CN1234522A - 软接触透镜 - Google Patents

软接触透镜 Download PDF

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CN1234522A
CN1234522A CN99103416A CN99103416A CN1234522A CN 1234522 A CN1234522 A CN 1234522A CN 99103416 A CN99103416 A CN 99103416A CN 99103416 A CN99103416 A CN 99103416A CN 1234522 A CN1234522 A CN 1234522A
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D·G·范德拉安
M·哈吉斯
S·威廉斯
I·努内兹
M·L·阿尔顿
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    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
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    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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Abstract

一种含聚硅酮水凝胶的软接触透镜,上述聚硅酮水凝胶是通过固化含聚硅酮单体的反应混合物制成的。

Description

软接触透镜
本发明涉及通过固化包括含聚硅酮单体的反应混合物所形成的以及用于形成软接触透镜的聚硅酮水凝胶。
水凝胶是含水量处于平衡状态的水合交联聚合物系统。水凝胶通常具有透氧性和生物适应性，使得它们成为制造医用装置特别是接触透镜或眼内透镜的最佳材料。
传统的水凝胶是用主要含亲水单体的单体混合物制备的，例如2-羟乙基甲基丙烯酸酯(HEMA)或N-乙烯基吡咯烷酮(NVP)。美国专利4,495,313、4,889,664和5,039,459公开了传统水凝胶的组成。这些传统的水凝胶材料的透氧性与材料的含水量有关，而且通常低于20-30barrers。对于由传统的水凝胶材料制成的接触透镜，这种水平的透氧性适合于短时间佩戴接触透镜，然而，这种水平的透氧性可能不足以在长时间佩戴接触透镜期间(例如30天不摘)保持角膜健康。因此，已经进行努力而且继续努力提高传统水凝胶的透氧性。
一种公知的提高水凝胶的透氧性的方法是向水凝胶的组分中加含聚硅酮单体，从而制成聚硅酮水凝胶。含聚硅酮的聚合物的透氧性通常比传统的水凝胶高。已经通过聚合包括至少一种含聚硅酮单体和至少一种亲水性单体的混合物制备出聚硅酮水凝胶。或者含聚硅酮单体或者亲水性单体可能作为交联剂(交联剂是具有多个可聚合官能团的单体)或者可能使用单独的交联剂。聚硅酮水凝胶的组成已经在美国专利4,954,587、5,010,141、5,079,319、5,115,056、5,260,000、5,336,797、5,358,995、5,387,632、5,451,617和5,486,579及WO96/31792中公开。
美国专利3,808,178公开了小的含聚硅酮单体与不同的亲水性单体的共聚物的形成。
美国专利5,034,461描述了用聚硅酮-聚氨酯大分子单体与亲水性单体例如HEMA或N,N-二甲基丙烯酰胺(DMA)的不同组合制备的聚硅酮水凝胶。加入甲基丙烯酰基氧丙基三(三甲基甲硅烷氧基)硅烷(TRIS)降低了这种水凝胶的模量，但是在许多例子中模量还是高于期望值。
美国专利5,358,995和5,387,632描述了用聚硅酮大分子单体、TRIS、N-乙烯基吡咯烷酮(NVP)与DMA的不同组合制备的水凝胶。用TRIS代替相当一部分聚硅酮大分子单体降低了水凝胶的模量。同一作者的两篇文章“The Role of BulkyPolysiloxanylalkyl Methacrylates in Polyuretyane-Polysiloxane Hydrogels”(发表在J.Appl.Poly.Sci.Vol.60,1193-1199(1996)和“The Role of Bulky PolysiloxanylalkylMethacrylates in Oxygen-Permeable Hydrogel Materials”(发表在J.Appl.Poly.Sci.Vol.56,317-324(1995)中也描述了实验结果，表明用含聚硅酮大分子单体和亲水性单体例如DMA的反应混合物制备水凝胶的模量随着加入TRIS而降低。
使用甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷(MBM)制造硬接触透镜在WO9110155和JP61123609中进行了描述。
当相当高水平的松散的含聚硅酮单体例如TRIS被加入到水凝胶中时，弹性或聚合物在受应力之后返回原来的形状的速度可能下降到接触透镜的佩戴者不能接受的程度，上述水凝胶是由含聚硅酮大分子单体和亲水性单体制成的。
本领域还需要足够软的聚硅酮水凝胶，以便制造具有高的透氧性、适当的含水量和足够的弹性以及使佩戴者感到舒适的软接触透镜。
本发明提供了通过固化包括具有如下结构的含聚硅酮单体的反应混合物制备的聚硅酮水凝胶：
结构Ⅰ
其中R51是H或CH3,q为1或2，而且对于每个q,R52、R53和R54分别是包括1至100个重复Si-O单元的乙基、甲基、苯甲基、苯基或一价硅氧烷链，p为1至10的数，r=(3-q),X为O或NR55，其中R55为H或具有1至4个碳的一价烷基团，a为0或1，以及L最好是包括2至5个碳的二价连接基团，所述二价连接基团也可选择包括醚或羟基基团，例如聚乙二醇链。
在最佳实施例中，聚硅酮水凝胶还包括第二含聚硅酮单体和亲水性单体。
本发明的优点在于在聚硅酮水凝胶中使用结构Ⅰ的含聚硅酮单体，降低了该水凝胶的模量，尤其是在包含作为交联剂的附加的含聚硅酮单体和结构Ⅰ的含聚硅酮单体的水凝胶中。当结构Ⅰ的单体比现有技术中描述的单体存在的量少时，就可以有效降低聚硅酮水凝胶的模量，从而允许使用低水平的结构Ⅰ的含聚硅酮单体，同时保持本发明的聚硅酮水凝胶的弹性。这一效果似乎很可能是因为该硅氧烷基团不如现有技术中使用的含聚硅酮单体例如TRIS松散。根据本发明制造的聚合物可以用于制造具有高的透氧性、好的弹性的软接触透镜，而且制造成本低、效率高。本发明的聚合物可以用于制造需要生物适应性和高透氧性的医用装置，最好是接触透镜。
这里使用的术语“单体”是指可以聚合的低分子量化合物(即通常具有平均分子量低700的化合物)和指含有还能够进一步聚合的官能团的高分子量化合物或聚合物介质，有时称为大分子单体(即通常具有平均分子量大于700的化合物或聚合物介质)。这样，就应该理解，术语“含聚硅酮单体”和“亲水单体”包括单体、大分子单体和预聚物。预聚物是部分聚合的单体或能够进一步聚合的单体。
“含聚硅酮单体”是在单体、大分子单体或预聚物中包括至少两个[-Si-O-]重复单元的单体、大分子单体或预聚物。较好，在含聚硅酮单体中存在的Si和连接O的总量大于含聚硅酮单体总分子量的百分之二十重量，而且更好大于百分之三十重量。
可以用于形成本发明的聚硅酮水凝胶的结构Ⅰ的含聚硅酮单体的例子有甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷、甲基丙烯酰基氧丙基五甲基二硅氧烷、(3-甲基丙烯酰基氧基-2-羟丙基氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷、和以一-甲基丙烯丙基终止的例如结构Ⅱ的聚二甲基硅氧烷：
Figure A9910341600061
结构Ⅱ
其中b=0至100。
较好的结构Ⅰ的含聚硅酮单体是甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷、甲基丙烯酰基丙氧基五甲基二硅氧烷和以一甲基丙烯酰基丙氧基终止的聚二甲基硅氧烷。更好的结构Ⅰ的含聚硅酮单体是甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷、和甲基丙烯酰基氧丙基五甲基二硅氧烷。最好的结构Ⅰ的含聚硅酮单体是甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷(MBM)。
最佳是附加的含聚硅酮单体与结构Ⅰ的含聚硅酮单体结合形成本发明的软接触透镜。任何已知的对制造聚硅酮水凝胶有用的含聚硅酮单体都可以用于与结构Ⅰ的含聚硅酮单体结合形成本发明的软接触透镜。申请日为1997年10月9日、序列号为No.08/948,128的美国专利申请中公开了许多用于这一目的的含聚硅酮单体，将该专利申请包括在这里作为参考。可以用于与结构Ⅰ的含聚硅酮单体结合形成本发明的聚硅酮水凝胶的最佳的附加的含聚硅酮单体是在序列号(VTN-0389)的美国专利申请中公开的羟烷基胺-官能团含聚硅酮单体，该专利申请名称为“聚硅酮水凝胶聚合物”，由Vanderlaan et al.与本申请一同申请，将该专利申请包括在此作为参考。包括如下结构的嵌段(block)或随机单体的较佳含聚硅酮线型或支链羟烷基胺-官能团单体：
Figure A9910341600071
结构Ⅲ
其中
n为0至500、m为0至500，而且(m+m)=10至500，而且较好为20至250；R2、R4、R5、R6和R7分别是一价烷基或芳基，所述一价烷基或芳基可以进一步用醇、酯、胺、酮、羧酸或醚基团取代，较好是未被取代的一价烷基或芳基；R1、R3和R8分别是一价烷基或芳基，所述一价烷基或芳基可以进一步用醇、酯、胺、酮、羧酸或醚基团取代，较好是未被取代的一价烷基或芳基，或者是下列含氮的结构：
Figure A9910341600072
结构Ⅳ
条件是R1、R3和R8中的至少一个是根据结构Ⅳ，其中R9是二价烷基基团，例如
-(CH2)5-，其中s为1至10，较好是3至6，而且最好为3。
R10和R11分别是氢、一价烷基或芳基，该基团可以进一步用醇、酯、胺、酮、羧酸或醚基团来取代或者具有如下结构：
结构Ⅴ
其中R14为H或包括丙烯酰基、甲基丙烯酰基、苯乙烯基、乙烯基、烯丙基或N-乙烯基内酰胺的一价可聚合基团，最好为H或甲基丙烯酰基；R16是氢、一价烷基或芳基，该基团可以进一步用醇、酯、胺、酮、羧酸或醚基团来取代，或者是包括丙烯酸酯、甲基丙烯酸酯、苯乙烯基、乙烯基、烯丙基或N-乙烯基内酰胺的可聚合基团，较好是用醇或甲基丙烯酸酯取代的烷基；R12、R13和R15分别是氢、一价烷基或芳基，该基团可以进一步用醇、酯、胺、酮、羧酸或醚基团来取代，或者R12与R15或R15与R13可以结合在一起形成环形结构，条件是至少单体中的一些结构Ⅳ的基团包括可聚合的基团。R12、R13和R15较好是H。
在另一实施例中，本发明的聚硅酮水凝胶包括结构Ⅰ的含聚硅酮单体，可以使用或不使用附加的含聚硅酮单体，较好包括亲水单体。所述附加的含聚硅酮单体不是根据结结构Ⅰ的所述的含聚硅酮单体。选择用来制造本发明的水凝胶聚合物的亲水单体可以是任何现有技术中公开的用于制造水凝胶的亲水单体。
用于制造本发明的聚合物的较佳亲水单体可能含乙烯或丙烯。这样的亲水单体本身可能被用作交联剂。术语“乙烯基-型”或“含乙烯基”的单体是指包括乙烯基基团(-CH=CH2)的单体，而且通常具有高的反应性。这样的亲水含乙烯基单体聚合时比较容易是公知的。“丙烯-型”或“含丙烯”的单体是指包括丙烯基基团的那些单体；
(CH2=CRCOX)
其中R是H或CH3,X是O或N，所述那些单体也易于聚合是公知的，例如N,N-二甲基丙烯酰胺(DMA)、2-羟乙基甲基丙烯酸酯(HEMA)、甘油甲基丙烯酸酯、2-羟乙基甲丙烯酰胺、聚一甲基丙烯酸乙二醇酯、甲基丙烯酸和丙烯酸。
可能结合至本发明的聚硅酮水凝胶中的亲水含乙烯基单体包括诸如N-乙烯基内酰胺(例如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-乙甲酰胺、N-乙烯基甲酰胺，具有NVP的为较佳。
可以用于本发明的其他亲水单体包括一个或多个末端为羟基基团被含有可聚合双键的官能团代替的聚氧乙烯多元醇。例子包括聚乙二醇、乙氧基化烷基糖苷、和乙氧基化双酚A与一个或多个摩尔当量的封端基团例如异氰酸根合乙基甲基丙烯酸酯(“IEM”)、甲基丙烯基酸酐、甲基丙烯酰氯、乙烯基苯甲酰氯、或类似物反应，以便产生聚乙烯多元醇，所述聚乙烯多元醇具有一个或多个末端可聚合的烯烃族基团通过连接部分例如如氨基甲酸酯或酯基团与聚乙烯多元醇结合。
还有例子是在美国专利号为5,070,215中公开的亲水碳酸乙烯酯或氨基甲酸乙烯酯单体，和在美国专利号为4,910,277中公开的亲水噁唑酮。其他适合的单体对于本领域的技术人员是显而易见的。
可能包含在本发明的聚合物中的较好的亲水单体包括诸如N,N-二甲基丙烯酰胺(DMA)、2-羟乙基甲基丙烯酸酯(HEMA)、甲基丙烯酸甘油酯、2-羟乙基甲丙烯酰胺、N-乙烯基吡咯烷酮(NVP)、聚一甲基丙烯酸乙二醇酯、甲基丙烯酸和丙烯酸的亲水单体，其中具有DMA的为最佳。
可以存在于形成本发明的聚硅酮水凝胶的反应混合物中的其他单体包括吸收紫外线的单体、反应性颜料或类似物。附加处理助剂例如脱模剂或湿润剂也可以加到反应混合物中。
在反应混合物中较好包括聚合反应催化剂。聚合反应催化剂可以是在中等高温下可以产生游离基的诸如过氧化月桂酰、过氧化甲苯酰、过碳酸异丙酯、偶氮二异丁腈或类似物，或者聚合反应催化剂可以是光引发剂系统，例如芳族α-羟基酮或叔胺加双酮。光引发剂系统的说明性例子是2-羟基-2-甲基-1-苯基-丙烷-1-酮，及樟脑醌与4-(N,N-二甲氨基)苯甲酸乙酯的组合物。催化剂以催化有效量例如每100份重量反应单体中占大约0.1份至0.2份重量用于反应混合物中。反应混合物的聚合反应可以根据所使用的聚合反应引发剂来适当选择使用加热或可见光或紫外光或其他方法来引发。较佳的引发剂是2-羟基-2-甲基-1-苯基-丙烷-1-酮，较佳聚合反应引发方法是紫外光。
通常在固化反应混合物后(该反应混合物定义为结构Ⅰ的含聚硅酮单体与选择使用的亲水单体及任何其他选择使用的组分，例如附加的含聚硅酮单体、稀释剂、交联剂、催化剂、脱模剂、颜料等等，所有这些在聚合之前混合在一起)，所产生的聚合物用溶剂处理以便除去稀释剂(如果使用的话)或任何微量的没有反应的成分，并把该聚合物水合化以形成水凝胶。使用的溶剂可能是水(或者水溶液例如生理盐水)，或者根据用于制造本发明的水凝胶的稀释剂(如果使用的话)的溶解度特性和任何剩余的未发生聚合反应单体的溶解度特性，开始使用的溶剂可以是有机液体例如乙醇、甲醇、异丙醇、它们的混合物或类似物、或者一种或多种这样的有机液体与水的混合物、然后用纯水(或生理盐水)萃取以制造含用水溶胀的上述单体的聚合物的聚硅酮水凝胶。在水合所述聚合物之后该聚硅酮水凝胶的含水量占聚硅酮水凝胶的总重量比较好是占百分之二至五十重量，更好是占百分之十五至四十五重量组分，最好是占百分之二十至四十重量。这些聚硅酮水凝胶尤其适合于制造接触透镜或眼内透镜，较好是制造软接触透镜。
已知在制造接触透镜过程中有许多用于模注反应混合物的方法，包括旋转模注和静止模注。旋转模注方法在美国专利号为3,408,429和3,660,545中公开，而静止模注方法在美国专利号为4,113,224和4,197,266中公开。制造包括本发明的聚合物的接触透镜的较佳方法是直接模注聚硅酮水凝胶，这样经济而且能够精确控制水合透镜的最后形状。对于这一方法，反应混合物放置在具有最后期望的聚硅酮水凝胶即水-溶胀聚合物的形状的模具中，而且反应混合物置于单体聚合的条件之下，从而制造出近似于最后期望产品的形状的聚合物。然后，这一聚合物混合物选择地用溶剂处理，然后用水处理，制造出最后的尺寸和形状非常近以于原始模注的聚合物制品的尺寸和形状的聚硅酮水凝胶。这一方法可以用于形成接触透镜，而且也在美国专利4,495,313、4,680,336、4,889,664和5,039,495中公开，包括在本专利中作为参考。在制造出聚硅酮水凝胶之后，最后把所述透镜用亲水膜镀膜。现有技术中已经公开了一些给透镜加亲水膜的方法，包括美国专利3,854,982、3,916,033、4,920,184和5,002,794；和WO91/04283，及EPO93810399。
组合的结构Ⅰ的含聚硅酮单体与附加的含聚硅酮单体(如果在反应混合物中有的话)占反应混合物中各反应成分重量的范围较好是大约百分之五至百分之一百重量，更好是占大约百分之十至百分之九十重量，最好是占大约百分之十五至百分之八十重量。选择的亲水单体(如果上述发明中有的话)占反应混合物中反应成分重量的范围较好是大约百分之五至百分之八十重量，更好是大约占百分之十至百分之六十重量，最好是大约占百分之二十至百分之五十重量。稀释剂占总反应混合物重量的范围较好是大约零至百分之七十重量，更好是大约零至百分之五十重量，最好是大约占零至百分之二十重量。需要稀释剂的量随着反应成分的性质和相对量而变化。
较好是反应成分重量的百分之十至六十重量、更好是百分之十五至五十重量是含聚硅酮单体，反应成分重量的百分之二十至五十是结构Ⅰ的含聚硅酮单体，反应成分重量的百分之十至五十重量是亲水单体，更好是DMA，反应成分重量的百分之零点一至百分之一重量是紫外或可见光-激活的光引发剂和总反应混合物重量的百分之零至百分之二十重量是仲醇或叔醇稀释剂，更好是叔醇。较佳实施例包括结构Ⅰ的含聚硅酮单体、亲水单体和附加的含聚硅酮单体，较好是根据结构Ⅲ的单体。最佳实施例包括较佳的结构Ⅰ的含聚硅酮单体、亲水单体和根据上面描述的结构Ⅲ的附加的含聚硅酮单体。
本发明的反应混合物可以通过本领域的技术人员公知的任何方法形成，例如摇晃或搅拌，并用来通过前面描述的方法来形成聚合物制品或装置。对于一些单体反应混合物，较好是在稍微高于室温的温度下，例如30-40℃，或低于室温的温度下，例如0-10℃，对反应混合物进行聚合，以便防止各成分的相分离。
下面的例子进一步描述了本发明。用于这些例子中的一些材料标记如下：
“DAROCURE1173”2-羟基-2-甲基-1-苯基-丙烷-1-酮，
“DMA”         N,N-二甲基丙烯酰胺
“MBM”         3-甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)-
                甲基硅烷
制备1-制备聚硅氧烷单体
把500克α,ω-双氢基丙基聚双甲基硅氧烷(分子量为5000)和68克甲基丙烯酸缩水甘油酯混合，并在100℃加热搅拌10小时。把生成物用1500ml乙腈萃取五次以便除去剩余甲丙烯酸缩水甘油酯，得到透明油IR:3441,2962,1944,1725,1638,1612,1412cm-1。该生成物将被称为“甲基丙烯酸缩水甘油酯与分子量为5000的α,ω-双氨基丙基聚双甲基聚硅酮的反应产物”或者称为双(N,N-二-2-羟基-3-甲基丙烯酰基氧丙基)氨基丙基聚双甲基硅氧烷。
实施例1
将38.2份重量的制备1的生成物与28.8份MBM、33份DMA和一份重量的DAROCURE1173混合并用3-甲基-3戊醇稀释制成反应混合物，其中稀释剂占全部反应混合物质量的9％。所得到的反应混合物是透明均匀的溶液。填充和封住聚丙烯接触透镜模具，并用来自荧光紫外光源的总辐射量为3.2J/cm2的紫外光照射30分钟时间段。打开模具并把透镜放入异丙醇中，然后转移到去离子水中。
所述透镜透明，拉伸模量为205±12g/mm2，断裂伸长度为133±37％，而且平衡含水量为24.2±0.2％。拉伸性能用InstronTM model1122拉伸实验器确定。平衡含水量(EWC)通过重量分析确定，并表示如下：
％EWC=100×(水合透镜的质量-干燥透镜的质量)/水合透镜的质量
实施例2-16
反应混合物用制备1的组分制备，但是用量列于表1中。所有的反应混合物和透镜都是透明的。
表1-聚硅酮水凝胶组分和性能
      实施例       1       2      3       4
       组分制备大分子单体MBMDMADarocur稀释剂的％EWC(％)模量(psi)断裂伸长度的％Dk(barres) 38.228.8330.4924.2±0.2205±12133±371423 33.533.5330.4723.3±0.3178±11156±39144.9 27.639.4330.4522.4±0.2136±4168±48145.1 22.344.7330.4424.2±0.3109±3200±581093
      实施例       5       6      7       8
       组分制备大分子单体MBMDMADarocur稀释剂的％EWC(％)模量(psi)断裂伸长度的％DK(barrers) 37.127.9350.41026.1±0.3179±5151±42118.8 32.532.5350.4725.8±0.3215±7106±30129.6 26.838.2350.4525.8±0.3132±6195±65116.5 21.743.3350.41125.8±0.1101±4179±47107.9
      实施例       9       10      11       12
       组分制备大分子单体MBMDMADarocur稀释剂的％EWC(％)模量(psi)断裂伸长度的％Dk(barrers) 35.426.6380.41229.4±0.3215±799±22106.6 3131380.4730.0±0.3175±7132±40115.7 25.536.5380.4726.6±0.213±51166±51104.9 20.741.3380.4526.7±0.3106±4204±55100.3
      实施例       13       14      15       16
       组分制备大分子单体MBMDMADarocur稀释剂的％EWC(％)模量(psi)断裂伸长度的％Dk(barrers) 34.225.8400.41232.1±0.1218±11110±34112.4 3030400.41131.2±0.217±6130±51104.6 24.7353400.4831.6±03131±4185±5390.8 2040400.4931.7±0.295±3203±4792.3
*总反应混合物的反应成分和稀释剂的％。
实施例17
21.5％平均分子量为5000g/mol的α,ω-双甲基丙烯酰基氧丙基聚双甲基硅氧烷与42.5％MBM、35％DMA和1％DAROCUR1173混合并用3-甲基-3戊醇稀释制成含有22％重量稀释剂的透明溶液。用与例1相同的方法制出透镜。该透镜性能列于表2中。
实施例18
使用实施例17中描述的方法和反应混合物制成透镜，但是用甲基丙烯酰基氧丙基五甲基二硅氧烷(MPD)代替MBM。该透镜性能列于表2中。
比较例1
使用例17中的组分制备反应混合物，但是用TRIS代替MBM，而且使用20％稀释剂。用例1的方法制出透镜。列于表2中的透镜性能表明当使用MBM(实施例17)或者甲基丙烯酰基氧丙基五甲基二硅氧烷(MPD)(例18)代替TRIS得到的拉伸模量比较低。
表2-聚硅酮水凝胶聚合物的组分和性能
    实施例17     比较例1     实施例18
    PDMS*      21.5      21.5      21.5
    TRIS      42.5
    MBM      42.5
    MPD      42.5
    DMA      35      35      35
 单体/稀释剂      78/22      80/20      78/22
   拉伸模量      65±2psi      87±3psi      55±2psi
  断裂伸长度      278±60％      307±88％      263±81％
      Dk      110barrers      147barrers      75.6barrers
      EWC      28.2±0.3％      28.9±0.3％      31.0±0.3％
PDMS*=α,ω-双-甲基丙烯酰基氧丙基聚双甲基硅氧烷，平均分子量为5000g/mol。
实施例19
29.0％平均分子量为5000g/mol的α,ω-双甲基丙烯酰基氧丙基聚双甲基硅氧烷与35％以一甲基丙烯酰基氧丙基终止的PDMS(T1，结构Ⅱ，分子量=800至1000)、35％DMA和1％DAROCURE1173混合并用3-甲基-3-戊醇稀释制成含有23.0％重量稀释剂的透明溶液。用与例1相同的方法制出透镜。该透镜性能列于表3中。
实施例20
29.0％平均分子量为5000g/mol的α,ω-双甲基丙烯酰基氧丙基聚双甲基硅氧烷与35％(3-甲基丙烯酰基氧-2-羟丙基氧)丙基双(三甲基甲硅烷氧基)甲基硅烷(T2)、35％DMA和1％DAROCUR1173混合并用3-甲基-3戊醇稀释制成含有37.6％重量稀释剂的透明溶液。用与实施例1相同的方法制出透镜。该透镜性能列于表3中。
表3-聚硅酮水凝胶聚合物的组分和性能
    实施例19     实施例20
   PDMS      29.0      29.0
   T1      35.0
   T2      35.0
   DMA      35.0      35.0
   DAROCUR1173      1.0      1.0
   ％稀释剂      23.0      37.6
   拉伸模量      193±15psi      175±11psi
   断裂伸长度      87.9±42％      108±54％
   Dk      171barrers      94barrers
   EWC      31.1±0.2％      33.4±0.2％
各例子表明使用结构Ⅰ的含聚硅酮单体制造的接触透镜所提供的接触透镜是清晰的并比根据比较例制造的接触透镜的拉伸模量低。希望接触透镜的拉伸模量低，以提供佩戴舒适的透镜。
参考具体的实施例已经描述了本发明，然而，在权利要求范围以内的其他实施例对于本领域的普通技术人员是显而易见的。

Claims (14)

1．一种含聚硅酮水凝胶的软接触透镜，上述聚硅酮水凝胶是通过固化如下结构的含聚硅酮单体的反应混合物制成的：
Figure A9910341600021
结构Ⅰ
其中R51是H或CH3,q为1或2，而且对于每个q,R52、R53和R54分别是包括1至100个重复Si-O单元的乙基、甲基、苯甲基、苯基或一价硅氧烷链，p为1至10的数，r=(3-q),X为O或NR55，其中R55是H或具有1至4个碳的一价烷基基团，a为0或1，以及L为二价链基团。
2．如权利要求1所述的软接触透镜，其中上述含聚硅酮单体是从如下组中选择，该组包括甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷、甲基丙烯酰基氧丙基五甲基二硅氧烷、(3-甲基丙烯酰基氧-2-羟基丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷、和以一甲基丙烯酰基氧丙基终止的如结构Ⅱ的聚二甲基聚硅酮：
结构Ⅱ
其中b=0至100。
3．如权利要求1所述的软接触透镜，其中上述含聚硅酮单体是甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷。
4．如权利要求1所述的软接触透镜，其中上述反应混合物进一步包括亲水单体。
5．如权利要求4所述的软接触透镜，其中上述亲水单体是从如下组中选择，该组包括N,N-二甲基丙烯酰胺、2-羟乙基甲基丙烯酸酯、甲基丙烯酸甘油酯、2-羟乙基甲丙烯酰胺、N-乙烯基吡咯烷酮、聚一甲基丙烯酸乙二醇酯、甲基丙烯酸和丙烯酸。
6．如权利要求1所述的软接触透镜，其中上述反应混合物进一步包括附加的含聚硅酮单体。
7．如权利要求6所述的软接触透镜，其中上述附加的含聚硅酮单体是羟基烷基胺-官能团含聚硅酮单体。
8．如权利要求4所述的软接触透镜，其中上述反应混合物进一步包括附加的含聚硅酮单体。
9．如权利要求8所述的软接触透镜，其中上述附加的含聚硅酮单体是羟基胺-官能团含聚硅酮单体。
10．如权利要求1所述的软接触透镜，其中上述反应混合物进一步包括稀释剂。
11．如权利要求10所述的软接触透镜，其中上述稀释剂是叔醇。
12．如权利要求8所述的软接触透镜，其中上述结构Ⅰ的含聚硅酮单体和附加的含聚硅酮单体在上述反应混合物中占上述反应混合物中的反应成分重量的百分之五至百分之一百重量，而所述亲水单体占上述反应混合物中反应成分重量的百分之五至百分之八十重量。
13．如权利要求8所述的软接触透镜，其中上述结构Ⅰ的含聚硅酮单体和附加的含聚硅酮单体在上述反应混合物中占上述反应混合物中的反应成分重量的百分之十至百分之六十重量，而上述亲水单体占上述反应混合物中的反应成分重量的百分之十至百分之五十重量。
14．如权利要求1所述的软接触透镜，其中上述反应混合物包括甲基丙烯酰基氧丙基双(三甲基甲硅烷氧基)甲基硅烷、N,N-二甲基丙烯酰胺、和甲基丙烯酸缩水甘油酯与分子量为5000的α,ω-双氨基丙基聚双甲基聚硅酮的反应生成物。
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