CN1702114A - 用于挤出加工的含有接枝聚合物的组合物 - Google Patents
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Abstract
本发明涉及包含接枝聚合物的模塑组合物,其具有良好的挤出加工性,不会产生特定的表面缺陷。
Description
技术领域
本发明涉及包含接枝聚合物的模塑组合物,其具有良好的挤出加工性,不会产生特定的表面缺陷。
背景技术
基于接枝聚合物,尤其是基于ABS类接枝聚合物的塑料作为工程塑料用于制备各种类型(参见,例如,Ullmann’s Encyclopedia of Industrial Chemistry,5th版,Vol.A 21,652-653页,VCH,Weinheim,1992)的模塑制品已使用多年,一个具体应用是通过注模或挤出进行加工。
根据加工方法的不同,所使用的模塑组合物必须满足不同的要求:举例来说,包含接枝聚合物且采用注模加工的模塑组合物不得引起任何模塑沉积(关于这一点,参考如专利EP869147中记载的用于解决这一问题的方案),而包含接枝聚合物且用于挤出加工的模塑组合物不得沉积在辊上。
挤出加工的一个特殊问题是在挤出片材、型材或吹塑或热成型部件表面形成了缺陷,这些缺陷以直径约为0.5~20mm的圆形或细长的形式存在。
发明内容
令人惊讶的是,现在已经发现使用特殊的添加剂混合物能够使包含接枝聚合物且具有良好的挤出加工性的模塑组合物不产生这些表面缺陷。
本发明提供了适用于挤出加工的模塑组合物,该组合物包括:
A)5~95wt%,优选10~90wt%,更优选20~75wt%的至少一种热塑性均聚、共聚或三元共聚的苯乙烯、α-甲基苯乙烯、环状取代苯乙烯、甲基丙烯酸甲酯、丙烯腈、甲基丙烯腈、马来酸酐、N-取代马来酰亚胺或它们的混合物,
B)95~5wt%(基于A+B),优选90~10wt%,更优选80~25wt%B.1)和B.2)的至少一种接枝聚合物,其中,B.1)接枝在B.2)上:
B.1)5~90重量份,优选20~80重量份,更优选25~60重量份的苯乙烯、α-甲基苯乙烯、环状取代苯乙烯、甲基丙烯酸甲酯、丙烯腈、甲基丙烯腈、马来酸酐、N-取代马来酰亚胺或它们的混合物,
B.2)95~10重量份,优选80~20重量份,更优选75~40重量份的至少一种玻璃化转变温度小于或等于10℃的橡胶,和
C)0.05~5重量份,优选0.1~3重量份,更优选0.2~2重量份(在所有情况下,每100重量份A+B)的至少一种部分氧化的聚烯烃,以及
D)0.05~2重量份,优选0.08~1.5重量份,更优选0.1~1重量份(在所有情况下,每100重量份A+B)的至少一种选自氧化镁和氧化钙的碱土金属氧化物。
根据发明,适合的热塑性聚合物A)是苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、卤代苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯腈、马来酸酐、N-取代马来酰亚胺或它们的混合物的聚合物。
聚合物A)是类树脂的、热塑性且不含橡胶的。特别优选的聚合物A)为由苯乙烯、甲基丙烯酸甲酯、苯乙烯/丙烯腈混合物、苯乙烯/丙烯腈/甲基丙烯酸甲酯混合物、苯乙烯/甲基丙烯酸甲酯混合物、丙烯腈/甲基丙烯酸甲酯混合物、α-甲基苯乙烯/丙烯腈混合物、苯乙烯/α-甲基苯乙烯/丙烯腈混合物、α-甲基苯乙烯/甲基丙烯酸甲酯/丙烯腈混合物、苯乙烯/α-甲基苯乙烯/甲基丙烯酸甲酯混合物、苯乙烯/α-甲基苯乙烯/甲基丙烯酸甲酯/丙烯腈混合物、苯乙烯/马来酸酐混合物、甲基丙烯酸甲酯/马来酸酐混合物、苯乙烯/甲基丙烯酸甲酯/马来酸酐混合物构成的那些聚合物。
聚合物A)是已知的,且能够通过自由基聚合,尤其通过乳液聚合、悬浮聚合、溶液聚合或本体聚合制备。其平均分子量MW优选为20000到200000,其特性粘度[η]优选为20~110ml/g(在二甲基甲酰胺中,25℃下测定)。
适于制备接枝聚合物B)的接枝单体B.1)与描述聚合物A)所用的那些相同。
尤其适于制备接枝聚合物B)的橡胶B.2)为聚丁二烯、丁二烯-苯乙烯共聚物、丁二烯-丙烯腈共聚物、聚异戊二烯或基于丙烯酸C1-C8烷基酯的丙烯酸烷基酯橡胶,尤其是丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙基己基酯。
如果适当,丙烯酸酯橡胶可以含有高达30wt%(基于橡胶的重量)的共聚单体,如醋酸乙烯酯、丙烯腈、苯乙烯、甲基丙烯酸甲酯和/或乙烯基醚。丙烯酸酯橡胶也可含有相对少量、优选最高5wt%(基于橡胶重量)具有交联作用的烯属不饱和共聚单体。交联剂的例子是:亚烷基二醇二丙烯酸酯和亚烷基二醇甲基丙烯酸酯、聚酯二丙烯酸酯和聚酯甲基丙烯酸酯、二乙烯基苯、三乙烯基苯、氰脲酸三烯丙基酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丁二烯或异戊二烯。接枝基体也可以是具有核/壳结构的丙烯酸酯橡胶,其核由交联二烯烃橡胶组成,所述交联二烯烃橡胶由一种或多种共轭二烯例如聚丁二烯构成,或由一种共轭二二烯与一种烯属不饱和单体例如苯乙烯和/或丙烯腈的共聚物组成。
其它适合的橡胶实例包括已知的EPDM橡胶(由乙烯、丙烯和一种非共轭二烯例如二环戊二烯组成的聚合物)、EPM橡胶(乙丙橡胶)和硅橡胶,同样的,如果适当,它们也可以是核/壳结构。
制备接枝聚合物B)的橡胶B.2)优选是二烯烃橡胶和丙烯酸烷基酯橡胶,还有EPDM橡胶。
橡胶B.2)至少在某种程度上以中值粒径(d50)为0.05~20μm,优选为0.1~2μm,更优选为0.1~0.8μm的交联粒子的形式存在。
中值粒径d50可按照W.Scholtan等,Kolloid-Z.u.Z.Polymere
250(1972),782-796用超高速离心器测定,或由电子显微镜测定。
聚合物B)可以通过单体B.1)在适于作为接枝基体的橡胶B.2)的存在下通过自由基接枝聚合制备。
接枝聚合物B)的优选制备方法有乳液聚合、溶液聚合、本体聚合或悬浮聚合以及这几种已知方法的结合。接枝聚合物B)尤其优选ABS聚合物。
特别优选的接枝聚合物B)是由重量比优选为10∶1~1∶1,尤其优选为5∶1~2∶1的苯乙烯和丙烯腈组成的混合物在中值粒径(d50)为100~450nm的橡胶的存在下通过自由基聚合制得的产品,所述橡胶主要由二烯烃单体构成,优选聚丁二烯,其可包含高达30wt%的苯乙烯和/或丙烯腈作为共聚单体,特别优选的是在中值粒径(d50)分别为150~300nm和350~450nm的两种橡胶B.2.a)和B.2.b)的存在下制得的产品,所述橡胶主要由二烯烃单体构成,在所有情况下优选聚丁二烯,其可包含高达30wt%的苯乙烯和/或丙烯腈作为共聚单体,其中B.2.a)∶B.2.b)的重量比为10∶90~90∶10,优选为30∶70~60∶40。
接枝聚合物B)中的橡胶含量优选为40~95wt%,尤其优选为50~90wt%,特别优选为55~85wt%。
根据本发明,合适的部分氧化的聚烯烃C)是,例如,部分氧化的聚乙烯和部分氧化的聚丙烯,或部分氧化的聚乙烯蜡和部分氧化的聚丙烯蜡。这种类型的化合物是已知的,如A.Thalhofer在Kunststoff-Handbuch[塑料手册],卷IV(聚烯烃),pp.161-165(Carl Hanser Verlag,Munich 1969)中所述。可以商购的这种类型的化合物的名称通常是极性聚烯烃蜡或极性聚乙烯蜡或极性聚丙烯蜡。
使用的组分D)包括氧化镁、氧化钙或其混合物。
除了本发明的添加剂混合物C)+D)之外,本发明的ABS组合物原则上可以包括其它能够改进加工性的添加剂成分。
这种类型的化合物的例子是长链羧酸酰胺化合物,如乙二胺双硬脂酰胺、芥酰胺、油酰胺、硬脂酰胺、琥珀酰胺、褐煤酰胺,长链羧酸酯化合物,如三硬脂酸甘油酯、三油酸甘油酯、三山萮酸甘油酯、三褐煤酸甘油酯、硬脂酸十八酯、油酸十八酯、山萮酸十八酯、褐煤酸十八酯、硬脂酸油酯、油酸油酯、山萮酸油酯、褐煤酸油酯、硬脂酸山萮酯、油酸山萮酯、山萮酸山萮酯、褐煤酸山萮酯、硬脂酸辛酯、硬脂酸异辛酯、硬脂酸十二烷酯、油酸十二烷酯、单硬脂酸甘油酯、双硬脂酸甘油酯、单油酸甘油酯、双油酸甘油酯、四硬脂酸季戊四醇酯、四油酸季戊四醇酯、四山萮酸季戊四醇酯、四褐煤酸季戊四醇酯、三硬脂酸季戊四醇酯、三油酸季戊四醇酯、三山萮酸季戊四醇酯、三褐煤酸季戊四醇酯、单硬脂酸季戊四醇酯、单油酸季戊四醇酯、单山萮酸季戊四醇酯、单褐煤酸季戊四醇酯,长链羧酸盐化合物,如硬脂酸镁、硬脂酸钙、硬脂酸锌、褐煤酸镁、褐煤酸钙、褐煤酸锌、山萮酸镁、山萮酸钙、山萮酸锌、油酸镁、油酸钙、油酸锌。
本发明的模塑组合物优选不含上述提及的长链羧酸衍生物。
特别优选地,本发明的模塑组合物由以下组分构成:
A)85~35wt%的由5~40重量份的丙烯腈和95~60重量份的苯乙烯、α-甲基苯乙烯、丙烯腈、N-苯基马来酰亚胺或它们的混合物组成的热塑性共聚物,
B)15~65wt%的由25~60重量份的苯乙烯、α-甲基苯乙烯、丙烯腈、N-苯基马来酰亚胺或它们的混合物接枝在75~40重量份的聚丁二烯上形成的接枝聚合物,所述聚丁二烯可含有高达30wt%的苯乙烯和/或丙烯腈作为共聚单体,
以及0.2~1.5重量份(每100重量份的A+B)由C)氧化的聚乙烯蜡和D)氧化镁构成的混合物。
本发明的模塑组合物包括A)、B)、C)和D),以及如果适当,还包括传统添加剂,如加工助剂、稳定剂、颜料、抗静电剂、填料,其通过在室温或更高温度下以已知方式同时或连续混合各组分,然后在150~300℃的温度下以传统设备,例如密闭式混合机、挤出机或双螺杆***热熔捏合或熔融挤出上述混合物而制得。
本发明的模塑组合物可用于制备任何类型的模塑制品,其可以使用传统制备方法,挤出是制备模塑制品的优选加工方法。
原则上也可通过注模法加工本发明的模塑组合物。
本发明还提供了一种制备模塑组合物的方法、其用于制备模塑制品的用途以及所得到的模塑制品。本发明进一步提供了由C)和D)本身组成的添加剂混合物。
具体实施方式
本发明由以下实施例说明。
实施例
热塑性树脂A
无规苯乙烯-丙烯腈共聚物(重量比为72∶28),重均分子量MW约为115000,由GPC(凝胶渗透色谱)法测定。
接枝聚合物B-I
通过乳液聚合,由42wt%的苯乙烯/丙烯腈混合物(重量比为73∶27)接枝到58wt%的由中值粒径(d50)分别为a)290nm和b)420nm的两种粒状聚丁二烯组成的1∶1(重量比)混合物上,之后通过乳胶与硫酸镁/乙酸混合物发生凝聚,再用水洗涤然后真空干燥制得的接枝产物。
接枝聚合物B-II
通过50wt%的苯乙烯/丙烯腈混合物(重量为73∶27)和50wt%的中值粒径(d50)为130nm的粒状聚丁二烯的乳液聚合制得的接枝产物,与B-I处理相同。
添加剂C:
氧化聚乙烯:Licowax PED 191(Clariant GmbH,Sulzbach,Germany)
添加剂D:
氧化镁
各组分按表1所述重量比在挤出机中混合,同时加入0.17重量份的酚类抗氧剂(Irganox1076,Ciba),0.30重量份含有硫磺的增效剂(IrganoxPS 802,Ciba)和0.15重量份的硅油。
然后所得材料在Breyer BR 60型挤出机中挤出,所述挤出机具有六区排气螺杆,螺杆直径为60mm,长33D,熔融泵,调节棒/可调唇式模头,宽350mm,模头3mm,三辊压延机和垂直排列辊,以挤出片材。挤出机温度为240℃,模头温度为240℃,引出速度为1.5m/min,在所有情况下,总挤出时间为8小时。
观察挤出物表面出现破裂开始形成约0.5~20mm圆形或细长缺陷的情况。如表1所示,仅当使用本发明的ABS组合物时,可实现挤出部件表面不破裂的长时间挤出加工。
表1:配方和性能
实施例 | A(重量份) | B-I(重量份) | B-II(重量份) | C(重量份) | D(重量份) | X小时后出现表面破裂 |
1 | 55 | 27 | 18 | 0.5 | 0.3 | 无表面破裂 |
2(对照) | 55 | 27 | 18 | - | - | 0.5h |
3(对照) | 55 | 27 | 18 | 0.5 | - | 2h |
4(对照) | 55 | 27 | 18 | - | 0.3 | 1h |
5 | 65 | 21 | 14 | 0.5 | 0.3 | 无表面破裂 |
6(对照) | 65 | 21 | 14 | - | - | 1h |
7(对照) | 65 | 21 | 14 | 05 | - | 2h |
8(对照) | 65 | 21 | 14 | - | 03 | 1.5h |
Claims (10)
1、模塑组合物,该组合物包括:
A)5~95wt%(基于A+B)的至少一种热塑性均聚、共聚或三元共聚的苯乙烯、α-甲基苯乙烯、环状取代苯乙烯、甲基丙烯酸甲酯、丙烯腈、甲基丙烯腈、马来酸酐、N-取代马来酰亚胺或它们的混合物,
B)95~5wt%(基于A+B)B.1)和B.2)的至少一种接枝聚合物,其中,B.1)接枝在B.2)上:
B.1)5~90重量份的苯乙烯、α-甲基苯乙烯、环状取代苯乙烯、甲基丙烯酸甲酯、丙烯腈、甲基丙烯腈、马来酸酐、N-取代马来酰亚胺或它们的混合物,
B.2)95~10重量份的至少一种玻璃化转变温度小于或等于10℃的橡胶,其形式为至少在某种程度上交联的粒子,具有0.05~20μm的中值粒径(d50),和
C)0.05~5重量份(每100重量份的A+B)的至少一种部分氧化的聚烯烃,以及
D)0.05~2重量份(每100重量份的A+B)的至少一种选自氧化镁和氧化钙的碱土金属氧化物。
2、模塑组合物,该组合物包括:
A)10~90wt%(基于A+B)的至少一种热塑性均聚、共聚或三元共聚的苯乙烯、α-甲基苯乙烯、环状取代苯乙烯、甲基丙烯酸甲酯、丙烯腈、甲基丙烯腈、马来酸酐、N-取代马来酰亚胺或它们的混合物,
B)90~10wt%(基于A+B)B.1)和B.2)的至少一种接枝聚合物,其中B.1)接枝在B.2)上:
B.1)20~80重量份的苯乙烯、α-甲基苯乙烯、环状取代苯乙烯、甲基丙烯酸甲酯、丙烯腈、甲基丙烯腈、马来酸酐、N-取代马来酰亚胺或它们的混合物,
B.2)80~20重量份的至少一种玻璃化转变温度小于或等于10℃的橡胶,
C)0.1~3重量份(在所有情况下,每100重量份的A+B)的至少一种部分氧化的聚烯烃,和
D)0.08~1.5重量份(在所有情况下,每100重量份的A+B)的至少一种选自氧化镁和氧化钙的碱土金属氧化物。
3、权利要求1或2的模塑组合物,其中A)为由苯乙烯和丙烯腈组成的共聚物。
4、权利要求1~3任一项的模塑组合物,其中B1)是一种由苯乙烯和丙烯腈组成的混合物。
5、权利要求1~4任一项的模塑组合物,其中B2)是一种中值粒径(d50)为100~450nm的橡胶,其由聚丁二烯组成,可含有高达30wt%的苯乙烯和/或丙烯腈作为共聚单体。
6、权利要求1~4任一项的模塑组合物,其中B2)包括两种橡胶B.2.a)和B.2.b),B.2.a)与B.2.b)的中值粒径(d50)分别为150~300nm和350~450nm,B.2.a)∶B.2.b)的重量比为10∶90~90∶10,它们均由聚丁二烯组成,可含有高达30wt%的苯乙烯和/或丙烯腈作为共聚单体。
7、权利要求1~6任一项的模塑组合物,其中D)为氧化镁。
8、权利要求1~7任一项的模塑组合物用于通过挤出制备片状产品的用途。
9、通过挤出权利要求1~7任一项的模塑组合物制得的模塑制品。
10、含有0.05~5重量份的至少一种部分氧化的聚烯烃C)和0.05~2重量份的至少一种选自氧化镁和氧化钙的碱土金属氧化物D)的制剂。
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DE102004024272A DE102004024272A1 (de) | 2004-05-15 | 2004-05-15 | Pfropfpolymerisathaltige Massen für die Extrusionsverarbeitung |
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CN100441630C (zh) * | 2006-04-30 | 2008-12-10 | 华侨大学 | 云母增强热塑化木材/马来酸酐接枝聚丙烯复合材料的制备方法 |
CN104193910A (zh) * | 2014-08-26 | 2014-12-10 | 河北工业大学 | 一种采用反应挤出制备接枝共聚物方法 |
CN108368209A (zh) * | 2015-12-31 | 2018-08-03 | 乐天尖端材料株式会社 | 橡胶改性乙烯基类接枝共聚物及包含其的热塑性树脂组合物 |
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JP2010519359A (ja) | 2007-02-23 | 2010-06-03 | ビーエーエスエフ ソシエタス・ヨーロピア | n−アルカノールの混合物及びその使用方法 |
ES2758794T3 (es) * | 2009-12-23 | 2020-05-06 | Fpt Motorenforschung Ag | Método y aparato para medir y controlar la tasa de EGR en un motor de combustión |
TWI500683B (zh) * | 2012-12-26 | 2015-09-21 | Chi Mei Corp | 熱可塑性樹脂組成物 |
CN112940204B (zh) * | 2021-02-04 | 2023-04-07 | 万华化学(四川)有限公司 | 一种用于附聚的聚丁二烯胶乳的制备方法及制备的abs树脂 |
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CN100441630C (zh) * | 2006-04-30 | 2008-12-10 | 华侨大学 | 云母增强热塑化木材/马来酸酐接枝聚丙烯复合材料的制备方法 |
CN104193910A (zh) * | 2014-08-26 | 2014-12-10 | 河北工业大学 | 一种采用反应挤出制备接枝共聚物方法 |
CN108368209A (zh) * | 2015-12-31 | 2018-08-03 | 乐天尖端材料株式会社 | 橡胶改性乙烯基类接枝共聚物及包含其的热塑性树脂组合物 |
US10767038B2 (en) | 2015-12-31 | 2020-09-08 | Lotte Advanced Materials Co., Ltd. | Rubber modified vinyl-based graft copolymer, and thermoplastic resin composition containing same |
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US20060116472A1 (en) | 2006-06-01 |
ATE353933T1 (de) | 2007-03-15 |
KR101225819B1 (ko) | 2013-01-23 |
EP1595916A1 (de) | 2005-11-16 |
DE102004024272A1 (de) | 2005-12-01 |
EP1595916B1 (de) | 2007-02-14 |
TWI391438B (zh) | 2013-04-01 |
CN100487045C (zh) | 2009-05-13 |
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