CN106084614A - 防止pbt合金材料翘曲的相容剂的制备方法及其制得的相容剂 - Google Patents
防止pbt合金材料翘曲的相容剂的制备方法及其制得的相容剂 Download PDFInfo
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Abstract
本发明涉及高分子材料领域,特别是涉及一种防止PBT合金材料翘曲的相容剂的制备方法及其制得的相容剂。本发明包括以下步骤:(1)熔融接枝树脂的制备:三元乙丙胶(EPDM)30‑35份、聚乙烯粉料(PE)50‑60份、接枝单体2‑5份、过氧化物0.2‑0.3份、分散剂0.2‑0.3份和加工助剂0.5‑1份;其中,接枝单体为甲基丙烯酸缩水甘油酯(GMA)或马来酸酐(MAH);熔融挤出;洗涤纯化;(2)相容剂的制备:熔融接枝树脂70‑90份和亚微米级二氧化硅微球10‑30份;熔融挤出。本发明可有效增加PBT与非结晶、半结晶聚合物的相容性,能防止PBT合金材料翘曲。
Description
技术领域
本发明涉及高分子材料领域,特别是涉及一种防止PBT合金材料翘曲的相容剂的制备方法及其制得的相容剂。
背景技术
聚对苯二甲酸丁二醇酯(PBT)为结晶型热塑性树脂,其分子链为线型结构,主链上没有侧链,结构对称,易紧密堆砌在一起,因此结晶速率快,具有较好的结晶性和较高熔融温度(一般在224℃一235℃)。PBT结构单元中有活动性较差的苯环和极性的醋基,极易形成一种共轭体系,能够使分子间变得紧密,分子间作用力增大,从而使分子链的刚性得到加强,同时减小了分子链的溶解性、柔曲性和吸水性,因此其具有优异的力学性能、电绝缘性、热稳定性和化学稳定性,自润滑性和加工性也较好。
由于PBT分子链中酯基的存在也使其对热湿气很敏感,因此在加工过程中,如有水分或受热温度过高和时间过长的情况时,PBT便会产生水解、热氧化降解等不良反应,导致相对分子质量减小,影响PBT制品的性能与应用范围,此外PBT对缺口冲击较为敏感,缺口冲击强度低。工业上往往对PBT进行阻燃和增强改性,以改善其缺点。目前其增强阻燃材料75%以上用于电子电器、汽车、机械及仪器仪表等领域,但其产品有严重的翘曲现象,影响其材料更广泛的使用。
发明内容
本发明要解决的技术问题是提供一种可有效增加PBT与非结晶、半结晶聚合物的相容性,能防止PBT合金材料翘曲的相容剂的制备方法及其制备的相容剂
为解决上述技术问题,本发明采用如下技术方案:
本发明防止PBT合金材料翘曲的相容剂的制备方法,包括以下步骤:
(1)熔融接枝树脂的制备:
a)备料:按照下列组分(重量份数)进行备料:
三元乙丙胶(EPDM)30-35份、聚乙烯粉料(PE)50-60份、接枝单体2-5份、过氧化物0.2-0.3份、分散剂0.2-0.3份和加工助剂0.5-1份;
其中,接枝单体为甲基丙烯酸缩水甘油酯(GMA)或马来酸酐(MAH);
其中,EPDM中10-15%(质量百分数)为粉状,数均分子量为45000-52000,其余为颗粒;b)熔融挤出:将以上各组分用高速混合,用双螺杆挤出机在170℃~220℃挤出;
c)洗涤纯化:将其颗粒以有机溶剂Ⅰ回流溶解后过滤,加入有机溶剂Ⅱ沉淀纯化,反复三次并收集其沉淀产物,干燥后待用;
(2)相容剂的制备:
①备料:按照下列组分(重量份数)进行备料:
熔融接枝树脂70-90份、亚微米级二氧化硅微球10-30份、抗氧剂0.3-0.6份、润滑剂0.4-0.6份、分散剂0.5-1.0份和加工助剂0.5-1份;
②将以上各组分用用高速搅拌机混合,用双螺杆挤出机在180℃~220℃挤出造粒,制得相容剂成品颗粒。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(1)中接枝单体为GMA时的熔融挤出的温度为170-190℃,接枝单体为MAH时的熔融挤出的温度为180-220℃。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(1)中接枝单体为GMA时的有机溶剂Ⅰ为甲苯,有机溶剂Ⅱ为丙酮,接枝单体为MAH时的有机溶剂Ⅰ为三氯甲烷,有机溶剂Ⅱ为甲醇。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(1)中EPDM粉的粒径为150-300μm。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(1)中过氧化物为过氧化二异丙苯或过氧化二苯甲酰。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(1)和步骤(2)中的分散剂为活性磷酸钙。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(1)和步骤(2)中的加工助剂为乙撑双硬脂酰胺和硅油。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(2)中抗氧剂包括主抗氧剂和辅抗氧剂,主抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯,辅抗氧剂为三(2.4-二叔丁基苯基)亚磷酸酯。
本发明防止PBT合金材料翘曲的相容剂的制备方法,进一步的,步骤(2)中润滑剂为季戊四醇硬脂酸酯。
本发明防止PBT合金材料翘曲的相容剂的制备方法与现有技术相比,具有如下有益效果:
本发明防止PBT合金材料翘曲的相容剂的制备方法选用了GMA和MAH为接枝单体,将其与EPDM和PE熔融共混制备出GMA-g-EPDM/PE和MAH-g-EPDM/PE接枝母粒,其中EPDM组分采用了粉料与颗粒料混合使用,粉料分子量较小,数均分子量在5万左右,大大降低了接枝的难度,粉料粒径为150-300μm,降低了加工操作的难度。同时控制熔融挤出的温度在一定范围内,避免温度过高造成活性较大的接枝材料反应速度过快,接枝率不高的情况发生,且利用液液萃取方式对制备出的接枝母粒进行彻底的清洗,以除去母粒中残留的过氧化物和接枝单体,避免其在后期的相容剂的制备过程中造成相容剂的分解和加工的不稳定性。本发明防止PBT合金材料翘曲的相容剂的制备方法将制备出的接枝母粒GMA-g-EPDM/PE和MAH-g-EPDM/PE与亚微米级二氧化硅微球熔融共混,能提高材料的刚韧平衡性能,可有效防止合金材料的翘曲,也大大提高了材料的阻燃性能。
本发明防止PBT合金材料翘曲的相容剂可提高PBT与丙烯腈-丁二烯-苯乙烯树脂(ABS),聚酰胺树脂(PA6/PA66),聚碳酸酯树脂(PC),聚丙烯(PP),聚乙烯(PE)树脂等的相容性,提高合金材料的力学性能,提高材料的阻燃性,并有效避免阻燃改性PBT合金材料的翘曲现象,避免了再加入更多的助剂,降低了成本消耗。
下面结合附图对本发明的防止PBT合金材料翘曲的相容剂的制备方法作进一步说明。
附图说明
图1为应用实施例3与其对照组合金材料的DSC图谱;
图中:1为应用实施例3制得的合金材料,2为对照组2制得的合金材料,3为对照组1制得的合金材料。
具体实施方式
制备实施例
A、按照以下方法制备本发明相容剂A
(1)GMA-g-EPDM/PE母粒的制备:
A)备料:按照表1所述组分(重量份数)进行备料:其中,接枝单体为甲基丙烯酸缩水甘油酯(GMA);
其中,EPDM粉的数均分子量为4.5-5.2万,粒径为150-300μm,其余为颗粒,数均分子量为10-15万;
其中,PE为高密度聚乙烯粉料;
B)熔融挤出:将以上各组分用高速混合,用长径比为44:1的双螺杆挤出机,在170℃~190℃挤出;
C)洗涤纯化:将其颗粒以甲苯回流溶解后过滤,加入丙酮中进行彻底的沉淀纯化,反复三次并收集其沉淀产物,60℃真空干燥后待用;
(2)相容剂A的制备:
①备料:按照表2所示组分(重量份数)进行备料:
②将以上各组分用用高速搅拌机混合,用长径比为44:1的双螺杆挤出机在180℃~200℃挤出造粒,制得相容剂A成品颗粒。
表1GMA-g-EPDM/PE的具体组分用量(重量份数)
表2相容剂A的具体组分用量(重量份数)
B、按照以下方法制备本发明相容剂B
(1)MAH-g-EPDM/PE母粒的制备:
A)备料:按照表3所示组分(重量份数)进行备料:其中,接枝单体为马来酸酐(MAH);其中,EPDM粉的数均分子量为4.5-5.2万,粒径为150-300μm,其余为颗粒,数均分子量为10-15万;
其中,PE为高密度聚乙烯粉料;
B)熔融挤出:将以上各组分用高速混合,用长径比为44:1的双螺杆挤出机,在180℃~220℃挤出;
C)洗涤纯化:将其颗粒用三氯甲烷溶解后,再加入过量的甲醇沉淀析出,将其沉淀产物用甲醇清洗2次以上,将其中残留的马来酸酐洗净,收集其沉淀产物,在80℃真空干燥后待用;(2)相容剂B的制备:
①备料:按照表4所述组分(重量份数)进行备料:
②将以上各组分用用高速搅拌机混合,用长径比为44:1的双螺杆挤出机在180℃~220℃挤出造粒,制得相容剂B成品颗粒。
表3MAH-g-EPDM/PE的具体组分用量(重量份数)
表4相容剂B的具体组分用量(重量份数)
应用实施例
将上述制备实施例制得的相容剂与PBT和合金树脂熔融共混,并在其中加入一定比例的玻璃纤维和阻燃剂,熔融挤出造粒,制得合金材料,具体配比如表5所示。同时为每组应用实施例设置了相应的对照组1和对照组2,对照组1不使用任何相容剂,其余组分的选择和用量与应用实施例相同,对照组2选用目前本领域内常用的相容剂佳易容SOG-002,生产厂家为上海日之升新技术发展有限公司,用量与应用实施例相同,其余组分的选择和用量也与应用实施例相同。
表5合金材料的制备组分配比(重量份数)
制得的合金材料的性能检测结果如表6所示。
表6合金材料的性能检测结果
由表6可知,与未使用相容剂的对照组1相比,使用本发明相容剂制得的合金材料的力学性能有大幅度的提高,应用例1-5的拉伸强度和弯曲强度分别提高了10-75%和40-80%,应用例3-5的缺口冲击强度提高了90-130%,阻燃性能得到了提升,与使用目前现有相容剂的对照组2相比,使用本发明相容剂制得的合金材料的力学性能及流动性都有所提升,应用例1-5的拉伸强度和弯曲强度分别提高了25-76%和45-80%,应用例3-5的缺口冲击强度提高了90-130%,应用例1-3、5的熔融指数提高了20-80%,同时提高了制得的合金材料的阻燃性能,并有效防止了现有相容剂也存在的合金材料翘曲的现象。
其中图1为应用实施例3及其对照组的DSC图谱,图1说明相容剂可显著提高PBT与树脂材料的相容性,且相容效果高于现有相容剂40-60%。
以上所述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:包括以下步骤:
(1)熔融接枝树脂的制备:
a)备料:按照下列组分(重量份数)进行备料:
三元乙丙胶(EPDM)30-35份、聚乙烯粉料(PE)50-60份、接枝单体2-5份、过氧化物0.2-0.3份、分散剂0.2-0.3份和加工助剂0.5-1份;
其中,接枝单体为甲基丙烯酸缩水甘油酯(GMA)或马来酸酐(MAH);
其中,EPDM中10-15%(质量百分数)为粉状,数均分子量为45000-52000,其余为颗粒;
b)熔融挤出:将以上各组分用高速混合,用双螺杆挤出机在170℃~220℃挤出;
c)洗涤纯化:将其颗粒以有机溶剂Ⅰ回流溶解后过滤,加入有机溶剂Ⅱ沉淀纯化,反复三次并收集其沉淀产物,干燥后待用;
(2)相容剂的制备:
①备料:按照下列组分(重量份数)进行备料:
熔融接枝树脂70-90份、亚微米级二氧化硅微球10-30份、抗氧剂0.3-0.6份、润滑剂0.4-0.6份、分散剂0.5-1.0份和加工助剂0.5-1份;
②将以上各组分用用高速搅拌机混合,用双螺杆挤出机在180℃~220℃挤出造粒,制得相容剂成品颗粒。
2.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(1)中接枝单体为GMA时的熔融挤出的温度为170-190℃,接枝单体为MAH时的熔融挤出的温度为180-220℃。
3.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(1)中接枝单体为GMA时的有机溶剂Ⅰ为甲苯,有机溶剂Ⅱ为丙酮,接枝单体为MAH时的有机溶剂Ⅰ为三氯甲烷,有机溶剂Ⅱ为甲醇。
4.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(1)中EPDM粉的粒径为150-300μm。
5.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(1)中过氧化物为过氧化二异丙苯或过氧化二苯甲酰。
6.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(1)和步骤(2)中的分散剂为活性磷酸钙。
7.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(1)和步骤(2)中的加工助剂为乙撑双硬脂酰胺和硅油。
8.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(2)中抗氧剂包括主抗氧剂和辅抗氧剂,主抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯,辅抗氧剂为三(2.4-二叔丁基苯基)亚磷酸酯。
9.根据权利要求1所述的防止PBT合金材料翘曲的相容剂的制备方法,其特征在于:步骤(2)中润滑剂为季戊四醇硬脂酸酯。
10.根据权利要求1-9任意一项所述的防止PBT合金材料翘曲的相容剂的制备方法制备得到的相容剂。
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