CN117384423B - 一种新型氟弹性体加工助剂及制备工艺 - Google Patents
一种新型氟弹性体加工助剂及制备工艺 Download PDFInfo
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Abstract
本发明涉及氟弹性体加工助剂技术领域,且公开了一种新型氟弹性体加工助剂及制备工艺,包括以下重量组分的原料:30‑50重量份的新型氟弹性体、10‑20重量份的硅氧烷、8‑12重量份的填料、5‑8重量份的硅藻土;本发明通过将新型氟弹性体、硅氧烷、氧化硅、硅藻土,加入双螺旋挤出机中,将挤出物进行粉碎,丙酮提取,过滤、干燥,得到新型氟弹性体加工助剂,消除和改善LLDPE熔体破裂的问题,改善制品表面光洁度。
Description
技术领域
本发明涉及氟弹性体加工助剂技术领域,具体为一种新型氟弹性体加工助剂及制备工艺。
背景技术
塑胶产品在满足产品结构力学特性的同时,在挤出和成形生产加工过程中经常会碰到一些问题,这些问题包含:汇聚物堆积在模头的孔口处、在开展挤出过程中高的背压,及其因为高挤出环境温度造成的汇聚物的过度溶解或低的熔体强度。这些问题使挤出加工工艺减慢,或是必须终止加工工艺来清理设备含氟汇聚物生产加工助剂能够处理这些问题。
近年来,随着聚烯烃和工程热塑性树脂应用领域的扩展,对聚烯烃和工程热塑性树脂加工助剂的研究和产品日趋增多,促进新颖、高效的加工助剂迅速发展。含氟聚合物加工助剂是新的一代加工助剂,它是由氟聚合物弹性体改进而来的,具有优异的改善加工性能的能力,如文献《氟弹性体加工助剂对LLDPE薄膜性能的影响》报道了在线型低密度聚乙烯(LLDPE)树脂中添加一定量的氟弹性体加工助剂(PPA)进行造粒、吹膜,在LLDPE中添加PPA,由于PPA在机筒、螺杆、机头等熔体通道的表面形成润滑层避免了设备缺陷给熔体表面带来的伤害,本发明采用氟性单体和乙烯醇形成共聚物,再和4-三氟甲氧基苄胺改性马来酸酐反应得到新型氟弹体,具有较好的润滑,推迟鲨鱼皮熔体破裂的效果。
发明内容
(一)解决的技术问题
针对现有技术的不足,本发明提供了一种新型氟弹性体加工助剂及制备工艺,解决了LLDPE熔体破裂,制品表面不光洁的问题。
(二)技术方案
为实现上述目的,本发明提供以下技术方案:一种新型氟弹性体加工助剂,所述包括以下重量组分的原料:30-50重量份的新型氟弹性体、10-20重量份的硅氧烷、8-12重量份的填料、5-8重量份的硅藻土。
优选的,所述新型氟弹性体的制备方法为:
(1)向N,N-二甲基甲酰胺溶剂中加入10-15重量份的氟弹性体进行溶解,溶解结束后向其加入5-10重量份的乙烯醇搅拌均匀,缓慢滴加1-3重量份的偶氮二异丁腈引发剂,在60-80℃下反应3-6h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到氟弹性体-乙烯醇聚合物;
(2)将氟弹性体-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加二丁基二月桂酸锡催化剂,在90-120℃下反应2-4h,反应后转移到丙酮中沉析4-6h,洗涤、过滤、干燥,得到新型氟弹体。
优选的,所述(1)中氟弹性体为四氟乙烯、六氟乙烯、六氟丙烯、偏二氟乙烯中的任一种。
优选的,所述(2)中氟弹性体-乙烯醇聚合物、4-三氟甲氧基苄胺改性马来酸酐、二丁基二月桂酸锡的重量比为1.2-1.5:1:0.01-0.03。
优选的,所述(2)中4-三氟甲氧基苄胺改性马来酸酐的制备方法为:向N,N-二甲基甲酰胺溶剂中加入4-三氟甲氧基苄胺和马来酸酐,进行酰胺化反应,再60-100℃下反应6-12h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐。
优选的,所述4-三氟甲氧基苄胺和马来酸酐的重量比为2.1-2.5:1。
优选的,所述填料为氧化钙、氧化硅、二氧化硅、二氧化钛中的任一种。
优选的,所述包括以下步骤:将新型氟弹性体、硅氧烷、填料、硅藻土加入双螺旋挤出机中,挤出温度为180-200℃,挤出速度为30-50min,将挤出物进行粉碎,丙酮提取6-10h,过滤、干燥,得到新型氟弹性体加工助剂。
优选的,所述氟弹性体在LLDPE中的添加量为0-1000ppm;LLDPE临界剪切速率为265-1899s-1。
(三)有益的技术效果
本发明通过将新型氟弹性体、硅氧烷、氧化硅、硅藻土,加入双螺旋挤出机中,将挤出物进行粉碎,丙酮提取,过滤、干燥,得到新型氟弹性体加工助剂。
向N,N-二甲基甲酰胺溶剂中加入四氟乙烯进行溶解,溶解后向其加入乙烯醇搅拌均匀,缓慢滴加偶氮二异丁腈引发剂,得到四氟乙烯-乙烯醇聚合物;向N,N-二甲基甲酰胺溶剂中加入4-三氟甲氧基苄胺和马来酸酐,进行酰胺化反应,得到4-三氟甲氧基苄胺改性马来酸酐;将四氟乙烯-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解后加入4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加二丁基二月桂酸锡催化剂,得到新型氟弹体。
新型氟弹体加工助剂中的氟化物具有较低的表面能,应用在LLDPE中可以减少其树脂分子间的摩擦,氟聚合物会向熔体外部迁移并覆盖在挤出口模表面形成润滑层,在降低熔体粘度的同时,推迟鲨鱼皮熔体破裂,使其表面更光滑;新型氟弹体和LLDPE也具有较好的相容性,减少LLDPE的分解;本发明也提高了加工速率,降低机械消耗,增大生产安全。
附图说明
图1是新型氟弹体反应式。
具体实施方式
实施例1
(1)向N,N-二甲基甲酰胺溶剂中加入1g的四氟乙烯进行溶解,溶解结束后向其加入0.5g的乙烯醇搅拌均匀,缓慢滴加0.1g的偶氮二异丁腈引发剂,在60℃下反应3h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到四氟乙烯-乙烯醇聚合物;反应过程如下:
(2)向N,N-二甲基甲酰胺溶剂中加入2.1g的4-三氟甲氧基苄胺和1g的马来酸酐,进行酰胺化反应,再60℃下反应6h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐;
(3)将1.2g的四氟乙烯-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入1g的4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加0.01g的二丁基二月桂酸锡催化剂,在90℃下反应2h,反应后转移到丙酮中沉析4h,洗涤、过滤、干燥,得到新型氟弹体;
(4)将3g的新型氟弹性体、1g的硅氧烷、0.8g的氧化钙、0.5g的硅藻土,氟弹性体在LLDPE中的添加量为0ppm,LLDPE临界剪切速率为265s-1,加入双螺旋挤出机中,挤出温度为180℃,挤出速度为30min,将挤出物进行粉碎,丙酮提取6h,过滤、干燥,得到新型氟弹性体加工助剂。
实施例2
(1)向N,N-二甲基甲酰胺溶剂中加入1.5g的六氟乙烯进行溶解,溶解结束后向其加入1g的乙烯醇搅拌均匀,缓慢滴加0.3g的偶氮二异丁腈引发剂,在80℃下反应6h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到六氟乙烯-乙烯醇聚合物;
(2)向N,N-二甲基甲酰胺溶剂中加入5g的4-三氟甲氧基苄胺和2g的马来酸酐,进行酰胺化反应,再100℃下反应12h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐;
(3)将3g的六氟乙烯-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入2g的4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加0.06g的二丁基二月桂酸锡催化剂,在120℃下反应4h,反应后转移到丙酮中沉析6h,洗涤、过滤、干燥,得到新型氟弹体;
(4)将5g的新型氟弹性体、2g的硅氧烷、1.2g的氧化硅、0.8g的硅藻土,氟弹性体在LLDPE中的添加量为1000ppm,LLDPE临界剪切速率为1899s-1,加入双螺旋挤出机中,挤出温度为200℃,挤出速度为50min,将挤出物进行粉碎,丙酮提取10h,过滤、干燥,得到新型氟弹性体加工助剂。
实施例3
(1)向N,N-二甲基甲酰胺溶剂中加入1.25g的六氟丙烯进行溶解,溶解结束后向其加入0.75g的乙烯醇搅拌均匀,缓慢滴加0.2g的偶氮二异丁腈引发剂,在70℃下反应4.5h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到六氟丙烯-乙烯醇聚合物;
(2)向N,N-二甲基甲酰胺溶剂中加入3.55g的4-三氟甲氧基苄胺和1.5g的马来酸酐,进行酰胺化反应,再80℃下反应9h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐;
(3)将2.1g的六氟丙烯-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入1.5g的4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加0.035g的二丁基二月桂酸锡催化剂,在105℃下反应3h,反应后转移到丙酮中沉析5h,洗涤、过滤、干燥,得到新型氟弹体;
(4)将4g的新型氟弹性体、1.5g的硅氧烷、1.0g的二氧化硅、0.65g的硅藻土,氟弹性体在LLDPE中的添加量为500ppm,LLDPE临界剪切速率为825s-1,加入双螺旋挤出机中,挤出温度为190℃,挤出速度为40min,将挤出物进行粉碎,丙酮提取8h,过滤、干燥,得到新型氟弹性体加工助剂。
实施例4
(1)向N,N-二甲基甲酰胺溶剂中加入1g的四氟乙烯进行溶解,溶解结束后向其加入0.5g的乙烯醇搅拌均匀,缓慢滴加0.1g的偶氮二异丁腈引发剂,在60℃下反应3h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到四氟乙烯-乙烯醇聚合物;
(2)向N,N-二甲基甲酰胺溶剂中加入2.1g的4-三氟甲氧基苄胺和1g的马来酸酐,进行酰胺化反应,再60℃下反应6h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐;
(3)将3g的六氟乙烯-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入2g的4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加0.06g的二丁基二月桂酸锡催化剂,在120℃下反应4h,反应后转移到丙酮中沉析6h,洗涤、过滤、干燥,得到新型氟弹体;
(4)将4g的新型氟弹性体、1.5g的硅氧烷、1.0g的二氧化硅、0.65g的硅藻土,氟弹性体在LLDPE中的添加量为500ppm,LLDPE临界剪切速率为825s-1,加入双螺旋挤出机中,挤出温度为190℃,挤出速度为40min,将挤出物进行粉碎,丙酮提取8h,过滤、干燥,得到新型氟弹性体加工助剂。
实施例5
(1)向N,N-二甲基甲酰胺溶剂中加入1.5g的六氟乙烯进行溶解,溶解结束后向其加入1g的乙烯醇搅拌均匀,缓慢滴加0.3g的偶氮二异丁腈引发剂,在80℃下反应6h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到六氟乙烯-乙烯醇聚合物;
(2)向N,N-二甲基甲酰胺溶剂中加入5g的4-三氟甲氧基苄胺和2g的马来酸酐,进行酰胺化反应,再100℃下反应12h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐;
(3)将2.1g的六氟丙烯-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入1.5g的4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加0.035g的二丁基二月桂酸锡催化剂,在105℃下反应3h,反应后转移到丙酮中沉析5h,洗涤、过滤、干燥,得到新型氟弹体;
(4)将3g的新型氟弹性体、1g的硅氧烷、0.8g的氧化钙、0.5g的硅藻土,氟弹性体在LLDPE中的添加量为200ppm,LLDPE临界剪切速率为450s-1,加入双螺旋挤出机中,挤出温度为180℃,挤出速度为30min,将挤出物进行粉碎,丙酮提取6h,过滤、干燥,得到新型氟弹性体加工助剂。
实施例6
(1)向N,N-二甲基甲酰胺溶剂中加入1.25g的六氟丙烯进行溶解,溶解结束后向其加入0.75g的乙烯醇搅拌均匀,缓慢滴加0.2g的偶氮二异丁腈引发剂,在70℃下反应4.5h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到六氟丙烯-乙烯醇聚合物;
(2)向N,N-二甲基甲酰胺溶剂中加入3.55g的4-三氟甲氧基苄胺和1.5g的马来酸酐,进行酰胺化反应,再80℃下反应9h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐;
(3)将1.2g的四氟乙烯-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入1g的4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加0.01g的二丁基二月桂酸锡催化剂,在90℃下反应2h,反应后转移到丙酮中沉析4h,洗涤、过滤、干燥,得到新型氟弹体;
(4)将5g的新型氟弹性体、2g的硅氧烷、1.2g的氧化硅、0.8g的硅藻土,氟弹性体在LLDPE中的添加量为800ppm,LLDPE临界剪切速率为1625s-1,加入双螺旋挤出机中,挤出温度为200℃,挤出速度为50min,将挤出物进行粉碎,丙酮提取10h,过滤、干燥,得到新型氟弹性体加工助剂。
对比例1
(1)将5g的氟弹性体、2g的硅氧烷、1.2g的氧化硅、0.8g的硅藻土,氟弹性体在LLDPE中的添加量为1000ppm,LLDPE临界剪切速率为1899s-1,加入双螺旋挤出机中,挤出温度为200℃,挤出速度为50min,将挤出物进行粉碎,丙酮提取10h,过滤、干燥,得到新型氟弹性体加工助剂。
采用实施例1-5和对比例1的新型氟弹性体加工助剂和LLDPE进行混合,在哈克流变仪上进行挤出试验,挤出时间与挤出扭矩、机头压力、熔体破裂现象测试结果如表1。
表1
由表1可知,本发明实施例1-5相较于对比例1的应用在LLDPE效果较好。
以上公开的本发明优选实施例只是用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节,也不限制该发明仅为所述的具体实施方式。显然,根据本说明书的内容,可作很多的修改和变化。本说明书选取并具体描述这些实施例,是为了更好地解释本发明的原理和实际应用,从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。
Claims (8)
1.一种氟弹性体加工助剂,其特征在于,所述包括以下重量组分的原料:30-50重量份的氟弹性体、10-20重量份的硅氧烷、8-12重量份的填料、5-8重量份的硅藻土;
所述氟弹性体的制备方法为:
(1)向N,N-二甲基甲酰胺溶剂中加入10-15重量份的氟弹性体进行溶解,溶解结束后向其加入5-10重量份的乙烯醇搅拌均匀,缓慢滴加1-3重量份的偶氮二异丁腈引发剂,在60-80℃下反应3-6h,反应后减压蒸馏除去溶剂,丙酮和去离子水依次洗涤,过滤并干燥得到氟弹性体-乙烯醇聚合物;
(2)将氟弹性体-乙烯醇聚合物加入到甲苯溶剂中搅拌溶解,溶解结束后加入4-三氟甲氧基苄胺改性马来酸酐继续搅拌,再缓慢滴加二丁基二月桂酸锡催化剂,在90-120℃下反应2-4h,反应后转移到丙酮中沉析4-6h,洗涤、过滤、干燥,得到氟弹体。
2.根据权利要求1所述的氟弹性体加工助剂,其特征在于,所述(1)中氟弹性体为四氟乙烯、六氟乙烯、六氟丙烯、偏二氟乙烯中的任一种。
3.根据权利要求1所述的氟弹性体加工助剂,其特征在于,所述(2)中氟弹性体-乙烯醇聚合物、4-三氟甲氧基苄胺改性马来酸酐、二丁基二月桂酸锡的重量比为1.2-1.5:1:0.01-0.03。
4.根据权利要求1所述的氟弹性体加工助剂,其特征在于,所述(2)中4-三氟甲氧基苄胺改性马来酸酐的制备方法为:向N,N-二甲基甲酰胺溶剂中加入4-三氟甲氧基苄胺和马来酸酐,进行酰胺化反应,再60-100℃下反应6-12h,过滤溶剂,使用蒸馏水和乙醇洗涤,得到4-三氟甲氧基苄胺改性马来酸酐。
5.根据权利要求4所述的氟弹性体加工助剂,其特征在于,所述4-三氟甲氧基苄胺和马来酸酐的重量比为2.1-2.5:1。
6.根据权利要求1所述的氟弹性体加工助剂,其特征在于,所述填料为氧化钙、二氧化硅、二氧化钛中的任一种。
7.一种如权利要求1-6任一项所述的氟弹性体加工助剂的制备工艺,其特征在于,所述包括以下步骤:将所述氟弹性体、硅氧烷、填料、硅藻土加入双螺旋挤出机中,挤出温度为180-200℃,挤出时间为30-50min,将挤出物进行粉碎,丙酮提取6-10h,过滤、干燥,得到氟弹性体加工助剂。
8.根据权利要求7所述的氟弹性体加工助剂的制备工艺,其特征在于,所述氟弹性体在LLDPE中的添加量为0-1000ppm;LLDPE临界剪切速率为265-1899s-1。
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CN102399407A (zh) * | 2010-09-15 | 2012-04-04 | 中国石油天然气股份有限公司 | 一种改性含氟加工助剂的制备方法 |
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