CN105273365A - 包含表面改性玻璃填料的片状模塑组合物 - Google Patents
包含表面改性玻璃填料的片状模塑组合物 Download PDFInfo
- Publication number
- CN105273365A CN105273365A CN201510059746.4A CN201510059746A CN105273365A CN 105273365 A CN105273365 A CN 105273365A CN 201510059746 A CN201510059746 A CN 201510059746A CN 105273365 A CN105273365 A CN 105273365A
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- Prior art keywords
- matrix
- silane coupling
- coupling agent
- resin
- microsphere
- Prior art date
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Abstract
本发明提供了一种模制品,有具有一表面的树脂基体,该树脂基体由交联聚酯树脂或乙烯基树脂形成。玻璃纤维与该树脂基体通过一种硅烷偶合剂与该基体反应而交联。提供了一种模制品,有具有一表面的树脂基体,该树脂基体由交联聚酯树脂或乙烯基树脂形成。玻璃纤维各自与至少一个微球体基体通过一种硅烷偶合剂与至少一个微球体的一表面反应而共价结合,其存在于提高纤维拉力强度。在此模制品的应用中,还提供了一种用于处理玻璃纤维的施胶组合物。
Description
相关申请
本申请要求于2014年6月30日递交的序列号为62/018,747的美国临时申请的优先权,其内容在此以引用被包含。
技术领域
本发明一般涉及片状模塑组合物(SMC),特别涉及玻璃纤维基体技术和纤维胶料。
背景技术
物体的表面特性大大的影响着它们与周围材质的相互作用。玻璃纤维强化对于由SMC形成的制品来说很常见,其用于增加制品的强度。常规使用的玻璃纤维具有硅氧基团丰富的表面以及具有施加于纤维束的施胶组合物。
典型地,在纤维成型期间,水性的施胶组合物被涂覆于纤维上。该纤维被烘干。在此烘干过程中,施胶组合物的固体具有根据在线轴中或其他大的装配中的纤维经历的温度函数移动的趋势。由于常规胶料和疏水基质之间相互作用的有限性,随着玻璃纤维普遍地被从基体材料上清除,纤维被观察到滑离基质,在制品失败中是很常见的。这种失败的类型暗示了玻璃纤维和基体之间的弱相互作用。这个问题被纤维表面不均一和“不充分”的胶料复杂化了,其可在导致与复合材料吸水性有关的脆化性的无涂层纤维树脂界面上吸水。
在玻璃纤维强化基质的情况下,相关的玻璃表面的自由能、形态学、和化学反应性显著地影响物理和化学特性,其包括但不限于,摩擦力、可湿性、氧化性、与其他分子的相互作用等等。SMC制品,包括以玻璃纤维加强的纤维聚合物基体,其用于形成各种汽车面板和部件。由于SMC材料取代了汽车构造中的钢铁和铝,其在提供减轻重量、耐腐蚀和可媲美的强度是十分重要的。在基体纤维界面的水份吸收会导致作为模制件的基片的分层,由于对于汽车零部件的涂装和表面处理通过烘箱是必须的。
当现有技术认识到有这个问题,玻璃纤维制造的再设计的解决方案被证实昂贵,且其性能改善的实现依赖于聚合物基体的特殊种类。
因此,存在一种对于添加了向生成制品提供承载特性的施胶组合物之后的表面处理的需要。还存在一种需要将颗粒填料与纤维填料结合以创造一种整体牢固的SMC制品,以改善经过涂层和要求零件在不同箱温下烘烤的其他处理的零件性能。
发明内容
提供了一种模制品,有具有一表面的树脂基体,该树脂基体由交联聚酯树脂或乙烯基树脂形成。玻璃纤维与该树脂基体通过一种硅烷偶合剂与该基体反应而交联。
提供了一种模制品,有具有一表面的树脂基体,该树脂基体由交联聚酯树脂或乙烯基树脂形成。玻璃纤维各自与至少一个微球体基体通过一种硅烷偶合剂与至少一个微球体的一表面反应而共价结合,其存在于提高纤维拉力强度。在此模制品的应用中,还提供了一种用于处理玻璃纤维的施胶组合物。
附图说明
附图,其中,其中贯穿这些单独视图中同样的参考编号指向相同的或功能相似的元件并且其并入和组成说明书一部分的附图,进一步解释了已公开的方法,与详细描述一起,用来解释本公开文件的原理。
图1为采用以反应基R1结尾的硅烷偶联剂处理的玻璃纤维与可固化树脂反应以形成SMC基体的示意图;
图2为采用双臂硅烷偶联剂处理的玻璃纤维与低密度玻璃微球体反应,以提高将此类的纤维从固化SMC基体上除去的需要的拉拔强度的示意图;以及
图3为由硅烷偶联剂分子在单个纤维之间形成结合而形成玻璃纤维集合的示意图。
具体实施方式
本发明作为纤维施胶组合物和一种采用改良的对周围片状模塑组合物(SMC)基体的纤维粘附力而形成玻璃纤维强化基体制品的办法而使用。通过采用硅烷偶联剂与玻璃纤维和周围SMC基体两者反应对纤维表面处理,在固化聚合SMC基体中纤维粘附的相关量,所得制品的承重特性相比常规SMC制品被加强了。在某些创造性实施例中,玻璃纤维的表面与玻璃微球体的表面、其他玻璃纤维或它们的组合通过硅烷偶联剂共价结合。在某些创造性实施例中,微球体,与玻璃纤维表面和周围基体均反应的硅烷偶联剂与其他常规纤维施胶组合物的成分结合,为的是在纤维生产过程中快速的高效地在靠近胶料上涂装置处理玻璃纤维。施胶组合物对于玻璃纤维的生产和应用众所周知。J.L.Thomasonetal.,Composites(J.L托马森以及其他人,复合材料):部分A32(2001),页码313~321。玻璃纤维以及基体件的结合量通过加入与周围基体用化学方法不反应硅烷偶联剂来控制。在部分或全部胶料被移除的缺席下硅烷偶联剂的活性位点的密度被大大降低,在胶料已经根据此认知被应用后与SMC基体反应的硅烷偶联剂也易于被加入未处理玻璃纤维中。
在一创造性的SMC中使用的玻璃纤维包括A类型玻璃、C类型玻璃、E类型玻璃、S类型玻璃、ECR类型玻璃纤维、无硼纤维毛料玻璃纤维、它们的短分段或它们的组合。
本发明实用于热固性制品的模塑,采用其能够通过严格的涂料附着力测试,提高了常规制品的机械特性。本发明一般十分适用于形成车辆部件,特别是得益于与粘附到周围SMC基体上的玻璃纤维有关的附加强度的汽车部件。本发明生产的典型的汽车零部件包括引擎盖、行李盖、挡泥板、车门、后顶盖侧板、和车身顶盖、车身底板护罩、车身底板结构板。
在例子中可以理解,一个范围值被提供,该范围适用于不仅包含范围的端点值而且还包括范围的中间值,其明确的被包括在范围中且随着范围的最终的有效数字而改变。举例来说,从1到4列举的范围适用于包括1-2,1-3,2-4,3-4,和1-4。
在这些非限制性实施例中讨论的该些特殊的值和配置可以被改变,引用其不过是为了解释公开的组合物和方法的实施例,且不是为了限制附加的权利要求的范围。
微机械机制,包括纤维基体的剥离和摩擦滑动,在纤维被拉出时可为大量能量吸收的来源。此外,该纤维基体界面相对于玻璃纤维强化SMC的整体耐久性起作用。实现玻璃纤维强化聚合复合材料装甲的结构和抗弹性能之间的最优平衡包括控制界面响应,特别是通过使用基于水性纤维胶料包硅烷偶联剂。
当硅烷偶联剂被用于保持纤维强化聚合物复合材料的耐久性时,该硅烷偶联剂还具有光滑或填充效果,未分级玻璃纤维的天然微粗糙度。施胶纤维的下降的粗糙度降低了在纤维基体剥离发生以后将纤维抽拔的穿过聚合物基体能量的量。
将玻璃微球体与纤维表面结合以中和由仅仅使用传统的硅烷偶合处理玻璃纤维表面而观察到的后剥离纤维拉拔能量的减少。穿过基体的粗糙玻璃纤维的划片需要与相同基体同样尺寸的平滑纤维有关的额外的能量。与用于将脱胶纤维抽过周围基体的能量有关的因素包括的部分为:平均纤维表面粗糙化颗粒尺寸、纤维表面被微粒覆盖的百分比、玻璃纤维和微粒之间的共价结合、纤维表面和微粒之间的结合的平均数量,纤维横截面直径、以及在给定的温度设置和纤维抽出速度条件下基体的可变形性。在不打算被特定理论束缚以及忽略会导致趋向分解某一值的抵触效果,将一剥离纤维抽出基体的能量的量趋向于随着除了纤维横截面直径以外的每个因素增加而增加。
如图1所示,从玻璃纤维10中延伸出的羟基与甲硅烷基结合,一基团R1从那里延伸不来。R1能够在SMC热固性树脂中与不饱和乙烯基反应以将玻璃纤维结合到基体上(未显示)。甲硅烷基团与反应基团R1之间的可选择连接未在图1中显示出来。
第二种硅烷偶联剂的实施例为以化学方法同时与玻璃纤维和基于聚合体SMC基体固化的上的烯属不饱和树脂(具有R1)反应,用于已公开的纤维施胶封装和施胶组合物包括但不限于:3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三乙氧基硅烷、1,1,1,3,5,5,5-七甲基-3-(3-缩水甘油醚氧基丙基)三硅氧烷、(3-环氧丙氧基丙基)二甲基乙氧基硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅烷、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷、甲基丙烯酰氧基甲基三乙氧基硅烷、甲基丙烯酰氧甲基三甲氧基硅烷、3-甲基丙烯酰氧丙基二甲基乙氧基硅烷、甲基丙烯酰氧基丙基二甲基甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、甲基丙烯酰氧基丙基三乙氧基硅烷、甲基丙烯酰基丙基二甲基氯硅烷、2-甲基丙烯酸-3-(甲基二氯硅基)丙(醇)酯、2-甲基-2-丙烯酸3-(三氯硅基)丙酯、异氰酸丙基二甲基一氯硅烷、异氰酸丙基三乙氧基硅烷、甲基丙烯酰氧基丙基三乙氧基硅烷、循环叠氮硅烷、以及他们组合。
一般地,具有丙烯醛基,氨基或缩水甘油基团的硅烷偶联剂与基体在基体固化条件下反应。包含硅烷基的硅烷偶联剂与玻璃纤维的羟基相反应。同样地,延伸出一烷基的硅烷偶联剂基于与玻璃纤维反应产生亲脂表面,其被基体材料弄湿但是不共价结合到那。与玻璃纤维反应同时不与基体反应的硅烷偶联剂的例子包括但不限于:丙基三甲氧基硅烷、丙基三乙氧基硅烷、正辛基三乙氧基硅烷、(甲氧基甲基)三甲基硅烷、三甲氧基(3-甲氧基丙基)硅烷。此些不反应的硅烷常用于SMC玻璃纤维胶料中。
可理解的是反应基团的封闭用来限制基体反应基团的反应,直到基体固化。反应基团的解除封闭代表性地被选在200°F和400°F之间的温度发生。合适的作为封阻剂来使用的基团为本领域人员所熟知,包括的基团如醇、内酰胺、肟、丙二酸酯、烷基乙酰乙酸盐、三唑、酚、胺、苄基叔丁胺。此些基团为特别众所周知的用于封闭异氰酸基体反应基团。酚醛封闭硅烷在此也是有效的,其在US6,413,646中详细说明。
图1描述了具有从表面延伸并以反应基团R1为结尾的硅烷偶联剂12的玻璃纤维10在树脂固化时反应以形成SMC基体。反应基团R1代表性的为上述提及的基体反应硅烷偶联剂的列表中的末端基团。
已公开的为用于改善纤维强化复合材料耐久度的方法,其通过将纤维结合到周围SMC基体上,同时在其他实施例中提高纤维的表面粗糙度。为了在纤维拔出的时候提高摩擦滑动能,该创造性施胶组合物包括与纤维表面或其他玻璃纤维结合的玻璃微球体。
一微球填料可以通过依赖具有两个与玻璃表面羟基反应的基团的硅烷偶联剂与纤维表面结合,为了将纤维共价结合到微球体上。图2描述了玻璃微球体12采用具有基体反应基团R1的双臂硅烷偶联剂结合到玻璃纤维10上。第二微球体14采用第二具有基体反应基团R1的双臂硅烷偶联剂结合微球体12上。在树脂固化时用于将一个玻璃纤维与另一个此类纤维或玻璃微球体、不饱和聚氨酯结合以形成基体的偶联剂解释性地包括:双(三甲氧基硅基甲基)乙烯、双(甲基三氯)乙烯、1,3-[双(3-三乙氧基硅烷丙氧基)聚乙烯氧]-2-亚甲基丙烷、1,6-双(三氯硅烷基)己烷、1,6-双(三氯硅烷基)甲烷、1,8-双(三氯硅烷基)辛烷、1,3-双(三氯硅烷基)丙烷、双(三乙氧基硅烷基)乙烷、双(三乙氧基硅烷基)甲烷、1,8-二(三乙氧基硅烷基)辛烷、1,2-双三甲氧基硅基乙烷、双(三甲氧基硅烷基)苯、1,6-双三甲氧基硅基己烷、1,4-双(三甲氧基硅烷甲基)苯、1,8-二三甲氧硅基辛烷;每个都是单独的、与其他双臂偶联剂结合或与单臂硅烷偶联剂结合。可理解为在双臂偶联剂的硅烷基团之间的可选择的偏好按对应于1到30线性脂肪碳原子的长度将甲硅烷基分开。不打算被特定理论束缚,可相信双臂偶联剂的单个硅烷集团交叉结合于:两玻璃纤维,(一玻璃纤维)-(一玻璃微球体),或两个微球体。包括硅烷偶联剂的反应基团为双臂或单臂的也被结合到一玻璃纤维或玻璃微球体上,然后与热固性树脂在固化时反应以将树脂或微球体结合到基体上去。
除了使用与不饱和树脂反应的硅烷偶联剂以固化形成基体之外,具有氨反应基团的硅烷偶联剂通过硅烷基团容易地被结合到玻璃纤维或玻璃微球体上,然后氨反应基团与二异氰酸酯反应以产生氰基基团能够与不饱和树脂在固化时反应。同样地,硅烷偶联剂的反应基团容易地通过现有技术形成从与玻璃纤维或玻璃微球体通过甲硅烷基结合的硅烷偶联剂上延伸出的反应氨基甲酸酯基或脲基团。氨基甲酸酯基或脲基团与不饱和树脂在通过包含固化剂的氮或甚至自动催化活动的树脂固化时反应。可理解的是异氰酸官能硅烷容易直接与玻璃纤维或微球体反应,或随后与二异氰酸酯(TDI,MDI)在固化之前反应。氨基硅烷偶联剂与烷醇胺官能硅烷偶联剂十分适合与配方中存在的多元醇在固化前混合,其作为异氰酸官能硅烷偶联剂与多元醇结合;烷醇胺官能硅烷与异氰酸反应以生成氨基甲酸酯键,同时氨基硅烷偶联剂与异氰酸反应生成脲键。
在另一实施例中,代替的,或是与硅烷偶联剂结合,二异氰酸酯或聚异氰酸酯用于作为偶联剂以生成脲键,其共价结合热固性基体到玻璃纤维或玻璃微球体的表面,或在有聚异氰酸酯的情况下在纤维、微球体或两者之间形成多个三维键,图3一般30处显示了一个三维基体,其中玻璃纤维10与具有双臂硅烷偶联剂的、上述提到的图中详细描述的那些具有相同的特性。可理解的是有机金属催化剂如有机锡化合物像二月桂酸二丁基锡促进氨基甲酸酯键从二异氰酸酯中的形成。
可理解此玻璃微球体也包括在某些实施例,基体与微球体表面延伸出的硅烷偶联剂反应。微球体上可水解的表面基团与纤维表面羟基反应,其十分适合于结合并解释性地包括无机氧原子。与纤维表面反应,可被添加到微球体表面的其他基团说明性的包括氧原子、三辛基氧化膦(TOPO)、硫醇、胺、羧基、或硅烷。可理解的是基体偶联硅烷被准备加入微球体中,从而使得玻璃纤维通过共价结合微球体间接地与SMC基体偶合。
根据本发明,微球体具有的平均直径在10和120微米之间。在某些实施例中,微球体为单分散的,同时在其他实施例中,尺寸的范围在5和200微米之间。可理解的是有较高压碎强度的微球体较少可能被与SMC配方有关的完全混合和流动压破坏。
此处使用的微球体被定义为包括中空微球体或实心珠,其具有的纵横比介于两个常规最大线性参数1和1.6之间。典型地,微球体颗粒由玻璃或热塑性材料形成。在某些创造性实施例中,微球体在球形的线性尺寸百分之10内,由玻璃形成。
在一实施例中,微球体被加入现有完整的纤维胶料包中,连同硅烷偶联剂一起诱导微球体和纤维之间的结合以促进生产的简易性。在其他实施例中,SMC基体反应偶联剂被加入其他常规胶料包装中。仍然在其他实施例中,在微球体表面上的具有基体反应耦合剂的微球体被加入现有的完整的纤维胶料包装中,与硅烷偶联剂一起诱导微球体和加入其他常规胶料包中的结合。
常规的纤维胶料包装组合物的成分包括成膜剂的水性分散体,表面活性剂,润滑剂、抗静电剂,以及单种硅烷偶联剂。一般来说,成膜剂为任何保护纤维在加工和处理中不受损坏的组合物。用于公开的纤维胶料包装和施胶组合物的成膜剂的种类包括但不限于,环氧树脂、聚醋酸乙烯酯、聚氨酯、聚烯烃、和不饱和聚酯树脂。一般来说,表面活性剂为加入成膜剂分散体的任何组合物。用于公开的纤维胶料包装和施胶组合物的表面活性剂的种类包括但不限于聚乙烯吡咯烷酮、聚氧化乙烯,或聚氧化乙烯-聚氧化丙烯-聚氧化乙烯嵌段共聚物表面活性剂。一般来说,润滑剂为加入纤维加工的任何组合物。用于公开的纤维胶料包装和施胶组合物的润滑剂的种类包括但不限于聚乙烯亚胺烷基酰胺、阳离子脂肪酸酰胺、四乙烯五胺以及聚乙二醇酯。一般来说,抗静电剂为任何在纤维处理中减少静电堆积和装载的组合物。用于公开的纤维胶料包装和施胶组合物的抗静电剂的种类包括但不限于阳离子有机季铵盐。
创造性的施胶组合物包括成膜剂、表面活性剂、不与基体反应的硅烷偶联剂、与基体反应的硅烷偶联剂,在某些实施例中,有微球体。该创造性施胶组合物可能包括但不限于此些组合物的范围,下列典型的成分以%重量组合物(基于其固体,排除水性组分):50~90wt%成膜剂;0~10wt%表面活性剂;0.1~15wt%基体非反应硅烷偶联剂;0.1~15wt%基体反应硅烷偶联剂;0~50wt%微球体。基体非反应/反应硅烷偶联剂以1:02~0.7的摩尔比存在。可选择性地,只有反应硅烷偶联剂存在。
根据本发明用于将玻璃纤维共价结合到SMC基体上的典型的混合胶料包包括以下组分,通过近似%的成分(基于固体,排除水性成分):55%环氧树脂成膜剂;5%聚氧化乙烯-聚环氧丙烷-聚氧化乙烯嵌段共聚物表面活性剂;15%3-(甲基丙烯酰氧)丙基三甲氧基硅烷;15%丙基三甲氧基硅烷;10%的聚乙二醇酯润滑剂。
根据本发明用于将玻璃纤维共价结合到微球体上的典型的混合胶料包装包括以下组分,通过近似%的成分(基于固体,排除水性成分):52%环氧树脂成膜剂;5%聚氧化乙烯-聚环氧丙烷-聚氧化乙烯嵌段共聚物表面活性剂;4%1,4-双(三甲氧基硅烷甲基)苯,6%丙基三甲氧基硅烷;10%聚乙二醇酯润滑剂;以及23%具有的比重为0.60、压碎强度为28,000psi的18微米直径玻璃微球体。
水性基的纤维胶料包装在有益于工业生产的浓度范围中按配方制造,一般在水中有5~10%的固体,包括成膜剂和表面活性剂。醋酸用于调节溶液的pH值到合适的4.5,用于水解硅烷偶联剂。产生的胶料十分适合于E玻璃,S玻璃;H玻璃;A玻璃,玄武岩纤维。
为了加强微球体和周围固化基体之间的相互作用,微球体与微球体表面偶联剂共价结合。此处提及为处理或预处理。在某些创造性实施例中,微球体采用表面涂层粘附到微球体表面进行预处理。在不打算被特定理论束缚下,该微球体表面通过共价结合以与亲水基反应而改性,如羟基,在微球体表面产生微球体表面上的疏水面功能以产生与周围基体更强的相互作用。
在某些创造性实施例中,表面活性剂分子与具有用于在固化时结合周围树脂基质的末端反应基团微球体表面共价结合。在不打算被特定理论束缚下,在固化树脂基体和微球体之间的共价结合提高生成的SMC或BMC在如ASTMD3359的测试中的脱层强度。选择性地,与常规材料相比,本发明的效能通过测量的吸水性的减少而测试出来。
与SMC树脂在固化时与SMC树脂反应的末端反应基团解释性地包括叔胺-;羟基-;亚胺基-;不饱和乙烯基,例如烯丙基-或丙烯醛基-;或氰基。可理解的是基体固化会通过如自由基固化,潮气固化以及他们的组合的机制发生。
可选择地,可理解的是玻璃纤维表面硅烷偶联剂易于与预固化SMC配方混合,玻璃纤维被加入其中以引起基体固化开始之前玻璃纤维表面的活化。典型地,硅烷偶联剂以每克玻璃纤维0.005到0.1克硅烷偶联剂的浓度存在。
为了得到想要的基体粘附度,硅烷偶联剂在玻璃纤维表面以形成纤维表面0.1到1之间的单层的量存在。基于DSC/TGA用于测定纤维表面硅烷的质量,表面覆盖度易于被测定。可理解的是,在纤维和固化SMC基体之间的粘附的改善与在0.1和1单层之间每单位玻璃纤维表面积的硅烷偶联剂分子的数量近似成正比。
SMC配方的主成分为可交联聚合树脂,如不饱和聚酯树脂或乙烯基酯树脂。该预聚聚合树脂的平均分子量典型地在400和100,100道尔顿之间。该聚酯预聚树脂典型地代表了来源于不饱和二元酸和/或多元醇酐的缩合产物。可理解的是,二元或多元酸也是采用反应的乙烯基不饱和点的较少等价性形成聚酯预聚物缩合过程的一部分。典型的SMC和BMC配方在美国专利号4,260,358;4,643,126;5,100,935;5,268,400;5,854,317;6,780,923;或7,829,637中描述。
乙烯基酯树脂也典型的作为聚合树脂用于SMC或BMC配方中。乙烯基预聚物树脂典型地为环氧树脂与具有单不饱和乙烯基的羧酸的反应产物。一般使用的特定的乙烯基酯树脂为环氧官能双酚A与丙烯酸、酚醛环氧基或甲酚环氧基的反应产物。作为预聚物合成法不同的结果,当聚酯树脂预聚物在预聚物骨架内部具有的主要的为不饱和乙烯基时,乙烯基酯树脂预聚物典型地与末端不饱和乙烯基结合。可理解的是双键既可以为内部键或末端键或两者的结合中的任一种。
聚合树脂预聚物悬浮或溶解于在热固过程中与树脂异分子聚合的不饱和乙烯单体中。可理解的是不止一种单体可以用于模塑组合物中。该单体提供的好处包括更低的预聚物粘度和不会形成挥发型副产物的热固。单体典型地占据模制品18.5的总质量百分比。
典型的模塑组合物包括自由基引发剂以引发聚合预聚物树脂与其自己或与如果存在的不饱和乙烯单体之间的交联。选出的典型的自由基引发剂在低温能阻止显著交联以控制热固化情况。常规的自由聚合引发剂包括过氧化物或偶氮基中的一个。此处使用的过氧化物说明性地包括过氧化苯甲酰、过氧化环己酮、二特丁基过氧化物、过氧化二异丙苯、过苯甲酸三级丁酯、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷。此处使用的偶氮种类说明性地包括偶氮二异丁腈以及叔丁基偶氮二异丁腈。当自由基聚合引发剂的存在的数量随着如想要的热固性温度和分解热力学的因素变化时,引发剂代表性地以0.1至3的总质量百分比存在。为了减少在想要的热固温度下的温度时的交联,阻聚剂总是包含在基本模塑配方中。对苯二酚和叔丁基邻苯二酚为常规抑制剂。抑制剂代表性地以0至1总重量百分比存在。
在某些创造性实施例中创造性的模塑组合物包括微粒状填料。在此类模塑组合物中使用的微粒状填料说明性地包括碳酸钙、硅酸钙、氧化铝、ATH、二氧化硅、滑石、白云石、蛭石、硅藻土、高岭土、石墨、金属和它们的组合。在选择微粒状填料上的相关因素说明性地包括填料成本、流动性的生成物粘度、生成物收缩率、表面抛光重量、可燃性、导电性、和热固性配方的耐化学性。微粒状填料的数量典型地为模塑组合物总质量的0到80质量百分比。标准的填料尺寸从0.1到50微米。
代表性地加入的其他纤维填料,说明性的包括碳、聚酰亚胺、聚酯、聚酰胺、以及天然纤维如棉、丝、和麻。纤维填料代表性地以0到80总质量百分比存在。可理解地是不同种纤维的混合易于做到以得到想要的强度以及制品密度。
脱模剂典型地用于促进脱模。脱模剂包括脂肪酸盐,说明性地包括油酸盐、棕榈酸盐、硬脂酸金属离子例如钠、锌、钙、镁、以及锂。脱模剂典型地以从0到5总质量百分比存在。
收缩剂选择性的用于改善所得模塑产品的表面性能以及尺寸稳定性。收缩剂说明性地包括热塑性塑料和弹性体,如聚乙烯、聚苯乙烯、聚乙烯甲苯、聚丙烯酸酯、聚乙烯醚聚合物、聚苯醚、聚醋酸乙烯酯、PMMA、聚苯乙烯、聚丁二烯、饱和多元酯和它们的组合。作为收缩剂使用的共聚物除了同样的共聚物,除了包括丁二烯、丙烯腈、氯乙烯以外,还包括以上所述的聚合物。收缩剂典型地以从0到50总质量百分比,更经常的从5到40总质量百分比存在。
纳米复合材料粘土为亲脂性的,具有的尺寸的区域不会对模制品表面粗糙度起作用。此处使用的烷基季铵膨润土纳米复合材料粘土为市售可得(南方粘度产品,10A)。粘土区域大约在50到150纳米,具有的薄片厚度为1到10纳米,可选择性的单独使用,或与聚合水分减少剂组合使用,以在减少吸湿率时加强创造性配方的加工性能。此类纳米材料粘土代表性地以多达10总质量百分比存在。
可理解的是本发明可选择地也包含另外添加剂,说明性的包括阻燃剂、增塑剂、着色剂、和其他本领域常规的加工助剂。
在不背离此处的精神和原则,很多变化、替换和改变能够对上述所述实施例作出。所有此类变化、替换、和改变此处确定被包括在公开文件和以下权利要求的范围内。
Claims (11)
1.一种模制品,其特征在于,包括:
具有一个表面的树脂基体,所述的树脂基体由交联聚酯树脂或乙烯基树脂形成;以及
与所述的树脂基体通过一种硅烷偶合剂与所述的基体反应而交联的玻璃纤维。
2.根据权利要求1所述的模制品,其特征在于,还包括多个微球体或填料微粒。
3.根据权利要求2所述的模制品,其特征在于,其中,所述的多个微球体或所述的多个填料微粒与所述的玻璃纤维共价结合。
4.根据权利要求1至3中任一项所述的模制品,其特征在于,其中,在固化所述的树脂以形成所述的基体时,硅烷偶合剂嵌段并与所述的树脂反应。
5.根据权利要求1至4中任一项所述的模制品,其特征在于,还包含一种与所述的树脂不反应的硅烷偶合。
6.一种模制品,其特征在于,包括:
具有一个表面的树脂基体,所述的树脂基体由交联聚酯树脂或乙烯基树脂形成,以及
各自与至少一个微球体基体通过一种硅烷偶合剂与所述的至少一个微球体的一表面反应而共价结合的玻璃纤维。
7.根据权利要求6所述的制品,其特征在于,还包括一种与所述的至少一种微球体以及所述的基体共价结合的硅烷偶合剂。
8.根据权利要求7所述的制品,其特征在于,其中,所述的硅烷偶联剂与所述的至少一个微球体共价结合,所述的基体被嵌段且与所述的树脂在所述的树脂固化以形成所述的基体时反应。
9.一种施胶组合物,其特征在于,包括:
成膜剂;
表面活性剂;
基体活性的硅烷偶合剂;以及
微球体。
10.根据权利要求9所述的组合物,其特征在于,还包括基体非活性硅烷偶合剂。
11.根据权利要求9和10中任一项所述的组合物,其特征在于,其中所述的基体活性硅烷偶合剂为嵌段的。
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CN109504075B (zh) * | 2017-09-14 | 2021-10-29 | 大众汽车有限公司 | 改进的纤维增强复合塑料 |
CN109935751A (zh) * | 2018-11-23 | 2019-06-25 | 万向一二三股份公司 | 一种电池模组固定面板及其制备方法 |
CN109935751B (zh) * | 2018-11-23 | 2022-07-19 | 万向一二三股份公司 | 一种电池模组固定面板及其制备方法 |
Also Published As
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CN105273365B (zh) | 2019-03-26 |
CN107698942B (zh) | 2020-06-02 |
EP3161072A4 (en) | 2017-07-19 |
CN107698942A (zh) | 2018-02-16 |
US20150376398A1 (en) | 2015-12-31 |
US9944788B2 (en) | 2018-04-17 |
MX2017000085A (es) | 2017-04-27 |
EP3161072A1 (en) | 2017-05-03 |
WO2016004059A1 (en) | 2016-01-07 |
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