CN109306120A - 一种共混法高阻隔性聚丙烯包装膜的生产方法 - Google Patents
一种共混法高阻隔性聚丙烯包装膜的生产方法 Download PDFInfo
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Abstract
本发明公开了一种共混法高阻隔性聚丙烯包装膜的生产方法，以等规聚丙烯‑b‑聚乙二醇两嵌段物作为等规聚丙烯和聚乙烯醇的相容剂，聚乙烯醇具有优秀的阻氧性能，等规聚丙烯‑b‑聚乙二醇两嵌段物作为相容剂后，使规聚丙烯和聚乙烯醇之间具有良好的相容性，使得聚乙烯醇相在聚丙烯树脂中能均匀分散，形成次连续相或片层状结构，从而显著提高共混膜的阻隔性能。
Description
技术领域
本发明涉及包装材料技术领域，具体讲是一种共混法高阻隔性聚丙烯包装膜的生产方法。
背景技术
现有技术的聚丙烯包装膜的阻隔性能不佳，氧气、二氧化碳、水蒸气、香气及有机小分子等物质易透过聚丙烯膜而影响到被包装物的性能与寿命。目前，制备高阻隔聚丙烯膜主要有四种方法：多层复合、表面镀膜、纳米复合改性及共混改性，这四种方法均存在各自的缺陷和不足，例如多层复合膜存在溶剂残留、废弃物分离及后处理困难等问题；表面镀膜设备昂贵、成本高、膜层不均匀；纳米复合易产生粒子团聚现象，导致透明性下降等诸多问题。共混改性是这些方法中工艺最简单、操作最方便、成本最低的制备方法，但现有的改性剂对提高聚丙烯的阻隔性效果不明显。
目前，通过共混的方法提高聚丙烯膜的阻隔性能通常是将聚丙烯与尼龙、聚酯、聚乙烯酵(PVA)或乙烯-酸般乙烯酯共聚物的部分水解物(EVOH)共混，生产出具有优异抗冲、射环境应力、开裂性能和阻隔性能优良的专用料或母料，再经适当配混后进行成型加工。由于所使用的阻隔性树脂均为极性聚合物，而聚丙烯为缺少功能性基团的非扱性聚合物，再加上其半结品性的特性，并且隔性树脂和聚丙烯的相容性很差，无法在聚丙烯基体中均匀分散，大大减弱了其阻隔作用。因此，需要对阻隔性树脂进行改性，提高其与聚丙烯的相容性。
发明内容
鉴于上述现有技术的缺陷，本发明的目的在于：提供一种共混法高阻隔性聚丙烯包装膜的生产方法。
为解决上述问题，本发明的技术解决方案是：一种共混法高阻隔性聚丙烯包装膜的生产方法，包括以下步骤：
(1)用MgCl2负载的TiCl4作为主催化剂，用烷基铝作为副催化剂，催化丙烯聚合，以C-donor为外给电子体，ZnEt2为链转移剂，制备等规聚丙烯；
(2)用干燥的氧气氧化等规聚丙烯，等规聚丙烯用盐酸水解并得到端羟基等规聚丙烯；
(3)将聚乙二醇单甲醚的甲苯溶液加到异佛尔酮二异氰酸酯的甲苯溶液中，制备端异氰酸酯基聚乙二醇；
(4)将端异氰酸酯基聚乙二醇添加到端羟基等规聚丙烯的甲苯溶液中，制备等规聚丙烯-b-聚乙二醇两嵌段物；
(5)以等规聚丙烯-b-聚乙二醇两嵌段物为相容剂，将基等规聚丙烯、等规聚丙烯-b-聚乙二醇两嵌段物、聚乙烯醇共混，共混后在螺杆挤出机中进行充分的熔融共混，再进行挤出、吹塑和双向拉伸，制备聚丙烯复合材料膜。
进一步地，步骤(1)具体为：在无水无氧的条件下，将有机溶剂、作为助催化剂的烷基铝、C-donor外给电子体以及链转移剂ZnEt2加入到Schlenk瓶中，最后加入主催化剂TiCl4/MgCl2，通入压力为0.1～1.1Mpa的丙烯，控制聚合温度为40～80℃，聚合时间为0.5～3h,制得等规聚丙烯。
进一步地，步骤(2)具体为：用干燥的氧气氧化等规聚丙烯，氧化温度为80～120℃，用1mol/L的盐酸水溶液进行淬灭，使催化剂失活，搅拌5-10min后用分液漏斗静置分液，除去上、中层清液；除去固体产物中的溶剂，再用蒸馏水和有机溶剂反复洗涤后真空干燥，制得端羟基等规聚丙烯。
进一步地，所述有机溶剂为甲苯、二甲苯、正庚烷、正辛烷或石油醚中的一种。
进一步地，步骤(3)具体为：在装有回流冷凝管的、干燥且经氮气抽排3次的Schlenk瓶中，加入聚乙二醇单甲醚、异佛尔酮二异氰酸酯、二月桂酸二丁基锡和甲苯，反应温度为25℃～60℃，反应时间为4～24h，聚乙二醇单甲醚与异佛尔酮二异氰酸酯在催化剂二月桂酸二丁基锡的作用下发生亲核取代反应，得到端异氰酸酯基聚乙二醇。
进一步地，步骤(4)具体为：在装有回流冷凝管的、干燥且经氮气抽排3次的Schlenk瓶中，加入端羟基等规聚丙烯、端异氰酸酯基聚乙二醇、甲苯和二月桂酸二丁基锡，端异氰酸酯基聚乙二醇与端羟基功能化等规聚丙烯在催化剂二月桂酸二丁基锡的作用下发生亲核加成反应，得到等规聚丙烯-b-聚乙二醇两嵌段物，反应温度为90℃～130℃，反应时间为4～24h。
进一步地，步骤(5)具体为：以等规聚丙烯-b-聚乙二醇两嵌段物为相容剂，将等规聚丙烯、等规聚丙烯-b-聚乙二醇两嵌段物、聚乙烯醇共混，混合后的原料经双螺杆挤出机塑化，将熔融态熔体送入模头，并在模头口挤出熔融态片材，挤出的片材置于对开模中，闭模后立即在型坯内通入压缩空气，冷却脱模后得到铸片，铸片再分别经过纵拉机和横向拉伸机，将片材拉制成薄膜，薄膜经厚度检测后进行冷却并收卷。
本发明的有益效果是：
(1)以TiCl4/MgCl2作为主催化剂，烷基铝作为助催化剂，ZnEt2为链转移剂制备分子量可控的等规聚丙烯，再将聚合物用干燥的氧气氧化，用盐酸水溶液水解制备端羟基等规聚丙烯，该合成方法合成的聚合物分子量可控，易于实现工业化；
(2)以异佛尔酮二异氰酸酯为偶联剂将端羟基等规聚丙烯与聚乙二醇单甲醚偶联起来，制备等规聚丙烯-b-聚乙二醇两嵌段物，该合成技术方法实施方便，成本较低，并且效率高，所使用的原料简单易得，价格低廉，可通过调节两种链段的长度，调控嵌段共聚物的性能，制备的等规聚丙烯-b-聚乙二醇两嵌段物中等规聚丙烯链段保持了很高的等规度；
(3)以等规聚丙烯-b-聚乙二醇两嵌段物作为等规聚丙烯和聚乙烯醇的相容剂，聚乙烯醇具有优秀的阻氧性能，等规聚丙烯-b-聚乙二醇两嵌段物作为相容剂后，使规聚丙烯和聚乙烯醇之间具有良好的相容性，使得聚乙烯醇相在聚丙烯树脂中能均匀分散，形成次连续相或片层状结构，从而显著提高共混膜的阻隔性能。
具体实施方式
为比较直观、完整地理解本发明的技术方案，现进行非限制性的特征说明如下：
实施例一：
一种共混法高阻隔性聚丙烯包装膜的生产方法，包括以下步骤：
(1)在无水无氧的条件下，将甲苯、作为助催化剂的烷基铝、C-donor外给电子体以及链转移剂ZnEt2加入到Schlenk瓶中，最后加入主催化剂TiCl4/MgCl2，通入压力为0.1～1.1Mpa的丙烯，控制聚合温度为50℃，聚合时间为1h,制得等规聚丙烯。
(2)用干燥的氧气氧化等规聚丙烯，在氧化温度为100℃环境下反应0.5h，用1mol/L的盐酸水溶液进行淬灭，使催化剂失活，搅拌10min后用分液漏斗静置分液，除去上、中层清液；除去固体产物中的溶剂，再用蒸馏水和甲苯反复洗涤后真空干燥，制得端羟基等规聚丙烯。
(3)在装有回流冷凝管的、干燥且经氮气抽排3次的Schlenk瓶中，加入聚乙二醇单甲醚、异佛尔酮二异氰酸酯、二月桂酸二丁基锡和甲苯，反应温度为30℃，反应时间为6h，聚乙二醇单甲醚与异佛尔酮二异氰酸酯在催化剂二月桂酸二丁基锡的作用下发生亲核取代反应，得到端异氰酸酯基聚乙二醇。
(4)在装有回流冷凝管的、干燥且经氮气抽排3次的Schlenk瓶中，加入端羟基等规聚丙烯、端异氰酸酯基聚乙二醇、甲苯和二月桂酸二丁基锡，端异氰酸酯基聚乙二醇与端羟基功能化等规聚丙烯在催化剂二月桂酸二丁基锡的作用下发生亲核加成反应，得到等规聚丙烯-b-聚乙二醇两嵌段物，反应温度为100℃，反应时间为6h。
(5)按以下质量百分比称取原料：等规聚丙烯60％、等规聚丙烯-b-聚乙二醇两嵌段物15％、聚乙烯醇25％；以等规聚丙烯-b-聚乙二醇两嵌段物为相容剂，将等规聚丙烯、等规聚丙烯-b-聚乙二醇两嵌段物、聚乙烯醇共混，混合后的原料经双螺杆挤出机塑化，将熔融态熔体送入模头，并在模头口挤出熔融态片材，挤出的片材置于对开模中，闭模后立即在型坯内通入压缩空气，冷却脱模后得到铸片，铸片再分别经过纵拉机和横向拉伸机，将片材拉制成薄膜，薄膜经厚度检测后进行冷却并收卷。
Claims (7)
1.一种共混法高阻隔性聚丙烯包装膜的生产方法，其特征在于包括以下步骤：
(1)用MgCl2负载的TiCl4作为主催化剂，用烷基铝作为副催化剂，催化丙烯聚合，以C-donor为外给电子体，ZnEt2为链转移剂，制备等规聚丙烯；
(2)用干燥的氧气氧化等规聚丙烯，等规聚丙烯用盐酸水解并得到端羟基等规聚丙烯；
(3)将聚乙二醇单甲醚的甲苯溶液加到异佛尔酮二异氰酸酯的甲苯溶液中，制备端异氰酸酯基聚乙二醇；
(4)将端异氰酸酯基聚乙二醇添加到端羟基等规聚丙烯的甲苯溶液中，制备等规聚丙烯-b-聚乙二醇两嵌段物；
(5)以等规聚丙烯-b-聚乙二醇两嵌段物为相容剂，将基等规聚丙烯、等规聚丙烯-b-聚乙二醇两嵌段物、聚乙烯醇共混，共混后在螺杆挤出机中进行充分的熔融共混，再进行挤出、吹塑和双向拉伸，制备聚丙烯复合材料膜。
2.根据权利要求1所述的一种共混法高阻隔性聚丙烯包装膜的生产方法，其特征在于步骤(1)具体为：在无水无氧的条件下，将有机溶剂、作为助催化剂的烷基铝、C-donor外给电子体以及链转移剂ZnEt2加入到Schlenk瓶中，最后加入主催化剂TiCl4/MgCl2，通入压力为0.1～1.1Mpa的丙烯，控制聚合温度为40～80℃，聚合时间为0.5～3h,制得等规聚丙烯。
3.根据权利要求2所述的一种共混法高阻隔性聚丙烯包装膜的生产方法，其特征在于步骤(2)具体为：用干燥的氧气氧化等规聚丙烯，氧化温度为80～120℃，用1mol/L的盐酸水溶液进行淬灭，使催化剂失活，搅拌5-10min后用分液漏斗静置分液，除去上、中层清液；除去固体产物中的溶剂，再用蒸馏水和有机溶剂反复洗涤后真空干燥，制得端羟基等规聚丙烯。
4.根据权利要求3所述的一种共混法高阻隔性聚丙烯包装膜的生产方法，其特征在于：所述有机溶剂为甲苯、二甲苯、正庚烷、正辛烷或石油醚中的一种。
5.根据权利要求1所述的一种共混法高阻隔性聚丙烯包装膜的生产方法，其特征在于步骤(3)具体为：在装有回流冷凝管的、干燥且经氮气抽排3次的Schlenk瓶中，加入聚乙二醇单甲醚、异佛尔酮二异氰酸酯、二月桂酸二丁基锡和甲苯，反应温度为25℃～60℃，反应时间为4～24h，聚乙二醇单甲醚与异佛尔酮二异氰酸酯在催化剂二月桂酸二丁基锡的作用下发生亲核取代反应，得到端异氰酸酯基聚乙二醇。
6.根据权利要求5述的一种共混法高阻隔性聚丙烯包装膜的生产方法，其特征在于步骤(4)具体为：在装有回流冷凝管的、干燥且经氮气抽排3次的Schlenk瓶中，加入端羟基等规聚丙烯、端异氰酸酯基聚乙二醇、甲苯和二月桂酸二丁基锡，端异氰酸酯基聚乙二醇与端羟基功能化等规聚丙烯在催化剂二月桂酸二丁基锡的作用下发生亲核加成反应，得到等规聚丙烯-b-聚乙二醇两嵌段物，反应温度为90℃～130℃，反应时间为4～24h。
7.根据权利要求1的一种共混法高阻隔性聚丙烯包装膜的生产方法，其特征在于步骤(5)具体为：以等规聚丙烯-b-聚乙二醇两嵌段物为相容剂，将等规聚丙烯、等规聚丙烯-b-聚乙二醇两嵌段物、聚乙烯醇共混，混合后的原料经双螺杆挤出机塑化，将熔融态熔体送入模头，并在模头口挤出熔融态片材，挤出的片材置于对开模中，闭模后立即在型坯内通入压缩空气，冷却脱模后得到铸片，铸片再分别经过纵拉机和横向拉伸机，将片材拉制成薄膜，薄膜经厚度检测后进行冷却并收卷。
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