CN1865305A - Hydrogenation method of nitrile butadiene rubber - Google Patents
Hydrogenation method of nitrile butadiene rubber Download PDFInfo
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- CN1865305A CN1865305A CN 200510071103 CN200510071103A CN1865305A CN 1865305 A CN1865305 A CN 1865305A CN 200510071103 CN200510071103 CN 200510071103 CN 200510071103 A CN200510071103 A CN 200510071103A CN 1865305 A CN1865305 A CN 1865305A
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- CN
- China
- Prior art keywords
- paracril
- hydrogenation
- butadiene rubber
- molecular weight
- nitrile rubber
- Prior art date
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- Granted
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 229920013649 Paracril Polymers 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003292 glue Substances 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229920005603 alternating copolymer Polymers 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 230000002902 bimodal effect Effects 0.000 abstract description 6
- 230000006835 compression Effects 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 5
- 230000003679 aging effect Effects 0.000 abstract description 2
- 229920006168 hydrated nitrile rubber Polymers 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010948 rhodium Substances 0.000 description 8
- 241001441571 Hiodontidae Species 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229920013644 Chemigum Polymers 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 halogenated aryl hydrocarbon Chemical class 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
The invention relates to a hydrogenation method of nitrile rubber, which comprises the steps of firstly dissolving nitrile rubber in an organic solvent, and then carrying out hydrogenation under the conditions of adding a catalyst and stirring, and is characterized in that liquid nitrile rubber is added into nitrile rubber to be hydrogenated, the adding amount is 5-20%, then a solution of a mixture of the nitrile rubber and the liquid nitrile rubber is added into a hydrogenation kettle, and hydrogenation reaction is carried out at the temperature of 40-100 ℃ and the pressure of 4.0-9.0 MPa, wherein the reaction time is 2-12 hours. The hydrogenation method has the advantages that the hydrogenated product HNBR has bimodal characteristics in molecular weight distribution, the molecular weight distribution is obviously widened, the Mooney viscosity is effectively reduced, the processability of HNBR, the mechanical property of the product, the compression permanent deformation and the hot air aging property are excellent.
Description
Technical field
The present invention relates to a kind of method of hydrotreating of paracril, particularly a kind ofly unsaturated carbon-carbon double bond on divinyl and acrylonitrile copolymer (NBR) molecular chain is carried out solution method select hydrogenation method.
Background technology
Obtain product hydrogenated nitrile-butadiene rubber (HNBR), its mooney viscosity after divinyl and acrylonitrile copolymer (NBR) hydrogenation
Be the important indicator of processing characteristics, the high performance of HNBR and workability are the targets of product development always.
The disclosed hydrogen addition technology of US4581417, its condition is: catalyzer is RhX (PPh
3)
3, consumption is 0.05-0.6% (weight by dry rubber .Wt%), the triphenyl phosphorus consumption be 2% (weight by dry rubber, Wt%), hydrogenation temperature 100-145 ℃.This patent does not clearly limit basic glue Mooney viscosity, in one example, having selected basic glue Mooney viscosity for use is 29 low Mooney paracril, acrylonitrile content 34.9%, it is very fast to rise with the final HNBR Mooney viscosity of the increase of catalyst consumption, and Mooney viscosity has a big increase.That is to say the HNBR product that will obtain more satisfactory Mooney viscosity, basis glue Mooney is the selection of comparison key, and this low Mooney basis glue is generally less in NBR industrialization bulk product, may need special synthetic, and requiring that oxygen level is less than 5PPm in the glue, operability is relatively poor.The liquid NBR hydrogen addition technology of disclosed a kind of low molecular mass among the US4829128, catalyst system therefor is RhX (PPh
3)
3, but the required strict degassing displacement of glue, the technology relative complex.In addition because liquid NBR molecular weight ratio is lower, its remaining mercaptan or when synthetic foreign matter content such as used initiator higher relatively, only depending on repeatedly that degassing displacement also is difficult to reach ideal effect, be unfavorable for improving catalyst efficiency.
Summary of the invention
The object of the present invention is to provide a kind of hydrogenation method of new paracril, by improving the Mooney viscosity of process adjustments hydrogenation with basic glue, thereby regulate and control final HNBR Mooney, has bimodal molecular weight distribution behind the hydrogenation, do not reduce its degree of hydrogenation, obtain product and on processing characteristics, be improved.
For achieving the above object, method of the present invention is, at first paracril is dissolved in the organic solvent, carry out hydrogenation under catalyzer and the stirring condition being added with then, it is characterized in that earlier liquid acrylonitrile butadiene rubber being added in the paracril that needs hydrogenation, add-on counts 5%～20% (with the dried glue weight of NBR in the dried glue weight of NBR, as follows), best add-on is 8%～15%, solution with above-mentioned paracril and liquid acrylonitrile butadiene rubber mixture adds in the hydrogenation still then, at 40～100 ℃, carry out hydrogenation reaction under pressure 4.0～9.0Mpa, 2～12 hours reaction times.
Do not limit the preparation method of paracril (NBR), liquid acrylonitrile butadiene rubber (LNBR) among the present invention.NBR can be an alternating copolymer, also can be random copolymers, and vinyl cyanide 18～50% (quality) is preferably 32～40% (quality); The nitrile (HTBN) molecular weight can be 1000～10000 (osmometry mensuration), is preferably 3000～8000, and acrylonitrile content is 28～45% (quality), is preferably 33～40% (quality).
Catalyzer used herein does not equally limit especially yet, can adopt general chemigum hydrogenation catalyzer and add-on, as being homogeneous phase solution hydrogenation catalyst system such as rhodium (Rh), ruthenium (Ru), palladium (Pd) and Ru-Rh, also can be heterogeneous hydrogenation catalyst systems such as appendix Pd.Preferably use RhX (PPh
3)
3, wherein X is Cl, Br, I, is preferably Cl; Or carboxylic acid palladium.Use the rhodium catalyst of homogeneous phase solution hydrogenation catalyst system the best to be RhCl (PPh
3)
3Catalyst levels 0.05%～0.20% (weight by dry rubber), be preferably 0.08～0.15%, the triphenylphosphine consumption is 0～1.6% (weight by dry rubber), is preferably in 50～100 ℃, carry out hydrogenation reaction under pressure 6.0～9.0Mpa, preferably the reaction times is 8～12 hours.Use the best palladium catalyst of homogeneous phase solution hydrogenation catalyst system to be palladium, consumption 1%～2.50% (weight by dry rubber) is preferably 1～1.5% (weight by dry rubber), be preferably in 40～70 ℃, carry out hydrogenation reaction under pressure 4～6Mpa, preferably the reaction times is 2～5 hours.
The solvent of paracril can be chlorobenzene, bromobenzene, toluene and dimethylbenzene isopolarity halogenated aryl hydrocarbon among the present invention, and aromatic hydrocarbon also can be acetone, butanone etc.Use RhX (PPh
3)
3The time be preferably chlorobenzene.Be preferably acetone when using palladium.Strength of solution is 6%～15% to be preferably 8～14%
By in paracril, adding liquid acrylonitrile butadiene rubber, regulate and control final HNBR Mooney, and it is had than wide molecular weight distribution in the present invention.The difference of add-on, proportioning and molecular weight by regulating liquid acrylonitrile butadiene rubber, and then the HNBR Mooney viscosity, the molecular weight distribution that obtain suiting.
The technology of the present invention exploitation can be regulated the Mooney of hydrogenation glue, has bimodal molecular weight distribution, and molecular weight distribution is obviously widened, and is keeping having reduced Mooney viscosity under the high hydrogenation degree prerequisite.Its advantage is:
1. the present invention can be used for producing high hydrogenation degree, the hydrogenated nitrile-butadiene rubber of low Mooney viscosity.
2. method of hydrotreating advantage of the present invention is that hydrogenation glue and hydrogenation product HNBR molecular weight distribution have double-peak feature, molecular weight distribution is obviously widened, and effectively reduces Mooney viscosity, has improved the processing characteristics of HNBR, the mechanical property of product, compression set and thermal aging property are good.
3. the present invention can be used for the chemigum hydrogenation of different Mooney viscosities and different acrylonitrile contents.
4. the catalyzer that uses among the present invention can be used the homogeneous complex of rhodium (Rh), ruthenium (Ru), palladium (Pd), preferably rhodium (Rh), palladium (Pd).
Description of drawings
Method of hydrotreating (embodiment 1) the gained hydrogenated nitrile-butadiene rubber (HNBR) that Figure 1 shows that application paracril of the present invention is made GPC figure, Figure 2 shows that using prior art (Comparative Examples 1) gained hydrogenated nitrile-butadiene rubber (HNBR) makes GPC figure.
Embodiment
Raw material:
1. paracril: N-36 CNPC Lanzhou Petrochemical Company is produced
N-33 CNPC Lanzhou Petrochemical Company is produced
N-40 CNPC Lanzhou Petrochemical Company is produced
2. liquid acrylonitrile butadiene rubber: LNBR CNPC Lanzhou Petrochemical Company is produced
3. catalyzer: RhCl (PPh
3)
3Xi'An Catalyst Chemical Co., Ltd.
Palladium Xi'An Catalyst Chemical Co., Ltd.
Analysis test method:
1. degree of hydrogenation: iodine number method
2. Mooney viscosity: carry out GBT1232
3. molecular weight distribution: gel permeation chromatography (GPC)
Embodiment 1
With the NBR of 3Kg (acrylonitrile content 35.1%,
58, hereinafter to be referred as N-36), the nitrile (HTBN) LNBR of 0.5Kg (molecular weight 5500, acrylonitrile content 36%), 6gRhCl (PPh
3)
3Be dissolved in the 35Kg chlorobenzene solvent with the 4.8g triphenylphosphine, and join in the 50L hydrogenation reaction kettle, under 85 ℃, logical hydrogen carries out hydrogenation reaction, and hydrogen pressure is 7.5Mpa, 10 hours reaction times.Hydrogenation the results are shown in Table 1.
Comparative Examples 1
LNBR among the embodiment 1 is removed, and other the results are shown in Table 1 with embodiment 1.
Embodiment 2
Change LNBR among the embodiment 1 into 0.7kg (a), other the results are shown in Table 1 with embodiment 1 0.3kg (b).
Embodiment 3
Change LNBR in the EXAMPLE l into (a) molecular weight 3000, the LNBR of acrylonitrile content 36%; (b) molecular weight 10000, acrylonitrile content 36%; (c) molecular weight 5500, the LNBR of acrylonitrile content 40%, and other the results are shown in Table 1 with embodiment 1
Embodiment 4
With the N-36 of 3Kg, 0.5KgLNBR (molecular weight 5500, acrylonitrile content 36%) and 50g palladium are dissolved in the 35Kg acetone solvent, join in the 50L hydrogenation reaction kettle, temperature is 55 ℃, pressure 5.3Mpa, 3.5 hours reaction times other with embodiment 1, the results are shown in Table 1.
Embodiment 5
Change LNBR among the embodiment 4 into 0.7kg (a), other the results are shown in Table 1 with embodiment 4 0.3kg (b).
Embodiment 6
Change LNBR among the embodiment 4 into (a) molecular weight 3000, the LNBR of acrylonitrile content 36%; (b) molecular weight 10000, acrylonitrile content 36%; (c) molecular weight 5500, the LNBR of acrylonitrile content 40%, and other the results are shown in Table 1 with embodiment 4.
Comparative Examples 2
LNBR among the embodiment 4 is removed, and other the results are shown in Table 1 with embodiment 4.
Table 1 embodiment 1～6 and Comparative Examples 1 and 2 hydrogenation situations are relatively
Embodiment 1 and Comparative Examples 1 gained hydrogenation products HNBR are done gpc analysis, as shown in Figure 1 and Figure 2.The method of hydrotreating gained hydrogenation products HNBR that uses paracril of the present invention can obviously find out molecular weight bimodal distribution characteristics.
Embodiment 7
Change N-36 among the embodiment 1 into acrylonitrile content 33% respectively, Mooney viscosity 45 (hereinafter to be referred as N-33) (a); Acrylonitrile content 40%, Mooney viscosity 78 (hereinafter to be referred as N-40) is (b); Other the results are shown in Table 2 with embodiment 1.
The hydrogenation situation of the NBR of the different acrylonitrile contents of table 2 relatively
The experiment of hydrogenated nitrile-butadiene rubber material property:
Take following prescription (mass parts), comparative evaluation embodiment 1 and Comparative Examples 1 the results are shown in Table 3.
HNBR 100
Zinc oxide 5
Stearic acid 1
Polyester plasticizer 5
Styrenated diphenylamine 1
N660 45
Cyanacrylate 1.5
2,5-dimethyl-2,5-di-t-butyl hexane peroxide 3.5
The tensile property of vulcanized rubber is pressed GB-528-1998 test sulfuration test piece (170 ℃ of cure conditions * 15min), heat aging performance is tested 72hr by the GB-3512-89 standard in 150 ℃ hot air aging case, compression set is tested by GB-7759-87 standard (A method).
Table 3 embodiment 1 and Comparative Examples 1 gained HNBR material properties test
| Embodiment 1 | Comparative Examples 1 | |
| Hardness, Shao A tensile strength, the MPa tensile yield, (150 ℃ * 72hr) hardness of % hot air agings, Shao A tensile strength, the MPa tensile yield, % compression set, % (the A method, 150 ℃ * 72hr) | 68 20.9 300 77 17.6 210 26.7 | 70 22.1 270 76 19.9 200 24.1 |
As can be seen, because the bimodal molecular weight distribution feature that HNBR has, mooney viscosity reduces from embodiments of the invention, and processing characteristics improves.The material property experiment shows that though the low molecular weight fraction that the HNBR of bimodal molecular weight distribution contains is many, compare with the HNBR cross-linked rubber that does not add LNBR, the compression set performance after its tensile strength and the hot air aging does not all have considerable change.
Claims (8)
1. the method for hydrotreating of a paracril, at first paracril is dissolved in the organic solvent, carry out hydrogenation under catalyzer and the stirring condition being added with then, it is characterized in that earlier liquid acrylonitrile butadiene rubber being added in the paracril that needs hydrogenation, add-on counts 5～20% with the dried glue weight of paracril, and the solution with above-mentioned paracril and liquid acrylonitrile butadiene rubber mixture adds in the hydrogenation still, at 40～100 ℃ then, carry out hydrogenation reaction under pressure 4.0～9.0Mpa, 2～12 hours reaction times.
2. method of hydrotreating according to claim 1 is characterized in that the liquid acrylonitrile butadiene rubber add-on counts 8%～15% with the dried glue weight of paracril.
3. method of hydrotreating according to claim 1 is characterized in that hydrogenation catalyst is RhX (PPh
3)
3, wherein X is Cl, Br, I, and solvent is chlorobenzene, bromine benzene,toluene,xylene, and the catalyzer add-on is 0.05～0.2% in the dried glue weight of paracril consumption.
4. method of hydrotreating according to claim 1 is characterized in that hydrogenation catalyst is a palladium, and solvent is an acetone, and the catalyzer add-on is 1.0～2.5% in the dried glue weight of paracril consumption.
5. method of hydrotreating according to claim 1 is characterized in that paracril can be an alternating copolymer, also can be random copolymers, and the mass percentage content of vinyl cyanide is 18～50%.
6. method of hydrotreating according to claim 1, the mass percentage content that it is characterized in that vinyl cyanide in the paracril is 32～40%.
7. method of hydrotreating according to claim 1 is characterized in that the liquid acrylonitrile butadiene rubber molecular weight is 1000～10000, and the mass percentage content of vinyl cyanide is 28～45%.
8. method of hydrotreating according to claim 1 is characterized in that the liquid acrylonitrile butadiene rubber molecular weight is 3000～8000, and the mass percentage content of vinyl cyanide is 33～40%.
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| CNB2005100711038A CN100376611C (en) | 2005-05-20 | 2005-05-20 | Hydrogenation method of nitrile butadiene rubber |
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|---|---|---|---|
| CNB2005100711038A CN100376611C (en) | 2005-05-20 | 2005-05-20 | Hydrogenation method of nitrile butadiene rubber |
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| CN100376611C CN100376611C (en) | 2008-03-26 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512993A (en) * | 2016-08-30 | 2017-03-22 | 北京化工大学 | Preparation and hydrogenation application of palladium-ruthenium dual-metal nano-catalyst |
| CN114149520A (en) * | 2021-12-09 | 2022-03-08 | 北京化工大学 | Method for preparing hydrogenated butyronitrile latex by one-pot method |
| WO2022057848A1 (en) * | 2020-09-16 | 2022-03-24 | 赞南科技(上海)有限公司 | Liquid hydrogenated nitrile-butadiene rubber, preparation method therefor and use thereof |
| CN115322268A (en) * | 2022-09-16 | 2022-11-11 | 安庆华兰科技有限公司 | Butyronitrile soft rubber with high acrylonitrile content and low Mooney force and preparation method thereof |
| CN115725007A (en) * | 2021-08-30 | 2023-03-03 | 中国石油化工股份有限公司 | Preparation method of hydrogenated nitrile rubber |
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| JP6500053B2 (en) * | 2017-03-22 | 2019-04-10 | 三菱電線工業株式会社 | Sealing material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1220300A (en) * | 1982-12-08 | 1987-04-07 | Polysar Limited | Polymer hydrogenation process |
| CS217291A3 (en) * | 1990-07-19 | 1992-02-19 | Dsm Nv | Catalyst systems based on palladium for selective hydrogenation of diene polymers and copolymers |
| CA2304501A1 (en) * | 2000-04-10 | 2001-10-10 | Bayer Inc. | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
-
2005
- 2005-05-20 CN CNB2005100711038A patent/CN100376611C/en not_active Expired - Fee Related
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| CN106512993A (en) * | 2016-08-30 | 2017-03-22 | 北京化工大学 | Preparation and hydrogenation application of palladium-ruthenium dual-metal nano-catalyst |
| CN106512993B (en) * | 2016-08-30 | 2018-11-16 | 北京化工大学 | Palladium-ruthenium bimetal nano catalyst preparation and plus hydrogen application |
| WO2022057848A1 (en) * | 2020-09-16 | 2022-03-24 | 赞南科技(上海)有限公司 | Liquid hydrogenated nitrile-butadiene rubber, preparation method therefor and use thereof |
| CN114262394A (en) * | 2020-09-16 | 2022-04-01 | 浙江赞昇新材料有限公司 | Liquid hydrogenated nitrile rubber and preparation method and application thereof |
| CN114262394B (en) * | 2020-09-16 | 2023-08-18 | 浙江赞昇新材料有限公司 | Liquid hydrogenated nitrile rubber and preparation method and application thereof |
| CN115725007A (en) * | 2021-08-30 | 2023-03-03 | 中国石油化工股份有限公司 | Preparation method of hydrogenated nitrile rubber |
| CN115725007B (en) * | 2021-08-30 | 2023-12-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenated nitrile rubber |
| CN114149520A (en) * | 2021-12-09 | 2022-03-08 | 北京化工大学 | Method for preparing hydrogenated butyronitrile latex by one-pot method |
| CN115322268A (en) * | 2022-09-16 | 2022-11-11 | 安庆华兰科技有限公司 | Butyronitrile soft rubber with high acrylonitrile content and low Mooney force and preparation method thereof |
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| CN100376611C (en) | 2008-03-26 |
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