CN1066757C - 医药包装和装置用的四组分射频敏感聚合物组合物 - Google Patents
医药包装和装置用的四组分射频敏感聚合物组合物 Download PDFInfo
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- CN1066757C CN1066757C CN94191203A CN94191203A CN1066757C CN 1066757 C CN1066757 C CN 1066757C CN 94191203 A CN94191203 A CN 94191203A CN 94191203 A CN94191203 A CN 94191203A CN 1066757 C CN1066757 C CN 1066757C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Abstract
制造成物件用的多组分聚合物组合物。尤其是包含:耐热性聚合物;射频(″RF″)敏感聚合物,相容化聚合物的聚合物组合物,该组合物具有以下的物理性质;a<40000psi;b≥70%;c<30%;d>1.0;e<0.1%;f<0.1%;g≥0.005;h≤60%;i=0,其中a是根据ASTM D-882测定的组合物之力学模量,b是在20%的初始变形后组合物在长度方向上的百分回复率;c是根据ASTMD-1003在厚度为9密耳时测定的组合物之光雾度;d是在熔融加工温度下在1Hz时量测的组合物之损耗角正切;e是组合物的元素卤之重量含量;f是组合物的低分子量水溶性部分;g是在温度从25至250℃和在1与60MHz之间时组合物的介电损耗;h是在27psi负荷下组合物的1英寸条在121℃下测定的试样蠕变;i指示出在约为20英寸(50厘米)/分的适中速度下将组合物拉伸到100%伸长率(二倍原始长度)时未产生应变增白(指示值为0),而产生应变增白时指示值为1。
Description
一般来说,本发明涉及用于制成薄膜、容器、管子和其他装置的热塑性聚合物合金。
在医药领域,药剂被收集、加工和贮存在容器中,输送并最终通过管子被施予给病人以达到治疗效果,通常制造容器和管子的材料必须具备各种性质的良好组合。例如,为了目检溶液以发现粒状污染物,容器或管子必须是光学透明的。为了从容器通过器壁塌陷注入溶液而不将空气引入到容器中,形成器壁的材料必须是充分柔软的。材料必须在宽广温度范围内是在起作用的。由于某些溶液,例如,某些预混的药剂是在容器中在温度例如-25至-30℃下被贮存和输送的以减少药剂降解,因此在低温时材料必须保持其柔性和韧性而仍起作用。材料还必须是在高温下仍在起作用的。以便能经受加热杀菌-这是大部分医药包装和营养产品在输送前必须经受的过程。杀菌过程通常包括将容器暴露在一般为121℃温度的蒸汽下并加压。因此材料需经受此温度和压力而不会严重变形(“耐热变形性”)。
为了易于制成有用的物件,材料最好是使用通常27.12MHz的射频(“R F”)而能封合的。因此,材料应具有充分的介电损耗性以便将RF能量转变成热能。
另一个要求是,在使用之后,当由此材料制造的物件被处理时,对环境的影响应减到最低限度。当这些物件被掩埋处理时,最好尽可能使用很少的材料并避免在物件结构中掺入低分子量可析出组分。因此,材料应该是重量轻的并具有良好的机械强度。另一好处是通过使用一种这样的材料而实现的,它可通过热塑性加工将消耗的物件转变成为其他有用的物件而被回收。
就那些经过焚化而被处理的容器来说,必须使用有助于消除生物损害危险和缩小或完全消除在焚化时形成无机酸类(它们是有害于环境的、刺激性的和腐蚀性的)或其他产物(它们是有害的、刺激性的或使人难以忍受的)的材料。
还向往的是,材料应不含或含有少量的低分子量添加剂例如增塑剂、稳定剂等等,这些添加剂可能会被释出而进入到药剂或生物液或细胞组织中,由此危及使用这样装置的病人或污染被贮存或配制在这样装置内的物质。就保存注入溶液的容器而言,这样的污染能使污染物进入到注入通道和病人身体内,引起病人的损伤或死亡。
惯用的软质聚氯乙烯料符合上述的许多要求以及在某些情况中符合上述的大部分要求。聚氯乙烯(“PVC”)还提供特殊的优点-它是成本最低的构成符合以上要求的装置的材料之一。然而,PVC在焚化时可能产生不能接受量的氯化氢(或当与水接触时为氢氯酸),引起对焚化设备的腐蚀。PVC有时含增塑剂,增塑剂可能析出而进入到与PVC相接触的药剂、生物液或细胞组织。因此,现已研制许多材料来取代PVC。然而,许多可供选用的材料由于太贵而无法取代PVC,并且它们也不符合全部的上述要求。
现有许多研制取代PVC的薄膜材料的尝试,但是大多数的尝试由于这样或那样的原因而没有成功。例如,在美国专利No.4966795中公开一种能经受蒸汽杀菌的多层薄膜结构,但是它不能通过射频电介质加热而被熔接,因此它不能被这种快速、低成本、可靠和实用的方法所结合。欧洲申请No.EP 0310143 A1公开的多层薄膜符合大部分的要求,并能够被RF熔接。然而,所公开的薄膜之各组分是通过辐照而交联的,因此,它不能通过标准的热塑性加工法而被回收利用。此外,由于在辐射步骤中可检出量的乙酸被释出和夹在材料中。当蒸汽杀菌时,乙酸作为污染物转移到包装的内含物中,并且改变内含物的pH值而起内含物的潜在的化学反应剂作用或起内含物降解的催化剂作用。
本发明的主要目的是创造一种热塑性材料,总的说来,这种材料优于已知的、迄今为止在本技术领域中被大量使用或销售的材料。这样材料的诸性质包括:柔软性、延展性和应变回复性,这些性质不仅仅在室温下存在,而且在整个的从室温到冷藏温度的宽广温度范围内也存在。材料应是充分光学透明的以便目视检测,并且在高达121℃的温度下是可蒸汽杀菌的。材料应能经受充分的应变而不会显示应变增白,应变增白表明物理和外观美容缺陷。本发明的另一目的是材料是能通过RF法而被结合的。另一目的在于材料不含可析出的低分子量添加剂,并且能通过焚化而被安全处理的,不会产生大量的腐蚀性的无机酸。再一个目的是在使用后,材料是可通过标准的热塑性塑料加工法而回收的。另一个希望的优点是,在制造过程中材料可掺混。重新研磨的回收边角料,以便降低材料或成本。最后,材料在成本上应可有效替换现在被用作医药装置的各种PVC配方。
当多于一种的聚合物被掺混以形成合金组合物时,要同时达到所有的上述目的是困难的。例如,在大多数情况合金组合物散射光,于是它们就不能符合光透明度的要求。光散射强度(以雾度来度量)取决于各组分的区域结构尺寸(在微米范围内)和各组分析射指数的近似度。通常,各组分的选择能令人满意地达到非常小的区域结构尺寸,然而同时要达到最小的折射指数失配是件很困难的任务。
本发明是为了解决这些和其他问题而提供的。
根据本发明现已研制出某些热塑性聚合物组合物,它们是对已知的组合物和物件的重大改进。这些组合物可被制成医药级的物件例如贮存药液的包或输送药液的管子,也可被用于制造其他制品或成品的组件例如连接件、管接头、导管、阀门、管道、导尿管、等等。
本发明的目的是制备具有以下物理性质的组合物:(1)当根据ASTM D-882测定时,力学模量小于40000psi、优选为小于25000psi,(2)在20%的初始变形后,组合物在长度方向上的回复率大于或等于70%,而更优选为大于或等于75%,(3)根据ASTM D-1003对厚度为9密耳的组合物测定,光雾度小于30%、更优选为小于15%,(4)在加工温度和1Hz时测定的损耗角正切为大于1.0、而更优选的为大于2.0,(5)元素卤的含量为小于0.1%、而更优选的为小于0.01%,(6)低分子量水溶性部分为小于0.1%、而更优选的为小于0.005%,(7)在温度为25~250℃范围和在160MHz之间时,最大介电损耗为大于或等于0.05,更优选的为大于或等于0.1,(8)在121℃和27psi负载下通过试样蠕变测定的耐热压成型性为小于或等于40%,而更优选为小于或等于20%以及(9)在约为20英寸(50厘米)/分的适中速度下被拉伸到约为100%伸长率后没有出现应变增白。
符合这些物理性质的本发明的聚合物基组合物包括多组分组合物。三组分组合物是由第一组分-提供耐热性和柔软性的软质聚烯烃、第二组分-赋予薄膜RF封合性的RF敏感的聚合物、和在前二组分之间赋予相容性的第三组分组成的。在下文中详细说明的RF敏感的聚合物应具有在频率范围为1~60MHz和温度范围为室温至250℃时为大于0.05的介电损耗。第一组分应占组合物的40-90%重量,第二组分应占组合物的5~50%重量,第三组分应占组合物的5~30%重量。
在三组分组合物的另一实施方案中,第一组分赋予耐高温性,第二组分是赋予组合物以RF封合性和赋予薄膜以柔软性的RF敏感聚合物,而第三组分在前二组分之间起相容剂作用。按组合物重量计第一组分应占30~60%,第二组分应占30~60%,第三组分应占5~30%。
四组分组合物包括:第一组分丙烯基聚烯烃、它可包括全同和间同立构的异构体,第二组分非丙烯基聚烯烃,第三组分-赋予组合物以RF封合性的RF敏感聚合物,以及相容化聚合物。最好,第一组分的聚烯烃是聚丙烯,它约占组合物的30~60%重量、而更优选为占45%。第二组分的聚烯烃优选为超低密度聚乙烯或聚丁烯-1,它约占组合物的25~50%重量、而更优选为占45%。RF组分优选为二聚脂肪酸聚酰胺(它应被理解还包括其氢化的衍生物),它约占组合物的5~40%重量,而更优选为10%。第四组分是相容化聚合物,它可选自苯乙烯与二烯或α-烯烃的各种嵌段共聚物;相容化聚合物可用少量的化学活性官能度进行改性。例如,相容化聚合物可以是苯乙烯/乙烯-丁烯/苯乙烯(“SEBS”)嵌段共聚物。第四组分应占组合物的5~40%重量,更优选为10%。
这些三组分和四组分组合物的每一种均可被混合和挤塑而形成RF活性的以致对自身是可RF封合的薄膜。例如,薄膜和管子可被用于生产无菌液体包装,血液和血成份、静脉内的和医药溶液、营养和呼吸治疗制品、以及渗析溶液用的容器。组合物还可被用于构成容器的出口管和进入装置。通过注塑、吹塑、热成型或其他已知的热塑性料加工方法,组合物还可被用于形成其他制品。
这些组合物是适于医药应用的,因为构成薄膜的各组分对于与组合物相接触的液体和内含物仅具有最小的可提取性。此外,薄膜对环境是安全的,当被焚化时不产生有害的降解物。最后,薄膜在成本上可取代PVC。
在对提出的优选实施方案的详细介绍中,可看出本发明的另外的特征和优点。
尽管本发明有许多不同形式的实施方案,但此处将公开被详细介绍的本发明之优选的实施方案。应该理解,这些公开的内容是为了说明本发明的原理,而不是将本发明的范围限制在所说明的实施方案之中。
更具体地说,根据本发明,向往的是提供可被热塑性加工成符合上述要求的物件、装置和制品的组合物。
就这点来说,如上所述,现已发现,从具有三、四或更多种组分的组合物可以制备具有这些特征的材料。以下将分别介绍三组分和四组分组合物。
三组分组合物
在三组分组合物的第一种实施方案中,第一组分赋予组合物以耐热性和柔软性。此组分可选自无定形的聚(α-烯烃)并且优选为软质聚烯烃。这些聚烯烃应对高达121℃温度的高温具有耐变形性,并且其峰值熔点为高于130℃,它是高柔软性的,其模量不大于20000psi。这样的软质聚烯烃是以产品牌号Rexene FPO90007销售的,其峰值熔点为145℃和模量为11000psi。此外,某些具有高间同立构规整度的聚丙烯还具有高熔点和低模量的特性。第一组分应占组合物的40~90%重量。
三组分组合物的第二组分是赋予组合物以RF封合性的RF敏感聚合物,并且选自二组极性聚合物中的任何一组。第一组的极性聚合物是由具有50~85%重量的乙烯与选自丙烯酸、甲基丙烯酸、甲基丙烯酸与1~10个碳原子的醇类的酯衍生物、丙烯酸与1~10个碳原子的醇类的酯衍生物、乙酸乙烯、以及乙烯醇的共聚用单体的乙烯共聚物。RF敏感聚合物还可选自由含聚氨基甲酸乙酯、聚酯、聚脲、聚酰亚胺、聚砜、以及聚酰胺的链段的共聚物组成的第二组中。这些官能度可占RF敏感聚合物的5~100%。RF敏感聚合物应占组合物的5~50%重量。最好,RF组分是乙烯/丙烯酸甲酯共聚物,其中丙烯酸甲酯占共聚物的10~25%重量。
三组分组合物的最后一种组分确保前二种组分间的相容性,并且选自苯乙烯嵌段共聚物、优选为马来酐官能化的苯乙烯嵌段共聚物。第三组分应占组合物的5~30%重量。
在三组分薄膜的第二种实施方案中,第一组分在整个需要温度范围内赋予薄膜以RF封合性和柔软性。第一组分赋予耐高温性(“耐温聚合物”)并选自聚酰胺、聚酰亚胺、聚氨酯、聚丙烯和聚甲基戊烯组成的组。最好,第一组分占组合物的30~60%重量,并且为聚丙烯。第一组分在整个需要温度范围内赋予薄膜以RF封合性和柔软性。RF聚合物选自与上述相同的第一组和第二组共聚物,但乙烯/乙烯醇共聚物除外。第二组分占组合物的30~60%重量。第三组分确保前二组分之间的相容性,并选自SEBS嵌段共聚物、优选为马来酐官能化的SEBS嵌段共聚物。第三组分应占组合物的5~30%重量。
四组分组合物
四组分薄膜的第一组分赋予薄膜以耐热性。此组分可选自聚烯烃、特别优选为聚丙烯、更具体地说为聚丙烯/α-烯烃无规共聚物(PPE)。最好,PPE类具有窄的分子量范围。PPE类具有被要求的刚性和在约121℃的热蒸煮温度下的抗弯曲性。然而,就其本身而言,PPE由于太硬而不符合柔软性要求。当与某些低分子量聚合物通过合金化相结合时,能够达到良好的柔软性。可使用的PPE的例子包括那些以牌号为Soltex 4208和Exxon EscorenePD9272销售的产品。
这些低分子共聚物包括乙烯基共聚物例如乙烯-乙酸乙烯共聚物(“EVA”)、乙烯-α-烯烃共聚物、或所谓的超低密度(通常低于0.90 kg/L)的聚乙烯(“ULDPE”)。这些ULDPE包括商业上可得到的TAFMERA485(Mitsui石油化学公司)、Exact4023~4024(Exxon化学公司)、Insite工业技术聚合物(陶氏化学公司)。此外,还有聚丁烯-1(“PB”),例如壳牌化学公司的PB-8010和PB-8310;SEBS基热塑性弹性体(壳牌化学公司);聚异丁烯(“PIB”)如Vistanex L-80、L-100、L-120和L-140(Exxon化学公司);乙二醇烷基丙烯酸酯,丙烯酸甲酯共聚物(“EMA”)例如EMAC 2707、DS-1130(Chevron),以及丙烯酸正丁酯(“ENBA”)(Quantum化学公司)也是可用的共聚物。乙烯共聚物诸如丙烯酸和甲基丙烯酸共聚物以及它们的部分中和的盐和离聚物,例如PRIMACOR(陶氏化学公司)和SURYLN(E.I.DuPont de Nemours & Company)也是令人满意的。通常,具有熔点为低于约110℃的乙烯基共聚物是不适于热压成型的。此外,如以下某些相反的例子(例如,实施例8G)所示,并不是所有的合金对是光学透明而符合目视检测要求的。而且,每种组分仅在有限范围的性质方面能同时满足柔软性和热压成型性的要求。
最好,第一组分选自含量约占组合物重量的30~60%、更优选为35~45%、而最优选为45%的聚丙烯的均态和与α-烯烃的无规共聚物。例如,乙烯含量为聚合物重量的0~6%、更优选为2~4%的丙烯/乙烯无规共聚物被优选作为第一组分。
四组分组合物的第二组分赋予柔软性和低温延展性,并且是与第一组分的聚烯烃不同的第二种聚烯烃,第二种聚烯烃不含聚丙烯重复单元(“非丙烯基聚烯烃”)。最好,它是乙烯共聚物包括ULDPE,聚丁烯,丁烯/乙烯共聚物,乙烯-乙酸乙烯共聚物(乙酸乙烯含量约为18~50%),乙烯-丙烯酸甲酯共聚物(丙烯酸甲酯含量约为20~40%),乙烯-丙烯酸正丁酯共聚物(丙烯酸正丁酯含量为20~40%),乙烯-丙烯酸共聚物(丙烯酸含量约高于15%)。被销售的这些产品的例子是Tafmer A-4085(Mitsui),EMAC DS-1130(Chevron),Exact 4023、4024和4028(Exxon)。更优选的是,第二组分是Mitsui石油化学公司以商品牌号TAFMER A-4085销售的ULDPE,或是壳牌化学公司牌号为PB 8010和PB 8310的聚乙烯-1,第二组分应占组合物重量的25~50%、更优选为35~45%、而最优选为45%。
为了赋予四组分组合物以RF介电损耗性,某些已知的高介电损耗成份(“RF敏感聚合物”)可被包含在组合物中。这些聚合物可选自上面提出的第一组和第二组中的RF聚合物。
其他RF活性材料包括PVC、偏二氯乙烯、以及偏二氟乙烯、双酚A与表氯醇的被称为PHENOXYS(联合碳化物公司)共聚物。然而,大量的这些含氯和氟的聚合物使组合物在焚化这样材料时产生对环境有害的无机酸。
聚酰胺类PF敏感聚合物最好选自由具有碳原子数为2~13的二胺的缩聚反应产生的脂族聚酰胺类、由具有碳原子数为2~13的二酸的缩聚反应产生的脂族聚酰胺类,由二聚脂肪酸的缩聚反应产生的脂族聚酰胺类,以及酰胺的共聚物(无规、嵌段、以及接枝共聚物)。聚酰胺类例如耐纶被广泛地用于薄膜材料中,因为它们使薄膜具有耐磨性。然而,耐纶很少被用于与医药溶液相接触的层中,因为它们通常由于析出到溶液中而污染溶液。然而,本发明的申请人发现,最优选的RF敏感聚合物是Henkel公司以产品牌号MACROMELT和VERSAMID销售的各种二聚脂肪酸聚酰胺,因为它们不会产生这样的污染。RF敏感聚合物最好应占组合物重量的约5~30%、更优选为7~13%、最优选为10%。
组合物的第四组分赋予组合物在极性与非极性组分之间的相容性(有时称为“相容化聚合物”),并且最好是带有烃软链段的苯乙烯嵌段共聚物。最优选的是,第四组分选自马来酐、环氧、或羧化物官能度改性的SEBS嵌段共聚物,特别是含马来酐官能基(“官能化的”)SEBS嵌段共聚物。这样的产品是由壳牌公司以牌号为KRATON RP-6509销售。相容化聚合物应占组合物重量的约5~40%、更优选为7~13%、而最优选为10%。
另外,添加第五组分的非官能化的SEBS嵌段共聚物也是有益的,这些共聚物是由壳牌化学公司以产品牌号KRATONG-1652和G-1657销售的。第五组分应占组合物重量的约5~40%、更优选为7~13%、最优选为10%。
对以上提出的每种组合物来说,如果需要的话,最好还可添加本技术领域已知的其他添加剂诸如滑爽剂、润滑剂、蜡、防粘连剂等,条件是使薄膜组合物能符合上述要求。
上述多组分组合物可被加工制造各种产品例如薄膜。这样的薄膜在工业上可使用若干种工艺来制造。例如,上述诸组合可以以干态形式在高强力混合机例如Welex掺混机中被掺混,然后送入到挤塑机。诸组分还可被重力喂料到双螺杆结构的高强力混合挤塑机例如Werner Pfleiderer中,然后产品在水浴中骤冷成多股线料,切料并干燥供使用。在第三种方法中通过将混合挤塑机的产品直接送入到薄膜挤塑机而省略切料步骤。还可以在薄膜挤塑机中配置高强力混合区以便使用单一挤塑机能生产出合金薄膜。使用其他的热塑性塑料转换机例如注塑或注塑-吹塑机可将此合金转换成其他物件或形状。当然有许多种将合金加工成薄膜的其他已知方法,因此,本发明不应被限制在通过这些示例性方法生产薄膜方面。
在以下实施例中陈述的具有不同组分和重量百分比的组合物是使用下列方法被制成薄膜并进行测试的。(1)热压处理性
耐热压处理性是根据试样蠕变,或在121℃和27psi负荷下经一小时后在试样长度方向上的增长而测定的。耐热压成型性必须低于或等于40%。(2)低温和室温延展性
(A)低温延展性
在装备有液氮冷却的低温环境室的冲击试验仪中,将约为7×7英寸(18cm×18cm)的薄膜试样安装在直径约为6英寸(15cm)的环形试样夹持器上。将装有应力传感器的半球形冲击头以高速(通常约为3米/秒)被驱入到薄膜中央。画出应力-位移曲线,并通过积分法计算冲击能。将冲击能明显地增加和断裂试样由脆性变成延性的高应变形态时的温度取作薄膜的低温特性(“L.Temp”)。
B)力学模量和回复率
将具有已知几何形状的热压成型薄膜试样,安装在带有十字头的伺服液压驱动的力学试验机上以伸长薄膜。以每分钟为10英寸(25厘米)的十字头速度将试样伸长到约为20%的伸长率。此时,十字头位移,然后以与初速拉伸薄膜的相反方向位移十字头。应力-应变性被记录在数字记录仪上。弹性模量(“E(Kpsi)”)取自应力-应变曲线上的初始斜率,而将以试样伸长百分率表示的过量的试样尺寸取作回复率。(3)RF加工性能
将相对于平的黄铜电极的尺寸约为0.25英寸(6.3mm)×4英寸(10cm)的矩形黄铜热合模连接到Callahan 27.12MHz、2KW射频发生器,黄铜电极也被连接到发生器。当将其间带有二片待封合材料的模头闭合后,施加不同幅度和持续时间的RF力。当RF循环结束后,打开模头并通过用手撕开二薄片来检验所得到的封口。封合强度(与薄膜强度相比较)和破坏形式(剥离、撕裂、或粘着破坏)被用来评价材料的RF敏感度。
另一方面,将待测的薄膜先用金或铂溅涂100埃的厚度以赋予表面传导性,然后将其切成圆形并安装在电介电容测量电池的二平行电极之间。使用Hewlett Packard 4092自动RF电桥在高达10MHz的不同频率和高达150℃的温度下测定介电常数和介电损耗。在RF场下由介电损耗可计算产生热。由计算或与RF封合试验的关系得到特性介电损耗。
如果是由Callahan封合器得到RF封合特性的话,下面的等级表是适用的:
(4)光学透明度
RF力 | RF时间 | 封合强度 | 级别 |
80%80%80%60%50%30% | 101005030303 | 无可剥离的可剥离的强强强 | 012345 |
首先将后热压成型的薄膜试样切成约2×2英寸(5×5厘米)的方块,将其安装在亨特色差计(Hunter Colorimeter)上并按照ASTM D-1003测定其内光雾度。一般说来,就这些厚度而言,要求内光雾度小于30%,优选为小于20%(“雾度%”)。(5)应变增白
以约每分钟20英寸(50厘米)的中等速度将热压成型薄膜拉伸至约100%的伸长率(二倍原始长度),并检查是否出现应变增白(出现应变增白以1表示,未出现应变增白以0表示)(“S.Whitening”)。(6)环境相容性
环境相容性包括三方面重要性质:(a)材料不含在处理时能析出到废渣填埋物中的低分子量增塑剂;(2)当实现输送药物的主要目的后材料可被热塑性加工回收成为有用物件;(3)当通过焚化处理以获得能源时,不会释放出大量有害环境的无机酸。(“Envir。”)。组合物还含少于0.1%重量的卤素。为了通过熔融加工方法促进再使用,制成的组合物在1Hz和加工温度下测定时,其损耗角正切应大于1。(7)溶液相容性
就溶液相容性而言,我们是指薄膜所装的溶液不会被组成组合物的诸组分所污染。(“S.Comp.”)组合物的低分子量水溶性部分应小于0.1%。
就三和四组分的组合物而言,使用上述的测试方法对以下的组合物进行测定。这些实施例说明,这些组合物具有意想不到的优点。
实施例1
(1)四和五组分组合物。PPE,PE共聚物。改性SEBS,以及RF活性聚合物。组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (K Pli) 增白 相容性 相容性A 合格 20 45 4级 0 -30 合格 合格B 合格 20 35 4级 0 -40 合格 合格C 合格 20 35 4级 0 -25 合格 合格D 合格 25 35 4级 0 -25 合格 合格E 合格 15 25 4级 0 -40 合格 合格F 合格 15 25 4级 0 -40 合格 合格G 合格 15 25 4级 0 -40 合格 合格H 合格 20 25 3级 0 -40 合格 合格I 合格 25 22 3级 0 -40 合格 合格A.60% Soltex 4208.20% Mitsui Talmer A-4085.15% Kraton RP6509.5% PA-12.B.50% Soltex 4208.30% Tafmer A-4085.15% Kraton G1657.5%PA-12.C.50% Soltex 4208.30% Chevron EMAC OS1130.10% Kraton RP6509.10% HenkelMM-6301.D.50% Soltex 4208.30% EMAC-DS1130.10% Xraton RP6509.5% PEU-103-200.5% MM-5301.E.45% Soltex 4208.35% Tafmar A-1085.10% Kraton RP6509.10% Henkal MM-5239.F.45% Soltex 4208.35% Exxon EXACT4028.10% Kraton RP6509.10% MM-6301.G.45% Soltex 4208.35% Exact-4024.10% Kraton RP6509.10% MM-6301.H.45% Soltex 4208.35% Exact-4023.10% Kraton RP6509.10%MM-5301.L.40% Soltex 4208.40% Tafmer A-4085.10% Kraton RP6509.10%聚乙酸乙烯
(40%被水解MW-72.000).
实施例2
(2)四组分组合物:PPE,聚丁烯-1(共聚物),改性SEBS和聚酰胺合金组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性A 合格 15 40 4级 0 -20 合格 合格B 合格 20 40 4级 0 -20 合格 合格C 合格 20 30 4级 0 -20 合格 合格D 合格 20 30 4级 0 -20 合格 合格E 合格 15 30 4级 1 -20 合格 合格F 合格 15 30 4级 1 -20 合格 合格G 合格 20 30 4级 1 -20 合格 合格A.55% Soltax 4208.35% Sheil PS8010.10% 5% Kraton EP6509.5% L-20.B.55% Soltex 4208.25% PS-8310.10% Xraton EP6509.1% Henkel MM-5301.C.45% Soltex 4208.35% PS8310.10% kraton RP6509.10% MM-6239.D.45% Exxon Ercorene PD8272.25% PS-8010.10% Xraron RP6509.10% MM-6301.E.45% Soltex 4208.35% PS-8010.10% Kraton-RP6509.10% MM-6301.F.45% Soltex 4208.35% PS-8010.10% RP6509.10% LinrRe2633.G.45% Soltex 4208.25% PS-8310.10% Kraton EP6509.10% MM-6301.
实施例3
(3)四组分组合物:PPE,聚异丁烯,改性SEBS和聚酰胺合金组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性A 合格 35 40 3级 1 -30 合格 合格B 合格 >50 30 3级 1 -30 合格 合格C 合格 25 30 4级 1 -25 合格 合格D 合格 40 30 4级 1 -25 合格 合格E 合格 >40 30 4级 1 -25 合格 合格F 合格 >40 30 4级 1 -25 合格 合格A.50% Soltex 4208.30% Exxon Vistanex L120.5% Kraton RP6509.10% Kraton
G.1657.5% PA-12.B.35% Soltex 4208.45% Vistanex L120.15% Kraton RP6509.5% PA-12C.45% Soltex 4208.35% Vistanex L-80. 10% Kraton RP6509.10% Hanxel MM-6301.D.45% Soltex 4208.35% Vistanex L-100. 10% Kraton RP6509.10% Henoel MM-6301.E.45% Soltex 4208.35% Vistanex L120.10% Kraton RP6509.10% Hankel MM-6301.F.45% Soltex 4208.25% Vistanex L-140.10% Kraton RP6509.10% Henkel MM-6301.
实施例4
(4)四和五组分组合物:PPE,EMA,改性SEBS,第四和第五组分合金组合物 热压减型性 强度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性A 合格 25 25 3级 1 -25 合格 合格B 合格 25 20 4级 0 -25 合格 合格C 合格 20 25 4级 0 -25 合格 合格D 合格 25 25 4级 0 -25 合格 合格A.35% Soltex 4208.45% EMAC2207.10% Kraton RP6509.10% Easmon PCCE9966.B.30% Soltex 4208.40% EMAC DS-1130.10% Xraton RP6509.15% PEU103-200.5% Eastman Ecctel 9966C.35% Soltex 40% EMAC DS1130.5% Kraton RP6509.10% PEU103-200.10% Kraton G1652.D.35% Soltex 4208.40% DS1130.10% Kraton RP6509.5% PEU103-200.10% Kraton G1652.
实施例5
(5)四组分组合物:PPE,EMA,改性SEBS,RF活性Enhancer合金(多于150种配方)组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性A 合格 20 30 3级 1 -20 合格 合格B 合格 20 25 3级 0 -25 合格 合格C 合格 20 20 4级 0 -30 合格 合格D 合格 20 20 4级 0 -30 合格 合格E 合格 25 30 4级 1 -25 合格 合格F 合格 20 25 4级 0 -30 合格 合格G 合格 >40 25 2级 1 -20 合格 合格A.45% Fina 7825.45% Chevron EMA(42%MA).10% Morton PEU 192-100.B.40% Soltex 4208.40% Chevron EMAC2250.10% Shell Kraton RP5509.10% PEU192-100.C.35% Soltex 4208.45% EMAC2250.10% Shell Kraton RP6509.10% PEU192-100.D.35% Soltex 4208.45% EMAC2260.10% Xraron G-1657.10% PEU103-200.E.40% Soltex 4208.40% EMAC2220T.10% Xraton RP6509.10% PEU103-200.F.35% Soltex 4208.40% E0S1130.10% kraton RP6509.15% PEU103-200.G.35% Mrtsuit MA moctitied PP ActmerSF700.40% EMAC DS1130.10% Kraton RP6509.15%.PEU103-200.
实施例6
(6)四组分组合物:PPE,ENBA,改性SEBS合金组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性A 合格 25 30 20 0 -20 合格 合格B 合格 25 30 20 0 -20 合格 合格A.40% Soltex 4208.40% Ouantum ENBABO807(35%BA).10% Kraton RP6509.10% PEU103-200.B.40% Soltex 4208.40% ENBABO808 (35%BA).10% Kraton.RP6509.10% PEU103-200
实施例7
(7)三和四组分组合物:PPE,乙烯/乙烯醇共聚物,聚酰胺,改性SEBS合金组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性A 合格 35 45 4 1 -30 合格 合格B 合格 25 40 2 1 -30 合格 合格C 合格 25 25 4 1 -30 合格 合格D 合格 35 50 4 1 -25 合格 合格E 合格 30 25 4 0 -30 合格 合格F 合格 25 45 4 0 -30 合格 合格G 合格 25 45 4 0 -30 合格 合格A.55% Soltex 4208.5% EVALCA LCE151A 40% Shell Kraton RP6509.B.55% Soltex 4208.5% EVALCA ES-G110A 5% Shell Xraton RP6509. 35% Shell Kraton 1652.C.50% Soltex 4208.5% EVALCA LCE1015A 42% Shell Xraton RP6509.3% PA-12.C.72% Soltex 4208.18% Xraton RP6509.10% EVALCA G-115AE.55% Soltex 4208.10% PA-12.35% Xraton G1901X.F.60% Soltex 4208.5% PA-12.35% Xraton RP6509.G.60% Soltex 4208.5% Verxxlon 1164.35% Kraton RP6509.
实施例8
(8)三和四组分组合物:PPE,EVA,酰胺基TPE,EMAA组合物(柔软组分和RF组分是相同的)组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Xpli) 增白 相容性 相容性A 合格 20% 20 4 0 -20C 合格 合格8 合格 30% 20 4 0 -25C 合格 合格C 合格 20 25 3 0 -25 合格 合格D 合格 25 25 3 0 -25 合格 合格E 合格 20 20 4 0 -30C 合格 合格F 合格 30 30 4 0 -20 合格 合格G 合格 >50% 约.60 3 1 -20 合格 合格H 合格 >50% 约.50 4 1 -25 合格 合格I 合格 >50% 约.55 4 1 -20 合格 合格J 合格 >50% 45 3 1 -25 合格 合格K 合格 >50% 40 4 1 -30 合格 合格L 合格 25 25 3 0 -30 合格 合格M 合格 20 25 4 1 -25 合格 合格O 合格 20 25 3 1 -30 合格 合格D 合格 20 25 3 1 -30 合格 合格C 合格 20 25 3 1 -30 合格 合格R 合格 20 25 3 1 -30 合格 合格A.35% Fina 7825.55% Dvoonl DVax 170 (35%VA).10% Shell Xraton RP6509.B.35% Soltex 4208.55% Evax 170.10% Kraton RP5509.C.40% Soltex 4208.50% Cuantum UE559.10% Kraton RP6509.D.40% Soltex 4208.50% UE634.10% Kraton RP6509.E.35% Soltax 4208.40% UE656.10% Xraton RP6609.10% Manon PEU 192-100.F.fmore ulan 100 fomutaoonsl.Fina. Soltex. BASF. REXENE PPs (45%).45% Cuanrum UE6-4. 10% Xrato RP6509.G.50% PEBAX 4033.35% Fina Z-7850.15% Shell Kraton G1901X.H.50% PEBAX 4033.20% Fina 8473.20% K-1901X.10% EVA (25% VA).L.50% PEBAX 2533.25% Fina 8473.15%K-1901X.10% EVA (28% VA).J.50% PEBAX 4033.20% EVA(28% VA).20% shell kraton G-1652.K.50% PEBAX 4033.20% PEBAX 2533.20% EVA(25% VA).L.30% Fina 7825.60% Monon PEU 103-200.10% Shell Kraton RP6509.M.35% Soltex 4208.55 Chevron DS1009.10% Shell Kraton RP6509.O.45% ltex 4208.45% Duoont Nucrel (EMAA) 925.10% Shell Xraton RP6509.P.45% Soltex 4208.45% Ouoont Nucrel -035.10% Kraton RP-6509.C.45% Soltax 4208.45% Duoont Evaloy EP4051 (ENBACO).10% Xraton RP-6509.
实施例9
(9)三组分组合物:PPE,EVA,酰胺基TPE合金(柔性和耐高温组分相同)组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性C 合格 25 30 3 0 -20 合格 合格D 合格 25 30 2 0 -20 合格 合格C.45% REXENE FPO 90007.45% Eivax170.10% Kraton RP6509.D.60% FPO 90007.30% EMAC(42%MA).10% Shell Kraton RP6509.
实施例10
(10)Tafmer,均态高无定形含量PP和PP无规共聚物组合物组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Kpli) 增白 相容性 相容性A 不合格 约25 22 0 0 -30 合格 合格B 合格 约20 31 0 0 -30 合格 合格C 不合格 约23 25 0 0 -30 合格 合格Novolene是BASF生产的高无定形含量同聚丙烯,Dypro8473是Cosden(Fina)生产的、乙烯含量约3.5%的丙烯和乙烯的无规共聚物。
实施例11(11)Tafmer,PP和聚丁烯-1合金组合物 热压减型性 雾度 强性 RF 应变 低温度 环境 溶液(%) (Xpli) 增白 相容性 相容性A 合格 约.25 17 0 0 -30 合格 合格B 合格 约.30 35 0 0 -30 合格 合格C 合格 约.20 15 0 0 -30 合格 合格Rexene 23M2是乙烯含量约为2%的无规聚丙烯-乙烯共聚物。PB-8010是壳牌化学公司生产的聚丁烯-乙烯共聚物。
Claims (6)
1.一种聚合物组合物,包含:
聚丙烯,含量占组合物重量的30-60%;
在1-60MHz和室温至250℃时介电损耗大于0.05的射频敏感聚合物,其含量为组合物重量的5-40%,该射频敏感聚合物选自ⅰ)聚酰胺、聚氨酯、聚酯、聚脲、聚酰亚胺、聚砜和ⅱ)具有50-85%重量乙烯的乙烯共聚物,其共单体选自乙酸乙烯酯和乙烯基醇;
相容化聚合物,为具有烃软段的苯乙烯嵌段共聚物,含量为5-40%重量;
能使该聚合物组合物具有柔韧性的增韧聚合物,其中的增韧聚合物选自超低密度聚乙烯、聚丁烯和丁烯-乙烯共聚物;
其中的增韧聚合物和聚丙烯一起占聚合物组合物重量的55%或更多;
其中相容化聚合物赋于耐热变形聚合物、射频敏感聚合物和增韧聚合物之间的相容性;
此组合物具有处于以下范围内的物理性质:
a<40000psi;
b≥70%;
c<30%;
d>1.0;
e<0.1%;
f<0.1%;
g≥0.05;
h≤60%;
其中:
a是根据ASTM D-882测定的组合物的力学模量;
b是在20%的初始变形后组合物在长度方向上的百分回复率;
c是根据ASTM D-1003在被加工成9密耳厚薄膜的组合物的光雾度;
d是在熔体加工温度下在1Hz时测定的组合物的损耗角正切;
e是组合物的元素卤的重量含量;
f是低分子量可溶物分数;
g是在温度从25至250℃和在1与60MHz之间时组合物的介电损耗;
h是1.89kg/cm2负荷下组合物2.54厘米条在121℃时测定的试样蠕变;以及其中
该组合物在50厘米/分的适中速度下被应变到100%伸长即二倍原始长度后未显示应变增白。
2.如权利要求1的组合物,其中的增韧聚合物是超低密度聚乙烯。
3.权利要求1或2的组合物,其中的聚酰胺选自由具有2-13个碳原子的二胺的缩合反应产生的脂肪族聚酰胺、由具有2-13个碳原子的二酸的缩合反应产生的脂肪族聚酰胺、由二聚脂肪酸的缩合反应产生的聚酰胺和含有酰胺的共聚物。
4.权利要求3的组合物,其中聚酰胺是二聚体的脂肪酸聚酰胺。
5.权利要求4的组合物,其中相容化聚合物是苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物。
6.权利要求5的组合物,其中相容化聚合物是马来酸酐官能化的苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物。
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US08/153,823 | 1993-11-16 | ||
US08/153,823 US5849843A (en) | 1993-11-16 | 1993-11-16 | Polymeric compositions for medical packaging and devices |
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CN1118604A CN1118604A (zh) | 1996-03-13 |
CN1066757C true CN1066757C (zh) | 2001-06-06 |
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1994
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- 1994-11-16 CZ CZ951745A patent/CZ174595A3/cs unknown
- 1994-11-16 EP EP00200435A patent/EP1008357A3/en not_active Ceased
- 1994-11-16 AU AU10998/95A patent/AU686697B2/en not_active Expired
- 1994-11-16 DE DE69425649T patent/DE69425649T2/de not_active Expired - Lifetime
- 1994-11-16 SG SG1995002070A patent/SG77527A1/en unknown
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- 1994-11-16 KR KR1019950702927A patent/KR100413572B1/ko not_active IP Right Cessation
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- 1994-11-16 DK DK95901945T patent/DK0679170T3/da active
- 1994-11-16 CA CA002153483A patent/CA2153483C/en not_active Expired - Lifetime
- 1994-11-16 CN CN94191203A patent/CN1066757C/zh not_active Expired - Lifetime
- 1994-11-16 WO PCT/US1994/013342 patent/WO1995014739A2/en not_active Application Discontinuation
- 1994-11-16 NZ NZ276644A patent/NZ276644A/en unknown
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1995
- 1995-06-05 US US08/461,050 patent/US5686527A/en not_active Expired - Lifetime
- 1995-06-05 US US08/463,983 patent/US5854347A/en not_active Expired - Fee Related
- 1995-06-05 US US08/464,453 patent/US6399704B1/en not_active Expired - Lifetime
- 1995-06-05 US US08/462,070 patent/US6881790B1/en not_active Expired - Fee Related
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1998
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Patent Citations (2)
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WO1983000158A1 (en) * | 1981-06-29 | 1983-01-20 | Abbott Lab | Clear, autoclavable thermoplastic formulation for medical liquid containers |
DE4142271A1 (de) * | 1991-12-20 | 1993-06-24 | Danubia Petrochem Deutschland | Verfahren zum schweissen von aus polyolefinen, polyamiden und haftvermittlern bestehenden formteilen durch hochfrequenzschweissung, sowie folien aus polyolefinen, polyamiden und haftvermittlern |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100462375C (zh) * | 2002-08-15 | 2009-02-18 | 弗纳技术股份有限公司 | 透明的抗冲击间规聚丙烯 |
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