CN111019045A - Method for preparing food-grade butylbenzene or butadiene solution polymerized rubber - Google Patents
Method for preparing food-grade butylbenzene or butadiene solution polymerized rubber Download PDFInfo
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- CN111019045A CN111019045A CN201911366322.7A CN201911366322A CN111019045A CN 111019045 A CN111019045 A CN 111019045A CN 201911366322 A CN201911366322 A CN 201911366322A CN 111019045 A CN111019045 A CN 111019045A
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- butadiene
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- styrene
- rubber
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 30
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 title claims abstract description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 42
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 16
- 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 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 239000012442 inert solvent Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 3
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 26
- 238000012360 testing method Methods 0.000 abstract description 21
- 235000013305 food Nutrition 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 229940112822 chewing gum Drugs 0.000 abstract description 8
- 235000015218 chewing gum Nutrition 0.000 abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 abstract description 6
- 101000801619 Homo sapiens Long-chain-fatty-acid-CoA ligase ACSBG1 Proteins 0.000 abstract description 5
- 102100033564 Long-chain-fatty-acid-CoA ligase ACSBG1 Human genes 0.000 abstract description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract description 5
- 235000010634 bubble gum Nutrition 0.000 abstract description 5
- 230000036541 health Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- 239000003921 oil Substances 0.000 description 27
- 229920003048 styrene butadiene rubber Polymers 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- 238000007334 copolymerization reaction Methods 0.000 description 12
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000013557 residual solvent Substances 0.000 description 9
- -1 fatty acid salt Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- 125000001979 organolithium group Chemical group 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011115 styrene butadiene Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 3
- 231100000086 high toxicity Toxicity 0.000 description 3
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 231100000481 chemical toxicant Toxicity 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000002044 hexane fraction Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IEOPZUMPHCZMCS-ZCFIWIBFSA-N (2r)-2-(methoxymethyl)oxolane Chemical compound COC[C@H]1CCCO1 IEOPZUMPHCZMCS-ZCFIWIBFSA-N 0.000 description 1
- AFVDZBIIBXWASR-UHFFFAOYSA-N (e)-1,3,5-hexatriene Chemical compound C=CC=CC=C AFVDZBIIBXWASR-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 1
- FRBJEDLSFZZCFY-UHFFFAOYSA-N 2,5-bis(methoxymethyl)oxolane Chemical compound COCC1CCC(COC)O1 FRBJEDLSFZZCFY-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- MXFRWBNCSXHXRE-UHFFFAOYSA-N [Li]\C=C\C Chemical compound [Li]\C=C\C MXFRWBNCSXHXRE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for preparing food-grade butylbenzene or butadiene solution polymerized rubber, which adopts organic lithium as initiator and adopts C which is dried and refined under the condition of polar additive existing4‑C8The rubber polymer is prepared by using saturated aliphatic hydrocarbon or a mixed solvent prepared from the saturated aliphatic hydrocarbon as a solvent, completely polymerizing an organic matter consisting of elements such as carbon, hydrogen, oxygen and the like in a rubber polymer chain as a crosslinking coupling agent, and using a food-grade antioxidant BHT as an antioxidant to polymerize butadiene and styrene or butadiene at relatively high monomer concentration and polymerization temperature. The method is simpleThe method is quick, flexible and low in cost, the obtained product is pure white, the white rat test is nontoxic, the chewing gum and bubble gum prepared by the method have good taste and no peculiar smell, and the method can be widely applied to the aspects of manufacturing children toys, chewing gum, bubble gum, medical treatment and health, food packaging, rubber accessories of food production machinery and other products.
Description
Technical Field
The invention relates to a method for preparing food-grade rubber, in particular to a method for preparing food-grade solution polymerized styrene-butadiene rubber or butadiene rubber.
Background
As is well known, most of the food grade rubbers currently used in bubble gum, chewing gum, and medical and health, food packaging, etc. are natural rubber or emulsion polymerized styrene-butadiene rubber which is further purified.
However, the purified natural rubber is food additive grade rubber, which is expensive and occupies considerable land resources for production. The synthetic rubber which is purified is not pure and harmless because a large amount of toxic and harmful chemical raw materials are added in the production, and the cost is higher. For example, food-grade emulsion polymerized styrene-butadiene rubber purified and produced by Goodyear company in America has light brown yellow color, and contains obvious impurity peak of emulsifier fatty acid salt through infrared spectrum analysis, and has peculiar smell in taste.
Although the solution polymerization (solution polymerization) rubber does not contain fatty acid salt impurities, the high-temperature copolymerization products without adding polar additives, such as solution polymerization styrene-butadiene rubber, contain a polystyrene block structure and have poor rubber performance; when the polar structure regulator is added to produce the copolymer rubber, the copolymerization temperature is relatively low and is usually within 110 ℃, so that the conversion of styrene monomer is not enough, and styrene with high toxicity has certain residue in the rubber. Meanwhile, cyclohexane is usually adopted as the copolymerization solvent of the glue, and benzene is also used as the solvent in the US patent 3,944,528, and the subsequent treatment and removal are difficult, so that benzene, cyclohexane and other solvents with high toxicity are easy to remain in the product glue.
Particularly, the coupling process of the solution polymerized styrene butadiene rubber stannic chloride which is generally popularized and produced in various countries in the world at present introduces metallic tin harmful impurities, and is unsatisfactory as food-grade rubber colloid. The synthetic rubber nickel polybutadiene produced by a solution polymerization method using transition metal as a catalyst has residual metal chemicals in the rubber which threaten human health and is not suitable for being used as food-grade rubber.
In recent years, some enterprises in China intend to produce food-grade rubber by adopting a method of chopping and washing industrial emulsion polymerized styrene-butadiene rubber, so that harmful organic matters among molecular chains of high-molecular polymers are substantially difficult to remove, and the complicated process increases the cost.
Chinese patent application No. CN1454910A (application No. 03140520.7) relates to a preparation method of food-grade butadiene or butadiene and styrene solution polymerized rubber, which adopts C4-C8 mixed saturated aliphatic hydrocarbon as a solvent in the presence of an organic lithium initiator and a polar additive, can completely polymerize an organic matter consisting of units such as carbon, hydrogen, oxygen and the like of a rubber macromolecular chain as a crosslinking coupling agent, adopts food-grade antioxidant BHT as an antioxidant, and polymerizes butadiene and styrene or butadiene at relatively high monomer concentration and polymerization temperature to prepare the food-grade rubber. The method is simple and efficient, and the safety is higher than the FCC international standard. However, at present, petrochemical enterprises are becoming large-scale at home and abroad, and the production scale of large devices is relatively small, so that the rapid industrialization is difficult to realize, and the production flexibility is not provided.
Moreover, the inventor of the application researches on safety and discovers that the copolymerization initiator butyl lithium is damaged by trace water, oxygen, carbon dioxide, carbon monoxide and other carbonyl compound impurities contained in the raw materials (including protective nitrogen in contact with the reaction) for the anionic copolymerization of the butylbenzene, so that the conversion rate fluctuation, the molecular weight change and even the polymerization are not caused; more seriously, for the production of food-grade rubber, safety and sanitation indexes are obviously damaged, and even if the reaction conversion rate test result is 100%, the raw materials and impurities in the system can promote the residue of chemicals in the product, especially the residue of styrene with high toxicity.
The inventor thinks that, can reach the food level rubber of gum, bubble gum raw materials standard, but wide application in children's toys raw materials, guarantee children are healthy to grow up, but more wide application in food machinery, packing promote that many trades accord with sanitary standard, green. Therefore, the feeding ratio of the butylbenzene is diversified, and the Mooney viscosity of the product is controlled to be 30-150 so as to adapt to different market requirements.
Disclosure of Invention
The invention is a result of further research on the basis of the invention patent CN1454910A, which integrates common solvents for industrial anion production, adopts raffinate oil or hydrogenated gasoline mixed solvent system, and realizes that the production device can flexibly switch and produce different anion copolymer varieties, such as industrial styrene butadiene rubber, SBS, styrene butadiene copolymer containing styrene block, high elongation SBS containing butadiene block, 1, 2-polybutadiene rubber and the like. The method of the invention is convenient for enlarging production conditions and reducing production cost; correspondingly, the food-grade rubber can be produced on SBS and industrial solution polymerized butadiene styrene rubber devices without adding solvent matching equipment such as a pipeline storage tank and the like. The invention limits the purity of the raw materials, improves the product quality, lightens the load of washing and other conventional methods for further reducing and eliminating toxic chemicals, achieves the high purity of the product and can produce various products by strict raw material refining and drying measures.
The inventor of the present application found in practice that the hexane fraction in the mixed solvent of cyclohexane and hexane used as the solvent of SBS can be completely replaced by inexpensive narrow-cut raffinate. The n-hexane is difficult to purify in production and quite expensive, the raffinate oil is rich in source and low in cost, and the cyclohexane and the raffinate oil can be prepared in any required proportion to meet the requirements of different solubilities, heat capacities, solvent freezing points and the like. According to the method of the invention, a mixed solvent composed of 10-100 wt% of distillate raffinate oil at 55-85 ℃ or hydrogenated gasoline and 0-90 wt% of cyclohexane is adopted, so that the method can be suitable for producing different rubber species such as food-grade solution polymerized styrene-butadiene rubber, styrene-butadiene block copolymer SBS, industrial solution polymerized styrene-butadiene rubber, butadiene homopolymer and the like with a low-cost solvent, thereby enlarging the source of raw materials, and the obtained product is more suitable for the food sanitation requirement, ensures the quality of the product, and has various indexes superior to national standard and FCC international standard.
The invention further verifies the technical characteristics of the solution polymerized styrene-butadiene rubber, and styrene-butadiene rubber with different styrene-butadiene ratios can be obtained by flexibly adjusting the feeding proportion of styrene and butadiene. The current emulsion polymerized styrene-butadiene production technology has difficulty in controlling the feeding proportion, for example, the preparation of chewing gum base needs to be prepared by mixing 25/75 and 50/50 food-grade emulsion polymerized styrene-butadiene rubber. The method can directly synthesize the required rubber, not only ensure the quality of the gum base, but also simplify the production procedure of the gum base chewing gum, and can also meet the requirements of different fields such as the manufacturing industry of nontoxic toys for children and the like.
Tests prove that impurities in the raffinate oil synthesis system and raw materials not only destroy the reaction, but also increase the chemical residue of the synthesized raw materials of the synthesized product, particularly increase the contents of styrene and lithium haxate, and easily cause the quality of the product to be unqualified. Therefore, the synthesis process needs to strictly control the refining of trace impurities contained in the raw materials. In particular, the solvent used in a large amount must be refined and dried so that the water content is 10ppm or less, so that the total content of impurities (including water, oxygen, carbon monoxide and carbon dioxide) in the reaction system is less than 20 ppm.
Cyclohexane is used as a solvent in the butylbenzene anion reaction, and 10-30% of hexane is prepared for antifreezing. The solvent used in the Chinese invention patent CN1454910A is C4-C8 mixed saturated aliphatic hydrocarbon, preferably platinum reformed raffinate oil or hydrogenated gasoline with the temperature of 55-85 ℃, and the freezing point is very low. The inventor of the application can prepare better food-grade rubber products and prevent freezing by adopting a mixed solvent consisting of 10-100 wt% of 55-85 ℃ distillate raffinate oil or hydrogenated gasoline and 0-90 wt% of cyclohexane, and particularly can directly share solvent raw materials and equipment with the production of SBS, industrial butadiene styrene rubber, high vinyl butadiene rubber and other polymer materials by adopting the mixed solvent of 67.8-68.8 ℃ narrow distillate raffinate oil to realize multi-variety production. The invention can simply and conveniently adjust the feeding amount of butadiene and styrene, and further directly synthesize the rubber containing styrene with different proportions, thereby solving the current production situation that the two proportions of rubber are required to be prepared in the preparation of the gum base of the chewing gum and simplifying the production process. The large-scale device and multi-variety industrialized flexible production can be realized, and remarkable benefits can be obtained.
The invention provides a method for preparing food-grade butylbenzene or butadiene solution polymerized rubber, which comprises the steps of carrying out active anion polymerization of butadiene and styrene or butadiene in an inert solvent in the presence of a polar additive by taking organic lithium as an initiator in a high-purity nitrogen atmosphere, then carrying out coupling by using a coupling agent, and then carrying out coagulation and drying to obtain a polymer, wherein the weight ratio of butadiene to styrene is 100-25: 0-75, monomer concentration of 2-70g total monomer/100 ml solvent; wherein the organolithium initiator is n-butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium or dilithium; the coupling agent is divinylbenzene or diethyl adipate; the polar additive is tetrahydrofuran, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether; the inert solvent is: raffinate oil with a boiling range of 55-100 ℃; hydrogenated gasoline with a boiling range of 55-100 ℃; or a mixed solvent consisting of 10-100 wt% of raffinate oil with a boiling range of 55-100 ℃ and 0-90 wt% of cyclohexane; wherein the molar ratio of the total monomer, the polar additive, the coupling agent and the organic lithium initiator is 100-10000: 0-500: 0-2: 1; the polymerization temperature is 60-180 ℃.
Preferably, the raffinate or hydrogenated gasoline boiling range is from 55 to 85 ℃ in the inert solvent. Preferably, for facilitating the industrial mass production of other types of rubber such as SBS, industrial butylbenzene, vinyl polybutadiene, etc., the raffinate in the mixed solvent is further preferably a narrow cut raffinate with a boiling range of 67.8-68.8 deg.C, and has a composition (by weight) such as, but not limited to, n-hexane 85.86%, methylcyclohexane 7.99%, 2-methylpentane 0.15%, 3-methylpentane 4.75%, and cyclohexane 1.25%. The ratio of this narrow cut raffinate oil to cyclohexane in the mixed solvent is preferably 30-10: 70-90.
In the preparation method of the food-grade styrene-butadiene or butadiene solution polymerized rubber, the polymerization comprises homopolymerization and copolymerization, the polymer refers to homopolymer and copolymer, and the solution polymerized rubber refers to rubber polymer prepared by solution polymerization in the presence of a solvent. The raffinate oil refers to the part of oil left after an oil refinery extracts aromatic hydrocarbons from the platinum reformed gasoline, and is hydrogenated and saturated in the platinum reforming process, generally referred to as raffinate oil for short, and has the same property as hydrogenated gasoline. Among them, no matter whether raffinate oil, hydrogenated gasoline or mixed solvent is used, since the solvent is used in the largest amount among all the solution polymerization raw materials, the total amount of impurities contained therein is the largest, and the residual influence on chemicals in the product is most significant, it is necessary to limit the content of impurities (including trace water, oxygen, carbon monoxide, carbon dioxide, etc.) in the raw materials, for example, the water content in the inert solvent used in a large amount must be limited to 10ppm or less, more preferably 5ppm or less, so that the total content of impurities (including water, oxygen, carbon monoxide and carbon dioxide) in the raw materials used for the reaction (including reaction monomers, inert solvent, polar additive, initiator, coupling agent, high purity nitrogen, etc.) is less than 20 ppm.
The amount of inert solvent used during the polymerization depends on the desired monomer concentration, which is generally from 2 to 70g of total monomers per 100ml of solvent, preferably from 5 to 50g of total monomers per 100ml of solvent, more preferably from 10 to 25g of total monomers per 100ml of solvent. The total monomer referred to herein means the total amount of butadiene and styrene or butadiene.
The butadiene and the styrene are both polymer-grade monomers and are dried and subjected to impurity removal treatment before use. The feed ratio of butadiene and styrene is generally from 100 to 25 by weight: 0 to 75; preferably 100 to 40: 0-60. When two monomers of butadiene and styrene are copolymerized, the product is called food-grade solution polymerized styrene-butadiene rubber. When the only polymerized monomer is butadiene, the product is food grade soluble polybutadiene rubber. The styrene feeding amount is increased, the product plasticity is enhanced, and the product is styrene-butadiene resin when the styrene content is more than 75 percent, which is not discussed in the present discussion.
The organolithium initiator may be generally an alkyllithium, for example, a monolithium such as methyllithium, ethyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, cyclohexyllithium, vinyllithium, propenyl lithium, and a dilithium such as tetramethyldilithium, pentamethyldilithium, hexamethylenedilithium, decamethyldilithium and the like, preferably n-butyllithium, isobutyllithium, tert-butyllithium, sec-butyllithium or dilithium, more preferably n-butyllithium. The amount of organolithium initiator used can be determined according to the process requirements, and generally the molar ratio of the total monomers (referring to the total amount of butadiene or butadiene and styrene) to the organolithium initiator is 100-10000.
The polar additive is generally an ether or a tertiary amine having a lewis basic property, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 2-methoxymethyltetrahydrofuran, 2, 5-dimethoxymethyltetrahydrofuran, and the like, and tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether are preferred, and tetrahydrofuran is more preferred. The polar additives may be used alone or in combination of two or more, and the mixing ratio thereof is not critical and may be any ratio. The molar ratio of the polar additive to the organolithium initiator is 0-500.
The coupling agent is polyvinyl compound, halide, ether, ester and the like composed of elements such as carbon, hydrogen, oxygen and the like, such as divinylbenzene, diethyl adipate, silicon tetravinyl, tetrachloroethane, silicon tetrachloride and the like, and the preferred coupling agent is divinylbenzene or diethyl adipate. In the solution polymerization of butadiene or butylbenzene, a proper organic coupling agent composed of elements such as carbon, hydrogen, oxygen and the like is selected and completely copolymerized into rubber molecules, so that the pollution of the solution polymerization coupling agent such as tin tetrachloride and the like to the product can be avoided, and the influence of raw material chemicals for synthesizing the high polymer rubber is further reduced. The molar ratio of the coupling agent to the organolithium initiator is 0-2.
In the process described herein, a food grade antioxidant such as 2, 6-di-t-butyl-4-methylphenol or 2, 6-di-t-butyl-p-cresol (referred to as BHT) is further added to the reaction system after the polymerization reaction is completed. The amount of the antioxidant added is 0.05-1%, preferably 0.1-0.5% of the weight of the polymer.
In the process described herein, a terminating agent is used after the polymerization, said terminating agent being a commonly used anionic polymerization terminating agent such as water, ethanol or isopropanol, etc., preferably water or ethanol.
The polymerization temperature is 60 to 180 ℃, preferably 80 to 140 ℃. As mentioned above, since the polymerization process of the present inventionIn the middle by C4-C8The mixed saturated aliphatic hydrocarbon is used as a solvent to carry out a solution polymerization process of butadiene or butadiene and styrene, anion active polymerization can be carried out at a higher temperature (60-180 ℃), the polymerization reaction rate is high and stable, the monomer conversion rate is close to 100 percent, the structure of the polymer is not changed, and the phenomenon of sudden polymerization overpressure is avoided, so that the polymerization reaction efficiency and stability are improved, the residual probability of toxic monomers in rubber is greatly eliminated, and the solution polymerization process is favorable for stable and high-quality product quality. The polymerization pressure is not critical as long as the polymerization reaction system is carried out in a liquid phase, and the polymerization pressure is usually 0.2 to 0.5 MPa.
The polymerization reactor used in the method for preparing food grade rubber of the present invention may be any reactor or reaction vessel suitable for solution polymerization, such as a stainless steel polymerization reactor (tank) with a stirrer.
Advantageous effects
1. The raffinate oil in the mixed solvent adopted by the method, in particular the narrow-cut raffinate oil consisting of equivalent hexane fraction with the boiling range of 67.8-68.8 ℃, has the content controlled to be 10-30 wt%, and the mixed solvent has the advantages of being equal to the solvent commonly used in lithium anion reaction, being capable of switching to produce different anionic copolymer varieties and preventing the cyclohexane solvent from freezing and hindering the production in winter. The application range of the anion synthesis main raw material solvent can be enlarged, the device and the solvent can be shared with SBS, industrial butadiene styrene rubber and the like, the production can be switched, and the production scale and conditions of the butadiene styrene material can be enlarged.
2. The food-grade styrene butadiene rubber with different styrene content proportions is directly produced according to the product requirements, and the production procedure of the gum base of the chewing gum is simplified.
3. The trace water content of the solvent with larger dosage is controlled below 10ppm, preferably below 5ppm, so that the total content of impurities such as trace water, oxygen, carbon dioxide and the like in the raw materials is less than 20 ppm. Ensures that the product reduces and eliminates the residual of toxic chemicals, and ensures that the toxic content of the product is lower than 10 percent of the FCC international standard. The product not only can meet the requirement of manufacturing chewing gum bubble gum base, but also can be widely applied to the fields of children toys, food-grade rubber and plastic material modification, rubber gasket sealing pieces of food machinery and the like, improves the safety of equipment materials of the children toys and contacting food, is beneficial to health and health guarantee, and has great social benefit.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples, in which the solvent mixture of raffinate oils in different proportions is used as the synthesis inert solvent, the water content in the inert solvent is controlled below 10ppm, and the total amount of water, oxygen, carbon monoxide and carbon dioxide impurities in the reaction system is controlled below 20 ppm.
Example 1
The test was carried out in a 10 liter polymerization kettle. After the polymerization system is replaced by high-purity nitrogen, 600g of butadiene, 200g of styrene, 448g of raffinate oil (boiling range: 55-85 ℃), 4032g of cyclohexane, 16ml of tetrahydrofuran, 16ml of 2.68% divinylbenzene and 26ml of n-butyllithium with the concentration of 0.317M are added into the kettle in sequence, and then copolymerization reaction is carried out. The polymerization temperature is 75-125 deg.C, and the reaction pressure is 0.24-0.47 Mpa. The reaction time is 12 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping are finished by deionized water, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is not detected, the residual styrene is not detected, the residual hachert is 0.0028% (by weight), the product Mooney viscosity is 55.5, the tensile strength is 21.5Mpa, and the elongation is 490%. Note: FCC international standard residual n-hexane is less than or equal to 0.01 percent, residual styrene is 0.002 percent, and residual hachert quantity is less than or equal to 0.0075 percent.
Example 2
The test was carried out in a 10 liter polymerization kettle. After the polymerization system is replaced by high-purity nitrogen, 600g of butadiene, 200g of styrene, 1344g of raffinate oil (boiling range: 55-85 ℃), 3136g of cyclohexane, 16ml of tetrahydrofuran, 16ml of 2.68% divinylbenzene and 26ml of n-butyllithium with the concentration of 0.317M are sequentially added into a kettle, and then copolymerization reaction is carried out. The polymerization temperature is 80-120 deg.C, and the reaction pressure is 0.25-0.47 Mpa. The reaction time is 13 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping are finished by deionized water, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is not detected, the residual styrene is not detected, the residual hachert is 0.0026% (by weight), the product Mooney viscosity is 55, the tensile strength is 22Mpa, and the elongation is 492%.
Example 3
The test was carried out in a 10 liter polymerization kettle. After the polymerization system is replaced by high-purity nitrogen, 600g of butadiene, 200g of styrene, 4480g of raffinate oil (boiling range: 55-85 ℃), 16ml of tetrahydrofuran, 16ml of 2.68% divinylbenzene and 26ml of n-butyl lithium with the concentration of 0.317M are sequentially added into a kettle, and then copolymerization reaction is carried out. The polymerization temperature is 80-120 deg.C, and the reaction pressure is 0.28-0.42 MPa. The reaction time is 13 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping are finished by deionized water, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is not detected, the residual styrene is not detected, the residual hachert is 0.0028% (by weight), the product Mooney viscosity is 55.2, the tensile strength is 21.6MPa, and the elongation is 495%.
Comparative example 1
The test was carried out in a 10 liter polymerization kettle. After the polymerization system is replaced by high-purity nitrogen, 600g of butadiene, 200g of styrene, 5400g of cyclohexane, 18ml of tetrahydrofuran and 26ml of n-butyllithium with the concentration of 0.317M are sequentially added into the kettle, and then copolymerization reaction is carried out. The polymerization temperature is 45-100 deg.C, and the reaction pressure is 0.25-0.37 MPa. After the reaction was complete, 0.45g SnCl was added4And (3) carrying out coupling reaction for 30 minutes, adding food-grade BHT, stopping washing and steam stripping by deionized water, and then carrying out hot-roll extrusion drying to obtain a sample. The test results show that the conversion rate is 99.5%, the residual solvent cyclohexane is 0.0072% (by weight), the residual styrene is 0.0021% (by weight), the residual hakel is 0.0068% (by weight), the Mooney viscosity of the product is 55, the tensile strength is 22Mpa, and the elongation is 498%.
Example 4
The test was carried out in a 10 liter polymerization kettle. After the polymerization system is replaced by high-purity nitrogen, 500g of butadiene, 500g of styrene, 5000g of raffinate oil (boiling range: 55-85 ℃), 20ml of tetrahydrofuran, 16ml of 3.5% divinylbenzene and 12.5ml of 0.9M n-butyl lithium are sequentially added into a kettle, and then copolymerization reaction is carried out. The polymerization temperature is 90-125 deg.C, and the reaction pressure is 0.28-0.42 MPa. The reaction time is 15 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping are finished by deionized water, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is 0.0015% (weight), the residual styrene is 0.0003% (weight), the residual hakel is 0.0027% (weight), the Mooney viscosity of the product is 57.0, the tensile strength is 22.6MPa, and the elongation is 495%.
Example 5
The test was carried out in a 10 liter polymerization kettle. After the polymerization system was replaced with high-purity nitrogen, 496g of butadiene, 304g of styrene, 1344g of raffinate oil (boiling range: 55-85 ℃), 3136g of cyclohexane, 15ml of tetrahydrofuran, 16ml of 2.68% divinylbenzene and 26ml of n-butyllithium at a concentration of 0.317M were sequentially added to the reactor, followed by copolymerization. The polymerization temperature is 85-125 deg.C, and the reaction pressure is 0.25-0.41 Mpa. The reaction time is 14 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping of deionized water are stopped, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is 0.001% (by weight), the residual styrene is 0.0002% (by weight), the residual hakel is 0.0027% (by weight), the Mooney viscosity of the product is 55.0, the tensile strength is 21.6MPa, and the elongation is 495%.
Example 6
The test was carried out in a 10 liter polymerization kettle. After the polymerization system was replaced with high-purity nitrogen, 800g of butadiene, 3136g of raffinate oil (boiling range: 55-85 ℃), 1344g of cyclohexane, 13ml of tetrahydrofuran, 13ml of 3.31% divinylbenzene, and 10.5ml of 0.9M n-butyllithium were sequentially added to the reactor, followed by polymerization. The polymerization temperature is 45-120 deg.C, and the reaction pressure is 0.28-0.48 Mpa. The reaction time is 12 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping are finished by deionized water, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is 0.001% (weight), the residual styrene is not detected, the residual hachert is 0.0018% (weight), the Mooney viscosity of the product is 45.0, the tensile strength is 19.8Mpa, and the elongation is 520%.
Example 7
The test was carried out in a 10 liter polymerization kettle. After the polymerization system is replaced by high-purity nitrogen, 600g of butadiene, 200g of styrene, 1344g of narrow-cut raffinate oil with a boiling range of 67.8-68.8 ℃, 3136g of cyclohexane, 16ml of tetrahydrofuran, 16ml of 2.68% divinylbenzene and 26ml of n-butyllithium with a concentration of 0.317M are sequentially added into a kettle, and then polymerization reaction is carried out. The polymerization temperature is 80-125 deg.C, and the reaction pressure is 0.28-0.48 Mpa. The reaction time is 13 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping are finished by deionized water, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is not detected, the residual styrene is not detected, the residual hachert is 0.0025% (by weight), the product Mooney viscosity is 55, the tensile strength is 22.7Mpa, and the elongation is 493%.
Comparative example 2
The test was carried out in a 10 liter polymerization kettle. After a polymerization system is replaced by industrial common nitrogen, 600g of butadiene, 200g of styrene, 1344g of raffinate oil with a boiling range of 55-85 ℃ and containing 22ppm of trace water, 3136g of cyclohexane, 16ml of tetrahydrofuran and 16ml of 2.68 percent divinylbenzene are sequentially added into a kettle, wherein the total amount of impurities of the trace water, the oxygen, the carbon monoxide and the carbon dioxide of the raw materials is more than 25 ppm. Then, 36ml of n-butyllithium was added thereto at a concentration of 0.317M to initiate polymerization. The polymerization temperature is 80-120 deg.C, and the reaction pressure is 0.28-0.48 Mpa. The reaction time is 15 minutes, after the reaction is finished, food-grade BHT is added, and after the washing and steam stripping are finished by deionized water, the sample is extruded and dried by hot rollers to obtain the sample. The test result shows that the conversion rate is 100%, the residual solvent n-hexane is 0.0015% (weight), the residual styrene is 0.0032% (weight), the residual hachert is 0.0081% (weight), the Mooney viscosity of the product is 55.5, the tensile strength is 21MPa, and the elongation is 480%.
Claims (1)
1. A method for preparing food-grade butylbenzene or butadiene solution polymerized rubber is characterized by comprising the following steps:
1) refining and drying monomers, inert solvents, polar additives, coupling agents and high-purity nitrogen used in a reaction system to control the total amount of trace impurities such as water, oxygen, carbon dioxide and carbon monoxide to be less than 20 ppm; the content of trace water in the inert solvent is less than 10 ppm;
2) in a high-purity nitrogen atmosphere, butyl lithium is used as an initiator, active anion polymerization of butadiene and styrene or butadiene is carried out in an inert solvent in the presence of a polar additive tetrahydrofuran, and then a coupling reaction is carried out by using a coupling agent divinylbenzene, wherein the weight ratio of butadiene to styrene is 100-40: 0-60, the molar ratio of the total monomer, the polar additive, the coupling agent and the lithium initiator is 100-10000: 0-500: 0-2: 1, the concentration of the monomer is 2-70g of total monomer/100 ml of solvent, and the polymerization reaction temperature is 80-140 ℃;
the inert solvent is: raffinate oil with a boiling range of 55-100 ℃, hydrogenated gasoline with a boiling range of 55-100 ℃ or a mixed solvent consisting of 10-100 wt% raffinate oil with a boiling range of 55-100 ℃ and 0-90 wt% cyclohexane;
3) and after the polymerization reaction is finished, adding a food-grade antioxidant into the reaction system, and then condensing and drying to obtain the food-grade butadiene styrene or butadiene solution polymerized rubber polymer, wherein the food-grade antioxidant is food-grade 2, 6-di-tert-butyl-4-methylphenol or 2, 6-di-tert-butyl-p-cresol, and the adding amount is 0.05-1% of the weight of the polymer.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266067A (en) * | 1999-03-03 | 2000-09-13 | 韩国轮胎株式会社 | Process of solution polymerizing for preparing styrene-butadiene or butadiene |
| CN1445252A (en) * | 2002-01-15 | 2003-10-01 | 北京燕山石油化工公司研究院 | Conjugated alkadiene polymer rubbers with no-color and low gelatin and its preparing method |
| CN1454910A (en) * | 2003-05-28 | 2003-11-12 | 张乃然 | Food-level butadiene or butadiene and styrene fused rubber manufacture method |
| CN101475674A (en) * | 2009-01-15 | 2009-07-08 | 浙江三博聚合物有限公司 | Preparation of phenylethylene-dialkene special copolymer |
| CN102485762A (en) * | 2009-11-03 | 2012-06-06 | 中国石油化工股份有限公司 | Colourless butylbenzene segmented copolymer with low gel content and preparation method thereof |
-
2015
- 2015-02-04 CN CN201510058761.7A patent/CN104628954A/en active Pending
- 2015-02-04 CN CN201911366322.7A patent/CN111019045A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266067A (en) * | 1999-03-03 | 2000-09-13 | 韩国轮胎株式会社 | Process of solution polymerizing for preparing styrene-butadiene or butadiene |
| CN1445252A (en) * | 2002-01-15 | 2003-10-01 | 北京燕山石油化工公司研究院 | Conjugated alkadiene polymer rubbers with no-color and low gelatin and its preparing method |
| CN1454910A (en) * | 2003-05-28 | 2003-11-12 | 张乃然 | Food-level butadiene or butadiene and styrene fused rubber manufacture method |
| CN101475674A (en) * | 2009-01-15 | 2009-07-08 | 浙江三博聚合物有限公司 | Preparation of phenylethylene-dialkene special copolymer |
| CN102485762A (en) * | 2009-11-03 | 2012-06-06 | 中国石油化工股份有限公司 | Colourless butylbenzene segmented copolymer with low gel content and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| "顺丁橡胶生产", 30 September 1978, 石油化学工业出版社, pages: 19 - 22 * |
| 任建新: "膜分离技术及其应用", 31 January 2003, 化学工业出版社, pages: 361 - 362 * |
| 张洋等: "聚合物制备工程", 31 January 2001, 中国轻工业出版社, pages: 129 * |
| 张洪敏等: "活性聚合", 31 January 1998, 中国石化出版社, pages: 104 * |
| 薛联宝等: "阴离子聚合的理论与应用", 31 December 1990, 中国友谊出版社, pages: 132 * |
| 黄健等: "镍系顺丁橡胶生产技术", 31 January 2008, 化学工业出版社, pages: 36 * |
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