CN108822757B - 一种发泡体材料用低粘pet保护膜 - Google Patents
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Abstract
本发明提供一种发泡体材料用低粘PET保护膜,由PET基材层、低粘中间层以及保护层组成,其制备工艺简单、易操作,适合于工业化生产。第一,高性能低粘胶的扩链剂成酸性,酸性物质能抑制缩二脲的生成反应,进而抑制交联反应,粘性降低;第二,催化剂为温和的酸性离子液体,其催化活性较低,有效地抑制了其对异氰酸酯的亲核进攻,从而降低了异氰酸酯与大分子二元醇羟基反应的活性,与乳化剂有较好的协同效应,降低产品的粘性,提高了高性能低粘胶贮存稳定性能。因此,本发明提供的PET保护膜具有低粘、易撕取、不残胶、贴合性好、耐高温性好且力学性能优异的特点。
Description
技术领域
本发明涉及保护膜技术领域,具体涉及一种发泡体材料用低粘PET保护膜。
背景技术
保护膜已渗透入各行各业,例如仪器、仪表、电子、机械、建筑、汽车制造及标牌等行业,保护膜的应用,不仅改善了产品的外观质量、方便了材料加工,同时也提高了材料的利用率,降低了产品的生产成本。
发泡体材料是指以塑料、橡胶、弹性体、天然高分子材料等聚合物为基础而其内部具有无数气泡的微孔材料,也可以视为以气体为填料的复合材料。发泡体材料具有隔音、保温、降低营运成本和节能环保等优势,广泛应用于体育用品、电子、精密仪器、家电、汽车等领域。随着社会的发展和人们需求的提升,发泡体材料对保护膜的需求逐步增大,然而市面上的保护膜普遍存在着一些诸如不耐高温、不易撕取、残胶剩余、贴合性差和粘性不稳定等问题。
因此,制备低粘、易撕取、不残胶、贴合性好、耐高温性好且力学性能优异的发泡体材料用低粘PET保护膜对于保护膜行业具有重要意义。
发明内容
本发明的主要目的在于提供一种发泡体材料用低粘PET保护膜,具有低粘、易撕取、不残胶、贴合性好、耐高温性好、力学性能优异的特点。
为达到以上目的,本发明采用的技术方案为:
一种发泡体材料用低粘PET保护膜,由依次层叠的PET基材层、低粘中间层以及保护层组成,所述低粘中间层由高性能低粘胶形成,高性能低粘胶由20-80重量份大分子多元醇、3-10重量份异氰酸酯、2-5重量份扩链剂、0.5-2重量份成盐剂、4-10重量份催化剂、10-30重量份有机溶剂以及100-150重量份去离子水组成,所述扩链剂为羧酸型离子液体1-乙酸咪唑阳离子二羟甲基丙酸阴离子盐,所述催化剂为离子液体1-甲基-3-乙基咪唑溴盐。
优选的,所述PET基材层厚度为50-200μm。
优选的,所述保护层为PET薄膜,厚度为20-100μm。
优选的,所述高性能低粘胶按照如下方法制备:将大分子多元醇在100-120℃下真空脱水1-5h,再冷却至60-80℃;然后加入异氰酸酯、有机溶剂和催化剂,在500-1500r/min条件下恒温反应2-6h;加入扩链剂扩链反应1-5h,冷却至30-50℃;
然后加入成盐剂和去离子水,在1000-3000r/min条件下高速剪切分散0.5-2h,得到高性能低粘胶。
优选的,所述大分子多元醇为聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇中的一种或几种。
优选的,所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯和4,4’-二苯基甲烷二异氰酸酯中的一种或几种。
优选的,所述扩链剂按照如下方法制备:将咪唑-1-乙酸与乙酸乙酯混合配制成质量分数为30-50%的溶液,然后加入与咪唑-1-乙酸等摩尔的溴乙烷,在450-750r/min条件下搅拌加热升温至50-80℃后反应6-18h,得到中间体;向所述中间体中加入与咪唑-1-乙酸等摩尔的二羟甲基丙酸,在300-500r/min条件下搅拌加热升温至60-90℃后反应8-24h,离心洗涤得到扩链剂。
优选的,所述成盐剂为三乙胺、NaOH、KOH和氨水中的一种或几种。
优选的,所述有机溶剂为丙酮、丁酮、N-甲基吡咯烷酮和N,N-二甲基甲酰胺中的一种或几种。
优选的,所述催化剂按照如下方法制备:将摩尔比为1:1的甲基咪唑和溴乙烷在450-750r/min条件下搅拌加热升温至50-80℃后反应6-18h,用乙酸乙酯洗涤多次,得到催化剂。
本发明提供一种发泡体材料用低粘PET保护膜,由PET基材层、低粘中间层以及保护层组成,其制备工艺简单、易操作,适合于工业化生产。第一,高性能低粘胶的扩链剂成酸性,酸性物质能抑制缩二脲的生成反应,进而抑制交联反应,从而使交联度降低,粘性降低;第二,高性能低粘胶的催化剂为温和的酸性离子液体,其催化活性较低,有效地抑制了其对异氰酸酯的亲核进攻,从而降低了异氰酸酯与大分子二元醇羟基反应的活性,与乳化剂有较好的协同效应,降低产品的粘性;同时控制了反应体系的粘度,避免产生爆聚或凝胶,提高了高性能低粘胶贮存稳定性能。因此,本发明提供的PET保护膜具有低粘、易撕取、不残胶、贴合性好、耐高温性好且力学性能优异的特点,同时PET薄膜还具有优良的耐热、耐寒性、良好的耐化学药品性和耐油性。
具体实施方式
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例,本领域技术人员可以想到其他显而易见的变型。
本发明提供一种发泡体材料用低粘PET保护膜,由依次层叠的PET基材层、低粘中间层以及保护层组成,所述低粘中间层由高性能低粘胶形成,高性能低粘胶由20-80重量份大分子多元醇、3-10重量份异氰酸酯、2-5重量份扩链剂、0.5-2重量份成盐剂、4-10重量份催化剂、10-30重量份有机溶剂以及100-150重量份去离子水组成,所述扩链剂为羧酸型离子液体1-乙酸咪唑阳离子二羟甲基丙酸阴离子盐,所述催化剂为离子液体1-甲基-3-乙基咪唑溴盐。
作为优选方案,所述PET基材层厚度为50-200μm;所述保护层为PET薄膜,厚度为20-100μm。
作为优选方案,所述高性能低粘胶按照如下方法制备:将大分子多元醇在100-120℃下真空脱水1-5h,再冷却至60-80℃;然后加入异氰酸酯、有机溶剂和催化剂,在500-1500r/min条件下恒温反应2-6h;加入扩链剂扩链反应1-5h,冷却至30-50℃;然后加入成盐剂和去离子水,在1000-3000r/min条件下高速剪切分散0.5-2h,得到高性能低粘胶。
作为优选方案,所述大分子多元醇为聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇中的一种或几种。所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯和4,4’-二苯基甲烷二异氰酸酯中的一种或几种。
作为优选方案,所述扩链剂按照如下方法制备:将咪唑-1-乙酸与乙酸乙酯混合配制成质量分数为30-50%的溶液,然后加入与咪唑-1-乙酸等摩尔的溴乙烷,在450-750r/min条件下搅拌加热升温至50-80℃后反应6-18h,得到中间体;向所述中间体中加入与咪唑-1-乙酸等摩尔的二羟甲基丙酸,在300-500r/min条件下搅拌加热升温至60-90℃后反应8-24h,离心洗涤得到扩链剂。
扩链剂对对高性能低粘胶的制备起了重要作用,扩链剂成酸性,酸性物质能抑制缩二脲的生成反应,进而抑制交联反应,从而使交联度降低,粘性降低。
作为优选方案,所述成盐剂优选为三乙胺、NaOH、KOH和氨水中的一种或几种。所述有机溶剂优选为丙酮、丁酮、N-甲基吡咯烷酮和N,N-二甲基甲酰胺中的一种或几种。
作为优选方案,所述催化剂按照如下方法制备:将摩尔比为1:1的甲基咪唑和溴乙烷在450-750r/min条件下搅拌加热升温至50-80℃后反应6-18h,用乙酸乙酯洗涤多次,得到催化剂。
催化剂对对高性能低粘胶的制备起了促进作用,催化剂为温和的酸性离子液体,其催化活性较低,有效地抑制了其对异氰酸酯的亲核进攻,从而降低了异氰酸酯与大分子二元醇羟基反应的活性,降低产品的粘性;同时控制了反应体系的粘度,避免产生爆聚或凝胶,提高了高性能低粘胶贮存稳定性能。
本发明同现有技术相比,具有以下优点和有益效果:
(1)本发明的发泡体材料用低粘PET保护膜由PET基材层、低粘中间层以及保护层组成,其制备工艺简单、易操作,适合于工业化生产;
(2)本发明的发泡体材料用低粘PET保护膜具有低粘、易撕取、不残胶、贴合性好、耐高温性好且力学性能优异的特点,同时PET薄膜还具有优良的耐热、耐寒性、良好的耐化学药品性和耐油性;
(3)高性能低粘胶的扩链剂成酸性,酸性物质能抑制缩二脲的生成反应,进而抑制交联反应,从而使交联度降低,粘性降低;
(4)高性能低粘胶的催化剂为温和的酸性离子液体,其催化活性较低,有效地抑制了其对异氰酸酯的亲核进攻,从而降低了异氰酸酯与大分子二元醇羟基反应的活性,与乳化剂有较好的协同效应,降低产品的粘性;同时控制了反应体系的粘度,避免产生爆聚或凝胶,提高了高性能低粘胶贮存稳定性能。
为了进一步理解本发明,下面结合实施例对本发明提供的技术方案进行详细说明,本发明的保护范围不受以下实施例的限制。
本发明实施例采用的化学试剂均为市购:大分子多元醇购自于青岛瑞诺化工有限公司;异氰酸酯购自于上海九邦化工有限公司;成盐剂及有机溶剂购自于常州市启迪化工有限公司;PET薄膜购自于浙江南洋科技股份有限公司。
实施例1:
本发明的发泡体材料用低粘PET保护膜由50μm的PET基材层、5μm的低粘中间层以及20μm的保护层组成。
低粘中间层由高性能低粘胶形成,高性能低粘胶由20重量份大分子多元醇聚醚多元醇、3重量份异氰酸酯甲苯二异氰酸酯、2重量份扩链剂、0.5重量份成盐剂三乙胺、4重量份催化剂、10重量份有机溶剂丙酮以及100重量份去离子水组成,具体制备方法如下:
(1)将大分子多元醇在100℃下真空脱水5h,再冷却至60℃;
(2)加入异氰酸酯、有机溶剂和催化剂,在500r/min条件下恒温反应6h;
(3)再加入扩链剂扩链反应1h,将上述反应产物冷却至30℃左右;
(4)加入成盐剂和去离子水,在1000r/min条件下高速剪切分散2h,得到高性能低粘胶,备用。
扩链剂羧酸型离子液体1-乙酸咪唑阳离子二羟甲基丙酸阴离子盐,具体制备方法如下:
(1)将咪唑-1-乙酸与乙酸乙酯混合配制成质量分数为30%的溶液后,再加入与咪唑-1-乙酸等摩尔的溴乙烷,在450r/min条件下搅拌加热升温至50℃后反应18h,得到中间体;
(2)再加入与咪唑-1-乙酸等摩尔的二羟甲基丙酸,在300r/min条件下搅拌加热升温至60℃后反应24h,离心洗涤得到扩链剂,备用。
所述催化剂为离子液体1-甲基-3-乙基咪唑溴盐,具体制备方法如下:
将等摩尔的甲基咪唑和溴乙烷,在450r/min条件下搅拌加热升温至50℃后反应18h,用乙酸乙酯洗涤多次,得到催化剂,备用。
实施例2:
本发明的发泡体材料用低粘PET保护膜由100μm的PET基材层、10μm的低粘中间层以及50μm的保护层组成。
低粘中间层由高性能低粘胶形成,高性能低粘胶由80重量份大分子多元醇聚酯多元醇、5重量份异氰酸酯4,4’-二苯基甲烷二异氰酸酯、3重量份扩链剂、0.5-2重量份成盐剂氨水、4-10重量份催化剂、10重量份有机溶剂N-甲基吡咯烷酮以及100重量份去离子水组成,具体制备方法如下:
(1)将大分子多元醇在120℃下真空脱水2h,再冷却至80℃;
(2)加入异氰酸酯、有机溶剂和催化剂,在1500r/min条件下恒温反应2h;
(3)再加入扩链剂扩链反应2h,将上述反应产物冷却至50℃左右;
(4)加入成盐剂和去离子水,在3000r/min条件下高速剪切分散0.5h,得到高性能低粘胶,备用。
扩链剂羧酸型离子液体1-乙酸咪唑阳离子二羟甲基丙酸阴离子盐,具体制备方法如下:
(1)将咪唑-1-乙酸与乙酸乙酯混合配制成质量分数为50%的溶液后,再加入与咪唑-1-乙酸等摩尔的溴乙烷,在750r/min条件下搅拌加热升温至80℃后反应6h,得到中间体;
(2)再加入与咪唑-1-乙酸等摩尔的二羟甲基丙酸,在500r/min条件下搅拌加热升温至90℃后反应8h,离心洗涤得到扩链剂,备用。
所述催化剂为离子液体1-甲基-3-乙基咪唑溴盐,具体制备方法如下:
将等摩尔的甲基咪唑和溴乙烷,在750r/min条件下搅拌加热升温至80℃后反应6h,用乙酸乙酯洗涤多次,得到催化剂,备用。
实施例3:
本发明的发泡体材料用低粘PET保护膜由200μm的PET基材层、20μm的低粘中间层以及50μm的保护层组成。
低粘中间层由高性能低粘胶形成,高性能低粘胶由80重量份大分子多元醇聚碳酸酯多元醇、10重量份二苯基甲烷二异氰酸酯、5重量份扩链剂、2重量份成盐剂KOH、10重量份催化剂、30重量份有机溶剂N,N-二甲基甲酰胺以及150重量份去离子水组成,具体制备方法如下:
(1)将大分子多元醇在120℃下真空脱水1h,再冷却至80℃;
(2)加入异氰酸酯、有机溶剂和催化剂,在1500r/min条件下恒温反应2h;
(3)再加入扩链剂扩链反应5h,将上述反应产物冷却至50℃左右;
(4)加入成盐剂和去离子水,在3000r/min条件下高速剪切分散0.5h,得到高性能低粘胶,备用。
扩链剂羧酸型离子液体1-乙酸咪唑阳离子二羟甲基丙酸阴离子盐,具体制备方法如下:
(1)将咪唑-1-乙酸与乙酸乙酯混合配制成质量分数为50%的溶液后,再加入与咪唑-1-乙酸等摩尔的溴乙烷,在750r/min条件下搅拌加热升温至50℃后反应18h,得到中间体;
(2)再加入与咪唑-1-乙酸等摩尔的二羟甲基丙酸,在500r/min条件下搅拌加热升温至90℃后反应8h,离心洗涤得到扩链剂,备用。
所述催化剂为离子液体1-甲基-3-乙基咪唑溴盐,具体制备方法如下:
将等摩尔的甲基咪唑和溴乙烷,在750r/min条件下搅拌加热升温至80℃后反应6h,用乙酸乙酯洗涤多次,得到催化剂,备用。
实施例4:
发泡体材料用低粘PET保护膜制备方法同实施例2,只是使用市购低粘胶。
实施例5:
发泡体材料用低粘PET保护膜制备方法同实施例2,只是使用市购扩链剂和催化剂。
实施例6:
发泡体材料用低粘PET保护膜制备方法同实施例2,只是使用市购扩链剂。
实施例7:
发泡体材料用低粘PET保护膜制备方法同实施例2,只是使用市购催化剂。
发泡体材料用低粘PET保护膜的粘结性能测试参照国家标准GB/T 2792-1995;耐高温性能是将试样贴敷于304SUS板,120℃保持60min;力学性能测试参照国家标准GB/T3398.2-2008。
本发明实施例制备的发泡体材料用低粘PET保护膜的性能测试结果如表1所示。
表1实施例1-6制备的发泡体材料用低粘PET保护膜主要性能指标
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。
Claims (4)
1.一种发泡体材料用低粘PET保护膜,其特征在于,由依次层叠的PET基材层、低粘中间层和保护层组成,所述低粘中间层由高性能低粘胶形成,高性能低粘胶由20-80重量份大分子多元醇、3-10重量份异氰酸酯、2-5重量份扩链剂、0.5-2重量份成盐剂、4-10重量份催化剂、10-30重量份有机溶剂以及100-150重量份去离子水组成,
所述扩链剂为羧酸型离子液体1-乙酸咪唑阳离子二羟甲基丙酸阴离子盐,所述催化剂为离子液体1-乙基-3-甲基咪唑溴盐,
所述PET基材层厚度为50-200 μm,
所述保护层为PET薄膜,厚度为20-100 μm,
所述高性能低粘胶按照如下方法制备:
将大分子多元醇在 100-120 ℃下真空脱水1-5 h,再冷却至 60-80 ℃;
然后加入异氰酸酯、有机溶剂和催化剂,在500-1500 r/min条件下恒温反应2-6 h;
加入扩链剂扩链反应1-5 h,冷却至30-50 ℃;
然后加入成盐剂和去离子水,在1000-3000 r/min条件下高速剪切分散 0.5-2 h,得到高性能低粘胶,
所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或几种,
所述有机溶剂为丙酮、丁酮、N-甲基吡咯烷酮和N,N-二甲基甲酰胺中的一种或几种。
2.根据权利要求1所述的发泡体材料用低粘PET保护膜,其特征在于,所述大分子多元醇为聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇中的一种或几种。
3.根据权利要求1所述的发泡体材料用低粘PET保护膜,其特征在于,所述成盐剂为三乙胺、NaOH、KOH和氨水中的一种或几种。
4.根据权利要求1所述的发泡体材料用低粘PET保护膜,其特征在于,所述催化剂按照如下方法制备:
将摩尔比为1:1的甲基咪唑和溴乙烷在450-750 r/min条件下搅拌加热升温至50-80℃后反应6-18h,用乙酸乙酯洗涤多次,得到催化剂。
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