CN111961178B - 一种自由基-阳离子型水性可混杂光固化树脂及其合成方法 - Google Patents
一种自由基-阳离子型水性可混杂光固化树脂及其合成方法 Download PDFInfo
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Abstract
本发明公开了一种自由基‑阳离子型水性可混杂光固化树脂及其合成方法,本方法合成得到光固化树脂解决了当前胺类中和型树脂刺激性气味问题,采用水性可混杂光固化树脂打印的制品可直接用水清洗,避免了使用化学品;同时利用自由基型和阳离子型两种树脂的优势,平衡了树脂的光固化速度,降低了3D打印制品的体积收缩,有效缓解了氧阻聚的发生,促进3D打印制品或者表面涂层的表干。
Description
技术领域
本发明属于光固化树脂有机高分子技术领域,具体涉及水性可混杂光固化树脂3D打印材料的合成制备方法。
背景技术
目前,市面上较常见的光固化3D打印材料为非水性光固化树脂,光固化3D打印设备使用这类树脂打印模型后,需要使用高浓度酒精或者异丙醇对模型进行清洗,这将产生大量的废弃酒精或者异丙醇,这些废弃物需要通过专门设备进行回收,回收成本高,对环境影响大。同时对于使用光固化3D打印设备进行工业化生产的操作人员来说,长期暴露在高浓度酒精或者异丙醇环境中不利于身体健康,也不符合相关环保政策的要求。对于普通消费者而言,高浓度酒精或者异丙醇属于化学品,缺少获取途径,也不具备专业知识去使用化学品,具有潜在的安全隐患,这些因素在一定程度上阻碍了3D打印技术的普及及应用。
目前大多数水性光固化树脂生产过程中需要使用胺进行中和,胺类化合物会给体系带来刺激性气味,消费者使用体验差,不利于身体健康,限制了此类水性光固化树脂材料在3D打印领域的使用。另外一方面光固化3D打印要求光固化树脂能够在紫外光照射下迅速固化成型,并能够避免产生大的体积收缩,从而保证打印制品的尺寸精度以及打印制品的力学性能。单一自由基体系树脂固化速度快,能够满足3D打印对于速度的要求,可是快速固化的同时会导致大的体积收缩,也伴随着较大的收缩应力,严重的还会导致打印制品翘曲变形;单一自由基体系固化时存在氧阻聚现象,会导致打印制品在清洗后仍出现表面发粘的情况,严重影响了打印制品的表面质量。而单一阳离子光固化体系则存在固化速度较慢的缺陷,但阳离子体系的优势也是明显的,固化体积收缩小、不存在氧阻聚现象,而且阳离子体系可以进行暗反应,能够进一步后固化提高打印制品的力学性能。
发明内容
发明目的:针对上述现有存在的问题和不足,本发明的目的是提供了一种自由基-阳离子型水性可混杂光固化树脂及其合成方法,可解决当前胺类中和型树脂刺激性气味问题,采用水性可混杂光固化树脂打印的制品可直接用水清洗,避免了使用化学品;同时利用自由基型和阳离子型两种树脂的优势,平衡了树脂的光固化速度,降低了3D打印制品的体积收缩,有效缓解了氧阻聚的发生,促进3D打印制品或者表面涂层的表干。
技术方案:为实现上述发明目的,本发明采用以下技术方案:一种自由基-阳离子型水性可混杂光固化树脂,具有以下分子结构通式:
其中,R为甲苯二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体、或甲苯二异氰酸酯-三羟甲基丙烷加成物;
R1为对羟基苯磺酸钠、2-羟基-2-丙磺酸盐、3-(N-吗啉)-2-羟基磺酸盐、3-氯-2-羟基丙磺酸盐、或3-烯丙氧基-2-羟基-1-丙磺酸盐;
n1和n2为1~30的自然数。
作为优选方案,n1+n2的值在5~30范围内。
本发明还提供了一种上述自由基-阳离子型水性可混杂光固化树脂的合成方法,包括以下步骤:
(1)反应釜预热至55℃后,将三官能度异氰酸酯投入反应釜内搅拌混合均匀;
(2)控制反应釜内温度在55℃~60℃,然后将羟基磺酸盐、活性稀释剂丙烯酸吗啉、阻聚剂对羟基苯甲醚和催化剂二月桂酸二丁基锡混合均匀后,滴加进入反应体系内,保温反应1~2h,测试异氰酸酯值到计算值时,得到中间产物A;
(3)控制反应体系温度在70~75℃,继续滴加混合均匀的聚氧化丙烯二醇、3-乙基-3-氧杂丁环甲醇和季戊四醇三丙烯酸酯,进行保温反应2~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,得到目标产物。
进一步的,所述三官能度异氰酸酯包含:甲苯二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体以及甲苯二异氰酸酯-三羟甲基丙烷加成物
进一步的,所述羟基磺酸盐为对羟基苯磺酸钠、2-羟基-2-丙磺酸钠、3-(N-吗啉)-2-羟基磺酸钠、3-氯-2-羟基丙磺酸钠、3-烯丙氧基-2-羟基-1-丙磺酸钠中的一种或几种的混合物。
进一步的,所述的聚氧化丙烯二醇分子量在600~4000,n1+n2=5~30。
有益效果:与现有技术相比,本发明具有以下优点:1、采用磺酸盐型化合物作为亲水基团,不存在刺激性气味;2、水性树脂打印完毕后可直接用水清洗,避免使用乙醇和异丙醇溶剂;3、使用异氰酸酯三聚体作为反应物,在一定程度上降低了生产操作风险(异氰酸酯的单体毒性较大);4、阳离子自由基混杂型树脂有效避免了氧阻聚,平衡了光固化速度,降低了3D打印制品的体积收缩,促进了3D打印制品或者涂层的表干。
具体实施方式
下面结合具体实施例,进一步阐明本发明,应理解这些实施例仅用于说明本发明而不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
本发明的自由基-阳离子型水性可混杂光固化树脂,其化学结构式如下:
其中,R选自甲苯二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体以及甲苯二异氰酸酯-三羟甲基丙烷加成物中不含异氰酸酯的部分;
R1选自对羟基苯磺酸钠、2-羟基-2-丙磺酸钠、3-(N-吗啉)-2-羟基磺酸钠、3-氯-2-羟基丙磺酸钠、3-烯丙氧基-2-羟基-1-丙磺酸钠中不含磺酸钠和羟基基团的部分。
本发明的自由基-阳离子型水性可混杂光固化树脂的合成反应路线如下:
(a)
(b)
以下通过具体实施例具体介绍本发明由基-阳离子型水性可混杂光固化树脂的合成具体步骤:
实施例1
反应釜预热至55℃后把甲苯二异氰酸酯-三羟甲基丙烷加成物60g投入反应釜内,然后滴加羟基磺酸钠18g、活性稀释剂丙烯酸吗啉25g、阻聚剂对羟基苯甲醚0.05g和催化剂二月桂酸二丁基锡0.01g的混合物,控制温度在55℃~60℃,保温反应1h~2h,测试异氰酸酯值到计算值时加入聚氧化丙烯二醇120g、3-乙基-3-氧杂丁环甲醇5g和季戊四醇三丙烯酸酯20g,控制温度在70℃~75℃,保温反应2h~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,得到可混杂光固化水性树脂。
实施例2
反应釜预热至55℃后把异佛尔酮二异氰酸酯三聚体90g投入反应釜内,然后滴加羟基磺酸钠25g、活性稀释剂丙烯酸吗啉58g、阻聚剂对羟基苯甲醚0.05g和催化剂二月桂酸二丁基锡0.01g的混合物,控制温度在55℃~60℃,保温反应1h~2h,测试异氰酸酯值到计算值时加入聚氧化丙烯二醇80g、3-乙基-3-氧杂丁环甲醇8g和季戊四醇三丙烯酸酯14g,控制温度在70℃~75℃,保温反应2h~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,得到可混杂光固化水性树脂。
实施例3
反应釜预热至55℃后把六亚甲基二异氰酸酯三聚体70g投入反应釜内,然后滴加羟基磺酸钠21g、活性稀释剂丙烯酸吗啉45g、阻聚剂对羟基苯甲醚0.05g和催化剂二月桂酸二丁基锡0.01g的混合物,控制温度在55℃~60℃,保温反应1h~2h,测试异氰酸酯值到计算值时加入聚氧化丙烯二醇150g、3-乙基-3-氧杂丁环甲醇10g和季戊四醇三丙烯酸酯16g,控制温度在70℃~75℃,保温反应2h~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,得到可混杂光固化水性树脂。
实施例4
反应釜预热至55℃后把甲苯二异氰酸酯三聚体45g、甲苯二异氰酸酯-三羟甲基丙烷加成物33g投入反应釜内,然后滴加羟基磺酸钠23g、活性稀释剂丙烯酸吗啉50g、阻聚剂对羟基苯甲醚0.05g和催化剂二月桂酸二丁基锡0.01g的混合物,控制温度在55℃~60℃,保温反应1h~2h,测试异氰酸酯值到计算值时加入聚氧化丙烯二醇80g、3-乙基-3-氧杂丁环甲醇7g和季戊四醇三丙烯酸酯13g,控制温度在70℃~75℃,保温反应2h~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,得到可混杂光固化水性树脂。
对比例1
反应釜预热至50℃后把甲苯二异氰酸酯17g投入反应釜内,然后滴加二羟甲基丙酸3g、活性稀释剂丙烯酸吗啉20g、阻聚剂对羟基苯甲醚0.05g和催化剂二月桂酸二丁基锡0.01g的混合物,控制温度在50℃~55℃,保温反应1h~2h,测试异氰酸酯值到计算值时加入聚氧化丙烯二醇100g、3-乙基-3-氧杂丁环甲醇5.8g和季戊四醇三丙烯酸酯14g,控制温度在70℃~75℃,保温反应2h~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,降温至室温加入三乙胺中和,得到光固化水性树脂。
对比例2
反应釜预热至50℃后把甲苯二异氰酸酯17g投入反应釜内,然后滴加二羟甲基丙酸3g、活性稀释剂丙烯酸吗啉20g、阻聚剂对羟基苯甲醚0.05g和催化剂二月桂酸二丁基锡0.01g的混合物,控制温度在50℃~55℃,保温反应1h~2h,测试异氰酸酯值到计算值时加入聚氧化丙烯二醇100g、季戊四醇三丙烯酸酯13g和丙烯酸羟乙酯6g,控制温度在70℃~75℃,保温反应2h~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,降温至室温加入三乙胺中和,得到水性光固化树脂。
分别取实施例1~4和对比例1及2中的样品针对液体气味进行测试,同时在固化条件为40W,365nmLED紫外灯,样品与紫外灯距离5cm的条件下进行固化表干情况测试,得到如下结果,表1。
表1:实施例和对比例样品的气味和表干情况测试对比
从测试结果可知:本发明得到的自由基-阳离子型水性可混杂光固化树脂不存在刺激性气味,且表干情况优秀,在降低3D打印体积收缩的同时能快速表面干燥。
Claims (4)
1.一种自由基-阳离子型水性可混杂光固化树脂的合成方法,包括以下步骤:
(1)反应釜预热至55℃后,将三官能度异氰酸酯投入反应釜内搅拌混合均匀;
(2)控制反应釜内温度在55℃~60℃,然后将羟基磺酸盐、活性稀释剂丙烯酸吗啉、阻聚剂对羟基苯甲醚和催化剂二月桂酸二丁基锡混合均匀后,滴加进入反应体系内,保温反应1~2h,测试异氰酸酯值到计算值时,得到中间产物A;
(3)控制反应体系温度在70~75℃,继续滴加混合均匀的聚氧化丙烯二醇、3-乙基-3-氧杂丁环甲醇和季戊四醇三丙烯酸酯,进行保温反应2~3h,测试异氰酸酯值,当异氰酸酯值为零时停止反应,得到目标产物。
2.根据权利要求1所述自由基-阳离子型水性可混杂光固化树脂的合成方法,其特征在于:所述三官能度异氰酸酯包含:甲苯二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体以及甲苯二异氰酸酯-三羟甲基丙烷加成物。
3.根据权利要求1所述自由基-阳离子型水性可混杂光固化树脂的合成方法,其特征在于:所述羟基磺酸盐为对羟基苯磺酸钠、2-羟基-2-丙磺酸钠、3-(N-吗啉)-2-羟基磺酸钠、3-氯-2-羟基丙磺酸钠、3-烯丙氧基-2-羟基-1-丙磺酸钠中的一种或几种的混合物。
4.根据权利要求1所述自由基-阳离子型水性可混杂光固化树脂的合成方法,其特征在于:所述的聚氧化丙烯二醇分子量在600~4000。
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