CN103788492B - 一种三层结构的高韧性高透光聚烯烃薄膜的制备方法 - Google Patents
一种三层结构的高韧性高透光聚烯烃薄膜的制备方法 Download PDFInfo
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Abstract
本发明涉及了一种三层结构的高韧性高透光聚烯烃薄膜的制备方法,该方法以均聚聚丙烯和丙烯-乙烯嵌段共聚物为基本原料,添加乙烯-辛烯嵌段共聚物、乙烯-丙烯酸甲酯共聚物,通过物料混合、三层共挤成型工艺加工而成。其中表层配方:均聚PP52~60重量份,PPB40~48重量份;中间夹层配方:PPB50~57重量份,OBC40~45重量份,EMA3~5重量份。本方法制成的薄膜,其断裂伸长率>850%,拉伸断裂强度>29MPa,透光率>91%,雾度<5%,零下35℃条件下30天不脆裂,具有柔韧性佳、透光率高、长时间耐低温性能好、热封强度高等特点,特别适用于寒冷地区物品包装以及食品超低温冷冻包装。
Description
技术领域
本发明涉及功能性塑料薄膜的制备方法,具体的说是一种三层结构的高韧性高透光聚烯烃薄膜的制备方法。
背景技术
聚丙烯(PP)是当今五大塑料品种中发展速度最快之一。PP具有优良的刚度、透光性、耐溶剂性、无毒性、电绝缘性、加工性、可回收再利用等优点。PP薄膜无毒无味、透光率高、光泽性好,已广泛用于食品、糖果、冷冻面食、航空食品、茶叶、药品、卫生用品、文具、服装、日用品等包装。PP薄膜虽然具有优异的性能,但也存在一些不足之处,其中最突出的缺点是柔韧性差、低温脆性大,尤其在冬天寒冷地区以及食品超低温冷冻包装储存过程中经常发生PP薄膜脆裂现象,使其应用领域受到限制。
近年来,国内外一些研究单位和生产企业对PP进行增韧改性,主要方法有:①橡胶及热塑性弹性体增韧改性PP:采用顺丁橡胶(BR)、乙丙橡胶(EPR)、三元乙丙橡胶(EPDM)、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)、苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)等与PP共混改性,改善PP的球晶形态,形成以弹性体微粒状的“海岛”结构,提高PP共混材料的抗冲击强度和耐低温性能;②茂金属聚烯烃弹性体增韧改性PP:采用茂金属三元乙丙弹性体、茂金属线型低密度聚乙烯(mLLDPE)、茂金属低密度聚乙烯(mLDPE)与PP共混改性,提高PP共混材料的断裂伸长率和柔韧性;③无机刚性粒子增韧改性PP:采用微米级或亚纳米级碳酸钙、滑石粉、二氧化硅、高岭土、云母、硅灰石、硫酸钡等无机刚性粒子对PP进行增韧改性,提高PP共混材料的刚性和韧性;上述改性方法对提高PP薄膜制品的抗冲击强度和耐低温性能均起到不同程度的效果,但是,增韧改性后PP薄膜制品的透光率明显下降、雾度上升。检索大量的专利文献和公开发表的研究论文,尚未见采用均聚聚丙烯(均聚PP)和丙烯-乙烯嵌段共聚物(PPB)为基本原料,添加乙烯-辛烯嵌段共聚物(OBC)、乙烯-丙烯酸甲酯共聚物(EMA),通过三层共挤成型工艺制成三层结构的高韧性高透光聚烯烃薄膜的报道。
发明内容
为了克服目前PP薄膜制品存在柔韧性差、低温脆性大,增韧改性后PP薄膜制品存在透光率明显下降、雾度上升等缺陷,本发明提供了一种三层结构的高韧性高透光聚烯烃薄膜的制备方法,本方法以均聚聚丙烯(均聚PP)和丙烯-乙烯嵌段共聚物(PPB)为基本原料,添加乙烯-辛烯嵌段共聚物(OBC)、乙烯-丙烯酸甲酯共聚物(EMA),通过物料混合、三层共挤成型工艺加工而成具有“表层-中间夹层-表层”三层复合结构的高韧性高透光聚烯烃薄膜;所制备的薄膜表层由均聚聚丙烯(均聚PP)与丙烯-乙烯嵌段共聚物(PPB)共混塑化组成,中间夹层由丙烯-乙烯嵌段共聚物(PPB)、乙烯-辛烯嵌段共聚物(OBC)、乙烯-丙烯酸甲酯共聚物(EMA)共混塑化组成。
采用本方法制成的薄膜,其断裂伸长率>850%,拉伸断裂强度>29MPa,透光率>91%,雾度<5%,零下35℃条件下30天不脆裂,具有柔韧性佳、透光率高、长时间耐低温性能好、热封强度高等特点,特别适用于寒冷地区物品包装以及食品超低温冷冻包装。
为了实现本发明目的所采用的技术方案是:
材料与配方
表层:均聚聚丙烯(均聚PP)52~60重量份,丙烯-乙烯嵌段共聚物(PPB)40~48重量份;
中间夹层:丙烯-乙烯嵌段共聚物(PPB)50~57重量份,乙烯-辛烯嵌段共聚物(OBC)40~45重量份,乙烯-丙烯酸甲酯共聚物(EMA)3~5重量份。
制备方法
将均聚聚丙烯(均聚PP)、丙烯-乙烯嵌段共聚物(PPB)计量后置于搅拌机中,控制搅拌机转速250r/min,温度95±1℃,物料混合5min后等量置于三层共挤成型机的1#、2#表层挤出机组料斗中;将丙烯-乙烯嵌段共聚物(PPB)、乙烯-辛烯嵌段共聚物(OBC)、乙烯-丙烯酸甲酯共聚物(EMA)计量后置于搅拌机中,控制搅拌机转速250r/min,温度95±1℃,物料混合5min后置于三层共挤成型机的3#中间夹层挤出机组料斗中;控制1#、2#表层挤出机组料筒温度:Ⅰ区175~180℃、Ⅱ区182~186℃、Ⅲ区187~192℃、Ⅳ区193~196℃、Ⅴ区195~198℃、Ⅵ区197~200℃;控制3#中间夹层挤出机组料筒温度:Ⅰ区170~175℃、Ⅱ区176~182℃、Ⅲ区183~188℃、Ⅳ区190~193℃、Ⅴ区193~196℃、Ⅵ区195~198℃;控制连接法兰温度198~201℃、模头温度195~198℃;同步启动1#、2#、3#挤出机组,进行共挤、下吹、淋膜,制成具有“表层-中间夹层-表层”三层复合结构的高韧性高透光聚烯烃薄膜。
本发明所述的均聚聚丙烯(均聚PP),其熔体流动速率为7g/10min、密度为0.91g/cm3。
本发明所述的丙烯-乙烯嵌段共聚物(PPB)中乙烯的质量分数为12%、熔体流动速率为5g/10min。
本发明所述的乙烯-辛烯嵌段共聚物(OBC),其熔体流动速率为3.5g/10min、密度为0.877g/cm3。
本发明所述的乙烯-丙烯酸甲酯共聚物(EMA)中丙烯酸甲酯的质量分数为20%、熔体流动速率为4.5g/10min。
本发明的有益效果是:①设计薄膜表层由均聚PP与PPB共混塑化组成,使得薄膜表层既保持较好的刚性和透明性,又大幅度提高耐低温性能;②设计薄膜中间夹层由PPB、OBC、EMA共混塑化组成,OBC的加入,大幅度提高PPB/OBC共混材料的缺口冲击强度和断裂伸长率,相容剂EMA的加入,使得PPB与OBC两相间界面结合力增强,PPB/OBC/EMA共混材料的柔韧性和耐低温性能显著提高;③采用本方法制成的薄膜,其断裂伸长率>850%,拉伸断裂强度>29MPa,透光率>91%,雾度<5%,零下35℃条件下30天不脆裂,具有柔韧性佳、透光率高、长时间耐低温性能好、热封强度高等特点,特别适用于寒冷地区物品包装以及食品超低温冷冻包装。
具体实施方式
实施例1:
将熔体流动速率为7g/10min、密度为0.91g/cm3的均聚PP55kg及乙烯质量分数为12%、熔体流动速率为5g/10min的PPB45kg置于搅拌机中,控制搅拌机转速250r/min,温度95℃,物料混合5min后等量置于三层共挤成型机的1#、2#表层挤出机组料斗中;将乙烯质量分数为12%、熔体流动速率为5g/10min的PPB54kg,熔体流动速率为3.5g/10min、密度为0.877g/cm3的OBC42kg,丙烯酸甲酯质量分数为20%、熔体流动速率为4.5g/10min的EMA4kg置于搅拌机中,控制搅拌机转速250r/min,温度95℃,物料混合5min后置于三层共挤成型机的3#中间夹层挤出机组料斗中;控制1#、2#表层挤出机组料筒温度:Ⅰ区177℃、Ⅱ区184℃、Ⅲ区190℃、Ⅳ区195℃、Ⅴ区197℃、Ⅵ区198℃;控制3#中间夹层挤出机组料筒温度:Ⅰ区173℃、Ⅱ区179℃、Ⅲ区185℃、Ⅳ区192℃、Ⅴ区195℃、Ⅵ区197℃;控制连接法兰温度199℃、模头温度197℃;同步启动1#、2#、3#挤出机组,进行共挤、下吹、淋膜,制成具有“表层-中间夹层-表层”三层复合结构的高韧性高透光聚烯烃薄膜。
本实施例制成的薄膜测试结果:断裂伸长率(纵/横向)886%/935%,拉伸断裂强度(纵/横向)31.5MPa/30.2MPa,透光率91.8%,雾度4.5%,零下35℃条件下30天不脆裂。
实施例2:
将熔体流动速率为7g/10min、密度为0.91g/cm3的均聚PP52kg及乙烯质量分数为12%、熔体流动速率为5g/10min的PPB48kg置于搅拌机中,控制搅拌机转速250r/min,温度94℃,物料混合5min后等量置于三层共挤成型机的1#、2#表层挤出机组料斗中;将乙烯质量分数为12%、熔体流动速率为5g/10min的PPB50kg,熔体流动速率为3.5g/10min、密度为0.877g/cm3的OBC45kg,丙烯酸甲酯质量分数为20%、熔体流动速率为4.5g/10min的EMA5kg置于搅拌机中,控制搅拌机转速250r/min,温度96℃,物料混合5min后置于三层共挤成型机的3#中间夹层挤出机组料斗中;控制1#、2#表层挤出机组料筒温度:Ⅰ区175℃、Ⅱ区182℃、Ⅲ区187℃、Ⅳ区193℃、Ⅴ区195℃、Ⅵ区197℃;控制3#中间夹层挤出机组料筒温度:Ⅰ区170℃、Ⅱ区176℃、Ⅲ区183℃、Ⅳ区190℃、Ⅴ区193℃、Ⅵ区195℃;控制连接法兰温度198℃、模头温度195℃;同步启动1#、2#、3#挤出机组,进行共挤、下吹、淋膜,制成具有“表层-中间夹层-表层”三层复合结构的高韧性高透光聚烯烃薄膜。
本实施例制成的薄膜测试结果:断裂伸长率(纵/横向)917%/963%,拉伸断裂强度(纵/横向)30.8MPa/29.7MPa,透光率91.5%,雾度4.7%,零下35℃条件下30天不脆裂。
实施例3:
将熔体流动速率为7g/10min、密度为0.91g/cm3的均聚PP60kg及乙烯质量分数为12%、熔体流动速率为5g/10min的PPB40kg置于搅拌机中,控制搅拌机转速250r/min,温度96℃,物料混合5min后等量置于三层共挤成型机的1#、2#表层挤出机组料斗中;将乙烯质量分数为12%、熔体流动速率为5g/10min的PPB57kg,熔体流动速率为3.5g/10min、密度为0.877g/cm3的OBC40kg,丙烯酸甲酯质量分数为20%、熔体流动速率为4.5g/10min的EMA3kg置于搅拌机中,控制搅拌机转速250r/min,温度94℃,物料混合5min后置于三层共挤成型机的3#中间夹层挤出机组料斗中;控制1#、2#表层挤出机组料筒温度:Ⅰ区180℃、Ⅱ区186℃、Ⅲ区192℃、Ⅳ区196℃、Ⅴ区198℃、Ⅵ区200℃;控制3#中间夹层挤出机组料筒温度:Ⅰ区175℃、Ⅱ区182℃、Ⅲ区188℃、Ⅳ区193℃、Ⅴ区196℃、Ⅵ区198℃;控制连接法兰温度201℃、模头温度198℃;同步启动1#、2#、3#挤出机组,进行共挤、下吹、淋膜,制成具有“表层-中间夹层-表层”三层复合结构的高韧性高透光聚烯烃薄膜。
本实施例制成的薄膜测试结果:断裂伸长率(纵/横向)873%/918%,拉伸断裂强度(纵/横向)32.3MPa/30.9MPa,透光率92.0%,雾度4.2%,零下35℃条件下30天不脆裂。
Claims (5)
1.一种三层结构的高韧性高透光聚烯烃薄膜的制备方法,其特征是:
配方
表层:均聚聚丙烯52~60重量份,丙烯-乙烯嵌段共聚物40~48重量份;
中间夹层:丙烯-乙烯嵌段共聚物50~57重量份,乙烯-辛烯嵌段共聚物40~45重量份,乙烯-丙烯酸甲酯共聚物3~5重量份;
制备方法
将均聚聚丙烯、丙烯-乙烯嵌段共聚物计量后置于搅拌机中,控制搅拌机转速250r/min,温度95±1℃,物料混合5min后等量置于三层共挤成型机的1#、2#表层挤出机组料斗中;将丙烯-乙烯嵌段共聚物、乙烯-辛烯嵌段共聚物、乙烯-丙烯酸甲酯共聚物计量后置于搅拌机中,控制搅拌机转速250r/min,温度95±1℃,物料混合5min后置于三层共挤成型机的3#中间夹层挤出机组料斗中;控制1#、2#表层挤出机组料筒温度:Ⅰ区175~180℃、Ⅱ区182~186℃、Ⅲ区187~192℃、Ⅳ区193~196℃、Ⅴ区195~198℃、Ⅵ区197~200℃;控制3#中间夹层挤出机组料筒温度:Ⅰ区170~175℃、Ⅱ区176~182℃、Ⅲ区183~188℃、Ⅳ区190~193℃、Ⅴ区193~196℃、Ⅵ区195~198℃;控制连接法兰温度198~201℃、模头温度195~198℃;同步启动1#、2#、3#挤出机组,进行共挤、下吹、淋膜,制成具有“表层-中间夹层-表层”三层复合结构的高韧性高透光聚烯烃薄膜。
2.根据权利要求1所述的三层结构的高韧性高透光聚烯烃薄膜的制备方法,其特征是所述的均聚聚丙烯,其熔体流动速率为7g/10min、密度为0.91g/cm3。
3.根据权利要求1所述的三层结构的高韧性高透光聚烯烃薄膜的制备方法,其特征是所述的丙烯-乙烯嵌段共聚物中乙烯的质量分数为12%、熔体流动速率为5g/10min。
4.根据权利要求1所述的三层结构的高韧性高透光聚烯烃薄膜的制备方法,其特征是所述的乙烯-辛烯嵌段共聚物,其熔体流动速率为3.5g/10min、密度为0.877g/cm3。
5.根据权利要求1所述的三层结构的高韧性高透光聚烯烃薄膜的制备方法,其特征是所述的乙烯-丙烯酸甲酯共聚物中丙烯酸甲酯的质量分数为20%、熔体流动速率为4.5g/10min。
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Effective date of registration: 20191106 Address after: 362000 first and third floor, AIII building, Central Industrial Zone, Quangang District, Quanzhou City, Fujian Province Patentee after: QUANZHOU QUANGANG DINGXIN COMMODITY CO.,LTD. Address before: 350108 science and Technology Department, Fujian Normal University, Fuzhou Town, Minhou County, Fujian Patentee before: Fujian Normal University |
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CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 |