CN1472232A - Method for preparing hydrogenated butyronitrile copolymer by butadiene-acrylonitrile copolymer latex hydrogenation - Google Patents
Method for preparing hydrogenated butyronitrile copolymer by butadiene-acrylonitrile copolymer latex hydrogenation Download PDFInfo
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- CN1472232A CN1472232A CNA021272883A CN02127288A CN1472232A CN 1472232 A CN1472232 A CN 1472232A CN A021272883 A CNA021272883 A CN A021272883A CN 02127288 A CN02127288 A CN 02127288A CN 1472232 A CN1472232 A CN 1472232A
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- hydrogenation
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- butadiene
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- hydrogenation method
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 101
- 239000004816 latex Substances 0.000 title claims abstract description 48
- 229920000126 latex Polymers 0.000 title claims abstract description 48
- 229920001577 copolymer Polymers 0.000 title claims abstract description 42
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 9
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 49
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003112 inhibitor Substances 0.000 claims abstract description 31
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract 7
- 239000007800 oxidant agent Substances 0.000 claims abstract 7
- 150000002989 phenols Chemical class 0.000 claims abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 20
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- YFHNDHXQDJQEEE-UHFFFAOYSA-N acetic acid;hydrazine Chemical compound NN.CC(O)=O YFHNDHXQDJQEEE-UHFFFAOYSA-N 0.000 claims description 2
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims 1
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims 1
- 239000012493 hydrazine sulfate Substances 0.000 claims 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 60
- 150000008363 butyronitriles Chemical class 0.000 description 49
- 239000000839 emulsion Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KURZCZMGELAPSV-UHFFFAOYSA-N [Br].[I] Chemical compound [Br].[I] KURZCZMGELAPSV-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- -1 aromatic amine compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明提供一种在具有水溶性的、无取代基的酚、醌、芳胺类凝胶抑制剂存在下，丁二烯－丙烯腈共聚物胶乳与(1)为肼或产生肼的化合物的还原剂，(2)氧化剂，和(3)催化剂进行加氢反应，制备无凝胶的氢化丁腈共聚物的方法。The present invention provides a kind of butadiene-acrylonitrile copolymer latex and (1) hydrazine or a compound that produces hydrazine in the presence of water-soluble, unsubstituted phenol, quinone, and aromatic amine gel inhibitors. A reducing agent, (2) an oxidizing agent, and (3) a catalyst carry out a hydrogenation reaction to prepare a gel-free hydrogenated nitrile copolymer.
Description
The present invention relates to have water miscible, the phenol of unsubstituted, quinone, arylamine gellike inhibitor exist down, perbutan latex is hydrazine or the reductive agent that produces the compound of hydrazine with (1), (2) oxygenant, (3) catalyst reaction, the method for the hydrogenated butyronitrile multipolymer of preparation gel-free.
Perbutan is widely used as a kind of oil resistant polymkeric substance, but because of the existence of unsaturated carbon-carbon double bond in the molecule, causes that it is heat-resisting, erosion resistance, ageing-resistant performance be relatively poor.Hydrogenated nitrile-butadiene rubber is the hydrogenation products of perbutan, it is when having kept the original oil-proofness of perbutan, heat-resisting, ageing-resistant, corrosion-resistant, high tensile and the little excellent over-all properties of long-term compression set have been obtained again, in fields such as automotive industry and oil exploration industry, be widely used, can be used as the oil resistant pipe of gasket, sealing-ring, connection engine of synchronous band, the engine of high-grade car and oil well well lid etc.
Industrial hydrogenated butyronitrile multipolymer is made through solution hydrogenation by perbutan, promptly the perbutan latex that is obtained by emulsion copolymerization is through breakdown of emulsion cohesion, dried product, with suitable organic solvent dissolution, organic coordination compound with precious metals such as rhodium, ruthenium, palladiums is a catalyzer, feeds hydrogen and carry out hydrogenation reaction in autoclave.This method is catalyzer cost height not only, and technical process is long, also has following deficiency: use high-tension apparatus and hydrogen, and the facility investment height, and have some unsafe factors; The concentration that feeds intake of perbutan glue is low, causes plant factor not high; Adopt noble metal catalyst, based on environmental protection, cost and product performance aspects factor, noble metal catalyst need remove and reclaim in follow-up process; Organic solvent must reclaim use, makes the flow process complexity, increases facility investment; Organic solvent is all unfavorable to people's health and environmental protection.
Compound with hydrazine or generation hydrazine is the technology of hydrogenation parent to the direct hydrogenation of perbutan emulsion, compare with traditional solution hydrogenation technology, overcome above-mentioned shortcoming, without high-tension apparatus and hydrogen, without noble metal catalyst and a large amount of organic solvents, flow process is simple, facility investment and production cost reduce, and is beneficial to environmental protection, and can obtain the hydrogenated butyronitrile copolymer emulsion, widened the range of application of hydrogenated butyronitrile multipolymer.
U.S. Pat 4,452,950 to disclose the employing hydrazine hydrate first be reductive agent, and oxygen or air or hydrogen peroxide are oxygenant, copper sulfate be the redox reaction catalyzer to perbutan latex hydrogenation, make degree of hydrogenation and be 80% hydrogenated butyronitrile copolymer emulsion.The problem of this method is that hydrogenant perbutan latex is seriously crosslinked in breakdown of emulsion, the generation of cohesion back, and product is insoluble to chloroform, makes crosslinked hydrogenated butyronitrile copolymer emulsion.
USP 5,039,737 disclose and carry out aftertreatment with ozone and eliminate the crosslinked method of hydrogenated products, promptly make two key chain ruptures of multipolymer with ozone, molecular weight and molecular weight, the wet product (product of undried) after breakdown of emulsion, the cohesion dissolves in chloroform again, but in drying process, the terminal aldehyde group that chain rupture place forms, end carboxyl take place crosslinked once more, make the product can't processing and utilization.
Therefore, USP 5,442,009 USP 5,039 that continues, and 737 have proposed to add azanol and the hydrogenated butyronitrile copolymer emulsion effect of having used the ozone aftertreatment, transfer the end group of hydrogenated butyronitrile copolymer molecule to oximido, avoid producing in the drying process crosslinked.
International monopoly WO 91/06579 discloses is not having metal ion (as bivalent cupric ion Cu
2+) under the situation of catalyzer, be redox system with hydrazine hydrate and hydrogen peroxide, adopt hydrazine hydrate and the mol ratio of C=C to go to overcome crosslinking reaction up to 8-15 method doubly, prepare the hydrogenated butyronitrile multipolymer of gel-free.But excessive greatly hydrazine hydrate need add acetone or 2-butanone again in last handling process reacts and removes, and this all is disadvantageous to economy and environmental protection aspect.
It is redox system that international monopoly WO 00/09576 discloses with hydrazine hydrate, hydrogen peroxide, substituting copper sulfate with boric acid is the catalyzer of redox system, perbutan latex is carried out hydrogenation, the characteristics of this method are to reduce the consumption of hydrazine hydrate greatly, the mol ratio of hydrazine hydrate and C=C can be reduced to 2: 1 even near 1: 1, the hydrogenated butyronitrile copolymer emulsion blots surface-moisture with filter paper after the breakdown of emulsion precipitation is separated out, can be dissolved in the chloroform at once.The degree of hydrogenation that records the wet product of undried with nuclear magnetic resonance method reaches 96%.
International monopoly WO 00/09568 points out that hydrogenated butyronitrile copolymer emulsion one drying that WO 00/09576 patent system gets just is insoluble in the chloroform, records that gel content reaches 60% in the hydrogenated butyronitrile multipolymer, and product lacks workability.And to disclose with hydrazine hydrate, hydrogen peroxide be redox system, and boric acid is catalyzer, and perbutan latex is carried out hydrogenation, reduces hydrogenated products produces gel in drying process method.This method is before hydrogenation reaction, in the reaction process or compounds such as azanol, oxime are added in the reaction back, the O-Phenylene Diamine acetone soln of adding 5% in the wet product of while after the cohesion of hydrogenated butyronitrile copolymer emulsion breakdown of emulsion, under 125 ℃, mediate, the gel content of hydrogenated butyronitrile multipolymer in drying process significantly reduced, but gel content still reach about 5-15%.
It is redox system with hydrazine hydrate, hydrogen peroxide that international monopoly WO 01/04162 A1 discloses a kind of, boric acid is catalyzer, perbutan latex is carried out hydrogenation, and the method that overcomes hydrogenated butyronitrile multipolymer generation gel is to add oxidation inhibitor in system.This method select for use fragrant and mellow, the quinoline that contains the above replacement of six carbon atom, imidazoles, and the derivative of arylamine be oxidation inhibitor, before hydrogenation reaction, be added in the latex, it is crosslinked to suppress product.Described oxidation inhibitor is water insoluble, will add after its emulsification; The above aryl amine derivatives of described six carbon is N-sec.-propyl-N '-phenyl-Ursol D, and N-1,4-3,5-dimethylphenyl-N-phenyl-Ursol D.This method is with 1% N-1 before hydrogenation, the emulsion of 4-3,5-dimethylphenyl-N-phenyl-Ursol D is added in the perbutan hydro genation system of WO00/09568 patent disclosure, the result records in the hydrogenated products gel content more than 80%, and after the cohesion of this hydrogenation latex breakdown of emulsion, add 5% O-Phenylene Diamine acetone soln again, mediate down at 150 ℃, this hydrogenated butyronitrile multipolymer can be dissolved in the chloroform.
The inventor finds under study for action, in the prior art with hydrazine hydrate/hydrogen peroxide/boric acid system to perbutan latex hydrogenation, wet product after its breakdown of emulsion cohesion dissolves in the chloroform, in case drying product then not exclusively be dissolved in chloroform (the visible insolubles is arranged in the chloroformic solution), and in storage process, the chloroform insolubles in the hydrogenated butyronitrile multipolymer can increase.The performance that contains the acrylonitrile-butadiene copolymer of gel like this must be affected, and its thermotolerance, ageing resistance, chemical resistance can descend.So prepare gel-free, i.e. the hydrogenated butyronitrile multipolymer of no visible insolubles in chloroform.
The purpose of this invention is to provide a kind of method for preparing the hydrogenated butadiene-acrylonitrile copolymer of gel-free.
The inventor finds after deliberation, in the presence of a kind of phenol with water miscible unsubstituted, quinone, arylamine gellike inhibitor, perbutan latex is hydrazine or the reductive agent that produces the compound of hydrazine with (1), (2) oxygenant, (3) catalyzer carries out hydrogenation reaction, can realize this purpose.
In the method for the invention, used gel inhibitor is selected from the phenol of quinone, monobasic, binary of unsubstituted and aromatic amine compounds and composition thereof, preferred phenol, pyrocatechol, Resorcinol, benzoquinones, aniline, O-Phenylene Diamine, Ursol D and composition thereof, more preferably Resorcinol, O-Phenylene Diamine or Ursol D, and composition thereof.
Said in the inventive method have water-soluble being meant and be slightly soluble in water at normal temperatures, is dissolved in the water in hot water.
According to the present invention, the general hydrogenation step of perbutan latex hydrogenation is:
In reactor, add perbutan latex and described gel inhibitor, stir.When being warming up to temperature of reaction, in the compound adding reactor with hydrazine or generation hydrazine, preferably add several defoamers, stir.Mixed solution with oxygenant and aqueous catalyst solution adds in the reactor simultaneously, preferably under agitation dropwise adds in the reactor.Oxygenant is a gas, can feed from reactor bottom.Behind the reaction certain hour, the naturally cooling stopped reaction obtains the hydrogenated butyronitrile copolymer emulsion.
Gained hydrogenated butyronitrile copolymer emulsion is condensed with emulsion splitter (for example calcium chloride, lime carbonate, sodium-chlor) breakdown of emulsion, and the product of separating out dewaters through extruding, and drying obtains the hydrogenated butyronitrile multipolymer.Measure its degree of hydrogenation and gel content.
According to the present invention, gel inhibitor or/and add in the hydrogenation process, or adds in hydrogenation process before hydrogenation in batches.Preferably before hydrogenation He in the hydrogenation process, add.
Among the present invention, the consumption of gel inhibitor is 0.5～8.0% of a copolymer quality, preferred 1.0～4.0%.
According to the present invention, used perbutan latex is that emulsion polymerization makes, and multipolymer is the latex state, can directly carry out hydrogenation reaction.Described copolymer emulsion is selected from butadiene-acrylonitrile copolymer latex, butadiene-acrylonitrile-vinylformic acid (or methacrylic acid) terpolymer latex, butadiene-acrylonitrile-N-(4-anilino phenyl) Methacrylamide terpolymer latex and butadiene-acrylonitrile-(3,5-di-t-butyl-4-phenolic group) Methacrylamide terpolymer latex, preferred butadiene-acrylonitrile copolymer latex.
According to the present invention, the butadiene content of perbutan is 30～90% (mass percents, down together) in the described latex, and acrylonitrile content is 70～10%; Preferred butadiene content is 50～85%, and acrylonitrile content is 50～15% perbutan latex.The solid content of latex is 1～55% quality, preferred 10～35% quality.
According to the present invention, reductive agent is hydrazine or the compound that produces hydrazine, preferred hydrazine hydrate, acetic acid hydrazine, hydrazonium sulfate and hydrazine hydrochloride, more preferably hydrazine hydrate.The mol ratio of the two keys of C=C is 0.5: 1～8: 1 in the compound of hydrazine or generation hydrazine and the multipolymer, preferred 0.9: 1～3: 1 mol ratios.
Among the present invention, used oxygenant is to add in the hydrogen system and can use any oxygenant that constitutes redox system with above-mentioned reductive agent at perbutan latex, preferably oxygen, air, ozone, hydrogen peroxide, Peracetic Acid, more preferably hydrogen peroxide.The mol ratio of the two keys of C=C is 0.5: 1～8: 1 in described oxygenant and the multipolymer, preferred 0.9: 1～3: 1 mol ratios.
Among the present invention, catalyzer is any catalyzer preferably sulfuric acid copper and boric acid that is applicable to perbutan latex hydrogenation, boric acid more preferably, the mol ratio of the two keys of C=C is 0.005: 1～1: 1 in this catalyzer and the multipolymer, is preferably 0.01: 1～0.5: 1 mol ratio.
The method according to this invention, hydrogenation reaction temperature are room temperature to 95 ℃, preferred 30～80 ℃.
The method according to this invention, the hydrogenation reaction time is 0.5～24 hour, preferred 2～12 hours.
Advantage of the present invention is: (1) has water miscible by adding before hydrogenation reaction or/and in the hydrogenation process, the phenol of unsubstituted, quinone, arylamine gellike inhibitor, the crosslinking reaction that not only can suppress perbutan latex in the hydrogenation process, make the hydrogenated butyronitrile copolymer emulsion of gel-free, but also it is crosslinked that hydrogenated butyronitrile copolymer emulsion breakdown of emulsion cohesion back is not also taken place in drying process, thereby make the hydrogenated butyronitrile multipolymer of gel-free.(2) the selected gel inhibitor of the present invention is to have water misciblely, can directly join in the hydrogenation reaction system of latex, does not need emulsification.Compare with prior art, it is good not only to suppress gel effect, and technology is simple.(3) add described gel inhibitor before reaction or/and in the reaction process, the hydrogenation reaction of perbutan latex and the degree of hydrogenation of product are not had negative impact substantially.
Among the present invention, the degree of unsaturation of polymkeric substance adopts bromine iodine method to measure, and its method is seen CNS GB-1776-81.Its degree of hydrogenation calculation formula is as follows:
Degree of hydrogenation=[(hydrogenation prepolymer degree of unsaturation-hydrogenation post polymerization thing degree of unsaturation)/hydrogenation prepolymer degree of unsaturation] * 100%.
Among the present invention, gel content adopts mass method to measure in the polymkeric substance, promptly accurately takes by weighing polymer quality W gram and is dissolved in the chloroform, is made into 1% chloroformic solution, and (quality is W to this solution through the G2 of constant weight sintered glass funnel
1) after the filtration, funnel is dried to constant weight, claim to such an extent that quality is W
2Its calculation formula is:
Gel content=[(W
2-W
1)/W] * 100%
Following embodiment is used to illustrate of the present invention, rather than is used for limiting the scope of the invention.
Among the application the per-cent of each material or ratio all in mass, except as otherwise noted.
The comparative example 1
With Nancar Latex perbutan latex (Nandi Chemical Industry Co Ltd's product, its solid content 26.3%, butadiene content 66.7%, acrylonitrile content 33.3%) 200ml, concentration is that 85% hydrazine hydrate aqueous solution 60ml (1.12mol) adds and is equipped with in the 1000ml reactor of mechanical stirring, reflux exchanger and constant pressure funnel, places water bath with thermostatic control, adds several defoamers, mixture is stirred, heat and keep 40 ℃.With concentration is that 30% aqueous hydrogen peroxide solution 99ml (0.96mol) and 5.57g boric acid aqueous solution (0.088mol) mix, and adds in the constant pressure funnel, stirs down dropwise to be added in the reactor, drips through 6 hours.With the perbutan latex behind the hydrogenation with the cohesion of 2% NaCl aqueous solution breakdown of emulsion, extruding dewaters, blot the water on hydrogenated butyronitrile multipolymer surface with filter paper after, wet hydrogenated butyronitrile multipolymer is dissolved in the chloroform, and the degree of hydrogenation that records wet hydrogenated butyronitrile multipolymer is 82%.Drying is after 6 hours down at 60 ℃ with this hydrogenated butyronitrile multipolymer, and with the chloroform dissolving, hydrogenated butyronitrile multipolymer swelling in chloroform records its gel content about 60%.
The comparative example 2
Repeat comparative example 1, different is before hydrogenation reaction, add emulsification in advance good 2,6-di-t-butyl 4-methylphenol, its consumption is 8% of an acrylonitrile-butadiene copolymer quality.Wet hydrogenated butyronitrile multipolymer is dissolved in the chloroform, and the degree of hydrogenation that records wet hydrogenated butyronitrile multipolymer is 82%.This hydrogenated butyronitrile multipolymer with the chloroform dissolving, recorded gel content in the hydrogenated butyronitrile multipolymer～30% after under 60 ℃ dry 6 hours.
Embodiment 1
Repeat comparative example 1, different is to add the gel inhibitor Resorcinol before hydrogenation reaction, and its consumption is 8% of an acrylonitrile-butadiene copolymer quality.Wet hydrogenated butyronitrile multipolymer is dissolved in the chloroform, and this hydrogenated butyronitrile multipolymer after under 60 ℃ dry 12 hours, still is dissolved in the chloroform, and the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 80%, and its gel content is 3%.
Embodiment 2
Repeat embodiment 1, different is to replace Resorcinol with O-Phenylene Diamine, and its consumption is 8% of an acrylonitrile-butadiene copolymer quality.Wet hydrogenated butyronitrile multipolymer is dissolved in the chloroform, and this hydrogenated butyronitrile multipolymer still was dissolved in chloroform after under 60 ℃ dry 12 hours, and the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 78%, and gel content is 3%.
Embodiment 3
Repeat embodiment 1, different is to replace Resorcinol with Ursol D, and its consumption is 2% of an acrylonitrile-butadiene copolymer quality, and temperature of reaction is 40 ℃, and the reaction times is 4 hours.Wet hydrogenated butyronitrile multipolymer is dissolved in the chloroform, and drying is after 6 hours down at 60 ℃ with this hydrogenated products, and the hydrogenated butyronitrile multipolymer is dissolved in chloroform, and the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 80.8%, and its gel content is 3.9%.
Embodiment 4
Repeat embodiment 3, the consumption of different is Ursol D is 4% of a perbutan quality, and the reaction times is 4 hours.Drying is after 6 hours down at 60 ℃ for the hydrogenated butyronitrile multipolymer, and this hydrogenated butyronitrile multipolymer is dissolved in chloroform, and the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 79.5%, and gel content is 2.7%.
Embodiment 5
Repeat embodiment 3, the consumption of different is Ursol D is 4% of an acrylonitrile-butadiene copolymer quality, and the reaction times is 6 hours.Drying is after 6 hours down at 60 ℃ for the hydrogenated butyronitrile multipolymer, and this hydrogenated butyronitrile multipolymer is dissolved in chloroform, and the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 84.8%, and gel content is 5.9%.
Embodiment 6
Repeat embodiment 5, the consumption of different is Ursol D is 4% of an acrylonitrile-butadiene copolymer quality, and divides two batches of addings.Add 50% of Ursol D consumption before the hydrogenation reaction earlier, add 50% of remainder in the reaction process before hydrogenation reaction is finished again, the reaction times also is 6 hours.Drying is after 6 hours down at 60 ℃ for the hydrogenated butyronitrile multipolymer, and the hydrogenated butyronitrile multipolymer is dissolved in chloroform, and the degree of hydrogenation that records polymkeric substance is 85%, and gel content is 2.7%.
Embodiment 7
Repeat comparative example 1, different is to add the gel inhibitor Ursol D before hydrogenation reaction, and its consumption is 4% of an acrylonitrile-butadiene copolymer quality.The prescription of reactant is: Nancar Latex perbutan latex 200ml, the mol ratio of hydrazine hydrate and carbon-carbon double bond (the two keys of C=C) is 1.6: 1.0, the mol ratio of hydrogen peroxide and carbon-carbon double bond (the two keys of C=C) is 1.5: 1.0, the mol ratio of boric acid and carbon-carbon double bond (the two keys of C=C) is 0.063: 1.0,40 ℃ of temperature of reaction, 5 hours reaction times.With the perbutan latex behind the hydrogenation with the cohesion of 2% calcium chloride water breakdown of emulsion after, wet hydrogenated butyronitrile multipolymer is dissolved in chloroform, descend drying after 6 hours at 60 ℃ this hydrogenated butyronitrile multipolymer, still be dissolved in chloroform, the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 76.6%, its gel content about 0.0%.
Embodiment 8
Repeat embodiment 7, different is to replace Ursol D with O-Phenylene Diamine, and the consumption of O-Phenylene Diamine also is that 4%, 40 ℃ of perbutan quality reacted 5 hours down.Drying is after 6 hours down at 60 ℃ for the hydrogenated butyronitrile multipolymer, and this hydrogenated butyronitrile multipolymer is dissolved in chloroform, and the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 61.3%, and gel content is 2.5%.
Embodiment 9
Repeat embodiment 7, different is to improve the hydrazine hydrate amount, and the mol ratio of hydrazine hydrate and carbon-carbon double bond (the two keys of C=C) is 2.0: 1.0.Hydrazine hydrate/H
2O
2Constant rate.Wet hydrogenated butyronitrile multipolymer is dissolved in chloroform, and this hydrogenated butyronitrile multipolymer after under 60 ℃ dry 6 hours, still is dissolved in chloroform, and the degree of hydrogenation that records the hydrogenated butyronitrile multipolymer is 81.0%, its gel content 2.6%.
Embodiment 10
The exsiccant hydrogenated butyronitrile multipolymer of the gel-free of embodiment 7 gained was placed in air more than the week, still be dissolved in chloroform, recording gel content is 0.6%.
The foregoing description 1-9 compares with comparative example 1, add before the reaction and have water miscible gel inhibitor of the present invention, to suppressing crosslinked in the perbutan hydrogenation unusual effect is arranged, gel inhibitor adds in batches and more helps reducing gel content, and adds gel inhibitor the degree of hydrogenation of product is not had influence substantially.
Embodiment 1-9 compares with comparative example 2, adding has phenol, quinone, the phenyl amines gel inhibitor that water miscible the present invention does not have replacement before the reaction, not only suppresses gel and has better effect, and have the water-soluble emulsification that need not because of it, simple to operate, easy to implement.
Embodiment 10 compares with embodiment 7, adds before the reaction to have water miscible gel inhibitor of the present invention, to suppressing crosslinked in the perbutan hydrogenation unusual effect is arranged, and hydrogenated products also is stable in storage process.
Above embodiment is exemplary, and the scientific and technical personnel of this area can be used for method of the present invention the hydrogenation of other unsaturated copolymer latex, butadiene-styrene copolymer latex hydrogenation for example, all within the scope of the invention.
Claims (27)
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Cited By (6)
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|---|---|---|---|---|
| CN101367887B (en) * | 2008-10-17 | 2010-06-02 | 北京化工大学 | A kind of hydrogenation method of nitrile latex |
| CN101993504A (en) * | 2009-08-26 | 2011-03-30 | 苏州大学 | Nano-sized hydrogenated diene-based latex particles |
| CN101704909B (en) * | 2009-10-16 | 2011-06-01 | 北京化工大学 | A kind of in-situ hydrogenation method of nitrile latex |
| CN110684254A (en) * | 2019-08-30 | 2020-01-14 | 北京化工大学 | High-performance hydrogenated nitrile rubber material and preparation method thereof |
| CN114014818A (en) * | 2021-12-08 | 2022-02-08 | 沈阳科创化学品有限公司 | Method for preparing pymetrozine intermediate triazine amide |
| CN115806643A (en) * | 2022-12-15 | 2023-03-17 | 西安凯立新材料股份有限公司 | Nitrile rubber hydrogenation method |
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2002
- 2002-07-31 CN CNB021272883A patent/CN1182167C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367887B (en) * | 2008-10-17 | 2010-06-02 | 北京化工大学 | A kind of hydrogenation method of nitrile latex |
| CN101993504A (en) * | 2009-08-26 | 2011-03-30 | 苏州大学 | Nano-sized hydrogenated diene-based latex particles |
| CN101993504B (en) * | 2009-08-26 | 2014-01-01 | 苏州大学 | Nanoscale Hydrogenated Diene-based Latex Particles |
| CN101704909B (en) * | 2009-10-16 | 2011-06-01 | 北京化工大学 | A kind of in-situ hydrogenation method of nitrile latex |
| CN110684254A (en) * | 2019-08-30 | 2020-01-14 | 北京化工大学 | High-performance hydrogenated nitrile rubber material and preparation method thereof |
| CN114014818A (en) * | 2021-12-08 | 2022-02-08 | 沈阳科创化学品有限公司 | Method for preparing pymetrozine intermediate triazine amide |
| CN114014818B (en) * | 2021-12-08 | 2024-02-02 | 沈阳科创化学品有限公司 | Method for preparing pymetrozine intermediate triazinamide |
| CN115806643A (en) * | 2022-12-15 | 2023-03-17 | 西安凯立新材料股份有限公司 | Nitrile rubber hydrogenation method |
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