CN106065049A - 高固含量环保型水性聚氨酯‑丙烯酸酯复合乳液及其制备方法 - Google Patents

高固含量环保型水性聚氨酯‑丙烯酸酯复合乳液及其制备方法 Download PDF

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CN106065049A
CN106065049A CN201610389905.1A CN201610389905A CN106065049A CN 106065049 A CN106065049 A CN 106065049A CN 201610389905 A CN201610389905 A CN 201610389905A CN 106065049 A CN106065049 A CN 106065049A
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何迪宏
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Nanxiong Rising Chemical Industrial Co Ltd
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Abstract

本发明涉及一种水性聚氨酯‑丙烯酸酯复合乳液的制备方法，具体是一种高固含量环保型水性聚氨酯‑丙烯酸酯复合乳液及其制备方法。在无任何金属催化剂和溶剂条件下由聚合物二元醇、二异氰酸酯、亲水性扩链剂合成水性聚氨酯预聚体，用乙烯基化合物封端，随后中和、加水自乳化、扩链，并在无外加乳化剂存在下，与(甲基)丙烯酸酯单体共聚，制备水性聚氨酯‑丙烯酸酯复合乳液。本发明制备水性聚氨酯‑丙烯酸酯复合乳液的特征是所得乳液固含量高(≥60％)、稳定性良好，且制备过程中不使用任何金属催化剂、溶剂和外加乳化剂。

Description

高固含量环保型水性聚氨酯-丙烯酸酯复合乳液及其制备 方法
技术领域
本发明涉及一种水性聚氨酯-丙烯酸酯复合乳液的制备方法，具体是一种高固含量环保型水性聚氨酯-丙烯酸酯复合乳液及其制备方法。
背景技术
聚氨酯是一种性能优异的高分子材料，具有耐低温、耐化学腐蚀、耐摩擦及柔性好等优点，目前已作为涂料、胶粘剂、织物整理剂等得到广泛应用。传统的聚氨酯材料以溶剂型为主，所用的有机溶剂一般具有易燃、易爆、气味大、有毒等缺点，在生产与使用过程中容易对人类健康与环境造成危害。上世纪七十年代开始出现并得到迅速发展的水性聚氨酯材料，与传统的溶剂型聚氨酯相比，具有毒性小、不易燃、低污染等优点。随着水性聚氨酯产品性能的不断提高，以及很多国家、部门在限制挥发性有机化合物(VOC)使用方面相关法令的颁布，从溶剂型聚氨酯到水性聚氨酯的转变已成必然。
然而，水性聚氨酯在具有优异的耐溶剂性、耐磨性及柔韧性等众多优点的同时，由于自身结构中引入了亲水基团，存在着耐水性变差、表面光泽度降低等缺陷，且生产成本较高。而被广泛应用于涂料、胶粘剂、印染等领域的聚丙烯酸酯材料，则有具有耐候、耐污染、耐酸、耐碱、透明性好等性能，且生产成本较低，但是也存在着低温易变脆、高温变黏、耐溶剂性差、抗拉伸性能不佳等缺点。因此，通过物理或化学方法将两者结合在一起，制备水性聚氨酯-丙烯酸酯复合乳液，不仅降低了生产成本，且兼具两者的优点，实现优势互补，改善产品性能。
目前国内报道的水性聚氨酯-丙烯酸酯复合乳液固含量较低，一般为40-50％，且在制备过程中，往往需要使用有机溶剂如丙酮等降低聚氨酯预聚体粘度，最后产物需脱除和回收有机溶剂。不使用有机溶剂，可省去溶剂脱除和回收后工序以提高生产效率，同时可避免生产与使用过程中对人类健康与环境造成的危害，符合清洁生产的概念；另一方面高固含量乳液具有干燥快、初粘好等优点，同时也降低生产、包装和运输成本。因此，不使用任何溶剂制备高固含量(60％以上)的水性聚氨酯-丙烯酸酯复合乳液，将具有重要的实际应用价值，相关途径鲜有报道。
发明的内容
为解决上述现有技术中存在的不足，本发明公开了一种不使用任何金属催化剂、溶剂和外加乳化剂的制备环保型高固含量水性聚氨酯-丙烯酸酯乳液及其制备方法。无任何金属催化剂和溶剂下由聚合物二元醇、二异氰酸酯、亲水性扩链剂合成水性聚氨酯预聚体，用乙烯基化合物封端，随后中和、加水自乳化、扩链，并在无外加乳化剂存在下，与(甲基)丙烯酸酯单体共聚，制备水性聚氨酯-丙烯酸酯复合乳液。本发明制备水性聚氨酯-丙烯酸酯复合乳液的特征是所得乳液固含量高(≥60％)、稳定性良好，且制备过程中不使用任何金属催化剂、溶剂和外加乳化剂。
为了实现上述目的，本发明在无金属催化剂和有机溶剂存在的情况下，将聚己二酸丁二醇酯(PBA)和/或聚丙二醇(PPG)与异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二羟甲基丁酸(DMBA)进行预聚，然后加入甲基丙烯酸羟乙酯(HEMA)封端，随后用三乙胺中和、加水自乳化、扩链，并在无外加乳化剂存在下，与(甲基)丙烯酸酯单体共聚，获得固含量较高(≥60％)、稳定性良好的水性聚氨酯-丙烯酸酯复合乳液。由于制备过程中不使用任何溶剂和金属催化剂，且无污染物排放，为清洁生产过程。所得水性环保型高固含量水性聚氨酯-丙烯酸酯复合乳液可用作胶粘剂、涂料等。
本发明所制备的一种高固含量环保型水性聚氨酯-丙烯酸酯复合乳液，其固形物含量为60％及以上；制备过程中不使用金属催化剂、有机溶剂和外加乳化剂。
所述复合乳液是通过将聚己二酸丁二醇酯和/或聚丙二醇与异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二羟甲基丁酸进行预聚，然后加入甲基丙烯酸羟乙酯封端，随后用三乙胺中和、加水自乳化、扩链，并在无外加乳化剂存在下，与丙烯酸酯单体和/或甲基丙烯酸酯单体共聚得到。
上述高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法中所用聚合物二元醇由聚己二酸丁二醇酯和聚丙二醇组成；所用二异氰酸酯由摩尔比2:3的六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯组成；所用亲水性扩链剂为二羟甲基丁酸，占水性聚氨酯质量≥4.1％；NCO/OH≥2.0，其中NCO为HDI和IPDI的总摩尔量，OH为聚合物二元醇和DMBA的总摩尔量；聚合在氮气氛围下进行。
所得的聚氨酯预聚体用甲基丙烯酸羟乙酯进行封端，反应温度为76℃，反应时间为3-3.5h；随后加入三乙胺进行中和，中和温度为65℃，中和时间为15min。
所得聚氨酯预聚体通过自乳化方式得到水性聚氨酯乳液，乳化用水通过滴加方式加入到预聚体中，乳化温度为65℃，乳化时间为15min，搅拌速度为500r/min；所得聚氨酯预乳液采用已二胺水溶液进行扩链，反应温度为65℃。
通过向聚氨酯预聚体乳液滴加溶有偶氮二异丁睛的丙烯酸酯单体，进行自由基聚合，反应温度为75℃，反应时间为7h；丙烯酸酯单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸丁酯和丙烯酸异辛酯中的一种或几种的混合物。
具体由以下步骤组成：
(1)将128g聚己二酸丁二醇酯和/或聚丙二醇在120℃条件下真空除水，所述聚己二酸丁二醇酯和聚丙二醇摩尔比为10:0，8:2，6:4，0:10中的一种；
(2)停真空、通氮，加入6.52g二羟甲基丁酸，继续加热至其全部溶解；
(3)冷却至80℃，加入10.90g六亚甲基二异氰酸酯和21.61g异佛尔酮二异氰酸酯，80℃下反应3.5h；
(4)降温至76℃，加入甲基丙烯酸羟乙酯4.1g，继续反应3.5h；再降温至65℃，加入4.25g三乙胺，反应15min；
(5)65℃下，向预聚体中滴加170mL水，500r/min下搅拌乳化15min得到预乳液；将1.325g乙二胺溶于20.5mL水后，向预乳液中滴加，反应30min；
(6)维持75℃、300r/min搅拌的条件下，再向其中滴加溶有10.2g偶氮二异丁睛的丙烯酸酯单体，3h滴完，继续反应2h，然后进行升温熟化；
(7)升温至82℃，反应1h，再升温至85℃，反应45min，再升温至90℃，反应15min；最后冷却至常温，出料。
进一步的，所述步骤(1)中将聚己二酸丁二醇酯和/或聚丙二醇在120℃条件下真空除水1h。
进一步的，所述步骤(6)中丙烯酸酯单体为质量比为2:1的甲基丙烯酸甲酯和丙烯酸丁酯，共113.4g。
一种高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的用途，用作胶粘剂或涂料。
本发明的有益效果如下：
与目前广泛采用的丙酮法合成水性聚氨酯-丙烯酸酯复合乳液工艺相比，本发明提供的方法不使用任何金属催化剂、溶剂和外加乳化剂。不使用有机溶剂，可省去需溶剂脱除和回收后工序以提高生产效率，同时可避免生产与使用过程中人类健康与环境造成的危害；不使用金属催化剂可避免残留金属毒性；不使用外加乳化剂可提高产物耐水性；高固含量乳液具有干燥快、初粘好等优点，同时也降低生产、包装和运输成本。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
一种高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，由以下步骤组成：
(1)将128g聚己二酸丁二醇酯(PBA)在120℃条件下真空除水1h；
(2)停真空、通氮，加入6.52g二羟甲基丁酸(DMBA)，继续加热至其全部溶解；
(3)冷却至80℃，加入10.90g六亚甲基二异氰酸酯(HDI)和21.61g异佛尔酮二异氰酸酯(IPDI)，80℃下反应3.5h；
(4)降温至76℃，加入甲基丙烯酸羟乙酯(HEMA)4.1g，继续反应3.5h；再降温至65℃，加入4.25g三乙胺(TEA)，反应15min；
(5)65℃下，向预聚体中滴加170mL水，500r/min下搅拌乳化15min得到预乳液；将1.325g乙二胺(EDA)溶于20.5mL水后，向预乳液中滴加，反应30min；
(6)维持75℃、300r/min搅拌的条件下，再向其中滴加溶有10.2g偶氮二异丁睛(AIBN)的丙烯酸酯单体，3h滴完，继续反应2h，其中丙烯酸酯单体为质量比为2:1的甲基丙烯酸甲酯和丙烯酸丁酯，共113.4g；
(7)升温至82℃，反应1h，再升温至85℃，反应45min，再升温至90℃，反应15min；最后冷却至常温，出料。
所得复合乳液固含量为60％，粘度为50.7cP，胶膜拉伸强度为13.59mPa，断裂伸长率为902.48％，25℃下24h吸水率为1.62％，60℃36h吸水率为7.12％。平均乳液粒径为104nm，储藏稳定性大于12月。
实施例2：
步骤(1)中将128g聚丙二醇(PPG)在120℃条件下真空除水1h，其余均与实施例1相同。
所得复合乳液固含量为62％，粘度为48.2cP，平均粒径为129nm，胶膜透明，拉伸强度为13.76mPa，断裂伸长率为523.68％，25℃下24h吸水率为3.22％，60℃36h吸水率为17.37％。
实施例3：
步骤(1)中将102.4gPBA和25.6g PPG在120℃条件下真空除水1h，其余均与实施例1相同。
所得复合乳液固含量为65％，粘度为87.6cP，平均粒径为97.3nm，拉伸强度为6.32mPa，断裂伸长率为837.56％，25℃下24h吸水率为1.98％，60℃36h吸水率为8.26％。

Claims (10)

1.一种高固含量环保型水性聚氨酯-丙烯酸酯复合乳液，其特征在于：所述复合乳液固形物含量为60％及以上；制备过程中不使用金属催化剂、有机溶剂和外加乳化剂。
2.如权利要求1所述的高固含量环保型水性聚氨酯-丙烯酸酯复合乳液，其特征在于：所述复合乳液是通过将聚己二酸丁二醇酯和/或聚丙二醇与异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二羟甲基丁酸进行预聚，然后加入甲基丙烯酸羟乙酯封端，随后用三乙胺中和、加水自乳化、扩链，并在无外加乳化剂存在下，与丙烯酸酯单体和/或甲基丙烯酸酯单体共聚得到。
3.一种高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，其特征在于：所用聚合物二元醇由聚己二酸丁二醇酯和聚丙二醇组成；所用二异氰酸酯由摩尔比2:3的六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯组成；所用亲水性扩链剂为二羟甲基丁酸，占水性聚氨酯质量≥4.1％；NCO/OH≥2.0，其中NCO为HDI和IPDI的总摩尔量，OH为聚合物二元醇和DMBA的总摩尔量；聚合在氮气氛围下进行。
4.如权利要求3所述的高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，其特征在于：所得的聚氨酯预聚体用甲基丙烯酸羟乙酯进行封端，反应温度为76℃，反应时间为3-3.5h；随后加入三乙胺进行中和，中和温度为65℃，中和时间为15min。
5.如权利要求3所述的高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，其特征在于：所得聚氨酯预聚体通过自乳化方式得到水性聚氨酯乳液，乳化用水通过滴加方式加入到预聚体中，乳化温度为65℃，乳化时间为15min，搅拌速度为500r/min；所得聚氨酯预乳液采用已二胺水溶液进行扩链，反应温度为65℃。
6.如权利要求3所述的高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，其特征在于：通过向聚氨酯预聚体乳液滴加溶有偶氮二异丁睛的丙烯酸酯单体，进行自由基聚合，反应温度为75℃，反应时间为7h；丙烯酸酯单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸丁酯和丙烯酸异辛酯中的一种或几种的混合物。
7.如权利要求3所述的高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，其特征在于由以下步骤组成：
(1)将128g聚己二酸丁二醇酯和/或聚丙二醇在120℃条件下真空除水，所述聚己二酸丁二醇酯和聚丙二醇摩尔比为10:0，8:2，6:4，0:10中的一种；
(2)停真空、通氮，加入6.52g二羟甲基丁酸，继续加热至其全部溶解；
(3)冷却至80℃，加入10.90g六亚甲基二异氰酸酯和21.61g异佛尔酮二异氰酸酯，80℃下反应3.5h；
(4)降温至76℃，加入甲基丙烯酸羟乙酯4.1g，继续反应3.5h；再降温至65℃，加入4.25g三乙胺，反应15min；
(5)65℃下，向预聚体中滴加170mL水，500r/min下搅拌乳化15min得到预乳液；将1.325g乙二胺溶于20.5mL水后，向预乳液中滴加，反应30min；
(6)维持75℃、300r/min搅拌的条件下，再向其中滴加溶有10.2g偶氮二异丁睛的丙烯酸酯单体，3h滴完，继续反应2h，然后进行升温熟化；
(7)升温至82℃，反应1h，再升温至85℃，反应45min，再升温至90℃，反应15min；最后冷却至常温，出料。
8.如权利要求3所述的高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，其特征在于：所述步骤(1)中将聚己二酸丁二醇酯和/或聚丙二醇在120℃条件下真空除水1h。
9.如权利要求3所述的高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的制备方法，其特征在于：所述步骤(6)中丙烯酸酯单体为质量比为2:1的甲基丙烯酸甲酯和丙烯酸丁酯，共113.4g。
10.一种高固含量环保型水性聚氨酯-丙烯酸酯复合乳液的用途，其特征在于：用作胶粘剂或涂料。
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CN109575192A (zh) * 2018-11-14 2019-04-05 华南理工大学 一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法
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