CN107236440B - 一种多重改性高耐盐雾丙烯酸分散体的制备方法 - Google Patents

一种多重改性高耐盐雾丙烯酸分散体的制备方法 Download PDF

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CN107236440B
CN107236440B CN201710561663.4A CN201710561663A CN107236440B CN 107236440 B CN107236440 B CN 107236440B CN 201710561663 A CN201710561663 A CN 201710561663A CN 107236440 B CN107236440 B CN 107236440B
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周静静
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Xingtai Fuyu New Material Co., Ltd
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Abstract

本发明公开了一种多重改性高耐盐雾丙烯酸分散体的制备方法。所述制备方法包括：溶剂升温；功能单体改性；多异氰酸酯改性；溶剂脱除；中和；高速分散。本发明制备的多重改性高耐盐雾丙烯酸分散体，通过与聚氨酯固化剂、氨基树脂配合，能够有效地减缓金属基材的电化学腐蚀，涂膜不仅具有优良的物理性能还具有优良的耐候性及耐盐雾性能。另外，本发明的产品溶剂含量低于5％，环保无污染，能够适应各行业的应用要求。

Description

一种多重改性高耐盐雾丙烯酸分散体的制备方法
技术领域
本发明涉及化工涂料技术领域，具体涉及一种多重改性高耐盐雾丙烯酸分散体的制备方法。
背景技术
随着科学技术的不断进步，用于装饰、防腐的涂料已由天然油脂涂料、大漆、天然树脂涂料、改性油脂涂料、改性天然树脂涂料发展到合成树脂涂料。但涂料工业的发展是以牺牲环境为代价的，传统溶剂型涂料中的VOC(有机挥发物)在涂装过程中至少有50％以上挥发到环境中，这些有机物对环境及人体均会造成巨大危害。据综合调查数据显示，1/3的白血病儿童发病与家庭装饰装修有直接关系。为了保护环境和人类健康，各国政府都出台了限制涂料VOC的排放法规，同时各国化学工作者也在大力研究各种环保型涂料。如何将高性能和水性涂料的低VOC含量结合起来备受瞩目，成为涂料工业领域研究的热点。
公开号为CN101457005B的中国专利一种含羟基丙烯酸水分散体，以溶液聚合方法合成羟基丙烯酸树脂；溶剂脱除；中和成盐；最后加去离子水分散。先通过一次性加料合成羟基丙烯酸树脂，真空蒸馏除去多余溶剂，将树脂降温，加入中和剂在圆盘分散机中分散进行中和反应，再投入去离子水进行分散得水分散体。但是，按此方法制得的水分散体，粘度高、粒径大、稳定性不高、涂膜性能差。公开号为CN101161701A的中国专利一种作为汽车中涂漆的聚酯水分散体及其制备方法，将多元酸与多元醇混合均匀进行熔融缩聚反应，在反应后期引入亲水基团到聚酷分子链上，然后通过中和成盐的方法制备了一种低酸值，高分子量的可作为汽车中涂漆的聚酷水分散体。这种涂料具有良好的耐水和耐溶剂性能，抗石击能力强，但是涂膜的光泽度和丰满度不高。
有鉴于此，本发明提供一种附着力强、稳定性好、高光泽的改性丙烯酸分散体。
发明内容
本发明的目的在于提供一种多重改性高耐盐雾丙烯酸分散体的制备方法，此方法不仅工艺和设备简单、操作方便，涂膜具有交联密度高，耐化学介质性能强，VOC含量低，光泽度好的特点。
为实现上述目的，本发明提供了一种多重改性高耐盐雾丙烯酸分散体的制备方法。具体地，该方法包括如下步骤：
步骤一、将溶剂置于反应釜中加热至120～130℃；
步骤二、将丙烯酸酯类单体、含羟基特殊功能单体、耐盐雾功能单体和引发剂混匀后，在3h内匀速滴加至所述溶剂中，保温1h；
步骤三、将所述反应釜降温至80～100℃，在1h内向所述反应釜中匀速滴加多异氰酸酯，保温1h；
步骤四、将所述反应釜加热至90℃，0.02Mpa负压条件下抽提至溶剂含量低于10％，制备得到抽提液；
步骤五、将所述抽提液降温至60℃，在0.5h内匀速滴加中和剂，保温搅拌15min，制得聚合物；
步骤六、将去离子水在0.5h内匀速滴加到1000r/min转速下的聚合物中，提高转速至1500r/min搅拌0.5h，即制得多重改性高耐盐雾丙烯酸分散体；
制备过程中所述各组分的质量份数为:
Figure BDA0001347267970000021
Figure BDA0001347267970000031
优选地，所述步骤六中去离子与聚合物的质量份数比为1：1。
优选地，所述溶剂为100#溶剂油、丙二醇甲醚、乙二醇丁醚、丙二醇丁醚或正丁醇中的一种或多种。
优选地，所述丙烯酸酯类单体为丙烯酸、甲基丙烯酸、丙烯酸丁酯、苯乙烯、甲基丙烯酸甲酯或丙烯酸异辛酯中的一种或多种。
优选地，所述含羟基特殊功能单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯中的一种或两种。
优选地，所述耐盐雾功能单体为2-羟乙基甲基丙烯酸酯磷酸酯。
优选地，所述引发剂为过氧化二异丙苯、过氧化叔丁基酯或过氧化叔戊基酯中的一种。
优选地，所述多异氰酸酯为甲苯二异氰酸酯或异弗尔酮二异氰酸酯中的一种。
优选地，所述中和剂为三乙胺或二甲基乙醇胺中的一种。
本发明具有如下优点：
1、本发明的多重改性高耐盐雾丙烯酸分散体的制备方法，利用羟基丙烯酸单体的后交联反应形成交联结构，使交联点增加，交联密度增大，进而提高了涂膜的耐性；同时，通过加入多异氰酸酯，进一步提高多重改性高耐盐雾丙烯酸分散体内部的交联度，从而增强涂膜的稳定性。
2、本发明的多重改性高耐盐雾丙烯酸分散体的制备方法，通过加入高耐盐雾功能单体，使磷酸酯基团在物体表面形成一层致密的磷酸盐保护膜，极大的提高了防腐、防锈性能。
3、本发明的多重改性高耐盐雾丙烯酸分散体的制备方法，生产工艺简单，反应条件温和，生产成本低，其产品溶剂含量低于5％，VOC含量低，光泽度好，稳定性强，不可燃，低异味，施工性能及涂膜的综合性能更能够适应各行业的应用要求。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1
本实施例的多重改性高耐盐雾丙烯酸分散体的制备方法，按以下步骤进行：
步骤一(溶剂升温)、将200g100#溶剂油、150g乙二醇丁醚置于反应釜中加热至125℃；
步骤二(功能单体改性)、将200g丙烯酸、200g丙烯酸异辛酯、150g丙烯酸羟乙酯、55g2-羟乙基甲基丙烯酸酯磷酸酯和12g过氧化二异丙苯混匀后，在3h内匀速滴加至所述溶剂中，保温1h；
步骤三(多异氰酸酯改性)、将所述反应釜降温至90℃，在1h内向所述反应釜中匀速滴加35g异弗尔酮二异氰酸酯，保温1h；
步骤四(溶剂脱除)、将所述反应釜加热至90℃，0.02Mpa负压条件下抽提至溶剂含量低于10％，制备得到抽提液；
步骤五(中和)、将所述抽提液降温至60℃，在0.5h内匀速滴加65g二甲基乙醇胺，保温搅拌15min，制得聚合物；
步骤六(高速分散)、将100g去离子水在0.5h内匀速滴加到1000r/min转速下的100g聚合物中，提高转速至1500r/min搅拌0.5h，即制得固含量为45％的多重改性高耐盐雾丙烯酸分散体。
实施例2
本实施例的多重改性高耐盐雾丙烯酸分散体的制备方法，按以下步骤进行：
步骤一(溶剂升温)、将400g正丁醇置于反应釜中加热至120℃；
步骤二(功能单体改性)、将220g丙烯酸丁酯、440g苯乙烯、400g甲基丙烯酸羟乙酯、120g2-羟乙基甲基丙烯酸酯磷酸酯和26g过氧化叔戊基酯混匀后，在3h内匀速滴加至所述溶剂中，保温1h；
步骤三(多异氰酸酯改性)、将所述反应釜降温至95℃，在1h内向所述反应釜中匀速滴加84g甲苯二异氰酸酯，保温1h；
步骤四(溶剂脱除)、将所述反应釜加热至90℃，0.02Mpa负压条件下抽提至溶剂含量低于10％，制备得到抽提液；
步骤五(中和)、将所述抽提液降温至60℃，在0.5h内匀速滴加170g三乙胺，保温搅拌15min，制得聚合物；
步骤六(高速分散)、将200g去离子水在0.5h内匀速滴加到1000r/min转速下的200g聚合物中，提高转速至1500r/min搅拌0.5h，即制得固含量为45％的多重改性高耐盐雾丙烯酸分散体。
实施例3
本实施例的多重改性高耐盐雾丙烯酸分散体的制备方法，按以下步骤进行：
步骤一(溶剂升温)、将150g100#溶剂油、120g丙二醇甲醚、120g乙二醇丁醚、120g丙二醇丁醚和120g正丁醇置于反应釜中加热至130℃；
步骤二(功能单体改性)、将270g丙烯酸、300g甲基丙烯酸、255g丙烯酸羟丙酯、45g2-羟乙基甲基丙烯酸酯磷酸酯和15g过氧化叔戊基酯混匀后，在3h内匀速滴加至所述溶剂中，保温1h；
步骤三(多异氰酸酯改性)、将所述反应釜降温至100℃，在1h内向所述反应釜中匀速滴加75g异弗尔酮二异氰酸酯，保温1h；
步骤四(溶剂脱除)、将所述反应釜加热至90℃，0.02Mpa负压条件下抽提至溶剂含量低于10％，制备得到抽提液；
步骤五(中和)、将所述抽提液降温至60℃，在0.5h内匀速滴加30g二甲基乙醇胺，保温搅拌15min，制得聚合物；
步骤六(高速分散)、将80g去离子水在0.5h内匀速滴加到1000r/min转速下的80g聚合物中，提高转速至1500r/min搅拌0.5h，即制得固含量为45％的多重改性高耐盐雾丙烯酸分散体。
实施例4
本实施例的多重改性高耐盐雾丙烯酸分散体的制备方法，按以下步骤进行：
步骤一(溶剂升温)、将160g丙二醇丁醚和240g正丁醇置于反应釜中加热至122℃；
步骤二(功能单体改性)、将40g丙烯酸、40g甲基丙烯酸、40g丙烯酸丁酯、40g苯乙烯、40g甲基丙烯酸甲酯、40g丙烯酸异辛酯、112g甲基丙烯酸羟丙酯、64g2-羟乙基甲基丙烯酸酯磷酸酯和7.2g过氧化叔丁基酯混匀后，在3h内匀速滴加至所述溶剂中，保温1h；
步骤三(多异氰酸酯改性)、将所述反应釜降温至85℃，在1h内向所述反应釜中匀速滴加16g甲苯二异氰酸酯，保温1h；
步骤四(溶剂脱除)、将所述反应釜加热至90℃，0.02Mpa负压条件下抽提至溶剂含量低于10％，制备得到抽提液；
步骤五(中和)、将所述抽提液降温至60℃，在0.5h内匀速滴加64g二甲基乙醇胺，保温搅拌15min，制得聚合物；
步骤六(高速分散)、将65g去离子水在0.5h内匀速滴加到1000r/min转速下的65g聚合物中，提高转速至1500r/min搅拌0.5h，即制得固含量为45％的多重改性高耐盐雾丙烯酸分散体。
实施例5
本实施例的多重改性高耐盐雾丙烯酸分散体的制备方法，按以下步骤进行：
步骤一(溶剂升温)、将500g丙二醇甲醚、625g正丁醇置于反应釜中加热至128℃；
步骤二(功能单体改性)、将250g丙烯酸丁酯、500g苯乙烯、500g丙烯酸异辛酯、250g甲基丙烯酸羟乙酯、50g甲基丙烯酸羟丙酯、100g2-羟乙基甲基丙烯酸酯磷酸酯和39g过氧化二异丙苯混匀后，在3h内匀速滴加至所述溶剂中，保温1h；
步骤三(多异氰酸酯改性)、将所述反应釜降温至80℃，在1h内向所述反应釜中匀速滴加100g异弗尔酮二异氰酸酯，保温1h；
步骤四(溶剂脱除)、将所述反应釜加热至90℃，0.02Mpa负压条件下抽提至溶剂含量低于10％，制备得到抽提液；
步骤五(中和)、将所述抽提液降温至60℃，在0.5h内匀速滴加250g三乙胺，保温搅拌15min，制得聚合物；
步骤六(高速分散)、将250g去离子水在0.5h内匀速滴加到1000r/min转速下的250g聚合物中，提高转速至1500r/min搅拌0.5h，即制得固含量为45％的多重改性高耐盐雾丙烯酸分散体。
验证试验
采用上述实施例中制得的多重改性高耐盐雾丙烯酸分散体制备涂料，对本发明的分散体的性能进行验证，涂料的原料及配比如表1所示，对所制得的涂料基本性质进行测定，测定结果如表2所示。
表1采用实施例1～5制得的分散体制备涂料的原料及配比
Figure BDA0001347267970000081
表2验证试验中制备涂料的基本性能
Figure BDA0001347267970000082
通过上述验证试验可知，采用本发明的多重改性高耐盐雾丙烯酸分散体用来制备得到的涂料具有较强的耐水、耐盐雾性能，并且硬度高、附着力强、有光泽。
此外，本发明制备方法操作简单，反应条件温和，生产成本低，产品溶剂含量低于5％，绿色环保，易于实现工业化。
虽然，上文中已经用一般性说明及具体实施例对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (1)

1.一种多重改性高耐盐雾丙烯酸分散体的制备方法，其特征在于：所述制备方法包括以下步骤：
步骤一、将溶剂置于反应釜中加热至120~130℃；
步骤二、将丙烯酸酯类单体、含羟基特殊功能单体、耐盐雾功能单体和引发剂混匀后，在3h内匀速滴加至所述溶剂中，保温1h；
步骤三、将所述反应釜降温至80~100℃，在1h内向所述反应釜中匀速滴加多异氰酸酯，保温1h；
步骤四、将所述反应釜加热至90℃，0.02Mpa负压条件下抽提至溶剂含量低于10%，制备得到抽提液；
步骤五、将所述抽提液降温至60℃，在0.5h内匀速滴加中和剂，保温搅拌15min，制得聚合物；
步骤六、将去离子水在0.5h内匀速滴加到1000r／min转速下的聚合物中，提高转速至1500r／min搅拌0.5h，即制得多重改性高耐盐雾丙烯酸分散体；
制备过程中所述各组分的质量份数为：
溶剂 20~50份；
丙烯酸酯类单体 30~50份；
含羟基特殊功能单体 12~20份；
耐盐雾功能单体 3~8份；
引发剂 0.9~1.56份；
多异氰酸酯 2~5份；
中和剂 2~10份，
所述步骤六中去离子水与聚合物的质量份数比为1：1；
所述溶剂为100#溶剂油、丙二醇甲醚、乙二醇丁醚、丙二醇丁醚或正丁醇中的一种或多种；
所述丙烯酸酯类单体为丙烯酸丁酯、甲基丙烯酸甲酯或丙烯酸异辛酯中的一种或多种；
所述含羟基特殊功能单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯中的一种或两种；
所述耐盐雾功能单体为2-羟乙基甲基丙烯酸酯磷酸酯；
所述引发剂为过氧化二异丙苯、过氧化叔丁基酯或过氧化叔戊基酯中的一种；
所述多异氰酸酯为甲苯二异氰酸酯或异弗尔酮二异氰酸酯中的一种；
所述中和剂为三乙胺或二甲基乙醇胺中的一种。
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