CN101616978B - 具有阻燃性和抗冲性的热塑性模塑组合物 - Google Patents
具有阻燃性和抗冲性的热塑性模塑组合物 Download PDFInfo
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- CN101616978B CN101616978B CN2007800517196A CN200780051719A CN101616978B CN 101616978 B CN101616978 B CN 101616978B CN 2007800517196 A CN2007800517196 A CN 2007800517196A CN 200780051719 A CN200780051719 A CN 200780051719A CN 101616978 B CN101616978 B CN 101616978B
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- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical group C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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Abstract
Description
发明领域
本发明涉及一种热塑性模塑组合物,尤其涉及具有阻燃性和抗冲性的聚碳酸酯组合物。
发明背景
含聚碳酸酯和聚对苯二甲酸亚烷基二醇酯的热塑性模塑组合物是已知的。在专利文献中已经揭示了多种这样的组合物。美国专利4,888,388中揭示了一种具有杰出的表面外观、色彩稳定性和热稳定性的耐冲击热塑性组合物。该组合物包含特定的接枝橡胶共聚物、聚碳酸酯和饱和聚酯。美国专利3,557,053揭示了一种自熄聚碳酸酯组合物,该组合物对降解稳定,且含有卤代的磷化合物。还已知的是包含磷化合物作为添加剂(主要作为阻燃剂)的组合物。已有文献揭示磷化合物与卤代添加剂的组合能赋予热塑性组合物阻燃性。在这方面应该注意美国专利5,276,077,该文献揭示了一种具有抗引燃性的组合物,该组合物包含聚碳酸酯、橡胶改性的单亚乙烯基芳族共聚物和橡胶芯/壳接枝共聚物的抗冲改性剂。
发明概述
揭示了一种具有阻燃性和抗冲性的热塑性组合物。包含聚碳酸酯、热塑性聚酯、卤化丙烯酸酯、抗冲改性剂、含磷化合物和氟化聚烯烃的组合物具有机械性质、加工性和阻燃性的良好组合。卤代丙烯酸酯包含符合以下结构式的重复结构单元:
其中,R1、R2、R3、R4和R5各自独立地表示氢、烷基或芳基,n是0-5,m是10-10000,R表示卤素。
发明详述
本发明的组合物包含:
(a)24-94重量%(pbw)、优选35-78重量%的(共)聚碳酸酯,
(b)4-74重量%、优选6-55重量%的热塑性聚酯,
(c)1-30重量%、优选5-15重量%的卤化丙烯酸酯,
(d)最多为20重量%的正量、优选3-15重量%的抗冲改性剂,
(e)最多为15重量%的正量、优选2-15重量%的至少一种含磷化合物,和
(f)最多为1重量%的正量、优选0.05-0.5重量%的氟化聚烯烃。
本发明的聚碳酸酯组分是众所周知的可购得的热塑性树脂。在许多出版物中揭示了其化学结构、性质和制备方法(在此方面参见专论H.Schnell,″聚碳酸酯的化学和物理(Chemistry and Physics of Polycarbonates)″,Interscience Publishers,纽约,纽约,1964,通过参考结合于此)。文中所用的术语“聚碳酸酯”一般指均聚碳酸酯或共聚碳酸酯。适用于本发明的聚碳酸 酯的重均分子量为10,000-200,000,优选为20,000-80,000,根据ASTMD-1238在300℃、1.2千克负荷下的熔体流动速率约为1-65克/10分钟,优选为2-15克/10分钟。这些树脂可以通过例如已知的两相界面缩聚法(参见上述Schnell的文献)或熔融酯交换法(参见D.G.LeGrand等,″聚碳酸酯科学和技术手册(Handbook of Polycarbonate Science and Technology)″,MarcelDekker Verlag,纽约,Basel,2000,第12页)制得。
适用于制备聚碳酸酯的芳族二羟基化合物符合通式HO-Z-OH,其中Z是具有6-30个碳原子的包含一个或多个芳基的二价有机基团。这类化合物的例子是双酚,包括二羟基联苯、二(二羟基苯基)烷烃、茚满双酚、二(羟基苯基)醚、二(羟基苯基)砜、二(羟基苯基)酮和α,α’-二(羟基苯基)二异丙基苯。其中,可提及的是氢醌、间苯二酚、二-(羟基苯基)-烷烃、二-(羟基苯基)-醚、二-(羟基苯基)-酮、二-(羟基苯基)-亚砜、二-(羟基苯基)-硫醚、二-(羟基苯基)-砜和α,α-二-(羟基苯基)-二异丙基苯。这些和其它合适的芳族二羟基化合物在例如美国专利3,028,356、2,999,835、3,148,172、2,991,273、3,271,367和2,999,846中描述,所有文献通过参考结合于此。其它合适的双酚的例子是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、1,1-二-(4-羟基苯基)-环己烷、α,α′-二-(4-羟基苯基)-对-二异丙基苯、2,2-二-(3-甲基-4-羟基苯基)-丙烷、2,2-二-(3-氯-4-羟基苯基)-丙烷、二-(3,5-二甲基-4-羟基苯基)-甲烷、2,2-二-(3,5-二甲基-4-羟基苯基)-丙烷、二-(3,5-二甲基-4-羟基苯基)-硫醚、二-(3,5-二甲基-4-羟基-苯基)-亚砜、二-(3,5-二甲基-4-羟基苯基)-砜、二羟基-二苯甲酮、2,4-二-(3,5-二甲基-4-羟基苯基)-环己烷、α,α′-二-(3,5-二甲基-4-羟基苯基)-对-二异丙基苯和4,4′-磺酰基联苯酚。
特别优选的芳族双酚的例子是2,2-二-(4-羟基苯基)-丙烷、2,2-二-(3,5-二甲基-4-羟基苯基)-丙烷和1,1-二-(4-羟基苯基)-环己烷。最优选的双酚是2,2-二-(4-羟基苯基)-丙烷(双酚A)。
适用于制备热塑性芳族聚碳酸酯的链终止剂包括例如苯酚和对叔丁基苯酚以及长链烷基苯酚,例如依据DE-A 2 842 005的4-(1,3-四甲基丁基)苯酚,或烷基取代基中总共含有8-20个碳原子的单烷基苯酚或二烷基苯酚, 诸如3,5-二叔丁基苯酚、对异辛基苯酚、对叔辛基苯酚、对十二烷基苯酚和2-(3,5-二甲基庚基)苯酚和4-(3,5-二甲基庚基)苯酚。以在特定情况下使用的二元酚的总摩尔量为基准计,链终止剂的用量通常为0.5-10摩尔%。
可以通过已知的方式使所述热塑性芳族聚碳酸酯支化,优选通过结合0.05-2.0摩尔%(以使用的二元酚的总量为基准计)的官能度大于或等于3的化合物,例如具有三个或更多个酚基的化合物进行支化。
合适的聚碳酸酯树脂可以例如商品名Makrolon从宾夕法尼亚州匹兹堡的拜尔材料科学有限公司(Bayer MaterialScience LLC of Pittsburgh,Pennsylvania)或德国勒沃库森的拜尔材料科学有限公司(BayerMaterialScience AG of Leverkusen,Germany)购得。
适合用作组分(b)的(共)聚酯包括均聚聚酯和共聚聚酯树脂,这些树脂是分子结构包括至少一个来自羧酸的键(优选排除来自碳酸的键)的树脂。这些树脂是已知的,可通过二醇组分和二元酸依据已知的方法发生缩合或酯交换聚合制得。例子是通过环己烷二甲醇和乙二醇与对苯二甲酸或对苯二甲酸和间苯二甲酸的组合进行缩合反应得到的酯。还适合的是环己烷二甲醇和乙二醇与1,4-环己烷二羧酸发生缩聚反应得到的聚酯。合适的树脂包括聚(二羧酸亚烷基二醇酯),特别是聚(对苯二甲酸乙二醇酯)(PET)、聚(对苯二甲酸1,4-丁二醇酯)(PBT)、聚(对苯二甲酸丙二醇酯)(PTT)、聚(萘二甲酸乙二醇酯)(PEN)、聚(萘二甲酸丁二醇酯)(PBN)、聚(对苯二甲酸环己烷二甲醇酯)(PCT)、聚(对苯二甲酸环己烷二甲醇-乙二醇酯)共聚物(PETG或PCTG)和聚(1,4-环己烷二甲基-1,4-环己烷二羧酸酯)(PCCD)。
美国专利2,465,319、3,953,394和3,047,539(均通过参考结合于此)揭示了制备这类树脂的合适方法。合适的聚对苯二甲酸亚烷基二醇酯的特征是特性粘度至少为0.2分升/克,优选至少约为0.4分升/克,该粘度值是通过在约25℃下、在8%的邻氯苯酚溶液中的相对粘度测得。上限值并不重要,但是其通常不超过约2.5分升/克。特别优选的聚对苯二甲酸亚烷基二醇酯是特性粘度在0.4-1.3分升/克范围内的那些聚对苯二甲酸亚烷基二醇酯。
适合用于本发明的聚对苯二甲酸亚烷基二醇酯中的亚烷基单元含有2-5个、优选2-4个碳原子。聚对苯二甲酸丁二醇酯(由1,4-丁二醇制备)和聚对 苯二甲酸乙二醇酯是优选用于本发明的聚对苯二甲酸亚烷基二醇酯。其它合适的聚对苯二甲酸亚烷基二醇酯包括聚对苯二甲酸丙二醇酯、聚对苯二甲酸异丁二醇酯、聚对苯二甲酸戊酯、聚对苯二甲酸异戊酯和聚对苯二甲酸新戊酯。亚烷基单元可以是直链或支链。
优选的聚对苯二甲酸亚烷基二醇酯除了含有对苯二甲酸基外,还含有最多20摩尔%的来自其它具有8-14个碳原子的芳族二羧酸或具有4-12个碳原子的脂族二羧酸的基团,例如来自邻苯二甲酸、间苯二甲酸、萘-2,6-二羧酸、4,4′-二苯基二羧酸、琥珀酸、己二酸、癸二酸、壬二酸或环己烷二乙酸的基团。
除了含有乙二醇或1,4-丁二醇基团外,优选的聚对苯二甲酸亚烷基二醇酯还含有最多20摩尔%的其它具有3-12个碳原子的脂族二醇或具有6-21个碳原子的脂环族二醇的基团,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-甲基-2,4-戊二醇、2-甲基-2,4-戊二醇、2,2,4-三甲基-1,3-戊二醇和2,2,4-三甲基-1,6-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-羟基乙氧基)-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-(3-β-羟基乙氧基-苯基)-丙烷和2,2-二-(4-羟基丙氧基苯基)-丙烷的基团(DE-OS 24 07 674、24 07 776、27 15 932)。
例如,依据DE-OS 19 00 270和美国专利3,692,744所述,通过结合少量三元醇或四元醇或三元羧酸或四元羧酸来使聚对苯二甲酸亚烷基二醇酯支化。优选的支化剂的例子包括均苯三酸、偏苯三酸、三羟甲基乙烷和三羟甲基丙烷、以及季戊四醇。较佳的是,相对于酸组分,支化剂的用量不超过1摩尔%。
特别优选的是仅仅由以下组分制备的聚对苯二甲酸亚烷基二醇酯:对苯二甲酸及其反应性衍生物(例如其二烯丙基酯)和乙二醇和/或1,4-丁二醇(聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯)和这些聚对苯二甲酸亚烷基二醇酯的混合物。
由上述酸组分中的至少两种和/或上述醇组分中的至少两种制备的共聚聚酯也是优选的聚对苯二甲酸亚烷基二醇酯,特别优选的共聚聚酯是聚(乙 二醇/1,4-丁二醇)-对苯二甲酸酯。
美国专利4,267,096、4,786,692、4,352,907、4,391,954、4,125,571、4,125,572、4,188,314和5,407,994中揭示了合适的聚对苯二甲酸亚烷基二醇酯,这些专利文献通过参考结合于此。
适合作为本发明的组分(c)的卤化丙烯酸酯包含符合以下结构式的重复结构单元:
其中,R1、R2、R3、R4和R5各自独立地表示氢、烷基或芳基,优选是C1-18-烷基或苯基;n是0-5,优选是0-3;m是10-10000,优选是50-1000。R是卤素,优选是溴或氯。苯环最多可被5个R基团取代。
最佳地,R1、R2、R3、R4和R5各自表示氢,n是1,R是溴。
优选的卤化丙烯酸酯是FR 1025P,一种来自新泽西州利堡的艾美姆公司(Ameribrom,Inc,of Fort Lee,New Jersey)的商品。
适合用于本发明的卤化丙烯酸酯可通过符合以下结构式的单体的自由基聚合反应制得:
其中,R1、R2、R3、R4和R5、n和R如上文所述。
适合作为本发明组合物的组分(d)的抗冲改性剂是一种接枝聚合物,由5-95重量%、优选30-90重量%至少一种乙烯基单体接枝到95-5重量%、优选70-10重量%一种或多种弹性交联接枝基料(graft base)上形成,所述接枝基料的玻璃化转变温度低于10℃,优选低于0℃,特别优选低于-20℃,所述百分数是相对于抗冲改性剂的重量的百分数。
接枝基料的中值粒度(d50)通常为0.05-10微米,优选为0.1-5微米,特别优选为0.2-1微米。
接枝相优选是以下组分的混合物:
A)50-99重量份的一种或多种乙烯基芳族化合物(例如苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、甲基丙烯酸(C1-C8)-烷基酯(优选是甲基丙烯酸甲酯和甲基丙烯酸乙酯),和
B)1-50重量份的一种或多种乙烯基氰化物(例如丙烯腈、甲基丙烯腈)、(甲基)丙烯酸(C1-C8)-烷基酯(优选的是甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和它们的衍生物(优选是不饱和羧酸的酸酐和酰亚胺)(优选是马来酸酐和N-苯基马来酰亚胺)。
优选包括在A中的单体是苯乙烯、α-甲基苯乙烯和甲基丙烯酸甲酯;优选的单体B包括丙烯腈、马来酸酐和甲基丙烯酸甲酯。特别优选的A是苯乙烯,特别优选的B是丙烯腈。
合适的接枝基料包括二烯橡胶、EP(D)M橡胶、丙烯酸酯、聚氨酯、硅酮和乙烯/乙酸乙烯酯橡胶。优选的接枝基料是二烯橡胶(例子是丁二烯和异戊二烯),特别优选的是聚丁二烯橡胶。
例如美国专利3 644 574、GB 1 409 275和Ullmann, derTechnischen Chemie,第19卷(1980),第280页(其内容都通过参考结合于此)描述的ABS聚合物也是合适的接枝聚合物。这类聚合物可通过自由基聚合反应制备,例如通过乳液聚合、悬浮聚合、溶液聚合或本体聚合制备,优选通过乳液聚合或本体聚合制备。特别优选的是乳液聚合得到的ABS。
特别合适的接枝橡胶还包括使用有机氢过氧化物和抗坏血酸的引发剂体系通过环氧还原引发制备的ABS聚合物(参见美国专利4,937,285,其内容通过参考结合于此)。
也适合作为接枝基料的是丙烯酸酯橡胶,优选是丙烯酸烷基酯的聚合物,任选地最多包含40%(相对于基料的重量)的其它可聚合烯键式不饱和单体。优选的可聚合丙烯酸酯包括C1-C8-烷基酯,例如甲基酯、乙基酯、丁基酯、正辛基酯和2-乙基己基酯,以及这些单体的混合物。
为了接枝基料的交联,可以使具有一个以上的可聚合双键的单体共聚。优选的交联单体的例子是:具有3-8个碳原子的不饱和一元羧酸的酯、具有3-12个碳原子的不饱和一元醇的酯,或具有2-4个OH基和2-20个碳原子的饱和多元醇的酯,例如二甲基丙烯酸乙二醇酯、甲基丙烯酸烯丙酯;多不饱和杂环化合物,例如氰尿酸三乙烯酯和氰尿酸三烯丙酯;多官能乙烯基化合物,例如二乙烯基苯和三乙烯基苯;以及磷酸三烯丙酯和邻苯二甲酸二烯丙酯。优选的交联单体是甲基丙烯酸烯丙酯、二甲基丙烯酸乙二醇酯、邻苯二甲酸二烯丙酯和具有至少三个烯键式不饱和基团的杂环化合物。特别优选的交联单体是环状单体,例如氰尿酸三烯丙酯、异氰脲酸三烯丙酯、三丙烯酰基六氢-s-三嗪、三烯丙基苯。以接枝基料的重量为基准计,交联单体的量优选为0.02-5%,特别优选为0.05-2%。
其它合适的接枝基料包括具有接枝活性位点的硅橡胶,如DE-A 3 704657、DE-A 3 704 655、DE-A 3 631 540和DE-A 3 631 539中所描述的。
中值粒度(d50)是这样一种粒径,各有50重量%的颗粒在该粒径以上和 该粒度以下。可通过超速离心测量确定该中值粒度(W.Scholtan,H.Lange,Kolloid,Z.und Z.Polymere 250(1972),7821796)。
本发明中的组分(e)是符合通式(III)或(IV)的磷酸酯化合物,膦酸胺、磷腈或磷酸酯/盐。
O=P-[-OCH2C(CH2 Br)3]3 (III)
式中:
R1、R2、R3和R4各自独立地表示C1-C8-烷基,或C5-C6-环烷基,C6-C20-芳基或C7-C12-芳烷基,这些基团各自任选地被烷基、优选C1-C4-烷基取代,
n各自独立地表示0或1,
优选是,
N是0.1-30,优选是0.5-10,更优选是0.7-5,
X表示具有6-30个碳原子的单核或多核芳族基团,或具有2-30个碳原子的脂族基团,所述脂族基团可以是直链或支链的。
在最优选的实施方式中,X表示以下所列中的任何一种:
较佳地,R1、R2、R3和R4各自独立地表示C1-C4烷基、苯基、萘基或苯基-C1-C4烷基,它们各自可被烷基、优选C1-C4-烷基取代。特别优选的芳基团是甲苯基、苯基、二甲苯基、丙基苯基或丁基苯基。
合适的通式(IV)的磷化合物中包括磷酸三丁酯、磷酸三苯酯、磷酸三甲苯酯、磷酸二苯基甲苯酯、磷酸二苯基辛酯、磷酸二苯基-2-乙基甲苯酯、三-(异丙基苯基)磷酸酯、甲基膦酸二甲酯、甲基膦酸二苯酯、苯基膦酸二乙酯、三苯基氧化膦、三甲苯基氧化膦。特别优选的单磷化合物是磷酸三苯酯。
特别有利的是符合通式(V)的化合物:
式中:
R1、R2、R3和R4、n和N如上文所定义,其中q各自独立地表示0、1、2、3或4,优选是0、1或2,R5和R6各自独立地表示C1-C4-烷基,优选是甲基,Y表示C1-C7-烷叉基(alkylidene)、C1-C7-亚烷基(alkylene)、C5-C12-亚环烷基、C5-C12-环烷叉基(cycloalkylidene)、-O-、-S-、-SO-、SO2或-CO-。
特别优选的是由双酚A或其甲基取代的衍生物得到的符合通式(V)的化合物。
上述磷化合物是已知的(参见EP-A 363 608、EP-A 640 655),可通过已知的方法制备(参见Ullmanns der technischen Chemie,第18卷,第301页1979;Houben-Weyl,Methoden der organischen Chemie,第12/1卷,第43页;Beilstein第6卷,第177页)。
膦酸胺符合通式(VI)
A3-y-NB1 y (VI)
其中:
A表示通式(VIa)或(VIb)的基团
R11和R12各自独立地表示C1-C10-烷基或C6-C10-芳基,
R13和R14各自独立地表示C1-C10-烷基或C6-C10-芳基,
y表示0、1或2,B1独立地表示氢、C2-C8-烷基或C6-C10-芳基,
B1表示氢、乙基、正丙基或异丙基、未取代的或C1-C4-烷基取代的C6-C10-芳基,特别是苯基或萘基。
R11、R12、R13和R14的烷基优选是甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基、戊基或己基,芳基优选是苯基、萘基或联萘基。
例子包括符合(VIa-1)的5,5,5′,5′,5″,5″-六甲基三(1,3,2-二氧杂磷杂环己烷-甲烷)氨基-2,2′,2″-三氧化物。
例如美国专利5,844,028描述了膦酸胺的制备方法,其内容通过参考结合于此。
也合适的是符合通式(VIIa)或(VIIb)的磷腈:
其中,R各自独立地表示C1-8-烷基或C1-8-烷氧基、C5-6-环烷基、C6-20-芳基、C6-20-芳氧基或C7-12-芳烷基,k表示0-15,优选为1-10。
例子包括丙氧基磷腈、苯氧基磷腈和甲基苯氧基磷腈。优选的是苯氧基磷腈。例如,在EP-A 728811、DE-A 1961668和WO 97/40092中描述了磷腈及其制备方法。本发明组合物的组分(f)氟化聚烯烃在组合物中的含量为0.05-0.5重量%。氟化聚烯烃是已知的(参见EP-A 640655)。一种可从杜邦公司(DuPont)购得商品是 30N。
氟化聚烯烃的使用形式还可以是氟化聚烯烃的乳液与接枝聚合物的乳液或与优选为苯乙烯-丙烯腈的共聚物的乳液的凝结混合物,将乳液形式的氟化聚烯烃与接枝聚合物或共聚物的乳液混合,然后混凝。氟化聚烯烃的使用形式还可以是其与接枝聚合物或与优选基于苯乙烯/丙烯腈的共聚物的预混物。将氟化聚烯烃以粉末形式与接枝聚合物或共聚物的粉末或颗粒混合,使用常规方式在200-330℃的温度熔融配混。
氟化聚烯烃的使用形式还可以是母料,该母料是通过在氟化聚烯烃的水 性分散体存在下使至少一种单烯键式不饱和单体发生乳液聚合而制得的。优选的单体组分是苯乙烯、丙烯腈和它们的混合物。凝结体、预混物和母料的氟化聚烯烃固体含量通常为5-95重量%,优选为7-60重量%。
该组合物还可含有一种或多种常规的功能添加剂,例如填料、其它相容性塑料、抗静电剂、抗氧化剂、润滑剂和紫外稳定剂。合适的填料包括滑石、粘土、纳米粘土(文中所用的前缀“纳米”指粒度小于约100纳米)、二氧化硅、纳米二氧化硅,以及增强剂如玻璃纤维。合适的紫外吸收剂包括羟基二苯甲酮、羟基苯并三唑、羟基苯并三嗪、氰基丙烯酸酯、N,N’-草酰二苯胺和苯并噁嗪酮,以及纳米尺寸的无机材料,例如二氧化钛、氧化铈和氧化锌。合适的稳定剂包括碳二亚胺,例如二-(2,6-二异丙基苯基)碳二亚胺和聚碳二亚胺;位阻胺光稳定剂;位阻酚(例如Irganox 1076(CAS号2082-79-3)、Irganox 1010(CAS号6683-19-8);亚磷酸酯(例如Irgafos 168,CAS号31570-04-4;Sandostab P-EPQ,CAS号119345-01-6;Ultranox 626,CAS号26741-53-7;Ultranox 641,CAS号161717-32-4;Doverphos S-9228,CAS号154862-43-8)、三苯基膦和亚磷酸。合适的水解稳定剂包括环氧化物,例如Joncryl ADR-4368-F、Joncryl ADR-4368-S、Joncryl ADR-4368-L、脂环族环氧树脂ERL-4221(CAS号2386-87-0)。
添加剂以有效的量使用,优选相对于树脂状组分的总重量,总共为0.01重量%至约30重量%。
在制备例举的组合物中,在双螺杆挤出机ZSK 30(温度分布为120-255℃)中将各组分和添加剂熔融配混。得到的粒料在强制通风的对流烘箱中在120℃干燥4-6小时。对部件进行注塑(熔融温度265-285℃,模具温度约75℃)。
使用厚度为1/8”或1/4”的样品进行艾佐德(Izod)冲击强度的测定。测量依据ASTM D-256进行。
依据ASTM 1238,在5千克负荷重量下,在256℃测量熔体流动指数。根据对厚度1/8”或1/16”的样品进行UL 94垂直燃烧(vertical burning)来测量阻燃性。
通过以下实施例进一步说明本发明,但本发明不受限于这些实施例,在 这些实施例中,除非另有指示,否则,所有份数和百分数都是以重量计的。
实施例
在制备下述组合物中,使用以下组分:
聚碳酸酯:基于双酚A的均聚碳酸酯,其依据ASTM D 1238的熔体流动速率约为4克/10分钟(在300℃,1.2千克)(Makrolon 3208,拜尔材料科学有限公司(Bayer MaterialScience LLC)的产品)
聚对苯二甲酸乙二醇酯,其特性粘度为0.94。
卤化丙烯酸酯:聚(五溴苄基丙烯酸酯)-FR 1025P,一种来自新泽西州利堡的艾美姆公司的产品。
卤化碳酸酯:四溴双酚A的低聚碳酸酯,肯姆瑞公司(ChemtruraCompany)的产品。
抗冲改性剂:包含约75%橡胶的ABS,莱克斯公司的(Lanxess AG)的产品。
磷化合物III:三溴新戊基磷酸酯,FR-370,来自新泽西州利堡的艾美姆公司的产品。
磷化合物IV:双酚A-二-(二苯基磷酸酯),Reofos BAPP,肯姆瑞公司的产品。
氟化聚烯烃:含等重量聚四氟乙烯和苯乙烯丙烯腈共聚物的凝结剂。
所有组合物含47.1%的聚碳酸酯、30.6%的热塑性聚酯、9.1%的ABS和0.1%的氟化聚烯烃。
实施例 | 1(本发明) | 2(对比例) | 3(对比例) | 4(本发明) |
卤化丙烯酸酯 | 10 | - | - | 10 |
卤化低聚碳酸 酯 | -- | 10 | 10 | -- |
磷化合物IV | -- | -- | 3 | 3 |
磷化合物III | 3 | 3 | -- | -- |
易燃性级别,UL 94 1.59mm | V-0 | V-2 | -- | -- |
易燃性级别,UL 94 3.2mm | V-0 | V-0 | V-0 | V-0 |
熔体流动指数, 克/10分钟 | 23.7 | 16.8 | 19.7 | 19 |
冲击强度,缺口 艾佐德(1/8”, 在23℃),英尺- 磅/英寸 | 22.0 | 17.1 | 15.6 | 17.2 |
冲击强度,缺口 艾佐德(1/8”, 在-20℃),英尺- 磅/英寸 | 11.9 | 6.4 | 4.2 | 13.1 |
冲击强度,缺口 艾佐德(1/4”,在 23℃),英尺-磅/ 英寸 | 14.1 | 11.2 | 10.6 | 13.3 |
参考具体实施方式的具体内容对本发明进行了描述。这些详细描述不应被认为是对本发明范围的限制,除非这些限制被包括在所附权利要求中。
Claims (3)
1.一种热塑性模塑组合物,其包含:
(a)35-78重量%的芳族聚碳酸酯,
(b)6-55重量%的热塑性聚酯,
(c)5-15重量%的卤化丙烯酸酯,其包含符合以下结构式的重复结构单元:
其中,R1、R2、R3、R4和R5各自独立地表示氢、烷基或芳基,n是0-5,m是10-10000,R表示卤素,
(d)3-15重量%的抗冲改性剂,其是一种接枝聚合物,其由5-95重量%的至少一种乙烯基单体接枝在95-5重量%的弹性的交联的接枝基料上形成,所述接枝基料的玻璃化转变温度低于10℃,所述重量百分数是相对于抗冲改性剂的重量的,
(e)2-15重量%的含磷酸酯的化合物,选自符合以下结构式(III)和(IV)的化合物;
O=P-[-OCH2C(CH2Br)3]3 (III)
式中:
R1、R2、R3和R4各自独立地表示C1-C8-烷基,或C5-C6-环烷基,C6-C20-芳基或C7-C12-芳烷基,这些基团各自任选地被C1-C4-烷基取代,
n各自独立地表示0或1,
N是0.1-30,
X表示具有6-30个碳原子的单核或多核芳族基团,或具有2-30个碳原子的脂族基团;和
(f)0.05-0.5重量%的氟化聚烯烃,
其中所述组合物中所有组分的百分数之和为100%,所有百分数都是相对于组合物的重量的。
2.如权利要求1所述的组合物,其特征在于,所述热塑性聚酯是聚对苯二甲酸亚烷基二醇酯。
3.如权利要求1所述的组合物,其特征在于,所述热塑性聚酯是聚对苯二甲酸乙二醇酯。
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