CN115536806B - 超高拉伸率涂层薄膜的水性聚氨酯乳液生产工艺 - Google Patents
超高拉伸率涂层薄膜的水性聚氨酯乳液生产工艺 Download PDFInfo
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Abstract
本发明公开了一种超高拉伸率涂层薄膜的水性聚氨酯乳液，包括聚醚多元醇3010E 0‑24份，聚醚多元醇PTMG‑2000 0‑20份，聚酯多元醇P2010 0‑20份，聚碳酸酯多元醇C1090 14‑31份，小分子扩链剂4.2份，亲水性扩链剂4.4份，异氰酸酯IPDI 37.62份；本发明提供了一种可以替代聚乙烯、聚氯乙烯等用于快递外包装材料的水性聚氨酯乳液涂层薄膜，以解决上述难以降解的塑料包装袋造成的白色污染问题；该工艺得到的涂层薄膜具有超高拉伸率，拉伸后的长度可以达到原先长度的19倍以上，可以在极大程度上，降低聚乙烯、聚氯乙烯等类包装袋的使用；同时，由于水性聚氨酯高分子链中存在酯键和酰胺键，回收后进行简单的处理，如适量的碱性条件下，可以逐步降解，消除白色污染的产生，避免对环境产生有害物质。
Description
技术领域
本发明属于水性聚氨酯乳液合成领域，具体涉及一种超高拉伸率涂层薄膜的水性聚氨酯乳液及其生产工艺。
背景技术
聚氨酯是聚氨基甲酸酯的简称。是一种高分子化合物，其特点是在聚合物链的分子结构中有重复的氨基甲酸酯基团（-NHCOO-）。聚氨酯自发明出来以后即成为用途广阔的高分子材料，可制成形态各异的产品，是一种“可剪裁”的“万能”的聚合物。
水性聚氨酯是以异氰酸酯和二元醇等进行缩聚反应，生成两端均为-NCO的预聚体后，再用含有亲水酸性基团的二胺为扩链剂，嵌到聚氨酯分子链上；根据反应所用的原料官能团数目的不同，可以制成线型或体型结构。由于预聚体中引入了亲水基团，使其具有一定程度的亲水性，而后成盐乳化，分散至水中制成水性聚氨酯，也称聚氨酯水分散体。水性PU具有无毒、不燃、不爆、环保等特点。
近年来，随着人们环保意识的不断增强，相比于传统的溶剂型聚氨酯，水性聚氨酯具有无污染、低有机挥发物排放量等特点，越来越多地受到学者的关注，成为研究的热点。水性聚氨酯具有独特的分子结构及聚集状态，使得它的胶膜具有优异的力学性能、耐磨性、附着力等特点，使其在服装、鞋业、皮包、家庭用品、家具、汽车和交通设施以及纺织助剂、造纸业助剂、涂料和粘合剂等领域中得到了广泛应用。由于在合成水性聚氨酯时，没有使用DMF、甲苯、MEK等溶剂，因此无公害；又具有不燃、安全、环保的独特性能和无毒、无污染等优点，可以满足无VOC排放的环保要求，因此水性聚氨酯乳液越来越受到重视；现代化工业发达国家已经采用水性聚氨酯树脂来代替溶剂聚氨酯进行生产。
如今随着经济的飞速发展，垃圾也随之增多，尤其是塑料垃圾。这类垃圾由于性质较为稳定，难以降解，散落于各处，俗称白色污染。这些来源之一是快递盒外层的塑料包装袋。目前常见的快递包裹外层包装材料为聚乙烯（PE）或聚氯乙烯（PVC）。目前对白色污染的处理方法一是回收再利用，另一方法是进行焚烧，例如作为能源焚烧进行发电等；但焚烧过程中不可避免的向大气中释放出致癌的二噁英，加剧了环境的污染。同时焚烧发电又增加了碳排放含量，不符合持续发展的要求。
发明内容
为解决上述问题，本发明公开了一种可以替代聚乙烯、聚氯乙烯等包装材料的水性聚氨酯乳液涂层薄膜，以解决上述难以降解的塑料包装袋造成的白色污染问题，且该涂层薄膜具有超高拉伸率。
为达到上述目的，本发明的技术方案如下：
采用预聚体法，将聚合物多元醇（聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇）小分子扩链剂、亲水性扩链剂和异氰酸酯进行反应，达到理论NCO%值后，加入中和剂成盐，最后加入去离子水和后扩链剂搅拌分散得到具有高拉伸率涂层薄膜的水性聚氨酯乳液。
具体包括以下步骤：
（1）将聚醚多元醇3010E、聚醚多元醇PTMG-2000、聚酯多元醇P2010和聚碳酸酯多元醇C1090混合，搅拌，进行一次升温反应；加入异氰酸酯后，进行二次升温反应；然后加入小分子扩链剂，进行三次升温反应；然后加入亲水性扩链剂，反应30分钟后，进行四次升温反应；得到预聚体；
（2）当预聚体达到理论NCO%值后，降温，加丙酮稀释，加入中和剂成盐，最后加入去离子水和后扩链剂搅拌分散得到具有高拉伸率涂层薄膜的水性聚氨酯乳液。
上述水性聚氨酯乳液制备工艺中，使用的原料按重量份计为：聚醚多元醇3010E0-24份，聚醚多元醇PTMG-2000 0-20份，聚酯多元醇P2010 0-20份，聚碳酸酯多元醇C109014-31份，小分子扩链剂4.2份，亲水性扩链剂4.4份，异氰酸酯37.62份；丙酮30份，中和剂3.3份，去离子水174-192份，后扩链剂2.6-3份。
进一步地，所述异氰酸酯为异佛尔酮二异氰酸酯（IPDI）。
进一步地，所述小分子扩链剂为1,4-丁二醇（BDO）。
进一步地，所述亲水性扩链剂为二羟甲基丙酸（DMPA）。
进一步地，所述中和剂为三乙胺。
进一步地，所述后扩链剂为水合肼。
进一步地，步骤（1）中，一次升温反应的温度为60℃-65℃，时间为30-40分钟；二次升温反应的温度为70℃-75℃，时间为30-40分钟；三次升温反应的温度为80℃-85℃，时间为20-30分钟；四次升温反应的温度为90-95℃，时间为30-35分钟。
本发明的有益效果为：
本发明各原料配比结合生产工艺得到水性聚氨酯乳液，制备的涂层薄膜具有超高拉伸率，拉伸后的长度可以达到原先长度的19倍以上，可以在极大程度上，降低聚乙烯、聚氯乙烯等类包装袋的使用。同时，由于本发明水性聚氨酯高分子链中存在酯键和酰胺键，回收后进行简单的处理，如适量的碱性条件下，就可以逐步降解，消除白色污染的产生，避免对环境产生有害物质。
具体实施方式
下面结合具体实施方式，进一步阐明本发明，应理解下述具体实施方式仅用于说明本发明而不用于限制本发明的范围。
实施例1
（1）称量24 g聚醚多元醇3010E，20 g聚醚多元醇PTMG2000，31 g聚碳酸酯多元醇C1090于四颈烧瓶中，启动搅拌，加热升温至60 ℃并保温30分钟，随后加入37.62 g IPDI，加热至70 ℃，继续反应30分钟左右，加入4.2 g BDO，升温至80 ℃并保温20分钟；随后再加入4.4 g DMPA，反应30分钟后，升温至90-95 ℃，继续反应30-35分钟，得到预聚体；
（2）反应过程中取样滴定知道NCO值，预聚体到达NCO%理论值2.82 %后，降温待预聚体冷却到60 ℃时加入丙酮30 g稀释，冷却至30 ℃，加入中和剂三乙胺3.3 g，成盐15分钟，最后加入去离子水191 g和2.6 g水合肼的混合物，搅拌分散30分钟，得到水性聚氨酯乳液。
实施例2
（1）称量24 g聚醚多元醇3010E，20 g聚醚多元醇PTMG2000，20 g聚酯多元醇P2010，14 g聚碳酸酯多元醇C1090于四颈烧瓶中，启动搅拌，加热升温至60 ℃并保温30分钟，随后加入37.62 g IPDI，加热至70 ℃，继续反应30分钟左右，加入4.2 g BDO，升温至80℃并保温20分钟；随后再加入4.4 g DMPA，反应30分钟后，升温至90-95 ℃，继续反应30-35分钟，得到预聚体；
（2）反应过程中取样滴定知道NCO值，到达NCO%理论值3.23 %后，降温待预聚体冷却到60 ℃时加入丙酮30 g稀释，冷却至30 ℃，加入中和剂三乙胺3.3 g，成盐15分钟，最后加入去离子水192 g和3.0 g水合肼的混合物，搅拌分散30分钟，得到水性聚氨酯乳液。
实施例3
（1）称量24 g聚醚多元醇3010E，20 g聚酯多元醇P2010，31 g聚碳酸酯多元醇C1090于四颈烧瓶中，启动搅拌，加热升温至60 ℃并保温30分钟，随后加入37.62 g IPDI，加热至70 ℃，继续反应30分钟左右，加入4.2 g BDO，升温至80 ℃并保温20分钟；随后再加入4.4 g DMPA，反应30分钟后，升温至90-95 ℃，继续反应30-35分钟，得到预聚体；
（2）反应过程中取样滴定知道NCO值，预聚体到达NCO%理论值2.82 %后，降温待预聚体冷却到60 ℃时加入丙酮30 g稀释，冷却至30 ℃，加入中和剂三乙胺3.3 g，成盐15分钟，最后加入去离子水191 g和2.6 g水合肼的混合物，搅拌分散30分钟，得到水性聚氨酯乳液。
实施例4
（1）称量20 g聚醚多元醇PTMG2000，20 g聚酯多元醇P2010，24 g聚碳酸酯多元醇C1090于四颈烧瓶中，启动搅拌，加热升温至60 ℃并保温30分钟，随后加入37.62 g IPDI，加热至70 ℃，继续反应30分钟左右，加入4.2 g BDO，升温至80 ℃并保温20分钟；随后再加入4.4 g DMPA，反应30分钟后，升温至90-95 ℃，继续反应30-35分钟，得到预聚体；
（2）反应过程中取样滴定知道NCO值，预聚体到达NCO%理论值3.58 %后，降温待预聚体冷却到60 ℃时加入丙酮30 g稀释，冷却至30 ℃，加入中和剂三乙胺3.3 g，成盐15分钟，最后加入去离子水174 g和3 g水合肼的混合物，搅拌分散30分钟，得到水性聚氨酯乳液。
对比实施例
（1）称量70.5 g聚醚多元醇3010E，51 g聚醚多元醇PTMG2000于四颈烧瓶中，启动搅拌，加热升温至60 ℃并保温30分钟，随后加入37.62 g IPDI，加热至70 ℃，继续反应30分钟左右，加入4.2 g BDO，升温至80 ℃并保温20分钟；随后再加入4.4 g DMPA，反应30分钟后，升温至90-95 ℃，继续反应30-35分钟，得到预聚体；
（2）反应过程中取样滴定知道NCO值，预聚体到达NCO%理论值2.82 %后，降温待预聚体冷却到60 ℃时加入丙酮30 g稀释，冷却至30 ℃，加入中和剂三乙胺3.3 g，成盐15分钟，最后加入去离子水191 g和2.6 g水合肼的混合物，搅拌分散30分钟，得到水性聚氨酯乳液。
性能测试试验：
取实施例1—实施例4制备得到的水性聚氨酯乳液涂布于镜面离心纸后，置120℃鼓风烘箱中烘干，得到聚氨酯涂层薄膜（测试薄膜厚度为0.09 mm）。48h后将薄膜外形剪裁为哑铃形，进行拉伸测试。
利用万能材料测试机(美特斯微机控制CMT6104型电子万能试验机)进行拉伸力测试（仪器运行速度：400 mm/min；哑铃形测试膜的厚度为0.09 mm）；测试结果显示本发明工艺制备的水性聚氨酯涂层薄膜均具有超高拉伸率，得到的数值显示当超过量程范围时，薄膜依然未断裂，见拉伸率测试数据表1。
表1断裂伸长率测试数据
薄膜降解实验
取实施例1—实施例4制备得到的水性聚氨酯涂层薄膜于4个烧杯中，加入5% NaOH溶液30 mL，启动搅拌并加热至80 ℃。10h后停止加热和搅拌，冷却至室温，整片薄膜消失，烧杯内出现蜡状固体沉淀和少量细小膜状碎片。说明聚氨酯涂层薄膜能够降解，可以以此代替聚乙烯、聚氯乙烯等包装材料，实现减少白色污染的目的。
需要说明的是，以上内容仅仅说明了本发明的技术思想，不能以此限定本发明的保护范围，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰均落入本发明权利要求书的保护范围之内。
Claims (2)
1.超高拉伸率涂层薄膜的水性聚氨酯乳液，其特征在于，按重量份计，包括以下原料：聚醚多元醇3010E 24份，聚醚多元醇PTMG-2000 20份，聚酯多元醇P2010 0-20份，聚碳酸酯多元醇C1090 14-31份，小分子扩链剂4.2份，亲水性扩链剂4.4份，异氰酸酯37.62份，丙酮30份，中和剂3.3份，去离子水174-192份，后扩链剂2.6-3份；
所述超高拉伸率涂层薄膜的水性聚氨酯乳液的制备方法如下：
（1）按以上重量份，将聚醚多元醇3010E、聚醚多元醇PTMG-2000、聚酯多元醇P2010和聚碳酸酯多元醇C1090混合，搅拌，进行一次升温反应；加入异氰酸酯后，进行二次升温反应；然后加入小分子扩链剂，进行三次升温反应；然后加入亲水性扩链剂，反应30分钟后，进行四次升温反应；得到预聚体；
（2）降温，加丙酮稀释，加入中和剂成盐，最后加入去离子水和后扩链剂搅拌分散得到具有高拉伸率涂层薄膜的水性聚氨酯乳液；
步骤（1）中，一次升温反应的温度为60℃-65℃，时间为30-40分钟；二次升温反应的温度为70℃-75℃，时间为30-40分钟；三次升温反应的温度为80℃-85℃，时间为20-30分钟；四次升温反应的温度为90-95℃，时间为30-35分钟；
所述异氰酸酯为异佛尔酮二异氰酸酯；
所述小分子扩链剂为1,4-丁二醇；
所述亲水性扩链剂为二羟甲基丙酸；
所述后扩链剂为水合肼。
2.根据权利要求1所述的超高拉伸率涂层薄膜的水性聚氨酯乳液，其特征在于，所述中和剂为三乙胺。
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