CN106496769B - 一种含有l-poss交联剂的同质异构交联法改性回收pp及其制备方法 - Google Patents
一种含有l-poss交联剂的同质异构交联法改性回收pp及其制备方法 Download PDFInfo
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Abstract
一种含有L‑POSS交联剂的同质异构交联法改性回收PP及其制备方法，涉及一种塑胶材料及其制备方法，本发明改性方法是：首先将回收PP在80℃条件下鼓风干燥3～4小时;将自制的微交联母料先放入万能粉碎机再放入行星式球磨机中研磨直至交联料的粒径达到10～50μm，然后按重量配比称取干燥好的回收PP、自制的微交联母料、增韧剂、无机填料投入到高混机中混合4～6min，用双螺杆挤出机于160℃‑230℃下挤出造粒即得再生料。本发明的技术方案能同时实现增强、增韧等力学性能改性PP的效果，而且同质异构交联法的引入可以使改性PP的再生过程中无需加入相容剂也可以使再生料的性能很好。
Description
技术领域
本发明涉及一种塑胶材料及其制备方法，特别是涉及一种含有L-POSS交联剂的同质异构交联法改性回收PP及其制备方法。
背景技术
聚丙烯是由丙烯聚合而制得的一种热塑性树脂，是目前所有塑料中最轻的品种之一，无毒、无臭、无味、具备优异的表面刚度、抗冲击强度和抗划痕等特性，并且PP不存在环境应力开裂问题，所以聚丙烯在包装薄膜、电器设备、家具领域应用广泛。
随着聚丙烯应用领域的扩大和使用量的增加，废旧聚丙烯也与日俱增，废旧聚丙烯发生老化降解，其物理性能远不及新料聚丙烯，它的应用也受到了极大的限制，只能用于制作低性能的产品。可废旧聚丙烯的再生使用，更有利于塑料行业的可持续发展，将废旧聚丙烯再生用于制造聚丙烯管材，既能满足市场对聚丙烯管材的需求，又能解决环境问题，节约资源，因此废旧聚丙烯回收改性技术是解决以上问题的根本。
回收PP需要一种优异性能的交联剂对其改性，因此我们合成了一种含L-POSS的硅烷交联剂对其改性。L-POSS是一种具有梯形结构的硅氧烷，其分子结构是以Si-O为无机内核，以含有键能较大的Si-O键和Si-C键连接形成的梯形网状分子结构构成，这种分子结构具有良好的耐高温和力学性能，其分子结构中的Si-H可与乙烯基硅烷交联剂中的乙烯基结合形成含L-POSS的硅烷交联剂，由于这种交联剂同时含有L-POSS和硅烷成份，因此这是一种兼具两者性能的交联剂，即同时具有耐高温和交联性能的新型交联剂，满足对PP进行改性回收。
发明内容
本发明的目的在于提供一种含有L-POSS交联剂的同质异构交联法改性回收PP及其制备方法，本发明通过用含有L-POSS交联剂的同质异构交联法改性回收PP，从而达到提高回收PP力学性能的目的，其工艺操作简单且可以将回收塑料进行大批量生产，满足市场的工业化要求和可持续发展。
本发明的目的是通过以下技术方案实现的：
一种含有L-POSS交联剂的同质异构交联法改性回收PP，含有L-POSS硅烷交联剂的结构式如下：
。
一种含有L-POSS交联剂的同质异构交联法改性回收PP，按质量重量份计，包括有：
回收PP 100份；
增韧剂 3 ～10份；
交联母料 10 ～30份；
无机填料 5 ～10份。
所述的一种含有L-POSS交联剂的同质异构交联法改性回收PP,所述的交联母料是由A料B料和产水剂三部分组成；
A料成份: PP
含L-POSS硅烷交联剂 ；
引发剂（过氧化二异丙苯（DCP））；
B料成份： PP
催化剂（二月桂酸二丁基锡）；
抗氧剂（抗氧剂1010）；
产水剂成份：酸和金属氧化物以（1：1）比例混合。
所述的一种含有L-POSS交联剂的同质异构交联法改性回收PP,所述的L-POSS硅烷交联剂是用L—POSS与乙烯基三甲氧基硅烷发生加成聚合反应的方法，合成出的硅烷衍生物；无机填料为碳酸钙、滑石粉中的至少一种，优选碳酸钙；引发剂为过氧化苯甲酰（BPO）和过氧化二异丙苯（DCP）中的至少一种，优选过氧化二异丙苯。
所述的一种含有L-POSS交联剂的同质异构交联法改性回收PP,所述的增韧剂为POE、聚醋酸乙烯乳液、聚乙烯醇中的至少一种，优选POE；抗氧剂为抗氧剂1010、抗氧剂1076中的至少一种，优选抗氧剂1010；催化剂为二月桂酸二丁基锡、三乙胺、三正丙胺、三正丁胺、N,N- 二甲基丁胺中至少一种，优选二月桂酸二丁基锡；产水剂为酸和金属氧化物以一定比例混合，优选硬脂酸和氧化锌。
一种含L-POSS交联剂的同质异构交联法改性回收PP的制备方法，包括以下步骤：
A、按质量分数称取95份A料，4.5份B料混合后放入双螺杆挤出机中挤出造粒，然后再与0.5份产水剂混合均匀放入双螺杆挤出机中挤出造粒形成微交联母料；
B、将A部中的微交联母料先放入万能粉碎机再放入行星式球磨机中研磨直至交联料的粒径达到10～50μm为止；
C、将回收PP在80℃条件下鼓风干燥3～4 小时，按重量配比将微交联母料、增韧剂、回收PP、无机填料投入到高速混合机中高速混合4～6 分钟，使其均匀混合；
D、将上述高速混合机中混合均匀的物料加入到螺杆长径比为36，转速为200r/min的双螺杆挤出机中，在熔融状态下利用双螺杆的强剪切力将微交联母料的平均粒径控制在10～50μm，同时将交联料、增韧剂、回收PP以及无机填料混合均匀，将上述混合料挤出造粒得到再生PP。
所述的一种含L-POSS交联剂的同质异构交联法改性回收PP的制备方法，所述双螺杆挤出机的螺杆温度控制在160℃-230℃之间。
本发明的优点与效果是：
本发明增强增韧改性是改善塑料力学性能的一种有效途径，其工艺操作简单且可以将回收塑料进行大批量生产，满足市场的工业化要求和可持续发展，因此，针对现有技术的缺陷本方法通过用含有L-POSS交联剂的同质异构交联法改性回收PP，从而达到提高回收PP力学性能的目的。
附图说明
图1为L-POSS与乙烯基三甲氧基硅烷反应合成出新型交联剂的方程式。
具体实施方式
下面结合实施例对本发明进行详细说明。
实施例1-3，各实施例中各组份的重量分配比如表1 所示。把各组份按配比称取，于高速搅拌机中混合5 分钟，出料，将混合料的原料置于双螺杆挤出机中造料，挤出机温度控制在160℃-230℃之间，转速为200r/min。制备样条，按相应的标准测试（见表2），性能结果见表3。
表1 ：实施例1-3 的配方组成(份）
表2 ：力学性能测试标准
表3 ：实施例1 －3 中PP回料的力学性能测试
从表3 实施例1-3 以及对比例1的性能测试结果，我们可知：在没使用微交联母料的时候，其它改性助剂的加入在提高回收PP冲击性能的同时会降低材料的拉伸性能，而把制得的微交联母料的粒径粉碎到10～50μm后再将交联料与回收PP、增韧剂、无机填料等投入到大长径比的双螺杆挤出机中剪切混合，这种方法在提高回收PP韧性的同时也可以提高其拉伸性能，实现了同质异构交联法对回收PP同时进行增韧、增强改性的效果。
以上通过具体实施例对本发明进行了进一步说明，不过这些实施例仅是范例性的，并不对本发明的保护范围构成任何限制。本领域技术人员理解，在不超出本发明的精神和保护范围的情况下，可以对本发明的技术方案及其实施方式进行多种等价替换、修饰或改进，这些均应落入本发明的保护范围内。本发明的保护范围以所附的权利要求为准。
Claims (5)
1.一种含有L-POSS交联剂的同质异构交联法改性回收PP，其特征在于，含有L-POSS交联剂的结构式如下：
；
含有L-POSS交联剂的同质异构交联法改性回收PP按重量份计算原料组成及含量如下：
回收PP 100份；
增韧剂 3 ～10份；
交联母料 10 ～30份；
无机填料 5 ～10份；
所述的交联母料是由A料、B料和产水剂三部分组成；
A料成份: PP
含L-POSS交联剂 ；
引发剂，所述的引发剂为过氧化二异丙苯DCP；
B料成份： PP
催化剂，所述的催化剂为二月桂酸二丁基锡；
抗氧剂，所述的抗氧剂为抗氧剂1010；
产水剂成份：酸和金属氧化物以1：1比例混合。
2.根据权利要求1所述的一种含有L-POSS交联剂的同质异构交联法改性回收PP, 其特征在于，所述的L-POSS交联剂是用L-POSS与乙烯基三甲氧基硅烷发生加成聚合反应的方法，合成出的硅烷衍生物；无机填料为碳酸钙、滑石粉中的至少一种。
3.根据权利要求1所述的一种含有L-POSS交联剂的同质异构交联法改性回收PP, 其特征在于，所述的增韧剂为POE、聚醋酸乙烯乳液、聚乙烯醇中的至少一种。
4.根据权利要求1所述的一种含L-POSS交联剂的同质异构交联法改性回收PP的制备方法，其特征在于，包括以下步骤：
A、按质量份数称取95份A料，4.5份B料混合后放入双螺杆挤出机中挤出造粒，然后再与0.5份产水剂混合均匀放入双螺杆挤出机中挤出造粒形成交联母料；
B、将A步中的交联母料先放入万能粉碎机再放入行星式球磨机中研磨直至交联母料的粒径达到10～50μm为止；
C、将回收PP在80℃条件下鼓风干燥3～4 小时，按重量配比将交联母料、增韧剂、回收PP、无机填料投入到高速混合机中高速混合4～6 分钟，使其均匀混合；
D、将上述高速混合机中混合均匀的物料加入到螺杆长径比为36，转速为200r/min的双螺杆挤出机中，在熔融状态下利用双螺杆的强剪切力将交联母料的平均粒径控制在10～50μm，同时将交联母料、增韧剂、回收PP以及无机填料混合均匀，将上述混合料挤出造粒得到含L-POSS交联剂的同质异构交联法改性回收PP。
5.根据权利要求4所述的一种含L-POSS交联剂的同质异构交联法改性回收PP的制备方法，其特征在于：所述双螺杆挤出机的螺杆温度控制在160℃-230℃之间。
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