CN1084335C - 用于降低硅氧烷水凝胶的模量的单体单元 - Google Patents
用于降低硅氧烷水凝胶的模量的单体单元 Download PDFInfo
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- CN1084335C CN1084335C CN96198808A CN96198808A CN1084335C CN 1084335 C CN1084335 C CN 1084335C CN 96198808 A CN96198808 A CN 96198808A CN 96198808 A CN96198808 A CN 96198808A CN 1084335 C CN1084335 C CN 1084335C
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Abstract
本发明公开了用于降低水凝胶模量的单体单元。包含本发明单体单元的硅氧烷水凝胶特别适用于制备生物医学制品如硅氧烷水凝胶隐形眼镜。式I中A为活性不饱和基团；R和D独立地为1-10个碳原子的烷基、亚烷基或卤代烷基，其中在所说的碳原子间可包括醚键；R1、R2、R3和R4独立地选自：烷基或卤代烷基，其中在碳原子间可包括醚键；硅氧烷基团；以及具有6-18个碳原子的碳环基团；m为1-500的整数；n为1-20的整数；x和y为0或1；z为1或2；并且x+y+z＝3；只要R1或R2中至少一个为1-10个碳原子的烷基。
Description
在先申请
本申请要求保护U.S.临时申请号为60/008,297，申请日为1995.12.7的申请的权益。
发明领域
本发明涉及一类含氟代硅氧烷的单体单元和它们在降低硅氧烷水凝胶的模量方面的用途。这种物质在制备隐形眼镜中有特殊应用。
发明背景
水凝胶表示一类用于多种生物医学应用领域的理想物质，包括用于制备隐形眼镜。水凝胶为包含平衡态水的水合且交联的聚合体系。硅氧烷水凝胶为一类公知的水凝胶，其特征是其中引入了硅氧烷。通常，硅氧烷水凝胶的含水量大于约5％(重量)，而一般为约10-80％(重量)。通常，将至少一种含硅氧烷的单体与至少一种亲水性单体的混合物进行聚合可制备这种物质。含硅氧烷的单体或亲水性单体均可用作交联剂(交联剂是指具有多个可聚合官能团的单体)，或者采用另一种单独的交联剂。在本领域中用于制备硅氧烷水凝胶的适用硅氧烷单体单元是公知的，在下述文献中提供了许多实例：U.S.专利4,136,250；4,153,641；4,740,533；5,034,461；5,070,215；5,260,000；5,310,779和5,358,995。适用的含硅氧烷的单体单元的实例包括：
(a)本体聚硅氧烷基烷基(甲基)丙烯酸单体，一般称之为“TRIS”单体，例如包括：甲基丙烯酰氧基丙基三(三甲基硅氧烷基)硅烷；
(b)聚(有机硅氧烷)单体单元；
(c)含硅氧烷单体，包括：含硅氧烷的乙烯基碳酸酯或乙烯基氨基甲酸酯单体，例如：1，3-双[4-乙烯基氧基羰基氧基)丁-1-基]四甲基-二硅氧烷；3-(三甲基甲硅烷基)丙基乙烯基碳酸酯；3-(乙烯基氧基羰基硫基)丙基-[三(三甲基甲硅烷氧基)硅烷]；3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基氨基甲酸酯；3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基烯丙基氨基甲酸酯；3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基碳酸酯；叔丁基二甲基甲硅烷氧基乙基乙烯基碳酸酯；三甲基甲硅烷基乙基乙烯基碳酸酯；三甲基甲硅烷基甲基乙烯基碳酸酯。其它适用的含硅氧烷的单体实例在本领域中是公知的。
含硅氧烷的单体可与各种亲水性单体进行共聚以生产各种硅氧烷水凝胶产物。例如，硅氧烷水凝胶特别适用于各种生物医学应用领域，包括制备成型制品和涂层，例如：膜、薄膜、人造输尿管、宫颈帽、子宫内用具、心脏瓣膜、血管替代品、手术用具、插管、护牙、牙线、眼内用具、弥补用具，特别是隐形眼镜。
适宜的用于硅氧烷水凝胶的亲水性单体包括：不饱和羧酸，如甲基丙烯酸和丙烯酸；丙烯酰取代的醇，如甲基丙烯酸2-羟基乙酯和丙烯酸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，如甲基丙烯胺和N，N-二甲基丙烯酰胺。其它实例为U.S.专利5,070,215描述的亲水性的乙烯基碳酸酯或乙烯基氨基甲酸酯单体以及U.S.专利4,910,277描述的亲水性噁唑酮单体。其它适宜的亲水性单体是本领域的技术人员公知的。
具体就隐形眼镜而言，业已表明，对某些用于形成硅氧烷水凝胶的单体进行氟化可降低用所述水凝胶制备的隐形眼镜上沉淀物的聚集，如U.S.专利4,954,587、5,079,319和5,010,141所述。进而，已发现，具有某些氟代侧基-(CF2)-H的含硅氧烷单体，可改善亲水性单体与含硅氧烷单体单元间的相容性，如U.S.专利5,387,662和5,321,108所述。
多数硅氧烷水凝胶的模量(杨氏弹性模量)相当高，例如常常超过300g/mm2(按照ASTM测试法D1938测量)。对于多数生物医学应用领域而言，最好是将水凝胶的模量降低如降低至约20-150g/mm2，更优选的是降低至30-100g/mm2。这对制备舒适的隐形眼镜是非常重要的，这是因为隐形眼镜材料的模量对于眼镜的“舒适度”有很大的影响。模量大的眼镜一般感觉较硬，其弹性回复力太大，使得戴上这样的眼镜后感觉不自然。
本体聚硅氧烷基烷基甲基丙烯酸酯，例如甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷(被称为：TRIS)是公知的可降低硅氧烷水凝胶即聚氨酯-聚硅氧烷水凝胶组合物模量的物质。例如参见：Lai，Yu Chin，The Role of Bulky Polysiloxanyl Methacrylates in PolyurethanePolysiloxane Hydrogels，Proceedings of the American Chemical SocietyDivision of Polymeric Materials：Science and Engineering，Vol 72，pg.118-119(1995)。TRIS化合物在硅氧烷水凝胶中的使用在U.S.专利5,358,995中也有描述。而在U.S.专利5,321,108和5,387,662中，公开了TRIS类化合物，其至少包括一个含末端氢的氟取代端基。这种物质可增加含硅氧烷的单体单元与亲水性单体单元间的相容性。
不幸的是，上述TRIS型氟代化合物的沸点非常高，这样就难于按照常规方法对其蒸馏。因而，这类物质也难于进行诸如气相色谱的分析。
因此，人们仍试图寻找既具有可接受的透氧性，同时模量又得以降低，易于进行合成、纯化及分析的硅氧烷水凝胶。进而，在许多应用领域中，这种水凝胶必须具有光学透明性和可加工性(如能被铸塑、机加工等)，可将其加工成如隐形眼镜的产品，还应具有生物相容性，并且形成沉淀的倾向较小。
发明概述
本发明涉及一种用于降低硅氧烷水凝胶的模量的单体单元，其用式I表示：
其中：
A为活性不饱和基团；
R和D独立地为1-10个碳原子的烷基、亚烷基或卤代烷基，其中在所说的碳原子间可包括醚键；
R1、R2、R3和R4独立地选自：烷基或卤代烷基，其中在碳原子间可包括醚键；硅氧烷基团；以及具有6-18个碳原子的碳环基团；
m为1-500的整数；n为1-20的整数；x和y为0或1；
z为1或2；并且x+y+z＝3；
只要R1或R2中至少一个为1-10个碳原子的烷基。
本发明还涉及包含这种单体单元的水凝胶组合物，涉及降低水凝胶模量的方法，涉及制备水凝胶的方法，还涉及由这种水凝胶制备的隐形眼镜。
本发明的优点在于，式I所述的单体单元可降低水凝胶的模量，同时不会显著降低形成的聚合组合物的透氧性。进而，该单体单元的合成、纯化和分析均相当容易，它们可被聚合成水凝胶而不会显著影响光学透明性。
发明详述
本发明涉及下式I表示的单体单元，以及这种单体单元降低硅氧烷水凝胶模量的用途。本发明的硅氧烷水凝胶通常是通过聚合单体混合物形成的，所说的单体混合物包含约10-89％(重量)但优选约25-50％(重量)的含硅氧烷的单体单元；约10-70％(重量)但优选约20-60％(重量)的亲水性单体单元；约1-50％(重量)但优选约5-20％(重量)的式I表示的单体单元：
其中：
A为活性不饱和基团；
R和D独立地为1-10个碳原子的烷基、亚烷基或卤代烷基，其中在所说的碳原子间可包括醚键；
R1、R2、R3和R4独立地选自：烷基或卤代烷基，(包含未取代的烷基，如1-18个碳原子的烷基；还包含取代的烷基，如卤代的烷基和羟基取代的烷基)，其中在碳原子间可包括醚键；硅氧烷基团；及具有6-18个碳原子的碳环基团，如可包含烷基侧基的环己基或苯基；
m为等于或大于1但优选小于500的整数，更优选1至10左右，首选1-3；
n为1-20的整数，但优选1-6；
x和y为0或1；
z为1或2；并且x+y+z＝3；
只要R1或R2中至少一个为1-10个碳原子的烷基。
式I表示的单体单元可通过本领域公知的技术合成。优选单体单元的具体制备方法在下述实施例中提供。
在某些优选实施方案中，z为1，R1-R4独立地选自烷基，如低级烷基，例如1-10个碳原子的烷基，如甲基、乙基、丙基等，以及氟代的低级烷基。优选的单体单元的具体实例包括式II表示的单体单元：
可用于形成硅氧烷水凝胶的含硅氧烷的单体单元在本领域中是公知的，其实例参见下述文献：U.S.专利4,136,250；4,153,641；4,740,533；5,034,461；5,070,215；5,260,000；5,310,779和5,358,995。可应用的含硅氧烷的单体单元包括用于组合物中的烯属“封端的”含硅氧烷单体单元，该单体单元由式III表示：
其中：
A′和A″为活性不饱和基团；
R′和R″独立地为1-10个碳原子的烷基或亚烷基，其中在碳原子间可包含醚键；
R8-R17独立地选自1-18个碳原子的单价烃基或卤代单价烃基，在碳原子间可包括醚键，但优选如R1-R4定义的那些基团；
a为等于或大于1的整数；
b和c为等于或大于0的整数；和
a+b+c＝1-1000的整数。
优选R8-R17独立地选自烷基，包括未取代的烷基和取代的烷基，如氟代的烷基。更优选的是，R8-R17中至少一个基团包括氟代的烷基，如由式-D′-(CF2)s-M′表示的基团其中：
D′为1-10个碳原子的烷基或亚烷基，在所说的碳原子间可包括醚键；
M′为氢、氟或烷基(如1-10个碳原子的烷基)，优选氢或氟；和
s为1-20的整数，优选1-6。
对A、A′和A″而言，术语“活性”用于描述不饱和基团，该基团至少包含一个可促进自由基聚合的取代基。优选活性基团促进在温和条件如室温下的聚合。虽然可采用各种这类基团，但A、A′和A″优选为由下面通式表示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，但也可包括其它基团，如氰基，Y表示-O-、-S-或-NH-，但优选-O-。其它适宜基团的实例包括乙烯基碳酸酯基、乙烯基氨基甲酸酯基、丙烯氰基和苯乙烯基。适宜的基团的其它实例包括N-乙烯基-2-吡咯烷酮-(3，4，或5)基，如下式所示：
D、R、R′和R″表示二价烃基，优选1-10个碳原子的烷基或亚烷基，在碳原子间可包括醚键。优选这种烷基或亚烷基包括1-6个碳原子。这种基团的实例包括亚甲基、亚丙基、亚丁基、亚戊基、1，5-亚己基等，1，6-亚芳基，如亚苯基和亚联苯基，和-O-(CH2)q-，其中q优选为1-6。
优选的单体单元的具体实例包括式IV和V表示的单体单元：
其中：
d、e、f和g为0-1000的整数，
d+e等于2-1000的整数，优选2-100，
f+g等于2-1000的整数，优选2-100，
其中e和g优选为约20-50的整数，
h为1至大约20的整数。
式III、IV和V表示的单体单元的合成方法是本领域中公知的。
其具体实例在下述实施例中提供。
适宜的含硅氧烷的单体的实例还包括式VI表示的本体聚硅氧烷基烷基(甲基)丙烯酸单体：
其中：
X代表-O-或-NR-；
R18独立地代表氢或甲基；
R19独立地代表低级烷基或苯基；和
h为1-10。
这种本体单体包括甲基丙烯酰氧基丙基三(三甲基甲硅烷氧基)硅烷。
另一类优选的含硅氧烷的单体包括式VII的含硅氧烷的乙烯基碳酸酯或乙烯基氨基甲酸酯单体：
其中：
Y′代表-O-，-S-或-NH-；
RSi代表含硅氧烷的有机基团；
R20代表氢或甲基；
d为1、2、3或4；和
q为0或1。
适宜的含硅氧烷的有机基团RSi包括：
-(CH2)n′Si[(CH2)m′CH3]3；
-(CH2)n′Si[OSi(CH2)m′CH3]3；和
其中：
R21代表
其中p′为1-6；
R22代表1-6个碳原子的烷基或氟代烷基；
e为1-200；
n′为1、2、3或4；和
m′为0、1、2、3、4或5。
含硅氧烷的乙烯基碳酸酯或乙烯基氨基甲酸酯单体包括：1，3-双[4-乙烯基氧基羰基氧基)丁-1-基]四甲基-二硅氧烷；3-(三甲基甲硅烷基)丙基乙烯基碳酸酯；3-(乙烯基氧基羰基硫基)丙基-[三(三甲基甲硅烷氧基)硅烷]；3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基氨基甲酸酯；3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基烯丙基氨基甲酸酯；3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基碳酸酯；叔丁基二甲基甲硅烷氧基乙基乙烯基碳酸酯；三甲基甲硅烷基乙基乙烯基碳酸酯；三甲基甲硅烷基甲基乙烯基碳酸酯；和由式VIII表示的“V2D25”。
另一类优选的含硅氧烷的单体包括式IX和X的单体：
(IX) E(*D*A*D*G)a *D*A*D*E′；或
(X) E(*D*G*D*A)a *D*G*D*E′；其中：
D代表6-30个碳原子的烷基双基、烷基环烷基双基、环烷基双基、芳基双基或烷基芳基双基；
G代表1-40个碳原子的烷基双基、烷基环烷基双基、环烷基双基、芳基双基或烷基芳基双基，且在其主链中可包含醚、硫或胺键；
*代表氨基甲酸乙酯或脲基键；
a至少为1；
A代表式XI的二价聚合基团：
其中：
RS独立地代表1-10个碳原子的烷基或氟代烷基，在碳原子间可包含醚键；
m′至少为1；和
p为提供400-10,000基团重量的数目；
E和E′独立地代表式XII表示的可聚合不饱和有机基团：
其中：
R23为氢或甲基；
R24为氢、1-6个碳原子的烷基或-CO-Y-R26基团，其中Y为-O-、-S-或-NH-；
R25为1-10个碳原子的二价亚烷基；
R26为1-12个碳原子的烷基；
X代表-CO-或-OCO-；
Z代表-O-或-NH-；
Ar代表6-30个碳原子的芳基；
w为0-6；
x为0或1；
y为0或1；
z为0或1。
优选的氨基甲酸乙酯单体由式(XIII)表示：其中，m至少为1，优选3或4，a至少为1，优选1，p为提供400-10,000分子量的数目，优选至少为30，R27为二异氰酸酯脱去异氰酸酯基团后的双基，如异佛尔酮二异氰酸酯的双基，每一个E″为下式表示的基团：
本发明的单体混合物可包括其它的成分，如交联剂、内湿润剂、亲水性单体单元、增韧剂(toughening agents)和其它本领域公知的成分。
虽然某些前述含硅氧烷的单体单元在聚合时会形成三维交联网络，但附加的交联剂仍可加至单体混合物中。适宜的交联剂的实例包括：多乙烯基，通常为二或三乙烯基单体，特别是二甘醇、三甘醇、丁二醇、1，6-己二醇的二或三(甲基)丙烯酸酯，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；N，N′-二羟基亚乙基双丙烯酰胺和双甲基丙烯酰胺；二烯丙基化合物，如对苯二甲酸二烯丙酯和氰脲酸三烯丙酯；二乙烯基苯；乙二醇二乙烯基醚；多元醇如三乙醇胺、甘油、季戊四醇、丁二醇、甘露糖醇和山梨醇的(甲基)丙烯酸酯。进而，还包括：N，N-亚甲基-双-(甲基)丙烯酰胺、磺化的二乙烯基苯和二乙烯基砜。还可以使用羟基烷基(甲基)丙烯酸酯与不饱和异氰酸酯的反应产物，例如甲基丙烯酸2-羟乙酯与2-异氰酸根合乙基甲基丙烯酸酯(IEM)的反应产物，如U.S.专利4,954,587所述。
其它公知的交联剂为U.S.专利4,192,827所述的聚醚-二氨基甲酸乙酯-二甲基丙烯酸酯，以及聚乙二醇、聚丙二醇和聚丁二醇与2-异氰酸根合甲基丙烯酸酯(IEM)或间异丙烯基-γ，γ，-二甲基苄基异氰酸酯(m-TMI)的反应产物，以及U.S.专利4,486,577和4,605,712所述的聚硅氧烷-二氨基甲酸乙酯-二甲基丙烯酸酯。其它公知的交联剂为聚乙烯醇、乙氧基化聚乙烯醇或聚乙烯醇与聚乙烯的共聚物与0.1-10mol％乙烯基异氰酸酯如IEM或m-TMI的反应产物。
虽然并不是必须的，但本发明的组合物还可包括增韧剂，优选其用量少于约80％(重量)，例如约5-80％(重量)，优选约20-60％(重量)。适宜的增韧剂的实例如U.S.专利4,327,203所述。这些增韧剂包括环烷基丙烯酸酯或甲基丙烯酸酯，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酯、丙烯酸异丙基环戊酯、甲基丙烯酸叔戊基环庚酯、丙烯酸叔丁基环己酯、丙烯酸异己基环戊酯、和丙烯酸甲基异戊基环辛酯。适宜的增韧剂的其它实例如U.S.专利4,355,147所述。这些参考文献公开了多环丙烯酸酯或甲基丙烯酸酯，例如：丙烯酸和甲基丙烯酸异冰片酯、丙烯酸和甲基丙烯酸二环戊二烯酯、丙烯酸和甲基丙烯酸金刚烷基酯、丙烯酸和甲基丙烯酸异松莰烷基酯。增韧剂的其它实例如U.S.专利5,270,418所述。这些文献公开了支链的烷基羟基环烷基丙烯酸酯、甲基丙烯酸酯、丙烯酰胺和甲基丙烯酰胺。其代表性实例包括：4-叔丁基，2-羟基环己基甲基丙烯酸酯(TBE)；4-叔丁基，2-羟基环戊基甲基丙烯酸酯；甲基丙烯酰氧基-4-叔丁基-2-羟基环己烷；6-异戊基-3-羟基环己基甲基丙烯酸酯；和甲基丙烯酰氧基氨基-2-异己基-5-羟基环戊烷。
内润湿剂也可用于增加本发明的水凝胶组合物的润湿性。其实例包括：N-链烯酰基三烷基甲硅烷基胺化物，如U.S.专利4,652,622所述。这些润湿剂可由下述通式表示：
CH2＝C(E)C(O)N(H)CH(G)(CH2)qC(O)OSi(V)3其中：
E为氢或甲基；
G为(CH2)rC(O)OSi(V)3或氢；
V为甲基、乙基或丙基；
q为1-15的整数；
r为1-10的整数；
q+r为1-15的整数，下文中将其称为NATA。
下文将丙烯酰氧基和甲基丙烯酰氧基，单和二元氨基酸称为NAA，它们可使聚硅氧烷聚合物具有所需的表面润湿性，但在完成聚合之前，它们会从硅氧烷单体混合物中沉淀出来。NAA可被改性以形成三烷基甲硅烷基酯，其更易于掺入聚硅氧烷聚合物中。优选的NATA为三甲基甲硅烷基-N-甲基丙烯酰氧基谷氨酸酯、三乙基甲硅烷基-N-甲基丙烯酰氧基谷氨酸酯、三甲基-N-甲基丙烯酰氧基6-氨基己酸酯、三甲基甲硅烷基-N-甲基丙烯酰氧-氨基十二烷酸酯和双-三甲基-甲硅烷基-N-甲基丙烯酰氧基天冬氨酸酯。
优选的润湿剂也可包括丙烯酸和甲基丙烯酸及其衍生物。通常，这种润湿剂的用量小于组合物重量的5％(重量)。
其它优选的内润湿剂包括噁唑酮，如U.S.专利4,810,764所述(1989年3月7日授权于Friends等)。这些物质可用下式表示：
其中：
R28和R29独立地选自氢或甲基，和
R30和R31独立地选自甲基或环己基。
这些优选的内润湿剂具体包括：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’-异丙烯基-2’-噁唑-5’-酮)(IPCO)环己烷-螺-4′-(2′-乙烯基-2′-噁唑-5′-酮)(VCD)和2-(1-丙烯基)-4，4-二甲基-噁唑-5-酮(PDMO)。这些噁唑酮的制备方法在现有技术中是公知的，如U.S.专利4,810,764所述。
这些优选的内润湿剂具有使其成为特别有用的润湿剂的两个重要特征：(1)相对而言，它们是非极性的，与疏水单体(聚硅氧烷和增韧剂)相容；(2)当进行适度水解后，它们会转化成为高极性氨基酸，这将赋予其显著的润湿性能。当在其它单体存在下进行聚合时，形成了共聚物。这些内润湿剂通过碳-碳双键与聚硅氧烷单体的端封基团聚合，并与增韧剂聚合形成特别适用于生物医学，尤其是隐形眼镜的共聚物材料。
如所指明的那样，本发明的水凝胶组合物包含亲水性单体单元。适用的亲水性单体单元的实例包括下述文献所述的那些：U.S.专利4,259,467；4,260,725；4,440,918；4,910,277；4,954,587；4,990,582；5,010,141；5,079,319；5,310,779；5,321,108；5,358,995；5,387,662；所有这些文献引入本文作参考。
优选的亲水性单体可为含丙烯酰或乙烯基的单体。这种亲水性单体自身可用作交联剂。术语“乙烯基类型”或“含乙烯基”单体是指包含乙烯基基团(CH2＝CQH)的单体，其通常具有高活性。这种含亲水性乙烯基的单体非常容易聚合。“丙烯酰型”或“含丙烯酰”的单体是指包含由下式表示的丙烯酰基团的单体：
其中，X优选氢或甲基，Y优选-O-、-OQ-、-NH-、-NQ-和-NH(Q)-，其中Q通常为烷基或取代烷基。这种单体易于聚合。
优选的可掺入本发明水凝胶中的含乙烯基亲水性单体包括：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，特别优选NVP。
优选的可掺入本发明水凝胶中的含丙烯酰的亲水性单体包括：N，N-二甲基丙烯酰胺(DMA)、基丙烯酸2-羟乙甲酯、甲基丙烯酸甘油酯、2-羟基乙基甲基丙烯酰胺、甲基丙烯酸和丙烯酸，首选DMA。
当含丙烯酰单体和含乙烯基单体同时掺入本发明中时，可使用即具有乙烯基又具有丙烯酰可聚合基团的交联剂，如U.S.专利5,310,779(1994.5.10授权)所述的交联剂，该文献引入本文作参考。这种交联剂有助于使形成的共聚物从整体上进行UV固化。但是，该共聚物也可仅通过加热进行固化，或者同时采用UV和加热手段。在单体混合物中将包括用于固化共聚物的光和/或热引发剂，其是本领域中公知的。其它可掺入含硅氧烷水凝胶中的交联剂包括前述的那些。
本发明也可采用其它增加组合物润湿性的技术，如本领域中公知的等离子体表面处理技术。
特别优选的水凝胶组合物包含约5-20％(重量)的式I表示的单体单元，5-60％(重量)的式IV表示的单体单元和20-60％(重量)的亲水性单体单元。
本发明中采用的单体混合物通过常规方法易于固化成铸塑形状，如用UV聚合或热聚合，或其组合的方法，这与聚合烯属不饱和化合物的方法相同。代表性的自由基热聚合引发剂为有机过氧化物，例如过氧化乙酰、过氧化月桂酰、过氧化癸酰、过氧化硬脂酰、过氧化苯甲酰。叔丁基过氧化新戊酸酯、过氧化二碳酸酯等，其用量为总单体混合物重量的约0.01-1％(重量)。代表性的UV引发剂是本领域公知的那些，例如，苯偶姻甲基醚、苯偶姻乙基醚，Darocur 1173、1164、2273、1116、2959、3331(EM Industries)和Igracur 651和184(Ciba-Geigy)。
本发明的单体单元与其它共聚单体的聚合通常在稀释剂存在下进行(加有交联剂)。然后，聚合产物将形成凝胶形式。如果稀释剂为非水稀释剂，则必须采用本领域技术人员公知的萃取和水合方法从凝胶中除去稀释剂以用水代替。聚合过程也可以在无稀释剂存在下进行，得到一种干凝胶。然后，如本领域公知的那样，将这些干凝胶水合以形成水凝胶。
除了上述聚合引发剂外，本发明的共聚物也可包括其它本领域技术人员公知的成分。例如，单体混合物可以包括着色剂或UV吸收剂，如公知的用于隐形眼镜领域中的那些成分。
本发明提供了可用于修复术的材料，例如心脏瓣膜、眼内镜片、薄膜、手术用具、血管替代品、子宫内用具、膜和其它薄膜、宫颈帽、外科移植物、血管、人造输尿管、人造乳房组织和用于与排出体外的体液进行接触的膜，如肾透析和心/肺机等用膜、插管、护牙、牙线、眼内用具、弥补用具，特别是隐形眼镜。
可以采用旋转铸塑法(如U.S.专利3,408,429及3,496,254所述)、铸压成型法或其它公知的制备隐形眼镜的方法将本发明的聚合物制成隐形眼镜。聚合过程可以在相应于所需隐形眼镜形状的旋转模具或静态模具中进行。必要时，镜片可作进一步精加工。聚合过程也可以在适宜的模具或容器中进行以形成钮扣坯、板或棒坯，将其再加工(如采用车床或激光进行切割或抛光)得到所需形状的隐形眼镜。
当水凝胶用于制备隐形眼镜时，优选其含水量为约20-70％(重量)。进而，优选该水凝胶的模量为约20-150g/mm2，更优选约30-100g/mm2。
以下用若干个实施例对本发明进行说明。这些实施例仅用于说明本发明，并不构成对本发明的限定。
实施例1
通过改变各组分的比例，制备若干水凝胶聚硅氧烷组合物，所述组分为：式V所示的烯属端封的含硅氧烷的单体单元(RD542)，亲水性单体单元、N，N-二甲基丙烯酰胺(DMA)及式II所示本发明的单体单元(MO)。下表I给出了每一种单体单元的具体比例。对各组合物进行各种机械性能测试，结果示于表I。
按照下述过程制备以下被称之为“RD542”的式V所示的单体单元，即聚(25mol％八氟戊氧基丙基甲基硅氧烷)-共-(75mol％二甲基硅氧烷)：(a)制备DP 100甲基丙烯酸酯端封的聚75mol％二甲基硅氧烷-共-25mol％甲基硅氧烷氢化物的预聚物
在干燥的氮气氛下，向1000ml的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-双甲基丙烯酰氧基丁基四甲基二硅氧烷(27.7g，0.7mol)。搅拌下，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的碳酸氢钠，再将反应混合物搅拌过夜。将形成的溶液进行过滤，并将其置于50℃及高真空下，除去未反应的环状化合物。用NMR光谱证实了预聚物的结构。(b)制备DP 100甲基丙烯酸酯端封的聚75mol％二甲基硅氧烷-共-25mol％(甲基八氟戊氧基丙基)硅氧烷的预聚物
在干燥的氮气氛下，向带有磁力搅拌器和水冷凝器的500ml的圆底烧瓶中加入15g(0.002mol)的硅氧烷氢化物预聚物(如上制备)，27.2g(0.1mol)的烯丙氧基八氟戊烷，60μl的四甲基二硅氧烷铂配合物(由Huels得到)和80ml的无水四氢呋喃以及80ml二噁烷。将反应混合物加热至75℃，通过IR光谱检测硅氧烷氢化物的损失。在硅氧烷氢化物反应后，将反应混合物冷却，通过在高真空及50℃下加热产物1小时以除去未反应的烯丙氧基八氟戊烷。用NMR光谱证实了形成的八氟取代的预聚物的结构。
按照下述过程制备以下被称之为“MO”的式II所示的单体单元，即1-(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：(a)制备三甲基甲硅烷基保护的羟丙基四甲基二硅氧烷
向1L的圆底烧瓶中加入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的(TRIS(三苯基膦)铑)氯化物和400ml的甲苯。将溶液在80℃下加热2小时，此时，通过1H-NMR光谱显示硅氧烷氢化物进行了反应。采用旋转蒸发器除去甲苯，将形成的油进行真空蒸馏(65℃/1.5mmHg)，得到127.5g(收率64.8％)的三甲基甲硅烷基保护的羟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：
向1L的圆底烧瓶中加入三甲基甲硅烷基保护的羟丙基四甲基二硅氧烷(60g，0.227mol)、烯丙氧基八氟戊烷(74.1g，0.272mol)、铂二乙烯基四甲基二硅氧烷配合物(113μl，0.02mol/μl催化剂)、200ml的THF和200ml的1，4-二噁烷。将溶液在80℃下加热3小时，使用旋转蒸发器除去溶剂。使形成的油通过50g的硅胶，使用10/1戊烷与二氯甲烷的混合物。使用旋转蒸发器除去溶剂，形成的油再进行真空蒸馏(120℃/0.2mmHg)，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(57.3g，0.1mol)溶解于540ml甲醇中。在室温下，向该溶液中加入8.8ml的10％的乙酸溶液。将混合物搅拌1小时，在40℃下用旋转蒸发器除去溶剂。将形成的油溶解于300ml的己烷中，用蒸馏水洗涤四次。收集有机层，用无水硫酸镁干燥，过滤。
将上述滤得的反应产物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)与三乙胺(11.1g，0.110mol)一道加至1L的圆底烧瓶中。将溶液冷却至0℃，再缓慢加入甲基丙烯酰氯(11.5g，0.11mol)。随后，将溶液升至室温，将其搅拌过夜。第二天，用1N HCl萃取2次，再用2N NaOH萃取2次，再用2N蒸馏水萃取2次。收集有机层，用硫酸镁干燥。将溶液过滤，使用旋转蒸发器除去溶剂。使形成的油通过50g的硅胶，使用10/1戊烷与二氯甲烷的混合物。用旋转蒸发器除去溶剂，形成的油再进行真空蒸馏(120℃/0.1mmHg)，得到34.1g(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。
该合成过程可用下述反应路径表示：用于制备MO的合成路线
以表I所列的比例将每一种试样的各组分以及一种UV引发剂混合约20分钟。再将各组合物分别铸塑成膜，采用下述过程对其机械性能进行评价。将每种组合物的膜铸塑在具有0.3mm特氟隆间隔物的硅烷化玻璃板间，固化条件为在UV强度3500μW/cm2下2小时。UV引发剂为Darocur 1173(浓度为0.5％)。将形成的膜在2-丙醇中提取16小时，在蒸馏水中提取2小时，随后在磷酸缓冲盐水(pH7.3)中水合16小时。膜的机械性能采用Instron Model 4500按照ASTM法1708和1938测定。透氧率(DK)采用极谱深测法(I.Fatt，J.E.Rasson和J.B.Melpolder，ICLC J.，14，38(1987))测定。水解稳定性试验由下述步骤组成：将于磷酸缓冲盐水中的试验膜在80℃下加热3、5、7和14天；检测重量和水含量的变化。表I提供了各组合物机械性能评价结果。
表I
| 组合物(重量％)RD542/MO/DMA | 杨氏模量(g/mm2) | 撕裂强度(g/mm) | 透氧率(barrers) | 含水率(％) |
| 70/0/30 | 192 | 3 | 104 | 34 |
| 50/20/30 | 100 | 3 | 70 | 33 |
| 30/40/30 | 29 | 5 | 64 | 34 |
表I给出了三种水凝胶组合物的模量、撕裂强度、透氧率(DK)和含水量。第一种组合物为对照样，它不包含式II所示的单体单元。第二种和第三种水凝胶组合物分别包括20和40wt％的式II所示的单体单元(MO)。表I的模量数据清楚表明，对照样组合物的模量显著大于包含MO的其它组合物。
实施例II
按照实施例1制备水凝胶聚硅氧烷组合物，只是含硅氧烷的单体单元被式XIII所示的含氨基甲酸乙酯-硅氧烷的单体单元代替。更具体地说，所用的氨基甲酸乙酯单体单元如U.S.专利5,034,461的实施例11所述。单体单元的制备是本领中公知的，也参见U.S.专利5,034,461。如实施例I，将各组合物进行表II所示的各种机械性能测试。
表II
| 组合物(wt％)氨基甲酸乙酯/MO/DMA | 杨氏模量(g/mm2) | 撕裂强度(g/mm) | DK | 拉伸强度(g/mm2) | 断裂伸长率％ | 含水率(％) |
| 70/0/30 | 344 | 3 | 120 | 67 | 29 | 23.4 |
| 60/10/30 | 255 | 3 | 92 | 46 | 25 | 22.8 |
| 50/20/30 | 206 | 3 | 73 | 44 | 31 | 23.9 |
| 40/30/30 | 142 | 4 | 65 | 51 | 60 | 23.3 |
表II给出了四种水凝胶组合物的模量、撕裂强度、透氧率(DK)、伸长和含水量。第一种组合物为对照样，它不包含式II所示的单体单元。第二种、第三种和第四种水凝胶组合物分别包括10、20和30wt％的式II所示的单体单元(MO)。表II的模量数据清楚表明，对照样组合物的模量显著大于包含MO的其它组合物。
实施例III
式III所示的单体单元的合成为本领域中公知的，以下提供式IV所示的具体物质的代表性合成方法。更具体地说，按照下述过程合成聚(65mol％三氟丙基甲基硅氧烷)-共-(35mol％二甲基硅氧烷)。
在室温下，将八甲基环四硅氧烷(39.4g，0.122mol)、三氟丙基环三硅氧烷(154.3g，0.33mol)和甲基丙烯酰氧基丁基四甲基二硅氧烷(6.3g，0.015mol)加至干燥氮气下的圆底烧瓶中。再加入三氟甲磺酸(0.54g，3.6mol)，将混合物搅拌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。中和后，加入氯仿(500ml)，溶液用硫酸镁干燥，用5μ微孔特氟隆过滤器过滤。将滤液置于旋转蒸发器中，除去氯仿。在快速搅拌下，向500ml的甲醇中滴加形成的预聚物，以除去未反应的环状化合物。收集聚合物层，并重复两次该过程。在第三次分馏后，收集聚合物，将其溶解于乙醚中，用硫酸镁干燥，再次用5μ过滤器过滤。形成的溶解置于旋转蒸发器中，除去乙醚。通过NMR光谱证实了纯化产物(150g，65％)的分子结构。
实施例IV
虽然式I所示单体单元的合成是本领域公知的，此处优然提供了其它代表性的合成方法。更具体地说，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)甲基硅烷的合成方法。
(a)制备甲基丙烯酰氧基丙基甲基二(甲基甲硅烷氧基)硅烷
向备有温度计和磁力搅拌器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)、二甲基氯硅烷(39.2g，0.415mol)、三乙胺(45.5g，0.450mol)和250ml无水乙醚。将反应混合物冷却至-15℃，缓慢加入蒸馏水(14.9g，0.830mol)。将反应混合物缓慢地升温至室温，将混合物搅拌过夜。将形成的溶液用蒸馏水洗涤三次。收集乙醚层，用硫酸镁干燥，过滤，使用旋转蒸发器除去乙醚。将形成的油蒸馏(105℃/0.15mm)，得到收率为50％、纯度为94％(通过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的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的铂二乙烯基配合物(huels)和80ml的四氢呋喃。将溶液回流1小时，此时1H-NMR显示硅氧烷氢化物发生了反应，使用旋转蒸发器(50℃/30mm)除去THF和未反应的烯丙氧基八氟戊烷，形成定量收率的甲基丙烯酰丙基二(八氟戊氧基丙基二甲基甲硅烷氧基)甲基硅烷。
对于本领域的技术人员而言，根据本发明的描述可对本发明进行各种改进和变化。因而，可以理解，在权利要求的保护范围之内，本发明可以采用本文描述的内容之外的形式实施。
Claims (19)
1、一种式I表示的单体单元：
其中：
A为烯属不饱和基团；
R和D独立地为1-10个碳原子的亚烷基或卤代亚烷基，其中在所说的碳原子间可包括醚键；
R1、R2、R3和R4独立地选自：烷基或卤代烷基，其中在碳原子间可包括醚键；硅氧烷基团；以及具有6-18个碳原子的碳环基团；
m为1-500的整数；n为1-20的整数；x和y为0或1；
z为1或2；并且x+y+z＝3；
只要R1或R2中至少一个为1-10个碳原子的烷基。
2、根据权利要求1的单体单元，其中z为1，R1和R2独立地选自1-10个碳原子的烷基。
3、根据权利要求1的单体单元，其中R1、R2、R3和R4中至少一个是氟代烷基。
4、根据权利要求1的单体单元，其中A为选自丙烯酸或甲基丙烯酸的酯或酰胺的基团。
5、根据权利要求1的单体单元，其中R和D为1-6个碳原子的亚烷基，其中在所说的碳原子间可包括醚键。
6、根据权利要求1的单体单元，其中R1、R2、R3和R4独立地选自1-10个碳原子的烷基。
7、根据权利要求1的单体单元，其中n为1-6；m为1-10。
8、根据权利要求1的单体单元，其用式II表示：
9、一种通过聚合含式I所示单体单元的单体混合物而形成的水凝胶组合物：
其中：
A为烯属不饱和基团；
R和D独立地为1-10个碳原子的亚烷基或卤代亚烷基，其中在所说的碳原子间可包括醚键；
R1、R2、R3和R4独立地选自：烷基或卤代烷基，其中在碳原子间可包括醚键；硅氧烷基团；以及6-18个碳原子的碳环基团；
m为1-500的整数；n为1-20的整数；x和y为0或1；
z为1或2；并且x+y+z＝3；
只要R1或R2中至少一个为1-10个碳原子的烷基。
10、根据权利要求9的组合物，其中z为1，R1、R2、R3和R4独立地选自1-10个碳原子的烷基。
11、根据权利要求9的组合物，它是通过聚合包含下述组分的单体混合物而形成的：
(a)10-89％(重量)的含硅氧烷的单体单元；
(b)10-70％(重量)的亲水性单体单元；和
(c)1-50％(重量)的式I表示的单体单元。
12、一种隐形眼镜，其包含通过聚合含式I所示单体单元的单体混合物而形成的水凝胶组合物：其中：
A为烯属不饱和基团；
R和D独立地为1-10个碳原子的亚烷基或卤代亚烷基，其中在所说的碳原子间可包括醚键；
R1、R2、R3和R4独立地选自：烷基或卤代烷基，其中在碳原子间可包括醚键；硅氧烷基团；以及具有6-18个碳原子的碳环基团；
m为1-500的整数；n为1-20的整数；x和y为0或1；
z为1或2；并且x+y+z＝3；
只要R1或R2中至少一个为1-10个碳原子的烷基。
13、根据权利要求12的隐形眼镜，其中z为1；R1、R2、R3和R4独立地选自1-10个碳原子的烷基；A为选自丙烯酸或甲基丙烯酸的酯或酰胺的基团；R和D为1-6个碳原子的亚烷基，其中在所说的碳原子间可包括醚键；n为1-6；m为1-10。
14、根据权利要求13的隐形眼镜，其中，式I表示的单体单元包括用式II表示的单体单元：
15、根据权利要求12的隐形眼镜，其中所说的硅氧烷水凝胶由包括下述组分的单体混合物聚合而成：
(a)10-89％(重量)的含硅氧烷的单体单元；
(b)10-70％(重量)的亲水性单体单元；和
(c)1-50％(重量)的式I表示的单体单元。
16、根据权利要求15的隐形眼镜，其中所说的含硅氧烷的单体单元包括由式III表示的单体单元：其中：
A′和A″为烯属不饱和基团；
R′和R″独立地为1-10个碳原子的亚烷基，其中在碳原子间可包含醚键；
R8-R17独立地选自R1-R4所述的基团；
a为等于或大于1的整数；
b和c为等于或大于0的整数；和
a+b+c等于1-1000的整数。
17、根据权利要求16的隐形眼镜，其中A′和A″选自：丙烯酸或甲基丙烯酸的酯或酰胺；R′和R″选自1-6个碳原子的亚烷基，其中在碳原子间可包含醚键；R8-R17独立地选自1-10个碳原子的烷基。
18、根据权利要求12的隐形眼镜，其中所说的组合物的杨氏弹性模量为约20-150g/mm2。
19、一种水凝胶组合物的制备方法，包括包含式I所示单体单元的单体混合物的聚合步骤：
其中：
A为烯属不饱和基团；
R和D独立地为1-10个碳原子的亚烷基或卤代亚烷基，其中在所说的碳原子间可包括醚键；
R1、R2、R3和R4独立地选自：烷基或卤代烷基，其中在碳原子间可包括醚键；硅氧烷基团；以及具有6-18个碳原子的碳环基团；
m为1-500的整数；n为1-20的整数；x和y为0或1；
z为1或2；并且x+y+z＝3；
只要R1或R2中至少一个为1-10个碳原子的烷基。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US829795P | 1995-12-07 | 1995-12-07 | |
| US60/008,297 | 1995-12-07 |
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| EP (1) | EP0865444B1 (zh) |
| JP (1) | JP2001518061A (zh) |
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- 1996-11-12 CA CA002239901A patent/CA2239901C/en not_active Expired - Fee Related
- 1996-11-12 CN CN96198808A patent/CN1084335C/zh not_active Expired - Fee Related
- 1996-11-12 EP EP96940792A patent/EP0865444B1/en not_active Expired - Lifetime
- 1996-11-12 WO PCT/US1996/018356 patent/WO1997020852A1/en active IP Right Grant
- 1996-11-12 US US08/745,538 patent/US5710302A/en not_active Expired - Lifetime
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- 1997-10-10 US US08/947,490 patent/US5908906A/en not_active Expired - Lifetime
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|---|---|
| US5710302A (en) | 1998-01-20 |
| HK1016184A1 (en) | 1999-10-29 |
| AU713509B2 (en) | 1999-12-02 |
| KR19990071887A (ko) | 1999-09-27 |
| WO1997020852A1 (en) | 1997-06-12 |
| US5908906A (en) | 1999-06-01 |
| CA2239901C (en) | 2001-10-30 |
| ES2164265T3 (es) | 2002-02-16 |
| MX9804471A (es) | 1998-09-30 |
| EP0865444A1 (en) | 1998-09-23 |
| DE69615393D1 (de) | 2001-10-25 |
| CA2239901A1 (en) | 1997-06-12 |
| KR100468803B1 (ko) | 2005-04-19 |
| DE69615393T2 (de) | 2002-07-04 |
| AU1076597A (en) | 1997-06-27 |
| EP0865444B1 (en) | 2001-09-19 |
| JP2001518061A (ja) | 2001-10-09 |
| CN1222155A (zh) | 1999-07-07 |
| BR9612119A (pt) | 1999-02-17 |
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