CN111320836A - 一种无卤阻燃abs复合材料及其制备方法 - Google Patents
一种无卤阻燃abs复合材料及其制备方法 Download PDFInfo
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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Abstract
本发明涉及一种无卤阻燃ABS复合材料及其制备方法,包括ABS树脂、阻燃剂组合物、增韧剂以及其他助剂。本发明采用的阻燃剂熔融温度适当,加工过程中可熔融,对材料的物性伤害小;整体添加量低,性能可调整范围大;可用于有阻燃要求的电子电气领域,替代原溴锑阻燃ABS复合材料的应用领域,以及其他需要用到阻燃ABS的领域。
Description
技术领域
本发明属于阻燃塑料材料领域,特别涉及一种无卤阻燃ABS复合材料及其制备方法。
背景技术
丙烯腈-丁二烯-苯乙烯共聚树脂,即ABS树脂,其性能介于工程塑料和通用塑料之间,综合机械性能和加工成型性能优异,在电子电气、机械、建筑等很多领域都有广泛的应用。但是,受其聚合物结构和组成成份的限制,ABS树脂也存在很多缺陷和不足,如不耐磨、耐热低、耐候差,只能达到HB级阻燃等。
现在市面上的阻燃ABS所使用的阻燃体系主要以溴锑协效体系为主。溴锑协效体系的溴主要是来自市面常见的溴系阻燃剂,如四溴双酚A、溴代三嗪、十溴二苯乙烷、溴化聚苯乙烯等;锑主要是来自含锑化合物阻燃协效剂,如锑氧化物、锑酸盐等。含锑阻燃协效剂中,最常用的是三氧化二锑。如中国专利CN102391608中,使用10-25%的溴系阻燃剂(十溴二苯乙烷和溴化环氧,单独使用或按照一定比例组合使用),复配2-8%的阻燃协效剂(含锑化合物的复配型阻燃协效剂)制备出了垂直燃烧等级达到1.6-3.0mm UL94 V-0级别的阻燃ABS;中国专利CN103289293中,使用10-25%溴系阻燃剂三(三-溴苯基)氰尿酸酯,复配0-1%锑系阻燃协效剂和1-5%磷系阻燃协效剂,可以制备出垂直燃烧等级达到1.5-3.0mm V-2等级以上,甚至1.5-3.0mm V-0等级的阻燃ABS材料。
为了满足阻燃ABS无卤化的要求,需要选择含磷、氮或其复配体系。现在使用最普遍的含磷阻燃剂及其组合物主要有微胶囊化红磷、磷酸酯、以聚磷酸铵为主体的膨胀型阻燃体系等。这些阻燃体系,都是通过固相机理来实现阻燃。与传统溴-锑复配阻燃体系比较,固相阻燃机理的含磷阻燃剂及其复配阻燃体系,具有阻燃效率低的缺点。螺环状磷酸酯是一类可以作用于气相的含磷阻燃剂,可以用于ABS体系和PP体系的无卤阻燃,阻燃剂单独使用时,需要比较大的添加量才可以达到UL 94V-0级阻燃,这样的方案不但成本高,对材料基体的物化性能的影响也比较大,不利于材料性能的优化发挥。
发明内容
本发明所要解决的技术问题是提供一种无卤阻燃ABS复合材料及其制备方法,该复合材料解决了现有阻燃ABS中阻燃剂添加量大、对材料整体物化性能影响大的缺陷。
本发明提供了一种无卤阻燃ABS复合材料,按重量百分比,包括如下组分:
酯类阻燃剂和含氮自由基引发剂组成;所述含氮自由基引发剂为SONGFLAME 203或
所述ABS树脂中丙烯腈的重量百分比为12-35%,丁二烯的重量百分比为8-35%,苯乙烯的重量百分比为30-80%。
所述ABS树脂可以选用具有核壳结构的一步法聚合工艺生产的ABS树脂,也可以选用乳液法接枝聚合的丁二烯接枝SAN共聚物掺混丙烯腈-苯乙烯共聚物(AS树脂,SAN)的两步法工艺生产的ABS树脂;可以选用市售的ABS树脂作为基体树脂,也可以选用丁二烯接枝SAN共聚物与SAN的掺混物作为基体树脂。
所述螺环状磷酸酯类阻燃剂的结构式如下所示:
优选的,所述饱和烷烃取代基团为C1-C10烷基取代基团;所述不饱和烯烃为C2-C15的烯烃;所述含有苯环结构的芳香族取代基团为苯基、甲苯基或多烷基取代苯基。较优选的,R、R’各自独立的为H、甲基、乙基、苯基或烯丙基。最优选的,R、R’同时为甲基或苯基。
进一步的,所述螺环状磷酸酯类阻燃剂和含氮自由基引发剂的质量比为2:1-50:1,优选5:1-30:1,更优选5:1-20:1。
进一步的,所述丁二烯接枝SAN共聚物由乳液法工艺进行接枝聚合,其中,丙烯腈的重量百分比为2-20%,丁二烯的重量百分比为50-80%,苯乙烯的重量百分比为18-30%;所述硅橡胶的重均分子量分布范围为5-100万,硅含量的范围为10-40重量%。
所述其他助剂包括抗氧剂、润滑剂、耐候剂、着色剂中的一种或几种。
所述抗氧剂包括受阻酚类抗氧剂和亚磷酸酯类抗氧剂。
所述润滑剂包括酰胺类润滑剂、硬脂酸盐类润滑剂、酯类润滑剂或硅酮类润滑剂。
所述耐候剂包括二苯甲酮类紫外线吸收剂、苯并***类紫外线吸收剂或受阻胺类光稳定剂。
所述着色剂包括颜料型、染料型或其他具有特殊美学效果的着色剂。
本发明还提供了一种无卤阻燃ABS复合材料的制备方法,包括:
按配比,将原料投入混合机中混合,将混合后的物料投入双螺杆挤出机的进料斗中,通过同向双螺杆挤出机进行熔融共混后,水冷拉条切粒,即得。
所述同向双螺杆挤出机的参数为:挤出机各段的温度设定范围为180-240℃,螺杆转速设定范围为200-800转/分钟。
有益效果
(1)本发明含氮自由基引发剂是通过结构筛选,将自由基引发结构(N-O-R、N=N、N-S、N-O-Si等)链接上可以提高热稳定性的基团制备而成的自由基引发剂。该类自由基引发剂可以在ABS树脂熔融共混改性过程中(200-280℃条件下)稳定存在,在燃烧发生时(350-600℃条件下)快速分解,产生自由基,协效气相作用的螺环状磷酸酯类阻燃剂一起淬灭自由基,共同实现ABS树脂的阻燃;
(2)本发明采用的阻燃剂熔融温度适当,加工过程中可熔融,对材料的物性伤害小;整体添加量低,性能可调整范围大;可用于有阻燃要求的电子电气领域,替代原溴锑阻燃ABS复合材料的应用领域,以及其他需要用到阻燃ABS的领域。
附图说明
图1为实施例中B-12的FTIR谱图。
图2为实施例中B-23的FTIR谱图。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
所使用的各组分原材料如下:
ABS树脂:
①两步法掺混ABS树脂,即乳液法ABS树脂,LG HI-121H,记为A-11;
②一步法ABS,即本体法ABS,DOW,记为A-12;
③SAN树脂,310TR,韩国锦湖;ABS接枝胶粉,MAG 50,苯领;两者按质量比7:3混合,记为A-21;两者按质量比3:7混合,记为A-22。
阻燃剂组合物:
①螺环状磷酸酯类阻燃剂的结构式如下所示:
B-11:R、R’同时为甲基;PCO 900,托尔化学;
B-12:R、R’同时为苯基。
B-12的FTIR谱图如图1所示,KBr压片;
合成方法:将31.6克(0.1mol)季戊四醇和31.6克(0.4mol)吡啶溶于300ml二氯甲烷(溶液1),将溶液1置于配有冷凝器、机械搅拌器和滴液漏斗的500ml圆底烧瓶中,将装有溶液的烧瓶置于冰水混合浴中并搅拌降温至0℃;将39克(0.2mol)苯基膦酰二氯溶于50ml二氯甲烷(溶液2),将溶液2置于滴液漏斗中,在保持冰水混合浴和搅拌的情况下,缓慢滴加入已降温至0℃的溶液1中;滴加完成后,在冰水混合浴中继续搅拌15min后,缓慢升温至50℃,并在该温度条件下回流反应6h。反应完成后,将溶剂蒸馏回收,反应产物经三次水洗过滤,并于70度真空烘干72h后,获得28.5克白色粉体,为阻燃剂B-12,产率75%。
②含氮自由基引发剂:
B-21:NOR 116,巴斯夫;
B-22:SONGFLAME 203,松原国际;
B-23的FTIR谱图如图2所示,KBr压片;
合成方法:在配有冷凝器、机械搅拌器和滴液漏斗的500ml圆底烧瓶中,加入300ml干燥后的二氯甲烷、16.4克(0.1mol)N-羟基邻苯二甲酰亚胺、2克三乙胺和20克碳酸钾,将烧瓶置于冰水混合浴中并搅拌降温至0℃;将24克(0.1mol)二苯基甲基氯硅烷置于滴液漏斗中,在保持冰水混合浴和搅拌的情况下,缓慢滴加入烧瓶溶液中;滴加完成后,在冰水混合浴中继续搅拌15min后,缓慢升温至30℃,并在该温度条件下反应12h。反应完成后,将溶剂蒸馏回收,反应产物经三次水洗过滤,并于70度真空烘干72h后,获得28.5克白色粉体,为阻燃剂B-23,产率80%。
③其他无卤阻燃剂
B-31:OP 1230,科莱恩;
B-32:PX-220,浙江万盛;
增韧剂:丁二烯接枝SAN共聚物、MBS、丙烯酸酯橡胶及硅橡胶等;
其他助剂:常用的加工助剂,如抗氧剂、润滑剂等,功能助剂,如抗滴落剂、耐候剂等,以及填料、颜料、染料等。
各性能测试方法:
阻燃等级测试:垂直燃烧,测试标准UL94,125mm*13mm*1.5mm的样条;
缺口冲击强度测试:注塑成符合ISO 180悬臂梁缺口冲击强度测试要求的棒状样条,在25℃下用于缺口冲击强度测试,结果记录样条被冲断时的强度数据。
制备方法,包括:按配比,将原料投入混合机中以1000转/分钟的转速混合5min后取出,将混合后的物料投入双螺杆挤出机的进料斗中,通过同向双螺杆挤出机(挤出机各段的温度设定范围为200℃,螺杆转速设定范围为600转/分钟)进行熔融共混后,水冷拉条切粒,即得。
从上表可以看出,本发明ABS复合材料阻燃性能与缺口冲击强度均较佳。从对比例1-2和实施例1-3可以看出,采用本发明中的含氮自由基引发剂和螺环状磷酸酯类阻燃剂作为协效阻燃剂组合物,在本发明的添加量范围内,可以提升复合材料的阻燃性能和缺口冲击强度,该体系的阻燃效率远比传统有机磷酸酯和有机次膦酸盐高,对缺口冲击强度的负面影响也小很多。从对比例3-6和实施例1-3可以看出,采用本发明中的自由基引发剂和螺环状磷酸酯类阻燃剂复配,对比NOR 116,可以有效提升复合材料的阻燃性能和缺口冲击强度。
Claims (9)
2.根据权利要求1所述的复合材料,其特征在于:所述ABS树脂中丙烯腈的重量百分比为12-35%,丁二烯的重量百分比为8-35%,苯乙烯的重量百分比为30-80%。
4.根据权利要求3所述的复合材料,其特征在于:所述饱和烷烃取代基团为C1-C10烷基取代基团;所述不饱和烯烃为C2-C15的烯烃;所述含有苯环结构的芳香族取代基团为苯基、甲苯基或多烷基取代苯基。
5.根据权利要求1所述的复合材料,其特征在于:所述增韧剂为丁二烯接枝SAN共聚物、硅橡胶中的一种或两种。
6.根据权利要求1所述的复合材料,其特征在于:所述其他助剂包括抗氧剂、润滑剂、耐候剂、着色剂中的一种或几种。
7.根据权利要求6所述的复合材料,其特征在于:所述抗氧剂包括受阻酚类抗氧剂和亚磷酸酯类抗氧剂;所述润滑剂包括酰胺类润滑剂、硬脂酸盐类润滑剂、酯类润滑剂或硅酮类润滑剂;所述耐候剂包括二苯甲酮类紫外线吸收剂、苯并***类紫外线吸收剂或受阻胺类光稳定剂;所述着色剂包括颜料型、染料型或其他具有特殊美学效果的着色剂。
8.一种如权利要求1所述的无卤阻燃ABS复合材料的制备方法,包括:
按配比,将原料投入混合机中混合,将混合后的物料投入双螺杆挤出机的进料斗中,通过同向双螺杆挤出机进行熔融共混后,水冷拉条切粒,即得。
9.一种如权利要求1所述的无卤阻燃ABS复合材料的应用。
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