CN114075322A - 一种水性聚氨酯树脂乳液及其制备方法 - Google Patents
一种水性聚氨酯树脂乳液及其制备方法 Download PDFInfo
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
本发明属于聚合物合成技术领域,具体为一种水性聚氨酯乳液及制备方法。本发明水性含聚氨酯乳液,由下述重量份的原料制成:聚酯与聚醚多元醇重量比为0.3~0.7的混合多元醇50~80份;异氰酸酯10~40份;亲水扩链剂1~3份;第一类醇类扩链剂1~6份;第二类扩链剂1~6份;催化剂0.01~0.05份;成盐剂1~3份。本发明在不影响聚氨酯树脂本身优异的力学性和化学性能的同时,通过调节多元醇中聚酯与聚醚多元醇的重量比,制备出固含量在30~45%的水性聚氨酯乳液,该乳液不仅具有良好的稳定性,而且有较高的抗拉伸强度和优异的成膜性,可广泛应用在涂料、油墨、胶粘剂及生活健康用品领域。
Description
技术领域
本发明属于聚合物合成技术领域,具体涉及一种水性聚氨酯乳液及制备方法。
背景技术
水性聚氨酯是一种低或零VOC排放的环保型树脂材料,因其具有良好的物理和化学性能,而被广泛应用于皮革、纺织、涂料等工业领域。但是目前一般采用预聚体法制备的水性聚氨酯乳液,在后期制备成膜时,成膜性能较差,主要表现为后期成膜后,膜出现发粘、卷曲、褶皱等缺陷,这些缺陷使水性聚氨酯树脂难以在工业和日常生活领域中得到应用。为此,人们常通过在水性树脂乳加入助剂等方式,来提高水性聚氨酯乳液的成膜性能。
为解决上述水性聚氨酯乳液在后期应用中所出现的缺陷,避免大量助剂的使用,本发明提供了一种水性聚氨酯乳液及制备方法。本发明提供的乳液环保、高稳定性、制备工艺简单、具有良好的成膜性能和机械强度。可被广泛应用在涂料、油墨、胶粘剂,食品包装及生活健康用品上。
发明内容
本发明的目标旨在提供一种具有良好成膜性及其稳定性的水性聚氨酯乳液及制备方法。
本发明提供水性聚氨酯树脂乳液,由下述重量份的原料制备得到:
多元醇 50~80份;
异氰酸酯 10~40份;
催化剂 0.01~0.05份;
第一类扩链剂 1~6份;
第二类扩链剂 1~6份;
亲水扩链剂 1~3份;
成盐剂 1~3份;
所述多元醇为聚酯多元醇与聚醚多元醇的混合物;所述聚酯多元醇的分子量为1000~2000,所述聚醚多元醇的分子量1500~3000;
所述聚酯多元醇与聚醚多元醇的重量比为0.3~0.7;
所述聚醚多元醇和聚酯多元醇优选聚四氢呋喃醚多元醇、聚氧化丙二醇、聚乙二醇、聚己二酸1,4-丁二醇酯和聚碳酸酯多元醇中的一种或多种。
本发明中,所述异氰酸酯单体选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯中的至少一种。
本发明中,所述催化剂单体选自二月桂酸二丁基锡、二丁酸二丁基锡、二辛酸锌、乙酰丙酮酸锆、2 ,2 ,6 ,6-四甲基-3 ,5-庚烷二酮酸锆,新癸酸铋和2-乙基己酸铋中的至少一种;优选地,所述催化剂选自二月桂酸二丁基锡、新癸酸铋和2-乙基己酸铋中的至少一种。
本发明中,所述亲水扩链剂单体选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸中的一种或多种。
本发明中,所述第一类扩链剂为小分子多羟基化合物,选自乙二醇、2-甲基-1 ,3-丙二醇、一缩二乙二醇、1 ,4-丁二醇、1 ,6-己二醇、新戊二醇、甲基丙三醇、二羟甲基环己烷、1 ,8-辛二醇、1 ,9-壬二醇、1 ,12-十二烷二醇、季戊四醇中的至少一种。
本发明中,所述第二类扩链剂为小分子胺类化合物,选自丙二胺、己二胺、对苯二胺、异佛尔酮二胺中的至少一种。
本发明中,所述成盐剂为三乙胺、氨水、氢氧化钾、氢氧化钠中的至少一种。
本发明中,所述水性聚氨酯乳液的制备方法,具体步骤为:
(1)将50~80份的多元醇在110~130℃温度下真空脱水60~120 min,混合多元醇中聚酯多元醇与聚醚多元醇的重量比为0.3~0.7;
(2)将步骤(1)中温度降至80~85℃,然后加入10~40份的二异氰酸酯和0.01~0.05份的催化剂,在惰性气体保护下预聚反应120~150 min;
(3)在上述温度下加入1~6份的第一类扩链剂,继续反应60~90 min;
(4)将上述温度降至65~75℃,然后加入1~6份的第二类扩链剂,反应30~40 min;
(5)将上述预聚合反应温度升至80~85℃,然后加入1~3份的亲水扩链剂,反应120~150 min;
(6)将上述反应温度降温至30~35℃,加入1~3份的成盐剂,中和15~20 min;
(7)在500~800 rpm/min的转速下加水乳化,乳化时间为25~30 min;
(8)转速降速至300~350 rpm/min,并升温至50~60℃,熟化反应60~90 min,得到固含量30~45%的水性聚氨酯纳米乳液。
本发明的有益成果
本发明通过调节多元醇组份中聚酯与聚醚多元醇的重量比,并通过第一与第二类扩链剂,两次分布扩链反应,制备出的水性聚氨酯具有链结构均一,其膜力学性能好,室温下成膜速率快的特点。本发明提供的水性聚氨酯乳液室温下(25~30℃)储存6~12月未出现絮凝现象,具有较好的稳定性;室温下膜表干时间7~15 min;本发明提供的乳液所制备的膜具有42~55 MPa的较高拉伸强度,其断裂伸长率在1050~1300%。
此外,本发明避免大量助剂的使用,因而具有低成本和优异的环保性。
具体实施方式
下面通过实施例对本发明进行具体的描述,只用于对本发明的进行进一步说明,不能理解为对本发明保护范围的限定,该技术的相关领域人员可根据该发明内容作出一些非本质的改进和调整。
本发明实施例中所用原料除以下标注说明的,其它均购自上海阿拉丁生化科技有限公司。异佛尔酮二异氰酸酯购自万华化学集团股份有限公司、聚四氢呋喃醚多元醇-2500(分子量2500)和聚碳酸酯多元醇-1000(分子量1000)购自拜耳公司,新癸酸铋催化剂购自巴斯夫公司。
实施例1
将78份的多元醇(聚四氢呋喃醚多元醇-2500和聚碳酸酯多元醇-1000)在温度110℃下真空脱水120 min,多元醇中聚酯多元醇与聚醚多元醇的重量比为0.36;将温度降至85℃后,再加入16份的异佛尔酮二异氰酸酯和0.03份的催化剂新癸酸铋,在惰性气体(氮气)保护下预聚反应150 min;加入2.08份的第一类扩链剂一缩二乙二醇,反应90 min;在温度降至65℃时,加入1.55份的第二类扩链剂异佛尔酮二胺,并反应30 min;再将预聚合反应温度升至85℃,加入2.37份的亲水扩链剂二羟甲基丁酸,反应120 min;后降温至35℃,加入与亲水扩链剂等摩尔量的成盐剂三乙胺,中和反应15 min,后在600 rpm/min的转速下加水乳化,乳化时间为25 min;后降速至350 rpm/min,并升温至50℃下熟化反应75 min,后制备出固含量42%的水性聚氨酯纳米乳液。
实施例2
将78份的多元醇(聚四氢呋喃醚多元醇-2500和聚碳酸酯多元醇-1000)在温度110℃下真空脱水120 min,多元醇中聚酯多元醇与聚醚多元醇的重量比为0.48;将温度降至85℃后,再加入16份的异佛尔酮二异氰酸酯和0.03份的催化剂新癸酸铋,在惰性气体(氮气)保护下预聚反应150 min;加入2.08份的第一类扩链剂一缩二乙二醇,反应90 min;在温度降至65℃时,加入1.55份的第二类扩链剂异佛尔酮二胺,并反应30 min;再将预聚合反应温度升至85℃,加入2.37份的亲水扩链剂二羟甲基丁酸,反应120 min;后降温至35℃,加入与亲水扩链剂等摩尔量的成盐剂三乙胺,中和反应15 min,后在600 rpm/min的转速下加水乳化,乳化时间为25 min;后降速至350 rpm/min,并升温至50℃下熟化反应75 min,后制备出固含量37%的水性聚氨酯纳米乳液。
实施例3
将78份的多元醇(聚四氢呋喃醚多元醇-2500和聚碳酸酯多元醇-1000)在温度110℃下真空脱水120 min,多元醇中聚酯多元醇与聚醚多元醇的重量比为0.62;将温度降至85℃后,再加入16份的异佛尔酮二异氰酸酯和0.03份的催化剂新癸酸铋,在惰性气体(氮气)保护下预聚反应150 min;加入2.08份的第一类扩链剂一缩二乙二醇,反应90 min;在温度降至65℃时,加入1.55份的第二类扩链剂异佛尔酮二胺,并反应30 min;再将预聚合反应温度升至85℃,加入2.37份的亲水扩链剂二羟甲基丁酸,反应120 min;后降温至35℃,加入与亲水扩链剂等摩尔量的成盐剂三乙胺,中和反应15 min,后在600 rpm/min的转速下加水乳化,乳化时间为25 min;后降速至350 rpm/min,并升温至50℃下熟化反应75 min,后制备出固含量35%的水性聚氨酯纳米乳液。
测试结果
根据轻工行业标准对由实施例1至3制备的水性聚氨酯树脂样品进行性能测试。表1为由实施例1至3获得的水性聚氨酯树脂样品的性能检测结果。
表1
Claims (7)
1.一种水性聚氨酯树脂乳液,其特征在于,其原料组分按重量份计,为:
多元醇 50~80份;
异氰酸酯 10~40份;
催化剂 0.01~0.05份;
第一类扩链剂 1~6份;
第二类扩链剂 1~6份;
亲水扩链剂 1~3份;
成盐剂 1~3份;
所述多元醇为聚酯多元醇与聚醚多元醇的混合物,所述聚酯多元醇的分子量为1000~2000,所述聚醚多元醇的分子量1500~3000;所述聚酯多元醇与聚醚多元醇的重量比为0.3~0.7;
所述第一类扩链剂为小分子多羟基化合物,选自乙二醇、2-甲基-1 ,3-丙二醇、一缩二乙二醇、1 ,4-丁二醇、1 ,6-己二醇、新戊二醇、甲基丙三醇、二羟甲基环己烷、1 ,8-辛二醇、1 ,9-壬二醇、1 ,12-十二烷二醇、季戊四醇中的至少一种;
所述第二类扩链剂为小分子胺类化合物,选自丙二胺、己二胺、对苯二胺、异佛尔酮二胺中的至少一种。
2.如权利要求1所述的水性聚氨酯树脂乳液,其特征在于,所述异氰酸酯单体选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯中的至少一种。
3.如权利要求1所述的水性聚氨酯树脂乳液,其特征在于,所述催化剂单体选自二月桂酸二丁基锡、二丁酸二丁基锡、二辛酸锌、乙酰丙酮酸锆、2 ,2 ,6 ,6-四甲基-3 ,5-庚烷二酮酸锆,新癸酸铋和2-乙基己酸铋中的至少一种。
4.如权利要求1所述的水性聚氨酯树脂乳液,其特征在于,所述亲水扩链剂单体选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸中的一种或多种。
5.如权利要求1所述的水性聚氨酯树脂乳液,其特征在于,所述成盐剂为三乙胺、氨水、氢氧化钾、氢氧化钠中的至少一种。
6.如权利要求1所述的水性聚氨酯树脂乳液,其特征在于,所述聚醚多元醇和聚酯多元醇选自聚四氢呋喃醚多元醇、聚氧化丙二醇、聚乙二醇、聚己二酸1,4-丁二醇酯和聚碳酸酯多元醇中的一种或多种。
7.一种如权利要求1~6任一所述水性聚氨酯树脂乳液的制备方法,其特征在于,具体步骤为:
(1)将50~80份的多元醇在110~130℃温度下真空脱水60~120 min,混合多元醇中聚酯多元醇与聚醚多元醇的重量比为0.3~0.7;
(2)将步骤(1)中温度降至80~85℃,然后加入10~40份的二异氰酸酯和0.01~0.05份的催化剂,在惰性气体保护下预聚反应120~150 min;
(3)在上述温度下加入1~6份的第一类扩链剂,继续反应60~90 min;
(4)将上述温度降至65~75℃,然后加入1~6份的第二类扩链剂,反应30~40 min;
(5)将上述预聚合反应温度升至80~85℃,然后加入1~3份的亲水扩链剂,反应120~150 min;
(6)将上述反应温度降温至30~35℃,加入1~3份的成盐剂,中和15~20 min;
(7)在500~800 rpm/min的转速下加水乳化,乳化时间为25~30 min;
(8)转速降速至300~350 rpm/min,并升温至50~60℃,熟化反应60~90 min,得到固含量30~45%的水性聚氨酯纳米乳液。
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