fatty alcool

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

The monohydric aliphatic alcohols of six or more carbon atoms are generally referred to as higher alcohols. Historically, the higher alcohols,particularly those of 12 or more carbon atoms, were derived from natural fats, oils, and waxes and were called fatty alcohols (see FATS AND FATTY OILS);but now similar alcohols are widely available from synthetic processes using petrochemical feedstocks (qv). Although the natural and syntheticalcohols are used interchangeably for many applications, for some applications the distinction still remains. The higher alcohols can be separated intothe plasticizer range alcohols, generally 6−11 carbon atoms, and the detergent range alcohols, 12 or more carbon atoms. There is, however,considerable overlap in use. Production of higher alcohols in North America, Europe, and Japan in 1985 was about 2,600,000 tons and United Statesproduction was 35% of that total. About three-fourths of the U.S. output was plasticizer range alcohols, which are used primarily as ester derivativesin plasticizers (qv) and lubricants (see LUBRICATION AND LUBRICANTS). The detergent range alcohols are used mainly as sulfate, ethoxy, and ethoxysulfatederivatives in a wide variety of detergent and surfactant applications (see DETERGENCY; SURFACTANTS).

Most higher alcohols of commercial importance are primary alcohols; secondary alcohols have more limited specialty uses. Detergent rangealcohols are apt to be straight chain materials and are made either from natural fats and oils or by petrochemical processes. The plasticizer rangealcohols are more likely to be branched chain materials and are made primarily by petrochemical processes. Whereas alcohols made from natural fatsand oils are always linear, some petrochemical processes produce linear alcohols and others do not. Industrial manufacturing processes are discussedin SYNTHETIC PROCESSES.

Detergent Range Alcohols. Natural or synthetic detergent range alcohols are usually described as middle cut (12−15 carbon atoms) orheavy cut (16−18 carbon atoms), corresponding to the distillation fractions of coconut alcohol from which these alcohols were first derived. Becausemiddle cut alcohols are preferred for most detergent applications, manufacturers maximize this production through feedstock choice (naturalalcohols), or by manipulating processing conditions (synthetic alcohols). The coproduct light cut (6−11 carbon atoms) and heavy cut alcohols arealso valuable products. Only a small percentage of detergent range alcohols are sold as pure single carbon chain materials.

The higher alcohols occur in minor quantities primarily as the wax ester (ester of a fatty alcohol and a fatty acid) in many oilseed and marinesources. Free alcohols octacosanol [557-61-9], C28H58O, and triacontanol [28351-05-5], C32H66O, have been isolated in very small amounts fromsugarcane and its products (1). Oil from the sperm whale is rich in wax esters of hexadecanol, octadecenol, and eicosenol; this oil was formerly amajor commerical source of these alcohols. The oil of the North Atlantic barracudina fish contains 85% wax esters that consist mainly ofhexadecanol and octadecenol (2). Minor amounts of alcohols having 12−26 carbon atoms have been found in both ancient and recent marinesediments, probably having their origin in ocean marine life (3). Wool grease from sheep also contains higher alcohols as wax esters, and is a minorcommercial source of alcohol. The seeds of the shrub jojoba which grows in the North American desert give an oil which contains esters ofeicosenol and docosenol [629-98-1], and the natural waxes such as carnauba wax [8015-86-9] and candelilla wax [8006-44-8] contain wax esters withalcohols of 26−34 carbon atoms (4). Although higher alcohols could be obtained from any of these plant sources by saponification of the esters, theyare not commercially important sources.

Plasticizer Range Alcohols. Commercial products from the family of 6−11 carbon alcohols that make up the plasticizer range areavailable both as commercially pure single carbon chain materials and as complex isomeric mixtures. Commercial descriptions of plasticizer rangealcohols are rather confusing, but in general a commercially pure material is called "-anol," and the mixtures are called "-yl alcohol" or "iso...ylalcohol." For example, 2-ethylhexanol [104-76-7] and 4-methyl-2-pentanol [108-11-2] are single materials whereas isooctyl alcohol [68526-83-0] is acomplex mixture of branched hexanols and heptanols. Another commercial product contains linear alcohols of mixed 6-, 8-, and 10-carbon chains.

Physical Properties

Table 1 provides physical property data for selected pure alcohols (5). The homologous series of primary normal alcohols exhibits definite trends inphysical properties: for each additional CH2 unit the normal boiling point increases by about 20°C, the specific gravity increases by about 0.003units, and the melting point increases by about 10°C in the lower end of the range and about 4°C in the upper end. The water solubility decreaseswith increasing molecular weight and the oil solubility increases. In general, the higher alcohols are soluble in lower alcohols such as ethanol andmethanol and in diethyl ether and petroleum ether. The solubility of water in 1-hexanol and 1-octanol is appreciable, but drops off rapidly as alcoholmolecular weight increases. Enough solubility remains, however, to make even 1-octadecanol slightly hygroscopic. Mixtures of alcohols, such as1-octadecanol and 1-hexadecanol, are considerably more hygroscopic. Below C12 the normal alcohols are colorless, oily liquids with light, ratherfruity odors. At room temperature pure 1-dodecanol solidifies to soft, crystalline platelets and the physical form of higher molecular weight alcoholsprogresses from these soft platelets to crystalline waxes. Although 1-dodecanol has a slight odor, the higher homologues are essentially odorless. Thesecondary and branched primary alcohols are oily liquids at room temperature and have light, fruity odors. They are soluble in alcohol solvents anddiethyl ether, and also show less affinity for water as molecular weights increase. The members of this group do not have well-defined freezingpoints; they set to a glass at very low temperatures. Physical properties are often ill-defined because of difficulties in obtaining pure samples.

Table 1. Physical Properties of Pure Alcohols

Solubility, %by wt

IUPAC name CASRegistryNumber

Molecular

formula

Other commonnames

Specific

gravity,20°Ca

Refractive

index,20°Ca

Bp, °C,101.3kPab

Mp,°C

Viscosity,

mPa¢sa,c

in water ofwater

Solubility in othersolvents

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

The monohydric aliphatic alcohols of six or more carbon atoms are generally referred to as higher alcohols. Historically, the higher alcohols,particularly those of 12 or more carbon atoms, were derived from natural fats, oils, and waxes and were called fatty alcohols (see FATS AND FATTY OILS);but now similar alcohols are widely available from synthetic processes using petrochemical feedstocks (qv). Although the natural and syntheticalcohols are used interchangeably for many applications, for some applications the distinction still remains. The higher alcohols can be separated intothe plasticizer range alcohols, generally 6−11 carbon atoms, and the detergent range alcohols, 12 or more carbon atoms. There is, however,considerable overlap in use. Production of higher alcohols in North America, Europe, and Japan in 1985 was about 2,600,000 tons and United Statesproduction was 35% of that total. About three-fourths of the U.S. output was plasticizer range alcohols, which are used primarily as ester derivativesin plasticizers (qv) and lubricants (see LUBRICATION AND LUBRICANTS). The detergent range alcohols are used mainly as sulfate, ethoxy, and ethoxysulfatederivatives in a wide variety of detergent and surfactant applications (see DETERGENCY; SURFACTANTS).

Most higher alcohols of commercial importance are primary alcohols; secondary alcohols have more limited specialty uses. Detergent rangealcohols are apt to be straight chain materials and are made either from natural fats and oils or by petrochemical processes. The plasticizer rangealcohols are more likely to be branched chain materials and are made primarily by petrochemical processes. Whereas alcohols made from natural fatsand oils are always linear, some petrochemical processes produce linear alcohols and others do not. Industrial manufacturing processes are discussedin SYNTHETIC PROCESSES.

Detergent Range Alcohols. Natural or synthetic detergent range alcohols are usually described as middle cut (12−15 carbon atoms) orheavy cut (16−18 carbon atoms), corresponding to the distillation fractions of coconut alcohol from which these alcohols were first derived. Becausemiddle cut alcohols are preferred for most detergent applications, manufacturers maximize this production through feedstock choice (naturalalcohols), or by manipulating processing conditions (synthetic alcohols). The coproduct light cut (6−11 carbon atoms) and heavy cut alcohols arealso valuable products. Only a small percentage of detergent range alcohols are sold as pure single carbon chain materials.

The higher alcohols occur in minor quantities primarily as the wax ester (ester of a fatty alcohol and a fatty acid) in many oilseed and marinesources. Free alcohols octacosanol [557-61-9], C28H58O, and triacontanol [28351-05-5], C32H66O, have been isolated in very small amounts fromsugarcane and its products (1). Oil from the sperm whale is rich in wax esters of hexadecanol, octadecenol, and eicosenol; this oil was formerly amajor commerical source of these alcohols. The oil of the North Atlantic barracudina fish contains 85% wax esters that consist mainly ofhexadecanol and octadecenol (2). Minor amounts of alcohols having 12−26 carbon atoms have been found in both ancient and recent marinesediments, probably having their origin in ocean marine life (3). Wool grease from sheep also contains higher alcohols as wax esters, and is a minorcommercial source of alcohol. The seeds of the shrub jojoba which grows in the North American desert give an oil which contains esters ofeicosenol and docosenol [629-98-1], and the natural waxes such as carnauba wax [8015-86-9] and candelilla wax [8006-44-8] contain wax esters withalcohols of 26−34 carbon atoms (4). Although higher alcohols could be obtained from any of these plant sources by saponification of the esters, theyare not commercially important sources.

Plasticizer Range Alcohols. Commercial products from the family of 6−11 carbon alcohols that make up the plasticizer range areavailable both as commercially pure single carbon chain materials and as complex isomeric mixtures. Commercial descriptions of plasticizer rangealcohols are rather confusing, but in general a commercially pure material is called "-anol," and the mixtures are called "-yl alcohol" or "iso...ylalcohol." For example, 2-ethylhexanol [104-76-7] and 4-methyl-2-pentanol [108-11-2] are single materials whereas isooctyl alcohol [68526-83-0] is acomplex mixture of branched hexanols and heptanols. Another commercial product contains linear alcohols of mixed 6-, 8-, and 10-carbon chains.

Physical Properties

Table 1 provides physical property data for selected pure alcohols (5). The homologous series of primary normal alcohols exhibits definite trends inphysical properties: for each additional CH2 unit the normal boiling point increases by about 20°C, the specific gravity increases by about 0.003units, and the melting point increases by about 10°C in the lower end of the range and about 4°C in the upper end. The water solubility decreaseswith increasing molecular weight and the oil solubility increases. In general, the higher alcohols are soluble in lower alcohols such as ethanol andmethanol and in diethyl ether and petroleum ether. The solubility of water in 1-hexanol and 1-octanol is appreciable, but drops off rapidly as alcoholmolecular weight increases. Enough solubility remains, however, to make even 1-octadecanol slightly hygroscopic. Mixtures of alcohols, such as1-octadecanol and 1-hexadecanol, are considerably more hygroscopic. Below C12 the normal alcohols are colorless, oily liquids with light, ratherfruity odors. At room temperature pure 1-dodecanol solidifies to soft, crystalline platelets and the physical form of higher molecular weight alcoholsprogresses from these soft platelets to crystalline waxes. Although 1-dodecanol has a slight odor, the higher homologues are essentially odorless. Thesecondary and branched primary alcohols are oily liquids at room temperature and have light, fruity odors. They are soluble in alcohol solvents anddiethyl ether, and also show less affinity for water as molecular weights increase. The members of this group do not have well-defined freezingpoints; they set to a glass at very low temperatures. Physical properties are often ill-defined because of difficulties in obtaining pure samples.

Table 1. Physical Properties of Pure Alcohols

Solubility, %by wt

IUPAC name CASRegistryNumber

Molecular

formula

Other commonnames

Specific

gravity,20°Ca

Refractive

index,20°Ca

Bp, °C,101.3kPab

Mp,°C

Viscosity,

mPa¢sa,c

in water ofwater

Solubility in othersolvents

SURVEY AND NATURAL ALCOHOLS MANUFACTURE Vol 1

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 1

Primary normal aliphatic1-hexanol [111-27-3] C6H14O n-hexyl alcohol 0.8212 1.4181 157 ¡44 5.9 0.5920 7.2 petroleum ether,

ethanol1-heptanol [111-70-6] C7H16O n-heptyl alcohol 0.8238 1.4242 176 ¡35 7.4 0.1018

1-octanol [111-87-5] C8H18O n-octyl alcohol 0.8273 1.4296 195 ¡15:5 8.4 0.0625 4.5 ethanol,petroleum ether

1-nonanol [143-08-8] C9H20O n-nonyl alcohol 0.8295 1.4338 213 ¡5 11.71-decanol [112-30-1] C10H22O n-decyl alcohol 0.8312 1.4371 230 7 13.8 2.8 glacial acetic acid,

benzene, ethanol,petro-leum ether

1-undecanol [112-42-5] C11H24O n-undecylalcohol

0.8339 1.4402 243 16 17.2 <0:02

1-dodecanol [112-53-8] C12H26O n-dodecylalcohol, laurylalcohol

0.83062

51.4428 1381.33 24 18.8 i 1.3 petroleum ether,

ethanol

1-tridecanol [112-70-9] C13H28O n-tridecylalcohol

0.82383

11552.0 30.5

1-tetradecanol [112-72-1] C14H30O n-tetradecylalco-hol,myristyl alcohol

0.81655

01.435850 1581.33 38 <0:02 nil petroleum ether,

ethanol

1-pentadecanol [629-76-5] C15H32O n-pentadecylalcohol

1.440850 44

1-hexadecanol [36653-82-4]

C16H34O cetyl alcohol,palmityl alcohol

0.81576

01.439260 1771.33 49 5375 0.0620 nil ethanol,

methanol, diethylether, benzene

1-heptadecanol [1454-85-9]

C17H36O margarylalcohol

0.81676

01.439260 54

1-octadecanol [112-92-5] C18H38O stearyl alcohol,n-octadecylalcohol

0.81376

01.438860 2031.33 58 i nil

1-nonadecanol [1454-84-8]

C19H40O n-nonadecylalcohol

62

1-eicosanol [629-96-9] C20H42O eicosyl alcohol,arachidylalcohol

2511.33 66 i nil benzene, ethanol,petroleum ether

1-hexacosanol [506-52-5] C26H54O ceryl alcohol 3052.67 79.5 i ethanol, ether1-hentriacontanol [26444-39-

3]C31H64O melissyl alcohol,

myricyl alcohol0.77849

587 nil

9-hexadecen-1-ol [10378-01-5]

C16H32O palmitoleylalcohol

205−2102.

0

9-octadecen-1-ol [143-28-2] C18H36O oleyl alcohol 0.85045

81.447360 ethanol, diethyl

ether10-eicosen-1-ol [28061-39-

4]C20H40O eicosoyl alcohol

Primary branched aliphatic2-methyl-1-pentanol [105-30-6] C6H14O 2-methylpentyl

alcohol0.8254 1.4190 148 6.6 0.31 5.4

2-ethyl-1-butanol [97-95-0] C6H14O 2-ethylbutylalcohol

0.8348 1.4224 146.5 ¡114

2-ethyl-1-hexanol [104-76-7] C8H18O 2-ethylhexylalcohol

0.8340 1.4316 184 ¡70 9.8 0.07 2.6 ethanol, diethylether

3,5-dimethyl-1-hexanol

[13501-73-0]

C8H18O 0.8297 1.4250 182.5

2,2,4-trimethyl-1-pentanol

[123-44-4] C8H18O 0.839 1.4300 168 ¡70 ethanol

Secondary aliphatic4-methyl-2-pentanol [108-11-2] C6H14O methylamyl

alco-hol,methyliso-butylcarbinol


2-octanol [123-96-6] C8H18O capryl alcohol 0:83515=4 1.4256 178−179 ¡38 8.2 0.09625 ethanol,petroleum ether

2,6-dimethyl-4-heptanol

[108-82-7] C9H20O diisobutylcar-binol

0.8121 1.4231 178 ¡65 14.3 0.06 0.99

ethanol, diethylether

2,6,8-trimethyl-4-non [123-17-1] C12H26O 0.8193 1.4345 225 ¡60 21 <0:02 0.6

Primary normal aliphatic1-hexanol [111-27-3] C6H14O n-hexyl alcohol 0.8212 1.4181 157 ¡44 5.9 0.5920 7.2 petroleum ether,

ethanol1-heptanol [111-70-6] C7H16O n-heptyl alcohol 0.8238 1.4242 176 ¡35 7.4 0.1018

1-octanol [111-87-5] C8H18O n-octyl alcohol 0.8273 1.4296 195 ¡15:5 8.4 0.0625 4.5 ethanol,petroleum ether

1-nonanol [143-08-8] C9H20O n-nonyl alcohol 0.8295 1.4338 213 ¡5 11.71-decanol [112-30-1] C10H22O n-decyl alcohol 0.8312 1.4371 230 7 13.8 2.8 glacial acetic acid,

benzene, ethanol,petro-leum ether

1-undecanol [112-42-5] C11H24O n-undecylalcohol

0.8339 1.4402 243 16 17.2 <0:02

1-dodecanol [112-53-8] C12H26O n-dodecylalcohol, laurylalcohol

0.83062

51.4428 1381.33 24 18.8 i 1.3 petroleum ether,

ethanol

1-tridecanol [112-70-9] C13H28O n-tridecylalcohol

0.82383

11552.0 30.5

1-tetradecanol [112-72-1] C14H30O n-tetradecylalco-hol,myristyl alcohol

0.81655

01.435850 1581.33 38 <0:02 nil petroleum ether,

ethanol

1-pentadecanol [629-76-5] C15H32O n-pentadecylalcohol

1.440850 44

1-hexadecanol [36653-82-4]

C16H34O cetyl alcohol,palmityl alcohol

0.81576

01.439260 1771.33 49 5375 0.0620 nil ethanol,

methanol, diethylether, benzene

1-heptadecanol [1454-85-9]

C17H36O margarylalcohol

0.81676

01.439260 54

1-octadecanol [112-92-5] C18H38O stearyl alcohol,n-octadecylalcohol

0.81376

01.438860 2031.33 58 i nil

1-nonadecanol [1454-84-8]

C19H40O n-nonadecylalcohol

62

1-eicosanol [629-96-9] C20H42O eicosyl alcohol,arachidylalcohol

2511.33 66 i nil benzene, ethanol,petroleum ether

1-hexacosanol [506-52-5] C26H54O ceryl alcohol 3052.67 79.5 i ethanol, ether1-hentriacontanol [26444-39-

3]C31H64O melissyl alcohol,

myricyl alcohol0.77849

587 nil

9-hexadecen-1-ol [10378-01-5]

C16H32O palmitoleylalcohol

205−2102.

0

9-octadecen-1-ol [143-28-2] C18H36O oleyl alcohol 0.85045

81.447360 ethanol, diethyl

ether10-eicosen-1-ol [28061-39-

4]C20H40O eicosoyl alcohol

Primary branched aliphatic2-methyl-1-pentanol [105-30-6] C6H14O 2-methylpentyl

alcohol0.8254 1.4190 148 6.6 0.31 5.4

2-ethyl-1-butanol [97-95-0] C6H14O 2-ethylbutylalcohol

0.8348 1.4224 146.5 ¡114

2-ethyl-1-hexanol [104-76-7] C8H18O 2-ethylhexylalcohol


3,5-dimethyl-1-hexanol

[13501-73-0]

C8H18O 0.8297 1.4250 182.5

2,2,4-trimethyl-1-pentanol

[123-44-4] C8H18O 0.839 1.4300 168 ¡70 ethanol

Secondary aliphatic4-methyl-2-pentanol [108-11-2] C6H14O methylamyl

alco-hol,methyliso-butylcarbinol


2-octanol [123-96-6] C8H18O capryl alcohol 0:83515=4 1.4256 178−179 ¡38 8.2 0.09625 ethanol,petroleum ether

2,6-dimethyl-4-heptanol

[108-82-7] C9H20O diisobutylcar-binol

0.8121 1.4231 178 ¡65 14.3 0.06 0.99

ethanol, diethylether

2,6,8-trimethyl-4-non [123-17-1] C12H26O 0.8193 1.4345 225 ¡60 21 <0:02 0.6



anol 0a Temperature, °C, if other than 20°C, is noted as superscript.b Pressure, kPa, if other than 101.3 kPa, is noted as superscript. To convert kPa to mm Hg, multiply by 7.50.c mPa¢s =cP.

Chemical Properties

The higher alcohols undergo the same chemical reactions as other primary or secondary alcohols. Similar to other chemicals having long carbonchains, however, reactivity decreases as molecular weight or chain branching increase. This lower reactivity and concommitant decreased solubility inwater and in other solvents means that more rigorous reaction conditions, or even use of different reaction schemes as compared to shorter chainalcohols, are generally required. Typical reactions of the higher alcohols are as shown.

Esterification

ROH+ R0COOH ! R0COOR+ H2O

Sulfation

ROH+ SO3 ! ROSO3H

alkyl sulfuric acid

ROSO3H+NaOH ! ROSO3Na + H2O

sodium alkyl sulfate

Etherification

Halogenation

3 ROH + PCl3 ! 3 RCl + P(OH) 3

Dehydration

RCH2CH2OH ! RCH||CH2 +H2O

Oxidation

RCH2OH+1=2 O2 ! RCH||O+H2O

Amination

ROH+ R0NH2 ! RNHR0 + H2O

Oxidation (6,7) and amination (8,9) are discussed in detail elsewhere.

Shipment and Storage

Detergent range alcohols are available in 208-L (55-gal) drums of approximately 160-kg or 23,000-L (6000-gal) tank trucks, in tank cars of 75,000 L(20,000 gal) containing about 60,000 kg, and in marine barges. The tank trucks and cars are usually insulated and equipped with an external heatingjacket; the barges have coils for melting and heating the alcohols. High melting alcohols such as hexadecanol and octadecanol are also available asflaked material in three-ply, polyethylene-lined 22.7 kg (50 lb) bags. Detergent range alcohols have a U.S. Department of Transportationclassification as nonhazardous for shipment. The perfume-grade alcohols, such as specially purified octanol and decanol, are available in bottles andcans; other plasticizer range materials are available in 208-L drums, 23,000-L tank trucks, 75,000-L tank cars, and in marine barges. Because of lowmelting points, most of these materials do not require transports having heating equipment. Bulk shipments are usually described by the commercialname of the material, such as methylisobutylcarbinol for 4-methyl-2-pentanol. The names hexyl, octyl, or decyl alcohol are used as freightdescriptions for the linear or branched alcohols of corresponding carbon number. Linear and branched alcohols of 6−9 carbon atoms, and mixturescontaining them, are classified as combustible for shipment by the U.S. DOT because of their low flash points. Alcohols of 10 carbons and aboveare classified as nonhazardous.

The higher alcohols are not corrosive to carbon steel, and equipment suitable for handling solvents or gasoline is also suitable for the

anol 0a Temperature, °C, if other than 20°C, is noted as superscript.b Pressure, kPa, if other than 101.3 kPa, is noted as superscript. To convert kPa to mm Hg, multiply by 7.50.c mPa¢s =cP.

Chemical Properties

The higher alcohols undergo the same chemical reactions as other primary or secondary alcohols. Similar to other chemicals having long carbonchains, however, reactivity decreases as molecular weight or chain branching increase. This lower reactivity and concommitant decreased solubility inwater and in other solvents means that more rigorous reaction conditions, or even use of different reaction schemes as compared to shorter chainalcohols, are generally required. Typical reactions of the higher alcohols are as shown.

Esterification

ROH+ R0COOH ! R0COOR+ H2O

Sulfation

ROH+ SO3 ! ROSO3H

alkyl sulfuric acid

ROSO3H+NaOH ! ROSO3Na + H2O

sodium alkyl sulfate

Etherification

Halogenation

3 ROH + PCl3 ! 3 RCl + P(OH) 3

Dehydration

RCH2CH2OH ! RCH||CH2 +H2O

Oxidation

RCH2OH+1=2 O2 ! RCH||O+H2O

Amination

ROH+ R0NH2 ! RNHR0 + H2O

Oxidation (6,7) and amination (8,9) are discussed in detail elsewhere.

Shipment and Storage

Detergent range alcohols are available in 208-L (55-gal) drums of approximately 160-kg or 23,000-L (6000-gal) tank trucks, in tank cars of 75,000 L(20,000 gal) containing about 60,000 kg, and in marine barges. The tank trucks and cars are usually insulated and equipped with an external heatingjacket; the barges have coils for melting and heating the alcohols. High melting alcohols such as hexadecanol and octadecanol are also available asflaked material in three-ply, polyethylene-lined 22.7 kg (50 lb) bags. Detergent range alcohols have a U.S. Department of Transportationclassification as nonhazardous for shipment. The perfume-grade alcohols, such as specially purified octanol and decanol, are available in bottles andcans; other plasticizer range materials are available in 208-L drums, 23,000-L tank trucks, 75,000-L tank cars, and in marine barges. Because of lowmelting points, most of these materials do not require transports having heating equipment. Bulk shipments are usually described by the commercialname of the material, such as methylisobutylcarbinol for 4-methyl-2-pentanol. The names hexyl, octyl, or decyl alcohol are used as freightdescriptions for the linear or branched alcohols of corresponding carbon number. Linear and branched alcohols of 6−9 carbon atoms, and mixturescontaining them, are classified as combustible for shipment by the U.S. DOT because of their low flash points. Alcohols of 10 carbons and aboveare classified as nonhazardous.

The higher alcohols are not corrosive to carbon steel, and equipment suitable for handling solvents or gasoline is also suitable for the



alcohols. However, special storage conditions are often needed to maintain alcohol quality. Lined carbon steel tanks having nitrogen blankets toexclude both moisture and oxygen are recommended for storage of detergent range alcohols (10). Preferred storage temperature is no higher than10°C above the alcohol melting point and repeated cycles of melting and solidifying must be avoided. Low pressure steam is generally used forheating; for the high melting hexadecanol and octadecanol, hot water can be used in order to reduce exposure to high temperature heating surfaces.Although they are generally considered quite stable, alcohols which are stored either for long periods of time or under improper conditions canundergo such subtle changes as deterioration of color, increase in carbonyl level, or a decrease in acid heat stability. It is sometimes preferable tostore high melting alcohols as flakes in bags at ambient temperature rather than melted in a tank at higher temperature.

To prevent rusting and moisture pickup resulting from the hygroscopic nature of plasticizer range alcohols, tanks should be protected frommoisture by such devices as a drying tube on the tank or a dry air blanket; nitrogen is usually not needed because ambient storage temperature isadequate for these lower melting materials. In general, plasticizer range alcohols are more storage-stable than the detergent range alcohols. However,to avoid the danger of fire resulting from the low flash points of plasticizer range alcohols, tanks should be grounded, have no interior sources ofignition, be filled from the bottom or have a filling line extending to the bottom to prevent static sparks, and be equipped with flame arrestors.

Economic Aspects

United States production of detergent range alcohol was 354,000 t in 1987, according to the U.S. International Trade Commission, compared to263,000 t in 1974. About 60% was sold as alcohol on the merchant market; most of the rest was ethoxylated by the producers, then sold as theethoxylated alcohol or sulfated and sold as the ethoxysulfate surfactant. In the 1960s and early 1970s ethylene-based synthetic alcohols appeared tobe the wave of the future. Increases in petroleum prices and stabilization in the price of coconut and palm kernel oils, the primary raw materials forhigher alcohols, have led back to natural production. Most alcohol capacity installed in the 1980s uses catalytic hydrogenolysis processes employingnatural fats and oils as feedstock to make alcohol. Fatty alcohol capacity is increasingly being built in the coconut and palm oil producing countries.A number of natural alcohol plants have started up or are in various stages of construction in the Philippines, Malaysia, and Indonesia. In the UnitedStates however, the lion's share of detergent range alcohol production is by synthetic processes; Shell Chemical is the largest producer in a planthaving a 270,000-t capacity. Linear synthetic alcohols can be used interchangeably with natural alcohols except where the presence of minor amountsof chain branching or secondary alcohols preclude use of the synthetics. The more highly branched alcohols are used where branching is not aproblem, is desired, or the alcohols are ethoxylated. Ethoxylation reduces the physical and chemical effects of chain branching. Domestic detergentrange alcohol producers are shown in Table 2; representative prices are given in Table 3. Manufacturers often adjust coproduct alcohol prices tocompensate for shortages or surpluses, keeping the price of the primary material stable.

Table 2. U.S. Manufacturers of Detergent Range Alcohols

Manufacturer Process Feedstock ProductsProcter & Gamble catalytic hydrogenolysis coconut and palm kernel oils,

tallow, palm oilC6¡C18

Sherex catalytic hydrogenolysis tallow C16, C18, oleylShell Chemical modified oxo ethylene/olefins C9−C15Vista Ziegler ethylene C6−C22Ethyl modified Ziegler ethylene C6−C22Exxon modified oxo olefins C13, C15

Table 3. Prices of Detergent Range Alcoholsa

Alcohol Price, U.S.$/kglauryl alcohol, fob 1.54dodecanol/tridecanol, delivered 1.26hexadecanol, fob 2.01octadecanol, fob 2.01

a November 1989 list prices.

United States production of plasticizer range alcohols was estimated to be 690,000 t in 1988 (11), 44% of which was 2-ethylhexanol.Domestic manufacturers and prices of representative plasticizer range alcohols are given in Table 4. The previous decade has seen a reduction in thenumber of manufacturers of 2-ethylhexanol and other branched chain alcohols. The volume of most branched alcohols has been static, however,and 2-ethylhexanol volume has doubled; the volume of linear alcohols has also grown. A substantial portion of these materials is used in plasticizersfor poly(vinyl chloride) (PVC), so plasticizer range alcohol fortunes are tied to variations in the PVC industry. The plasticizers are mainly diesters ofthe alcohols and phthalic acid; di(2-ethylhexyl) phthalate [117-81-7] is the highest volume product. Recent price and volume history of2-ethylhexanol is given in Table 5. Other branched alcohols tend to be priced at, or slightly above, the price of 2-ethylhexanol; the linear alcohols areseveral cents per kilogram higher. Production costs of plasticizer range alcohols, manufactured either by oxo or Ziegler processes, are stronglydependent on the cost of the ethylene or propylene feedstocks, making them dependent on the cost of crude oil and natural gas.

alcohols. However, special storage conditions are often needed to maintain alcohol quality. Lined carbon steel tanks having nitrogen blankets toexclude both moisture and oxygen are recommended for storage of detergent range alcohols (10). Preferred storage temperature is no higher than10°C above the alcohol melting point and repeated cycles of melting and solidifying must be avoided. Low pressure steam is generally used forheating; for the high melting hexadecanol and octadecanol, hot water can be used in order to reduce exposure to high temperature heating surfaces.Although they are generally considered quite stable, alcohols which are stored either for long periods of time or under improper conditions canundergo such subtle changes as deterioration of color, increase in carbonyl level, or a decrease in acid heat stability. It is sometimes preferable tostore high melting alcohols as flakes in bags at ambient temperature rather than melted in a tank at higher temperature.

To prevent rusting and moisture pickup resulting from the hygroscopic nature of plasticizer range alcohols, tanks should be protected frommoisture by such devices as a drying tube on the tank or a dry air blanket; nitrogen is usually not needed because ambient storage temperature isadequate for these lower melting materials. In general, plasticizer range alcohols are more storage-stable than the detergent range alcohols. However,to avoid the danger of fire resulting from the low flash points of plasticizer range alcohols, tanks should be grounded, have no interior sources ofignition, be filled from the bottom or have a filling line extending to the bottom to prevent static sparks, and be equipped with flame arrestors.

Economic Aspects

United States production of detergent range alcohol was 354,000 t in 1987, according to the U.S. International Trade Commission, compared to263,000 t in 1974. About 60% was sold as alcohol on the merchant market; most of the rest was ethoxylated by the producers, then sold as theethoxylated alcohol or sulfated and sold as the ethoxysulfate surfactant. In the 1960s and early 1970s ethylene-based synthetic alcohols appeared tobe the wave of the future. Increases in petroleum prices and stabilization in the price of coconut and palm kernel oils, the primary raw materials forhigher alcohols, have led back to natural production. Most alcohol capacity installed in the 1980s uses catalytic hydrogenolysis processes employingnatural fats and oils as feedstock to make alcohol. Fatty alcohol capacity is increasingly being built in the coconut and palm oil producing countries.A number of natural alcohol plants have started up or are in various stages of construction in the Philippines, Malaysia, and Indonesia. In the UnitedStates however, the lion's share of detergent range alcohol production is by synthetic processes; Shell Chemical is the largest producer in a planthaving a 270,000-t capacity. Linear synthetic alcohols can be used interchangeably with natural alcohols except where the presence of minor amountsof chain branching or secondary alcohols preclude use of the synthetics. The more highly branched alcohols are used where branching is not aproblem, is desired, or the alcohols are ethoxylated. Ethoxylation reduces the physical and chemical effects of chain branching. Domestic detergentrange alcohol producers are shown in Table 2; representative prices are given in Table 3. Manufacturers often adjust coproduct alcohol prices tocompensate for shortages or surpluses, keeping the price of the primary material stable.

Table 2. U.S. Manufacturers of Detergent Range Alcohols

Manufacturer Process Feedstock ProductsProcter & Gamble catalytic hydrogenolysis coconut and palm kernel oils,

tallow, palm oilC6¡C18

Sherex catalytic hydrogenolysis tallow C16, C18, oleylShell Chemical modified oxo ethylene/olefins C9−C15Vista Ziegler ethylene C6−C22Ethyl modified Ziegler ethylene C6−C22Exxon modified oxo olefins C13, C15

Table 3. Prices of Detergent Range Alcoholsa

Alcohol Price, U.S.$/kglauryl alcohol, fob 1.54dodecanol/tridecanol, delivered 1.26hexadecanol, fob 2.01octadecanol, fob 2.01

a November 1989 list prices.

United States production of plasticizer range alcohols was estimated to be 690,000 t in 1988 (11), 44% of which was 2-ethylhexanol.Domestic manufacturers and prices of representative plasticizer range alcohols are given in Table 4. The previous decade has seen a reduction in thenumber of manufacturers of 2-ethylhexanol and other branched chain alcohols. The volume of most branched alcohols has been static, however,and 2-ethylhexanol volume has doubled; the volume of linear alcohols has also grown. A substantial portion of these materials is used in plasticizersfor poly(vinyl chloride) (PVC), so plasticizer range alcohol fortunes are tied to variations in the PVC industry. The plasticizers are mainly diesters ofthe alcohols and phthalic acid; di(2-ethylhexyl) phthalate [117-81-7] is the highest volume product. Recent price and volume history of2-ethylhexanol is given in Table 5. Other branched alcohols tend to be priced at, or slightly above, the price of 2-ethylhexanol; the linear alcohols areseveral cents per kilogram higher. Production costs of plasticizer range alcohols, manufactured either by oxo or Ziegler processes, are stronglydependent on the cost of the ethylene or propylene feedstocks, making them dependent on the cost of crude oil and natural gas.



Table 4. Prices and Manufacturers of Plasticizer Range Alcohols

Material Price, U.S.$/kga Manufacturerhexanol 1.74 Ethyl

Vista4-methyl-2-pentanol 1.32 Union Carbideoctanol 2.01 Ethyl

Vistaoctanol, perfumer's grade 3.09isooctyl alcohol 0.97 Exxon2-ethylhexanol 0.93 BASF

EastmanShell ChemicalTenn-USSUnion Carbide

decanol 1.34 EthylVista

decanol, perfumer's grade 1.65a Delivered price May 1989. The listed price is not necessarily the price listed by the indicated manufacturer.

Table 5. Price and Production Volume of 2-Ethylhexanola

Year Price, U.S.$/kg Volume, 103 t/yr1988 0.73 3371987 0.60 3001986 0.55 2591985 0.60 2431984 0.71 2451983 0.71 175

a Ref. 12.

Most manufacturers sell a portion of their alcohol product on the merchant market, retaining a portion for internal use, typically for themanufacture of plasticizers. Sterling Chemicals' linear alcohol of 7, 9, and 11 carbons is all used captively. Plasticizer range linear alcohols derivedfrom natural fats and oils, for instance, octanol and decanol derived from coconut oil and 2-octanol derived from castor oil, are of only minorimportance in the marketplace. The 13−carbon tridecyl alcohol is usually considered to be a plasticizer range alcohol because of its manufacture bythe oxo process and its use in making plasticizers. On the other hand, some types of linear 9- and 11-carbon alcohols find major application indetergents.

Analysis

Because the higher alcohols are made by a number of processes and from different raw materials, analytical procedures are designed to yield threekinds of information: the carbon chain length distribution, or combining weight, of the alcohols present; the purity of the material; and the presenceof minor impurities and contaminants that would interfere with subsequent use of the product. Analytical methods and characterization of alcoholshave been summarized (13).

For the detergent range alcohols, capillary gas chromatography, fast, accurate, and simple to use, is by far the most useful method fordetermining composition and purity (14). By the proper choice of the capillary stationary phase, carbon chain distribution and the amount ofunsaturated, chain branched, or secondary alcohols, as well as the level of minor materials such as esters and hydrocarbons, can be determined.Hydroxyl Value (HV = mg of KOH equivalent to the hydroxyl content of 1 g of alcohol) measures the |OH end group and reflects both thecombining weight and the purity of the sample. Saponification Value (SV = mg of KOH required to saponify the esters and acids in 1 g of alcohol),Acid Value (AV = mg of KOH required to neutralize the free fatty acid in 1 g of alcohol), and Ester Value (EV = SV minus AV) are measures of thecarboxylic acid impurities present as the free acids or esters. Iodine Value (IV = g of iodine absorbed by 100 g of alcohol) is a measure ofcarbon−carbon unsaturation present in the alcohol. HV, SV, AV, EV, and IV can all be calculated from the capillary GC analysis. Moisture is also animportant criterion of alcohol quality, and the color of the alcohol, usually determined by the APHA (Pt−Co) method, should be as close towater-white as possible. A number of other tests measure attributes important to specific uses. Examples are melting point for the heavy cutalcohols, cloud point of unsaturated alcohols, odor, carbonyl content, peroxide content, and various color stability tests. One of these last is the acidheat stability test. It determines the color change of middle cut alcohol in contact with concentrated sulfuric acid at an elevated temperature as anindex of the color of alkyl sulfates that would be made from the alcohol. Test outcome is affected by carbonyl at a level of a few hundred parts permillion, and by traces of iron, rust, and dirt particles.

As for detergent range alcohols, extensive use of capillary gas chromatography is also made for composition and purity determination of theplasticizer range materials. For those products that are a broad mixture of various isomers, however, distillation range and Hydroxyl Value are moreuseful characterizations. From the HV the combining weight can be calculated for subsequent chemical reactions. Carbonyl content is important,

Table 4. Prices and Manufacturers of Plasticizer Range Alcohols

Material Price, U.S.$/kga Manufacturerhexanol 1.74 Ethyl

Vista4-methyl-2-pentanol 1.32 Union Carbideoctanol 2.01 Ethyl

Vistaoctanol, perfumer's grade 3.09isooctyl alcohol 0.97 Exxon2-ethylhexanol 0.93 BASF

EastmanShell ChemicalTenn-USSUnion Carbide

decanol 1.34 EthylVista

decanol, perfumer's grade 1.65a Delivered price May 1989. The listed price is not necessarily the price listed by the indicated manufacturer.

Table 5. Price and Production Volume of 2-Ethylhexanola

Year Price, U.S.$/kg Volume, 103 t/yr1988 0.73 3371987 0.60 3001986 0.55 2591985 0.60 2431984 0.71 2451983 0.71 175

a Ref. 12.

Most manufacturers sell a portion of their alcohol product on the merchant market, retaining a portion for internal use, typically for themanufacture of plasticizers. Sterling Chemicals' linear alcohol of 7, 9, and 11 carbons is all used captively. Plasticizer range linear alcohols derivedfrom natural fats and oils, for instance, octanol and decanol derived from coconut oil and 2-octanol derived from castor oil, are of only minorimportance in the marketplace. The 13−carbon tridecyl alcohol is usually considered to be a plasticizer range alcohol because of its manufacture bythe oxo process and its use in making plasticizers. On the other hand, some types of linear 9- and 11-carbon alcohols find major application indetergents.

Analysis

Because the higher alcohols are made by a number of processes and from different raw materials, analytical procedures are designed to yield threekinds of information: the carbon chain length distribution, or combining weight, of the alcohols present; the purity of the material; and the presenceof minor impurities and contaminants that would interfere with subsequent use of the product. Analytical methods and characterization of alcoholshave been summarized (13).

For the detergent range alcohols, capillary gas chromatography, fast, accurate, and simple to use, is by far the most useful method fordetermining composition and purity (14). By the proper choice of the capillary stationary phase, carbon chain distribution and the amount ofunsaturated, chain branched, or secondary alcohols, as well as the level of minor materials such as esters and hydrocarbons, can be determined.Hydroxyl Value (HV = mg of KOH equivalent to the hydroxyl content of 1 g of alcohol) measures the |OH end group and reflects both thecombining weight and the purity of the sample. Saponification Value (SV = mg of KOH required to saponify the esters and acids in 1 g of alcohol),Acid Value (AV = mg of KOH required to neutralize the free fatty acid in 1 g of alcohol), and Ester Value (EV = SV minus AV) are measures of thecarboxylic acid impurities present as the free acids or esters. Iodine Value (IV = g of iodine absorbed by 100 g of alcohol) is a measure ofcarbon−carbon unsaturation present in the alcohol. HV, SV, AV, EV, and IV can all be calculated from the capillary GC analysis. Moisture is also animportant criterion of alcohol quality, and the color of the alcohol, usually determined by the APHA (Pt−Co) method, should be as close towater-white as possible. A number of other tests measure attributes important to specific uses. Examples are melting point for the heavy cutalcohols, cloud point of unsaturated alcohols, odor, carbonyl content, peroxide content, and various color stability tests. One of these last is the acidheat stability test. It determines the color change of middle cut alcohol in contact with concentrated sulfuric acid at an elevated temperature as anindex of the color of alkyl sulfates that would be made from the alcohol. Test outcome is affected by carbonyl at a level of a few hundred parts permillion, and by traces of iron, rust, and dirt particles.

As for detergent range alcohols, extensive use of capillary gas chromatography is also made for composition and purity determination of theplasticizer range materials. For those products that are a broad mixture of various isomers, however, distillation range and Hydroxyl Value are moreuseful characterizations. From the HV the combining weight can be calculated for subsequent chemical reactions. Carbonyl content is important,



especially for those alcohols manufactured from aldehydes by the oxo process. It is often expressed similarly to HV: as the mg of KOH equivalentto the carbonyl oxygen in 1 g of sample. Acidity, expressed in terms of the equivalent weight percent of acetic acid, is used to determine the qualityof the alcohol, as are moisture and APHA color. As with the detergent range alcohols, tests which measure color stability in the presence of sulfuricacid are employed to predict the color changes that may occur in subsequent reactions utilizing acid catalysts. Additionally, analytical determinationssuch as odor, chloride level, hydrocarbon content, and trace metal content, are required for specific uses.

Specifications and Standards

Most of the detergent range alcohols used commercially consist of mixtures of alcohols, and a wide variety of products is available. Table 6 showsthe approximate carbon chain length composition of both the commonly used mixtures and single carbon materials; typical properties are given inTable 7. The range of commercially available materials is further described in sales brochures published by the manufacturers (15), who usually canalso provide specially tailored blends to meet individual customer needs. Although only even-carbon alcohols are available from natural fats and oilsand the Ziegler process, the development of the oxo process for linear alcohols has made odd-carbon alcohols a commercial reality, albeit with somechain branching. Commercial mixtures of these latter alcohols contain both odd and even numbered chain lengths. The major production ofdetergent range alcohols is in the 12−18 carbon range. Alcohols with 20 carbons and above are available in mixtures such as Vista's Alfol 20+ andEthyl's Epal 20+. Behenyl alcohol (docosanol) [661-19-8], C22H46O, can be made from rapeseed oil. Except for oleyl alcohol, all commercialalcohols are fully saturated.

Table 6. Composition of Commercial Detergent Range Alcoholsa

Alcoholcommercial name

Representative trade name Derived from C12 C13 C14 C16 C18 C20

lauryl CO-1214b [67762-41-8] coconut, palm kernel 68 26 6

Alfol 1214c ethylene 55 45

Epal 1214d ethylene 66 27 7

Neodol 23e ethylene 41 57 1Epal 1218 [67762-25-8] ethylene 49 20 17 14Lauryl Alcohol Special-Typef coconut 72 27 1Epal 12 ethylene 99 1

myristyl Alfol 14 ethylene 1 99 1cetyl CO-1695 [36653-82-4] vegetable oil 98 2

Epal 16 ethylene 1 98 1tallow TA-1618b [67762-30-5] tallow 2 27 70h 1

Adol 64g fats 4 26 70stearyl CO-1897 vegetable oil 1 98 1oleyl HD Oleyl Alcohol Df fats 5 94i 1

Adol 80 fats 4 14 81i 1a Approximate composition by wt %, 100% alcohol basis.b Registered trademark for Procter & Gamble alcohols.c Registered trademark for Vista alcohols.d Registered trademark for Ethyl Corporation alcohols.e Registered trademark for Shell alcohols.f Registered trademark for Henkel alcohols.h Includes 1% C17 alcohol.g Registered trademark for Sherex alcohols.i Primarily unsaturated.

Table 7. Properties of Commercial Linear Detergent Range Alcohols

Commercialdescriptive name

Hydroxyl Value

SaponificationValue

AcidValu

e

Iodine

Value

Meltingpoint,°C

Color,APH

A

Moisture,%

lauryl (99% C12) 301 0.2 0.02 0.2 23−25 5 0.03lauryl (68% C12) 285 0.2 0.01 0 22 3 0.04

C12−C13a 289 0.02 18−22 5 0.02

cetyl 229 0.4 0 0.6 49 6−10 0.04tallow 208 1.8 0 0.5 53 10−20 0.03

especially for those alcohols manufactured from aldehydes by the oxo process. It is often expressed similarly to HV: as the mg of KOH equivalentto the carbonyl oxygen in 1 g of sample. Acidity, expressed in terms of the equivalent weight percent of acetic acid, is used to determine the qualityof the alcohol, as are moisture and APHA color. As with the detergent range alcohols, tests which measure color stability in the presence of sulfuricacid are employed to predict the color changes that may occur in subsequent reactions utilizing acid catalysts. Additionally, analytical determinationssuch as odor, chloride level, hydrocarbon content, and trace metal content, are required for specific uses.

Specifications and Standards

Most of the detergent range alcohols used commercially consist of mixtures of alcohols, and a wide variety of products is available. Table 6 showsthe approximate carbon chain length composition of both the commonly used mixtures and single carbon materials; typical properties are given inTable 7. The range of commercially available materials is further described in sales brochures published by the manufacturers (15), who usually canalso provide specially tailored blends to meet individual customer needs. Although only even-carbon alcohols are available from natural fats and oilsand the Ziegler process, the development of the oxo process for linear alcohols has made odd-carbon alcohols a commercial reality, albeit with somechain branching. Commercial mixtures of these latter alcohols contain both odd and even numbered chain lengths. The major production ofdetergent range alcohols is in the 12−18 carbon range. Alcohols with 20 carbons and above are available in mixtures such as Vista's Alfol 20+ andEthyl's Epal 20+. Behenyl alcohol (docosanol) [661-19-8], C22H46O, can be made from rapeseed oil. Except for oleyl alcohol, all commercialalcohols are fully saturated.

Table 6. Composition of Commercial Detergent Range Alcoholsa

Alcoholcommercial name

Representative trade name Derived from C12 C13 C14 C16 C18 C20

lauryl CO-1214b [67762-41-8] coconut, palm kernel 68 26 6

Alfol 1214c ethylene 55 45

Epal 1214d ethylene 66 27 7

Neodol 23e ethylene 41 57 1Epal 1218 [67762-25-8] ethylene 49 20 17 14Lauryl Alcohol Special-Typef coconut 72 27 1Epal 12 ethylene 99 1

myristyl Alfol 14 ethylene 1 99 1cetyl CO-1695 [36653-82-4] vegetable oil 98 2

Epal 16 ethylene 1 98 1tallow TA-1618b [67762-30-5] tallow 2 27 70h 1

Adol 64g fats 4 26 70stearyl CO-1897 vegetable oil 1 98 1oleyl HD Oleyl Alcohol Df fats 5 94i 1

Adol 80 fats 4 14 81i 1a Approximate composition by wt %, 100% alcohol basis.b Registered trademark for Procter & Gamble alcohols.c Registered trademark for Vista alcohols.d Registered trademark for Ethyl Corporation alcohols.e Registered trademark for Shell alcohols.f Registered trademark for Henkel alcohols.h Includes 1% C17 alcohol.g Registered trademark for Sherex alcohols.i Primarily unsaturated.

Table 7. Properties of Commercial Linear Detergent Range Alcohols

Commercialdescriptive name

Hydroxyl Value

SaponificationValue

AcidValu

e

Iodine

Value

Meltingpoint,°C

Color,APH

A

Moisture,%

lauryl (99% C12) 301 0.2 0.02 0.2 23−25 5 0.03lauryl (68% C12) 285 0.2 0.01 0 22 3 0.04

C12−C13a 289 0.02 18−22 5 0.02

cetyl 229 0.4 0 0.6 49 6−10 0.04tallow 208 1.8 0 0.5 53 10−20 0.03



stearyl 206 0.5 0 0.7 58 6−15 0.03oleyl 206 0.5 94 4

a Neodol 23 (registered trademark for Shell alcohols).

Both detergent range and plasticizer range alcohols and their derivatives have been accepted by the U.S. government for use in a number ofdrug and food contact or food additive areas, and plasticizer range alcohols have been accepted as flavoring agents in foods (16). They must meetrigid manufacture, quality control, and record keeping requirements. Hexadecanol and octadecanol are used extensively in drug and cosmetic areaswhich require drug-grade raw materials. For this application they are produced to the specifications of the National Formulary (NF) in facilitiesregistered by the U.S. Food and Drug Administration. The NF requirements for hexadecanol are 45−50°C melting point, 2.0 max AV, 5.0 max IV,and 218−238 HV. The NF requirements for octadecanol are 55−60°C melting point, 2.0 max AV, 2.0 max IV, 200−220 HV, and 90% min.octadecanol.

Besides the linear detergent range alcohols, a number of highly branched alcohols of 12 or more carbon atoms made by the oxo process areof commercial importance. Tridecyl alcohol [27458-92-0], C13H28O, consisting mainly of tetramethyl-1-nonanols, is one such material; it is generallyconsidered to be a plasticizer range alcohol because of its manufacturing process and use in making plasticizers. Primary alcohols made by theGuerbet process, consisting of alcohols characterized as 2,2-dialkyl-1-ethanols, are available as hexadecyl [68526-87-4], C16H34O, octadecyl[27458-93-1], C18H38O, eicosyl [52655-10-4], C20H42O, and hexacosyl [70693-05-9], C26H54O, materials sold by Exxon under the Exxal brand name(17). They should not be confused with linear alcohols having similar names. Isostearyl alcohol [27458-93-1] is a highly branched natural alcoholcontaining a mixture of C18 alcohols derived from isostearic acid.

The sales brochures of the manufacturers describe the plasticizer range alcohols available on the merchant market (18). Typical properties ofseveral commercial plasticizer range alcohols are presented in Table 8. Because in most cases these are mixtures of isomers or alcohols with severalcarbon chains, the properties of a particular material can vary somewhat from manufacturer to manufacturer. Both odd and even carbon chainalcohols are available, in both linear and highly branched versions. Examples of the composition of several mixtures are given in Table 9.

Table 8. Typical Properties of Commercial Plasticizer Range Alcohols

Name Molecularformula

Hydroxyl Value

Acidity, %as acetic

Carbonyl,wt % O

Boiling range,°C

Color,APH

A

Moisture,%

Flash pointa,°C

hexyl (C6H14O) 0.001 <0:003 152−160 5 0.05 632-ethylhexanol C8H18O) 431 <0:007 <0:02 182−186 <10 <0:10 84b

isooctyl (C8H18O) 0.001 <0:003 184−190 5 0.05 84isononyl (C9H20O) 0.001 <0:003 202−213 5 0.05 91hexyl decyl 408 <0:004 0.003 168−203 5 0.01 81c

octanol (C8H18O) 431 <0:005 0.003 184−195 5 0.03 88c

decanol (C10H22O) 355 <0:01 0.003 226−230 5 0.03 113tridecyl (C13H28O) 283 0.001 <0:003 254−263 5 <0:05 127

a Pensky-Martens closed cup unless otherwise noted.b Cleveland open cup.c Tag close cup.

Table 9. Composition of Commercial Plasticizer Range Alcohols

Material Component Composition, wt %isooctyl 3,4-dimethyl-1-hexanol [19138-79-5]

3,5-dimethyl-1-hexanol [69778-63-8]4,5-dimethyl-1-hexanol [60564-76-3]

9=; 54

3-methyl-1-heptanol [31367-46-1]5-methyl-1-heptanol [7212-53-5]

¾25

3-ethyl-1-hexanol [41065-95-6] 13other primary alcohols 8

hexyl decyl hexanol 10(Epal 610) octanol 44

decanol 46octyl decyl octanol 42(Alfol 810) decanol 58

stearyl 206 0.5 0 0.7 58 6−15 0.03oleyl 206 0.5 94 4

a Neodol 23 (registered trademark for Shell alcohols).

Both detergent range and plasticizer range alcohols and their derivatives have been accepted by the U.S. government for use in a number ofdrug and food contact or food additive areas, and plasticizer range alcohols have been accepted as flavoring agents in foods (16). They must meetrigid manufacture, quality control, and record keeping requirements. Hexadecanol and octadecanol are used extensively in drug and cosmetic areaswhich require drug-grade raw materials. For this application they are produced to the specifications of the National Formulary (NF) in facilitiesregistered by the U.S. Food and Drug Administration. The NF requirements for hexadecanol are 45−50°C melting point, 2.0 max AV, 5.0 max IV,and 218−238 HV. The NF requirements for octadecanol are 55−60°C melting point, 2.0 max AV, 2.0 max IV, 200−220 HV, and 90% min.octadecanol.

Besides the linear detergent range alcohols, a number of highly branched alcohols of 12 or more carbon atoms made by the oxo process areof commercial importance. Tridecyl alcohol [27458-92-0], C13H28O, consisting mainly of tetramethyl-1-nonanols, is one such material; it is generallyconsidered to be a plasticizer range alcohol because of its manufacturing process and use in making plasticizers. Primary alcohols made by theGuerbet process, consisting of alcohols characterized as 2,2-dialkyl-1-ethanols, are available as hexadecyl [68526-87-4], C16H34O, octadecyl[27458-93-1], C18H38O, eicosyl [52655-10-4], C20H42O, and hexacosyl [70693-05-9], C26H54O, materials sold by Exxon under the Exxal brand name(17). They should not be confused with linear alcohols having similar names. Isostearyl alcohol [27458-93-1] is a highly branched natural alcoholcontaining a mixture of C18 alcohols derived from isostearic acid.

The sales brochures of the manufacturers describe the plasticizer range alcohols available on the merchant market (18). Typical properties ofseveral commercial plasticizer range alcohols are presented in Table 8. Because in most cases these are mixtures of isomers or alcohols with severalcarbon chains, the properties of a particular material can vary somewhat from manufacturer to manufacturer. Both odd and even carbon chainalcohols are available, in both linear and highly branched versions. Examples of the composition of several mixtures are given in Table 9.

Table 8. Typical Properties of Commercial Plasticizer Range Alcohols

Name Molecularformula

Hydroxyl Value

Acidity, %as acetic

Carbonyl,wt % O

Boiling range,°C

Color,APH

A

Moisture,%

Flash pointa,°C

hexyl (C6H14O) 0.001 <0:003 152−160 5 0.05 632-ethylhexanol C8H18O) 431 <0:007 <0:02 182−186 <10 <0:10 84b

isooctyl (C8H18O) 0.001 <0:003 184−190 5 0.05 84isononyl (C9H20O) 0.001 <0:003 202−213 5 0.05 91hexyl decyl 408 <0:004 0.003 168−203 5 0.01 81c

octanol (C8H18O) 431 <0:005 0.003 184−195 5 0.03 88c

decanol (C10H22O) 355 <0:01 0.003 226−230 5 0.03 113tridecyl (C13H28O) 283 0.001 <0:003 254−263 5 <0:05 127

a Pensky-Martens closed cup unless otherwise noted.b Cleveland open cup.c Tag close cup.

Table 9. Composition of Commercial Plasticizer Range Alcohols

Material Component Composition, wt %isooctyl 3,4-dimethyl-1-hexanol [19138-79-5]

3,5-dimethyl-1-hexanol [69778-63-8]4,5-dimethyl-1-hexanol [60564-76-3]

9=; 54

3-methyl-1-heptanol [31367-46-1]5-methyl-1-heptanol [7212-53-5]

¾25

3-ethyl-1-hexanol [41065-95-6] 13other primary alcohols 8

hexyl decyl hexanol 10(Epal 610) octanol 44

decanol 46octyl decyl octanol 42(Alfol 810) decanol 58



Toxicological Properties

The higher alcohols are among the less toxic of commonly used chemicals and, in general, their toxic effects are reduced as the number of carbonatoms is increased. Table 10 gives data representative of the toxicological properties of the higher alcohols (19−23). Slight differences in materialpurity, methodology, and grading of results may account for variations in data from different sources, and these data should not be regarded asrepresenting a consistent series. Because the data pertain to animals and not necessarily to humans, they should be used only as a guide. The valuesfor acute oral toxicity may be compared to an LD50 of about 3.75 g/kg for sodium chloride ingested by rats. A substance with an LD50 of 15 g/kg orabove is generally considered to be "practically nontoxic."

Table 10. Toxicological Properties of Higher Alcohols

Material Acute oral LD50 rats,

g/kgaEye irritation, rabbitsb Primary skin irritation,

rabbitsc

hexanol 3.2−4.4 severe moderateoctanol 18 severe moderatedecanol 20−26 severe moderatedodecanol >40 moderate slighttetradecanol >8 mild mildhexadecanol >20 mild mildoctadecanol >20 mild mild4-methyl-2-pentanol 2.6 slight moderate2-ethylhexanol 3.7 severe moderatemixed isomershexyl 3.7 severe moderateisooctyl >2 severe moderatedecyl 4.7 severe moderatetridecyl 4.7 moderate moderate

a The lethal dose for 50% of the test animals, expressed in terms of g of material per kg of body weight.b Evaluation of the irritation elicited from 0.1 mL of the material applied to the eyes without rinsing.c Evaluation of the irritation elicited from an application of full-strength alcohol left in contact with the skin for 24 h.

Primary human skin irritation of tetradecanol, hexadecanol, and octadecanol is nil; they have been used for many years in cosmetic creamsand ointments (24). Based on human testing and industrial experience, the linear, even carbon number alcohols of 6−18 carbon atoms are nothuman skin sensitizers, nor are the 7-, 9- and 11-carbon alcohols and 2-ethylhexanol. Neither has industrial handling of other branched alcohols ledto skin problems. Inhalation hazard, further mitigated by the low vapor pressure of these alcohols, is slight. Sustained breathing of alcohol vapor ormist should be avoided, however, as aspiration hazards have been reported (25).

Manufacture from Fats and Oils

Fats and oils from a number of animal and vegetable sources are the feedstocks for the manufacture of natural higher alcohols. These materialsconsist of triglycerides: glycerol esterified with three moles of a fatty acid. The alcohol is manufactured by reduction of the fatty acid functionalgroup. A small amount of natural alcohol is also obtained commercially by saponification of natural wax esters of the higher alcohols, such as woolgrease.

The carbon chain lengths of the fatty acids available from natural fats and oils range from 6−22 and higher, although a given material has anarrower range. Each triglyceride has a random distribution of fatty acid chain lengths and unsaturation, but the proportion of the various acids isfairly uniform for fats and oils from a common source. Any triglyceride or fatty acid may be utilized as a raw material for the manufacture ofalcohols, but the commonly used materials are coconut oil, palm kernel oil, lard, tallow, rapeseed oil, and palm oil, and to a lesser extent soybean oil,corn oil and babassu oil. Coconut and palm kernel oil are the primary sources of dodecanol and tetradecanol; lard, tallow, and palm oil are theprimary sources of hexadecanol and octadecanol. Producers of natural fatty alcohols typically make a broad range of alcohol products having variouscarbon chain lengths. They vary feedstocks to meet market needs for particular alcohols and to take advantage of changes in the relative costs of thevarious feedstock materials.

The first commercial production of fatty alcohol in the 1930s employed the sodium reduction process using a methyl ester feedstock. Theprocess was used in plants constructed up to about 1950, but it was expensive, hazardous, and complex. By about 1960 most of the sodiumreduction plants had been replaced by those employing the catalytic hydrogenolysis process. Catalytic hydrogenation processes were investigated asearly as the 1930s by a number of workers; one of these is described in reference 26.

Hydrogenolysis Process. Fatty alcohols are produced by hydrogenolysis of methyl esters or fatty acids in the presence of aheterogeneous catalyst at 20,700−31,000 kPa (3000−4500 psi) and 250−300°C in conversions of 90−98%. A higher conversion can be achieved usingmore rigorous reaction conditions, but it is accompanied by a significant amount of hydrocarbon production.

RCOOCH3 + 2 H2 ¡¡¡¡¡¡¡! catalysthigh pressure RCH2OH+CH3OH

RCH2CH2OH+ H2 ! RCH2CH3 + H2O

Toxicological Properties

The higher alcohols are among the less toxic of commonly used chemicals and, in general, their toxic effects are reduced as the number of carbonatoms is increased. Table 10 gives data representative of the toxicological properties of the higher alcohols (19−23). Slight differences in materialpurity, methodology, and grading of results may account for variations in data from different sources, and these data should not be regarded asrepresenting a consistent series. Because the data pertain to animals and not necessarily to humans, they should be used only as a guide. The valuesfor acute oral toxicity may be compared to an LD50 of about 3.75 g/kg for sodium chloride ingested by rats. A substance with an LD50 of 15 g/kg orabove is generally considered to be "practically nontoxic."

Table 10. Toxicological Properties of Higher Alcohols

Material Acute oral LD50 rats,

g/kgaEye irritation, rabbitsb Primary skin irritation,

rabbitsc

hexanol 3.2−4.4 severe moderateoctanol 18 severe moderatedecanol 20−26 severe moderatedodecanol >40 moderate slighttetradecanol >8 mild mildhexadecanol >20 mild mildoctadecanol >20 mild mild4-methyl-2-pentanol 2.6 slight moderate2-ethylhexanol 3.7 severe moderatemixed isomershexyl 3.7 severe moderateisooctyl >2 severe moderatedecyl 4.7 severe moderatetridecyl 4.7 moderate moderate

a The lethal dose for 50% of the test animals, expressed in terms of g of material per kg of body weight.b Evaluation of the irritation elicited from 0.1 mL of the material applied to the eyes without rinsing.c Evaluation of the irritation elicited from an application of full-strength alcohol left in contact with the skin for 24 h.

Primary human skin irritation of tetradecanol, hexadecanol, and octadecanol is nil; they have been used for many years in cosmetic creamsand ointments (24). Based on human testing and industrial experience, the linear, even carbon number alcohols of 6−18 carbon atoms are nothuman skin sensitizers, nor are the 7-, 9- and 11-carbon alcohols and 2-ethylhexanol. Neither has industrial handling of other branched alcohols ledto skin problems. Inhalation hazard, further mitigated by the low vapor pressure of these alcohols, is slight. Sustained breathing of alcohol vapor ormist should be avoided, however, as aspiration hazards have been reported (25).

Manufacture from Fats and Oils

Fats and oils from a number of animal and vegetable sources are the feedstocks for the manufacture of natural higher alcohols. These materialsconsist of triglycerides: glycerol esterified with three moles of a fatty acid. The alcohol is manufactured by reduction of the fatty acid functionalgroup. A small amount of natural alcohol is also obtained commercially by saponification of natural wax esters of the higher alcohols, such as woolgrease.

The carbon chain lengths of the fatty acids available from natural fats and oils range from 6−22 and higher, although a given material has anarrower range. Each triglyceride has a random distribution of fatty acid chain lengths and unsaturation, but the proportion of the various acids isfairly uniform for fats and oils from a common source. Any triglyceride or fatty acid may be utilized as a raw material for the manufacture ofalcohols, but the commonly used materials are coconut oil, palm kernel oil, lard, tallow, rapeseed oil, and palm oil, and to a lesser extent soybean oil,corn oil and babassu oil. Coconut and palm kernel oil are the primary sources of dodecanol and tetradecanol; lard, tallow, and palm oil are theprimary sources of hexadecanol and octadecanol. Producers of natural fatty alcohols typically make a broad range of alcohol products having variouscarbon chain lengths. They vary feedstocks to meet market needs for particular alcohols and to take advantage of changes in the relative costs of thevarious feedstock materials.

The first commercial production of fatty alcohol in the 1930s employed the sodium reduction process using a methyl ester feedstock. Theprocess was used in plants constructed up to about 1950, but it was expensive, hazardous, and complex. By about 1960 most of the sodiumreduction plants had been replaced by those employing the catalytic hydrogenolysis process. Catalytic hydrogenation processes were investigated asearly as the 1930s by a number of workers; one of these is described in reference 26.

Hydrogenolysis Process. Fatty alcohols are produced by hydrogenolysis of methyl esters or fatty acids in the presence of aheterogeneous catalyst at 20,700−31,000 kPa (3000−4500 psi) and 250−300°C in conversions of 90−98%. A higher conversion can be achieved usingmore rigorous reaction conditions, but it is accompanied by a significant amount of hydrocarbon production.

RCOOCH3 + 2 H2 ¡¡¡¡¡¡¡! catalysthigh pressure RCH2OH+CH3OH

RCH2CH2OH+ H2 ! RCH2CH3 + H2O



Fatty esters (wax esters), formed by ester interchange of the product alcohol and the starting material in the hydrogenolysis reactors, are laterseparated from the product by distillation. Unreacted methyl esters are also converted to fatty esters in the distillation step

RCOOCH3 +R0OH ! RCOOR0 +CH3OH

so that they too can be separated from the product. Fatty esters are recycled to the hydrogenolysis reactors since they can undergo hydrogenation ina manner similar to methyl esters, in this case yielding two moles of fatty alcohol per mole of ester. Fatty acids can also be used for the higheralcohol production. The fatty acid is pumped into the high pressure reactor and esterified in situ using previously made fatty alcohol; the resultingfatty ester then undergoes hydrogenolysis to two moles of fatty alcohol. A recently disclosed process uses the naturally occurring triglyceride ester asthe feedstock for hydrogenolysis (27). Although the manufacturing process is simplified by eliminating the production of a methyl ester or fatty acid,degradation of glycerol to 1,2-propanediol also occurs in the high temperature of the reaction and thus degrades a valuable coproduct.

To prepare methyl ester feedstock for making fatty alcohols, any free fatty acid must first be removed from the fat or oil so that the acid doesnot react with the catalyst used in the subsequent alcoholysis step. Fatty acid removal may be accomplished either by refining or by converting theacid directly to a methyl ester (28). Refining is done either chemically, by removal of a soap formed with sodium hydroxide or sodium carbonate(alkali refining), or physically, by steam distillation of the fatty acids (steam refining) (29). In the case of chemical refining, the by-product soap isacidified to give a fatty acid and these "foots" are used as animal feed or upgraded for industrial fatty acid use. The by-product fatty acid from steamrefining is of a higher grade than acidified foots and is used directly as an industrial fatty acid or as animal feed. In either case, the fatty acid can alsobe converted to the methyl ester and used as additional alcohol feedstock. Refined oil is dried to prevent the reaction of water with the catalystduring alcoholysis.

Alcoholysis (ester interchange) is performed at atmospheric pressure near the boiling point of methanol in carbon steel equipment. Sodiummethoxide [124-41-4], CH3ONa, the catalyst, can be prepared in the same reactor by reaction of methanol and metallic sodium, or it can bepurchased in methanol solution. Usage is approximately 0.3−1.0 wt % of the triglyceride.

C3H5 (OOCR) 3 + 3 CH3OH ¡¡¡¡¡! NaOCH 3 3 RCOOCH3 + C3H5(OH)3

The alcoholysis reaction may be carried out either batchwise or continuously by treating the triglyceride with an excess of methanol for 30−60 min ina well-agitated reactor. The reactants are then allowed to settle and the glycerol [56-81-5] is recovered in methanol solution in the lower layer. Thesodium methoxide and excess methanol are removed from the methyl ester, which then may be fed directly to the hydrogenolysis process.Alternatively, the ester may be distilled to remove unreacted material and other impurities, or fractionated into different cuts. Fractionation of eitherthe methyl ester or of the product following hydrogenolysis provides alcohols that have narrow carbon-chain distributions.

High Pressure Hydrogenolysis. There are three major hydrogenolysis processes in worldwide use: the methyl ester, slurry catalystprocess operated by Procter & Gamble, Henkel, and Kao; the methyl ester, fixed-bed catalyst process operated by Henkel and Oleofina; and thefatty acid, slurry catalyst process developed by Lurgi and operated by several licensees. Each process typically uses a copper chromite or copper−zinccatalyst that is modified to meet the needs of the individual producer. Copper chromite when prepared is nominally a complex mixture of primarilycopper(II) oxide and copper(II) chromite. But in use it is believed to be reduced to a mixture of metallic copper, copper(II) oxide, and copper(II)chromite, the metallic copper playing an important, but as yet undefined, role in the catalysis of the reaction. The catalyst is made by reaction ofcopper nitrate and chromic oxide with ammonia followed by vacuum filtering of the precipitate, water washing, and then roasting in air. Theresulting material is a very fine black powder. The roasting operation is continuous, utilizing accurate temperature control to give a catalyst of longlife and high activity. Barium, manganese, or other metal ions are sometimes added to improve stability, and silica or other binders may be put in tomake a physically strong, fixed-bed catalyst pellet. Hydrogen [1333-74-0] is usually generated on site from methane or propane. The hydrogen shouldbe of high purity to avoid catalyst poisons, such as sulfur and carbon dioxide, and to prevent buildup of inert gases in the system; pressure swingadsorption (PSA) is often used to remove gaseous impurities.

Methyl Ester Hydrogenolysis. The flow sheet for the continuous methyl ester, catalyst slurry process is shown in Figure 1. The drymethyl ester, hydrogen, and catalyst slurry are fed cocurrently to a series of four vertical reactors operated at 250−300°C and 20,700 kPa (3000 psi).The reactors are unagitated, empty tubes, designed to provide adequate residence time, minimum backmixing, and a reasonable column height.Fresh catalyst powder is slurried with fatty alcohol and recycled catalyst in a weigh tank and metered into the bottom of the first reactor atapproximately 3% of the ester feed rate. The heated hydrogen is fed through a distributor in the bottom of the first reactor. Besides serving as thereducing agent, the hydrogen also provides the principal source of heat and agitation for the reaction, and its flow conveys the mixture of ester,alcohol, and catalyst from one reactor to another. Approximately 30 moles of hydrogen are fed per mole of ester. The product stream from the lastreactor, consisting of fatty alcohol, methanol, hydrogen, catalyst, and unreacted ester, enters a gravity separator where the vapor portion, consistingof hydrogen, methanol, and some fatty alcohol, goes overhead. The underflow stream of crude alcohol and catalyst is heat-interchanged with esterfeed and depressurized, and the catalyst is removed. Most of the catalyst slurry is recycled but a small amount, to match the amount of fresh catalystfeed, is purged. This keeps a constant catalyst activity. The purged catalyst can be regenerated (30) or sold to a reclaimer to recover copper values.The overhead stream is heat-interchanged with hydrogen feed, cooled, and separated from hydrogen before being depressurized and filtered. Anatmospheric stripping column removes methanol from the combined underflow/overhead stream of crude alcohol, and the methanol is recycled tothe alcoholysis process. The stripped crude fatty alcohol is distilled in a vacuum column, or fractionated in a series of vacuum columns, to give thefinished alcohol. The still bottoms, primarily fatty ester, are mainly recycled, and a small amount of still bottoms is removed from the system as apurge.

Fatty esters (wax esters), formed by ester interchange of the product alcohol and the starting material in the hydrogenolysis reactors, are laterseparated from the product by distillation. Unreacted methyl esters are also converted to fatty esters in the distillation step

RCOOCH3 +R0OH ! RCOOR0 +CH3OH

so that they too can be separated from the product. Fatty esters are recycled to the hydrogenolysis reactors since they can undergo hydrogenation ina manner similar to methyl esters, in this case yielding two moles of fatty alcohol per mole of ester. Fatty acids can also be used for the higheralcohol production. The fatty acid is pumped into the high pressure reactor and esterified in situ using previously made fatty alcohol; the resultingfatty ester then undergoes hydrogenolysis to two moles of fatty alcohol. A recently disclosed process uses the naturally occurring triglyceride ester asthe feedstock for hydrogenolysis (27). Although the manufacturing process is simplified by eliminating the production of a methyl ester or fatty acid,degradation of glycerol to 1,2-propanediol also occurs in the high temperature of the reaction and thus degrades a valuable coproduct.

To prepare methyl ester feedstock for making fatty alcohols, any free fatty acid must first be removed from the fat or oil so that the acid doesnot react with the catalyst used in the subsequent alcoholysis step. Fatty acid removal may be accomplished either by refining or by converting theacid directly to a methyl ester (28). Refining is done either chemically, by removal of a soap formed with sodium hydroxide or sodium carbonate(alkali refining), or physically, by steam distillation of the fatty acids (steam refining) (29). In the case of chemical refining, the by-product soap isacidified to give a fatty acid and these "foots" are used as animal feed or upgraded for industrial fatty acid use. The by-product fatty acid from steamrefining is of a higher grade than acidified foots and is used directly as an industrial fatty acid or as animal feed. In either case, the fatty acid can alsobe converted to the methyl ester and used as additional alcohol feedstock. Refined oil is dried to prevent the reaction of water with the catalystduring alcoholysis.

Alcoholysis (ester interchange) is performed at atmospheric pressure near the boiling point of methanol in carbon steel equipment. Sodiummethoxide [124-41-4], CH3ONa, the catalyst, can be prepared in the same reactor by reaction of methanol and metallic sodium, or it can bepurchased in methanol solution. Usage is approximately 0.3−1.0 wt % of the triglyceride.

C3H5 (OOCR) 3 + 3 CH3OH ¡¡¡¡¡! NaOCH 3 3 RCOOCH3 + C3H5(OH)3

The alcoholysis reaction may be carried out either batchwise or continuously by treating the triglyceride with an excess of methanol for 30−60 min ina well-agitated reactor. The reactants are then allowed to settle and the glycerol [56-81-5] is recovered in methanol solution in the lower layer. Thesodium methoxide and excess methanol are removed from the methyl ester, which then may be fed directly to the hydrogenolysis process.Alternatively, the ester may be distilled to remove unreacted material and other impurities, or fractionated into different cuts. Fractionation of eitherthe methyl ester or of the product following hydrogenolysis provides alcohols that have narrow carbon-chain distributions.

High Pressure Hydrogenolysis. There are three major hydrogenolysis processes in worldwide use: the methyl ester, slurry catalystprocess operated by Procter & Gamble, Henkel, and Kao; the methyl ester, fixed-bed catalyst process operated by Henkel and Oleofina; and thefatty acid, slurry catalyst process developed by Lurgi and operated by several licensees. Each process typically uses a copper chromite or copper−zinccatalyst that is modified to meet the needs of the individual producer. Copper chromite when prepared is nominally a complex mixture of primarilycopper(II) oxide and copper(II) chromite. But in use it is believed to be reduced to a mixture of metallic copper, copper(II) oxide, and copper(II)chromite, the metallic copper playing an important, but as yet undefined, role in the catalysis of the reaction. The catalyst is made by reaction ofcopper nitrate and chromic oxide with ammonia followed by vacuum filtering of the precipitate, water washing, and then roasting in air. Theresulting material is a very fine black powder. The roasting operation is continuous, utilizing accurate temperature control to give a catalyst of longlife and high activity. Barium, manganese, or other metal ions are sometimes added to improve stability, and silica or other binders may be put in tomake a physically strong, fixed-bed catalyst pellet. Hydrogen [1333-74-0] is usually generated on site from methane or propane. The hydrogen shouldbe of high purity to avoid catalyst poisons, such as sulfur and carbon dioxide, and to prevent buildup of inert gases in the system; pressure swingadsorption (PSA) is often used to remove gaseous impurities.

Methyl Ester Hydrogenolysis. The flow sheet for the continuous methyl ester, catalyst slurry process is shown in Figure 1. The drymethyl ester, hydrogen, and catalyst slurry are fed cocurrently to a series of four vertical reactors operated at 250−300°C and 20,700 kPa (3000 psi).The reactors are unagitated, empty tubes, designed to provide adequate residence time, minimum backmixing, and a reasonable column height.Fresh catalyst powder is slurried with fatty alcohol and recycled catalyst in a weigh tank and metered into the bottom of the first reactor atapproximately 3% of the ester feed rate. The heated hydrogen is fed through a distributor in the bottom of the first reactor. Besides serving as thereducing agent, the hydrogen also provides the principal source of heat and agitation for the reaction, and its flow conveys the mixture of ester,alcohol, and catalyst from one reactor to another. Approximately 30 moles of hydrogen are fed per mole of ester. The product stream from the lastreactor, consisting of fatty alcohol, methanol, hydrogen, catalyst, and unreacted ester, enters a gravity separator where the vapor portion, consistingof hydrogen, methanol, and some fatty alcohol, goes overhead. The underflow stream of crude alcohol and catalyst is heat-interchanged with esterfeed and depressurized, and the catalyst is removed. Most of the catalyst slurry is recycled but a small amount, to match the amount of fresh catalystfeed, is purged. This keeps a constant catalyst activity. The purged catalyst can be regenerated (30) or sold to a reclaimer to recover copper values.The overhead stream is heat-interchanged with hydrogen feed, cooled, and separated from hydrogen before being depressurized and filtered. Anatmospheric stripping column removes methanol from the combined underflow/overhead stream of crude alcohol, and the methanol is recycled tothe alcoholysis process. The stripped crude fatty alcohol is distilled in a vacuum column, or fractionated in a series of vacuum columns, to give thefinished alcohol. The still bottoms, primarily fatty ester, are mainly recycled, and a small amount of still bottoms is removed from the system as apurge.



Fig. 1. Methyl ester, slurry catalyst process.

The process is controlled by the reaction temperature, feed rate (residence time), catalyst rate, and fresh catalyst usage. It is operated toprovide the highest production rate commensurate with high yield and product quality, as well as lowest temperature and fresh catalyst usage. Heatinterchange is used wherever possible to minimize energy consumption; low pressure steam is generated from coolers and condensers for useelsewhere in the process. Recycling from the two blowdown tanks recovers the hydrogen dissolved in those streams and reduces the usage ofhydrogen feedstock. A fat trap is used to recover minor amounts of fatty alcohol and ester from process water streams and spills to reduce COD(chemical oxygen demand) loadings in the process sewer. The recovered material is then recycled to the process. A minor amount of still bottomsand unusable process remnants is burned as fuel.

The methyl ester, fixed-bed catalyst process is shown in Figure 2. A large excess of hydrogen is mixed with the methyl ester, part of whichvaporizes and is carried through one or more fixed beds of catalyst at 200−250°C and a pressure similar to that used in the slurry process (31). Afterleaving the reactor, the mixture is cooled, then separated into a gaseous phase of mostly hydrogen, which is recycled, and a liquid phase of methanoland fatty alcohol. The liquid phase is depressurized into a blowdown tank, which removes the methanol; the fatty alcohol that remains does notrequire further purification. The alcohol is fractionated, however, if a product having a narrower carbon chain distribution is desired. The high rateof recirculating hydrogen in this process is claimed to provide fast removal of heat, providing high yields and minimizing side reactions such ashydrocarbon formation.

Fig. 1. Methyl ester, slurry catalyst process.

The process is controlled by the reaction temperature, feed rate (residence time), catalyst rate, and fresh catalyst usage. It is operated toprovide the highest production rate commensurate with high yield and product quality, as well as lowest temperature and fresh catalyst usage. Heatinterchange is used wherever possible to minimize energy consumption; low pressure steam is generated from coolers and condensers for useelsewhere in the process. Recycling from the two blowdown tanks recovers the hydrogen dissolved in those streams and reduces the usage ofhydrogen feedstock. A fat trap is used to recover minor amounts of fatty alcohol and ester from process water streams and spills to reduce COD(chemical oxygen demand) loadings in the process sewer. The recovered material is then recycled to the process. A minor amount of still bottomsand unusable process remnants is burned as fuel.

The methyl ester, fixed-bed catalyst process is shown in Figure 2. A large excess of hydrogen is mixed with the methyl ester, part of whichvaporizes and is carried through one or more fixed beds of catalyst at 200−250°C and a pressure similar to that used in the slurry process (31). Afterleaving the reactor, the mixture is cooled, then separated into a gaseous phase of mostly hydrogen, which is recycled, and a liquid phase of methanoland fatty alcohol. The liquid phase is depressurized into a blowdown tank, which removes the methanol; the fatty alcohol that remains does notrequire further purification. The alcohol is fractionated, however, if a product having a narrower carbon chain distribution is desired. The high rateof recirculating hydrogen in this process is claimed to provide fast removal of heat, providing high yields and minimizing side reactions such ashydrocarbon formation.



Fig. 2. Methyl ester, fixed-bed catalyst process.

Fatty Acid Hydrogenolysis. The fatty acid, slurry catalyst process operates at 315°C and a pressure of 31,000 kPa (4500 psi); it isshown in Figure 3 (32,33). This process uses a single large reactor with internal baffles and a complex flow system. First, previously prepared fattyalcohol reacts with the acid feed to make a fatty ester via the alcoholysis reaction. A mole of water is also released. Then, the fatty ester reacts withhydrogen to give two moles of fatty alcohol per mole of ester. One exits the reactor, the other is recycled to react with the fatty acid feed. In twostages of cooling and separation, the excess hydrogen is separated from the reactor effluent for recycle, the reaction water is separated, and thecatalyst containing fatty alcohol is recovered. The catalyst is removed as a slurry in a centrifugal separator for recycle. A small amount of catalyst iscontinuously purged from the process; an equivalent amount of fresh catalyst is added. After a final polish filtration, the crude fatty alcohol is sent todistillation: single-stage distillation for a broad range of carbon alcohols; fractionation for a narrower range of carbon alcohols.

Fig. 3. Fatty acid, slurry catalyst process.

Fig. 2. Methyl ester, fixed-bed catalyst process.

Fatty Acid Hydrogenolysis. The fatty acid, slurry catalyst process operates at 315°C and a pressure of 31,000 kPa (4500 psi); it isshown in Figure 3 (32,33). This process uses a single large reactor with internal baffles and a complex flow system. First, previously prepared fattyalcohol reacts with the acid feed to make a fatty ester via the alcoholysis reaction. A mole of water is also released. Then, the fatty ester reacts withhydrogen to give two moles of fatty alcohol per mole of ester. One exits the reactor, the other is recycled to react with the fatty acid feed. In twostages of cooling and separation, the excess hydrogen is separated from the reactor effluent for recycle, the reaction water is separated, and thecatalyst containing fatty alcohol is recovered. The catalyst is removed as a slurry in a centrifugal separator for recycle. A small amount of catalyst iscontinuously purged from the process; an equivalent amount of fresh catalyst is added. After a final polish filtration, the crude fatty alcohol is sent todistillation: single-stage distillation for a broad range of carbon alcohols; fractionation for a narrower range of carbon alcohols.

Fig. 3. Fatty acid, slurry catalyst process.



Production of Unsaturated Alcohols

Unsaturated higher alcohols may be produced by saponification, sodium reduction, or hydrogenolysis of unsaturated fatty acids or esters.Saponification of oil from the sperm whale was a former source, but bans on the slaughter of whales by some nations and a general reduction inwhaling have made this method obsolete. Alcohol made by saponification of wool grease (lanolin) is a minor product; sodium reduction ofunsaturated esters is no longer an economic process for manufacturing unsaturated alcohols. Hydrogenolysis of unsaturated fatty acids or esters toproduce alcohol without loss of the double bond has been a subject of interest for many years. Literature through the mid-1960s has been reviewed(34); and there has also been other work reported (35). In general, the key to double bond retention is a specially designed catalyst to give selectivitycoupled with reaction conditions adjusted for the poorer reactivity of this catalyst compared to the copper−chromite catalysts. Cadmium modifiedcatalysts are claimed to be effective, as are zinc chromite and a zinc−lanthanum catalyst (36). A zinc−aluminum catalyst reportedly avoidsisomerization of the cis double bond of octadecenoic acid, soybean fatty acid, and linseed fatty acid methyl esters during hydrogenolysis (37). Theknown commercial hydrogenolysis processes for the production of octadecenol and other unsaturated alcohols are practiced by Sherex ChemicalCompany in the United States, Henkel K.-G.a.A. in Germany, and the New Japan Chemical Company in Japan. In at least one procedure (38), anunsaturated fatty acid reacts in a continuous process over a fixed catalyst bed at 270−290°C and 19,600 kPa (2800 psi). The catalyst is a complexaluminum−cadmium−chromium oxide that has high activity and exceptionally long life. The process is claimed to give a conversion of ester toalcohol of about 99% retaining essentially all of the original double bonds.

Uses of Detergent Range Alcohols

The detergent range alcohols and their derivatives have a wide variety of uses in consumer and industrial products either because of surface-activeproperties, or as a means of introducing a long chain moiety into a chemical compound. The major use is as surfactants (qv) in detergents andcleaning products. Only a small amount of the alcohol is used as-is; rather most is used as derivatives such as the poly(oxyethylene) ethers and thesulfated ethers, the alkyl sulfates, and the esters of other acids, eg, phosphoric acid and monocarboxylic and dicarboxylic acids. Major use areas aregiven in Table 11.

Table 11. Uses of Detergent Range Alcohols

Industry Use as alcohol Use as derivativedetergent emollient, foam control, opacifier,

softenersurfactant, softener

petroleum and lubrication drilling mud emulsifier, lubricant, dispersant, viscosityindex improver, oil field chemical,pour-point depressant, drag reducing agent

agriculture evaporation suppressant pesticide, emulsifier, soil conditionerplastics mold release agent, antifoam, emulsion

polymerization agent, lubricantplasticizer, emulsion polymerizationsurfactant, lubricant dispersant,antioxidant, stabilizer, uv absorber

textile lubricant, foam control, anti-static agent,ink ingredient

emulsifier, finish, softener, lubricant,scouring agent

cosmetics softener, emollient emulsifier, biocide, hair conditioner,emollient

pulp and paper foam control deresination agent, de-inking agentfood emulsifier, antioxidant, disinfectantrubber plasticizer, dispersant plasticizerpaint and coatings foam control emulsifiermetal working lubricant, rolling oil degreaser, lubricantmineral processing flotation agent surfactant

Surfactants. The detergent range alcohols can be used as building blocks for all of the surfactant types: anionics, cationics, nonionics,and zwitterionics. These alcohols are used for their emulsifying, dispersing, wetting, and cleaning properties and most surfactants (qv) made fromthem are readily biodegradable. Formulation of nonphosphate heavy duty liquid laundry detergents was made possible by use of these materials asthe primary surfactant. The alkyl sulfates derived from C12 through C15 alcohols are widely used in consumer products such as shampoos,toothpastes, hand dishwashing detergents, and light duty household cleaners. Sodium dodecyl sulfate [151-21-3] is the optimum material for manycleaning compounds because of cleaning ability, mildness, and foaming capability. The alkyl sulfates of C16 and C18 alcohols are used in powderlaundry detergents and other heavy-duty cleaners. Minor amounts of unsulfated alcohol left in the alkyl sulfate detergents serve as foam stabilizers.Surfactants made from polyethoxylated alcohols are in wider use than the alkyl sulfates. They tend to be less irritating to the skin than the alkylsulfates and perform better in liquid systems such as hand dishwashing detergents and liquid laundry detergents. The ethoxylated materials may beused underivatized as nonionic surfactants. Alternatively, they may be sulfated and then neutralized using a base such as sodium or ammoniumhydroxide to give ethoxysulfate anionic surfactants, the largest usage category of detergent range alcohols. Although the amount of ethylene oxide[75-21-8], C2H4O, can range from 1 to about 45 moles per mole of alcohol, the degree of ethoxylation of the anionic surfactants is typically 6 to 12,whereas that of the ethoxysulfates typically ranges from 3 to 12. Additionally, ethoxylation yields a broad range of species: for instance, a nominal3-mole ethoxylate has some alcohol molecules containing up to 14 units of ethylene oxide, yet it also includes about 15% unreacted alcohol, givingthe effect of a mixed surfactant system. Varying the number of parent alcohol carbons, the amount of ethylene oxide used, and to some extent the

Production of Unsaturated Alcohols

Unsaturated higher alcohols may be produced by saponification, sodium reduction, or hydrogenolysis of unsaturated fatty acids or esters.Saponification of oil from the sperm whale was a former source, but bans on the slaughter of whales by some nations and a general reduction inwhaling have made this method obsolete. Alcohol made by saponification of wool grease (lanolin) is a minor product; sodium reduction ofunsaturated esters is no longer an economic process for manufacturing unsaturated alcohols. Hydrogenolysis of unsaturated fatty acids or esters toproduce alcohol without loss of the double bond has been a subject of interest for many years. Literature through the mid-1960s has been reviewed(34); and there has also been other work reported (35). In general, the key to double bond retention is a specially designed catalyst to give selectivitycoupled with reaction conditions adjusted for the poorer reactivity of this catalyst compared to the copper−chromite catalysts. Cadmium modifiedcatalysts are claimed to be effective, as are zinc chromite and a zinc−lanthanum catalyst (36). A zinc−aluminum catalyst reportedly avoidsisomerization of the cis double bond of octadecenoic acid, soybean fatty acid, and linseed fatty acid methyl esters during hydrogenolysis (37). Theknown commercial hydrogenolysis processes for the production of octadecenol and other unsaturated alcohols are practiced by Sherex ChemicalCompany in the United States, Henkel K.-G.a.A. in Germany, and the New Japan Chemical Company in Japan. In at least one procedure (38), anunsaturated fatty acid reacts in a continuous process over a fixed catalyst bed at 270−290°C and 19,600 kPa (2800 psi). The catalyst is a complexaluminum−cadmium−chromium oxide that has high activity and exceptionally long life. The process is claimed to give a conversion of ester toalcohol of about 99% retaining essentially all of the original double bonds.

Uses of Detergent Range Alcohols

The detergent range alcohols and their derivatives have a wide variety of uses in consumer and industrial products either because of surface-activeproperties, or as a means of introducing a long chain moiety into a chemical compound. The major use is as surfactants (qv) in detergents andcleaning products. Only a small amount of the alcohol is used as-is; rather most is used as derivatives such as the poly(oxyethylene) ethers and thesulfated ethers, the alkyl sulfates, and the esters of other acids, eg, phosphoric acid and monocarboxylic and dicarboxylic acids. Major use areas aregiven in Table 11.

Table 11. Uses of Detergent Range Alcohols

Industry Use as alcohol Use as derivativedetergent emollient, foam control, opacifier,

softenersurfactant, softener

petroleum and lubrication drilling mud emulsifier, lubricant, dispersant, viscosityindex improver, oil field chemical,pour-point depressant, drag reducing agent

agriculture evaporation suppressant pesticide, emulsifier, soil conditionerplastics mold release agent, antifoam, emulsion

polymerization agent, lubricantplasticizer, emulsion polymerizationsurfactant, lubricant dispersant,antioxidant, stabilizer, uv absorber

textile lubricant, foam control, anti-static agent,ink ingredient

emulsifier, finish, softener, lubricant,scouring agent

cosmetics softener, emollient emulsifier, biocide, hair conditioner,emollient

pulp and paper foam control deresination agent, de-inking agentfood emulsifier, antioxidant, disinfectantrubber plasticizer, dispersant plasticizerpaint and coatings foam control emulsifiermetal working lubricant, rolling oil degreaser, lubricantmineral processing flotation agent surfactant

Surfactants. The detergent range alcohols can be used as building blocks for all of the surfactant types: anionics, cationics, nonionics,and zwitterionics. These alcohols are used for their emulsifying, dispersing, wetting, and cleaning properties and most surfactants (qv) made fromthem are readily biodegradable. Formulation of nonphosphate heavy duty liquid laundry detergents was made possible by use of these materials asthe primary surfactant. The alkyl sulfates derived from C12 through C15 alcohols are widely used in consumer products such as shampoos,toothpastes, hand dishwashing detergents, and light duty household cleaners. Sodium dodecyl sulfate [151-21-3] is the optimum material for manycleaning compounds because of cleaning ability, mildness, and foaming capability. The alkyl sulfates of C16 and C18 alcohols are used in powderlaundry detergents and other heavy-duty cleaners. Minor amounts of unsulfated alcohol left in the alkyl sulfate detergents serve as foam stabilizers.Surfactants made from polyethoxylated alcohols are in wider use than the alkyl sulfates. They tend to be less irritating to the skin than the alkylsulfates and perform better in liquid systems such as hand dishwashing detergents and liquid laundry detergents. The ethoxylated materials may beused underivatized as nonionic surfactants. Alternatively, they may be sulfated and then neutralized using a base such as sodium or ammoniumhydroxide to give ethoxysulfate anionic surfactants, the largest usage category of detergent range alcohols. Although the amount of ethylene oxide[75-21-8], C2H4O, can range from 1 to about 45 moles per mole of alcohol, the degree of ethoxylation of the anionic surfactants is typically 6 to 12,whereas that of the ethoxysulfates typically ranges from 3 to 12. Additionally, ethoxylation yields a broad range of species: for instance, a nominal3-mole ethoxylate has some alcohol molecules containing up to 14 units of ethylene oxide, yet it also includes about 15% unreacted alcohol, givingthe effect of a mixed surfactant system. Varying the number of parent alcohol carbons, the amount of ethylene oxide used, and to some extent the



breadth of the ethylene oxide distribution, gives wide latitude in the hydrophile−lipophile balance (HLB) of the resulting surfactant, which may beused as a nonionic surfactant or sulfated to give an anionic one. This versatility accounts for the broad use of ethoxylates in consumer cleaningproducts and in industrial applications as wetting agents, cleaning products, dispersing agents, and emulsifiers.

Alkyl glyceryl ether sulfonates are very mild, high foaming surfactants used in bar soaps and shampoos; they are made from the sulfonatedalkyl chlorohydrin ether of detergent range alcohols. Alkyldimethyl amines are made from alcohols and then oxidized to give the amine oxide whichis used as a mild surfactant in hand dishwashing products, shampoos, and some cosmetic applications. Some specialty cationic quaternary nitrogensurfactants are also made from the alcohols. Specialty phosphate ester surfactants are made from detergent range alcohols and ethoxylated alcohols;these find use mainly as lubricants and wetting agents in the textile industry.

In other surfactant uses, dodecanol−tetradecanol is employed to prepare porous concrete (39), stearyl alcohol is used to make a polymerconcrete (40), and lauryl alcohol is utilized for froth flotation of ores (41). A foamed composition of hexadecanol is used for textile printing (42) anda foamed composition of octadecanol is used for coating polymers (43). On the other hand, foam is controlled by detergent range alcohols inapplications: by lauryl alcohol in steel cleaning (44), by octadecanol in a detergent composition (45), and by eicosanol−docosanol in various systems(46).

Cosmetics and Pharmaceuticals. The main use of hexadecanol (cetyl alcohol) is in cosmetics (qv) and pharmaceuticals (qv), where itand octadecanol (stearyl alcohol) are used extensively as emollient additives and as bases for creams, lipsticks, ointments, and suppositories.Octadecenol (oleyl alcohol) is also widely used (47), as are the nonlinear alcohols. The compatibility of heavy cut alcohols and other cosmeticmaterials or active drug agents, their mildness, skin feel, and low toxicity have made them the preferred materials for these applications. Higheralcohols and their derivatives are used in conditioning shampoos, in other personal care products, and in ingested materials such as vitamins (qv) andsustained release tablets (see CONTROLLED RELEASE TECHNOLOGY).

Lubricants and Petroleum. Methacrylate esters of detergent range alcohols find use as viscosity index improvers, pour-pointdepressants, and dispersants (qv) in automobile engine lubricants. The free alcohol, particularly dodecanol (lauryl alcohol), is widely used inaluminum rolling, and also in other metalworking (48). A composition of octadecenol and sodium lauryl sulfate is used for petroleum oil recovery(49). Esters of docosanol are used as drag reducing agents for pipelining of crude petroleum oil, which reduces the power requirements for pumping.

Other Applications. Alkylbenzyldimethylammonium salts are made from alcohols in the C12−C16 range and find use as biocides anddisinfectants in a number of areas. Dodecanol, tetradecanol, octadecanol, and tridecyl alcohol esters of thiodipropionic acid are employed as part ofthe antioxidant system of polyolefin plastics. Higher alcohols are used as antistatic agents (qv), mold release agents, and as additives in olefinpolymerization (50); other uses have been reviewed (51). Esters of detergent range alcohols and fatty acids, lactic acid, and maleic acid are used forcosmetics and lubricants. Phosphites and phosphates of detergent range alcohols are also articles of commerce. Triacontanol (C32) has activity as aplant growth regulator, but results have not been consistent enough for commercial use (52). Hexadecanol and octadecanol can be used to retardevaporation of water from reservoirs in arid regions (53). Detergent range alcohols also find application in antifoulant coatings, adhesives, and fabricsofteners (54).

Uses of Plasticizer Range Alcohols

The plasticizer range alcohols are utilized primarily in plasticizers, but they also have a wide range of uses in other industrial and consumer products,as shown in Table 12. As in the case of the detergent range alcohols, the plasticizer range materials are little used as is, but rather are employed as theester derivatives of acids such as phthalic, adipic, and trimellitic.

Table 12. Uses of Plasticizer Range Alcohols

Industry Use as alcohol Use as derivativeplastics emulsion polymerization plasticizer, flame retardant, oxidation and uv

stabilizer, heat stabilizer, polymerizationinitiator

petroleum and lubrication defoamer lubricant, grease, lubricant additive, hydraulicfluid, diesel fuel additive

agriculture stabilizer, tobacco sucker control, herbicide,fungicide

surfactant, insecticide, herbicide

mineral processing solvent, extractant, antifoam extractant, surfactanttextile leveling agent, defoamer surfactantcoatings solvent, smoothing agent surfactant, drying agent, solventmetal working solvent, lubricant, protective coating lubricant, surfactantchemical processing antifoam, solvent solventfood flavoring agentcosmetics perfume ingredient

Plasticizers. Over 70% of plasticizer range alcohols are ultimately consumed as plasticizers for PVC and other resins. Of this amount,80% is used as the diester of phthalic acid, for instance di-2-ethylhexyl phthalate (DOP) or diisodecyl phthalate (DIDP) [26761-40-0]. Otherplasticizers made from these alcohols are the diesters of adipic acid, azeleic acid, and sebacic acid, plus the triesters of phosphoric acid and trimelliticacid. A small amount of alcohol is used as the terminating agent in specialty polyester plasticizers. The adipates, azelates, and sebacates are employedas specialty materials in some food contact applications and in areas where low temperature flexibility is important, such as automobile interiors; eg,the diadipate ester of hexanol is the plasticizer in poly(vinyl butyral) used for automobile safety glass. The phosphates find application as good lowtemperature plasticizers and as flame retardant additives, whereas the trimellitates are used for high temperature applications such as the insulation ofelectrical wiring. The phthalates, however, are the general purpose plasticizers. Phthalate esters of alcohols from 4−13 carbons are available although

breadth of the ethylene oxide distribution, gives wide latitude in the hydrophile−lipophile balance (HLB) of the resulting surfactant, which may beused as a nonionic surfactant or sulfated to give an anionic one. This versatility accounts for the broad use of ethoxylates in consumer cleaningproducts and in industrial applications as wetting agents, cleaning products, dispersing agents, and emulsifiers.

Alkyl glyceryl ether sulfonates are very mild, high foaming surfactants used in bar soaps and shampoos; they are made from the sulfonatedalkyl chlorohydrin ether of detergent range alcohols. Alkyldimethyl amines are made from alcohols and then oxidized to give the amine oxide whichis used as a mild surfactant in hand dishwashing products, shampoos, and some cosmetic applications. Some specialty cationic quaternary nitrogensurfactants are also made from the alcohols. Specialty phosphate ester surfactants are made from detergent range alcohols and ethoxylated alcohols;these find use mainly as lubricants and wetting agents in the textile industry.

In other surfactant uses, dodecanol−tetradecanol is employed to prepare porous concrete (39), stearyl alcohol is used to make a polymerconcrete (40), and lauryl alcohol is utilized for froth flotation of ores (41). A foamed composition of hexadecanol is used for textile printing (42) anda foamed composition of octadecanol is used for coating polymers (43). On the other hand, foam is controlled by detergent range alcohols inapplications: by lauryl alcohol in steel cleaning (44), by octadecanol in a detergent composition (45), and by eicosanol−docosanol in various systems(46).

Cosmetics and Pharmaceuticals. The main use of hexadecanol (cetyl alcohol) is in cosmetics (qv) and pharmaceuticals (qv), where itand octadecanol (stearyl alcohol) are used extensively as emollient additives and as bases for creams, lipsticks, ointments, and suppositories.Octadecenol (oleyl alcohol) is also widely used (47), as are the nonlinear alcohols. The compatibility of heavy cut alcohols and other cosmeticmaterials or active drug agents, their mildness, skin feel, and low toxicity have made them the preferred materials for these applications. Higheralcohols and their derivatives are used in conditioning shampoos, in other personal care products, and in ingested materials such as vitamins (qv) andsustained release tablets (see CONTROLLED RELEASE TECHNOLOGY).

Lubricants and Petroleum. Methacrylate esters of detergent range alcohols find use as viscosity index improvers, pour-pointdepressants, and dispersants (qv) in automobile engine lubricants. The free alcohol, particularly dodecanol (lauryl alcohol), is widely used inaluminum rolling, and also in other metalworking (48). A composition of octadecenol and sodium lauryl sulfate is used for petroleum oil recovery(49). Esters of docosanol are used as drag reducing agents for pipelining of crude petroleum oil, which reduces the power requirements for pumping.

Other Applications. Alkylbenzyldimethylammonium salts are made from alcohols in the C12−C16 range and find use as biocides anddisinfectants in a number of areas. Dodecanol, tetradecanol, octadecanol, and tridecyl alcohol esters of thiodipropionic acid are employed as part ofthe antioxidant system of polyolefin plastics. Higher alcohols are used as antistatic agents (qv), mold release agents, and as additives in olefinpolymerization (50); other uses have been reviewed (51). Esters of detergent range alcohols and fatty acids, lactic acid, and maleic acid are used forcosmetics and lubricants. Phosphites and phosphates of detergent range alcohols are also articles of commerce. Triacontanol (C32) has activity as aplant growth regulator, but results have not been consistent enough for commercial use (52). Hexadecanol and octadecanol can be used to retardevaporation of water from reservoirs in arid regions (53). Detergent range alcohols also find application in antifoulant coatings, adhesives, and fabricsofteners (54).

Uses of Plasticizer Range Alcohols

The plasticizer range alcohols are utilized primarily in plasticizers, but they also have a wide range of uses in other industrial and consumer products,as shown in Table 12. As in the case of the detergent range alcohols, the plasticizer range materials are little used as is, but rather are employed as theester derivatives of acids such as phthalic, adipic, and trimellitic.

Table 12. Uses of Plasticizer Range Alcohols

Industry Use as alcohol Use as derivativeplastics emulsion polymerization plasticizer, flame retardant, oxidation and uv

stabilizer, heat stabilizer, polymerizationinitiator

petroleum and lubrication defoamer lubricant, grease, lubricant additive, hydraulicfluid, diesel fuel additive

agriculture stabilizer, tobacco sucker control, herbicide,fungicide

surfactant, insecticide, herbicide

mineral processing solvent, extractant, antifoam extractant, surfactanttextile leveling agent, defoamer surfactantcoatings solvent, smoothing agent surfactant, drying agent, solventmetal working solvent, lubricant, protective coating lubricant, surfactantchemical processing antifoam, solvent solventfood flavoring agentcosmetics perfume ingredient

Plasticizers. Over 70% of plasticizer range alcohols are ultimately consumed as plasticizers for PVC and other resins. Of this amount,80% is used as the diester of phthalic acid, for instance di-2-ethylhexyl phthalate (DOP) or diisodecyl phthalate (DIDP) [26761-40-0]. Otherplasticizers made from these alcohols are the diesters of adipic acid, azeleic acid, and sebacic acid, plus the triesters of phosphoric acid and trimelliticacid. A small amount of alcohol is used as the terminating agent in specialty polyester plasticizers. The adipates, azelates, and sebacates are employedas specialty materials in some food contact applications and in areas where low temperature flexibility is important, such as automobile interiors; eg,the diadipate ester of hexanol is the plasticizer in poly(vinyl butyral) used for automobile safety glass. The phosphates find application as good lowtemperature plasticizers and as flame retardant additives, whereas the trimellitates are used for high temperature applications such as the insulation ofelectrical wiring. The phthalates, however, are the general purpose plasticizers. Phthalate esters of alcohols from 4−13 carbons are available although



most are in the C8 through C10 range. All plasticizers are chosen on the basis of performance, cost, and ease of processing; DOP and DIDP are theworkhorses of the industry. When compared to DOP, phthalates of mixed linear alcohols (for instance, mixed heptyl, nonyl, and undecyl alcohols)give improved low temperature properties and resistance to volatile loss whereas those made of higher molecular weight alcohols (for instance,isodecyl or tridecyl alcohols) give improved resistance to extraction and volatile loss but exhibit some loss of plasticizing ability. In general, esters ofmixtures of alcohols are favored as plasticizers because they give a broader range of properties than esters of a single alcohol.

Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics: hexanol and 2-ethylhexanol are used as partof the catalyst system in the polymerization of acrylates, ethylene, and propylene (55); the peroxydicarbonate of 2-ethylhexanol is utilized as apolymerization initiator for vinyl chloride; various trialkyl phosphites find usage as heat and light stabilizers for plastics; organotin derivatives areused as heat stabilizers for PVC; octanol improves the compatibility of calcium carbonate filler in various plastics; 2-ethylhexanol is used to makeexpanded polystyrene beads (56); and acrylate esters serve as pressure sensitive adhesives.

Lubricants, Fuels, and Petroleum. The adipate and azelate diesters of C6 through C11 alcohols, as well as those of tridecyl alcohol,are used as synthetic lubricants, hydraulic fluids, and brake fluids. Phosphate esters are utilized as industrial and aviation functional fluids and to asmall extent as additives in other lubricants. A number of alcohols, particularly the C8 materials, are employed to produce zincdialkyldithiophosphates as lubricant antiwear additives. A small amount is used to make viscosity index improvers for lubricating oils. 2-Ethylhexylnitrate [24247-96-7] serves as a cetane improver for diesel fuels and hexanol is used as an additive to fuel oil or other fuels (57). Various enhanced oilrecovery processes utilize formulations containing hexanol or heptanol to displace oil from underground reservoirs (58); the alcohols and derivativesare also used as defoamers in oil production.

Agricultural Chemicals. Plasticizer range alcohols are used as intermediates in the manufacture of a number of herbicides (qv) andinsecticides, the largest use being that of 2-ethylhexanol and isooctyl alcohol to make the octyl ester of 2,4-dichlorophenoxyacetic acid (2,4-D)[94-75-7] for control of broadleaf weeds. Surfactants made from these alcohols are used as emulsifiers and wetting agents for agricultural chemicals.A mixture of octanol and decanol and the proper surfactants is able to kill the young meristemic tissue of some plants without harming more maturetissue. This is the basis for formulations that kill unwanted buds (suckers) in tobacco (59) and other plants and serve as a selective herbicide. Bothdecanol and 4-methyl-2-pentanol can be used as fungicides (qv) (60).

Surfactants. A number of surfactants are made from the plasticizer range alcohols, employing processes similar to those for thedetergent range materials such as sulfation, ethoxylation, and amination. These surfactants find application primarily in industrial and commercialareas: ether amines and trialkyl amines are used in froth flotation of ores, and the alcohols are also used to dewater mineral concentrates or breakemulsions (61). The dialkyl sulfosuccinates of many of the C8 through C13 alcohols also have surfactant applications. Octanol has found anapplication in a cleaning composition for engine carburetors, and decanol in a detergent for cleaning cotton (62).

Other Applications. The alcohols through C8 have applications as specialty solvents, as do derivatives of linear and branched hexanols.Inks, coatings, and dyes for polyester fabrics are other application areas for 2-ethylhexanol (63). Di(2-ethylhexyl) phthalate is used as a dielectric fluidto replace polychlorinated biphenyls. Trialkyl amines of the linear alcohols are used in solder fluxes, and hexanol is employed as a solvent in asoldering flux (64). Quaternary ammonium compounds of the plasticizer range alcohols are used as surfactants and fungicides, similarly to those ofthe detergent range alcohols.

BIBLIOGRAPHY

"Alcohols, Higher" in ECT 1st ed., Vol. 1, pp. 315−321, by H. B. McClure, Carbide and Carbon Chemicals Corporation, Unit of Union Carbide andCarbon Corporation; "Alcohols, Higher, Fatty" in ECT, 2nd ed., Vol. 1, pp. 542−559, by K. R. Ericson and H. D. Van Wagenen, The Procter& Gamble Company; "Alcohols, Higher, Synthetic" in ECT, 2nd ed., Vol. 1, pp. 560−569, by R. W. Miller, Eastman Chemical Products, Inc."Alcohols, Higher Aliphatic, Survey and Natural Alcohols Manufacture" in ECT 3rd ed., Vol. 1, pp. 716−739, by R. A. Peters, Procter & GambleCompany. 1. Braz. Pat. Pedido 86 2469A (Jan. 27, 1987), S. Inada and co-workers (to Seitetsu Kagaku Co., Ltd., Shinko Seito Co., Ltd., and Shinko

Sugar Production Co., Ltd.); Chem. Abstr. 107, 236087n (1987). 2. R. G. Ackman, S. N. Hooper, S. Epstein, and M. Kelleher, J. Am. Oil Chem. Soc. 49, 378−382 (1972). 3. J. Sever and P. L. Parker, Science 164, 1052−1054 (1969). 4. T. K. Miwa, J. Am. Oil Chem. Soc. 48, 259 (1971); A. P. Tulloch, J. Am. Oil Chem. Soc. 50, 367−371 (1973). 5. R. C. Wilhoit and B. J. Zwolinski, J. Phys. Chem. Ref. Data 2 (1) (1973). 6. U.S. Pat. 4,097,535 (June 27, 1978), K. Yang, K. L. Motz, and J. D. Reedy (to Continental Oil Co.). 7. D. Landini, F. Montanari, and F. Rolla, Synthesis 2, 134−136 (1979). 8. Eur. Pat. Appl. EP 281,417 (Sept. 14, 1988), P. Y. Fong, K. R. Smith, and J. D. Sauer (to Ethyl Corp.). 9. U.S. Pat. 4,683,336 (July 28, 1987), C. W. Blackhurst (to Sherex Chemical Co.). 10. Storage and Handling of Shell Neodol Detergent Alcohols, Ethoxylates, and Ethoxysulfates, SC:133−179, Shell Chemical Company, Houston, Tex.,

1979. 11. T. Gibson, CEH Marketing Research Report: Plasticizer Alcohols, SRI International, Menlo Park, Calif, 1989. 12. Data from U.S. International Trade Commission. 13. J. A. Monick, Alcohols, Their Chemistry, Properties and Manufacture, Reinhold Book Corp., New York, 1968, pp. 519−579. 14. R. E. Oborn and A. H. Ullman, J. Am. Oil Chem. Soc. 63, 95−97 (1986). 15. Products from the Chemicals Division, Procter & Gamble Company, Cincinnati, Ohio, 1987; Adol Fatty Alcohols, Sherex Chemical Company,

Dublin, Ohio, 1986; Vista Surfactants, Industrial Chemicals, and Plastics, Vista Chemical Company, Houston, Texas, 1987; Epal Linear PrimaryAlcohols, Ethyl Corporation, Baton Rouge, Louisiana, 1985; Neodol, Shell Chemical Company, Houston, Texas, 1987; Henkel Fat RawMaterials, Henkel K.-G.a.A., Düsseldorf, Fed. Rep. Germany.

16. The United States Pharmacopeia, 21st rev. The National Formulary, 16th ed., United States Pharmacopeial Convention, Rockville, Md., 1984; FoodChemicals Codex, 3rd ed., National Academy Press, Washington, D.C., 1981.

most are in the C8 through C10 range. All plasticizers are chosen on the basis of performance, cost, and ease of processing; DOP and DIDP are theworkhorses of the industry. When compared to DOP, phthalates of mixed linear alcohols (for instance, mixed heptyl, nonyl, and undecyl alcohols)give improved low temperature properties and resistance to volatile loss whereas those made of higher molecular weight alcohols (for instance,isodecyl or tridecyl alcohols) give improved resistance to extraction and volatile loss but exhibit some loss of plasticizing ability. In general, esters ofmixtures of alcohols are favored as plasticizers because they give a broader range of properties than esters of a single alcohol.

Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics: hexanol and 2-ethylhexanol are used as partof the catalyst system in the polymerization of acrylates, ethylene, and propylene (55); the peroxydicarbonate of 2-ethylhexanol is utilized as apolymerization initiator for vinyl chloride; various trialkyl phosphites find usage as heat and light stabilizers for plastics; organotin derivatives areused as heat stabilizers for PVC; octanol improves the compatibility of calcium carbonate filler in various plastics; 2-ethylhexanol is used to makeexpanded polystyrene beads (56); and acrylate esters serve as pressure sensitive adhesives.

Lubricants, Fuels, and Petroleum. The adipate and azelate diesters of C6 through C11 alcohols, as well as those of tridecyl alcohol,are used as synthetic lubricants, hydraulic fluids, and brake fluids. Phosphate esters are utilized as industrial and aviation functional fluids and to asmall extent as additives in other lubricants. A number of alcohols, particularly the C8 materials, are employed to produce zincdialkyldithiophosphates as lubricant antiwear additives. A small amount is used to make viscosity index improvers for lubricating oils. 2-Ethylhexylnitrate [24247-96-7] serves as a cetane improver for diesel fuels and hexanol is used as an additive to fuel oil or other fuels (57). Various enhanced oilrecovery processes utilize formulations containing hexanol or heptanol to displace oil from underground reservoirs (58); the alcohols and derivativesare also used as defoamers in oil production.

Agricultural Chemicals. Plasticizer range alcohols are used as intermediates in the manufacture of a number of herbicides (qv) andinsecticides, the largest use being that of 2-ethylhexanol and isooctyl alcohol to make the octyl ester of 2,4-dichlorophenoxyacetic acid (2,4-D)[94-75-7] for control of broadleaf weeds. Surfactants made from these alcohols are used as emulsifiers and wetting agents for agricultural chemicals.A mixture of octanol and decanol and the proper surfactants is able to kill the young meristemic tissue of some plants without harming more maturetissue. This is the basis for formulations that kill unwanted buds (suckers) in tobacco (59) and other plants and serve as a selective herbicide. Bothdecanol and 4-methyl-2-pentanol can be used as fungicides (qv) (60).

Surfactants. A number of surfactants are made from the plasticizer range alcohols, employing processes similar to those for thedetergent range materials such as sulfation, ethoxylation, and amination. These surfactants find application primarily in industrial and commercialareas: ether amines and trialkyl amines are used in froth flotation of ores, and the alcohols are also used to dewater mineral concentrates or breakemulsions (61). The dialkyl sulfosuccinates of many of the C8 through C13 alcohols also have surfactant applications. Octanol has found anapplication in a cleaning composition for engine carburetors, and decanol in a detergent for cleaning cotton (62).

Other Applications. The alcohols through C8 have applications as specialty solvents, as do derivatives of linear and branched hexanols.Inks, coatings, and dyes for polyester fabrics are other application areas for 2-ethylhexanol (63). Di(2-ethylhexyl) phthalate is used as a dielectric fluidto replace polychlorinated biphenyls. Trialkyl amines of the linear alcohols are used in solder fluxes, and hexanol is employed as a solvent in asoldering flux (64). Quaternary ammonium compounds of the plasticizer range alcohols are used as surfactants and fungicides, similarly to those ofthe detergent range alcohols.

BIBLIOGRAPHY

"Alcohols, Higher" in ECT 1st ed., Vol. 1, pp. 315−321, by H. B. McClure, Carbide and Carbon Chemicals Corporation, Unit of Union Carbide andCarbon Corporation; "Alcohols, Higher, Fatty" in ECT, 2nd ed., Vol. 1, pp. 542−559, by K. R. Ericson and H. D. Van Wagenen, The Procter& Gamble Company; "Alcohols, Higher, Synthetic" in ECT, 2nd ed., Vol. 1, pp. 560−569, by R. W. Miller, Eastman Chemical Products, Inc."Alcohols, Higher Aliphatic, Survey and Natural Alcohols Manufacture" in ECT 3rd ed., Vol. 1, pp. 716−739, by R. A. Peters, Procter & GambleCompany. 1. Braz. Pat. Pedido 86 2469A (Jan. 27, 1987), S. Inada and co-workers (to Seitetsu Kagaku Co., Ltd., Shinko Seito Co., Ltd., and Shinko

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Wiley & Sons, Inc., New York, 1982, pp. 4257−4708. 23. MSDS for Alfol Alcohols, Vista Chemical Company, Houston, Texas, 1984, 1985. 24. J. Am. Coll. Toxicol. 7, 359−423 (1988). 25. H. W. Gerarde and D. B. Ahlstrom, Arch. Environ. Health 13, 457−461 (1966). 26. U.S. Pat. 2,091,800 (Aug. 31, 1937), H. Adkins, K. Folkers, and R. Connor (to Rohm & Haas Co.). 27. Ger. Offen. 3,624,812 (Jan. 28, 1988), F.-J. Carduck, J. Falbe, T. Fleckenstein, and J. Pohl (to Henkel K.-G.a.A.). 28. U.S. Pat. 4,608,202 (Aug. 26, 1986), H. Lepper and L. Friesenhagen (to Henkel K.-G.a.A.). 29. F. E. Sullivan, Chem. Eng. New York 81, 56 (April 15, 1974). 30. U.S. Pat. 4,533,648 (Aug. 6, 1985), P. J. Corrigan, R. M. King, and S. A. Van Diest (to The Procter & Gamble Co.). 31. U. R. Kreutzer, J. Am. Oil Chem. Soc. 61, 343−348 (1984). 32. H. Buchold, Chem. Eng. New York 90, 42, 43 (1983). 33. U.S. Pat. 4,259,536 (Mar. 31, 1981), T. Voeste, H. J. Schmidt, and F. Marschner (to Metallgesellschaft A.-G.). 34. H. Bertsch, H. Reinheckel, and K. Haage, Fette Seifen Anstrichm. 66, 763−773 (1964); E. S. Lower, Spec. Chem. 2(1), 30 (1982). 35. U.S. Pat. 3,193,586 (July 6, 1965), W. Rittmeister (to Dehydag, Deutsche Hydrierwerke); J. D. Richter and P. J. Van Den Berg, J. Am. Oil

Chem. Soc., 46, 158−162, 163−166 (1969). 36. Brit. Pat. 1,076,855 (July 26, 1967), A. J. Pantulu, K. T. Achaya, G. S. Sidhu, and S. H. Laheer (to Council of Scientific and Industrial

Research, India); Jpn. Kokai 58 210,035 (Dec. 7, 1983) (to Kao Corp.); Ger. Pat. 2,513,377 (Sept. 9, 1976), G. Demmering (to Henkel& Cie.).

37. U.S. Pat. 3,729,520 (Apr. 24, 1973), H. Rutzen and W. Rittmeister (to Henkel & Cie.). 38. Brit. Pat. 1,335,173 (Oct. 24, 1973) (to New Japan Chemical Co.). 39. Eur. Pat. Appl. 296,941 (Dec. 28, 1988), G. Dion Biro and R. De Bona Biro; Ger. Offen. 3,807,250 (Sep. 15, 1988), J. Sulkiewicz (to

Anthes Industries, Inc.). 40. Jpn. Kokai 63 176,345 (July 20, 1988), C. Tomizawa and S. Narisawa (to Sumitomo Chemical Co.). 41. Ger. Offen. 3,517,154 (Nov. 13, 1986), W. Von Rybinski and R. Koester (to Henkel K.-G.a.A.). 42. Ger. Offen. 3,535,454 (Apr. 9, 1987), W. Braeuer and P. Diewald (to Bayer A.-G.). 43. Jpn. Kokai 53 101,061 (Sep. 4, 1978), E. Sugawara, S. Shioume, and K. Yorikane (to Dainichi Nippon Cables, Ltd.). 44. Jpn. Kokai 58 221,300 (Dec. 22, 1983) (to Nippon Kokan K.K. and Kao Corp.). 45. Eur. Pat. Appl. 210,721 (Feb. 4, 1987), P. M. Burrill (to Dow Corning Corp.). 46. Ger. Offen. 3,001,387 (July 23, 1981), R. Peppmoeller (to Chemische Fabrik Stockhausen und Cie.). 47. U. Ploog, Seife. Oele. Fette. Wachse, 109, 225−229 (1983). 48. Eur. Pat. Appl. 182,552 (May 28, 1986), M. K. Budd and M. H. Foster (to Alcan International Ltd.); Jpn. Kokai 63 393 (Jan. 5, 1988), K.

Nabatake, M. Ogawa, Y. Iwasaki, and T. Mizuta (to Nippon Steel Corp. and Daido Chemical Industry Co., Ltd.); N. P. Korotkova, I. G.Turyanchik, G. I. Cherednichenko, and V. P. Temnenko, Neftepererab. Neftekhim. (Kiev), 34, 16−18 (1988); Chem. Abstr. 110, 98392s (1989).

49. U.S. Pat. 4,213,500 (July 22, 1980), R. L. Cardenas and J. T. Carlin (to Texaco, Inc.). 50. Jpn. Kokai 59 217,782 (Dec. 7, 1984) (to Lion Corp.); U.S. Pat. 4,239,862 (Dec. 16, 1980), D. N. Matthews, W. Nudenberg, and H. A.

Petersen (to Uniroyal, Inc.); Jpn. Kokai 61 138,606 (June 26, 1986), T. Tsutsui, M. Kioka, and N. Kashiwa (to Mitsui PetrochemicalIndustries, Ltd.).

51. E. S. Lower, Polym. Paint Colour J. 173, 506 (1983). 52. S. K. Ries, CRC Crit. Rev. Plant Sci. 2, 239−285 (1985); S. K. Ries and R. Houtz, HortScience 18, 654−662 (1983). 53. U.S. Pat. 3,415,614 (Dec. 10, 1968), R. R. Egan and S. R. Sheeran (to Ashland Oil and Refining Co.). 54. Jpn. Kokai 62 13,471 (Jan. 22, 1987), Y. Yonehara and Y. Nanishi (to Kansai Paint Co., Ltd.); Jpn. Kokai 58 101,182 (June 16, 1983) (to

Toshiba Silicone Co., Ltd.); Belg. Pat. 904,142 (July 30, 1986), J. P. Grandmaire and A. Jacques (to Colgate-Palmolive Co.). 55. Eur. Pat. Appl. 190,892 (Aug. 13, 1986), C. J. Chang (to Rhom and Haas Co.); Jpn. Kokai 62 135,501 (June 18, 1987), Y. Kondo, M. Mori,

Y. Naito, and T. Chigusa (to Toyo Soda Mfg. Co., Ltd.); Jpn. Kokai 63 89,507 (Apr. 20, 1988), M. Terano, H. Soga, and M. Inoue (to TohoTitanium Co., Ltd.).

56. Jpn. Kokai 58 122,935 (July 21, 1983) (to Sekisui Kaseihin Kogyo K. K. and Eslen Kako K. K.); Fr. Demande 2,531,971 (Feb. 24, 1984),H. P. Schlumpf, C. Stock, and P. Trouve (to Pluess-Staufer A.-G.).

57. Ger. Offen. 2,910,011 (Sep. 20, 1979), M. J. Rose; Ger. Offen. 3,626,102 (Feb. 11, 1988), M. L. Nelson and O. L. Nelson, Jr. (to PolarMolecular Corp.).

58. U.S. Pat. 4,485,871 (Dec. 4, 1984), B. W. Davis (to Chevron Research Co.); Brit. Pat. 1,542,166 (Mar. 14, 1979), Y.-C. Chiu (to ShellInternationale Research Maatschappij B.V.); U.S. Pat. 4,193,452 (Mar. 18, 1980), P. M. Wilson and J. Pao (to Mobil Oil Corp.).

59. Off-Shoot-T, Cochrane Corporation, Memphis, Tenn., 1984. 60. U.S. Pat. 3,778,509 (Dec. 11, 1973), H. L. Lewis (to Cotton, Inc.); Ger. Offen. 2,330,596 (Jan. 10, 1974), E. L. Frick and R. T. Burchill (to

National Research Development Corp.).

17. Exxal Guerbet Alcohols, Exxon Corporation, Houston, Texas, 1988. 18. Vista Surfactants, Industrial Chemicals, and Plastics, Vista Chemical Company, Houston, Texas, 1987; Epal Linear Primary Alcohols, Ethyl

Corporation, Baton Rouge, Louisiana, 1985; Exxal Alcohols, Exxon Chemical Company, Houston, Texas, 1988; Aristech Alcohols,2-Ethlyhexanol, Aristech Chemical Corporation, Pittsburgh, Pa., 1988; Technical Bulletin, 2-Ethylhexanol, BASF Corporation, Parsippany, N.J.,1987.

19. D. L. J. Opdyke, ed., Monographs on Fragrance Raw Materials, Pergamon Press, Oxford, 1974, pp. 8, 35, 39, 42. 20. R. A. Scala and E. G. Burtis, J. Am. Ind. Hyg. Assn. 34, 493−499 (1973). 21. Epal Linear Primary Alcohols, Ethyl Corporation, Baton Rouge, Louisiana, 1985. 22. V. K. Rowe and S. B. McCollister in G. D. Clayton and F. E. Clayton, eds., Patty's Industrial Hygiene and Toxicology, Vol. 2C, 3rd ed., John

Wiley & Sons, Inc., New York, 1982, pp. 4257−4708. 23. MSDS for Alfol Alcohols, Vista Chemical Company, Houston, Texas, 1984, 1985. 24. J. Am. Coll. Toxicol. 7, 359−423 (1988). 25. H. W. Gerarde and D. B. Ahlstrom, Arch. Environ. Health 13, 457−461 (1966). 26. U.S. Pat. 2,091,800 (Aug. 31, 1937), H. Adkins, K. Folkers, and R. Connor (to Rohm & Haas Co.). 27. Ger. Offen. 3,624,812 (Jan. 28, 1988), F.-J. Carduck, J. Falbe, T. Fleckenstein, and J. Pohl (to Henkel K.-G.a.A.). 28. U.S. Pat. 4,608,202 (Aug. 26, 1986), H. Lepper and L. Friesenhagen (to Henkel K.-G.a.A.). 29. F. E. Sullivan, Chem. Eng. New York 81, 56 (April 15, 1974). 30. U.S. Pat. 4,533,648 (Aug. 6, 1985), P. J. Corrigan, R. M. King, and S. A. Van Diest (to The Procter & Gamble Co.). 31. U. R. Kreutzer, J. Am. Oil Chem. Soc. 61, 343−348 (1984). 32. H. Buchold, Chem. Eng. New York 90, 42, 43 (1983). 33. U.S. Pat. 4,259,536 (Mar. 31, 1981), T. Voeste, H. J. Schmidt, and F. Marschner (to Metallgesellschaft A.-G.). 34. H. Bertsch, H. Reinheckel, and K. Haage, Fette Seifen Anstrichm. 66, 763−773 (1964); E. S. Lower, Spec. Chem. 2(1), 30 (1982). 35. U.S. Pat. 3,193,586 (July 6, 1965), W. Rittmeister (to Dehydag, Deutsche Hydrierwerke); J. D. Richter and P. J. Van Den Berg, J. Am. Oil

Chem. Soc., 46, 158−162, 163−166 (1969). 36. Brit. Pat. 1,076,855 (July 26, 1967), A. J. Pantulu, K. T. Achaya, G. S. Sidhu, and S. H. Laheer (to Council of Scientific and Industrial

Research, India); Jpn. Kokai 58 210,035 (Dec. 7, 1983) (to Kao Corp.); Ger. Pat. 2,513,377 (Sept. 9, 1976), G. Demmering (to Henkel& Cie.).

37. U.S. Pat. 3,729,520 (Apr. 24, 1973), H. Rutzen and W. Rittmeister (to Henkel & Cie.). 38. Brit. Pat. 1,335,173 (Oct. 24, 1973) (to New Japan Chemical Co.). 39. Eur. Pat. Appl. 296,941 (Dec. 28, 1988), G. Dion Biro and R. De Bona Biro; Ger. Offen. 3,807,250 (Sep. 15, 1988), J. Sulkiewicz (to

Anthes Industries, Inc.). 40. Jpn. Kokai 63 176,345 (July 20, 1988), C. Tomizawa and S. Narisawa (to Sumitomo Chemical Co.). 41. Ger. Offen. 3,517,154 (Nov. 13, 1986), W. Von Rybinski and R. Koester (to Henkel K.-G.a.A.). 42. Ger. Offen. 3,535,454 (Apr. 9, 1987), W. Braeuer and P. Diewald (to Bayer A.-G.). 43. Jpn. Kokai 53 101,061 (Sep. 4, 1978), E. Sugawara, S. Shioume, and K. Yorikane (to Dainichi Nippon Cables, Ltd.). 44. Jpn. Kokai 58 221,300 (Dec. 22, 1983) (to Nippon Kokan K.K. and Kao Corp.). 45. Eur. Pat. Appl. 210,721 (Feb. 4, 1987), P. M. Burrill (to Dow Corning Corp.). 46. Ger. Offen. 3,001,387 (July 23, 1981), R. Peppmoeller (to Chemische Fabrik Stockhausen und Cie.). 47. U. Ploog, Seife. Oele. Fette. Wachse, 109, 225−229 (1983). 48. Eur. Pat. Appl. 182,552 (May 28, 1986), M. K. Budd and M. H. Foster (to Alcan International Ltd.); Jpn. Kokai 63 393 (Jan. 5, 1988), K.

Nabatake, M. Ogawa, Y. Iwasaki, and T. Mizuta (to Nippon Steel Corp. and Daido Chemical Industry Co., Ltd.); N. P. Korotkova, I. G.Turyanchik, G. I. Cherednichenko, and V. P. Temnenko, Neftepererab. Neftekhim. (Kiev), 34, 16−18 (1988); Chem. Abstr. 110, 98392s (1989).

49. U.S. Pat. 4,213,500 (July 22, 1980), R. L. Cardenas and J. T. Carlin (to Texaco, Inc.). 50. Jpn. Kokai 59 217,782 (Dec. 7, 1984) (to Lion Corp.); U.S. Pat. 4,239,862 (Dec. 16, 1980), D. N. Matthews, W. Nudenberg, and H. A.

Petersen (to Uniroyal, Inc.); Jpn. Kokai 61 138,606 (June 26, 1986), T. Tsutsui, M. Kioka, and N. Kashiwa (to Mitsui PetrochemicalIndustries, Ltd.).

51. E. S. Lower, Polym. Paint Colour J. 173, 506 (1983). 52. S. K. Ries, CRC Crit. Rev. Plant Sci. 2, 239−285 (1985); S. K. Ries and R. Houtz, HortScience 18, 654−662 (1983). 53. U.S. Pat. 3,415,614 (Dec. 10, 1968), R. R. Egan and S. R. Sheeran (to Ashland Oil and Refining Co.). 54. Jpn. Kokai 62 13,471 (Jan. 22, 1987), Y. Yonehara and Y. Nanishi (to Kansai Paint Co., Ltd.); Jpn. Kokai 58 101,182 (June 16, 1983) (to

Toshiba Silicone Co., Ltd.); Belg. Pat. 904,142 (July 30, 1986), J. P. Grandmaire and A. Jacques (to Colgate-Palmolive Co.). 55. Eur. Pat. Appl. 190,892 (Aug. 13, 1986), C. J. Chang (to Rhom and Haas Co.); Jpn. Kokai 62 135,501 (June 18, 1987), Y. Kondo, M. Mori,

Y. Naito, and T. Chigusa (to Toyo Soda Mfg. Co., Ltd.); Jpn. Kokai 63 89,507 (Apr. 20, 1988), M. Terano, H. Soga, and M. Inoue (to TohoTitanium Co., Ltd.).

56. Jpn. Kokai 58 122,935 (July 21, 1983) (to Sekisui Kaseihin Kogyo K. K. and Eslen Kako K. K.); Fr. Demande 2,531,971 (Feb. 24, 1984),H. P. Schlumpf, C. Stock, and P. Trouve (to Pluess-Staufer A.-G.).

57. Ger. Offen. 2,910,011 (Sep. 20, 1979), M. J. Rose; Ger. Offen. 3,626,102 (Feb. 11, 1988), M. L. Nelson and O. L. Nelson, Jr. (to PolarMolecular Corp.).

58. U.S. Pat. 4,485,871 (Dec. 4, 1984), B. W. Davis (to Chevron Research Co.); Brit. Pat. 1,542,166 (Mar. 14, 1979), Y.-C. Chiu (to ShellInternationale Research Maatschappij B.V.); U.S. Pat. 4,193,452 (Mar. 18, 1980), P. M. Wilson and J. Pao (to Mobil Oil Corp.).

59. Off-Shoot-T, Cochrane Corporation, Memphis, Tenn., 1984. 60. U.S. Pat. 3,778,509 (Dec. 11, 1973), H. L. Lewis (to Cotton, Inc.); Ger. Offen. 2,330,596 (Jan. 10, 1974), E. L. Frick and R. T. Burchill (to

National Research Development Corp.).



61. Ger. Offen. 3,018,758 (Dec. 17, 1981), R. Peppmoeller (to Chemische Fabrik Stockhausen und Cie.); U.S. Pat. 4,206,063 (June 3, 1980), C.Dugan, M. E. Lewellyn, and S. S. Wang (to American Cyanamid Co.).

62. Jpn. Kokai 60 155,299 (Aug. 15, 1985), H. Murata and R. Hidaka (to Nitto Chemical Industry Co., Ltd.); U.S. Pat. 4,056,355 (Nov. 1,1977), J. H. Kolaian, F. C. McCoy, and J. A. Patterson (to Texaco, Inc.).

63. U.S. Pat. 4,711,802 (Dec. 8, 1986), H. P. Tannenbaum (to E. I. du Pont de Nemours & Co., Inc.); Ger. Offen. 3,508,419 (Sep. 11, 1986),G. Neubert, M. Melan, and W. Schultze (to BASF A.-G.); Ger. Offen. 2,413,866 (Oct. 2, 1975), M. Vescia, M. Daeuble, and R. Widder (toBASF A.-G.).

64. Ger. Offen. 3,513,424 (Oct. 23, 1986), W. Kellberg (to Siemens A.-G.).

General References

Fatty Alcohols, Raw Materials, Methods, Uses, Henkel K.-G.a.A., Düsseldorf, 1982. Also published in German as Fettalkohole.J. A. Monick, Alcohols, Their Chemistry, Properties and Manufacture, Reinhold Book Corp., New York, 1968.E. J. Wickson, ed., Monohydric Alcohols, ACS Symp. Ser. 159, American Chemical Society, Washington, D.C., 1981.

Richard A. PetersThe Procter & Gamble Company



fatty alcool

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fatty alcohols

linear alcohols

similar alcohols

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