CN1856545A - 聚苯硫醚组合物及其应用 - Google Patents
聚苯硫醚组合物及其应用 Download PDFInfo
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- CN1856545A CN1856545A CNA2004800272227A CN200480027222A CN1856545A CN 1856545 A CN1856545 A CN 1856545A CN A2004800272227 A CNA2004800272227 A CN A2004800272227A CN 200480027222 A CN200480027222 A CN 200480027222A CN 1856545 A CN1856545 A CN 1856545A
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- China
- Prior art keywords
- pps
- weight
- barrier layer
- acidifying
- olefin polymer
- Prior art date
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Abstract
提供聚苯硫醚(PPS)基共混物的组合物及其应用。PPS基共混物可包括约40-95%(重)的PPS树脂和约5-60%(重)的烯烃共聚物和弹性体。PPS基共混物的抗冲击性、断裂伸长率和柔韧性较PPS有所提高,可用于制造一些除具有PPS常规性能外还需要这些性能的制品。PPS基共混物可作为用来形成工业制品(包括单件式或多件式制品)的多层结构的最后一层引入。组装时,PPS基层接合,得到的PPS基制品整体包括各构造部件的接合处具有蒸气和液体不渗透性。
Description
相关申请的互相参照
本申请要求2003年8月18日申请的临时申请60/496,097的优先权。
技术领域
本发明广义涉及柔韧性较PPS有所改进的弹性聚苯硫醚(PPS)组合物,具体地说,本发明技术涉及适合用作柔韧性包覆层、纤维和阻隔层的弹性PPS组合物。
技术背景
本节意欲向读者介绍与下文描述和/或权利要求的本发明技术各方面相关的各种先有技术。相信这里所讨论的内容将有助于给读者提供一些背景信息来更好地理解本发明的各个方面。因此,应当明白这些陈述是就事论事,并没有任何将构成先有技术的要素纳入本发明的意思。
在市售和生产的制品和包装材料中通常会引入热塑性聚合物如一些加热时可模塑或成型而冷却时能硬化成所需形状的塑料和其它聚合物。特种热塑性材料一般在其特性如阻燃性、抗冲击性、柔韧性、耐化学腐蚀性、耐热性等方面会有所不同。因此,通常要根据所需求或限定的应用场合来选用合适的热塑性材料,但有时,一种其它性能都很适合应用场合的热塑性材料会因为某一不恰当的特性而不被接受。
例如,聚苯硫醚(PPS)是一种具有优良热稳定性、尺寸稳定性、耐化学腐蚀性、阻燃性和电绝缘性的高性能热塑性工程塑料。但是,对于某些期望高柔韧性或高抗冲击性的应用场合来说PPS太不柔韧或是说太刚性了。例如,PPS的刚性使其不可能用作一些必须弯曲或随形的基材如电线或电缆的包覆层,或是用作一些必须要抗冲击损伤的容器构造或其它制品的部件。
但是,柔韧性、弹性或抗冲击性能很好且具有PPS其它理想品质的PPS基组合物却能很好地满足这类用途。具体地说,柔韧性和或抗冲击损伤性能高于纯PPS的PPS基组合物是非常令人期望的。类似地,引入这类组合物的制品或物品无论是包覆层还是结构部件也是非常令人期望的。
附图简介
阅读下文的详细描述并参照下列附图可以很清楚地看到本发明的优点:
图1例示按本技术的一个方面,包覆有PPS基共混物的电线;
图2例示按本技术的一个方面,引入阻隔层的多层结构;
图3例示按本技术的一个方面,将型坯挤入吹塑模具;
图4例示闭合模具并将图3的型坯吹胀;
图5例示将图4的吹塑成型制品冷却;
图6例示将图5的吹塑成型制品脱模;
图7例示按本技术的一个方面,由图2多层结构所构成的多件式制品的一件;
图8例示按本技术的一个方面,由图2多层结构所构成的,插入一或多个成品中要包括的内插件后的多件式制品的一件;
图9例示按本技术的一个方面,由如图7和8所述部件构成的多件式制品;
图9A例示按本技术的一个方面,图9多件式制品的两件构造接合处局部放大图;
图10例示按本技术的一个方面,借助真空成型方法将图7部件成型;
图11例示按本技术的一个方面,借助热平板焊接方法将图7和/或图8的部件组装成一个多件式制品;
图12例示按本技术的一个方面,图7和/或图8的部件经热平板焊接或者其它粘接或接合技术处理后组装成一个多件式制品;
图13例示一辆放有按本技术一个方面构造的燃料箱的机动车
实施本发明的模式
A.引言
基于聚苯硫醚(PPS)的热塑性共混物可应用于加工、商业和/或消耗品用途的不同场合。特别地,结晶性PPS是一种高性能的热塑性塑料,可用于生产各种需要具有PPS机械和/或电性能的制品。例如,PPS适合应用于需要高模塑性、硬度、热稳定性、尺寸稳定性、耐化学腐蚀性、阻燃性和/或电绝缘性的场合。PPS可单独或是以共混物(即PPS与一或多种其它组分如其它热塑性材料、弹性材料、共聚物树脂、增强剂、添加剂等的组合物)组分之一形式引入成为加工件。
特别地,当希望具有某一组分如PPS的特殊性能但该组分其它性能不是太理想时则使用热塑性共混物比较好。确实,由于可使用的热塑性材料非常广泛,通常希望开发一些能突出某一组分的理想性能同时使该组分的任何不理想性能最小化的适合特定用途的热塑性共混物。例如,PPS基共混物能很好地用作柔韧性基材如电缆或电线的包覆层、用作可织入布料或纺织品的纤维构造、或用来构造储存挥发性液体容器的结构件。因此,最好是形成一个热塑性共混物,其中包括适当等级和足够量的PPS以保留PPS的理想化学、电、热和/或机械性能,同时还包括一或多种其它组分来使共混物的柔韧性和/或抗冲击损伤性达到理想程度。
B.适用的PPS基共混物
通过将处理过的PPS树脂、烯烃共聚物和弹性体混合来形成具有柔韧性和抗冲击损伤性较PPS有所改进且具有基本的化学、电和/或阻燃性的PPS基共混物的实例。PPS基共混物可包括约40-95%(重)处理过的PPS树脂、约5-50%(重)烯烃共聚物和约1-20%(重)弹性体。在PPS基共混物的一个具体方案中,共混物包括少于10%(重)烯烃共聚物。烯烃共聚物与弹性体的重量比一般约为3∶1-20∶1,本领域普通技术人员应该知道,共混物各组分所选的量应使它们合计的共混物组成为100%。
在与共混物其它组分混合物之前,可将PPS进行处理来改善活性端基,例如对端基进行酸化处理。特别地,最好是除去活性端基所带的离子如钠离子或氯离子。可采用各类技术来完成脱离子过程,包括用酸、热水、有机溶剂或是一些组合处理法来处理PPS。脱离子处理过程可紧接在聚合过程和PPS回收过程后进行,如为湿PPS松散物和颗粒时进行。处理过程可在热和/或搅拌(若需要)条件下进行来提高处理效率。如下文所述,脱离子处理也可在PPS聚合过程终止之前即在聚合条件下进行。脱离子过程后,则处理过的PPS的离子含量如钠离子含量可低于900ppm,如果不能低于500ppm的话。
要处理的PPS可包括较低分子量的PPS树脂以及基本为线型的较高分子量聚合物。在某些情况中,如用较低分子量树脂时,可在聚合过程后通过有氧存在或交联剂如过氧化物存在的条件下将PPS聚合物加热的方法来提高PPS聚合物的聚合度。尽管通过任何方法制成的PPS都可用于本技术,但最好是用基本为线型的较高分子量聚合物来形成PPS共混物。
本技术所用的PPS包括至少70mole%且通常是90mole%或更多的下列结构式所示的重复单元:
且可包括多至30mole%的一或多个下列结构式所示的重复单元:
为改进上述PPS树脂与烯烃共聚物的亲和性,要将PPS树脂进行如上所述的脱离子处理。通常,要处理的PPS为粉末颗粒状,特别是微粒状,以便处理过程和任何后续洗涤过程更为有效。
就酸处理过程而言,是在适当搅拌或加热条件下将聚合后的PPS包括新聚合的或湿的PPS浸渍于酸或酸性溶液中。例如,可用pH=4的乙酸水溶液来处理PPS。可将乙酸性溶液加热到约80-90℃并在搅拌条件下将PPS浸渍约30分钟。然后例如用加压条件下加热到100℃或更高温的蒸馏水或去离子水洗涤处理过的PPS一或多次。通常,可用的酸包括那些不会使PPS分解或降解的酸。除乙酸外,这类酸的实例包括盐酸、硫酸、磷酸、硅酸、碳酸和丙酸。
可采用有机溶剂处理法来替代或补充酸处理法,以改进PPS树脂与烯烃共聚物的亲和性。可在搅拌和/或适当加热的条件下将PPS浸渍于一或多种溶剂中来实现用此技术处理PPS的过程。将回收的PPS经洗涤并干燥之后或者仍带有聚合溶剂或洗涤水的湿态时进行处理。实际上,可将PPS聚合混合物与有机一种或多种溶剂或溶剂混合来对PPS进行处理。用有机溶剂处理时的温度可依溶剂而变,从室温到约300℃不等。但在约25-150℃条件下可达到充分的有机溶剂处理。视有机溶剂和温度,处理过程可在高压下进行以避免溶剂沸腾。尽管有机溶剂的接触时间并没有严格限定,但通常无论是间歇还是连续模式处理约5分钟或更多时间能达到理想效果。处理后,可视水的溶解度和有机溶剂的沸点将PPS用蒸馏水或去离子水洗涤一或多次。若进行水洗,则要在加压条件高至100℃或更高温度下实施。
有机溶剂处理法对所用有机溶剂并不限定,只要该有机溶剂不会使PPS分解或降解即可。有机溶剂的实例包括但不限于含氮极性溶剂(如N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1,3-二甲基咪唑烷酮、六甲基磷酰胺、哌啶烷酮类等)。另外可用的有机溶剂包括亚砜和砜类溶剂(如二甲基亚砜、二甲基砜、环丁砜等)和酮类溶剂(如丙酮、甲乙酮、二乙酮和苯乙酮)。其它可用的有机溶剂包括醚类溶剂(二乙醚、二丙醚、二烷和四氢呋喃)和含卤类溶剂(如氯仿、二氯甲烷、三氯乙烯、二氯乙烯、全氯乙烯、一氯乙烷、二氯乙烷、四氯乙烷、全氯乙烷、氯苯等)。也可使用醇和酚类溶剂(如甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇、丙二醇、苯酚、甲酚、聚乙二醇、聚丙二醇等)和芳烃类溶剂(如苯、甲苯、二甲苯等)。
此外,可用热水如蒸馏水或去离子水处理PPS来改进PPS树脂与烯烃共聚物的亲和性。热水处理法可用100℃或更高温度的水进行操作。170℃或更高温的水能更有效地提供理想的化学改性。例如,可将给定量的PPS(包括湿态或新聚合的PPS)加入到给定量的水中,然后在一个压力容器中加热到例如170℃或更高并搅拌。尽管PPS与水的比例可变动,但该比例通常为每升水200gPPS或更低。一般来说,水处理法是在惰性气氛下实施。水处理过程后,可将PPS洗涤一或多次来除去任何不想要的成分。
尽管上述这些处理方法可实现PPS端基脱离子或酸化的目标,但在某些情况下,最好是在聚合条件下的反应器内完成此过程。特别地,这样的处理方法可减少PPS生产过程的步骤数如洗涤和回收步骤和/或减少所回收PPS中的灰分即杂质的含量。这样的方法公开于美国专利5352768中,并入本文作为参考。
例如,可在聚合条件下将酸或酸性溶液加入到聚合反应混合物中。可在聚合反应进行到适当程度后聚合反应终止之前将酸或酸性溶液加入。一般来说,酸或酸性溶液可在聚合反应即将终止前的一刻加入。将足量的酸或酸性溶液加入到聚合混合物中来降低聚合混合物的碱性。具体来说,酸与PPS的摩尔比在0.025∶1到0.1∶1范围内,一般为0.4∶1到0.8∶1范围内。
可使用与聚合混合物中的极性有机化合物或溶剂如N-甲基-2-吡咯烷酮相溶或混溶的有机或无机酸。适用有机酸的实例包括但不限于乙酸、甲酸、草酸、富马酸和邻苯二甲酸氢钾。类似地,适用的无机酸包括盐酸、磷酸二氢铵、硫酸、磷酸、硼酸、硝酸、磷酸二氢钠、磷酸二氢铵、碳酸和H2SO。
加入酸或酸性溶液后,可终止聚合反应。可通过将聚合混合物的温度降到基本不会进行聚合反应的温度以下,一般是低于235℃来实现终止。聚合反应终止后,可采用传统技术即过滤、洗涤、闪蒸回收等方法将PPS回收。回收的PPS通过酸处理法有效地脱去离子使所回收的PPS成为改性的PPS,这可与本文所述技术联用。
例如,可如下所述将聚合混合物用酸处理来制备PPS聚合物。首先,制备一个由32.40kg(71.42磅)的50%(重)氢氧化钠(NaOH)水溶液与39.34kg(86.74磅)的含60%(重)硫氢化钠(NaSH)和0.4%(重)硫化钠(Na2S)的溶液组成的混合物。将该溶液、11.34kg(25磅)乙酸钠(NaOAc)粉末和104.1L(27.5加仑)N-甲基-2-吡咯烷酮(NMP)加入到一个搅拌的(400rpm)反应器中,然后用氮气吹扫。随后将该混合物加热到约172℃(342)并脱水处理来移出水,同时将温度升到约211℃(411)。将于22.7L(6加仑)NMP中的63.27kg(139.49磅)对二氯苯(DCB)装入反应器。加热混合物到约282℃(540)并维持1.5小时。然后将2000ml冰乙酸随3.97L(1加仑)NMP一起加入反应器并使其于279℃(535)下与反应混合物反应约5分钟。
然后,将反应混合物于约282℃(540)下闪蒸处理来移出NMP并使PPS聚合物固体化。室温下将干燥的带盐聚合物用454.25L(120加仑)去离子水洗涤两次,过滤,然后于177℃(350)下再用302.83L(80加仑)去离子水洗涤30分钟。过滤溶液,回收约26.76kg(59磅)PPS。回收的PPS显示的灰分含量约为0.23或更低。
前述脱离子技术适用于制备活性端基已通过例如酸化处理得到改性的脱离子PPS。但是,本领域普通技术人员应知道,也可采用其它脱离子技术,这也在本公开内容范围内。并且,所述的不同脱离子技术可单独或组合使用。例如,可将已经酸处理的PPS接着在有机溶剂条件下或用热水等进行处理。
除了对PPS进行脱离子和/或酸化处理外,还可将PPS与各种添加剂如抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂混合,添加剂的量应对PPS或所得PPS基共混物的期望性能没有影响。各种其它的聚合物也可以不影响期望性能的量存在。影响交联反应的试剂如交联剂、交联加速剂和/或交联抑制剂也可混入PPS。
将有或没有上述添加剂的处理过的PPS并入PPS基共混物。除处理过的PPS和任何需要的添加剂外,PPS基共混物还可包括烯烃聚合物,如共聚物和三元共聚物。烯烃聚合物可包括至少约50%(重)的α-烯烃如乙烯、丙烯、丁烯-1等和少于约50%(重)的缩水甘油酯。可用于本技术的缩水甘油酯的实例包括丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、乙基丙烯酸缩水甘油酯等。烯烃聚合物可包括40%(重)或更少的另一种可共聚不饱和单体如乙烯基醚、乙酸乙烯酯、丙酸乙烯酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯腈、苯乙烯等。
除烯烃共聚物外,可将一或多种弹性体与PPS混合。一般来说,弹性体包括至少50%(重)的乙烯。可用的弹性体包括但不限于相应的乙烯/丙烯、乙烯/丁烯、乙烯/丙烯/二烯共聚物和氢化苯乙烯/丁二烯/苯乙烯嵌段共聚物。其它可用的弹性体包括乙烯与丙烯酸、甲基丙烯酸或是其烷基酯和/或金属盐的共聚物以及聚酰胺弹性体。本领域普通技术人员应知道,还有其它一些共聚物也适合用作弹性体。
就弹性体包括乙烯与丙烯酸、甲基丙烯酸及其烷基酯和/或金属盐的共聚物的情况而言,烷基一般选用1-5个碳原子。这类弹性体的实例包括但不限于乙烯/丙烯酸酯共聚物如相应的乙烯/丙烯酸甲酯、乙烯/丙烯酸乙酯、乙烯/丙烯酸丙酯和乙烯/丙烯酸丁酯的共聚物。类似地,适用的乙烯/甲基丙烯酸酯共聚物的实例包括乙烯/甲基丙烯酸甲酯、乙烯/甲基丙烯酸乙酯、乙烯/甲基丙烯酸丙酯和乙烯/甲基丙烯酸丁酯的共聚物。如上所述,弹性体也可包括或由乙烯/丙烯酸和/或乙烯/甲基丙烯酸的共聚物组成。同样,本领域普通技术人员应知道,弹性体共聚物的金属盐如钠、锌、钾、钙、锂、铝和镁盐也要包括在广义描述的共聚物中。
可将所选的弹性体与烯烃共聚物、酸化的PPS和相关添加剂混合起来生成PPS基共混物。如上所述,PPS基共混物包括约40-95%(重)脱离子的即酸化的PPS树脂、约5-50%(重)烯烃共聚物和约1-20%(重)弹性体。在一个方案中,共混物包括少于10%(重)烯烃共聚物。烯烃共聚物与弹性体的重量比一般约为3∶1-20∶1。PPS基共混物还可包括一或多种如下所述的增强剂,其量为400重量份/100重量份PPS、烯烃共聚物和弹性体总重量或更少。若需要的话,增强剂在并入PPS剂共混物之前可用偶联剂如硅烷或钛酸酯处理。增强剂的实例包括纤维增强剂如无机纤维和碳纤维以及中空或颗粒状增强剂如硅酸盐、金属氧化物、碳酸盐、硫酸盐、玻璃珠、氧化硅、氮化硼、碳化硅等。
PPS基共混物可通过本领域普通技术人员熟知的各种技术进行熔融共混。例如,可在高剪切和高于PPS熔点的温度如280-340℃下将PPS、烯烃共聚物、弹性体和任何所需增强剂或试剂在挤出机中进行熔融共混。可将各组分预混或计量,同时或分别加入到混合和捏合设备中。然后将得到的混合物挤出造粒以便于运输和将来的加工。
PPS基共混物通常是化学惰性的、阻燃的、通常不能渗透液体和/或蒸气和柔韧性的。PPS基共聚物的柔韧性可通过共混物相应的断裂伸长率(以样品断裂时的伸长与原长的百分比表示)来证实。具体地说,PPS基共混物的断裂伸长率一般大于150%,对于柔韧性包覆层如电线包覆层来说这通常是很理想的。但是,本领域普通技术人员应知道,弹性体或其它组分的百分比可依据所期望的具体方案进行改变来产生其它断裂伸长率范围。例如,使用较低百分比的弹性体可产出断裂伸长率在100%-150%范围的PPS基共混物。类似地,使用较高百分比的弹性体可产出断裂伸长率在150%-200%范围的PPS基共混物。
C.柔韧性和/或抗冲击性PPS基共混物的应用
1.柔韧性基材的包覆层
造粒后PPS基共混物可用于构造商品或制品,或是作为出售的构造材料或是复合构造材料的一个组分。例如,PPS基共混物可如图1所示用作电线24或其它柔韧性介质的包覆层22。例如,将PPS基共混物的各组分例如在一个挤出机中进行熔融共混,之后造粒。然后将造粒后的共混物熔融并挤出到要包覆的基材如电线24或电缆上,冷却硬化成为包覆层22。
尽管电线24和电缆是可由PPS基共混物包覆的柔韧性介质实例,但其它柔韧性基材也可类似地被包覆。例如,可将包括PPS基共混物的涂覆层施涂于制品如燃料箱、化学罐、厨具等的里面和外面。这些表面因其组成的缘故本身是柔韧性的,且可受益于柔韧性PPS基共混物的包覆层。包覆层例如通过提供机械、化学、热或电方面的保护起到底层基材保护层的作用,同时具有一定的抗冲击性。
尽管作为另外基材的包覆层是PPS基共混物的一个可能用途,但PPS基共混物本身可以是构造的主材。例如,可成型为化学惰性和/或阻燃性且具有一定柔韧性的单件或多件式容器或制品。为构造成这些制品,可采用已知技术将PPS基共混物模塑或成型,包括但不限于注塑、挤塑、压塑、传递模塑和下述成型技术。
2.纤维
PPS基共混物也可单独或与其它组分联用来形成绳线或纤维,再将PPS基共混物纤维编织成布或织物,用来制成过滤材料、帆布、衣物和绝缘材料如电绝缘材料。例如,可将PPS基共混物挤出或成型为丝或线,包括本身就是纤维或者长度方向即纵向连接来形成纤维。一旦形成PPS基共混物纤维,就可将其纺成织品、织物或布,或是其它方法连系起来形成例如过滤材料或绝缘材料。由于纤维是由PPS基共混物形成的,故纤维和纤维所制成的材料比纯PPS具有更高的柔韧性和更低的脆性。纤维的柔韧性还与纤维或纱线中PPS聚合物的长度有关。
3.多层结构
或者,可将PPS基共混物引入到一个暴露表面具有另外期望性能或不同性能的多层结构的一或多层。例如,参看图2,示出一个引入阻隔层52的多层结构50。阻隔层52的组成如下:仅有PPS、如上所述的PPS基共混物、不同的热塑性材料如聚丙烯或是具有所期望性能如蒸汽不渗透性的热塑性共混物。可以固体层、膜或分散细颗粒状形成PPS或PPS基共混物阻隔层52。本领域普通技术人员很容易理解,多层结构50的其它层也可包括纯态或是PPS基共混物组分之一形式的PPS。
多层结构50可包括能赋予多层结构50抗冲击性和/或可成型性的其它层。例如,外层54可起到保护涂层的作用,外层54还可提供期望的结构和/或机械性能。外层54可由PPS、PPS基共混物、聚乙烯(PE)、高密度聚乙烯(HDPE)、聚丙烯(PP)、尼龙、聚(对苯二甲酸丁二酯)(PBT)、聚(对苯二甲酸乙二酯)(PET)或其它具有所期望性能的聚合物组成。外层54还可包括聚合物共混物或者可包括具有所期望性能的回收聚合物如回收HDPE。
另外,如图2所示,多层结构50中还可包括辅助层56。辅助层56可为内层如阻隔层52提供附加保护作用,或者可为多层结构50提供所期望的结构和/或机械性能。因此,辅助层56(若存在)可与外层54具有相同或类似的组成。或者,辅助层56可赋予多层结构50不同于外层54的性能,因此根据所期望的性能可有不同或不相似的组成。尽管为简便起见图2所示的多层结构50是由有限层数组成的,但结构50所包括的层数可减少或增加以适应最终用途。例如,根据多层结构50整体所需的化学、结构、电、机械和/或阻燃性可存在更多层数。
依据阻隔层52、外层54和辅助层56(若存在)的组成,多层结构50中可存在一或多层粘结层58以利于各层之间彼此粘合。例如,例如可用XtelXE3200(自Chevron Phillips Chemical Company LP处获得的PPS基共混物)和/或线型低密度聚乙烯(LDPE)来构造粘结层58。粘结层58的组成可由相邻层的性质如预期环境中相邻层在整个温度范围内的尺寸稳定性决定。例如,XtelXE3200构成的粘结层58最好是与PPS或PPS基共混物构成的阻隔层52相邻。类似地,线型LDPE构成的粘结层58最好是与HDPE或回收HDPE构成的外层54或辅助层56相邻。若需要的话,可使用多层上述粘结层58,以便适配于相邻层的不同组成。在这些情况下,粘结层58可与一个面对粘到一起以实现将其它相异的内层和外层结合的目的。
可有多个方法补充或替代引入粘结层58的方法来形成多层结构50。例如,阻隔层52、外层54和任何更多的层经加热并加压即层压技术处理使两或多层结合在一起。或者用诸如UV、IR、热或等离子体的能源将各层的表面或层间放置的粘合剂活化来使各层接合起来。另一个替换方案是多层结构50的一层做成借助喷涂或等离子喷涂技术沉积而成的或者借助溶剂蒸发留下溶质残留层技术沉积而成的层模。
尽管前述技术采用由所需聚合物或聚合物共混物组成的两或多个分开的片材或膜来构造多层结构50,但也可换一种方法来形成多层结构50,即采用共挤出工艺或是多层挤出工艺。例如,可用挤出法通过标准吹塑工艺或是各层顺次熔敷的注塑工艺来构造多层结构50。但是,本领域普通技术人员应知道,上述各方法并不互相排斥且可将这些方法组合用于整体多层结构50的构造过程。
a.用多层结构来制造部件或制品
多层结构50构造好后,就可将其通过定型或铸型技术形成所想要的一或多个制品或部件。这些制品包括需要化学惰性、不渗透性和/或阻燃性内阻隔层的用于储存和/或运输燃料、化学品或饮料的容器。例如,可用如图3-6所示的吹塑技术或通过其它技术来构造一个包括多层结构50的单件构造制品80。
参看图3,通过将挤出机84中的熔融聚合物(或多种聚合物)经环型口模86加力挤出而形成一个多层结构的型坯即聚合物的熔融管坯82。将型坯82放入其内部形状按所期望制品80的模具88中。如图4所示,模具88环绕要模塑的型坯82闭合,用例如从气嘴90吹入的气流将型坯82吹胀。型坯82吹胀到与模具88内部形状一致即所期望的制品形状。然后如图5所示将制品80冷却到不软和/或不变形的程度。冷却后,将制品80从模具88脱出,收集起来并应用。若型坯82为多层的,则所形成的制品80也应包括多层结构50。举个最简单例子,制品80可包括内阻隔层52如PPS或PPS即共混物的阻隔层52和外层54如包括HDPE的外层54。
尽管由多层结构50来形成单件制品80是众多方式之一,但更希望由多层结构50来构造一个多件式制品100。例如,希望构造一个包含内插件或是因太大而无法采用单件制造技术的燃料箱或化学罐。在这些情况下,可将多层结构50成型为所期望的一些部件如主体部件、加油颈管等等,接着再组装成所期望的多件式制品100。
例如,可用一种吹塑成型法即在图3-6所示吹塑法基础上变动的方法的来制造多件式制品100的各个部件。在该吹塑成型法中,将多层结构的型坯82挤出并成型为所期望的制品。成型制品可切成两或多件如图7所示的半边容器102。可用成型刀具或机器进一步形成两或多件如所示的容器上半边102。若需要的话,可如图8所示将诸如燃料泵、燃料水平传感器、过滤器、分流器、防喷溅挡板等的内插件104插入半边容器如容器下半边103或另一件中。然后可如图9所示将两或多件接合起来形成一个如下所讨论的有或没有内插件104的不渗透性多件式制品100。图9A示出多件式制品100中两件间接合处的局部放大图。可对多件式制品100进行修整以达到所期望的尺寸或形状。
或者,可采用其它成型方法如图10所示的真空成型技术将多层结构50制成容器半边102、103或多件式制品100的其它部件。在真空成型技术中,要产生一个真空以使可延展的多层结构50与所需形状的模具110一致。对引入一或多个含PPS层的多层结构50而言,真空成型过程一般是在构造后结构50仍是热的和可延展时进行。多件式结构100的各件分别真空成型后,将内插件104插入某一件如容器半边102、103,并将各件接合形成多件式制品100。将多件式制品100进行修整以达到所期望的尺寸或形状。
多件式制品100的部件如容器半边102、103还可通过其它方法形成。例如,可在成型过程中如注射压塑过程中构造多层结构50。为在成型过程的同时构造多层结构50,可先将阻隔层52插入、沉积或施涂于模具成为膜、片、颗粒涂层等。下一层如辅助层56、粘结层或外层54借助注射压塑技术施加到阻隔层54上。注射压塑法的加热和加压工艺促进了不同层的粘合。也可类似地施加上更多层,直到制造出包括多层结构50在内的所期望部件。多件式制品的各部件制成后就可如上所述进行多件式制品100的组装工作,包括插入任何所需的内插件104。尽管已描述了通过吹塑成型、真空成型和注射压塑成型技术来制造各部件的方法,但本领域普通技术人员应知道,其它成形技术如模压成型和冷成型技术也可用来制造多件式制品100的部件。
b.组装多件式制品
可通过各种技术,包括但不限于热平板焊接、IR或UV活化表面或粘合、EMA粘结和热气焊接技术将多件式制品100的不同部件组装起来。例如,如图11所示,准备好要进行热平板焊接的容器上半边102和下半边103,加热板114用来加热准备接合的半边102、103相应的互补表面116。加热充分后,可移去加热板114,可如图12所示将互补表面116压合到一起,形成一个熔接面118或焊缝,如图9A的接合处局部放大图所示。如上所述,组装过程后可对制品100进行修整以达到所期望的高规格尺寸。
如图9A所示,若多件式制品100的部件如容器的半边102、103已构造成有阻隔层52放在制品100内表面上,则互补表面116将由阻隔层52组成。在此情况下,阻隔层52的融接和焊接操作会导致形成一个包括阻隔材料如PPS或PPS即共混物的、具有阻隔层52不渗透性的熔接面118或焊缝。按此方式可获得不会渗透所装液体或蒸气的接合面118或焊缝。
尽管本说明书为简单起见以两件式容器的方式对多件式制品100进行了描述,但本领域普通技术人员应很清楚地知道,本技术也能很容易地适用于具有更多部件或更复杂部件的制品100。实际上,多件式制品100的部件数量一般是由加工经济性和体型体积决定的,本技术可很容易地适用于更复杂的多件式制品100。例如,可制成燃料箱130并放入机动车132中,如放入轿车、卡车、摩托车、船、飞机中等,如图13所示,这样就可将机动车发动机燃料储存在燃料箱130中。由本技术制成的燃料箱130具有整个组装部件间形成的熔接面118不渗透或基本不渗透燃料蒸气的优点。该燃料箱130可包括PPS或PPS基共混物阻隔层52和一或多层HDPE抗冲击层即外层54和/或辅助层56以及任何所需的粘结层58。本领域普通技术人员应知道,也可使用其它阻隔材料或层材料,视所需的结构、机械性能和不渗透性能而定。类似地,使用本文所公开的技术也可构造出其它各种形状和尺寸的化学容器。
尽管前面的讨论主要集中在包括一或多层PPS或PPS基共混物层的多层结构用来形成单件式或多件式制品的可能性,但也可类似地使用单层PPS。例如,可用单层PPS或各层均是PPS或PPS基共混物的多层结构来制造容器或燃料箱。这样的容器或燃料箱若按上述技术制造即能形成一个不渗透的PPS或PPS基共混物的焊缝或熔接面118则具有如上所述的不渗透特性。采用上述技术如吹塑成型、真空成型等来制成相应的PPS部件,并采用所公开的技术如热平板焊接或热空气焊剂法将它们组装起来。
尽管本发明容许有各种改动和替换方式,通过画图例举方法已示出了一些具体方案并在本文进行了详细描述,但应知道,本发明并不想局限于所公开的特定形式,相反,本发明将覆盖所附权利要求定出的本发明精神实质和范围内的所有改动方案、等价方案和替换方案。
Claims (72)
1.一种组合物,包括
约5-50%(重)的包括乙烯和缩水甘油酯的烯烃聚合物;
约40-95%(重)的酸化PPS;和
约1-20%(重)的弹性体,包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物。
其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
2.权利要求1所述的组合物,其中酸化PPS的钠离子含量低于900ppm。
3.权利要求1所述的组合物,其中组合物的断裂伸长率大于150%。
4.权利要求1所述的组合物,其中酸化PPS与抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂中的至少一种并用。
5.权利要求1所述的组合物,其中酸化PPS与一或多种增强剂并用。
6.权利要求1所述的组合物,其中组合物包括少于10%(重)的烯烃聚合物。
7.一种生产PPS基共混物的方法,包括如下步骤:
将包括至少一种硫源、至少一种二卤代芳族化合物和极性有机化合物的聚合反应混合物在聚合条件下进行反应,生成PPS聚合物;
将PPS聚合物的一或多个端基酸化,生成酸化PPS聚合物;
终止聚合反应;
回收酸化PPS聚合物;和
将酸化PPS聚合物、至少乙烯和缩水甘油酯的烯烃聚合物以及一种包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物的弹性体在酸化PPS聚合物熔点以上的温度下进行共混,生成PPS基共混物,其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
8.权利要求7所述方法,其中将一或多个端基酸化的步骤是在聚合反应终止前进行。
9.权利要求7所述方法,其中将一或多个端基酸化的步骤是在聚合条件下进行的。
10.权利要求7所述方法,其中将一或多个端基酸化的步骤是在PPS聚合物回收步骤后进行。
11.权利要求7所述方法,包括将PPS基共混物造粒的步骤。
12.权利要求7所述方法,其中将一或多种增强剂与酸化PPS聚合物、烯烃共聚物和弹性体共混。
13.权利要求7所述方法,其中PPS基共混物包括约5-50%(重)烯烃共聚物。
14.权利要求7所述方法,其中PPS基共混物包括少于10%(重)的烯烃聚合物。
15.权利要求7所述方法,其中PPS基共混物包括约40-90%(重)的酸化PPS。
16.权利要求7所述方法,其中PPS基共混物包括约1-20%(重)弹性体。
17.一种PPS共混物纤维,包括:
多根丝,其中每根丝包括:
约5-50%(重)的至少乙烯和缩水甘油酯的烯烃聚合物;
约40-95%(重)的酸化PPS;和
约1-20%(重)的弹性体,包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物;
其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
18.权利要求17的PPS共混物纤维,其中酸化PPS的钠离子含量低于900ppm。
19.权利要求17的PPS共混物纤维,其中酸化PPS与抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂中的至少一种并用。
20.权利要求17的PPS共混物纤维,其中酸化PPS与一或多种增强剂并用。
21.权利要求17的PPS共混物纤维,其中丝包括少于10%(重)的烯烃聚合物。
22.一种包覆制品,包括
可变形基材;
置于可变形基材一或多个表面的包覆层,包覆层包括:
约5-50%(重)的包括乙烯和缩水甘油酯的烯烃聚合物;
约40-95%(重)的酸化PPS;和
约1-20%(重)的弹性体,包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物;
其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
23.权利要求22所述的包覆制品,其中酸化PPS的钠离子含量低于900ppm。
24.权利要求22所述的包覆制品,其中包覆层的断裂伸长率大于150%。
25.权利要求22所述的包覆制品,其中酸化PPS与抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂中的至少一种并用。
26.权利要求22所述的包覆制品,其中酸化PPS与一或多种增强剂并用。
27.权利要求22所述的包覆制品,其中包覆层包括少于10%(重)的烯烃聚合物。
28.一种多层结构,包括
至少一个基层;和
置于所述至少一个基层上的阻隔层,阻隔层包括:
约5-50%(重)的至少乙烯和缩水甘油酯的烯烃聚合物;
约40-95%(重)的酸化PPS;和
约1-20%(重)的弹性体,包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物;
其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
29.权利要求28所述的多层结构,其中基层包括一个外层。
30.权利要求28所述的多层结构,其中多层结构包括一种有内表面和外表面的容器。
31.权利要求30所述的多层结构,其中阻隔层形成内表面,基层形成外表面。
32.权利要求28所述的多层结构,包括置于阻隔层和基层间的一或多个粘结层。
33.权利要求28所述的多层结构,其中至少一个粘结层包括XtelXE3200和线型低密度聚乙烯的至少一种。
34.权利要求28所述的多层结构,其中基层至少包括聚乙烯、高密度聚乙烯、聚丙烯、尼龙、聚(对苯二甲酸丁二酯)、聚(对苯二甲酸乙二酯)之一。
35.权利要求28所述的多层结构,其中阻隔层包括膜、固体层和颗粒分散体之一。
36.权利要求28所述的多层结构,包括置于阻隔层与基层间的一或多个辅助层。
37.权利要求28所述的多层结构,其中酸化PPS与抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂中的至少一种并用。
38.权利要求28所述的多层结构,其中阻隔层包括一或多种增强剂。
39.权利要求28所述的多层结构,其中阻隔层包括少于10%(重)的烯烃聚合物。
40.一种不渗透蒸气的结构,包括:
至少两个由复合片材形成的结构部件,复合片材包括:
阻隔层;
外层;
在两个相邻的结构部件间的至少一个蒸气不渗透的密封部分,该蒸气不渗透的密封部分包括一个由各邻接结构部件的阻隔层融合所形成的融接区。
41.权利要求40所述的蒸气不渗透结构,其中阻隔层包括:
约5-50%(重)的乙烯和缩水甘油酯的烯烃聚合物;
约40-90%(重)的酸化PPS;和
约1-20%(重)的弹性体,包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物;
其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
42.权利要求41所述的蒸气不渗透结构,其中阻隔层包括少于10%(重)的烯烃聚合物。
43.权利要求40所述的蒸气不渗透结构,其中复合片材包括一或多个置于阻隔层和外层间的粘结层。
44.权利要求43所述的蒸气不渗透结构,其中至少一个粘结层包括Xtel XE3200和线型低密度聚乙烯的至少一种。
45.权利要求40所述的蒸气不渗透结构,其中外层至少包括聚乙烯、高密度聚乙烯、聚丙烯、尼龙、聚(对苯二甲酸丁二酯)、聚(对苯二甲酸乙二酯)之一。
46.权利要求40所述的蒸气不渗透结构,其中阻隔层包括膜、固体层和颗粒分散体之一。
47.权利要求40所述的蒸气不渗透结构,其中复合片材包括置于阻隔层与外层间的一或多个辅助层。
48.权利要求40所述的蒸气不渗透结构,其中阻隔层至少包括抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂之一。
49.权利要求40所述的蒸气不渗透结构,其中阻隔层包括一或多种增强剂。
50.一种蒸气不渗透部件,包括
由复合片材形成的部件主体,复合片材包括:
阻隔层;和
外层;
其中部件主体的至少一个边缘与第二部件的配接边缘匹配,以使部件主体和第二部件的阻隔层能接合。
51.权利要求50所述的蒸气不渗透部件,其中阻隔层包括:
约5-50%(重)的乙烯和缩水甘油酯的烯烃聚合物;
约40-90%(重)的酸化PPS;和
约1-20%(重)的弹性体,包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物;
其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
52.权利要求51所述的蒸气不渗透部件,其中阻隔层包括少于10%(重)的烯烃聚合物。
53.权利要求50所述的蒸气不渗透部件,其中复合片材包括一或多个置于阻隔层和外层间的粘结层。
54.权利要求53所述的蒸气不渗透结构,其中至少一个粘结层包括Xtel XE3200和线型低密度聚乙烯的至少一种。
55.权利要求50所述的蒸气不渗透部件,其中外层至少包括聚乙烯、高密度聚乙烯、聚丙烯、尼龙、聚(对苯二甲酸丁二酯)、聚(对苯二甲酸乙二酯)之一。
56.权利要求50所述的蒸气不渗透部件,其中阻隔层包括膜、固体层和颗粒分散体之一。
57.权利要求50所述的蒸气不渗透部件,其中复合片材包括置于阻隔层与外层间的一或多个辅助层。
58.权利要求50所述的蒸气不渗透部件,其中阻隔层至少包括抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂之一。
59.权利要求50所述的蒸气不渗透部件,其中阻隔层包括一或多种增强剂。
60.一种燃料箱,包括:
一个围出燃料箱内体的燃料箱箱体,燃料箱箱体包括:
两或多个箱体部件,每个部件是由各自的复合片材制成,各复合片材包括:
阻隔层;
外层;和
在两个相邻箱体部件间的至少一个蒸气不渗透的密封部分,蒸气不渗透的密封部分包括一个由相应邻接箱体部件的阻隔层融合所形成的融接区。
61.权利要求60的燃料箱,包括一或多个置于燃料箱内的内插件。
62.权利要求61的燃料箱,其中一或多个内插件至少包括泵、过滤器和分流器之一。
63.权利要求60的燃料箱,其中阻隔层包括:
约5-50%(重)的乙烯和缩水甘油酯的烯烃聚合物;
约40-90%(重)的酸化PPS;和
约1-20%(重)的弹性体,包括乙烯与丙烯酸、甲基丙烯酸、其相应的1-5个碳原子烷基的烷基酯及金属盐中至少一种所形成的共聚物;
其中烯烃聚合物与弹性体的重量比在约3∶1-20∶1范围。
64.权利要求63所述的燃料箱,其中阻隔层包括少于10%(重)的烯烃聚合物。
65.权利要求60所述的燃料箱,其中复合片材包括一或多个置于阻隔层和外层间的粘结层。
66.权利要求65所述的燃料箱,其中至少一个粘结层包括XtelXE3200和线型低密度聚乙烯的至少一种。
67.权利要求60所述的燃料箱,其中外层至少包括聚乙烯、高密度聚乙烯、聚丙烯、尼龙、聚(对苯二甲酸丁二酯)、聚(对苯二甲酸乙二酯)之一。
68.权利要求60所述的燃料箱,其中阻隔层包括膜、固体层和颗粒分散体之一。
69.权利要求60所述的燃料箱,其中复合片材包括置于阻隔层与外层间的一或多个辅助层。
70.权利要求60所述的燃料箱,其中阻隔层至少包括抗氧剂、热稳定剂、润滑剂、成核剂、UV稳定剂、炭黑、金属钝化剂、增塑剂、二氧化钛、颜料、粘土、云母、阻燃剂、加工助剂、粘合剂和增粘剂之一。
71.权利要求60所述的燃料箱,其中阻隔层包括一或多种增强剂。
72.权利要求60所述的燃料箱,包括一个能通向燃料箱内部空间的加油颈管。
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- 2004-08-18 EP EP20040781586 patent/EP1660583A1/en not_active Withdrawn
- 2004-08-18 MX MXPA06001901A patent/MXPA06001901A/es unknown
- 2004-08-18 BR BRPI0413751 patent/BRPI0413751A/pt not_active IP Right Cessation
- 2004-08-18 KR KR1020067003258A patent/KR20060065698A/ko not_active Application Discontinuation
- 2004-08-18 US US10/922,139 patent/US20050089688A1/en not_active Abandoned
- 2004-08-18 JP JP2006524038A patent/JP2007502894A/ja active Pending
- 2004-08-18 CA CA 2536098 patent/CA2536098A1/en not_active Abandoned
- 2004-08-18 WO PCT/US2004/026927 patent/WO2005019341A1/en not_active Application Discontinuation
- 2004-08-18 CN CNA2004800272227A patent/CN1856545A/zh active Pending
Cited By (7)
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CN102560734A (zh) * | 2011-12-29 | 2012-07-11 | 深圳市中晟创新科技股份有限公司 | 一种抗氧化增韧改性聚苯硫醚单丝及其制备方法 |
CN102560734B (zh) * | 2011-12-29 | 2013-05-01 | 深圳市中晟创新科技股份有限公司 | 一种抗氧化增韧改性聚苯硫醚单丝及其制备方法 |
CN104302704A (zh) * | 2012-04-13 | 2015-01-21 | 提克纳有限责任公司 | 动态硫化的聚芳硫醚组合物 |
CN110283457A (zh) * | 2013-09-26 | 2019-09-27 | Dic株式会社 | 聚芳硫醚树脂组合物及其成形品、以及表面安装电子部件 |
CN104109380A (zh) * | 2014-06-27 | 2014-10-22 | 惠州市昌亿新材料有限公司 | 一种聚苯硫醚用增强剂及由其制备的高强度聚苯硫醚 |
CN104109380B (zh) * | 2014-06-27 | 2017-07-07 | 惠州市集和光电科技有限公司 | 一种聚苯硫醚用增强剂及由其制备的高强度聚苯硫醚 |
WO2022016788A1 (zh) * | 2020-07-21 | 2022-01-27 | 金发科技股份有限公司 | 一种超高断裂伸长率的pps复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
MXPA06001901A (es) | 2006-05-31 |
US20050089688A1 (en) | 2005-04-28 |
KR20060065698A (ko) | 2006-06-14 |
EP1660583A1 (en) | 2006-05-31 |
WO2005019341A1 (en) | 2005-03-03 |
BRPI0413751A (pt) | 2006-10-31 |
CA2536098A1 (en) | 2005-03-03 |
JP2007502894A (ja) | 2007-02-15 |
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