CN109312084B - 改善非-邻苯二甲酸二(2-乙基己基)酯聚氯乙烯与丙烯酸类或abs类聚合物的粘合性的方法 - Google Patents

改善非-邻苯二甲酸二(2-乙基己基)酯聚氯乙烯与丙烯酸类或abs类聚合物的粘合性的方法 Download PDF

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CN109312084B
CN109312084B CN201780034926.4A CN201780034926A CN109312084B CN 109312084 B CN109312084 B CN 109312084B CN 201780034926 A CN201780034926 A CN 201780034926A CN 109312084 B CN109312084 B CN 109312084B
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abs
acrylic
polymer
acrylic polymer
impact modifier
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CN109312084A (zh
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泽赫拉·西贝尔·塞温奇
林忠建
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Baxter Healthcare SA
Baxter International Inc
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Abstract

本公开提供了改善非邻苯二甲酸二(2‑乙基己基)酯(DEHP)增塑的聚氯乙烯(PVC)与丙烯酸类聚合物或ABS类聚合物的粘合性的方法。这样的方法可以包括:将丙烯酸类聚合物或ABS类聚合物与抗冲改性剂掺合,使得丙烯酸类聚合物或ABS类聚合物中的橡胶含量大于12%(w/w)。还提供了通过所公开的方法制造的装置(例如,医疗装置)的组件。

Description

改善非-邻苯二甲酸二(2-乙基己基)酯聚氯乙烯与丙烯酸类 或ABS类聚合物的粘合性的方法
背景技术
聚氯乙烯(PVC)是医疗应用例如静脉注射(IV)袋和血液袋、手术管材和相关组件、导管等中最普遍使用的聚合物之一。单独时,PVC是一种硬且刚性的物质。然而,当PVC用增塑剂增塑时,PVC变得柔韧但坚固、抗扭结,并且可以使用溶剂例如环己酮容易地与其它聚合物组件进行溶剂焊接。然而,PVC的使用在一定程度上受到它与其它聚合物例如丙烯酸类或ABS类聚合物粘结的强度随时间衰退的阻碍。
发明内容
本公开提供了改善非-邻苯二甲酸二(2-乙基己基)酯(DEHP)增塑的聚氯乙烯(PVC)、包括基于非-DEHP PVC的聚合物掺合物以及包含这些聚合物和掺合物的制品或装置与丙烯酸类聚合物或ABS类聚合物、包括含有这些聚合物的制品或装置的粘合性的方法。
本公开的方法可以包括将所述丙烯酸类聚合物或ABS类聚合物与抗冲改性剂掺合,使得所述丙烯酸类聚合物或ABS类聚合物中的橡胶含量大于12%(w/w)。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述非DEHP增塑的PVC是对苯二甲酸二-2-乙基己酯(DEHT)增塑的PVC。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,非DEHP增塑的PVC包括增塑剂,所述增塑剂包含非DEHP增塑剂,所述非DEHP增塑剂的量的范围为基于增塑剂的总重量从15%(w/w)至46%(w/w)。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,非DEHP增塑的PVC包括增塑剂,所述增塑剂包含非DEHP增塑剂,所述非DEHP增塑剂的量的范围为从6%(w/w)至42%(w/w),不包括环氧化油。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述丙烯酸类聚合物是抗冲改性的丙烯酸类多元共聚物。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述ABS类聚合物是抗冲改性的ABS类多元共聚物。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述丙烯酸类聚合物是丙烯酸三元共聚物。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述丙烯酸三元共聚物是甲基丙烯酸甲酯/苯乙烯/丙烯酸乙酯三元共聚物。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述ABS类聚合物选自:(1)含ABS的甲基丙烯酸酯聚合物,(2)透明级的ABS,和(3)甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯(MABS)。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述丙烯酸类聚合物的聚(甲基丙烯酸甲酯)含量大于98%(w/w)。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述丙烯酸类聚合物是透明的。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述抗冲改性剂选自:聚(丙烯酸丁酯),聚(甲基丙烯酸丁酯),聚丁二烯,甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS),丙烯酸橡胶,以及
Figure BDA0001892994130000031
AC。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,将所述丙烯酸类聚合物或所述ABS类聚合物与聚丁二烯型抗冲改性剂掺合。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,将所述丙烯酸类聚合物与聚丁二烯型抗冲改性剂和/或聚(丙烯酸丁酯)抗冲改性剂掺合。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述丙烯酸类聚合物或ABS类聚合物中的橡胶含量大于12%(w/w)并至多40%(w/w)。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述丙烯酸类聚合物或ABS类聚合物中的橡胶含量为至少15%(w/w)。
本发明还提供了将包含非DEHP增塑的PVC聚合物、包括非DEHP增塑的PVC聚合物掺合物的第一构件(member)与包含丙烯酸类聚合物或ABS类聚合物的第二构件粘结的方法,所述方法包括:将所述丙烯酸类聚合物或所述ABS类聚合物与抗冲改性剂掺合,使得所述丙烯酸类聚合物或ABS类聚合物中的橡胶含量大于12%(w/w);形成包含所述丙烯酸类聚合物或所述ABS类聚合物的第二构件;将所述第一构件与所述第二构件溶剂粘结。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述基于非DEHP增塑PVC的聚合物(例如,非-DEHP PVC聚合物掺合物)和丙烯酸类聚合物具有大于5.5lbf的粘结力达至少5年。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,将所述丙烯酸类聚合物或所述ABS类聚合物与聚丁二烯型抗冲改性剂掺合。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,将所述丙烯酸类聚合物与聚丁二烯型抗冲改性剂和/或聚(丙烯酸丁酯)抗冲改性剂掺合。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,所述第一构件是管,并且所述第二构件是模制部件。
在上述或下述实施方式中的每一个或任何一个的一些实施方式中,利用环己酮或环己酮与甲基乙基酮(MEK)的混合物将所述第一构件和所述第二构件溶剂粘结。
本公开还提供了一种由下述方法制造的装置的组件,所述方法包括:将所述丙烯酸类聚合物或所述ABS类聚合物与抗冲改性剂掺合,使得所述丙烯酸类聚合物或ABS类聚合物中的橡胶含量大于12%(w/w);形成包含所述丙烯酸类聚合物或所述ABS类聚合物的第二构件;将所述第一构件与所述第二构件溶剂粘结。
本公开还提供了一种装置的组件,所述组件包括:包含非DEHPPVC的第一构件;和包含丙烯酸类聚合物或ABS类聚合物模制部件的第二构件,其中所述第一构件与所述第二构件溶剂粘结,并且其中所述丙烯酸类聚合物或ABS类聚合物包含抗冲改性剂,使得所述丙烯酸类聚合物或ABS类聚合物中的橡胶含量大于12%(w/w)。
附图说明
当结合附图阅读时,将更好地理解前述的发明内容以及本公开的以下详细描述。出于说明本公开的目的,图中显示的是目前优选的实施方式。然而,应该理解,本公开不限于所显示的精确布置、示例和手段。
图1显示了根据本公开的一个实施方式的模制部件的横截面视图,所述模制部件具有用于溶剂粘结管材的孔穴。
具体实施方式
本公开提供了改善非-邻苯二甲酸二(2-乙基己基)酯(DEHP)聚氯乙烯(PVC)(例如,非-DEHP PVC聚合物掺合物)与丙烯酸类聚合物或ABS类聚合物的粘合性的方法。在医学应用中,含PVC的制品经常与包含丙烯酸类聚合物或ABS类聚合物的制品溶剂粘结。在这样的应用中,鉴于日益增长的对于PVC制品中DEHP浸出的担忧,不含DEHP的PVC组合物(例如,非-DEHP PVC聚合物掺合物)是有利的。然而,这种粘结随时间衰退,因此包含这种粘结的医疗装置或组件没有合适的储存期。令人惊讶的是,发现通过将丙烯酸类聚合物或ABS类聚合物与抗冲改性剂掺合和/或使用高分子量的丙烯酸类聚合物或ABS类聚合物,可以改善非-邻苯二甲酸二(2-乙基己基)酯(DEHP)聚氯乙烯(PVC)(例如,非-DEHP PVC聚合物掺合物)与所述丙烯酸类聚合物或ABS类聚合物的粘合性(例如,粘结强度和/或粘结寿命)。所述方法可用于制造医疗装置或医疗装置的组件,其中所述医疗装置或组件包括包含非-DEHP PVC(例如,非-DEHP PVC聚合物掺合物)的制品与包含丙烯酸类聚合物或ABS类聚合物的制品。
本文公开了改善非-邻苯二甲酸二(2-乙基己基)酯(DEHP)聚氯乙烯(PVC)与丙烯酸类聚合物或ABS类聚合物的粘合性的方法,所述方法包括将所述丙烯酸类聚合物或ABS类聚合物与抗冲改性剂掺合和/或使用高分子量的丙烯酸类聚合物或ABS类聚合物。用于本文中时,术语“改善粘合性”是指增加、提高或维持接合强度(例如,不会显著劣化粘结拉力(例如,3.5lbf、4.0lbf、4.5lbf、5.0lbf、5.5lbf、6.0lbf、6.5lbf、7.0lbf、7.5lbf、8.0lbf、8.5lbf、9.0lbf、9.5lbf、10.0lbf或更高)和/或粘结寿命(例如,减少或维持粘结衰退),包括,例如,在一定年限内(例如,1、2、3、4、5、6、7、8、9、10或更多年)。优选地,所述粘结维持至少5.5lbf的拉力达至少5年。
适用于本公开的非-DEHP增塑PVC化合物或掺合物包括医疗级和食品级聚氯乙烯均聚物。所述PVC树脂可以按照任何合适的量、例如约35%(w/w)至约90%(w/w)范围内的量包含在组合物或制品中。所述PVC树脂的量与所有添加剂的合并量相比的优选重量比可以是任何合适的比率,例如在约0.5至约5、或约1至3、或约1至2范围内的比率。
PVC的K值与PVC的分子量相关,并且经常用作分子量的替代值。用于本文所述的组合物中的PVC树脂的特征可以在于如本领域中已知的适合目标PVC制品最终用途的任何K值,任选地K值在约35至约80的范围内,任选地在约60至约80的范围内,例如70。
本公开的非-DEHP增塑PVC聚合物,包括聚合物掺合物,可包括其它任选的添加剂成分,包括但不限于增塑剂、润滑剂、抗冲改性剂、杀生物剂、填料、着色剂、抗氧化剂和其它功能性成分,例如以适用于它们的预期目的的量。
本公开的非-DEHP增塑PVC聚合物(例如非-DEHP PVC聚合物掺合物)可包括主增塑剂和任选的次增塑剂。用于PVC组合物中的增塑剂是本领域公知的。适合用作主增塑剂或次增塑剂的增塑剂包括邻苯二甲酸酯增塑剂,例如邻苯二甲酸二-2-乙基己酯(DEHP)、对苯二甲酸二(2-乙基己基)酯(DEHT)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸丁基苄酯(BBP)和邻苯二甲酸二(异壬基)酯(DINP),环氧化植物油,例如大豆和亚麻籽油,偏苯三酸酯,例如偏苯三酸三甲酯(TMTM)、偏苯三酸三(2-乙基己基)酯(TOTM)和偏苯三酸正辛酯(OTM),聚酯,磷酸酯,例如磷酸异癸基二苯酯(DDP)和磷酸三(2-乙基己基)酯(TOF),柠檬酸酯,例如丁酰柠檬酸三己酯(BTHC)和乙酰柠檬酸三丁酯(ATBC),苯甲酸酯,例如二苯甲酸二丙二醇酯(DPGDP),磺酸酯,例如十五烷基磺酸的苯基甲苯酯,基于环己烷的羧酸酯,例如二(异壬基)环己烷-1,2-二羧酸酯,蓖麻油衍生物,以及己二酸酯,例如,己二酸二-2-乙基己酯(DEHA)、己二酸二甲酯(DMAD)和己二酸二辛酯(DOA)。
所述主增塑剂可以按照任何合适的量包含在所述非-DEHP PVC组合物中,所述量例如在约30phr至约70phr、或约35phr至约65phr、或约30phr至约60phr、或约25phr至约55phr的范围内。在一些实施方式中,所述PVC组合物将包含次增塑剂。次增塑剂可以按照任何合适的量包含在所述PVC组合物中,例如,至多约30phr。在使用更少的增塑剂时,PVC制品可变得更脆,而在使用更多的增塑剂时,PVC制品可失去强度。
用于本公开的非DEHP增塑的PVC组合物中的润滑剂是本领域公知的。合适的润滑剂包括但不限于聚乙烯、石蜡和阿克蜡(acrawax),例如N,N'-亚乙基双硬脂酰胺。润滑剂可以按照至多约0.5phr的量包含在所述PVC组合物中。在一个实施方式中,本公开的非DEHP增塑的PVC组合物可以不需要任何加工助剂,例如润滑剂。
本文所述的非-DEHP PVC组合物可以形成PVC制品。PVC制品可以使用任何合适的设备和方法、包括本领域中已经普遍知道的各种方法制造。所述PVC制品可以被热加工。例如,所述PVC制品可以用一个或多个加工步骤制造,所述加工步骤包括但不限于:挤塑,挤压吹塑,注塑,注射吹塑,嵌件成型,旋转铸塑,热成型,真空成型,拉挤成型,树脂传递模塑,以及焊接。
所述基于非DEHP增塑的PVC的聚合物可以是两种或更多种聚合物的掺合物,并且可以能够制成管材(例如,用于医疗应用的管材),包括例如多层管材、或双腔管材。所述管材可具有一种或多种以下物理性质:弹性模量小于约20,000psi、更优选小于约10,000psi、最优选小于约5,000psi,当根据ASTM D1003测量时内部雾度(internal haze)小于约25%,能够以大于约100ft/min、更优选地大于约200ft/min、更加优选地大于约250ft/min并最优选地等于或大于约300ft/min的生产速率制造;屈服强度为约400psi至约1500psi、更优选约600psi至约800psi,并且屈服曲线周围的拉伸曲线应该是平滑的,能够在通常约5lb的闭塞力下使用医用管夹的情况下重复使用且不会显著损坏所述管材,以及能够与刚性组件溶剂粘结。在一个实施方式中,所述管材可以暴露于辐射。
所述基于非DEHP PVC的聚合物可使用标准聚合物加工技术例如挤塑、共挤塑、吹胀挤塑、吹塑、注塑等制成管材。类似地,可使用标准聚合物加工技术,例如挤塑、共挤塑、吹胀挤塑、吹塑、压塑注塑、层压、热成型、压延(calendaring)等,将所述掺合物制成膜或片材。
对于要与输液泵、尤其是向管材侧壁施加能量的泵一起使用的管材,希望所述管材能够响应通过医用输液泵施加于所述管材上的能量来输送流体长达24小时周期,流速变化不超过10%,更优选变化不超过5%。还希望泵相容的管材具有原始横截面直径并在用5lb重物拉伸所述管材10秒后保持95%的原始横截面直径。
所述基于非DEHP增塑的PVC的聚合物可与一种或多种添加剂掺合以制备管材材料。例如,所述基于非DEHP的聚合物可包含聚烯烃的掺合树脂,更特别是α-烯烃的均聚物和共聚物。这些添加剂可以按管材材料的5至约95重量%的量掺合到所述管材材料中。所述α-烯烃可含有2至约20个碳原子或者其中的任何范围或范围组合。更优选含有2至约10个碳原子的α-烯烃。因此,所述烯烃聚合物可以源自于诸如乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-辛烯、1-癸烯、4-乙基-1-己烯等的烯烃,或这些烯烃中两种或多种的混合物。特别有用的烯烃聚合物的例子包括乙烯-丁烯共聚物以及乙烯和丙烯共聚物以及乙烯和辛烯-1共聚物,它们将被称为超低密度聚乙烯(ULDPE)。这样的ULDPE的密度优选等于或低于0.910g/cm3,并优选使用金属茂催化剂体系生产。这样的催化剂被称为“单位点”催化剂,因为它们具有单一的、空间上和电子上等同的催化剂位置,与已知具有多个催化剂位点的Ziegler-Natta型催化剂相反。
在一些实施方式中,可以将辐射敏感性添加剂添加到所述管材材料中,其对暴露于辐射例如γ射线、电子束、紫外光、可见光或其它电离能源起反应。合适的辐射敏感性添加剂包括有机过氧化物,例如过氧化二异丙苯(DiCup)和其它产生自由基的化合物。其它自由基敏感官能团包括丙烯酸酯、酸、二烯及其共聚物和三元共聚物、酰胺、胺、硅烷、氨基甲酸酯、羟基、环氧基、酯、吡咯烷酮、乙酸酯、一氧化碳、酮、咪唑啉、光和UV引发剂、含氟化合物等。这些官能团可以在聚合和非聚合的化合物中。更特别合适的添加剂包括乙烯乙酸乙烯酯、乙烯丙烯酸甲酯(EMA)、乙烯丙烯酸(EAA)、脂肪酰胺、低粘度官能化和非官能化苯乙烯-丁二烯共聚物及其氢化衍生物、官能化和非官能化聚丁二烯、聚异戊二烯、乙烯丙烯二烯单体三元共聚物、聚丁烯、氨基甲酸酯丙烯酸酯、环氧丙烯酸酯、光引发剂等。乙烯-丙烯三元共聚物具有链非共轭二烯烃的第三组分,例如,1,4-戊二烯、1,4-己二烯、1,5-己二烯或环状多烯例如二环戊二烯、亚甲基降冰片烯、亚乙基降冰片烯、环辛二烯、甲基四氢茚等。
所述辐射敏感性添加剂应以有效量添加到所述管材材料中,优选以单层或外层的0.01-20.0重量%、更优选0.01-10.0重量%并最优选0.02-5.0重量%的量。
任选地,所述管材材料可以通过掺入极性添加剂来进一步改性,以提高它们与粘合剂例如氰基丙烯酸酯型粘合剂的相容性,并改善其它表面特性,例如摩擦(润滑)。所述极性添加剂优选选自主链中具有大于5个碳原子但小于500、更优选小于200个碳并最优选小于100个碳的非聚合脂族或芳族烃。此外,所述添加剂应具有选自以下的负电性基团:胺;酰胺;羟基;酸;乙酸盐,铵盐;有机金属化合物,例如金属醇化物、金属羧酸盐和许多1,3二羰基化合物的金属络合物;苯基膦;吡啶;吡咯烷酮;咪唑啉和噁唑啉。所述改性添加剂也可以是聚合物乳液或溶液。
所述极性添加剂的含量应为所述管材材料的约0.001-10.00重量%,更优选0.01-2.0重量%。
所述管材的内径尺寸可以在0.003-0.4英寸的范围内,外径尺寸在0.12-0.50英寸的范围内。所述管材应该是柔性的,其弹性模量小于50,000psi,更优选小于30,000、更加优选小于10,000并最优选小于4,000psi,或其中的任何范围或范围组合。
通过将丙烯酸类聚合物或ABS类聚合物与抗冲改性剂掺合和/或增加所述丙烯酸类聚合物或ABS类聚合物的分子量,可以改善所述非-DEHP PVC与所述丙烯酸类聚合物或ABS类聚合物的粘合性。
可与丙烯酸类聚合物或ABS类聚合物掺合的抗冲改性剂可包括,例如,一种或多种选自以下的抗冲改性剂:聚(丙烯酸丁酯),聚(甲基丙烯酸丁酯),聚丁二烯,甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS),丙烯酸橡胶,或
Figure BDA0001892994130000101
AC。在另一个实施方式中,丙烯酸类聚合物或ABS类聚合物可以与聚丁二烯型抗冲改性剂掺合,包括例如大于12%(w/w)并至多40%(w/w)的所述抗冲改性剂。在又一个实施方式中,丙烯酸类聚合物可以与聚丁二烯型抗冲改性剂和/或聚(丙烯酸丁酯)抗冲改性剂掺合,包括例如大于12并至多40%(w/w)的所述抗冲改性剂。
与抗冲改性剂掺合的所述丙烯酸类聚合物或ABS类聚合物优选具有大于12%(w/w)、例如至少15%(w/w)的橡胶含量。取决于特定应用的使用要求或偏好,所述丙烯酸类聚合物或ABS类聚合物中的橡胶含量小于12%(w/w)可能无法提供必要的粘合强度。
包含基于非DEHP PVC的聚合物的制品可以与包含例如如本文公开的丙烯酸类或ABS类聚合物的其他制品溶剂粘结。用于制造组件的合适聚合物可额外包含聚丙烯、聚酯、聚酰胺、聚碳酸酯、含有环烯烃的聚合物和含有桥联多环烯烃的聚合物的均聚物和共聚物。合适的是含有环烯烃的聚合物和含有桥联多环烯烃的聚合物。
参照图1,包含本发明的丙烯酸类或ABS类聚合物的制品可以是刚性制品,例如通常用于腹膜透析或I.V.给药装置的连接器或其它装置。所述制品可具有大于约30,000psi的弹性模量。
溶剂粘结技术可用于将刚性、半刚性和柔性部件的任何组合接合在一起,包括接合两个刚性组件、一个刚性部件组件与一个半刚性组件、一个刚性组件与一个柔性组件、一个半刚性组件与一个柔性组件、一个半刚性组件与另一个半刚性组件、以及某些柔性组件彼此之间。溶剂粘结是指将由一种所述聚合物制成的制品之一暴露于溶剂中以熔化、溶解或溶胀所述产品,然后可附着于另一个聚合物组件以形成永久性粘结。例如,包含基于非DEHP PVC的聚合物的制品可以暴露于溶剂以将它与刚性制品例如包含丙烯酸类或ABS类聚合物的制品粘结。
合适的溶剂通常包括溶解度参数小于约20(MPa)1/2、更优选小于约19(MPa)1/2、最优选小于约18(MPa)1/2的溶剂,并且包括但不限于脂族烃、芳族烃、脂族烃混合物、芳族烃混合物、以及芳族和脂族烃的混合物。合适的脂族烃包括取代和未取代的己烷、庚烷、环己烷、环庚烷、萘烷等。合适的芳族烃包括取代和未取代的芳族烃溶剂,如二甲苯、萘满、甲苯和异丙苯。合适的烃取代基包括具有1-12个碳的脂族取代基,并包括丙基、乙基、丁基、己基、叔丁基、异丁基及其组合。合适的溶剂的分子量也将小于约200克/摩尔,更优选小于约180克/摩尔,最优选小于约140克/摩尔。
本公开还提供了溶剂粘结的组件,例如用于腹膜透析、血液透析或血液透析滤过的装置的组件。所述组件可以如下所述被溶剂粘结在一起:提供包含基于非DEHP PVC的聚合物的制品,提供包含丙烯酸类聚合物或ABS类聚合物的制品,向所述第一制品或第二制品之一施加溶剂以限定界面区域;并沿所述界面区域将所述第一制品与所述第二制品粘结。
所述第一制品可以是刚性、半刚性和柔性医疗产品,其选自Y型部位(Y-site)、过滤器外壳、滴斗、肝素锁、注射部位、导管、刺针、注射器针筒、封闭物、管材、氧合器、泵匣、阀、滴定管以及任何医疗制品或组件。所述第二制品可以是刚性、半刚性和柔性聚合物材料,选自丙烯酸类聚合物或ABS类聚合物。所述第二制品可以是针对所述第一制品阐述的同一装置的部件。
也可以希望改善溶剂粘结,以提供在管材将被粘结的区域(界面区域)或沿着整个管材外表面具有纹理化、磨砂或以其它方式变粗糙的外表面的管材。
本公开还提供了将包含非DEHP增塑的PVC的第一构件与包含丙烯酸类聚合物或ABS类聚合物的第二构件粘结的方法。所述方法可包括:将所述丙烯酸类聚合物或所述ABS类聚合物与抗冲改性剂掺合或增加所述丙烯酸类聚合物或ABS类聚合物的分子量;形成包含丙烯酸类聚合物或ABS类聚合物的第二构件;以及将所述第一构件与所述第二构件溶剂粘合。或者,所述方法可以包括将包含非DEHP PVC的第一构件与第二构件粘结,所述第二构件包含具有抗冲改性剂的丙烯酸类聚合物或具有抗冲改性剂的ABS类聚合物,所述方法包括:提供包含非DEHP PVC的第一构件和第二构件,所述第二构件包含具有抗冲改性剂的丙烯酸类聚合物或具有抗冲改性剂的ABS类聚合物;以及将所述第一构件与所述第二构件溶剂粘结。还提供了装置(例如,用于腹膜透析、血液透析或血液透析滤过的装置)的组件,所述组件包含根据本文所公开的方法与第二构件粘结的第一构件。
用于本文时并且除非另有说明,术语“wt.%”和“wt%”旨在以整个组合物的“干”(无水)重量份表示所鉴定的要素的组成(当适用时)。
尽管阐述本公开的广义范围的数值范围和参数是近似值,但具体示例中阐述的数值是尽可能精确地报告的。然而,任何数值固有地包含必然由它们各自的检验测量中存在的标准偏差引起的某些误差。除非另有说明,用于说明书和权利要求中表示成分的量、性质例如分子量、反应条件等的所有数值应理解为在所有情况下都被术语“约”修饰。
除非在本文中另有说明或上下文明显相矛盾,否则在描述本公开的上下文中(尤其是在权利要求的上下文中)使用的不带数量指示的、“所述”和类似的指称物应被解释为涵盖单数和复数两者。本文中列举的数值范围仅旨在用作单独地提及落入该范围内的每个分开的值的简写方法。除非本文另有说明,否则将每个单独的值并入本说明书中,如同其在本文中被单独地列举一样。除非本文另有说明或上下文明显矛盾,否则本文所述的所有方法均可以按照任何合适的顺序进行。本文提供的任何和所有示例或示例性语言(例如,“诸如”)的使用仅旨在更好地阐明本公开,而不对原本要求保护的本公开的范围造成限制。说明书中的任何语言都不应被解释为指示对于实践本公开而言必不可少的任何未要求保护的要素。
本文公开的替选元素或实施方式的分组不应被解释为限制。每个组成员可以单独地或以与该组中的其它成员或本文中存在的其它要素的任何组合被提及和要求保护。据预期,组中的一个或多个成员可以出于方便和/或可专利性的原因被包括在组中或从组中删除。当发生任何这样的包括或删除时,本说明书被认为包含经修改的组,从而满足权利要求中使用的所有马库什组的书面描述。
本文描述了本公开的某些实施方式,包括发明人已知的实施本公开的最佳模式。当然,在阅读前面的描述后,在这些描述的实施方式上的变化对于本领域普通技术人员将变得显而易见。本发明人预期熟练技术人员会酌情采用这些变化,并且发明人打算以不同于本文具体描述的方式来实践本公开。因此,本公开包括适用的法律所允许的权利要求中主题的所有修改和等同体。此外,除非本文另有说明或上下文明显矛盾,否则本公开涵盖上述要素的所有可能变化形式的任何组合。
本文公开的具体实施方式可以在权利要求中使用“由...组成”或“基本上由...组成”的语言进一步限制。当在权利要求中使用时,无论是提交还是按照修改添加时,过渡术语“由...组成”排除权利要求中未指定的任何要素、步骤或成分。过渡术语“基本上由...组成”将权利要求的范围限制在指定的材料或步骤以及不会对基本和新颖特征产生实质性影响的材料或步骤。如此要求保护的本公开的实施方式在本文中被内在地或明确地描述和实现。
应理解,本文公开的公开内容的实施方式是对本公开的原理的说明。可以采用的其它修改落入本公开的范围内。因此,作为示例而非限制,可以根据本文的教导采用本公开的替选性配置。因此,本公开不限于精确地示出和描述的那些内容。
虽然本文通过参考各种具体的材料、程序和示例描述和说明了本公开,但应理解,本公开不限于为此目的选择的材料和程序的特定组合。如本领域技术人员将领会,可以暗含这样的细节的许多变化。本说明书和示例旨在仅被认为是例示性的,本公开的真实范围和精神由权利要求书指示。本申请中提及的所有参考文献、专利和专利申请均通过引用以整体并入本文。

Claims (17)

1.一种改善非邻苯二甲酸二(2-乙基己基)酯(DEHP)增塑的聚氯乙烯(PVC)与丙烯酸类聚合物或ABS类聚合物的粘合性的方法,所述方法包括:
将所述丙烯酸类聚合物或ABS类聚合物与抗冲改性剂掺合,使得所述丙烯酸类聚合物或ABS类聚合物中所述抗冲改性剂的含量大于12%(w/w)并至多40%(w/w),其中所述抗冲改性剂选自以下中的至少一者:聚(丙烯酸丁酯),聚(甲基丙烯酸丁酯),甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS),丙烯酸橡胶,以及
Figure FDA0003339811240000011
AC。
2.权利要求1的方法,其中所述非-DEHP PVC是对苯二甲酸二辛酯(DEHT)PVC。
3.权利要求1的方法,其中所述丙烯酸类聚合物是抗冲改性的丙烯酸类多元共聚物。
4.权利要求1的方法,其中所述ABS类聚合物是抗冲改性的ABS类多元共聚物。
5.权利要求1的方法,其中所述丙烯酸类聚合物是丙烯酸三元共聚物。
6.权利要求5的方法,其中所述丙烯酸三元共聚物是甲基丙烯酸甲酯/苯乙烯/丙烯酸乙酯三元共聚物。
7.权利要求1的方法,其中所述ABS类聚合物选自:(1)含ABS的甲基丙烯酸酯聚合物,(2)透明级的ABS,和(3)甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯(MABS)。
8.权利要求1的方法,其中所述丙烯酸类聚合物的聚(甲基丙烯酸甲酯)含量大于98%(w/w)。
9.权利要求1的方法,其中所述丙烯酸类聚合物是透明的。
10.权利要求1的方法,其中将所述丙烯酸类聚合物与聚(丙烯酸丁酯)抗冲改性剂掺合。
11.一种将包含非DEHP PVC的第一构件与包含丙烯酸类聚合物或ABS类聚合物的第二构件粘结的方法,所述方法包括:
将所述丙烯酸类聚合物或所述ABS类聚合物与抗冲改性剂掺合,使得所述丙烯酸类聚合物或ABS类聚合物中所述抗冲改性剂的含量大于12%(w/w)并至多40%(w/w),其中所述抗冲改性剂选自以下中的至少一者:聚(丙烯酸丁酯),聚(甲基丙烯酸丁酯),甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS),丙烯酸橡胶,以及
Figure FDA0003339811240000021
AC;
形成包含所述丙烯酸类聚合物或所述ABS类聚合物的第二构件;以及
将所述第一构件与所述第二构件溶剂粘结。
12.权利要求11的方法,其中所述非DEHP PVC与丙烯酸类聚合物具有大于5.5lbf的粘结力达至少5年。
13.权利要求11的方法,其中将所述丙烯酸类聚合物与聚(丙烯酸丁酯)抗冲改性剂掺合。
14.权利要求11的方法,其中所述第一构件是管,并且所述第二构件是模制部件。
15.权利要求11的方法,其中利用环己酮或环己酮与MEK的混合物将所述第一构件和所述第二构件溶剂粘结。
16.一种将包含非DEHP PVC的第一构件与包含丙烯酸类聚合物或ABS类聚合物的第二构件粘结的方法,所述方法包括:
将所述丙烯酸类聚合物或所述ABS类聚合物与抗冲改性剂掺合,使得所述丙烯酸类聚合物或ABS类聚合物中所述抗冲改性剂的含量为至少15%(w/w)并至多40%(w/w),其中所述抗冲改性剂选自以下中的至少一者:聚(丙烯酸丁酯),聚(甲基丙烯酸丁酯),甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS),丙烯酸橡胶,以及
Figure FDA0003339811240000032
AC;
形成包含所述丙烯酸类聚合物或所述ABS类聚合物的第二构件;以及
将所述第一构件与所述第二构件溶剂粘结。
17.一种装置的组件,所述组件包括:
包含非DEHP PVC的第一构件;和
包含丙烯酸类聚合物或ABS类聚合物模制部件的第二构件,其中所述第一构件与所述第二构件溶剂粘结,其中所述丙烯酸类聚合物或ABS类聚合物包含抗冲改性剂,使得所述丙烯酸类聚合物或ABS类聚合物中所述抗冲改性剂的含量大于12%(w/w)并至多40%(w/w),并且其中所述抗冲改性剂选自以下中的至少一者:聚(丙烯酸丁酯),聚(甲基丙烯酸丁酯),甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS),丙烯酸橡胶,以及
Figure FDA0003339811240000031
AC。
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