CN101296960B - 具有抗冲改性剂粒度的双峰分布的抗冲改性丙烯酸类材料 - Google Patents

具有抗冲改性剂粒度的双峰分布的抗冲改性丙烯酸类材料 Download PDF

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CN101296960B
CN101296960B CN2006800395404A CN200680039540A CN101296960B CN 101296960 B CN101296960 B CN 101296960B CN 2006800395404 A CN2006800395404 A CN 2006800395404A CN 200680039540 A CN200680039540 A CN 200680039540A CN 101296960 B CN101296960 B CN 101296960B
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H·R·班亚
B·埃奇库姆
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Abstract

本发明涉及一种抗冲改性的丙烯酸类片材组合物，其具有抗冲改性剂粒度的双峰分布。所述组合物在熔融加工后具有冲击性能和外观的最佳平衡。

Description

具有抗冲改性剂粒度的双峰分布的抗冲改性丙烯酸类材料
发明领域
本发明涉及一种抗冲改性的丙烯酸基的组合物，其具有抗冲改性剂粒度的双峰分布。所述组合物在熔融加工后具有冲击性能和外观的最佳平衡。
背景技术
橡胶增强丙烯酸树脂广泛用于希望发挥丙烯酸有益性能(透明、耐候性等)的应用领域，但是，标准的未改性丙烯酸不具有希望的冲击强度。增强丙烯酸树脂的通常方式是在丙烯酸基体中引入冲击改性剂。
大粒度的冲击改性剂(＞220nm体积平均粒度)通常提供优良的冲击性能，但会导致差的外观，例如热成型形成的表面雾度(低光泽度)。小粒度的改性剂(＜220nm体积平均粒度)在熔融加工后提供良好的外观，但却不能提供优良的冲击性能。
如美国专利5,985,997、6,323,282、和6,6660,808中所述的，具有双峰粒度分布的橡胶颗粒已经被用于聚苯乙烯和聚丙烯聚合物中以获得高光泽度、冲击强度和硬度的平衡。这些文献中描述了具有双峰分布的二烯烃共聚物橡胶颗粒的用途，但没有提及基于丙烯酸的基体材料中的丙烯酸冲击改性剂。
不同平均粒度从而性能不同的粒子群的共混通常制得具有平均物理性能的产品，或制得具有所述粒子群中最差物理性能的产品。
令人惊奇地发现，含有具有适当的双峰粒度分布的抗冲改性剂的丙烯酸类组合物能够在熔融加工后提供冲击性能和外观的最佳平衡。通过用大粒度抗冲改性剂代替一定量的小粒度抗冲改性剂使得树脂中大粒度抗冲改性剂的比例低于20％，经热成型后，部分可以同时获得优良的冲击性能和外观。使用具有双峰粒度分布的抗冲改性剂提供了独特的性能平衡，这不是单独一种改性剂或任何单一粒度的方式能够实现的。
发明概要
本发明涉及一种抗冲改性的丙烯酸类组合物，其包括丙烯酸类聚合物基体和具有双峰平均粒度分布的抗冲改性剂。
本发明还涉及一种多层制品，包括基底层，在该基底层上直接粘合有抗冲改性的丙烯酸类组合物，所述丙烯酸类组合物包含丙烯酸类聚合物基体和具有双峰平均粒度分布的抗冲改性剂。
发明详述
本发明涉及具有双峰粒度分布的抗冲改性剂在制备具有冲击强度和外观(光泽度和图像的清晰度)的最佳平衡的丙烯酸基的基体中的应用。
本发明的丙烯酸基聚合物基体包括主要由甲基丙烯酸烷基酯和丙烯酸烷基酯单体及其混合物形成的聚合物(这里包括均聚物、共聚物、和三种以上单体形成的聚合物如三聚物)。甲基丙烯酸烷基酯单体优选甲基丙烯酸甲酯，其可以占单体混合物的60-100wt％，单体混合物还可以含有0-40wt％的其它丙烯酸酯和甲基丙烯酸酯单体。用于单体混合物的其它甲基丙烯酸酯和丙烯酸酯单体包括，但不限于，丙烯酸甲酯、丙烯酸乙酯和甲基丙烯酸乙酯、丙烯酸丁酯和甲基丙烯酸丁酯、甲基丙烯酸异辛酯和丙烯酸异辛酯、丙烯酸月桂酯和甲基丙烯酸月桂酯、丙烯酸十八烷酯和甲基丙烯酸十八烷酯、丙烯酸异冰片酯和甲基丙烯酸异冰片酯、丙烯酸甲氧基乙酯和甲基丙烯酸甲氧基乙酯、丙烯酸2-乙氧基乙酯和甲基丙烯酸2-乙氧基乙酯、丙烯酸二甲氨基乙酯和甲基丙烯酸二甲氨基乙酯单体。烷基(甲基)丙烯酸如甲基丙烯酸和丙烯酸可以用于所述单体混合物。也可以使用少量多官能单体作为交联剂。合适的交联单体包括，但不限于，例如，甲基丙烯酸烯丙酯、丙烯酸烯丙酯、二乙烯基苯、二甲基丙烯酸乙二醇酯和二丙烯酸乙二醇酯、三丙烯酸乙二醇酯和三甲基丙烯酸乙二醇酯、二甲基丙烯酸丁二醇酯、甲基丙烯酸缩水甘油酯、异氰脲酸三烯丙酯、N-羟甲基丙烯酰胺、N，N-亚甲基二丙烯酰胺和N，N-亚甲基二甲基丙烯酰胺、柠檬酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、二甘醇二乙烯基醚等。苯乙烯类单体如苯乙烯和α-甲基苯乙烯也可以少量引入聚合物中。
丙烯酸基的基体也可以由一种或多种其它热塑性聚合物与丙烯酸类聚合物的共混物组成。丙烯酸基的基体可以包括至少20wt％，优选至少40wt％，更优选至少50wt％，再优选至少60wt％，和最优选至少70wt％的丙烯酸类聚合物。用于所述丙烯酸基的基体的其它热塑性聚合物的例子包括，但不限于，聚偏二氟乙烯(PVDF)、聚氯乙烯和氯化聚氯乙烯(PVC和CPVC)、聚碳酸酯(PC)、聚偏二氯乙烯和苯乙烯/丙烯腈(SAN)。
丙烯酸基的聚合物基体可以包括5-70wt％一种或多种抗冲改性剂。优选的抗冲改性剂是芯壳型多层聚合物和具有至少一个硬嵌段和至少一个软嵌段的嵌段共聚物。芯壳型(多层)抗冲改性剂可以具有软的(橡胶或弹性体)芯和硬的壳；用软的弹性体层包覆的硬芯，和硬壳；现有技术已知的其它芯壳形态。橡胶层由低玻璃化转变温度(Tg)的聚合物组成，它包括，但不限于，丙烯酸丁酯(BA)、丙烯酸乙基己酯(EHA)、丁二烯(BD)、BD/苯乙烯、丙烯酸丁酯/苯乙烯、和许多其它组合。
用于本发明的抗冲改性剂具有双峰粒度分布。对于如何获得双峰分布没有限制。每种“模式”粒度的粒子可以具有相同或不同的化学组成。在一个实施方式中，共混两种具有两种不同平均粒度的不同的抗冲改性剂，所述抗冲改性剂可以具有相同或不同的组成。在另一个实施方式中，单种抗冲改性剂通过如筛选等已知方法分离成不同的粒度，粒度范围不同的组分然后又被共混在一起。在另一种实施方式中，通过US6852812B2所述的单聚合法获得双峰分布。
大粒度抗冲改性剂提供优良的冲击性能，但在熔融加工(例如热成型、挤出和注塑)后具有差的外观，如高表面雾度、低光泽度和差的图像清晰度。小粒度抗冲改性剂在熔融加工后具有优良的外观但不能提供优良的冲击性能。通过用大粒度抗冲改性剂代替少量的小粒度抗冲改性剂，热成型后可以同时获得优良的冲击性能和外观。较大体积平均粒度的抗冲改性剂的量占丙烯酸类树脂总重量的2-20wt％，优选4-15wt％。全部双峰抗冲改性剂由20-80wt％的大体积平均粒度颗粒和20-80wt％的小体积平均粒度颗粒制成。
较小粒度抗冲改性剂的体积平均粒度是60-220nm，优选100-200nm。较高粒度抗冲改性剂的体积平均粒度是220-700nm，优选250-400nm。颗粒的体积平均粒度可以由抗冲改性剂颗粒在水中或稀释胶乳中的动态光散射技术测定。本领域技术人员可以理解其它技术例如显微镜法能够获得稍有不同的平均值。
除抗冲改性剂之外，本发明的丙烯酸类基体可以含有其它常用的聚合物添加剂，如抗氧化剂、染料、着色剂、UV吸收剂、润滑剂和填料。
丙烯酸基的聚合物基体和抗冲改性剂可以通过本领域已知的方法共混。在一个实施方式中，丙烯酸基的聚合物和抗冲改性剂通过挤出进行熔融配混，然后直接注塑成制品，或形成可以进一步加工成制品的片材、膜、型材(profiles)、或粒料。
本发明的抗冲改性组合物尤其适用于膜、模内装饰应用、高性能应用、面料(capstock)和注塑高光泽度部件。
在一个终端应用中，含有UV吸收剂的本发明的抗冲改性丙烯酸基薄膜被用作如ABS基底的保护面料以形成多层复合材料。这可以通过共挤出、使用粘合剂、或层压法实现。可以用本发明的抗冲改性丙烯酸类涂敷的其它基底包括塑料、金属、木材、玻璃、和石头。所述基底可以是单层，或其本身含有多层。优选的塑料基底包括聚丙烯腈-丁二烯-苯乙烯、聚丙烯腈-苯乙烯-丙烯酸类、聚碳酸酯/聚丙烯腈-丁二烯-苯乙烯、高抗冲聚苯乙烯、聚氯乙烯、热塑性烯烃、聚烯烃、聚苯乙烯、聚苯乙烯-丙烯腈、聚碳酸酯、聚对苯二甲酸乙二醇酯、和乙醇酸化(glycolised)聚酯。
实施例
两种不同粒度的抗冲改性剂(表1中的改性剂A和改性剂B)以不同比率与具有黑色着色剂的PMMA基体混合。抗冲改性剂在丙烯酸基组合物中总的重量百分含量被控制在40％。表2列出了抗冲改性剂A的总量，余量是改性剂B。所述材料经挤出熔融配混，然后注塑形成平板。所述样板通过装有仪表化落镖过程测试抗冲击性、制成时的光泽度和热成型后的光泽度。结果示于表2。
表1
  组合物   体积平均粒度(nm)
 改性剂A   层1芯MMA、EA、甲基丙烯酸烯丙酯＝96/3.8/0.2的共聚物层2丙烯酸丁酯、苯乙烯、甲基丙烯酸烯丙酯＝81/17/2.0的共聚物层3MMA、EA、甲基丙烯酸烯丙酯＝96/3.8/0.2的共聚物   175
 改性剂B   层1芯MMA、EA、甲基丙烯酸烯丙酯＝96/3.8/0.2的共聚物   310
  层2丙烯酸丁酯、苯乙烯、甲基丙烯酸烯丙酯＝81/17/2.0的共聚物层3MMA、EA、甲基丙烯酸烯丙酯＝96/3.8/0.2的共聚物
表2
Figure S2006800395404D00051

Claims (6)

1.一种抗冲改性的丙烯酸类组合物，包括丙烯酸基聚合物基体和基于组合物总重量为5-70wt％的具有双峰粒度分布的抗冲改性剂，其中，较小粒度的抗冲改性剂具有50-200nm的体积平均粒度，和所述大粒度的抗冲改性剂具有220-500nm的体积平均粒度，以及丙烯酸基聚合物基体包括60-100wt％的甲基丙烯酸甲酯单体单元。
2.根据权利要求1所述的抗冲改性的丙烯酸类组合物，其中，抗冲改性剂包括20-80wt％的大粒度颗粒，和20-80wt％的小粒度颗粒，其总量为100％。
3.根据任一前述权利要求所述的抗冲改性的丙烯酸类组合物，其中，大粒度抗冲改性剂和小粒度抗冲改性剂的化学组成相同。
4.根据权利要求1或2所述的抗冲改性的丙烯酸类组合物，所述组合物还包括至少一种选自抗氧化剂、染料、着色剂、UV吸收剂、润滑剂和填料的添加剂。
5.根据权利要求1或2所述的抗冲改性的丙烯酸类组合物，其中，所述丙烯酸基的基体是丙烯酸类聚合物和至少一种其它热塑性聚合物的共混物。
6.根据权利要求5所述的抗冲改性的丙烯酸类组合物，其中，所述其它热塑性聚合物选自聚偏二氟乙烯、聚碳酸酯、聚氯乙烯、聚偏二氯乙烯、苯乙烯/丙烯腈(SAN)及其混合物。
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