CN107383323A - 松香基芳香族型水性聚氨酯的制备方法 - Google Patents

松香基芳香族型水性聚氨酯的制备方法 Download PDF

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CN107383323A
CN107383323A CN201710688203.8A CN201710688203A CN107383323A CN 107383323 A CN107383323 A CN 107383323A CN 201710688203 A CN201710688203 A CN 201710688203A CN 107383323 A CN107383323 A CN 107383323A
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余彩莉
边峰
张发爱
陈勇
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Guilin University of Technology
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Abstract

本发明公开了一种松香基芳香族型水性聚氨酯的制备方法。将丙酮溶解的丙烯酸松香GMA酯化物、聚乙二醇‑1000、催化剂二丁基二月桂酸锡加入至反应釜中，N2保护下加热至30℃，加入甲苯‑2，4‑二异氰酸酯进行预聚反应，用丙酮‑二正丁胺法测定‑NCO含量降为理论值时加2，2‑二羟甲基丙酸，将体系升温至55℃，待‑NCO含量为零时将体系降温至18℃，向反应器中加入三乙胺中和10分钟，在1300 r/min下加入去离子水进行乳化分散30分钟，减压蒸馏除去溶剂丙酮。本发明以RAG/PEG‑1000为多元醇，水为溶剂制备得到水性聚氨酯树脂，涂膜具有光泽度高、柔韧性和附着力好、硬度和耐冲击强度高等优良特性。

Description

松香基芳香族型水性聚氨酯的制备方法
技术领域
本发明涉及松香基芳香族型水性聚氨酯的制备方法。
背景技术
水性聚氨酯是指在聚氨酯的主链或者侧链引入亲水性基团，或者釆用外加乳化剂的方法使得聚氨酯能溶于水，或者分散于水中而形成的聚氨酯水分散体。水性聚氨酯符合生态环境的要求，健康、环保、高效，可广泛应用于涂料、胶粘剂、织物涂层与整理剂、皮革涂饰剂、纸张表面处理剂和纤维表面处理剂等，成为聚氨酯工业发展的重要方向。传统的溶剂型聚氨酯在合成过程中需要使用大量的有机溶剂，在生产和应用过程中产生大量的挥发性有机物，不仅对环境造成污染，而且严重危害人体健康。随着人们环保意识的提高，以水为介质的安全、清洁聚氨酯分散体应用技术得到快速发展，聚氨酯材料的水性化日益受到重视，未来顺应市场潮流的水性聚氨酯将成为低投入、高产出、低消耗、少污染、可持续发展的朝阳产业。
松香作为一种丰富的天然可再生林产资源，在日常生活、工业生产、科学研究等领域得到广泛应用。利用松香分子结构中的共轭双键和羧基两个反应活性中心，通过改性可以将松香引入到高分子材料中，制备出物理性能和机械性能优异的高分子材料，从而扩大松香的应用领域。本发明以松香为原料，通过改性得到丙烯酸松香，以其中的两个羧基与甲基丙烯酸缩水甘油酯（GMA）反应，得到含有两个羟基的丙烯酸松香GMA酯化物（RAG），再与聚乙二醇-1000以及甲苯-2，4-二异氰酸酯（TDI）、亲水性扩链剂2，2-二羟甲基丙酸（DMPA）等反应制备水性聚氨酯，本发明为合理开发利用松香资源提供新的应用途径。
发明内容
本发明的目的是提供一种具有良好涂膜性能的松香基芳香族型水性聚氨酯的制备方法。
本发明的具体步骤为：
将440~510质量份丙酮溶解的100.0质量份丙烯酸松香GMA酯化物、15.0~40.0质量份聚乙二醇-1000、0.6~1.0质量份催化剂二丁基二月桂酸锡加入至反应釜中，N2保护下加热至30℃进行反应，加入40.0~48.0质量份甲苯-2，4-二异氰酸酯进行预聚反应，用丙酮-二正丁胺法测定-NCO含量降为理论值时加入15.0~22.0质量份2，2-二羟甲基丙酸，并将体系升温至55℃，待-NCO含量为零时将体系降温至18℃，向反应器中加入12.0~16.0质量份三乙胺中和10分钟，在1300 r/min下快速加入770~ 885质量份去离子水进行乳化分散30分钟，减压蒸馏除去溶剂丙酮，得到松香基芳香族型水性聚氨酯。
所述化学试剂：丙烯酸松香GMA的酯化物（RAG），自制，酸值为4.0 mg KOH·g-1，固体质量百分比为92.0%；甲苯-2，4-二异氰酸酯、二丁基二月桂酸锡和聚乙二醇-1000为化学纯；1，4-丁二醇、丙酮、二正丁氨、盐酸和三乙胺为分析纯。
本发明与其它相关技术相比，最显著的特点是以天然可再生林产资源—松香为原料，经改性得到丙烯酸松香GMA酯化物（RAG），再以RAG/PEG-1000为多元醇，与TDI以及DMPA等聚合得到芳香族型水性聚氨酯树脂，将其应用在涂料领域，得到光泽度高、柔韧性好、附着力好、硬度较高、耐冲击强度高等优良特性的聚氨酯漆膜。不仅赋予了松香更为广泛的应用，而且还得到了综合性能优良的聚氨酯树脂。
具体实施方式
下述化学试剂：丙烯酸松香GMA的酯化物（RAG），自制，酸值为4.0 mg KOH·g-1，固体质量百分比为92.0%；甲苯-2，4-二异氰酸酯、二丁基二月桂酸锡和聚乙二醇-1000为化学纯；1，4-丁二醇、丙酮、二正丁氨、盐酸和三乙胺为分析纯。
实施例1：
将500质量份丙酮溶解的100.0质量份丙烯酸松香GMA酯化物（RAG）、38.0质量份聚乙二醇-1000（PEG-1000）、0.9质量份催化剂二丁基二月桂酸锡（DBTDL）加入至反应釜中，N2保护下加热至30℃，加入46.3质量份甲苯-2，4-二异氰酸酯（TDI）进行预聚反应，用丙酮-二正丁胺法测定-NCO含量降为理论值时加入20.3质量份2，2-二羟甲基丙酸（DMPA），并将体系升温至55℃，待-NCO含量为零时将体系降温至18℃，向反应器中加入15.3质量份三乙胺（TEA）中和10分钟，在1300 r/min下快速加入875.0质量份去离子水进行乳化分散30分钟，，减压蒸馏除去溶剂丙酮，得到松香基芳香族型水性聚氨酯。加入去离子水调节其固体质量百分比为18.0%，均匀地涂布在玻璃板和马口铁板上，在25℃条件下干燥48小时，得到厚度为20.0um的漆膜，测得其光泽度为143.8，铅笔硬度为HB，柔韧性为1 mm，附着力为1级，冲击强度达到50 cm·Kg。
实施例2：
将470.6质量份丙酮溶解的100.0质量份丙烯酸松香GMA酯化物（RAG）、26.8质量份聚乙二醇-1000（PEG-1000）、0.9质量份催化剂二丁基二月桂酸锡（DBTDL）加入至反应釜中，N2保护下加热至30℃，加入43.5质量份甲苯-2，4-二异氰酸酯（TDI）进行预聚反应，用丙酮-二正丁胺法测定-NCO含量降为理论值时加入18.7质量份2，2-二羟甲基丙酸（DMPA），并将体系升温至55℃，待-NCO含量降为零时将体系降温至18℃，向反应器中加入14.1质量份三乙胺（TEA）中和10分钟，在1300 r/min下快速加入823.5质量份去离子水进行乳化分散30分钟，，减压蒸馏除去溶剂丙酮，得到松香基芳香族型水性聚氨酯。加入去离子水调节其固体质量百分比为18.0%，均匀地涂布在玻璃板和马口铁板上，在25℃条件下干燥48小时，得到厚度为20.0 um的漆膜，测得其光泽度为145.9，铅笔硬度为H，柔韧性为1 mm，附着力为1级，冲击强度达到50 cm·Kg。
实施例3：
将444.4质量份丙酮溶解的100.0质量份丙烯酸松香GMA酯化物（RAG）、16.9质量份聚乙二醇-1000（PEG-1000）、0.8质量份催化剂二丁基二月桂酸锡（DBTDL）加入至反应釜中，N2保护下加热至30℃，加入41.1质量份甲苯-2，4-二异氰酸酯（TDI）进行预聚反应，用丙酮-二正丁胺法测定-NCO含量降为理论值时加入17.4质量份2，2-二羟甲基丙酸（DMPA），并将体系升温至55℃，待-NCO含量为零时将体系降温至18℃，向反应器中加入13.1质量份三乙胺（TEA）中和10分钟，在1300 r/min下快速加入777.7质量份去离子水进行乳化分散30分钟，减压蒸馏除去溶剂丙酮，得到松香基芳香族型水性聚氨酯。加入去离子水调节其固体质量百分比为18.0%，均匀地涂布在玻璃板和马口铁板上，在25℃条件下干燥48小时，得到厚度为20.0um的漆膜，测得其光泽度为148.3，铅笔硬度为2H，柔韧性为3 mm，附着力为2级，冲击强度达到40 cm·Kg。

Claims (1)

1.一种松香基芳香族型水性聚氨酯的制备方法，其特征在于具体步骤为：
将440~510质量份丙酮溶解的100.0质量份丙烯酸松香GMA酯化物、15.0~40.0质量份聚乙二醇-1000、0.6~1.0质量份催化剂二丁基二月桂酸锡加入至反应釜中，N2保护下加热至30℃进行反应，加入40.0~48.0质量份甲苯-2，4-二异氰酸酯进行预聚反应，用丙酮-二正丁胺法测定-NCO含量降为理论值时加入15.0~22.0质量份2，2-二羟甲基丙酸，并将体系升温至55℃，待-NCO含量为零时将体系降温至18℃，向反应器中加入12.0~16.0质量份三乙胺中和10分钟，在1300 r/min下快速加入770~ 885质量份去离子水进行乳化分散30分钟，减压蒸馏除去溶剂丙酮，得到松香基芳香族型水性聚氨酯；
所述化学试剂：丙烯酸松香GMA的酯化物，自制，酸值为4.0 mg KOH·g-1，固体质量百分比为92.0%；甲苯-2，4-二异氰酸酯、二丁基二月桂酸锡和聚乙二醇为化学纯；1，4-丁二醇、丙酮、二正丁氨、盐酸和三乙胺为分析纯。
CN201710688203.8A 2017-08-12 2017-08-12 松香基芳香族型水性聚氨酯的制备方法 Pending CN107383323A (zh)

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Citations (3)

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JP2001200029A (ja) * 2000-01-21 2001-07-24 Nicca Chemical Co Ltd ロジン含有水性アクリル−ウレタン共重合物、塗工剤及び接着剤
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Application publication date: 20171124