CN104870181A - 含氟弹性体和耐热丙烯酸酯弹性体的层合体 - Google Patents
含氟弹性体和耐热丙烯酸酯弹性体的层合体 Download PDFInfo
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- CN104870181A CN104870181A CN201380065809.6A CN201380065809A CN104870181A CN 104870181 A CN104870181 A CN 104870181A CN 201380065809 A CN201380065809 A CN 201380065809A CN 104870181 A CN104870181 A CN 104870181A
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- polyamide
- curable
- acrylate copolymer
- lamilated body
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Abstract
本文公开了一种层合体结构,其包含可固化的含氟弹性体组合物层和聚酰胺填充的可固化的聚丙烯酸酯弹性体组合物层。还公开了一种用于制造此类层合体的方法。
Description
技术领域
本发明涉及包含含氟弹性体层和热稳定的丙烯酸酯弹性体层的层合体。
背景技术
对于它们对热空气老化优异的抗性,以及对燃料,诸如汽油、柴油和生物柴油的渗透性和溶胀的抗性,含氟弹性体为人们所熟知。含氟弹性体的主要缺点是它们的使用成本高。
聚丙烯酸酯弹性体具有对热空气老化和对燃料适度的抗性,但具有比含氟弹性体更低的使用成本。因此,已知在层合体结构中组合含氟弹性体层和聚丙烯酸酯弹性体层,使得含氟弹性体层与高温环境和/或燃料接触,而聚丙烯酸酯弹性体层对制品提供机械强度。此类构造尤其可用于机动车软管。然而,聚丙烯酸酯弹性体层适度的高温抗性可限制此类层合体在高温环境中的使用。
令人惊讶地,现已发现当在层合结构中的聚丙烯酸酯层包含10重量%至60重量%的具有高于160℃峰值熔融温度的聚酰胺分散体时,层合体表现出增强的特性。具体地,聚丙烯酸酯的热空气老化抗性显著地改善,从而使层合体将被用于更极端的使用条件。
发明内容
在一个方面,本发明提供了聚酰胺填充的聚丙烯酸酯共聚物弹性体和含氟弹性体的可固化的层合体,其包含:
A.可固化的含氟弹性体组合物层;和
B.可固化的聚丙烯酸酯共聚物弹性体组合物层,其包含
a.聚合物共混物,其包含
i.至少一种聚丙烯酸酯共聚物弹性体,其包含1)基于所述聚丙烯酸酯共聚物弹性体的总重量计至少50重量%的至少一种具有以下结构的单体的聚合单元
其中R1为H或C1-C10烷基,并且R2为C1-C12烷基、C1-C20烷氧基烷基、C1-C12氰基烷基或C1-C12氟代烷基;和
2)选自以下的固化位点单体的共聚单元:不饱和羧酸、不饱和羧酸的酸酐、不饱和环氧化物、以及它们中两种或更多种的混合物;和
ii.10-60重量%的一种或多种聚酰胺,其具有至少160℃的熔融峰温度;
其中A)所述聚合物共混物具有根据ASTM D6746-10测定的小于约2MPa的生胶强度,B)所述一种或多种聚酰胺作为不连续相存在于所述聚合物共混物中,并且C)所述一种或多种非晶态丙烯酸酯共聚物和一种或多种聚酰胺的重量百分比是基于聚合物共混物中的所述一种或多种非晶态丙烯酸酯共聚物和一种或多种聚酰胺的总重量计的;和
b)胺固化剂。
本发明的另一个方面为用于制备可固化的层合体的方法,所述可固化的层合体具有聚酰胺填充的丙烯酸酯共聚物弹性体组合物层和可固化的含氟弹性体组合物层,所述方法包括以下步骤
A.提供一种或多种丙烯酸酯共聚物弹性体,其包含
a)基于所述非晶态丙烯酸酯共聚物的总重量计至少50重量%的至少一种具有以下结构的单体的聚合单元
其中R1为H或C1-C10烷基,并且R2为C1-C12烷基、C1-C20烷氧基烷基、C1-C12氰基烷基或C1-C12氟代烷基;和
b)选自以下的固化位点单体的共聚单元:不饱和羧酸、不饱和羧酸的酸酐、不饱和环氧化物、以及它们中两种或更多种的混合物;
B.提供一种或多种具有至少160℃熔融峰温度的聚酰胺;
C.在高于所述一种或多种聚酰胺熔的融峰温度的温度下将所述聚丙烯酸酯共聚物弹性体和聚酰胺混合,从而形成基于所述一种或多种聚酰胺和一种或多种聚丙烯酸酯的总重量计包含10重量%至60重量%聚酰胺的聚合物共混物;
D.将所述聚合物共混物冷却至低于一种或多种聚酰胺结晶峰温度的温度,从而形成聚酰胺填充的聚丙烯酸酯共聚物弹性体组合物,其i)包含连续的非晶态丙烯酸酯共聚物弹性体相和不连续的聚酰胺相并且ii)具有根据ASTM D 6746-10测定的小于约2MPa的生胶强度;
E.在低于聚酰胺峰值熔融温度的温度下将胺固化剂加入所述聚合物共混物中以形成可固化的聚丙烯酸酯弹性体组合物;
F.提供可固化的含氟弹性体组合物;以及
G.形成包含所述可固化的聚丙烯酸酯弹性体组合物层和所述可固化的含氟弹性体组合物层的层合体结构。
具体实施方式
本发明涉及包含可固化的含氟弹性体组合物层和可固化的聚酰胺填充的聚丙烯酸酯弹性体组合物层的层合体。所述两层可直接接触或粘合剂和/或接合层可介于含氟弹性体层和聚酰胺填充的聚丙烯酸酯弹性体层之间。
由于它们优异的高耐温性和低燃料渗透性,本发明的层合体可用于软管、振动膜、垫圈、密封圈和填料。
适用于本发明的含氟弹性体为多羟基或二胺可固化的那些可由有机过氧化物和多官能团助剂固化的那些。
“多羟基可固化”是指已知与多羟基固化剂如双酚AF交联的含氟弹性体。“二胺可固化”是指已知与二胺固化剂例如己二胺氨基甲酸盐交联的含氟弹性体。此类含氟弹性体包括沿着弹性体聚合物主链具有多个碳-碳双键的那些,以及包含易于脱氟化氢的位点的含氟弹性体。后一种含氟弹性体包括但不限于包含邻近的偏二氟乙烯(VF2)和六氟丙烯(HFP)共聚单元的那些,以及包含邻近的VF2(或四氟乙烯)和氟化共聚单体共聚单元的含氟弹性体,所述氟化共聚单体具有酸性氢原子,如2-氢五氟丙烯;1-氢五氟丙烯;三氟乙烯;2,3,3,3-四氟丙烯;或3,3,3-三氟丙烯。优选的多羟基可固化含氟弹性体包括i)偏二氟乙烯与六氟丙烯以及任选的四氟乙烯(TFE)的共聚物;ii)偏二氟乙烯与全氟(烷基乙烯基醚)如全氟(甲基乙烯基醚)、2-氢五氟乙烯以及任选的四氟乙烯的共聚物;iii)四氟乙烯与丙烯和3,3,3-三氟丙烯的共聚物;iv)四氟乙烯、全氟(甲基乙烯基)醚和六氟-2-(五氟苯氧基)-1-(三氟乙烯氧基)丙烷的共聚物;以及v)乙烯与四氟乙烯、全氟(甲基乙烯基)醚和3,3,3-三氟丙烯的共聚物。
除含氟弹性体之外,本发明的多羟基可固化的含氟弹性体组合物还包含多羟基固化体系,其是指多羟基固化剂和硫化(或固化)促进剂。
可固化组合物包含每100重量份含氟弹性体0.4至4重量份(优选1至2.5份),即0.4-4phr(优选1-2.5phr)的多羟基固化剂(或其衍生物)。典型的多羟基交联剂包括二羟基、三羟基和四羟基的苯、萘和蒽,以及下式的双酚
其中A为1-13个碳原子的双官能的脂族、脂环族或芳族基团,或者硫基、氧基、羰基、亚磺酰基或磺酰基;A可任选被至少一个氯原子或氟原子取代;x为0或1;n为1或2;并且多羟基化合物的任何芳环可任选地被至少一个氯原子或氟原子、氨基、-CHO基团或羧基或酰基取代。优选的多羟基化合物包括六氟亚异丙基-双(4-羟基-苯)(即双酚AF或BPAF);4,4′-亚异丙基二酚(即双酚A);4,4′-二羟基二苯砜;以及二氨基双酚AF。关于以上所示的双酚式,当A为亚烷基时,其可以是例如亚甲基、亚乙基、氯代亚乙基、氟代亚乙基、二氟亚乙基、亚丙基、亚异丙基、三亚丁基(tributylidene)、七氯亚丁基、七氟亚丁基、亚戊基、亚己基、以及1,1-环亚己基。当A为亚环烷基时,其可以是例如1,4-亚环己基、2-氯-1,4-亚环己基、亚环戊基或2-氟-1,4-亚环己基。此外,A可以是亚芳基如间亚苯基、对亚苯基、邻亚苯基、甲基亚苯基、二甲基亚苯基、1,4-亚萘基、3-氟-1,4-亚萘基以及2,6-亚萘基。下式的多羟基酚
或者
其中R为H或具有1-4个碳原子的烷基或包含6-10个碳原子的芳基,并且R′为包含1-4个碳原子的烷基,它们也用作有效的交联剂。此类化合物的示例包括对苯二酚、儿茶酚、间苯二酚、2-甲基间苯二酚、5-甲基间苯二酚、2-甲基对苯二酚、2,5-二甲基对苯二酚、2-叔丁基对苯二酚;以及这样的化合物如1,5-二羟基萘和2,6-二羟基萘。
另外的多羟基固化剂包括双酚阴离子的碱金属盐、双酚阴离子的季铵盐、双酚阴离子的叔锍盐、以及双酚阴离子的季盐。具体示例包括双酚AF的二钠盐、双酚AF的二钾盐、双酚AF的单钠单钾盐、以及双酚AF的苄基三苯基盐。
双酚阴离子的季铵盐和季盐描述于美国专利4,957,975和5,648,429中。具有式R1R2R3R4N+的季铵离子的双酚AF盐(1∶1摩尔比)是优选的,其中R1-R4是C1-C8烷基,并且R1-R4中至少三个是C3或C4烷基。这些优选组合物的具体示例包括四丙基铵双酚AF、甲基三丁基铵双酚AF和四丁基铵双酚AF的1∶1摩尔比的盐。此类盐可通过多种方法制备。例如,可将双酚AF的甲醇溶液与季铵盐的甲醇溶液混合,然后用甲醇钠升高pH值,促使无机的钠盐沉淀。在过滤后,可通过蒸去甲醇将四烷基铵/BPAF盐从溶液中分离出来。作为另外一种选择,可使用氢氧化四烷基铵的甲醇溶液代替季铵盐溶液,因此免去了无机盐的沉淀并且不需要在蒸发溶液之前将其除去。
此外,衍生的多羟基化合物如单酯或二酯、以及三甲基甲硅烷基醚是有用的交联剂。此类组分的示例包括,但不限于间苯二酚单苯甲酸酯、双酚AF的二乙酸酯、磺酰联苯酚的二乙酸酯、以及对苯二酚的二乙酸酯。
可用于可固化含氟弹性体组合物中的硫化促进剂(也被称为固化促进剂)包括叔锍盐,例如[(C6H5)2S+(C6H13)][Cl]-、和[(C6H13)2S(C6H5)]+[CH3CO2]-以及式R5R6R7R8Y+X-的季铵盐、盐、盐和锑鎓盐,其中Y为磷、氮、砷、或者锑;R5、R6、R7、和R8各自为C1-C20烷基、芳基、芳烷基、链烯基,以及它们的氯、氟、溴、氰基、-OR和-COOR取代的类似物(同时R为C1-C20烷基、芳基、芳烷基、链烯基),并且其中X是卤离子、氢氧根、硫酸根、亚硫酸根、碳酸根、五氯硫酚根、四氟硼酸根、六氟硅酸根、六氟磷酸根、二甲基磷酸根,以及C1-C20烷基、芳基、芳烷基和链烯基羧酸根和二羧酸根。尤其优选氯化苄基三苯基溴化苄基三苯基四丁基硫酸氢铵、氢氧化四丁基铵、氢氧化四丙基铵、溴化四丁基铵、氯化三丁基烯丙基氯化三丁基-2-甲氧基丙基1,8-二氮杂二环[5.4.0]十一碳-7-烯、以及氯化苄基二苯基(二甲基氨基)其它有用的促进剂包括甲基三辛基氯化铵、甲基三丁基氯化铵、四丙基氯化铵、苄基三辛基溴化苄基三辛基氯化甲基三辛基乙酸四辛基溴化甲基三苯基四氟硼酸四苯基溴化锑、4-氯苄基三苯基氯化8-苄基-1,8-二氮杂二环(5.4.0)-7-十一碳烯铵氯化物、二苯基甲基三苯基氯化烯丙基三苯基氯化四丁基溴化间三氟甲基苄基三辛基氯化以及公开在美国专利5.591.804、4,912,171、4,882,390、4,259,463、4,250,278和3,876,654中的其他四价化合物。所用促进剂的量介于每百重量份含氟弹性体0.05和2重量份(0.05-2phr)之间。优选地,每一百份含氟弹性体使用0.1至1.0份促进剂。
“过氧化物可固化”是指包含沿聚合物链、在链末端或同时在这两个位置上的Br或I固化位点的含氟弹性体。
沿含氟弹性体链的固化位点通常是由于包含溴或碘原子的共聚的固化位点单体的存在。合适的固化位点单体的示例包括但不限于:i)含溴烯烃;ii)含碘烯烃;iii)含溴乙烯基醚;以及iv)含碘乙烯基醚;
溴化的固化位点单体可包含其它卤素,优选氟。溴化烯烃固化位点单体的示例是CF2=CFOCF2CF2CF2OCF2CF2Br;溴化三氟乙烯;4-溴-3,3,4,4-四氟丁烯-1(BTFB);以及其它的,例如溴乙烯,1-溴-2,2-二氟乙烯;全氟丙烯基溴;4-溴-1,1,2-三氟-1-丁烯;4-溴-1,1,3,3,4,4,-六氟丁烯;4-溴-3-氯-1,1,3,4,4-五氟丁烯;6-溴-5,5,6,6-四氟己烯;4-溴全氟-1-丁烯和3,3-二氟丙烯基溴。可用于本发明的溴化乙烯基醚固化位点单体包括2-溴-全氟乙基全氟乙烯醚和CF2Br-Rf-O-CF=CF2(Rf为全氟亚烷基)类氟化化合物如CF2BrCF2O-CF=CF2,以及ROCF=CFBr或ROCBr=CF2(其中R为低级烷基或氟代烷基)类氟代乙烯基醚如CH3OCF=CFBr或CF3CH2OCF=CFBr。
适宜的碘化固化位点单体包括具有下式的碘化烯烃:CHR=CH-Z-CH2CHR-I,其中R为-H或-CH3;Z为任选地包含一个或多个醚氧原子的直链或支化的C1-C18(全)氟亚烷基,或如美国专利5,674,959中所公开的(全)氟聚氧化亚烷基。有用的碘化固化位点单体的其它示例是下式的不饱和醚:I(CH2CF2CF2)nOCF=CF2和ICH2CF2O[CF(CF3)CF2O]nCF=CF2等等,其中n=1-3,诸如美国专利5,717,036中所公开的。此外,包括碘乙烯、4-碘-3,3,4,4-四氟丁烯-1(ITFB);3-氯-4-碘-3,4,4-三氟丁烯;2-碘-1,1,2,2-四氟-1-(乙烯氧基)乙烷;2-碘-1-(全氟乙烯氧基)-1,1,-2,2-四氟乙烯;1,1,2,3,3,3-六氟-2-碘-1-(全氟乙烯氧基)丙烷;2-碘乙基乙烯基醚;3,3,4,5,5,5-六氟-4-碘戊烯;和碘三氟乙烯在内的适宜的碘化固化位点单体公开于美国专利4,694,045中。烯丙基碘和2-碘-全氟乙基全氟乙烯醚也是有用的固化位点单体。
除了(或代替)含Br或I的固化位点单体以外,由于在含氟弹性体制备期间使用链转移剂或分子量调节剂,因此含碘端基、含溴端基或它们的混合物可任选存在于含氟弹性体聚合物链的一端或两端。当使用时,计算链转移剂的量以使得含氟弹性体中碘或溴的含量在0.005-5重量%,优选0.05-3重量%范围内。
链转移剂的示例包括含碘化合物,其致使键合的碘原子结合在聚合物分子的一端或两端上。二碘甲烷;1,4-二碘全氟-正丁烷;和1,6-二碘-3,3,4,4-四氟己烷是此类剂的代表。其它碘化链转移剂包括1,3-二碘全氟丙烷;1,6-二碘全氟己烷;1,3-二碘-2-氯全氟丙烷;1,2-双(碘二氟甲基)-全氟环丁烷;一碘全氟乙烷;一碘全氟丁烷;2-碘-1-氢全氟乙烷等等。还包括欧洲专利0868447A1中所公开的氰基-碘链转移剂。尤其优选二碘化链转移剂。
溴化链转移剂的示例包括1-溴-2-碘全氟乙烷;1-溴-3-碘全氟丙烷;1-碘-2-溴-1,1-二氟乙烷以及其它(诸如美国专利5,151,492中所公开的)。
适用于本发明组合物中的有机过氧化物包括但不限于1,1-双(叔丁过氧基)-3,5,5-三甲基环己烷;1,1-双(叔丁过氧基)环己烷;2,2-双(叔丁过氧基)辛烷;正丁基-4,4-双(叔丁过氧基)戊酸酯;2,2-双(叔丁过氧基)丁烷;2,5-二甲基己烷-2,5-二羟基过氧化物;二叔丁基过氧化物;过氧化叔丁基异丙苯;过氧化二异丙苯;α,α′-双(叔丁过氧基间异丙基)苯;2,5-二甲基-2,5-二(叔丁过氧基)己烷;2,5-二甲基-2,5-二(叔丁过氧基)己烯-3;过氧化苯甲酰、叔丁基过氧基苯;2,5-二甲基-2,5-二(过氧化苯甲酰)-己烷;叔丁基过氧化马来酸;以及叔丁基过氧化异丙基碳酸。有机过氧化物的优选的示例包括2,5-二甲基-2,5-二(叔丁过氧基)己烷、过氧化二异丙苯,以及α,α′-双(叔丁过氧基间异丙基)苯。复合量一般在每100重量份含氟弹性体0.05-5重量份的范围内,优选地在0.1-3重量份的范围内。此外,所述有机过氧化物可以单独使用或以两种或更多种的组合使用。
本发明可固化组合物中使用的助剂为多官能团的不饱和化合物,例如氰尿酸三烯丙酯、异氰脲酸三甲基丙烯酯、异氰脲酸三烯丙酯、异氰脲酸三甲烯丙酯、二甲氧基甲烷三丙烯酯、偏苯三酸三烯丙酯、N,N′-间亚苯基双马来酰亚胺、邻苯二甲酸二烯丙基酯、四烯丙基对苯二甲酰胺、三(二烯丙基胺)-均三嗪、三烯丙基亚磷酸盐、双烯烃以及N,N-二烯丙基丙烯酰胺。复合量一般在每100重量份含氟弹性体0.1-10重量份的范围内。优选的助剂范围为每100重量份含氟弹性体0.2-6重量份。所述不饱和的化合物可以单独使用或以两种或更多种的组合使用。
适用于本发明层合体的可固化的含氟弹性体组合物通过在密炼机或橡胶磨中组合含氟弹性体、固化剂和任何其它成分制成。优选含氟弹性体为可用过氧化物固化的含氟弹性体。
可用于本文所述的本发明实践中的聚丙烯酸酯共聚物弹性体包含a)至少一种丙烯酸的烷基酯和/或烷氧基烷基酯和b)固化位点单体的共聚单元。此类适宜的丙烯酸的烷基酯和/或烷氧基烷基酯的示例包括丙烯酸烷基酯和丙烯酸烷氧基烷基酯以及其中丙烯酸被C1-C10烷基取代的物质。此类物质的示例包括甲基丙烯酸烷基酯、乙基丙烯酸烷基酯、丙基丙烯酸烷基酯、以及己基丙烯酸烷基酯、甲基丙烯酸烷氧基烷基酯、乙基丙烯酸烷氧基烷基酯、丙基丙烯酸烷氧基烷基酯、以及己基丙烯酸烷氧基烷基酯。此外,丙烯酸酯的烷基酯基团还可被氰基或一个或多个氟原子取代。即,酯基将为C1-C12氰基烷基或C1-C12氟代烷基。丙烯酸酯共聚物还可包含多于一种烷基酯和/或烷氧基烷基酯,例如两种丙烯酸烷基酯的共聚单元。
丙烯酸的烷基酯和烷氧基烷基酯以及取代的丙烯酸优选为丙烯酸或甲基丙烯酸的C1-C12烷基酯或丙烯酸或甲基丙烯酸的C1-C20烷氧基烷基酯。此类酯的示例包括丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸2-乙基己基酯、乙基丙烯酸2-甲氧基酯、乙基丙烯酸2-乙氧基酯、乙基丙烯酸2-(正丙氧基)酯、乙基丙烯酸2-(正丁氧基)酯、丙基丙烯酸3-甲氧基酯以及丙基丙烯酸3-乙氧基酯。包含C1-C12氰基烷基和氟代烷基的酯的示例包括甲基丙烯酸氰基酯、乙基丙烯酸1-氰基酯、丙基丙烯酸2-氰基酯、丙基丙烯酸3-氰基酯、丁基丙烯酸4-氰基酯、甲基丙烯酸1,1-二氢全氟乙基酯、丙烯酸1,1-二氢全氟乙基酯、甲基丙烯酸1,1-二氢全氟丙基酯、丙烯酸1,1-二氢全氟丙基酯、和(甲基)丙烯酸1,1,5-三氢全氟己基酯以及甲基丙烯酸1,1,5-三氢全氟己基酯。优选地,酯基将包含C1-C8烷基。更优选地,酯基将包含C1-C4烷基。尤其有用的丙烯酸烷基酯为丙烯酸甲酯、丙烯酸乙酯以及丙烯酸丁酯。尤其有用的甲基丙烯酸烷基酯为甲基丙烯酸甲酯。在不脱离本发明的范围的情况下,可在聚合物中掺入微量不饱和乙酸酯诸如乙酸乙烯酯、或乙酸3-丁烯酯。所谓微量是指基于丙烯酸酯共聚物的重量计小于1重量%。
包含丙烯酸酯共聚物中的共聚单元的酯一般可由下式表示:
其中R1为H或C1-C10烷基,并且R2为C1-C12烷基、C1-C20烷氧基烷基、C1-C12氰基烷基、或C1-C12氟代烷基。
在某些实施例中,丙烯酸酯共聚物可衍生自多于一种的丙烯酸酯单体,例如第一丙烯酸烷基酯、第二丙烯酸烷基酯、以及任选地1,4-丁烯二酸的单烷基酯的共聚。此类组合物的示例包括丙烯酸甲酯和丙烯酸丁酯的共聚物以及丙烯酸甲酯、丙烯酸丁酯、以及1,4-丁烯二酸的单乙基酯的共聚物。
存在于这些丙烯酸酯共聚物中的丙烯酸酯共聚单体的浓度将为基于所述共聚物的重量计至少50重量%。优选地,浓度将为至少55重量%,并且更优选至少60重量%。如果丙烯酸酯的浓度低于50重量%,则例如在为乙烯丙烯酸酯共聚物的聚合物中,存在一些结晶度的可能性高。丙烯酸酯共聚物中的结晶度使固化后的组合物的弹性性能下降。此外,高含量的非极性单体如乙烯降低了丙烯酸酯共聚物与聚酰胺的相容性,并因此将影响固化后的组合物的物理性能,诸如拉伸和抗撕强度。
用于本发明实践的丙烯酸酯共聚物包含选自以下的共聚固化位点单体单元:不饱和羧酸、不饱和羧酸的酸酐、不饱和环氧化物、以及它们中两种或更多种的混合物。这些固化位点单体单元包含与胺和/或其它含氮物质如氨基甲酸盐反应的化学基团(例如羧基和环氧基)。
不饱和羧酸包括例如丙烯酸和甲基丙烯酸、1,4-丁烯二酸、柠康酸、以及1,4-丁烯二酸的单烷基酯。在聚合前,1,4-丁烯二酸可以顺式或反式或两者,即马来酸或富马酸的形式存在。有用的可聚合固化位点单体还包括不饱和羧酸的酸酐,例如马来酸酐、柠康酸酐以及衣康酸酐。优选的固化位点单体包括马来酸及其半酸酯(单酯)或二酯中任一种,具体地甲基或乙基半酸酯(例如马来酸单乙酯);富马酸及其半酸酯或二酯中的任一种,具体地甲基、乙基、或丁基半酸酯;以及衣康酸的单烷基和单芳烷基酯。这些共聚固化位点单体的存在产生表现出良好烧焦安全性的可固化的丙烯酸酯共聚物组合物,这是指固化位点在小于约120℃的温度下与胺缓慢反应或根本不反应,但是仍然允许在较高温度下快速交联。
有用的不饱和环氧化物的示例包括例如(甲基)丙烯酸缩水甘油酯、烯丙基缩水甘油醚、缩水甘油基乙烯基醚、以及包含脂环族环氧树脂的(甲基)丙烯酸酯。
优选地,基于所述共聚物中单体的总摩尔数计,丙烯酸酯共聚物胶状橡胶包含至少0.3mol%,更优选地至少0.4mol%,并且最优选地多于0.5mol%的含胺反应性基团的固化位点单体单元。尽管丙烯酸酯共聚物中的固化位点含量必须足以在固化和后固化过程期间产生交联网络,但是高含量的固化位点单体趋于不利地影响本发明固化后的组合物的热老化性能。优选地,丙烯酸酯共聚物包含小于1.4mol%固化位点,更优选地小于1.2mol%,并且最优选地小于1.0mol%。很多实施例的优选范围为0.3mol%-1.0mol%固化位点单体单元。当两种或更多种丙烯酸酯共聚物存在于本发明聚酰胺填充的组合物的丙烯酸酯共聚物组分中时,约0.3至1.0mol%胺反应性固化位点的范围适用于固化位点占各个丙烯酸酯共聚物的摩尔百分比的重均分子量。当存在多于一种丙烯酸酯共聚物时,这适用于固化位点单体的其它mol%范围。
在很多实施例中,用于本发明实践中的丙烯酸酯共聚物还将包含附加共聚单体的共聚单元,例如乙烯和/或其它烯烃诸如丙烯、1-丁烯、1-己烯、1-辛烯等。基于所述丙烯酸酯共聚物的重量计,烯烃将以小于50重量%,更优选地小于45重量%,并且最优选地约40重量%或更小的浓度存在。具有胺可硫化基团的乙烯丙烯酸烷基酯共聚物橡胶是尤其适用于本文所述的组合物和方法中的丙烯酸酯共聚物。此类橡胶的示例为乙烯丙烯酸弹性体,购自E.I.du Pont de Nemours and Company。
由于聚合物链主链中存在包含环氧树脂、羧酸、羧酸酐和/或羧酸酯部分的共聚单体单元,因而用于本发明实践的丙烯酸酯共聚物是可固化,即可交联的。在芳族聚酰胺或脂族聚酰胺,优选二胺的存在下,此类化学基团可参与热引发的化学反应。
包含本文所述可固化的丙烯酸酯共聚物组合物中的一种组分的聚合物共混物组合物包含一种或多种聚酰胺,所述聚酰胺具有根据ASTM D3418-08测定的至少约160℃,优选地小于270℃的熔融峰温度。更优选地,一种或多种聚酰胺具有至少180℃,最优选至少200℃的熔融峰温度。优选地,聚酰胺在丙烯酸酯弹性体固化温度下为固体,意味着固化温度小于熔融峰温度。不受理论的束缚,当聚酰胺在固化温度下不是固体时,固化剂容易扩散入聚酰胺中,致使共混物难以固化。聚酰胺树脂在本领域中为人们所熟知并涵盖那些重均分子量为至少5,000的半结晶树脂,并包括那些通常称为尼龙的组合物。从而,用于本发明实践中的聚酰胺组分包括聚酰胺和聚酰胺树脂,诸如尼龙6、尼龙7、尼龙6/6、尼龙6/10、尼龙6/12、尼龙11、尼龙12、包含芳族单体的聚酰胺、以及聚酰胺嵌段共聚物诸如共聚(酰胺-醚)或共聚(酰胺-酯)。树脂可以任何物理形式,诸如任意形状或大小的粒料或颗粒,包括纳米颗粒。
聚酰胺树脂的粘度在满足本发明目的同时可广泛变化。为确保聚酰胺在丙烯酸酯弹性体的连续相内分散,希望聚酰胺具有根据ASTM D2857-95,使用96重量%硫酸作为溶剂于25℃的测试温度下所测量的,大于0.9dL/g,更优选地大于1.1dL/g,并且最优选地大于1.3dL/g的特性粘度。
一般来讲,因为丙烯酸酯共聚物共混物中的聚酰胺浓度增加,所以更期望使用较高特性粘度的聚酰胺。在某些实施例中,可能期望具有约60meq/Kg或更大的高含量胺端基的聚酰胺并允许使用特性粘度为约0.89dL/g的低粘度聚酰胺。这种高胺端基含量导致了丙烯酸酯橡胶的固化位点与聚酰胺胺端基之间的接枝反应,所述反应可有助于聚酰胺分散在丙烯酸酯橡胶中。然而,在一些情况下,使用这种高胺含量的聚酰胺可导致丙烯酸酯橡胶在与聚酰胺熔融混合期间凝胶,从而使得后续加工更加困难。当丙烯酸酯共聚物中的聚酰胺浓度增加时,丙烯酸酯弹性体的凝胶更加成为问题。
聚酰胺树脂可通过等摩尔量的包含4至12个碳原子的饱和二羧酸与二胺缩聚而制备,其中二胺包含4至14个碳原子。为提升丙烯酸酯橡胶与尼龙之间的粘附性,优选地聚酰胺将包含一些胺端基。由二酸和二胺聚合获得的聚酰胺类型可包含一些具有两个胺基的分子。在这种情况下,聚酰胺与丙烯酸酯橡胶的某些组合可略微交联或凝胶,以便产生具有失能挤出可加工性的组合物。通过开环聚合反应而制得的聚酰胺类型,诸如尼龙6,或仅基于氨基羧酸的诸如尼龙7或11的那些是最优选的,因为其避免了在与丙烯酸橡胶共混期间交联的可能性。此类聚酰胺类型各自包含具有最多一个胺基的分子。
聚酰胺的示例包括聚己二酰己二胺(66尼龙)、聚壬二酰己二胺(69尼龙)、聚癸二酰己二胺(610尼龙)、以及聚十二烷二酰己二胺(612尼龙)、通过内酰胺的开环而产生的聚酰胺即聚己内酰胺、聚月桂酸内酰胺、聚-11-氨基十一烷酸以及双(对氨基环己基)甲烷十二烷酰胺。还可使用通过上述聚合物中的两种共聚或上述聚合物或其组分三元共聚而制得的聚酰胺,例如己二酸间苯二甲酸己二胺共聚物。
通常,聚酰胺为一种或多种二羧酸和一种或多种二胺,和/或一种或多种氨基羧酸的缩合产物,和/或一种或多种环状内酰胺的开环聚合反应产物。聚酰胺可为全脂族或半芳族的。
用于本发明实践中的全脂族聚酰胺由脂族和脂环族单体(诸如二胺、二羧酸、内酰胺、氨基羧酸、以及它们的反应性等同物)形成。合适的氨基羧酸为11-氨基十二烷酸。合适的内酰胺为己内酰胺和月桂内酰胺。在本发明的上下文中,术语“全脂族聚酰胺”也指来源于两种或更多种此类单体的共聚物以及两种或更多种全脂族聚酰胺的共混物。可使用直链、支化和环状的单体。
全脂族聚酰胺中包含的羧酸单体包括但不限于脂族羧酸,诸如例如己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、十三烷二酸、十四烷二酸和十五烷二酸。二胺可选自具有四个或更多个碳原子的二胺,包括但不限于丁二胺、己二胺、辛二胺、癸二胺、十二碳二胺、2-甲基戊二胺、2-乙基-丁二胺、2-甲基辛二胺、三甲基己二胺、间苯二甲基二胺、和/或它们的混合物。
半芳族聚酰胺也适用于本发明。此类聚酰胺为由包含芳基的单体形成的均聚物、二聚物、三聚物或高阶聚合物。一种或多种芳族羧酸可为对苯二甲酸或对苯二甲酸与一种或多种其他羧酸(诸如间苯二甲酸、邻苯二甲酸、2-甲基对苯二甲酸和萘二甲酸)的混合物。此外,一种或多种芳族羧酸可与一种或多种脂族二羧酸混合。作为另外一种选择,可使用芳族二胺(如间苯二甲基二胺)提供半芳族聚酰胺,其示例为包含间苯二甲基二胺和己二酸的均聚物。
嵌段共聚(酰胺)共聚物也适合用作聚酰胺组分,所述组分具有的聚酰胺嵌段的熔融峰温度为至少160℃。如果低软化点材料包含嵌段共聚(酰胺)共聚物,例如聚醚低聚物或聚亚烷基醚如聚环氧乙烷,则嵌段聚合物将为共聚(酰胺-醚)。如果嵌段共聚(酰胺)共聚物的低软化点材料包含酯,例如聚内酯如聚己内酯,则嵌段共聚物将为共聚(酰胺-酯)。任何此类低软化点材料可用于形成嵌段共聚(酰胺)共聚物。任选地,嵌段共聚(酰胺)共聚物的低软化点材料可包括混合物,例如上述低软化点材料中任一种的混合物。此外,所述低软化点材料的混合物可以无规或嵌段排列的形式存在,或以它们的混合物的形式存在。优选地,嵌段共聚(酰胺)共聚物为嵌段共聚(酰胺-酯)、嵌段共聚(酰胺-醚)、或它们的混合物。更优选地,嵌段共聚(酰胺)共聚物为至少一种嵌段共聚(酰胺-醚)或它们的混合物。适宜的可商购获得的热塑性共聚(酰胺-醚)包括得自Elf-Atochem的聚醚嵌段酰胺,其包括4033和6333。最优选地,聚酰胺不是嵌段共聚(酰胺-醚)或共聚(酰胺-酯)。其它聚酰胺一般具有更高的熔融峰温度并且在增强丙烯酸酯弹性体方面更有效。与缺少聚醚嵌段的常规聚酰胺相比,聚(酰胺-醚)还表现出较差的热空气老化。
优选的聚酰胺为均聚物或共聚物,其中术语共聚物是指具有两种或更多种酰胺和/或二酰胺分子重复单元的聚酰胺。
聚酰胺组分可包含一种或多种聚酰胺,其选自组I聚酰胺,所述组I聚酰胺具有至少约160℃但是小于约210℃的熔融峰温度,并包含脂族或半芳族聚酰胺,例如聚(癸二酰戊二胺)、聚(十二烷二酰戊二胺)、聚(ε-己内酰胺/己二酰己二胺)、聚(ε-己内酰胺/癸二酰己二胺)、聚(12-氨基十二烷酰胺)、聚(12-氨基十二烷酰胺/对苯二甲丁酰胺)、以及聚(十二烷二酰十二碳二胺);组(II)聚酰胺,其具有至少约210℃的熔融峰温度,并包含选自以下的脂族聚酰胺:聚(己二酰丁二胺)、聚(ε-己内酰胺)、聚(己二酰己二胺)、聚(十二烷二酰己二胺)、以及聚(十四烷二酰己二胺);组(III)聚酰胺,其具有至少约210℃的熔融峰温度,并且包含约20至约35摩尔%的半芳族重复单元,所述半芳族重复单元衍生自选自以下中的一种或多种的单体:(i)具有8至20个碳原子的芳族二羧酸,和具有4至20个碳原子的脂族二胺;以及约65至约80摩尔%的脂族重复单元,所述脂族重复单元衍生自选自以下中的一种或多种的单体:具有6至20个碳原子的脂族二羧酸和具有4至20个碳原子的所述脂族二胺;以及具有4至20个碳原子的内酰胺和/或氨基羧酸;组(IV)聚酰胺,其包含约50至约95摩尔%的半芳族重复单元,所述半芳族重复单元衍生自选自以下中的一种或多种的单体:具有8至20个碳原子的芳族二羧酸,和具有4至20个碳原子的脂族二胺;以及约5至约50摩尔%的脂族重复单元,所述脂族重复单元衍生自选自以下中的一种或多种的单体:具有6至20个碳原子的脂族二羧酸和具有4至20个碳原子的所述脂族二胺;以及具有4至20个碳原子的内酰胺和/或氨基羧酸;组(V)聚酰胺,其具有至少约260℃的熔融峰温度,包含大于95摩尔%的半芳族重复单元,所述半芳族重复单元衍生自选自以下中的一种或多种的单体:具有8至20个碳原子的芳族二羧酸和具有4至20个碳原子的脂族二胺;以及小于5摩尔%的脂族重复单元,所述脂族重复单元衍生自选自以下中的一种或多种的单体:具有6至20个碳原子的脂族二羧酸和具有4至20个碳原子的所述脂族二胺;以及具有4至20个碳原子的内酰胺和/或氨基羧酸。聚酰胺还可为两种或更多种聚酰胺的共混物。
优选的聚酰胺包括尼龙6、6/6、以及熔融峰温度小于约270℃并且胺端基浓度为60meq或更小的组IV聚酰胺。这些聚酰胺具有足够高的熔融峰温度,以便不限制可固化的聚酰胺填充的丙烯酸酯共聚物的应用范围,但是不太高使得共混物的制备造成丙烯酸酯共聚物的显著降解。还优选通过氨基羧酸的开环或缩合而形成的聚酰胺。
适用于本发明中的聚酰胺可广泛地商购获得,例如购自E.I.du Pont deNemours and Company,Wilmington,Delaware,USA的树脂,购自Lanxess,Germany的树脂,以及购自BASF,USA的树脂。
优选地,填充的丙烯酸酯共聚物组合物的聚酰胺组分以大约球形颗粒的形式存在于丙烯酸酯共聚物中。颗粒的尺寸相对不重要,但是当大多数颗粒的直径为约1微米或更小时,固化后的组合物的拉伸强度变得最佳。可使用常规技术将此类组合物混合、模塑和/或挤出以制备可固化的组合物,所述可固化的组合物可与常规固化剂体系交联以形成各种弹性体制品。
聚合物共混物组合物为本发明可固化的聚酰胺填充的丙烯酸酯共聚物组合物的组分,其包含基于所述丙烯酸酯共聚物和聚酰胺组分的总重量计40-90重量%的本文所述的非晶态丙烯酸酯共聚物组分和10-60重量%的本文所述的聚酰胺组分。非晶态丙烯酸酯共聚物组分可由适用于本发明实践中的一种或多种本文所述类型的丙烯酸酯共聚物组成。相似地,聚酰胺组分可由适用于本发明实践中的一种或多种本文所述类型的聚酰胺组成。优选地,可固化的组合物将包含基于所述丙烯酸酯共聚物和聚酰胺组分的总重量计50至80重量%丙烯酸酯共聚物组分和20至50重量%聚酰胺组分。更优选地,可固化的组合物将包含基于所述丙烯酸酯共聚物和聚酰胺组分的总重量计55至70重量%丙烯酸酯共聚物组分和30至45重量%聚酰胺组分。这些比率提供聚酰胺填充的丙烯酸酯共聚物组合物,使得由此制成的固化后的制品表现出足够的肖氏硬度A,从而为进一步增加固化后的组合物的硬度需要很少或不需要增强填料。另外,聚合物共混物表现出根据ASTM D6746-10测定的小于约2MPa的生胶强度,并且当与固化剂配混以形成可固化组合物时,具有根据ISO 6502:1999a测定使用得自AlphaTechnologies的MDR 2000,在0.5°弧度下操作的,并在180℃的测试条件下保持15分钟测定的,优选至少2.5dN-m,还更优选至少4dN-m的良好固化响应,其中ML是指测量的最小扭矩值,并且MH是指测量ML后获得的最大扭矩值。
可固化的聚酰胺填充的丙烯酸酯共聚物组合物的聚合物共混物组分可通过如下形成:在不产生丙烯酸酯共聚物的动态固化的条件下,在高于聚酰胺的熔融峰温度的温度下,将聚酰胺组分混合到丙烯酸酯共聚物组分中,然后将由此制备的聚合物共混物冷却以形成聚酰胺填充的丙烯酸酯共聚物组合物。即,当将聚酰胺组分和丙烯酸酯共聚物组分混合时,胺固化剂将不存在。这是因为指定的混合温度高于丙烯酸酯共聚物的交联和/或凝胶将在其下发生的温度。
通过将丙烯酸酯共聚物组分和聚酰胺组分混合而形成的组合物的冷却用于结晶聚酰胺域,使得聚酰胺成为固体并因此在后续混合时(例如当与胺固化剂混合形成可固化的组合物时)不能聚结以形成连续相。可通过根据ASTM D3418-08测量结晶峰温度来确定共混物必须被冷却至低于其的温度。聚酰胺填充的丙烯酸酯共聚物组合物可表现出多个结晶峰温度。在这种情况下,最低的结晶峰温度被认为是共混物必须被冷却至低于其的温度以将聚酰胺组分完全固化。一般来讲,将共混物冷却至40℃或更小,其足以固化用于本发明实践中的聚酰胺。
本文所述的可固化的丙烯酸酯共聚物组合物还包含胺固化剂。优选地,所述胺固化剂为二胺固化剂或某些其他含氮固化剂,如产生二胺的二胺氨基甲酸盐。固化剂将通常以0.1至10份/百份丙烯酸酯共聚物,优选地0.3-2份,更优选地0.4-1份的量存在。
适宜的芳族胺的示例包括:4,4’-双(4-氨基苯氧基)联苯、4,4’-二氨基二苯硫醚、1,3-双(4-氨基苯氧基)-2,2-二甲基丙烷、4,4’-二氨基苯砜、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、4,4’-二氨基二苯醚、4,4’-二氨基二苯甲烷、4,4’-二氨基苯酰替苯胺、1,3-双(4-氨基苯氧基)苯、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、以及苯二胺。适宜的脂族胺和其他固化剂的示例包括:己二胺、氨基甲酸己二胺、N,N’-亚肉桂基-1,6-己二胺、乙二胺,二亚乙基三胺、环己二胺、丙二胺以及丁二胺。
在可固化的丙烯酸酯共聚物组合物中,多胺固化剂中的伯胺基与聚合物中的羧酸或羧酸酐或环氧树脂固化位点单体残基的优选摩尔比在0.2至2.0的范围内,更优选地在0.5至1.5的范围内,并且最优选地在0.75至1.0的范围内。
向聚酰胺增强的丙烯酸酯共聚物组合物中加入固化剂将有利地在低于固化剂的分解温度的温度下,并且在低于与丙烯酸酯共聚物的羧基、酸酐基或环氧基发生交联反应的温度下进行。一般来讲,所述添加将在低于140℃的温度下,优选地在不高于120℃的温度下进行。固化剂的添加可与任选的加工成分的添加同时进行,所述加工成分诸如着色剂、常规炭黑、或无机增强剂、抗氧化剂、加工助剂、填料以及增塑剂,或其可为与其他成分的添加分开的操作。所述添加可在双辊橡胶磨上进行,或通过使用适用于配混天然橡胶组合物的密炼机进行,所述密炼机包括密炼机、Haake搅拌器、Brabender搅拌器、Farrel连续搅拌器、以及单螺杆或双螺杆挤出机。
促进剂为用于某些实施例中的添加剂的示例。即,胺固化的速率可由于存在通常在本领域中已知的基础硫化促进剂而提高。所述促进剂可为胍、芳基胍、烷基胍、脒、它们的混合物和盐、或如美国专利3,883,472中所公开的其他材料。代表性的促进剂包括四甲基胍、四乙基胍、二苯基胍、二邻甲苯基胍以及1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)。胍或脒型促进剂的浓度一般在丙烯酸酯共聚物的0.5至5phr,优选地1至3phr的范围内。优选的促进剂为DBU和有机酸的DBU盐,这是由于它们的低毒性和良好的固化加速度。
例如,典型的固化方法可利用基于100份丙烯酸酯共聚物弹性体计1.0phr的氨基甲酸己二胺和1phr的DBU盐,连同其它成分。在辊磨机上共混后,可在至少10MPa的压力下于175℃下进行10分钟的固化步骤。
为实现最佳的耐热老化性,有利地在固化前向可固化的丙烯酸酯共聚物组合物中加入抗氧化剂。有用的抗氧化剂包括但不限于芳族胺、酚类、咪唑、以及亚磷酸酯。从而,在一些实施例中,抗氧化剂可为磷酯抗氧化剂、受阻酚抗氧化剂、胺抗氧化剂、或这些化合物中的两种或更多种的混合物。组合物中抗氧化剂化合物的比例通常为0.1至5phr,优选地约0.5至2.5phr。混合物中酚类或胺抗氧化剂与磷化合物的重量比为约0.5至3,并且优选地所述比率为约1。
可为有用的抗氧化剂的芳族胺的示例包括:4,4’-双(α,α-二甲基苄基)二苯胺、二苯胺以及烷基化二苯胺、4-氨基二苯胺(其也用作减焦剂)、以及N-苯基-N’-(对甲苯磺酰基)对苯二胺。酚类抗氧化剂的示例包括:4,4′-亚丁基双(6-叔丁基间甲酚)、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯以及4,4′-硫代双(3-甲基-6-叔丁基苯酚)。亚磷酸盐抗氧化剂的示例包括:三苯基亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、以及三(2,4-二叔丁基苯基)亚磷酸酯。咪唑抗氧化剂的示例包括2-巯基甲基苯并咪唑、和2-巯基苯并咪唑。一般来讲,可基于化合物中的100份丙烯酸酯共聚物橡胶计介于0.5和5phr之间的含量使用抗氧化剂的组合。
适宜的受阻酚类抗氧化剂可为例如4,4’-亚丁基二(6-叔丁基间甲酚)、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、2,6-二叔丁基-α-二甲基氨基对甲酚以及4,4′-硫代双(3-甲基-6-叔丁基苯酚)。
优选的抗氧化剂组合物包含与4,4’-亚丁基二(6-叔丁基间甲酚)或4,4’-双(α,α-二甲基苄基)二苯胺混合的三(混合的单-和二壬基苯基)磷酸酯。优选的抗氧化剂组合物包含4,4’-双(α,α-二甲基苄基)二苯胺(可以445从Chemtura Corp商购获得)。尤其优选的抗氧化剂组合物包括4-氨基苯基胺,其含量为基于丙烯酸酯共聚物(即丙烯酸酯橡胶)组分计至多约2phr(份/百份橡胶)。抗氧化剂可在丙烯酸酯橡胶与聚酰胺熔融混合的同时,或在共混物冷却之后添加。
本发明的组合物还可包含附加的聚合物,前提条件是此类聚合物的添加在高于聚酰胺的熔融峰温度的温度下发生,此类聚合物的存在不使所得的聚酰胺填充的丙烯酸酯组合物的生胶强度增加至高于约2MPa。例如,可通过任何混合方法,在高于或低于聚酰胺的熔融峰温度下,将本发明的聚酰胺填充的丙烯酸酯共聚物组合物与丙烯酸酯共聚物共混,以稀释本发明组合物的聚酰胺含量。用于共混加工的丙烯酸酯共聚物可与本发明组合物的丙烯酸酯共聚物相同或不同,并且还可包含填料、固化剂或其它成分。优选地,此类稀释在低于聚酰胺的熔融峰温度的温度下发生,并且如果存在固化剂,则低于引发固化所需的温度。
此外,可固化的丙烯酸酯共聚物组合物可任选地包含附加的组分,所述组分包括增塑剂、加工助剂、蜡、颜料和着色剂。基于所述丙烯酸酯橡胶的重量计,此类任选组分一般将以约0.1phr至约30phr的量存在。此类任选组分的添加可在制备聚酰胺/丙烯酸酯共聚物共混物期间或在固化剂与共聚物共混物混合时进行。
一般来讲,由丙烯酸酯共聚物橡胶与聚酰胺混合获得的组合物可包含各种不同的共混物形态,其范围从其中离散的不连续聚酰胺颗粒存在于连续的非晶态丙烯酸酯共聚物基质中的那些,到其中存在高纵横比的聚酰胺“线”的组合物,到包含共连续结构的组合物,到包含聚酰胺连续相中的离散的丙烯酸酯共聚物域的组合物。这些组合物中的大部分具有不适用于本发明中的形态,因为共混物具有非常高的门尼粘度,即大于约120的门尼粘度(ML 1+4,100℃),和/或较差的弹性性能,诸如低拉伸断裂伸长率和高压缩形变。然而,如果如本文所述,选择组分的比率,则可制备聚酰胺填充的丙烯酸酯共聚物组合物,其具有低于约120的门尼粘度(ML1+4,100℃)和良好的弹性性能。此类本发明的聚酰胺填充的丙烯酸酯共聚物组合物以及适用于本发明方法中的那些组合物的特征在于,具有由根据ASTM D6746-10的测量测定的,小于约2MPa的生胶强度。所得的组合物具有良好的可加工性和弹性性能。生胶强度值小于约2MPa是本发明组合物的基本特征并且验证了聚酰胺填充的丙烯酸酯共聚物组合物中存在连续的丙烯酸酯共聚物相和不连续的聚酰胺相。所谓“不连续的聚酰胺相”是指聚酰胺以分散颗粒的形式、或被连续非晶态丙烯酸酯共聚物基质包围的域的形式存在于本发明的聚合物共混物组合物中。一般来讲,聚酰胺域可在连续的非晶态丙烯酸酯共聚物基质内完全彼此分离。然而,在某些情况下,聚合物共混物组合物中可存在一小部分(小于约5%)的局部位点,其中聚酰胺域聚集或彼此连接。就本发明的目的而言,认为生胶强度小于约2MPa的此类聚合物共混物组合物包含不连续的聚酰胺相。优选地,聚酰胺填充的丙烯酸酯共聚物的生胶强度将低于约1MPa。
大于2MPa的生胶强度指示共混物具有高门尼粘度、较差的挤出可加工性、或较差的固化后弹性性能。这些缺陷可能出现,因为共混物的聚酰胺相连续或与丙烯酸酯共聚物共连续,或因为聚酰胺的端基与丙烯酸酯共聚物的固化位点反应至丙烯酸酯聚合物凝胶的程度,或两者的任意组合。
本发明的层合体通过形成一种制品制成,所述制品包括聚酰胺填充的可固化的聚丙烯酸酯弹性体组合物层和可固化的含氟弹性体组合物层。层合体可为管、软管、片材或模塑制品的形式。层压制品可由一般实践用于制备多层制品的方法产生。例如,所述层可为共挤出的,或它们可使用单独的操作成型为膜或片材,然后在后面的步骤中组合从而形成层合体。组合所述层从而形成层合体的方法可与施加加热和压力以交联所述制品同时进行,即在模具或高压釜中,或所述层可在交联所述制品之前结合。作为另外一种选择,所述层可通过顺序挤出工艺形成,即形成第一层,然后使用十字头口模或其它挤压涂布方法施加第二层。
本发明的层合体通过施加加热和压力被固化以产生成品。温度通常在150℃至200℃的范围内达约两分钟至一小时的时间。层合体优选在至少0.5MPa的压力下,在密闭的模具或高压釜中固化。施加压力改善介于层合体层之间的粘附性程度,并且另外防止制品的海绵化。在固化后,制品可在约150℃至250℃的温度下被后固化达至多约24小时以完成固化过程并完全发展制品的特性。
实例
测试方法
固化响应:按照ISO 6502:1999a使用在0.5°弧度下操作的得自AlphaTechnologies的MDR 2000而测量。测试条件为180℃并达15分钟。ML是指在测试期间测量的最小扭矩值,而MH是指ML后获得的最大扭矩值。T50和T90是指到MH和ML之间扭矩差的50%和90%分别所需的时间。
生胶强度:根据ASTM D6746-10,在添加任何其它成分之前,对丙烯酸酯共聚物和聚酰胺的未固化的共混物进行测量。在辊磨机上将共混物切片成约2.5mm厚度,然后在尺寸为2mm×76.2mm×.152.4mm的腔体中模塑。模塑条件为在30吨的压力下于100℃保持5分钟。从压机中取出之后,将模塑块在金属片之间于室温下冷却30分钟。然后在平行于研磨片材纹理的方向上,从模塑块中切割出ASTM D412模具C拉伸样本。报告了中值屈服应力。测试温度为23℃±2℃。
剥离强度:按照ISO 36:2005测量,但在测试片的模塑中不具有织物。含氟弹性体和聚丙烯酸酯化合物被压制到一起并在密闭的模具中在165℃下固化达20分钟。释放膜布置在介于两层的一部分之间以提供用于抓持测试片的材料。ISO 6133:1998的方法A被用来计算中值剥离强度。数据以三个试样的中值报道。
材料
A-1 包含55重量%共聚合的甲基丙烯酸酯单元,43重量%乙烯单元(约70摩尔%)和约2重量%(约0.6摩尔%)马来酸单乙酯共聚合单元的甲基丙烯酸酯和乙烯的共聚物,门尼粘度(ML 1+4,100℃)为33。
PA-1 聚酰胺6,特性粘度为1.450dL/g,熔融峰温度为大约220℃,以B40购自BASF。
FKM-1 包含偏二氟乙烯(VF2)、六氟丙烯(HFP)、四氟乙烯(TFE)和0.4重量%的含溴固化部位单体的含氟弹性体,具有门尼粘度(ML 1+10,121℃)为28。
FKM-2 包含VF2、HFP、TFE和0.6重量%的含溴固化位点单体的含氟弹性体。由于含碘的链转移剂,聚合物另外包含02重量%的碘。门尼粘度(ML1+10,121℃)为26。
FKM-3 包含VF2、HFP、TFE和碘固化位点的含氟弹性体。门尼粘度(ML1+10,121℃)为65。以GBL600S购自DuPont。
其它材料
促进剂 ACT-55,以70重量%的量吸收在二氧化硅载体上的叔胺复合材料,购自Safic-Alcan。
AO-1 抗氧化剂,以445购自Chemtura Corp.。
AO-2 抗氧化剂,以正-苯基对苯二胺购自Sigma-Aldrich Corp.。
Ca(OH)2 氢氧化钙,以CF购自Rhein Chemie Corp.。
炭黑N550: SO炭黑,购自Cabot Corp.。
炭黑N990: 以N990购自Cancarb Corp.。
助剂-1 异氰尿酸三烯丙酯,以7购自DuPont。
助剂-2 三官能的甲基丙烯酸酯,以517购自Sartomer Corp.。
固化剂1 苄基三苯基氯化膦与双酚AF反应的盐,以固化剂50购自DuPont。
固化剂2 1,6-己二胺的氨基甲酸酯,以DiakTM 1购自DuPont。
MgO 氧化镁,以170购自Akrochem Corp.。
过氧化物 2,5-二甲基-2,5-二(叔丁过氧基)己烷,其以按重量计45%的与碳酸钙和二氧化硅的活性共混物来提供。购自Sigma-Aldrich Corp.。
增塑剂 酯类型增塑剂,以Alcanplast PO 80购自Safic Alcan。
加工助剂 以Vam购自R.T.Vanderbilt。
释放助剂 十八酸,购自Sigma-Aldrich Corp.。
减焦剂 以18D购自Akzo-Nobel N.V.。
TBABr 溴化四丁基铵,购自Sigma-Aldrich Corp.。
蜡 卡洛巴蜡,购自Akrochem Corp.。
钙硅石 以Tremin 283MST购自Quarzwerk GMBH。
实例1
如下制备包含45重量%聚酰胺PA-1和55重量%聚丙烯酸酯共聚物A-1的共混物B-1。通过减重喂料机将聚酰胺计量到具有十二个圆筒部分的43mm同向双螺杆挤出机的第一圆筒部分中,所述双螺杆挤出机在250rpm的螺杆转速下操作。同时,经由专门配置的挤出机和用于精确进料速率的熔体泵,将丙烯酸酯共聚物计量到挤出机的第四部分中。聚酰胺/丙烯酸酯共聚物共混物的熔体温度达到约280℃。离开第十二圆筒部分之后,在进一步加工之前,将所得的聚酰胺填充的丙烯酸酯共聚物制粒并冷却至25℃。发现B-1具有0.5MPa的生胶强度。
表1示出了对于聚丙烯酸酯共聚物可固化的化合物CA-1和CA-2的配方和固化响应。CA-1为常规的聚丙烯酸酯化合物,并且仅仅依赖炭黑用于增强。CA-2包含聚酰胺和炭黑增强填料两者。CA-1和CA-2两者均通过多官能的胺固化。CA-1通过将成分装入密炼机,并且混合达约5分钟直至批料温度达到100℃制备。然后将批料再装入到双辊开炼机上,并压片成适用于模塑剥离测试样品的厚度。CA-2通过将除了固化剂2以外的所有成分装入至密炼机,混合达约5分钟,直至批料温度达到100℃制备。然后去除批料,冷却并随着固化剂2返回到搅拌器中,并混合直至批料温度达到80℃。然后以如CA-1中相同的方式将CA-2在双辊开炼机上成片。
表1
表2示出了含氟弹性体可固化的化合物CF-1和CF-2的配方和固化响应。CF-1包含多元醇可固化的含氟弹性体化合物,然而CF-2包含可用过氧化物固化的含氟弹性体化合物。CF-1和CF-2两者均以上文所述的CA-1的方式制备。
表2
表3示出了对于常规的聚丙烯酸酯化合物CA-1和聚酰胺填充的聚丙烯酸酯化合物CA-2针对多元醇固化的含氟弹性体化合物CF-1以及另外聚酰胺填充的聚丙烯酸酯化合物CA-2针对过氧化物固化的含氟弹性体化合物CF-2的剥离测试结果。对两种类型的含氟弹性体化合物,CA-2均表现出可用的粘附性水平。表3中的“R”是指橡胶组件的失效。
表3
x-用于剥离样品的化合物
Claims (18)
1.聚酰胺填充的聚丙烯酸酯共聚物弹性体和含氟弹性体的可固化的层合体,其包含
A.可固化的含氟弹性体组合物层;和
B.可固化的聚丙烯酸酯共聚物弹性体组合物层,其包含
a.聚合物共混物,其包含
i.至少一种聚丙烯酸酯共聚物弹性体,其包含1)基于所述聚丙烯酸酯共聚物弹性体的总重量计至少50重量%的至少一种具有以下结构的单体的聚合单元
其中R1为H或C1-C10烷基,并且R2为C1-C12烷基、C1-C20烷氧基烷基、C1-C12氰基烷基或C1-C12氟代烷基;和2)选自以下的固化位点单体的共聚单元:不饱和羧酸、不饱和羧酸的酸酐、不饱和环氧化物、以及它们中两种或更多种的混合物;和
ii.10-60重量%的一种或多种聚酰胺,其具有至少160℃的熔融峰温度;
其中A)所述聚合物共混物具有根据ASTM D6746-10测定的小于约2MPa的生胶强度,B)所述一种或多种聚酰胺作为不连续相存在于所述聚合物共混物中,并且C)所述一种或多种非晶态丙烯酸酯共聚物和一种或多种聚酰胺的重量百分比是基于所述聚合物共混物中的所述一种或多种非晶态丙烯酸酯共聚物和一种或多种聚酰胺的总重量计的;和
b)胺固化剂。
2.根据权利要求1所述的可固化的层合体,其中所述一种或多种聚酰胺具有至少200℃的熔融峰温度。
3.根据权利要求1所述的可固化的层合体,其中所述可固化的聚丙烯酸酯共聚物组合物表现出当根据ISO 6502:1999a使用来自AlphaTechnologies的MDR 2000在0.5°弧和180℃下运行15分钟测试时至少2.5dN-m的扭矩MH-ML提高。
4.根据权利要求1所述的可固化的层合体,其中基于所述聚合物共混物中的聚丙烯酸酯共聚物和聚酰胺的总重量计,所述可固化的聚丙烯酸酯共聚物组合物包含20至50重量%的聚酰胺。
5.根据权利要求1所述的可固化的层合体,其中所述可固化的聚丙烯酸酯组合物包含聚酰胺,所述聚酰胺具有根据ASTM D2857-95,使用96重量%的硫酸作为溶剂在25℃的测试温度下测量的至少0.9dL/g的特性粘度。
6.根据权利要求1所述的可固化的层合体,其中所述可固化的聚丙烯酸酯组合物包含聚丙烯酸酯共聚物,所述聚丙烯酸酯共聚物包含至少0.5摩尔%的胺反应性固化位点单体。
7.根据权利要求1所述的可固化的层合体,其中所述可固化的含氟弹性体化合物包括可用过氧化物固化的含氟弹性体。
8.根据权利要求1所述的可固化的层合体,其中所述一种或多种聚酰胺包括聚酰胺6/6。
9.根据权利要求1所述的可固化的层合体,其中所述聚合物共混物具有根据ASTM D 6746-10测定的小于约1MPa的生胶强度。
10.用于制备可固化的层合体的方法,所述可固化的层合体具有聚酰胺填充的丙烯酸酯共聚物弹性体组合物层和可固化的含氟弹性体组合物层,所述方法包括以下步骤
A.提供一种或多种丙烯酸酯共聚物弹性体,其包含
a)基于所述非晶态丙烯酸酯共聚物的总重量计至少50重量%的至少一种具有以下结构的单体的聚合单元
其中R1为H或C1-C10烷基,并且R2为C1-C12烷基、C1-C20烷氧基烷基、C1-C12氰基烷基或C1-C12氟代烷基;和
b)选自以下的固化位点单体的共聚单元:不饱和羧酸、不饱和羧酸的酸酐、不饱和环氧化物、以及它们中两种或更多种的混合物;
B.提供一种或多种具有至少160℃熔融峰温度的聚酰胺;
C.在高于所述一种或多种聚酰胺的熔融峰温度的温度下将所述聚丙烯酸酯共聚物弹性体和聚酰胺混合,从而形成基于所述一种或多种聚酰胺和一种或多种聚丙烯酸酯的总重量计包含10重量%至60重量%聚酰胺的聚合物共混物;
D.将所述聚合物共混物冷却至低于所述一种或多种聚酰胺的结晶峰温度的温度,从而形成聚酰胺填充的聚丙烯酸酯共聚物弹性体组合物,其i)包含连续的非晶态丙烯酸酯共聚物弹性体相和不连续的聚酰胺相并且ii)具有根据ASTM D 6746-10测定的小于约2MPa的生胶强度;
E.在低于所述聚酰胺的峰值熔融温度的温度下将胺固化剂加入所述聚合物共混物中以形成可固化的聚丙烯酸酯弹性体组合物;
F.提供可固化的含氟弹性体组合物;以及
G.形成包含所述可固化的聚丙烯酸酯弹性体组合物层和所述可固化的含氟弹性体组合物层的层合体结构。
11.根据权利要求10所述的用于制备可固化的层合体的方法,其中所述一种或多种聚酰胺具有至少200℃的熔融峰温度。
12.根据权利要求10所述的用于制备可固化的层合体的方法,其中步骤E)的所述可固化的聚丙烯酸酯共聚物组合物表现出当根据ISO6502:1999a使用来自Alpha Technologies的MDR 2000在0.5°弧和180℃下运行15分钟测试时至少2.5dN-m的扭矩MH-ML提高。
13.根据权利要求10所述的用于制备可固化的层合体的方法,其中基于所述聚合物共混物中的聚丙烯酸酯共聚物和聚酰胺的总重量计,所述可固化的聚丙烯酸酯共聚物组合物包含20至50重量%的聚酰胺。
14.根据权利要求10所述的用于制备可固化的层合体的方法,其中所述可固化的聚丙烯酸酯组合物包含聚酰胺,所述聚酰胺具有根据ASTMD 2857-95使用96重量%的硫酸作为溶剂在25℃的测试温度下测量的至少0.9dL/g的特性粘度。
15.根据权利要求10所述的用于制备可固化的层合体的方法,其中所述可固化的聚丙烯酸酯组合物包含聚丙烯酸酯共聚物,所述聚丙烯酸酯共聚物包含至少0.5摩尔%的胺反应性固化位点单体。
16.根据权利要求10所述的用于制备可固化的层合体的方法,其中所述可固化的含氟弹性体化合物包括可用过氧化物固化的含氟弹性体。
17.根据权利要求10所述的用于制备可固化的层合体的方法,其中所述一种或多种聚酰胺包括聚酰胺6/6。
18.根据权利要求10所述的用于制备可固化的层合体的方法,其中步骤D)的所述聚合物共混物组合物具有根据ASTM D 6746-10测定的小于约1MPa的生胶强度。
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CN110694352A (zh) * | 2019-11-01 | 2020-01-17 | 石家庄辰泰滤纸有限公司 | 一种纳米纤维、其制备方法及制成的复合滤材和应用 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9654076B2 (en) | 2014-03-25 | 2017-05-16 | Apple Inc. | Metadata for ducking control |
EP3165360B1 (en) * | 2014-07-18 | 2019-05-08 | Zeon Corporation | Laminate |
CN111848994B (zh) * | 2019-04-24 | 2022-04-05 | 歌尔股份有限公司 | 一种微型发声装置 |
CN111866670B (zh) * | 2019-04-24 | 2022-04-22 | 歌尔股份有限公司 | 一种用于微型发声装置的振膜和微型发声装置 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0337977A2 (en) * | 1988-04-11 | 1989-10-18 | Advanced Elastomer Systems, L.P. | High temperature stable, low solvent swelling thermoplastic elastomer compositions |
US5777033A (en) * | 1996-07-26 | 1998-07-07 | Advanced Elastomer Systems, L.P. | Co-cured rubber-thermoplastic elastomer compositions |
WO2012124544A1 (ja) * | 2011-03-11 | 2012-09-20 | 東海ゴム工業株式会社 | 車両用耐熱ホース |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3876654A (en) | 1970-12-23 | 1975-04-08 | Du Pont | Fluoroelastomer composition |
US3883472A (en) | 1973-08-09 | 1975-05-13 | Du Pont | Fast curing heat stable elastomeric compositions |
DK553478A (da) | 1977-12-14 | 1979-06-15 | Montedison Spa | Vulkaniserbare blandinger paa basis af vinylidenfluoridelastomere samt fremgangsmaade til vulkanisering af saadanne blandinger |
JPS5923578B2 (ja) | 1978-05-01 | 1984-06-02 | ダイキン工業株式会社 | フツ素ゴム組成物 |
US4694045A (en) | 1985-12-11 | 1987-09-15 | E. I. Du Pont De Nemours And Company | Base resistant fluoroelastomers |
US4957975A (en) | 1988-03-14 | 1990-09-18 | E. I. Du Pont De Nemours And Company | Fluoroelastomer composition with low tendency to foul molds |
US4912171A (en) | 1988-04-01 | 1990-03-27 | Minnesota Mining And Manufacturing Company | Fluoroelastomer curing process with phosphonium compound |
US4882390A (en) | 1988-04-01 | 1989-11-21 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition with organo-onium compounds |
JPH04288305A (ja) | 1991-03-15 | 1992-10-13 | Nippon Mektron Ltd | パーオキサイド加硫可能な含フッ素エラストマ−の製造方法 |
JPH06228402A (ja) * | 1992-12-08 | 1994-08-16 | Japan Synthetic Rubber Co Ltd | アクリルゴム組成物 |
IT1269514B (it) | 1994-05-18 | 1997-04-01 | Ausimont Spa | Fluoroelastomeri vulcanizzabili per via perossidica,particolarmente adatti per la fabbricazione di o-ring |
IT1269846B (it) | 1994-05-27 | 1997-04-15 | Ausimont Spa | Composizioni fluoroelastomeriche vulcanizzabili |
JP3327016B2 (ja) | 1994-12-06 | 2002-09-24 | ダイキン工業株式会社 | 低温シール性に優れたフッ素ゴム共重合体及びその硬化用組成物 |
US6166157A (en) | 1995-12-20 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Iodonitriles as chain transfer agents in the manufacture of perfluoropolymers |
US5591804A (en) | 1995-12-21 | 1997-01-07 | Minnesota Mining And Manufacturing Company | Fluorinated onium salts, curable compositions containing same, and method of curing using same |
AU2631100A (en) * | 1999-03-02 | 2000-09-21 | 3M Innovative Properties Company | Compositions for fluoropolymer bonding to non-fluorinated polymers |
US6686012B1 (en) * | 2000-08-23 | 2004-02-03 | 3M Innovative Properties Company | Multi-layer articles including a fluoroplastic layer |
US6759129B2 (en) * | 2002-04-18 | 2004-07-06 | 3M Innovative Properties Company | Adhesion and bonding of multi-layer articles including a fluoropolymer layer |
JP4081711B2 (ja) * | 2002-06-17 | 2008-04-30 | 旭硝子株式会社 | 積層ゴムホース |
EP1896514B1 (en) * | 2005-06-30 | 2017-04-12 | E. I. du Pont de Nemours and Company | Ethylene/alkyl acrylate copolymers and compounds and vulcanizates thereof |
WO2012177879A1 (en) * | 2011-06-21 | 2012-12-27 | E. I. Du Pont De Nemours And Company | Heat-stabilised polyamide-filled acrylate copolymer and process for its production |
CN103732682B (zh) * | 2011-06-21 | 2016-11-09 | 纳幕尔杜邦公司 | 用于制备热稳定聚酰胺填充的丙烯酸酯聚合物的方法 |
-
2013
- 2013-12-10 KR KR1020157015840A patent/KR20150096661A/ko not_active Application Discontinuation
- 2013-12-10 US US14/652,327 patent/US20150328866A1/en not_active Abandoned
- 2013-12-10 WO PCT/US2013/073971 patent/WO2014099454A1/en active Application Filing
- 2013-12-10 JP JP2015549451A patent/JP6272349B2/ja not_active Expired - Fee Related
- 2013-12-10 CN CN201380065809.6A patent/CN104870181B/zh not_active Expired - Fee Related
- 2013-12-10 EP EP13814713.7A patent/EP2934878B1/en not_active Not-in-force
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0337977A2 (en) * | 1988-04-11 | 1989-10-18 | Advanced Elastomer Systems, L.P. | High temperature stable, low solvent swelling thermoplastic elastomer compositions |
US5777033A (en) * | 1996-07-26 | 1998-07-07 | Advanced Elastomer Systems, L.P. | Co-cured rubber-thermoplastic elastomer compositions |
WO2012124544A1 (ja) * | 2011-03-11 | 2012-09-20 | 東海ゴム工業株式会社 | 車両用耐熱ホース |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110694352A (zh) * | 2019-11-01 | 2020-01-17 | 石家庄辰泰滤纸有限公司 | 一种纳米纤维、其制备方法及制成的复合滤材和应用 |
CN110694352B (zh) * | 2019-11-01 | 2022-08-12 | 石家庄辰泰滤纸有限公司 | 一种纳米纤维、其制备方法及制成的复合滤材和应用 |
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