CN100558800C - 阻燃性聚酯组合物 - Google Patents

阻燃性聚酯组合物 Download PDF

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CN100558800C
CN100558800C CNB2004800374697A CN200480037469A CN100558800C CN 100558800 C CN100558800 C CN 100558800C CN B2004800374697 A CNB2004800374697 A CN B2004800374697A CN 200480037469 A CN200480037469 A CN 200480037469A CN 100558800 C CN100558800 C CN 100558800C
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Abstract

一种组合物，其包括：聚对苯二甲酸丁二醇酯；含氮阻燃剂，其选自三嗪、胍类、氰尿酸盐、异氰尿酸盐和包括上述含氮阻燃剂中至少一种的混合物；次膦酸盐或二次膦酸盐；和炭化聚合物。

Description

阻燃性聚酯组合物
相关申请的交叉引用
本申请要求编号为60/530147的美国临时申请的优先权，该临时申请于2003年12月17日提交，其全部内容在本文中引入作为参考。
背景技术
热塑性聚酯组合物，如聚(对苯二酸亚烷基酯)，具有重要的特征，包括强度、韧度、高光泽和耐溶剂性。因此聚酯可用于许多应用的材料，从汽车零件到电气电子设备。因为其广泛的用途，特别是在电子应用领域，所以期望向聚酯提供阻燃性。通常接受的并且用作阻燃性标准的一组特定的规则由美国保险业实验所(UnderwritersLaboratories，Inc.)规定。Bulletin 94规定了某些规则，通过这些规则来对材料的自熄特性进行评级。另一组通常接受的并且用作阻燃性标准(特别在欧洲)的规则是辉光灯丝试验(GWT)，其根据国际标准IEC695-2-1/2进行。许多聚酯阻燃剂是已知的，但许多包含卤素、通常为溴。由于对生态友好配料的需求逐渐增加，卤代阻燃剂是很少期望的。也可以使用不含卤素的阻燃剂如基于磷和氮的化合物，但是它们缺乏对薄片的良好阻燃性。
需要这样的聚酯组合物，即，其结合了良好的阻燃性能(不仅在厚度大于1.5mm而且在厚度不大于0.8mm时)和至少基本上保持了机械性能和/或热性能。
发明内容
一个或多个上述缺点和不利情况可以通过一种组合物而缓解或最小化，该组合物包括：聚酯；选自三嗪、胍类、氰尿酸盐(cyanurate)、异氰尿酸盐(isocyanurate)和其混合物中至少一种的含氮阻燃剂；次膦酸盐(phosphinic acid salt)和/或二次膦酸盐(diphosphinic acidsalt)和/或其聚合物；和炭化聚合物(charring polymer)。
包括制备该组合物的方法的其他实施方案将在下文进行描述。
具体实施方式
根据一个实施方案，一种组合物包括聚酯如聚对苯二甲酸丁二醇酯；选自三嗪、胍类、氰尿酸盐、异氰尿酸盐和其混合物中至少一种的含氮阻燃剂；如下所述的式I的次膦酸盐和/或式II的二次膦酸盐和/或其聚合物；和炭化聚合物。
优选的聚酯通过二醇组分和酸组分的共聚合而获得，所述酸组分包括至少约70mol％，优选至少约80mol％的对苯二甲酸或其形成聚酯的衍生物。优选的二醇(丁二醇)组分可以包含高达约30mol％，优选高达约20mol％的另一种二醇，如乙二醇、丙二醇、2-甲基-1，3-丙二醇、己二醇、癸二醇、环己烷二甲醇、新戊二醇等，和包括上述二醇中至少一种的混合物。优选的酸组分可以包含高达约30mol％，优选高达约20mol％的另一种酸如间苯二甲酸、2，6-萘二羧酸、2，7-萘二羧酸、1，5-萘二羧酸、4，4’-联苯二羧酸、4，4’-联苯氧基乙烷二羧酸、癸二酸、己二酸等，和其形成聚酯的衍生物，和包括上述酸或酸衍生物中至少一种的混合物。
优选的聚酯的数均分子量可以是约10,000原子质量单位(AMU)-约200,000AMU，如使用聚苯乙烯标准样品通过凝胶渗透色谱法测量的。在此范围内，优选数均分子量为至少约20,000AMU。还在此范围内，优选数均分子量为至多约100,000AMU，更优选数均分子量为至多约50,000AMU。
在该组合物中，该聚酯可占组合物总重量的约20-约90wt％。在此范围内，优选使用至少约25wt％，更优选至少约30wt％的聚酯如聚对苯二甲酸丁二醇酯。
在进一步的实施方案中，该组合物可以包含不同于第一种聚酯的第二种聚酯树酯。对于第二种聚酯，合适的树脂包括衍生自C2-C10脂族或脂环族二醇或其混合物和至少一种芳族二羧酸的树脂。优选的聚酯衍生自脂族二醇和具有以下通式的重复单位的芳族二羧酸：
Figure C20048003746900041
其中n是2-6的整数，R是C6-C20二价芳基，其包括衍生自芳族二羧酸的脱羧基残基。
由脱羧基残基R表示的芳香族二羧酸的实例是间苯二甲酸、对苯二甲酸、1，2-二(对-羧苯基)乙烷、4，4′-二羧基二苯醚、4，4′双苯甲酸等和其混合物。全部这些酸包含至少一个芳香核。包含稠环的酸还可以例如以1，4-、1，5-、或2，6-萘二羧酸的形式存在。优选的二羧酸包括对苯二甲酸、间苯二甲酸、萘二羧酸等和包括上述二羧酸中至少一种的混合物。
脂族或脂环族多元醇包括二醇，如乙二醇、丙二醇、丁二醇、对苯二酚、间苯二酚、丙二醇、2-甲基-1，3-丙二醇、1，4-丁二醇、己二醇、癸二醇、1，4-环己烷二甲醇或新戊二醇。
在本文中还预期上述聚酯与较少量的，例如约0.5-约30wt％的，衍生自脂族酸和/或脂族多元醇的单元形成共聚聚酯。该脂族多元醇包括二醇，如聚(乙二醇)。这种聚酯可遵循例如美国专利2465319(whinfield等人)和3047539(Pengilly)的教导而制备。
嵌段共聚聚酯树脂组分也是有用的，并且可以通过以下物质的酯交换制备：(a)直链或支链的聚(对苯二酸亚烷基酯)和(b)线性脂族二羧酸和任选的芳香族二元酸如对苯二甲酸或间苯二甲酸与一种或多种直链或支链的二羟基脂族二醇的共聚聚酯。当高熔体强度重要时，特别有用的是分支的高熔体粘度的树脂，其包括少量的，例如，基于酸单元的高达5mol％的含至少3个成酯基团的分支组分。分支组分可以是在聚酯的酸单元部分、在二醇单元部分中提供分支的物质，或者它可以是一种包括酸和醇两种官能团的混合支化剂。这种分支组分的例子是三元羧酸，如均苯三酸，和其低级烷基酯等；四元羧酸，如均苯四酸，和其低级烷基酯等；或优选地，多元醇，尤其优选地，四醇，如季戊四醇；三醇，如三羟甲基丙烷；二羟基羧酸；和羟基二羧酸及衍生物，如羟基对苯二甲酸二甲酯等。分支的聚(对苯二酸亚烷基酯)树脂及其制备方法例如描述于美国专利3,953,404(Borman)中。除对苯二甲酸单元之外，还可以存在少量的(例如0.5-15mol％)其他芳香族二羧酸如间苯二甲酸或萘二羧酸、或脂族二羧酸如己二酸，以及较少量的非1，4-丁二醇所衍生的二醇组分，如乙二醇或环己烯二甲醇等，以及较少量的三官能或更高官能的分支组分，例如，季戊四醇、均苯三酸三甲酯等。
阻燃聚酯组合物包括阻燃量的一种含氮阻燃剂或含氮阻燃剂混合物，所述含氮阻燃剂如三嗪、胍类、氰尿酸盐和异氰尿酸盐。优选的三嗪具有下式结构：
Figure C20048003746900061
其中R1、R2和R3独立地是C1-C12烷基、C1-C12烷氧基、C6-C12芳基、氨基、C1-C12烷基取代的氨基、或氢。非常优选的三嗪包括2，4，6-三胺-1，3，5-三嗪(三聚氰胺，CAS登记号108-78-1)、三聚氰胺衍生物、蜜白胺、蜜勒胺、氰尿酰胺、氰尿二酰胺(CAS登记号645-92-1)、三聚氰酸一酰胺(CAS登记号645-93-2)、2-脲基三聚氰胺、乙酰胍胺(CAS登记号542-02-9)、苯胍胺(CAS登记号91-76-9)等。这些化合物与硼酸或磷酸的盐/加合物可用于该组合物中。实例包括三聚氰胺焦磷酸盐和三聚氰胺多磷酸盐。优选的氰尿酸盐/异氰尿酸盐化合物包括三嗪化合物与三聚氰酸的盐/加合物，如三聚氰胺氰尿酸盐和三聚氰胺盐的任何混合物。
优选的胍化合物包括胍；氨基胍等；和其与硼酸、碳酸、磷酸、硝酸、硫酸等的盐和加合物；和包括上述胍化合物中至少一种的混合物。
在该组合物中，含氮阻燃剂可占组合物总重量的约1-约25wt％。在此范围内，优选使用至少约5wt％，更优选至少约8wt％的含氮阻燃剂。还在此范围内，优选使用高达约20wt％。
该含氮阻燃剂与一种或多种次膦酸盐组合使用。次膦酸盐和二次膦酸盐包括美国专利6255371(Schosser等人)中所述的那些。将该专利说明书第1列第46行至第3列第4行引入本说明书作为参考。所提及的具体的次膦酸盐包括二乙基次膦酸铝(DEPAL)和二乙基次膦酸锌(DEPZN)。这些次膦酸盐为式(I)
[(R1)(R2)(PO)-O]m -Mm+
和式II
[(O-POR1)(R3)(POR2-O)]2 2-Mx m+，
和/或包括所述式I或II的聚合物，其中R1和R2是相同的或不同的并且是H，直链或支链的C1-C6-烷基，和/或芳基；R3是C1-C10、亚烷基、直链或支链的，C6-C10-亚芳基、-烷基亚芳基或-芳基亚烷基；M是任何金属，但优选是镁、钙、铝或锌，m是1、2或3；n是1、2或3；x是1或2。式I和II的结构特别从Schosser的专利中引入本申请作为参考。注意，除了在该专利中阐述的取代基外，R1和R2可以是H。这导致次磷酸盐、次膦酸盐的亚类，如次磷酸钙、次磷酸铝等。
炭化聚合物是这样的化合物，当在氮气环境下使用热解重量分析法(TGA)以20℃/分钟的加热速率加热时，在400-500℃，其重量损失不大于约85％。典型的炭化聚合物包括聚醚酰亚胺、聚苯醚、聚苯硫醚、聚砜、聚醚砜、聚苯硫醚聚苯醚(poly(phenylenesulphide oxide))(PPSO)、聚酚醛树脂(polyphenolic)(例如线型酚醛清漆)。炭化聚合物的含量为该组合物的约0.1-约15wt％。
该组合物可以任选地进一步包含补强性填料。合适的补强性填料包括二氧化硅；硅酸盐如滑石或云母；炭黑；和补强纤维如碳纤维、芳族聚酰胺纤维、玻璃纤维等；和包括上述填料中至少一种的混合物。在优选实施方案中，补强性填料包括玻璃纤维。对于最终用于电气用途的组合物而言，优选使用含相对不含钠的石灰-硼硅酸铝玻璃的玻璃纤维，其通常被称为“E”玻璃。然而，在电气性能不是十分重要的情况下，其他玻璃也是有用的，例如，低钠玻璃，其通常被称为“C”玻璃。玻璃纤维可以通过标准方法来制造，如蒸汽吹制或气流吹制、火焰吹制和机械牵引。优选的用于塑料增强的玻璃纤维可通过机械牵引制成。玻璃纤维的直径通常是约1-约50微米，优选约1-约20微米。直径越小的纤维通常越昂贵，直径为约10-约20微米的玻璃纤维目前提供了所希望的成本和性能的平衡。玻璃纤维可被集束为纤维，而纤维又被集束为纱、绳或粗纱，或被织造成毡片等，如该组合物的特定的最终用途所要求的。在制备模塑组合物中，合宜使用约1/8-约2英寸长的切短玻璃丝形式的丝状玻璃，其通常在模塑配混料中呈现单丝长度为约0.0005-约0.25英寸。这种玻璃纤维通常由厂商提供，使用了与该组合物的聚合物组分相容的表面处理，如硅氧烷、钛酸酯或聚氨酯上浆等。
当组合物中存在补强性填料时，该补强性填料可以以该组合物总重量的约10-约60wt％的量使用。在此范围内，优选使用至少约20wt％的补强性填料。还在此范围内，优选使用高达约50wt％，更优选高达约40wt％的补强性填料。
该组合物可以进一步包含一种或多种防滴剂，当树脂经受燃烧状况时，其防止或延迟树脂滴下。这种试剂的具体实例包括硅油、二氧化硅(其还作为一种补强性填料)、石棉和原纤化型含氟聚合物。含氟聚合物的实例包括氟化聚烯烃，例如，聚(四氟乙烯)、四氟乙烯/六氟丙烯共聚物、四氟乙烯/乙烯共聚物、聚偏1，1-二氟乙烯、聚(三氟氯乙烯)等，和包括上述防滴剂中至少一种的的混合物。优选的防滴剂是聚(四氟乙烯)。当使用防滴剂时，基于组合物的总重量计，所述防滴剂含量为约0.02-约2wt％，更优选约0.05-约1wt％。
该组合物可以，任选地，进一步包含其他用于聚酯聚合物组合物中的常规添加剂，如非补强性填料、稳定剂、脱模剂、增塑剂和加工助剂。可以加入用于其通常所用目的的其他配料如染料、颜料、抗氧化剂等。
该组合物可以由许多方法制备。在一种示范性的方法中，该聚酯组合物、任选的非晶态添加剂、耐冲击性改进剂和填料和/或补强玻璃与树脂组分被放入挤压配混机而生产模塑粒料。在该方法中，树脂及其他配料分散于树脂基质中。在另一种方法中，配料和任何补强玻璃通过干混而与树脂混合，然后在辊炼机中熔融并且被粉碎，或挤出和切断。该组合物和任何任选的配料还可以被混合并且直接模塑，例如，通过注塑或压铸技术。优选地，全部配料尽可能地不含水。此外，应该进行配混以保证在机器中短的停留时间；密切控制温度；利用摩擦热；获得树脂组合物和任何其他配料之间的均质共混料。
优选地，配料被预配混，造粒，然后模塑。预配混可以在常规设备中进行。例如，在预先干燥聚酯组合物(例如在约120℃，约4小时)后，可将配料的干燥共混料进料到单螺杆挤出机，使用具有长过渡段的螺杆以确保适当的熔融。或者，可以在进料口将树脂和添加剂进料给具有啮合同向旋转螺杆的双螺杆挤塑机，而补强添加剂(及其他添加剂)可在下游进料。但不论是哪种情况，通常合适的熔融温度总是为约230℃-约300℃。预配混的组合物可以被挤压并且通过标准技术被切断成模塑配混料如常规颗粒、粒料等。然后该组合物可以在任何通常用于热塑性组合物的设备如Newbury型注塑机中模塑，常规的料桶温度为约230℃-约280℃而常规的模具温度为约55℃-约95℃。该组合物提供了冲击强度和阻燃性间的极好的平衡。
另一种优选实施方案包含由该组合物制成的模制品，如电气和电子零件，包括例如连接器、断路器和电源播头。
显然本发明包含上述组合物的反应产物。
本发明进一步通过以下非限制性实施例举例说明。
实施例和对比例
全部制剂是通过将除四苯基BPA-二磷酸酯(BPA-DP)和玻璃纤维外的配料干混制成。随后在Werner-Pfleiderer 25毫米同向旋转挤出机上将该共混料配混，其中BPA-DP和玻璃分别在该共混料的下游进料。挤出机温度设定(上游至下游)为50-140-265-260-260-260-260-260-275℃；施加0.45巴的真空度，螺杆转速是300RPM。
零件的模塑在35吨Engel注塑机上进行，温度设定为245-255-265-265℃(从进料喉至注嘴)，基于PBT的制剂的模具温度为70℃。在模塑前，粒料在120℃预干燥2-4小时。
虽然参考优选实施方案已经描述了本发明，但是本领域技术人员应该理解的是，在不偏离本发明范围的情况下可以进行各种变化并且等价物可代替其要素。此外，可进行许多改进以在不偏离本发明基本范围的条件下使特定情况或材料适应本发明的教导。因此，意图是，本发明不限于作为实施本发明所预期的最佳方式的、所公开的、特定的实施方案，而是本发明将包括属于所附权利要求范围的全部实施方案。
根据ISO 180评价试验样品的伊佐德无缺口冲击(IUI)强度，结果用单位kJ/m2表示。UL94试验用于阻燃性试验。使用ISO 527评价拉伸强度。所用的聚对苯二甲酸丁二醇酯(PBT)是GE的PBT-315和GE的PBT-195，其重量比为2∶1。MC-25是获自Ciba的三聚氰胺氰尿酸盐。TSAN获自GE并且是在苯乙烯丙烯腈中的原纤化型Teflon。BPA-DP是获自Albemarle的双酚A二磷酸酯。PPO是获自GE的聚苯醚(2，6-二甲苯酚的聚苯醚)。Ultem 1010是获自GE的聚醚酰亚胺。使用标准稳定剂如Irganox 1010和/或环氧树脂。所用的标准颜料包括硫化锌。
不同制剂的结果列于下表中。
Figure C20048003746900101
对比样品A和B表明，使用P-配混料如BPA-DP，未获得良好热稳定性的产品，在140℃一周后，拉伸强度保持率低于50％。对于基于次膦酸盐的配方，该保持率高于80％。
属于本发明的样品1和2表明，同对比样品C相比，在0.8mm UL性能为V0。所以加入炭化聚合物产生了更好的UL性能，同时拉伸强度保持率仍然是良好的。同PPO相比，炭化聚合物Ultem(获自GE的聚醚酰亚胺)是优选的，由于更高的冲击值。
当使用较少量的三聚氰胺氰尿酸盐时，能够看出冲击性提高，但需要炭化聚合物(制剂3)以在1.5mm下保持V0性能；对比样品D和E仅产生V1性能。当进一步降低阻燃剂量时，在这种情况下是次膦酸盐的量，能够看出对于对比样品F，UL性能下降到NC(未分类)或NR(未定等)，但对于样品4，该材料仍然具有V1性能。此外就次磷酸钙(次膦酸钙)来说，加入炭化聚合物(制剂5)导致更好的UL性能而对拉伸强度保持率无消极作用。
从这些结果可以得出结论，在含氮化合物存在下，次膦酸盐化合物与炭化聚合物的组合使得性能如UL性能和烘箱老化时拉伸强度保持率达到最佳平衡。没有炭化剂或者就其它磷化合物(如BPA-DP)来说，不能获得这些结果。

Claims (3)

1.一种组合物，其包括：
聚酯；
三聚氰胺氰尿酸盐；
二乙基次膦酸锌和/或其聚合物；和
炭化聚合物，其为聚醚酰亚胺。
2.权利要求1的组合物，其中当在氮气环境下利用热解重量分析法以20℃/分钟的加热速率加热时，在400-500℃，所述炭化聚合物重量损失不大于85％。
3.权利要求1的组合物，其中该炭化聚合物的含量为0.1-15wt％。
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US8034870B2 (en) 2011-10-11
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WO2005059018A1 (en) 2005-06-30
EP1697451B1 (en) 2011-06-29
KR20070003786A (ko) 2007-01-05
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ATE514739T1 (de) 2011-07-15
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