european patent office - ep 2839107 b1
TRANSCRIPT
Note: Within nine months of the publication of the mention of the grant of the European patent in the European PatentBulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with theImplementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has beenpaid. (Art. 99(1) European Patent Convention).
Printed by Jouve, 75001 PARIS (FR)
(19)E
P2
839
107
B1
TEPZZ 8¥9_Z7B_T(11) EP 2 839 107 B1
(12) EUROPEAN PATENT SPECIFICATION
(45) Date of publication and mention of the grant of the patent: 05.07.2017 Bulletin 2017/27
(21) Application number: 13778762.8
(22) Date of filing: 12.04.2013
(51) Int Cl.:C08L 15/00 (2006.01) E21B 33/12 (2006.01)
C08L 33/10 (2006.01)
(86) International application number: PCT/US2013/036345
(87) International publication number: WO 2013/158487 (24.10.2013 Gazette 2013/43)
(54) HIGH TEMPERATURE STABLE WATER SWELLABLE RUBBER COMPOSITION
HOCHTEMPERATURBESTÄNDIGE IN WASSER QUELLFÄHIGE KAUTSCHUKMISCHUNG
COMPOSITION DE CAOUTCHOUC GONFLANT À L’EAU ET STABLE À HAUTE TEMPÉRATURE
(84) Designated Contracting States: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
(30) Priority: 16.04.2012 US 20121344761114.01.2013 US 201313741040
(43) Date of publication of application: 25.02.2015 Bulletin 2015/09
(73) Proprietor: ZEON CHEMICALS L.P.Louisville, KY 40211 (US)
(72) Inventors: • CHOI, Soobum
Louisville, KY 40241 (US)
• JUSTICE, Lawrence, J.Louisville, KY 40241 (US)
(74) Representative: Nevant, Marc et alCabinet Beau de Loménie 158, rue de l’UniversitéF-75007 Paris (FR)
(56) References cited: EP-A1- 1 978 071 WO-A1-2010/039131JP-A- 2001 123 028 US-A- 5 293 938US-A- 5 723 551 US-A1- 2004 214 961US-A1- 2008 194 717 US-A1- 2009 084 550US-A1- 2009 159 267 US-A1- 2009 234 054US-A1- 2010 243 235 US-A1- 2011 028 593US-A1- 2011 054 093 US-B1- 6 281 293US-B1- 7 030 194 US-B1- 7 762 329
EP 2 839 107 B1
2
5
10
15
20
25
30
35
40
45
50
55
Description
[0001] The present invention relates to a water swellable rubber (or elastomer) composition which is swellable withwater or aqueous fluids, in particular saline fluids or brines.[0002] There has been growing interest in recent years in developing water swellable elastomers, in particular for usein oil fields and similar subterranean applications. For this purpose, U.S. Patent No. 4,590,227 discloses a homogeneousmixture of an elastomer, a water-absorbent resin and a water soluble resin. JP 3111510 B discloses a water swellablevulcanized rubber which is an ethylene oxide-propylene oxide-allyl glycidyl ether copolymer having 40 - 90 mole% ofethylene oxide. JP 2004-123887 discloses a water swellable vulcanizable rubber composition comprising an epichloro-hydrin elastomeric polymer, a natural or synthetic rubber, and a vulcanizing agent. U.S. patent application publicationNo. 2009/0084550 A1 discloses a water swellable rubber composition comprising a base rubber, a cellulose component,and an acrylate copolymer. JP 2001-123028 discloses a rubber composition comprising a polyether polymer, a dienerubber and an ethylene/propylene/diene rubber.[0003] Most oil field applications require good stability of swell and high volume swell under hostile environments,such as high electrolyte concentration, in particular electrolytes such as binary salts which are not conducive to swellingof the rubber, and high temperatures. The standard evaluations of water swellable rubber compositions for use in suchhostile environments are the measurements of volume swell, weight swell and stability of swell at high temperature, atdifferent salinity concentrations and in different electrolyte types. One aspect of the invention disclosed herein takes intoconsideration the fact that, in some applications such as in an oil wellbore, the element made from the rubber compositionis not free (at some point during its installation or use) to swell in all directions, but its swelling is physically constrainedbecause a portion of the surface of the rubber element is pressed against a solid surface and thus has no or little contactwith water. The invention disclosed herein takes into consideration "free swell" as well as "constrained swell" of therubber composition.[0004] In "free swell" applications the water swellable rubber compositions disclosed in the above cited documentsdo not perform well under prolonged exposure to high temperature or under saline conditions. The composition accordingto JP 3111510 B exhibits high water absorbency at room temperature. However, with this composition it is difficult toachieve a weight swell of over 200% at a temperature above 80°C, as is required for most oil field applications. With thecomposition according to U.S. Patent No. 4,590,227, after swelling at high temperature most of the water soluble resinwas moved to the water phase, and the swelling capacity of the remaining rubber mixture was thus reduced. Thecomposition according to U.S. patent application publication No. 2009-0084550 A1 has a very low swelling capacity inmoderately high concentration of monovalent saline solution (3.5% NaCl) or divalent saline solution (3.5% CaCl2), evenat room temperature.[0005] The present inventors worked to solve the problems above with respect to the free swell capacity of the rubbercomposition, i.e., low swell at high temperature, low swell even under moderately high saline conditions, and loss ofswelling under prolonged exposure at high temperature. An object of the invention is to provide a water swellable rubbercomposition having high and sustained free swell at elevated temperatures, and high free swell under saline conditions.[0006] The water-swellable rubber compositions disclosed in the above documents also do not perform well underconstrained swell conditions in different saline environments. The composition according to JP 3111510 B exhibits highwater absorbency under free swell conditions at room temperature. However, with this composition it is difficult to achievea satisfactory constrained swell at a temperature above 80°C, as is required for most oil field applications. The compositionaccording to U.S. Patent No. 4,590,227 also does not achieve sufficient constrained swell for oil field applications. Thecomposition according to U.S. patent application publication No. 2009-0084550 A1 has a very low constrained swellingcapacity in moderately high concentrations of saline solution (3.5% NaCl and 6.0% NaCl), even at room temperature.[0007] The present inventors also worked to solve the problems described above for swelling under constrainedconditions, i.e., low constrained swell under low and high saline conditions, distortion or destruction of the shape of therubber element upon swelling under constrained conditions, and low constrained swell at high temperature. An objectof the invention is to provide a water-swellable rubber composition having high constrained swell with good shaperetention upon swelling at elevated temperatures and under highly saline conditions.
BRIEF SUMMARY OF THE INVENTION
[0008] The above objects of the invention were achieved with a water swellable rubber composition comprising (a)100 phr of a non-water swellable base rubber which is at least one selected from the group consisting of hydrogenatedacrylonitrile-butadiene rubber (HNBR) and epichlorohydrin rubber, (b) 10 - 200 phr of a crosslinkable ethylene oxidebased hydrophilic elastomer having at least one curable functional group selected from the group consisting of hydroxyl,carboxyl, epoxy, amino, oxime, vinyl, oxazoline, anhydride, and amide, and (c) 50 - 200 phr of a water swellable non-elastomeric material which is partially neutralized/crosslinked polyacrylic acid salt. The water swellable rubber compo-sition may also contain a compatibilizing agent.
EP 2 839 107 B1
3
5
10
15
20
25
30
35
40
45
50
55
[0009] This water swellable rubber composition is characterized by high and sustained swelling at elevated temper-ature, as well as a high degree of swelling at elevated temperatures in electrolytes (saline or acidic) of different typesand concentrations. The invention has overcome the problem of low swelling in multivalent salt solutions at high tem-perature, and the problem of loss of swelling over time at high temperature.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010]
FIGS. 1A and 1B show schematically a water swellable packer arranged around a pipe inside a wellbore in asubterranean formation.FIGS. 2A and 2B show schematically two variations of a method for measuring one-dimensional constrained swellusing a constrained pipe sample.Fig. 3 is a graph of % weight increase over 30 days of free swell for the compositions of Example 1- Example 4 andComparative Example 1- Comparative Example 3 in 3.5 % NaCl solution at 176°F (80°C).FIG. 4 is a graph of % weight increase over 30 days of free swell for the composition of Example 4 in 3.5 % NaClsolution at 176°F (80°C), and also at 200°F (93°C).FIG. 5 is a graph of % weight increase over 260 hours of free swell for the composition of Example 4 in 15 % HClsolution at 150°F (66°C).FIG. 6 is a graph of % weight increase for the composition of Example 5 in 3.5 % NaCl solution over 10 days of freeswell at 100°F (38°C), followed by 10 days of free swell at 200°F (93°C).FIG. 7 is a graph of constrained swell over 14 days for the compositions of Example 6- Example 7 and ComparativeExample 4 - Comparative Example 5 in tap water at 122°F (50°C).FIG. 8 shows photographs of constrained swell shapes for the compositions of Example 6- Example 7 and Com-parative Example 4 - Comparative Example 5 in tap water at 122°F (50°C) after 14 days.FIG. 9 is a graph of constrained swell over 14 days for the compositions of Example 6- Example 7 and ComparativeExample 4 - Comparative Example 5 in 3.5% NaCl solution at 180°F (82°C).FIG. 10 is a graph of constrained swell over 14 days for the compositions of Example 6- Example 7 and ComparativeExamples 4 - Comparative Example 5 in 6% NaCl solution at 180°F (82°C).FIG. 11 is a graph of constrained swell over 14 days for the compositions of Example 6- Example 7 and ComparativeExample 4 - Comparative Example 5 in 12% NaCl solution at 180°F (82°C).
DETAILED DESCRIPTION
[0011] The water swellable rubber composition of the invention comprises (a) 100 phr of a non-water swellable baserubber which is at least one selected from the group consisting of hydrogenated acrylonitrile-butadiene rubber (HNBR)and epichlorohydrin rubber, (b) 10 -200 phr of a crosslinkable ethylene oxide based hydrophilic elastomer having atleast one curable functional group selected from the group consisting of hydroxyl, carboxyl, epoxy, amino, oxime, vinyl,oxazoline, anhydride, and amide, and (c) 50 - 200 phr of a water swellable non-elastomeric material which is partiallyneutralized/crosslinked polyacrylic acid salt. This water swellable rubber composition is characterized by high and sus-tained swelling at elevated temperature, as well as a high degree of swelling at elevated temperature in electrolytes(saline or acidic) of different types and concentrations.[0012] Many oil field applications require wrapping a layer of water swellable rubber (also known as a "packer") 3around the surface of a pipe 4 (also known as a tubular) to prevent water intake into the annular space 6 between thepipe 4 and the internal wall 2 of the wellbore 1, as shown in Figs. 1A and 1B. The two ends of the wrapped water swellablerubber are restricted by anti-extrusion rings 5. The swelling mechanism in this application is of the one-dimensional type,originating from the contact surface between the water swellable rubber and the water phase. Known water swellablerubber technology tends to focus on free swell measured with a slab type sample (1 inch x 2 inches x 0.08 inch) or abutton type sample (1.2 inches of diameter x 0.5 inch of thickness). In free swell, which is three-dimensional, the swellingrate and the swell capacity are proportional to the contact surface area. The main driving force in free swell is the osmoticpressure resulting from the ionic difference between the water swellable rubber and the solvent in contact with theswellable rubber. The performance of a swellable rubber composition under free swell conditions is not an adequateindicator of its performance under constrained swell conditions. To overcome this gap in known technology, the inventorshave developed a method for measuring one-dimensional constrained swell using a constrained pipe sample as shownin Figs. 2A and 2B.[0013] In constrained swell, the driving force of the initial swell is the osmotic pressure between the water swellablerubber and the solvent. However, the main driving force of the continued swell is the diffusion or migration of water insidethe water swellable rubber. It is understood that this diffusion or migration of water is based on the affinity between the
EP 2 839 107 B1
4
5
10
15
20
25
30
35
40
45
50
55
water present in the rubber and the hydrophilic portion of the water swellable rubber.
a. Non-water swellable base rubber
[0014] The non-water swellable base rubber (a) is used in the composition to provide the elastic property needed formaintaining a tight seal after swelling of the composition at elevated temperature. The base rubber also improves theprocessability of the water swellable rubber composition.[0015] The base rubber (a) used in this invention is at least one selected from hydrogenated acrylonitrile - butadienerubber (HNBR) and epichlorohydrin rubber (ECO).
b. Ethylene oxide based hydrophilic elastomer
[0016] The ethylene oxide elastomer (b) used in the composition has at least one curable functional group recurringthroughout the polymer chain and/or in side groups of the polymer chain. These occurrences of the curable functionalgroup provide crosslinkable sites for the polymer. The monomers comprising this elastomer (b) having crosslinkablesites must include at a minimum (1) ethylene oxide; and (2) at least one monomer providing the mentioned crosslinkablesite after polymerization with ethylene oxide, selected from the group consisting of hydroxyl, carboxyl, epoxy, amino,oxime, vinyl, oxazoline, anhydride, and amide. Ethylene oxide based hydrophilic elastomers having a carboxylic acidgroup or a vinyl group are commonly available and may be used as component (b) of the composition of the invention.Examples of the monomer (2) are acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, vinyl glycidylether, and allyl glycidyl ether. Other glycidyl ethers bearing vinyl groups may be used, including 4-vinylcyclohexyl glycidylether, 4-vinylbenzyl glycidyl ether, 4-allylbenzyl glycidyl ether, ethylene glycol vinyl glycidyl ether, diethylene glycol allylglycidyl ether, diethylene glycol vinyl glycidyl ether, triethylene glycol vinyl glycidyl ether, α-terpenyl glycidyl ether, oli-goethylene glycol vinyl glycidyl ether, and oligoethylene glycol allyl glycidyl ether. Other epoxy compounds bearing vinylgroups such epoxybutene, 3,4-epoxy-1-pentene, 1,2-epoxy-5,9-cyclododecadiene, 3,4-epoxy-1-vinylcyclohexene, and1,2-epoxy-5-cyclooctene may also be used as the monomer (2). The ethylene oxide elastomer (b) may be comprisedof other monomers in addition to (1) ethylene oxide and (2) the monomer providing the crosslinkable site. The ethyleneoxide elastomer (b) may be a single ethylene oxide elastomer having at least one curable functional group, or may bea mixture of two or more of such ethylene oxide elastomers having at least one curable functional group.[0017] The elastomer (b) must contain a sufficiently high amount of ethylene oxide for the desired degree of waterswell to be achieved. For many applications, an ethylene oxide content in the range of at least 65 mole %, preferably75 mole%, is suitable.[0018] The amount of crosslinking sites in the elastomer (b) is selected to achieve the desired properties:
(i) a higher degree of crosslinking helps to stabilize water swell under exposure to elevated temperatures;(ii) however, if the increase in the number of crosslinking sites is accomplished by using more of the monomer havinga crosslinking site and less of ethylene oxide, the reduction in ethylene oxide will be accompanied by a decreasein water swell at elevated temperatures; and(iii) no crosslinking or a low degree of crosslinking facilitates shape retention for the rubber composition underconstrained swell conditions.
[0019] Based on the above understanding of the effects of the ethylene oxide content and crosslinking density, theappropriate elastomer (b) may be selected to achieve the water swell characteristics desired for specific applications.For many applications, the content of the monomer having a crosslinkable site in the elastomer (b) may be in the rangeof at least 0.1 mole % up to and including 20 mole%.[0020] In the aspect of the invention where the rubber composition has satisfactory shape retention under constrainedswell as well as a high degree of constrained swelling at elevated temperatures in different saline concentrations, theethylene oxide based hydrophilic elastomer (b) must have a low content of crosslinkable functional group, specificallyfrom zero to less than 5% mole ratio of crosslinkable functional group.[0021] Ethylene oxide terpolymers are suitable for use as the elastomer (b) in the composition of this invention. Non-limiting suitable examples are ethylene oxide - propylene oxide - allyl glycidyl ether terpolymers. These suitable terpol-ymers have at least 65 mole %, preferably 75 mole %, ethylene oxide and at least 0.1 mole % up to and including 20mole % allyl glycidyl ether. If the amount of ethylene oxide is lower than 65 mole %, the degree of swelling is remarkablyreduced. If the amount of crosslinkable site (from the allyl glycidyl ether) is lower than 0.1 mole %, it is very difficult toobtain stability of swelling at high temperature under conditions of free swell. Also, if the amount of the crosslinkablesite is higher than 20 mole %, the relative amount of ethylene oxide is reduced so that the initial swelling rate at atemperature over 60 °C is reduced. Suitable examples of this material include, but are not limited to, terpolymers ofethylene oxide-propylene oxide-allyl glycidyl ether available from Zeon Chemicals L.P. under the names ZEOSPAN
EP 2 839 107 B1
5
5
10
15
20
25
30
35
40
45
50
55
8010 and ZEOSPAN 8030, which have a crosslinkable vinyl group in a side chain.[0022] Ethylene oxide copolymers having at least 65 mole %, preferably 75 mole %, ethylene oxide are also suitablefor use as the elastomer (b) in the composition of this invention. If the amount of ethylene oxide is lower than 65 mole%, the degree of swelling is remarkably reduced. Non-limiting suitable examples are ethylene oxide - propylene oxidecopolymers. For obtaining good shape retention and high swell under constrained swell conditions, the amount ofcrosslinkable sites in the copolymer must be from zero to less than 5 mole %. For satisfactory performance in constrainedswell, it may be possible to use a combination of copolymer and terpolymer as long as the total amount of crosslinkingsites is less that 5 mole % based on the total amount of ethylene oxide polymers. Suitable examples of this materialinclude, but are not limited to, an ethylene oxide-propylene oxide copolymer available from Zeon Chemicals L.P. underthe names ZEOSPAN 8100, which has a non-crosslinkable functional group, or a combination of this copolymer ZE-OSPAN 8100 with the ethylene oxide-propylene oxide-ally glycidyl ether terpolymer ZEOSPAN 8030, or a combinationof the ethylene oxide-propylene oxide copolymer ZEOSPAN 8100 with the ethylene oxide-allyl glycidyl ether copolymerZEOSPAN 8010, such that the amount of crosslinkable groups is less than 5mole % based on the total amount ofethylene oxide polymers.[0023] Finally, homopolymers of ethylene oxide may be used as the elastomer (b).
c. Water swellable non-elastomeric material
[0024] The water swellable non-elastomeric material (c) contributes to the high volume swell at high temperature whichcharacterizes the water swellable rubber composition according to this invention. A water swellable non-elastomericmaterial having at least 20 times swelling in distilled water at a temperature above 50 °C may be used as component(c). This water swellable non-elastomeric material (c) is a partially neutralized/crosslinked polyacrylic acid salt, whichincludes the materials known as "super absorbent polymer" (SAP). The water swellable non-elastomeric material (c)may be a single water swellable non-elastomeric material, or may be a mixture of two or more of such water swellablenon-elastomeric materials.[0025] For use under conditions of free swell, the following proportions are used:
(a) Non-water swellable base rubber: 100 phr(b) Crosslinkable ethylene oxide based hydrophilic elastomer: 10 - 200 phr, preferably 20 - 180 phr and morepreferably 50 - 150 phr.(c) Water swellable non-elastomeric material: 50 - 200 phr, preferably 70 - 180 phr and more preferably 90 - 170 phr.
Compatibility
[0026] An important consideration in the compounding of the water swellable rubber composition according to thisinvention is the compatibility of the base rubber (a) with the crosslinkable ethylene oxide based hydrophilic polymer (b)and the water swellable material (c). A significant factor in this compatibility is the degree of polarity of the base rubber(a) and the amount of the base rubber (a) relative to the amounts of the hydrophilic polymer (b) and the water swellablematerial (c). In compositions where the base rubber (a) is non-polar or is present in large quantity, the addition of acompatibilizing agent helps to produce a composition having stable water swell properties. The polarity characteristicsof rubbers are known, and the inclusion of a compatibilizing agent may be based on the polarity of the base rubber usedin a particular composition. Another approach in determining whether to use a compatibilizing agent is to prepare a testmixture of the three components (a), (b) and (c). If it is evident from visual observation of the mixture that the rubber (a)is not sufficiently blended with components (b) and (c), for example when there is visible phase separation, then acompatibilizing agent may be added.[0027] In general, when a compatibilizing agent is used, its amount should be no more than 40 phr for 100 phr of non-water swellable base rubber (a). In many compositions an amount of no more than 30 phr of the compatibilizing agentfor 100 phr of base rubber is suitable.[0028] With respect to compatibility with the crosslinkable ethylene oxide based hydrophilic polymer (b), hydrogenatedacrylonitrile-butadiene rubber (HNBR) and epichlorohydrin rubber (ECO) are particularly suitable as the base rubber(a), and may be compounded without a compatibilizing agent. A water swellable non-elastomeric material (c) particularlysuitable for use with HNBR or ECO is a super absorbent polymer based on partially neutralized polyacrylic acid sodiumsalt. The resulting composition is characterized by a high degree of swelling and stability of swelling derived from theinternal compatibility among its components at high temperature in different electrolyte types and at different electrolyteconcentrations.[0029] Compatibilizing agents which may be used in the water swellable rubber composition of this invention arematerials having both polar and non-polar moieties in their molecules. A single compatibilizing agent or a mixture of twoor more compatibilizing agents may be used. Examples of such materials having both polar and non-polar moieties are
EP 2 839 107 B1
6
5
10
15
20
25
30
35
40
45
50
55
aromatic triesters, monoesters of tricarboxylic acids, and diesters. The diesters may be aliphatic or aromatic diesters,or they may be diesters of: a dialkyl ether, a polyglycol, or an alkyl alkylether. Examples of suitable compatibilizing agentsfor use in the water swellable rubber composition of this invention are trioctyl trimellitate, ditridecyl adipate, and dialkyldiether glutarate. The plasticizers PLASTHALL TOTM and PLASTHALL DTDA, both available from Hallstar, are examplesof compatibilizing agents which may be used in this invention.
Additives
[0030] The water swellable rubber composition according to the invention may be formulated to include additivessuitably selected by one of ordinary skill in the art, which may include but are not limited to fillers, curing agents, activators,retarders, accelerators, antioxidants, antiozonants, processing aids, etc.[0031] Various fillers such as carbon black, silica, clays, calcium carbonate, bentonite and other filler material may beused, alone or in combination with one or more other filler. The amount of filler is not specifically restricted and may beselected readily by one of ordinary skill in this art. A suitable range for many applications is from 3 to 100 phr.[0032] A variety of curatives or curing agents may be used, such as a sulfur type curing package or a peroxide typecuring package, with their respectively preferred accelerators. The amount of curatives and their accelerators may bein the range from 0.05 to 5.0 phr. In one aspect of the invention the water swellable rubber composition comprises aperoxide cure system or a sulfur cure system; when a sulfur cure system is used, the rubber composition preferablycomprises at least one accelerator for said system.[0033] Examples of suitable activators include zinc oxide (ZnO), zinc stearate, stearic acid, magnesium oxide (MgO)and combinations thereof. The amount of activators may be in the range from 1 to 10 phr.[0034] Examples of suitable antioxidants include any of the phenyl amines (e.g. NAUGARD type, NOCRAC type,AGERITE type) and any of the mercaptobenzimidazoles (e.g. VANOX type). The amount of antioxidant may be in therange from 0.1 to 5.0 phr.[0035] Processing aids may be used in the range from 0.1 to 20 phr.
Processing
[0036] The addition, blending or compounding of all components of the composition of the invention may be carriedout with conventional equipment, for example a mill and/or a Brabender mixer or other internal mixer. Curing conditionssuch as cure temperature and cure time may be selected according to conventional practice in rubber technology.[0037] The water swellable rubber composition of the invention exhibits good stability and improved volume swell athigh temperature, in different electrolyte types and at different electrolyte concentrations, compared with conventionalwater swellable rubber compositions.[0038] The water swellable rubber composition of the invention, either cured or uncured, can be used in the manufactureof an article. Examples of such an article include a seal, a gasket, a component of a well packer, a component of adevice for controlling fluid flow, a component of a device for detecting water, a component of a device for detectingdepletion of water, a component for an activating mechanism in a control device, a toy, or a game element.[0039] The invention also relates to a method for impeding an aqueous fluid flow through a space defined by solidwalls, comprising the steps of placing the water swellable rubber composition of the invention in said space in contactwith the aqueous fluid flow, whereby the composition swells by absorption of water from the aqueous fluid, fills up saidspace and impedes the flow of the aqueous fluid through the space. In one aspect, the solid walls are smooth. In anotheraspect the solid walls have uneven surfaces or minor discontinuous areas.[0040] The following examples further illustrate aspects of the invention but do not limit the invention. Unless otherwiseindicated, all parts, percentages, ratios, etc., in the Examples, Comparative Examples and in the rest of the specificationare in terms of weight.
Free swell
[0041] The degree of free swell in the Examples and Comparative Examples is defined and measured as follows:
wherein
A: weight before swelling.
EP 2 839 107 B1
7
5
10
15
20
25
30
35
40
45
50
55
B: weight after swelling.
[0042] The size of a sample affects the measurement of the initial swelling, which depends on the surface area of thecontact with water. In the free swell tests reported for this invention, the sample is a slab type sample (1 inch width x 2inches length x 0.08 inch thickness) unless otherwise indicated.
Constrained swell
[0043] The degree of constrained swell in the Examples and Comparative Examples was measured as follows. A pipeof 1 inch diameter was filled completely from end to end with the swellable rubber composition and immersed in the testsolution.
Length of pipe: 1 inch for testing in 6 - 12% NaCl solutions1.5 inch for testing in 3.5% NaCl solution
[0044] For measuring constrained swell in saline concentrations, both ends of the pipe were open. As illustrated inFig. 2A, the total growth in constrained swell of the pipe sample is the difference in the measurements A and B.
wherein
A: length of rubber sample in pipe before constrained swellingB: length of rubber sample measured between the points of maximum extension at each end of the sample afterconstrained swelling.
[0045] As shown in Fig. 2B, a variation of this test was used in testing for constrained swell in tap water. The swellingin tap water was so large that the swollen rubber sample was pulled out of one end the pipe and the extended length ofthe sample could not be measured accurately. Therefore, the measurement was made with one end of the pipe beingclosed, leaving only one open end from which the swollen rubber extended beyond the pipe. For the purpose of comparisonwith the results of constrained swell measured with both ends of the pipe open, the growth obtained with this modifiedmethod was multiplied by 2 to adjust the results for testing with only one end of the pipe open.
wherein
A: length of rubber sample in pipe before constrained swelling.B: length of rubber sample measured from closed end of pipe to point of maximum extension of rubber sample atopen end of pipe after constrained swelling.
Free swell
Example 1
[0046] In this example the non-water swellable base rubber is a hydrogenated acrylonitrile-butadiene rubber (ZETPOL2020EP from Zeon Chemicals LP). The ethylene oxide based hydrophilic elastomer having a curable functional groupis ZEOSPAN 8030 (from Zeon Chemicals LP). The water swellable non-elastomeric material is a partially neutral-ized/crosslinked polyacrylic acid sodium salt (AQUA KEEP 10SH-NF: Sumitomo Seika Chemicals Co. Ltd.). Othercomponents are shown in Table 1. These components were blended in a 270 mL Brabender bowl at 70 °C for 15 minuteswithout curing agent or accelerator. The curing agent and accelerator shown in the table were added during the millprocess under cooling. After measuring with MDR 2000 at 100 cpm 0.5° arc for 45 minutes at 160 °C, curing was carriedout at 160 °C for 15 minutes. To measure the degree of swelling in different electrolyte types and concentrations atdifferent temperatures, button type samples (1 inch diameter x 0.5 inch thickness) were made and tested. The resultsare shown in Fig. 3.
EP 2 839 107 B1
8
5
10
15
20
25
30
35
40
45
50
55
Example 2
[0047] The composition of Example 2 was prepared according to the same procedure as in Example 1 except thatPLASTHALL 7050 was added. All components and their amounts are shown in Table 1. To measure the degree ofswelling in different electrolyte types, at different electrolyte concentrations and at different temperatures, button typesamples (1 inch diameter x 0.5 inch thickness) were made and tested. The results are shown in Fig. 3.
Example 3
[0048] The composition of Example 3 was prepared according to the same procedure as in Example 1 except thatPLASTHALL TOTM was added. All components and their amounts are shown in Table 1. To measure the degree ofswelling in different electrolyte types, at different electrolyte concentrations and at different temperatures, button typesamples (1 inch diameter x 0.5 inch thickness) were made and tested. The results are shown in Fig. 3.
Example 4
[0049] The composition of Example 4 was prepared according to the same procedure as in Exa7mple 1 except thatPLASTHALL DTDA was added. All components and their amounts are shown in Table 1. To measure the degree ofswelling in different electrolyte types, at different electrolyte concentrations and at different temperatures, button typesamples (1 inch diameter x 0.5 inch thickness) were made and tested. The results are shown in Figs. 3, 4 and 5.
Example 5
[0050] The composition of Example 5 was prepared according to the same procedure as in Example 4 except that aperoxide cure agent (DI-CUP 40c) and an accelerator (MBM) suitable for a peroxide cure system were used instead ofsulfur and accelerators suitable for a sulfur cure system (OBTS, TMTD, and TETD). All components and their amountsare shown in Table 1. After measuring MDR 2000 at 160 °C, a slab (5.88 inches x 5.88 inches x 0.08 inch) of thecomposition was cured for 22 minutes at 160 °C. To measure the degree of swelling in 3.5% NaCl solution at 100 °Fand 200 °F, slab type specimens (1 inch x 2 inch x 0.08 inch) were cut from the cured slab and tested. The results areshown in Fig. 6.
Comparative Example 1
[0051] The composition of Comparative Example 1 was prepared according to the same procedure as in Example 2except that ZEOSPAN 8030 was omitted. All components and their amounts are shown in Table 1. To measure thedegree of swelling in different electrolyte types, at different electrolyte concentrations and at different temperatures,button type samples (1 inch diameter x 0.5 inch thickness) were made and tested. The results are shown in Fig. 3.
Comparative Example 2
[0052] The composition of Comparative Example 2 was prepared according to the same procedure as in Example 2except that ZETPOL 2020EP and SAP were omitted. All components and their amounts are shown in Table 1. Tomeasure the degree of swelling in different electrolyte types, at different electrolyte concentrations and at differenttemperatures, button type samples (1 inch diameter x 0.5 inch thickness) were made and tested. The results are shownin Fig. 3.
Comparative Example 3
[0053] The composition of Comparative Example 3 was prepared according to the same procedure as in Example 2,except that ZETPOL 2020EP was omitted. All components and their amounts are shown in Table 1. To measure thedegree of swelling in different electrolyte types, at different electrolyte concentrations and at different temperatures,button type samples (1 inch diameter x 0.5 inch thickness) were made and tested. The results are shown in Fig. 3.
EP 2 839 107 B1
9
5
10
15
20
25
30
35
40
45
50
55
TA
BLE
1
Ingr
edie
ntE
xam
ple
1 (p
hr)
Exa
mpl
e 2
(phr
)E
xam
ple
3 (p
hr)
Exa
mpl
e 4
(phr
)E
xam
ple
5 (p
hr)
Com
para
tive
Exa
mpl
e 1
(phr
)C
ompa
rativ
e E
xam
ple
2 (p
hr)
Com
para
tive
Exa
mpl
e 3
(phr
)
ZE
TP
OL
2020
EP
a10
0.0
100.
010
0.0
100.
010
0.0
100.
0Z
EO
SP
AN
80
30b
93.0
93.0
93.0
93.0
93.0
100.
010
0.0
SA
Pc
164.
016
4.0
164.
016
4.0
164.
018
5.7
122.
2
PLA
ST
HA
LL
7050
d5.
49.
13.
27.
1P
LAS
TH
ALL
TO
TM
e21
.0P
LAS
TH
ALL
DT
DA
f21
.021
.0
N55
0g21
.421
.421
.421
.421
.428
.63.
913
.3M
gO0.
40.
40.
40.
40.
40.
1
AG
ER
ITE
R
ES
IN D
h1.
81.
81.
81.
81.
81.
40.
41.
1S
tear
ic a
cid
1.8
1.8
1.8
1.8
1.8
1.4
0.4
1.1
KA
DO
X 9
20ci
5.7
5.7
5.7
5.7
5.7
4.3
1.1
4.0
Spi
der
Sul
fur
0.4
0.4
0.4
0.4
0.3
0.1
0.2
OB
TS
j1.
81.
81.
81.
81.
40.
41.
1
TM
TD
k1.
81.
81.
81.
81.
40.
41.
1T
ET
D1
1.8
1.8
1.8
1.8
1.4
0.4
1.1
DI-
CU
P 4
0cm
3.9
VA
NO
X M
BM
n3.
6
EP 2 839 107 B1
10
5
10
15
20
25
30
35
40
45
50
55
(con
tinue
d)
Ingr
edie
ntE
xam
ple
1 (p
hr)
Exa
mpl
e 2
(phr
)E
xam
ple
3 (p
hr)
Exa
mpl
e 4
(phr
)E
xam
ple
5 (p
hr)
Com
para
tive
Exa
mpl
e 1
(phr
)C
ompa
rativ
e E
xam
ple
2 (p
hr)
Com
para
tive
Exa
mpl
e 3
(phr
)
TO
TA
L39
9.3
399.
341
4.9
414.
942
3.6
335.
011
7.4
252.
3
a ZE
TP
OL
2020
EP
: hyd
roge
nate
d ni
trile
rub
ber
havi
ng 3
6 %
of a
cryl
onitr
ile a
nd 9
1 %
of h
ydro
gena
tion
(Zeo
n C
hem
ical
s LP
)b Z
EO
SP
AN
803
0: e
thyl
ene
oxid
e-pr
opyl
ene
oxid
e-al
lyl g
lyci
dyl e
ther
terp
olym
er h
avin
g 91
% o
f eth
ylen
e ox
ide
and
6 m
ole
% o
f ally
l gly
cidy
l eth
er (
Zeo
n C
hem
ical
s LP
)c S
AP
: a p
artia
lly n
eutr
aliz
ed/c
ross
linke
d po
lyac
rylic
aci
d so
dium
sal
t (A
qua
Kee
p 10
SH
-NF
: Sum
itom
o S
eika
Che
mic
als
Co.
Ltd
)d P
LAS
TH
ALL
705
0: d
ialk
yl d
ieth
er g
luta
rate
(T
he H
alls
tar
com
pany
)e P
LAS
TH
ALL
TO
TM
: trio
ctyl
trim
ellit
ate
(The
Hal
lsta
r co
mpa
ny)
f PLA
ST
HA
LL D
TD
A: d
itrid
ecyl
adi
pate
(T
he H
alls
tar
com
pany
)g N
550:
car
bon
blac
k (C
abot
Cor
pora
tion)
h AG
ER
ITE
RE
SIN
D: a
ntio
xida
nt (
poly
mer
ized
1,2
-dih
ydro
-2,2
,4-t
rimet
hylq
uino
line,
from
R.T
. VA
ND
ER
BIL
T C
OM
PA
NY
, IN
)i K
AD
OX
920
c: Z
inc
Oxi
de A
ctiv
e (H
orse
head
Cor
p.)
j OB
TS
: N-o
xydi
ethy
lene
-2-b
enzo
thia
zole
sul
fena
mid
e (a
ccel
erat
or o
f sul
fur:
Akr
oche
m C
orp.
)k T
MT
D: t
etra
met
hylth
iura
m d
isul
fide
(acc
eler
ator
of s
ulfu
r: A
kroc
hem
Cor
p.)
l TE
TD
: tet
raet
hylth
iura
m d
isul
fide
(acc
eler
ator
of s
ulfu
r: A
kroc
hem
Cor
p.)
n DI-
CU
P 4
0c: D
icum
yl p
erox
ide
on a
car
rier
of c
alci
um c
arbo
nate
(A
rkem
a)n V
AN
OX
MB
M: m
-phe
nyle
nedi
mal
eim
ide
(R.T
. Van
derb
ilt C
ompa
ny, I
nc.)
EP 2 839 107 B1
11
5
10
15
20
25
30
35
40
45
50
55
[0054] As seen in Fig. 3, compositions according to the invention (Examples 1-4) showed improved free swell (byweight) in 3.5% NaCl solution that did not deteriorate with time over the duration of the test (30 days). In contrast, thecomposition of Comparative Example 1 (lacking the ethylene oxide elastomer) and the composition of ComparativeExample 2 (lacking the water swellable non-elastomeric material) had consistently lower free swell over the duration ofthe test. The composition of Comparative Example 3 (lacking the non-water swellable rubber) showed a remarkableincrease in free swell during the first five days of the test, but this free swell declined to the same level as for ComparativeExample 1 and Comparative Example 2 after 15 days of testing.[0055] Fig. 4 shows that the free swell (by weight) for the composition of Example 4 according to the invention remainedconsistently high even towards the end of the 30-day test, and even when measured at a higher temperature of 93°C.A similar performance was exhibited by the composition of Example 4 when tested in 15% HCl solution, as shown in Fig. 5.[0056] Finally, Fig. 6 shows that the free swell (by weight) for the composition of Example 5 did not drop greatly afterexposure for ten days at 100 °F when the temperature was increased to 200 °F for another ten days.
Constrained swell
Example 6
[0057] In this example the non-water swellable base rubber is a hydrogenated acrylonitrile-butadiene rubber (ZETPOL2020EP from Zeon Chemicals LP). The ethylene oxide based hydrophilic elastomer having no curable functional groupis ZEOSPAN 8100 (from Zeon Chemicals LP). The water-swellable non-elastomeric material is a partially neutral-ized/crosslinked polyacrylic acid sodium salt (AQUA KEEP 10SH-NF: Sumitomo Seika Chemicals Co. Ltd.). Othercomponents are shown in Table 2. These components were blended in a 270 mL Brabender bowl at 70 °C for 15 minuteswithout curing agent or accelerator. The curing agent and accelerator shown in the table were added during the millprocess under cooling. After measuring with MDR 2000 at 100 cpm 0.5° arc for 45 minutes at 160 °C, curing was carriedout at 160 °C for 15 minutes. To measure the degree of constrained swelling in different electrolyte concentrations atdifferent temperatures, pipe samples (1 inch diameter x 1 inch length) were made and tested. The results are shown inFigs. 7-11.
Example 7
[0058] The composition of Example 7 was prepared according to the same procedure as in Example 6, except thatthe amount of ZEOSPAN 8100 was changed from 100 phr to 50 phr. All components and their amounts are shown inTable 2. To measure the degree of constrained swell in different electrolyte concentrations at different temperatures,pipe samples (1 inch diameter x 1 inch length) were made and tested. The results are shown in Fig. 7 - 11.
Comparative Example 4
[0059] The composition of Comparative Example 5 was prepared according to the same procedure as in Example 6except that ZEOSPAN 8010 was used instead of ZEOSPAN 8100. All components and their amounts are shown inTable 3. To measure the degree of constrained swelling in different electrolyte concentrations at different temperatures,pipe samples (1 inch diameter x 1 inch length) were made and tested. The results are shown in Fig. 7 - 11.
Comparative Example 5
[0060] The composition of Comparative Example 6 was prepared according to the same procedure as in Example 6,except that the amount of ZEOSPAN 8100 was changed from 100 phr to 10 phr. All components and their amounts areshown in Table 3. To measure the degree of constrained swelling in different electrolyte concentrations at differenttemperatures, pipe samples (1 inch diameter x 1 inch length) were made and tested. The results are shown in Fig. 7 - 11.
Table 2. Examples (constrained swell tests)
Ingredients Example 6 Example 7
ZETPOL 2020EPa 100.0 100.0ZEOSPAN 8100b 100.0 50.0ZEOSPAN 8010c
SAPd 100.0 100.0
PLASTHALL DTDAe 15.0 15.0
EP 2 839 107 B1
12
5
10
15
20
25
30
35
40
45
50
55
[0061] As seen in Fig. 7, Example 6 showed highly improved constrained swell in tap water over the duration of thetest (14 days). The compositions of Example 7 and Comparative Example 4 both showed improved constrained swellin tap water over the duration of the test (14 days). However, the sample of Comparative Example 4 (having 13% moleratio of crosslinkable functional group in the ethylene oxide elastomer) displayed a distorted and broken shape afterswelling, as seen in Fig 8. Even though there was no crosslinkable functional group in the ethylene oxide elastomer inthe composition of Comparative Example 5, that sample (having an insufficient amount of only 10 parts of the ethyleneoxide elastomer) showed remarkably low constrained swell in tap water over the duration of the test (14 days).[0062] Fig. 8 shows that constrained swell shapes for the compositions of Example 6 and Example 7 had consistentlygood shape retention in tap water at 122°F (50°C) after 14 days. In contrast, the sample of Comparative Example 4displayed broken shapes after swelling. The sample of Comparative Example 5 exhibited a negligible degree of con-strained swell in tap water at 122 °F after 14 days.[0063] Fig. 9 - Fig. 11 show the constrained swell of the tested compositions in different saline concentrations at 180
(continued)
Ingredients Example 6 Example 7
N550f 40.0 40.0
Maglite Dg 0.5 0.5AGERITE RESIN Dh 1.5 1.5KADOX 920Ci 4.0 4.0Di-CUP 40KEj 4.0 4.0VANOX MBMk 2.5 2.5
Total 367.5 317.5
Table 3. Comparative Examples (constrained swell tests)
Ingredients Comparative Example 4 Comparative Example 5
ZETPOL 2020EPa 100.0 100.0ZEOSPAN 8100b 10.0ZEOSPAN 8010c 100.0
SAPd 100.0 100.0PLASTHALL DTDAe 15.0 15.0N550f 40.0 40.0Maglite Dg 0.5 0.5AGERITE RESIN Dh 1.5 1.5
KADOX 920Ci 4.0 4.0Di-CUP 40KEj 4.0 4.0VANOX MBMk 2.5 2.5
Total 367.5 277.5
aZETPOL 2020EP: hydrogenated nitrile rubber having 36 % of acrylonitrile and 91 % of hydrogenation (Zeon Chem-icals LP)bZEOSPAN 8100: ethylene oxide-propylene oxide copolymer having 90 % of ethylene oxide (Zeon Chemicals LP)cZEOSPAN 8010: ethylene oxide- allyl glycidyl ether copolymer having 13 % of allyl glycidyl ether (Zeon Chemicals LP)dSAP: a partially neutralized/crosslinked polyacrylic acid sodium salt (Aqua Keep 10SH-NF: Sumitomo Seika Chem-icals Co. Ltd)ePLASTHALL DTDA: ditridecyl adipate (The Hallstar company)fN550: carbon black (Cabot Corporation)gMaglite D: Magnesium Oxide (C. P. Hall Company)hAGERITE RESIN D: antioxidant (polymerized 1,2-dihydro-2,2,4-trimethylquinoline, from R.T. VANDERBILT COM-PANY, IN)iKADOX 920c: Zinc Oxide Active (Horsehead Corp.)jDI-CUP 40KE: Dicumyl peroxide in a clay carrier (Arkema Inc.)kVANOX MBM: m-phenylenedimaleimide (R.T. Vanderbilt Company, Inc.)
EP 2 839 107 B1
13
5
10
15
20
25
30
35
40
45
50
55
°F. The absolute values of constrained swell changed with the saline concentration. However, the relative order of theamount of constrained swell for the four compositions did not change.[0064] The water swellable rubber composition of the invention may be produced in various forms suitable for its enduse, such as slabs, sheets, strips, tubes, pellets and crumbs. It can be produced also as a rope, a string, a tape, a slug,a powder, a slurry, or a dispersion for a paint or coating. The composition may be adapted to any other form or shapethat allows it to be used to produce an article, or implement a step in a process which takes advantage of its high andsustained water swell characteristics.[0065] An important aspect of the water swelling of the rubber composition of the invention which contains crosslinkablesites is that the swelling process is reversible. Swelling decreases when the rubber is no longer exposed to water andthe absorbed water is released from the rubber. Eventually the rubber returns to a shape very close to its original shape.[0066] The water swellable rubber composition of the invention may be formed into articles by various methods suchas compression, transfer, extrusion, injection, and wrapping, and then cured. The composition also may be cured andthen divided into smaller pieces for its end use. In a particular embodiment, the composition may be cured and thendivided into pieces or particles of a size suitable for delivery by a fluid carrier to a space defined by solid walls underwater. As the particles thus deposited in that space absorb water, expand in size and press against the walls surroundingthe space, they eventually fill up the space and close it.[0067] The water swellable rubber composition of the invention has excellent water swell characteristics under con-ditions of free contact surface and/or constrained geometry, under prolonged exposure to high temperature and tovarious electrolyte solutions (including high salinity as well as acid conditions). The composition is suitable for useswhere such properties are advantageous, for example control and prevention of a fluid flow through a defined space,caulking, sealing, preserving airtightness in machinery or apparatus. As already mentioned above, the water swellablerubber composition is suitable as a sealing element for a well packer in well drilling. The water swellable rubber compositionmay also be made into a seal, a gasket, a component of a device for controlling fluid flow, a component of a device fordetecting water by the swelling of the component, or a component for activating a mechanism in a control device afterwater is absorbed into the component and changes its shape. The rubber composition may also be used for toys andgame elements.[0068] In a particular application the rubber composition of the invention may be used for impeding or stopping anaqueous fluid flow through a space defined by solid walls by placing the rubber composition inside the space in contactwith the aqueous fluid flow. As the rubber swells by absorption of water from the aqueous fluid, the expanding rubberfills up the space and presses against the walls, the flow of the aqueous fluid through the space is impeded and eventuallystopped. This method may be used in spaces such as cavities or cracks defined by solid walls which may be smooth,or uneven, or even discontinuous in some areas. These cavities or cracks may be in natural formations in the environment,or may be in man made devices or installations.[0069] The reversible aspect of the swelling by water of the rubber composition of the invention which contains crosslink-ing sites lends itself to additional applications and uses. For example, the rubber composition may be made into a partof a device for detecting water depletion when a indicator mechanism is activated when the part made from the rubbercomposition shrinks upon drying out and is no longer in contact with a portion of the device. A toy which operates onthe basis of water swelling the rubber composition of the invention may be re-used since the swelling is reversible andthe part made from the rubber composition returns to its original shape. The rubber composition of the invention mayalso be used for removing unwanted water from a material or an environment contaminated with such water, with possiblereuse of the rubber composition after the swelling by water is reversed upon drying.[0070] Other embodiments and uses of the present invention will be apparent to those skilled in the art from consid-eration of the specification and practice of the invention disclosed herein. It is intended that the specification and examplesbe considered as illustrative only, with the true scope and spirit of the invention being indicated by the following claims.
Claims
1. A water swellable rubber composition comprising:
(a) 100 phr of a non-water swellable base rubber which is at least one selected from the group consisting ofhydrogenated acrylonitrile-butadiene rubber (HNBR) and epichlorohydrin rubber,(b) 10 -200 phr of a crosslinkable ethylene oxide based hydrophilic elastomer having at least one curablefunctional group selected from the group consisting of hydroxyl, carboxyl, epoxy, amino, oxime, vinyl, oxazoline,anhydride, and amide, and(c) 50 - 200 phr of a water swellable non-elastomeric material which is partially neutralized/crosslinked polyacrylicacid salt.
EP 2 839 107 B1
14
5
10
15
20
25
30
35
40
45
50
55
2. A water swellable rubber composition according to claim 1, wherein the ethylene oxide based hydrophilic elastomer(b) is an ethylene oxide-propylene oxide-allyl glycidyl ether terpolymer having at least 75 % mole ratio of ethyleneoxide and 0.1 - 20 % mole ratio of allyl glycidyl ether.
3. A water swellable rubber composition according to claim 1, wherein the ethylene oxide based hydrophilic elastomer(b) is an ethylene oxide homopolymer.
4. A water swellable rubber composition according to claim 1, further comprising: (d) a compatibilizing agent.
5. A water swellable rubber composition according to claim 4, comprising: (d) up to 40 phr of the compatibilizing agent.
6. A water swellable rubber composition according to claim 5, wherein the compatibilizing agent is at least one selectedfrom the group consisting of trioctyl trimellitate, ditridecyl adipate, and dialkyl diether glutarate.
7. A water swellable rubber composition according to claim 1, comprising a peroxide cure system or a sulfur cure system.
8. A water swellable rubber composition according to claim 7, comprising at least one accelerator for the cure system.
9. An article comprising the composition of claim 1.
10. An article according to claim 9, wherein the composition is cured.
11. An article according to claim 9, wherein the composition is uncured.
12. An article according to claim 9, which is a seal, a gasket, a component of a well packer, a component of a devicefor controlling fluid flow, a component of a device for detecting water, a component of a device for detecting depletionof water, a component for an activating mechanism in a control device, a toy, or a game element.
13. A method for impeding an aqueous fluid flow through a space defined by solid walls, comprising the steps of placingthe composition of claim 1 in said space in contact with the aqueous fluid flow, whereby the composition swells byabsorption of water from the aqueous fluid, fills up said space and impedes the flow of the aqueous fluid throughthe space.
14. A method as in claim 13, wherein the solid walls are smooth.
15. A method as in claim 13, wherein the solid walls have uneven surfaces or minor discontinuous areas.
Patentansprüche
1. Wasserquellbare Gummizusammensetzung, umfassend:
(a) 100 phr eines nicht wasserquellbaren Basisgummis, welches wenigstens eines ist, das aus der aus hydro-geniertem Arcylonitril-Butadien-Gummi (HNBR) und Epichlorhydrin-Gummi bestehenden Gruppe ausgewähltist,(b) 10-200 phr eines quervernetzbaren ethylenoxidbasierten hydrophilen Elastomers, das wenigstens einehärtbare funktionelle Gruppe aufweist, die aus der aus Hydroxyl, Carboxyl, Epoxy, Amino, Oxim, Vinyl, Oxazolin,Anhydrid und Amid bestehenden Gruppe ausgewählt ist, und(c) 50-200 phr eines wasserquellbaren nicht elastomeren Materials, das teilweise neutralisiertes/quervernetztesPolyacrylsäuresalz ist.
2. Wasserquellbare Gummizusammensetzung nach Anspruch 1, wobei das ethylenoxidbasierte hydrophile Elastomer(b) ein Ethylenoxid-Propylenoxid-Allylglydidylether-Terpolymer ist, das wenigstens 75 % Molverhältnis Ethylenoxidund 0,1-20 % Molverhältnis Allylglydidylether aufweist.
3. Wasserquellbare Gummizusammensetzung nach Anspruch 1, wobei das ethylenoxidbasierte hydrophile Elastomer(b) ein Ethylenoxid-Homoplymer ist.
EP 2 839 107 B1
15
5
10
15
20
25
30
35
40
45
50
55
4. Wasserquellbare Gummizusammensetzung nach Anspruch 1, ferner umfassend:
(d) ein Kompatibilisierungsmittel.
5. Wasserquellbare Gummizusammensetzung nach Anspruch 4, umfassend:
(d) bis zu 40 phr des Kompatibilisierungsmittels.
6. Wasserquellbare Gummizusammensetzung nach Anspruch 5, wobei das Kompatibilisierungsmittel wenigstens ei-nes ist, das aus der aus Trioctyltrimellitat, Ditridecyladipat und Dialkyldietherglutarat bestehenden Gruppe ausge-wählt ist.
7. Wasserquellbare Gummizusammensetzung nach Anspruch 1, umfassend ein Peroxidhärtungssystem oder einSchwefelhärtungssystem.
8. Wasserquellbare Gummizusammensetzung nach Anspruch 7, umfassend wenigstens einen Beschleuniger für dasHärtungssystem.
9. Gegenstand, umfassend die Zusammensetzung nach Anspruch 1.
10. Gegenstand nach Anspruch 9, wobei die Zusammensetzung ausgehärtet ist.
11. Gegenstand nach Anspruch 9, wobei die Zusammensetzung nicht ausgehärtet ist.
12. Gegenstand nach Anspruch 9, der eine Dichtung, ein Dichtungsring, eine Komponente eines Brunnenpackers, eineKomponente einer Vorrichtung zum Regulieren eines Flüssigkeitsstroms, eine Komponente einer Vorrichtung zumDetektieren von Wasser, eine Komponente einer Vorrichtung zum Detektieren von Wasserverlust, eine Komponentefür einen Aktivierungsmechanismus in einer Steuervorrichtung, ein Spielzeug oder ein Spielelement ist.
13. Verfahren zum Unterbrechen des Flusses einer wässrigen Flüssigkeit durch einen von festen Wänden definiertenHohlraum, umfassend die Schritte des Platzierens der Zusammensetzung nach Anspruch 1 in dem Hohlraum inKontakt mit dem Fluss wässriger Flüssigkeit, wodurch die Zusammensetzung mittels Wasserabsorption aus derwässrigen Flüssigkeit aufquellt, den Hohlraum auffüllt und den Fluss der wässrigen Flüssigkeit durch den Hohlraumunterbricht.
14. Verfahren nach Anspruch 13, wobei die festen Wände glatt sind.
15. Verfahren nach Anspruch 13, wobei die festen Wände unebene Oberflächen oder kleinere diskontinuierliche Be-reiche aufweisen.
Revendications
1. Composition de caoutchouc gonflable dans l’eau comprenant :
(a) 100 parties en poids (phr) d’un caoutchouc de base non-gonflable dans l’eau qui est au moins un choisidans le groupe constitué de caoutchouc acrylonitrile-butadiène hydrogéné (HNBR) et de caoutchouc d’épichlo-rhydrine,(b) 10-200 parties en poids (phr) d’un élastomère hydrophile à base d’oxyde d’éthylène réticulable ayant aumoins un groupe fonctionnel durcissable choisi dans le groupe constitué d’un groupe hydroxyle, carboxyle,époxy, amino, oxime, vinyle, oxazoline, anhydride, et amide, et(c) 50-200 parties en poids (phr) d’un matériau non élastomère gonflable dans l’eau qui est un sel de poly(acideacrylique) partiellement neutralisé/réticulé.
2. Composition de caoutchouc gonflable dans l’eau selon la revendication 1, dans laquelle l’élastomère hydrophile àbase d’oxyde d’éthylène (b) est un terpolymère oxyde d’éthylène-oxyde de propylène-allylglycidyléther ayant unrapport molaire d’oxyde d’éthylène d’au moins 75 % et un rapport molaire d’allylglycidyléther de 0,1 - 20 %.
EP 2 839 107 B1
16
5
10
15
20
25
30
35
40
45
50
55
3. Composition de caoutchouc gonflable dans l’eau selon la revendication 1, dans laquelle l’élastomère hydrophile àbase d’oxyde d’éthylène (b) est un homopolymère d’oxyde d’éthylène.
4. Composition de caoutchouc gonflable dans l’eau selon la revendication 1, comprenant de plus :
(d) un agent de compatibilité.
5. Composition de caoutchouc gonflable dans l’eau selon la revendication 4, comprenant :
(d) jusqu’à 40 parties en poids (phr) de l’agent de compatibilité.
6. Composition de caoutchouc gonflable dans l’eau selon la revendication 5, dans laquelle l’agent de compatibilité estau moins un choisi dans le groupe constitué de triméllitate de trioctyle, adipate de ditridécyle et glutarate de dialk-yldiéther.
7. Composition de caoutchouc gonflable dans l’eau selon la revendication 1, comprenant un système de durcissementde type peroxyde ou un système de durcissement de type soufre.
8. Composition de caoutchouc gonflable dans l’eau selon la revendication 7, comprenant au moins un accélérateurpour le système de durcissement.
9. Article comprenant la composition selon la revendication 1.
10. Article selon la revendication 9, dans lequel la composition est durcie.
11. Article selon la revendication 9, dans lequel la composition est non durcie.
12. Article selon la revendication 9, lequel est un scellement, un joint, un constituant d’un garnissage d’étanchéité depuits, un constituant d’un dispositif destiné au contrôle de l’écoulement de fluide, un constituant d’un dispositifdestiné à la détection de l’eau, un constituant d’un dispositif destiné à la détection d’appauvrissement en eau, unconstituant destiné à l’activation d’un mécanisme dans un dispositif de contrôle, un jouet ou un élément de jeu.
13. Procédé pour empêcher un écoulement de fluide aqueux à travers un espace défini par des parois solides, com-prenant l’étape de mise en contact de la composition selon la revendication 1 avec l’écoulement de fluide aqueux,par laquelle la composition gonfle par absorption d’eau à partir du fluide aqueux, remplit ledit espace et empêchel’écoulement du fluide aqueux à travers l’espace.
14. Procédé selon la revendication 13, dans lequel les parois solides sont lisses.
15. Procédé selon la revendication 13, dans lequel les parois solides présentent des surfaces irrégulières ou des zonesdiscontinues mineures.
EP 2 839 107 B1
17
EP 2 839 107 B1
18
EP 2 839 107 B1
19
EP 2 839 107 B1
20
EP 2 839 107 B1
21
EP 2 839 107 B1
22
EP 2 839 107 B1
23
EP 2 839 107 B1
24
EP 2 839 107 B1
25
EP 2 839 107 B1
26
EP 2 839 107 B1
27
EP 2 839 107 B1
28
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the Europeanpatent document. Even though great care has been taken in compiling the references, errors or omissions cannot beexcluded and the EPO disclaims all liability in this regard.
Patent documents cited in the description
• US 4590227 A [0002] [0004] [0006]• JP 3111510 B [0002] [0004] [0006]• JP 2004123887 A [0002]
• US 20090084550 A1 [0002] [0004] [0006]• JP 2001123028 A [0002]