CN1275991C - 形状记忆苯乙烯共聚物 - Google Patents
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Abstract
一种形状记忆聚合物,其是苯乙烯、乙烯基化合物、多官能团交联剂和引发剂的反应产物。该形状记忆聚合物具有作为隐形眼镜模具的特定应用。
Description
相关申请的交叉参考
本申请要求了在2001年1月24日申请的序列号为60/263,968的临时申请的优先权,该申请在这里被全部引入作为参考。
1.技术领域
本发明涉及一种形状记忆聚合物,其包含苯乙烯、乙烯基化合物、多官能团交联剂和引发剂的反应产物。更特定地,本发明涉及与隐形眼镜用的聚合物具有相容性并且从而在隐形眼镜制造中具有用作隐形眼镜模具的特殊实用性的形状记忆聚合物热固性树脂。
2.背景技术
近年来,隐形眼镜的应用增长十分迅速。这使得相应的隐形眼镜制造能力的发展逐步增加。由许多制造业中的改进所产生的制造业的发展已经实现了制造能力的发展,其中所说的改进包括在实际的隐形眼镜制造中关键步骤的改进。
目前制造隐形眼镜的方法是模塑法,在该方法中用的外层阳性和阴性金属内插物提供了阳性和阴性塑性模具,其中所说的内插物是用如菱形点切削法来进行制备的,从而确保了其具有非常光滑的表面。该隐形眼镜实际上是在该塑性的阳性和阴性模具部件之间进行模塑的。本发明的主题就是隐形眼镜制造的这种方式。
虽然塑性模具部件的应用消除了许多隐形眼镜的质量问题,但是这种解决方法目前是以很高的制造成本来实现的。具体而言,隐形眼镜的脱模步骤涉及在该阳性和阴性模具部件之间插入撬杠。当该撬杠用力撬开时,模具部件被分离开。但是,这项技术有时会使隐形眼镜模具部件边缘形成磨损或缺口,从而使得随后制造出不能接受的隐形眼镜。
目前隐形眼镜模具的另一种不足还在于它们在制造时需要高的热力学条件。目前隐形眼镜模具的制造是用注塑法在高温和高压下完成的。降低形成隐形眼镜模具时的温度和压力将降低制造成本并且同时能生产出质量更好的隐形眼镜。
除了与任何特定隐形眼镜设计方案的制造有关的上述生产问题外,必需意识到目前与隐形眼镜制造的“定制”性质有关的制造成本十分高昂。必需提供许多注塑内插物,对于眼睛矫正的每种类型都必需提供一种内插物:动力(power)、圆柱体和轴。此外,进一步定制的隐形眼镜的制造操作还需要另外的内插物,其中所说的进一步定制的隐形眼镜的制造操作包括使眼镜适应于角膜的局部解剖学或矫正波前象差。
需要制造极大量的金属内插物的方法是一种高成本并费时的耗损性方法。此外,在生产运行中改变金属内插物又消耗了相当多的时间和成本。因此,现有技术中迫切需要对隐形眼镜模塑技术进行改进。
在现有技术中已经对用于形成隐形眼镜的工具形状进行了修改,US 6,086,204公开了一种可改变其形状从而制造热塑性眼镜的加热的冲模。当然,这种发展并没有解决上面所提出的具体问题。不仅从模具制造上除去冲模还很遥远,而且在热固性隐形眼镜的制造中也不能使用‘204专利的可调节形状的冲模。
在大约20年前就已经研制出了形状记忆聚合物(SMPs)并且其一直是近10年来商业化开发的主题。SMPs的名称得自于其在产生变形后可回复最初所“记忆”的形状的固有能力。在低于或高于其玻璃化转变温度(Tg)时,已经预成型的SMPs可以变形成任何所需的形状。如果低于其Tg,则该过程被称为冷变形。当在其Tg之上发生塑性变形时,该过程被称为热变形。在两种情况中,当维持热成型的形状以在变形中进行“锁定”时,SMP必需保持在低于或被骤冷至低于其Tg。一旦该变形被锁定,则由于热障而使得该聚合物网络不能回复至松弛的状态。该SMP将无限期地维持其变形的形状直至其被加热至Tg温度之上的温度,在该温度下SMP储存的机械应变被释放出来,SMP回复至其预成型的状态。
一些种类的聚合物表现出形状记忆性。最公知的并被最好地进行了研究的表现出形状记忆性的聚合物可能是聚氨酯类聚合物。Gordon,Proc of First Intl.Conf.Shape Memory and SuperelasticTech.,115-120(1994)和Tobushi等人,Proc of First Int1.Conf.Shape Memory and Superelastic Tech.,109-114(1994)列举了涉及形状记忆聚氨酯类的性质和应用研究。S.Ota,
Radiat.Phys. Chem.,18,81(1981)报道了另一种以交联聚乙烯均聚物为基础的聚合物体系。Japan Kokai,JP 63-179955还描述了一种表现出形状记忆性质的苯乙烯-丁二烯热塑性共聚物体系。在Japan Kokai,JP 62-192440中还声称聚异戊二烯也表现出形状记忆的性质。由Kagami等人,Macromol.Rapid Communication,17,539-543(1996)所公开的另一种公知的聚合体系是一类丙烯酸十八酯和丙烯酸或丙烯酸甲酯的共聚物。现有技术中公知的其它SMP聚合物包括降冰片烯或二甲烷八氢萘均聚物或共聚物所形成的制品,其在专利号为4,831,094的美国专利中进行了描述。
最近已经确认了形状记忆聚合物的一种新应用。这种应用是作为在隐形眼镜制造中所用的隐形眼镜模具的制造材料。在与本申请同时提交的序列号为____(VTN-575)的待审专利中描述了这种新应用,其在这里被引入作为参考。此外,正如在这里被引入作为参考的序列号为(VTN-575)的待审专利和序列号为09/649,635(9VTN-504)的美国专利中所描述的那样,形状记忆聚合物还可以在灵活模具中用作该灵活模具的模塑表面。
总之,并没有打算用现有技术中的形状记忆聚合物来满足与隐形眼镜模具的有效操作有关的特定需要。因此,形状记忆聚合物的这种新应用预示了现有技术中对本发明新型形状记忆聚合物应用的迫切需要。
发明简述
已经研制了一种在隐形眼镜制造中有特殊应用的新型的形状记忆聚合物。具体地,本发明的形状记忆聚合物特别是可与制备隐形眼镜的聚合物相容。
本发明提供了一种用于隐形眼镜模具制造中的新型的形状记忆聚合物。这种新的形状记忆聚合物是由苯乙烯、除苯乙烯外的乙烯基化合物、一种多官能团的交联剂和一种引发剂的反应产物所制备的。
详细说明
本发明独特地用形状记乙聚合物作为隐形眼镜制造中模具部件的构造材料。在隐形眼镜模具部件的制造中可以使用具有上述性质的形状记忆聚合物。因此,可以使用包括降冰片烯均聚物以及降冰片烯和烷基化、氰基、烷氧基化、单-或二酯化的酰亚胺或羧酸衍生物的共聚物。此外,该共聚物可以包括作为共聚单体的二甲烷八氢萘(DMON)。另一种供替代的选择是,使用DMON的均聚物以及DMON和苯乙烯、醋萘或双环戊二烯的共聚物,其可被氢化或卤化。
虽然这些已知的形状记忆聚合物在本发明的考虑范围之内,但优选地,在形成本发明的隐形眼镜时所用的形状记忆聚合物是一种新型的SMP——苯乙烯和除苯乙烯外的乙烯基化合物的共聚物。
这种新的共聚物优选地是由一种反应混合物来进行制备的,该反应混合物除了苯乙烯和该乙烯基化合物外还包含一种交联剂和一种引发剂。实际上,通过仔细地对该反应混合物进行制备,可以合成出具有与隐形眼镜制造过程的操作温度相匹配的玻璃化转变温度Tg的所得形状记忆聚合物。
在本发明的一个优选实施方案中,除了最初的第一单体——苯乙烯外,反应混合物还包括第二单体——一种除苯乙烯外的乙烯基化合物、交联剂——一种多官能团的化合物、以及引发剂、第五种组分、改性聚合物。
第二种单体——除苯乙烯外的乙烯基化合物优选地是新癸酸乙烯酯、苯甲酸乙烯酯、丙酸乙烯酯、硬脂酸乙烯酯、甲基苯乙烯,其可以是一种混合物、3-甲基苯乙烯或4-甲基苯乙烯、乙烯基吡啶,其可以是一种混合物、2-乙烯基吡啶、3-乙烯基吡啶或4-乙烯基吡啶、月桂酸乙烯酯、丁酸乙烯酯、醋酸乙烯酯、硬脂酸乙烯酯、乙烯基2-furate、苯乙酸乙烯酯、乙烯基咔唑、醋酸4-乙烯基苄基酯、4-乙烯基苯甲酸、乙烯基甲基砜、乙烯基十八烷基醚、乙烯基异辛基醚、N-乙烯基-2-吡咯烷酮、N-乙烯基-N-甲基乙酰胺、1-乙烯基咪唑、N-乙烯基甲酰胺、N-乙烯基己内酰胺、乙烯基噁唑酮、N-乙烯基脲、硬脂酸4-(乙烯氧基)丁酯、苯甲酸4-(乙烯氧基)丁酯、苯甲酸4-(乙烯氧基甲基)环己基甲酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸叔-丁酯、甲基丙烯酸丁酯、甲基丙烯酸叔-丁酯、丙烯酸己酯、丙烯酸、甲基丙烯酸、丙烯酸苄酯、甲基丙烯酸苄酯、甲基丙烯酸2-正-丁氧酯、丙烯酸2-氰基乙酯、丙烯酸环己酯、甲基丙烯酸环己酯、丙烯酸癸酯、丙烯酸二环戊烯酯、丙烯酸二环戊烯氧基乙酯、甲基丙烯酸二环戊烯氧基乙酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、甲基丙烯酸2-乙氧基乙酯、丙烯酸2-乙基己酯、甲基丙烯酸乙酯、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸2-(2-甲氧基乙氧基)乙酯、甲基丙烯酸2-(2-甲氧基乙氧基)-乙酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸2-甲氧基乙酯、丙烯酸2-甲氧基丙酯、甲基丙烯酸2-甲氧基丙酯、甲基丙烯酸辛酯、丙烯酸2-苯氧基乙酯、甲基丙烯酸2-苯氧基乙酯、丙烯酸苯酯、丙烯酸2-苯基乙酯、甲基丙烯酸2-苯基乙酯、甲基丙烯酸苯酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸硬脂基酯、甲基丙烯酸硬脂基酯、丙烯酸2,4,6-三溴苯酯、丙烯酸十一烷基酯或甲基丙烯酸十一烷基酯。
在该乙烯基化合物中优选的用于本发明形状记忆聚合物的反应混合物中的化合物有新癸酸乙烯酯、苯甲酸乙烯酯、丙酸乙烯酯、硬脂酸乙烯酯、甲基苯乙烯、硬脂酸4-(乙烯氧基)丁酯或乙烯基吡啶。
该形状记忆聚合物反应混合物的交联剂是多官能团的,即该交联剂具有至少为2的聚合官能度。实际上,优选双官能团的交联剂。本发明范围内的交联剂包括延胡索酸二烯丙酯、二烯丙基二甘醇碳酸酯、甲基丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、辛二酸二烯丙酯、四溴邻苯二甲酸二烯丙酯、二甘醇二丙烯酸酯、二甘醇二甲基丙烯酸酯、二甘醇二乙烯基醚、N,N′-二甲基丙烯酰基哌嗪、2,2-二甲基丙二醇二甲基丙烯酸酯、戊丙烯酸二季戊四醇酯、一缩二丙二醇二甲基丙烯酸酯、四丙烯酸二-三羟甲基丙酯、二乙烯基二醇、癸二酸二乙烯基酯、甘油三甲基丙烯酸酯、1,5-己二烯(haxadiene)、1,6-己二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、N,N′-亚甲基双甲基丙烯酰胺、1,9-壬二醇二甲基丙烯酸酯、四丙烯酸季戊四醇酯、三丙烯酸季戊四醇酯、季戊四醇三烯丙基醚、1,5-戊二醇二甲基丙烯酸酯、聚(丙二醇)二甲基丙烯酸酯、四甘醇二甲基丙烯酸酯、三甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、三甘醇二乙烯基醚、三甲基丙烯酸1,1,1-三羟甲基乙酯、1,1,1-三羟甲基丙烷二烯丙基醚、三丙烯酸1,1,1-三羟甲基丙酯、三甲基丙烯酸1,1,1-三羟甲基丙酯、三丙二醇二丙烯酸酯、1,2,4-三乙烯基环己烷、二乙烯基苯、双(2-甲基丙烯酰氧基乙基)磷酸酯、2,2-二(4-甲基丙烯酰氧基苯基)丙烷、1,3-丁二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,4-丁二醇二乙烯基醚、1,4-环己二醇二甲基丙烯酸酯、二[4-(乙烯氧基)丁基]间苯二酸酯、二[4-(乙烯氧基甲基)环己基甲基]戊二酸酯、二[-(乙烯氧基)丁基]琥珀酸酯、二((4-((-乙烯氧基)甲基)环己基)甲基)间苯二酸酯、二(4(乙烯氧基)丁基)对苯二甲酸酯、二[[(4-[乙烯氧基)甲基)环己基]甲基]对苯二甲酸酯、二[4-乙烯氧基)丁基]己二酸酯、二[4-(乙烯氧基)丁基](亚甲基二-1,4-亚苯基)二氨基甲酸酯、二[4-(乙烯氧基)丁基](4-甲基-1,3-亚苯基)二氨基甲酸酯、二[4-(乙烯氧基)丁基]1,6-己二基二氨基甲酸酯或三[4-(乙烯氧基)丁基]三苯六甲酸酯。
在这些优选的交联剂中,特别优选地是二乙烯基苯、二[4-(乙烯氧基)丁基]对苯二甲酸酯和二[[4-[(乙烯氧基)甲基]环己基]甲基对苯二甲酸酯。在这些物质中更特别地优选二乙烯基苯作为交联剂。
该反应混合物的引发剂可以是自由基或离子引发剂。本发明范围内的自由基引发剂包括有机过氧化物和偶氮化合物。虽然可以使用任何商业上可获得的有机过氧化物,但特别优选叔-丁基过氧化物、叔-丁基氢过氧化物、过氧化苯甲酰、过氧化二枯基和过氧化月桂酰。类似地,虽然可以使用任何商业上可获得的偶氮引发化合物,但特别优选2,2′-偶氮二异丁腈。离子引发剂优选地是阳离子引发剂。优选的阳离子引发剂包括三氟化硼、三氟化硼二乙基醚合物、三氟化铝和氯化锡(IV)。
如上所述,该SMP反应混合物可以包括第五种任选的组分。该形状记忆聚合物反应混合物的第五种组分是可以包含或不包含的任选组分。该任选组分可以是改性聚合物。该改性聚合物可作为粘度调节剂并且还可以为所得的形状记忆聚合物提供所必需的硬度。该固化的形状记忆聚合物所必需的硬度是符合ASTM标准试验方法D5045和D6068中所述的质量要求的硬度。
该形状记忆聚合物反应混合物的改性聚合物是可以与苯乙烯和乙烯基化合物的反应产物所形成的聚合物相容的热塑性聚合物。优选的可相容的聚合物包括烯烃聚合物和苯乙烯聚合物。特别优选的可相容的聚合物包括聚苯乙烯、聚(苯乙烯-共-丁二烯)、聚乙烯和聚丙烯。在这些物质中,特别优选地在该形状记忆聚合物反应混合物中作为改性聚合物的是聚苯乙烯。
形状记忆聚合物反应混合物组分中苯乙烯单体组分的存在量为约30%至约95%,乙烯基单体组分为约5%至约60%,交联剂组分为约0.5%至约5%,引发剂的浓度在约0.1%至约4%的范围内并且如果存在的话,改性聚合物为约0.5%至约60%,上述所有百分比都是以该形状记忆聚合物反应混合物的总重量为基础的重量百分比。
优选地,该形状记忆聚合物反应混合物的组分是以如下的浓度范围存在的,还是以该反应混合物的总重量为基础以重量百分比来表示:苯乙烯单体,约40%至约85%;乙烯基单体,约5%至约20%;交联剂,约0.6%至约3%;引发剂,约0.5%至约3%;并且如果存在的话,改性聚合物,约5%至约50%。
更优选地,该形状记忆聚合物反应混合物的组分包括约50%至约80%苯乙烯单体;约5%至约14%乙烯基单体;约1%至约2.5%引发剂;并且如果存在的话,约10%至约40%改性聚合物。跟前面一样,这些百分比都是以该形状记忆聚合物的总重量为基础的重量百分比。
该形状记忆聚合物反应混合物是在约20℃至约150℃的温度范围和约14.7psi至约50psi的压力范围内在约2秒至约4天的时间内进行聚合的,从而制备出一种交联的形状记忆聚合物。
在一个优选的实施方案中,该制备本发明热固性形状记忆聚合物的聚合反应是在约50℃至约110℃的温度范围内和约14.7psi至约25psi的压力下在约1分钟至约3天的时间内进行的。
更优选地,由该形状记忆聚合物反应混合物形成热固性形状记忆聚合物的聚合反应条件如下:温度在约65℃至约75℃的范围内,压力为约14.7psi,反应时间为约4小时至约1.25天。
当几何形状的热可逆性是所需目的时,其在Tg附近的形状记忆现象和通过在很宽的温度范围内改变组成来设定Tg值的能力使得在多种应用中都有大量的用途。用指导和非限制性的方式列举了本发明形状记忆聚合物的如下应用:
眼镜如隐形眼镜、眼镜、眼内透镜制造用模具;灵活工具如用于制造眼镜的灵活工具的可变形表面;复合制造用模具;用于远程体统的结构解聚(deployment)装置;游戏和玩具;家用物品;艺术品和装饰品;医学和与医学有关的仪器和装置;热敏仪器和安全装置;办公装置;园艺设备;教育物品;魔术、曲艺和新奇的物品;建筑辅助设备;卫生辅助设备;汽车辅助设备;用于可回收的外壳和包装的膜和片;不同直径管子的连接材料;建筑部件辅助品;折叠部件;比例模型的附件;浴室玩具;靴子和鞋的镶嵌物;滑雪辅助设备;真空吸尘器的空吸装置;制备糕点的辅助品;宿营物品;可调节的衣架;可收缩的膜和网;灵敏的窗帘;绝缘接头和闭塞区段绝缘节;报警装置;雕刻辅助品;可调节的美发辅助品;可被抹去的用于盲字的板;医用假肢;矫形装置;家具;可变形的标尺;以及可回收的印刷字型塑料板。
用如下的实施例来对本发明进行举例说明。因为这些实施例的目的仅仅是为了进行举例说明,所以不应认为其会对本发明形成限制。
实施例1
通过将新癸酸乙烯酯(7%)、二乙烯基苯(1%)、以及苯乙烯(90%)以任意次序进行混合产生一种澄清的溶液来制备一种聚合反应混合物。然后向所得的溶液中加入过氧化苯甲酰(2%)(所有组分%都是重量百分比)。在使用前将所得的溶液放在冰箱中冷藏。为了制备该形状记忆聚合物(SMP),用注射器将上面所制备的反应混合物注入到用两个通过用Viton垫片所分离开的14″×14″的玻璃板制备的模具中。然后用夹子将两个玻璃板沿着边缘夹紧。该Viton垫片在该模具中也作为密封片。然后将该样品在维持大气压和温度为75℃的烘箱中加热24小时。在将样品固化特定的时间后,将其从烘箱中取出并立即将其转移到一个温水浴中。所用水的温度为约60℃。通过在该模具的边缘施加轻微的撬起的压力而在该温水中将所形成的SMP片脱模。然后将所释放出来的SMP片进行干燥并使之冷却至室温。
在这种聚合反应结束时获得一种透明的被固化的形状记忆聚合物片。
实施例2
通过将新癸酸乙烯酯(7%)、二乙烯基苯(1%)、以及苯乙烯(60%)以任意次序进行混合得到一种无色溶液来制备一种聚合反应混合物。然后向所得溶液中加入聚苯乙烯颗粒(30%)。然后将所得的混合物在室温下放置,偶尔进行搅拌直至所有的聚苯乙烯颗粒都被溶解从而得到一种澄清的粘性溶液。然后向所得的溶液中加入过氧化苯甲酰(2%)(所有的组分%都是重量百分比)。将所得的混合物在室温下超声15分钟,得到一种澄清的溶液。在使用前将所得的溶液在冰箱中冷藏。为了制备该形状记忆聚合物(SMP),用注射器将上面所制备的反应混合物注入到用两个通过用Viton垫片所分离开的14″×14″的玻璃板制备的模具中。然后用夹子将两个玻璃片沿着边缘夹紧。该Viton垫片在该模具中也作为密封片。然后将该样品在维持大气压和温度为75℃的烘箱中加热24小时。在将样品固化特定的时间后,将其从烘箱中取出并立即将其转移到一个温水浴中。所用水的温度为约60℃。通过在该模具的边缘施加轻微的撬起的压力而在该温水中将所形成的SMP片脱模。然后将所释放出来的SMP片进行干燥并使之冷却至室温。
在这种聚合反应结束时获得一种透明的被固化的形状记忆聚合物片。
上述实施方案和实施例对本发明的范围和主旨进行了举例说明。由这些实施方案和实施例得到其它的实施方案和实施例对于现有技术中的技术人员而言是显而易见的。这些其它的实施方案和实施例也在本发明考虑的范围之内。因此,本发明仅受所附的权利要求的限制。
Claims (14)
1.一种形状记忆聚合物,其包含苯乙烯、除苯乙烯外的乙烯基化合物、0.5wt%至5wt%的多官能团交联剂和一种引发剂的反应产物,其中所说乙烯基化合物是新癸酸乙烯酯、苯甲酸乙烯酯、丙酸乙烯酯、硬脂酸乙烯酯、甲基苯乙烯、硬脂酸4-(乙烯氧基)丁酯或乙烯基吡啶;其中所说苯乙烯占30%至95%;所说乙烯基化合物占5%至60%;所说多官能团交联剂占0.5%至5%并且所说引发剂占0.1%至4%,所说百分比是以所说形状记忆聚合物反应混合物的总重量为基础的重量百分比并且所有组分之和为100%。
2.如权利要求1所述的形状记忆聚合物,其中所说交联剂是双官能团的。
3.如权利要求2所述的形状记忆聚合物,其中所说双官能团交联剂是二乙烯基苯、二(4-(乙烯氧基)丁基)对苯二甲酸酯或二(4-((乙烯氧基)甲基)环己基)甲基对苯二甲酸酯。
4.如权利要求1所述的形状记忆聚合物,其中所说引发剂是一种自由基引发剂或离子引发剂。
5.如权利要求4所述的形状记忆聚合物,其中所说引发剂是一种自由基引发剂。
6.如权利要求5所述的形状记忆聚合物,其中所说自由基引发剂是一种有机过氧化物。
7.如权利要求4所述的形状记忆聚合物,其中所说引发剂是一种阳离子引发剂。
8.如权利要求1所述的形状记忆聚合物,其中所说反应混合物是在20℃至150℃的温度范围和101.4kPa至344.8kPa的压力范围内在2秒至4天的时间内进行聚合的。
9.如权利要求5或7所述的形状记忆聚合物,其中所说自由基或阳离子引发剂选自叔-丁基过氧化物、叔-丁基氢过氧化物、过氧化苯甲酰、过氧化二枯基、过氧化月桂酰、2,2′-偶氮二异丁腈、三氟化硼、三氟化硼二乙基醚合物、三氟化铝和氯化锡(IV)。
10.如权利要求9所述的形状记忆聚合物,还包括改性聚合物,其是可与所说苯乙烯和所说乙烯基化合物的反应产物相容的热塑性聚合物。
11.如权利要求10所述的形状记忆聚合物,其中所说热塑性聚合物是聚苯乙烯或聚烯烃。
12.如权利要求9所述的形状记忆聚合物,其中所说乙烯基化合物是新癸酸乙烯酯,所说双官能团交联剂是二乙烯基苯并且所说引发剂选自过氧化二枯基、过氧化苯甲酰和过氧化月桂酰。
13.如权利要求12所述的形状记忆聚合物,其中所说形状记忆聚合物包括聚苯乙烯。
14.如权利要求10所述的形状记忆聚合物,其中所说苯乙烯占40%至85%;所说乙烯基化合物占5%至20%;所说多官能团交联剂占0.6%至3%并且所说引发剂占0.5%至3%;并且所说热塑性聚合物占5%至50%,所说百分比是以所说形状记忆聚合物反应混合物的总重量为基础的重量百分比。
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WO2002059169A1 (en) | 2002-08-01 |
WO2002059169A9 (en) | 2003-01-09 |
DE60208775D1 (de) | 2006-04-06 |
CN1498233A (zh) | 2004-05-19 |
US6759481B2 (en) | 2004-07-06 |
BR0206685B1 (pt) | 2012-01-24 |
DE60208775T2 (de) | 2006-08-31 |
BR0206691A (pt) | 2004-02-03 |
KR100874602B1 (ko) | 2008-12-19 |
HK1058681A1 (en) | 2004-05-28 |
KR20040011456A (ko) | 2004-02-05 |
JP2004521172A (ja) | 2004-07-15 |
CN1266174C (zh) | 2006-07-26 |
CA2435808C (en) | 2011-01-04 |
EP1373340B1 (en) | 2005-10-19 |
US20020137864A1 (en) | 2002-09-26 |
JP2004530573A (ja) | 2004-10-07 |
AU2002245314B2 (en) | 2006-03-09 |
KR20040024542A (ko) | 2004-03-20 |
WO2002059170A1 (en) | 2002-08-01 |
DE60206739T2 (de) | 2006-07-20 |
HK1058680A1 (en) | 2004-05-28 |
EP1373339B1 (en) | 2006-01-18 |
EP1373339A1 (en) | 2004-01-02 |
CA2435809A1 (en) | 2002-08-01 |
BR0206685A (pt) | 2004-02-03 |
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