CN1124031A - 可用于生物医学设备的含有机硅的材料 - Google Patents
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Abstract
含有机硅的材料可用于诸如生物医学设备(包括接触透镜)之类的制品中。
Description
发明背景
有多种制品包括生物医学设备都是由含有机硅的材料制成的。一类可用于生物医学设备(例如软接触透镜)的有机硅材料是含聚硅氧烷的水凝胶材料。水凝胶是含有平衡态水的水合的交联聚合物体系。水凝胶接触透镜提供较高的氧透过率以及所需的生物相容性和舒适性。而在水凝胶配方中包含含聚硅氧烷的材料通常提供更高的氧透过率,这是由于基于硅氧烷的材料比水具有更高的氧透过率。
另一类有机硅材料是用于硬接触透镜的硬的透气性材料。这些材料通常由硅氧烷或氟代硅氧烷共聚物形成。这些材料是可透过氧的,而且比用于软接触透镜的材料更硬。
可用于生物医学设备,包括接触透镜的含有机硅的材料公开于下列美国专利:4,686,267(Eillis等人)、5,034,461(Lai等人)和5,070,215(Bam bury等人)。
本发明提供可用于诸如生物医学设备(包括接触透镜)之类的制品的新的含有机硅材料。
发明概述
第一方面,本发明涉及含式(I)重复单元的聚合物:
各个Y是-O-或NR30-,其中R30是H或C1~C6烷基;
各个R1、R2、R3、R4和R5独立地选自H、C1~C6烷基、C1~C6卤代烷基、C2~C6烷基(其中至少一个亚甲基被-O-代替)、C2~C6卤代烷基(其中至少一个亚甲基被-O-代替)和-RSi;
m和n独立地为0或整数1~6;
各RSi独立地为有机硅基团;
R为α,ω-二羟基化合物或α,ω-二氨基化合物的二价残基。
第二方面,本发明涉及包含式(I)重复单元的大分子单体(macromonomer);其中大分子单体以至少一个烯不饱和基团封端。此外,本发明包括含有以至少一个烯不饱和基团封端的式(I)的单一单元的单体。优选的大分子单体由式(II)代表,而优选的单体由式(III)代表:
其中各R50是烯不饱和基团;各R、R1、R2、R3、R4、R5、RSi、Y、m和n定义如式(I)中定义;x的平均值大于1。
第三方面,本发明包括由含有式(I)重复单元的聚合物形成的制品。根据优选实施方案,所述制品是含上述大分子单体或单体和亲水性单体的混合物的聚合产物。优选的制品是光学透明的,并可用作接触透镜。
本发明再一方面还涉及可用作制备各种目标聚合物的中间体的化合物。这些化合物具有下式:其中:
各个X为-OH、C1~C6烷氧基或卤素;
其中各R11独立地选自C1~C8烷基、苯基和-O-Si(R12)3,各R12独立地选自C1~C8烷基和苯基。
发明详述
各个Y是-O-或NR30-,其中R30是H或C1~C6烷基;
各个R1、R2、R3、R4和R5独立地选自H、C1~C6烷基、C1~C6卤代烷基、C2~C6烷基(其中至少一个亚甲基被-O-代替)、C2~C6卤代烷基(其中至少一个亚甲基被-O-代替)和-RSi;
m和n独立地为0或整数1~6;
各RSi独立地为有机硅基团;
R为α,ω-二羟基化合物或α,ω-二氨基化合物的二价残基。这里所用的术语“聚合物”指式(I)的重复单元平均数大于1的材料。
更具体讲,所述聚合物包括含式(Ia)重复单元的聚酯:
特别优选的是其中各个R1、R2、R3、R4和R5若存在则为氢的聚酯或聚酰胺。优选的R、RO和RN二价基团包括:C1~C10亚烷基、C1~C10卤代亚烷基例如C1~C10氟代亚烷基、C2~C10亚烷基醚、C6~C10亚芳基、C6~C10卤代亚芳基、C7~C10亚芳基烷基、C7~C10卤代亚芳烷基和C5~C10亚环烷基。
优选的RSi基团是下式的有机硅基团:
其中各个R10独立地选自C1~C8烷基、苯基和下式基团:其中各个R11独立地选自C1~C8烷基、苯基和-O-Si(R12)3,其中各个R12独立地选自C1~C8烷基和苯基;
L选自单键和二价连接基团。
此外,优选至少一个RSi基团是下式的含硅氧烷基团:其中各变量如前面定义。
可以理解,上式中的L基团将有机硅基团的硅原子连接在二元酸或二酯衍生物的酸部分中的脂肪链上。优选的L基团包括下式的二价基团:
其中q是2至6的整数,各个R7和R8独立地选自H、C1-C6烷基、C1-C6卤代烷基、其中至少一个亚甲基被-0-所替代的C2-C6烷基和其中至少一个亚甲基被-0-所替代的C2-C6卤代烷基。
特别优选的有机硅基团RSi包括:三甲基甲硅烷基-1,2-亚乙基、五甲基二硅噁烷基亚甲基、七甲基三硅噁烷基(trisiloxanyl)-1,2-亚乙基、苯基四甲基二硅噁烷基-1,2-亚乙基、三苯基二甲基二硅噁烷基亚甲基、异丁基六甲基三硅噁烷基亚甲基、正丙基八甲基四硅噁烷基-1,2-亚丙基、甲基(二[三甲基甲硅烷氧基])甲硅烷基亚甲基、二甲基(二[三甲基甲硅烷氧基]甲基硅氧烷基(siloxanyl))甲硅烷基亚甲基、二甲基(三[三甲基甲硅烷氧基]硅氧烷基)甲硅烷基-1,2-亚丙基、三(三甲基甲硅烷氧基)甲硅烷基亚甲基、三(三甲基甲硅烷氧基)甲硅烷基-1,2-亚丙基、三(苯基二甲基甲硅烷氧基)甲硅烷基-1,2-亚丙基、三(五甲基二硅噁烷基)甲硅烷基-1,2-亚丙基、三[三(三甲基二甲硅烷氧基)]甲硅烷基-1,2-亚丙基、和三[二(三甲基二甲硅烷氧基)甲基硅氧烷基]甲硅烷基-1,2-亚丙基。
各种优选的RSi可用下式表示:
-(CH2)qSi(OSi(R11)3)3其中各R11独立地选自C1-C8烷基和苯基,且q为2~6的整数。
上面反应路线中,式(IV)中各X优选为C1~C6烷氧基。式(Ib)中RO为α,ω-二羟基化合物的残基,且相应于α,ω-二羟基反应剂中的R基团。二羟基化合物的代表性实例包括新戊二醇、1,2-乙二醇、1,6-己二醇、三甘醇、双酚A、1,4-环己烷二甲醇、1,2-丙二醇和2,2,3,3,4,4-六氟戊烷-1,5-二醇。
式(Id)中RN是α,ω-二羟基化合物的残基,并相应于α,ω-二氨基反应剂的R基团。二氨基化合物的代表性实例包括:1,2-乙二胺、1,4-苯二胺、1,6-己二胺和1,4-环己二胺。
在式(Ib)和(Id)中,x的平均值大于1。重复单元的平均数可根据已知方法通过控制聚酯化或聚酰胺化程度来改变。
式(IV)化合物可通过向酸部分含α,β-不饱和基团的二羧酸或其二酯上经由反应活性的烯丙基甲硅烷加烯丙基基团来制备。用于该氢化硅烷化(hydrosilation)反应的α,β-不饱和二羧酸或二酯原料的代表性实例包括下面的丙二酸酯衍生物(Va)和丁二酸酯衍生物(Vb):
这样的α,β-不饱和二羧酸或二酯可通过本领域已知的方法制备。例如,在文献中(G.Majetich等,“使用三甲基烯丙基甲硅烷和氟化物催化剂的通用烯丙基化方法”,J.Org.Chem.Vol.51(10),1986,第1745页,其公开文本并入本文作为参考)描述了通过三甲基烯丙基甲硅烷的氟离子催化加成或通过二烯丙基铜锂的共轭加成制备α,β-不饱和T二酸酯衍生物(Vb)。此外,α,β-不饱和丙二酸酯衍生物(Va)的制备在下面的实施例1中叙述。
相应地,可根据下述的总反应路线制备式(IV)化合物。为说明代表性反应路线起见,将α,β-不饱和丙二酸酯衍生物(Va)用有机硅HSi(R10)3化合物氢化硅烷化,形成RSi基团对应于-L-Si(R10)3基团的式(IV)化合物,其中-L-为-(CH2)3-。
所述含式(I)重复单元的聚酯或聚酰胺可通过常规方法直接成型为各种形状的制品。但根据优选实施方案,包括接触透镜在内的本发明的成形制品是通过将含式(I)重复单元并用至少一个烯不饱和基团封端的大分子单体聚合制得的。因而,本发明的第二方面涉及这样的大分子单体,这里所用的“大分子单体”(macromonomer)指其中式(I)重复单元的平均数大于1的烯不饱和材料。
优选的大分子单体包括用两个烯不饱和基团封端的含有聚酯的大分子单体,如式(IIa)中所示:以及用两个烯不饱和基团封端的含聚酰胺的大分子单体,如式(IIb)所示:在式(IIa)和(IIb)中,各个R50为烯不饱和基团,x平均值大于1。
代表性的R50基团包括下式的烯不饱和基团:其中:
R31是氢或甲基;
R32选自氢、具有1~6个碳原子的烷基和其中Y′为-O-或-NH-的-CO-Y′-R34基团。
各个R34和R35独立地选自-COO-、-CONH-、-NHCO-、-OCOO-、-NHCOO-和-OCONH-基团;
Ar是具有6~30个碳原子的芳基;
各个t和y独立地为0或1~6的整数;
各个u、v和w独立地为0或1。
更优选的R50基团具有下式:
本发明的大分子单体可通过按照本领域已知的通用方法,用烯不饱和基团将前述的聚酯(例如式(Ib)的聚酯)或聚酰胺(例如式(Id)的聚酰胺)封端来制备。或者,缺乏有机硅基团RSi的聚酯或聚酰胺也可用烯不饱和基团封端,其中产生的大分子单体随后用有机硅基团氢化硅烷化,见下述实施例11~14所述。
加合终端烯不饱和基团的各种方法是本领域已知的。例如,含终端羟基官能团的聚酯(如式(Ib)的聚酯)可与甲基丙烯酸异氰酸根合乙酯反应形成终端基团CH2=CH(CH3)-COO-(CH2)2-NHCOO-。或者含终端羟基官能团的聚酯也可与(甲基)丙烯酰氯反应以提供(甲基)丙烯酸酯终端基团或与氯甲酸乙烯酯反应以提供碳酸乙烯酯终端基团。含终端氨基官能团的聚酰胺(例如式(Id)的聚酰胺)可与(甲基)丙烯酰氯反应以提供终端(甲基)丙烯酰胺基团,或与氯甲酸乙烯酯反应以提供氨基甲酸乙烯酯端基。
应当理解,通过控制酯化或酰胺化,可以制得仅包含一个式(I)单元的材料。因而,本发明还包括含有用至少一个烯不饱和基基团封端的式(I)单一单元的单体。
所得到的含烯不饱和有机硅的大分子单体或单体可通过自由基聚合过程而聚合成为各种含有机硅的成型制品,包括生物医学设备。已发现这样的聚合成型制品具有足够高的氧透过性、透明度和强度,可用作接触透镜材料。
例如,本发明的大分子单体可与至少一种亲水单体共聚以形成可用作软的水凝胶接触透镜材料的亲水的光学透明共聚物。或者,所述大分子单体也可与诸如甲基丙烯酸甲酯、衣康酸酯或其氟化衍生物之类的单体共聚合以形成硬的透气性接触透镜材料。
所述大分子单体可与宽范围的亲水性单体共聚合以形成可用作水凝胶接触透镜的材料。合适的亲水性单体包括:不饱和羧酸例如甲基丙烯酸和丙烯酸类;(甲基)丙烯酸取代的醇例如甲基丙烯酸2-羟乙酯和丙烯酸2-羟乙酯;乙烯基内酰胺如N-乙烯基吡咯烷酮;和丙烯酰胺类如甲基丙烯酰胺和N,N-二甲基丙烯酰胺。进一步的实例是美国专利Nos.5,070,215中所公开的亲水性碳酸乙烯酯或氨基甲酸乙烯酯单体,以及美国专利No4,910,277中所公开的亲水性噁唑酮类单体。其它合适的亲水性单体对本领域技术人员来讲是显而易见的。在起始单体混合物中所述大分子单体优选占约10~90%(重量),而且至少一种亲水性单体占约90%(重量)。
含有机硅的大分子单体或亲水性单体可用作交联剂(交联剂定义为具有多个可聚合官能团的材料)。或者,也可在起始混合物中使用另外的交联剂以提供交联聚合制品。
可通过自由基聚合过程使单体混合物聚合,通常在热或紫外照射条件下进行。在单体混合物中可包含少量自由基引发剂,通常约0.1~5%(重量)。
在生产接触透镜时,起始单体混合物可在管中固化以提供棒形制品,然后将其切成园片。然后将该园片车削成接触透镜。或者,接触透镜也可用单体混合物直接在模中浇注,例如通过旋转浇注或静态浇注法。旋转浇注法公开在美国专利Nos3,408,429和3,660,545中,而静态浇注法公开在美国专利Nos4,113,224和4,197,266中。作为另一种方法,美国专利No455,732也公开了这样一种工艺:将过量的单体混合物通过旋转浇注在模中固化形成具有前透镜表面和较厚的成形制品,而随后将固化的旋转浇注制品的后表面车削以提供具有所需厚度和后透镜表面的接触透镜。
下列实施例用于说明本发明的各种优选实施方案。
实施例1烯丙基丙二酸二乙酯(Va)的制备
在70℃,将新蒸馏的烯丙基溴(13.74g,0.12mol)加到含丙二酸二乙酯阴离子(CH3CH2OOCCHCOOCH2CH3,通过烯丙基丙二酸酯与钠在乙醇中反应制得)的无水乙醇溶液中。通过气相色谱(GC)测得两小时反应完全。将反应混合物冷却,用庚烷(25ml)稀释,并用蒸馏水洗涤两次。有机萃取液用硫酸镁干燥,并用旋转蒸发仪除去庚烷。将所得粗产物通过蒸馏纯化,得到烯丙基丙二酸二乙酯(Va)(收率80%,20mmHg b.p.115~120℃,GC测量纯度99.0%)。
实施例22-[3-(三(三甲基甲硅烷氧基)甲硅烷基)丙基]丙二酸二乙酯的制备
将烯丙基丙二酸二乙酯(8.0g,0.04mol)、三(三甲基甲硅烷氧基)甲硅烷(HSi[OSi(CH3)3]3,11.8g,0.04mol)、125ml无水甲苯和氯铂酸(0.02g,在尽可能少量的2-丙醇中)在100℃加热3小时。反应通过GC和红外光谱监测。三小时内反应完全。用旋转蒸发仪除去甲苯,将粗产物真空蒸馏,得到2-[3-(三(三甲基甲硅烷氧基)甲硅烷基)丙基]丙二酸二乙酯(收率:99.0%,0.05mmHg b.p.135~140℃,GC测量纯度99.0%)。
实施例3由含三(三甲基甲硅烷氧基)甲硅烷基的丙二酸酯和新戊二醇制备羟基封端的聚酯
在氮气气氛下,将2-[3-(三(三甲基甲硅烷氧基)甲硅烷基)丙基]丙二酸二乙酯(10g,0.02mol)和新戊二醇(2.5g,0.25mol)加入到园底烧瓶中。将混合物加热至170℃并维持三小时,期间由反应混合物中蒸出8ml乙醇。然后将反应混合物在30mm减压下加热至190℃并维持两小时。冷却后,得到数均分子量3300的透明粘稠聚酯。1HNMR分析证明得到希望的结构。实施例4和5由含三(三甲基甲硅烷氧基)甲硅烷基的丙二酸酯和1,6-己二醇或三甘醇制备羟基封端的聚酯
按照实施例3的通用方法,通过分别用1,6-己二醇和三甘醇替代新戊二醇,得到聚酯。
实施例6由羟基封端的含有机硅的聚酯制备含有机硅的大分子单体
于5℃,将实施例3中制得的羟基封端的聚酯(5.5g,0.022mol)溶于15ml二氯甲烷中。将甲基丙烯酸异氰酸根合乙酯(0.82g,5.28mmol)与18μl二月桂酸二丁基锡(0.3%w/w)一起缓慢加入。使混合物自行升温至室温,然后在60℃回流16小时。将所得混合物用蒸馏水洗涤两次,再用饱和碳酸氢盐溶液洗涤两次。收集有机层,用MgSO4干燥,并用旋转蒸发仪除去溶剂。1HNMR谱分析表明最终产物具有所预期的结构。
实施例7含有机硅的大分子单体的制备
根据实施例6的通用制备方法,由实施例5的羟基封端的聚酯即包含三甘醇残基的聚酯制备大分子单体。
实施例8和9浇注薄膜
通过将实施例6的大分子单体(80重量份)、N,N-二甲基丙烯酰胺(20重量份)和Darocur 1173引发剂(0.5%)混合制备第一混合物。
通过将实施例7的大分子单体(80重量份)、N,N-二甲基丙烯酰胺(20重量份)和Darocur 1173引发剂(0.5%)混合制备第二混合物。
通过用紫外光照射混合物两小时而在玻璃板之间由两种混合物浇注制得两个系列薄膜。由玻璃板干脱模后,将浇注薄膜在室温下在乙醇中萃取过夜,然后在缓冲盐水中萃取接着再在磷酸盐缓冲盐水中进行水合,得到水合水凝胶。所述薄膜是透明的,其性质列于表1中,包括水合后水的百分数(重量%)、模量(g/mm2)、撕裂强度(g/mm)和氧透过率(DK,Barrers)。模量和撕裂强度通过ASTM法1708和1938测定,而氧透过率通过极谱探针法(I.Fatt等人,International Contact Lens Clinio,vol.14,第38页(1987))测定。
表1组合物 水% 模量 撕裂强度 DK实施例8 14.6 275 7.2 70实施例9 43.6 122 1.0 33
实施例102-[3-(三(三甲基甲硅烷氧基)甲硅烷基)丙基]丁二酸二甲酯和羟基封端的聚酯以及含2-[3-(三(三甲基甲硅烷氧基)甲硅烷基)丙基]有机硅基团的大分子单体的合成方法
根据实施例2的通用方法,通过将烯丙基丁二酸二甲酯(Vb)代替烯丙基丙二酸二乙酯可制备2-[3-(三(三甲基甲硅烷氧基)甲硅烷基)丙基]丁二酸二甲酯。
羟基封端的聚酯可通过使2-[3-(三(三甲基甲硅烷氧基)甲硅烷基)丙基]丁二酸二甲酯与α,ω-二羟基化合物反应制备,而含有机硅的大分子单体可通过羟基封端的聚酯制备。
实施例11烯丙基丙二酸的合成方法
将氢氧化钾(15.6g,0.28mol)、15ml蒸馏水和50ml庚烷加到园底烧瓶中。在搅拌下向反应混合物中缓慢加入烯丙基丙二酸二乙酯(22.0g,1.1mol),并回流足够长的时间以完全水解。用旋转蒸发仪除去乙醇。将所得产物在一烧杯中冷却,并用硫酸酸化。最终溶液用乙醚萃取。收集乙醚层,用MgSO4干燥,并用旋转蒸发仪除去乙醚。粗品烯丙基丙二酸用石油醚结晶。
实施例12由烯丙基丙二酸和1,6-己二胺合成氨基封端的聚酰胺的方法
在氮气气氛下,在装有蒸馏头的园底烧瓶中将烯丙基丙二酸(35.3g,0.245mol)和1,6-己二胺(34.17g,0.3mol)混合。将混合物在220℃加热约2小时,期间水由反应混合物中蒸馏出来。然后将反应混合物在30mm的减压下加热至250℃并维持约3小时。将所得混合物冷却,结晶得聚酰胺。
实施例13由氨基封端的聚酰胺合成含烯丙基大分子单体的方法
在5℃,将氨基封端的聚酰胺(5.5g,2.2mmol)溶于15ml二氯甲烷中。将甲基丙烯酸异氰酸根合乙酯(0.82g,5.28mmol)与18ml二月桂酸二丁基锡(0.3%w/w)一起缓慢加入。使混合物自行升温至室温,然后回流过夜。随后再将所得混合物用蒸馏水和饱和碳酸氢盐溶液洗涤。收集有机层,并用MgSO4干燥,用旋转蒸发仪除去溶剂。
实施例14含有机硅的大分子单体的合成方法
将甲基丙烯酸酯封端的大分子单体(10g,0.048mol)、七甲基二硅氧烷(7.1g,0.48mol)和0.02ml氯铂酸溶于乙酸乙酯(25ml)中,并加热至80℃,保持足够长的时间以完全反应,得到硅氧烷取代的大分子单体。
该大分子可与亲水性单体共聚,如实施例8和9。
虽然已叙述了某些优选的实施方案,应该明白本发明并不限于此,而各种改进和变化对于本领域技术人员来讲都是显而易见的。
Claims (32)
2.权利要求1的聚合物,其中各Y是-O-。
3.权利要求1的聚合物,其中各Y是-NR30-。
4.权利要求1的聚合物,其中R选自C1~C10亚烷基、C1~C10卤代亚烷基、C2~C10亚烷基醚、C6~C10亚芳基、C6~C10卤代亚芳基、C7~C10亚芳基烷基、C7~C10卤代亚芳烷基、C5~C10亚环烷基和C6~C10烷基亚环烷基。
5.权利要求1的聚合物,其中m是0和n是0或1。
8.权利要求1的聚合物,其中所述重复单元是下式基团:
其中RO为α,ω-二羟基化合物的二价残基。
9.权利要求8的聚合物,其中RSi为:其中各R11独立地选自C1~C8烷基和苯基,且q为2~6的整数。
10.权利要求1的聚合物,具有下式:其中x平均值大于1,而RO为α,ω-二羟基化合物的残基。
14.权利要求13的大分子单体,其中所述聚合物以两个烯不饱和基团封端。
16.权利要求12的大分子单体,其中各个Y是-O-。
17.权利要求12的大分子单体,其中各Y是-NR30。
18.权利要求12的大分子单体,其中R选自C1~C10亚烷基、C1~C10卤代亚烷基如C1~C10氟代亚烷基、C2~C10亚烷基醚、C6~C10亚芳基、C6~C10卤代亚芳基、C7~C10亚芳基烷基、C7~C10卤代亚芳烷基、C5~C10亚环烷基和C6~C12烷基亚环烷基。
19.权利要求12的大分子单体,其中m是0和n是0或1。
21.权利要求20的大分子单体,其中各L独立地为二价连接基团。其中q是2至6的整数,R7和R8独立地选自H、C1~C6烷基、C1-C6卤代烷基、其中至少一个亚甲基被-O-所替代的C2~C6烷基和其中至少一个亚甲基被-O-所替代的C2~C6卤代烷基。
23.权利要求22的大分子单体,其中RSi为其中各个R11独立地选自C1~C8烷基和苯基,而q是2至6的整数。
29.权利要求27的制品,它是光学透明的,并成型为接触透镜。
32.权利要求31的化合物,其中所述至少一个RSi基团具有下式:其中各个R11独立地选自C1~C8烷基、苯基,q是2~6的整数。
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1994
- 1994-03-21 ES ES94913939T patent/ES2122273T3/es not_active Expired - Lifetime
- 1994-03-21 AU AU66201/94A patent/AU675132B2/en not_active Ceased
- 1994-03-21 JP JP52320094A patent/JP3236621B2/ja not_active Expired - Fee Related
- 1994-03-21 WO PCT/US1994/003109 patent/WO1994024187A2/en active IP Right Grant
- 1994-03-21 EP EP94913939A patent/EP0693089B1/en not_active Expired - Lifetime
- 1994-03-21 DE DE69412084T patent/DE69412084T2/de not_active Expired - Fee Related
- 1994-03-21 KR KR1019950704367A patent/KR100290202B1/ko not_active IP Right Cessation
- 1994-03-21 CA CA002159710A patent/CA2159710C/en not_active Expired - Fee Related
- 1994-03-21 CN CN94192171A patent/CN1048738C/zh not_active Expired - Fee Related
- 1994-03-21 BR BR9406057A patent/BR9406057A/pt not_active IP Right Cessation
-
1995
- 1995-05-11 US US08/439,215 patent/US5510442A/en not_active Expired - Lifetime
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- 1998-12-22 HK HK98114815A patent/HK1013424A1/xx not_active IP Right Cessation
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CN101687960B (zh) * | 2007-07-10 | 2013-10-30 | 博士伦公司 | 交联剂及双基固化聚合物 |
Also Published As
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JP3236621B2 (ja) | 2001-12-10 |
US5510442A (en) | 1996-04-23 |
BR9406057A (pt) | 1995-12-26 |
WO1994024187A3 (en) | 1995-01-05 |
US5616757A (en) | 1997-04-01 |
HK1013424A1 (en) | 1999-08-27 |
DE69412084T2 (de) | 1998-12-17 |
JPH08508780A (ja) | 1996-09-17 |
EP0693089A1 (en) | 1996-01-24 |
AU675132B2 (en) | 1997-01-23 |
WO1994024187A2 (en) | 1994-10-27 |
KR100290202B1 (ko) | 2001-05-15 |
EP0693089B1 (en) | 1998-07-29 |
AU6620194A (en) | 1994-11-08 |
ES2122273T3 (es) | 1998-12-16 |
CA2159710A1 (en) | 1994-10-27 |
CA2159710C (en) | 1998-08-18 |
CN1048738C (zh) | 2000-01-26 |
DE69412084D1 (de) | 1998-09-03 |
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