CN101094882B - 具有高折射率的硅酮抗冲改性剂及其制备方法 - Google Patents

具有高折射率的硅酮抗冲改性剂及其制备方法 Download PDF

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CN101094882B
CN101094882B CN2005800455928A CN200580045592A CN101094882B CN 101094882 B CN101094882 B CN 101094882B CN 2005800455928 A CN2005800455928 A CN 2005800455928A CN 200580045592 A CN200580045592 A CN 200580045592A CN 101094882 B CN101094882 B CN 101094882B
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siloxane
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vinylbenzene
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李汉洙
闵星植
李秉春
李炳道
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Lotte Advanced Materials Co Ltd
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Abstract

根据本发明的具有高折射率的硅酮抗冲改性剂包括：(A)橡胶核，其由(a)具有50～400nm粒径的有机硅氧烷交联(共)聚合物和(a)丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物构成；以及(B)塑料壳，其由乙烯(共)聚合物构成。本发明的硅酮抗冲改性剂的折射率为1.49～1.59。

Description

具有高折射率的硅酮抗冲改性剂及其制备方法
技术领域
本发明涉及一种具有高折射率的硅酮抗冲改性剂及其制备方法。更具体地，本发明涉及一种硅酮抗冲改性剂，其包括由有机硅氧烷-丙烯酸烷基酯-苯乙烯芳香族化合物交联共聚物构成的橡胶核和由乙烯基(共)聚合物构成的塑料壳，并且提供一种具有优异着色性、抗冲击性、热稳定性和耐候性的热塑性树脂。
背景技术
一般地，聚碳酸酯树脂由于其相比于其它树脂的优异的抗冲击强度、自熄性、尺寸稳定性和耐热性而已被用作工程塑料。因此，该树脂已被广泛应用于办公自动化(OA)设备、电器产品或电子产品等。
然而，聚碳酸酯树脂由于其高熔点而具有较差的流动性，使得该树脂需要较高加工温度。这样的较高加工温度引起所得模制品具有抗冲击性劣化的问题。因此，将聚碳酸酯树脂与各种抗冲改性剂加以混合以提高抗冲击性。
尽管这些抗冲改性剂提高聚碳酸酯树脂的抗冲击强度，但是使用这样的抗冲改性剂进一步导致问题产生。例如，通常用于聚碳酸酯树脂的丁二烯橡胶基抗冲改性剂在高于300℃的模制工艺过程中趋于降解或烧焦，这导致热稳定性和耐候性劣化，因此应用受限。在丙烯酸酯橡胶基抗冲改性剂的情况下，可以提供良好的热稳定性和耐候性，但是着色性和低温下的抗冲击性较差。
美国专利第4,994,522号和第5,132,359号披露了用于氯乙烯树脂的硅酮抗冲改性剂。然而，当将这些抗冲改性剂用于聚碳酸树脂时，着色性仍然会劣化。
因此，本发明的发明人开发了一种抗冲改性剂，其提供一种具有优异着色性、抗冲击性、热稳定性和耐候性的热塑性树脂，其中该热塑性树脂通过在具有特定粒径和折射率的有机硅氧烷交联(共)聚合物存在下交联聚合丙烯酸烷基酯-苯乙烯芳香化合物来制备橡胶核以及将乙烯基单体接枝(共)聚合到该橡胶核上由此形成塑料壳来获得。本发明的抗冲改性剂的折射率比传统硅酮抗冲改性剂具有的1.45～1.47的折射率值更高。
发明内容
技术问题
本发明的一个目的是提供一种可改善聚碳酸酯树脂的着色性同时没有降低其它本质特性的抗冲改性剂。
本发明的另一目的是提供一种可为聚碳酸酯提供良好热稳定性、低温抗冲击性和耐候性的抗冲改性剂。
根据随后的披露内容和所附权利要求，本发明的其它目的和优点将显而易见。
技术方案
本发明涉及一种硅酮抗冲改性剂，其包括：(A)橡胶核，由(a1)具有50～400nm粒径的有机硅氧烷交联(共)聚合物和(a2)丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物构成；以及(B)塑料壳，由乙烯基(共)聚合物构成，并且该硅酮抗冲击改性剂的折射率为1.49～1.59。
而且，本发明涉及硅酮抗冲改性剂，其包括：(A)橡胶核，由(a1)具有50～400nm粒径的有机硅氧烷交联(共)聚合物和(a2)丙烯酸烷基酯交联聚合物构成；以及(B)塑料壳，由乙烯基(共)聚合物构成并且具有的折射率为1.49～1.59。
具体实施方式
(A)橡胶核
在本发明的一个具体实施方式中，橡胶核包括(a1)有机硅氧烷交联(共)聚合物和(a2)丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物。
有机硅氧烷交联(共)聚合物具有1.41～1.50的折射率和50～400nm的粒径。如果有机硅氧烷交联(共)聚合物的折射率小于1.41，则该抗冲改性剂的折射率不能达到1.49的水平，并且如果有机硅氧烷交联(共)聚合物的折射率大于1.50，则该有机硅氧烷聚合物的玻璃化转变温度升高，使得对于有机溶剂的亲合性增加，这会导致其它性能劣化。因此，考虑到物理性能平衡，有机硅氧烷交联(共)聚合物的折射率范围优选为1.41～1.50，更优选为1.41～1.45。
而且，如果有机硅氧烷交联(共)聚合物的粒径小于50nm或大于400nm，则抗冲改性作用降低。因此，优选有机硅氧烷交联(共)聚合物的粒径范围为50～400nm。
在本发明的另一个具体实施方式中，橡胶核包括(a1)具有50～400nm的粒径的有机硅氧烷交联(共)聚合物和(a2)丙烯酸烷基酯交联聚合物。当橡胶核包括有机硅氧烷交联(共)聚合物和丙烯酸烷基酯交联聚合物而没有任何苯乙烯芳香化合物时，有机硅氧烷交联(共)聚合物的折射率为1.44～1.55。
如果有机硅氧烷交联(共)聚合物的折射率低于1.44，则抗冲改性剂的折射率不能达到1.49的水平。
本发明的有机硅氧烷交联(共)聚合物(a1)是具有交联结构的有机硅氧烷(共)聚合物。该有机硅氧烷交联(共)聚合物的实例包括聚二甲基硅氧烷、聚甲基苯基硅氧烷、聚二苯基硅氧烷等。通过共聚合两种或多种有机硅氧烷单体/低聚物，有可能将有机硅氧烷交联共聚物的折射率调节至1.41～1.50。优选地，本发明的有机硅氧烷(共)聚合物是交联的。如果有机硅氧烷(共)聚合物不是交联的，则其会不希望地丧失橡胶性能，这会导致抗冲击性降低，并且着色性也会由于有机硅氧烷(共)聚合物扩散到产品的表面而劣化。
交联的程度可通过有机硅氧烷交联(共)聚合物在有机溶剂中的溶解性来确定。交联度越高，在有机溶剂中的溶解性越低。作为有机溶剂，可以使用丙酮或甲苯。因此，其优选在甲苯或丙酮中具有不溶部分。有机硅氧烷交联(共)聚合物在甲苯中的不溶部分的含量优选高于30％。
丙烯酸烷基酯的实例包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯等。最优选的实例是丙烯酸正丁酯，由于其较低的玻璃化转变温度。
苯乙烯芳香化合物的实例包括苯乙烯、α-甲基苯乙烯、二乙烯基苯、乙烯基甲苯等。在它们之中，优选使用苯乙烯。
丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物通过在交联剂存在下共聚合丙烯酸烷基酯和苯乙烯芳香化合物而制备。
(a1)有机硅氧烷交联(共)聚合物与(a2)丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物或丙烯酸烷基酯交联共聚物的重量比优选为1∶6～6∶1。
如果有机硅氧烷交联(共)聚合物(a1)与丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物(a2)的重量比低于1∶6，则低温时的抗冲改性作用降低，并且如果该重量比高于6∶1，则有机硅氧烷交联(共)聚合物的含量相对增高，这会使树脂和抗冲改性剂之间的亲合性降低，以便降低抗冲改性作用并且需要更高的生产成本。
丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物(a2)中的丙烯酸烷基酯与苯乙烯芳香化合物的重量比优选为1∶1～20∶1。
如果丙烯酸烷基酯与苯乙烯芳香化合物的重量比低于1∶1，则丙烯酸烷基酯的玻璃化转变温度会极度增高，使得抗冲改性作用被降低，并且如果该重量比高于20∶1，则折射率和着色性被劣化。
(B)塑料壳
本发明的塑料壳是乙烯基(共)聚合物并通过将乙烯基单体接枝(共)聚合到橡胶核上而形成在该橡胶核的表面上。
乙烯基单体的实例包括甲基丙烯酸烷基酯、丙烯酸酯和烯键式不饱和芳香化合物等。例如，优选甲基丙烯酸甲酯、苯乙烯、丙烯腈或它们的两种或多种的混合物。
在本发明中，橡胶核(A)与塑料壳(B)的重量比为5∶5～9∶1。
如果橡胶核(A)与塑料壳(B)的重量比低于5∶5，则橡胶含量相对减少，使得对冲击强度的提高作用被降低。如果该比率高于9∶1，则树脂和抗冲改性剂之间的相容性降低，使得抗冲改性作用也被降低并且产生更高的生产成本。
本发明的抗冲改性剂具有在1.49至1.59，优选在1.50至1.57范围内的折射率。如果折射率低于1.49，则该抗冲改性剂和聚碳酸酯之间的折射率差异将增大，使着色性变差。
现在将详细描述制备本发明的硅酮抗冲改性剂的方法。
在本发明的一个具体实施方式中，制备本发明的硅酮抗冲改性剂的方法包括：通过将丙烯酸烷基酯和苯乙烯芳香化合物添加到具有50～400nm粒径和1.41～1.50折射率的有机硅氧烷交联(共)聚合物的交联聚合而制备橡胶核；以及将乙烯基单体接枝(共)聚合到该橡胶核上从而形成塑料壳。
在本发明的另一个具体实施方式中，制备本发明的硅酮抗冲改性剂的方法包括：通过将丙烯酸烷基酯添加到具有50～400nm粒径和1.44～1.55折射率的有机硅氧烷交联(共)聚合物的交联聚合而制备橡胶核；以及将乙烯基单体接枝(共)聚合到该橡胶核上从而形成塑料壳。
在本发明中，使用的有机硅氧烷交联(共)聚合物是分散状态的(称为“硅酮胶乳”)，其通过在乳化剂存在下将有机硅氧烷交联(共)聚合物分散到经离子交换的水中加以制备。
有机硅氧烷选自由二甲基硅氧烷、甲基苯基硅氧烷、二苯基硅氧烷、以及它们的混合物或共聚物组成的组。基于反应物的总重量，本发明的有机硅氧烷交联(共)聚合物的用量为5～90重量份，优选10～50重量份。
作为乳化剂，可以使用阴离子乳化剂，如含4到30个碳原子的烷基磺酸钠、钾、或铵盐。乳化剂的实例包括十二烷基磺酸钠、十二烷基苯磺酸钠等。在它们之中，由于其在较宽pH范围内的通用性，所以更优选十二烷基苯磺酸钠。基于反应物的总重量，乳化剂的用量为0.1～5重量份，优选0.1～2重量份。
在氮气流下向硅酮胶乳中加入丙烯酸烷基酯单体、苯乙烯芳香化合物和交联剂，并加热至50～100℃。通过丙烯酸烷基酯单体、苯乙烯芳香化合物和交联剂使有机硅氧烷交联(共)聚合物溶胀。然后通过加入聚合引发剂在50～100℃下实施聚合以获得橡胶核。
丙烯酸烷基酯单体的实例包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯等。最优选实例是具有低玻璃化转变温度的丙烯酸正丁酯。基于反应物的总重量，丙烯酸烷基酯单体的用量为5～90重量份，优选10～50重量份。
苯乙烯芳香化合物的实例包括苯乙烯、α-甲基苯乙烯、二乙烯基苯、乙烯基甲苯及其混合物。在它们之中，优选使用苯乙烯。基于反应物的总重量，苯乙烯芳香化合物的用量为0.01～50重量份，优选1～30重量份。
交联剂的实例包括甲基丙烯酸烯丙酯、氰尿酸三烯丙酯、异氰尿酸三烯丙酯、二乙烯基苯等。在它们之中，优选甲基丙烯酸烯丙酯和异氰尿酸三烯丙酯。基于反应物的总重量，交联剂的用量为0.1～10重量份，优选0.1～5重量剂。
作为聚合引发剂，可以使用通过热分解或氧化-还原反应产生自由基的自由基引发剂。合适的聚合引发剂包括过硫酸钾、过硫酸镁、过氧化苯甲酰、过氧化氢、过氧化二苯甲酰、氢过氧化枯烯、叔丁基过氧化氢等。在它们之中，水溶性的引发剂如过硫酸钾是优选的。聚合引发剂的用量是0.1～5重量份，优选0.1～2重量份。
在50～100℃下，向橡胶核连续地逐滴加入聚合引发剂和乙烯基单体以形成塑料壳，接着通过加凝结剂凝结并过滤以制备具有高折射率的硅酮抗冲改性剂。
乙烯基单体的实例包括甲基丙烯酸烷基酯、丙烯酸酯和烯键式不饱和芳香化合物等。在它们之中，优选甲基丙烯酸甲酯、苯乙烯、丙烯腈或其两种或更多种的混合物。基于反应物的总重量，本发明的乙烯基单体的用量是5～90重量份，优选10～50重量份。
作为凝结剂，可以使用金属盐如氯化镁、氯化钙、硫酸镁、硫酸钙等。
由此获得的抗冲改性剂具有1.49～1.59的高折射率。本发明的抗冲改性剂可以提供具有良好热稳定性、抗冲击性(即使在低温下)、耐候性以及优异着色性的热塑性树脂。对可用于本发明的热塑性树脂没有特别限制。热塑性树脂的实例包括氯乙烯树脂、苯乙烯树脂、苯乙烯-丙烯腈树脂、丙烯酸类树脂、聚酯树脂、ABS树脂、聚碳酸酯树脂等。尤其是，当在用于电子设备的外壳的聚碳酸酯树脂中使用本发明的抗冲改性剂时，其作用被扩大。
当热塑性树脂是聚碳酸酯树脂时，以每100重量份的聚碳酸酯树脂，将0.5～30重量份的本发明的硅酮抗冲改性剂混合到组合物中。
通过参照以下实施例可以更好地理解本发明，这些实施例是用于描述目的而不能被解释为以任何方式限制由所附权利要求所限定的本发明的范围。
实施例
实施例1
将90g二甲基硅氧烷-二苯基硅氧烷交联共聚物(折射率为1.43、粒径为170nm并且在甲苯中有65％的不溶部分)和1.4g十二烷基苯硫酸钠分散在760g经离子交换的水中以获得硅酮胶乳。在室温下将190g丙烯酸正丁酯、36g苯乙烯和9g异氰尿酸三烯丙酯加入到该硅酮胶乳中并混合。保持温度在75℃，向该混合物中加入1.8g过硫酸钾并实施聚合反应4小时。并向其中再加入0.7g过硫酸钾，然后在15分钟内逐滴加入由101.25g苯乙烯和33.75g丙烯腈组成的混合溶液。在75℃反应4小时后，将该体系冷却至室温。转化率为97.4％。获得的胶乳在1.5％的保持在75℃的含水MgSO4溶液中进行凝结，然后洗涤该凝结胶乳并干燥以获得呈粉末形式的抗冲改性剂。
实施例2
将112.5g二甲基硅氧烷-二苯基硅氧烷交联共聚物(折射率为1.45、粒径为210nm并且在甲苯中有60％的不溶部分)和2.7g十二烷基苯硫酸钠分散在980g经离子交换的水中以获得硅酮胶乳。在室温下将112.5g丙烯酸正丁酯、90g苯乙烯和9g异氰尿酸三烯丙酯加入到该硅酮胶乳并混合。随后的步骤以与实施例1中相同的方式进行，以获得呈粉末形式的抗冲改性剂。转化率为95.8％。
实施例3
将112.5g二甲基硅氧烷-二苯基硅氧烷交联共聚物(折射率为1.49、粒径为130nm并且在甲苯中有55％的不溶部分)和2.7g十二烷基苯硫酸钠分散在980g经离子交换的水中以获得硅酮胶乳。在室温下将107.8g丙烯酸正丁酯、90g苯乙烯和4.7g甲基丙烯酸烯丙酯加入到该硅酮胶乳并混合。随后的步骤以与实施例1中相同的方式进行，以获得呈粉末形式的抗冲改性剂。转化率为95.2％。
实施例4
将67.5g二甲基硅氧烷交联聚合物(折射率为1.41、粒径为250nm并且在甲苯中有68％的不溶部分)和3.2g十二烷基苯硫酸钠分散在980g经离子交换的水中以获得硅酮胶乳。在室温下将171g丙烯酸正丁酯、76.5g苯乙烯和4.5g甲基丙烯酸烯丙酯加入到该硅酮胶乳并混合。保持温度在75℃，向该混合物中加入1.8g过硫酸钾并实施聚合反应4小时。并向其中再加入0.68g过硫酸钾，然后在15分钟内逐滴加入由49.5g苯乙烯、36g丙烯腈和49.5g甲基丙烯酸甲酯组成的混合溶液。随后的步骤以与实施例1中相同的方式进行，以获得呈粉末形式的抗冲改性剂。转化率为95.2％。
比较实施例1
将157.5g二甲基硅氧烷交联聚合物(折射率为1.41、粒径为300nm并且在甲苯中有69％的不溶部分)和3.15g十二烷基苯硫酸钠分散在976g经离子交换的水中以获得硅酮胶乳。在室温下将153g丙烯酸正丁酯和4.5g甲基丙烯酸烯丙酯加入到该硅酮胶乳并混合。随后的步骤以与实施例1中相同的方式进行，以获得呈粉末形式的抗冲改性剂。转化率为97.6％。
比较实施例2
使用由日本的Mitsubishi Rayon公司生产的MetablenSRK-200(产品名)作为硅酮抗冲改性剂。
比较实施例3
比较实施例3以与实施例1中相同的方式进行，只是使用了90g二甲基硅氧烷-二苯基硅氧烷线性共聚物(折射率为1.43、粒径为220nm并且在甲苯中低于5％的不溶部分)来代替二甲基硅氧烷-二苯基硅氧烷交联共聚物。转换率为94.6％。
如下测量在以上实施例和比较实施例中获得的硅酮抗冲改性剂的物理性能：
(1)折射率：利用通过将所获得的抗冲改性剂热压至1mm厚度而制备的样品，通过利用由Sairon Tech.公司制造的棱镜耦合器型激光折射计(产品名：SPA-4000)发出的波长为632.8nm的激光来测量折射率。
(2)着色性能：利用通过以97∶3∶0.2的比例混合聚碳酸酯、抗冲改性剂和碳黑制备的模制样品来评价着色性(通过肉眼观察)。同样，模制样品的亮度(L*)通过由Konica Minota公司制造的分光光度计(CM-3600d)来测量。
(3)抗冲击性：以97∶3∶0.2的比例混合聚碳酸酯、抗冲改性剂和碳黑并通过双螺杆挤出机挤出为Φ＝45mm的小球。将该小球在110℃下干燥3小时，然后利用在260～330℃的10盎司注塑成形机和60～100℃的压辊温度分别模制成1/8”悬臂梁式试验条和板试样(厚度：3mm)。根据ASTM D-256，通过悬臂梁抗冲击性试验和通过落球冲击试验来评价抗冲击性。
表1
Figure GSB00000221760100121
a)亮度(L*)越低，着色性越好。
如上所示，实施例1-5的抗冲改性剂与比较实施例1-2的抗冲改性剂相比表现出更高的折射率(高于1.49)和更好的着色性同时没有冲击强度的劣化。尤其是，比较实施例3(其采用线性有机硅氧烷共聚物)的抗冲改性剂即使具有1.500的高折射率，但也表现出较差的冲击强度和较差的着色性能。
本领域的普通技术人员可容易地实现本发明。许多更改和变化可以视为属于由所附权利要求所限定的本发明范围内。

Claims (8)

1.一种硅酮抗冲改性剂，包括：
(A)橡胶核，由(a1)具有粒径为50～400nm的有机硅氧烷交联(共)聚合物和(a2)丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物构成；以及
(B)塑料壳，由乙烯基(共)聚合物构成；
其中，所述硅酮抗冲改性剂的折射率为1.49～1.59，所述橡胶核(A)与所述塑料壳(B)的重量比为5∶5～9∶1，所述有机硅氧烷交联(共)聚合物(a1)的折射率为1.41～1.50，所述(a1)有机硅氧烷交联(共)聚合物与所述(a2)丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物的重量比为1∶6～6∶1；并且在所述丙烯酸烷基酯-苯乙烯芳香化合物交联共聚物(a2)中所述丙烯酸烷基酯与所述苯乙烯芳香化合物的重量比为1∶1～20∶1。
2.一种制备根据权利要求1所述的硅酮抗冲改性剂的方法，包括：
通过将丙烯酸烷基酯和苯乙烯芳香化合物加入到具有粒径为50～400nm的有机硅氧烷交联(共)聚合物中进行交联聚合来制备橡胶核；以及
将乙烯基单体接枝(共)聚合到所述橡胶核上以形成塑料壳。
3.根据权利要求2所述的制备硅酮抗冲改性剂的方法，其中，所述有机硅氧烷选自由二甲基硅氧烷、甲基苯基硅氧烷、二苯基硅氧烷、以及它们的混合物或共聚物组成的组；所述丙烯酸烷基酯是丙烯酸正丁酯；所述苯乙烯芳香化合物选自由苯乙烯、α-甲基苯乙烯、二乙烯基苯、乙烯基甲苯及其混合物组成的组；所述乙烯基单体选自由甲基丙烯酸甲酯、苯乙烯、丙烯腈及其混合物组成的组。
4.根据权利要求2所述的制备硅酮抗冲改性剂的方法，其中，所述交联聚合是通过使用甲基丙烯酸烯丙酯或异氰尿酸三烯丙酯作为交联剂来进行的。
5.根据权利要求2所述的制备硅酮抗冲改性剂的方法，其中，所述有机硅氧烷交联(共)聚合物的量为5～90重量份，所述丙烯酸烷基酯的量为5～90重量份，所述苯乙烯芳香化合物的量为0.01～50重量份，以及所述乙烯基单体的量为5～90重量份。
6.一种热塑性树脂组合物，包括根据权利要求1所述的硅酮抗冲改性剂和热塑性树脂。
7.根据权利要求6所述的热塑性树脂组合物，其中，所述热塑性树脂选自由氯乙烯树脂、苯乙烯树脂、苯乙烯-丙烯腈树脂、丙烯酸类树脂、聚酯树脂、ABS树脂以及聚碳酸酯树脂组成的组。
8.根据权利要求7所述的热塑性树脂组合物，其中，所述热塑性树脂是聚碳酸酯树脂，并且所述硅酮抗冲改性剂是以每100重量份的所述聚碳酸酯树脂0.5～30重量份的量混合到所述组合物中。
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US7956105B2 (en) 2011-06-07
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