CN1162472C - 接触镜片材料 - Google Patents
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Abstract
通过采用由三甲代甲硅烷基封端的单体聚硅氧烷降低聚合物硅氧烷水凝胶组合物的模量以降低该水凝胶的交联密度的方法。合成方法是同一反应器酸催化开环聚合且可用于生产适用于水凝胶接触镜片材料的共聚物。
Description
发明背景
本发明总体上涉及适用于生物医疗元件例如接触镜片和人工晶状体的硅氧烷水凝胶组合物。
聚合硅氧烷材料一直广泛用在各种生物医疗用途中,其包括例如在接触镜片和人工晶状体中。此种材料通常可分为水凝胶和非水凝胶。硅氧烷水凝胶构成交联的聚合体系,其能够以一平衡状态吸收和保持水分且通常水含量高于约5重量%且更通常在约10-80重量%之间。此种材料通常是通过聚合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而制得的。所述含硅氧烷的单体或亲水性单体均可用作交联剂(交联剂是定义为具有多个可聚合官能度的单体)或者可采用另外的交联剂。
硅氧烷水凝胶结合了水凝胶的有利性能和含硅氧烷的聚合物的有利性能(Kunzler和McGee,“Contact Lens Materials”,Chemistry &Industry,pp.651-655,21 August 1995)。硅氧烷水凝胶一直用于制备同时结合聚二甲基硅氧烷材料的透氧性和常规非离子型水凝胶的舒适性、润湿性和耐沉积性的接触镜片。
发现特别适用于制备含硅氧烷接触镜片的单体是见于US4,136,250;4,153,641;4,189,546;4,208,506;4,217,038;4,277,595;4,327,203;4,355,147;4,740,533;4,780,515;5,034,461;5,070,215;5,310,779;5,346,976;5,374,662;5,358,995;5,387,632;5,420,324;和5,496,871。
US4,153,641(Deichert等人)公开了由通过二价烃基而α,ω端基连接至聚合的活性不饱和基团的聚(有机硅氧烷)单体制得的接触镜片。含各种疏水性硅氧烷的预聚物例如1,3-二(甲基丙烯酰氧基烷基)-聚硅氧烷是与公知的亲水性单体例如甲基丙烯酸2-羟乙酯共聚。这些材料是用于生产具有低水含量和高模量(大于300g/mm2)的镜片。
US5,358,995(Lai等人)介绍了一种硅氧烷水凝胶,其是由丙烯酸酯封端的聚硅氧烷预聚物与松散的聚硅氧烷基烷基(甲基)丙烯酸酯和至少一种亲水性单体聚合而制成。丙烯酸酯封端的聚硅氧烷预聚物通常表示为M2Dx,其是由两个丙烯酸酯端基和“x”个二甲基硅氧烷重复单元组成。优选的松散的聚硅氧烷基烷基(甲基)丙烯酸酯是TRIS-型(甲基丙烯酰氧基丙基三(三甲代甲硅烷氧基)硅烷),且亲水性单体是含丙烯酸基或乙烯基。当这些镜片的性能是可接受时,这些镜片的模量可以是高的,这可能导致上皮层的损坏且舒适性差。
设计以M2Dx作为原料预聚物的硅氧烷类水凝胶主要包括将所述预聚物与亲水性单体例如二甲基丙烯酰胺和N-乙烯基吡咯烷酮共聚。硅氧烷是疏水性的且与亲水性单体具有差的相容性,特别是当M2Dx预聚物具有高的分子量时更是如此。差的相容性导致得到相分离的、不透明材料。当制备用于光学透明的接触镜片的水凝胶时这是特别成问题的。
降低M2Dx预聚物的分子量能够改进不相容性。不幸地,低分子量的M2Dx预聚物通常得到高模量的水凝胶。这是这些低分子量的M2Dx类水凝胶的交联密度更高的直接结果。
在设计基于低分子量的M2Dx预聚物的低模量的硅氧烷水凝胶时,一种方法可以是使用高浓度的亲水性单体。这些材料的更低模量是较高水含量和较低交联密度的结果。这种方法的主要缺点是较高水含量材料具有较低的透氧性,由于在这些材料中硅氧烷的浓度较低。低透氧性是不适合于连续佩戴接触镜片应用的。
在开发基于低分子量M2Dx预聚物的低模量硅氧烷水凝胶时的第二种方法是通过引入甲基丙烯酰氧基丙基三(三甲代甲硅烷氧基)硅烷(“TRIS”)的单体。TRIS的更高浓度导致更低模量的水凝胶,但是用高TRIS量制得的镜片在临床研究中总体上倾向于表现不好。
基于低分子量M2Dx预聚物的低模量水凝胶的开发可通过添加硅氧烷大分子而实现,例如由Y.Kawakami在Polymer Journal,v.14,P.913,1982中所教示的那些。高含量的硅氧烷大分子可通过降低所得水凝胶的交联密度而降低模量,而透氧性没有明显的降低。这种方法的主要缺点是甲基丙烯酸酯类硅氧烷大分子是极难合成的。硅氧烷大分子的合成要求几个步骤。
发明概述
一直需求这样一种接触镜片,其具有含聚硅氧烷预聚物的高透氧性,但具有足够低以用于接触镜片的低模量。在本发明中采用的方法改变了含硅氧烷的单体以影响聚合物性能。通过降低M2Dx的甲基丙烯酸酯官能度,可降低交联密度。这可通过除去在预聚物的末端上的一定百分比的甲基丙烯酸酯基而完成。
这些改进的聚合物硅氧烷水凝胶组合物是由含有具有下列通式的硅氧烷预聚物的单体混合物的聚合产物制成的:
其中,
A是活性不饱和基;
A′是活性不饱和基或烷基;
R1-R10各自独立地是具有1-10个碳的烷基、氟代烷基、醇、醚或氟代醚基,或者具有6-18碳原子的芳基;
m,n和p各自独立地是0-200,m+n+p是约15-200;
a是1-10;和
b是0-10,
其中所述硅氧烷预聚物是通过二甲基丙烯酸酯基二硅氧烷(M2)和环状硅氧烷(D)在催化剂的存在下反应而制得,其改进之处包括将至少一种具有下列通式的二硅氧烷(T2)添加至用于制成硅氧烷预聚物的反应混合物:
其中R11-R16各自独立地是具有1-5个碳原子的烷基。
具体地说,本发明涉及一种制备由通式II所示的三甲代甲硅烷基(TMS)封端的M2Dx类预聚物:
其中,m+n+p是15-200。
注意的是,通式II的预聚物是通式I中b是零且R9,R10和A′是甲基的一类。
申请人发现,制备预聚物的上述方法在改进聚合硅氧烷材料的柔韧性方面是特别有效的且因此降低了硅氧烷水凝胶共聚物的模量,不同于先前的由甲基丙烯酸酯封端而非用三甲基甲硅烷基封端的硅氧烷化合物。M2Dx,TMS封端的预聚物的合成是容易的,比先前的方法要求更少的步骤和组分。
所述的水凝胶材料在生物医疗元件例如软接触镜片、人工晶状体、心脏瓣膜和其它假体中是特别适用的。
优选实施方案的详细描述
本发明介绍了一种设计基于M2Dx预聚物的低模量硅氧烷水凝胶的新方法。本发明的M2Dx预聚物包含“内设的”模量降低官能度:三甲代甲硅烷基(TMS)端帽。增加TMS端帽的浓度(或降低甲基丙烯酸酯帽的浓度)导致更低的模量、透明的硅氧烷水凝胶而没有降低输水性或透氧性。
这些改进的聚合物硅氧烷水凝胶组合物是由包含具有下列通式的硅氧烷预聚物的单体混合物的聚合产物制成的:
其中,
A是活性不饱和基;
A′是活性不饱和基或烷基;
R1-R10各自独立地是具有1-10个碳的烷基、氟代烷基、醇、醚或氟代醚基,或者具有6-18碳原子的芳基;
m,n和p各自独立地是0-200,m+n+p是约15-200;
a是1-10;和
b是0-10,
其中所述硅氧烷预聚物是通过二甲基丙烯酸酯基二硅氧烷(M2)和环状硅氧烷(D)在催化剂的存在下反应而制得,其改进之处包括将至少一种具有下列通式的二硅氧烷(T2)添加至用于制成硅氧烷预聚物的反应混合物中:
其中R11-R16各自独立地是具有1-5个碳原子的烷基。
至于通式I的A,A′,术语“活性”是用于描述包括至少一个有助于自由基聚合的取代基的不饱和基团,优选是烯属不饱和基团。这包括了由下列通式表示的丙烯酸或甲基丙烯酸的酯或酰胺:
其中X优选是氢或甲基,但可包括其它基团例如氰基,且Y表示-O-,-S-或-NH-,但是优选是-O-,其它合适的活性不饱和基的实例包括碳酸乙烯酯、氨基甲酸乙烯酯、富马酸酯、富马酸酰胺、马来酸酯、丙烯腈基、乙烯酯和苯乙烯基。
二甲基丙烯酸酯基二硅氧烷(M2)是由下列通式表示:
环状硅氧烷(D)可以是含有至少3个硅氧基团的环状化合物和取代的同类物。实例包括1,1,3,3-四甲基-1,3-二硅-2-氧环戊烷,六甲基环三硅氧烷和钯甲基环四硅氧烷或它们的混合物。优选的D是八甲基环四硅氧烷(D4)。
优选的T2是六甲基二硅氧烷和是由下列通式表示的:
所用的催化剂必须能够裂断Si-O键。这些试剂包括酸性粘土、氟化氢酸、HCl-FeCl3(盐酸-氯化铁(III)络合物)、浓硫酸和三氟代甲烷磺酸。优选的酸是浓硫酸和三氟代甲烷磺酸。
本发明旨在将聚硅氧烷预聚物混合物与松散的聚硅氧烷基烷基(甲基)丙烯酸酯和至少一种亲水性单体聚合。在本发明中使用的聚硅氧烷预聚物是m+n+p等于约15-200个二甲基硅氧烷重复单元的那些。优选的聚硅氧烷预聚物是具有约25-50个二甲基硅氧烷重复单元的那些。更优选的聚硅氧烷预聚物是具有25个二甲基硅氧烷重复单元的那些。
优选的是,预聚物的总浓度是用1-70摩尔%三烷基甲硅烷基、优选25-20摩尔%三烷基甲硅烷基且更优选40-50摩尔%三烷基甲硅烷基封端。由此,这类使用的“预聚物”表示具有通式(I)和(II)的化合物:
这些M2Dx,TMS-封端的预聚物是极易合成的。合成步骤包括在同一反应器中进行的酸催化和开环聚合。环状硅氧烷(D)、封端剂(M2)和二硅氧烷(T2)是同合适的催化剂一起被简单地添加至一反应器中并在室温下搅拌一段时间。
本发明的硅氧烷水凝胶是能够以平衡状态吸收和保持水分的交联聚合体系。这些聚合体系是基于至少一种含硅氧烷的单体和至少一种亲水性单体。优选地,本发明的硅氧烷水凝胶是通过聚合包含本发明的预聚物混合物、第二种不饱和含硅氧烷的单体和至少一种亲水性单体的单体而制成的。更优选地,所述第二种不饱和含硅氧烷的单体可以包括单官能的含硅氧烷单体。最优选地,单官能的含硅氧烷单体是由通式(III)表示的松散的聚硅氧烷基烷基(甲基)丙烯酸单体之中的至少之一:
其中:X表示-COO-,-CONR4-,-OCOO-,或-OCONR4-,其中每个R4独立地是H或低级烷基;R3表示氢或甲基;h是1-10;且每个R2独立地表示低级烷基,苯基或通式为-Si(R5)3的基团,其中每个R5独立地是低级烷基或苯基。
此种松散的单体具体地包括甲基丙烯酰氧基丙基三(三甲代甲硅烷氧基)硅烷(“TRIS”)、五甲基二硅氧烷基甲基甲基丙烯酸酯、三(三甲代甲硅烷氧基)甲基丙烯酰氧基丙基硅烷、苯基四甲基-二硅氧烷基乙基丙烯酸酯、甲基二(三甲代甲硅烷氧基)甲基丙烯酰氧基甲基硅烷、3-[三(三甲代甲硅烷氧基)甲硅烷基]丙基乙烯基氨基甲酸酯、3-[三(三甲代甲硅烷氧基)甲硅烷基]丙基烯丙基氨基甲酸酯和3-[三(三甲代甲硅烷氧基)甲硅烷基]丙基乙烯基碳酸酯。
优选的亲水性单体可以是含丙烯酸基或乙烯基。术语“乙烯基型”或“含乙烯基”单体是指含有乙烯基(CH2=CHR)的且通常是反应性的单体。已知此种亲水性含乙烯基的单体较容易地聚合。含丙烯酸基的单体是含有丙烯酸基(CH2=CRCOX)的单体,其中R=H或CH3和X=O或NH,公知该单体也是容易聚合的。
合适的亲水性单体的实例包括:不饱和的羧酸,例如甲基丙烯酸和丙烯酸;丙烯酸取代醇,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,例如N-乙烯基吡咯烷酮;且丙烯酰胺,例如甲基丙烯酰胺,最优选是N,N-二甲基丙烯酰胺(DMA)。其它单体包括甲基丙烯酸甘油酯和2-羟乙基甲基丙烯酰胺。
本发明的硅氧烷水凝胶通常是通过聚合如下的一种单体混合物形成的,该单体混合物包含:约10-90重量%,优选20-70重量%,更优选20-50重量%的由通式I和通式II表示的单体组成的预聚物,其中所述预聚物的总浓度是用约1-70摩尔%的三甲代甲硅烷基、优选约25-50摩尔%的三甲代甲硅烷基,更优选约40-50摩尔%的三甲代甲硅烷基封端:约10-50重量%的单官能烯属不饱和的含硅氧烷的单体,优选约20-50重量%的单官能烯属不饱和的含硅氧烷的单体,约20-40重量%的单官能烯属不饱和的含硅氧烷的单体;和约5-70重量%的亲水性单体,优选约10-50重量%的亲水性单体,更优选约20-40重量%的亲水性单体。由本发明制得的硅氧烷水凝胶的实例可以是由50摩尔%TMS封端的约20份预聚物,约35份亲水性单体、约25份单官能烯属不饱和的含硅氧烷的单体。可加入其它组分例如稀释剂并将在下面讨论。
本发明的单体混合物可以包括其它的组分例如紫外线吸收剂、内润滑剂、亲水性单体单元、增韧剂、或颜料,例如公知用在接触镜片技术中的那些添加剂。
在聚合烯属不饱和化合物例如紫外线聚合、热聚合或者它们的组合中所用的常规聚合方法可用于铸塑这些单体混合物。代表性的自由基热聚合引发剂可以是有机过氧化物且通常以总的单体混合物的约0.01-1重量%的浓度存在。代表性的紫外线引发剂在本领域是公知的,例如苯偶姻甲基醚、苯偶姻乙基醚、1164、2273、1116、2959、3331(EMindustries)和Irgacure 651和184(Ciba-Geigy)。在优选的实施方案中,紫外线引发剂是Darocur 1173。
本发明的预聚物与其它共聚物的聚合通常是在稀释剂的存在下进行。该稀释剂通常在聚合之后除去且在本领域熟练人员熟知的抽提和水合步骤中用水替换。代表性的吸收剂是二醇、醇、醇/水混合物、乙二醇、甘油、液态聚乙二醇、低分子量线性聚甲基丙烯酸羟乙酯、乳酸的乙二醇酯、甲酰胺、酮类、二烷基亚砜、丁基卡必醇等等。优选的稀释剂包括己醇和壬醇。
也可能在无稀释剂的情况下进行聚合以制得干凝胶。如本领域所熟知,这些干凝胶然后可以水合形成水凝胶。
单体混合物可以包括调色剂,其是当加入至最终的镜片中赋予镜片一定程度的颜色的试剂。常规的调色剂是本领域熟知的,包括不可聚合的试剂或可聚合的试剂,该可聚合的试剂包括与镜片制备单体反应的活性不饱和基团的试剂。这个后一类的优选实例是化合物1,4-二(4-(2-甲基丙烯酰氧基乙基)苯基氨基)蒽醌,其是在US4,997,897(Melpolder)中公开的显蓝色调色剂。
所述单体混合物可以包括紫外线吸收剂,其是在200至400纳米的通常范围内降低光的试剂。用于接触镜片用途的代表性可聚合的紫外线吸收材料是见于US4,304,895(Loshaek),4,528,311(Beard等人),4,716,234(Dunks等人),4,719,248(Bambury等人),3,159,646(Milionis等人)和3,761,272(Maneus等人)。紫外线吸收化合物的实例包括苯并***和二苯甲酮。
用于将水凝胶聚合物混合物模塑成接触镜片的各种技术在本领域是公知的,包括旋转铸塑和静态铸塑。旋转铸塑方法是公开在US3,408,429和3,496,254中。静态铸塑包括将一定量的可聚合单体混合物加入至模具组件中且对同时保留在模具组件中的单体混合物进行固化以形成镜片,例如,通过单体混合物的自由基聚合。固化镜片材料的自由基反应技术的实例包括热辐射、红外辐射、电子束辐射、伽玛辐射、紫外线辐射等等;可结合这些技术。所述模具组件限定了一个用于铸塑镜片的模腔,包括用于限定前镜片表面的前模具和用于限定后镜片表面的后模具。
US5,271,875介绍了一种静态铸塑方法,其使得在由后模具和前模具限定的模腔中模塑最终的镜片。
本发明的水凝胶是透氧性的、水解稳定的、生物惰性的和透明的。当在制备接触镜片中使用时,优选的是,所述水凝胶具有约5-70重量%的水含量。更优选是约25-50重量%。另外,优选的是,此种水凝胶的模量为约20g/mm2至约200g/mm2,且更优选是约75g/mm2至约175g/mm2。
如前所述,M2Dx,TMS封端的预聚物是极易合成的。比先已公知的方法需要较少的步骤和组分。这降低了生产水凝胶或接触镜片所必须的成本和时间。
作为本发明的说明,下面提供了几个实施例。这些实施例仅仅用于进一步说明本发明的性质且不应用于限制本发明。
实施例1
制备1,3-二(4-甲基丙烯酰氧基丁基)四甲基二硅氧烷(M2)
向装配有机械搅拌器、迪安-斯达克汽水阀、加热罩、水冷却冷凝器和温度计的一个5升四口树脂烧瓶中加入1,1-二甲基-1-硅-2-氧环己烷(521克,4.0摩尔),甲基丙烯酸(361克,4.2摩尔)和浓硫酸(25.5克)。然后向反应混合物中加入1升环己烷和氢醌(0.95克,8.6毫摩尔)作为聚合抑制剂。将反应混合物加热至回流5小时,在此期间收集28毫升水。然后将反应混合物冷却,分选并通过两个填充有1千克氧化铝的色谱柱(使用环己烷作为淋洗液)。环己烷是使用旋转式蒸发器除去且所得的M2是在真空(0.2毫米汞柱)下于80℃放置1小时(产率,80%;气相色谱法测得的纯度,96%)。
实施例2
合成甲基丙烯酸酯封端的聚二甲基硅氧烷(M2D25)
向一1000毫升圆底烧瓶在干氮气下添加八甲基环四硅氧烷(D4)(371.0克、1.25摩尔)和M2(27.7克、0.7摩尔)。添加入三氟代甲烷磺酸(0.25%,1.25克,8.3毫摩尔)作为引发剂。在室温下将反应混合物剧烈地搅拌24小时。然后添加碳酸氢钠(10克,0.119摩尔)且将反应混合物再搅拌24小时。将所得溶液通过0.3微米孔径Teflon过滤器过滤。将滤液进行真空汽提并在真空(>0.1毫米汞柱)下于50℃放置以除去未反应的硅氧烷环状化合物。所得的硅烷官能化的硅氧烷是粘性的、清澈的液体:产率,70%。
对比例3-16
具有不同比率的水凝胶的配方
制备具有下列组成的配方:α,ω-二(甲基丙烯酰氧基烷基)聚硅氧烷(M2D25),甲基丙烯酰氧基丙基三(三甲代甲硅烷基)硅烷(“TRIS”)和N,N-二甲基丙烯酰胺(DMA)。每个配方包含恒定量的己醇作为溶剂(20份)和Darocur-1173作为光引发剂(0.5份)。所有配方是在室温下于两个玻璃板之间进行紫外线固化2小时。将所得的薄膜分离、随后用乙醇抽提16小时且沸水水合4小时,然后放置在硼酸盐缓冲的盐水中。注意到,各种成分的比率是随所得性能变化的。
对根据上述的步骤铸塑的薄膜的水含量和异丙醇抽提物是进行重量测量。抗张和剪切性能是在缓冲盐水中测定的,分别按照标准的ASTM步骤1708和1938。透氧性是通过考虑了边缘效应的极谱方法测定。(参见Fatt,Rasson和Melpolder,Int′l Contact Lens Clinic,V.14,389(1987))。
表1使用用0摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
实施例 | DMA(份) | TRIS(份) | M2D25(份) | DK(Barrers) | H2O(%) | 重量损失(%) | 模量(g/mm2) | H2Otrans |
3 | 20.00 | 39.50 | 20.00 | 179.00 | 11.61 | 17.83 | 181 | 1.05 |
4 | 23.95 | 33.10 | 22.45 | 131.60 | 17.94 | 19.25 | 223 | 14.91 |
5 | 35.00 | 24.50 | 20.00 | 85.00 | 32.70 | 21.19 | 212 | 79.96 |
6 | 35.00 | 20.00 | 24.50 | 196.00 | 32.19 | 21.48 | 290 | 91.35 |
7 | 20.00 | 29.50 | 30.00 | 181.90 | 10.65 | 17.72 | 306 | 9.03 |
8 | 20.00 | 39.50 | 20.00 | 189.30 | 10.12 | 18.81 | 204 | 4.53 |
9 | 20.00 | 34.50 | 25.00 | 139.40 | 11.56 | 18.65 | 238 | 6.93 |
10 | 35.00 | 20.00 | 24.50 | 91.10 | 32.21 | 19.83 | 305 | 70.4 |
11 | 29.50 | 20.00 | 30.00 | 129.40 | 23.67 | 19.93 | 355 | 45.21 |
12 | 24.75 | 24.75 | 30.00 | 120.20 | 17.36 | 21.80 | 327 | 19.46 |
13 | 35.00 | 24.50 | 20.00 | 85.40 | 34.70 | 21.35 | 219 | 74.07 |
14 | 20.00 | 29.50 | 30.00 | 201.90 | 12.19 | 21.10 | 314 | 4.59 |
15 | 31.45 | 23.35 | 24.70 | 113.30 | 29.55 | 21.85 | 274 | 51.83 |
16 | 27.90 | 26.70 | 24.90 | 125.20 | 23.42 | 21.55 | 260 | 22.25 |
用上述组分制得的硅氧烷水凝胶制得通常具有高透氧性的薄膜。注意到,这些薄膜的某些的模量对于软接触镜片用途是太高的。
实施例17-30
用10摩尔%三甲代甲硅烷基封端的制得的M2D25薄膜
这个预聚物是通过与上述相同的步骤制得,例外之处是采用下列含量:M2 9.08克,D4 40.57克,T2(六甲基二硅氧烷)0.35克和三氟代甲烷磺酸0.125克。
表2使用用10摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
实施例 | DMA(份) | TRIS(份) | M2Dx(份) | DK(Barrers) | H2O(%) | 重量损失(%) | 模量(g/mm2) | H2Otrans |
17 | 20.00 | 39.50 | 20.00 | 200.00 | 11.69 | 17.42 | 163 | 1.16 |
18 | 23.95 | 33.10 | 22.45 | 160.40 | 18.04 | 19.47 | 191 | 9.53 |
19 | 35.00 | 24.50 | 20.00 | 80.40 | 32.62 | 19.48 | 179 | 91.35 |
20 | 35.00 | 20.00 | 24.50 | 77.80 | 33.89 | 24.61 | 263 | 2.68 |
21 | 20.00 | 29.50 | 30.00 | 187.30 | 10.65 | 17.72 | 246 | 2.79 |
22 | 20.00 | 39.50 | 20.00 | 208.00 | 9.97 | 18.70 | 164 | 6.04 |
23 | 20.00 | 34.50 | 25.00 | 198.60 | 11.93 | 19.15 | 215 | 7.72 |
24 | 35.00 | 20.00 | 24.50 | 84.50 | 31.80 | 19.27 | 250 | 90.99 |
25 | 29.50 | 20.00 | 30.00 | 120.20 | 23.33 | 19.19 | 329 | 40.44 |
26 | 24.75 | 24.75 | 30.00 | 164.10 | 17.43 | 19.55 | 275 | 20.54 |
27 | 35.00 | 24.50 | 20.00 | 75.80 | 34.06 | 21.03 | 190 | 79.86 |
28 | 20.00 | 29.50 | 30.00 | 158.30 | 11.88 | 20.16 | 284 | 2.91 |
29 | 31.45 | 23.35 | 24.70 | 102.70 | 27.03 | 22.14 | 272 | 59.79 |
30 | 27.90 | 26.70 | 24.90 | 119.70 | 22.97 | 21.11 | 232 | 22.55 |
相比于实施例3-16,含有用10摩尔%三甲代甲硅烷基封端的M2D25的薄膜表现出模量降低。透氧性是可接受的。
实施例31-44
用25摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
这个预聚物是通过与上述相同的步骤制得,例外之处是采用下列含量:M2 8.98克,D4 40.14克,T2 0.88克和三氟代甲烷磺酸0.125克。
表3使用用25摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
实施例 | DMA(份) | TRIS(份) | M2D25(份) | DK(Barrers) | H2O(%) | 重量损失(%) | 模量(g/mm2) | H2Otrans |
31 | 20.00 | 39.50 | 20.00 | 126.60 | 12.17 | 18.34 | 137 | 0.65 |
32 | 23.95 | 33.10 | 22.45 | 134.40 | 18.21 | 18.68 | 158 | 7.47 |
33 | 35.00 | 24.50 | 20.00 | 92.50 | 33.67 | 18.84 | 161 | 69.93 |
34 | 35.00 | 20.00 | 24.50 | 79.00 | 35.04 | 21.71 | 227 | 90.15 |
35 | 20.00 | 29.50 | 30.00 | 67.30 | 12.44 | 24.39 | 250 | 1.96 |
36 | 20.00 | 39.50 | 20.00 | 156.50 | 9.56 | 20.23 | 139 | 4.53 |
37 | 20.00 | 34.50 | 25.00 | 169.90 | 11.08 | 18.77 | 181 | 8.43 |
38 | 35.00 | 20.00 | 24.50 | 87.40 | 32.65 | 20.96 | 232 | 91.11 |
39 | 29.50 | 20.00 | 30.00 | 129.50 | 25.59 | 20.36 | 282 | 68.92 |
40 | 24.75 | 24.75 | 30.00 | 201.10 | 18.96 | 20.84 | 241 | 17.73 |
41 | 35.00 | 24.50 | 20.00 | 87.50 | 34.89 | 21.93 | 155 | 89.85 |
42 | 20.00 | 29.50 | 30.00 | 126.70 | 12.80 | 21.54 | 165 | 2.57 |
43 | 31.45 | 23.35 | 24.70 | 92.80 | 29.32 | 21.91 | 209 | 59.53 |
44 | 27.90 | 26.70 | 24.90 | 142.00 | 24.58 | 21.56 | 197 | 29.18 |
相比于实施例17-30,用由25摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜表现出模量降低。
实施例45-46
用由40摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
这个预聚物是通过与上述相同的步骤制得,例外之处是采用下列含量:M2 8.89克,D4 39.72克,T2 1.39克和三氟代甲烷磺酸0.125克。
表4使用由40摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
实施例 | DMA(份) | NVP(份) | TRIS(份) | M2D25(份) | DK(Barrers) | H2O(%) | 重量损失(%) | 模量(g/mm2) |
45 | 17.50 | 17.50 | 24.50 | 20.00 | 72.90 | 35.05 | 32.50 | 126 |
46 | 17.50 | 17.50 | 24.50 | 20.00 | 76.30 | 36.03 | 23.81 | 120 |
相比于实施例31-44,含有用40摩尔%三甲代甲硅烷基封端的M2D25的薄膜表现出模量降低。
实施例47-48
用由50摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
这个预聚物是通过与上述相同的步骤制得,例外之处是采用下列含量:M2 8.82克,D4 39.45克,T2 1.73克和三氟代甲烷磺酸0.125克。
表5使用由50摩尔%三甲代甲硅烷基封端的M2D25制得的薄膜
实施例 | DMA(份) | NVP(份) | TRIS(份) | M2D25(份) | DK(Barrers) | H2O(%) | 重量损失(%) | 模量(g/mm2) |
47 | 17.50 | 17.50 | 24.50 | 20.00 | 65.30 | 36.55 | 24.33 | 109 |
48 | 17.50 | 17.50 | 24.50 | 20.00 | 76.30 | 35.53 | 24.86 | 103 |
相比于实施例45,46,含有用50摩尔%三甲代甲硅烷基封端的M2D25的薄膜表现出模量降低。
考虑到上述的教示,本领域熟练人员是能够对本发明进行许多其它改进和变换。因此应理解的是,在所附权利要求的范围之内,本发明可以除上述具体描述以外的方法实施。
Claims (41)
1、一种由含有具有下列通式的硅氧烷预聚物的单体混合物的聚合产物制备水凝胶的方法:
其中,
A是甲基丙烯酸酯基;
A′是甲基丙烯酸酯基;
R1-R10各自独立地是具有1-10个碳的烷基、氟代烷基、醇、醚或氟代醚基,或者具有6-18碳原子的芳基;
m,n和p各自独立地是0-200,m+n+p是15-200;
a是1-10;和
b是0-10;
其中所述硅氧烷预聚物是通过由下列通式表示的二甲基丙烯酸酯基二硅氧烷(M2)和环状硅氧烷(D)在催化剂的存在下反应而制得,其改进之处包括将至少一种具有下列通式的二硅氧烷(T2)添加至用于制成硅氧烷预聚物的反应混合物中:
其中R11-R16各自独立地是具有1-5个碳原子的烷基。
2、如权利要求1所述的方法,其中所述水凝胶的交联密度随着所述T2的量增长而降低。
3、如权利要求1所述的方法,其中所述聚硅氧烷预聚物的m+n+p是在25-50的范围内。
4、如权利要求3所述的方法,其中所述聚硅氧烷预聚物的m+n+p是25。
5、如权利要求1所述的方法,其中所述聚硅氧烷预聚物用1-70摩尔%的三甲代甲硅烷基封端。
6、如权利要求5所述的方法,其中所述预聚物用25-50摩尔%的三甲代甲硅烷基封端。
7、如权利要求6所述的方法,其中所述预聚物用40-50摩尔%的三甲代甲硅烷基封端。
8、如权利要求5所述的方法,其中所述聚硅氧烷预聚物的m+n+p是25且是用50摩尔%的三甲代甲硅烷基封端。
9、如权利要求1所述的方法,其中D是八甲基环四硅氧烷。
10、如权利要求1所述的方法,其中D是1,1,3,3-四甲基-1,3-二硅-2-氧环戊烷。
11、如权利要求1所述的方法,其中D是六甲基环三硅氧烷。
12、如权利要求1所述的方法,其中所述催化剂是三氟代甲烷磺酸。
13、如权利要求1所述的方法,其中T2是六甲基二硅氧烷。
14、如权利要求1所述的方法,其中所述单体混合物还包含亲水性单体。
15、如权利要求14所述的方法,其中所述亲水性单体是含丙烯酸基的单体。
16、如权利要求15所述的方法,其中所述亲水性单体是N,N-二甲基丙烯酰胺。
17、如权利要求14所述的方法,其中所述亲水性单体是含乙烯基的单体。
18、如权利要求17所述的方法,其中所述亲水性单体是N-乙烯基吡咯烷酮。
19、如权利要求14所述的方法,还包括一种单官能的、烯属不饱和的含硅氧烷的单体。
21、如权利要求1所述的方法,其中所述单体混合物还包含紫外线引发剂。
22、如权利要求1所述的方法,其中所述单体混合物还包含稀释剂。
23、如权利要求22所述的方法,其中所述稀释剂是己醇。
24、一种由包含下列组分的单体混合物的聚合产物制成的含硅氧烷水凝胶:
(a)由下列通式表示的聚硅氧烷预聚物
其中,
A是甲基丙烯酸酯基;
A′是甲基丙烯酸酯基;
R1-R10各自独立地是具有1-10个碳的烷基、氟代烷基、醇、醚或氟代醚基,或者具有6-18碳原子的芳基;
m,n和p各自独立地是0-200,m+n+p是15-200;
a是1-10;和
b是0-10,
其中所述硅氧烷预聚物是通过由下列通式表示的二甲基丙烯酸酯基二硅氧烷(M2)和环状硅氧烷(D)在催化剂的存在下反应而制得,其改进之处包括将至少一种具有下列通式的二硅氧烷(T2)添加至用于制成硅氧烷预聚物的反应混合物中:
其中R11-R16各自独立地是具有1-5个碳原子的烷基,
(b)亲水性单体;和
(c)单官能的、烯属不饱和的含硅氧烷的单体。
25、如权利要求24所述的水凝胶,其中所述聚硅氧烷预聚物的m+n+p是在25-50的范围内。
26、如权利要求25所述的水凝胶,其中所述聚硅氧烷预聚物的m+n+p是25。
27、如权利要求24所述的水凝胶,其中所述聚硅氧烷预聚物是用1-70摩尔%的三甲代甲硅烷基封端。
28、如权利要求27所述的水凝胶,其中所述预聚物是用25-50摩尔%的三甲代甲硅烷基封端。
29、如权利要求28所述的水凝胶,其中所述预聚物是用40-50摩尔%的三甲代甲硅烷基封端。
30、如权利要求24所述的水凝胶,其中所述聚硅氧烷预聚物的m+n+p是25且是用50摩尔%的三甲代甲硅烷基封端。
31、如权利要求24所述的水凝胶,其中T2是六甲基二硅氧烷。
32、如权利要求24所述的水凝胶,其中所述亲水性单体是含丙烯酸基的单体。
33、如权利要求32所述的水凝胶,其中所述亲水性单体是N,N-二甲基丙烯酰胺。
34、如权利要求24所述的水凝胶,其中所述亲水性单体是含乙烯基的单体。
35、如权利要求34所述的水凝胶,其中所述亲水性单体是N-乙烯基吡咯烷酮。
37、如权利要求24所述的水凝胶,其中所述单体混合物还包含紫外线引发剂。
38、如权利要求24所述的水凝胶,其中所述单体混合物还包含稀释剂。
39、如权利要求38所述的水凝胶,其中所述稀释剂是己醇。
40、含有权利要求24所述的水凝胶的接触镜片。
41、含有权利要求24所述的水凝胶的人工晶状体。
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US60/145,908 | 1999-07-27 |
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- 2000-06-20 EP EP00944740A patent/EP1196499B1/en not_active Expired - Lifetime
- 2000-06-20 CA CA002379244A patent/CA2379244C/en not_active Expired - Fee Related
- 2000-06-20 KR KR1020027001119A patent/KR20020016922A/ko active IP Right Grant
- 2000-06-20 WO PCT/US2000/016891 patent/WO2001007523A1/en active IP Right Grant
- 2000-06-20 ES ES00944740T patent/ES2206270T3/es not_active Expired - Lifetime
- 2000-06-20 BR BR0013052-4A patent/BR0013052A/pt not_active Application Discontinuation
- 2000-06-20 CN CNB008108412A patent/CN1162472C/zh not_active Expired - Fee Related
- 2000-06-29 TW TW089112849A patent/TW500769B/zh active
- 2000-07-21 MY MYPI20003343 patent/MY133494A/en unknown
- 2000-07-21 AR ARP000103751A patent/AR026868A1/es not_active Application Discontinuation
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2002
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- 2002-11-12 US US10/293,056 patent/US6762264B2/en not_active Expired - Lifetime
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Cited By (3)
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CN106065075A (zh) * | 2015-04-23 | 2016-11-02 | 信越化学工业株式会社 | 硅酮、聚合物、眼科器件及硅酮的制造方法 |
CN106065075B (zh) * | 2015-04-23 | 2019-07-19 | 信越化学工业株式会社 | 硅酮、聚合物、眼科器件及硅酮的制造方法 |
CN106279699A (zh) * | 2015-06-05 | 2017-01-04 | 永胜光学股份有限公司 | 一种硅水胶镜片基材的制备工艺 |
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AR026868A1 (es) | 2003-03-05 |
CA2379244A1 (en) | 2001-02-01 |
HK1048331B (zh) | 2004-08-13 |
JP2003505728A (ja) | 2003-02-12 |
MY133494A (en) | 2007-11-30 |
CN1373794A (zh) | 2002-10-09 |
BR0013052A (pt) | 2002-04-09 |
WO2001007523A1 (en) | 2001-02-01 |
EP1196499A1 (en) | 2002-04-17 |
US6921802B2 (en) | 2005-07-26 |
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TW500769B (en) | 2002-09-01 |
DE60004854D1 (de) | 2003-10-02 |
HK1048331A1 (en) | 2003-03-28 |
AU766109B2 (en) | 2003-10-09 |
AU5879100A (en) | 2001-02-13 |
US20040152859A1 (en) | 2004-08-05 |
CA2379244C (en) | 2007-09-18 |
US6762264B2 (en) | 2004-07-13 |
KR20020016922A (ko) | 2002-03-06 |
DE60004854T2 (de) | 2004-06-09 |
US20030109637A1 (en) | 2003-06-12 |
EP1196499B1 (en) | 2003-08-27 |
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