CN1071360C - 阻燃性热塑性聚碳酸酯模塑组合物 - Google Patents
阻燃性热塑性聚碳酸酯模塑组合物 Download PDFInfo
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- CN1071360C CN1071360C CN95119058A CN95119058A CN1071360C CN 1071360 C CN1071360 C CN 1071360C CN 95119058 A CN95119058 A CN 95119058A CN 95119058 A CN95119058 A CN 95119058A CN 1071360 C CN1071360 C CN 1071360C
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Abstract
本发明涉及由聚碳酸酯和接枝共聚物制得的不含囟素的阻燃性热塑性模塑组合物,它可选地含有热塑性共聚物和/或聚对苯二甲酸亚烷基酯。所用的阻燃剂是硅氧烷树脂和聚苯醚的增效组合。
Description
本发明涉及由聚碳酸酯和接枝共聚物制得的不含卤素的阻燃性热塑性模塑组合物,它可选地含有热塑性共聚物和/或聚对苯二甲酸亚烷基酯。所用的阻燃剂是硅氧烷树脂和聚苯醚与特定的磷化合物的增效组合。
US-PS5061745和US-P5030675描述了由芳族聚碳酸酯、ABS聚合物、共聚物或聚对苯二甲酸亚烷基酯分别以一磷酸酯和氟化聚烯烃作为阻燃剂和防滴剂制得的耐燃性热塑性模塑组合物。氟化聚烯烃的缺点之一是在燃烧时其卤素成分和氟化氢的释放。然而,迄今为止,从芳族聚碳酸酯、可选的热塑性共聚物和热塑性聚对苯二甲酸亚烷基酯和接枝共聚物生产级别为V-0(以1.6mm厚的试样,按照UL-94测定)的自熄性模塑组合物的唯一方法是特别使用聚四氟乙烯。
EP-0363608描述了由芳族聚碳酸酯、共聚物和接枝共聚物以及低聚磷酸酯制得的以例如氢醌和间苯二酚作阻燃添加剂的聚合物共混物。V0/1.6mm(UL-94)的有效的阻燃性仅在聚四氟乙烯的存在下方能达到。
美国专利4273691,4387176,4536529,4871795和5242774要求保护了一种含有阻燃体系的热塑性塑料,该体系是由硅油或由硅油的混合物与硅氧烷树脂以及金属皂(硬脂酸镁)和可选的氢氧化镁制备的。还可进一步列出的阻燃添加剂是含有卤素的阻燃剂(十溴代二苯基醚)与三氧化锑和焦磷酸铵与多元醇。主要的热塑性塑料是聚丙烯和其它聚合物,例如一般可提及聚碳酸酯和例如某些聚酯。这里应当指出,镁化合物的使用会使聚碳酸酯的良好机械性能明显降低,只有在也使用卤素(US-PS4387176,第二栏,第12-20行)而不使用磷酸酯时才可能达到V-0/3.2mm。
EP-A0520186描述了由聚碳酸酯混以ABS成分制备的阻燃性模塑组合物,它含有磷化合物、硼化合物、聚有机硅氧烷和/或含氟树脂作为阻燃剂。从实施例和比较例可明显看出,只有在结合使用磷酸三苯酯、硼酸锌和聚二甲基硅烷和/或聚四氟乙烯时,才有可能得到V-0/1.6mm的所需的阻燃性;而不用硼酸锌和磷酸三苯酯只用聚二甲基硅氧烷,则不能达到V-0/1.6mm(参见EP-A0520186,比较例4);而用聚四氟乙烯代替聚有机硅氧烷仅达到V-1/1.6mm(参见EP-A0520186,比较例5)。
DE-OS4301730以实际上类似于EP-A520186的方法用羧酸的锌盐(例如乙酸锌)代替硼化合物(硼酸锌)给聚碳酸酯模塑组合物提供了有效的阻燃性能。当不合有该成分时,用磷酸三苯酯和二甲基硅氧烷也不能达到V-0/1.6mm(参见DE-OS4301730)。
US-PS5100958要求保护这样的方法:由硅氧烷树脂和ABS型接枝共聚物制得共沉淀产物,然后将此共沉淀产物与聚碳酸酯和苯乙烯/丙烯腈共聚物共混。为达到V-0/1.6mm的有效阻燃性,也必须使用磷酸三苯酯作为附加的阻燃剂,并且聚碳酸酯必须再含有10%(重量)四溴代双酚A(参见US-PS5100958,表Ⅰ,第7栏,第23行)。如果不含卤素,则US-PS5100958的模塑组合物不能获得阻燃性。
特别是从芳族聚碳酸酯、聚苯醚、接枝共聚物、苯乙烯共聚物与0-20%(重量)有机磷酸酯和0-2%(重量)聚四氟乙烯聚合物制备的热塑性模塑组合物可从DE-OS4200247得知。该方法的目的是提供具有良好的综合性能、特别是具有较高耐热性的热塑性聚碳酸酯模塑组合物。DE-OS4200247的实施例1和2相对于比较例可说明这一点。从实施例2显而易见,用聚苯醚、磷酸三苯酯和聚四氟乙烯可达到UL-94 V-0的阻燃性。未描述为达到UL-94 V-0/1.6mm的阻燃性,仅使用聚苯醚和磷酸酯而不使用聚四氟乙烯的方法。
EP-A522653描述了以ABS/接枝橡胶与聚苯醚或酚醛清漆特别是以二磷酸酯作为阻燃剂。也可以使用一般的共聚物或聚碳酸酯。该特殊共混物的阻燃性以氧指数(根据ASTM的LOI值)表达。在EP-A522653中,实施例3表3中用ABS和聚碳酸酯(各占40%(重量))、聚苯醚和氢醌二(磷酸二苯酯)(各占10%(重量))提供阻燃性,LOI值是23.5(该值相对较低,未描述滴流行为)。从EP-A522653的描述不能假设通过用间苯二酚二(磷酸二苯酯)代替氢醌并且使用易燃的一般的共聚物可以达到V-0/1.6mm的无滴流现象,即无滴流的明显较高的阻燃性(不含卤素,不使用聚四氟乙烯)。
US-PS5204395描述了含有经硅油处理的填充剂的聚苯醚模塑组合物。特定填充剂与硅油的组合可导致燃烧时间的减少。未提到用磷化合物作为阻燃剂。
根据EP-A0171826,向聚碳酸酯/聚苯醚共混物中加入少量多氢硅氧烷会使得熔体稳定性明显变好。
已经发现,通过使用0.5-5%(重量)硅氧烷树脂和2-15%(重量)聚苯醚与3-18%(重量)下述成分E)的磷化合物的组合,由热塑性芳族聚碳酸酯、可选的热塑性共聚物和热塑性聚对苯二甲酸亚烷基酯以及接枝聚合物制备的模塑组合物能够达到自熄性无燃烧滴流(按照UL-94),用1.6mm厚的试样测定的级别为V-0至V-1。不需要至今仍用作防滴剂的聚四氟乙烯。因此,本发明的模塑组合物是完全不含卤素的、高度有效的和着火时能够自熄的模塑组合物。按照本发明的硅氧烷树脂和聚苯醚的组合的协同作用可使所需的阻燃剂的量明显降低。本发明的组合物明显地有利于冲击强度、耐应力开裂性和耐热性。
本发明提供在燃烧时不产生燃烧滴流的、不含囟素的阻燃性热塑性模塑组合物,它包含:A)50-95%(重量)、优选60-90%(重量)的热塑性芳族聚碳酸酯,B)0-20%(重量)、优选1-15%(重量)包含下述成分的共聚物或缩
聚产物:
B.1)由下述化合物制成的热塑性共聚物:
B.1.1)50-95%(重量)苯乙烯、α-甲基苯乙烯、环被烷基化的
苯乙烯、丙烯酸C1-C8烷基酯、甲基丙烯酸C1-C8烷基酯
或其混合物和
B.1.2)5-50%(重量)丙烯腈、甲基丙烯腈、丙烯酸C1-C8烷基酯
、甲基丙烯酸C1-C8烷基酯、马来酸酐、N-取代的马来酰
亚胺、乙酸乙烯酯及其混合物和/或
B.2)热塑性聚对苯二甲酸亚烷基酯,C)3-18%(重量)、优选5-15%(重量)由下述成分组成的接枝共聚
物:
C.1)5-90%(重量)、优选30-80%(重量)下述成分制成的混合物:
C.1.1)50-95%(重量)苯乙烯、α-甲基苯乙烯、环被烷基化的
苯乙烯、丙烯酸C1-C8烷基酯、甲基丙烯酸C1-C8烷基酯
或其混合物和
C.1.2)5-50%(重量)丙烯腈、甲基丙烯腈、丙烯酸C1-C8烷基酯
、甲基丙烯酸C1-C8烷基酯、马来酸酐、N-取代的马来酰
亚胺或其混合物
C.2)10-95%(重量)、优选20-70%(重量)玻璃化转变温度Tg
≤10℃的橡胶D)1-20%(重量)、优选2-15%(重量)包含下述成分的具有阻燃剂
作用的组合:
D.1)5-50%(重量)、优选5-25%(重量)硅氧烷树脂和
D.2)50-95%(重量)、优选75-95%(重量)热塑性聚苯醚,E)3-18%(重量)、优选5-15%(重量)由下述化合物制备的磷酸酯:
式中,n=1-5,R1是甲基,l=0-5,优选0和1-3,或者E.2)式(Ⅰ)磷化合物与式(Ⅱ)磷化合物的混合物,式(Ⅱ)
式中,R2是甲基,m是0或1-5,优选0和1-3;其中式(Ⅱ)磷化合物在由E.1)和E.2)制备的磷酸酯混合物中的量为至多为35%(重量)、优选至多30%(重量)。成分A)
A可以是单键、C1-C5亚烷基、C2-C5亚烯基、可选地被甲基、
-O-、-S-和-SO2-取代的C5-C6亚环烷基。
成分A)聚碳酸酯可以是线型和支化的,它们可含有接在芳环上的甲基并且不含卤素。成分A)可以单独使用也可以以混合物的形式使用。
式(Ⅲ)二酚可从文献得知或者可采用文献所述的方法制备。类似地,本发明适用的成分A)聚碳酸酯的生产可从文献得知,并可以例如用碳酰氯采用相界面法或者用碳酰氯采用均相法(所谓吡啶法)进行,其中用适量的已知的链转移剂按照已知的方法获得期望的分子量。
适宜的式(Ⅲ)二酚是例如氢醌、间苯二酚、4,4′-二羟基联苯、2,2-二(4-羟基苯基)丙烷(双酚A)、2,4-二(4-羟基苯基)-2-甲基丁烷、2,2-二(4-羟基-3,5-二甲基苯基)丙烷、1,1-二(4-羟基苯基)环己烷或1,1-二(4-羟基苯基)-3,3,5-三甲基环己烷。优选的式(Ⅰ)二酚是2,2-二(4-羟基苯基)丙烷、1,1-二(4-羟基苯基)环己烷。也可以使用二酚的混合物,例如双酚A与不超过60%(摩尔)的1,1-二(4-羟基苯基)-3,3,5-三甲基环己烷的混合物。
均聚碳酸酯和共聚碳酸酯都是适宜的。对于本发明的共聚碳酸酯A)的制备,也可以使用1-25%(重量)、优选2.5-25%(重量)(基于欲使用的二酚的总量计)的式(Ⅲa)二酚:式中,-A-的意义与式(Ⅲ)中的相同,n是1或0,各R相同或不同,是线型C1-C20烷基、支链C3-C20烷基或C6-C20芳基,优选甲基,m是5-100之间的整数,优选20-80。
按照式(Ⅲa)的含有羟基芳氧基端基的聚二有机硅氧烷是已知的(例如参见美国专利第349634号)或者可按照文献所述的方法制备。含有共聚碳酸酯的聚二有机硅氧烷的制备例如被描述于DE-OS3334782中。
聚碳酸酯A)可部分或完全地用芳族聚酯碳酸酯代替。
适宜的链终止剂是例如苯酚或对叔丁基苯酚,还有长链烷基苯酚如DE-OS 2842005中的4-(1,3-四甲基丁基)苯酚或者在按照DE-OS3506472的在烷基取代基上总共具有8-20个碳原子的一烷基苯酚或二烷基苯酚,例如对壬基苯酚、2,6-二叔丁基苯酚、对叔辛基苯酚、对十二烷基苯酚、2-(3,5-二甲基庚基)苯酚和4-(3,5-二甲基庚基)苯酚。链转移剂的用量一般均在所用的二酚(Ⅲ)的总量的0.5-10%(摩尔)之间。
适用于本发明的成分A)聚碳酸酯可以是用已知方法支化的,即最好通过混入所用的二酚总量的0.05-2.0%(摩尔)的三官能或三官能以上的化合物,例如具有三个或三个以上酚OH的化合物。
适用于本发明的聚碳酸酯的重均分子量(例如用超速离心法或光散射法测定的Mw)为10000-200000,优选20000-80000。成分B.1)
本发明的可用的成分B.1)乙烯基(共)聚物是树脂状、热塑性的,并且不含橡胶。它们是从至少一种选自苯乙烯、α-甲基苯乙烯、环烷被基取代的苯乙烯、丙烯酸C1-C8烷基酯、甲基丙烯酸C1-C8烷基酯(成分B.1.1)的单体与至少一种选自丙烯腈、甲基丙烯腈、丙烯酸C1-C8烷基酯、甲基丙烯酸C1-C8烷基酯、马来酸酐和/或N-取代的马来酰亚胺和/或乙酸乙烯酯(成分B.1.2)的单体制备的化合物。
丙烯酸C1-C8烷基酯或甲基丙烯酸C1-C8烷基酯分别是丙烯酸和甲基丙烯酸与具有1-8个碳原子的多元醇的酯。特别优选甲基丙烯酸的甲酯、乙酯和丙酯。甲基丙烯酸甲酯被认为是特别优选的甲基丙烯酸酯。
具有成分B.1)的组成的热塑性共聚物可以作为生产成分C)过程中的副产物出现,尤其是如果大量单体被接枝到少量橡胶上时。本发明所用的共聚物B.1)的量不包括这些接枝聚合的副产物。
热塑性共聚物B.1)含有50-95%(重量)、优选60-90%(重量)的成分B.1.1)和5-50%(重量)、优选10-40%(重量)的成分B.1.2)。
特别优选的共聚物B.1)是那些由苯乙烯与丙烯腈并可选地与甲基丙烯酸甲酯制备的共聚物、由α-甲基苯乙烯与丙烯腈并可选地与甲基丙烯酸甲酯制备的共聚物或者由苯乙烯和α-甲基苯乙烯与丙烯腈并可选地与甲基丙烯酸甲酯制备的共聚物。
成分B.1)苯乙烯/丙烯腈共聚物是已知的并且可通过自由基聚合制备,特别是通过乳液聚合、悬浮聚合、溶液聚合或本体聚合制备。成分B.1)共聚物的分子量(重均分子量
Mw,用光散射法或沉降法测定)优选在15000-200000之间。
特别优选的本发明的成分B.1)也是由苯乙烯、马来酸酐和/或N-取代的马来酰亚胺制备的无规共聚物,它可由对应的单体通过连续本体聚合或溶液聚合转化不完全地制备。
适用于本发明的无规苯乙烯/马来酸酐共聚物的两个成分的比例可在很宽的范围内变动。优选的马来酸酐的含量在5-25%(重量)之间。
适用于本发明的成分B.1)无规苯乙烯/马来酸酐共聚物的分子量(数均分子量
Mn)可在很宽的范围内变动。特别优选60000-200000的范围。这些产物的优选的特性粘度是0.3-0.9dl/g(在二甲基甲酰胺中,于25℃测定)。
乙烯基共聚物B.1)也可不含苯乙烯,而含有环被取代的苯乙烯如乙烯基甲苯、2,4-二甲基苯乙烯和其它不含卤素的取代的苯乙烯,例如α-甲基苯乙烯。成分B.2)
成分B.2)聚对苯二甲酸亚烷基酯是由芳族二元羧酸或其活性衍生物如二甲酯或酸酐与脂族、环脂族或芳脂族二醇制备的反应产物,并混有这些反应产物的混合物。
优选的聚对苯二甲酸亚烷基酯含有至少80%(重量)、优选至少90%(重量)(相对于二元羧酸成分计)对苯二甲酸残基和至少80%(重量)、优选至少90%(摩尔)(相对于二元醇成分计)乙二醇和/或1,4-丁二醇残基。
优选的聚对苯二甲酸亚烷基酯除了含有对苯二甲酸残基外,还可含有不超过20%(摩尔)、优选不超过10%(摩尔)其它具有8-14个碳原子的芳族或环脂族二元羧酸的残基或者具有4-12个碳原子的脂族二元羧酸的残基,例如邻苯二甲酸、间苯二甲酸、萘-2,6-二甲酸、4,4-联苯二甲酸、琥珀酸、己二酸、癸二酸、壬二酸和环己烷二乙酸的残基。
优选的聚对苯二甲酸亚烷基酯除了含有乙二醇或1,4-丁二醇残基外,还可含有不超过20%(摩尔)、优选不超过10%(摩尔)其它具有3-12个碳原子的脂族二元醇或具有6-12个碳原子的环脂族二元醇或具有6-21个碳原子的环脂族二元醇残基,例如1,3-丙二醇、2-乙基-1,3-丙二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、环己烷-1,4-二甲醇、3-乙基-2,4-戊二醇、2-甲基-2,4-戊二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2,2-二乙基-1,3-丙二醇、2,5-己二醇、1,4-二(β-羟乙基)苯、2,2-二(4-羟基环己基)丙烷、2,4-二羟基-1,1,3,3-四甲基环丁烷、2,2-二(4-β-羟基乙氧基苯基)丙烷和2,2-二(4-羟基丙氧基苯基)丙烷(DE-OS 2407674,2407776,2715932)的残基。
该聚对苯二甲酸亚烷基酯可以通过混入相对少量的三或四元醇或三或四元羧酸的方法(例如按照DE-OS 1900270和US-PS 3692744的方法)支化。优选的支化剂的例子有1,3,5-苯三酸、1,2,4-苯三酸、三乙基乙烷和三乙基丙烷和季戊四醇。
特别优选的聚对苯二甲酸亚烷基酯是那些仅用对苯二甲酸及其活性衍生物(例如其二烷基酯)与乙二醇和/或1,4-丁二醇制得的聚对苯二甲酸亚烷基酯,以及这些聚对苯二甲酸亚烷基酯的混合物。
优选的混合物含有1-50%(重量)、优选1-30%(重量)聚对苯二甲酸乙二醇酯和50-99%(重量)、优选70-99%(重量)聚对苯二甲酸丁二醇酯。
优选使用的聚对苯二甲酸亚烷基酯的特性粘度通常为0.4-1.5dl/g、优选0.5-1.2dl/g(在苯酚/二氯苯(重量比1∶1)中,于25℃用乌氏粘度计测定)。
所述聚对苯二甲酸亚烷基酯可按照已知的方法制备(参见例如Kunststoff-Handbuch,第Ⅷ卷,第695页等,Carl-Hanser Verlag,Mnnich 1973)。成分C)
接枝聚合物C)是通过由C.1.1)和C.1.2)制备的单体混合物C.1)在待接枝橡胶C.2)的存在下的自由基共聚合制备的,并且是公知的。接枝聚合物C)的优选的制备方法是乳液聚合、溶液聚合、本体聚合或悬浮聚合。特别优选的接枝聚合物C)是所谓的ABS聚合物。
根据C.1.1),单体C.1)的例子是苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、甲基丙烯酸甲酯或其混合物。C.1.2)的单体的例子是丙烯腈、甲基丙烯腈、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯、马来酸酐、N-取代的马来酰亚胺或其混合物。优选的C.1.1)的单体是苯乙烯、α-甲基苯乙烯和甲基丙烯酸甲酯。优选的C.1.2)的单体是丙烯腈、马来酸酐和甲基丙烯酸甲酯。特别优选的单体是苯乙烯和丙烯腈。
适宜的用来制备成分C)接枝聚合物的橡胶C2)特别是聚丁二烯、聚异戊二烯、苯乙烯/丁二烯共聚物橡胶、凝胶含量(于20℃测定)大于30%(重量)的丙烯腈/丁二烯共聚物橡胶、EPDM(乙烯/丙烯/二烯单体)橡胶和硅橡胶。
优选的橡胶C.2)是二烯橡胶(例如基于丁二烯、异戊二烯等的橡胶)或二烯橡胶的混合物或二烯橡胶或其混合物与其它可共聚合单体(例如C.1.1)和C.1.2)的单体)的共聚物,条件是成分C.2)的玻璃化转变温度低于10℃,优选低于-10℃。
特别优选的聚合物C)是例如ABS聚合物,参见DE-OS 2035390或DE-OS 2248242所述。
适宜的丙烯酸酯橡胶C2)是那些基于丙烯酸C1-C8烷基酯的橡胶,特别是基于丙烯酸乙酯、丁酯、乙基己酯的橡胶。这些丙烯酸烷基酯橡胶可选地含有相对于橡胶重量不超过30%(重量)的共聚合单体例如乙酸乙烯酯、丙烯腈、苯乙烯、α-甲基苯乙烯、环被烷基化的苯乙烯、甲基丙烯酸甲酯、丙烯酰胺和/或乙烯基醚。这些丙烯酸烷基酯橡胶还可再含有少量、优选不超过5%(重量)(相对于橡胶的重量计)的具有交联作用的乙烯基不饱和单体。该交联剂是例如亚烷基二醇二(甲基)丙烯酸酯、聚酯二(甲基)丙烯酸酯、二乙烯基苯、三乙烯基苯、三烯丙基氰脲酸酯、(甲基)丙烯酸烯丙酯、丁二烯或异戊二烯。
优选的交联单体是甲基丙烯酸烯丙酯、乙二醇二甲基丙烯酸酯、邻苯二甲酸二烯丙酯和具有至少三个烯不饱和基团的杂环化合物。特别优选的这种交联单体是三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、三乙烯基氰脲酸酯、三丙烯酰基-六氢-s-三嗪、三烯丙基苯。交联单体的用量优选0.02-5.0%(重量),尤其是0.05-2.0%(重量)(相对于接枝主链C.2)计)。对于具有至少三个乙烯基不饱和基团的环状交联单体,将该用量限制在低于接枝主链C.2)的1%(重量)是有利的。
丙烯酸酯橡胶接枝主链也可以是含有由一种或多种共轭二烯制备的交联二烯橡胶芯的产物如聚丁二烯,或者是共轭二烯与烯不饱和单体的共聚物例如苯乙烯和/或丙烯腈。
优选的制备接枝聚合物C)的橡胶是纯二烯和丙烯酸酯橡胶。
C.2)的其它的适宜的接枝主链是具有活性接枝部位的硅橡胶,如DE-OS 3704657,DE-OS 3704655和DE-OS 3631539所述。
在接枝聚合物C)中的橡胶以平均粒径为0.1-3.0μm、特别是0.2-0.6μm的至少部分交联的颗粒形式存在。它们至少是部分交联的,即它们的凝胶含量大于20%(重量)、特别是大于50%(重量)、特别优选在73-98%(重量)的范围内(在甲苯酯中测定)。成分D)
起阻燃剂作用的成分D)由相对于组合物A)至C)有效量的硅氧烷树脂D.1)和热塑性聚苯醚组成。组合物D)为5-50%(重量)、优选5-25%(重量)D.1)和50-95%(重量)、优选75-95%(重量)D.2)。
本发明的硅氧烷树脂D.1)是固体、粉状物,并含有羟基。其实验式为:其中,R代表一价烃残基,它可选地带有取代基,但尤其是甲基或苯基,R3是烷基,优选甲基,或氢残基,x的值为0.75-1.75,y的值为0.0001-0.5,且其中,硅氧烷树脂是由式SiO4/2,RSiO3/2,R2SiO2/2和/或R3SiO1/2单元合成的。
式(Ⅳ)硅氧烷树脂的制备是已知的。为了进一步加工或使用,它们是在适当溶剂(也可以是在聚二甲基硅氧烷溶液)中的溶液形式,含有溶剂的水性乳液的形式或纯物质的形式。再一种有利于使用的形式是由聚合物和接枝聚合物与含溶剂的硅氧烷树脂的乳液制备的分散体的共沉淀产物。这样便可确保在塑料模塑组合物中最细碎的分布。
成分D.2)聚苯醚具有下式(Ⅴ)结构:式中,每一个单元中的醚氧原子接在相邻单元的芳环上,n是大于20的正整数,R4和R5相互独立地代表氢、不带α-叔碳原子的烃残基和烃氧残基,例如甲基、乙基、丙基、甲氧基、乙氧基、丙氧基。
US-PS 3306874,3306875,3257357和3257358和DE-OS 3035599和Honben-Weyl,Methoden der Organischen Chemie,第E20卷(1987),第1320-1388页描述了上式聚苯醚及其制备方法,即将苯酚和含氧气体在金属胺复合催化剂的存在下进行催化氧化偶联。
适宜的聚苯醚是例如聚(2,6-二甲基-1,4-亚苯基)醚、聚(2,6-二乙基-1,4-亚苯基)醚、聚(2-甲基-6-乙基-1,4-亚苯基)醚、聚(2-甲基-6-丙基-1,4-亚苯基)醚、聚(2,6-二异丙基-1,4-亚苯基)醚、聚(2-二乙基-6-丙基-1,4-亚苯基)醚或共聚物如含有2,3,6-三甲基苯酚的共聚物,以及各种聚苯醚的混合物。聚(2,6-二甲基-1,4-亚苯基)醚或由2,6-二甲基苯酚与2,3,6-三甲基苯酚制得的共聚物是优选的。所述聚苯醚的特性粘度通常为0.3-0.7dl/g(以氯仿溶液于25℃测定)。成分E.1)
本发明的聚合物共混物包含下式(Ⅰ)磷化合物作为阻燃剂:式中,n,R1和l具有上文所述的意义。
也可以使用各种磷酸酯的混合物作本发明的成分E.1)。在这种情况下,n的平均值在1-5之间,优选在1-2之间。
优选使用的式(Ⅰ)磷化合物是亚苯基二(磷酸二苯酯),其中n=1和2或在1-2之间。成分E.2)
本发明的共混物可再含有式(Ⅰ)磷化合物与式(Ⅱ)磷化合物的混合物作阻燃剂,式(Ⅱ)为:式中,R2和m具有上文所述的意义。
优选将磷酸三苯酯用作式(Ⅱ)磷化合物。
所述混合物最好含有2-30%(重量)的式(Ⅱ)磷化合物(相对于100%(重量)E.1和E.2计)。
该磷酸酯一般可用已知的方法制备(参见例如
Ullmann,Enzyklopadie der Technischen Chemie,volume 18,pages 301et seq.,1979;Houben-Weyl,Methoden der Organischen Chemie,volume 12/1,page 43;Beilstein,volume 6,page 177)。
本发明的模塑组合物可以再含有一种或多种下述阻燃剂:-对聚碳酸酯具有燃烧抑制作用的盐-具有协同作用的金属化合物。
优选的盐是二苯基砜磺酸的钾盐。
本发明的组合物可再含有常规添加剂,例如润滑剂和脱模剂、增塑剂、抗静电剂、稳定剂、填充剂、和增强材料以及颜料和染料。优选的增强材料是玻璃纤维;优选的填充剂是玻璃珠、云母、石英、滑石、硅灰石;优选的颜料是碳黑和二氧化钛。
含有成分A)至E)的本发明的热塑性模塑组合物是通过将各成分以已知的方式混合并且在200℃到300℃的温度下,在常规设备如内捏合机、挤出机或双螺杆挤出机中将其熔融混合。
各成分的混合可以已知的方式依次和连续地进行,实际上在较高的温度下进行。
从而,本发明还提供制备由成分A)至E)组成的热塑性聚碳酸酯模塑组合物的方法,其特征在于将特定的上述成分以已知的方式混合,然后在200℃至300℃的温度下,在常规设备中熔融混合或熔融挤塑。
本发明的模塑组合物可用于任何种类的模塑制品的制造。尤其是通过注塑的方法制造模塑制品。可以制造的模塑制品的例子有各种外壳部件(例如日用品和办公设备的外壳部件)或建筑行业用的盖子和汽车行业用的部件。它们也可用于电器工程领域,因为它们具有很好的电气性能。
本发明的模塑组合物特别适合于产生薄壁模塑制品(例如数据处理设备外壳部件),其中对所用的塑料的缺口冲击强度、应力开裂行为和尺寸稳定性提出了特别苛刻的要求。
颗粒尺寸总是指按照W.Scholtan等人在Kolloid-Z.& Z.Polymere 250(1972),782-796中所述的方法通过超速离心测量法测定的平均粒径d50。
实施例所用的材料成分A)
相对溶液粘度为1.34(在二氯甲烷中于25℃测定,浓度为0.5g/100ml)的基于双酚A的聚碳酸酯。成分B)
苯乙烯/丙烯腈比为72∶28且特性粘度为55dl/g(在二甲基甲酰胺中于25℃测定)的苯乙烯/丙烯腈共聚物。成分C)
通过乳液聚合制备的接枝在55%(重量)的粒状交联聚丁二烯橡胶上的45%(重量)苯乙烯/丙烯腈(比率为72∶28)接枝聚合物(平均粒径d50=0.4μm)。成分D.1)
Baysilone树脂M 120 XB,溶剂已用旋转蒸发器除去,100%(Bayer AG的甲基硅氧烷树脂)。成分D.1)
SFR100(由General Electric Silicones得到的聚甲基硅氧烷形式的甲基硅氧烷树脂)。成分D.2)
由2,6-二甲基苯酚按照DE-OS 3035599制备的聚苯醚,特性粘度为0.42dl/g(在氯仿中,于25℃测定)。成分E.1)
得自Akzo B.V.的Fyroflex RDP(含有大约60-65%间亚苯基二(磷酸二苯酯)的低聚物混合物)。成分E.2)
75.0%(重量)Fyroflex RDP(见成分E.1)和25.0%(重量)磷酸三苯酯(Bayer AG的Disflamoll TP)的混合物。模塑组合物的生产和测试
在W50E型小规模捏合机(Brabender OHG公司,Duisberg制造)中进行捏合制得耐燃性热塑性模塑组合物,捏合温度为210-230℃,转速为60min-1;捏合时间为10分钟。用电加热的Polystat 200T实验室压塑机(Schwabenthan公司制造)将所得模塑组合物压塑为4.0或1.6mm的片材,压制温度为200℃;压力为200巴;压制5分钟。
从片材上锯下所需的试样,进行下述测试:-用尺寸为80×10×4mm的棒按照DIN 53460(Vicat B)测定耐热性,-用厚度为1.6mm的棒按照Underwriters′Laboratories方法(
UL-94)进行可燃性测试。
应力开裂行为用尺寸为80×10×4mm的棒来研究,压制温度为220℃。所用的试验介质是60%(体积)甲苯与40%(体积)异丙醇的混合物。将试样在圆弧性模板上预拉伸(初始伸长百分数),在室温下存放于试验介质中。通过评定在试验介质中暴露5分钟断裂随初始伸长率的变化测定应力开裂行为。
表:模塑组合物的组成和性能
| 成分(重量份) | ||||||||||
| A | B | C | D1 | D2 | E1 | E2 | ESC断裂伸长率[%] | Vicat B 120[℃] | UL94V1.6mm | |
| 实施例 | ||||||||||
| 1 | 69 | 4 | 10 | 1 | 1 | - | 15 | 1.6 | 89 | V-0 |
| 2 | 69 | 5 | 10 | 1 | 1 | - | 14 | 1.8 | 91 | V-0 |
| 3 | 69 | 6 | 10 | 1 | 1 | - | 13 | 2.0 | 93 | V-0 |
| 4 | 69 | 4 | 10 | 1 | 1 | 15 | - | 1.4 | 91 | V-0 |
| 5 | 69 | 5 | 10 | 1 | 1 | 14 | - | 1.6 | 93 | V-0 |
| 6 | 69 | 6 | 10 | 1 | 1 | 13 | - | 1.8 | 95 | V-0 |
本发明的模塑组合物(实施例1-6)表现出很好的包括阻燃性、耐热性和应力开裂行为在内的综合性能。在实施例1-3和4-6中,即使仅加入少量聚苯醚和硅氧烷树脂也可在不损害V-0级别的情况下明显地降低磷酸酯的用量。由于这一协同作用,结果提高了耐热性并改善了ESC行为。
如果使用成分E.1)与一磷酸酯例如磷酸三苯酯的混合物代替间苯二酚二磷酸酯,则可获得本发明的模塑组合物的上述有利的综合性能。这些模塑组合物的再一个优点是它们具有提高的耐应力开裂性(参见实施例1-3与4-6的比较)。单独使用一磷酸酯作为磷酸酯成分E将导致耐热性的严重损害。
Claims (10)
1.不含卤素的阻燃性热塑性模塑组合物,它包含以下成分:A)50-95%(重量)热塑性芳族聚碳酸酯,B)0-20%(重量)包含下述成分的共聚物或缩聚产物:
B.1)由下述化合物制成的热塑性共聚物:
B.1.1)50-95%(重量)苯乙烯、α-甲基苯乙烯、环被烷基化
的苯乙烯、丙烯酸C1-C8烷基酯、甲基丙烯酸C1-C8烷
基酯或其混合物和
B.1.2)5-50%(重量)丙烯腈、甲基丙烯腈、丙烯酸C1-C8烷
基酯、甲基丙烯酸C1-C8烷基酯、马来酸酐、N-取代的
马来酰亚胺、乙酸乙烯酯或其混合物和/或
B.2)热塑性聚对苯二甲酸亚烷基酯,C)3-18%(重量)由下述成分制成的接枝共聚物:
C.1)5-90%(重量)由下述成分制成的混合物:
C.1.1)50-95%(重量)苯乙烯、α-甲基苯乙烯、环被烷基
化的苯乙烯、丙烯酸C1-C8烷基酯、甲基丙烯酸C1-C8
烷基酯或其混合物和
C.1.2)5-50%(重量)丙烯腈、甲基丙烯腈、丙烯酸C1-C8烷
基酯、甲基丙烯酸C1-C8烷基酯、马来酸酐、N-取代的
马来酰亚胺或其混合物
C.2)10-95%(重量)玻璃化转变温度Tg≤10℃的橡胶,D)1-20%(重量)由下述成分制成的具有阻燃作用的组合:
D.2)50-95%(重量)热塑性聚苯醚,
E)3-18%(重量)由下述化合物制备的磷酸酯:
E.1)式(Ⅰ)磷化合物:
式中,n=1-5,R1是甲基,l=0-5,或者E.2)式(Ⅰ)磷化合物与式(Ⅱ)磷化合物的混合物,式(Ⅱ)
式中,R2是甲基,m是0-5,
其中式(Ⅱ)磷化合物在由E.1)和E.2)制备的磷酸酯混合物中的量为至多为35%(重量),
其中所有成分之和为100%(重量)。
2.根据权利要求1的热塑性模塑组合物,其中各成分的含量为:
60-90%(重量)的A);
1-15%(重量)的B);
5-15%(重量)的C);
2-15%(重量)的D);
5-15%(重量)的E);
其中所有成分之和为100%。
4.根据权利要求1的热塑性模塑组合物,其特征在于以间亚苯基二(磷酸二苯酯)和磷酸三苯酯作为成分E)。
5.根据权利要求1的热塑性模塑组合物,它含有对聚碳酸酯具有燃烧抑制作用的盐和/或具有协同作用的金属化合物作为附加的阻燃剂。
6.根据权利要求1的热塑性模塑组合物,它还含有添加剂,其选自润滑剂和脱模剂、增塑剂、抗静电剂、稳定剂、填充剂和增强材料、颜料和/或染料。
7.权利要求1-3之任一项的热塑性模塑组合物,其中式(Ⅳ)中的R基团为甲基或苯基。
8.生产权利要求1的热塑性模塑组合物的方法,其中将成分A)至E)以已知的方式混合,然后在200℃到300℃的温度下,在常规设备内熔融混合或熔融挤塑。
9.权利要求1的热塑性模塑组合物在制造模塑制品中的用途。
10.由权利要求1的热塑性模塑组合物制得的模塑制品。
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| DEP4443164.3 | 1994-12-05 | ||
| DE4443164A DE4443164A1 (de) | 1994-12-05 | 1994-12-05 | Flammgeschützte, thermoplastische Polycarbonat-Formmassen |
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| DE4200247A1 (de) * | 1992-01-08 | 1993-07-15 | Basf Ag | Thermoplastische polycarbonatformmassen |
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- 1995-11-22 DE DE59510937T patent/DE59510937D1/de not_active Expired - Lifetime
- 1995-11-24 US US08/562,585 patent/US5621029A/en not_active Expired - Lifetime
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| EP0522653A1 (en) * | 1991-07-12 | 1993-01-13 | Dsm N.V. | Flame-retardant polymer composition |
| DE4200247A1 (de) * | 1992-01-08 | 1993-07-15 | Basf Ag | Thermoplastische polycarbonatformmassen |
| EP0594021A2 (de) * | 1992-10-22 | 1994-04-27 | Bayer Ag | Flammwidrige Formmassen |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100577738C (zh) * | 2001-11-30 | 2010-01-06 | 宝理塑料株式会社 | 阻燃性树脂组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3376571B2 (ja) | 2003-02-10 |
| CN1130198A (zh) | 1996-09-04 |
| DE59510937D1 (de) | 2004-09-30 |
| US5621029A (en) | 1997-04-15 |
| DE4443164A1 (de) | 1996-06-13 |
| JPH093312A (ja) | 1997-01-07 |
| EP0716125A2 (de) | 1996-06-12 |
| EP0716125A3 (de) | 1996-08-28 |
| EP0716125B1 (de) | 2004-08-25 |
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