CN105175671A - 一种阴阳离子型聚氨酯树脂及其制备方法 - Google Patents
一种阴阳离子型聚氨酯树脂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种阴阳离子型聚氨酯树脂。本发明还公开了上述阴阳离子型聚氨酯树脂的制备方法,包括以下步骤:将对苯二甲酸酐聚酯二元醇和聚己二酸新戊二醇-1,6-己二醇酯二醇升温熔融,保温,接着真空脱水得到第一物料;将六亚甲基二异氰酸酯加入第一物料中,升温,保温,降温后加入一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂和N,N-二甲基甲酰胺,再加入三氯化铁,升温,保温,得到第二物料;将第二物料降温后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,升温,保温得到第三物料;向第三物料中加入乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
Description
技术领域
本发明涉及聚氨酯技术领域,尤其涉及一种阴阳离子型聚氨酯树脂及其制备方法。
背景技术
聚氨酯,即聚氨基甲酯,是分子链中含有重复氨基甲酯(-NHCOO-)结构的高分子材料的总称。聚氨酯一般由二异氰酸酯和二元醇或多元醇为基本材料经过加聚反应而成,根据原料的官能团数不同,可以制成线性或体形结构的聚合物,其具有良好的力学性能、粘结性能及耐磨性等,在各领域得到了广泛应用。
但是目前聚氨酯树脂绝大部分还是采用溶剂型聚氨酯树脂,而大规模频繁发生的持续性雾霾天气不禁让人们认识到VOC排放的严重性。水性聚氨酯树脂由于其无毒、低污染等优点越来越受到市场的认可和青睐。目前聚氨酯的水性化已逐步取代溶剂型,成为聚氨酯工业发展的重要方向。水性聚氨酯可广泛应用于涂料、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。
为了提高水性聚氨酯的综合性能,国内外做了大量研究进行改性和采用不同活性的异氰酸酯改变合成进度,以提高水性聚氨酯的断裂伸长率、拉伸强度、粘结强度等。但目前阳离子型水性聚氨酯生产过程中容易暴聚凝胶,而常用的阴离子型水性聚氨酯硬度不高、附着力一般,因此急需要研发一种高附着力高硬度的产品来满足市场的需要。
发明内容
基于背景技术存在的技术问题,本发明提出了一种阴阳离子型聚氨酯树脂及其制备方法,方法简单,所得阴阳离子型聚氨酯树脂具有高附着力,而且硬度高,能满足市场的需要。
本发明提出的一种阴阳离子型聚氨酯树脂的制备方法,包括以下步骤:
S1、将对苯二甲酸酐聚酯二元醇和聚己二酸新戊二醇-1,6-己二醇酯二醇升温熔融,保温,接着真空脱水得到第一物料;
S2、将六亚甲基二异氰酸酯加入第一物料中,升温,保温,降温后加入一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂和N,N-二甲基甲酰胺,再加入三氯化铁,升温,保温,得到第二物料;
S3、将第二物料降温后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,升温,保温得到第三物料;
S4、向第三物料中加入乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
优选地,S1中,将对苯二甲酸酐聚酯二元醇和聚己二酸新戊二醇-1,6-己二醇酯二醇升温至110~125℃,保温1.5~3h,接着真空脱水得到第一物料。
优选地,S2中,将六亚甲基二异氰酸酯加入第一物料中,升温至88~94℃,保温2.5~3.5h,降温至48~56℃后,加入一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂和N,N-二甲基甲酰胺,再加入三氯化铁,升温至80~86℃,保温3~6h,得到第二物料。
优选地,S3中,将第二物料降温至40~50℃后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,滴加时间为0.7~1h,升温至65~75℃,保温0.7~1h得到第三物料。
优选地,对苯二甲酸酐聚酯二元醇与聚己二酸新戊二醇-1,6-己二醇酯二醇的重量比为45~65:20~35。
优选地,对苯二甲酸酐聚酯二元醇、六亚甲基二异氰酸酯、一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂、N,N-二甲基甲酰胺和三氯化铁的重量比为45~65:40~55:10~13:0.7~1:3~6:30~40:0.5~0.8。
优选地,S3中,含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液包括:N-乙基二乙醇胺、双(2-羟丙基)苯胺和N,N-二甲基甲酰胺。
优选地,N-乙基二乙醇胺、双(2-羟丙基)苯胺、N,N-二甲基甲酰胺和三氯化铁的重量比为4~8:4.5~5.5:14~18:0.5~0.8。
优选地,N-乙基二乙醇胺、乙酸和水的重量比为4~8:6.5~7:320~360。
本发明还提出的一种阴阳离子型聚氨酯树脂,采用上述阴阳离子型聚氨酯树脂的制备方法制得。
由于同等条件下对苯二甲酸酐聚酯二元醇合成的水性聚氨酯胶膜硬度较高,本发明采用高硬度的对苯二甲酸酐聚酯二元醇为软段,N-乙基二乙醇胺和双(2-羟丙基)苯胺配合作为阳离子型亲水扩链剂,2-(羟基甲基)苯硼酸半酯作为磺酸盐型阴离子亲水扩链剂,分段逐步聚合的方式合成了硬度高、附着力强、封闭性好、抗渗油和抗色素渗出性能优越、耐水性好的阴阳离子型聚氨酯树脂,而且阴阳离子联用并控制反应速度,提高乳液的稳定性和固含量,克服阳离子水性聚氨酯生产过程中容易暴聚凝胶的缺陷,降低生产凝胶风险。本发明所得水性聚氨酯具有批次稳定性好,生产风险小。
与现有技术相比,本发明具有以下优点:
1)本发明硬度高,附着力强,封闭性好,抗渗油和抗色素渗出性能优越,耐水性好;
2)本发明润湿性好,防止润湿剂对渗油性的影响;
3)本发明成膜速度快,漆膜透明,铅笔硬度达H~2H,耐水48h无异常,附着力为0级;
4)本发明渗透性强,抗渗油性好,漆膜表面与其他树脂相容性好;
5)本发明制备方法工艺稳定,反应易于控制,生产风险小。
附图说明
图1为本发明提出的一种阴阳离子型聚氨酯树脂的制备方法的流程示意图。
具体实施方式
如图1所示,图1为本发明提出的一种阴阳离子型聚氨酯树脂的制备方法的流程示意图。
参照图1,本发明提出的一种阴阳离子型聚氨酯树脂的制备方法,包括以下步骤:
S1、将对苯二甲酸酐聚酯二元醇和聚己二酸新戊二醇-1,6-己二醇酯二醇升温熔融,保温,接着真空脱水得到第一物料;
S2、将六亚甲基二异氰酸酯加入第一物料中,升温,保温,降温后加入一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂和N,N-二甲基甲酰胺,再加入三氯化铁,升温,保温,得到第二物料;
S3、将第二物料降温后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,升温,保温得到第三物料;
S4、向第三物料中加入乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种阴阳离子型聚氨酯树脂的制备方法,包括以下步骤:
S1、按重量份将45份对苯二甲酸酐聚酯二元醇和35份聚己二酸新戊二醇-1,6-己二醇酯二醇升温至110℃,保温3h,接着真空脱水得到第一物料;
S2、将40份六亚甲基二异氰酸酯加入第一物料中,升温至94℃,保温2.5h,降温至56℃后,加入10份一缩二丙二醇、1份2-(羟基甲基)苯硼酸半酯、3份环氧树脂和40份N,N-二甲基甲酰胺,再加入0.5份三氯化铁,升温至86℃,保温3h,得到第二物料;
S3、将第二物料降温至50℃后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,其中混合溶液包括4份N-乙基二乙醇胺、5.5份双(2-羟丙基)苯胺和14份N,N-二甲基甲酰胺,滴加时间为1h,升温至65℃,保温1h得到第三物料;
S4、向第三物料中加入6.5份乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
实施例2
本发明提出的一种阴阳离子型聚氨酯树脂的制备方法,包括以下步骤:
S1、按重量份将65份对苯二甲酸酐聚酯二元醇和20份聚己二酸新戊二醇-1,6-己二醇酯二醇升温至125℃,保温1.5h,接着真空脱水得到第一物料;
S2、将55份六亚甲基二异氰酸酯加入第一物料中,升温至88℃,保温3.5h,降温至48℃后,加入13份一缩二丙二醇、0.7份2-(羟基甲基)苯硼酸半酯、6份环氧树脂和30份N,N-二甲基甲酰胺,再加入0.8份三氯化铁,升温至80℃,保温6h,得到第二物料;
S3、将第二物料降温至40℃后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,其中混合溶液包括8份N-乙基二乙醇胺、4.5份双(2-羟丙基)苯胺和18份N,N-二甲基甲酰胺,滴加时间为0.7h,升温至75℃,保温0.7h得到第三物料;
S4、向第三物料中加入7份乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
实施例3
本发明提出的一种阴阳离子型聚氨酯树脂的制备方法,包括以下步骤:
S1、按重量份将60份对苯二甲酸酐聚酯二元醇和25份聚己二酸新戊二醇-1,6-己二醇酯二醇升温至120℃,保温2h,接着真空脱水得到第一物料;
S2、将50份六亚甲基二异氰酸酯加入第一物料中,升温至90℃,保温3.2h,降温至50℃后,加入12份一缩二丙二醇、0.8份2-(羟基甲基)苯硼酸半酯、5份环氧树脂和35份N,N-二甲基甲酰胺,再加入0.7份三氯化铁,升温至82℃,保温5h,得到第二物料;
S3、将第二物料降温至42℃后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,其中混合溶液包括7份N-乙基二乙醇胺、5份双(2-羟丙基)苯胺和16份N,N-二甲基甲酰胺,滴加时间为0.8h,升温至72℃,保温0.8h得到第三物料;
S4、向第三物料中加入6.8份乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
实施例4
本发明提出的一种阴阳离子型聚氨酯树脂的制备方法,包括以下步骤:
S1、按重量份将50份对苯二甲酸酐聚酯二元醇和30份聚己二酸新戊二醇-1,6-己二醇酯二醇升温至115℃,保温2.5h,接着真空脱水得到第一物料;
S2、将45份六亚甲基二异氰酸酯加入第一物料中,升温至92℃,保温2.8h,降温至54℃后,加入11份一缩二丙二醇、0.9份2-(羟基甲基)苯硼酸半酯、4份环氧树脂和38份N,N-二甲基甲酰胺,再加入0.6份三氯化铁,升温至84℃,保温4h,得到第二物料;
S3、将第二物料降温至46℃后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,其中混合溶液包括5份N-乙基二乙醇胺、5.2份双(2-羟丙基)苯胺和15份N,N-二甲基甲酰胺,滴加时间为0.9h,升温至68℃,保温0.9h得到第三物料;
S4、向第三物料中加入6.6份乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种阴阳离子型聚氨酯树脂的制备方法,其特征在于,包括以下步骤:
S1、将对苯二甲酸酐聚酯二元醇和聚己二酸新戊二醇-1,6-己二醇酯二醇升温熔融,保温,接着真空脱水得到第一物料;
S2、将六亚甲基二异氰酸酯加入第一物料中,升温,保温,降温后加入一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂和N,N-二甲基甲酰胺,再加入三氯化铁,升温,保温,得到第二物料;
S3、将第二物料降温后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,升温,保温得到第三物料;
S4、向第三物料中加入乙酸进行中和后,真空蒸馏得到阴阳离子型聚氨酯树脂。
2.根据权利要求1所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,S1中,将对苯二甲酸酐聚酯二元醇和聚己二酸新戊二醇-1,6-己二醇酯二醇升温至110~125℃,保温1.5~3h,接着真空脱水得到第一物料。
3.根据权利要求1或2所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,S2中,将六亚甲基二异氰酸酯加入第一物料中,升温至88~94℃,保温2.5~3.5h,降温至48~56℃后,加入一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂和N,N-二甲基甲酰胺,再加入三氯化铁,升温至80~86℃,保温3~6h,得到第二物料。
4.根据权利要求1-3任一项所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,S3中,将第二物料降温至40~50℃后,再滴加含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液,滴加时间为0.7~1h,升温至65~75℃,保温0.7~1h得到第三物料。
5.根据权利要求1-4任一项所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,对苯二甲酸酐聚酯二元醇与聚己二酸新戊二醇-1,6-己二醇酯二醇的重量比为45~65:20~35。
6.根据权利要求1-5任一项所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,对苯二甲酸酐聚酯二元醇、六亚甲基二异氰酸酯、一缩二丙二醇、2-(羟基甲基)苯硼酸半酯、环氧树脂、N,N-二甲基甲酰胺和三氯化铁的重量比为45~65:40~55:10~13:0.7~1:3~6:30~40:0.5~0.8。
7.根据权利要求1-6任一项所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,S3中,含N-乙基二乙醇胺和双(2-羟丙基)苯胺的混合溶液包括:N-乙基二乙醇胺、双(2-羟丙基)苯胺和N,N-二甲基甲酰胺。
8.根据权利要求7所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,N-乙基二乙醇胺、双(2-羟丙基)苯胺、N,N-二甲基甲酰胺和三氯化铁的重量比为4~8:4.5~5.5:14~18:0.5~0.8。
9.根据权利要求1-8任一项所述阴阳离子型聚氨酯树脂的制备方法,其特征在于,N-乙基二乙醇胺、乙酸和水的重量比为4~8:6.5~7:320~360。
10.一种阴阳离子型聚氨酯树脂,其特征在于,采用权利要求1-9任一项所述阴阳离子型聚氨酯树脂的制备方法制得。
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