CN107200794B - A kind of method of hydrotreating of NBR latex - Google Patents
A kind of method of hydrotreating of NBR latex Download PDFInfo
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- CN107200794B CN107200794B CN201610149598.XA CN201610149598A CN107200794B CN 107200794 B CN107200794 B CN 107200794B CN 201610149598 A CN201610149598 A CN 201610149598A CN 107200794 B CN107200794 B CN 107200794B
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- 229920000126 latex Polymers 0.000 title claims abstract description 99
- 239000004816 latex Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 225
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000003446 ligand Substances 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 230000035484 reaction time Effects 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 57
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 46
- 150000002825 nitriles Chemical class 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 29
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229940117389 dichlorobenzene Drugs 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- -1 aliphatic tertiary amine Chemical class 0.000 claims description 5
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000003375 sulfoxide group Chemical group 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 46
- 229920000459 Nitrile rubber Polymers 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 229910019891 RuCl3 Inorganic materials 0.000 description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000007600 charging Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UUDAMDVQRQNNHZ-UHFFFAOYSA-N (S)-AMPA Chemical group CC=1ONC(=O)C=1CC(N)C(O)=O UUDAMDVQRQNNHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
Abstract
The present invention relates to hydrogenation of NBR latex fields, disclose a kind of method of hydrotreating of NBR latex, this method comprises the following steps: (1) mixing NBR latex, hydrogenation catalyst and ligand；(2) mixture that step (1) obtains successively is subjected to the first hydrogenation reaction and the second hydrogenation reaction in presence of hydrogen, the reaction temperature of first hydrogenation reaction is 0-30 DEG C, and the reaction temperature of second hydrogenation reaction is 50-180 DEG C；(3) solvent in the reaction product that removal step (2) obtains.NBR latex is carried out using method of the invention to add hydrogen, it can be improved the hydrogenation reaction activity of hydrogenation catalyst and the degree of hydrogenation of hydrogenation products, hydrogenation products increase compared with for the nitrile rubber added before hydrogen in NBR latex without obvious gel, and it is easy to operate, the reaction time is short, it is easy implement, be hydrogenated into it is low.
Description
Technical Field
The invention relates to the field of nitrile latex hydrogenation, in particular to a hydrogenation method of nitrile latex.
Background
In recent years, with the development of industries such as automobile manufacturing, machining, metallurgical sealing, engineering construction, and petroleum industry, the demand for high-end polymers has been increasing. Hydrogenated nitrile rubber not only has good performances of wear resistance, low temperature resistance, oxidation resistance, ozone resistance and the like, but also has excellent thermal stability, so that the hydrogenated nitrile rubber occupies a good place in high-end polymers, and the dosage of the hydrogenated nitrile rubber is increased year by year.
But for hydrogenated nitrile rubber, the popularization and application of the hydrogenated nitrile rubber in various industries in China are restricted due to the high price of the hydrogenated nitrile rubber. The main reasons for the long-term high price of hydrogenated nitrile rubber are as follows: (1) the hydrogenation catalyst is expensive; (2) the existing synthesis means is mainly solution hydrogenation, and the technological process is complex; (3) catalyst removal is difficult. For general nitrile rubber, the nitrile rubber is mainly prepared by an emulsion polymerization method, and if emulsion hydrogenation can be directly carried out, the production process flow of hydrogenated nitrile rubber is greatly shortened, and the production cost is reduced. However, for the hydrogenation of nitrile rubber emulsion (i.e. nitrile latex), the existing emulsion hydrogenation method has the disadvantages of high production cost, high reaction temperature, high energy consumption, low reaction activity of hydrogenation catalyst, high gel content of product, and high hydrogenation degree of hydrogenation product.
Disclosure of Invention
The invention aims to overcome the defects of high production cost, difficult implementation (high reaction temperature and high energy consumption), low reaction activity of a hydrogenation catalyst, low hydrogenation degree of a hydrogenation product, and high gel content of a product in the hydrogenation process of the butyronitrile latex in the prior art, and provides the hydrogenation method of the butyronitrile latex, which has the advantages of low production cost, easy implementation (low reaction temperature, simple operation and low energy consumption), high hydrogenation activity of the hydrogenation catalyst, obviously improved hydrogenation degree of the hydrogenation product, and no obvious gel growth of the hydrogenation product.
The inventor of the invention unexpectedly discovers in research that in the process of nitrile latex hydrogenation, nitrile latex, a hydrogenation catalyst and a ligand are mixed, then the mixture is subjected to a first hydrogenation reaction at a reaction temperature of 0-30 ℃ and a second hydrogenation reaction at a reaction temperature of 50-180 ℃ in the presence of hydrogen in sequence, and the low-temperature hydrogenation reaction and the high-temperature hydrogenation reaction are combined for use, so that the reaction is easier to implement (the reaction temperature is lower, the operation is simple, and the energy consumption is low), the hydrogenation activity of the hydrogenation catalyst can be obviously improved, the reaction speed is higher, the reaction time is shortened, the hydrogenation degree of a hydrogenation product can be obviously improved, the hydrogenation product has no obvious gel growth, and the hydrogenation cost of the nitrile latex can be effectively reduced.
Accordingly, in order to achieve the above objects, the present invention provides a process for hydrogenating a nitrile latex, comprising the steps of:
(1) mixing the butyronitrile latex, a hydrogenation catalyst and a ligand;
(2) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the mixture obtained in the step (1) in the presence of hydrogen, wherein the reaction temperature of the first hydrogenation reaction is 0-30 ℃, and the reaction temperature of the second hydrogenation reaction is 50-180 ℃;
(3) and (3) removing the solvent in the reaction product obtained in the step (2).
The hydrogenation method of the butyronitrile latex can improve the hydrogenation reaction activity of the hydrogenation catalyst, obtain faster reaction speed, shorten the reaction time, obviously improve the hydrogenation degree of the hydrogenation product, and the hydrogenation product has no obvious gel growth compared with the butyronitrile rubber in the butyronitrile latex before hydrogenation. Meanwhile, the method has the advantages of simple operation, short reaction time, easy implementation (low reaction temperature, simple operation, low energy consumption) and the like, and can effectively reduce the hydrogenation cost of the butyronitrile latex.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a hydrogenation method of butyronitrile latex, which comprises the following steps:
(1) mixing the butyronitrile latex, a hydrogenation catalyst and a ligand;
(2) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the mixture obtained in the step (1) in the presence of hydrogen, wherein the reaction temperature of the first hydrogenation reaction is 0-30 ℃, and the reaction temperature of the second hydrogenation reaction is 50-180 ℃;
(3) and (3) removing the solvent in the reaction product obtained in the step (2).
In step (1) of the process of the present invention, the method for mixing the nitrile latex, the hydrogenation catalyst and the ligand is not particularly limited, and various methods commonly used in the art may be used as long as the above-mentioned materials are mixed, and for example, the nitrile latex may be added to a reaction vessel, followed by charging, discharging, degassing, and then adding the hydrogenation catalyst and the ligand, followed by mixing. It will be understood by those skilled in the art that the degassing by venting occurs prior to the hydrogenation reaction, meaning that the air in the reaction vessel is replaced with an inert gas, such as nitrogen, or hydrogen. The method for charging, discharging and degassing is not particularly limited, and may be various methods commonly used in the art, which are well known to those skilled in the art and will not be described herein.
In order to improve the hydrogenation reaction activity of the hydrogenation catalyst and increase the hydrogenation degree of the hydrogenation product, the solid content of the butyronitrile latex is preferably 0.5-5%. It will be understood by those skilled in the art that the solid content (solids content) of the nitrile latex is the mass of the remaining solid material in percent of the mass of the nitrile latex after drying the nitrile rubber latex.
For the nitrile latex with a solid content of 0.5% to 5%, in general, the commercially available nitrile latex has a high solid content (mostly above 40%), so that the preparation needs to be carried out again to obtain the nitrile latex with a desired solid content, and the specific method for the preparation is not particularly limited, and may be various methods commonly used in the art as long as the obtained nitrile latex has a solid content of 0.5% to 5%. Preferably, the preparation method of the butyronitrile latex with the solid content of 0.5-5% comprises the following steps: adding an organic solvent into the butyronitrile latex with the solid content of not more than 35 percent to prepare the butyronitrile latex with the solid content of 0.5 to 5 percent; more preferably, the solid content of the butyronitrile latex with the solid content of not more than 35 percent is 2 to 35 percent, and more preferably 2 to 15 percent; or,
the preparation method of the butyronitrile latex with the solid content of 0.5 to 5 percent comprises the following steps: adding water into the butyronitrile latex with the solid content of more than 35% to prepare butyronitrile latex with the solid content of not more than 35%, and then adding an organic solvent into the butyronitrile latex with the solid content of not more than 35% to prepare the butyronitrile latex with the solid content of 0.5% -5%; more preferably, the butyronitrile latex with the solid content of not more than 35 percent has the solid content of 2 to 35 percent, and more preferably 2 to 15 percent. It will be understood by those skilled in the art that the nitrile latex with a solid content of not more than 35% can be prepared, then the nitrile latex with a solid content of 0.5% -5% can be prepared, and then the hydrogenation catalyst and the ligand can be added and mixed.
The organic solvent is not particularly limited, and may be any of various organic solvents which are miscible with the nitrile latex in the art and dissolve the hydrogenation catalyst and the ligand (and the auxiliary), and preferably one or more of aromatic hydrocarbon, derivatives of aromatic hydrocarbon substituted by alkyl or halogen, halogenated alkane, ketone and amide; further preferably, the organic solvent is one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, acetone, butanone and N, N-dimethylformamide; still more preferably, the organic solvent is a mixed solvent of one of benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene and one of acetone and butanone, and the volume ratio of the former (i.e., any one of benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene) to the latter (acetone or butanone) is 3:1 to 1: 3.
The nitrile latex is not particularly limited, and may be any of various kinds of binary nitrile latexes known in the art, and preferably, the nitrile latex is a binary nitrile latex of one of butadiene and isoprene and one of acrylonitrile and methacrylonitrile, and more preferably, a binary nitrile latex of butadiene and acrylonitrile. Specifically, the method for synthesizing the nitrile rubber latex is not particularly limited, and may be any of various methods commonly used in the art, as long as one of butadiene and isoprene and one of acrylonitrile and methacrylonitrile are formed by polymerization, for example, a binary nitrile rubber latex directly prepared by emulsion polymerization, or a binary nitrile rubber latex formed by emulsifying nitrile rubber, which are well known to those skilled in the art and will not be described herein again. The aforementioned binary nitrile latices are also commercially available. The content of butadiene or isoprene in the nitrile latex may be 50 to 80 wt% and the content of acrylonitrile or methacrylonitrile may be 20 to 50 wt%, based on the weight of the solid content of the nitrile latex.
In step (1) of the process of the present invention, the hydrogenation catalyst to be added is not particularly limited, and may be any of various catalysts commonly used in the art for hydrogenation of nitrile rubber, and preferably, the hydrogenation catalyst has the following general formula: (R)mA)zRhXnWherein each R is independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C15 aryl or C7-C15 aralkyl; a is selected from the group consisting of phosphorus, arsenic, sulfur or a sulfoxide group S ═ O; x is selected from hydrogen or an anion; z is 2, 3 or 4; m is 2 or 3; n is 1, 2 or 3. In order to further increase the hydrogenation reaction activity of the hydrogenation catalyst and increase the hydrogenation degree of the hydrogenation product, it is further preferred that the hydrogenation catalyst is (PPh)3)3RhCl. The above hydrogenation catalyst (R) of the present inventionmA)zRhXnMay be obtained commercially.
Preferably, the hydrogenation catalyst has the general formula: m1 aM2 bXmLnWherein M is1Is rhodium, M2Is ruthenium, X is one or more of chlorine, bromine and hydrogen, L is one or more of organic monophosphine, organic diphosphine, organic cerium and organic compound containing nitrogen, sulfur or oxygen, a is more than or equal to 1 and less than or equal to 6, b is more than or equal to 1 and less than or equal to 3, m is more than or equal to 3 and less than or equal to 7, and n is more than or equal to 6 and less than or equal to 21. In order to further improve the hydrogenation reaction activity of the hydrogenation catalyst and increaseDegree of hydrogenation of the large hydrogenation product, more preferably, in the hydrogenation catalyst, M1Is rhodium, M2Ruthenium, X is chlorine, L is an organic monophosphine; still further preferably, a: b: m: n is (1-3): 1: (3-5): (6-12), most preferably, L is triphenylphosphine, a: b: m: n is 3: 1: 5: 12.
hydrogenation catalyst M1 aM2 bXmLnCan be prepared by a process comprising the steps of:
(1) adding the L and the solvent into a reaction bottle, and refluxing and dissolving under stirring;
(2) will M1And M2The metal halide is dissolved in a hot solvent after being mixed, and is added into a reaction bottle for reaction at the reflux temperature;
(3) and removing the solvent to obtain the crystalline or powdery hydrogenation catalyst.
In order to increase the hydrogenation reaction activity of the hydrogenation catalyst and increase the hydrogenation degree of the hydrogenation product, the amount of the hydrogenation catalyst added is preferably 0.01 to 5%, more preferably 0.05 to 1%, of the mass of the solid content in the nitrile latex.
In step (1) of the method of the present invention, in order to increase the hydrogenation degree of the hydrogenation product, it is preferable that the ligand is one or more of organic monophosphine, organic diphosphine, organic cerium and organic compound containing nitrogen, sulfur or oxygen; further preferably, the ligand is an organic monophosphine and/or an organic diphosphine; more preferably, the ligand is at least one of triphenylphosphine, 1, 3-bis (diphenylphosphino) propane and 1, 4-bis (diphenylphosphino) butane; still further preferably, the ligand is triphenylphosphine.
The organic monophosphine, organic diphosphine, organic cerium and nitrogen, sulfur or oxygen containing organic compound in the hydrogenation catalyst and ligand are not particularly limited, and can be various organic monophosphine, organic diphosphine, organic cerium and nitrogen, sulfur or oxygen containing organic compounds commonly used in the art, which are well known to those skilled in the art and will not be described in detail herein.
In order to increase the hydrogenation degree of the hydrogenation product, the amount of the ligand added is preferably 1 to 20 times, more preferably 4 to 15 times, the mass of the hydrogenation catalyst.
In step (1) of the method of the present invention, in order to increase the hydrogenation degree and reduce the gel content, it is preferable to add an auxiliary agent during mixing, that is, in step (1), the nitrile latex, the hydrogenation catalyst, the ligand and the auxiliary agent are mixed. The auxiliary is not particularly limited, and may be various auxiliary commonly used in the art, and preferably, the auxiliary is an aliphatic tertiary amine and/or an aromatic tertiary amine; more preferably, the auxiliary agent is triethylamine (i.e. N, N-diethylethylamine) and/or diisopropylethylamine (i.e. N, N-diisopropylethylamine).
In order to further increase the hydrogenation degree and reduce the gel content, the addition amount of the auxiliary is preferably 0.5 to 10 times the mass of the hydrogenation catalyst, and more preferably 1 to 5 times the mass of the hydrogenation catalyst.
In step (2) of the process of the present invention, in order to further increase the hydrogenation activity of the hydrogenation catalyst and increase the hydrogenation degree of the hydrogenation product, preferably, the conditions of the first hydrogenation reaction include: the reaction temperature is 0-30 ℃, and the preferable temperature is 10-25 ℃; the hydrogen pressure is 0.05-15MPa, preferably 1-5 MPa; the reaction time is 1 to 120 minutes, and more preferably 20 to 40 minutes.
In step (2) of the process of the present invention, in order to further increase the hydrogenation degree of the hydrogenation product, it is preferable that the conditions of the second hydrogenation reaction include: the reaction temperature is 50-180 ℃, and the preferable temperature is 80-150 ℃; the hydrogen pressure is 0.1-15MPa, preferably 4-12 MPa; the reaction time is 1 to 20 hours, and more preferably 4 to 16 hours.
In step (3) of the process of the present invention, the method for removing the solvent from the reaction product obtained in step (2) is not particularly limited, and may be any of various methods commonly used by those skilled in the art, for example, a method comprising removing most of the solvent from the reaction product obtained in step (2) by ethanol coagulation, steam distillation, or the like to precipitate a hydrogenation product, and then drying the hydrogenation product to remove a small portion of the solvent contained in the hydrogenation product. The method for removing the solvent contained in the hydrogenation product is not particularly limited, and may be various methods commonly used by those skilled in the art, and preferably, the method for removing the solvent is vacuum drying under conditions including: the temperature is 50-100 ℃ and the time is 1-10 hours.
Examples
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In the following examples and comparative examples, the method of measuring the degree of hydrogenation was carried out according to the literature (nuclear magnetic analysis method for calculating the microstructure and the degree of hydrogenation of hydrogenated nitrile rubber. petrochemical, 2014,43,403).
The method for measuring the gel content comprises the following steps: weighing w 1g of dry glue, adding chlorobenzene to prepare a solution of 1g/100mL, pouring the solution into a filter screen with constant weight (w2 g) for filtration after dissolving for 24 hours, and drying the filter screen containing insoluble substances to constant weight, wherein the weight is recorded as w3 g, and the gel content is as follows: (w3-w2)/w1 106ppm。
Hydrogenation catalyst (PPh)3)3RhCl was purchased from Acros and designated C1.
RhCl3.H2O、RuCl3.H2O is available from kunming platinum metals materials ltd.
The butyronitrile latex with the solid content of 43.5 percent is purchased from Taiwan south emperor chemical industry Co., Ltd, and is named NANTEX-640, the weight of solid content is taken as a reference, the content of butadiene is 63 percent, the content of acrylonitrile is 37 percent, the viscosity is 50 centipoises, the pH is 8.2, and the latex is marked as S1; the gel content of the nitrile rubber after removal of the solvent was found to be 397 ppm.
Preparation example 1
Book systemPreparation example is illustrative of hydrogenation catalyst M1 aM2 bXmLn(C2) In which M is1Is rhodium, M2Is ruthenium, X is chlorine, L is triphenylphosphine, a: b: m: n is 2: 1: 4: 9.
4.5 g of PPh3Dissolving in 70 ℃ hot ethanol solution under the protection of argon, and adding the dissolved solution into a reaction bottle; 0.5 g of RhCl was weighed3.H2O and 0.23 gram RuCl3.H2Dissolving O in ethanol solution under the protection of argon, heating and refluxing at 78 ℃, and dissolving RhCl in the ethanol solution3.H2O and RuCl3.H2And dropwise adding the ethanol solution of O into a reaction bottle for reacting for 2.5 hours, cooling to 25 ℃, performing suction filtration, and washing with diethyl ether to obtain powdered Rh: ru 2:1 hydrogenation catalyst, noted C2.
Preparation example 2
This preparation example is illustrative of hydrogenation catalyst M1 aM2 bXmLn(C3) In which M is1Is rhodium, M2Is ruthenium, X is chlorine, L is triphenylphosphine, a: b: m: n is 3: 1: 5: 12.
mixing 6 g of PPh3Dissolving in 70 ℃ hot ethanol solution under the protection of argon, and adding the dissolved solution into a reaction bottle; 0.75 g of RhCl was weighed out3.H2O and 0.23 gram RuCl3.H2Dissolving O in ethanol solution under the protection of argon, heating and refluxing at 78 ℃, and dissolving RhCl in the ethanol solution3.H2O and RuCl3.H2And dropwise adding the ethanol solution of O into a reaction bottle for reacting for 2.5 hours, cooling to 25 ℃, performing suction filtration, and washing with diethyl ether to obtain powdered Rh: ru — 3:1 hydrogenation catalyst, noted C3.
Preparation example 3
This preparation example is illustrative of hydrogenation catalyst M1 aM2 bXmLn(C4) In which M is1Is rhodium, M2In the case of ruthenium, the compound is a ruthenium compound,x is chlorine, L is triphenylphosphine, a: b: m: n is 1: 1: 3: 6.
3 g of PPh3Dissolving in 70 ℃ hot ethanol solution under the protection of argon, and adding the dissolved solution into a reaction bottle; 0.25 g of RhCl was weighed out3.H2O and 0.23 gram RuCl3.H2Dissolving O in ethanol solution under the protection of argon, heating and refluxing at 78 ℃, and dissolving RhCl in the ethanol solution3.H2O and RuCl3.H2And dropwise adding the ethanol solution of O into a reaction bottle for reacting for 2.5 hours, cooling to 25 ℃, performing suction filtration, and washing with diethyl ether to obtain powdered Rh: ru 1:1 hydrogenation catalyst, noted C4.
Examples 1 to 13
Examples 1 to 13 of the present invention are intended to illustrate the hydrogenation process of the nitrile latex of the present invention.
(1) Adding deionized water into the binary butyronitrile latex S1 to prepare butyronitrile latex with p% of solid content, and discharging and degassing;
(2) adding an organic solvent into butyronitrile latex with p% of solid content to prepare butyronitrile latex with q% of solid content, and then adding the prepared butyronitrile latex with q% of solid content into a reaction kettle;
(3) adding a hydrogenation catalyst, a ligand and an auxiliary agent into a reaction kettle, and mixing;
(4) filling hydrogen, stirring and reacting, wherein the reaction conditions comprise: the reaction temperature is b ℃, the hydrogen pressure is aMPa, and the reaction time is c minutes;
(5) heating to e ℃, keeping the hydrogen pressure at d MPa, and reacting for f hours;
(6) the hydrogenation product was precipitated by ethanol condensation and dried under vacuum at 60 ℃ for 8 hours.
In examples 1 to 13, the results of measuring the solid content p%, the solid content q%, the hydrogenation catalyst, the ligand, the auxiliary, the catalyst/solid content in the nitrile latex (i.e., the mass ratio of the hydrogenation catalyst to the solid content in the nitrile latex), the ligand/catalyst (i.e., the mass ratio of the ligand to the hydrogenation catalyst), the auxiliary/catalyst (i.e., the mass ratio of the auxiliary to the hydrogenation catalyst), a to f, and the hydrogenation degree and gel content of the obtained hydrogenation product are shown in table 1.
Comparative examples 1 to 6
In comparative examples 1 to 4, the binary acrylonitrile-butadiene latex, the solid content p%, the solid content q%, the hydrogenation catalyst, the ligand, the auxiliary, the catalyst/the solid content in the acrylonitrile-butadiene latex (i.e., the mass ratio of the hydrogenation catalyst to the solid content in the acrylonitrile-butadiene latex), the ligand/the catalyst (i.e., the mass ratio of the ligand to the hydrogenation catalyst), and the auxiliary/the catalyst (i.e., the mass ratio of the auxiliary to the hydrogenation catalyst) are respectively the same as in examples 1 to 4, except that the processes of comparative examples 1 to 4 do not have a low-temperature hydrogenation reaction. Comparative example 5 is compared with comparative example 1, except that the reaction time f of comparative example 1 is extended. Comparative example 6 compares with example 1 except that the low temperature hydrogenation reaction is changed to a high temperature hydrogenation reaction. In comparative examples 1 to 6, the solid content p%, the solid content q%, the hydrogenation catalyst, the ligand, the auxiliary, the catalyst/solid content in the nitrile latex (i.e., the mass ratio of the hydrogenation catalyst to the solid content in the nitrile latex), the ligand/catalyst (i.e., the mass ratio of the ligand to the hydrogenation catalyst), the auxiliary/catalyst (i.e., the mass ratio of the auxiliary to the hydrogenation catalyst), a to f, and the results of measurement of the hydrogenation degree and gel content of the obtained hydrogenation product are shown in table 2.
Comparative example 7
The method of example 1 is followed, except that (1) the hydrogenation catalyst, ligand and auxiliary agent are added into the reaction kettle, mixed, charged and degassed; (2) filling hydrogen, stirring and reacting, wherein the reaction conditions comprise: the reaction temperature is 20 ℃, the hydrogen pressure is 3MPa, and the reaction time is 30 minutes; (3) adding deionized water into S1 to prepare butyronitrile latex with solid content of 10.9%, then adding an organic solvent into the butyronitrile latex with solid content of 10.9% to prepare butyronitrile latex with solid content of 1.5%, adding the prepared butyronitrile latex with solid content of 1.5% into a reaction kettle, and mixing; (4) heating to 90 ℃, keeping the hydrogen pressure at 6MPa, and reacting for 8 hours; (5) the hydrogenation product was precipitated by ethanol condensation and dried under vacuum at 60 ℃ for 8 hours. Wherein the conditions of the organic solvent, the hydrogenation catalyst, the ligand, the auxiliary agent, the solid content in the catalyst/butyronitrile latex, the ligand/catalyst and the auxiliary agent/catalyst are the same as those in example 1.
The hydrogenation degree of the hydrogenation product was found to be 87.2% and the gel content was found to be 640 ppm.
Compared with the examples 5 to 6, when the temperature of the low-temperature hydrogenation reaction in the step (3) is 10 to 25 ℃, the hydrogenation degree of the hydrogenation product can be further improved, and the gel content of the hydrogenation product can be further reduced.
Comparing example 1 with examples 7-8, the hydrogenation degree of the hydrogenation product can be further improved when the temperature of the high-temperature hydrogenation reaction in step (4) is 80-150 ℃.
Comparing example 1 with examples 9-10, when the organic solvent is a mixed solvent of one of benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene and one of acetone and butanone, the hydrogenation degree of the hydrogenation product can be further improved, and the gel content of the hydrogenation product can be further reduced.
Hydrogenation catalyst M comparing example 4 with examples 11-121aM2bXmLn(M1 is rhodium, M2 is ruthenium, X is chlorine, L is triphenylphosphine) in a: b: m: n is 3: 1: 5: 12, the degree of hydrogenation of the hydrogenated product can be further increased.
When example 1 is compared to example 13, PPh is chosen as ligand3When the auxiliary agent is triethylamine, the hydrogenation degree of the hydrogenation product can be further increased, and the gel content of the hydrogenation product can be further reduced.
Comparing examples 1-4 with comparative examples 1-4, respectively, it can be seen that the addition of the low temperature hydrogenation step at a reaction temperature of 0-30 ℃ prior to the high temperature hydrogenation step can effectively increase the reaction rate and increase the hydrogenation degree of the hydrogenated product.
Comparing example 1 with comparative example 5, if there is no step of low temperature hydrogenation reaction with a reaction temperature of 0-30 ℃ before the high temperature hydrogenation reaction, similar hydrogenation degree can not be obtained under the reaction condition of prolonging the reaction time f by 2 hours, which indicates that the reaction rate of hydrogenation reaction can be obviously improved by successively carrying out low temperature hydrogenation reaction and high temperature hydrogenation reaction, the hydrogenation degree of hydrogenation product can be effectively improved, and the gel content of hydrogenation product can be further reduced.
Compared with the comparative example 6, the low-temperature hydrogenation reaction is changed into the high-temperature hydrogenation reaction, the hydrogenation degree of the product is not improved, and the reaction rate of the hydrogenation reaction can be obviously improved by successively carrying out the low-temperature hydrogenation reaction and the high-temperature hydrogenation reaction, so that the hydrogenation degree of the hydrogenation product is effectively improved, and the gel content of the hydrogenation product can be further reduced.
Compared with the comparative example 7, the change of the feeding sequence of the butyronitrile latex and the hydrogenation catalyst in the example 1 can cause the reduction of the hydrogenation effect of the combination of the low-temperature hydrogenation reaction and the high-temperature hydrogenation reaction, eliminate the possibility that the hydrogenation catalyst reacts with hydrogen in the low-temperature hydrogenation reaction to change the catalyst structure so as to change the catalytic activity of the catalyst, and simultaneously increase the gel content in the hydrogenation product.
The hydrogenation method of the butyronitrile latex can improve the hydrogenation reaction activity of the hydrogenation catalyst, obtain faster reaction speed, shorten the reaction time, obviously improve the hydrogenation degree of the hydrogenation product, and the hydrogenation product has no obvious gel growth compared with the butyronitrile rubber in the butyronitrile latex before hydrogenation. Meanwhile, the method has the advantages of simple operation, short reaction time, easy implementation (low reaction temperature, simple operation, low energy consumption) and the like, and can effectively reduce the hydrogenation cost of the butyronitrile latex.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (31)
1. A hydrogenation method of butyronitrile latex is characterized by comprising the following steps:
(1) mixing the butyronitrile latex, a hydrogenation catalyst and a ligand;
(2) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the mixture obtained in the step (1) in the presence of hydrogen, wherein the reaction temperature of the first hydrogenation reaction is 0-30 ℃, and the reaction temperature of the second hydrogenation reaction is 50-150 ℃;
(3) removing the solvent in the reaction product obtained in the step (2);
the hydrogenation catalyst has the following general formula: m1 aM2 bXmLnWherein M is1Is rhodium, M2Is ruthenium, X is one or more of chlorine, bromine and hydrogen, L is one or more of organic monophosphine, organic diphosphine, organic cerium and organic compound containing nitrogen, sulfur or oxygen, a is more than or equal to 1 and less than or equal to 6, b is more than or equal to 1 and less than or equal to 3, m is more than or equal to 3 and less than or equal to 7, and n is more than or equal to 6 and less than or equal to 21; or
The hydrogenation catalyst has the following general formula: (R)mA)zRhXnWherein each R is independently selected from C1-C8 alkyl, C4-C8 cycloalkyl, C6-C15 aryl or C7-C15 aralkyl; a is selected from the group consisting of phosphorus, arsenic, sulfur or sulfoxide groups S = O; x is selected from hydrogen or an anion; z is 2, 3 or 4; m is 2 or 3; n is 1, 2 or 3.
2. The process of claim 1, wherein the conditions of the first hydrogenation reaction comprise: the reaction temperature is 0-30 ℃; the hydrogen pressure is 0.05-15 Mpa; the reaction time is 1-120 minutes.
3. The process of claim 2, wherein the conditions of the first hydrogenation reaction comprise: the reaction temperature is 10-25 ℃; the hydrogen pressure is 1-5 Mpa; the reaction time is 20-40 minutes.
4. The process of claim 1, wherein the conditions of the second hydrogenation reaction comprise: the reaction temperature is 50-150 ℃; the hydrogen pressure is 0.1-15 Mpa; the reaction time is 1-20 hours.
5. The process of claim 4, wherein the conditions of the second hydrogenation reaction comprise: the reaction temperature is 80-150 ℃; the hydrogen pressure is 4-12 Mpa; the reaction time is 4-16 hours.
6. A process according to any one of claims 1 to 5, wherein in step (1), the nitrile latex has a solids content of from 0.5% to 5%.
7. The method of claim 6, wherein the nitrile latex is formulated by a method comprising: adding an organic solvent into the butyronitrile latex with the solid content of not more than 35 percent to prepare the butyronitrile latex with the solid content of 0.5 to 5 percent; or,
the preparation method of the butyronitrile latex comprises the following steps: adding water into the butyronitrile latex with the solid content of more than 35% to prepare the butyronitrile latex with the solid content of not more than 35%, and then adding an organic solvent into the butyronitrile latex with the solid content of not more than 35% to prepare the butyronitrile latex with the solid content of 0.5% -5%.
8. A process as claimed in claim 7, wherein the nitrile latex having a solids content of not more than 35% has a solids content of 2-15%.
9. The process of claim 7 or 8, wherein the organic solvent is one or more of an aromatic hydrocarbon, an alkyl or halogen substituted derivative of an aromatic hydrocarbon, a halogenated alkane, a ketone, and an amide.
10. The method of claim 9, wherein the organic solvent is one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, acetone, butanone, and N, N-dimethylformamide.
11. The method according to claim 10, wherein the organic solvent is a mixed solvent of one of benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene and one of acetone and butanone in a volume ratio of 3:1-1: 3.
12. A process according to any one of claims 1 to 5, wherein the nitrile latex is a binary nitrile latex of butadiene with one of acrylonitrile and methacrylonitrile.
13. A process according to claim 12, wherein the nitrile latex is a binary nitrile latex of butadiene and acrylonitrile.
14. The process of any of claims 1-5, wherein the hydrogenation catalyst is (PPh)3)3RhCl。
15. The method of any one of claims 1-5, wherein M is1Is rhodium, M2Is ruthenium, X is chlorine and L is an organic monophosphine.
16. The method of claim 15, wherein a: b: m: n is 1 to 3: 1: 3-5: 6-12.
17. The method of claim 16, wherein L is triphenylphosphine, a: b: m: n is 3: 1: 5: 12.
18. the process according to any one of claims 1 to 5, wherein the hydrogenation catalyst is added in an amount of 0.01 to 5% by mass of the solids content of the nitrile latex.
19. The process according to claim 18, wherein the amount of the hydrogenation catalyst added is 0.05-1% by mass of the solids in the nitrile latex.
20. The method of any one of claims 1-5, wherein the ligand is one or more of an organic monophosphine, an organic bisphosphine, an organic cerium, and an organic compound containing nitrogen, sulfur, or oxygen.
21. The method of claim 20, wherein the ligand is an organomonophosphine and/or an organobisphosphine.
22. The method of claim 21, wherein the ligand is at least one of triphenylphosphine, 1, 3-bis (diphenylphosphino) propane, and 1, 4-bis (diphenylphosphino) butane.
23. The method of claim 22, wherein the ligand is triphenylphosphine.
24. The process according to any one of claims 1 to 5, wherein the ligand is added in an amount of 1 to 20 times the mass of the hydrogenation catalyst.
25. The process of claim 24 wherein the ligand is added in an amount of 4 to 15 times the mass of the hydrogenation catalyst.
26. The method according to any one of claims 1 to 5, wherein in step (1), an auxiliary agent is further added during mixing, and the auxiliary agent is an aliphatic tertiary amine and/or an aromatic tertiary amine.
27. The process according to claim 26, wherein the auxiliary agent is triethylamine and/or diisopropylethylamine.
28. The process of claim 26, wherein the amount of promoter added is 0.5 to 10 times the mass of the hydrogenation catalyst.
29. The process of claim 28 wherein the promoter is added in an amount of 1 to 5 times the mass of the hydrogenation catalyst.
30. The process of claim 27 wherein the promoter is added in an amount of 0.5 to 10 times the mass of the hydrogenation catalyst.
31. The process of claim 30 wherein the promoter is added in an amount of 1 to 5 times the mass of the hydrogenation catalyst.
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| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | Unsaturated copolymer hydrogenating method and bimetal containing catalyst system therefor |
| CN104271607A (en) * | 2012-04-28 | 2015-01-07 | 朗盛德国有限责任公司 | Hydrogenation of nitrile rubber |
| CN105175581A (en) * | 2015-09-25 | 2015-12-23 | 北京化工大学 | Preparation method for hydrophilic aminated hydrogenated butadiene-acrylonitrile rubber and prepared product |
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|---|---|---|---|---|
| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | Unsaturated copolymer hydrogenating method and bimetal containing catalyst system therefor |
| CN104271607A (en) * | 2012-04-28 | 2015-01-07 | 朗盛德国有限责任公司 | Hydrogenation of nitrile rubber |
| CN105175581A (en) * | 2015-09-25 | 2015-12-23 | 北京化工大学 | Preparation method for hydrophilic aminated hydrogenated butadiene-acrylonitrile rubber and prepared product |
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