[acs symposium series] green polymer chemistry: biocatalysis and materials ii volume 1144 ||...

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Chapter 21 Biobased Industrial Products from Soybean Biorefinery E. Hablot, D. Graiver, and R. Narayan * Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing, Michigan 48824, U.S.A. * E-mail: [email protected] The use of biomass as raw materials for the production of fuels and chemicals to displace fossil resources has been the focus of many research activities in recent years. These activities are motivated by the desire for a sustainable resource supply, enhanced national security, and macroeconomic benefits for rural communities and the society at large. The use of plastic materials in the modern world has been increasing rapidly due to the relatively low cost of production and specific set of properties that can be derived from them. Until recently crude oil was the major source of these basic chemicals and value-added polymeric materials. Sustainable economics requires a similar wide range of processes that can utilize every component of these renewable resources. In our work with soybeans, we have used all parts of the bean (meal, oil and hulls) as a source of materials that can be converted economically to value-added products. The focus of this paper is to provide a few examples of this biorefinery concept that includes a catalyzed ozonation process of oil triglycerides to produce polyols, the conversion process of proteins in the meal to rigid polyurethane foams and the production of isocyanate-free polyurethanes from dimer acids. We will also review a novel silylation process that yields moisture activated RTV coatings from vegetable oils. © 2013 American Chemical Society Downloaded by UNIV OF AUCKLAND on October 29, 2014 | http://pubs.acs.org Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch021 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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Page 1: [ACS Symposium Series] Green Polymer Chemistry: Biocatalysis and Materials II Volume 1144 || Biobased Industrial Products from Soybean Biorefinery

Chapter 21

Biobased Industrial Products fromSoybean Biorefinery

E. Hablot, D. Graiver, and R. Narayan*

Department of Chemical Engineering and Materials Science,Michigan State University, East Lansing, Michigan 48824, U.S.A.

*E-mail: [email protected]

The use of biomass as raw materials for the production of fuelsand chemicals to displace fossil resources has been the focusof many research activities in recent years. These activitiesare motivated by the desire for a sustainable resource supply,enhanced national security, and macroeconomic benefits forrural communities and the society at large. The use of plasticmaterials in the modern world has been increasing rapidlydue to the relatively low cost of production and specific setof properties that can be derived from them. Until recentlycrude oil was the major source of these basic chemicals andvalue-added polymeric materials. Sustainable economicsrequires a similar wide range of processes that can utilize everycomponent of these renewable resources. In our work withsoybeans, we have used all parts of the bean (meal, oil and hulls)as a source of materials that can be converted economicallyto value-added products. The focus of this paper is to providea few examples of this biorefinery concept that includes acatalyzed ozonation process of oil triglycerides to producepolyols, the conversion process of proteins in the meal torigid polyurethane foams and the production of isocyanate-freepolyurethanes from dimer acids. We will also review a novelsilylation process that yields moisture activated RTV coatingsfrom vegetable oils.

© 2013 American Chemical Society

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Introduction

The use of biomass as raw materials for production of fuels and chemicals todisplace fossil resources has been the focus of many research activities in recentyears. These activities are motivated by the possibility of positive contributions toa sustainable resource supply and macroeconomic benefits for local communitiesand the society at large. Much of these activities are directed following thebiorefinery concept which integrates biomass conversion and equipment toproduce fuels, energy and chemicals. Industrial biorefineries have been identifiedas the most promising route to the creation of a new domestic biobased industry.By producing a large range of products, a biorefinery can take advantage ofthe diversity in biomass components and intermediates to increase the valuederived from the biomass feedstock. Furthermore, a viable biorefinery shouldproduce low-volume but high-value chemicals with high profit margins as wellas high-volume but low-value products such as biofuel and commodity products.The biofuel can be used to meet the national energy needs as well as providingenergy for in-house use to reduce process costs and minimize CO2 emission fromfossil fuel.

Soybean is an attractive candidate for such biorefinery transformation sinceit is readily available and its relatively low price ($430/T in the USA in 2010(1)). The soybean is primarily an industrial crop cultivated for its oil and proteinsand both can be used as raw materials for industrial products and intermediates.A typical soybean composition is presented in Figure 1. Although the exactcomposition of the bean depends on many variables including trait, climate, soil,geographical location, maturity, the extraction process, etc. it is apparent thatthe protein content in the bean is almost twice the content of the oil (about 38%compared with only 18% oil).

Despite the relatively low oil content in the bean, soybeans are the largestsingle source of edible oil and account for 52% of the total oil seed production ofthe world. According to FAO estimates over 260 million tonnes of soybean wasproduced worldwide in the year 2010 (1). Soybeans are grown predominantlyin North and South America (Brazil and Argentina) where 34% and 47%,respectively, of the 2010/11 world’s supply of beans was harvested (2).

The recovery of oil from the bean has been done for many years but both theprocess and the equipment have undergone continuous evolution through this time.Currently, the most commonmethods are hydraulic pressing, expeller pressing andsolvent extraction. Presently, the solvent extraction process is the most commonprocess using hexane as the solvent. The oil is found as triglycerides, which aretri-esters of glycerol with the fatty acids that are listed in Table I. It should be notedthat the concentration of these fatty acids in the bean varies depending on the traitof the soy, the season and the growing conditions (humidity, light, soil, etc.) (3).In general, the soybean oil contains a significant amount of unsaturation on theorder of 4.6 double bonds per triglyceride. These double bonds can be used asa starting point for various chemical modifications to modify the oil and producenew derivatives and chemicals.

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Figure 1. Typical soybean composition.

Table I. Typical soybean oil fatty acid composition

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Traditionally, soybean oil has been considered as a major agricultural cropof great importance for the food and feed market. Nowadays however, it isincreasingly used as a feedstock for a wide variety of industrial products includinglubricants, candles, cleaning products, hydraulic fluids, paint strippers, dustsuppressants, solvents and printing inks (4–6). Recently, an increasing amountof soybean oil is also being used for biodiesel (7), which has led to increasesoybean oil production and consequently a need to define new applications forthe soymeal.

The left-over product from the oil extraction process is known as soymealand is composed of proteins (44%), carbohydrates (36.5%), moisture (12%),fiber (7%) and fat (0.5%) (8). Most of the soymeal is processed toward animalfeed primarily for poultry, swine, cattle, and aquaculture as soy flour, soyconcentrates, or soy isolates. A relatively small portion is also processed forhuman consumption and even a smaller portion (about 0.5%) is used for industrialapplications, primarily as adhesives for plywood and particle board. Someother minor applications also include additives in textured paints, insecticides,dry-wall tape compounds, linoleum backing, paper coatings, fire-fighting foams,fire-resistant coatings, asphalt emulsions, cosmetics and printing inks (9).

Figure 2. Technology platform for value-added industrial products from asoybean refinery.

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In our work, we developed a multiple biorefinery processes that utilizedboth the oil and the meal of the soybean as the starting materials for variousintermediates and industrial products. The general technology platformsare shown schematically in Figure 2. Special attention was directed towardcomplying with the ‘green chemistry’ principles for all the synthetic strategiesthat we employed. These include the use of non-hazardous reagents, solvent-lessprocesses, and safe operating procedures. A brief description of some of theseprocesses is described below.

Polyols by Ozonation of Soybean Oil

Polyols suitable for polymerization into polyurethane resins have beenprepared in the past directly from hydroxyl containing castor oil (10, 11). Theseearly open cell foams were later improved by DuPont (12) and were made overa wide density range (2-20 lb./ft3). However, castor oil contains secondaryalcohol groups and a fairly low hydroxyl number. Consequently, polyurethaneresins prepared from castor oil tend to be rubbery with inferior properties and arerelatively expensive due to the relatively high cost of the oil.

Several methods are described in the literature that have been used toprepare polyols from soy oil. Alcoholysis of triglycerides with glycerol (13),α-methylglucoside or pentaerytol (14) has been used in the past. In this processthe hydroxyl number of the product is determined by the ratio of the reagents.However, usually, this process requires an elevated temperature (250°C) and basecatalysis such as sodium hydroxide (which must be carefully neutralized beforeadding the isocyanate to prepare the polyurethane). Problems due to prematuredegradation limit the use of the process.

Vegetable oil polyols are commonly prepared by epoxidation (15) wherebythe oil is first reacted with peroxyacid acid (e.g. peracetic acid) for severalhours and then hydroxylated (16). Although significant improvements havebeen realized since these reactions were first proposed, side-reactions includingcyclization, transesterification, polymerization and undesirable by-productsalso occur. More importantly, secondary alcohols are obtained by this processwhich are inherently less reactive than primary alcohols and can adverselyimpact the polymerization process. Hydroformylation of vegetable oils leads toprimary polyols. Here, an aldehyde functional oil is first obtained which is thenhydrogenated to yield primary alcohols (17). Polyurethanes prepared from suchpolyols had different mechanical properties depending on the hydroformylationcatalyst that was used. Thus, rigid materials at room temperature were obtainedwith a rhodium catalyst while cobalt catalyzed hydroformylation led to rubberymaterials.

Various oxidation methods are available and all lead to primary alcohols.These methods utilize air at elevated temperatures, molecular oxygen (18),organic hydroperoxide in the presence of OsO4 and a NaBr cocatalyst (19)or ozonation followed by decomposing ozonides to alcohols using NaBH4or similar reducing agents. Ozonation is most effective method due to thehigh reactivity of the ozone toward double bonds. In the past it was used to

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determine the structure of olefins and identify the position of the double-bond.These analyses were based on the generally agreed mechanism (20) that thereaction occurs in several steps (Figure 3) starting with the formation of a 1,3-dipolar cycloaddition product from the insertion of ozone to the double bond.This cycloaddition product eventually decomposes into a mixture of aldehydesand carbonyl oxides which can be reduced to alcohols. Currently, it is usedcommercially by Emery-Oleochimicals group which produces around 10,000tons per year of azelaic acid (nonane-1,9-dioic acid) along with pelargonic acid(nonanoic acid) by ozonolysis of oleic acid (21). Industrial scale ozonolysis iscarried out in pelargonic acid run countercurrent to ozone at 25-45°C followed bydecomposition at 60-100°C in excess oxygen (22, 23).

Figure 3. Generalized ozonolysis reaction where carbonyl oxide and aldehyde(structure 1) recombine to yield an ozonide intermediate (structure 2) which

further reacts with an alcohol to yield an ester (structure 3).

Ozone, as an oxidation agent, has several distinct advantages over otheroxidation agents. Since ozone is produced and used on-site, issues related to safestorage and transportation are avoided. Unreacted ozone is simply decomposedback to oxygen and no separation or removal of by products is needed as isthe case with other oxidation agents. Production of ozone is fairly simple andinvolves passing an oxygen containing atmosphere through an ozone generator.Modern ozone generators are readily available; they are relatively inexpensiveand are much more efficient than old models. However, care must be used sinceozone is highly reactive and the ozonide intermediate can decompose violently.Thus, previous ozonation reactions were conducted at low temperatures (-78 °C)in dilute solutions usually with a chlorinated solvent and in small batches.

We investigated this reaction and devised a continuous process that can berun safely close to room temperature to produce vegetable oil polyols (24–27).In this process, the chain-ends that are formed by the cleavage of the double

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bonds are coupled with low molecular weight alcohols containing multiplehydroxyl groups (e.g. ethylene glycol, glycerol, etc.). As shown in Figure 4, thecleavage of the double bonds and the subsequent esterification reaction to yieldthe new chain-ends hydroxyl groups lead to a product distribution containinghydroxyl terminated short molecular weight triglycerides and linear mono- anddifunctional hydroxylated species. Thus, oleic acid would be cleaved at thedouble bond in the 9th carbon leaving 2-hydroxy nonanoate residue on thetriglyceride and 2-hydroxyethyl nonanoate (Figure 4A). Similarly, linoleic acidwould be cleaved at the double bonds to yield 2-hydroxy nonanoate residue onthe triglyceride, 2-hydroxyethyl hexanoate and bis(2-hydroxyethyl) malonate(Figure 4B). Linolenic acid, which contains multiple unsaturations at the 9th,12th, and 15th positions would yield the same 2-hydroxy nonanoate residue onthe triglyceride, 2-hydroxyethyl propionoate and bis(2-hydroxyethyl) malonate(Figure 4C). The saturated fatty acids (e.g. palmitic and stearic) are not cleavedby the ozone and remain intact. The statistical distribution of these polyols isshown in Figure 5 whereby 2-hydroxy nonanoate is designated as N, palmitate asP, stearate as S, bis(2-hydroxyethyl) malonate as EE, (2-hydroxyethyl) nonanoateas E1, (2-hydroxyethyl) hexanoate as E2 and (2-hydroxyethyl) propionoate as E3.

Figure 4. Polyols composition of triglycerides containing (A) oleic acid, (B)linoleic acid, and (C) linolenic acid by catalyzed ozonolysis of soy oil with

ethylene glycol.

Several important conclusions are apparent from this statistical analysis: (1).Overall, the polyol triglyceride mixture is much more uniform than the originalsoy triglyceride composition since the double bonds of all the unsaturated fattyacid in the 9th position leading to a significant concentration of NNN polyol. (2).About 24 wt% of the product mixture contains triols (NNN), 13 wt.% containsdiols (NNP and NNS), less than 3 wt.% contains mono functional alcohols (NPS,PPN and SSN) and only a very small component (less than 0.2 wt.%) of unreactive

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triglycerides having no hydroxyl groups is present in the mixture. The very smallquantity of unreactive components is very important since upon polymerizationit is not reactive and thus could diffuse out of the polymer over time resultingin undesirable changes in its properties. (3). About half of the polyols productmixture is composed of triglycerides. The other half is composed of the lowmolecular weight diol (EE) and mono functional alcohols (E1, E2 and E3). Ifneeded, these lowmolecular weight species can be removed and separated from thepolyol triglycerides. However, in most cases this is not necessary as these polyolsare reactive and will participate in the polymerization. It is also important to notethat all these polyols are composed of primary hydroxyls, which aremore desirablethan secondary alcohols in the preparation of polyurethanes and polyesters.

Figure 5. Statistical distribution of soy polyols obtained by alkaline catalyticozonolysis of soy oil with ethylene glycol.

As expected, the FTIR spectrum of the soy polyol mixture is characterized bya broad hydroxyl stretching peak around 3500 cm–1, the complete disappearance ofthe C=C band at 3005 cm-1, and the C=C stretch at 1650 cm–1. The FTIR spectrumfurther indicates that at the end of the ozonolysis reaction the carbonyl stretch at1743 cm–1 is broad, suggesting the formation of new carbonyl compounds. Noabsorptions around 2900–2700 cm–1were noted indicating the absence of aldehydegroups. Further confirmation of the soy polyol structure was obtained from 13C-NMR (Figure 6). The characteristic double peak of double bonds at 130 ppm,related to the unsaturated fatty acids in the soybean oil, didn’t appear in the soybeanpolyol spectrum, indicating complete cleavage of the double bonds. The carbonylester peaks (177 ppm) and the various methylene peaks (between 25 and 36 ppm)remained unchanged as did the glycerol carbons (64 and 69 ppm). Additionally,new resonance peaks appeared at 66 ppm, which were related to ethylene oxide

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carbons, as well as peaks at 60 ppm, related to the new C–OH functional groups. Itwas apparent from the NMR data that the hydroxylation of soybean oil progressedas expected to yield the desired polyols.

Figure 6. 13C-NMR of soy oil (A) and soy polyol obtained by catalyzed ozonolysisof soy oil with ethylene glycol (B).

Polyols from SoymealOnly limited effort has been directed toward using the protein biomass

to produce value added industrial products due to difficulties associated withprocessing the meal and the high sensitivity of the proteins to moisture. Weavoided these problems by first hydrolyzing the meal to its individual amino acidsand then protecting the carboxylic acid and converting the amines to hydroxylterminated urethanes (28, 29). Our approach is shown in Figure 7 for L-Argininethat was used as a model compound and includes protecting the carboxylic acid by

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reacting it with ethylene diamine to form an amido-amine terminated intermediatefollowed by reaction of the terminal amines with ethylene carbonate (30–36)to yield hydroxy-terminated urethane prepolymers. These urethane polyols canbe further polycondensed to high molecular weight poly(amide-urethane)s. Theuse of ethylene diamine and ethylene carbonate has several advantages: thesereactants are relatively inexpensive compounds, their respective reactions arewell known and proceed smoothly to high yields and both reactants are readilyavailable. The preparation process was studied and optimized using glycine andL-Arginine as model compounds. Glycine was chosen as it is the simplest aminoacid composed of one amine and one carboxylic acid. L-Arginine was chosensince it is present in the soy meal at relatively high concentrations and its structureis relatively complex (e.g. it contains two primary amines, one secondary amineand one imine group). Both of these amino acids exist as zwitterions, which limittheir reactivity.

Figure 7. Preparation of hydroxyl-terminated urethane pre-polymers.

In the first step, a large excess of ethylene diamine was used to react withthe carboxylic acid in order to minimize possible dimerization reactions andensure the formation of amine terminated products. NMR and FTIR were usedto identify the structure of these products and provided clear indication thatthe amidation reaction proceeded as desired. Furthermore, end-group analyses(Table II) provided additional evidence and showed a significant increase in theamine value after the conversion of the carboxylic acid groups in the aminoacid to the diamine derivative. A subsequent reaction with ethylene carbonateled to the formation of the desired hydroxyl terminated urethane prepolymers(Arg-ED-EC) as indicated by the significant decrease in the amine value and thehigh hydroxyl value. The reaction of amines with ethylene carbonate to yieldhydroxyl terminated urethanes is well known (30–38). It should be noted herethat the amine value did not decrease to zero due to the presence of the lessreactive secondary amines and imine groups.

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Table II. End-group analysis

Amine value [mg KOH/g] Acid value [mg KOH/g] OH value [mg KOH/g]Sample

Calc. Exp. Calc. Exp. Calc. Exp.

Arg 644.1 336.6 322.0 - 0.0 -

Arg-ED 778.1 665.1 0.0 0.0 0.0 -

Arg-ED-EC 0.0 103.1 0.0 0.0 480.5 448.2

Arg-ED-EC-PO 0.0 74.7 0.0 0.0 - 533.0

SMS 483.7 33.7 549.4 64.9 0.0 -

SMS-ED 726.7 650.4 0.0 0.0 0.0 -

SMS-ED-EC 0.0 58.9 0.0 0.0 456.2 454.4

SMS-ED-EC-PO 0.0 49.3 0.0 0.0 - 623.0

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Similar polyols were then synthesized from the soymeal following the sameprocedure after acid hydrolysis of the proteins to the corresponding amino acids.The composition of the amino acids in the soy proteins is well known and doesnot vary much (37). In order to minimize any degradation of the amino acids,a relatively weak HCl solution (3N) was used in the hydrolysis step. The finalhydrolyzate was filtered to remove unreacted humin, treated with activated carbonto remove some of the dark brown color, neutralized with NaOH and then vacuumdistilled to remove water. The amino acid mixture thus obtained was reacted withethylene diamine and ethylene carbonate as described before to yield hydroxylterminated pre-polyurethanes. It should be noted that instead of separating thecarbohydrates already present in the meal, they were converted to reactive polyolsby reacting them with propylene oxide. This propoxylation reaction is fairly fastand provided better economics since it eliminated the separation step and allowedhigher yield polyols. The hydrolyzed mixture of amino acids from the soy meal(SMS) showed a marked increase in the amine value after the reaction withethylene diamine (SMS-ED) followed by high hydroxyl value after the reactionwith ethylene carbonate (SMS-ED-EC). The propoxylation reaction led to asignificant increase in the hydroxyl value and a notable decrease in the viscositymaking these polyols particularly suitable for rigid polyurethane foams. Indeed,water-blown pour-in-place rigid foams were prepared from these soymeal polyolsby reacting them with polymeric methylene diphenyl diisocyanate (Rubinate M,eq. wt. = 135.5) targeting a foam density of 2 pcf (Table III). The foams were thenevaluated against similar foams prepared with a commercial sucrose-based polyol.

It was noted that the reaction of the soymeal polyols with polymericmethylenediphenyl diisocyanate (MDI) was noticeably faster than the reaction of sucrose-based polyols with MDI most likely because the tertiary amines and imines inthe soymeal polyols catalyzed this reaction. The reaction profile of these foamsis listed in Table IV and clearly shows that the cream time, gel time, rise timeand tack-free time were all significantly shorter than the control polyol. It wasnoted that due to this self-catalytic reaction and the high reactivity of the soymealpolyols, no amine-based catalysts were needed to produce foams.

Typical properties of rigid foams prepared from soymeal polyols with wateras the blowing agent as well as with 1,1,1,3,3-Pentafluoropropane (HFC-245fa)blowing agent are listed in Table IV and compared with a control foam preparedwith a sucrose/glycerin-based polyol. It was noted that the two polyols werecompletely miscible allowing us to prepare a series of foams with variousconcentrations of these polyols. However, it was noted that the physical properties(e.g. density, compressive strength, compressive strain and friability) of foamsprepared with various blends of these polyols were comparable. Similarly, resultsof the dimensional stability in aging tests at -30°C and 70°C up to 2 weeks andflammability measured as burning rate (with no flame retardant additives) wereessentially identical to the control foams.

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Table III. Typical formulation of rigid foams derived from L-arginine-polyol

Sample Eq. Wt. Control Foam 1 Foam 2 Foam 3

Polyol system*

Jeffol SG-360 155.40 100 50 50 50

Argenine-based polyol 114.48 0 50 50 50

Water 9.00 4.5 4.5 4.5 4.5

Dabco DC193 2.0 2.0 2.0 2.0

Dabco 33LV 1.8 0 0.8 0

Niax A-1 0.1 0 0 0

Dabco T-12 0 0 0 0.05

Isocyanate System

Rubinate M 135.50 165.55 179.41 180.49 179.41

Isocyanate Index 105 105 105 105

Reaction Profile

Mix time, sec. 10 10 5 5

Cream time, sec. 13 6 5 6

Gel time, sec. 60 - - -

Rise time, sec. 95 - 45 55

Tack-free time, sec. 105 120 50 50

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Table IV. Properties of rigid PU foams prepared from soymeal urethanep olyols

Sample designation Control polyol* Soymeal polyol Control polyol* Soymeal polyol

Type of blowing agent H2O H2O H2O+HFC245fa H2O+HFC245fa

Soy meal polyol [%] 0 25 0 50

Density, pcf 2.13 ± 0.19 1.62 ± 0.01 2.32 ± 0.03 2.03 ± 0.07

Compressive Strength, psi 23.98 ± 2.11 17.84 ± 2.06 27.65 ± 2.1 23.40 ± 2.5

Compressive Strain, [%] 6.06 ± 0.38 5.44 ± 0.31 5.83 ± 0.34 4.93 ± 0.71

Friability, mass loss [%] 5.28 ± 0.03 12.99 ± 1.88 4.41 ± 0.73 8.02 ± 0.26

Mass and Volume Change [%] with Aging and Water Immersion Tests

Mass Vol. Mass Vol. Mass Vol. Mass Vol.

Aging Test @ -30°C

after 1 day (24h) 0.61 0.66 -0.19 0.60 -0.42 0.43 -0.43 0.72

after 1 week (168 h) 1.69 0.88 0.93 0.17 0.98 0.11 -0.14 0.49

after 2 weeks (336 h) 1.53 -0.55 1.12 0.24 1.41 0.10 -0.14 -0.30

Aging Test @ 70°C

after 1 day (24h) -0.31 0.78 0.19 -0.29 -1.23 0.09 -1.04 -0.33

after 1 week (168 h) -0.31 0.78 0.19 -0.29 -1.23 -0.29 -1.04 -0.32

after 2 weeks (336 h) 0.47 0.92 -0.19 -0.83 0.14 1.58 -1.19 -1.51

Water Absorption @ 25°C

after 4 days (96 h) 217.5 0.39 304.5 2.17 165.4 -0.2 252.0 6.5

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Mass and Volume Change [%] with Aging and Water Immersion Tests

Mass Vol. Mass Vol. Mass Vol. Mass Vol.

after 1 week (168 h) 229.73 0.73 325.84 2.14 162.04 0.14 300.15 2.44

Burning rate, mm/min 387 ± 55 380 ± 47 377 ± 35 242 ± 15

K-factor, BTUs - - 0.170 -

Density K-factor, pcf - - 2.62 -

* Control polyol: Poly-G 74-376, Sucrose/glycerine-based polyol; Hydroxyl value=361 from Arch Chemical

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Isocyanate-Free Poly(amide-urethane)s from Dimer Fatty Acids

Dimer fatty acids (also known as dimerized acids) are obtained from fattyacids by a condensation reaction of unsaturated fatty acids using a combination ofpressure, temperature and catalysis. These dimer acids are suitable for preparationof linear polymers by polycondensation since they are composed of two functionalcarboxylic acids. We have used these dimer acids to develop isocyanate-freepolyurethane resins (29, 39).

Polyurethanes are an important class of polymers having widespreadindustrial applications in automotive, construction, packaging, furniture, medicineandmany other markets (40). Traditionally they are synthesized by a condensationof polyols with isocyanates. However, the use of isocyanate is problematic dueto its high toxicity as well as its preparation method from the corrosive andtoxic phosgene gas (41, 42). Consequently, much attention has been focused ondeveloping procedures to synthesize polyurethanes by safer and environmentallyfriendlier methods that do not involve isocyanates, phosgenation or carbamates.One such method involves the reaction of cycloalkyl carbonates with aliphaticamines to yield hydroxyalkylurethanes (43–55). It is expected that avoidingisocyanate in the preparation of polyurethanes and using renewable resources inthe process would offer a safe and environmentally responsible synthetic strategywhich could dramatically improve the LCA profile (56) of the process. It has beenshown that under certain conditions high molecular weight polyurethanes canbe prepared by a urethane-exchange reaction with no need for isocyanate in theprocess. However, only few studies have been published in the literature dealingwith polycondensation by such urethane-exchange reactions from renewableresources. One notable example is the preparation of poly(trimethylene carbonatehydroxyl-urethane)s from glycerol carbonate (57). Our work was focused on asolvent-free process to obtain poly (urethane amides) from dimer acids followingthe three steps described in Figure 8. In the first step the dimer fatty acid (DA) iscondensed with ethylene diamine (ED) to produce amine terminated oligomersintermediates (P1). In the second step these intermediates are reacted withethylene carbonate (EC) to yield hydroxyl terminated di-urethanes (P2). Thethird step involves urethane-exchange polycondensation reaction where terminalethylene glycols ares removed and the molecular weight is increased (P3) (29,39). The final polymer was a transparent, flexible material at ambient temperatureand contained 88 wt% renewable carbon.

The conversion of the carboxylic acid to amide in P1 was studied bymonitoring the amine and the acid values as a function of the reaction time. Itwas observed that 71% of the amine groups and 95% of the acid groups wereconsumed after 3 hrs indicating a calculated degree of polymerization DPn=4.3and a number average molecular weight (Mn) = 2640 g/mol (Table V). Theseresults were confirmed by FTIR (Figure 9) where the C=O peak (carboxylic acid)at 1710 cm-1 of the dimer acid disappeared and new peaks appeared at 1640and 1560 cm-1 corresponding to C=O deformation of amide groups and N-Hdeformation of amine groups, respectively. FTIR spectroscopy was also used tomonitor the reaction of P1 with ethylene carbonate to yield P2 in the 2nd step ofthis synthesis. It is apparent from the data in Figure 9 that ethylene carbonate

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was consumed as indicated by the disappearance of the peak at 1800 cm-1 anda new peak at 1695 cm-1 appeared corresponding to the C=O deformation ofthe urethane groups. The completion of this reaction was further confirmed bya significant decrease in the amine value to 4.0 mg KOH/g and a correspondingincrease in the hydroxyl value to 32.5 mg KOH/g, suggesting that 90% of P1chain-ends were reacted with EC in this step. The calculated Mn was 2570 g/mol,which was in good agreement with the experimental value determined by GPC.

Figure 8. Representation of the general approach for the synthesis of poly(amideurethane)s from dimer fatty acids.

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Finally, P2 was polymerized in the bulk by the urethane exchange reaction andthe molecular weight increased as ethylene glycol was removed and the hydroxylvalue decreased. The final hydroxyl value was 12.7 mg KOH/g corresponding tocalculated Mn = 8330 g/mol in fairly good agreement with the GPC results (Mn= 7700 g/mol, Mw = 14000 g/mol). The polyurethane P3 exhibited a Tg at -10°C and a melting point at +73 °C with a corresponding melting enthalpy at 0.04W/g. TGA under nitrogen atmosphere showed the onset of degradation at 288°C followed by a main degradation at 465 °C. These new poly (amide urethane)scontain high biomass content, yet, they can be formulated and used as coatings,adhesives and elastomers similarly to conventional polyurethanes prepared fromfossil resources.

Figure 9. FTIR spectra of dimer acid (A), P1 (B), ethylene carbonate (C), P2(D) and P3 (E).

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Table V. Molecular parameters of P1, P2 and P3

Calc.DPn

Calc. Mn(g/mol)

Exp Mn(g/mol)

Exp Mw(g/mol) PD

P1 4.3 2640 1) 720 1) 880 1) 1.22

2) 2810 2) 3370 2) 1.20

P2 0.9 2570 1) 1660 1) 1770 1) 1.06

2) 4220 2) 4890 2) 1.16

P3 3.3 8330 7700 14000 1.80

Coatings from Silylated Soybean Oil

It is well know that vegetable oils have been used as important componentsin alkyd resins. The cured coatings obtained from such resins were noted for theiranticorrosion properties, excellent water barrier, enhanced chemical protection andhigh wear and UV resistance. The “drying” character of these oils is achieved byair oxidation when the double bonds in the fatty acids undergo cross linking uponexposure to oxygen. The presences of certain metal salts in trace, such as cobaltnaphteneate, are used as a catalyst to accelerate the cure time. Similarly, linseedoil is known as a fast drying oil due to the high unsaturation content and is widelyused in coatings but its use is limited due to high costs and limited availability.In practice, curable oils must be diluted in an organic solvent or emulsified inwater. If solvents are used as diluents, they are considered as volatile organiccontent (VOC) and will evaporate upon application to pollute the air. When theoil is dispersed in water as a suspension, the use of surfactant stabilizing agentsis required. These surfactants remain in the finished coatings and tend to degradethe physical properties of the coating as well as its aesthetic appearance (58).

A more convenient approach, that we have developed in our work as partof the soybean refinery concept is a one-component moisture activated cure. Thiscure strategy is based on a well known limited hydrolytic stability of alkoxy silanesthat is widely used in various silicone sealants (27, 59–62). Our work was basedon grafting vinyltrimethoxysilane (VTMS) onto the unsaturation sites of the fattyacids in the triglycerides of the oil by the well known as ‘Ene-reaction’ as shown inFigure 10 (62). This reaction is catalyzed by peroxides and is based on the fact thatVTMSdoes not undergo free radical polymerized like other vinylmonomers due tothe stabilization of the free radicals by the silicon atom. Furthermore, this one-stepaddition reaction does not require a solvent and no by-products are produced thatrequire neutralization or purification at the end of the reaction. Since only smallconcentrations of VTMS are needed for crosslinking, the physical properties of themodified oil remains unchanged. Most notably, the product is a low viscosity oilthat requires no solvent or diluent and it can be applied by any common techniquesuch as brushing, spraying, dip-coating or casting using conventional equipment.

The success of the grafting reaction and the structure of the silane modifiedoil were determined by FTIR, GC and NMR. Representative 1H-NMR spectrum(Figure 11) clearly shows that the grafting reaction was successful. Figure 11

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(A) represents the partial 1H-NMR spectrum of soybean oil. The resonancepeaks with a chemical shift near 5.25 ppm are associated with the proton atomslocated in the unsaturation linkages of soybean oil. Figure 11 (B) shows the1H NMR spectrum of the intermediate product soybean oil-VTMOS reactionproduct. It is clear that the proton atoms located in unsaturation linkages inVTMOS exhbitis a group of resonance peaks near 6.0 ppm. We can also noticethat the shape of the resonance peak changed because of the reaction proceeding.The final consumption of unsaturations present in VTMOS by ene reaction wassupported by the partial 1H-NMR presented in Figure 11 (C). It clearly showedthe disappearance of 6.0 ppm resonance peak associated with the proton atomslocated in the unsaturation linkages in VTMOS. Further confirmation of thestructure was obtained by 13C-NMR and iodine number titration. Moreover, theextent of the grafting reaction was found to directly proportional to the reactiontime and the reaction temperature (11, 58, 62).

Figure 10. Grafting VTMS onto soy oil.

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Figure 11. 1H-NMR of (A) soybean oil, (B) the intermediate soybean oil-VTMOSreaction product, (C) the final silylated soybean oil.

Upon exposure of moisture, hydrolysis of the alkoxysilanes readily takesplace to yield silanols which are condensed to form stable siloxane crosslinks asshown in Figure 12. The rate of cure is proportional to the relative humidity, thetemperature and the presence of any cure accelerators (for example, dibutyltindiacetate). exhibits the partial spectrum of final cured product. The properties ofthe protective coating is largely controlled by the crosslink density and the typeof silane used. This cure system is very convenient as it does not require mixingdifferent components prior to curing and, essentially, has an infinite shelf life aslong as it is stored away from moisture. The major drawback of this system is thefact that the cure is controlled by diffusion of moisture into the bulk and diffusionof the by-product alcohol out of the bulk. Thus, the thickness of the sample iscritical, making this system particularly suitable for coatings or adhesives thatrequire only thin layers.

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Figure 12. Moisture activated cure mechanism of soybean oil grafted with VTMS.

These coatings exhibited excellent adhesion to steel, concrete, wood, paperand glass. The hardness of the coating was greatly enhanced when the oil wasformulated with fine particle size silica. Formulation with silica is particularlyaffective since good interface is obtained between the filler particles and the matrixthrough silanol interactions between the surface of the silica and the oil graftedsilanes. It was shown that these coatings can be used as a moisture barrier toprotect substrates such as wood, paper and concrete against water.

Conclusions

This work provides a few examples of our biorefinery concept where the oiland the meal of soybeans were used to produce useful intermediates for industrialproducts. In all cases safe processes were used following the ‘green chemistry’principles. These examples include:

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• New polyols from soy oil prepared by continuous ozonation process thatcan be further used in the synthesis of polyesters and polyurethanes.

• New hydroxyl terminated urethane prepolymers prepared fromsoymeal that were obtained by converting the amine in amino acids tourethanes. These high hydroxyl value polyols were further used in rigidpolyurethane foams.

• A new class of poly(amide urethane)s were prepared from dimer fattyacid by isocyanate-free polymerization. The properties of these polymersmake them suitable for coating and adhesive applications.

• We have also successfully demonstrated a novel moisture activated cureof soy oil by grafting onto the oil reactive silanes. Upon exposure tomoisture the low viscosity oil is cured into a transparent film that providesexcellent protective coating over a wide range of substrates.

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In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.