CN101402711A - 三元乙丙橡胶接枝马来酸酐的方法 - Google Patents
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Abstract
本发明是一种三元乙丙橡胶接枝马来酸酐的方法，其特征在于，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM－g－MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为15－33∶1，挤出机转速为30－180转/分，挤出机模口温度为60－180℃。本发明方法可使三元乙丙橡胶(EPDM)不发生凝胶，有利于它与极性聚合物(工程塑料)的相容；接枝产物的接枝率高，可达到1.2－3.6％；采用辐射接枝无环境污染，节约能源，降低生产成本可达30％左右。
Description
技术领域
本发明涉及一种三元乙丙橡胶的改性方法，特别是一种三元乙丙橡胶接枝马来酸酐的方法。
背景技术
三元乙丙橡胶(EPDM)具有优良的物理化学性能，在工程塑料增韧和抗臭氧老化等方面的应用十分突出。但是，由于三元乙丙橡胶(EPDM)属于非极性橡胶，难于与极性聚合物共混。因此对三元乙丙橡胶(EPDM)进行改性以增强其与极性聚合物的相容性显得尤为重要。
发明内容
本发明所要解决的技术问题是针对现有技术的不足，提供一种新的、有效增强三元乙丙橡胶与极性聚合物相容性的三元乙丙橡胶接枝马来酸酐的方法。
本发明所要解决的技术问题是通过以下的技术方案来实现的。本发明是一种三元乙丙橡胶接枝马来酸酐的方法，其特点是，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为15-33∶1，挤出机转速为30-180转/分，挤出机模口温度为60-180℃。
在以上所述的本发明技术方案中：
1、所述的增塑剂可以选用常规的增塑剂，优选芳烃油、环烷烃油、苯二甲酸酯类或脂肪酸酯类增塑剂。
2、所述的补强剂也可以选用常规的补强剂，优选炭黑、白炭黑、碳酸钙、高岭土或滑石粉。
3、所述的硫化延迟剂优选水杨酸、N-环己基硫代邻苯二甲酰亚胺或N-吗啉硫化邻苯二甲酰亚胺。
4、进行高能射线辐射时所述的高能射线可以为现有技术中任何一种高能射线，优选辐射源为钴Co60或电子加速器产生的γ射线。
5、原料三元乙丙橡胶、马来酸酐、增塑剂、补强剂与硫化延迟剂的重量比可以采用任何常规比例；优选：三元乙丙橡胶占原料重总量的90-30％，马来酸酐、增塑剂、补强剂和硫化延迟剂占原料总重量的10-70％；其中，马来酸酐、增塑剂、补强剂和硫化延迟剂之间可以采用任意比例。
本发明在三元乙丙橡胶(EPDM)接枝马来酸酐(MAH)的反应中，由于不加入硫化剂而加入硫化延迟剂，且采用辐射接枝的技术，可以有效地防止三元乙丙橡胶(EPDM)在马来酸酐(MAH)活性基团的作用，防止过度产生交联而造成的凝胶现象。经发明人按现有技术中的常规方法进行测定以及按常规方法进行检验与试验，发现本发明方法与现有技术相比的优点在于：它使三元乙丙橡胶(EPDM)不发生凝胶，有利于它与极性聚合物(工程塑料)的相容；接枝产物的接枝率高，可达到1.2-3.6％；采用辐射接枝无环境污染，节约能源，降低生产成本可达30％左右。
具体实施方式
以下进一步描述本发明的具体技术方案，以便于本领域的技术人员进一步地理解本发明，而不构成对其权利的限制。
实施例1。一种三元乙丙橡胶接枝马来酸酐的方法，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为15∶1，挤出机转速为30转/分，挤出机模口温度为60℃。
实施例2。一种三元乙丙橡胶接枝马来酸酐的方法，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为33∶1，挤出机转速为180转/分，挤出机模口温度为180℃。
实施例3。一种三元乙丙橡胶接枝马来酸酐的方法，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为20∶1，挤出机转速为70转/分，挤出机模口温度为100℃。
在本实施例中，增塑剂为脂肪酸酯类增塑剂；补强剂为滑石粉；硫化延迟剂为水杨酸；所述的辐射源为钴Co60或电子加速器产生的γ射线；三元乙丙橡胶占原料重总量的50％，马来酸酐、增塑剂、补强剂和硫化延迟剂占原料总重量的50％。
实施例4。一种三元乙丙橡胶接枝马来酸酐的方法，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为25∶1，挤出机转速为120转/分，挤出机模口温度为120℃。
在本实施例中，增塑剂为苯二甲酸酯类增塑剂；补强剂为碳酸钙或高岭土；硫化延迟剂为N-吗啉硫化邻苯二甲酰亚胺；三元乙丙橡胶占原料重总量的60％，马来酸酐、增塑剂、补强剂和硫化延迟剂占原料总重量的40％。
实施例5。一种三元乙丙橡胶接枝马来酸酐的方法，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为28∶1，挤出机转速为150转/分，挤出机模口温度为150℃。
在本实施例中，增塑剂为环烷烃油；补强剂为白炭黑；硫化延迟剂为N-环己基硫代邻苯二甲酰亚胺；所述的辐射源为钴Co60或电子加速器产生的γ射线；三元乙丙橡胶占原料重总量的30％，马来酸酐、增塑剂、补强剂和硫化延迟剂占原料总重量的70％。
实施例6。一种三元乙丙橡胶接枝马来酸酐的方法，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为30∶1，挤出机转速为50转/分，挤出机模口温度为70℃。
在本实施例中，增塑剂为芳烃油；补强剂为炭黑；硫化延迟剂为水杨酸；所述的辐射源为钴Co60或电子加速器产生的γ射线；三元乙丙橡胶占原料重总量的90％，马来酸酐、增塑剂、补强剂和硫化延迟剂占原料总重量的10％。
Claims (6)
1、一种三元乙丙橡胶接枝马来酸酐的方法，其特征在于，它以三元乙丙橡胶为原料，以马来酸酐作接枝单体，加入增塑剂、补强剂和硫化延迟剂，混合均匀后将混合物投入挤出机熔融共混剂出造粒，制得三元乙丙橡胶与马来酸酐的接枝物EPDM-g-MAH；在混合物熔融剂出前通过辐射源对其进行高能射线辐射；造粒时，挤出机的螺杆长径比为15-33∶1，挤出机转速为30-180转/分，挤出机模口温度为60-180℃。
2、根据权利要求1所述的方法，其特征在于，所述的增塑剂选自芳烃油、环烷烃油、苯二甲酸酯类或脂肪酸酯类增塑剂。
3、根据权利要求1所述的方法，其特征在于，所述的补强剂选自炭黑、白炭黑、碳酸钙、高岭土或滑石粉。
4、根据权利要求1所述的方法，其特征在于，所述的硫化延迟剂选自水杨酸、N-环己基硫代邻苯二甲酰亚胺或N-吗啉硫化邻苯二甲酰亚胺。
5、根据权利要求1所述的方法，其特征在于，所述的辐射源为钴Co60或电子加速器产生的γ射线。
6、根据权利要求1所述的方法，其特征在于，三元乙丙橡胶占原料重总量的90-30％，马来酸酐、增塑剂、补强剂和硫化延迟剂占原料总重量的10-70％。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167889A (zh) * | 2010-02-26 | 2011-08-31 | 张万鹏 | 乙丙橡胶接枝马来酸酐改性聚酯增韧母料及其制法 |
| CN102167888A (zh) * | 2010-02-26 | 2011-08-31 | 张万鹏 | 乙丙橡胶接枝马来酸酐改性聚酯板材及其制法 |
| CN102786632A (zh) * | 2012-07-17 | 2012-11-21 | 山东东宏管业有限公司 | 一种用于钢丝网骨架聚乙烯复合管的粘接树脂 |
| CN108570128A (zh) * | 2017-03-10 | 2018-09-25 | 中国石油化工股份有限公司 | 一种改性三元乙丙橡胶及制备方法 |
| CN108570129A (zh) * | 2017-03-10 | 2018-09-25 | 中国石油化工股份有限公司 | 一种改性三元乙丙橡胶及制备方法 |
| CN109111550A (zh) * | 2018-07-11 | 2019-01-01 | 合肥远科服装设计有限公司 | 一种鞋底回收再生橡胶粉的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167889A (zh) * | 2010-02-26 | 2011-08-31 | 张万鹏 | 乙丙橡胶接枝马来酸酐改性聚酯增韧母料及其制法 |
| CN102167888A (zh) * | 2010-02-26 | 2011-08-31 | 张万鹏 | 乙丙橡胶接枝马来酸酐改性聚酯板材及其制法 |
| CN102786632A (zh) * | 2012-07-17 | 2012-11-21 | 山东东宏管业有限公司 | 一种用于钢丝网骨架聚乙烯复合管的粘接树脂 |
| CN108570128A (zh) * | 2017-03-10 | 2018-09-25 | 中国石油化工股份有限公司 | 一种改性三元乙丙橡胶及制备方法 |
| CN108570129A (zh) * | 2017-03-10 | 2018-09-25 | 中国石油化工股份有限公司 | 一种改性三元乙丙橡胶及制备方法 |
| CN108570128B (zh) * | 2017-03-10 | 2020-10-23 | 中国石油化工股份有限公司 | 一种改性三元乙丙橡胶及制备方法 |
| CN108570129B (zh) * | 2017-03-10 | 2020-10-23 | 中国石油化工股份有限公司 | 一种改性三元乙丙橡胶及制备方法 |
| CN109111550A (zh) * | 2018-07-11 | 2019-01-01 | 合肥远科服装设计有限公司 | 一种鞋底回收再生橡胶粉的制备方法 |
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