GB1558491A - Hydrogenation of polymers - Google Patents
Hydrogenation of polymers Download PDFInfo
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- GB1558491A GB1558491A GB3596976A GB3596976A GB1558491A GB 1558491 A GB1558491 A GB 1558491A GB 3596976 A GB3596976 A GB 3596976A GB 3596976 A GB3596976 A GB 3596976A GB 1558491 A GB1558491 A GB 1558491A
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- copolymer
- hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
(54) HYDROGENATION OF POLYMERS
(71) We, BAYER AKTIENGESELLSCHAFT, of 509 Leverkusen, Germany, a body - corporate organised under the laws of Germany, do hereby declare the invention, for which
we pray that a patent may be granted to us, and the method by which it is to be performed,
to be particularly described in and by the following statement:
This invention relates to a process for the production of partially hydrogenated
copolymers of an a,ss-unsaturated carboxylic acid or derivatives thereof and a hydrocarbon
containing conjugated double bonds.
Random copolymers of monomers such as these are known from German Patent
Specifications Nos. 570,980 and 658,172. They are obtained by the emulsion copolymerisa
tion of, for example, acrylonitrile with conjugated dienes, such as butadiene.
It is known from US-PS 3,700,637 that regularly alternating copolymers can be produced -from butadiene and acrylonitrile and can be hydrogenated by means of rhodium complexes
as catalysts with the nitrile groups left intact.
In the context of the present invention, copolymers are both regularly alternating and
also random copolymers of an a,ss-unsaturated carboxylic acid or derivative thereof and an
unsaturated hydrocarbon containing conjugated double bonds. The back-bone of the
copolymer consists entirely of carbon atoms.
Suitable carboxylic acids and their derivatives are, for example, (meth)acrylic acid,
fumaric acid, their esters and amides, and also the corresponding carboxylic acid nitriles,
such as (meth)acrylonitrile. Suitable conjugated dienes are, for example, butadiene,
isoprene, dimethyl butadiene and piperylene. The process according to the invention is
preferably used for the partial hydrogenation of copolymers of (meth)acrylic acid or
derivatives thereof and butadiene. Copolymers of 90 to 45% by weight of butadiene and 10
to 55% by weight of acrylonitrile (based in each case on the copolymer total) are
particularly preferred.
-In addition to the functional groups emanating from the carboxylic acid or its derivatives,
for example the nitrile group, unsaturated structural units present in the above-mentioned
copolymers are the vinyl groups formed during 1.2-bonding of the dienes used and the cis
or trans-configuration olefinic double bonds formed during 1,4-bonding.
According to the invention, the copolymers are dissolved in suitable organic solvents and
are-hydrogenated in the presence of a rhodium complex and, optionally, a ligand of the
complex, e.g. triphenyl phosphine. at elevated temperature and pressure with any other
functional groups, e.g. the nitrile group. left intact. In this connection, it has surprisingly
been found that, in cases where chlorobenzene is used as solvent, the vinyl groups and the
trans-configuration double bonds in the above-mentioned copolymers are completely
hydrogenated in a selective manner. If on the other hand other solvents are used, the vinyl
groups are completely hydrogenated, whereas the trans-configuration double bonds are
only partially hydrogenated. The degree of hydrogenation of the trans-configuration double
bonds amounts to between 10 and 90 %, based on the quantity of these double bonds,
depending upon the solvent used. It was by no means foreseeable to the expert that the
controlled use of certain solvents in a hydrogenation reaction carried out under identical
conditions would enable the vinyl groups to be completely hydrogenated and the
trans-configuration double bond to be completely or partially hydrogenated in a selective
manner.
The present invention relates to a process for selective hydrogenation of the vinyl groups
and trans-configuration double bonds in copolymers of an a p-unsaturated carboxylic acid
or a derivative thereof and an unsaturated hydrocarbon containing conjugated double
bonds, the back-bone of the copolymer consisting entirely of carbon atoms, distinguished by the fact that a 1 to 20 % solution of the copolymer in a suitable organic solvent is
hydrogenated at 50 to 1500C and at 5 to 300 atms (absolute pressure) in the presence of 0.01
to 10 % by- weight of a catalyst of a complex compound of a monovalent or trivalent
rhodium halide, and, optionally, 5 to 25 % by weight of the ligand bound in the complex
(based in each case on dissolved copolymer). Selective hydrogenation of the vinyl groups
and trans-configuration double bonds in the copolymers may be carried out in a
chlorine-substituted aromatic solvent with from 6 to 12 carbon atoms, preferably
chlorobenzene, as solvent. In this medium the polar groups (for example nitrile groups) do
not undergo any demonstrable hydrogenation. If solutions of the copolymers in other
solvents, such as for example toluene, benzene, xylene, dimethyl formamide, ethyl acetate,
methyl ethyl ketone, tetrahydrofuran, cyclohexanone or methylene chloride, are used in
accordance with the invention, complete hydrogenation of the vinyl groups is accompanied
by only partial hydrogenation of the trans-configuration double bonds.
The degree of hydrogenation of these double bonds is governed by the type of solvent
used and decreases from around 90 to about 10 % in the order benzene > dimethylforma
mide ~ xylene > ethyl acetate > toluene > methyl ethyl ketone > cyclohexanone >
tetrahydrofuran > methylene chloride. Although not necessary, it is of course also possible
to use solvent mixtures for the process according to the invention.
The solutions contain from 1 to 20 % by weight and preferably from 2.5 to 10 % by
weight of the copolymers, based on- the particular above-described solvent used for the
process according to the invention.
From 0.01 to 10 % by weight and preferably from 0.1 to 5 % by weight (based on the
dissolved copolymer) of a complex compound of monovalent or trivalent rhodium halides
are added to the solutions of the copolymers as a catalyst for the hydrogenation reaction.
Suitable complex compounds correspond to the general formula (I): (RmB)3 Rh X, (I) in which R = C1-C8 alkyl, C6-C15 aryl or C7-C1.5 aralkyl,
B = P, As, S or S=0,
X = Cl or Br, m = 2 or 3, and
n = 1 or 3.
Preferred complex compounds of this type are tris-(triphenyl phosphine)-rhodium(I)
chloride, tris-(triphenyl phosphine)-rhodium(III)-chloride and tris-(dimethyl sulphoxide) rhodium(III)-chloride.
The pressure under which the hydrogenation reaction according to the invention is
carried out may be varied within a wide range. Suitable pressures are in the range of from 5
to 300 atms and preferably in the range of from 50 to 100 atms. The hydrogenation reaction
is carried out at temperatures in the range of from 50 to 1500C, and preferably at
temperatures in the range of from 75 to 115"C. Under these conditions, the selective
hydrogenation reaction is over after about 3 to 7 hours.
The catalyst may be separated off by the method described in DT-AS 1,558,395.
The hydrogenation product is separated off from the reaction solution by treatment with
steam or by pouring into methanol and is subsequently dried under reduced pressure at a
temperature of approximately 70"C.
Qualitative and quantitative determination of the hydrogenated double bonds and
double bonds still present in the copolymers hydrogenated in accordance with the invention
is carried out by IR-spectroscopic analysis. For further characterisation the iodine number
and the glass transition temperature of the hydrogenation products are determined (in case
of the glass transition temperature by thermomechanical analysis (TMA) and shear
modulus measurement);
The copolymers hydrogenated by the process according to the invention show increased
tensile strength for increased elongation at break and. in addition. improved elasticity.
They are vulcanisable rubbers which may be used as temperature-resistant materials, for
example in the sealing field.
Three different acrylonitrile-butadiene copolymers are used in the following Examples.
The percentages quoted are always per cent by weight.
The quantities of catalysts and triphenyl phosphine quoted in the Examples are based in
each case on the dissolved copolymer.
Copolymer I: of 82% of butadiene and 18% of acrylonitrile
Copolymer II: of 72% of butadiene and 28% of acrylonitrile
Copolymer III: of 62% of butadiene and 38% of acrylonitrile
(based in each case on the copolymer total).
Example 1
1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer I in chlorobenzene, followed by hydrogenation for 5.5 hours at 100 C/60 atms.
On completion of hydrogenation, the catalyst is separated off in accordance with DT-AS 1,558,395. The reaction products are precipitated by pouring the reaction solution into methanol, and are subsequently dried under reduced pressure at approximately 70 C.
The hydrogenation product obtained has the following properties:
Degree of hydrogenation: 100% of the vinyl and 100% of the
trans-double bonds
Glass transition temperature: Tg = -31 C
Iodine Number: INo. = 14
The hydrogenation products of the following Examples are worked up and characterised in the same way as described in Example 1.
Example 2
1% of [(C6H5)3P]RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer
II in chlorobenzene, followed by hydrogenation for 4.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl and 100% of the
trans-double bonds
Glass transition temperature: Tg = -30 C
Iodine Number: INo. = 26
Example 3
1% of [(C6H5)3P]3 RhlllCl3 and 10% of (C6Hs)3P are added to a 2.5% solution of copolymer II in chlorobenzene, followed by hydrogenation for 5.5 hours at 1000C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 100% of
the trans-double bonds
Glass transition temperature: Ta -30 C Iodine number: o. = 22
Example 4
1% of [(C6H5)3P]3Rh'Cl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer
III in chlorobenzene, followed by hydrogenation for 6 hours at 1000C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 100% of the
trans-double bonds
Glass transition temperature: Tg = -27 C
Iodine Number: INo. = 22
Example 5
1% of [(C6H5)3P]3 RhICl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer I in the toluene, followed by hydrogenation for 4.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 48% of the
trans-double bond
Glass transition temperature: Tg = -43 C
Iodine Number: INo. = 50
Example 6
1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in the toluene, followed by hydrogenation for 5.2 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 42% of the
trans-double bonds
Glass transition temperature: Tg = -26 C
Iodine Number: INo. = 95
Example 7
1% of [(C6H5)3P]3 RhICl and 10% (C6H5)3P are added to a 2.5% solution of copolymer
III in toluene, followed by hydrogenation for 5 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 30% of the
trans-double bonds
Glass transition temperature: Tg = -26 C
Iodine number: INo. = 60
Example 8
1% of [(CH3)2S=0]3 RhIIICl3 and 10% of (CH3)2S=0 are added to a 2.5% solution of copolymer II in chlorobenzene, followed by hydrogenation for 7.5 hours at 1000C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 100% of
the trans-double bonds
Glass transition temperature: T = -290C
Iodine number: INo. = 29
Example 9
1% of [(C6H5)3P]3 RhIIICl3 and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in benzene, followed by hydrogenation for 6.2 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 90% of the
trans-double bonds
Glass transition temperature: Ta = -30 C
Iodine number: INo. = 19
Example 10
1% of [(C6H5)3P]3 RhlCl and 10% of (C6H5)P are added to a 2.5% solution of copolymer II in ethyl acetate, followed by hydrogenation for 5.5 hours at 1000C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 50% of the
trans-double bonds
Glass transition temperature: T = -38 C
Iodine number: INo. = 77
Example 11
1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in methyl ethyl ketone, followed by hydrogenation for 6 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 40% of the
trans-double bonds
Glass transition temperature: Tg = -39 C
Iodine number: INo. = 119
Example 12
1% of [C6G5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in xylene, followed by hydrogenation for 6.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 59% of the
trans-double bonds
Glass transition temperature: T = -39 C Iodine number: INo. = 73
Example 13
1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in dimethyl formamide, followed by hydrogenation for 4 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of vinyl- and 59% of the
trans-double bonds
Glass transition temperature: Tg = -42 C
Iodine number: INo. = 144
Example 14
1% of [(C6H5)3P]3 RhCl and 1 % of (C6H5)3P are added to a 2.5% solution of copolymer
II in cyclohexanone, followed by hydrogenation for 4 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of vinyl- and 38% of the
trans-double bonds
Glass transition temperature: Tg = -41 C
Iodine number: INo. = 114
Example 15
1% of[C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer
II in tetrahydrofuran, followed by hydrogenation for 3.2 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 31% of the
trans-double bonds
Glass transition temperature: Tg = -39 C
Iodine number: INo. = 113
Example 16
1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in methylene chloride, followed by hydrogenation for 6.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties:
Degree of hydrogenation: 100% of the vinyl- and 12% of the
trans-double bonds
Glass transition temperature: Tg = -40 C
Iodine number: INo. = 160 The results of Examples 1 to 16 are summarized in Table 1 below:
TABLE 1
Co- Degree of hydrogenation(%)
Example polymer Solvent Catalyst vinyl- trans-double bonds Tg INo.
1 I chlorobenzene [(C6H5)3P]3RhICl 100 100 -31 14 2 II " " 100 100 -30 26 3 II " [(C6H5)3P]RhIIICl3 100 100 -30 22 4 III " [(C6H5)3P]3RhICl 100 100 -27 22 5 I toluene " " 100 48 - 43 50 6 II " " 100 42 -26 95 7 III " " 100 38 -26 60 8 II chlorobenezene [(CH3)2S=0]3RhIIICl3 100 100 -29 29 9 II benzene [(C6H5)3P]3RhIIICl3 100 90 -30 19 10 II ethyl acetate [(C6H5)3P[3RhICl 100 50 -38 77 11 II methyl ethyl " 100 40 -39 119 ketone 12 II xylene " 100 59 -39 73 13 II dimethyl " 100 59 -42 144 formamide 14 II cyclohexanone " 100 38 -41 114 15 II tetrahydrofuran " 100 31 -39 113 16 II methylene " 100 12 -40 160 chloride
Claims (12)
1. A process for the selective hydrogenation of the vinyl groups and trans-configuration double bonds in a copolymer of an a,ss-unsaturated carboxylic acid or a derivative thereof and an unsaturated hydrocarbon containing conjugated double bonds, the back-bone of the copolymer consisting entirely of carbon atoms, which comprises hydrogenating a 1 to 20% solution of the copolymer in an organic solvent at a temperature of from 50 to 1500C and at pressure of from 5 to 300 atmospheres in the presence of from 0.01 to 10% by weight of a complex of a monovalent or trivalent rhodium halide as a catalyst and, optionally, from 5 to 25% by weight of the ligand bound in the complex (based in each case on the dissolved copolymer).
2. A process as claimed in Claim 1, wherein the solvent is a chlorine-substituted aromatic solvent with from 6 to 12 carbon atoms, and the vinyl groups and the trans-configuration double bonds are completely hydrogenated in a selective manner.
3. A process as claimed in Claim 1, wherein the solvent is toluene, benzene, ethyl acetate, methyl ethyl ketone, xylene, dimethyl formamide, cyclohexanone, tetrahydrofuran or methylene chloride, and from 10 and 90% of the trans-configuration double bonds, in addition to the vinyl groups, are hydrogenated, depending upon the solvent used.
4. A process as claimed in any of Claims 1 to 3, wherein the copolymer to be hydrogenated is a copolymer of (meth)acrylic acid, an ester or amide thereof or (meth)acrylonitrile, with butadiene, isoprene, dimethyl butadiene or piperylene.
5. A process as claimed in any of Claims 1 to 4, wherein the copolymer is a butadiene-acrylonitrile copolymer of from 90 to 45% by weight of butadiene and from 10 to 55% by weight of acrylonitrile (based in each case on the copolymer total).
6. A process as claimed in any of claims 1 to 5, wherein the complex corresponds to the general formula (I): (RmB)3 Rh Xn (I) in which R = C-C8 alkyl, C6-C15 aryl or C7C15 aralkyl,
B = P, As, S or S=0,
X = Cl or Br,
m = 2 or 3, and
n = 1 or 3.
7. A process as claimed in any of Claims 1 to 6, wherein the hydrogenation is carried out in the presence of from 0.1 to 5% of the complex.
8. A process as claimed in any of Claims 1 to 7, wherein the hydrogenation temperature is from 75 to 1150C.
9. A process as claimed in any of Claims 1 to 8, wherein the hydrogenation pressure is from 50 to 100 atmospheres.
10. A process as claimed in any of claims 1 to 9, wherein the rhodium complex has sulphur-containing ligands.
11. A process as claimed in Claim 1, substantially as herein described with reference to any of the specific Examples.
12. A copolymer when hydrogenated by a process as claimed in any of Claims 1 to 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752539132 DE2539132C2 (en) | 1975-09-03 | 1975-09-03 | Use of hydrogenated diene copolymers as temperature-resistant materials in the sealing sector |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1558491A true GB1558491A (en) | 1980-01-03 |
Family
ID=5955476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3596976A Expired GB1558491A (en) | 1975-09-03 | 1976-08-31 | Hydrogenation of polymers |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5232095A (en) |
| BE (1) | BE845775A (en) |
| DE (1) | DE2539132C2 (en) |
| FR (1) | FR2322878A1 (en) |
| GB (1) | GB1558491A (en) |
| IT (1) | IT1121670B (en) |
| NL (1) | NL186327C (en) |
Cited By (77)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3229871A1 (en) * | 1981-08-11 | 1983-02-24 | Nippon Zeon Co., Ltd., Tokyo | OIL-RESISTANT RUBBER COMPOSITION |
| DE3232692A1 (en) * | 1981-09-02 | 1983-03-17 | Nippon Zeon Co., Ltd., Tokyo | CO-VULCANIZABLE RUBBER COMPOSITION |
| DE3248378A1 (en) * | 1981-12-28 | 1983-07-14 | Nippon Zeon Co., Ltd., Tokyo | Oil- and degradation-resistant rubber article |
| GB2123837A (en) * | 1982-07-13 | 1984-02-08 | Bayer Ag | Shaped articles for use in the exploration for and/or production of petroleum and natural gas |
| US4581417A (en) * | 1983-08-19 | 1986-04-08 | Bayer Aktiengesellschaft | Production of hydrogenated nitrile rubbers |
| US4675248A (en) * | 1983-10-29 | 1987-06-23 | Bayer Aktiengesellschaft | Polymer mixtures and co-vulcanizates produced therefrom |
| AU567132B2 (en) * | 1982-12-08 | 1987-11-12 | Polysar Ltd. | Sulphur vulcanizable nitrile rubber composition |
| EP0270020A2 (en) * | 1986-12-01 | 1988-06-08 | Polysar Limited | Resin cure |
| US4812528A (en) * | 1987-07-06 | 1989-03-14 | University Of Waterloo | Polymer hydrogenation process |
| US4857632A (en) * | 1988-06-13 | 1989-08-15 | Polysar Limited | Residue removal process |
| EP0111412B1 (en) * | 1982-12-08 | 1989-08-30 | Polysar Limited | Polymer hydrogenation process |
| US4876314A (en) * | 1988-11-09 | 1989-10-24 | Shell Oil Company | Hydrogenation process |
| US4879352A (en) * | 1988-12-30 | 1989-11-07 | Polysar Limited | Adducts of an aminoalcohol and nitrile rubber |
| US4879349A (en) * | 1987-11-05 | 1989-11-07 | Shell Oil Company | Selective hydrogenation process |
| US4892928A (en) * | 1988-10-12 | 1990-01-09 | Shell Oil Company | Hydrogenation process |
| US4914160A (en) * | 1988-06-23 | 1990-04-03 | Hormoz Azizian | Deuteration of unsaturated polymers and copolymers |
| US4944926A (en) * | 1988-08-01 | 1990-07-31 | Polysar Limited | Method to treat rhodium-containing solutions |
| US4970254A (en) * | 1988-09-22 | 1990-11-13 | Shell Oil Company | Method for hydrogenating functionalized polymer and products thereof |
| US4978771A (en) * | 1985-11-19 | 1990-12-18 | Bayer Aktiengesellschaft | Process for the selective hydrogenation of unsatuated compounds |
| US4985540A (en) * | 1989-11-20 | 1991-01-15 | Polysar Limited | Process for removing rhodium-containing catalyst residue from hydrogenated nitrile rubber |
| US5001199A (en) * | 1987-11-05 | 1991-03-19 | Shell Oil Company | Selective hydrogenation process |
| US5030779A (en) * | 1989-06-08 | 1991-07-09 | Shell Oil Company | Hydrogenation catalyst and hydrogenation process wherein said catalyst is used |
| US5057582A (en) * | 1988-12-23 | 1991-10-15 | Shell Oil Company | Hydrogenation catalyst and hydrogenation process wherein said catalyst is used |
| US5057581A (en) * | 1990-05-02 | 1991-10-15 | University Of Waterloo | Polymer hydrogenation process |
| US5075388A (en) * | 1990-12-13 | 1991-12-24 | Rempel Garry L | Amine modified hydrogenation of nitrile rubber |
| US5208296A (en) * | 1992-09-02 | 1993-05-04 | Polysar Rubber Corporation | Nitrile rubber hydrogenation |
| US5210151A (en) * | 1992-09-02 | 1993-05-11 | Polysar Rubber Corporation | Hydrogenation of nitrile rubber |
| US5241013A (en) * | 1992-09-02 | 1993-08-31 | Polysar Rubber Corporation | Catalytic hydrogenation of nitrile rubber |
| US5244965A (en) * | 1988-01-19 | 1993-09-14 | Polysar Limited | Polymer solution treatment process |
| US5258467A (en) * | 1992-09-02 | 1993-11-02 | Polysar Rubber Corporation | Catalytic solution hydrogenation of nitrile rubber |
| USRE34548E (en) * | 1985-11-19 | 1994-02-15 | Bayer Aktiengesellschaft | Process for the selective hydrogenation of unsaturated compounds |
| US5314741A (en) * | 1992-10-07 | 1994-05-24 | The Goodyear Tire & Rubber Company | Rubber article having protective coating |
| US6214922B1 (en) | 1998-03-06 | 2001-04-10 | Bayer Inc. | Nitrile polymer vulcanizate and process for the production thereof |
| US6307624B1 (en) | 1997-08-21 | 2001-10-23 | Bayer Ag | Process for the preparation of partially hydrogenated acrylonitrile-butadiene rubbers (HNBR) with on-line application of Raman spectroscopy |
| EP1219640A2 (en) * | 2000-12-28 | 2002-07-03 | Bayer Inc. | Hydrogenation of nitrile rubber |
| WO2002100905A1 (en) | 2001-06-12 | 2002-12-19 | Bayer Inc. | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
| US6538071B1 (en) | 1999-09-07 | 2003-03-25 | Bayer Aktiengesellschaft | Rubber mixtures for roller coatings |
| US6573333B2 (en) | 2000-08-22 | 2003-06-03 | Bayer Aktiengesellschaft | Mixtures of olefin polymers and nitrile rubbers |
| US6646059B2 (en) | 2000-11-06 | 2003-11-11 | Bayer Inc. | Process for removing iron-and rhodium-containing catalyst residues from hydrogenated nitrile rubber |
| WO2004113389A2 (en) * | 2003-06-26 | 2004-12-29 | Versamatrix A/S | High capacity poly(alkylene)glycol based amino polymers |
| US6844412B2 (en) | 2002-07-25 | 2005-01-18 | Lord Corporation | Ambient cured coatings and coated rubber products therefrom |
| US6929769B2 (en) | 2002-01-23 | 2005-08-16 | Bayer Aktiengesellschaft | Nitrile rubber mixtures with a low tendency towards mold contamination |
| US6946526B2 (en) | 2002-01-31 | 2005-09-20 | Bayer Inc. | Nitrile polymer vulcanizate and process for the production thereof |
| US7037982B2 (en) | 2001-01-17 | 2006-05-02 | Bayer Aktiengesellschaft | Rubber mixtures for roll coverings |
| US7091284B2 (en) | 2000-08-25 | 2006-08-15 | Bayer Ag | Hydrogenated nitrile rubbers with improved low-temperature properties |
| US7265185B2 (en) * | 2000-04-10 | 2007-09-04 | Lanxess Inc. | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
| US7345115B2 (en) * | 2005-03-18 | 2008-03-18 | Lanxess Inc. | Organic solvent-free hydrogenation of diene-based polymers |
| US7385010B2 (en) * | 2005-03-18 | 2008-06-10 | Lanxess Inc. | Hydrogenation of diene-based polymer latex |
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| DE2303753A1 (en) * | 1972-01-31 | 1973-08-09 | Schwermasch Liebknecht Veb K | Sealing cpds - with good oil resistance based on butadiene -acrylonitrile rubber |
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- 1976-08-31 NL NL7609679A patent/NL186327C/en not_active IP Right Cessation
- 1976-09-01 JP JP10377476A patent/JPS5232095A/en active Pending
- 1976-09-01 IT IT5109676A patent/IT1121670B/en active
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- 1976-09-03 FR FR7626671A patent/FR2322878A1/en active Granted
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Also Published As
| Publication number | Publication date |
|---|---|
| NL7609679A (en) | 1977-03-07 |
| FR2322878B1 (en) | 1980-05-23 |
| BE845775A (en) | 1977-03-02 |
| DE2539132C2 (en) | 1987-04-09 |
| NL186327C (en) | 1990-11-01 |
| DE2539132A1 (en) | 1977-03-17 |
| JPS5232095A (en) | 1977-03-10 |
| IT1121670B (en) | 1986-04-10 |
| FR2322878A1 (en) | 1977-04-01 |
| NL186327B (en) | 1990-06-01 |
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