CN115093670B - 一种pc用多功能复合助剂 - Google Patents
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Abstract
本发明涉及一种PC用多功能复合助剂,由如下重量份的原料组成:ABS树脂20‑30份、甲基丙烯酸丙酯笼型倍半硅氧烷10‑15份、耐寒增塑剂4‑6份、纳米填料4‑6份、相容剂2‑4份、复合阻燃剂1‑3份、复合抗氧化剂1‑5份、润滑剂3‑10份。本发明各个原料成分选择合理,原料配比合理,ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、纳米填料相互聚合交联,提升耐寒增塑剂的耐迁移性能,用于改善PC树脂与耐寒增塑剂所形成的共混体系的力学性能,使两者之间具有良好的相容性,从而得到在低温环境下仍具有很好的机械性能和很强的冲击性能的改性PC复合材料,还能够明显改善PC材料的阻燃性能和抗氧化性能,从整体上提升了PC材料的产品性能,使其能够很好的满足使用需求。
Description
技术领域
本发明属于高分子材料助剂技术领域,特别是涉及一种PC用多功能复合助剂。
背景技术
聚碳酸酯(PC)作为一种热塑性高分子材料,由于其兼具高抗冲、高透光和高耐热的优点,而被广泛应用于航空航天、汽车车窗及照明系统等领域。PC在加工过程中,为了改善 PC材料的外观、物理性能和机械性能,通常需要在PC材料中添加多种助剂,防止PC材料的劣化,保证PC材料的产品质量。
现有技术中用于PC材料的助剂大致分为三大类,分别为高温加工保护助剂抗氧剂、材料加工成型用润滑剂、调节颜色的有机颜料。然而,将上述助剂与PC材料混合后制备得到的PC制品仍然存在一些缺点:(一)PC制品的耐寒性能差,PC制品在低温环境下的机械性能较差,特别是冲击性能大幅降低,虽然现有技术中也会通过添加耐寒增塑剂的方法对PC 制品进行低温韧性改性,但是,在实际使用过程中,耐寒增塑剂与PC之间的相容性较差,耐寒增塑剂容易发生迁移和抽出,耐寒增塑剂迁移和抽出严重时会使PC制品发生较大变化,引起PC制品软化、发粘,甚至表面破裂,析出物往往会造成PC的制品污染,还会影响PC制品的二次加工;而且,在耐寒增塑剂向外迁移的过程中还会带出一些抗氧剂、稳定剂等成分,导致PC制品的性能大大降低;(二)阻燃性能较低;虽然现有技术中也会通过添加阻燃剂的方法来改善PC制品的阻燃性能,但阻燃剂的添加量大,对PC制品的物理性能有一定影响,所得产品的拉伸强度、弯曲强度和弯曲模量均较低,同时还会增加企业的成本,不利于企业的长期发展。
发明内容
本发明的目的是提供一种PC用多功能复合助剂,用以解决现有的PC用助剂不能有效地改善PC材料的耐寒性和阻燃性能,影响到PC材料的产品质量的技术问题。
本发明提供一种PC用多功能复合助剂,该多功能复合助剂由如下重量份的原料组成: ABS树脂20-30份、甲基丙烯酸丙酯笼型倍半硅氧烷10-15份、耐寒增塑剂4-6份、纳米填料4-6份、相容剂2-4份、复合阻燃剂1-3份、复合抗氧化剂1-5份、润滑剂3-10份。
优选地,该多功能复合助剂由如下重量份的原料组成:ABS树脂25份、甲基丙烯酸丙酯笼型倍半硅氧烷12份、耐寒增塑剂5份、纳米填料4份、相容剂3份、复合阻燃剂2份、复合抗氧化剂3份、润滑剂5份。
优选地,所述耐寒增塑剂为己二酸二辛酯、癸二酸二辛酯、乙二酸二(2-乙基己)酯中的任意一种或多种。
优选地,所述纳米填料为纳米二氧化硅、纳米氧化锌、纳米碳纤维中的任意一种或多种。
优选地,所述相容剂为苯乙烯接枝马来酸酐、丁二烯-苯乙烯共聚物接枝马来酸酐、丙烯酸酯类聚合物、氯化聚乙烯中的任意一种。
优选地,所述复合阻燃剂为磷酸三(2,4-二异丁基苯)酯与氧化锑、八溴二苯醚的混合物或磷酸二甲苯酯与三氧化二锑、十溴二苯乙烷的混合物。
优选地,所述复合抗氧化剂为抗氧剂1076与抗氧剂DSTP的混合物或抗氧剂1010与抗氧剂DSTP的混合物或抗氧剂1076与抗氧剂168的混合物。
优选地,所述润滑剂为聚酯蜡、PE蜡、微晶石蜡中的任意一种。
优选地,该多功能复合助剂应用于PC树脂制备得到一种改性PC复合材料,PC树脂与多功能复合助剂的重量份比为100/10-15。
本发明还提供一种改性PC复合材料的制备方法,包括以下步骤:(1)按重量份比依次称取各个原料,将ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、耐寒增塑剂置于高速混合机中充分混合,搅拌均匀;(2)在双螺杆挤出机中以240-280℃的加工温度进行共混挤出、冷却、切粒,制备得到改性ABS树脂颗粒;(3)依次将PC树脂、纳米填料、相容剂、复合阻燃剂、复合抗氧化剂、润滑剂、步骤(2)制备得到的改性ABS树脂颗粒置于高速混合机中充分混合,搅拌均匀;(4)在双螺杆挤出机中以250-300℃的加工温度进行共混挤出、冷却、切粒,制备得到改性PC复合材料。
本发明的有益效果:(1)通过添加ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、纳米填料,甲基丙烯酸丙酯笼型倍半硅氧烷与ABS树脂发生聚合得到改性ABS树脂,由于改性ABS树脂含有笼型倍半硅氧烷结构,笼型倍半硅氧烷是具有三维立体结构的笼型分子,其分子中心有一个类似二氧化硅的无机核,被有机基团所包围,笼型倍半硅氧烷很容易与耐寒增塑剂之间发生化学交联,不仅增大了耐寒增塑剂的分子量,分子之间的化学交联还使得分子链的运动能力大大降低,从而起到阻碍耐寒增塑剂迁移的屏障作用,使其耐迁移性更好,而纳米填料则由于尺寸极小,表面有很多悬空键,具有不饱和性,很容易吸附在改性ABS树脂表面的空隙中,而且由于纳米粒子本身不迁移,可以阻碍和抑制耐寒增塑剂分子的运动;ABS 树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、纳米填料相互配合发生协同作用,用于改善PC树脂与耐寒增塑剂所形成的共混体系的力学性能,使其具有良好的相容性,从而得到在低温环境下仍具有很好的机械性能和很强的冲击性能的改性PC复合材料;(2)加入纳米填料、复合阻燃剂和复合抗氧化剂,在保证阻燃效果的基础上,还提高了聚碳酸酯的屈服强度和弹性模量,大大提高了聚碳酸酯的力学性能,增强了耐磨性,还提高了PC材料的抗氧化性和抗光老化性,具有良好的耐候性和热稳定性,保持了PC材料的优良性能,延长了制品的使用寿命,使本发明制得的改性PC复合材料具有优异的综合性能和广阔的应用前景。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
本发明提供了一种PC用多功能复合助剂,该多功能复合助剂由如下重量份的原料组成: ABS树脂20-30份、甲基丙烯酸丙酯笼型倍半硅氧烷10-15份、耐寒增塑剂4-6份、纳米填料4-6份、相容剂2-4份、复合阻燃剂1-3份、复合抗氧化剂1-5份、润滑剂3-10份。甲基丙烯酸丙酯笼型倍半硅氧烷是由甲基丙烯酸丙酯与多面体笼型倍半硅氧烷之间发生聚合反应制备得到的。
该多功能复合助剂由如下重量份的原料组成:ABS树脂25份、甲基丙烯酸丙酯笼型倍半硅氧烷12份、耐寒增塑剂5份、纳米填料4份、相容剂3份、复合阻燃剂2份、复合抗氧化剂3份、润滑剂5份。
所述耐寒增塑剂为己二酸二辛酯、癸二酸二辛酯、乙二酸二(2-乙基己)酯中的任意一种或多种。能够赋予PC制品优良的低温柔软性。
所述纳米填料为纳米二氧化硅、纳米氧化锌、纳米碳纤维中的任意一种或多种。纳米氧化锌作为一种光稳定剂,能够反射或吸收太阳光紫外线,在PC聚合物与光源之间设置一道屏障,阻止紫外线深入PC聚合物内部,从而可使PC聚合物得到保护,提高了PC材料的抗氧化性和抗光老化性。纳米二氧化硅和纳米碳纤维提高了聚碳酸酯的屈服强度和弹性模量,大大提高了聚碳酸酯的力学性能,增强了耐磨性。
所述相容剂为苯乙烯接枝马来酸酐、丁二烯-苯乙烯共聚物接枝马来酸酐、丙烯酸酯类聚合物、氯化聚乙烯中的任意一种。相容剂用于改善PC树脂与复合助剂所形成的共混体系的力学性能,使其具有良好的相容性,从而得到具有较高的抗冲强度的改性PC复合材料。
所述复合阻燃剂为磷酸三(2,4-二异丁基苯)酯与氧化锑、八溴二苯醚的混合物或磷酸二甲苯酯与三氧化二锑、十溴二苯乙烷的混合物。在复合材料燃烧的过程中,磷酸三(2,4-二异丁基苯)酯和磷酸二甲苯酯在热解过程中形成的磷酸类化合物促进了聚碳酸酯的成炭,能在复合材料的表面形成致密的成炭层,起到隔热、隔氧和阻止聚碳酸酯分解产物挥发的作用,防止了聚碳酸酯的降解,提高了复合材料的阻燃性,八溴二苯醚和十溴二苯乙烷受热分解产生的 HBr稀释了复合材料分解产生的可燃气体,从而起到阻燃的作用,氧化锑与三氧化二锑在燃烧时能够形成泡沫层,隔绝氧气从而起到阻燃的作用,三者相互配合,不仅阻燃效果好,而且相对于单一的阻燃剂而言,还能够最大限度的降低添加阻燃剂对产品机械性能的影响,提高PC制品的机械性能。
所述复合抗氧化剂为抗氧剂1076与抗氧剂DSTP的混合物或抗氧剂1010与抗氧剂DSTP 的混合物或抗氧剂1076与抗氧剂168的混合物。其中,抗氧剂1076、抗氧剂1010作为主抗氧剂,化合物结构中均含有-OH,-OH与PC树脂争夺自动氧化中形成的过氧自由基,通过氢原子的转移,形成一个稳定的抗氧剂自由基,该自由基又具有捕获活性自由基的能力,从而抑制PC树脂氧化过程的发生,从而改善PC产品的颜色。抗氧剂DSTP与抗氧剂168作为辅助抗氧剂,作为良好的螯合剂,能够与反应体系中残存的有害金属离子如Fe2+、Mn2+等形成螯合物,避免了有色金属离子与PC分子中的酚羟基反应形成深颜色的复合物,与抗氧剂1076、抗氧剂1010复配后,能够起到很好的抗氧化协同作用,保证了PC的外观颜色,提高了产品的透明性。
所述润滑剂为聚酯蜡、PE蜡、微晶石蜡中的任意一种。聚酯蜡具有非常强的极性中心和很长的非极性碳链,聚酯蜡在极性上与PC聚合物相容的部分起到内润滑的作用,聚酯蜡在极性上与PC聚合物不相容的部分起到外润滑和脱模的作用,改善PC材料的加工流动性,方便加工成型。
该多功能复合助剂应用于PC树脂制备得到一种改性PC复合材料,PC树脂与多功能复合助剂的重量份比为100/10-15。
本发明还提供一种改性PC复合材料的制备方法,包括以下步骤:(1)按重量份比依次称取各个原料,将ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、耐寒增塑剂置于高速混合机中充分混合,搅拌均匀;(2)在双螺杆挤出机中以240-280℃的加工温度进行共混挤出、冷却、切粒,制备得到改性ABS树脂颗粒;(3)依次将PC树脂、纳米填料、相容剂、复合阻燃剂、复合抗氧化剂、润滑剂、步骤(2)制备得到的改性ABS树脂颗粒置于高速混合机中充分混合,搅拌均匀;(4)在双螺杆挤出机中以250-300℃的加工温度进行共混挤出、冷却、切粒,制备得到改性PC复合材料。
实施例1
一种PC用多功能复合助剂,该多功能复合助剂由如下重量份的原料组成:ABS树脂20 份;甲基丙烯酸丙酯笼型倍半硅氧烷10份;己二酸二辛酯4份;纳米二氧化硅4份;苯乙烯接枝马来酸酐2份;磷酸三(2,4-二异丁基苯)酯与氧化锑、八溴二苯醚的混合物共计1份;抗氧剂1076与抗氧剂DSTP的混合物共计1份、聚酯蜡3份。
实施例2
一种PC用多功能复合助剂,该多功能复合助剂由如下重量份的原料组成:ABS树脂30 份;甲基丙烯酸丙酯笼型倍半硅氧烷15份;己二酸二辛酯、癸二酸二辛酯、乙二酸二(2-乙基己)酯的混合物共计6份;纳米二氧化硅、纳米氧化锌、纳米碳纤维的混合物共计6份;丁二烯-苯乙烯共聚物接枝马来酸酐4份;磷酸二甲苯酯与三氧化二锑、十溴二苯乙烷的混合物共计3份;抗氧剂1010与抗氧剂DSTP的混合物共计5份、PE蜡10份。
实施例3
一种PC用多功能复合助剂,该多功能复合助剂由如下重量份的原料组成:ABS树脂25 份;甲基丙烯酸丙酯笼型倍半硅氧烷12份;癸二酸二辛酯5份;纳米氧化锌4份;丙烯酸酯类聚合物3份;磷酸三(2,4-二异丁基苯)酯与氧化锑、八溴二苯醚的混合物共计2份;抗氧剂1076与抗氧剂168的混合物共计3份、微晶石蜡5份。
实施例4
一种PC用多功能复合助剂,该多功能复合助剂由如下重量份的原料组成:ABS树脂28 份;甲基丙烯酸丙酯笼型倍半硅氧烷14份;乙二酸二(2-乙基己)酯4份;纳米碳纤维5份;丙烯酸酯类聚合物4份;磷酸二甲苯酯与三氧化二锑、十溴二苯乙烷的混合物共计3份;抗氧剂1076与抗氧剂DSTP的混合物共计2份、聚酯蜡8份。
实施例5
一种PC用多功能复合助剂,该多功能复合助剂由如下重量份的原料组成:ABS树脂22 份;甲基丙烯酸丙酯笼型倍半硅氧烷11份;己二酸二辛酯、癸二酸二辛酯的混合物共计6份;纳米二氧化硅、纳米氧化锌的混合物共计6份;氯化聚乙烯3份;磷酸二甲苯酯与三氧化二锑、十溴二苯乙烷的混合物共计1份;抗氧剂1010与抗氧剂DSTP的混合物共计3份、PE 蜡6份。
将实施例1-5所述的多功能复合助剂分别与PC树脂按照重量份比为10-15/100的比例制备得到五种不同的改性PC复合材料;
并将实施例1所述的配方中去掉ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、纳米二氧化硅,将得到的复合助剂制备而成的PC复合材料作为对比例1;
将实施例2所述的配方中去掉ABS树脂;甲基丙烯酸丙酯笼型倍半硅氧烷;纳米二氧化硅、纳米氧化锌、纳米碳纤维的混合物,将得到的复合助剂制备而成的PC复合材料作为对比例2;
将实施例3所述的配方中去掉ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、纳米氧化锌,将得到的复合助剂制备而成的PC复合材料作为对比例3;
将实施例1所述的配方中去掉氧化锑、八溴二苯醚,将得到的复合助剂制备而成的PC 复合材料作为对比例4;
将实施例1所述的配方中去掉抗氧剂DSTP,将得到的复合助剂制备而成的PC复合材料作为对比例5;
对实施例1-5以及对比例1-5分别进行综合性能测试,测试结果见表1。
表1
由实施例1-5和对比例1-3可以看出,添加ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、纳米填料后,能够显著改善PC树脂与耐寒增塑剂所形成的共混体系的力学性能,使其具有良好的相容性,不仅使其在室温下具有优异的力学性能,而且在低温环境下仍具有很好的机械性能和很强的冲击性能,提高PC材料的屈服强度和弹性模量,延长产品的使用寿命。由实施例1-5和对比例4可以看出,本申请将三种阻燃剂复配,三者之间相互结合发生协同作用,相对于单一成分的阻燃剂,阻燃效果好。由实施例1-5和对比例5可以看出,本申请所述的复合氧化剂能够起到很好的抗氧化协同作用,相对于单一成分的抗氧剂,能够降低色差料的产生,降低产品颜色发黄的概率,提高产品的透明度,提高了PC材料的表面性能,保持了PC材料的优良性能。
以上所述的仅是本发明的一些实施方式。对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (6)
1.一种PC用多功能复合助剂,其特征在于:由如下重量份的原料组成:ABS树脂20-30份、甲基丙烯酸丙酯笼型倍半硅氧烷10-15份、耐寒增塑剂4-6份、纳米填料4-6份、相容剂2-4份、复合阻燃剂1-3份、复合抗氧化剂1-5份、润滑剂3-10份;
所述耐寒增塑剂为己二酸二辛酯、癸二酸二辛酯、乙二酸二(2-乙基己)酯中的任意一种或多种;所述复合阻燃剂为磷酸三(2,4-二异丁基苯)酯与氧化锑、八溴二苯醚的混合物或磷酸二甲苯酯与三氧化二锑、十溴二苯乙烷的混合物;所述复合抗氧化剂为抗氧剂1076与抗氧剂DSTP的混合物或抗氧剂1010与抗氧剂DSTP的混合物或抗氧剂1076与抗氧剂168的混合物;
该PC用多功能复合助剂的制备方法,包括以下步骤:(1)按重量份比依次称取各个原料,将ABS树脂、甲基丙烯酸丙酯笼型倍半硅氧烷、耐寒增塑剂置于高速混合机中充分混合,搅拌均匀;(2)在双螺杆挤出机中以240-280℃的加工温度进行共混挤出、冷却、切粒,制备得到改性ABS树脂颗粒;(3)依次将PC树脂、纳米填料、相容剂、复合阻燃剂、复合抗氧化剂、润滑剂、步骤(2)制备得到的改性ABS树脂颗粒置于高速混合机中充分混合,搅拌均匀;(4)在双螺杆挤出机中以250-300℃的加工温度进行共混挤出、冷却、切粒,制备得到改性PC复合材料。
2.根据权利要求1所述的一种PC用多功能复合助剂,其特征在于:由如下重量份的原料组成:ABS树脂25份、甲基丙烯酸丙酯笼型倍半硅氧烷12份、耐寒增塑剂5份、纳米填料4份、相容剂3份、复合阻燃剂2份、复合抗氧化剂3份、润滑剂5份。
3.根据权利要求1所述的一种PC用多功能复合助剂,其特征在于:所述纳米填料为纳米二氧化硅、纳米氧化锌、纳米碳纤维中的任意一种或多种。
4.根据权利要求1所述的一种PC用多功能复合助剂,其特征在于:所述相容剂为苯乙烯接枝马来酸酐、丁二烯-苯乙烯共聚物接枝马来酸酐、丙烯酸酯类聚合物、氯化聚乙烯中的任意一种。
5.根据权利要求1所述的一种PC用多功能复合助剂,其特征在于:所述润滑剂为聚酯蜡、PE蜡、微晶石蜡中的任意一种。
6.根据权利要求1-5中任一项所述的一种PC用多功能复合助剂,其特征在于:该多功能复合助剂应用于PC树脂制备得到一种改性PC复合材料,PC树脂与多功能复合助剂的重量份比为100/10-15。
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