WO2006102050A2 - Process for the production of monodisperse and narrow disperse monofunctional silicones - Google Patents
Process for the production of monodisperse and narrow disperse monofunctional silicones Download PDFInfo
- Publication number
- WO2006102050A2 WO2006102050A2 PCT/US2006/009666 US2006009666W WO2006102050A2 WO 2006102050 A2 WO2006102050 A2 WO 2006102050A2 US 2006009666 W US2006009666 W US 2006009666W WO 2006102050 A2 WO2006102050 A2 WO 2006102050A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- reacting
- monodisperse
- endgroup
- terminated polydimethylsiloxane
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 77
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229920001296 polysiloxane Polymers 0.000 title description 3
- -1 polydimethylsiloxane methacrylate Polymers 0.000 claims abstract description 99
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 62
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 61
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 56
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 27
- 150000001450 anions Chemical class 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 21
- 239000012454 non-polar solvent Substances 0.000 claims description 21
- 150000002118 epoxides Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 15
- 150000003254 radicals Chemical group 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 239000005046 Chlorosilane Substances 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 150000002576 ketones Chemical group 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- AIRGGFRDSLSIGU-UHFFFAOYSA-N (3-chloro-3-dimethylsilylpropyl) 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCC([SiH](C)C)Cl AIRGGFRDSLSIGU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003926 acrylamides Chemical class 0.000 claims description 3
- 150000001299 aldehydes Chemical group 0.000 claims description 3
- 150000002170 ethers Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical group ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- TURGQPDWYFJEDY-UHFFFAOYSA-N 1-hydroperoxypropane Chemical compound CCCOO TURGQPDWYFJEDY-UHFFFAOYSA-N 0.000 claims 5
- 238000005194 fractionation Methods 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 23
- 238000003786 synthesis reaction Methods 0.000 abstract description 23
- 238000000746 purification Methods 0.000 abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 238000013459 approach Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- 238000007142 ring opening reaction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011552 falling film Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 230000001902 propagating effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010936 aqueous wash Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- XYXCXCJKZRDVPU-UHFFFAOYSA-N hexane-1,2,3-triol Chemical compound CCCC(O)C(O)CO XYXCXCJKZRDVPU-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011995 wilkinson's catalyst Substances 0.000 description 2
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical compound [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(*)N(C)C Chemical compound CC(C)(*)N(C)C 0.000 description 1
- YNBJCOQSMZJEPG-UHFFFAOYSA-N CCOC(C)(C)N(C)C Chemical compound CCOC(C)(C)N(C)C YNBJCOQSMZJEPG-UHFFFAOYSA-N 0.000 description 1
- VBIJPDMYAMPTHA-UHFFFAOYSA-N C[Si]1(C)O[Si+](C)(C)O[Si+](C)(C)O1 Chemical compound C[Si]1(C)O[Si+](C)(C)O[Si+](C)(C)O1 VBIJPDMYAMPTHA-UHFFFAOYSA-N 0.000 description 1
- ABHZIJLNNJKTPJ-UHFFFAOYSA-N C[Si]1(C)O[Si+](C)(C)O[Si](C)(C)O1 Chemical compound C[Si]1(C)O[Si+](C)(C)O[Si](C)(C)O1 ABHZIJLNNJKTPJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000157855 Cinchona Species 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- UIEXFJVOIMVETD-UHFFFAOYSA-N P([O-])([O-])[O-].[Pt+3] Chemical class P([O-])([O-])[O-].[Pt+3] UIEXFJVOIMVETD-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- LDKSTCHEYCNPDS-UHFFFAOYSA-L carbon monoxide;dichloroplatinum Chemical compound O=C=[Pt](Cl)(Cl)=C=O LDKSTCHEYCNPDS-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical group C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012670 controlled anionic polymerization Methods 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical class C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method 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
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical class P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003410 quininyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- 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
-
- 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
- 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
-
- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08G77/32—Post-polymerisation treatment
- C08G77/36—Fractionation
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Definitions
- the present application relates to methods for the synthesis and purification of monodisperse and narrow disperse polymeric compositions of matter that comprise monofunctional polydimethylsiloxane derivatives (herein referred to as mPDMS).
- mPDMS polymers of this invention are of use in biomaterial and other applications.
- the mPDMS polymers of this invention are particularly useful in the manufacture of contact lenses.
- Methods for producing mPDMS polymers having higher molecular weights with a greater number of siloxane units have used anionic polymerization techniques and solvents such as tetrahydrofuran (THF), and mixtures of cyclohexane and benzene with THF.
- THF tetrahydrofuran
- This invention provides a general method for the synthesis and purification of free radical reactive, substituted and unsubstituted alkyl-terminated polydimethylsiloxane compositions for both monodisperse low molecular weight oligomers and higher molecular weight polymers with polydispersities approaching 1.
- the present invention relates to a method comprising the steps of: (a) reacting, in at least one non-polar solvent, hexamethylcyclotrisiloxane with a molar excess of or a salt of trialkylsilanol or at least one functionalized or unfunctionalized organometallic compound, such as an alkyl lithium compound of the formula RLi wherein R is an alkyl group of 1-8 carbon atoms to form a silanolate anion having mono or low dispersity.
- the silanolate anion may be further reacted with a molar excess of a chlorosilane compound of formula I:
- R 1 is selected from H, Cl to CS alkyl or substituted Cl to C8 alkyl, wherein said substituents include aprotic subtstituents, such as a protected hydroxyl group, free radical reactive groups and combinations thereof.
- silane terminated polydimethylsilxone compounds may be further reacted with (a) substituted or unsubstituted allyl alkyl (meth)acrylates to form substituted or unsubstituted alkyl terminated polydimethylsiloxanes, or (b) substituted epoxides, which then undergo a ring opening reaction to form substituted or unsubstituted alkyl terminated polydimethylsiloxanes.
- mPDMS derivatives are described herein, including “monodisperse” and “narrow disperse” free radical reactive, substituted or unsubstituted alkyl-terminated polydimethylsiloxanes, such as mono and narrow disperse hydroxy mPDMS propylglycerol (meth)acrylate compositions and mPDMS propyl (meth)acrylate compositions.
- mPDMS refers to monofunctional polydimethylsiloxanes.
- monodisperse refers to a siloxane polymer product in which at least about 98% of the polymer present has the same molecular weight.
- narrow disperse refers to a siloxane polymer product in which at least about 85%, at least about 90% of said siloxane polymer is the desired molecular weight.
- (meth)acrylate includes both acrylates and methacrylates.
- hexamethylcyclotrisiloxane (D 3 ) is reacted with a either functionalized or unfunctionalized organometallic compounds or a salt of trialkylsilanol such as those having the formula MOSiR 2 RsR 4 , wherein R 2 -R 4 are independently selected from alkyl groups having 1-8 carbon atoms, and M is an species capable of bearing a positive charge, such as metals and tetra alkyl ammonium ions.
- Suitable examples a salt of trialkylsilanol include tetrabutylammonium salt of trimethylsilanol.
- Suitable examples of functionalized or unfunctionalized organometallic compounds include alkyl lithium compound of the formula RLi wherein R is an alkyl group of 1-8 carbon atoms in the presence of at least one non-polar solvent.
- Suitable non-polar solvents include hydrocarbon liquids which do not contain an abstractable proton. Examples of non-polar solvents include pentane, cyclohexane, hexane, heptane, benzene, toluene, higher non-polar hydrocarbons, mixtures thereof and the like. In one embodiment the non-polar solvents include pentane, cyclohexane, hexane, mixtures thereof and the like. The use of non-polar solvents in the initiation stage of the ring opening reaction produces mono or narrow dispersed silanolate anion.
- Hexamethylcylcotrisiloxane is commercially available.
- the alkyl lithium compound is selected from nbutyl lithium or sec-butyl lithium.
- the hexamethylcyclotrisiloxane and alkyl lithium compound are used in a stiochiometric amount based upon the number of dimethylsiloxane repeating units which are desired in the final mPDMS derivative. So for example, if an mPDMS derivative having one dimethylsiloxane repeating unit is desired, the mole ratio of alkyl lithium compound to hexamethylcyclotrisiloxane used is about 1:1.1 to about 1:1.5.
- the ratio of alkyl lithium compound to hexamethylcyclotrisiloxane decreases.
- Other molar ratios may be calculated by those of skill in the art using the teachings of the present invention.
- the reaction is conducted at temperatures between about 5 to about 6O 0 C, and in some embodiments from about 5 to about 3O 0 C.
- the reaction is conducted for about 1 to 4 hours. Ambient pressure may be used.
- a polar chain propagating solvent such as THF 5 diethyl ether, dioxane, DMSO, DMF, hexamethylphosphortriamide, mixtures thereof and the like is added after the initial reaction is complete.
- THF, dioxane, DMSO or mixtures thereof is used as the polar chain propagating solvent
- the polar chain propagating solvent comprises THF.
- the polar chain propagating solvent is added under controlled conditions and the reaction is allowed to proceed for a period from about 2 to about 24 hours at a temperature between about 5 and 60 0 C, and in some embodiments from about 5 to about 30 0 C,
- the conversion of the hexamethylcyclotrisiloxane is measured via gas chromatographic analysis.
- R 1 is selected from H, Cl to C8 alkyl or substituted Cl to C8 alkyl, wherein said substituents include aprotic subtstituents, such as a protected hydroxyl group, free radical reactive groups and combinations thereof.
- free radical reactive group includes (meth)acrylates, styryls, vinyls, vinyl ethers, Cj-galkylacrylates, acrylamides, Q-ealkylacrylamides, N-vinyllactams, N- vinylamides, C 2- i 2 alkenyls, C 2-12 alkenylphenyls, C 2 -i 2 alkenylnaphthyls, or
- the free radical reactive groups include (meth)acrylates, acryloxys, (rneth)acrylarnides, the like and mixtures thereof.
- the free radical reactive group is a methacrylate or acrylate group.
- chlorosilane An excess of the chlorosilane is used. While any molar ratio of chlorosilane compound to silanolate anion may be used, ratios from about 1.1 : 1 to about 5 to 1 , and in some embodiments from about 1.1 : 1 to about 2 to 1 are used for reasons of economy.
- the reaction of the chlorosilane with the silanolate anion is exothermic. Accordingly, the reaction temperature is maintained by known means, such as controlled addition of the chlorosilane or decreasing the temperature of the reaction mixture prior to chlorosilane addition. This termination reaction may be conducted at temperatures below about 7O 0 C, and in some embodiments at temperatures between about O 0 C and 70 0 C for times from about 15 minutes to about 4 hours.
- the termination reaction produces the desired narrow or monodisperse substituted or unsubstituted alkyl-mPDMS derivatives.
- the chlorosilane is dimethylchlorosilane the termination reaction produces a silane terminated polydimethyl siloxane.
- the silane terminated PDMS can be purified before further reaction or may be used directly.
- Impurities may be removed by numerous methods, including, filtration of LiCl; evaporation of excess chlorodimethylsilane; washing of the residual material with aqueous base (dilute sodium bicarbonate) to remove residual HCl followed by aqueous wash; and drying (anhydrous sodium sulfate) and distillation (using falling film or wiped film evaporators or other distillation methods known to those skilled in the art) to remove water and any residual traces of D 3 or higher cyclics.
- any of a number of methods can be used, such as distillation, so long as the conditions selected, such as residence time, the number of plates used, vacuum and temperature are sufficient to provide a silane terminated PDMS having at least a narrow disperse molecular weight as defined herein.
- the silane terminated PDMS may be purified by evaporation of the chlorosilane followed by aqueous extraction (using aqueous base) of the LiCl and distillation as described above.
- the process of the present invention further comprises a hydrosilylation step.
- the silane terminated PDMS may then be reacted with an allyl (meth)acrylate or a substituted epoxide via a hydrosilylation reaction, such as that disclosed in US2006/0047134, the disclosures of which is incorporated in its entirety herein by reference.
- the allyl (meth)acrylate is used in a molar excess of about 10 to about 100% excess.
- Suitable allyl (meth)acrylates include allyl (meth)acrylate , allyloxyhydroxypropyl methacrylate and allyloxyhydroxypropylacrylate. It should be appreciated that allyl glycerol (meth)acrylate exist in equilibrium as mixtures of the primary and secondary alcohol. In any reaction disclosed herein, the equilibrium mixture of allyl glycerol (meth)acrylate maybe used.
- Suitable substituted epoxides include monos ⁇ bstituted epoxides having a terminal vinyl group. Specific examples include epoxides of formula III
- B is a group which can hydrogen bond with another moiety or a carboxylic acid derivative.
- B include heteroatoms, including O, S, N, P, and the like, carbonyl, alkylene having 1 to 6 carbon atoms which may be unsubstituted or substituted with hydroxy, amines, amides, ethers, esters, aldehydes, ketones, aromatics, alkyl groups and combinations thereof.
- B is O or a hydroxyl substituted alkyl group having 1-4 carbon atoms.
- a specific example of a substituted epoxide includes allyl glycidyl ether.
- Suitable hydrosilylation catalysts include metal halides, including chlorides, bromides and iodides of chromium, cobalt, nickel, germanium, zinc, tin, mercury, copper iron, ruthenium, platinum, antimony, bismuth, selenium and tellurium.
- platinum chloride-olefin complexes as described in USP 3516946 are useful.
- catalysts other than platinum compounds include RhCl(PPh 3 ) 3 , RhCl 3 , Rh/Al 2 O 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2 ⁇ 2H 2 O, NiCl 2 and TiCl 4 (Ph indicating a phenyl group).
- Rhodium-based catalyst such as Wilkinson's catalyst may also be used.
- the hydrosilylation catalyst is used in suitable amounts including between about 1 and about 500 ppm, and preferably about 5 and about lOOppm.
- the reaction is conducted under mild conditions, such as temperatures between about 0 to about 100 0 C, preferably between about 0° and about 60 0 C, and more preferably from about 5 to about 4O 0 C. It has been found that these reaction temperatures reduce by-products by an appreciable amount even if the time of reaction is increased. Pressure is not critical, and atmospheric pressure may be used. Reaction times of up to about 24 hours, preferably up to about 12 hours and more preferably between about 4 and about 12 hours may be used.
- the components may be mixed neat (without solvent) or in solvents, such as aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, mixtures thereof and the like.
- Suitable examples in each class include, aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, octane or higher saturated hydrocarbons; ether solvents such as ethyl ether, butyl ether and tetrahydrofuran; alcohols, such as isopropanol and ethanol, and halogenated hydrocarbon solvents such as trichloroethylene and mixtures thereof.
- aromatic hydrocarbon solvents such as benzene, toluene and xylene
- aliphatic hydrocarbon solvents such as pentane, hexane, octane or higher saturated hydrocarbons
- ether solvents such as ethyl ether, butyl ether and tetrahydrofuran
- alcohols such as isopropanol and ethanol
- halogenated hydrocarbon solvents such as trichloroethylene and
- the resulting alkyl epoxy -PDMS may be undergo an epoxide ring opening reaction under conditions disclosed in US Serial No. 10/862074.
- the substituted epoxide is reacted with at least one acrylic acid and at least one lithium salt of said acrylic acid.
- Suitable acrylic acids comprise between 1 and 4 carbon atoms.
- the acrylic acid is methacrylic acid.
- the reaction between the substituted epoxide and the acrylic acid may be equimolar, however, it maybe advantageous to add an excess of acrylic acid. Accordingly, the acrylic acid may be used in amounts between about 1 and about 3 moles of acrylic acid per mole of the epoxide.
- the lithium salts comprise lithium and at least one acrylic acid comprising between 1 and 4 carbon atoms, hi one embodiment the lithium salt is the Li salt of methacrylic acid.
- the lithium salt is added in an amount sufficient to catalyze the reaction, and preferably in an amount up to about 0.5 equivalents, based upon the epoxide.
- An inhibitor may also be included with the reactants. Any inhibitor which is capable of reducing the rate of polymerization may be used. Suitable inhibitors include sulfides, thiols, quinines, phenothiazine, sulfur, phenol and phenol derivatives, mixtures thereof and the like. Specific examples include, but are not limited to hydroquinone monomethyl ether, butylated hydroxytoluene, mixtures thereof and the like. The inhibitor may be added in an amount up to about 10,000 ppm, and preferably in an amount between about 1 and about 1,000 ppm.
- Inhibitors may also be used, appropriate amounts, in any of the other process steps disclosed herein including free radical reactive compounds.
- the epoxide ring opening reaction is conducted at elevated temperatures, preferably greater than about 60 0 C and more preferably between about 80 0 C and about 110 0 C. Suitable reaction times include up to about a day, in some embodiments between about 4 and about 20 hours, and in other embodiments between six hours and about 20 hours. It will be appreciated by those of skill in the art the temperature and reaction time are inversely proportional, and that higher reaction temperatures may allow for decreased reaction times and vice versa. However, in the process of the present invention it is desirable to run the reaction to or near completion (for example, greater than about 95% conversion of substituted epoxide, and preferably greater than about 98% conversion of substituted epoxide).
- substituted or unsubstituted alkyl-mPDMS derivatives which may be produced by the process of the present invention include mono-(3-methacryloxy-2- hydroxypropyloxy) ⁇ ropyl terminated, mono-butyl terminated polydimethylsiloxane and monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxanes.
- the distribution of average MW may be confirmed by gel permeation chromatography, NMR IH and 29Si) and mass spectral (MALDI-TOFS) analysis.
- the resulting narrow disperse product can be further purified under controlled temperature and vacuum conditions using fractional distillation methods such as packed column or multi-plate distillation, and other methods known in the art such as chromatography known to those skilled in the art.
- fractional distillation methods such as packed column or multi-plate distillation, and other methods known in the art such as chromatography known to those skilled in the art.
- chromatography known to those skilled in the art.
- the present invention has been described above. In order to illustrate the invention the following exemplary reaction schemes are included. These exemplary reaction descriptions do not limit the invention. They are meant only to suggest a method of practicing the invention. Those knowledgeable in the field of synthesis of silicone compounds as well as other specialties may find other methods of practicing the invention. However, those methods are deemed to be within the scope of this invention.
- the first step is the anionic ring opening reaction involving the ring opening of commercially available D 3 using a molar excess of an alkyllithium reagent such as n-butylLi or sec-butylLi (mole ratio OfBuLIiD 3 from about 1.1:1 to 2:1) in a nonpolar solvent such as cyclohexane or hexane at a temperature of between about 5 and about 6O 0 C for about 1 to about 4 hours) followed by termination of generated alkyldimethylsilanolate anion with an excess of chlorodimethylsilane (typically 1.1 - 5 times the amount of alkyllithium reagent used).
- an alkyllithium reagent such as n-butylLi or sec-butylLi (mole ratio OfBuLIiD 3 from about 1.1:1 to 2:1) in a nonpolar solvent such as cyclohexane or hexane at a temperature of between about 5 and about 6O
- the resulting reaction product can be purified by: filtration of LiCl; evaporation of excess chlorodimethylsilane; washing of the residual material with aqueous base (dilute sodium bicarbonate) to remove residual HCl followed by aqueous wash; and drying (anhydrous sodium sulfate) and distillation (using falling film or wiped film evaporators or other distillation methods known to those skilled in the art) to remove water and any residual traces OfD 3 or higher cyclics.
- the resulting product is the n-butyl- or sec-butyl- monofunctional dimethylsiloxanyl dimethylsilane derivative with MW of 190 g/mole.
- Method B To obtain narrow disperse and monodisperse mPDMS-H compositions with MW above 190 g/mole , the reaction is conducted with calculated amounts of D 3 to the alkyllithium reagent (such as n-butylLi or sec-butylLi) in cyclohexane or hexane at temperatures of between about 5 and about 6O 0 C for between about 1 and about 4 hours. This is followed by a addition of a polar chain propagating aprotic solvent such as THF under controlled conditions (time between about 2 and about 24 hours and a temperature between about 5 and about 60 0 C) until near complete conversion OfD 3 is observed by gas chromatography analysis. The generated alkylpolydimethylsiloxonalate anion is terminated with an excess of chlorodimethylsilane.
- the alkyllithium reagent such as n-butylLi or sec-butylLi
- the resulting reaction product can be purified by: filtration of LiCl; evaporation of excess chlorodimethylsilane; washing of the residual material with aqueous base (dilute sodium bicarbonate) to remove residual HCl followed by aqueous wash; and drying (anhydrous sodium sulfate) and distillation (using falling film or wiped film evaporators or other distillation methods known to those skilled in the art) to remove water and any residual traces OfD 3 or higher cyclics.
- Step 2 Synthesis and Purification of Hydroxy-mPDMS via Hydrosilylation
- the purified narrow disperse or monodisperse hydride-terminated product obtained from step 1 (Method A or Method B) is reacted with a molar excess of allyloxy hydroxypropyl methacrylate (AHM) or allyloxy hydroxypropyl acrylate (AHA) in the presence of a hydrosilylation catalyst.
- Suitable catalysts include rhodium-based catalyst such as Wilkinson's catalyst and platinum-based catalysts such as Karstedt catalyst, Pt(0)tetramethyltetravinylcyclotetrasiloxanes, chloroplatinic acid, Pt/C, and PtO 2 .
- the reaction may be conducted at a temperature between about 5 and about 4O 0 C) under an atmosphere of dry compressed air, nitrogen, or argon and for a duration until almost complete consumption of the starting mPDMS-H is detected (from FTIR analysis).
- the mixture is deactivated using a small amount of diethylethylenediamine, typically from about 10 to about 100 times the moles of active Pt catalyst.
- the "as-synthesized" reaction product is then washed several times with ethylene glycol to remove unreacted AHM or AHA (typically until ⁇ 0.1 % of AHM or AHA is left behind in the product).
- the product after ethylene glycol wash may be diluted with methanol (1:3 - 1:5 volume ratio).
- methanol (1:3 - 1:5 volume ratio).
- the resultant turbid solution upon settling has two phases.
- the process may be repeated until mPDMS-H is not detected in the washed product by FTIR.
- the above washing/extraction process can be accelerated using a batch centrifugal separator, a continuous contactor unit, or other separation equipment known to those skilled in the art.
- the second approach for the synthesis of alkyl-hydroxy-mPDMS in accordance with the present invention involves a three-step sequence.
- the strategy for this approach is outlined in Scheme 3 for a final product MW of ⁇ 613 g/mole.
- the first synthesis step in Approach 2 follows the same anionic ring opening protocol described in step 1 (Method B) of Approach 1.
- Step 2 Synthesis/Purification of Alkyl-Epoxy-mPDMS derivative via Hvdrosilylation
- the resulting alkyl-epoxy-mPDMS derivative may be distilled using a falling film evaporator or wiped film evaporator under high vacuum and at moderate/high temperatures to yield very high purity epoxy derivative.
- Step 3 Synthesis/Purification of Alkyl-Hydroxy-mPDMS via Oxirane Ring Opening Reaction
- the first step is the hydrosilylation reaction between AHM or AHA with commercially available chlorodimethylsilane. Purification of the resulting product under inert/dry conditions and by distillation techniques known to those skilled in the art provides high purity product that is an effective chain terminating agent or "capping agent" for the next reaction step.
- the second step is the controlled ring opening of hexamethylcyclotrisiloxane (D 3 ) by procedures described above in stepl of Approach 1, followed by terminating the siloxanolate anion with the "capping agent".
- D 3 hexamethylcyclotrisiloxane
- the disclosed methodologies covers novel synthesis and purification of hydroxy-monofunctional PDMS propylglycerol (meth)acrylate derivatives of the type described herein with different molecular weights and having different molecular distribution from monodisperse to narrow disperse to polydisperse product.
- the reaction scheme for synthesis of novel monodisperse mPDMS derivatives is outlined in Scheme 5.
- the ring opening reaction OfD 3 under controlled anionic polymerization in nonpolar and/or polar aprotic solvents followed by reaction of the in situ generated siloxanolate anion with commercially available chlorodimethylsilyl-propyl methacrylate is capable of yielding narrow disperse and monodisperse mPDMS derivatives bearing terminal methacrylate functionality.
- the synthesis protocol employs the hydrosilylation reaction between monodisperse or narrow disperse Alkyl-PDMS-H and commercially available allyl methacrylate under conditions described for the synthesis of alkylhydroxy-mPDMS.
- the synthesis steps to obtain final product with MW of- 982 g/mole and with narrow polydispersity are illustrated in Scheme 6.
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Abstract
Description
Claims
Priority Applications (5)
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EP06738699A EP1963402A2 (en) | 2005-03-17 | 2006-03-16 | Process for the production of monodisperse and narrow disperse monofunctional silicones |
JP2008502083A JP2008537966A (en) | 2005-03-17 | 2006-03-16 | Process for producing monodisperse and narrowly dispersed monofunctional silicones |
BRPI0606287-3A BRPI0606287A2 (en) | 2005-03-17 | 2006-03-16 | process for the production of limited monodisperse and dispersed monofunctional silicones |
CA002601533A CA2601533A1 (en) | 2005-03-17 | 2006-03-16 | Process for the production of monodisperse and narrow disperse monofunctional silicones |
AU2006227418A AU2006227418A1 (en) | 2005-03-17 | 2006-03-16 | Process for the production of monodisperse and narrow disperse monofunctional silicones |
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US66255605P | 2005-03-17 | 2005-03-17 | |
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US68241005P | 2005-05-19 | 2005-05-19 | |
US60/682,410 | 2005-05-19 |
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US (1) | US20060229423A1 (en) |
EP (1) | EP1963402A2 (en) |
JP (1) | JP2008537966A (en) |
KR (1) | KR20070112857A (en) |
AU (1) | AU2006227418A1 (en) |
BR (1) | BRPI0606287A2 (en) |
CA (1) | CA2601533A1 (en) |
WO (1) | WO2006102050A2 (en) |
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JP2008537966A (en) | 2008-10-02 |
EP1963402A2 (en) | 2008-09-03 |
WO2006102050A3 (en) | 2009-05-22 |
KR20070112857A (en) | 2007-11-27 |
AU2006227418A1 (en) | 2006-09-28 |
US20060229423A1 (en) | 2006-10-12 |
CA2601533A1 (en) | 2006-09-28 |
BRPI0606287A2 (en) | 2009-06-09 |
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