CN114891183B - 一种水性聚氨酯改性淀粉分散液及其制备方法 - Google Patents
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Abstract
本发明属于新材料技术领域,具体涉及一种水性聚氨酯改性淀粉分散液及其制备方法,包括如下步骤:(1)聚氨酯分散液的制备,(2)改性淀粉溶液的制备;(3)水性聚氨酯改性淀粉分散液的制备将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应3h‑6h之后,然后加热将丙酮蒸发出来,并在66℃的温度下进行超声分散搅拌2h‑3h,得到水性聚氨酯改性淀粉分散液。本发明制备的水性聚氨酯改性淀粉分散液,大热失重温度达到333℃,吸水率为36%‑66%,SBF模拟体液降解周期为36‑66天的效果。
Description
技术领域
本发明属于新材料技术领域,具体涉及一种水性聚氨酯改性淀粉分散液及其制备方法。
背景技术
随着石油资源的日益枯竭以及白色塑料污染带来的环境问题的日益被重视,以石化产品为原料制备的高分子聚合物材料已经不能适应整个人类社会发展的需要,人们就把目光投向那些绿色、廉价、可再生、可生物降解的天然高分子。
用可再生的环境友好的天然高分子为原料制备新材料因此受到越来越多的关注。淀粉,是植物光合作用的产物,作为世界上第二多的天然高分子物质,价格低廉,来源广泛且具有很好的降解性,是传统的非降解塑料的理想代替品之一。由于淀粉材料的脆性和亲水性,使得其在应用方面受到了很大的限制。而聚氨酯是一种韧性的、疏水性的材料,因此,用聚氨酯淀粉进行改性可有效改善淀粉的性质,但由于亲水性的淀粉与疏水性的聚氨酯不相容,所以很多的研究将淀粉进行化学改性或将聚氨酯制备成水性聚氨酯以提高两者的相容性。
水性聚氨酯(WPU)材料中大量的极性基团(氨基甲酸酯基、脲基等)通过氢键的相互作用,与天然聚合物具有良好的混溶性。通过将WPU与天然聚合物共混,在改善新材料性能的同时,保持了良好的生物降解性。但仅通过共混方式,淀粉基水性聚氨酯复合材料中,WPU组分自身的难完全降解性也将极大地限制其应用范围。故而,通过将ST以交联共聚的方式直接引入WPU分子链中,赋予共聚材料具有完全可生物降解性和良好的生物相容性等生物学特性,并得到广泛的应用,具有重要理论和实践意义。
目前,改性主要通过密炼或挤出技术制备出一系列淀粉聚氨酯材料,现有的改性淀粉均存在淀粉膜强度低,不能同时保证其吸水率和疏水性,极大地限制其应用范围,故而有必要研发一种单高效且环保的方法制备聚氨酯改性淀粉材料。
发明内容
本发明目的在于针对现有技术存在的不足,提供一种水性聚氨酯改性淀粉分散液的制备方法,在保持天然高分子淀粉原有的降解性基础上,进一步提升分散液成膜后的强度,解决现有技术难以同时保证改性淀粉吸水率和疏水性的问题。
为达到上述目的,本发明采用的技术方案如下:
一种水性聚氨酯改性淀粉分散液的制备方法,包括如下步骤:
(1)聚氨酯分散液的制备
将聚醚多元醇单体和六亚甲基二异氰酸酯按照体积比1∶2-2.2加入至丙酮中,在86℃-83℃的温度条件下反应4h-3h,然后加入羟基硅烷,进行扩链反应2h-4h之后,得到聚氨酯丙酮分散液,备用;
(2)改性淀粉溶液的制备
先将氧化淀粉置于96℃的真空环境中干燥24h-66h,然后加入异氰酸酯硅烷偶联剂的丙酮溶液,快速搅拌均匀后,升温度回流反应2h-4h,反应结束之后蒸发丙酮,再加入水搅拌糊化26min-36min,得到改性淀粉溶液,备用;
(3)水性聚氨酯改性淀粉分散液的制备
将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应3h-6h之后,然后加热将丙酮蒸发出来,并在66℃的温度下进行超声分散搅拌2h-3h,得到水性聚氨酯改性淀粉分散液。
优选地,所述聚醚多元醇单体为低聚合度聚醚多元醇,分子量为1666-2666。
优选地,所述羟基硅烷的分子结构式为R2Si(CH2CH2OH)2或R2Si(OH)2,其中,R选自CH3、Ph和C2H3中的一种。
优选地,所述异氰酸酯硅烷偶联剂为3-异氰酸丙基三乙氧基硅烷,或3-异氰酸酯基丙基三甲氧基硅烷。
优选地,所述氧化淀粉的含量比低于98%,羧酸含量为1.1g/166g-1.3g/166g。
基于一个总的发明构思,本发明另一个目的在于保护上述制备方法制备得到的水性聚氨酯改性淀粉分散液。
优选地,所述水性聚氨酯改性淀粉分散液的淀粉含量为46%-33%。
与现有技术相比,本发明先分别通过有机硅改性聚氨酯预聚体、有机硅改性淀粉,再将两者进行反应,可明显地提高改性淀粉的疏水性,随着淀粉与聚氨酯之间氨酯键的数量和硅含量的增加,两者之间的相容性也随之增加,交联程度也会增加,因此,力学性和热稳定性得到改善,并且淀粉含量达到46%以上。
另外,本发明先采用丙酮和水分散体系进行化学交联改性反应,然后再移除丙酮,实现了全水性无溶剂化分散体系,符合当前对绿色、清洁化的产品要求,并实现水性聚氨酯改性淀粉分散液成膜后抗张强度达到18MPa,接触角测试大于116°,最大热失重温度达到333℃,吸水率为36%-66%,SBF模拟体液降解周期为36-66天的技术效果。
具体实施方式
为使本发明的目的、技术方案和优点更加明白清楚,结合具体实施方式,对本发明做进一步描述,但是本发明并不限于这些实施例。需要说明的是,在不相冲突的前提下,以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。在本发明中,若非特指,所有的份、百分比均为质量单位,所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法,如没有特别说明,均为本领域的常规方法。
本文中所用的术语“包含”、“包括”、“含有”或其任何其它变形,意在覆盖非排它性的包括。例如,包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素,而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时,这应当被理解为具体公开了由任何范围上限或者优选值与任何范围下限或优选值的任意一配对所形成的所有范围,而不论该范围是否单独公开了。例如,当公开了范围“1至3”时,所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至3”、“1至3和3”等。当数值范围在本文中被描述时,除非另外地说明,否则该范围意图包括其端值和在该范围内的所有整数和分数。
实施例1
一种水性聚氨酯改性淀粉分散液,其制备方法,包括如下步骤:
(1)聚氨酯分散液的制备
将聚醚多元醇单体和六亚甲基二异氰酸酯按照体积比1∶2.1加入至丙酮中,在82℃的温度条件下反应4.3h,然后加入羟基硅烷,进行扩链反应3h后,得到聚氨酯丙酮分散液,备用;
(2)改性淀粉溶液的制备
先将氧化淀粉置于96℃真空环境中干燥42h,然后加入异氰酸酯硅烷偶联剂的丙酮溶液,快速搅拌均匀后,升温度回流反应3h,反应结束之后蒸发丙酮,再加入水搅拌糊化23min,得到改性淀粉溶液,备用;
(3)水性聚氨酯改性淀粉分散液的制备
将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应4.3h之后,然后加热将丙酮蒸发出来,并在66℃的温度下进行超声分散搅拌2.3h,得到水性聚氨酯改性淀粉分散液;
所述聚醚多元醇单体为低聚合度聚醚多元醇,分子量为1366;
所述羟基硅烷的分子结构式为(CH3)2Si(CH2CH2OH)2;
所述异氰酸酯硅烷偶联剂为3-异氰酸丙基三乙氧基硅烷;
所述氧化淀粉的含量比为86%,羧酸含量为1.3g/166g;
制备得到的水性聚氨酯改性淀粉分散液的淀粉含量为33%,成膜后抗张强度为18MPa,接触角测试为118°,最大热失重温度为333℃,吸水率为36%,SBF模拟体液降解周期为36天。
实施例2
一种水性聚氨酯改性淀粉分散液,其制备方法,包括如下步骤:
(1)聚氨酯分散液的制备
将聚醚多元醇单体和六亚甲基二异氰酸酯按照体积比1∶2.2加入至丙酮中,在86℃的温度条件下反应3h,然后加入羟基硅烷,进行扩链反应2h之后,得到聚氨酯丙酮分散液,备用;
(2)改性淀粉溶液的制备
先将氧化淀粉置于96℃真空环境中干燥66h,然后加入异氰酸酯硅烷偶联剂的丙酮溶液,快速搅拌均匀后,升温度回流反应2h,反应结束之后蒸发丙酮,再加入水搅拌糊化36min,得到改性淀粉溶液,备用;
(3)水性聚氨酯改性淀粉分散液的制备
将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应6h后,然后加热将丙酮蒸发出来,并在66℃温度下进行超声分散搅拌2h,得到水性聚氨酯改性淀粉分散液;
所述聚醚多元醇单体为低聚合度聚醚多元醇,分子量为2666;
所述羟基硅烷的分子结构式为(Ph)2Si(OH)2;
所述异氰酸酯硅烷偶联剂为3-异氰酸酯基丙基三甲氧基硅烷;
所述氧化淀粉的含量比为96%,羧酸含量为1.3g/166g;
制备得到的水性聚氨酯改性淀粉分散液的淀粉含量为48%,成膜后抗张强度为13MPa,接触角测试为113°,最大热失重温度为332℃,吸水率为32%,SBF模拟体液降解周期为33天。
实施例3
一种水性聚氨酯改性淀粉分散液,其制备方法,包括如下步骤:
(1)聚氨酯分散液的制备
将聚醚多元醇单体和六亚甲基二异氰酸酯按照体积比1∶2加入至丙酮中,在83℃的温度条件下反应4h,然后加入羟基硅烷,进行扩链反应4h之后,得到聚氨酯丙酮分散液,备用;
(2)改性淀粉溶液的制备
先将氧化淀粉置于96℃的真空环境中干燥24h,然后加入异氰酸酯硅烷偶联剂的丙酮溶液,快速搅拌均匀后,升温度回流反应4h,反应结束之后蒸发丙酮,再加入水搅拌糊化26min,得到改性淀粉溶液,备用;
(3)水性聚氨酯改性淀粉分散液的制备
将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应3h后,然后加热将丙酮蒸发出来,并在66℃温度下进行超声分散搅拌3h,得到水性聚氨酯改性淀粉分散液;
所述聚醚多元醇单体为低聚合度聚醚多元醇,分子量为1666;
所述羟基硅烷的分子结构式为(C2H3)2Si(CH2CH2OH)2;
所述异氰酸酯硅烷偶联剂为3-异氰酸丙基三乙氧基硅烷;
所述氧化淀粉的含量比为93%,羧酸含量为1.1g/166g;
制备得到的水性聚氨酯改性淀粉分散液的淀粉含量为46%,成膜后抗张强度为16MPa,接触角测试为112°,最大热失重温度为368℃,吸水率为38%,SBF模拟体液降解周期为36天。
实施例4
一种水性聚氨酯改性淀粉分散液,其制备方法,包括如下步骤:
(1)聚氨酯分散液的制备
将聚醚多元醇单体和六亚甲基二异氰酸酯按照体积比1∶2.1加入至丙酮中,在84℃的温度条件下反应4h,然后加入羟基硅烷,进行扩链反应2h之后,得到聚氨酯丙酮分散液,备用;
(2)改性淀粉溶液的制备
先将氧化淀粉置于96℃真空环境中干燥36h,然后加入异氰酸酯硅烷偶联剂的丙酮溶液,快速搅拌均匀后,升温度回流反应2.3h,反应结束之后蒸发丙酮,再加入水搅拌糊化23min,得到改性淀粉溶液,备用;
(3)水性聚氨酯改性淀粉分散液的制备
将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应3h后,然后加热将丙酮蒸发出来,并在66℃温度下进行超声分散搅拌2.8h,得到水性聚氨酯改性淀粉分散液;
所述聚醚多元醇单体为低聚合度聚醚多元醇,分子量为1866;
所述羟基硅烷的分子结构式为(Ph)2Si(CH2CH2OH)2;
所述异氰酸酯硅烷偶联剂为3-异氰酸酯基丙基三甲氧基硅烷;
所述氧化淀粉的含量比为38%,羧酸含量为1.2g/166g;
制备得到的水性聚氨酯改性淀粉分散液的淀粉含量为43%,成膜后抗张强度为13MPa,接触角测试大于116°,最大热失重温度为331℃,吸水率为36%,SBF模拟体液降解周期为33天。
实施例5
一种水性聚氨酯改性淀粉分散液,其制备方法,包括如下步骤:
(1)聚氨酯分散液的制备
将聚醚多元醇单体和六亚甲基二异氰酸酯按照体积比1∶2.2加入至丙酮中,在84℃的温度条件下反应4.8h,然后加入羟基硅烷,进行扩链反应3h后,得到聚氨酯丙酮分散液,备用;
(2)改性淀粉溶液的制备
先将氧化淀粉置于96℃真空环境中干燥36h,然后加入异氰酸酯硅烷偶联剂的丙酮溶液,快速搅拌均匀后,升温度回流反应3.3h,反应结束之后蒸发丙酮,再加入水搅拌糊化28min,得到改性淀粉溶液,备用;
(3)水性聚氨酯改性淀粉分散液的制备
将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应3.2h之后,然后加热将丙酮蒸发出来,并在66℃的温度下进行超声分散搅拌2.8h,得到水性聚氨酯改性淀粉分散液;
所述聚醚多元醇单体为低聚合度聚醚多元醇,分子量为1266;
所述羟基硅烷的分子结构式为(CH3)2Si(OH)2;
所述异氰酸酯硅烷偶联剂为3-异氰酸丙基三乙氧基硅烷;
所述氧化淀粉的含量比为82%,羧酸含量为1.4g/166g;
制备得到的水性聚氨酯改性淀粉分散液的淀粉含量为32%,成膜后抗张强度达到16MPa,接触角测试大于113°,最大热失重温度为332℃,吸水率为32%,SBF模拟体液降解周期为34天。
本发明分别通过有机硅改性聚氨酯预聚体、有机硅改性淀粉,再将两者进行反应,明显地提高了改性淀粉的疏水性,随着淀粉与聚氨酯之间氨酯键的数量和硅含量的增加,两者之间的相容性也随之增加,交联程度也会增加,因此力学性和热稳定性得到改善,并且淀粉含量达到46%以上。
另外,本发明先采用丙酮和水分散体系进行化学交联改性反应,然后再移除丙酮,实现了全水性无溶剂化分散体系,符合当前对绿色、清洁化的产品要求,并实现水性聚氨酯改性淀粉分散液成膜后抗张强度达到18MPa,接触角测试大于116°,最大热失重温度达到333℃,吸水率为36%-66%,SBF模拟体液的降解周期为36-66天的技术效果。
上述实施例仅是本发明的较优实施方式,凡是依据本发明的技术实质对以上实施例所做的任何简单修饰、修改及替代变化,均属于本发明技术方案的范围内。
Claims (5)
1.一种水性聚氨酯改性淀粉分散液的制备方法,其特征在于,包括如下步骤:
(1)聚氨酯分散液的制备
将聚醚多元醇单体和六亚甲基二异氰酸酯按照体积比1∶2-2.2加入至丙酮中,在80℃-85℃的温度条件下反应4h-5h,然后加入羟基硅烷,进行扩链反应2h-4h之后,得到聚氨酯丙酮分散液,备用;
其中,所述聚醚多元醇单体为低聚合度聚醚多元醇,分子量为1000-2000;所述羟基硅烷的分子结构式为R2Si(CH2CH2OH)2或R2Si(OH)2,其中,R选自CH3、Ph和C2H5中的一种;
(2)改性淀粉溶液的制备
先将氧化淀粉置于90℃的真空环境中干燥24h-60h,然后加入异氰酸酯硅烷偶联剂的丙酮溶液,快速搅拌均匀后,升温度回流反应2h-4h,反应结束之后蒸发丙酮,再加入水搅拌糊化20min-30min,得到改性淀粉溶液,备用;
(3)水性聚氨酯改性淀粉分散液的制备
将步骤(1)制备的聚氨酯丙酮分散液,缓慢地加入至步骤(2)制备的改性淀粉溶液中,在室温下反应3h-6h之后,然后加热将丙酮蒸发出来,并在60℃的温度下进行超声分散搅拌2h-3h,得到水性聚氨酯改性淀粉分散液。
2.根据权利要求1所述的一种水性聚氨酯改性淀粉分散液的制备方法,其特征在于,所述异氰酸酯硅烷偶联剂为3-异氰酸丙基三乙氧基硅烷,或3-异氰酸酯基丙基三甲氧基硅烷。
3.根据权利要求1所述的一种水性聚氨酯改性淀粉分散液的制备方法,其特征在于,所述氧化淀粉的含量比低于98%,羧酸含量为1.1g/100g-1.5g/100g。
4.权利要求1-3任一项所述制备方法制备得到的水性聚氨酯改性淀粉分散液。
5.根据权利要求4所述的一种水性聚氨酯改性淀粉分散液,其特征在于,所述水性聚氨酯改性淀粉分散液的淀粉含量为40%-55%。
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