CN101184801A - 甲硅烷基化的热塑性硫化橡胶组合物 - Google Patents
甲硅烷基化的热塑性硫化橡胶组合物 Download PDFInfo
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- CN101184801A CN101184801A CNA2006800189318A CN200680018931A CN101184801A CN 101184801 A CN101184801 A CN 101184801A CN A2006800189318 A CNA2006800189318 A CN A2006800189318A CN 200680018931 A CN200680018931 A CN 200680018931A CN 101184801 A CN101184801 A CN 101184801A
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Abstract
一种制备热塑性硫化橡胶的方法,包括将热塑性第一聚合物、弹性第二聚合物、羧酸酐、自由基发生剂和增粘剂共混,以提供粘性第一共混物,所述粘性第一共混物包含所述热塑性第一聚合物和接枝的弹性第二聚合物,并具有分散在其中的增粘剂;然后,使所述第一共混物与硅烷进行反应,以提供非粘性热塑性硫化橡胶产物。
Description
背景技术
当前存在这样的密封剂/粘合剂应用,其中显示出改善的粘合性、拉伸强度和耐热性的硅烷交联的热熔体是工业化组装和构造的理想性能。这些应用的代表是用于汽车车窗玻璃装配和中空玻璃单元工业化组装的密封剂/粘合剂。另外的密封剂/粘合剂的要求包括足够的湿强度和节省的固化时间,以便于在组装期间易于处理,而随之在热循环期间保持粘合性。所述密封剂/粘合剂的理想性能包括200psi或更大的拉伸强度、100psi或更大的100%模量、200%或更大的伸长率、和30或更大的肖氏A硬度。能够用作单一密封的密封剂/粘合剂由于利用自动化施加而成本较低。
在中空玻璃制造行业中存在两种类型的粘合剂和密封剂。这些物质包括热固性和热塑性的组合物。化学固化的热固性组合物包括多硫化物、聚氨酯和有机硅。热塑性组合物包括基于热熔体丁基橡胶的组合物。热熔体丁基组合物的可取性在于其低的导湿(MVT)性能。然而,这些物质由于高低温度的波动容易使粘合性和抗蠕变性变得较差,从而导致组装构造的变形。
Schombourg,J.F.等人的美国专利6,448,343(引入本文以供参考)中公开了硅烷硫化的热塑性弹性体,其凝胶含量为10至50wt%,和伸长率为400%。所要求保护的组合物由聚合物或共聚物、自由基发生剂、羧酸酐和氨基硅烷的分散相反应产物,以及第二聚合物连续相组成。然而,该项专利中公开的方法未能提供通过甲硅烷氧基水解和缩合而充分交联所述分散相所需的化学计量数量的水。其说明书中教导到不需要额外的水源。此外,没有提到要引入增塑剂、树脂增粘剂、硅烷、缩合催化剂和/或聚合添加剂。
Arhart,R.J.等人的美国专利公开20030032728公开了水分可固化的、可熔融处理的接枝乙烯共聚物。通过将甲基丙烯酸环氧缩水甘油基酯共聚到所述聚合物骨架中制备甲硅烷基接枝的乙烯,这提供了用于氨基硅烷的接枝位点。可以预计粘合性将得到改善。然而,没有公开将通过所述甲硅烷氧基的交联作为该方法的一部分。需要增加固化时间以达到最终性能的后固化步骤。制备共聚材料的必要性增加了成本,并限制了甲硅烷氧基交联度变化的适应性。没有提到水分释放添加剂、缩合催化剂或增粘剂。
Laughner,M.K.等人的美国专利公开20020151647公开了热塑性聚合物共混组合物,其包括基本没有交联的热塑性基质树脂相和分散的硅烷接枝弹性体相。这些组合物是通过多步骤工艺制备的,首先熔融混合热塑性树脂和弹性体,所述热塑性树脂和弹性体在熔融混合温度下具有类似的粘度。优选将能促进硅烷交联、支化或能促进上述两者的催化剂,当所述熔体混合相呈熔融态时或在将它们以固态回收之后,加入到所述熔体混合相中,但这不是必要的。然后在所述熔体混合相转化为成型物体之前或之后,使该熔体混合相和任选的催化剂与水分接触,从而实现所分散的弹性体相在域内的支化和交联。所述交联和支化可以构建弹性体分子量和稳定分散域形状。所述弹性体相可以包含非弹性体聚合物。第二非接枝的弹性体相也可以被包括在所述热塑性聚合物的共混物组合物中。这样的多步骤工艺需要特殊的存放和处理,以防止预交联、后水分固化,这将增大成本及复杂性。
Baratuci,J.L.等人在美国专利5,851,609和6,355,328中描述了一种用于多格窗的组合物中的单一的隔离物/密封剂,其中核心材料和粘合剂为基于异丁烯的聚合物、增塑剂、填料、粘合促进剂和无定形聚α-烯烃聚合物。还公开的有通过动态硫化而制备的热塑性塑料或热塑性弹性体。没有提到通过甲硅烷氧基的交联、释放用于甲硅烷氧基水解和缩合的水分的添加剂,也没有公开用于核心材料或粘合剂组合物的缩合催化剂。
目前对于热熔体组合物尚有需求,该热熔体组合物具有扩大范围的热熔体密封剂/粘合剂组合物的分散相和改善的抗蠕变性能。
发明内容
制备热塑性硫化橡胶的方法包括使热塑性第一聚合物、弹性第二聚合物、羧酸酐、自由基发生剂和增粘剂共混,以提供粘性第一共混物,所述粘性第一共混物包含所述热塑性第一聚合物和接枝的弹性第二聚合物,并具有分散在其中的增粘剂;然后,使所述第一共混物与硅烷进行反应,以提供非粘性热塑性硫化橡胶产物。
有利的是在本发明中引入树脂增粘剂,优选还有释放水分的添加剂。增粘剂树脂的引入可以扩大分散相的范围,并在其中进一步提高抗蠕变性能。在指定温度下的释放水分的添加剂的引入有利于烷氧基水解和缩合的完成,从而增加所述交联相,这一特点提高了抗蠕变性能,如通过熔体流动的减少的可确定的那样。
发明详述
本发明涉及甲硅烷基化的热塑性硫化橡胶(TPVSi)组合物,所述组合物基于羧酸酐改性的或过氧化物接枝的弹性体的分散相、连续相热塑性塑料、有机树脂增粘剂、添加剂和缩合催化剂,所述分散相进一步与硅烷、优选氨基硅烷进行反应,所述添加剂释放水分,以促进所述分散相的烷氧基甲硅烷基水解和缩合交联。这些组合物显示出优于现有技术的扩大范围的机械性能,以及如通过熔体流动的减少可以确定的抗蠕变性能的改善。所公开的热塑性硫化橡胶组合物具有丁基橡胶基密封剂/粘合剂的优异MVT性质,该性质适合于中空玻璃的制造。此外,与在中空玻璃的制造期间固化的组合物相比,本文公开的TPVSi组合物的挥发性物质减少,因而减少了化学雾。
在本发明的实施方案中,TPVSi组合物为以下物质的共混物:(a)结晶或部分结晶的热塑性第一聚合物,(b)弹性第二聚合物(橡胶相);(c)羧酸酐,其作为在弹性第二聚合物中的共聚单体,或者用诸如过氧化物的自由基发生剂或其它合适的方法接枝到弹性第二聚合物上的共聚单体引入;(d)硅烷,优选的是氨基硅烷;和有机树脂增粘剂。在一个实施方案中,所述组合物还包括水分源物质。
根据本发明的一个实施方案,基于组合物总重量,所述组合物包括约5wt%至约40wt%的热塑性第一聚合物、约60wt%至约95wt%的弹性第二聚合物、约0.01wt%至约1.0wt%的羧酸酐、约0.005wt%至约0.5wt%的过氧化物、约0.25wt%至约2.5wt%的硅烷、和约5wt%至约25wt%的增粘剂。
根据本发明另一个实施方案,基于组合物总重量,所述组合物包括约10wt%至约30wt%的热塑性第一聚合物、约70wt%至约90wt%的弹性第二聚合物、约0.05wt%至约0.5wt%的羧酸酐、约0.025至约0.25wt%的过氧化物、约0.5wt%至约2.0wt%的硅烷和约10wt%至约25wt%的增粘剂。
根据本发明另一个实施方案,基于组合物总重量,所述组合物包括约15wt%至约25wt%的热塑性第一聚合物、约75wt%至约85wt%的弹性第二聚合物、约0.1wt%至约0.4wt%的羧酸酐、约0.05至约0.2wt%的过氧化物、约1.0wt%至约2.0wt%的硅烷和约15wt%至约20wt%的增粘剂。
在另一个实施方案中,所述组合物还包括(基于组合物总重量)约1wt%至约60wt%、更优选为约10wt%至约50wt%、最优选为约15wt%至约20wt%的水分源物质。
根据优选的实施方案,与制备TPV的现有技术方法相反,本发明的方法是在单一操作下进行的。接枝、交联及偶联在共混装置中连续进行。如果需要的话,该方法也适用于间歇式混配系统中,例如Banbury或Krupp混合机。
合适的热塑性聚合物(a)包括但不限于聚丙烯(PP);聚乙烯,特别是高密度的(PE);聚苯乙烯(PS);丙烯腈丁二烯苯乙烯(ABS);苯乙烯丙烯腈(SAN);聚甲基丙烯酸甲酯(PMMA);热塑性聚酯(PET,PBT);聚碳酸酯(PC);聚酰胺(PA);聚苯撑醚(PPE)或聚苯醚(PPO)。
可以通过本领域中已知的任何方法制备这些聚合物,包括但不限于本体相、浆液相、气相、溶剂相、界面的聚合(自由基、离子、金属引发的(例如,金属茂、Ziegler-Natta))、缩聚、加聚或这些方法的组合。
合适的聚烯烃橡胶相组分(b)包括但不限于可以进行反应从而生成包含羧酸酐的聚合物的任何聚合物,例如,乙烯丙烯共聚物(EPR);乙烯丙烯二烯三元共聚物(EPDM)、丁基橡胶(BR);天然橡胶(NR);氯化聚乙烯(CPE);硅橡胶;异戊二烯橡胶(IR);丁二烯橡胶(BR);苯乙烯-丁二烯橡胶(SBR);苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物(SEBS)、乙烯-乙酸乙烯酯(EVA);乙烯丙烯酸丁酯(EBA)、乙烯-丙烯酸甲酯(EMA)、乙烯-丙烯酸乙酯(EEA)、乙烯-α烯烃共聚物(例如,EXACT和ENGAGE,LLDPE(线性低密度聚乙烯))、高密度聚乙烯(HPE)和丁腈橡胶(NBR)。聚丙烯作为该相是不合适的,因为它在交联期间具有降解的趋势;然而,如果所述聚丙烯是聚丙烯与酸酐的共聚物或接枝聚合物的话就可以使用。优选的是,所述聚合物为具有至少50%乙烯含量(单体计)的乙烯聚合物或共聚物,更优选至少70%的单体是乙烯。
可以使用于所述两相的聚合物相同,其中将酸酐与过氧化物一道预添加,或者用其它方法将其接枝到聚合物的一部分上,其中预反应的聚合物将作为TPV内的橡胶相。这种预添加包括了使所述酸酐作为在所述聚合物中的共聚单体或使所述酸酐与所述聚合物预反应的可能性。无论处于这两种情况中的哪一种下,添加单独的酸酐都是不必要的,因为其存在于所述聚合物中。该过程可以在单个连续混合机、串列布置的若干混合机、间歇式混合机或通常用于加工弹性体和热塑性聚合物的任何其它合适的混合机中完成。
第三种可选方案是,橡胶相和热塑性塑料相的聚合物可以是相同的聚合物,只是将酸酐加入到作为整体的聚合物当中。在这种情况下,当加入硅烷时,部分聚合物会形成橡胶相,而另一部分将不反应(假定存在相对少量的酐和硅烷)。重要的是在该过程期间造成橡胶相和热塑性塑料相之间的适当相分离度。该过程可以在单个连续混合机、串列布置的若干混合机、间歇式混合机或通常用于加工弹性体和热塑性聚合物的任何其它合适的混合机中完成。
在两种不同聚合物的情况下,将对酸酐反应性更强的聚合物用酸酐进行接枝,并用作在TPV中的橡胶相。然而,该方法是灵活的,并且如果需要的话,可以通过在该过程中选择性地加入添加剂来对该方法进行改进。
欲成为橡胶相的聚合物必须是可挤出的,且在其制造期间应能够用酸酐进行接枝或被酸酐改性。
热塑性塑料相的熔点应低于氨基硅烷的分解温度以及酸酐的分解温度(除非酸酐是所述聚合物中的共聚单体)。
所述聚合物可以具有单峰、双峰或多峰式的分子量分布。所述聚合物的熔体流动可以为任何在本领域中已知用于形成热塑性塑料及橡胶的那些。
可以使用能够通过任何可行的方式进行接枝或反应到达将要成为橡胶相的聚合物之上或之内的任何羧酸酐。优选的是,为了完成该接枝过程,在聚合物中或者更优选在酸酐中存在不饱和结构。如果存在的话,所述羧酸酐的不饱和结构可以在环结构的内部或外部,只要其可以与聚合物反应。所述酸酐可以包括卤化物。可以使用不同羧酸酐的混合物。适用于本发明中的典型不饱和羧酸酐包括但不限于异丁烯基琥珀酸、(+/-)-2-辛烯-1-基琥珀酸、衣康酸、2-十二烯-1-基琥珀酸、顺-1,2,3,6-四氢邻苯二甲酸、顺-5-降冰片烯-内-2,3-二羧酸、内-双环[2.2.2]辛-5-烯-2,3-二羧酸、甲基-5-降冰片烯-2,3-二羧酸、外-3,6-环氧-1,2,3,6-四氢邻苯二甲酸、马来酸、柠康酸、2,3二甲基马来酸、1-环戊烯-1,2-二羧酸、3,4,5,6-四氢邻苯二甲酸、溴代马来酸和二氯代马来酸的酸酐。
这些酸酐可以作为在橡胶相的聚合物中的共聚单体而存在,或者可以接枝到将成为所述橡胶相的聚合物上。
基于聚合物存在的总量,所用的酸酐的量为约0.01至约1.0wt%。所述自由基发生剂(优选过氧化物)的存在量通常是约所述羧酸酐重量百分比的一半,当然在适当的时候也可以使用其它的百分比。
在本发明的配方中既使用硅烷交联剂又使用增粘剂所提供的产品具有三维的聚合物结构,该产品用于粘合及密封是有利的,例如作为玻璃制品的玻璃油灰(glazing compound)。所述共混物最初是粘性的,直到例如通过与硅烷反应而被固化,于是失去其粘性,直到再加热所述TPV配混物,例如当用作热熔体粘合剂时。当熔融时所述热熔体配混物恢复其粘性,用以施加到欲粘结的表面(例如,玻璃)上,然后当冷却时再变成非粘性的。若没有硅烷固化,所述配混物将长久地保持粘性,这在诸如窗玻璃油灰的许多应用当中是不合适的。
本文中所用的硅烷优选为氨基硅烷,该氨基硅烷具有至少一个可水解的基团,例如烷氧基、乙酰氧基或卤基,优选烷氧基。优选的是,存在能经历交联缩合反应的至少两个这样的可水解基团,从而使得到的化合物能经历这种交联。可以使用不同氨基硅烷的混合物。
所述胺必须具有与所述酸酐的足够的反应速率。一般来说,叔胺不能与所述酸酐进行适当的反应,应避免使用。所述氨基可以通过支链基团桥接到硅原子上,以减少所得组合物的泛黄。
所述硅烷可以由式YNHBSi(OR)a(X)3-a表示,其中a=1至3,优选为3,Y是氢、烷基、烯基、羟基烷基、烷芳基、烷基甲硅烷基、烷基胺、C(=O)OR或C(=O)NR,R是酰基、烷基、芳基或烷芳基,X可以是R或卤基。B是二价桥基,其优选为亚烷基,该亚烷基可以是支化的(例如,亚新己基)或环状的。B可以包含杂原子桥,例如醚键。优选B为亚丙基。优选R为甲基或乙基。包含甲氧基的硅烷与包含乙氧基的相比可以确保更好的交联性能。优选Y为氨基烷基、氢或烷基。更优选Y是氢或伯氨基烷基(例如,氨基乙基)。优选X是Cl或甲基,更优选为甲基。典型的硅烷为γ-氨基丙基三甲氧基硅烷(得自GE的SILQUESTA-1110);γ-氨基丙基三乙氧基硅烷(SILQUESTA-1100);γ-氨基丙基甲基二乙氧基硅烷;4-氨基-3,3-二甲基丁基三乙氧基硅烷、4-氨基-3,3-二甲基丁基甲基二乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷(SILQUESTA-1120)、H2NCH2CH2NHCH2CH2NH(CH2)3Si(O-CH3)3(SILQUESTA-1130)和N-β-(氨基乙基)-γ-氨基丙基甲基二甲氧基硅烷(SILQUESTA-2120)。其它合适的氨基硅烷如下:3-(N-烯丙基氨基)丙基三甲氧基硅烷、4-氨基丁基三乙氧基硅烷、4-氨基丁基三甲氧基硅烷、(氨基乙基氨基甲基)-苯乙基三甲氧基硅烷、氨基苯基三甲氧基硅烷、3-(1-氨基丙氧基)-3,3,二甲基-1-丙烯基三甲氧基硅烷、双[(3-三甲氧基甲硅烷基)-丙基]乙二胺、N-甲基氨基丙基三甲氧基硅烷、双(γ-三乙氧基甲硅烷基丙基)胺、(SILQUESTA-1170)和N-苯基-γ-氨基丙基三甲氧基硅烷(SILQUESTY-9669)。
如果所述氨基硅烷是隐性氨基硅烷,即脲基硅烷或氨基甲酸根合硅烷,则共混温度必须足以使各自的保护基团从所述胺上脱离,并允许所述胺与所述酸酐官能团进行反应,约150至230EC。这种隐性氨基硅烷的例子有叔丁基-N-(3-三甲氧基甲硅烷基丙基)氨基甲酸酯、脲基丙基三乙氧基硅烷和脲基丙基三甲氧基硅烷。其它可以使用的氨基甲酸酯基硅烷公开在美国专利5,220,047中,该文献通过引用结合到本文中。优选的是,为了避免去保护基的额外复杂性,所述氨基硅烷不采用这种隐性氨基硅烷。
基于两种聚合物的重量,所述氨基硅烷应为250至25,000ppm。其与酸酐的摩尔当量比还应当为约0.1比10,更优选为0.9比1.1,最优选的是约1∶1的比例。
可以将所述硅烷负载在诸如多孔聚合物、二氧化硅、二氧化钛或碳黑的载体上,从而使得在混合过程中易于添加到所述聚合物当中。所述硅烷还可以与相容性的加工油或蜡共混。这在已经包含油和/或将得益于使用油作为加工助剂、增塑剂、降低油吸收制剂和/或软化剂的配方中是特别有用的。典型的材料为ACCUREL聚烯烃(Akzo Nobel)、STAMYPOR聚烯烃(DSM)和VALTEC聚烯烃(Montell)、SPHERILENE聚烯烃(Montell)、AEROSIL二氧化硅(Degussa)、MICRO-CEL E(Manville)和ENSACO 350G碳黑(MMM Carbon)。白油,即石蜡基油,石蜡基蜡,是对于所述硅烷的有用载体,但可以使用与所述硅烷相容的任何油及复合制剂。
合适的可商购增粘剂包括,例如商标名称EASTOTAC系列的部分氢化的脂环族石油烃树脂,包括例如购自Eastman Chemical Co.(Kingsport,Tenn.)的EASTOTAC H-100、H-115、H-130和H-142,可以得到E、R、L和W的级别,其具有不同的氢化程度,从最少氢化(E)至最多氢化(W),购自Exxon Chemical Co.(Houston,Tex.)的商标名称ESCOREZ系列,包括例如ESCOREZ 5300和ESCOREZ 5400,以及购自Hercules(Wilmington,Del.)的商标名称HERCOLITE 2100系列;以商标名称ESCOREZ 5600购自Exxon Chemical Co.的部分氢化的芳族改性石油烃树脂;以商标名称WINGTACK EXTRA购自GoodyearChemical Co.(Akron,Ohio)的脂族-芳族石油烃树脂;由d-柠檬烯制备的苯乙烯化萜烯树脂,以商标名称ZONATAC 105 LITE购自ArizonaChemical Co.(Panama City,Fla.);以商标名称REGALREZ 1094购自Hercules的芳族氢化烃树脂;以及以商标名称KRISTALEX 3070、3085和3100购自Hercules的α-甲基苯乙烯树脂,分别具有70EC、85EC和100EC的软化点。
适用于本发明中的水分源物质中含有水,并优选的是这样的化合物,其在分子结构中结合有水,但在进行共混处理的温度下将水释放出来。这种包含结合水的化合物包括例如无机化合物的水合物,如水合无机氧化物、氢氧化物和盐。具体的例子包括三水合铝、Al(OH)3、Mg(OH)2、Ca(OH)2等。
如果是通过自由基机理将所述羧酸酐接枝到所述聚合物上则需要自由基发生剂,但是当通过另外的机理接枝酸酐或者酸酐为所述聚合物的共聚单体时则不需要它。合适的自由基催化剂可以选自:水溶性或油溶性过氧化物,例如过氧化氢、过硫酸铵、过硫酸钾,各种有机过氧催化剂,例如二烷基过氧化物,如二异丙基过氧化物、二月桂基过氧化物、二叔丁基过氧化物、二(2-叔丁基过氧基异丙基)苯、3,3,5-三甲基1,1-二(叔丁基过氧基)环己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己-3-炔、过氧化二异丙苯,烷基过氧化氢,例如叔丁基过氧化氢、叔戊基过氧化氢、异丙苯基过氧化氢,二酰基过氧化物,例如过氧化乙酰、过氧化月桂酰、过氧化苯甲酰,过氧基酯,例如过氧基苯甲酸乙酯,以及偶氮化合物,例如2-偶氮双(异丁腈)。
基于所述酸酐的摩尔数量,所述自由基发生剂可以为1/100至1/1的量。
可以将例如(UV、光或老化)稳定剂、抗氧化剂、金属减活剂、加工助剂、蜡、填料(二氧化硅、TiO2、CaCO3、碳黑、二氧化硅等)和着色剂的标准添加剂加入到TPVSi中。此外,可以将发泡剂添加到聚合物中,从而使得当它们被挤出时所述聚合物会形成泡沫。这些发泡剂的例子为挥发性烃、氢氟碳化合物和氯氟碳化合物。如偶氮碳酰胺或碳酸氢钠的常见发泡剂在高温下分解产生气态产物。这些都是化学发泡方法。也可以通过将液态或气态发泡剂注入到所述聚合物熔体中产生泡沫。例子有例如丁烷、CO2、氮、水、氦等。这种发泡剂的量应当为所述聚合物的0.1至50重量%。
在第一个反应中(最优选通过自由基机理)将所述羧酸酐接枝到所述橡胶相聚合物上。该反应可以在两种聚合物都存在或两种聚合物分离的情况下完成,虽然优选是在两种聚合物都存在的情况下完成这一步。如前所述,或者可以通过将所述羧酸酐作为共聚单体包含在所述橡胶相聚合物中来有效地实现这一步(在这种情况下自由基发生剂不是必要的)。所述聚合物应在与氨基硅烷的反应之前用羧酸酐进行接枝/共聚,这是因为在酸酐与氨基硅烷之间的反应产物只具有较差的接枝效率。在氨基硅烷与酸酐之间的在先反应会导致形成半酰胺,其可能具有差的接枝性能。在这种情况下将不会发生交联。相反,所述聚合物的部分降解和/或所述半酰胺的增塑效果可能导致熔体流动指数(MFI)的增加。
优选在所述接枝步骤期间添加自由基发生剂与所述酐,从而引发将所述酸酐到所述橡胶相聚合物上的接枝。
如果所述热塑性聚合物在接枝期间不存在的话,则应在添加氨基硅烷之前将其与所述接枝的橡胶相聚合物一起共混入;然而,从得到的TPVSi的机械性能方面讲,这种方法存在缺陷。
第二步是将所述氨基硅烷添加到所述橡胶相接枝的聚合物/热塑性聚合物共混物中。与美国专利6,448,343中公开的方法不同,优选加入水分源物质。
在将所述氨基硅烷接枝到所述一种聚合物上以后,应使其进行交联,从而形成所述交联聚合物的凝胶相。不需要发生单独的水分固化。可以使用缩合催化剂以加速所述交联过程,虽然所述半酰胺应该是一种充分的催化剂。在约60EC至约200EC的高温下一至十分钟应可以确保发生这种交联。
所述添加剂的总量只有组合物总计的约0.4%,这大约比过氧化物或乙烯基硅烷固化所需的量少约5倍。这在两种方式上是有益的:总成本的降低和可造成安全问题的易挥发过氧化物的减少。
有利的是,本发明的方法可以作为连续的过程在单一的步骤中操作进行。或者该方法可以为间歇的过程。可以使用适合于本文所述目的的任何混合机。优选的混合机为螺杆式混合机,具有至少两个进料点,一个位于沿着混合机桶的上游位置,并且第二个进料点位于沿着所述桶的下游位置。所述混合机可以是挤出机(单螺杆、双螺杆等)、BUSS KO-KNEADER混合机或简单的内部式混合机。混合的条件取决于聚合物及交联度。
所得到的产品为具有优良机械性能的热塑性硫化橡胶。所述交联的材料具有相当的凝胶含量,比起起始聚合物来说MFI要低得多,这将会提高抗蠕变性能,提供更高的断裂拉伸强度,和提供的材料比非交联的聚合物共混物更硬。终端产物具有弹性性质(即,断裂伸长率大于400%),但可以采用热塑性塑料领域中通常已知的方法进行熔融加工。所述最终产物的优选凝胶含量(即,橡胶含量)为约10wt%至约50wt%,最优选为约25wt%至约35wt%。纵向和横向上的拉伸及弹性模量得以提高,这是材料的落镖冲击强度。
所述TPVSi组合物是可涂漆的,且具有更好的耐油性。它们可以用于例如粘合剂和密封剂、电缆绝缘、管道、断面、模塑部件、发泡部件、片材等。
所述氨基硅烷橡胶相改性的聚合物往往与所述热塑性聚合物更相容,这可以提供更坚固的TPVSi。
实施例
下面给出实施例和比较例。实施例(数字编号)用来例示本发明。不使用硅烷的比较例(字母编号)仅用于比较的目的,不是用来例示本发明。
在实施例中使用下述组分:购自ExxonMobil的名称为Butyl 268和Butyl 165的异丁烯-异戊二烯共聚物(丁基橡胶)、购自ExxonMobilChemical的名称为Escorez 1304的烃增粘剂树脂、以名称VistanexL-100和L-140购得的高分子量聚异丁烯、购自Kraton polymers的名称为Kraton FG 1901和Kraton FG 1924X的马来酸酐改性的苯乙烯乙烯-丁烯苯乙烯嵌段共聚物、购自Hardman Co.的名称为Kalene 800的液态合成的解聚丁基橡胶、购自Arizona chemical Co.的名称为SylvarezTR1085的萜烯-酚增粘剂、购自DuPont的名称为Elvax460的乙烯-乙酸乙烯酯树脂、购自Eastman Chemical Co.的名称为Eastotac H-100W的部分氢化的脂环族石油烃树脂增粘剂以及购自Pfizer的名称为Ultra-pflex和Hi-pflex的碳酸钙。
实施例1-4和比较例A-H
使用Braybender在160℃、150rpm的条件下制备表1中比较例A至D的组合物,没有酸酐的接枝与氨基硅烷的后续反应。这些例子中显示出较高的熔体流动速率,其中100%模量低于100psi,这对于显示出蠕变增大的热熔丁基橡胶基密封剂/粘合剂组合物来说是典型的。所述伸长率及撕裂的结果进一步表明其为软韧性的密封剂/粘合剂,其不具有中空玻璃装配应用中所需的力学性能。
比较例E、F、G和H的组合物(分别)为相对于实施例1、2、3和4的比较配方,其中马来酸酐接枝的SEBS橡胶(共聚(苯乙烯-乙烯/丁烯-苯乙烯)是在连续丁基橡胶相中的分散相。这些配方表明,当引入硅烷氨基硅烷交联剂时抗蠕变性能得以提高,通过熔体流动的减少可以观察到这一点,还有力学性能得以改善,适合于中空玻璃密封剂/粘合剂的应用。
例如,实施例1-4每个的撕裂强度和100%模量高于相应的比较例E-H,并且熔体流动更低。
表1
成分 | 配方(%) | |||||||||||
实施/比较例 | A* | B* | C* | D* | E* | 1 | F* | 2 | G* | 3 | H* | 4 |
Butyl 268 | 9.05 | 9.05 | 9.05 | 9.01 | 9.05 | 9.01 | ||||||
Butyl 165 | 9.05 | 9.05 | 9.05 | 9.01 | 9.05 | 9.01 | ||||||
VistanexL-100 | 12.07 | 12.07 | ||||||||||
VistanexL-140 | 12.07 | 12.07 | ||||||||||
Kraton FG* | ||||||||||||
KratonFG1901 | 12.07 | 12.02 | 12.07 | 12.02 | ||||||||
Kraton FG1924X | 12.07 | 12.02 | 12.07 | 12.02 | ||||||||
Kalene 800 | 12.07 | 12.07 | 12.07 | 12.07 | 12.07 | 12.02 | 12.07 | 12.02 | 12.07 | 12.02 | 12.07 | 12.02 |
Escorez 1304 | 30.17 | 30.17 | 30.17 | 30.17 | 30.17 | 30.04 | 30.17 | 30.04 | 30.17 | 30.04 | 30.17 | 30.04 |
SylvarezTR1085 | 15.09 | 15.09 | 15.09 | 15.09 | ||||||||
EastotacH-100W | 15.09 | 15.02 | 15.09 | 15.02 | 15.09 | 15.02 | 15.09 | 15.02 | ||||
Elvax 460 | 8.62 | 8.62 | 8.62 | 8.62 | 8.62 | 8.58 | 8.62 | 8.58 | 8.62 | 8.58 | 8.62 | 8 58 |
滑石 | 4.31 | 4.31 | 4.31 | 4.31 | 4.31 | 4.29 | 4.31 | 4.29 | 4.31 | 4.29 | 4.31 | 4 29 |
Ultra-pflex | 4.31 | 4.31 | 4.31 | 4.31 | 4.31 | 4.29 | 4.31 | 4.29 | 4.31 | 4.29 | 4.31 | 4 29 |
Hi-pflex | 4.31 | 4.31 | 4.31 | 4.31 | 4.31 | 4.29 | 4.31 | 4.29 | 4.31 | 4.29 | 4.31 | 4 29 |
A-1100 | 0.43 | 0.43 | 0.43 | 0.43 | ||||||||
熔体流动1,g/10min. | 23.4 | 14.3 | 27.8 | 12.2 | 10.6 | 8.7 | 13.9 | 11.3 | 9.8 | 6.9 | 14.6 | 11.2 |
拉伸2,psi | 152 | 148 | 265 | 204 | 353 | 273 | 288 | 286 | 460 | 335 | 349 | 339 |
100%模量2,psi | 19 | 58 | 83 | 63 | 145 | 172 | 132 | 188 | 132 | 147 | 99 | 145 |
伸长率2,% | 1250 | 1137 | 1057 | 1243 | 556 | 443 | 449 | 479 | 449 | 809 | 857 | 843 |
撕裂B3,磅/英寸 | 49 | 27 | 62 | 76 | 101 | 101 | 80 | 95 | 80 | 93 | 81 | 92 |
1熔体流动,按ASTM 1238测量,使用Tinius Olsen ExtrusionPlastometer Model MP993a,140℃,2.16Kg重。
2ASTM D412-86
3ASTM D624-80
*比较例
实施例5和6
如上面实施例1-4中那样制备实施例5和6的配方。在实施例5和6中氨基硅烷交联的分散相增加,并且引入的水分导致熔体流动的进一步减少,预示着抗蠕变性的提高。增粘剂树脂的选择改进了机械性能而不改变熔体流动或耐撕裂性。
表2
成分 | 配方(%) | |
实施例 | 5 | 6 |
Butyl 268 | 6.29 | 6.29 |
Kraton FG 1924X | 14.68 | 14.68 |
Kalene 800 | 11.98 | 11.98 |
Escorez 1304 | 29.96 | 14.98 |
Sylvarez TR1085 | 14.98 | |
Eastotac H-100W | 14.98 | 14.98 |
Elvax 460 | 8.59 | 8.59 |
滑石 | 4.29 | 4.29 |
水 | 0.20 | 0.20 |
Ultra-pflex | 4.30 | 4.30 |
Hi-pflex | 4.30 | 4.30 |
A-1100 | 0.43 | 0.43 |
熔体流动1g/10min. | 5 | 5.1 |
拉伸2,psi | 392 | 300 |
100%模量2,psi | 175 | 122 |
伸长率2,% | 496 | 622 |
撕裂B3,磅/英寸 | 97 | 91 |
肖氏A硬度4 | 48 | 33 |
4ASTM D2240-86
比较例I和实施例7-9
使用Haake Rheometer在160℃、150rpm条件下制备比较例I和实施例7-9的配方,然后于不加热的情况下在EEMCO两辊磨粉机上进行碾磨,采用0.25英寸的间距设定。将实施例8制成下面的另外例子,然后于200℃下在Haake Rheometer中进一步混合以释放水分。比较例I和实施7是没有硅烷的组合物与带有硅烷和水分的组合物的对比。硅烷与水分的引入提高了耐撕裂性能和肖氏A硬度,显示出所述分散相的交联。实施例8在200℃下用释放水分的添加剂(~30wt%)代替水作为水分源物质,结果与实施例7的类似。实施例9显示出引入缩合催化剂的益处。在实施例14中,将20ppm二月桂酸二丁基锡与所述氨基硅烷混合。可以观察到,水分释放剂和缩合催化剂的加入产生了对于机械性能的显著改善,这预示着所述分散相的进一步交联。
表3
成分 | 配方(%) | |||
实施/比较例 | I | 7 | 8 | 9 |
Butyl 268 | 15.0 | 14.9 | 14.9 | 14.9 |
Kraton FG1924X | 18.7 | 18.6 | 18.6 | 18.6 |
Kalene 800 | 11.2 | 11.2 | 11.2 | 11.2 |
Escorez 1304 | 11.2 | 11.2 | 11.2 | 11.1 |
SvlvarezTR1085 | 11.2 | 11.2 | 11.2 | 11.1 |
EastotacH-100W | 11.2 | 11.2 | 11.2 | 11.1 |
Elvax 460 | 8.5 | 8.5 | 8.5 | 8.5 |
滑石 | 4.3* | 4.2 | ||
水 | 0.8 | |||
三水合铝 | 4.2 | 4.3 | ||
Ultra-pflex | 4.3* | 4.2 | 4.2 | 4.3 |
Hi-pflex | 4.3* | 4.2 | 4.2 | 4.3 |
A-1100 | 0.65 | 0.65 | 0.65t | |
拉伸2,psi | 103 | 127 | 120 | 230 |
100%模量2,psi | 65 | 66 | 61 | 64 |
伸长率2,% | 358 | 435 | 406 | 756 |
撕裂B3,磅/英寸 | 44 | 52 | 47 | 77 |
肖氏A硬度4 | 18 | 21 | 21 | 18 |
*150EC干燥2小时
20ppm月桂酸二丁基锡加入到氨基硅烷中
从以上可以看出,实施例7-9产品的撕裂强度和拉伸强度高于比较例I的产品。而肖氏硬度至少与实施例7和8一样好,并且好于比较例I的肖氏硬度。
比较例J和实施例10-13
按实施例7至9制备实施例10至13,并有进一步的组成变化,以达到适合于IG玻璃热熔体玻璃装配/粘合剂应用的机械性能。
表3
成分 | 配方(%) | ||||
10 | J* | 11 | 12 | 13 | |
Butyl 268 | 23.8 | 8.5 | 5.9 | 5.9 | 5.2 |
Kraton FG1924X | 29.7 | 42.7 | 29.7 | 29.7 | 25.9 |
Kalene 800 | 5.9 | 25.6 | 5.9 | 5.9 | 15.5 |
Escorez1304 | 17.8 | 15.5 | |||
SylvarezTR1085 | 17.8 | 17.8 | |||
EastotacH-100W | 17.8 | 17.8 | 15.5 | ||
Elvax 460 | 8.3 | 8.4 | 8.3 | 8.3 | 8.3 |
滑石 | 4.3 | 4.3 | 4.3 | 4.3 | 4.2 |
水 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
Ultra-pflex | 4.3 | 4.3 | 4.3 | 4.3 | 4.2 |
Hipflex | 4.3 | 4.3 | 4.3 | 4.3 | 4.2 |
A-1100 | 1.05 | 1.5 | 1.05 | 1.05 | 0.91 |
拉伸2,psi | 152 | 241 | 325 | 467 | 204 |
100%模量2,psi | 103 | 133 | 120 | 134 | 104 |
伸长率2,% | 261 | 265 | 452 | 468 | 406 |
撕裂B3,磅/英寸 | 58 | 59 | 33 | 36 | 26 |
肖氏A硬度 | 33 | 38 | 91 | 124 | 70 |
*比较例
从以上可以看出,比较例J不含增粘剂,并需要约50%以上的硅烷才能达到相当的结果。
虽然上述的描述中包含了许多具体细节,但这些具体细节不应该被视为对本发明的限制,它们只是其优选实施方案的范例。本领域的技术人员可以设想出许多其它的实施方案,它们都在通过本发明所附的权利要求所界定的范围和实质之内。
Claims (20)
1.一种制备热塑性硫化橡胶的方法,所述方法包括:
a)使热塑性第一聚合物、弹性第二聚合物、羧酸酐、自由基发生剂和增粘剂共混,以提供粘性第一共混物,所述粘性第一共混物包含所述热塑性第一聚合物和接枝的弹性第二聚合物,并具有分散在其中的增粘剂;然后
b)使所述第一共混物与硅烷进行反应,以提供非粘性热塑性硫化橡胶产物。
2.权利要求1的方法,其中所述热塑性第一聚合物包括选自如下均聚物和共聚物的一种或多种聚合物:聚丙烯、聚乙烯、聚苯乙烯、丙烯腈-丁二烯-苯乙烯、苯乙烯-丙烯腈、聚甲基丙烯酸甲酯、热塑性聚酯、聚碳酸酯、聚酰胺、聚苯撑醚、聚苯醚、及其组合。
3.权利要求1的方法,其中所述弹性第二聚合物包括选自如下的一种或多种聚合物:乙烯-丙烯共聚物、乙烯-丙烯-二烯三元共聚物、丁基橡胶、天然橡胶、氯化聚乙烯、硅橡胶、异戊二烯橡胶、丁二烯橡胶、苯乙烯-丁二烯橡胶、SEBS、乙烯-乙酸乙烯酯、乙烯-丙烯酸丁酯、乙烯-丙烯酸甲酯、乙烯-丙烯酸乙酯、乙烯-α烯烃共聚物、高密度聚乙烯、和丁腈橡胶。
4.权利要求1的方法,其中所述羧酸酐选自异丁烯基琥珀酸、(+/-)-2-辛烯-1-基琥珀酸、衣康酸、2-十二烯-1-基琥珀酸、顺-1,2,3,6-四氢邻苯二甲酸、顺-5-降冰片烯-内-2,3-二羧酸、内-双环[2.2.2]辛-5-烯-2,3-二羧酸、甲基-5-降冰片烯-2,3-羧酸、外-3,6-环氧-1,2,3,6-四氢邻苯二甲酸、马来酸、柠康酸、2,3-二甲基马来酸、1-环戊烯-1,2-二羧酸、3,4,5,6-四氢邻苯二甲酸、溴代马来酸、和二氯代马来酸的酸酐。
5.权利要求1的方法,其中所述硅烷如下式所示
YNHBSi(OR)a(X)3-a’
其中a=1至3,Y是氢、烷基、烯基、羟基烷基、烷芳基、烷基甲硅烷基、烷基胺、C(=O)OR或C(=O)NR,R是酰基、烷基、芳基或烷芳基,X是R或卤素,其中R是甲基或乙基,B是二价直链、支链或环烃桥连基团,或者B可以包含杂原子桥。
6.权利要求5的方法,其中R是甲基,Y是氨基烷基、氢或烷基,X是Cl或甲基。
7.权利要求1的方法,其中所述硅烷选自γ-氨基丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、γ-氨基丙基甲基二乙氧基硅烷、4-氨基-3,3-二甲基丁基三乙氧基硅烷、4-氨基-3,3-二甲基丁基甲基二乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷、H2NCH2CH2NHCH2CH2NH(CH2)3Si(OCH3)3、N-β-(氨基乙基)-γ-氨基丙基甲基二甲氧基硅烷、3-(N-烯丙基氨基)丙基三甲氧基硅烷、4-氨基丁基三乙氧基硅烷、4-氨基丁基三甲氧基硅烷、(氨基乙基氨基甲基)-苯乙基三甲氧基硅烷、氨基苯基三甲氧基硅烷、3-(1-氨基丙氧基)-3,3,二甲基-1-丙烯基三甲氧基硅烷、双[(3-三甲氧基甲硅烷基)-丙基]乙二胺、N-甲基氨基丙基三甲氧基硅烷、双(γ-三乙氧基甲硅烷基丙基)胺、苯基-γ-氨基丙基三甲氧基硅烷、叔丁基-N-(3-三甲氧基甲硅烷基丙基)氨基甲酸酯、脲基丙基三乙氧基硅烷和脲基丙基三甲氧基硅烷。
8.权利要求1的方法,其中将所述硅烷负载在多孔粒子载体上或用聚合物进行预处理。
9.权利要求8的方法,其中所述多孔粒子载体选自二氧化硅、二氧化钛、碳黑和聚烯烃。
10.权利要求1的方法,其中所述增粘剂包括一种或多种增粘剂树脂,所述增粘剂树脂选自部分或完全氢化的脂环族石油烃树脂、部分或完全氢化的芳族改性石油烃树脂;脂族-芳族石油烃树脂;由d-柠檬烯和α-甲基苯乙烯树脂制备的苯乙烯化萜烯树脂。
11.权利要求1的方法,进一步包括在步骤(a)中使水分源物质与所述第一聚合物、第二聚合物、羧酸酐、自由基发生剂和增粘剂进行共混。
12.权利要求11的方法,其中所述水分源物质是水。
13.权利要求11的方法,其中所述水分源物质包括水合的无机化合物。
14.权利要求13的方法,其中所述水合的无机化合物选自Al(OH)3、Mg(OH)2和Ca(OH)2。
15.权利要求1的方法,其中所述共混作为连续的过程进行。
16.权利要求1的方法,进一步包括还将选自UV稳定剂、抗氧化剂、金属减活剂、加工助剂、蜡、填料、着色剂和发泡剂的一种或多种组分共混。
17.权利要求1的方法,其中所述自由基发生剂包括选自以下的化合物:过氧化氢,过硫酸铵,过硫酸钾,各种有机过氧催化剂,如二烷基过氧化物,例如二异丙基过氧化物,二月桂基过氧化物,二叔丁基过氧化物,二(2-叔丁基过氧基异丙基)苯,3,3,5-三甲基1,1-二(叔丁基过氧基)环己烷,2,5-二甲基-2,5-二(叔丁基过氧基)己烷,2,5-二甲基-2,5-二(叔丁基过氧基)己-3-炔,过氧化二异丙苯,叔丁基过氧化氢,叔戊基过氧化氢,异丙苯基过氧化氢,过氧化乙酰,过氧化月桂酰,过氧化苯甲酰,过氧基苯甲酸乙酯和2-偶氮双(异丁腈)。
18.权利要求1的方法,其中所述共混是在螺杆型混合-挤出机中进行的。
19.按照权利要求1的方法制备的热塑性硫化橡胶。
20.按照权利要求1的方法制备的热熔性粘合剂。
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- 2006-04-07 EP EP06749533A patent/EP1874857A1/en not_active Withdrawn
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- 2006-04-07 JP JP2008506543A patent/JP2008537973A/ja not_active Withdrawn
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- 2006-04-07 RU RU2007142004/04A patent/RU2007142004A/ru not_active Application Discontinuation
- 2006-04-07 CN CNA2006800189318A patent/CN101184801A/zh active Pending
- 2006-04-07 AU AU2006236876A patent/AU2006236876A1/en not_active Abandoned
- 2006-04-14 TW TW095113296A patent/TW200704694A/zh unknown
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NO20075591L (no) | 2007-11-12 |
TW200704694A (en) | 2007-02-01 |
EP1874857A1 (en) | 2008-01-09 |
JP2008537973A (ja) | 2008-10-02 |
CA2604958A1 (en) | 2006-10-26 |
ZA200709708B (en) | 2008-11-26 |
US20060235156A1 (en) | 2006-10-19 |
AU2006236876A1 (en) | 2006-10-26 |
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