CN112457578A - 一种硅灰石改性聚丙烯母粒及其制备方法 - Google Patents
一种硅灰石改性聚丙烯母粒及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种硅灰石改性聚丙烯母粒及其制备方法,涉及塑料技术领域。所述硅灰石改性聚丙烯母粒包含如下重量份的成分:聚丙烯树脂75‑95份和经甜菜碱改性的硅灰石5‑25份;所述经甜菜碱改性的硅灰石的制备方法为:将硅灰石和甜菜碱在70~90℃下混合均匀,得到所述经甜菜碱改性的硅灰石。以所述配方制备的硅灰石改性聚丙烯母粒具有良好的强度、韧性和耐温性。并且制备方法仅为简单的物理共混,对设备的要求较小,适用于现有的生产条件。
Description
技术领域
本发明涉及塑料技术领域,尤其涉及一种硅灰石改性聚丙烯母粒及其制备方法。
背景技术
聚丙烯(PP)是五大通用塑料之一,能有效代替部分钢铁在工程领域的应用,但由于其强度不高,热稳定性差,缺口敏感性高,尤其是在低温情况下冲击性更差等缺点严重阻碍了其在工程领域的应用,所以对PP改性成为了国内外学者研究的热点。
物理改性是聚丙烯的主要改性途径,常用的方法有增强、共混和填充。物理改性其本质为,加入目的辅助剂从而改变其微观结构,但不改变聚丙烯分子链结构,使聚丙烯具有满足要求的新性能。与工艺流程、性能指标、生产成本和环境保护等方面的局限较大的化学改性相比,物理改性具有工艺简单、针对性强、成本小、产品设计空间大等优点。所以近年来PP的物理改性得到蓬勃发展,在提高PP使用性能的同时也降低PP原材料的成本。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种高强度、高韧性、耐腐蚀、绝缘且稳定性良好的硅灰石改性聚丙烯母粒及其制备方法。
为实现上述目的,本发明所采取的技术方案为:一种硅灰石改性聚丙烯母粒,其特征在于,包含如下重量份的成分:聚丙烯树脂75-95份和经甜菜碱改性的硅灰石5-25份;所述经甜菜碱改性的硅灰石的制备方法为:将硅灰石和甜菜碱在70~90℃下混合均匀,得到所述经甜菜碱改性的硅灰石。
硅灰石凭借其针状与纤维状的晶体结构,能部分代替有毒的石棉、昂贵的碳纤维与玻璃纤维等增强材料。此外,硅灰石还具有高电阻、低吸油率和低热膨胀系数等优点。因此硅灰石作为填充剂填充塑料时,能有效改善塑料产品绝缘性,耐磨性,耐蠕变性与尺寸稳定性,同时也防止了产品的翘曲。
硅灰石表面呈化学惰性,填充聚丙烯时,很难与基体基团发生反应。而且硅灰石的表面自由能与聚丙烯相差较大,影响其在聚丙烯中的分散均匀性。这些因素都对其复合材料力学性能有较大的影响,因此本发明采用极性与聚丙烯基体相似的有机表面活性剂甜菜碱对硅灰石表面进行处理,以增加硅灰石与基体聚丙烯树脂的相容性,使其在复合体系中形成较好的结合界面,并且分散均匀。
优选地,所述硅灰石改性聚丙烯母粒包含如下重量份的成分:聚丙烯树脂80-90份和经甜菜碱改性的硅灰石10-20份。
优选地,所述硅灰石改性聚丙烯母粒包含如下重量份的成分:聚丙烯树脂85份和经甜菜碱改性的硅灰石15份。本发明申请人经多次实验证实,以所述配比制备出的聚丙烯母粒具有最优的综合力学性能。
优选地,所述甜菜碱包含椰油酰胺丙基甜菜碱、十二烷基甜菜碱、椰油酰胺丙基羟磺酸甜菜碱中的至少一种;所述甜菜碱的质量分数为硅灰石的0.8-1.2%。
椰油酰胺丙基甜菜碱是一种两性表面活性剂,具有良好的清洗、调理作用;十二烷基甜菜碱是一种两性表面活性剂,具有良好的洗涤和调理作用,可广泛与阴离子、阳离子和非离子表面活性剂配伍;椰油酰胺丙基羟磺酸甜菜碱有优异的增稠性,具有低刺激性和杀菌性。
优选地,所述甜菜碱为椰油酰胺丙基甜菜碱和十二烷基甜菜碱的复配物。
优选地,所述硅灰石改性聚丙烯母粒还包含如下重量份的成分:增韧剂3-8份、抗静电剂1.5-2份、抗氧剂0.1-0.3份和加工助剂0.3-0.5份。
优选地,所述增韧剂包含乙烯辛烯共聚物、三元乙丙橡胶、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物中的至少一种,以其中的任意一种作为增韧剂都能显著增加聚丙烯树脂的韧性,显著提高其制品的常温和低温冲击性能。
优选地,所述抗静电剂为二烷基二甲基季铵盐。其在混炼过程中和基体树脂混合在一起,经过一段时间后迁移到表面,形成表面抗静电剂分子层。由于它们与树脂组成物是混为一体的,所以耐久性好。
优选地,所述抗氧剂包含多元受阻酚类抗氧剂和亚磷酸酯类抗氧剂中的至少一种。
优选地,所述抗氧剂为多元受阻酚类抗氧剂和亚磷酸酯类抗氧剂的复配物。所述多元受阻酚类抗氧剂作为主抗氧剂、亚磷酸酯类抗氧剂作为辅助性抗氧剂,复合后有良好的抗黄变性和高透明性,是低挥发性有机合成抗氧阻聚剂。这两种抗氧剂可协同抗氧化。
优选地,所述抗氧剂中,多元受阻酚类抗氧剂和亚磷酸酯类抗氧剂的重量比为:多元受阻酚类抗氧剂:亚磷酸酯类抗氧剂=2:1。本发明申请人经多次实验证实,抗氧剂以所述配比复配制备出的硅灰石改性聚丙烯母粒具有最优的抗氧化性能。
优选地,所述加工助剂包含硬脂酸、硬脂酸钙、硬脂酸锌中的至少一种。
同时,本发明公开了一种所述硅灰石改性聚丙烯母粒的制备方法,所述制备方法包含如下步骤:
(1)制备经甜菜碱改性的硅灰石:将硅灰石和甜菜碱在70~90℃下混合均匀,得到经甜菜碱改性的硅灰石;
(2)混料:将聚丙烯树脂、经甜菜碱改性的硅灰石、增韧剂、抗静电剂、抗氧剂和加工助剂混合均匀;
(3)挤出造粒:将步骤(2)得到的物料加入双螺杆挤出机中,熔融、混炼、挤出、冷却、烘干、造粒,得到所述硅灰石改性聚丙烯母粒。
相比于现有技术,本发明的有益效果为:
1)添加橡胶或者弹性体虽然能使复合材料的韧性明显改善,但同时也使复合材料的刚度,强度、加工性与耐热性能大幅降低,而刚性粒子硅灰石的引入能在改善复合材料韧性的同时维持复合材料的刚性、强度与耐热性。对刚性共混体系来说,单向拉伸时,当刚性粒子所受的应力超过其屈服值时,刚性粒子有较好的韧性效果,这就是有机刚性粒子冷拉机理。
2)硅灰石表面呈化学惰性,填充聚丙烯时,很难与基体基团发生反应。而且硅灰石的表面自由能与聚丙烯相差较大,影响其在聚丙烯中的分散均匀性。这些因素都对其复合材料力学性能有较大的影响,因此本发明采用极性与聚丙烯基体相似的有机表面活性剂甜菜碱对硅灰石表面进行处理,以增加硅灰石与基体聚丙烯树脂的相容性,并在复合体系中形成较好的结合界面而且分散均匀。
3)同时体系中再辅以适量弹性粒子和抗静电剂,使刚、韧达到平衡的同时体系又具有抗静电性。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
实施例中所用聚丙烯树脂在230℃,2.16kg负荷下,其熔体质量流动速率(MFR)为1~60g/10min,密度为0.89~0.91g/cm3。硅灰石粒径为200目,长径比为1:12,为片状、放射状或纤维状集合体,白色微带灰色,洛氏硬度为4.5~5.5R,密度为2.75~3.10g/cm3,市售。
实施例1~5
实施例1~5为本发明所述硅灰石改性聚丙烯母粒,其配方如表1所示,甜菜碱为椰油酰胺丙基甜菜碱和十二烷基甜菜碱重量比为1:1的复配物;抗氧剂为抗氧剂1010和抗氧剂626重量比为2:1的复配物;增韧剂为乙烯辛烯共聚物;抗静电剂为二烷基二甲基共聚物;加工助剂为硬脂酸。
实施例1~5的制备方法如下:
(1)将硅灰石放入高速混合机中,加入甜菜碱,在80℃下混合7min,混炼速度为800rpm;
(2)按比例称取聚丙烯树脂、经甜菜碱改性的硅灰石、增韧剂、抗静电剂、抗氧剂和加工助剂,在高速混合器中进行干混处理,混炼转速为1100rpm,混炼时间为6min;
(3)挤出造粒:将步骤(2)中的物料加入双螺杆挤出机中,经熔融、混炼、挤出、冷却、吹干、造粒,制得硅灰石改性聚丙烯母粒;所述双螺杆挤出机为同向双螺杆挤出机,且挤出机最高段温度为210℃。
表1实施例1~5的配方(重量份)
实施例6~12
实施例6~12为本发明所述的硅灰石改性聚丙烯母粒,其配方除甜菜碱的组成与实施例3不同外,其余均与实施例3相同,制备方法与实施例1~5也相同,实施例6~12中甜菜碱的配方如表2所示。
表2实施例6~12中甜菜碱的配方(质量百分数%)
实施例13~18
实施例13~18为本发明所述的硅灰石改性聚丙烯母粒,其配方除抗氧剂的组成与实施例3不同外,其余均与实施例3相同,制备方法与实施例1~5也相同,实施例13~18中抗氧剂的配方如表3所示。
表3实施例13~18中抗氧剂的配方(质量百分数%)
对比例1
一种硅灰石改性聚丙烯母料,其硅灰石未经甜菜碱改性,配方中无甜菜碱,其余配方与实施例3相同,制备方法与实施例3相近,除了没有第一步对硅灰石的改性外,其余步骤与实施例3相同。
性能测试
对实施例1~18和对比例1进行性能测试,测试标准如下:
1、熔体质量流动速率(g/10min):参照GB/T 3682;
2、拉伸屈服强度(MPa):参照GB/T 1040;
3、弯曲模量(KJ/m2):参照GB/T 9341;
4、悬臂梁缺口冲击强度(MPa):参照GB/T 1843;
5、洛氏硬度R:参照GB/T 3682;
6、表面电阻率(Ω·m):参照GB/T 1410;
7、表面电阻率(Ω·m,常温500h):参照GB/T 1410;
9、悬臂梁低温冲击强度(KJ/m2,-20℃):参照GB/T 1843
表4性能测试结果
从表4中可知,对比例1的综合力学性能明显低于本发明,说明甜菜碱有助于改进硅灰石与聚丙烯树脂的接触性能,使硅灰石与聚丙烯树脂均匀混合,在保证制备出的母粒具有优良的韧性的同时,提高聚丙烯母粒的强度。此外,从实施例1~5的测试结果可知,实施例3的综合性能明显优于其余实施例,说明聚丙烯树脂与经甜菜碱改性的硅灰石的最优重量比为85:15。另外,从实施例3和实施例6~12的测试结果可知,实施例6~12的综合性能均差于实施例3,表明,甜菜碱的最优配方为椰油酰胺丙基甜菜碱和十二烷基甜菜碱重量比为1:1的复配物。最后,从实施例3和实施例13~18的测试结果可知,抗氧剂的最优配方为抗氧剂1010和抗氧剂626重量比为2:1的复配物。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,但并不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种硅灰石改性聚丙烯母粒,其特征在于,包含如下重量份的成分:聚丙烯树脂75-95份和经甜菜碱改性的硅灰石5-25份;所述经甜菜碱改性的硅灰石的制备方法为:将硅灰石和甜菜碱在70~90℃下混合均匀,得到所述经甜菜碱改性的硅灰石。
2.如权利要求1所述的硅灰石改性聚丙烯母粒,其特征在于,包含如下重量份的成分:聚丙烯树脂80-90份和经甜菜碱改性的硅灰石10-20份。
3.如权利要求2所述的硅灰石改性聚丙烯母粒,其特征在于,包含如下重量份的成分:聚丙烯树脂85份和经甜菜碱改性的硅灰石15份。
4.如权利要求1所述的硅灰石改性聚丙烯母粒,其特征在于,所述甜菜碱包含椰油酰胺丙基甜菜碱、十二烷基甜菜碱、椰油酰胺丙基羟磺酸甜菜碱中的至少一种;所述甜菜碱的质量分数为硅灰石的0.8-1.2%。
5.如权利要求4所述的硅灰石改性聚丙烯母粒,其特征在于,所述甜菜碱为椰油酰胺丙基甜菜碱和十二烷基甜菜碱的复配物。
6.如权利要求1所述的硅灰石改性聚丙烯母粒,其特征在于,还包含如下重量份的成分:增韧剂3-8份、抗静电剂1.5-2份、抗氧剂0.1-0.3份和加工助剂0.3-0.5份。
7.如权利要求6所述的硅灰石改性聚丙烯母粒,其特征在于,所述增韧剂包含乙烯辛烯共聚物、三元乙丙橡胶、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物中的至少一种;所述抗静电剂为二烷基二甲基季铵盐;所述抗氧剂包含多元受阻酚类抗氧剂和亚磷酸酯类抗氧剂中的至少一种;所述加工助剂包含硬脂酸、硬脂酸钙、硬脂酸锌中的至少一种。
8.如权利要求7所述的硅灰石改性聚丙烯母粒,其特征在于,所述抗氧剂为多元受阻酚类抗氧剂和亚磷酸酯类抗氧剂的复配物。
9.如权利要求8所述的硅灰石改性聚丙烯母粒,其特征在于,所述抗氧剂中,多元受阻酚类抗氧剂和亚磷酸酯类抗氧剂的重量比为:多元受阻酚类抗氧剂:亚磷酸酯类抗氧剂=2:1。
10.一种如权利要求6~9任一项所述的硅灰石改性聚丙烯母粒的制备方法,其特征在于,包含如下步骤:
(1)制备经甜菜碱改性的硅灰石:将硅灰石和甜菜碱在70~90℃下混合均匀,得到经甜菜碱改性的硅灰石;
(2)混料:将聚丙烯树脂、经甜菜碱改性的硅灰石、增韧剂、抗静电剂、抗氧剂和加工助剂混合均匀;
(3)挤出造粒:将步骤(2)得到的物料加入双螺杆挤出机中,熔融、混炼、挤出、冷却、烘干、造粒,得到所述硅灰石改性聚丙烯母粒。
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