CN114634598B - 一种用于甲油胶的丙烯酸聚氨酯的制备方法 - Google Patents
一种用于甲油胶的丙烯酸聚氨酯的制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于甲油胶的丙烯酸聚氨酯的制备方法。它是由二乙二醇、己二酸和1,4‑环己烷二甲醇先制备预聚体,再与聚己内酯二醇和异佛尔二酮二异氰酸酯进行反应,进而用二羟基甲基丁酸扩链,并用甲基丙烯酸羟乙酯封端制备而成。将本发明的丙烯酸聚氨酯用于制作甲油胶,在光泽、硬度、柔韧性和附着力等性能指标优良,可以作为底胶、加固胶和延长胶的通用型树脂。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种用于甲油胶的丙烯酸聚氨酯的制备方法。
背景技术
聚氨酯分子结构中,在单元结构氨基甲酸酯键(-NH-CO-)链中含有交替的软链段和硬链段。丙烯酸聚氨酯兼有丙烯酸酯和聚氨酯两种材料的特性,其反应活性高、固化速率快,表现出优良的柔性、附着力和耐磨性等,尤其是利用聚氨酯分子设计的原理,通过反应原料、反应进程等条件的控制和优化,可以制备出在具有独特结构特征基础上,体现出性能独特的丙烯酸聚氨酯材料,从而满足不同领域的应用需求。
美甲是一种手部装饰的美化艺术,美甲技术也由油性指甲油阶段和水性指甲油阶段,发展到UV-LED甲油胶阶段,它具有的技术优势是:(1)高效,(2)环境友好,(3)性能良好。丙烯酸聚氨酯材料以其结构多样性和性能可调性,在甲油胶应用领域具有强大的技术优势,再加上光固化技术优点:固化速率快、效率高、能量利用率高、节约能源、有机挥发分少等,UV-LED甲油胶已经成为指甲美化的主要技术手段。指甲上胶包括底胶、加固胶和延长胶三步工艺,由于目前市场上用于光固化甲油胶的基础树脂,在干燥速度、附着力、硬度和光泽等技术指标方面不能兼顾,底胶、加固胶和延长胶需要用不同的基础树脂调配,导致整套指甲上胶工艺繁琐。如何在保证甲油胶综合性能优化基础上,尽可能让指甲上胶工艺简单快速,即采用一种基础树脂就可以调配出满足底胶、加固胶和延长胶不同的性能,是亟待需要解决的问题。
发明内容
为了解决上述技术问题,本发明提供了一种用于甲油胶的丙烯酸聚氨酯的制备方法。本发明的主要技术路线如下:
其中:
以上技术路线不包括其他可能的反应途径。
本发明的一种用于甲油胶的丙烯酸聚氨酯的制备方法,包括以下步骤:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值<1;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到7.4%-7.9%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.3%-3.8%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量<0.1%以后,停止反应;
(5)在步骤(4)的反应液中,加入5%-10%的甲基丙烯酸羟乙酯,搅拌均匀,出料。
所述的有机锡为二月桂酸二丁基锡,其用量为异佛尔酮二异氰酸酯质量的0.05%-0.1%;
所述的钛酸四异丙酯用量是二乙二醇、己二酸和1,4-环己烷二甲醇总质量的0.01%-0.025%;
所述的聚己内酯二醇的分子量为530。
将本发明的一种丙烯酸聚氨酯作为基础树脂,辅以稀释剂、流平剂和光引发剂,通过刷涂方法,涂覆在塑料甲片或人体指甲上,在36WLED甲油胶灯照60s,固化成甲油胶膜,进行性能测试。甲油胶配方为:基础树脂87.9%,稀释剂甲基丙烯酸羟乙酯10.0%,光引发剂TPO2.0%和流平剂丙烯酸酯0.1%。
本发明的有益效果是,通过丙烯酸聚氨酯分子结构的优化设计,原料类型和比例的优化以及精准控制反应条件,制备了分子量约1000的预聚体,在此基础上,制备了分子链上含不同官能团和不同碳链结构的宽分子量分布的丙烯酸聚氨酯。将该丙烯酸聚氨酯作为甲油胶的基础树脂,可以实行附着力、硬度和光泽等的有效兼顾和统一,从而实行将底胶、加固胶和延长胶三合一的目标。其中,二乙二醇具有抗氧阻聚和促进快速表干的作用,1,4-环己烷二甲醇有利于提高光泽和硬度,聚己内酯二醇在丙烯酸聚氨酯中主要起到调节柔韧性的作用,尤其是1,4-环己烷二甲醇和一定分子量的聚己内酯二醇协同,可以有效做到硬度和柔性的统一,二羟基甲基丁酸在扩链以提高分子量的基础上,还有利于附着力的提高。
具体实施方式
以下结合具体实施例对本发明作进一步的详细描述,但不应该将此理解为本发明上述主题的范围仅限于下述实施例。
实施例1:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入0.020%钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值0.70;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入0.07%有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到7.5%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.4%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量0.03%以后,停止反应;
(5)在步骤(4)的反应液中,加入7%的甲基丙烯酸羟乙酯,搅拌均匀,出料。
实施例2:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入0.025%钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值0.6;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入0.05%有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到7.7%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.8%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量0.07%以后,停止反应;
(5)在步骤(4)的反应液中,加入10%的甲基丙烯酸羟乙酯,搅拌均匀,出料。
实施例3:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入0.025%钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值0.8;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入0.060%有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到7.8%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.7%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量0.06%以后,停止反应;
(5)在步骤(4)的反应液中,加入8%的甲基丙烯酸羟乙酯,搅拌均匀,出料。
实施例4:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入0.020%钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值0.2;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入0.10%有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到7.4%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.4%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量0.03%以后,停止反应;
(5)在步骤(4)的反应液中,加入5%的甲基丙烯酸羟乙酯,搅拌均匀,出料。对比例1:
(1)按照二乙二醇、己二酸的摩尔比2.6:2.0投料,加入0.025%钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值0.9;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入0.050%有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到7.8%时结束反应;
(3在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.6%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量0.05%以后,停止反应;
(5)在步骤(4)的反应液中,加入10%的甲基丙烯酸羟乙酯,搅拌均匀,出料。
对比例2:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入0.020%钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值0.70;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇(分子量830)和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入0.08%有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到6.3%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.0%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量0.06%以后,停止反应;
(5)在步骤(4)的反应液中,加入10%的甲基丙烯酸羟乙酯,搅拌均匀,出料。
对比例3:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入0.020%钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值0.70;
(2)将0.2mol步骤(1)的反应液、0.2mol聚己内酯二醇(分子量530)和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入0.08%有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到6.0%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到2.8%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量0.06%以后,停止反应;
(5)在步骤(4)的反应液中,加入10%的甲基丙烯酸羟乙酯,搅拌均匀,出料。
由实施例1-实施例4和对比例1、对比例2、对比例3制备的丙烯酸聚氨酯,作为制作甲油胶的基础树脂,按以下配方制作成甲油胶:基础树脂87.9%,稀释剂甲基丙烯酸羟乙酯10.0%,光引发剂TPO2.0%和流平剂丙烯酸酯0.1%。
将本发明的一种丙烯酸聚氨酯作为基础树脂,辅以稀释剂、流平剂和光引发剂,通过刷涂方法,涂覆在塑料甲片或人体指甲上,再在36WLED甲油胶灯照60s,固化成甲油胶膜,进行色相、透明度、固化速度、光泽、柔性、硬度、附着力的测试,其中,色相和透明度由观察评价,固化速度由甲油胶灯照60s后指触法检测表干程度,光泽用祈色4#测试纸,黑色面涂30微米光固化后60度入射角测定,柔性是对折固化膜在塑料甲片断裂情况,硬度是用邵氏硬度计测定,附着力用人体指甲观察脱落时间。
实施例1-实施例4和对比例1、对比例2、对比例3的相关性能指标见下表:
表1实施例和对比例的测试结果
由测试结果可以看出,实施例1-实施例4制作的甲油胶,不仅固化速度快,而且在色相、光泽、柔性、硬度和附着力等综合性能上优良。对比例1预聚体无碳环结构,制作的甲油胶在光泽和硬度、附着力方面明显较差,且色相微黄;对比例2用分子量较高的聚己内酯二醇,导致甲油胶的低温出现轻微结晶现象,且硬度和表干性也变差;对比例3将预聚体与聚己内酯二醇的比例改变,导致甲油胶的色相、硬度变差,附着力明显低于实施例。
以上所述的仅为本发明的若干具体实施例。对于本领域的技术人员来说,还可以做出许多变形和改进,这些都属于本发明的保护范围。
Claims (3)
1.一种用于甲油胶的丙烯酸聚氨酯的制备方法,其特征在于,包括以下步骤:
(1)按照二乙二醇、己二酸和1,4-环己烷二甲醇的摩尔比1.6:2.0:1.0投料,加入钛酸四异丙酯,搅拌下逐步升温至220℃,脱水,至无水蒸汽产生后,再采用真空脱水至体系酸值<1;
(2)将0.1mol步骤(1)的反应液、0.3mol聚己内酯二醇和0.8mol异佛尔酮二异氰酸酯计量好后加至反应瓶搅拌均匀,再加入有机锡为催化剂,升温至65℃,保温反应3h,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到7.4%-7.9%时结束反应;
(3)在步骤(2)的反应液中,加入0.2mol的二羟基甲基丁酸,并升温至85℃进行反应,反应3h后,取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量达到3.3%-3.8%时结束反应;
(4)在步骤(3)的反应液中,加入0.41mol的甲基丙烯酸羟乙酯,继续在85℃进行反应,直至取样用二正丁胺-二甲苯溶液滴定至体系-NCO值重量百分含量<0.1%以后,停止反应;
(5)在步骤(4)的反应液中,加入5%-10%的甲基丙烯酸羟乙酯,搅拌均匀,出料;
其中,所述的聚己内酯二醇的分子量为530。
2.根据权利要求1所述的一种用于甲油胶的丙烯酸聚氨酯的制备方法,其特征在于,所述的有机锡为二月桂酸二丁基锡,其用量为异佛尔酮二异氰酸酯质量的0.05%-0.1%。
3.根据权利要求1所述的一种用于甲油胶的丙烯酸聚氨酯的制备方法,其特征在于,所述的钛酸四异丙酯用量是二乙二醇、己二酸和1,4-环己烷二甲醇总质量的0.01%-0.025%。
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