CN1399657A - 新型环丙硅氧烷、新型硅氧烷聚合物和它们的制备方法 - Google Patents
新型环丙硅氧烷、新型硅氧烷聚合物和它们的制备方法 Download PDFInfo
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 16
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical class O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- -1 halo siloxanes Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004032 superbase Substances 0.000 claims description 5
- 150000007525 superbases Chemical class 0.000 claims description 5
- 229910003849 O-Si Inorganic materials 0.000 claims description 4
- 229910003872 O—Si Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006318 anionic polymer Polymers 0.000 claims description 2
- 229920000831 ionic polymer Polymers 0.000 claims description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 229910008051 Si-OH Inorganic materials 0.000 abstract description 4
- 229910006358 Si—OH Inorganic materials 0.000 abstract description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 3
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000005046 Chlorosilane Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000555268 Dendroides Species 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000569 multi-angle light scattering Methods 0.000 description 2
- NSRBCQCXZAYQHF-UHFFFAOYSA-N n-[[tert-butylimino-bis[[tris(dimethylamino)-$l^{5}-phosphanylidene]amino]-$l^{5}-phosphanyl]imino-bis(dimethylamino)-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)(N(C)C)=NP(=NC(C)(C)C)(N=P(N(C)C)(N(C)C)N(C)C)N=P(N(C)C)(N(C)C)N(C)C NSRBCQCXZAYQHF-UHFFFAOYSA-N 0.000 description 2
- 238000000710 polymer precipitation Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- OQCFWECOQNPQCG-UHFFFAOYSA-N 1,3,4,8-tetrahydropyrimido[4,5-c]oxazin-7-one Chemical compound C1CONC2=C1C=NC(=O)N2 OQCFWECOQNPQCG-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-MICDWDOJSA-N 1-deuteriopropan-2-one Chemical compound [2H]CC(C)=O CSCPPACGZOOCGX-MICDWDOJSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- DWZRSINBNVWODQ-UHFFFAOYSA-N C1(=CC=CC=C1)[SiH](C)C.[O] Chemical compound C1(=CC=CC=C1)[SiH](C)C.[O] DWZRSINBNVWODQ-UHFFFAOYSA-N 0.000 description 1
- HOPKHJSQWOIIQO-UHFFFAOYSA-N C[SiH2]C.[O] Chemical compound C[SiH2]C.[O] HOPKHJSQWOIIQO-UHFFFAOYSA-N 0.000 description 1
- UALZKYDLONOZNL-UHFFFAOYSA-N C[Si](N[Si](C)(C)C)(C)C.C[Si]([Si](C)(C)C)(C)C Chemical compound C[Si](N[Si](C)(C)C)(C)C.C[Si]([Si](C)(C)C)(C)C UALZKYDLONOZNL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
本发明涉及用具有官能团Si-OH的环丙硅氧烷的阴离子聚合制备超支化硅氧烷的方法,和用具有乙烯基封端官能团的环丙硅氧烷阳离子或阴离子聚合制备线性硅氧烷聚合物的方法。更进一步,本发明涉及用于制备上述聚合物的新型环丙硅氧烷。
Description
本发明涉及新型环丙硅氧烷、新型超支化或线性硅氧烷聚合物,以及它们的制备方法。
发明背景
本发明中所使用的公开出版物和其他材料阐述了发明背景,而且特别地提供了与实践有关的其他细节,引入本文作为参考。
有机硅树枝状和超支化聚合物是众所周知的。树枝状物核通常是由四烯丙基-或乙烯基硅烷制备的,然后通过氢化硅烷化反应(1,2)衍生得到的。另一方面,超支化聚碳硅烷常常是由乙烯基三(二甲基甲硅烷氧基)硅烷通过氢化硅烷化反应制备的。典型地,在副反应(3)中8~10mol%的起始物质发生环化。见图1。
没有几个超支化或树枝状聚硅氧烷的实例,例如聚合物,它的主链仅仅由-SiRR’-O-键组成。由Uchicda等(4)编写了可能是最重要的论文,描述了多步途径制备分子量约15,000g/mol的高规整第三代树枝状聚硅氧烷。见图2。
Rebrov(5)使用一种不同的手段,他让MeSiCl3与3当量的NaOSiMe(OEt)2发生反应。乙氧基然后通过与亚硫酰二氯反应定量地转化成氯。所得到的产物再与NaOSiMe(OEt)2进行处理,然后重复发生由Si-OEt向Si-Cl基团转化过程,得到收率>75%的第四代聚合物。见图3。
发明目的和发明概述
本发明的目的是提供通过具有官能团Si-OH的环丙硅氧烷的阴离子聚合制备超支化硅氧烷聚合物的方便方法,和通过具有乙烯基封端官能团的环丙硅氧烷的阳离子或阴离子聚合制备线性硅氧烷聚合物的方便方法。本发明的另外一个目的是提供对制备前述聚合物有用的新型环丙硅氧烷。
因此,根据一个目的,本发明涉及通式(I)的新型环丙硅氧烷,其中Y是OSi(R)2H、OSi(R)2OH或O-Si(R)2-OSi(R)2-CH=CH2,和R取代基可以相同或不同,任一R取代基选自苯基、1~6个碳原子的未被取代或取代烷基,其中视需要存在的取代基是苯基或一个或多个氟原子,条件是烷基链的α或β位不能被氟取代。
根据另外一个目的,本发明涉及制备超支化硅氧烷聚合物的方法,其中通式(II)的化合物在本体或在合适溶剂如THF中进行阴离子聚合,得到通式为(IIIa1,IIIa2,IIIa3)或(IIIb1,IIIb2,IIIIb3)的超支化聚合物,其中Y是OH或OSi(R)2OH,和R取代基可以相同或不同,任一R取代基选自苯基、1~6个碳原子的未被取代的或取代烷基,其中视需要存在的取代基是苯基或一个或多个氟原子,条件是烷基链的α或β位不能被氟取代。其中取代基R如上述所定义的,和其中IIIa1-a3中的每个Z是基团IIIa1-a3之一,以及IIIb1-b3中的每个Z是基团IIIb1-b3之一,或Z是封端基。所述封端基可以相同或不同,可以是由中和得到的氢,或由卤代硅烷或卤代硅氧烷例如氯代硅烷或氯代硅氧烷衍生的基团,其中所述卤代硅烷或者卤代硅氧烷可以承载官能或非官能基团。所述官能或非官能团的实例可以是所提及的氢、乙烯基、如上述所定义的取代基R、氨基、烷氧基或聚环氧烷。聚合物的封端也可以通过使用不同化合物的混合物实现。通过封端基的合适选择,聚合物表面可以希望的方式进行改性。
根据另一个目的,本发明涉及用于制备线性硅氧烷聚合物的方法,其中通式(IV)的化合物进行阳离子或阴离子聚合物得到具有通式(V)的线性聚合物,其中Y是O-Si(R)2-OSi(R)2-CH=CH2,和R取代基可以相同或不同,任一R取代基选自苯基、1~6个碳原子的未被取代的或取代烷基,其中视需要存在的取代基是苯基或一个或多个氟原子,条件是烷基链的α或β位不能被氟取代。其中取代基R与在化合物(IV)中的是相同的和m是3~9000。
本发明也涉及新型超支化或线性硅氧烷聚合物。
发明详述
根据优选的实施方案,在通式(I)的环丙硅氧烷中每个R取代基是相同的而且是1~4个碳原子的烷基。最优选地,每个R取代基是甲基。
Si-OH官能化环丙硅氧烷(化合物(II))的阴离子聚合可以在含有锂的碱存在下进行,例如烷基锂如正丁基锂或三苯基甲基锂,或二异丙基酰胺锂。可以在本体或在合适溶剂中进行聚合。可以作为合适溶剂的实例是所提到的THF。
替换地,阴离子聚合可以通过将Si-OH官能化的环丙硅氧烷接触催化量的超强碱如磷腈实现。特别有用的超强碱是磷腈碱P4-t-Bu-[1-叔丁基-4,4,4-三(二甲基氨基)-2,2-双〔三(二甲基氨基)正膦基亚基氨基〕-2λ5,4λ5-链状二(磷腈)]
线性硅氧烷聚合物的制备可以通过用酸如三氟甲磺酸引发的阳离子聚合或者通过用碱如二苯基硅烷醇二锂或四甲基硅氧烷二醇二锂引发的阴离子聚合来实现。
本发明将在下述非限定性实施例中的实验部分得到更详细的描述。
实验
光谱分析
1H、13C和29Si NMR谱是在以FT方式操作的Bruker AMX-500MHz分光镜上得到的。1H NMR谱是在5%w/v氯仿-d溶液中进行实验。丙酮-d6中的40%w/v溶液用于获得29Si和13C NMR谱。获得的13C NMR谱具有宽带质子偶联。用60秒延迟的翻转门偶联脉冲序列以获得29SiNMR谱。四甲基硅烷(TMS)用作1H、13C和29Si NMR谱的内标。
NaCl片上光滑膜的IR谱被记录在Perkin Elmer Spectrum2000FT-IR分光镜上。聚合物分子量分布的GPC分析在装配有折射指数检测器的Waters系统上实现的。用<5μ的二乙烯基苯交联的聚苯乙烯HR4和HR2堆积的两个7.8mm×300mm串联Styragel柱用于分析中。洗脱溶剂是流速为0.3ml/min的甲苯。保留时间用已知单分散聚苯乙烯标样进行校准。聚合物的TGA是在Shimadzu TGA-50仪器上测量的。程序升温为以4℃/min的速度从25℃升高到850℃。
聚合物的Tg是在Perkin-Elmer DSC-7上用DSC确定的。分析用程序升温开始于-150℃。温度以10℃/分钟的速度升高。光散射CPS/MALLS用Wyatt Dawn-DSP MALLS检测器进行,其插入到GPC柱和R410RI检测器中间。用Wyatt Astra系统分析数据。THF用作洗脱液。
所有反应是在氩气气氛下火焰烘干的玻璃器皿中进行的。
实施例1
1-二甲基甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷的制备
a)1,1-二氯代-1,3,3-三甲基二硅氧烷
1,3-二氢化四甲基二硅氧烷(1,3-Dihydridotetramethyldisiloxane)(57g,0.42mol)和甲基三氯代硅烷(96g,0.64mol)被放入200mL装配有用Teflon覆盖的磁搅拌棒并用橡胶隔膜密封的rb烧瓶中。在室温(RT)下将催化剂溶液(500μL)注入到烧瓶中。没有反应发生。干燥HCL气体慢慢鼓泡进入溶液。过剩压力通过扎入装填有燥石膏的干燥管中的注射器针排放。发生放热反应。10分钟后烧瓶中物质被加热到约35℃。持续加入气态HCl气体2小时。反应混合物通过装填有不锈钢鞍形物的50cm真空夹套塔进行蒸馏。收集一个馏分,33.6g(42%收率),沸点116℃。
1H NMRδ:0.32(d,6H,J=3Hz),0.84(s,3H),4.77(七重峰,1H,J=3Hz);13C NMRδ:-0.17,5.97;29Si NMRδ:-17.10(1Si),0.94(1Si).IRν:2966,2151,1414,1258,1088,904,797 cm-1.
b)四甲基二硅氧烷-1,3-二醇
通过二甲基二氯代硅烷(5)的控制水解制备该化合物。
c)1-二甲基甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷
室温(RT)下经过1小时,在30mL的Et2O中的1,1-二氯代-1,3,3-三甲基二硅氧烷(25.0g,0.13mol)和在30mL的Et2O中的四甲基二硅氧烷-1,3-二醇(22.0g,0.13mol)被一滴滴地加入到溶液Et3N(28.0g,0.28mol)和170mL的Et2O中。搅拌2小时后,反应混合物被过滤和用水、稀H3PO4溶液和饱和NaHCO3洗涤。经过无水MgSO4进行干燥、过滤,并在减压下通过蒸发去除挥发物。通过10cm真空夹套塔逐级蒸馏得到一个馏分,26.9g(72%的收率),沸点81℃(40mmHg)。
1H NMRδ:0.09(s,3H),0.12(s,6H),0.14(s,6H),0.20(d,6H,J=3Hz),4.75(七重峰,1H,J=3Hz).13C NMRδ:-3.11,0.52,0.72,0.82.29Si NMRδ:-56.20(1Si),-8.50(2Si),-5.72(1Si).IRν:2966,2907,2133,1406,1260,1089,1020,907,862,810,770,624 cm-1.
实施例2
1-(羟基二甲基甲硅烷氧基)-1,3,3,5,5-五甲基环丙硅氧烷
均相溶液是从实施例1得到的1-二甲基甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷(20.0g,70mmol)、250mL二噁烷和30mL蒸馏水形成的。室温下钯催化剂(10% Pd/C,0.5g)按照三等分部分加入到溶液中,而且系统允许反应12小时。当加入少量额外催化剂时不放出更多H2。过滤后通过蒸发去除挥发物,逐级蒸馏得到一个馏分:19.6g(66mmol,93%收率),沸点52℃(0.1mmHg)。
1H NMRδ:0.10(6H),0.11(3H),0.12(6H),0.15(6H),5.15(1H).13C NMRδ:-2.81,0.34,0.78,0.85.29Si NMRδ:-57.63(1Si),-12.45(1Si),-8.32(2Si).IRν:3339(br),2966,2907,1411,1262,1092,1023,880,867,809,764,624 cm-1.
实施例3
1-二甲基甲硅烷氧基-1-苯基-3,3,5,5-四甲基环丙硅氧烷
根据实施例1中描述的步骤由1-苯基-1,1-二氯代-3,3-二甲基二硅氧烷(22.0g,88mmol)、四甲基二硅氧烷-1,3-二醇(14.56g,88mmol)和Et3N(18.6g,184mmol)在210mL二乙醚中进行制备,13.02g(收率43%),沸点86℃(1mmHg)。
1H NMRδ:0.17(s,6H),0.24(s,6h),0.26(d,6H,J=2.5Hz),4.82(七重峰,1H,J=2.5Hz),7.42(m,3h),7.65(m,2H).13C NMRδ:0.80,0.98,1.23,128.42,130.86,133.73,134.30.19F NMRδ:29Si NMRδ:-70.00(1Si),-7.27(2Si),-3.90(1Si).IRν:2964,2133,1431,1261,1133,1084,1021,998,902,851,808,771,699,641 cm-1.
实施例4
1-(羟基二甲基甲硅烷氧基)-1-苯基-3,3,5,5-四甲基环丙硅氧烷
根据实施例2中描述的步骤由实施例2中的1-二甲基甲硅烷氧基-1-苯基-3,3,5,5-四甲基环丙硅氧烷(8.34g,24mmol)、蒸馏水(10mL),用0.4g 10% Pd/C催化进行制备,6.18g(收率71%),沸点94℃(0.2mmHg)。
1H NMRδ:0.13(s,6H),0.16(s,6H),0.23(s,6H),5.37(s,1H),7.41(m,3H),7.67(m,2H).13C NMRδ:0.62,0.90,1.10,128.31,130.72,134.38.29Si NMRδ:-71.73(1Si),-11.97(1Si),-7.35(2Si).IRν:3392,2964,1595,1431,1262,1133,1189,1020,998,879,852,808,745,717,699,641,593cm-1.
实施例5
3’-乙烯基-1’,1’,3’,3’-四甲基二甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷
室温下经过20分钟,将10mL的Et2O中的乙烯基二甲基氯代硅烷(4.0g,33mmol)滴加入在实施例2中制备的1-二甲基羟基甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷(4.85g,16mmol)溶液、60mL的Et2O和Et3N(4.0g,40mmol)中。5小时后,过滤反应,滤液用水、H3PO4的含水稀溶液和饱和NaHCO3洗涤,去除氯化三乙基铵,用无水MgSO4进行干燥并过滤。通过50℃/(0.15mmHg)下经过逐级蒸馏得到最终产物4.91g(0.13mol,收率79%),
1H NMRδ:0.09(s,6H),0.11(s,3H),0.13(s,6H),0.15(d,6H,J=0.5Hz),0.17(s,6H),5.76(dd,1H,J=21和4Hz),5.93(dd,1H,J=15和4Hz),6.14(dd,1H,J=21和15Hz).13C NMRδ:-2.73,0.36,0.77,0.93,1.07,132.08,139.69.29Si NMRδ:-58.11(1Si),-20.30(1Si),-8.40(2Si),-3.53(1Si).IRν:3052,2965,2906,1596,1408,1261,1068,1021,862,839,808,763,710,625cm-1.
实施例6
通过阳离子聚合制备线性硅氧烷聚合物
实施例5中的在250μL的1,1,2-三氯代三氟代乙烷中的3’-乙烯基-1’,1’,3’,3’-四甲基二甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷(1.0g,2.6mmol)冷却至-78℃,并将5μL的三氟甲磺酸注入到溶液中。当系统变得太粘而不能搅拌时,加入额外的1,1,2-三氯代三氟代乙烷(3×250μL)。0.5小时后加入20mg、0.12mmol六甲基二硅烷(hexamethyldisilazane)使反应淬灭,由Et2O/MeOH混合物中聚合物沉淀三次,并在真空下干燥12小时。在该方法中,得到0.48g聚合物(48%收率),
Mn/Mw=83,900/28,300.1HNMRδ:0.08-0.18(m,27H),5.75(dd,1H,J=20.5和4Hz),5.92(dd,1H,J=15和4Hz),6.13(dd,1H,J=20.5和15Hz).13C NMRδ:-2.04,-2.02,-0.39,1.11,1.15,1.18,1.20,1.23,1.28,131.96,139.57.29Si NMRδ:-67.17,-67.11,-21.93,-21.92,-21.84,-21.76,-21.75,-21.68,-21.04,-3.95,-3.94.IRν:3053,2964,2906,1596,1408,1261,1094,1030,956,839,799,756,707,518 cm-1.
实施例7
用阴离子聚合法制备线性硅氧烷聚合物
a)引发剂
在THF中通过用正丁基锂处理二苯基硅烷二醇制备二苯基硅烷醇二锂,苯乙烯用作引发剂(8)。
b)阴离子聚合
室温下将引发剂(20μL,10μmol)注入到实施例5中得到3’-乙烯基-1’,1’,3’,3’-四甲基二甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷(1.0g,2.6mmol)在250μL THF中的溶液中,24小时完成聚合,然后用乙烯基二甲基氯代硅烷(0.1g,0.8mmol)淬灭。用Et2O/MeOH将聚合物沉淀三次并在真空中干燥10小时,产物产量0.92g(收率92%),Mw/Mn=29,100/12,400。TGA:从425℃开始降解,530℃剩余90%物质,655℃时损失总重量的一半,850℃时还有45%的剩余物。
实施例8
使用超强碱通过阴离子聚合制备线性硅氧烷聚合物
室温下将超强碱(磷腈碱P4-t-Bu(在正己烷中1M)(2μL,2μmol)注入到在250μL THF中的3’-乙烯基-1’,1’,3’,3’-四甲基二甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷(1.0g,2.6mmol)的溶液中。0.5小时后,用二甲基乙烯基氯代硅烷(0.1g,0.8mmol)将反应淬灭,真空去除挥发物,反应产物是低粘度液体,Mw/Mn=8700/2100。
实施例9
通过阴离子聚合制备超支化聚合物
单体(1-二甲基羟基甲硅烷氧基-1,3,3,5,5-五甲基环丙硅氧烷)2.0g,6.7mmol和1.0mL的THF被冷却到-9℃,注入碱(P4-t-Bu)(8μL,8μmol)。4小时后,加入1mL的THF、Et3N(2mL,7.3mmol)和1mL乙烯基二甲基氯代硅烷,持续搅拌12小时,聚合物被萃取到六甲基二硅氧烷中,用NaCl水溶液洗涤并由THF/MeOH沉淀三次,产量2.47g(96%),
Mw/Mn=15400/5900.1H NMRδ:0.05-0.20(m,27H),5.74(dd,0.65H,J=20.5和4.5Hz),5.76(dd,0.35H,J=20.5和4.5Hz),5.91(dd,0.65H,J=14和4.5Hz),5.92(dd,0.35H,J=14和4.5Hz),6.13(dd,0.65H,J=20.5和14.5Hz),6.13(dd,0.35H,20.5和14.5Hz).13CNMRδ:-2.79,-2.11,0.25,0.36,0.75-1.23(m),131.84,131.97,139.27,139.49.29SiNMRδ:-67.27,067.20,-67.14,-67.06,-66.20,-66.14,-66.06,-22.05,-21.97,-21.89,-21.82,-21.80,-21.76,-21.74,-21.11,-8.55,-4.00,-3.66,-3.64.IRν:3053,2964,2906,1596,1408,1261,1093,1028,956,839,799,756,707,519 cm-1.
实施例10
由1-羟基-1,3,3,5,5-五甲基环丙硅氧烷、苯基二甲基甲硅烷氧基封端的超支化聚合物的制备
将THF(0.3mL)和磷腈碱P4-t-Bu溶液(10μL,Fluka ChemieAG)放入装配有Teflon覆盖的磁搅拌棒和用橡胶隔膜密封的试管中,冷却到-15℃,经过30分钟将五甲基环丙硅氧烷-1-醇(1.70g,7.57mmol)慢慢地加入进去。将系统在-15℃下反应5小时后室温下反应4天,然后加入Et3N(1.5mL,10.8mmol)、苯基二甲基氯代硅烷(1.5mL,9.07mmol)和3mLTHF以封端聚合物。24小时后,过滤溶液并去除铵盐。在真空下蒸发掉挥发物并将聚合物由Et2O/MeOH中沉淀三次,产量1.72g(63.3%)
Mw/Mn=32,020/11,320(GPC),Mw/Mn=62,980/13,240(光散射).Tg=-98℃,Tm=-56℃.1H NMRδ:0.13(m,15.8H),0.37(m,5.2H),7.29(s,2.6H),7.56(s,0.9H),7.59(s,0.8H).13C NMRδ:-2.01(m),0.80(m),1.20(m),127.97,129.57,129.60,133.21,133.27,133.29,139.41,139.44,139.64,139.68.29Si NMRδ:-67.78,-67.34,-67.25,-66.29,-65.86,-65.79,-21.73,-21.58,-21.53,-21.37,-21.34,-20.53,-8.29,-8.15,-2.25,-2.12,-1.76,-1.62.IRν:3091,3072,3053,3025,3012,2963,2905,1592,1488,1429,1412,1261,1120,1090,1027,999,857,831,800,755,726,699,668 cm-1.TGA:在437℃剩余95%,576℃剩余50%,600℃后剩余物为25%。
应该意识到的是本发明的方法可以用各种各样实施方案的形式引用,本发明中仅仅公开了几个。显然对于本领域专家来说还存在其他实施方案而且不背离本发明宗旨。因此所描述的实施方案是描述性的而并不能认为是限制性的。
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Claims (12)
2.根据权利要求1的化合物,其中通式(I)中R-取代基的每一个是相同的并且是1~4个碳原子的烷基。
3.根据权利要求2的化合物,其中每一个R-取代基都是甲基。
4.用于制备超支化硅氧烷聚合物的方法,其中通式(II)的化合物在本体或者在合适溶剂中进行阴离子聚合以得到具有通式(IIIa1,IIIa2,IIIa3)或者(IIIb1,IIIb2,IIIIb3)的超支化聚合物,其中Y是OH或OSi(R)2OH,和R取代基可以相同或不同,任一R取代基选自苯基、1~6个碳原子的未被取代的或取代烷基,其中任选的取代基是苯基或一个或多个氟原子,条件是烷基链的α或β位不能被氟取代,其中取代基R如上述所定义,和其中IIIa1-a3中的每个Z是基团IIIa1-a3之一,以及IIIb1-b3中的每个Z是基团IIIb1-b3之一,或Z是封端基,可以相同或者不同,并且是氢或由卤代硅烷或卤代硅氧烷衍生出来的基团,其中所述卤代硅烷或者卤代硅氧烷可以承载官能或非官能基团。
5.根据权利要求4的方法,其中化合物(II)用含锂的碱处理。
6.根据权利要求5的方法,其中含锂的碱是烷基锂如正丁基锂或者三苯基甲基锂或者二异丙基酰胺锂。
7.根据权利要求4的方法,其中化合物(II)用超强碱处理。
8.通式(IIIa1,IIIa2,IIIa3)或者(IIIb1,IIIb2,IIIb3)的聚合物衍生的超支化硅氧烷,其中取代基R和Z与权利要求4中所定义的相同。
10.根据权利要求9的方法,其中聚合是通过使用三氟甲磺酸而引发的阳离子聚合。
11.根据权利要求9的方法,其中聚合是通过使用二苯基硅氧烷醇二锂而引发的阴离子聚合。
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