CN1204338A - 用于降低低水聚硅氧烷组合物的模量的单体 - Google Patents
用于降低低水聚硅氧烷组合物的模量的单体 Download PDFInfo
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- CN1204338A CN1204338A CN96198877A CN96198877A CN1204338A CN 1204338 A CN1204338 A CN 1204338A CN 96198877 A CN96198877 A CN 96198877A CN 96198877 A CN96198877 A CN 96198877A CN 1204338 A CN1204338 A CN 1204338A
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- Prior art keywords
- monomer
- carbon atom
- alkyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 46
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 76
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Chemical group 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 141
- -1 Siloxanes Chemical class 0.000 claims description 125
- 150000001721 carbon Chemical group 0.000 claims description 69
- 229910052799 carbon Inorganic materials 0.000 claims description 69
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 125000001118 alkylidene group Chemical group 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 4
- 125000004185 ester group Chemical group 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 19
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000002837 carbocyclic group Chemical group 0.000 abstract 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract 1
- 239000000463 material Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000080 wetting agent Substances 0.000 description 14
- 239000000017 hydrogel Substances 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 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 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- YWAKXRMUMFPDSH-UHFFFAOYSA-N propyl ethylene Natural products CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 5
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- LVLANIHJQRZTPY-UHFFFAOYSA-N vinyl carbamate Chemical compound NC(=O)OC=C LVLANIHJQRZTPY-UHFFFAOYSA-N 0.000 description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- VFGDTKZITOJUHZ-UHFFFAOYSA-N 3-[methyl(trimethylsilyloxy)silyl]propan-1-ol Chemical compound C[Si](C)(C)O[SiH](C)CCCO VFGDTKZITOJUHZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000005336 allyloxy group Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 2
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HNGIZKAMDMBRKJ-UHFFFAOYSA-N 2-acetamido-3-(1h-indol-3-yl)propanamide Chemical compound C1=CC=C2C(CC(NC(=O)C)C(N)=O)=CNC2=C1 HNGIZKAMDMBRKJ-UHFFFAOYSA-N 0.000 description 2
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical group CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 2
- HOPKHJSQWOIIQO-UHFFFAOYSA-N C[SiH2]C.[O] Chemical compound C[SiH2]C.[O] HOPKHJSQWOIIQO-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
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- 239000004809 Teflon Substances 0.000 description 2
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- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 238000000605 extraction Methods 0.000 description 2
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- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 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
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- 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
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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Abstract
本文涉及用于降低聚硅氧烷模量的单体。包含本发明的单体的低水材料在形成生物医药设备,如低水聚硅氧烷隐形眼镜中,是非常有用的。在式Ⅰ中,A是一个活化的不饱和基团;R和D可以分别是具有1至10个碳原子烷基,亚烷基,或者卤代烷基,其中在碳原子之间可能包含醚键卤代烷基;M是氢,氟,或者烷基;R1,R2,R3,R4可以分别是碳原子之间可能包含醚键的烷基、卤代烷基,硅氧烷基,有6至18个碳原子的碳环;m是从1到500的整数;n是从1到20的整数;x和y是0或1;z是1或2;x+y+z=3;R1或R2中至少有1个是有1至10个碳原子烷基。
Description
在先申请
本申请享受1995年12月7日递交的美国临时专利申请60/088329的优先权。
发明所属领域
本发明主要是有关氟代的含硅氧烷的单体和它们在降低低水聚硅氧烷组合物的模量方面的应用。该材料特别适用于制备隐形眼镜。
发明背景
聚硅氧烷材料广泛应用于生物医药领域,包括,例如制备隐形眼镜。这种材料一般主要划分为两类:水凝胶和非水凝胶(本文称其为“低水”材料)。硅水凝胶构成了能平衡吸收并保持水分的交联聚合体系,其中水的含量通常大于5%(重量),常见的是在10%到80%(重量)之间。这种材料一般由包含至少一个聚硅氧烷单体和一个亲水性单体的混合物聚合得到。可以使用聚硅氧烷单体或者是亲水性单体作为交联剂(交联剂被定义为具有多个可聚合官能基的单体),或者使用分离的交联剂。用于聚硅氧烷水凝胶的制备中的可用的含硅氧烷的单体是本领域周知的,许多美国专利也提及了大量的实施例:USP 4136250;4153641;4740533;5034461;5070215;526000;5310779;5358995。可使用的含硅氧烷的单体的特殊例子包括:
(a)大体积的烷基(甲基)硅氧烷基丙烯酰基单体(通常表示为TRIS),例如甲基丙烯酰氧丙基三(三甲基硅氧基)硅烷单体;
(b)有机聚硅氧烷单体;
(c)含硅氧烷的单体,包括含硅氧烷的碳酸乙烯基酯和氨基甲酸乙烯基酯单体,例如:1,3-二[4-乙烯氧基羰基氧基-丁基]四甲基-二硅氧烷,碳酸3-(三甲基甲硅烷基)丙基-乙烯基酯,3-(乙氧基羰基硫基)-丙基-[三(三甲基甲硅烷氧基)硅烷],氨基甲酸的3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯酯,氨基甲酸的3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基烯丙基酯,碳酸的3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯酯,碳酸的叔-丁基二甲基甲硅烷氧基乙烯酯,碳酸的三甲基甲硅烷基乙基乙烯酯,碳酸的三甲基甲硅烷基甲基乙烯酯;
(d)包含氨基甲酸乙酯和脲基的有机聚硅氧烷单体。其他可使用的含硅氧烷的单体是本领域周知的。
在聚硅氧烷水凝胶中使用的合适的亲水性单体包括:不饱和羧酸,如甲基丙烯酸和丙烯酸;丙烯酸取代的醇,如丙烯酸2-羟基乙基甲酯和丙烯酸2-羟基乙酯;乙烯基内酰胺,如N-乙烯基吡咯烷酮和丙烯酰胺,如甲基丙烯酰胺,N,N-二甲基丙烯酰胺。其它的例子有美国专利Nos.5070215所公开的亲水性的碳酸乙烯基酯和氨基甲酸乙烯基酯单体,美国专利Nos.4910277所公开的亲水性的噁唑酮单体。其它合适的亲水性单体是本领域熟练技术人员所周知的。
USP 4954587,5079319,5010141中描述了:对于形成隐形眼镜所使用的硅氧烷水凝胶,其中某些单体的氟化减少了隐形眼镜上沉积物的积累。而且使用有氟化侧基,例如-(CF2)-H的含硅氧烷的TRIS-型单体,提高了亲水性单体和含硅氧烷的单体之间的相容性,如USP5,387,662和5,321,108所述。
低水聚硅氧烷材料,和其水凝胶对应物相类似,包含同一种类的含硅氧烷的单体;然而,不同于硅氧烷水凝胶,“低水”聚硅氧烷材料不包含大量的亲水性单体和/或内湿润剂(一般少于5%-10%(重量))。因此,低水聚硅氧烷材料,如其名称所暗示的那样,并没有吸收或保留大量的水,例如少于5%(重量),更典型的是少于1%到2%(重量)。USP4,810,764和5,142,009中披露了氟化的低水聚硅氧烷的例子。为了使表面材料具有更高的亲水性,一般都对其进行表面处理,例如等离子体表面处理。不管是否进行表面处理或使用亲水性单体和/或内湿润剂,在低水聚硅氧烷组合物中水的浓度小于5%(重量)。
虽然低水聚硅氧烷组合物具有非常好的透氧性,但通常具有相对高的模量(杨氏弹性模量),例如,采用ASTM标准测试方法D1938,该模量经常超过300g/mm2。在许多生物医药应用领域,希望提供低模量,例如模量在20g/mm2到150g/mm2,优选是从30g/mm2到100g/mm2的低水组合物。这点在形成软性隐形眼镜中特别重要,因为透镜材料模量对透镜的舒适有重要的影响。具有高模量的透镜经常使人感到僵硬、弹性恢复性差和不自然。
虽然聚甲基丙烯酸硅氧烷基烷基酯,例如甲基丙烯酰基氧丙基三(三甲基硅氧基)硅烷,常表示为TRIS的使用降低了一些聚硅氧烷水凝胶,例如聚氨基甲酸乙酯-聚硅氧烷水凝胶的模量,(例如:lai,Yu Chin,The Role of Bulky Polysiloxanylalkyl Methacrylates inpolyurethane-polysiloxane Hydrogels,Proceedings of AmericanChemical Society Division of polymeric Materials:Science andEngineering,Vol 72,pg.118-119,(1995));在低水聚硅氧烷中TRIS单体的使用通常提高了目标材料的模量。因此,TRIS单体一般无助于降低“低水”聚硅氧烷模量。
美国专利Nos.5321108和5387662披露了端基包含氢且至少有一个氟取代的TRIS-类型的单体。据称该单体提高了在形成聚硅氧烷水凝胶时的含聚硅氧烷和亲水性单体的相容性。借助于TRIS,所述的单体具有三个(三)硅氧烷支链的巨大的聚硅氧烷烷基结构。使用传统技术不能蒸馏这些TRIS类型的氟化单体。因此,此类材料的纯化是困难的。基于同一理由,这些材料也较难分析,例如使用气相色谱。
总之,正在寻找具有相对低的模量,例如从20g/mm2到150g/mm2的低水聚硅氧烷材料。而且,在例如形成隐形眼镜材料的应用中,这些低水材料必须是光学透明的,具有可加工性(例如能被模具制造,机械加工等),并具有透氧性,生物相容性和抵抗沉积物形成的能力。而且,低水材料容易合成、纯化和分析。
发明简述
其中:
A是一个活化的不饱和基;
R和D相互独立,为具有1至10个碳原子的烷基,烯基,或者卤代烷基,其中所述的碳原子之间可能包含醚键;
M是氢,氟,或者烷基;
R1,R2,R3,R4相互独立,选自碳原子之间可能包含醚键的烷基,卤代烷基;硅氧烷基;以及具有6至18个碳原子的基团;
m是大于等于1的整数;n是从1到20的整数;x和y是0或1;
z是1或2;x+y+z=3;
R1或R2中至少有一个是有1至10个碳原子的烷基。
本发明还涉及含有本发明的单体的低水聚硅氧烷组合物,制备该低水聚硅氧烷组合物的方法,用该组合物制得的隐形眼镜,以及降低低水聚硅氧烷组合物的模量的方法。
本发明的优点是,以式Ⅰ表示的单体在没有明显降低所得到的聚合物的透氧性的前提下,降低了低水聚硅氧烷组合物的模量。而且,该单体相对容易合成、纯化和分析,在没有明显影响光学清晰度的情况下,可以在含硅氧烷的单体中聚合形成低水聚硅氧烷材料。
发明的详细说明
本发明涉及以式Ⅰ表示的单体(如下所述)和该单体在降低低水聚硅氧烷组合物的模量中的应用。低水聚硅氧烷组合物是通过聚合一种单体混合物而得到的,该混合物包含约1%到约99%(重量),优选约30%至60%(重量)的含硅氧烷的单体和1%到约50%(重量),优选约5%至30%(重量)的由式Ⅰ代表的单体:
其中:
A是一个活化的不饱和基;
R和D分别为具有1至10个碳原子的烷基,烯基,或者卤代烷基,其中,所述的碳原子之间可能包含醚键;
M是氢,氟,或者烷基;
R1,R2,R3,R4分别是碳原子之间可能包含醚键的烷基,卤代烷基;硅氧烷基;以及具有6至18个碳原子的含芳环的基团(例如环烷基和芳香基,例如苯基);
m是大于等于1的整数;n是从1到20的整数;x和y是0或1;
z是1或2;并且x+y+z=3;
R1或R2中至少有一个是有1至10个碳原子的烷基。
使用本领域中已知的工艺可合成以式Ⅰ代表的单体,制造优选单体的具体方法如实施例所述。
在一些优选的方案中,z为1,R1,R2,R3,R4分别选自烷基,例如低级烷基如具有1至10个碳原子的低级烷基,例如甲基,乙基,丙基等和氟取代的低级烷基,这样的单体易于合成和分析。优选单体的具体例子包括由式Ⅱ和Ⅲ代表的单体:
在低水聚硅氧烷组合物的制备中可以使用的含硅氧烷的单体是本领域周知的,美国专利Nos.4136250;4153641;4740533;5034461;5070215;526000;5310779;5358995中提供了许多这些单体的例子。可用于本发明的组合物中的含硅氧烷的单体的具体例子包括以式Ⅳ代表的烯属封端的含硅氧烷的单体:
其中:
A’和A”是活化的不饱和基团;
R’和R”分别是具有1至10个碳原子、碳原子之间可能包含醚键的烷基或亚烷基;
R8到R17分别选自单价烃基或卤素取代的单价烃基,其具有1至18个碳原子,碳原子之间可能包含醚键,优选选自R1到R4所代表的基团;a是大于等于1的整数;b和c是大于等于0的整数;a+b+c等于从1到1000的一个整数。
R8到R17优选选自烷基和氟取代的烷基。特别优选的是,R8到R17中至少有一个是氟取代的烷基,例如以下式代表的基团:
-D’-(CF2)s-M’
其中:
D’是具有1至10个碳原子、碳原子之间可能包含醚键的烷基或亚烷基;
M’是氢,氟或烷基,优选氢,氟;
s是从1到1000的一个整数,最好是1到6。
关于A’、A”和A,术语“活化”用于描述包含至少一个促进自由基聚合的取代基的不饱和基团。优选的是,所述的活化基团在温和条件下如室温下促进聚合。虽然有一系列这样的基团可以使用,但优选的是,A,A”,A是以下式代表的丙烯酸或甲基丙烯酸的酯或酰胺:
其中:X优选为氢或甲基但也可以是其它基团,例如氰基,Y优选为-O-,-S-,-NH-,更优选为-O-。其它合适基团的例子包括碳酸乙烯基酯,氨基甲酸乙烯基酯,丙烯氰基,苯乙烯基。合适基团的其它的例子包括N-乙烯基-2-吡咯烷酮-(3,4,或5)-基,如下式所示:
D,R,R’和R”代表二价烃基团,优选为具有1至10个碳原子、碳原子之间可能包含醚键的烷基或亚烷基,优选的此类烷基或亚烷基基包括具有1至6个碳原子的烷基或亚烷基。此类基团的例子包括亚甲基,亚丙基,亚丁基,1,5-亚戊基,1,6-亚己基等,亚芳基,例如亚苯基和二亚苯基,和-O-(CH2)q-,q为1到6。
d,e,f和g是0到1000的整数;
d+e等于一个2到1000的整数,优选是2到100;
f+g等于一个2到1000的整数,优选是2到100;
其中e,g优选是20到50的整数;以及
h是1到20的整数;
由式Ⅳ,Ⅴ,Ⅵ代表的单体和与其类似的单体的合成是本领域公知的。下面的实施例中提供了具体例子。
X代表-O-或-NR-;每个R18分别代表氢或甲基;每个R19分别代表低级烷基或苯基;h是1到20。
这种大体积的单体包括甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷。
另一种优选的含硅氧烷的单体包括以式Ⅷ代表的含硅氧烷的碳酸乙烯基酯和氨基甲酸乙烯基酯单体:其中:Y’代表-O-或-NR-;RSi代表含硅氧烷的有机基团;R20代表氢或甲基;d为1,2,3,4;q为0或1。合适的含硅氧烷的有机基团RSi包括下述基团:
-(CH2)n,Si[(CH2)m,CH3]3;
其中:
其中p’为1到6;
R22代表具有1至6个碳原子的烷基或氟取代的烷基;
e为1到200;n’为1,2,3或4;m’为1,2,3,4或5。
含硅氧烷的碳酸乙烯基酯和氨基甲酸乙烯基酯的单体包括:1,3-双[(4-乙烯氧基羰基氧基)-丁-1-基]四甲基-二硅氧烷,碳酸3-(三甲基甲硅烷基)丙基乙烯酯,3-(乙烯氧基羰基巯基)丙基-[三(三甲基甲硅烷氧基)硅烷],氨基甲酸3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基酯,氨基甲酸3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基烯丙基酯,碳酸3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基酯,碳酸叔丁基二甲基甲硅烷氧基乙基乙烯酯,碳酸三甲基甲硅烷基乙基乙烯基酯,碳酸三甲基甲硅烷基甲基乙烯基酯以及由式Ⅸ代表的“V2D25”:
一类更优选的含硅氧烷的单体包括由式Ⅹ和Ⅺ代表的:
(Ⅹ)E(*D*A*D*G)a *D*A*D*E’;或
(b)E(*D*G*D*A)a *D*G*D*E’;
其中:
D代表具有6到30个碳原子的烷基双基,烷基环烷基双基,环烷基双基,芳基双基,烷基芳基双基;
G代表具有1到40个碳原子的烷基双基,环烷基双基,烷基环烷基双基,芳基双基,烷基芳基双基,在其主链上可能包含醚、巯或胺键;
*代表氨基甲酸乙酯或脲基键;
a至少为1;
其中:
每个Rs分别代表具有1至10个碳原子的烷基或氟取代的烷基,该基团的碳原子之间可能含有醚键;
m’至少为1;以及
p是使括号部分的分子量为400到10000的一个数;
其中:
R23为氢或甲基;
R24为氢或具有1到6个碳原子的烷基,或-CO-Y-R26,其中Y为-O-,-S-,或-NH-;
R25为具有1到10个碳原子的二价亚烷基;R26为具有1到12个碳原子的烷基;X代表-CO-或-OCO-;Z代表-O-或-NH-;Ar代表具有6到30个碳原子的芳基;w为0到6;x为0或1;z为0或1。
其中m至少为1,优选为3或4,a至少为1,优选为1,p是使括号部分分子量为400到10000的一个数,优选至少为30,R27j是二异氰酸酯在去掉异氰酸酯基后的二价基团,如异佛尔酮二异氰酸酯的二价基团,每个E”为下式代表的基团:
本发明的单体混合物也可以包含其他组分例如交联剂,内湿润剂,亲水性单体,增韧剂和本领域公知的其它添加剂。
尽管以前描述了烯属封端的含硅氧烷的单体聚合时形成交联的三维网状结构,也可以将其他的交联剂添加到单体混合物中。合适的交联剂的例子包括:多乙烯基单体、典型的为二或三-乙烯基单体,最常用的为二或三(甲基)丙烯酸的二羟基乙二醇酯,三乙二醇酯,丁二醇酯,己烷-1,6-二醇酯,二丙烯酸硫代乙二醇酯和甲基丙烯酸酯;二丙烯酸新戊二醇酯;三丙烯酸三羟甲基丙烷酯等;N,N’-二羟基亚甲基-二丙烯酰胺和二甲基丙烯酰胺;和二烯丙基化合物,如邻苯二甲酸二烯丙基酯,氰尿酸三烯丙基酯;二乙烯基苯;乙二醇二乙烯基醚;和多元醇的(甲基)丙烯酸酯,如三乙醇胺,丙三醇,季戊四醇,丁二醇,甘露糖醇和山梨糖醇的(甲基)丙烯酸酯。而且还包括N,N-亚甲基-二-(甲基)丙烯酰胺,磺化二乙烯基苯和二乙烯基砜。(甲基)丙烯酸羟基烷基和不饱和异氰酸盐的反应产物也是有用的,例如美国专利No4954587所披露的甲基丙烯酸2-羟基乙基酯和甲基丙烯酸二异氰酸乙基酯的反应产物。
其它已知的交联剂如美国专利No4192827披露的聚醚-二氨基甲酸乙酯-二甲基丙烯酸酯,以及如美国专利No4486577和4605712所披露的交联剂,所述的交联剂由聚乙二醇,聚丙二醇和聚四亚甲基二醇与甲基丙烯酸2-异氰酸乙基酯(IEM)或异氰酸m-异丙烯-γ,γ-二甲基苄基酯(m-TMI)反应得到。还有一些其它的交联剂,其是聚乙烯醇,乙氧基化聚乙烯醇或乙烯醇-乙烯共聚物与0.1%到10%(摩尔)的异氰酸乙烯基酯,如IEM或m-TMI的反应产物。
尽管不是必须的,本发明的组合物也可以包括增韧剂,其用量优选是小于80%(重量),典型的是在20%到60%(重量)之间。美国专利No4327203描述了合适的增韧剂。这些试剂包括:丙烯酸环烷基酯或甲基丙烯酸环烷基酯,例如:丙烯酸甲酯和甲基丙烯酸甲酯,甲基丙烯酸叔丁基环己基酯,丙烯酸异丙基环戊基酯,甲基丙烯酸叔戊基环庚基酯,丙烯酸叔丁基环己基酯,丙烯酸异己基环戊基酯和丙烯酸甲基异戊基环辛基酯。美国专利No4355147中提到了其它合适的增韧剂的例子。该参考文献描述了多环丙烯酸酯或甲基丙烯酸酯例如:丙烯酸异冰片基酯和甲基丙烯酸异冰片基酯,丙烯酸联环戊二烯酯和甲基丙烯酸联环戊二烯酯,丙烯酸金刚烷基酯和甲基丙烯酸金刚烷基酯,以及丙烯酸异松蒎醇酯和甲基丙烯酸异松蒎醇酯。美国专利No5270418提供了其他的增韧剂的例子。该参考文献描述了支链烷基羟基环烷基的丙烯酸酯,甲基丙烯酸酯,丙烯酸酰胺和甲基丙烯酸酰胺。代表性的例子包括:甲基丙烯酸4-叔-丁基-2-羟基环己基酯(TBE);甲基丙烯酸4-叔-丁基-2-羟基环戊基酯;甲基丙烯酸氧氨基-4-叔-丁基-2-羟基环己烷;甲基丙烯酸6-异戊基-3-羟基环戊基酯;和甲基丙烯酸氧氨基-2-异己基-5-羟基环戊烷。
为了提高低水材料的润湿性能,此类材料中一般使用内湿润剂。内湿润剂的用量通常不多于20%(重量),更经常的是不多于10%(重量),这当然取决于所使用的润湿剂或其组合。在任何情况下,所得到的组合物的总水含量小于5%(重量),更经常的是小于1%或2%(重量)。合适的润湿剂的例子包括美国专利No4652622所描述的N-烷基乙氧基-三烷基甲硅烷基胺化物。这些试剂可以用下述通式代表:
CH2=C(E)C(O)N(H)CH(G)(CH2)qC(O)OSi(V)3
其中:
E是氢或甲基,
G是(CH2)rC(O)OSi(V)3或氢,
V是甲基,乙基或丙基,
q是1到15的整数,
r是1到10的整数,
q+r是1到15的整数,下文中称其为NATA。
丙烯酰氧基和甲基丙烯酰氧基单和二羧酸氨基酸,下文称其为NAA可使聚硅氧烷表面有合适的表面湿度,但在聚合完成之前会从硅氧烷单体混合物中析出。NAA能转化为能更容易加入到聚硅氧烷聚合物中的三烷基甲硅烷基酯。优选的NATA有:三甲基甲硅烷基-N-甲基丙烯酰氧谷氨酸酯,三乙基甲硅烷基-N-甲基丙烯酰谷氨酸酯,三甲基-N-甲基丙烯酰氧-6-氨基己酸,酯三甲基甲硅烷基-N-甲基丙烯酰氧-氨基十二烷酸酯,和二-三甲基-甲硅烷基-N-甲基丙烯酰氧天冬氨酸酯。
优选的内湿润剂还包括丙烯酸和甲基丙烯酸,及其衍生物。通常,这些试剂在组合物中的含量少于5%(重量)。
其中:
R28和R29分别选自氢或甲基,和
R30和R31分别选自甲基或环己基。
这些优选的内湿润剂特别包括:2-异丙烯基-4,4-二甲基-2-噁唑啉-5-酮(IPDMO),2-乙烯基-4,4-二甲基-2-噁唑啉-5-酮(VDMO),环己烷-螺-4’-(2’-异丙基-2’-噁唑啉-5-酮(IPCO),环己烷-螺-4’-(2’-乙烯基-2’-噁唑啉-5-酮(VCO),和2-(-1-丙烯基)-4,4-二甲基-噁唑啉-5-酮(PDMO)。此类噁唑酮的制备是本领域公知的并在美国专利No4810764中有描述。
这些优选的内湿润剂具有两个很重要的特征,这两个特征使其能成为特别希望的润湿剂:(1)它们相对来说是非极性的,且和疏水性单体(聚硅氧烷和增韧剂)是相容的;(2)它们在温和水解时,转化为高极性的氨基酸,从而提供较强的润湿性。当有其它成分存在时,发生聚合形成共聚体。这些内湿润剂通过碳碳双键与聚硅氧烷单体的端基聚合,并与增韧剂聚合,而形成在生物医疗设施,特别是隐形眼镜中有用的共聚体。
其他的内湿润剂的例子包括亲水性单体,例如在美国专利Nos.4259467,4260725,4440918,4910277,4954587,4990582,5010141,5079319,5310779,5321108,5358995,5387662中所披露的那些单体,这些专利文献在此引用作为参考文献。此类亲水性单体的例子包括含丙烯酸基和含乙烯基的单体。
优选的亲水性单体可以是含丙烯酸基和含乙烯基的单体。此类亲水性单体本身可用做交联剂。术语“乙烯基型”和“含乙烯基”的单体指的是包含类乙烯基基团(CH2=CQH)的单体,其反应活性通常较高。此类含乙烯基的亲水性单体通常是比较容易聚合的。“丙烯酸基型”和“含丙烯酸基”的单体是以下式表示的含有丙烯酸基的单体:
其中X优选为氢或甲基,Y优选为-O-,-OQ-,-NH-,-NQ-和-NH(Q)-,其中Q典型地是烷基或取代烷基。已经知道这些单体容易聚合。
可以结合到本发明的低水组合物中的含乙烯基的亲水性单体优选包括下述单体,如N-乙烯基内酰胺(N-乙烯基吡咯酮(NVP)),N-乙烯基-N-甲基乙酰胺,N-乙烯基-N-乙基乙酰胺,N-乙烯基-N-乙基甲酰胺,N-乙烯基甲酰胺,NVP是最优选的。
可以结合到本发明的水凝胶中的含丙烯酸基的亲水性单体优选包括下述亲水性单体,如N,N-二甲基丙烯酰胺(DMA),甲基丙烯酸2-羟乙基酯,甲基丙烯酸丙三醇酯,2-羟基乙基甲基丙烯酰胺,甲基丙烯酸和丙烯酸,其中DMA是最优选的。
当本发明同时使用含丙烯基单体和含乙烯基单体时,可进一步使用一种具有既能使丙烯基聚合也能使乙烯基聚合的基团的交联剂,如1994年5月10日授权的美国专利5,310,779中的那些交联剂,该美国专利全文在此引作参考资料。这些交联剂有助于使得到的共聚物可完全用紫外光固化。但该共聚物也可只通过加热而固化,或是经UV和加热固化。对于本领域的熟练技术人员来说,将固化该共聚物所需要的光和/或热引发剂加入到单体混合物中是周知的。可加入到含硅氧烷的水凝胶中的其它的交联剂包括以前描述的那些交联剂。
用于增加组合物的润湿性的其他技术也可以用于本发明,如本领域熟知的等离子体表面处理技术。
特别优选的低水组合物包括5%到40%(重量)由式Ⅰ代表的单体,30%到60%(重量)由式Ⅳ代表的单体,和15%到40%(重量)的增韧剂。此类配方也可以包括其他附加组分,如八氟戊基甲基丙烯酸盐(OFPMA)。此类单体可以用本领域公知的技术合成。有关资料可参考美国专利No 4810764,该专利在此引用作为参考。
通过一些通常用于聚合乙烯基不饱和化合物的传统方法,如紫外聚合法,热聚合,或两者的共用,可以将本发明所使用的单体混合物能很容易地固化成形。典型的自由基热聚合引发剂是一些有机过氧化物,例如过氧化乙缩醛,过氧化月桂酰,过氧化癸酰,过氧化硬酯酰,过氧化苯甲酰,过新戊酸叔丁基酯,过氧化二碳酸酯等,其用量为单体总重量的约0.01%-1%(重量)。典型的紫外引发剂是本领域熟知的,例如苯偶姻甲基醚,苯偶姻乙基醚,Darocure 1173,1164,2273,1116,3331(EM Industries)和Igracure 651,184(Ciba-Geigy)。
本发明的单体和其它的共聚单体的聚合(带有交联剂)通常是在有稀释剂存在下进行。聚合产物通常是胶体形式。如果稀释剂是非水的,必须通过本领域的熟练技术人员公知的萃取和水合法从胶体中去掉稀释剂,并用水取代之。
除了以上提到的聚合引发剂外,本发明的共聚物也可包括对本领域的熟练技术人员来说显而易见的其它单体。例如所述的单体混合物可包括着色剂,紫外吸收剂等隐形眼镜领域中周知的成分。
本发明提供的材料可用于人造器官,如心脏瓣膜,眼内晶状体,角膜,外科设备,人造血管,尿道内设备,横隔膜,外科移植,人造输尿管,人造胸腔器官,可用于体液在体外使用的装置,例如,用于肾坏死和心脏/肺装置的薄膜,插入导管,口腔保护,牙线,眼内装置,尤其是隐形眼镜的薄膜。
本发明的聚合物可通过旋转铸塑法(如美国专利3408429和3496254所披露的)、铸压法和其它方法制成隐形眼镜。聚合既可以在具有与所需隐形眼镜的形状相对应的旋转模具中进行,也可以在具有与所需隐形眼镜的形状相对应的静态模具中进行。隐形眼镜偶尔还需要进行机械抛光。聚合也可以在适当的模具或容器中进行,形成扣状,盘状,棒状物,然后将其加工(例如,通过机床或激光来切割或抛光)成具有所需形状的隐形眼镜。
当用于制造隐形眼镜时,优选的是水凝胶中的水含量小于5%(重量),更优选的是小于1%(重量)。而且,这些水凝胶的弹性模量优选在20g/mm2与150g/mm2之间,更优选的是在30g/mm2与100g/mm2之间。
为了说明本发明,下面提供了一些实施例。这些实施例仅仅用于进一步说明本发明,而不是限制本发明。
实施例Ⅰ
制备了十种低水聚硅氧烷组合物,每一种组合物由以下三种主要组分按照不同比例组成:以式Ⅴ代表的烯属封端的含硅氧烷的单体,以式Ⅱ代表的单体和甲基丙烯酸八氟戊基酯,以下称其为OFPMA。
以式Ⅴ代表的单体,即65%(摩尔)三氟丙基甲基硅氧烷和35%(摩尔)二甲基硅氧烷的共聚物,称为“65-TFP”,是按以下方法制备的。
将八甲基环四硅氧烷(39.4g,0.133mol),三氟丙基环三硅氧烷(15.3g,0.33mol)和甲基丙烯酰氧基丁基四甲基二硅氧烷(6.3g,0.015mol)在室温下加到干氮气气氛的圆底烧瓶中,再加入三氟甲基磺酸(0.54g,3.6mmol),并将反应混合物搅拌24小时。然后向粘稠的反应产物中加入碳酸氢钠,继续搅拌16小时。经中和处理后,再加入氯仿(500ml),溶液用硫酸镁干燥,用5μ特氟隆过滤器过滤。滤液用旋转蒸发器蒸去氯仿。快速搅拌下将得到的预聚物滴加到500ml氯仿中,以除去没有反应的环状化合物。收集聚合物层,并重复以上过程两次。第三次分馏后,收集聚合物并将其溶于乙醚中,用硫酸镁干燥后,用5μ的过滤器过滤。滤液用旋转蒸发器蒸去乙醚。将得到的清液在80℃(抽真空(0.2mm Hg)4小时,以除去低分子量的环状化合物。通过NMR可以确认纯化的65-TFP(150g,75%)的分子结构。
式Ⅱ代表的单体,即1-(甲基丙烯酰氧丙基)-3-(3-(2,2,3,3,4,4,5,5-八氟戊氧基)-丙基)四甲基二硅氧烷,以下称其为“MO”,是按照下面的方法制备的。
(a)制备用三甲基甲硅烷保护的羟基丙基四甲基二硅氧烷
将1,3-四甲基二硅氧烷(100g,0.774mol),烯丙氧基三甲基硅烷(97.0g,0.779mol),0.008g氯化(TRIS(三苯基膦)铑)和400ml甲苯加入到1L圆底烧瓶中。将溶液于80℃加热2小时,通过1H-NMR光谱仪可证实,在这一期间水合聚硅氧烷发生了反应。用旋转蒸发器蒸去甲苯,得到的油状物经真空蒸馏(65℃/1.5mm Hg)得到127.5g(64.8%)三甲基甲硅烷保护的羟基丙基四甲基二硅氧烷。
(b)制备1-(3-三甲基甲硅烷氧基丙基)-3-(3-(2,2,3,3,4,4,5,5-八氟戊氧基)-丙基)四甲基二硅氧烷
将三甲基甲硅烷基保护的羟基丙基四甲基二硅氧烷(60g,0.227mol),烯丙氧基八氟戊烷(74.10g,0.272mol),铂二乙烯基四甲基二硅氧烷配合物(113uL,0.002mol/ul催化剂),200ml THF,200ml1,4-二噁烷加入到1L圆底烧瓶中。将溶液于80℃加热3小时,同时用旋转蒸发器蒸去溶剂。使得到的油状物通过50g硅胶,用10/1的戊烷和二氯甲烷混合物洗脱。用旋转蒸发除去溶剂,得到的油状物经真空蒸馏(120℃/0.2mm Hg)得到103g纯度为97%的1-(3-三甲基甲硅烷氧基丙基)-3-(3-(2,2,3,3,4,4,5,5-八氟戊氧基)-丙基)四甲基二硅氧烷。
(c)制备1-(甲基丙烯酰氧基)-3-(3-(2,2,3,3,4,4,5,5-八氟戊氧基)-丙基)四甲基二硅氧烷
将1-(3-三甲基甲硅烷氧基丙基)-3-(3-(2,2,3,3,4,4,5,5-八氟戊氧基)-丙基)四甲基二硅氧烷(53.7g,0.1mol)溶于540ml甲醇中。室温下向该溶液中加入8.8ml浓度为10%的乙酸溶液。将该混合物搅拌1小时,并用旋转蒸发器在40℃除去溶剂。将得到的油状物溶于200ml己烷中并用蒸馏水洗涤四次。收集有机层,并用硫酸镁干燥后过滤。
将以上过滤后得到的反应产物,(1-(3-羟丙基)-3-(3-(2,2,3,3,4,4,5,5-八氟戊氧基-丙基)四甲基二硅氧烷),(46.3g,0.1mol)加到1L的盛有三乙胺(11.1g,0.11mol)的圆底烧瓶中。将该溶液冷却至0℃,缓慢加入(11.5g,0.11mol)甲基丙烯酰氯。加入甲基丙烯酰氯后,将溶液温度恢复至室温并搅拌过夜。第二天,将得到的溶液分别用1N HCl,2N NaOH和蒸馏水萃取两次。收集有机层,用硫酸镁干燥后过滤。滤液用旋转蒸发器蒸去溶剂。将得到的油状物通过50克使用10/1戊烷和二氯甲烷的硅胶柱。通过旋转蒸发器蒸去溶剂,将得到的油状物真空蒸馏(120℃/0.1mm Hg)后得到34.1克(收率为64%)纯度为95%的1-(3-甲基丙烯酰氧基丙基)-3-(3-(2,2,3,3,4,4,5,5-八氟戊氧基)-丙基)四甲基二硅氧烷。
表Ⅰ列出了十种组合物中65TFP,MO和OFPMA的比例。
每一样品的每一组分都是按照表Ⅰ的比例混合,经紫外引发剂引发混合近20分钟。然后将它们都做成薄膜,并按照下述过程进行机械性质的评估。将薄膜放在中间有0.3mm的Teflon垫板的两层硅烷化玻璃板之间,在强度为3500μm/cm2的紫外光下照射2小时后固化成型。紫外引发剂是Darocur 1173(浓度为0.5%)。将得到的薄膜在2-丙醇中萃取16小时,在蒸馏水中萃取2小时,随后在磷酸盐缓冲溶液(pH7.3)中水合16小时。在Instron Model 4500上用ASTM 1708和1938法测定薄膜的机械性质。透氧率是用极谱探针法(I.Fatt,J.E.Rasson,and J.B.Melpolder,ICLC J14,389(1987))来测定的。水解稳定性测试是在磷酸盐缓冲溶液中,将测试薄膜加热到80℃,分别测试3,5,7,14天后其重量和水含量的变化。对每种样品组合物的机械性质的评估结果列于表Ⅰ中。
表1
组成%(重量)65TFP/MO/OFPMA | 杨氏模量(g/mm2) | 撕裂强度(g/mm) | 透氧性(barrers) |
80/0/20 | 110 | 5 | 360 |
75/5/20 | 79 | 3 | 275 |
70/10/20 | 74 | 3 | 240 |
60/20/20 | 58 | 2 | 220 |
60/0/40 | 351 | 29 | 213 |
55/5/40 | 188 | 29 | 190 |
50/10/40 | 121 | 36 | NA |
45/15/40 | 68 | 24 | 155 |
40/20/40 | 73 | 26 | NA |
30/30/40 | 44 | 29 | 145 |
实施例Ⅱ
以基本上与实施例Ⅰ相同的方式制备和评估了三种低水聚硅氧烷组合物,只是用式Ⅲ代表的单体代替式Ⅱ的单体。即,用1-(甲基丙烯酰氧基丙基)-3-(三氟丙基)四甲基二硅氧烷(MTFP)代替MO。每一组分的比例和机械评估结果列于表Ⅱ中。
表Ⅱ
组成%(重量)65TFP/MTFP/OFPMA | 杨氏模量(g/mm2) | 撕裂强度(g/mm) | 透氧性(barrers) |
60/0/40 | 351 | 29 | 213 |
50/10/40 | 189 | 58 | 178 |
40/20/40 | 89 | 40 | 148 |
表Ⅰ和表Ⅱ列出了按65TFP/MO/OFPMA和65TFP/MTFP/OFPMA配方所得薄膜的模量、断裂强度和透氧性的数据。这些数据清晰表明,在两种低水配方中本发明的单体,即MO和MTFP(分别由式Ⅰ和Ⅱ代表)会明显地降低两种配方的低水组合物的模量。
实施例Ⅲ
在前后两个聚丙烯模具之间,使用65TFP/MO/OFPMA(45/15/40)和紫外引发剂Darocur1173按以上所列固化条件,铸塑成透镜。固化后,用甲苯使其脱模,并在室温下用甲苯萃取一夜。使用常规的空气等离子体技术对该透镜进行等离子体处理得到隐形眼镜,其具有很好的润湿特性。
实施例Ⅳ
尽管由式Ⅰ代表的单体的合成是本领域所熟知的,本发明还是提供了另外一种代表性的合成方法。更具体地,下面提供了甲基丙烯酰丙基二(八氟戊氧基丙基二甲基甲硅烷氧基)甲基硅烷的制备。
(a)制备甲基丙烯酰氧基丙基甲基二(甲基甲硅烷氧基)硅烷
向装有温度计和电磁搅拌的三颈圆底烧瓶中加入甲基丙烯酰氧基丙基二氯甲基硅烷(25g,0.104mol),二甲基氯硅氧烷(39.2g,0.419mol),三乙胺(45.5g,0.450mol)和250ml无水乙醚。将反应混合物冷却至-15℃,慢慢加入蒸馏水(14.9g,0.830mol)。然后慢慢升到室温,搅拌过夜。将得到的溶液用蒸馏水洗涤三次,收集乙醚层。用硫酸镁干燥后过滤,用旋转蒸发器除去乙醚。将得到的油状物真空蒸馏(105℃/0.15mmHg)得到50%(产率)纯度为94%(GC测定)的甲基丙烯酰氧基丙基三(二甲基甲硅烷氧基)硅烷。
(b)制备甲基丙烯酰丙基二(八氟戊氧基丙基二甲基甲硅烷氧基)甲基硅烷
向200ml圆底烧瓶中加入甲基丙烯酰氧基丙基三(二甲基甲硅烷氧基)硅烷(8.0g,0.0249mol),烯丙氧基八氟戊烷(15g,0.055moL),0.030ml铂二乙烯基配合物和80ml四氢呋喃。将溶液回流一个小时,同时利用1H-NMR观察到硅氧烷水合物发生反应。用旋转蒸发器(50℃/30mm)蒸去THF和未反应的烯丙氧基八氟戊烷,得到定量转化的甲基丙烯酰基丙基二(八氟戊氧基丙基二甲基甲硅烷氧基)甲基硅烷。
对于本领域的熟练技术人员来,根据本发明的描述,可以对本发明进行修改和变化。因此,应该理解的是,在权利要求所限定的范围内,也可以以本文中所特别说明的方式以外的方式实施本发明。
Claims (28)
2、如权利要求1所述的单体,其中z为1,并且R1或R2分别选自具有1至10个碳原子的烷基。
3、如权利要求2所述的单体,其中至少有一个所述的烷基是氟取代的烷基。
4、如权利要求1所述的单体,其中A是选自丙烯酸或甲基丙烯酸的酯基或酰胺基。
5、如权利要求1所述的单体,其中R和D为具有1至6个碳原子的烷基,其中所述的碳原子之间可能包含醚键。
6、如权利要求1所述的单体,其中R1,R2,R3,R4分别选自具有1至10个碳原子的烷基
7、如权利要求1所述的单体,其中n为1-6,m为1-10。
9、由包含式Ⅰ表示的单体的单体混合物聚合形成的低水聚硅氧烷组合物:
其中:
A是一个活化的不饱和基团;
R和D分别为具有1至10个碳原子的烷基、亚烷基、或者是卤代烷基,其中所述的碳原子之间可能包含醚键;
M是氢、氟或者烷基;
R1,R2,R3,R4分别选自烷基、卤代烷基,其中的碳原子之间可能包含醚键;硅氧烷基;以及含有6至18个碳原子的碳环基团;
m是从1到500的整数;n是从1到20的整数;x和y是0或1;
z是1或2;并且x+y+z=3;
R1或R2中至少有一个是有1至10个碳原子的烷基。
10、如权利要求9所述的组合物,其中z为1;R1,R2,R3,R4分别选自带有1至10个碳原子的烷基;A是丙烯酸或甲基丙烯酸的酯或酰胺基团;R和D是具有1至6个碳原子并且在碳原子之间可能包含醚键的烷基;m是从1到10的整数;n是从1到6的整数。
12、如权利要求所述的通过聚合单体混合物形成的组合物,所述单体混合物包括:
(a)大约1%(重量)到99%(重量)的式Ⅰ代表的单体之外的其它含硅氧烷的单体;和
(b)大约1%到50%(重量)由式Ⅰ代表的单体。
14、如权利要求13所述的组合物,其中,A’和A”是丙烯酸或甲基丙烯酸的酯或酰胺基团;R’和R”分别是具有1至6个碳原子、碳原子之间可能包含醚键的烷基;R8到R17分别是具有1至10个碳原子的烷基,并且R8到R17中至少有一个是氟取代的烷基。
17、如权利要求16所述的隐形眼镜,其中z为1;R1,R2,R3,R4分别独立地选自带有1至10个碳原子的烷基;A是丙烯酸或甲基丙烯酸的酯或酰胺基团;R和D是具有1至6个碳原子并且在碳原子之间可能包含醚键的烷基;m是从1到10的整数;n是从1到6的整数。
19、如权利要求16所述的隐形眼镜,其中所述的组合物是通过聚合一单体混合物而形成的,所述的单体混合物包括:
(a)大约1%(重量)到99%(重量)的式Ⅰ代表的单体之外的其它含硅氧烷的单体;和
(b)大约1%到50%(重量)由式Ⅰ代表的单体。
21、如权利要求20所述的隐形眼镜,其中,A’和A”是丙烯酸或甲基丙烯酸的酯或酰胺基团;R’和R”分别是具有1至6个碳原子、碳原子之间可能包含醚键的烷基;R8到R17分别是具有1至10个碳原子的烷基,并且R8到R17中至少有一个是氟取代的烷基。
23、如权利要求16所述的隐形眼镜,其中,所述的组合物的杨氏弹性模量在20g/mm2与150g/mm2之间。
25、如权利要求24所述的方法,其中z为1;R1,R2,R3,R4分别独立地选自带有1至10个碳原子的烷基;A是丙烯酸或甲基丙烯酸的酯或酰胺基团;R和D是具有1至6个碳原子并且在碳原子之间可能包含醚键的烷基;m是从1到10的整数;n是从1到6的整数。
26、如权利要求24所述的方法,其中所述的聚合单体混合物的步骤进一步包括制备一种单体混合物,该混合物包括:
(a)大约1%(重量)到99%(重量)的式Ⅰ代表的单体之外的其它含硅氧烷的单体;和
(b)大约1%到50%(重量)由式Ⅰ代表的单体。
28、如权利要求27所述的方法,其中,A’和A”是丙烯酸或甲基丙烯酸的酯或酰胺基团;R’和R”分别是具有1至6个碳原子、碳原子之间可能包含醚键的烷基;R8到R17分别是具有1至10个碳原子的烷基。
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US832995P | 1995-12-07 | 1995-12-07 | |
US60/008,329 | 1995-12-07 |
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CN (1) | CN1070494C (zh) |
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- 1996-11-12 US US08/745,537 patent/US5714557A/en not_active Expired - Lifetime
- 1996-11-12 KR KR10-1998-0704173A patent/KR100462450B1/ko not_active IP Right Cessation
- 1996-11-12 DE DE69625941T patent/DE69625941T2/de not_active Expired - Fee Related
- 1996-11-12 WO PCT/US1996/018307 patent/WO1997020851A1/en active IP Right Grant
- 1996-11-12 CN CN96198877A patent/CN1070494C/zh not_active Expired - Fee Related
- 1996-11-12 ES ES96941356T patent/ES2191779T3/es not_active Expired - Lifetime
- 1996-11-12 EP EP96941356A patent/EP1019416B1/en not_active Expired - Lifetime
- 1996-11-12 JP JP09521279A patent/JP2000502329A/ja not_active Ceased
- 1996-11-12 BR BR9611859A patent/BR9611859A/pt active Search and Examination
- 1996-11-12 CA CA002239902A patent/CA2239902C/en not_active Expired - Fee Related
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1998
- 1998-06-04 MX MX9804475A patent/MX9804475A/es unknown
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2001
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CN110914282A (zh) * | 2017-08-01 | 2020-03-24 | 信越化学工业株式会社 | 硅氧烷化合物及其制备方法 |
CN111278927A (zh) * | 2017-10-27 | 2020-06-12 | 美国陶氏有机硅公司 | 可固化聚有机硅氧烷组合物、通过固化所述组合物获得的固化体以及包含其的电子装置 |
CN111278927B (zh) * | 2017-10-27 | 2022-06-03 | 美国陶氏有机硅公司 | 可固化聚有机硅氧烷组合物、通过固化所述组合物获得的固化体以及包含其的电子装置 |
US11390746B2 (en) | 2017-10-27 | 2022-07-19 | Dow Silicones Corporation | Curable polyorganosiloxane composition, cured body obtained by curing said compositions, and electronic device comprising the same |
Also Published As
Publication number | Publication date |
---|---|
AU711848B2 (en) | 1999-10-21 |
CN1070494C (zh) | 2001-09-05 |
BR9611859A (pt) | 1999-05-04 |
EP1019416B1 (en) | 2003-01-22 |
CA2239902A1 (en) | 1997-06-12 |
KR100462450B1 (ko) | 2005-07-18 |
KR19990071888A (ko) | 1999-09-27 |
DE69625941D1 (de) | 2003-02-27 |
WO1997020851A1 (en) | 1997-06-12 |
ES2191779T3 (es) | 2003-09-16 |
JP2000502329A (ja) | 2000-02-29 |
US5714557A (en) | 1998-02-03 |
MX9804475A (es) | 1998-09-30 |
AU1052397A (en) | 1997-06-27 |
EP1019416A1 (en) | 2000-07-19 |
HK1030951A1 (en) | 2001-05-25 |
DE69625941T2 (de) | 2003-06-18 |
CA2239902C (en) | 2001-08-07 |
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