CN112341592A - 一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法 - Google Patents

一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法 Download PDF

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CN112341592A
CN112341592A CN202010999763.7A CN202010999763A CN112341592A CN 112341592 A CN112341592 A CN 112341592A CN 202010999763 A CN202010999763 A CN 202010999763A CN 112341592 A CN112341592 A CN 112341592A
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吴广峰
李迎春
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Changchun University of Technology
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Abstract

本发明是一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法。首先用聚己内酯二醇、葡萄糖、异氟尔酮二异氰酸酯和有机锡催化剂反应一定时间后，将小分子扩链剂二羟甲基丙酸加入体系中继续反应制备聚氨酯预聚体。第二步将定量的去离子水加入到预聚体中进行高速分散，分散后滴入扩链剂2‑[(2‑氨基乙基)氨基]乙磺酸钠水溶液，最后得到一种可降解水性聚氨酯。本发明的优点是利用天然无毒可降解的葡萄糖作为内交联剂，同时利用磺酸型亲水单体，制备出一种可降解的水性聚氨酯。本制备方法工艺简单，只需要添加很少量的有机溶剂，不需加消泡剂，得到的聚氨酯乳液稳定性好，聚氨酯胶膜具有优异的土埋和生物降解性。

Description

一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法
技术领域
本发明涉及一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法。
背景技术
磺酸型水性聚氨酯具有很好的发展优势和应用前景。磺酸型水性聚氨酯具有亲水扩链剂用量少，乳液固含量高，胶膜致密等特点，因此其耐水性、耐电解质性、耐酸碱性、耐高低温性能较好。磺酸型水性聚氨酯在应用过程中具有很多优势且常选用活性高的氨基磺酸盐作为扩链剂，氨基磺酸盐反应活性高于醇类磺酸盐，且研究表明：与醇类小分子扩链剂相比，将胺类扩链剂引入聚氨酯分子链后材料的耐高温性能，强度以及硬度均有很大提高。另外，线型水性聚氨酯由于本身结构构造等因素，成膜后的成品存在着力学性能差、耐水性低和热稳定性差等缺点，交联改性可在本质上将聚氨酯设计成立体网状结构，能从结构上弥补其不足。葡萄糖中含有五个活性羟基，有利于氢键化，促进微相分离，多羟基的引入可提高水性聚氨酯的交联度，宏观上能改善胶膜的耐水性、力学性能和耐溶剂性能。另外，葡萄糖价格低廉和来源丰富，并且具有天然生物可降解等性能，是一种分布在自然界中最广的单糖。葡萄糖可以作为水性聚氨酯的一种交联改性剂，且廉价易得安全环保可再生，有着很好的发展优势和应用前景。
发明内容
为了克服现有水性聚氨酯制备技术上在降解性上的缺陷，本发明的目的在于公开一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法。
本发明的一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的材料和质量配比如下：
二异氰酸酯为异氟尔酮二异氰酸酯，其在合成预聚体中占29.23—30.16%
多元醇为聚己内酯二醇，其在合成预聚体中占64.77—66.84%
内交联剂为葡萄糖，葡萄糖在合成预聚体中占0—3.00%
有机锡催化剂为二月桂酸二丁基锡，在预聚体中占0.01%
羧酸型亲水扩链剂为二羟甲基丙酸，在合成预聚体中占3.00%
后扩链剂为质量分数为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液，2-[(2-氨基乙基)氨基]乙磺酸钠质量占比为0.92—6.23%
中和剂三乙胺，质量占比为2.08—2.19%
所述的聚己内酯二醇分子量Mn为1000 g/mol，预聚体是由聚己内酯二醇、葡萄糖、异氟尔酮二异氰酸酯，有机锡催化剂和小分子扩链剂二羟甲基丙酸反应后得到。
本发明的一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法，步骤和条件如下：
（1）将聚己内酯二醇和葡萄糖加入反应容器中搅拌10 min后将异氟尔酮二异氰酸酯加入反应容器中再搅拌10 min后加入催化剂，在80℃水浴加热及260 r/min的机械搅拌下，保温反应90 min；当反应体系中NCO质量分数达到22—51 %时，将反应体系温度降至40℃，将二羟甲基丙酸加入到反应容器中，再向反应体系中加入10%（预聚体质量为100%）的丙酮调节体系粘度，再升温至70℃下水浴加热及260 r/min的机械搅拌下保温反应90 min，当反应体系中NCO含量达到5—34 %时，将反应体系温度降至35℃，之后加入三乙胺保温反应30min，得到NCO端基的预聚体；
（2）将温度为35℃的去离子水加入到NCO端基的预聚体中进行分散，搅拌速度为850 r/min；同时将2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3 g/min的滴加速度滴入水性聚氨酯分散体中反应30 min；
（3）在一定条件下（温度40℃，真空度-0.09 MPa）脱去体系内丙酮，得到葡萄糖和磺酸盐改性的可降解水性聚氨酯。
有益效果：本发明的一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法其优点如下：（1）磺酸型亲水扩链剂反应活性高，引入聚氨酯分子链后材料的耐高温性能，强度以及硬度均有很大提高，且用量很少时便能达到最好的分散的效果，乳液分散后稳定，可存放一年以上时间。（2）本发明使用的内交联剂为葡萄糖，含有五个活性羟基，有利于氢键化，促进微相分离，多羟基的引入可提高水性聚氨酯的交联度，宏观上能改善胶膜的耐水性、力学性能和耐溶剂性能且葡萄糖本身是一种廉价易得安全环保可再生可降解的材料。本发明使用的多元醇为聚己内酯二醇，是一种容易降解的材料，能够增加聚氨酯的结晶性及弹性力学性能。（3）本发明的葡萄糖和磺酸盐改性的可降解水性聚氨酯制备过程简单，只用少量的有机溶剂且最终被脱除，产品具有优异的降解性和乳液稳定性（大于一年）。
具体实施方式
实施例1
葡萄糖和磺酸盐改性的可降解水性聚氨酯的材料和质量配比如下:
异氟尔酮二异氰酸酯在预聚体中占30.00%；聚己内酯二醇在预聚体中占66.49%；葡萄糖在预聚体中占0.50%；二月桂酸二丁基锡，在预聚体中占0.01%，二羟甲基丙酸在预聚体中占3.00%；三乙胺2.10%；2-[(2-氨基乙基)氨基]乙磺酸钠5.39%。
具体的加入量如下：异氟尔酮二异氰酸酯，质量10 g；聚己内酯二醇，质量22.16g；葡萄糖，质量0.167 g；二月桂酸二丁基锡，质量0.003 g;二羟甲基丙酸，质量1.002 g；三乙胺，质量0.755 g；2-[(2-氨基乙基)氨基]乙磺酸钠，质量1.94 g。
其制备方法：
（1）聚己内酯二醇和葡萄糖加入反应容器中以260 r/min的机械搅拌10 min，再将异氟尔酮二异氰酸酯加入反应容器中搅拌10 min后加入催化剂，在80℃水浴加热及260 r/min的机械搅拌下，保温反应90 min；当反应体系中NCO质量分数达到46%时，将反应体系温度降至40℃，将二羟甲基丙酸加入到反应容器中，再向反应体系中加入10%（预聚体质量为100%）的丙酮调节体系粘度，再升温至70℃下水浴加热及260 r/min的机械搅拌下保温反应90min，当反应体系中NCO含量达到30%时，将反应体系温度降至35℃，之后加入三乙胺保温反应30 min，得到NCO端基的预聚体；
（2）将温度为35℃的去离子水加入到NCO端基的预聚体中进行分散，搅拌速度为850 r/min；同时将2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3 g/min的滴加速度滴入水性聚氨酯分散体中反应30 min；
（3）在一定条件下（温度40℃，真空度-0.09 MPa）脱去体系内丙酮，得到葡萄糖和磺酸盐改性的可降解水性聚氨酯。
实施例2
葡萄糖和磺酸盐改性的可降解水性聚氨酯的原料和原料占单体总数的质量配比如下:
异氟尔酮二异氰酸酯在预聚体中29.69%；聚己内酯二醇在预聚体中占65.80%；葡萄糖在预聚体中占1.50%；二月桂酸二丁基锡，在预聚体中占0.01%；二羟甲基丙酸在预聚体中占3.00%；三乙胺2.13%；2-[(2-氨基乙基)氨基]乙磺酸钠3.65%。
具体的加入量如下：异氟尔酮二异氰酸酯，质量10 g；聚己内酯二醇，质量22.16g；葡萄糖，质量0.505；二月桂酸二丁基锡，质量0.003 g；二羟甲基丙酸，质量1.01 g；三乙胺，质量0.762 g；2-[(2-氨基乙基)氨基]乙磺酸钠，质量1.306 g。
其制备方法：
（1）聚己内酯二醇和葡萄糖加入反应容器中260 r/min的机械搅拌10 min钟，再将异氟尔酮二异氰酸酯加入反应容器中搅拌10 min后加入催化剂，在80℃水浴加热及260 r/min的机械搅拌下，保温反应90 min；当反应体系中NCO质量分数达到37%时，将反应体系温度降至40℃，将二羟甲基丙酸加入到反应容器中，再向反应体系中加入10%（预聚体质量为100%）的丙酮调节体系粘度，再升温至70℃下水浴加热及260 r/min的机械搅拌下保温反应90min，当反应体系中NCO含量达到20%时，将反应体系温度降至35℃，之后加入三乙胺保温反应30 min，得到NCO端基的预聚体；
（2）将温度为35℃的去离子水加入到NCO端基的预聚体中进行分散，搅拌速度为850 r/min；同时将2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3 g/min的滴加速度滴入水性聚氨酯分散体中反应30 min；
（3）在一定条件下（温度40℃，真空度-0.09 MPa）脱去体系内丙酮，得到葡萄糖和磺酸盐改性的可降解水性聚氨酯。
实施例3
葡萄糖和磺酸盐改性的可降解水性聚氨酯的原料和原料占单体总数的质量配比如下:
异氟尔酮二异氰酸酯在预聚体中29.38%；聚己内酯二醇在预聚体中占65.11%；葡萄糖在预聚体中占2.57%；葡萄糖在预聚体中占2.50%；二月桂酸二丁基锡，在预聚体中占0.01%；二羟甲基丙酸在预聚体中占3.00%；三乙胺2.17%；2-[(2-氨基乙基)氨基]乙磺酸钠1.86%。
具体的加入量如下：异氟尔酮二异氰酸酯，质量10 g；聚己内酯二醇，质量22.16g；葡萄糖，质量0.851 g；二月桂酸二丁基锡，质量0.003 g；二羟甲基丙酸，质量1.021 g；三乙胺，质量0.770 g；2-[(2-氨基乙基)氨基]乙磺酸钠，质量0.658 g。
其制备方法：
（1）聚己内酯二醇和葡萄糖加入反应容器中260 r/min的机械搅拌10 min，再将异氟尔酮二异氰酸酯加入反应容器中搅拌10 min后加入催化剂，在80℃水浴加热及260 r/min的机械搅拌下，保温反应90 min；当反应体系中NCO质量分数达到27%时，将反应体系温度降至40℃，将二羟甲基丙酸加入到反应容器中，再向反应体系中加入10%（预聚体质量为100%）的丙酮调节体系粘度，再升温至70℃下水浴加热及260 r/min的机械搅拌下保温反应90 min，当反应体系中NCO含量达到10%时，将反应体系温度降至35℃，之后加入三乙胺保温反应30min，得到NCO端基的预聚体；
（2）将温度为35℃的去离子水加入到NCO端基的预聚体中进行分散，搅拌速度为850 r/min；同时将2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3 g/min的滴加速度滴入水性聚氨酯分散体中反应30 min；
（3）在一定条件下（温度40℃，真空度-0.09 MPa）脱去体系内丙酮，得到葡萄糖和磺酸盐改性的可降解水性聚氨酯。

Claims (2)

1.一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法，其特征在于，一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的材料和质量配比如下：
二异氰酸酯为异氟尔酮二异氰酸酯，其在合成预聚体中占29.23—30.16%
多元醇为聚己内酯二醇，其在合成预聚体中占64.77—66.84%
内交联剂为葡萄糖，葡萄糖在合成预聚体中占0—3.00%
有机锡催化剂为二月桂酸二丁基锡，在预聚体中占0.01%
羧酸型亲水扩链剂为二羟甲基丙酸，在合成预聚体中占3.00%
后扩链剂为质量分数为50%的2-[(2-氨基乙基)氨基]乙磺酸钠水溶液，2-[(2-氨基乙基)氨基]乙磺酸钠质量占比为0.92—6.23%
中和剂三乙胺，质量占比为2.08—2.19%
所述的聚己内酯二醇分子量Mn为1000 g/mol，预聚体是由聚己内酯二醇、葡萄糖、异氟尔酮二异氰酸酯，有机锡催化剂和小分子扩链剂二羟甲基丙酸反应后得到。
2.根据权利要求1所述的一种葡萄糖和磺酸盐改性的可降解水性聚氨酯的制备方法，步骤和条件如下：
（1）将聚己内酯二醇和葡萄糖加入反应容器中搅拌10 min后将异氟尔酮二异氰酸酯加入反应容器中再搅拌10 min后加入催化剂，在80℃水浴加热及260 r/min的机械搅拌下，保温反应90 min；当反应体系中NCO质量分数达到22—51 %时，将反应体系温度降至40℃，将二羟甲基丙酸加入到反应容器中，再向反应体系中加入10%（预聚体质量为100%）的丙酮调节体系粘度，再升温至70℃下水浴加热及260 r/min的机械搅拌下保温反应90 min，当反应体系中NCO含量达到5—34 %时，将反应体系温度降至35℃，之后加入三乙胺保温反应30min，得到NCO端基的预聚体；
（2）将温度为35℃的去离子水加入到NCO端基的预聚体中进行分散，搅拌速度为850 r/min；同时将2-[(2-氨基乙基)氨基]乙磺酸钠水溶液以2-3 g/min的滴加速度滴入水性聚氨酯分散体中反应30 min；
（3）在一定条件下（温度40℃，真空度-0.09 MPa）脱去体系内丙酮，得到葡萄糖和磺酸盐改性的可降解水性聚氨酯。
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