CN106574054A - 用于聚合物/纤维模制化合物的使用聚合物分散液的连续方法 - Google Patents

用于聚合物/纤维模制化合物的使用聚合物分散液的连续方法 Download PDF

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CN106574054A
CN106574054A CN201580042736.8A CN201580042736A CN106574054A CN 106574054 A CN106574054 A CN 106574054A CN 201580042736 A CN201580042736 A CN 201580042736A CN 106574054 A CN106574054 A CN 106574054A
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resin
weight
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A·K·乔杜里
E·L·马驰班克斯
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Abstract

一种加工与无机纤维混合的热固性树脂的方法，所述方法包含组合热固性树脂、无机纤维和水以产生分散液。

Description

用于聚合物/纤维模制化合物的使用聚合物分散液的连续 方法
技术领域
本发明大体上涉及一种制备含有无机纤维和热固性树脂的模制组合物的方法。
背景技术
典型地，通过将纤维与热固性树脂混合来配制基于纤维的模制化合物需要高温来维持模制化合物的可管理粘度。高温可能导致热固性树脂的稳定性降低。高粘度可能限制模制化合物的纤维含量。美国公开案第2006/0128895号公开了一种由纤维和热固性树脂制成的模制化合物，但未提出对前述问题的任何解决方案。
具有降低的粘度和更好稳定性的聚合物/纤维模制化合物将是有利的。
发明内容
本发明是针对一种加工与无机纤维混合的热固性树脂的方法。所述方法包含组合热固性树脂、无机纤维和水以产生树脂与纤维分散液。
具体实施方式
除非另外指示，否则所有百分比都是重量百分比(“重量％”)并且温度以℃为单位。热固性树脂是可以典型地通过加热或通过添加反应性催化剂而不可逆地固化以形成不溶性聚合物网络的有机材料。优选地，树脂在20到100℃的温度下是液体。热固性树脂包括例如环氧树脂、聚酯树脂和乙烯酯树脂。优选的热固性树脂是环氧树脂。优选地，环氧树脂是表氯醇与二醇或多元醇的缩合物。优选地，环氧树脂是芳香族环氧树脂，优选双酚A树脂、酚醛环氧树脂或噁唑烷酮环氧树脂。优选地，环氧树脂的环氧当量(克/当量)是200到1500、优选至少225、优选至少250；优选不超过800、优选不超过600。
无机纤维的实例包括碳纤维和玻璃纤维。优选的纤维是碳纤维。可以使用连续和/或短切纤维。优选地，纤维的直径是3到20微米、优选至少4微米、优选至少5微米；优选不超过15微米、优选不超过10微米。优选地，短切纤维的平均长度(算术平均值)是0.1到50mm、优选至少0.5mm、优选至少1mm；优选不超过25mm、优选不超过15mm。
优选地，将至少一种热固性树脂分散于水中以产生水性树脂分散液，随后与纤维混合。优选地，水性树脂分散液中树脂的浓度是30到70重量％、优选45到65重量％、优选50到60重量％。优选地，添加至少一种表面活性剂以帮助分散热固性树脂。优选地，表面活性剂以1到15重量％、优选2到12重量％、优选2到10重量％、优选2.5到8重量％、优选3到6重量％的总量存在于水性树脂分散液中。优选地，水性树脂分散液包含2到10重量％、优选2到8重量％、优选2.5到5重量％的量的阳离子表面活性剂。优选地，分散液包含0.2重量％到5重量％、优选0.5重量％到3重量％、优选0.7重量％到2重量％的量的乙氧基化脂肪胺表面活性剂。优选地，热固性树脂是环氧树脂。优选地，水性分散液包含5到65重量％、优选至少10重量％、优选至少20重量％；优选不超过50重量％、优选不超过35重量％的量的酚醛环氧树脂。
优选地，组合水性树脂分散液与纤维(树脂与纤维分散液)包含30到60重量％、优选至少35重量％、优选至少37重量％、优选至少39重量％、优选至少41重量％、优选至少43重量％；优选不超过55重量％、优选不超过53重量％、优选不超过51重量％的纤维(以树脂与纤维分散液的总重量计)。
树脂与纤维分散液可以含有其它添加剂，包括例如脱模剂、韧化剂(橡胶材料)、催化剂和硬化剂。
当热固性树脂是环氧树脂时，添加环氧固化剂作为催化剂。环氧固化剂是能够在20到200℃的温度下固化具有环氧官能团的树脂的任何催化剂。优选地，催化剂含有胺官能团。优选地，胺固化剂包括多官能胺。优选地，胺固化剂包含含胺聚合物(包括低分子量聚乙烯亚胺，例如三亚乙基四胺)或具有咪唑环的化合物(例如，2-乙基-4-甲基咪唑)。优选地，环氧固化剂是硬化剂与催化剂的组合，所述组合仅当在高温(例如，高于120℃、优选高于130℃；优选不超过180℃)下活化时促进环氧树脂的固化。催化剂/硬化剂组合的优选实例是双氰胺与封端脲的组合。环氧固化剂为本领域中所熟知并且描述于例如WO 2005/080481中。当热固性树脂是具有可聚合烯系官能团的树脂时，优选地，催化剂是自由基聚合引发剂，例如过氧化物、偶氮化合物、过硫酸盐。
优选的用于产生本发明分散液的混合装置包括例如挤压机(例如，双螺杆、单螺杆)或其它变化形式(法劳(Farrel)连续混合器、特利丹(Teledyne)连续混合器、班伯里(Banbury)混合器、分批混合器)。优选地，水性树脂分散液当其与纤维混合时的温度是20到100℃、优选至少25℃、优选至少30℃、优选至少35℃、优选至少40℃、优选至少45℃；优选不超过95℃、优选不超过85℃、优选不超过80℃、优选不超过75℃。在这些温度下，聚合不发生或仅在极有限的程度上发生。
优选地，在混合过程期间例如在双螺杆挤压机中从水性树脂分散液与纤维的混合物去除水。优选地，树脂/纤维混合物中的残余水含量小于5重量％、优选小于2重量％、优选小于0.5重量％。可以在去除水之前或之后添加用于树脂的催化剂和/或硬化剂。优选地，在去除水之后，挤压最终树脂/纤维混合物。
在挤压之后，可以将最终树脂/纤维混合物模制成任何形式，例如团粒、圆材、薄片、团块等。如上文所述，通过加热来固化模制树脂/纤维混合物。
实例
在100与150℃之间的温度下如表1中所描述制备环氧树脂掺合物的水性分散液，然后将其冷却到环境温度。D.E.R.TM6508和D.E.N.438是由陶氏化学公司(The DowChemical Company)生产的环氧树脂。D.E.R.6508是双酚A、表氯醇与二苯基甲烷二异氰酸酯聚合物，并且D.E.N.438是基于酚-醛酚醛清漆与表氯醇的反应产物的液体环氧树脂。硬化剂和催化剂分别是来自AC Catalysts的Technicure NanoDicy双氰胺和来自EmeraldPerformance Materials的Omicure U-410M甲苯双二甲基脲。E-PEG 4600是由陶氏化学公司生产的阳离子表面活性剂，并且Ethox TAM-20DQ由Ethox Chemicals生产。
表1：环氧树脂的水性分散液的组成.
树脂配制品的组分 重量％
D.E.R.6508 27.3
D.E.N.438 27.3
E-PEG 3.3
TAM-20DQ 1.1
水 41.0
挤压过程/样品制备
然后将表1的水性分散液与碳纤维、催化剂和硬化剂一起引入到双螺杆挤压机中，以制备环氧-碳纤维无规复合物馈料(详述于表2中)。将纤维混合区段中的温度维持在40到70℃，取决于纤维的重量分率和混合速度。在水去除区段中，温度是90到100℃。在25mm TSE中制备环氧-碳纤维复合物，并且以圆柱形圆材形状收集。
表2：25mm双螺杆挤压机中制备的无规复合物馈料的组成.
复合物的组分 重量％
D.E.R.6508 20.75
D.E.N.438 20.75
E-PEG 2.5
TAM-20DQ 0.8
Technicure NanoDicy 3.5
Omicure U-410M 1.7
碳纤维 50.0
然后使得使用连续挤压过程制备的无规复合物馈料经历如下文所提及的压缩模制过程：
通过首先将约350g馈料预加热到70±10℃，继而将馈料放置在预加热到150℃的Lih Woei(300吨)压缩模制器内的模具中间，将在以上实例中制备的复合物馈料压缩模制成10"×10"×1/8"(30.5cm×30.5cm×0.3cm)扁平薄板。使模具接近25000lbs(200×105N/m2)的负荷持续5分钟。复合物立即脱模(在150℃下)。

Claims (10)

1.一种加工与无机纤维混合的热固性树脂的方法，所述方法包含组合热固性树脂、无机纤维和水以产生分散液。
2.根据权利要求1所述的方法，其中所述热固性树脂包含至少一种环氧树脂。
3.根据权利要求2所述的方法，其中所述无机纤维是碳纤维或玻璃纤维。
4.根据权利要求3所述的方法，其中将所述热固性树脂与水组合以形成水性树脂分散液。
5.根据权利要求4所述的方法，其中所述热固性树脂构成所述水性分散液的30到70重量％。
6.根据权利要求1所述的方法，其中将所述热固性树脂与水组合以形成水性树脂分散液，并且将所述水性树脂分散液与无机纤维组合以形成水性树脂与纤维分散液。
7.根据权利要求6所述的方法，其中所述水性树脂与纤维分散液包含30到60重量％纤维。
8.根据权利要求7所述的方法，其中所述无机纤维是碳纤维或玻璃纤维。
9.根据权利要求8所述的方法，其中所述热固性树脂是环氧树脂。
10.根据权利要求9所述的方法，其中所述热固性树脂构成所述水性分散液的30到70重量％。
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