CN106928391A - Preparation method of isobutylene, isoprene and alkylstyrene polymer - Google Patents
Preparation method of isobutylene, isoprene and alkylstyrene polymer Download PDFInfo
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- CN106928391A CN106928391A CN201511021343.7A CN201511021343A CN106928391A CN 106928391 A CN106928391 A CN 106928391A CN 201511021343 A CN201511021343 A CN 201511021343A CN 106928391 A CN106928391 A CN 106928391A
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- ether
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- isoprene
- tgδ
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- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 42
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- -1 amine salt Chemical class 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 150000003983 crown ethers Chemical group 0.000 claims description 26
- 230000000977 initiatory effect Effects 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 150000003440 styrenes Chemical class 0.000 claims description 14
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical group CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 claims description 5
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical group CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims 1
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical class CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims 1
- 150000001399 aluminium compounds Chemical class 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000013016 damping Methods 0.000 abstract description 38
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229940050176 methyl chloride Drugs 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 19
- 230000009477 glass transition Effects 0.000 description 17
- 239000002585 base Substances 0.000 description 13
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 12
- 229920005549 butyl rubber Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000002460 imidazoles Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 208000005156 Dehydration Diseases 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229940049706 benzodiazepine Drugs 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920005555 halobutyl Polymers 0.000 description 4
- 125000004968 halobutyl group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- VAPKHDZBJXRVNG-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene;1-ethenyl-4-methylbenzene Chemical group CC1=CC=C(C=C)C=C1.CC1=CC=CC(C=C)=C1 VAPKHDZBJXRVNG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- MNEIJGDSFRHGMS-UHFFFAOYSA-N 1-(phenylmethyl)benzimidazole Chemical class C1=NC2=CC=CC=C2N1CC1=CC=CC=C1 MNEIJGDSFRHGMS-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of a polymer of isobutene, isoprene and alkylstyrene, which comprises the steps of replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-50 to-100 ℃, adding methyl chloride as a solvent, adding an ionic liquid solution of the isobutene, the isoprene and the alkylstyrene, stirring for 10 to 30min, adding aniline, adding an initiator for 3 to 5 times, reacting for 30min to 3h, adding a terminator to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The polymer has good flexibility and good rigidity, so that the polymer has excellent processing performance and damping performance.
Description
Technical field
The present invention relates to the preparation method of a kind of isobutene, isoprene and ring-alkylated styrenes polymer, tool
Body is a kind of method that utilization solwution method prepares isobutene, isoprene and ring-alkylated styrenes polymer.
Background technology
Because its sub-chain motion can not completely keep up with vibration velocity when elastomeric material is in glass transition region
Produce triboabsorption partial vibration in strand to be dissipated with form of thermal energy again and effectively realize the mesh of vibration and noise reducing
's.With the development of auto industry and aerospace industry, automobile noise vibration, ride comfort sex chromosome mosaicism and
Amortization is increasingly paid close attention to by people, and rubber can change into vibrational energy and acoustic energy as one kind
The new function material that thermal energy consumption is fallen, damping material has turned into study hotspot.
CN201410078284.6 is related to poly- (isobutene-co- p-methylstyrenes) random copolymer preparation side
Method, it is third component to use hexahydropyridine, using alkyl aluminum as initiator, is closed by cationic copolymerization
Poly- (isobutene-co- p-methylstyrenes) random copolymer is successfully synthesized；Possess preferable molecular weight
And molecular weight distribution.There is provided one kind poly- (isobutene-co- p-methylstyrenes) random copolymer of synthesis
Method, the synthetic method is applied to slurry process and solwution method is prepared poly- (isobutene-co- p-methylstyrenes)
Random copolymer.A kind of isoolefin copolymers preparation methods of CN201010514252.8；Halogenated hydrocarbons,
In hydrocarbon compound or their mixture, under catalyst action, isoolefin monomer, polyene are carried out
The polymerisation of monomer and optional other copolymerisable monomers, described catalyst is the sesquialter chlorination of aluminium ethide
The mixture of thing and water；The present invention synthesizes the side of isoolefin copolymers by a kind of solwution method of environment-friendly high-efficiency
Method, can solve the problem that the low problem of solwution method butyl rubber product yield, while extending the continuous poly- of reactor
The conjunction time, wash number is reduced, (- 20~-80 DEG C) are polymerized under both economical polymerization temperature,
Be conducive to energy-conservation；Ring is conducive to instead of the chloromethanes used in slurry process as solvent using saturated alkane
Protect.A kind of preparation methods of butyl rubber of CN201310546657.3, including prepare：Raw material is by isobutyl
Alkene and isoprene are formulated；Polymerization：Above-mentioned raw materials are added into polymeric kettle, is then sequentially added
The catalyst and diluent, carry out being polymerized instead finally at -10~-25 DEG C, under the conditions of 1~14KPa
Answer 2~4 hours；Terminate：Terminator isopropanol is added after polymerisation, resulting polymers flash distillation is removed
Unreacted monomer and solvent are removed, then by dehydration, extruding, dry and briquetting, obtains butyl rubber
Finished product.A kind of methods for preparing halobutyl elastomeric graft copolymer of CN201310056027.8, bag
Include：Make halogenation in the presence of the alkali metal salt soln for combining oxygen or sulphur nucleopilic reagent on polymer substrate
The solution of butyl elastomers is mixed with phase transfer catalyst, and by the nucleophilic in allyl halide site
Be grafted to polymer substrate on halobutyl elastomeric by substitution, wherein the halobutyl elastomeric is included
Isoolefin monomer and at least one C4 to C14 multi-olefin monomers derived from least one C4 to C7
Repeat unit, the halobutyl elastomeric has allyl halide site.CN201210332453.5
A kind of method for preparing butyl rubber solution, comprises the following steps：Butyl rubber micelle aqueous mixtures are led to
Cross vibratory sieve dehydration；Micelle aqueous mixtures after dehydration derived above are dissolved in the alkane as solvent
And/or in cycloalkane, obtain aqueous glue；Aqueous glue obtained above is dehydrated by gravitational settling
One-level dehydration is carried out, aqueous glue is obtained；And aqueous glue obtained above is carried out by electric dehydration
Two grades of dehydrations, obtain butyl rubber solution of the water content less than 0.3 weight %, molten based on the butyl rubber
The gross weight of liquid.
CN201310521634.7 discloses a kind of based on imidazole type ion liquid/dimethyl sulfoxide (DMSO) system system
The method of standby collagen microfibrils.With animal's leather as raw material, with imidazole type ion liquid/dimethyl sulfoxide (DMSO)
Mixture is inorganic agent, and suspension is obtained after being processed at 90~130 DEG C, is precipitated through high speed centrifugation
Thing, by obtained sediment undergoes washing and freeze-drying, you can obtain collagen microfibrils.
A kind of 2- of CN201210196327.1 (((1H- benzos [d] imidazoles -2- bases) methyl) (1- benzyl -1H- benzos [d]
Imidazoles -2- bases) amino) acetic acid preparation method, more specifically to 2- (((1H- benzos [d] imidazoles -2-
Base) methyl) (1- benzyl -1H- benzo [d] imidazoles -2- bases) amino) centre that is related in acetic acid and synthesis
The preparation method of body compound.What the present invention was provided prepares a kind of new double benzene with potential source biomolecule activity
And imidazole amino acid compound 2- (((1H- benzos [d] imidazoles -2- bases) methyl) (1- benzyl -1H- benzo [d] miaows
Azoles -2- bases) amino) acetic acid (VII) method, for the synthesis of similar compound provides thinking, while
For its follow-up pharmacological research provides raw material.A kind of chiral pyrrolidine functions of CN201310533308.8
Imidazole salts of change and its preparation method and application.The imidazole salts of described chiral pyrrolidine functionalization are brominations
1- [2- (S)-(pyrrolidinyl) methyl] -3- phenacyl imidazoles hydrobromates.Its preparation method：With
Natural amino acid L-PROLINE be initiation material, through Boc acylations, carboxylic acid reduction, hydroxysulfonamide,
The nucleophilic displacement of fluorine of imidazoles anion, the quaternization of halogenated hydrocarbons and go Boc protect etc. multistep it is routinely organic
Synthetic reaction is obtained the imidazole salts of chiral pyrrolidine functionalization.A kind of swimming high of CN201310253407.0 is saturating
Power cathode electrophoresis dope emulsion resin and preparation method thereof, described emulsion resin is by three component structures
Into：Modified epoxy, accounts for the 50-70% of emulsion resin solid weight；Closing is isocyanate terminated, accounts for
The 20-40% of emulsion resin solid weight；Imidazole salt compound, accounts for the 10- of emulsion resin solid weight
20%, sequentially add modified epoxy resin, close isocyanate terminated, imidazole salt compound and molten
Agent, after being warming up to 60 DEG C, after stirring and being incubated 30 minutes, adds organic acid to neutralize, at 60 DEG C
Stirring 1 hour, deionized water is slowly added under stirring, is continued to stir 30 minutes after adding and is made
Obtain resin emulsion.
It is by 6 to 22 from α that EP2285851 (B1), JP5409774 (B2) are referred to from a polymer
The olefin unit of individual carbon atom is formed has formula A-B block copolymers and polymer unit, B be by
Isobutene units are basically formed, and are related to their preparation method, its lubricant oil composite for using and including
The lubricant compositions of this block copolymer.The resin combination product that JP2000319461 (A) is obtained
With excellent impact resistance, the polymer includes transparent acrylic resin and isobutene polymer, contains
There is the copolymer of ethene and alpha-olefin.KR20010049193 (A) provides one kind and contains polyvinyl
And preparation method thereof, it can be used as a kind of replacement α polyisobutene and poly-1-olefin and can be used for
Production lubricating oil.
Ullmanns Encyclopedia of Industrial Chemistry (A volumes, page 23,1993) institute
The slurry process stated with dichloromethane as solvent, with alchlor as initiator, while adding a small amount of water or chlorine
Change hydrogen, make isobutene that cationic copolymerization occur with isoprene and react, the polymerisation of above-mentioned slurry process
Temperature requirement is at -100 DEG C.The solvent method butyl rubber of foreign literature report is that isobutene exists with isoprene
Dicyandiamide solution is that chloroethanes, isopentane and catalyst system and catalyzing are common by cation under ethyl aluminum dichloride etc. is catalyzed
The product that polymerization is obtained.The CN1253141A of Beyer Co., Ltd proposes that one kind prepares molecular weight and is at least 40
The method of ten thousand butyl rubber polymer, makes temperature of C4~C14 multi-olefin monomers at about -100 DEG C~+50 DEG C
In the range of degree, first contacted in the presence of aliphatic diluent and a kind of catalyst mixture, the catalysis
Agent composition includes major amount of aluminum dialkyl monohalide, has the disadvantage that the control of polymerisation has limitation
Property.Canadian Patent 1019095 uses aluminum alkyl halide, such as ethyl sesquichloride, co-catalyst
It is water or hydrogen sulfide, and solvent isopentane.WO0185810, CN01143371.X report utilization
Aluminum alkyl halide and alcoxyl aluminium, used as aided initiating, one kind that aliphatic hydrocarbon makees solvent prepares fourth to alcoxyl aluminium
The improved method of base rubber.RU2071481 is reported and is utilized aluminum alkyl halide and water using solwution method
The initiation system of butyl rubber is prepared, and using monoethanolamine, diethanol amine, triethanolamine as the 3rd group
Point, the consumption of monoethanolamine is the 25-75% of copolymerization catalyst consumption, is favorably improved monomer conversion
And reaction temperature.
The content of the invention
Present invention aim at the preparation for providing a kind of isobutene, isoprene and ring-alkylated styrenes polymer
Method, obtained polymer has excellent processing characteristics and damping capacity.
The preparation method of a kind of isobutene, isoprene and ring-alkylated styrenes polymer, comprising following
Step：(1) first alkylstyrene monomers are dissolved in ionic liquid；(2) under normal pressure, by polymeric kettle
By nitrogen displacement three times, -50~-100 DEG C are then cooled to, add chloromethanes as solvent, added
Isobutene, isoprene and step (1) gained ring-alkylated styrenes solution, stir 10~30min, add
Aniline, then divides 3~5 addition initiators, reacts 30min~3h, adds terminator terminating reaction,
Solution after termination is through flashing, filtering and dry finished product.
Ring-alkylated styrenes of the present invention is o-methyl styrene, a methyl styrene, to methylbenzene second
Alkene, adjacent ethyl styrene, an ethyl styrene, p -ethyl-styrene, adjacent propylstyrene, a propyl group
Styrene, it is the one kind in the styrene of C4~C10, preferably o-methyl-benzene to propylstyrene or side chain
Ethene；Consumption is 10~20g.
Ionic liquid of the present invention is imidazole salts, such as double (the fluoroforms of 1- butyl -3- methylimidazoles
Sulphonyl) inferior amine salt, 1- octyl group -3- methylimidazoles double (fluoroform sulphonyl) inferior amine salt, 1- hexyl -3- first
One kind or its mixture in double (fluoroform sulphonyl) inferior amine salts of base imidazoles, consumption is 10~20g.
Isobutene consumption of the present invention is 200~400g.
Isoprene consumption of the present invention is 1~2g.
Preferably -70~-100 DEG C of polymeric reaction temperature of the present invention.
Chloromethanes of the present invention, is monochloro methane or dichloromethane；Consumption is 500~1000g.
Aniline consumption of the present invention is 1~2g.
Initiator of the present invention is the initiation system comprising main initiator and aided initiating.
The preparation method of initiation system of the present invention is：In the glove box of anhydrous and oxygen-free, in-
At 20~-80 DEG C, main initiator is added in flask, be subsequently adding aided initiating, aided initiating and main initiation
Agent mass ratio is 8~2:1, shake up 8~20min of ageing.
Main initiator of the present invention is tertiary butyl chloride (t-BuCl), HCL gases, dicumyl chlorine
(DCC) one kind in, consumption is 1~5g.
Aided initiating of the present invention is the complex compound of alkyl aluminum compound and ether, the alkyl aluminum chemical combination
Thing is tert-butyl group aluminium chloride, isobutyl aluminium dichloride, ethyl aluminum dichloride, the aluminium of ethylaluminum two etc., excellent
Select isobutyl aluminium dichloride；The ether is aliphatic ether, cyclic ethers, crown ether etc., such as methyl ether, ethyl methyl ether, four
Hydrogen furans, phendioxin 5- crown ethers -5,4'- amino benzo -18- crown ethers -6 etc., preferably crown ether, alkyl calorize
Compound is complexed mass ratio 1 with ether：1~3.
The preparation method of aided initiating of the present invention is：In the glove box of anhydrous and oxygen-free, in-
At 20~-80 DEG C, shaken up during 0.5~30g ethers, 0.5~20g alkyl aluminum compounds are added into flask, be complexed
3~8min.
Terminator of the present invention is methyl alcohol, and consumption is 1~3g.
Polymer performance index obtained by the present invention：Polymer molecular weight reaches 50,000~150,000,
Molecular weight distribution is 2.0~4.0, and ring-alkylated styrenes molar content is more than 3%, vulcanization in copolymer
Glue tensile strength >=13MPa, glass transition temperature is≤- 50 DEG C, damping capacity：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 45 DEG C~-5 DEG C |
| tgδ≥0.3 | - 43 DEG C~-8 DEG C |
| tgδ≥0.5 | - 40 DEG C~-10 DEG C |
The beneficial effects of the invention are as follows：(1) prepare butyl rubber relative to current solwution method and with the addition of
Three component ring-alkylated styrenes, isobutene is linear polymeric polymer, alkylbenzene with the copolymerization of isoprene
The addition of ethene increased the rigid structure of molecule, therefore polymer had not only had good pliability but also had
Good rigidity；(2) addition of ring-alkylated styrenes is so that the processing characteristics of rubber more preferably, is first dissolved into
It is more easy to add in ionic liquid, in polymerization；Aniline is nucleophilic functional group, and its addition causes polymer
Molecular weight distribution is narrower, and processing characteristics is more stablized, and aniline is due to containing rigid structure, it plus
Enter to also improve the mechanical property of polymer；(3) initiator is added by several times, stable reaction, controllable；
Resulting polymers of the present invention are a kind of brand-new material, and polymer has preferable damping capacity.
Specific embodiment
The present invention is described further with reference to embodiments.It should be noted that following embodiments are not
Can as limiting the scope of the invention, any improvement made on the basis of the present invention all without prejudice to
Spirit of the invention.
Required medicine is commercially available industrial goods；
Polymer molecular weight is determined using gel permeation chromatography (GPC) method, using nuclear magnetic resonance spectroscopy
Ring-alkylated styrenes molar content in polymer is determined, tensile strength is surveyed according to GB GB/T528-1998
Examination, according to GB/T528-2009 standard testings, dynamic mechanical is by viscoelastic spectra for glass transition temperature
Instrument (DMA) is tested, and testing standard is GJB 981-1990.
Embodiment 1
(1) 10g o-methyl styrene monomers are first dissolved in 10g ionic liquid 1-butyl-3-methyl imidazoliums
In double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In anhydrous and oxygen-free
In glove box, under the conditions of -20 DEG C of temperature, 2g crown ethers are added in a flask, add 2g isobutyl groups
Al dichloride is complexed with crown ether, shakes up complexing 5min；The main initiator uncles of 1g are added in an other flask
Butyl chloride (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with crown ether is added to master
In initiator, ageing 10min is shaken up；(3) under normal pressure, by polymeric kettle by nitrogen displacement three times,
Then -50 DEG C are cooled to, it is solvent to add 500g chloromethanes, adds 200g isobutenes, 1g isoamyls
Diene and step (1) gained o-methyl styrene solution, add 1g aniline, then divide 3 times and add step
Suddenly (2) gained initiator, reacts 30min, adds 3g methyl alcohol terminating reactions, the solution warp after termination
Flash, filter and dry finished product.Polymer molecular weight is 60,000, and molecular weight distribution is 2.5,
O-methyl styrene molar content is 3.5% in copolymer, and vulcanizate tensile strength is 13.5MPa,
Glass transition temperature is -70 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 43 DEG C~-9 DEG C |
| tgδ≥0.3 | - 40 DEG C~-10 DEG C |
| tgδ≥0.5 | - 38 DEG C~-11 DEG C |
Comparative example 1
Experiment condition does not add 10g o-methyl styrenes simply with embodiment 1, as a result for：Polymer
Molecular weight is 30,000, and molecular weight distribution is 3.5, and vulcanizate tensile strength is 9MPa, glass transition
Temperature is -45 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 30 DEG C~-2 DEG C |
| tgδ≥0.3 | - 28 DEG C~-5 DEG C |
| tgδ≥0.5 | - 35 DEG C~-8 DEG C |
Embodiment 2
(1) methyl styrene monomer between 10g is first dissolved in 10g ionic liquid 1-butyl-3-methyl imidazoliums
In double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In anhydrous and oxygen-free
In glove box, under the conditions of -40 DEG C of temperature, 10g crown ethers are added in a flask, add 5g isobutyl groups
Al dichloride is complexed with crown ether, shakes up complexing 8min；The main initiator uncles of 5g are added in an other flask
Butyl chloride (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with crown ether is added to master
In initiator, ageing 20min is shaken up；(3) at ambient pressure, by polymeric kettle by nitrogen displacement three
It is secondary, -50 DEG C are then cooled to, it is solvent to add 1000g chloromethanes, adds 400g isobutenes, 2g
Methyl styrene solution between isoprene and step (1) gained, adds 2g aniline, then divides 4 times and adds
Enter step (2) gained initiator, react 3h, add 3g methyl alcohol terminating reactions, the solution after termination
Through flashing, filtering and dry finished product.Polymer molecular weight is 80,000, and molecular weight distribution is
2.3, methyl styrene molar content is 3.2% in the middle of copolymer, and vulcanizate tensile strength is
15MPa, glass transition temperature is -70 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 45 DEG C~-5 DEG C |
| tgδ≥0.3 | - 43 DEG C~-9 DEG C |
| tgδ≥0.5 | - 40 DEG C~-10 DEG C |
Comparative example 2
Experiment condition does not add methyl styrene between 10g simply with embodiment 2, as a result for：Polymer
Molecular weight is 50,000, and molecular weight distribution is 3.2, and vulcanizate tensile strength is 10MPa, glass transition
Temperature is -40 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 35 DEG C~-5 DEG C |
| tgδ≥0.3 | - 33 DEG C~-9 DEG C |
| tgδ≥0.5 | - 30 DEG C~-10 DEG C |
Embodiment 3
(1) 20g p-methylstyrene monomers are first dissolved in 10g ionic liquid 1- octyl group -3- methylimidazoles
In double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In anhydrous and oxygen-free
In glove box, under the conditions of -60 DEG C of temperature, 7.5g crown ethers are added in a flask, add 2.5g isobutyls
Base al dichloride is complexed with crown ether, shakes up complexing 4min；The main initiators of 5g are added in an other flask
Tertiary butyl chloride (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with crown ether is added to
In main initiator, ageing 8min is shaken up；(3) at ambient pressure, by polymeric kettle by nitrogen displacement three
It is secondary, be then cooled to -100 DEG C, it is solvent to add 1000g chloromethanes, add 400g isobutenes,
1g isoprene and step (1) gained p-methylstyrene solution, add 2g aniline, then divide 5
Secondary addition step (2) gained initiator, reacts 2h, 2g methyl alcohol terminating reactions is added, after termination
Solution is through flashing, filtering and dry finished product.Polymer molecular weight is 150,000, molecular weight distribution
It is 2.2, p-methylstyrene molar content is 3.1% in copolymer, vulcanizate tensile strength is
16.3MPa, glass transition temperature is -69 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 45 DEG C~-5 DEG C |
| tgδ≥0.3 | - 43 DEG C~-8 DEG C |
| tgδ≥0.5 | - 39 DEG C~-10 DEG C |
Comparative example 3
Experiment condition does not add 20g p-methylstyrenes simply with embodiment 3, as a result for：Polymer
Molecular weight is 90,000, and molecular weight distribution is 3.9.Vulcanizate tensile strength is 10MPa, glass transition
Temperature is -50 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 27 DEG C~0 DEG C |
| tgδ≥0.3 | - 25 DEG C~-5 DEG C |
| tgδ≥0.5 | - 20 DEG C~-10 DEG C |
Embodiment 4
(1) 10g o-methyl styrene monomers are first dissolved in 10g ionic liquid 1- octyl group -3- methylimidazoles
Double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In the hand of anhydrous and oxygen-free
In casing, under the conditions of -80 DEG C of temperature, 6g crown ethers are added in a flask, add 2g isobutyl groups two
Aluminium chloride is complexed with crown ether, shakes up complexing 8min；The 1g tertiary fourths of main initiator are added in an other flask
Base chlorine (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with crown ether is added to master and draws
In hair agent, ageing 8min is shaken up；(3) at ambient pressure, by polymeric kettle by nitrogen displacement three times, so
After be cooled to -100 DEG C, it is solvent to add 1000g chloromethanes, adds 200g isobutenes, 1g isoamyls
Diene and step (1) gained o-methyl styrene solution, add 2g aniline, then divide 3 times and add step
Suddenly (2) gained initiator, reacts 1h, adds 3g methyl alcohol terminating reactions, and the solution after termination is through dodging
Steam, filter and dry finished product.Polymer molecular weight is 150,000, and molecular weight distribution is 2.3, altogether
O-methyl styrene molar content is 3.5% in polymers, and vulcanizate tensile strength is 15.8MPa, glass
Glass conversion temperature is -73 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 43 DEG C~-5 DEG C |
| tgδ≥0.3 | - 40 DEG C~-9 DEG C |
| tgδ≥0.5 | - 39 DEG C~-10 DEG C |
Comparative example 4
Experiment condition does not add 10g o-methyl styrenes simply with embodiment 4, as a result for：Polymer
Molecular weight is 90,000, and molecular weight distribution is 4.5, and vulcanizate tensile strength is 8MPa, glass transition
Temperature is -46 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 25 DEG C~5 DEG C |
| tgδ≥0.3 | - 23 DEG C~2 DEG C |
| tgδ≥0.5 | - 20 DEG C~-0 DEG C |
Embodiment 5
(1) methyl styrene monomer between 20g is first dissolved in 10g ionic liquid 1- octyl group -3- methylimidazoles
Double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In the hand of anhydrous and oxygen-free
In casing, under the conditions of -30 DEG C of temperature, 3.75g crown ethers are added in a flask, add 1.25g isobutyls
Base al dichloride is complexed with crown ether, shakes up complexing 6min；The main initiators of 1g are added in an other flask
Tertiary butyl chloride (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with crown ether is added to
In main initiator, ageing 15min is shaken up；(3) at ambient pressure, by polymeric kettle by nitrogen displacement three
It is secondary, -70 DEG C are then cooled to, it is solvent to add 500g chloromethanes, adds 400g isobutenes, 2g
Methyl styrene solution between isoprene and step (1) gained, adds 1g aniline, then divides 4 times and adds
Enter step (2) gained initiator, react 2h, add 2g methyl alcohol terminating reactions, the solution after termination
Through flashing, filtering and dry finished product.Polymer molecular weight is 100,000, and molecular weight distribution is
2.3, methyl styrene molar content is 3.4% in the middle of copolymer, and vulcanizate tensile strength is
16.1MPa, glass transition temperature is -65 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 44 DEG C~-5 DEG C |
| tgδ≥0.3 | - 43 DEG C~-8 DEG C |
| tgδ≥0.5 | - 39 DEG C~-10 DEG C |
Comparative example 5
Experiment condition does not add 1g aniline simply with embodiment 5, as a result for：Polymer molecular weight is
90,000, molecular weight distribution is 3.8, vulcanizate tensile strength be 10.3MPa, glass transition temperature for-
50 DEG C, damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 25 DEG C~-5 DEG C |
| tgδ≥0.3 | - 23 DEG C~-8 DEG C |
| tgδ≥0.5 | - 20 DEG C~-10 DEG C |
Embodiment 6
(1) 20g p-methylstyrene monomers are first dissolved in 10g ionic liquid 1- octyl group -3- methylimidazoles
Double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In the hand of anhydrous and oxygen-free
In casing, under the conditions of -50 DEG C of temperature, 15g crown ethers are added in a flask, add 15g isobutyl groups
Al dichloride is complexed with crown ether, shakes up complexing 8min；The main initiator uncles of 5g are added in an other flask
Butyl chloride (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with ether is added to master and draws
In hair agent, ageing 20min is shaken up；(3) at ambient pressure, by polymeric kettle by nitrogen displacement three times,
Then -90 DEG C are cooled to, it is solvent to add 1000g chloromethanes, adds 400g isobutenes, 2g isoamyls
Diene and step (1) gained p-methylstyrene solution, add 2g aniline, then divide 5 times and add step
Suddenly (2) gained initiator, reacts 1h, adds 3g methyl alcohol terminating reactions, and the solution after termination is through dodging
Steam, filter and dry finished product.Polymer molecular weight is 140,000, and molecular weight distribution is 2.2, altogether
P-methylstyrene molar content is 3.3% in polymers, and vulcanizate tensile strength is 14.8MPa, glass
Glass conversion temperature is -75 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 45 DEG C~-8 DEG C |
| tgδ≥0.3 | - 43 DEG C~-10 DEG C |
| tgδ≥0.5 | - 40 DEG C~-12 DEG C |
Comparative example 6
Experiment condition does not add 2g aniline simply with embodiment 6, as a result for：Polymer molecular weight is
130,000, molecular weight distribution is 4.9, and vulcanizate tensile strength is 10.3MPa, glass transition temperature
It it is -55 DEG C, damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 27 DEG C~-5 DEG C |
| tgδ≥0.3 | - 25 DEG C~-7 DEG C |
| tgδ≥0.5 | - 24 DEG C~-10 DEG C |
Embodiment 7
(1) 15g o-methyl styrene monomers are first dissolved in 10g ionic liquid 1- octyl group -3- methylimidazoles
Double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In the hand of anhydrous and oxygen-free
In casing, under the conditions of -70 DEG C of temperature, 15g crown ethers are added in a flask, add 5g isobutyl groups two
Aluminium chloride is complexed with crown ether, shakes up complexing 5min；The 5g tertiary fourths of main initiator are added in an other flask
Base chlorine (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with crown ether is added to master and draws
In hair agent, ageing 10min is shaken up；(3) at ambient pressure, by polymeric kettle by nitrogen displacement three times,
Then -100 DEG C are cooled to, it is solvent to add 500g chloromethanes, adds 300g isobutenes, 1.5g different
Pentadiene and step (1) gained o-methyl styrene solution, add 2g aniline, then divide 3 additions
Step (2) gained initiator, reacts 3h, adds 2g methyl alcohol terminating reactions, the solution warp after termination
Flash, filter and dry finished product.Polymer molecular weight is 150,000, and molecular weight distribution is 2.0,
O-methyl styrene molar content is 3.3% in copolymer, and vulcanizate tensile strength is 16.8MPa,
Glass transition temperature is -72 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 45 DEG C~-6 DEG C |
| tgδ≥0.3 | - 43 DEG C~-8 DEG C |
| tgδ≥0.5 | - 40 DEG C~-11 DEG C |
Comparative example 7
Experiment condition does not add 2g aniline simply with embodiment 7, as a result for：Polymer molecular weight is
130,000, molecular weight distribution is 4.6, and vulcanizate tensile strength is 10.6MPa, and glass transition temperature is
- 48 DEG C, damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 30 DEG C~-5 DEG C |
| tgδ≥0.3 | - 28 DEG C~-7 DEG C |
| tgδ≥0.5 | - 25 DEG C~-10 DEG C |
Embodiment 8
(1) methyl styrene monomer between 15g is first dissolved in 10g ionic liquid 1- octyl group -3- methylimidazoles
Double (fluoroform sulphonyl) inferior amine salts；(2) preparation of initiator complex：In the hand of anhydrous and oxygen-free
In casing, under the conditions of -60 DEG C of temperature, 14g crown ethers are added in a flask, add 7g isobutyl groups two
Aluminium chloride is complexed with crown ether, shakes up complexing 8min；The 3g tertiary fourths of main initiator are added in an other flask
Base chlorine (t-BuCl)；Then the isobutyl aluminium dichloride aided initiating that will be complexed with crown ether is added to master and draws
In hair agent, ageing 10min is shaken up；(3) at ambient pressure, by polymeric kettle by nitrogen displacement three times,
Then -50 DEG C are cooled to, it is solvent to add 500g chloromethanes, adds 400g isobutenes, 1.5g different
Methyl styrene solution between pentadiene and step (1) gained, adds 1g aniline, then divides 3 additions
Step (2) gained initiator, reacts 3h, adds 1g methyl alcohol terminating reactions, the solution warp after termination
Flash, filter and dry finished product.Polymer molecular weight is 60,000, and molecular weight distribution is 2.5,
Methyl styrene molar content is 3.2% in the middle of copolymer, and vulcanizate tensile strength is 16.4MPa,
Glass transition temperature is -69 DEG C, and damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 45 DEG C~-5 DEG C |
| tgδ≥0.3 | - 43 DEG C~-8 DEG C |
| tgδ≥0.5 | - 40 DEG C~-10 DEG C |
Comparative example 8
Experiment condition does not add 1g aniline simply with embodiment 8, as a result for：Polymer molecular weight is
50,000, molecular weight distribution is 3.8, vulcanizate tensile strength be 12.3MPa, glass transition temperature for-
52 DEG C, damping capacity is：
| Tg δ value scopes | Damping temperature range DEG C |
| tgδ≥0.2 | - 33 DEG C~-5 DEG C |
| tgδ≥0.3 | - 30 DEG C~-8 DEG C |
| tgδ≥0.5 | - 28 DEG C~-10 DEG C |
Certainly, the present invention can also have other various embodiments, without departing substantially from spiritual and its essence of the invention
In the case of, those of ordinary skill in the art can make various corresponding changes and deformation according to the present invention,
But these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (18)
1. a kind of preparation method of isobutene, isoprene and ring-alkylated styrenes polymer, its feature exists
In comprising the steps of：(1) first alkylstyrene monomers are dissolved in ionic liquid；(2) normal pressure
Under, by polymeric kettle by nitrogen displacement three times, -50~-100 DEG C are then cooled to, add chloromethanes conduct
Solvent, adds isobutene, isoprene and step (1) gained ring-alkylated styrenes ionic liquid molten
Liquid, stirs 10~30min, adds aniline, then divides 3~5 addition initiators, polymerisation
30min~3h, adds terminator terminating reaction, and the solution after termination is through flash distillation, filtering and dries prepared
Finished product.
2. method according to claim 1, it is characterised in that the ring-alkylated styrenes is adjacent first
Base styrene, a methyl styrene, p-methylstyrene, adjacent ethyl styrene, an ethyl styrene,
P -ethyl-styrene, adjacent propylstyrene, a propylstyrene, to propylstyrene or side chain it is
One kind in the styrene of C4~C10, consumption is 10~20g.
3. method according to claim 1, it is characterised in that described ionic liquid, is miaow
Azoles salt, such as 1- butyl -3- methylimidazoles double (fluoroform sulphonyl) inferior amine salt, 1- octyl group -3- methyl miaows
Double (fluoroform sulphonyl) inferior amine salts of azoles, double (fluoroform sulphonyl) imines of 1- hexyl -3- methylimidazoles
One or more in salt, consumption is 10~20g.
4. method according to claim 1, it is characterised in that the isobutene consumption is
200~400g.
5. method according to claim 1, it is characterised in that the isoprene consumption is
1~2g.
6. method according to claim 1, it is characterised in that the polymeric reaction temperature for-
70~-100 DEG C.
7. method according to claim 1, it is characterised in that the chloromethanes is monochloro methane
Or dichloromethane, consumption is 500~1000g.
8. method according to claim 1, it is characterised in that the aniline consumption is 1~2g.
9. method according to claim 1, it is characterised in that the terminator is methyl alcohol, uses
It is 1~3g to measure.
10. method according to claim 1, it is characterised in that the initiator is to draw comprising master
Hair agent and the initiation system of aided initiating.
11. methods according to claim 10, it is characterised in that the preparation of the initiation system
Method is：In the glove box of anhydrous and oxygen-free, in adding main initiator at -20~-80 DEG C, in flask,
Aided initiating is subsequently adding, aided initiating is 8~2 with main initiator quality ratio:1, shake up ageing
8~20min.
12. methods according to claim 10, it is characterised in that described main initiator is uncle
One kind in butyl chloride, HCL gases, dicumyl chlorine, consumption is 1~5g.
13. methods according to claim 10, it is characterised in that described aided initiating is alkane
The complex compound of base aluminium compound and ether, alkyl aluminum compound is complexed mass ratio 1 with ether：1~3.
14. methods according to claim 13, it is characterised in that the system of described aided initiating
Preparation Method is：In the glove box of anhydrous and oxygen-free, at -20~-80 DEG C, by 0.5~30g ethers,
0.5~20g alkyl aluminum compounds shake up in adding flask, are complexed 3~8min.
15. methods according to claim 13, it is characterised in that the alkyl aluminum compound is
One kind in tert-butyl group aluminium chloride, isobutyl aluminium dichloride, ethyl aluminum dichloride, the aluminium of ethylaluminum two.
16. methods according to claim 13, it is characterised in that the alkyl aluminum compound is
Isobutyl aluminium dichloride.
17. methods according to claim 13, it is characterised in that the ether is methyl ether, first and second
One kind in ether, tetrahydrofuran, phendioxin 5- crown ethers -5,4'- amino benzo -18- crown ethers -6.
18. methods according to claim 13, it is characterised in that the ether is crown ether.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110483671A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of butyl rubber and its production technology |
| CN110734516A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing isobutylene and isoprene polymer from ionic liquid modified fluorinated graphene |
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| CN1034006A (en) * | 1987-12-28 | 1989-07-19 | 波利萨有限公司 | Improved rubber combination |
| CN101357960A (en) * | 2008-06-30 | 2009-02-04 | 江苏圣杰实业有限公司 | Resource-saving preparation method of isoolefine and conjugated diene copolymer |
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| CN1034006A (en) * | 1987-12-28 | 1989-07-19 | 波利萨有限公司 | Improved rubber combination |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734516A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing isobutylene and isoprene polymer from ionic liquid modified fluorinated graphene |
| CN110734516B (en) * | 2018-07-19 | 2022-03-01 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing isobutylene and isoprene polymer by using ionic liquid modified fluorinated graphene |
| CN110483671A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of butyl rubber and its production technology |
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