CN110105498B - Mono-silicon-hydrogen functionalized star polymer suitable for hydrosilylation chemical reaction and preparation method thereof - Google Patents
Mono-silicon-hydrogen functionalized star polymer suitable for hydrosilylation chemical reaction and preparation method thereof Download PDFInfo
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- CN110105498B CN110105498B CN201910407333.9A CN201910407333A CN110105498B CN 110105498 B CN110105498 B CN 110105498B CN 201910407333 A CN201910407333 A CN 201910407333A CN 110105498 B CN110105498 B CN 110105498B
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- Prior art keywords
- hydrogen
- polymer
- monosilicon
- hydrosilylation
- phenyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 138
- 239000001257 hydrogen Substances 0.000 title claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 59
- 238000006459 hydrosilylation reaction Methods 0.000 title claims description 41
- 238000006243 chemical reaction Methods 0.000 title claims description 23
- 238000005285 chemical preparation method Methods 0.000 title description 2
- 239000002243 precursor Substances 0.000 claims abstract description 70
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- 238000005859 coupling reaction Methods 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 230000008878 coupling Effects 0.000 claims abstract description 17
- 238000010168 coupling process Methods 0.000 claims abstract description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 86
- -1 alkyl lithium Chemical compound 0.000 claims description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 31
- 229920001195 polyisoprene Polymers 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- CUESDWVNRYJUMY-UHFFFAOYSA-N dimethyl-[4-(1-phenylethenyl)phenyl]silane Chemical compound C[SiH](C1=CC=C(C=C1)C(=C)C1=CC=CC=C1)C CUESDWVNRYJUMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010559 graft polymerization reaction Methods 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 150000004754 hydrosilicons Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- HQPVOBKJDNOIRC-UHFFFAOYSA-N C(C)(C)(C)[SiH](C1=CC=C(C=C1)C(=C)C1=CC=CC=C1)C(C)(C)C Chemical compound C(C)(C)(C)[SiH](C1=CC=C(C=C1)C(=C)C1=CC=CC=C1)C(C)(C)C HQPVOBKJDNOIRC-UHFFFAOYSA-N 0.000 claims description 2
- DDWWAAYHCNEHLJ-UHFFFAOYSA-N C(CC)[SiH](C1=CC=C(C=C1)C(=C)C1=CC=CC=C1)CCC Chemical compound C(CC)[SiH](C1=CC=C(C=C1)C(=C)C1=CC=CC=C1)CCC DDWWAAYHCNEHLJ-UHFFFAOYSA-N 0.000 claims description 2
- HREAUFZNXNJVDJ-UHFFFAOYSA-N CC(C)[SiH](C1=CC=C(C=C1)C(=C)C2=CC=CC=C2)C(C)C Chemical compound CC(C)[SiH](C1=CC=C(C=C1)C(=C)C2=CC=CC=C2)C(C)C HREAUFZNXNJVDJ-UHFFFAOYSA-N 0.000 claims description 2
- WOJAQKBPJPAFJO-UHFFFAOYSA-N CC[SiH](CC)C1=CC=C(C=C1)C(=C)C2=CC=CC=C2 Chemical compound CC[SiH](CC)C1=CC=C(C=C1)C(=C)C2=CC=CC=C2 WOJAQKBPJPAFJO-UHFFFAOYSA-N 0.000 claims description 2
- FNLWMLUALQWLQV-UHFFFAOYSA-N C[SiH](C)C1=CC=CC(=C1)C(=C)C2=CC=CC=C2 Chemical compound C[SiH](C)C1=CC=CC(=C1)C(=C)C2=CC=CC=C2 FNLWMLUALQWLQV-UHFFFAOYSA-N 0.000 claims description 2
- WESOVJLBLVINQM-UHFFFAOYSA-N C[SiH](C1=C(C=CC=C1)C(=C)C1=CC=CC=C1)C Chemical compound C[SiH](C1=C(C=CC=C1)C(=C)C1=CC=CC=C1)C WESOVJLBLVINQM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 238000012545 processing Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 description 28
- 229910000077 silane Inorganic materials 0.000 description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 12
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 238000007306 functionalization reaction Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229910052990 silicon hydride Inorganic materials 0.000 description 3
- RFBNEESZDICKQI-UHFFFAOYSA-N 1-bromo-4-(1-phenylethenyl)benzene Chemical group C1=CC(Br)=CC=C1C(=C)C1=CC=CC=C1 RFBNEESZDICKQI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The monosilicon-hydrogen functionalized star polymer is prepared by coupling linear precursor polymer chains with specific sequence structures and microstructures, wherein the linear precursor is a binary or multicomponent copolymer of monosilicon-hydrogen DPE derivative monomers and general monomers, and the number average molecular weight of the functionalized star polymer is 1 multiplied by 104～800×104g/mol. The linear precursor with a preset structure can be obtained by changing the feeding ratio of the monosilicon hydrogen DPE derivative monomer and the general monomer and using different types and equivalent regulators, and the linear precursor is coupled into star polymers with different arm numbers by adding a coupling agent. The invention realizes the introduction of the silicon-hydrogen functional groups into the star polymer and effectively controls the number of the silicon-hydrogen functional groups, and compared with the linear polymer with the same molecular weight, the star polymer has the characteristics of smaller dynamic mechanical size in solution and low solution and bulk viscosityHas important significance for processing polymers.
Description
Technical Field
The invention belongs to the technical field of synthesis and preparation of high molecular materials, and particularly relates to monosubstituted 1, 1' -Diphenylethylene (DPE) derivatives for high-efficiency hydrosilylation, which are characterized in that qualitative, quantitative and positioning introduction of a hydrosilylation functional group into a star polymer is realized through the monosilicon functionalization DPE derivatives.
Background
The linear, comb and star are three typical polymer chain topologies, the linear polymer is equivalent to the comb polymer with extremely short side chain length, and the star polymer is equivalent to the comb polymer with extremely short main chain length. With the continuous development of polymerization technology, the possibility is provided for synthesizing various polymers with non-linear structures, star polymers have unique structures and functions different from linear analogues thereof, and the synthesis and performance research of the star polymers are attracted extensive attention in recent years. The research of the star polymer has important reference value on the relationship between the structure and the performance of the high molecular weight polymer and the influence of branching on the overall performance of a polymer solution or a solution. Moreover, star polymers have smaller dynamic mechanical dimensions in solution and lower solution and bulk viscosities than linear analogs of the same molecular weight, so star polymers have better processability and mechanical properties than linear polymers and can be used for applications such as: fluid improvers, pressure sensitive adhesives, etc., which are of great importance for the processing of polymers. The star polymer has only one branch point, is the simplest branched polymer in the branched chain arrangement situation, is an ideal model polymer for understanding the solution property and rheological behavior theory of the branched polymer, and has important academic and industrial values for scientists and polymer workers.
Star polymers are largely classified into two types from the synthetic method: the nucleus-first and arm-second method and the nucleus-first and arm-second method. (1) Nucleus-first and arm-second methods: the star polymer with determined arm number and arm length can be obtained by initiating monomer polymerization through a polyfunctional initiator, wherein the arm number is determined by the number of initiating groups, and the arm length is determined by the ratio of the initial monomer to the initiator concentration. (2) Arm first and nucleus second method: the polymer is prepared by synthesizing monofunctional linear macromolecules (i.e., "arms" of star polymers, which are usually living polymer macromolecular chains prepared by living polymerization methods), and adding a polyfunctional coupling agent for reaction. Chlorosilanes or divinylbenzene are generally used as coupling agents. In recent years, in order to synthesize a polymer having more vivid properties, polymer scientists have never stopped exploring the relationship between the structure and properties of a polymer to provide the desired properties to the polymer, and functionalizing a polymer is one of the most effective means for providing the desired properties to the polymer. Star polymers have the advantage of being more efficient, both in-chain and at-chain end, due to their unique structure. The introduction of the silicon-hydrogen functional group into the star polymer has important significance for the post-functionalization of the star polymer, and the existence of the silicon-hydrogen bond provides more convenient conditions for the post-functionalization and efficient grafting reaction of the star polymer because the silicon-hydrogen bond and the unsaturated double bond or triple bond can both generate efficient silicon-hydrogen addition reaction. The star polymer is synthesized by a living polymerization method, so that the linear precursors of the star polymer have the same molecular weight and structure, and the functionalized polymer in the star chain synthesized by an anionic polymerization method can meet the requirements of definite qualitative, accurate quantitative and precise positioning to the greatest extent. At present, the university of the great physics has reported that a hydrosilation functional group is introduced into a linear polymer, the linear polymer is copolymerized with styrene by using a monosilation DPE derivative, and the polymer is subjected to hydrosilylation polymerization to form a linear comb-shaped polymer. [1 ] Huang W, Ma H, Han L, et al, synthetic polymerization of Styrene and Dimethyl- [4- (1-phenylvinyl) phenyl ] silane (DPE-SiH) [ J ] Macromolecules, 2018: acs. macromolecular polymerization. 8b00666 ]
The introduction of a silicon-hydrogen functional group into a star polymer is rarely reported, and the existence of the silicon-hydrogen functional group brings great convenience to the post-functionalization and graft polymerization of the silicon-hydrogen functionalized star polymer. The DPE derivative comonomer containing the hydrosilation functional group has a weak electron-withdrawing group, so that the DPE derivative has high polymerization activity in anionic copolymerization, and the DPE derivative has a functional site for high-efficiency hydrosilation addition and has the advantage of high-efficiency functionalization. The silicon-hydrogen functionalized star polymer can improve the efficiency of subsequent functionalization and graft polymerization due to the quantitative and positioning introduction of silicon-hydrogen functional groups, and improves the service performance of the star polymer.
Disclosure of Invention
The invention aims to provide a mono-silicon-hydrogen functionalized star polymer suitable for a silicon-hydrogen addition chemical reaction, which has the characteristics of high branching, high molecular weight and narrow distribution, and simultaneously has excellent physical and mechanical properties and excellent processing performance. Another object of the present invention is to provide a simple and efficient process for preparing the above-mentioned hydrosilylated star polymer.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the monosilicon-hydrogen functionalized star polymer is formed by coupling linear precursor polymer chains with specific sequence structures and microstructures, and the linear precursor polymer chain or the chain end of the linear precursor polymer chain contains not less than 2 monosilicon-hydrogen DPE derivative units. The linear precursor polymer chain is prepared from monosilicon-hydrogen DPE derivative monomer and general monomer (phenylethylene)Alkene, butadiene or isoprene, etc.), and the mass fraction of the monosilicon hydrogen DPE derivative in the copolymer is 2-78%. The number average molecular weight of the monosilicon hydrogen functionalized star polymer is 1 multiplied by 104~800×104 g/mol。
The star polymer is obtained by coupling a functional linear copolymer containing polysiloxane hydrogen in a chain by using a coupling agent, the arm number range is 3-80, and the single-arm number average molecular weight is 0.2 multiplied by 104~10×104g/mol. The linear precursor polymer chain of the hydrosilation functionalized star polymer with a preset structure can be obtained by changing the feeding proportion of the monosilation DPE derivative monomer and a general monomer (styrene, butadiene or isoprene, etc.) and using different types and equivalents of polarity regulators, and then the linear precursor polymer chain is coupled into the monosilation functionalized star polymer with different arm numbers and suitable for the hydrosilation chemical reaction by adding different types and equivalents of coupling agents. Namely, the invention can lead the linear precursor polymer chain to present different microstructures and sequence structures by changing the type and the dosage of the polarity regulator, wherein the content of 3,4 structures is 0-45 percent based on 100 percent of the microstructures in the linear precursor polymer chain,cisthe content of-1, 4 structure is 30-80%,transthe content of the-1, 4 structure is 10-60%.
The general monomer is styrene, butadiene or isoprene.
The monosilicon hydrogen DPE derivative monomer is a 1,1 '-diphenylethylene derivative monomer containing a single hydrosilicon hydrogen functional group, and the hydrosilicon hydrogen functional group of the monosilicon hydrogen DPE derivative unit can be connected with para position, meta position or ortho position of phenyl in 1, 1' -diphenylethylene; the hydrosilyl functional group is selected from a functional group with a structure of-SiH (R) R ', R and R ' are selected from methyl, ethyl, propyl, isopropyl, tert-butyl and phenyl, and R ' can be the same or different. The hydrosilation functionalized 1, 1' -diphenylethylene derivative containing a single hydrosilation functional group is selected from one or a mixture of more of dimethyl- [4- (1-phenylvinyl) phenyl ] silane, dimethyl- [3- (1-phenylvinyl) phenyl ] silane, dimethyl- [2- (1-phenylvinyl) phenyl ] silane, diethyl- [4- (1-phenylvinyl) phenyl ] silane, dipropyl- [4- (1-phenylvinyl) phenyl ] silane, diisopropyl- [4- (1-phenylvinyl) phenyl ] silane and di-tert-butyl- [4- (1-phenylvinyl) phenyl ] silane. The monosilicohydroDPE derivative monomer is preferably selected from dimethyl- [4- (1-phenylvinyl) phenyl ] silane, the dimethylsilyl group may be in the para, meta or ortho position of the phenyl group in 1, 1' -diphenylethylene.
Each single silicon hydrogen DPE derivative unit in the star-shaped copolymer contains a silicon hydrogen bond, so the star-shaped copolymer synthesized by utilizing the 1, 1' -diphenylethylene derivative contains the silicon hydrogen bond, the silicon hydrogen bond in the copolymer can be utilized to carry out high-efficiency silicon hydrogen addition reaction with an unsaturated compound, wherein the unsaturated compound can be a functionalized micromolecule or an unsaturated copolymer, and the unsaturated compound with double bonds or triple bonds can be grafted on a linear precursor polymer chain of the star-shaped copolymer through high-efficiency silicon hydrogen addition click chemical reaction. The hydrosilylation reaction efficiency is generally more than 95 percent, and an unsaturated compound is connected to the same monosilicon DPE derivative unit in the star copolymer after the hydrosilylation reaction. That is, the star polymer chain contains a hydrosilation functional group suitable for high-efficiency hydrosilation, and can perform a hydrosilation reaction with an unsaturated compound: if the unsaturated compound is a functionalized small molecule, a required functional group can be introduced into the star copolymer, so that the star copolymer can be post-functionalized; if the unsaturated compound is a macromolecular chain, a macromolecular chain can be connected to each monosilicon hydrogen DPE derivative unit in the star-shaped copolymer chain to form a star-shaped comb-shaped polymer taking the linear precursor polymer chain of the star-shaped copolymer as a main chain and the unsaturated macromolecular chain as a side chain.
Compared with the reported synthesis method of the star polymer, the essential difference of the invention is that the comonomer monosilicon hydride DPE derivative used in the invention successfully introduces the hydrosilicon hydride functional group into the star polymer, thereby providing convenience for the post-functionalization and high-efficiency graft polymerization of the star polymer. The method comprises the following specific steps: under the protection of nitrogen or argon, adding an organic solvent and a monosilicon hydrogen DPE derivative monomer into a polymerization reaction bottle; adding an alkyl lithium initiator at the temperature of 20-45 ℃ to initiate for half an hour; and adding general monomers for copolymerization, adding coupling agents of different types and equivalent weight to couple the linear precursor polymer chains of the star polymer after the polymerization reaction is finished to obtain the mono-silicon-hydrogen functionalized star polymer with different arm numbers and suitable for the silicon-hydrogen addition chemical reaction, performing post-treatment on a polymer sample by adopting a traditional method, and analyzing the structure and the performance of a product after drying.
Determining the type and the dosage of a polarity regulator used in the precursor synthesis process according to the sequence structure and the microstructure of the precursor of the silicon-hydrogen functionalized star polymer: when no polarity regulator is added, the linear precursor is in a gradient structure, and the content of the copolymerized diene (butadiene or isoprene) 1,4 is higher; the linear precursor is in an alternating structure due to the use of the polarity regulator, and the linear precursor is in different microstructures due to different types of polarity additives, such as: high 3,4 content and highcisA content of-1, 4 or highertrans-1,4 content; the amount of polarity modifier used depends on the microstructure content of the diene in the copolymer or, in the case of copolymerization with the general monomer styrene, on the styrene block content. The purpose of selecting the polarity regulator is mainly to regulate and control the sequence structure of styrene, butadiene, isoprene and silicon hydride functionalized 1,1 '-diphenylethylene derivative binary copolymer in the precursor of the silicon hydride functionalized star polymer, regulate and control the distribution of the silicon hydride functionalized 1, 1' -diphenylethylene derivative in the linear precursor of the star polymer, and then regulate the content of a diene microstructure in the precursor.
The lithium alkyl initiator is selected from monofunctional lithium alkyl initiator or bifunctional lithium alkyl initiator, wherein the monofunctional lithium alkyl initiator is any initiator or mixture of several initiators disclosed in the prior art and can be used for butadiene, isoprene or styrene anion polymerization, and is generally selected from: one or a mixture of several monofunctional lithium initiators in RLi and TRLi, wherein R is a hydrocarbon group with 2-20 carbon atoms, R can be an alkane group or an aromatic hydrocarbon group, T is a metal atom or a nitrogen atom, is generally a metal element such as tin Sn, silicon Si, lead Pb, titanium Ti, germanium Ge and the like, and is preferably selected from the following: ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tin-containing or nitrogen atom-containing monofunctional lithium initiators, and the like.
The organic solvent is selected from one or a mixture of several hydrocarbon solvents in nonpolar aromatic hydrocarbon and nonpolar aliphatic hydrocarbon, and is generally selected from: benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons (e.g. mixed xylenes), mixed aliphatic hydrocarbons (e.g. raffinate), preferably from: benzene, toluene, hexane, cyclohexane.
The polarity regulator is selected from one or more of oxygen-containing, nitrogen-containing, sulfur-containing and phosphorus-containing polar compounds and metal alkoxide compounds, such as: (1) an oxygenate, typically selected from: diethyl ether, Tetrahydrofuran (THF), R1OCH2CH2OR2(wherein: R1、R2Is an alkyl group having 1 to 6 carbon atoms, R1、R2May be the same or different, with R1、R2The difference is preferably as follows: ethylene glycol dimethyl ether, ethylene glycol diethyl ether), R1OCH2CH2OCH2CH2OR2 (wherein: R1、R2Is an alkyl group having 1 to 6 carbon atoms, R1、R2May be the same or different, with R1、R2The difference is preferably as follows: diethylene glycol dimethyl ether, diethylene glycol dibutyl ether), crown ethers; (2) a nitrogen-containing compound, generally selected from: triethylamine, Tetramethylethylenediamine (TMEDA), dipiperidine ethane (DPE); (3) a phosphorus-containing compound, typically selected from hexamethylphosphoric triamide (HMPA); (4) the metal alkoxide compound is generally selected from the group consisting of ROMs, wherein: r is an alkyl group having 1 to 6 carbon atoms, O is an oxygen atom, M is metallic sodium (Na) or potassium (K), and is preferably selected from: potassium tert-butoxide, potassium tert-pentoxide, sodium 2, 3-dimethyltripentanolate (NaODP).
The coupling agent is selected from chromium complex coupling agent, silane coupling agent, titanate coupling agent, bimetallic coupling agent and lignin coupling agentAnd a tin coupling agent. Such as: (1) a chromium complex coupling agent, typically selected from the group consisting of metallic chromium complexes of unsaturated organic acids with trivalent chromium metal ions; (2) silane coupling agent: is generally selected from the structures RSiX3In the compound of (1), R is generally selected from amino, mercapto, vinyl, epoxy, cyano, methacryloxy and the like, and X is generally selected from hydrolyzable alkoxy groups such as methoxy, ethoxy and the like.
Under the protection of argon, 20 ml of solvent toluene and 0.676 g of monosilicon-functionalized star-shaped copolymer suitable for hydrosilylation click chemistry reaction are sequentially added into a polymerization reactor which is dried and deaerated, a grafted macromolecular chain adopts polyisoprene blocked by alkynyl, and the feeding ratio of the alkynyl to a silicon-hydrogen bond is 1.1: 1 adding 108.56 g of grafted macromolecular chain, adding a Kanst catalyst, and carrying out graft polymerization to obtain a star-shaped comb-shaped polymer.
The invention contains the monosilicon-hydrogen functionalized star polymer suitable for the hydrosilylation chemical reaction, and on one hand, the invention realizes the sequence control of the copolymerization unit in the linear precursor of the star copolymer and the control of the microstructure content based on the specific activity of the monosilicon-hydrogen DPE derivative. On the other hand, each monosilicon hydrogen DPE derivative unit has a functional site, and the multifunctional site grafting of the star-shaped copolymer can be realized. The mono-silicon-hydrogen functionalized star polymer suitable for the silicon-hydrogen addition chemical reaction contains silicon-hydrogen bonds which can carry out efficient silicon-hydrogen addition reaction with unsaturated compounds, so that the silicon-hydrogen functionalized star polymer is efficiently subjected to post-functionalization and graft polymerization, and the silicon-hydrogen addition efficiency is generally over 95 percent, so that the number of arms after grafting is basically equal to the number of silicon-hydrogen functional groups in the star copolymer, and a star-shaped comb-shaped polymer is formed.
The invention has the advantages that: the method adopts a comonomer (monosilicon DPE derivative) containing a single hydrosilicon functional group to prepare the hydrosilicon functionalized star macromolecules, and the star macromolecules are combined with the hydrosilylation reaction to form the star comb-shaped macromolecules, so the process flow is simple and efficient, and the cost is lower; the high molecular weight and narrow distribution effectively improve the physical and mechanical properties of the star polymer; meanwhile, the high-branching structure effectively improves the processing performance of the high-molecular-weight narrow-distribution silicon-hydrogen functionalized star polymer.
Detailed Description
The following examples are presented as further illustrations and are not intended to limit the scope of the claims. The copolymer composition sequence distribution and microstructure were analyzed by nuclear magnetic resonance spectroscopy, and the molecular weight and molecular weight distribution of the copolymer were analyzed by gel permeation chromatography.
Example 1
54.72 g of methyltriphenylphosphonium bromide were placed in a three-necked flask under argon protection and dissolved in 350 ml of tetrahydrofuran which was completely dried. 18.65 g of potassium tert-butoxide is dissolved in 200 ml of completely dry tetrahydrofuran and dropped into the tetrahydrofuran solution of triphenyl phosphonium bromide in a water bath at-20 ℃ to prepare wittig reagent, 25 g of 4-bromobenzoyl benzene is dissolved in 250 ml of completely dry tetrahydrofuran and dropped into the wittig reagent to react to form 4-bromodiphenylethylene. 34.12 g of dimethylchlorosilane were dissolved in 250 ml of tetrahydrofuran which was completely dried, and added dropwise to a flask containing 12.33 g of magnesium and a small amount of iodine to prepare a Grignard reagent. 22.2 g of 4-bromodiphenylethylene dissolved in completely dry tetrahydrofuran are slowly added dropwise to the Grignard reagent under argon protection and the tetrahydrofuran in solution is heated to reflux and reacts to form dimethyl- [4- (1-phenylvinyl) phenyl ] silane.
Example 2
Under the protection of argon, 20 ml of hexane solvent and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]4.347 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 2.0 kg/mol, and reacting for 30 min at the temperature of 20 ℃; isoprene (dimethyl- [4- (1-phenylvinyl) phenyl) is added]The molar ratio of silane to isoprene is equal to 1.0), coupling by adding 0.6g of divinylbenzene after the end of the polymerization, terminating the reaction by adding isopropanol, precipitating the reaction mixture in an excess of anhydrous ethanol, obtaining a polymerDrying in a vacuum oven to constant weight. The results of the product structure analysis are as follows: the isoprene content in the linear precursor molecular chain of the binary star copolymer is more than that of dimethyl- [4- (1-phenyl vinyl) phenyl]The content of silane is in a gradient structure; the number average molecular weight of the single arm is 2.0 kg/mol, and the molecular weight distribution is 1.03; the number average molecular weight of the star copolymer was 16.0 kg/mol, the molecular weight distribution was 1.06, and the number of arms of the star polymer was 8. The linear precursor of the star polymer is dimethyl- [4- (1-phenyl vinyl) phenyl ] in the total amount of 100 percent]35.9 percent of silane and 64.1 percent of isoprene. The 3, 4-polyisoprene content is 3.2 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 29.8%,cisthe 1, 4-polyisoprene content was 67.0%.
Example 3
Under the protection of argon, 20 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]4.40 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 100 kg/mol, and reacting for 30 min at the temperature of 45 ℃; isoprene (dimethyl- [4- (1-phenylvinyl) phenyl) is added]The molar ratio of silane to isoprene was equal to 1.0), coupling was carried out by adding 11.8 g of divinylbenzene after the end of the polymerization, termination by adding isopropanol after the end of the coupling, precipitation of the reaction mixture in excess absolute ethanol, and drying of the resulting polymer to constant weight in a vacuum oven. The results of the product structure analysis are as follows: the isoprene content in the linear precursor molecular chain of the binary star copolymer is more than that of dimethyl- [4- (1-phenyl vinyl) phenyl]The content of silane is in a gradient structure; the number average molecular weight of the single arm is 100.1 kg/mol, and the molecular weight distribution is 1.04; the number average molecular weight of the star copolymer was 7998.8 kg/mol, the molecular weight distribution was 1.09, and the number of arms of the star polymer was 80. The linear precursor of the star polymer is dimethyl- [4- (1-phenyl vinyl) phenyl ] in the total amount of 100 percent]The mass portion of the silane is 34.3 percent, and the mass portion of the isoprene is 65.7 percent. The 3, 4-polyisoprene content is 5.5 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 22.5%,cisthe 1, 4-polyisoprene content was 72.0%.
Example 4
Under the protection of argon, 20 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]4.4 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 3.5 kg/mol, and reacting for 30 min at the temperature of 30 ℃; and then, sequentially adding 25 mass parts of styrene and 75 mass parts of isoprene, reacting for 6 days, adding 3.5g of divinylbenzene for coupling, adding isopropanol to terminate the coupling reaction, precipitating the reaction mixture in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 mass percent, the molecular chain of the linear precursor of the ternary star-shaped copolymer contains 26.6 percent of styrene, 71.0 percent of isoprene and dimethyl- [4- (1-phenyl vinyl) phenyl]The silane content was 2.4%; the linear precursor has a number average molecular weight of 3.5 kg/mol, a molecular weight distribution of 1.05, a star copolymer number average molecular weight of 51.3 kg/mol, a molecular weight distribution of 1.09 and an arm number of 15, and the linear precursor terpolymer is dimethyl- [4- (1-phenylvinyl) phenyl ] terpolymer]Silane terminated, styrene and isoprene block structures. The 3, 4-polyisoprene content is 9.5 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 13.2%,cisthe 1, 4-polyisoprene content was 77.3%.
Example 5
Under the protection of argon, 20 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]4.4 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 3.5 kg/mol, and reacting for 30 min at the temperature of 30 ℃; and then, sequentially adding 25 mass percent of styrene, 75 mass percent of isoprene and 1.35 g of polarity regulator TMEDA, reacting for 5 days, adding 3.0 g of divinylbenzene for coupling, adding isopropanol for terminating the coupling reaction, precipitating the reaction mixture in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 mass percent, the molecular chain of the linear precursor of the ternary star-shaped copolymer contains 24.2 percent of styrene, 70.1 percent of isoprene and dimethyl- [4- (1-phenyl vinyl) phenyl]Having a silane content of5.7 percent; the number average molecular weight of the linear precursor is 3.6 kg/mol, the molecular weight distribution is 1.04, the number average molecular weight of the star copolymer is 30.5kg/mol, the molecular weight distribution is 1.08, the number of arms is 9, and the linear precursor terpolymer is dimethyl- [4- (1-phenyl vinyl) phenyl]Silane terminated, styrene and isoprene block structures. The 3, 4-polyisoprene content is 45.2 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 22.2%,cisthe 1, 4-polyisoprene content was 32.6%.
Example 6
Under the protection of argon, 200 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]130.5 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 11.1 kg/mol, and reacting for 30 min at the temperature of 30 ℃; and then sequentially adding 30.0 g of isoprene and 1.85 g of polarity regulator TMEDA, reacting for 5 days, adding 5.0 g of tetrachlorosilane for coupling, adding isopropanol to terminate the coupling reaction, precipitating the reaction mixture in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of mass fraction, the mass fraction of isoprene in the molecular chain of the linear precursor of the binary star-shaped copolymer is 21.8 percent, and the molecular chain is dimethyl- [4- (1-phenyl vinyl) phenyl]The mass fraction of silane is 78.2%; the number average molecular weight of the linear precursor is 11.1 kg/mol, the molecular weight distribution is 1.05, the number average molecular weight of the star copolymer is 32.9kg/mol, the molecular weight distribution is 1.08, the number of arms is 3, and the linear precursor terpolymer is dimethyl- [4- (1-phenyl vinyl) phenyl]Silane terminated, styrene and isoprene block structures. The 3, 4-polyisoprene content is 6.3 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 56.8%,cisthe 1, 4-polyisoprene content was 36.9%.
Example 7
Under the protection of argon, 200 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]130.0 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 11.0 kg/mol, and reacting for 30 min at the temperature of 30 ℃; then, 30.0 g and 3.05 g of isoprene were added in this orderAnd (3) adding 4.5 g of divinylbenzene into the regulator TMEDA after reacting for 5 days for coupling, adding isopropanol to terminate the coupling reaction after the coupling reaction is finished, precipitating the reaction mixture in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight. The results of the product structure analysis are as follows: the linear precursor number average molecular weight is 10.9 kg/mol, the molecular weight distribution is 1.04, the star copolymer number average molecular weight is 88.2 kg/mol, the molecular weight distribution is 1.08, the arm number is 8, and the linear precursor binary copolymer is in an alternating structure. Based on 100 percent of mass portion, the mass portion of isoprene in the molecular chain of the linear precursor of the binary star-shaped copolymer is 21.9 percent, and the molecular chain of the linear precursor of the binary star-shaped copolymer is dimethyl- [4- (1-phenyl vinyl) phenyl]The mass fraction of silane is 78.1%; the 3, 4-polyisoprene content is 6.5 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 15.2%,cisthe 1, 4-polyisoprene content was 78.3%.
Example 8
Under the protection of argon, 200 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]130.0 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 11.0 kg/mol, and reacting for 30 min at the temperature of 30 ℃; then adding 29.8 g of isoprene and 20.0 g of polarity regulator THF in sequence, reacting for 5 days, adding 3.8 g of divinylbenzene for coupling, adding isopropanol to terminate the coupling reaction, precipitating the reaction mixture in excessive absolute ethanol, and drying the obtained polymer in a vacuum oven to constant weight. The results of the product structure analysis are as follows: the linear precursor number average molecular weight is 11.1 kg/mol, the molecular weight distribution is 1.05, the star copolymer number average molecular weight is 112.3 kg/mol, the molecular weight distribution is 1.07, the arm number is 10, and the linear precursor binary copolymer is in an alternating structure. Based on 100 percent of mass portion, the mass portion of isoprene in the molecular chain of the linear precursor of the binary star-shaped copolymer is 22.7 percent, and the molecular chain of the linear precursor of the binary star-shaped copolymer is dimethyl- [4- (1-phenyl vinyl) phenyl]The mass fraction of silane is 77.3%; the 3, 4-polyisoprene content is 6.5 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 60.6%,cisthe 1, 4-polyisoprene content was 32.9%.
Example 9
Under the protection of argonAdding 200 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] into a polymerization reaction bottle which is dried and deaerated in sequence]129.6 g of silane, namely adding an initiator sec-butyl lithium according to the designed molecular weight of 11.0 kg/mol, and reacting for 30 min at the temperature of 30 ℃; then 29.9 g of isoprene and 22.1 g of potassium tert-butoxide as a polarity regulator are added in sequence, 5.3 g of divinylbenzene are added for coupling after 5 days of reaction, isopropanol is added for termination after the coupling reaction is finished, the reaction mixture is precipitated in excess absolute ethanol, and the obtained polymer is dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: the linear precursor number average molecular weight is 11.0 kg/mol, the molecular weight distribution is 1.04, the star copolymer number average molecular weight is 169.2 kg/mol, the molecular weight distribution is 1.06, the arm number is 15, and the linear precursor binary copolymer is in an alternating structure. Based on 100 percent of mass fraction, the mass fraction of isoprene in the molecular chain of the linear precursor of the binary star-shaped copolymer is 18.2 percent, and the molecular chain is dimethyl- [4- (1-phenyl vinyl) phenyl]The mass fraction of silane is 81.8%; the 3, 4-polyisoprene content is 5.3 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polyisoprene is 55.5%,cisthe 1, 4-polyisoprene content was 39.2%.
Example 10
Under the protection of argon, 200 ml of benzene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]129.0 g of silane, namely adding an initiator sec-butyl lithium according to the designed molecular weight of 11.0 kg/mol, and reacting for 30 min at the temperature of 30 ℃; then, 29.8 g of butadiene and 24.2 g of THF (polar regulator) were sequentially added, after 5 days of reaction, 4.0 g of divinylbenzene was added for coupling, after the coupling reaction was completed, isopropanol was added to terminate the coupling reaction, the reaction mixture was precipitated in excess anhydrous ethanol, and the obtained polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: the linear precursor number average molecular weight is 10.8 kg/mol, the molecular weight distribution is 1.04, the star copolymer number average molecular weight is 216.2 kg/mol, the molecular weight distribution is 1.05, the arm number is 20, and the linear precursor binary copolymer is in an alternating structure. Based on 100 percent of mass fraction, the mass fraction of butadiene in the molecular chain of the linear precursor of the binary star-shaped copolymer is 23.7 percent, and the molecular chain of the linear precursor of the binary star-shaped copolymer is dimethyl- [4- (1-phenyl vinyl) phenyl]The mass portion of the silane is76.3 percent; the 1, 2-polybutadiene content is 6.3% based on 100% of the butadiene microstructure,transthe content of 1, 4-polybutadiene is 50.2%,cisthe 1, 4-polybutadiene content was 43.5%.
Example 11
Under the protection of argon, adding 200 ml of cyclohexane solvent and 4.36 g of dimethyl- [4- (1-phenyl vinyl) phenyl ] silane into a polymerization reaction bottle which is dried and deaerated in sequence, adding sec-butyl lithium serving as an initiator into the polymerization reaction bottle according to the designed molecular weight of 2.0 kg/mol, and reacting for 30 min at the temperature of 30 ℃; then adding styrene (the molar ratio of dimethyl- [4- (1-phenyl vinyl) phenyl ] silane to the styrene is equal to 1.0) in sequence, adding 3.8 g of divinylbenzene for coupling after reacting for 5 days, adding isopropanol for terminating the coupling reaction, precipitating the reaction mixture in excessive absolute ethanol, and drying the obtained polymer in a vacuum oven to constant weight. The results of the product structure analysis are as follows: the linear precursor number average molecular weight is 2.1 kg/mol, the molecular weight distribution is 1.04, the star copolymer number average molecular weight is 10.6 kg/mol, the molecular weight distribution is 1.07, the arm number is 5, and the linear precursor binary copolymer is in a gradient structure. The weight portion of styrene in the molecular chain of the linear precursor of the binary star-shaped copolymer is 67.7 percent and the weight portion of dimethyl- [4- (1-phenyl vinyl) phenyl ] silane is 32.3 percent, calculated by 100 percent.
Example 12
Under the protection of argon, 20 ml of toluene and dimethyl- [4- (1-phenyl vinyl) phenyl ] are sequentially added into a polymerization reaction bottle which is dried and deaerated]4.35 g of silane, adding an initiator sec-butyl lithium according to the designed molecular weight of 2.0 kg/mol, and reacting for 30 min at the temperature of 30 ℃; isoprene (dimethyl- [4- (1-phenylvinyl) phenyl) is added]The molar ratio of silane to isoprene was equal to 1.0), 3.6 g of divinylbenzene were added for coupling after 5 days of reaction, isopropanol was added for termination after the coupling reaction was complete, the reaction mixture was precipitated in excess anhydrous ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: the linear precursor has a number average molecular weight of 2.1 kg/mol, a molecular weight distribution of 1.05, a star copolymer number average molecular weight of 44.9 kg/mol, a molecular weight distribution of 1.08, and an arm number of 21, and the linear precursor binary copolymer is in a gradient junctionAnd (5) forming. Based on 100 percent of mass fraction, the mass fraction of isoprene in the molecular chain of the linear precursor of the binary star-shaped copolymer is 65.2 percent, and the molecular chain is dimethyl- [4- (1-phenyl vinyl) phenyl]The mass fraction of silane is 34.8%; the 3, 4-polyisoprene content is 7.8 percent based on 100 percent of the isoprene microstructure,transthe content of 1, 4-polybutadiene is 25.6%,cisthe 1, 4-polybutadiene content was 66.6%.
Example 13
Under the protection of argon, 20 ml of solvent toluene and 0.676 g of monosilicon hydrogen functionalized star-shaped copolymer suitable for hydrosilylation click chemical reaction are sequentially added into a polymerization reactor subjected to drying and oxygen removal, a grafted macromolecular chain adopts polyisoprene blocked by alkynyl, and the feeding ratio of the alkynyl to the silicon hydrogen bond is 1.1: 1 adding 108.56 g of grafted macromolecular chain, adding a Kanst catalyst, and carrying out graft polymerization to obtain a star-shaped comb-shaped polymer. The results of the product structure analysis are as follows: the molecular weight of the polymer was 313.4X 104g/mol, the glass transition temperature of the polymer is-57 ℃, and the number of the grafting arms of the star-shaped comb-shaped polymer is basically close to the number of the silicon-hydrogen functional groups in the linear precursor of the polymer.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (9)
1. A monosilicon-functionalized star polymer suitable for a hydrosilylation chemical reaction is characterized in that: the mono-silicon-hydrogen functionalized star polymer is formed by coupling linear precursor polymer chains with specific sequence structures and microstructures, wherein the linear precursor polymer chain or the chain end contains not less than 2 mono-silicon-hydrogen DPE derivative units; the linear precursor polymer chain is a binary or multi-component copolymer of a monosilicon-hydrogen DPE derivative monomer and a general monomer, and the mass fraction of the monosilicon-hydrogen DPE derivative in the copolymer is 2-78%; the number average molecular weight of the monosilicon hydrogen functionalized star polymer is 1 multiplied by 104~800×104 g/mol；
Changing the feeding ratio of a monosilicon hydrogen DPE derivative monomer and a general monomer, using different types and equivalent of polarity regulators to obtain a linear precursor of the hydrosilicon hydrogen functionalized star polymer with a preset structure, and adding different types and equivalent of coupling agents to couple the linear precursor into the monosilicon hydrogen functionalized star polymer with different arm numbers and suitable for the hydrosilylation chemical reaction;
the general monomer is styrene, butadiene or isoprene;
the monosilicon hydrogen DPE derivative monomer is a 1,1 '-diphenylethylene derivative monomer containing a single hydrosilicon hydrogen functional group, and the hydrosilicon hydrogen functional group of the monosilicon hydrogen DPE derivative unit is connected with para position, meta position or ortho position of phenyl in 1, 1' -diphenylethylene; the hydrosilyl functional group is selected from a functional group with a structure of-SiH (R) R ', and R' are selected from methyl, ethyl, propyl, isopropyl, tert-butyl and phenyl;
the number of the arms is 3-80, and the number average molecular weight of the single arm is 0.2 multiplied by 104~10×104 g/mol;
The 1, 1' -diphenylethylene derivative containing a single hydrosilation functional group is selected from one or a mixture of more of dimethyl- [4- (1-phenylvinyl) phenyl ] silane, dimethyl- [3- (1-phenylvinyl) phenyl ] silane, dimethyl- [2- (1-phenylvinyl) phenyl ] silane, diethyl- [4- (1-phenylvinyl) phenyl ] silane, dipropyl- [4- (1-phenylvinyl) phenyl ] silane, diisopropyl- [4- (1-phenylvinyl) phenyl ] silane and di-tert-butyl- [4- (1-phenylvinyl) phenyl ] silane.
2. A class of monohydrosilylated star polymers suitable for use in hydrosilylation chemistry according to claim 1, wherein: the star polymer chain contains a hydrosilation functional group suitable for high-efficiency hydrosilation and performs a hydrosilation reaction with an unsaturated compound.
3. A class suitable for use in hydrosilylation chemistry according to claim 1 or 2A reacted monosilicon-hydrogen functionalized star polymer characterized by: when the universal monomer contains isoprene, the linear precursor polymer chain is made to have different microstructures and sequence structures by changing the type and the dosage of the polarity regulator, wherein the content of 3 and 4 structures is 0-45 percent based on 100 percent of the microstructures in the linear precursor polymer chain,cisthe content of-1, 4 structure is 30-80%,transthe content of the-1, 4 structure is 10-60%.
4. A preparation method of the mono-hydrosilylation functionalized star polymer suitable for hydrosilylation chemical reaction according to any claim 1 to 3, characterized by comprising the following steps: under the protection of nitrogen or argon, adding an organic solvent and a monosilicon hydrogen DPE derivative monomer into a polymerization reaction bottle; adding an alkyl lithium initiator at the temperature of 20-45 ℃ to initiate for half an hour; adding general monomers for copolymerization, adding coupling agents of different types and equivalent weight to couple the linear precursor polymers of the star polymers after the polymerization reaction is finished to obtain mono-silicon-hydrogen functionalized star polymers with different arm numbers and suitable for the hydrosilylation chemical reaction, then carrying out post-treatment on polymer samples by adopting a traditional method, and analyzing the structure and the performance of products after drying; and determining the type and the dosage of the polarity regulator used in the precursor synthesis process according to the sequence structure and the microstructure of the linear precursor polymer chain of the silicon-hydrogen functionalized star polymer.
5. The method of claim 4 for preparing mono-hydrosilylation functionalized star polymers suitable for use in hydrosilylation chemistry, wherein: the alkyl lithium initiator is selected from monofunctional alkyl lithium or bifunctional alkyl lithium initiator.
6. The method of claim 4 for preparing mono-hydrosilylation functionalized star polymers suitable for use in hydrosilylation chemistry, wherein: the polarity regulator is one or a mixture of several of tetrahydrofuran, tetramethyl ethylenediamine, potassium tert-butoxide and sodium 2, 3-dimethyl tripentanolate.
7. The method of claim 4 for preparing mono-hydrosilylation functionalized star polymers suitable for use in hydrosilylation chemistry, wherein: the coupling agent is one or a mixture of more of a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, a bimetallic coupling agent, a lignin coupling agent and a tin coupling agent.
8. The method of claim 4 for preparing mono-hydrosilylation functionalized star polymers suitable for use in hydrosilylation chemistry, wherein: the organic solvent is selected from one or a mixture of several organic solvents of benzene, toluene, hexane and cyclohexane.
9. A method of post-functionalizing the monosilicon-hydride functionalized star polymer of claim 3, characterized by: under the protection of argon, 20 ml of solvent toluene and 0.676 g of monosilicon-functionalized star polymer suitable for hydrosilylation click chemistry reaction are sequentially added into a polymerization reactor subjected to drying and oxygen removal, a grafted macromolecular chain adopts polyisoprene blocked by alkynyl, and the feeding ratio of the alkynyl to the silicon-hydrogen bond is 1.1: 1 adding 108.56 g of grafted macromolecular chain, adding a Kanst catalyst, and carrying out graft polymerization to obtain a star-shaped comb-shaped polymer.
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