CN114045025A - 一种sis衍生物改性水性聚氨酯-环氧树脂及其制备方法 - Google Patents
一种sis衍生物改性水性聚氨酯-环氧树脂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种SIS衍生物改性水性聚氨酯‑环氧树脂及其制备方法,按重量份计,其组成为:二异氰酸酯50.0~80.0份、环氧树脂10.0~30.0份、SIS衍生物6.0~12.0份、过氧化苯甲酰0.2~0.8份、低聚物多元醇30.0~70.0份、多元醇2.0~8.0份、二羟甲基丙酸4.5~10.0份、丙烯酸羟乙酯1.5~4.0份、二月桂酸二丁基锡0.01~0.1份、丙酮15.0~60.0份、乙酸乙酯12.0~30.0份、中和剂3.0~15.0份、聚乙烯醇2.0~6.0份、去离子水180.0~350.0份;所述的SIS衍生物为甲基丙烯酸丁酯接枝SIS弹性体,其采用溶液法接枝制得;本发明制得的一种SIS衍生物改性水性聚氨酯‑环氧树脂,其交联密度高,具有优异的附着力、柔韧性和耐磨性,无需额外添加抗流挂剂,其具有良好的抗流挂性以及抗弯曲性能。
Description
技术领域
本发明涉及一种改性水性聚氨酯-环氧树脂,尤其涉及到一种SIS衍生物改性水性聚氨酯-环氧树脂及其制备方法,属于特种水性树脂技术领域。
背景技术
传统的单一材料已远不能满足市场对其性能越来越高的要求。聚氨酯树脂是由低聚物多元醇、小分子多元醇、多异氰酸酯和扩链剂反应而成,反应原料及工艺因素对聚氨酯材料形态有很大影响。聚氨酯具有良好的耐溶剂性和耐磨性,因而被广泛应用于涂料、胶黏剂、泡沫塑料、油墨及橡胶等领域,但由于其耐水性差、力学性能弱、抗流挂性差等不足之处,限制了水性聚氨酯的应用范围及进一步发展。所以通过对其改性,来增强水性聚氨酯的综合性能就非常关键。
环氧树脂具有力学性能好、耐热性能强、耐溶剂、耐腐蚀性能优良等性能。通过环氧树脂改性的水性聚氨酯兼具环氧树脂和聚氨酯的优异性能,具有广泛的应用前景。
中国专利CN113444221A公开了一种环氧树脂改性水性聚氨酯的制备方法,即将聚己二酸丁二醇酯二醇脱水后,与二苯基甲烷二异氰酸酯和催化剂在70~80℃搅拌反应2h,加入二羟甲基丙酸的N-甲基吡咯烷酮溶液,于70℃搅拌反应1.5h,加入1,4-丁二醇于70℃搅拌反应1h,过程中加入适量丙酮调节粘度。加入环氧树脂E-44于65~75℃搅拌反应1.5h。降温至30℃后加入三乙胺中和搅拌0.5h,再加入去离子水高速剪切乳化0.5h。真空除去丙酮后,得环氧树脂改性水性聚氨酯乳液,具有优异的耐水性、耐溶剂性,良好的力学性能及硬度等性质,可用于涂料和胶粘剂等领域,但其抗流挂性能不佳、柔韧性不够。
发明内容
针对上述所述的技术问题,本发明首先合成以双键封端的聚氨酯-环氧树脂,然后加入SIS衍生物,SIS衍生物中含有双键,SIS衍生物与聚氨酯-环氧树脂通过化学键相连,从而得到SIS衍生物改性水性聚氨酯-环氧树脂。
本发明的目的旨在提供一种SIS衍生物改性水性聚氨酯-环氧树脂。
本发明的另一目的提供一种SIS衍生物改性水性聚氨酯-环氧树脂的其制备方法。
为满足本发明的一种SIS衍生物改性水性聚氨酯-环氧树脂,按重量份计,其组成为:二异氰酸酯50.0~80.0份、环氧树脂10.0~30.0份、SIS衍生物6.0~12.0份、过氧化苯甲酰0.2~0.8份、低聚物多元醇30.0~70.0份、多元醇2.0~8.0份、二羟甲基丙酸4.5~10.0份、丙烯酸羟乙酯1.5~4.0份、二月桂酸二丁基锡0.01~0.1份、丙酮15.0~60.0份、乙酸乙酯12.0~30.0份、中和剂3.0~15.0份、聚乙烯醇2.0~6.0份、去离子水180.0~350.0份;所述的SIS衍生物为甲基丙烯酸丁酯接枝SIS弹性体,其采用溶液法接枝制得。
所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯中的一种或几种的组合。
所述的低聚物多元醇为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚环氧乙烷多元醇、聚乙二醇中的一种或几种的组合;所述的低聚物多元醇分子量为1000~3000。
所述的多元醇为丁二醇、1,4-环己二甲醇、新戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、三羟甲基丙烷中的一种或几种的组合。
所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
所述的环氧树脂为脱水双酚A环氧树脂。
所述的SIS衍生物改性水性聚氨酯-环氧树脂,其制备工艺如下:
a)、在滴定罐中按配方重量份,将SIS衍生物和过氧化苯甲酰溶于乙酸乙酯中,得到混合液Ⅰ;
b)、在四口反应器中,按配方重量份,依次加入低聚物多元醇、多元醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
c)、降温,缓慢加入二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止;
d)、缓慢滴加滴加上述混合液Ⅰ,滴加完毕后,保温反应1.5h,并加入适量的聚乙烯醇;
e)、继续搅拌,除去部分溶剂,降温缓慢滴加中和剂,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到SIS衍生物改性水性聚氨酯-环氧树脂。
本发明制得的一种SIS衍生物改性水性聚氨酯-环氧树脂,其交联密度高,具有优异的附着力、柔韧性和耐磨性,无需额外添加抗流挂剂,其具有良好的抗流挂性能以及抗弯曲性能。
具体实施方式
本发明结合以下实施例对SIS衍生物改性水性聚氨酯-环氧树脂做进一步的描述。可以理解的是,此处所描述的具体实施例仅仅用于解释相关发明,而非对该发明的限定。
实施例1
一种SIS衍生物改性水性聚氨酯-环氧树脂,按重量份计,其组成为:甲苯二异氰酸酯50.0份、环氧树脂15.0份、SIS衍生物8.0份、过氧化苯甲酰0.5份、聚碳酸酯二元醇45.0份、丁二醇2.5份、二羟甲基丙酸6.0份、丙烯酸羟乙酯2.5份、二月桂酸二丁基锡0.06份、丙酮40.0份、乙酸乙酯16.0份、三乙胺6.5份、聚乙烯醇4.0份、去离子水250.0份。
本实施例中一种SIS衍生物改性水性聚氨酯-环氧树脂的制备方法,包括以下步骤:
a)、在滴定罐中按配方重量份,将SIS衍生物和过氧化苯甲酰溶于乙酸乙酯中,得到混合液Ⅰ;
b)、在四口反应器中,按配方重量份,依次加入聚碳酸酯二元醇、丁二醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
c)、降温,缓慢加入甲苯二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止;
d)、缓慢滴加滴加上述混合液Ⅰ,滴加完毕后,保温反应1.5h,并加入适量的聚乙烯醇;
e)、继续搅拌,除去部分溶剂,降温缓慢滴加三乙胺,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到SIS衍生物改性水性聚氨酯-环氧树脂。
实施例2
一种SIS衍生物改性水性聚氨酯-环氧树脂,按重量份计,其组成为:异佛尔酮二异氰酸酯70.0份、环氧树脂20.0份、SIS衍生物10.0份、过氧化苯甲酰0.7份、聚四氢呋喃二元醇60.0份、1,4-环己二甲醇4.0份、二羟甲基丙酸7.5份、丙烯酸羟乙酯3.0份、二月桂酸二丁基锡0.07份、丙酮50.0份、乙酸乙酯20.0份、氨水5.5份、聚乙烯醇5.0份、去离子水350.0份。
本实施例中一种SIS衍生物改性水性聚氨酯-环氧树脂的制备方法,包括以下步骤:
a)、在滴定罐中按配方重量份,将SIS衍生物和过氧化苯甲酰溶于乙酸乙酯中,得到混合液Ⅰ;
b)、在四口反应器中,按配方重量份,依次加入聚四氢呋喃二元醇、1,4-环己二甲醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
c)、降温,缓慢加入异佛尔酮二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止;
d)、缓慢滴加滴加上述混合液Ⅰ,滴加完毕后,保温反应1.5h,并加入适量的聚乙烯醇;
e)、继续搅拌,除去部分溶剂,降温缓慢滴加氨水,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到SIS衍生物改性水性聚氨酯-环氧树脂。
实施例3
一种SIS衍生物改性水性聚氨酯-环氧树脂,按重量份计,其组成为:六亚甲基二异氰酸酯60.0份、环氧树脂10.0份、SIS衍生物7.5份、过氧化苯甲酰0.5份、聚己内酯二元醇60.0份、新戊二醇6.0份、二羟甲基丙酸6.0份、丙烯酸羟乙酯3.0份、二月桂酸二丁基锡0.05份、丙酮40.0份、乙酸乙酯15.0份、二甲基乙醇胺9.5份、聚乙烯醇5.0份、去离子水300.0份。
本实施例中一种SIS衍生物改性水性聚氨酯-环氧树脂的制备方法,包括以下步骤:
a)、在滴定罐中按配方重量份,将SIS衍生物和过氧化苯甲酰溶于乙酸乙酯中,得到混合液Ⅰ;
b)、在四口反应器中,按配方重量份,依次加入聚己内酯二元醇、新戊二醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
c)、降温,缓慢加入六亚甲基二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止;
d)、缓慢滴加滴加上述混合液Ⅰ,滴加完毕后,保温反应1.5h,并加入适量的聚乙烯醇;
e)、继续搅拌,除去部分溶剂,降温缓慢滴加二甲基乙醇胺,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到SIS衍生物改性水性聚氨酯-环氧树脂。
实施例4
一种SIS衍生物改性水性聚氨酯-环氧树脂,按重量份计,其组成为:苯二亚甲基二异氰酸酯70.0份、环氧树脂22.0份、SIS衍生物9.0份、过氧化苯甲酰0.6份、聚环氧乙烷多元醇60.0份、三羟甲基丙烷1.0份、2-丁基-2-乙基-1,3-丙二醇3.5份、二羟甲基丙酸7.0份、丙烯酸羟乙酯3.0份、二月桂酸二丁基锡0.05份、丙酮45.0份、乙酸乙酯18.0份、三乙胺7.0份、聚乙烯醇5.0份、去离子水330.0份。
本实施例中一种SIS衍生物改性水性聚氨酯-环氧树脂的制备方法,包括以下步骤:
a)、在滴定罐中按配方重量份,将SIS衍生物和过氧化苯甲酰溶于乙酸乙酯中,得到混合液Ⅰ;
b)、在四口反应器中,按配方重量份,依次加入聚环氧乙烷多元醇、三羟甲基丙烷、2-丁基-2-乙基-1,3-丙二醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
c)、降温,缓慢加入苯二亚甲基二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止;
d)、缓慢滴加滴加上述混合液Ⅰ,滴加完毕后,保温反应1.5h,并加入适量的聚乙烯醇;
e)、继续搅拌,除去部分溶剂,降温缓慢滴加三乙胺,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到SIS衍生物改性水性聚氨酯-环氧树脂。
对比例1
一种常规改性水性聚氨酯-环氧树脂,按重量份计,其组成为:甲苯二异氰酸酯50.0份、环氧树脂15.0份、聚碳酸酯二元醇45.0份、丁二醇2.5份、二羟甲基丙酸6.0份、丙烯酸羟乙酯2.5份、二月桂酸二丁基锡0.06份、丙酮40.0份、三乙胺6.5份、聚乙烯醇4.0份、去离子水250.0份。
本实施例中一种常规改性水性聚氨酯-环氧树脂的制备方法,包括以下步骤:
a)、在四口反应器中,按配方重量份,依次加入聚碳酸酯二元醇、丁二醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
b)、降温,缓慢加入甲苯二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止,加入适量的聚乙烯醇;
d)、继续搅拌,除去部分溶剂,降温缓慢滴加三乙胺,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到常规改性水性聚氨酯-环氧树脂。
对比例2
一种SIS衍生物改性水性聚氨酯-环氧树脂,按重量份计,其组成为:异佛尔酮二异氰酸酯70.0份、环氧树脂20.0份、SIS衍生物10.0份、过氧化苯甲酰0.7份、聚四氢呋喃二元醇60.0份、1,4-环己二甲醇4.0份、二羟甲基丙酸7.5份、丙烯酸羟乙酯3.0份、二月桂酸二丁基锡0.07份、丙酮50.0份、乙酸乙酯20.0份、氨水5.5份、去离子水350.0份。
本实施例中一种SIS衍生物改性水性聚氨酯-环氧树脂的制备方法,包括以下步骤:
a)、在滴定罐中按配方重量份,将SIS衍生物和过氧化苯甲酰溶于乙酸乙酯中,得到混合液Ⅰ;
b)、在四口反应器中,按配方重量份,依次加入聚四氢呋喃二元醇、1,4-环己二甲醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
c)、降温,缓慢加入异佛尔酮二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止;
d)、缓慢滴加滴加上述混合液Ⅰ,滴加完毕后,保温反应1.5h;
e)、继续搅拌,除去部分溶剂,降温缓慢滴加氨水,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到SIS衍生物改性水性聚氨酯-环氧树脂。
性能指标测试:将上述实施例1、实施例2、实施例3、实施例4以及对比例1、对比例2的样品,按照表1的原料配方制备成涂料,对应的涂料样品分别记为涂料1、涂料2、涂料3、涂料4以及涂料5、涂料6,并分别测试其性能。
表1:涂料配方
原料名称 | 规格 | 用量/% |
水 | 去离子水 | 5 |
润湿剂 | pe100 | 0.5 |
水性树脂 | 上述水性树脂 | 88.0 |
成膜助剂 | 醇酯十二 | 6.0 |
流平剂 | BYK-333 | 0.5 |
将按照相关标准,对配置好的涂料进行性能指标测试,测试结果如表2所示。
其中,附着力:按照GB/T1720-1988的规定,使用划格法进行测试;
耐冲击性:按照GB/T1732-2020的规定进行检测;
抗流挂性:按照GB/T9264-2012的规定进行检测;
柔韧性:按照GB/T1731-1993的规定进行检测。
表2:涂层的性能技术指标
由表2可以看出本发明的涂料1、涂料2、涂料3、涂料4和涂料6的附着力、抗流挂性、耐冲击性以及柔韧性等性能要好于涂料5(常规改性水性聚氨酯-环氧树脂),也就是说实施例1、实施例2、实施例3、实施例4样品和对比例2样品的附着力、抗流挂性、耐冲击性以及柔韧性等性能要好于对比例1常规改性水性聚氨酯-环氧树脂的相应性能,这表明SIS衍生物的加入能有效提高漆膜的附着力、抗流挂性、耐冲击性以及柔韧性等性能。
而涂料1、涂料2、涂料3、、涂料4和涂料5的贮存稳定性要明显好于涂料6的贮存稳定性,而涂料6没有加入聚乙烯醇,这表明在本发明体系中,聚乙烯醇能有效提高其贮存稳定性。
尽管本发明已作了详细说明并引证了实施例,但对于本领域的普通技术人员,显然可以按照上述说明而做出的各种方案、修改和改动,都应该包括在权利要求的范围之内。
Claims (7)
1.一种SIS衍生物改性水性聚氨酯-环氧树脂,其特征在于,按重量份计,其组成为:二异氰酸酯50.0~80.0份、环氧树脂10.0~30.0份、SIS衍生物6.0~12.0份、过氧化苯甲酰0.2~0.8份、低聚物多元醇30.0~70.0份、多元醇2.0~8.0份、二羟甲基丙酸4.5~10.0份、丙烯酸羟乙酯1.5~4.0份、二月桂酸二丁基锡0.01~0.1份、丙酮15.0~60.0份、乙酸乙酯12.0~30.0份、中和剂3.0~15.0份、聚乙烯醇2.0~6.0份、去离子水180.0~350.0份;所述的SIS衍生物为甲基丙烯酸丁酯接枝SIS弹性体,其采用溶液法接枝制得。
2.根据权利要求1所述的SIS衍生物改性水性聚氨酯-环氧树脂,其特征在于,所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯中的一种或几种的组合。
3.根据权利要求1所述的SIS衍生物改性水性聚氨酯-环氧树脂,其特征在于,所述的低聚物多元醇为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚环氧乙烷多元醇、聚乙二醇中的一种或几种的组合;所述的低聚物多元醇分子量为1000~3000。
4.根据权利要求1所述的SIS衍生物改性水性聚氨酯-环氧树脂,其特征在于,所述的多元醇为丁二醇、1,4-环己二甲醇、新戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、三羟甲基丙烷中的一种或几种的组合。
5.根据权利要求1所述的SIS衍生物改性水性聚氨酯-环氧树脂,其特征在于,所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
6.根据权利要求1所述的SIS衍生物改性水性聚氨酯-环氧树脂,其特征在于,所述的环氧树脂为脱水双酚A环氧树脂。
7.根据权利要求1所述的SIS衍生物改性水性聚氨酯-环氧树脂,其特征在于,所述的SIS衍生物改性水性聚氨酯-环氧树脂,其制备工艺如下:
a)、在滴定罐中按配方重量份,将SIS衍生物和过氧化苯甲酰溶于乙酸乙酯中,得到混合液Ⅰ;
b)、在四口反应器中,按配方重量份,依次加入低聚物多元醇、多元醇、二羟甲基丙酸,升温至110~120℃,真空下脱水2.0h;
c)、降温,缓慢加入二异氰酸酯,然后加入环氧树脂,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,升温到80~82℃搅拌反应,然后加入丙烯酸羟乙酯,视体系粘度补充丙酮,检测,当NCO值达到规定的设计值时为止;
d)、缓慢滴加滴加上述混合液Ⅰ,滴加完毕后,保温反应1.5h,并加入适量的聚乙烯醇;
e)、继续搅拌,除去部分溶剂,降温缓慢滴加中和剂,高速搅拌分散条件下,加入计算量去离子水,再一次除溶剂,过滤,得到SIS衍生物改性水性聚氨酯-环氧树脂。
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