CN1116326C - 氟硅氧烷水凝胶 - Google Patents

氟硅氧烷水凝胶 Download PDF

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CN1116326C
CN1116326C CN94191165A CN94191165A CN1116326C CN 1116326 C CN1116326 C CN 1116326C CN 94191165 A CN94191165 A CN 94191165A CN 94191165 A CN94191165 A CN 94191165A CN 1116326 C CN1116326 C CN 1116326C
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J·F·孔斯勒
R·M·奥扎克
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Bausch and Lomb Inc
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/38Polysiloxanes modified by chemical after-treatment
    • C08G77/382Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • CCHEMISTRY; METALLURGY
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    • C08F30/04Homopolymers 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
    • C08F30/08Homopolymers 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/045Polysiloxanes containing less than 25 silicon atoms
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Abstract

公开了新的含氟硅氧烷的单体,所述单体特别适合用于制备诸如接触透镜一类的生物医学材料。

Description

氟硅氧烷水凝胶
                         本发明的背景
技术领域
本发明涉及新的聚合组合物,更具体地说,涉及由此制得的接触透镜。本发明进一步具体地涉及带有至少一个极性氟化侧链的含聚硅氧烷的单体。这里所述的单体可用于制备“硬”或“软”接触透镜、眼内植入物以及其它修补物,尤其是“软”水凝胶接触透镜。
背景技术
在接触透镜领域里,必须综合考虑各种因素以得到具有适宜性能的材料。透氧性、湿润性、材料强度和稳定性只是欲得到可使用的接触透镜所必须仔细权衡的诸多因素中的几个。由于角膜仅仅通过与大气接触获得其氧源,因而良好的透氧性对于任何接触透镜材料来说都是一个关键的性能。湿润性也很重要,这是由于若透镜的湿润性不足,便不会保持润滑,从而无法舒适地配戴于眼内。因此,最佳的接触透镜应该兼具极好的透氧性和极好的泪液湿润性。
由于聚硅氧烷材料具有极好的透氧性和其它一些性能,因而它们可用于制备接触透镜,参见美国专利4,153,641和4,189,546。但聚硅氧烷通常是亲水性的。可将某些亲水官能团连接到含聚硅氧烷的单体或预聚物上以改善其湿润性,参见美国专利4,260,725和4,259,467。但是,已知许多亲水性共聚单体在单体混合物中与含聚硅氧烷的单体不相容,为使单体混合物适当地聚合,需要加入加溶剂或相容剂。如果没有相容剂,可能根本得不到共聚物,有产生不同程度的相分离之虞,使得聚合的材料不透明。
除了透氧性、湿润性和相容性方面的要求外,接触透镜还必须能够抗沉积。某些聚硅氧烷材料易于积聚沉积。已知将某些聚硅氧烷单体氟化可改善抗沉积性。参见例如美国专利4,440,918、4,990,582、4,954,587、5,079,319和5,010,141。
美国专利4,810,764和5,142,009公开了具有可用于非水凝胶接触透镜的性能的氟化聚硅氧烷。用这些材料进行进一步实验后确认,具有硅氧烷基团赋予的透氧性优点和氟化基团赋予的类脂抑制性的水凝胶是特别有利的。但是,因为氟化聚硅氧烷单体难以溶于所用的亲水单体中,所以利用这种方法难以得到用于接触透镜的可行的水凝胶制剂。如果共聚单体不能充分互溶,便会发生相分离,导致聚合材料不透明。这种结果对于诸如接触透镜一类必须是透明的材料来说是不合要求的。
已经采用相容剂或加溶剂(如甲乙酮(MEK))使某些含氟化硅氧烷的单体进入溶液以用来成膜或制透镜。但是这类加溶剂和相容剂往往影响纯度,因而必须从得到的聚合物中提取出来。这种提取需要额外的加工步骤。另外,如果含硅氧烷的单体和亲水性单体极性相差大,即使加入加溶剂(如MEK)也不能使共聚单体保持在溶液中。
因此,具有含聚硅氧烷的单体的透氧性和材料强度高的优点及氟化侧基的抗沉积性好的优点而不使用相容剂或加溶剂的水解稳定性聚合体系对于水凝胶制剂来说是极其有利的。
                   本发明的概述
现已发现,通过在含聚硅氧烷的单体的硅氧烷基团上连接其二氟取代的端碳原子上连有氢原子的极性氟化接枝基团或侧基,可以大大改善氟化聚硅氧烷在亲水性单体中的相容性和溶解性。当二氟取代的端碳原子上连有氧原子时,氟化聚硅氧烷能够溶于亲水性单体,因而不需要另外加入相容剂或加溶剂。当端氢原子被氟取代时,溶解性受到严重影响,以致亲水性单体不能溶于含全氟化硅氧烷的单体中。
                 本发明的详细说明
本发明公开的含氟化聚硅氧烷的单体令人惊奇地展示了极好的相容性。即在各种亲水性化合物(如N-乙烯基吡咯烷酮(NVP)和N,N-二甲基丙烯酰胺(DMA)中具有高度溶解性,不需要另外加入相容剂或加溶剂。
这里所用的术语“侧基”是指任何引自硅氧烷基团的支链,当硅氧烷位于聚合结构的骨架上时,侧基便是侧链。当硅氧烷基团不在骨架上时,从硅氧烷基团上接枝出来的氟化链变成硅氧烷侧链的侧链。
“端”碳原子是指位于距硅氧烷基团最远的位置的碳原子,所述硅氧烷基团上连有氟化侧基。
本发明人发现并公开的是:当极性氟化基团-(CF2)zH位于与含硅氧烷的单体相连的侧基的末端时,连有侧基的整个硅氧烷单体在亲水性单体(如NVP)中具有高度溶解性。当氟化端碳原子上的氢原子被氟取代时,含硅氧烷的单体在所用的亲水性单体中的溶解性明显变差,或根本不溶。
在本发明的一个实施方案中,含氟化硅氧烷的单体具有至少一个氟化侧基,所述侧基用下面通式(I)表示:
I.
                          -D-(CF2)zH其中,
z为1-20;
D为具有1-10个碳原子且碳原子间可有醚键的烷基或亚烷基。
在另一个实施方案中,含氟化硅氧烷的单体具有至少一个氟化侧基,且含有下面通式(II)所示的部分:其中,
D为具有1-10个碳原子且碳原子间可有醚键的烷基或亚烷基;
x≥0;
y≥1;
x+y=2-1000;
z为1-20。
更优选的是如下面通式(III)所示的含氟化硅氧烷的单体:
Figure C9419116500092
其中,
R为具有1-10个碳原子且碳原子间可有醚键的烷基或亚烷基;
R1-R4可独立地为具有1-18个碳原子且碳原子间可有醚键的一价烃基或卤素取代的一价烃基;
x≥0;
y≥1;
x+y=2-1000;
z为1-20;
R5为下面通式所示的氟化侧链:
              -D-(CF2)z-H其中z为1-20;
D为具有1-10个碳原子且碳原子间可有醚键的烷基或亚烷基;
A为活性不饱和基团,如丙烯酸或甲基丙烯酸的酯或酰胺基团,或下面通式所示的基团:
Figure C9419116500101
其中,
Y为-O-、-S-或-NH-;
优选的氟化侧基由下式表示:
             -CH2-CH2-CH2-O-CH2-(CF2)z-H其中z为1-20。
一种优选的含氟化硅氧烷的单体按照下述反应式制备:其中,
y为10、25和40;
x+y为100;
z为4或6。
在本发明的另一个实施方案中,含氟化硅氧烷的单体是下面通式所示的(甲基)丙烯酸氟化大聚硅氧烷基烷基酯单体:
Figure C9419116500112
其中,
A为活性不饱和基团,如丙烯酸或甲基丙烯酸的酯或酰胺基团;
R6为CH3或H;
R为具有1-10个碳原子且碳原子间可有醚键的烷基或亚烷基;
D为具有1-10个碳原子且碳原子间可有醚键的烷基或亚烷基;
x为1、2或3;
y为0、1或2;
x+y=3。
下式所示的氟化大聚硅氧烷基烷基单体也是优选的:其中,
R7为CH2
x为1、2或3;
y为0、1或2:
x+y=3。
本发明的含氟化聚硅氧烷的单体综合了已知亲水性侧链聚硅氧烷的所需性质,如与亲水性单体的相对相容性,和源于氟化基团的改善的抗沉积性。所需的透镜性能可以改变和控制。例如,通过改变共聚单体的相对比例(即上述氟化聚硅氧烷单体与亲水性单体的比例),可以改变聚合的氟化聚硅氧烷共聚物的某些水凝胶特性。
通过降低或提高用活性不饱和基团封端的聚硅氧烷单体的分子量,或通过改变所用的共聚单体的比例,可以改变由本发明所得的聚合物制成的接触透镜的相对柔软度或硬度。一般来说,随着聚硅氧烷单元与封端单元的比例的增加,材料的柔软度提高。
本发明期望将氟化聚硅氧烷单体同时用于“硬”和“软”接触透镜,据认为所公开的制剂尤其适用于“软”水凝胶接触透镜。如果一个透镜能够折迭而不断裂,则认为该透镜是“软”透镜。
水凝胶是一种含处于平衡状态水的水合交联聚合物体系。硅氧烷水凝胶(即含硅氧烷的水凝胶)通过将含有至少一种含硅氧烷的单体和至少一种亲水性单体的混合物聚合来制备。含硅氧烷的单体和亲水性单体均可作为交联剂,这里交联剂定义为具有多个可聚合的官能度的单体。也可以另外加入交联剂。
这里当术语“活性的”与术语“不饱和基团”联用时,意味着活性不饱和基团是带有促进自由基聚合反应的取代基的基团。这些活性不饱和基团聚合后形成本发明的聚合物。优选的是适宜在温和条件(如室温)下进行聚合的活性基团。
这里所用的术语“聚合”是指用可聚合的不饱和基团封端的聚硅氧烷的双键的聚合,该聚合反应得到交联的三维网络。
另外,这里所用的诸如“(甲基)丙烯酸酯”或“(甲基)丙烯酰胺”一类的用语是指可任选带有甲基取代基。例如,(甲基)丙烯酸酯包括丙烯酸酯和甲基丙烯酸酯,N-烷基(甲基)丙烯酰胺包括N-烷基丙烯酰胺和N-烷基甲基丙烯酰胺。
术语“预聚物”表示一个可以是含有至少两个可聚合的基团的高分子量单体的单体。本发明的单体混合物中所用的单体可以是单体或预聚物。因此应该理解,术语“含硅氧烷的单体”和“亲水性单体”包括相应的预聚物。这类单体的实例可参见美国专利4,136,250、4,153,641、4,740,533、5,034,461和5,070,215。
术语“生物医用成型制品”或“生物医学装置或材料”是指本发明公开的水凝胶材料的物化性能使其适合与活组织、血液和粘膜长时间接触。
本发明的单体可用来制备具有理想的刚度、透氧性和其它物理性能的高湿润性水凝胶。这种含硅氧烷的水凝胶非常适合用于诸于接触透镜一类的生物医学装置。
某些交联的聚合物材料,如本发明考虑的材料,可聚合形成不含水的硬干凝胶。干凝胶被认为是未水合的水凝胶制剂,该制剂可通过物理方法例如经机械加工得到光学性能,然后水合并保持其水含量和光学性能。
本发明优选的丙烯酸类封端的聚硅氧烷单体具有约1至约200个硅烷氧基重复单元,更优选具有约100个硅烷氧基重复单元。
本发明的含(甲基)丙烯酸氟化大聚硅氧烷基烷基酯的单体是用于可以是也可以不是水凝胶的“硬”和“软”两种体系的极好材料。优选的含(甲基)丙烯酸大聚硅氧烷基烷基酯的单体是例如甲基丙烯酰氧丙基三(八氟戊氧丙基二甲基甲硅烷氧基)甲硅烷。
优选的氟化侧基是烷基氟化铡链,如丙氧基八氟戊烷、丙氧基四氟丙烷和丙氧基十二氟庚烷基团,最优选丙氧基八氟戊烷基团。
在本发明的一个优选的实施方案中,使单体混合物中一种以上聚硅氧烷单体(其中一种聚硅氧烷单体具有至少一个极性氟化硅氧烷基团)与至少两种亲水性单体聚合制备接触透镜材料。
本发明的聚合组合物中还可加入其它亲水性单体来形成水凝胶。这类优选的亲水性单体可以是含丙烯酸类基团或含乙烯基的单体,也可用作交联剂。术语“乙烯基型”或“含乙烯基的”单体是指含有乙烯基(CH2=CH2)的非丙烯酸类单体。已知这类含乙烯基的亲水性单体较易聚合。“丙烯酸型”或“含丙烯酸类基团的”单体是指含有丙烯酸类基团(其中R为H或CH3,x为O或NH)的单体。
优选的可用于本发明的水凝胶的含乙烯基的亲水性单体包括例如N-乙烯基内酰胺(如N-乙烯基吡咯烷酮(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,最优选NVP。
优选的可用于本发明的水凝胶的含丙烯酸类基团的亲水性单体包括诸如N,N-二甲基丙烯酰胺(DMA)、甲基丙烯酸2-羟基乙酯、甲基丙烯酸甘油酯、2-羟乙基甲基丙烯酰胺、甲基丙烯酸和丙烯酸一类的亲水性单体,最优选DMA。
含硅氧烷的单体占共聚单体混合物总量的相对比例(重量%)优选为约10%至约85%,更优选为约20%至约70%,最优选为约25%至约40%。亲水性单体占共聚单体混合物总量的相对比例(重量%)优选为约20%至约90%,更优选为约30%至约80%,最优选为约50%至约60%。
优选的含硅氧烷的碳酸乙烯酯或氨基甲酸乙烯酯单体包括:1,3-二[(4-乙烯氧基羰氧基)丁-1-基]四甲基二硅氧烷、碳酸3-(三甲基甲硅烷基)丙基乙烯基酯、3-(乙烯氧基羰硫基)丙基-[三(三甲基甲硅烷氧基)甲硅烷]、氨基甲酸3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯酯、氨基甲酸3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基烯丙酯、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乙基乙烯基酯、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下式所示的“V2D25”:
Figure C9419116500161
其中,
X为具有1-10个碳原子且碳原子间可有醚键的烷基或亚烷基;
z为1-20。
由于乙烯基亲水性单体和丙烯酸类亲水性单体的反应竞聚率不同,其共聚速率有很大差别,或者根本不共聚,所以当需要同时将含丙烯酸类基团的亲水性单体和含乙烯基的亲水性单体引入本发明的含硅氧烷的聚合物中时,可以再加入一种同时具有乙烯基和丙烯酸类可聚合基团的交联剂。这种可促进共聚单体共聚的交联剂(如碳酸甲基丙烯酰氧乙基乙烯基酯(HEMAVC)和氨基甲酸甲基丙烯酰乙基乙烯酯)是共同未决和共同转让的美国专利申请07/922,452(1992年7月30日提交)的主题。这种交联剂可用下面的示意性化学式表示:
Figure C9419116500162
其中,
V表示下式所示的含乙烯基的基团:
Figure C9419116500171
A′表示下式所示的含丙烯酸类基团的基团:
S表示下式所示的含苯乙烯基团的基团:
Figure C9419116500173
其中、
R11是由下述化合物衍生而来的烷基:取代和未取代的烃、聚烯化氧、聚(全氟)烯化氧、二烷基封端的聚二甲基硅氧烷、用氟烷基或氟代醚基团改性的二烷基封端的聚二甲基硅氧烷;
R12-R20独立地为H或1-5个碳原子的烷基;
Q是含有6-30个碳原子的芳族基团的有机基团;
X、Y和Z独立地为O、NH或S;
v为1或更大的数;
a、s独立地为大于或等于0的数,且
a+s大于或等于1。
这种交联剂使得所得的共聚物完全是紫外光固化性的。但是,共聚物也可以仅通过加热固化,或结合使用紫外光和加热的方法来固化。当然,本领域技术人员显然都明白这其中还可包括固化共聚物所需的必要的光引发剂和热引发剂。
可以引入本发明的含硅氧烷的水凝胶的其它交联剂包括多乙烯基通常是二或三乙烯基单体,最常见的是二甘醇、三甘醇、丁二醇、1,6-己二醇的二或三(甲基)丙烯酸酯类;硫代二甘醇二丙烯酸酯和甲基丙烯酸酯;新戊二醇二丙烯酸酯;三羟甲基丙烷三丙烯酸酯等等;N,N′-二羟基亚乙基双丙烯酰胺和双甲基丙烯酰胺类;二烯丙基化合物,如邻苯二甲酸二烯丙酯和氰尿酸三烯丙酯;二乙烯基苯:乙二醇二乙烯基醚;以及诸如三乙醇胺、丙三醇、季戊四醇、丁二醇、甘露糖醇和山梨醇一类的多元醇的(甲基)丙烯酸酯类。其他实例有N,N-亚甲基双(甲基)丙烯酰胺、磺化二乙烯基苯和二乙烯基砜。还可以使用(甲基)丙烯酸羟烷基酯与不饱和异氰酸酯的反应产物,例如美国专利4,954,587公开的甲基丙烯酸2-羟基乙酯与甲基丙烯酸2-异氰酸基乙酯(IEM)的反应产物。
其它已知的交联剂有聚醚-双氨基甲酸乙酯-二甲基丙烯酸酯类(美国专利4,192,827),通过聚乙二醇、聚丙二醇和聚丁二醇与甲基丙烯酸2-异氰酸基乙酯(IEM)或间异丙烯基-γ,γ-二甲基苄基异氰酸酯类(m-TMI)反应得到的交联剂,以及聚硅氧烷-双氨基甲酸乙酯-二甲基丙烯酸酯类(美国专利4,486,577和4,605,712)。已知的交联剂还有聚乙烯醇、乙氧基化的聚乙烯醇或聚乙烯醇-乙烯共聚物与0.1-10%(摩尔)乙烯基异氰酸酯类(如IEM或m-TMI)的反应产物。
通过常规方法,如烯类不饱和化合物聚合中常用的紫外光聚合、利用自由基热引发剂或加热、或这些方法的组合方法,可以容易地将本发明的共聚物固化而浇铸成型。代表性的自由基热聚合引发剂有有机过氧化物,如过氧化缩醛、过氧化月桂酰、过氧化癸酰、过氧化硬脂酰、过氧化苯甲酰、过氧新戊酸叔丁酯、过二碳酸酯等等,所用的热引发剂浓度约为单体混合物总重量的0.01-1%。代表性的紫外光引发剂即本领域已知的那些,如苯偶姻甲醚、苯偶姻乙醚、Darocure1173、1164、2273、1116、2959、3331(EM工业)和Igracure651和184(Ciba-Geigy)。
除了上述聚合引发剂和交联剂外,本发明的单体混合物和所得的共聚物还可如接触透镜领域公知的那样含有其它物质,如着色剂、增韧剂、紫外线吸收剂和其它物质。
本发明得到的聚合物可按离心浇铸法(如美国专利3,408,429和3,496,254所述)及其它常规的方法如美国专利4,084,459和4,197,266公开的压塑法制成接触透镜。
聚合可在相应于所需的接触透镜形状的旋转模或固定模中进行。这样制得的接触透镜还可以根据需要进行机械精加工。也可以在适宜的模具或反应器中聚合而得到扣状、片状或棒状透镜材料,然后将其加工(如用车床或激光切削或抛光)得到具有所需形状的接触透镜。
本发明制得的水凝胶为输氧型、水解稳定、生物惰性、且是透明的。按照本发明使用的单体和共聚物易于聚合形成三维网络,从而可以输送氧气,并且是光学透明的、强度大且亲水。
本发明提供的材料可用于制备光学接触透镜或膜形式的修复材料,如心脏瓣膜和眼内透镜。本发明尤其涉及接触透镜。
本发明还提供了可用于生物医学装置的制品,如外科器械、心脏瓣膜、脉管替代物、子宫内节育器、膜和其它薄膜、隔膜、外科植入物、血管、人造输尿管、人造胸组织、用于与体外的体液接触的膜(如用于肾透析和心/肺机等的膜)、导管、口腔防护器、托牙分离剂、眼内装置(特别是接触透镜)。
例如,已知当血与人造物体表面接触时易于迅速破坏。对于与血液接触使用的修复物和装置的合成物表面进行抗血栓形成和非溶血性的设计是必要的。
下述实施例仅用来进一步说明本发明,不应认为是对本发明的限制。
                        实施例1烯丙氧基八氟戊烷的制备
向装有机械搅拌器和温度计的三颈圆底烧瓶中加入烯丙基溴(16.9克(g),0.14摩尔(mol))。八氟-1-戊醇(27.2g,0.1mol)、硫酸氢四丁铵(1.7g,0.005mol)、10毫升(ml)50%的氢氧化钠和125ml四氢呋喃。在70℃下回流6小时后,GC检测表明下式所示的反应完成。所得溶液用蒸馏水洗涤两次。收集产物层并蒸馏(68℃/30mm),得到31g(70%)烯丙氧基八氟戊烷。
Figure C9419116500201
当z为4和6时,分别得到的是烯丙氧基八氟戊烷和烯丙氧基十二氟戊烷侧链。
                        实施例2DP 100的甲基丙烯酸酯封端的75%(mol)聚二甲基硅氧烷-25% (mol)氢化甲基硅氧烷共聚预聚物的制备
在干燥氮气氛下,向1000ml圆底烧瓶中加入八甲基环四硅氧烷(371.9g,1.25mol)、四甲基环四硅氧烷(100.4g,0.42mol)和1,3-双甲基丙烯酰氧丁基四甲基二硅氧烷(27.7g,0.7mol)。加入三氟甲磺酸(0.25%,1.25g)作为引发剂。将反应混合物在室温下搅拌过夜。然后加入10g碳酸氢钠,再将反应混合物搅拌过夜。然后将所得溶液过滤并置于50℃、高真空下以除去未反应的环状化合物。单体结构由1H-NMR谱确认。
                     实施例3DP 100的甲基丙烯酸酯封端的75%(mol)聚二甲基硅氢烷-25% (mol)聚甲基八氟戊氧丙基硅氧烷共聚物单体(Octa-25)的制备
在氮气氛下,向装有磁性搅拌器和水冷凝器的500ml圆底烧瓶中加入氢化硅氧烷单体(按实施例2所述制备)(15g,0.002mol)、实施例1的烯丙氧基八氟戊烷(27.2g,0.1mol)、2.5ml四甲基二硅氧烷铂配合物(Huels-3%Pt/二甲苯)、150ml无水四氢呋喃(THF)和75ml二噁烷。将下面所示的反应混合物加热至75℃,反应通过红外光谱监测氢化硅氧烷的减少。当氢化硅氧烷消失时(3-4小时),冷却反应混合物,并在50℃、高真空下加热1小时以除去未反应的烯丙氧基八氟戊烷。单体结构由1H-NMR谱确认。其中,
y为10、25和40;
x+y为100;
z为4和6。
                     实施例4甲基丙烯酰氧丙基三(二甲基甲硅烷氧基)甲硅烷的制备
向装有温度计和磁性搅拌器的三颈圆底烧瓶中加入甲基丙烯酰氧丙基三氯甲硅烷(2.5g,0.01mol)、二甲基氯硅烷(6.53g,0.069mol)、三乙胺(7.69g,0.076mol)和25ml无水乙醚。将反应混合物冷却至-15℃并慢慢加入水(5g,0.28mol)稀释。使反应混合物慢慢回到室温并将其搅拌过夜。所得溶液用蒸馏水洗涤三次。收集乙醚层,用硫酸镁干燥,过滤并用旋转蒸发器除去乙醚。将所得油状物真空蒸馏(83-93℃/1mm),得到纯度为97.5%(GC法测定)的甲基丙烯酰氧丙基三(二甲基甲硅烷氧基)甲硅烷(产率为51.4%)。
                     实施例5甲基丙烯酰氧丙基三(八氟戊氧丙基二甲基甲硅烷氧基)甲硅烷的制
向200ml圆底烧瓶中加入甲基丙烯酰氧丙基三(二甲基甲硅烷氧基)甲硅烷(5.0g,0.013mol)、烯丙氧基八氟戊烷(21.4g,0.079mol)、0.005ml二乙烯基铂配合物(Huels)和50ml四氢呋喃。将溶液回流1小时,这时1H-NMR谱表明氢化硅氧烷已反应完。用旋转蒸发器(50℃/30mm)除去四氢呋喃和未反应的烯丙氧基八氟戊烷,得到甲基丙烯酰氧丙基三(八氟戊氧丙基二甲基甲硅烷氧基)甲硅烷(定量产率)。
                     实施例6由25%(mol)八氟硅氧烷(octa-25)与二甲基丙烯酰胺(DMA) 浇铸制得的膜的物理性能
用于评估物理和机械性能的所有膜均按下述方法制备。采用特氟隆垫片在两块硅烷化的玻璃片之间铸膜。紫外光引发剂为Darocur1173(浓度为0.5%)。固化条件为用紫外灯在3700uW/cm2的强度下照射2小时。固化后,将膜用2-丙醇在室温下提取过夜(膨胀300%),在室温下干燥2小时,然后用缓冲盐水煮2小时。评价膜的机械性能、透氧性和水解稳定性。水解稳定性测试即将测试样品在80℃下于缓冲盐水中加热并监测3、5和7天时的重量损失。
表1示出了由DP 100甲基丙烯酸酯封端的25%(mol)八氟硅氧烷(octa-25)与二甲基丙烯酰胺(DMA)制得的膜的提取性、水含量、透氧性和机械性能数据。不需要助溶剂来溶解组分。膜是透明的。
                      表1
        由八氟硅氧烷/DMA制剂得到的膜的提取
        性、水含量、氧气渗透性和机械性能数据混       提取百  水百分                伸长百  拉伸    撕裂合物     分数    含量      DK   模量   分数    强度    强度100/0    11.97   0.00     530    55     40      18     1.590/10    8.57    6.39     397    188    38      48     1.580/20    7.24    18.18    223    219    34      48     3.375/25    6.80    25.56    134    222    29      44     4.170/30    5.78    30.94    138    210    63      68     3.1
                        实施例7比较例——与不含-CF2H端基的硅氧烷相比25%(mol)八氟硅氧 烷(octa-25)与亲水性单体的溶解性的改善
由70份DP 100的甲基丙烯酸酯封端的聚二甲基硅氧烷和30份DMA配成制剂。该制剂为相分离的混合物。聚二甲基硅氧烷和DMA不相容。没法用该混合物制膜。另外,由含25%(mol)九氟侧链的DP100的甲基丙烯酸酯封端的聚二甲基硅氧烷(即-CF2H端基被全氟-CF3端基代替)和30份DMA制备溶液时也得到相分离的混合物。DMA和该聚硅氧烷不相容,也没法用该混合物制膜。
                              实施例8膜数据——氟硅氧烷/DMA/VDMO
表2示出了由DP 100的甲基丙烯酸酯封端的25%(mol)八氟硅氧烷与亲水性单体DMA和乙烯基二甲基噁唑烷酮(VDMO)制得的膜的提取性、水含量、透氧性和机械性能数据。所制备的所有膜均是透明的。
                           表2
          25%(mol)八氟硅氧烷/DMA/VDMO制剂的性能混         提取百   水百分               伸长百   拉伸   撕裂合物        分数     含量    DK   模量    分数    强度   强度70/30       5.8       34    145   180      40      47    3.170/30/1     6.4       33    132   156      39      37    2.970/30/3     5.9       37    102   106      36      22    2.570/30/5     5.0       42    66    103      50      30    2.6
                            实施例9膜数据——氟硅氧烷/TRIS/DMA/NVP
表3和4示出了由25%(mol)八氟硅氧烷与甲基丙烯酰氧丙基三(三甲基甲硅烷氧基)甲硅烷(TRIS)、DMA和N-乙烯基吡咯烷酮(NVP)(表3)以及乙二醇二甲基丙烯酸酯(EGDMA)(表4)制得的膜的提取性、水含量、透氧性和机械性能数据。
                        表3
       25%(mol)八氟硅氧烷/TRIS/DMA/NVP制剂的性能混           水百分                       撕裂合物          含量      DK      模量     强度80/0/20/0      17      186      155      1.880/0/15/5      17      212      170      2.480/0/10/10     15      183      195      1.980/0/5/15      16      186      190      2.070/0/30/0      28      108      190      3.070/0/20/10     25      112      217      3.570/0/10/20     27      130      212      2.575/0/5/25      24      160      179      1.440/10/10/40    52      52       71       2.3
                      表4
25%(mol)八氟硅氧烷/TRIS/DMA/NVP/EGDMA制剂的性能混                 水百分                   撕裂合物                 含量    DK     模量     强度50/0/10/40/0.2       41      65     171      2.440/10/10/40/0.2      46      63     83       2.325/25/10/40/0.2      51      81     32       4.510/40/10/40/0.2      54      76     20       9.2所有制剂均含有20份己醇。
                        实施例10膜数据——三(氟硅氧烷)/DMA
用DMA作共聚单体由八氟取代的三甲基丙烯酸酯(按实施例5所述制备)的聚合物浇铸制膜。70/30八氟取代的三甲基丙烯酸酯/DMA制剂的水含量为25%、DK为42,模量为107g/mm2,撕裂强度为3.7g/mm。另外,由八氟取代的三甲基丙烯酸酯和NVP的混合物浇铸制膜。在单体混合物中无助溶剂存在的条件下所得膜即是透明的。70/30/0.5八氟取代的三甲基丙烯酸酯/NVP/EGDMA制剂的水含量为25%,DK为45,模量为107g/mm2,撕裂强度为3.7g/mm。
                        实施例11八氟硅氧烷基透镜的铸塑
利用实施例8所述的固化条件,用DP 100的甲基丙烯酸酯封端的25%(mol)八氟侧链硅氧烷/DMA/Darocur 1173(70/30/0.5)制剂铸塑制备透镜。美容上可接受的透镜的总合格率为40%。用2-丙醇和缓冲盐水提取后,所得透镜显示出极好的湿润性。
所有制剂都含有20份己醇。用碳酸甲基丙烯酰氧乙基乙烯基酯(HEMAVC)和二甘醇甲基丙烯酸酯(EDGMA)作交联剂。
根据本发明所公开的内容,本领域技术人员可以对本发明作出许多其它的改变和变动。当然,在权利要求的范围内,可不局限于用这里具体描述的方式实施本发明。

Claims (17)

1.一种改善含硅氧烷的单体在亲水性单体中的溶解性的方法,该方法包括在含硅氧烷的单体上连接其二氟取代的端碳原子上连有氢原子的极性氟化侧基,所述氟化侧基用下面的示意性化学式表示:
             -D-(CF2)zH
其中,
z为1-20;
D为具有1-10个碳原子且碳原子间任选有醚键的烷基或亚烷基。
2.一种如下面通式所示的含有至少一个氟化侧基的含硅氧烷的单体:
Figure C9419116500021
其中,
R为具有1-10个碳原子且碳原子间任选有醚键的烷基或亚烷基;
R1-R4独立地为具有1-18个碳原子且碳原子间任选有醚键的一价烃基或卤素取代的一价烃基;
x≥0;
y≥1;
x+y=2-1000;
R5为下面通式所示的氟化侧基;
            -D-(CF2)zH
其中z为1-20;
D为具有1-10个碳原子且碳原子间任选有醚键的烷基或亚烷基;
A为活性不饱和基团。
3.按照权利要求2所述的单体,其中A为丙烯酸或甲基丙烯酸的酯或酰胺基团,或下面通式所示的基团:其中,
Y为-O-、-S-或-NH-。
4.按照权利要求2所述的单体,其中所述氟化侧基包含烷氧基全氟烷基基团。
5.按照权利要求4所述的单体,其中所述氟化侧基选自丙氧基八氟戊烷、丙氧基四氟丙烷和丙氧基十二氟庚烷基团。
6.按照权利要求4所述的含硅氧烷的单体,其中所述氟化侧基由下式表示:
-CH2-CH2-CH2-O-CH2-(CF2)z-H
其中z为1-20。
7.按照权利要求2所述的含硅氧烷的单体,其中所述含硅氧烷的单体由约1至约200个硅烷氧基重复单元构成。
8.按照权利要求2所述的含硅氧烷的单体,其中所述含硅氧烷的单体由100个硅烷氧基重复单元构成。
9.一种如下面通式所示的含有至少一个氟化侧基的含(甲基)丙烯酸氟化大体积聚硅氧烷基烷基酯的单体:其中,
A为活性不饱和基团;
R6为CH3或H;
R为具有1-10个碳原子且碳原子间任选有醚键的烷基和亚烷基;
D为具有1-10个碳原子且碳原子间任选有醚键的烷基或亚烷基;
x为1、2或3;
y为0、1或2;
x+y=3。
10.按照权利要求9所述的单体,其中A为丙烯酸或甲基丙烯酸的酯或酰胺基团。
11.按照权利要求9所述的单体,其中所述氟化侧基包含烷氧基全氟烷基基团。
12.按照权利要求11所述的单体,其中所述氟化侧基选自丙氧基八氟戊烷、丙氧基四氟丙烷和丙氧基十二氟庚烷基团。
13.按照权利要求11所述的单体,其中所述氟化侧基由下式表示:
           -CH2-CH2-CH2-O-CH2-(CF2)z-H
其中z为1-20。
14.一种如下式所示的含氟化大体积聚硅氧烷基烷基的单体:其中,
R7为CH2
x为1、2或3;
y为0、1或2;
x+y=3。
15.一种含有至少一种含硅氧烷的单体和至少一种亲水性单体的单体混合物,其中含硅氧烷的单体含有其二氟取代的端碳原子上连有氢原子的极性氟化侧基,所述氟化侧基由下面通式表示:
       -D-(CF2)zH其中,
z为1-20;
D为具有1-10个碳原子且碳原子间任选有醚键的烷基或亚烷基。
16.按照权利要求15所述的单体混合物,其中所述单体混合物还含有至少另外一种含硅氧烷的单体。
17.按照权利要求15所述的单体混合物,其中所述单体混合物还含有至少另外一种交联剂。
CN94191165A 1993-02-12 1994-01-28 氟硅氧烷水凝胶 Expired - Lifetime CN1116326C (zh)

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ES2114181T3 (es) 1998-05-16
SG47856A1 (en) 1998-04-17
KR100295147B1 (ko) 2001-09-17
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AU6167094A (en) 1994-08-29
US5539016A (en) 1996-07-23
CA2154660A1 (en) 1994-08-18
JP4173193B2 (ja) 2008-10-29
CN1273978A (zh) 2000-11-22
MX9401067A (es) 1994-08-31
US5387662A (en) 1995-02-07
AU669058B2 (en) 1996-05-23
CN1252143C (zh) 2006-04-19
US5321108A (en) 1994-06-14
JPH08506841A (ja) 1996-07-23
HK1008746A1 (en) 1999-05-14
BR9405839A (pt) 1995-12-05
DE69407573T2 (de) 1998-04-16
JP2008001905A (ja) 2008-01-10
DE69407573D1 (de) 1998-02-05
WO1994018253A1 (en) 1994-08-18
EP0683799A1 (en) 1995-11-29
EP0683799B1 (en) 1997-12-29
KR960701112A (ko) 1996-02-24

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