CN101094879B - 用于生物医学器件的聚硅氧烷预聚物 - Google Patents
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Abstract
本发明涉及可用于形成生物医学器件且包含嵌段(I)和(II)并且在每个末端由烯键式不饱和基封端的聚硅氧烷预聚物:(*Dii*Diol*Dii*PS)x(I)(*Dii*PS)y(II),其中:每个Dii独立地为二异氰酸酯的双基残基;每个Diol独立地为具有1-10个碳原子的二醇的双基残基;每个PS独立地为含聚硅氧烷的二醇或二胺的双基残基;每个*独立地为-NH-CO-NH-、-NH-COO-或-OCO-NH-;x代表嵌段(I)的个数且至少为2;y代表嵌段(II)的个数且至少是1。
Description
技术领域
本发明涉及可用于形成生物医学器件,尤其是包括接触镜、人工晶状体和眼内植入物的眼科器件的聚硅氧烷预聚物。本发明还涉及由该预聚物形成的共聚物,特别是水凝胶共聚物。
背景技术
水凝胶代表一类用来制造各种生物医学器件,包括眼科器件如接触镜的理想的材料。水凝胶是水合交联聚合物体系,其在平衡状态下含有水。水凝胶透镜具有想要的生物相容性和舒适度。有机硅水凝胶是一类已知的水凝胶,其特征在于包括含有机硅的材料。通常,含有机硅的单体与亲水性单体通过自由基聚合进行共聚合,其中或者含有机硅的单体或者亲水性单体用作交联剂(交联剂定义为含有多个可聚合官能度的单体),或者可使用单独的交联剂。有机硅水凝胶与非有机硅水凝胶相比的优点在于由于包括含有机硅的单体而使有机硅水凝胶通常具有较高的透氧性。
已经公开了多种含有脲或氨基甲酸酯联接的基于聚硅氧烷的预聚物作为用于有机硅水凝胶的潜在含有机硅的单体。这些各种预聚物在其制备方法和物理特征/性质上可以不同,并因此可以在与用于水凝胶共聚物的其它单体结合时显示出不同的性质。
一类含氨基甲酸酯或含脲的聚硅氧烷预聚物涉及由具有异氰酸酯基的烯键式不饱和单体如甲基丙烯酸异氰酸根合乙酯(IEM)封端的聚硅氧烷-二醇或聚硅氧烷-二胺。例如,通过使IEM与羟基封端的聚二甲基硅氧烷反应而形成预聚物。通常,该类预聚物作为不含氨基甲酸酯联接的相应预聚物显示出与亲水性单体类似的相容性,尤其是对于较高分子量预聚物。此外,这些预聚物在室温下通常为液体。该类预聚物的实例可在美国专利4,605,712(Mueller等)中找到。
第二类含氨基甲酸酯的聚硅氧烷预聚物使用二异氰酸酯以产生氨基甲酸 酯联接。通常,这些预聚物通过使2摩尔二异氰酸酯与羟基封端的聚二甲基硅氧烷反应,然后用甲基丙烯酸2-羟乙酯(HEMA)封端而制备。这类预聚物根据聚硅氧烷的分子量而在与亲水性单体如N,N-二甲基丙烯酰胺(DMA)相容性上显示出轻微的改进。此外,这类预聚物在室温下通常为液体。该类预聚物的实例可在美国专利4,136,250(Mueller等)中找到。
美国专利5,034,461(Lai等)公开了多种含聚硅氧烷的氨基甲酸酯或脲预聚物。通常,这些预聚物衍生于短链二醇、羟基封端的聚二甲基硅氧烷和二异氰酸酯,从而使结构类似于嵌段聚氨酯弹性体;这些预聚物用可聚合的烯键式不饱和基来封端,如HEMA与异氰酸酯反应。这些预聚物可以与亲水性共聚单体进行共聚合以形成可用作接触镜材料或其它生物医学器件应用的有机硅水凝胶共聚物。US 5,034,461的优选预聚物由软聚硅氧烷链段(在该专利的分子式中由A表示)和极硬链段(在该专利的分子式中由*D*G*D表示)组成并且由可聚合的烯键式不饱和基封端。
本发明的含聚硅氧烷的预聚物包含如US 5,034,461的柔链段和极硬链段。然而,本发明的预聚物除软链段和极硬链段外还包含较不硬链段。已经发现这导致几个优点。首先,本发明预聚物在室温下趋于具有更低的粘度,这使它们与公开于US 5,034,461中的预聚物相比在合成过程中和浇铸生物医学器件中更易于加工。第二,该排列允许形成具有更高有机硅含量的预聚物,从而允许形成比US 4,136,250或4,605,712中公开的预聚物具有更高的透氧性的共聚物,而同时保持与亲水性单体良好的相容性并形成透明的水凝胶。第三,由于各种链段的排列,可以得到具有更高透氧性且没有高模量的共聚物。
发明内容
本发明提供可用于形成生物医学器件的聚硅氧烷预聚物。该预聚物包含嵌段(I)和(II)并且在每端由烯键式不饱和基封端:
(*Dii*Diol*Dii*PS)x (I)
(*Dii*PS)y (II)
其中:
每个Dii独立地为二异氰酸酯的双基残基;
每个Diol独立地为具有1-10个碳原子的二醇的双基残基;
每个PS独立地为聚硅氧烷-二醇或二胺的双基残基;
每个*独立地为-NH-CO-NH-、-NH-COO-或-OCO-NH-;
x代表嵌段(I)的个数且至少为2,
y代表嵌段(II)的个数且至少是1
优选的预聚物由以下通式表示:
M(*Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii*M (III)或者
M(*Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii*Diol*Dii*M (IV)
其中Dii、Diol、PS、*、x和y如上所定义,并且M独立地为可聚合的烯键式不饱和基。
本发明还提供共聚物,其为包含所述预聚物与共聚单体的单体混合物的聚合产物。一个优选的共聚单体为亲水性单体,另一个优选共聚单体为含有机硅的单官能单体。优选的共聚物为水凝胶,即包含该预聚物的单体混合物与亲水性共聚单体的水合聚合产物。特别优选水凝胶共聚物含水量至少为20重量%,模量不大于100g/mm2和/或透氧性至少为100barrer。
本发明还提供包含所述共聚物的生物医学器件,尤其是眼科器件如接触镜或人工晶状体。
具体实施方式
本发明的预聚物包含如上所示的式(I)和(II)的嵌段。通常式(I)的嵌段可以被表征为由极硬链段(由*Dii*Diol*Dii*代表)和软链段(由PS代表)组成。通常,通常式(II)的嵌段可以被表征为由较不硬链段(由*Dii*代表)和软链段(由PS代表)组成。这些较不硬链段和极硬嵌段(I)和(II)的分布可以为随机的或交替的,其中x和y表示预聚物中各结构的嵌段总数,换句话说,在式(III)和(IV)中所有式(I)的嵌段不需要相互直接联接。这些嵌段的分布可以通过在预聚物制备过程中添加聚硅氧烷、二异氰酸酯和短链二醇组分的顺序来控制。
该预聚物包括含聚硅氧烷的软链段,其在式(I)、(II)、(III)和(IV)中由PS表示。更具体而言,该含聚硅氧烷的链段衍生于由羟基或氨基封端的聚硅氧烷:
其中每个A为羟基或氨基;
每个R独立地选自具有1-10个碳原子的亚烷基,其中碳原子之间可以包括醚、氨基甲酸酯或脲联接;
每个R’独立地选自氢、一价烃基或卤素取代的一价烃基,其中烃基具有其间可以包括醚联接的1-20个碳原子,和
a至少为1。
优选的R基为任选由醚基取代的亚烷基。优选的R’基包括烷基、苯基、氟取代的烷基和烯基、任选取代的醚基。特别优选的R’基包括烷基如甲基;或任选包括醚联接的氟代烷基如-CH2-CH2-CH2-O-CH2-(CF2)z-H,其中z为1-6。
优选a为约10-100,更优选约15-80。PS的Mn为1000-8000,更优选2000-6000。
各种聚硅氧烷-二醇和聚硅氧烷-二胺可以市购。此外,在本实施例中给出了聚硅氧烷的代表性合成。
该预聚物的极硬链段包括二醇的残基,在式(I)、(III)和(IV)中由Diol表示。优选的二醇基包括具有1-10个碳原子且在主链上可以含醚、硫醚或胺联接的烷基二醇、环烷基二醇和烷基环烷基二醇、芳族二醇或烷基芳基二醇的双基残基。代表性二醇包括2,2-(4,4’-二羟基二苯基)丙烷(双酚-A)、4,4’-异亚丙基二环己醇、乙氧基化及丙氧基化双酚-A、2,2-(4,4’-二羟基二苯基)戊烷、1,1’-(4,4’-二羟基二苯基)-对二异丙基苯、1,3-环己烷二醇、1,4-环己烷二醇、1,4-环己烷二甲醇、新戊二醇、1,4-丁二醇、1,3-丙二醇、1,5-戊二醇、乙二醇、二甘醇和三甘醇。特别优选具有1-10个碳原子的亚烷基二醇和醚化亚烷基二醇。
上述含聚硅氧烷的链段和二醇残基链段经由与含聚硅氧烷链段和二醇的羟基官能团或氨基官能团反应的二异氰酸酯而联接。通常,可以使用任何二异氰酸酯。这些二异氰酸酯可以为脂族或芳族的,包括优选在脂族或芳族部分中具有6-30个碳原子的烷基、烷基环烷基、环烷基、烷基芳基和芳基二异 氰酸酯。具体实例包括异佛尔酮二异氰酸酯、六亚甲基-1,6-二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、4,4’-二苯基二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、对亚苯基二异氰酸酯、1,4-亚苯基4,4’-二苯基二异氰酸酯、1,3-二(4,4’-异氰酸甲基)环己烷和环己烷二异氰酸酯。
通常,更高的x值导致预聚物具有更高数量的极性氨基甲酸酯/脲联接,预聚物的极性对确保与亲水性共聚单体的相容性是重要的。通常,更高的y值导致预聚物具有更高比例的硅,这导致更高的透氧性。然而,x和y的比例应该平衡。因此,x和y的比例优选为至少0.6(即x∶y至少为0.6∶1),更优选至少0.75。
所述预聚物在两端用在式(III)和(IV)中由M表示的可聚合的烯键式不饱和基封端。代表性的M基可以通过下式表示:
其中:
R23为氢或甲基;
每个R24为氢、具有1-6个碳原子的烷基或-CO-Y-R26基,其中Y为-O-、-S-或-NH-;
R25为具有1-10个碳原子的二价亚烷基;
R26为具有1-12个碳原子的烷基;
Q表示-CO-、-OCO-或-COO-;
X表示-O-或-NH-;
Ar表示具有6-30个碳原子的芳基;b为0-6;c为0或1;d为0或1并且e为0或1。
形成M基的合适封端前体包括羟基封端的(甲基)丙烯酸酯,如甲基丙烯酸2-羟乙酯、丙烯酸2-羟乙酯和甲基丙烯酸3-羟丙酯;和氨基封端的(甲基)丙烯酸酯,如甲基丙烯酸叔丁基氨基乙酯和甲基丙烯酸氨基乙酯;和(甲基)丙烯酸(如这里所用,术语“(甲基)”表示任选的甲基取代基,因此术语如“(甲基)丙烯酸酯”表示甲基丙烯酸酯或丙烯酸酯,“(甲基)丙烯酸”表示甲基丙烯酸或丙烯酸)。
形成预聚物的第一代表性反应路线如下。首先使二异氰酸酯与二醇分别以2∶1的摩尔比反应。
2xOCN-Dii-NCO+xHO-Diol-OH→xOCN-Dii*Diol*Dii-NCO
在该路线中,*表示尿烷基-NH-COO-或-OCO-NH-。通常该反应在催化剂如二月桂酸二丁基锡存在下并在溶剂如二氯甲烷中和在回流下进行。然后,加入二异氰酸酯和聚硅氧烷-二醇,总二异氰酸酯(x+y)对聚硅氧烷-二醇的比例至少为1.1(通常2<x+y≤11;x>0;y>0)。
x OCN-Dii-*-Diol-*-Dii-NCO+(x+y-1)HO-PS-OH+y OCN-Dii-NCO→
OCN-(Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii-NCO
最后,该产物由可聚合的烯键式不饱和基封端。
OCN-Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii-NCO+2M-OH→
M(*Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii*M
形成预聚物的第二种代表性反应路线如下。首先使二异氰酸酯与聚硅氧烷-二醇分别以如下所示的摩尔比反应,其中(1+1/m)优选为1.05-1.9,最优选1.2-1.5。
(m+1)OCN-Dii-NCO+m HO-PS-OH→OCN-(Dii*PS)m*Dii-NCO
在该路线中,*再次表示尿烷基-NH-COO-或-OCO-NH-。通常该反应在催化剂如二月桂酸二丁基锡存在下并在溶剂如二氯甲烷中和在回流下进行。然后,加入二醇,摩尔比的选择基于所需极硬链段和较不硬链段的比例,随着回流的继续,其中z1/z2等于或低于2但大于1。
z1OCN-(Dii-*-PS)m-*-Dii-NCO+z2HO-Diol-OH→
OCN-Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii-NCO
最后,该产物由可聚合的烯键式不饱和基封端。
OCN-Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii-NCO+2M-OH→
M(*Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii*M
在以上反应路线中,二醇与二异氰酸酯的反应生成尿烷基(-NH-COO-或-OCO-NH-)。或者,二胺与二异氰酸酯的反应生成脲基(NH-CO-NH-)。其它形成氨基甲酸酯或脲聚合物的方法在现有技术中是已知的并且在本实施例中描述了代表性的合成。
本发明的共聚物通过使本发明的预聚物与一种或多种共聚单体共聚合而形成。由于预聚物由可聚合烯键式不饱和基封端,它们可通过自由基聚合进行聚合。用于本发明的单体混合物包括常规的形成透镜的单体或形成器件的单体。(如这里所用,术语“单体”或“单体的”等表示可通过自由基聚合而聚合的低分子量化合物,而较高分子量的化合物也称为“预聚物”,“大分子单体”等相关术语)。对于共聚物,单体混合物中包括5-95重量%,优选20-70重量%的所述预聚物。
例如,若需要获得更亲水的共聚物或形成水凝胶共聚物,则可在含有所述预聚物的起始单体混合物中包括亲水性共聚单体。代表性的亲水性共聚单体包括不饱和羧酸,如甲基丙烯酸和丙烯酸;(甲基)丙烯酸取代的醇,如甲基丙烯酸2-羟乙酯、丙烯酸2-羟乙酯和甘油甲基丙烯酸酯;乙烯基内酰胺,如N-乙烯基吡咯烷酮;和(甲基)丙烯酰胺,如甲基丙烯酰胺和N,N-二甲基丙烯酰胺。水凝胶为可以在平衡态吸收并保留水的交联聚合物体系。对于水凝胶共聚物,单体混合物中包括20-60重量%,优选25-50重量%的至少一种亲水性单体。
另一类形成透镜或形成器件的单体为含有机硅的单体。换句话说,例如,若需要获得具有更高透氧性的共聚物,则除所述预聚物外在起始单体混合物中可以包括另外含有机硅的共聚单体。
一类合适的含有机硅的单体包括由式(V)代表的已知的大的单官能的聚硅氧烷基烷基单体:
X表示-COO-、-CONR4-、-OCOO-或-OCONR4-,其中每个R4为H或低级烷基;R3表示氢或甲基;h为0-10;每个R2独立地表示低级烷基或卤代烷基、苯基或下式的基:
-Si(R5)3
其中每个R5独立地为低级烷基或苯基。该大单体具体包括甲基丙烯酰氧丙基三(三甲基甲硅烷氧基)硅烷(TRIS)、五甲基二硅烷氧基甲基丙烯酸甲酯、三(三甲基甲硅烷氧基)甲基丙烯酰氧丙基硅烷、甲基二(三甲基甲硅烷氧基)甲基丙烯酰氧甲基硅烷、3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基氨基甲酸酯和3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基乙烯基碳酸酯。
多种双官能和多官能含有机硅的单体在现有技术中是已知的并且需要的话可以用作共聚单体。
存在的话,除所述预聚物外所述单体混合物还可以包括0-50重量%、优选5-30重量%的有机硅共聚单体。
在有机硅水凝胶的情况下,单体混合物包括交联单体(交联单体定义为具有多个可聚合官能度的单体)。由于所述预聚物在两端用可聚合基封端,该预聚物将起到交联剂的作用。任选地,可以将补充交联单体加入起始单体混合物中。代表性的交联单体包括二乙烯基苯、甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、四甘醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、二醇二甲基丙烯酸酯的乙烯基碳酸酯衍生物和甲基丙烯酰氧乙基乙烯基碳酸酯。在使用补充交联剂时,在单体混合物中可以包括0.1-20重量%、更优选0.2-10重量%的该单体材料。
在人工晶状体的情况下,单体混合物还可以包括增加所得共聚物的折射率的单体。该单体的实例为芳族(甲基)丙烯酸酯,例如(甲基)丙烯酸苯酯、(甲基)丙烯酸苯基乙酯和(甲基)丙烯酸苄酯。
在起始单体混合物中可以包括有机稀释剂。如这里所用,术语“有机稀释剂”包括与起始混合物中的组分基本不反应的有机化合物,并且常用于将在该混合物中的单体组分的不相容性最小化。代表性的有机稀释剂包括一元醇,例如C2-C10一元醇;二醇,例如乙二醇;多元醇,例如甘油;醚,例如二甘醇一乙醚;酮,例如甲乙酮;酯,例如庚酸甲酯;以及烃,例如甲苯。
在形成透镜或其它生物医学器件中,可以将单体混合物加入模具中,然后进行加热和/或光照(如UV辐照)以实现模具中的单体混合物的固化或自由基聚合。在接触镜或其它生物医学器件生产中用于固化单体混合物的多种方法是已知的,包括旋转浇铸和静态浇铸。旋转浇铸的方法涉及将单体装入模具中并且以可控的方式使模具旋转同时将单体混合物曝于光。静态浇铸的 方法涉及将单体混合物装入形成模具空穴的两个模具部分之间,所述模具空穴提供所需物体形状,并且通过曝于热和/或光而使单体混合物固化。在接触镜的情况下,使一个模具部分成型以形成前透镜表面并将另一模具部分成型以形成后透镜表面。需要的话,在将模具中的单体混合物固化之后可以进行机器操作以产生接触镜或具有所需最终构造的物体。该方法描述于美国专利3,408,429、3,660,545、4,113,224、4,197,266、5,271,875和5,260,000中,这些公开在此引入作为参考。此外,可以将单体混合物浇铸成杆形或钮扣形,然后将其车床切割成所需形状,例如切割成透镜形状的物体。
所述预聚物的一个优选应用为水凝胶接触镜。对于接触镜应用,优选水凝胶共聚物在完全水合时含水量如重量测定的至少为20重量%。
此外,优选水凝胶共聚物的拉伸模量不大于100g/mm2,更优选模量为约40-80g/mm2。模量可以用Instron(型号4502)仪器根据ASTM D-1708a测量,其中将水凝胶共聚物膜样品浸入在硼酸盐缓冲盐水中。膜样品的合适尺寸为规格长度为22mm且宽度为4.75mm,其中样品还具有形成狗骨(dogbone)形状的末端以容下用Instron仪器的夹具夹住样品,且具有厚度为200±50微米。
优选水凝胶共聚物的透氧性至少为100barrer,更优选至少150barrer。透氧性(也称为Dk)通过以下程序进行测定。有机硅水凝胶的透氧性通过极谱法(ANSI Z80.20-1998)使用O2透气量仪201T型仪器(Createch,Albany,CalifoniaUSA)测量,其中所述201T型仪器具有在其末端含有中心的环形金阴极和与阴极隔离的银阳极的探测器。测量仅在已预检测的无孔的平面聚硅氧烷水凝胶膜样品上进行,所述样品具有三个范围为150-600微米的不同的中心厚度。膜样品的中心厚度可以使用Rehder ET-1电子厚度仪测量。通常,膜样品具有圆盘形状。将膜样品和探测器浸入含有在35℃+/-0.2°下平衡的循环磷酸盐缓冲盐水(PBS)的浴中进行测量。在将探测器和膜样品浸入PBS浴之前,将膜样品放置在已用平衡PBS进行预润湿的阴极的中心上,以确保在阴极和膜样品之间没有气泡或过剩PBS存在,然后将膜样品用固定帽固定在探测器上并仅使探测器的阴极部分接触膜样品。对于有机硅水凝胶膜,通常有用的是在探测器阴极和膜样品之间使用例如具有圆盘形状的Teflon聚合物膜。在这种情况下,首先将Teflon膜置于预润湿的阴极上,然后将膜样品置于Teflon膜上,以确保在Teflon膜或膜样品下没有气泡或过剩PBS存在。一旦采集测量数据,仅相关系数值(R2)为0.97或更高的数据应进入Dk值的计算。对每个厚度获得至少两个满足R2值的Dk测量。使用已知的回归分析,由具有至少三个不同厚度的膜样品计算透氧性(Dk)。首先将任何与不是PBS的溶液水合的膜样品浸没在纯化水中并允许平衡至少24个小时,然后浸没在PHB中并允许平衡至少另外12个小时。定期地清洁仪器并定期使用RGP标样对其进行校准。通过计算由William J.Benjamin等人建立的贮存值(repository value)的+/-8.8%来建立上限和下限,The Oxygen Permeability of Reference Materials,Optom VisSci 7(12s):95(1997),其中对所述贮存值的公开在此完整引入。
材料名称 | 贮存值 | 下限 | 上限 |
Fluoroperm 30 | 26.2 | 24 | 29 |
Menicon EX | 62.4 | 56 | 66 |
Quanum II | 92.9 | 85 | 101 |
在根据本发明的预聚物的一个实施方案中,每个M为甲基丙烯酰氧乙基;每个Dii为异佛尔酮二异氰酸酯的双基残基;每个Diol为二甘醇的双基残基;每个PS为Mn至少为2000的聚二甲基硅氧烷-二醇的双基残基;和每个*为-NH-COO-或-OCO-NH-。
以下实施例说明本发明的各种优选的实施方案。
实施例1 α,ω-二(4-羟丁基)聚二甲基硅氧烷的制备(Mn约5000)
将以下化合物加入配有一个回流冷凝器的2升的三口圆底烧瓶中:51.26g1,3-二羟丁基四甲基二硅氧烷;1085g二甲氧基二甲基硅烷;157.8g蒸馏水;和18.4mL浓盐酸。将该混合物在60℃下加热1小时。然后在5小时内蒸馏出甲醇,并收集到了552mL。然后,加入349ml蒸馏水和349ml浓盐酸,并将混合物在100℃下回流3小时。然后将粗产物与水层分离。然后,加入600mL乙醚(醚)和400mL去离子水,并将该溶液用400mL碳酸氢钠溶液(0.5%)萃取两次,然后用蒸馏水萃取直至洗液pH为中性。然后将产物(655.8g)缓慢加入甲醇/水(508.2g/147.97g)的混合物中。下面的有机层被分离,加入乙醚并用硫酸镁干燥。然后在真空和室温下反萃取醚,将剩余物在真空(0.07-mm torr)和80℃下进一步反萃取。回收最终产物。通过H-NMR测定的分子量(Mn)为4800。
实施例2 α,ω-二(4-羟丁基)聚二甲基硅氧烷的制备(Mn约2700)
遵循实施例1的一般程序来制备该聚硅氧烷,不同之处为1,3-二羟丁基四甲基二硅氧烷对二甲氧基二甲基硅烷的摩尔比改为约1∶28。通过滴定测量的产物的分子量(Mn)为2730。
实施例3使用实施例1的PDMS制备基于聚二甲基硅氧烷的预聚物
将干燥的3口、500mL圆底烧瓶与氮气入口管和回流冷凝器连接。一次性向该烧瓶中加入以下化合物:异佛尔酮二异氰酸酯(2.111g,9.497mol)(IPDI);二甘醇(0.498g,4.696mol)(DEG);二月桂酸二丁基锡(0.161g);和150mL二氯甲烷。回流该内容物。过夜后,通过滴定测得异氰酸酯的量减少至43.3%。然后,将实施例1的α,ω-二(4-羟丁基)聚二甲基硅氧烷(45.873g,9.557mmol)(PDMS)加入烧瓶中。将回流持续过夜,通过滴定测得没有剩下未反应的异氰酸酯。然后加入IPD(1.261g,5.673mol)并将回流持续过夜。通过滴定测得异氰酸酯的量减少至22.9%。将内容物冷却至环境温度。然后加入1,1’-二-2-萘酚(0.008g)和甲基丙烯酸2-羟乙酯(0.429g,3.296mmol),并将内容物在环境温度下搅拌直至在2267cm-1处的异氰酸酯峰从产物的IR谱中消失(约20小时)。然后在减压下反萃取溶剂并回收产物(44.55g)。理论上,该预聚物具有三个极硬链段,四个较不硬链段(x约为3,y约为4)。
实施例4使用实施例1的PDMS制备基于聚二甲基硅氧烷的预聚物
将干燥的3口、500mL圆底烧瓶与氮气入口管和回流冷凝器连接。一次性向该烧瓶加入以下化合物:异佛尔酮二异氰酸酯(7.825g,35.202mol)(IPDI);实施例1的α,ω-二(4-羟丁基)聚二甲基硅氧烷(94.31g,19.648mmol)(PDMS);二月桂酸二丁基锡(0.297g);和250mL二氯甲烷。将内容物回流。过夜后,通过滴定测得异氰酸酯的量减少至44.5%。然后将二甘醇(1.421g,13.391mmol)(DEG)加入烧瓶中。将回流持续过夜,通过滴定测得异氰酸酯的量降至起始的5.1%。然后将内容物冷却至环境温度。然后加入1,1’-二-2-萘酚(0.013g)和甲基丙烯酸2-羟乙酯(0.819g,6.293mmol),并将内容物在环境温度下搅拌直至在2267cm-1处的异氰酸酯峰从产物的IR谱中消失(约20小时)。然后在减压下反萃取溶剂并回收82g产物。理论上,该预聚物具有四个极硬链段,三个较不硬链段(x约为4,y约为3)。
实施例5使用实施例1的PDMS制备基于聚二甲基硅氧烷的预聚物
制备了具有与实施例4类似摩尔比的组分的预聚物。该合成与实施例4相似,不同之处为使用了第二批约相同分子量的聚硅氧烷。组分的量为:异佛尔酮二异氰酸酯(8.716g,39.209mol)(IPDI);α,ω-二(4-羟丁基)聚二甲基硅氧烷(105.23g,21.923mmol);二月桂酸二丁基锡(0.307g);250mL二氯甲烷;二甘醇(1.496g,14.093mmol);1,1’-二-2-萘酚(0.0146g)和甲基丙烯酸2-羟乙酯(1.033g,7.938mmol)。
实施例6使用实施例2的PDMS制备基于聚二甲基硅氧烷的预聚物
将干燥的3口、500mL圆底烧瓶与氮气入口管和回流冷凝器连接。一次性向该烧瓶加入以下化合物:IPDI(10.3311g,46.475mol);实施例2的α,ω-二(4-羟丁基)聚二甲基硅氧烷(84.68g,31.023mmol);二月桂酸二丁基锡(0.300g);和200mL二氯甲烷。将内容物回流。过夜后,通过滴定测得异氰酸酯的量减少至33.6%。然后将DEG(1.092g,10.288mmol)加入烧瓶中。将回流持续60小时,通过滴定测得异氰酸酯的量降至起始的11.4%。然后将内容物冷却至环境温度。然后加入1,1’-二-2-萘酚(0.012g)和甲基丙烯酸2-羟乙酯(1.639g,12.595mmol),并将内容物在环境温度下搅拌直至在2267cm-1处的异氰酸酯峰从产物的IR谱中消失(约20小时)。然后在减压下反萃取溶剂以生成透明的液体产物(96.67g)。理论上,该预聚物具有六个PDMS嵌段和二个极硬链段(x约为2,y约为5)。
实施例7-12由实施例3的预聚物制备共聚物
通过将列于表1中的下列组分以重量计的量混合制备单体混合物:实施例3和4的预聚物;甲基丙烯酰氧丙基三(三甲基甲硅烷氧基)硅烷(TRIS);N,N-二甲基丙烯酰胺(DMA);甲基丙烯酸2-羟乙酯(HEMA);N-乙烯基吡咯烷酮(NVP);和甲基丙烯酰氧乙基乙烯基碳酸酯(HemaVC)。此外,每个单体混合物包括1,4-二(2-甲基丙烯酰氨基乙氨基)蒽醌作为染色(150ppm);己醇作为稀释剂(10重量份);和Darocur-1173TM UV引发剂(Ciba Specialty Chemical,Ardsley NY)(0.5重量%)。
将单体混合物浇铸在用硅烷处理过的玻璃板之间,然后在UV光下固化1 小时。将每种单体混合物浇铸在三套玻璃板之间,每套玻璃板通过不同厚度的TeflonTM聚合物带分隔,从而对每种单体混合物得到三套膜厚度为约200微米、400微米和600微米的膜样品。然后用异丙醇萃取固化的膜过夜,随后在去离子(DI)水中水合,在DI水中蒸煮4小时,然后在硼酸盐缓冲盐水或磷酸盐缓冲盐水中饱和以得到水凝胶膜。重量测定含水量。机械测试如以上讨论在硼酸盐缓冲盐水中根据ASTM D-1708a进行。以Dk单位(或barrer)报导的透氧性如以上讨论在磷酸盐缓冲盐水中使用具有三个不同厚度的可用膜在35℃下测量。
表1
实施例 | 7 | 8 | 9 | 10 | 11 | 12 |
实施例3的预聚物 | 65 | 65 | 60 | 65 | 65 | 60 |
Tris | 10 | 10 | 15 | 10 | 10 | 15 |
DMA | 25 | 12 | 12 | 12 | 12.4 | 0 |
NVP | -- | 13 | 10 | 10 | 10 | 22 |
Hema | -- | 5 | 5 | 2.65 | 2.4 | 5 |
HemaVC | -- | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
%水 | 34.2 | ND | ND | 31.7 | 33.9 | 36.5 |
Dk(barrer) | --(1) | ND | ND | 251 | 208 | 169(2) |
模量(g/mm2) | 45 | ND | ND | 57 | -- | -- |
在实施例8和9中制备的单体混合物为混浊的,因此没有浇铸膜。然而,在将更少HEMA用作亲水性共聚单体(如在实施例9、10、11)或用NVP完全代替DMA(如在实施例6)时,混合物为透明的并且所有水凝胶膜为透明的。(1)没有得到三个厚度数据点。(2)得到四个厚度数据点。
实施例13-18由实施例4的预聚物制备共聚物
遵循实施例7-12的一般程序,使用实施例4的预聚物制备单体混合物,浇铸共聚物膜,并评价性能。结果总结于表2。
表2
实施例 | 13 | 14 | 15 | 16 | 17 | 18 |
实施例4的预聚物 | 65 | 65 | 60 | 65 | 60 | 65 |
Tris | 10 | 10 | 15 | 10 | 15 | 10 |
DMA | 25 | 12 | 12 | 12 | 0 | 0 |
NVP | -- | 10 | 10 | 10 | 22 | 22 |
Hema | -- | 0 | 5 | 5 | 5 | 5 |
HemaVC | -- | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
%水 | 31.7 | 28.5 | 29.6 | 34.7 | 48.2 | 47.8 |
Dk(barrer) | 158 | 208 | 218 | 209 | 215 | 183 |
模量(g/mm2) | 60 | 66 | 54 | 61 | 73 | 76 |
在对比实施例3和实施例4的预聚物时,发现实施例4的预聚物可用于与5份HEMA配制,而与实施例3的预聚物配制的HEMA仅为2.5份。据信这是由于实施例4的预聚物比实施例3的预聚物具有更强的硬链段含量。
实施例19-24由实施例5的预聚物衍生的共聚物
遵循实施例7-12的一般程序,使用实施例5的预聚物制备单体混合物,浇铸共聚物膜,并评价性能。结果总结于表3。
表3
实施例 | 19 | 20 | 21 | 22 | 23 | 24 |
实施例5的预聚物 | 65 | 65 | 65 | 65 | 60 | 60 |
Tris | 10 | 10 | 10 | 10 | 15 | 15 |
DMA | 4 | 8 | 12 | 12 | 0 | 0 |
NVP | 18 | 14 | 10 | 10 | 22 | 25 |
Hema | 3 | 3 | 3 | 5 | 5 | 5 |
HemaVC | 0.9 | 0.7 | 0.5 | 0.5 | 1.0 | 0.5 |
%水 | 26.9 | 27.8 | 28.0 | 28.8 | 26.8 | 36.4 |
Dk(barrer) | -- | -- | -- | -- | 287 | -- |
模量(g/mm2) | 96 | 84 | 74 | 73 | 107 | 73 |
实施例25-27由实施例6的预聚物衍生的共聚物
遵循实施例7-12的一般程序,使用实施例6的预聚物制备单体混合物,浇铸共聚物膜,并评价性能。结果总结于表4。
表4
实施例 | 25 | 26 | 27 |
实施例6的预聚物 | 65 | 65 | 60 |
Tris | 10 | 10 | 15 |
DMA | 25 | 12 | 12 |
NVP | -- | 10 | 10 |
Hema | -- | 5 | 5 |
HemaVC | -- | 0.5 | 0.5 |
%水 | 29.8 | 23.6 | 25.8 |
Dk(barrer) | 122 | 165 | 161 |
模量(g/mm2) | 81 | 119 | 84 |
有了所描述的本发明的各种优选实施方案,本领域技术人员在不背离所附权利要求中提出的本发明的精神和范围的情况下应可以对本发明做各种改进、增加和变化。
Claims (26)
1.一种由以下通式表示的预聚物:
M(*Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii*M或者
M(*Dii*Diol*Dii*PS)x(*Dii*PS)y*Dii*Diol*Dii*M
其中:
每个M独立地为可聚合的烯键式不饱和基;
每个Dii独立地为二异氰酸酯的双基残基;
每个Diol独立地为具有1-10个碳原子的二醇的双基残基;
每个PS独立地为聚硅氧烷-二醇或聚硅氧烷-二胺的双基残基;
每个*独立地为-NH-CO-NH-、-NH-COO-或-OCO-NH-;
x至少是2;和
y至少是1;以及2<x+y≤11,
其中每个PS独立地为由下式表示的聚硅氧烷的双基残基:
其中每个A为羟基或氨基;
每个R独立地选自具有1-10个碳原子的亚烷基,其中碳原子之间可以包括醚、氨基甲酸酯或脲联接;
每个R’独立地选自氢、一价烃基或卤素取代的一价烃基,其中烃基具有其间可以包括醚联接的1-20个碳原子;和
a至少为1;以及
每个M独立地为下式的可聚合烯键式不饱和基:
其中:
R23为氢或甲基;
每个R24为氢、具有1-6个碳原子的烷基或-CO-Y-R26基,其中Y为-O-、-S-或-NH-;
R25为具有1-10个碳原子的二价亚烷基;
R26为具有1-12个碳原子的烷基;
Q为-CO-、-OCO-或-COO-;
X为-O-或-NH-;
Ar为具有6-30个碳原子的芳基;
b为0-6;c为0或1;d为0或1并且e为0或1。
2.权利要求1的预聚物,其中每个Dii独立地为在脂族或芳族部分中具有6-30个碳原子的脂族或芳族二异氰酸酯的双基残基。
3.权利要求2的预聚物,其中每个Dii为选自以下组中的二异氰酸酯的双基残基:异佛尔酮二异氰酸酯、六亚甲基-1,6-二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、4,4’-二苯基二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、对亚苯基二异氰酸酯、1,4-亚苯基4,4’-二苯基二异氰酸酯、1,3-二(4,4’-异氰酸甲基)环己烷和环己烷二异氰酸酯。
4.权利要求1的预聚物,其中每个Diol独立地为选自以下组中的二醇的双基残基:具有1-10个碳原子且在主链上可以含醚、硫醚或胺联接的烷基二醇、环烷基二醇和烷基环烷基二醇、芳基二醇或烷基芳基二醇。
5.权利要求4的预聚物,其中所述二醇独立地选自1,3-环己烷二醇、1,4-环己烷二醇、1,4-环己烷二甲醇、新戊二醇、1,4-丁二醇、1,3-丙二醇、1,5-戊二醇、乙二醇、二甘醇和三甘醇。
6.权利要求1的预聚物,其中每个R为具有1-10个碳原子的亚烷基,每个R’独立地为烷基或任选具有醚联接的氟代烷基,且具有1-20个碳原子。
7.权利要求1的预聚物,其中PS的Mn为1000-8000。
8.权利要求1的预聚物,其中x对y的比例至少为0.6。
9.权利要求1的预聚物,其中:
每个M为甲基丙烯酰氧乙基;
每个Dii为异佛尔酮二异氰酸酯的双基残基;
每个Diol为二甘醇的双基残基;
每个PS为Mn至少为2000的聚二甲基硅氧烷-二醇的双基残基;和
每个*为-NH-COO-或-OCO-NH-。
10.一种包含嵌段(I)和(II)并且在每个末端由可聚合烯键式不饱和基封端的预聚物:
(*Dii*Diol*Dii*PS)x (I)
(*Dii*PS)y (II)
其中:
每个Dii独立地为二异氰酸酯的双基残基;
每个Diol独立地为具有1-10个碳原子的二醇的双基残基;
每个PS独立地为聚硅氧烷-二醇的双基残基;
每个*独立地为-NH-CO-NH-或-OCO-NH-;
x代表嵌段(I)的个数且至少为2;
y代表嵌段(II)的个数且至少是1;以及
2<x+y≤11,
其中每个PS独立地为由下式表示的聚硅氧烷的双基残基:
其中每个A为羟基或氨基;
每个R独立地选自具有1-10个碳原子的亚烷基,其中碳原子之间可以包括醚、氨基甲酸酯或脲联接;
每个R’独立地选自氢、一价烃基或卤素取代的一价烃基,其中烃基具有其间可以包括醚联接的1-20个碳原子;和
a至少为1,
其中,所述可聚合烯键式不饱和基由下式表示:
其中:
R23为氢或甲基;
每个R24为氢、具有1-6个碳原子的烷基或-CO-Y-R26基,其中Y为-O-、-S-或-NH-;
R25为具有1-10个碳原子的二价亚烷基;
R26为具有1-12个碳原子的烷基;
Q为-CO-、-OCO-或-COO-;
X为-O-或-NH-;
Ar为具有6-30个碳原子的芳基;
b为0-6;c为0或1;d为0或1并且e为0或1。
11.一种共聚物,其为包含权利要求1的预聚物和共聚单体的单体混合物的聚合产物。
12.权利要求11的共聚物,其中所述单体混合物包含亲水性共聚单体。
13.权利要求12的共聚物,其中所述单体混合物包含至少一种选自烯键式不饱和羧酸、(甲基)丙烯酸取代的醇、乙烯基内酰胺及(甲基)丙烯酰胺的亲水性单体。
14.权利要求13的共聚物,其中所述单体混合物包含至少一种选自甲基丙烯酸、丙烯酸、甲基丙烯酸2-羟乙酯、甘油甲基丙烯酸酯、N-乙烯基吡咯烷酮、甲基丙烯酰胺和N,N-二甲基丙烯酰胺的亲水性单体。
15.权利要求12的共聚物,其中所述单体混合物还包含单官能的含有机硅的单体。
16.权利要求15的共聚物,其中所述单体混合物还包含甲基丙烯酰氧丙基三(三甲基甲硅烷氧基)硅烷。
17.一种水凝胶共聚物,其为包含权利要求1的预聚物和亲水性共聚单体的单体混合物的水合聚合产物。
18.权利要求17的水凝胶共聚物,其含水量至少为20重量%。
19.权利要求17的水凝胶共聚物,根据ASTM D-1708a测量其模量不大于100g/mm2。
20.权利要求19的水凝胶共聚物,根据ASTM D-1708a测量其模量为40-80g/mm2。
21.权利要求17的水凝胶共聚物,根据ANSI Z80.20-1998测量其透氧性至少为100barrer。
22.权利要求21的水凝胶共聚物,根据ANSI Z80.20-1998测量其透氧性至少为150barrer。
23.权利要求17的水凝胶共聚物,其含水量至少为20重量%,根据ASTMD-1708a测量模量为40-80g/mm2且根据ANSI Z80.20-1998测量透氧性至少为150barrer。
24.一种包含权利要求17的共聚物的生物医学器件。
25.一种包含权利要求17的共聚物的眼科器件。
26.权利要求25的眼科器件,其为接触镜或人工晶状体。
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- 2005-11-14 CN CN2005800454592A patent/CN101094879B/zh not_active Expired - Fee Related
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WO2006071387A1 (en) | 2006-07-06 |
EP1838748A1 (en) | 2007-10-03 |
DE602005013298D1 (de) | 2009-04-23 |
JP2008525614A (ja) | 2008-07-17 |
JP4933448B2 (ja) | 2012-05-16 |
ATE425198T1 (de) | 2009-03-15 |
MX2007007804A (es) | 2007-09-14 |
US20060142524A1 (en) | 2006-06-29 |
EP1838748B1 (en) | 2009-03-11 |
CA2592206A1 (en) | 2006-07-06 |
US7423074B2 (en) | 2008-09-09 |
CN101094879A (zh) | 2007-12-26 |
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