CN105968316A - 一种3d打印用双重固化树脂的制备方法 - Google Patents

一种3d打印用双重固化树脂的制备方法 Download PDF

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CN105968316A
CN105968316A CN201610331878.2A CN201610331878A CN105968316A CN 105968316 A CN105968316 A CN 105968316A CN 201610331878 A CN201610331878 A CN 201610331878A CN 105968316 A CN105968316 A CN 105968316A
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陈春灵
张哲�
王向军
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Wuyi University
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Abstract

本发明属于3D打印耗材领域，特别涉及一种3D打印用双重固化树脂的制备方法。具体包括：（1）将亚麻油、豆油酸、季戊四醇、苯酐、脂肪油（酸），在8%wt二甲苯作为回流溶剂下，进行反应，制得干性油醇酸树脂；（2）将HEA（丙烯酸羟乙酯）、IPDI（异佛尔酮二异氰酸酯），在0.1‑0.8%wt阻聚剂（MEHQ）、0.1%wt T‑12催化剂下反应，制成一端含有HEA，另一端含有NCO 基团的半加成物（HEA‑IPDI‑NCO）；（3）利用步骤（1）和步骤（2）制得的干性油醇酸树脂和半加成物（HEA‑IPDI‑NCO）进行反应，即得到所述3D打印用双重固化树脂。本发明制备的3D打印用双重固化树脂，同时具有UV固化和氧化固化两种固化方式，具有低粘度、低能量、快速固化和附着力大等特点，并且与颜料具有较好的润湿性。

Description

一种3D打印用双重固化树脂的制备方法
技术领域
本发明涉及3D打印用耗材的制备领域，具体涉及一种3D打印用双重固化树脂的制备方法。
背景技术
三维打印材料类似于喷墨打印材料，是与喷头技术和材料性质相结合的。在喷头技术不断提高下，可以打印的材料日益广泛，包括金属材料、无机非金属材料、高分子材料。不管是什么样的喷射材料，都要求与喷头相适应，因此选择合适的材料是问题的关键。国内市场现有的3D打印材料，在高分子材料方向主要以热塑性材料为主，主要涉及聚乳酸-聚乙醇酸共聚物、聚L-乳酸和ABS、尼龙等。其中聚乳酸-聚乙醇酸共聚物、聚L-乳酸、改性淀粉具有很好的生物相容性，因此被用于组织工程支架材料，它们也经常通过3D打印来成形。相对与热塑性材料的高能耗、挥发性气味等对周边环境可能产生的不利影响，光固化3D打印材料就属于更为绿色的成型技术。无需加热，即时家庭使用也无安全隐患，并且该材料成分为液体组合物，可以通过彩色打印机的配色原理打印出各种颜色制品，使得应用范围更加的广泛。
用于3D打印的光敏材料，在固化过程中产生收缩应力，导致其层间附着力较差。同时光敏树脂又由于氧阻聚的作用导致其在低能量下不能完全固化，最终导致表面发粘，无法成型。也有采用光热重固化机理制备的打印材料，需要额外加热装置，消耗能源，产品施工性不佳，同时储存稳定性不好。
发明内容
为解决上述技术问题，本发明提供了一种3D打印用双重固化树脂的制备方法，该树脂含有干性油（亚麻油等）的共轭碳碳双键，在催干剂的作用下，可在空气中氧气的作用下进行氧化交联，树脂末端的双键可在UV作用下固化，实现UV和氧化干燥双重固化模式，具备有低粘度、低能量、快速固化和较好的层间附着力等特点，并且与颜料具有较好的润湿性。具体包括以下步骤：
1）干性油醇酸树脂的制备：
将原料按质量份计：亚麻油200份、豆油酸305份、季戊四醇276份、苯酐148份、脂肪油（酸）100份加入到带有温度计、搅拌桨、回流和分水设备的反应器中，以8%wt二甲苯作为回流溶剂，添加0.1%wt酯化催化剂，在氮气或二氧化碳保护气氛下，升温至180-200℃，保温1-2h，在1h内缓慢升到200-220℃，抽样检测，当酸值为10-20mgKOH/g，反应终止，冷却到90℃，减压抽提溶剂，冷却至60℃备用，得到干性油醇酸树脂A；
2）半加成物（HEA-IPDI-NCO）的制备：
按物质的量比1：1称取HEA（丙烯酸羟乙酯）、IPDI（异佛尔酮二异氰酸酯），混合后加入0.1-0.8%wt阻聚剂（MEHQ）、0.1%wt T-12催化剂，在60℃下反应1h，制成一端含有HEA，另一端含有NCO 基团的半加成物（HEA-IPDI-NCO）B；
3）干性油醇酸树脂改性聚氨酯丙烯酸树脂的制备：
将3000质量份A与338质量份B混合，在90-120℃反应3h，当NCO含量小于0.1-0.5%wt时停止反应，降温至60℃后过滤包装，即得到所述3D打印用双重固化树脂。
进一步，步骤1）中，所述酯化催化剂为单丁基氧化锡；所述干性油醇酸树脂A：油度45-55%、羟值112-128mgKOH/g、分子量为2500-3000。
更进一步，步骤2）中，半加成物B中NCO含量为12-14%wt。
实施例：
为了便于本领域技术人员的理解，下面结合实施例对本发明作进一步的说明，实施方式提及的内容并非对本发明的限定。
实施例1
一种UV固化光敏材料的制备方法，包括如下步骤：
1）干性油醇酸树脂的制备：
将亚麻油200g、豆油酸305g、季戊四醇276g、苯酐148g、脂肪油（酸）100g加入到带有温度计、搅拌桨、回流和分水设备的反应器中，以8%wt二甲苯作为回流溶剂，添加0.1%wt单丁基氧化锡催化剂，在氮气或二氧化碳保护气氛下，升温至180℃，保温1h，在1h内缓慢升到200℃，抽样检测，当酸值为10mgKOH/g，反应终止，冷却到90℃，减压抽提溶剂，冷却至60℃备用，得到干性油醇酸树脂A；所述干性油醇酸树脂A：油度45%、羟值112mgKOH/g、分子量为2500-3000；
2）半加成物（HEA-IPDI-NCO）的制备：
称取1 molHEA（丙烯酸羟乙酯）、1molIPDI（异佛尔酮二异氰酸酯），混合后加入0.1%wt阻聚剂（MEHQ）、0.1%wt T-12催化剂，在60℃下反应1h，制成一端含有HEA，另一端含有NCO 基团的半加成物（HEA-IPDI-NCO）B，半加成物中NCO含量为12-14%wt；
3）干性油醇酸树脂改性聚氨酯丙烯酸树脂的制备：
将30gA与33.8gB混合，在90℃反应3h，当NCO含量小于0.1%wt时停止反应，降温至60℃后过滤包装，即得到所述3D打印用双重固化树脂。

Claims (4)

1.一种3D打印用双重固化树脂的制备方法，其特征在于，包括以下步骤：
1）干性油醇酸树脂的制备：
将原料按质量份计：亚麻油200份、豆油酸305份、季戊四醇276份、苯酐148份、脂肪油（酸）100份加入到带有温度计、搅拌桨、回流和分水设备的反应器中，以8%wt二甲苯作为回流溶剂，添加0.1%wt酯化催化剂，在氮气或二氧化碳保护气氛下，升温至180-200℃，保温1-2h，在1h内缓慢升到200-220℃，抽样检测，当酸值为10-20mgKOH/g，反应终止，冷却到90℃，减压抽提溶剂，冷却至60℃备用，得到干性油醇酸树脂A；
2）半加成物（HEA-IPDI-NCO）的制备：
按物质的量比1：1称取HEA（丙烯酸羟乙酯）、IPDI（异佛尔酮二异氰酸酯），混合后加入0.1-0.8%wt阻聚剂（MEHQ）、0.1%wt T-12催化剂，在60℃下反应1h，制成一端含有HEA，另一端含有NCO 基团的半加成物（HEA-IPDI-NCO）B；
3）干性油醇酸树脂改性聚氨酯丙烯酸树脂的制备：
将3000质量份A与338质量份B混合，在90-120℃反应3h，当NCO含量小于0.1-0.5%wt时停止反应，降温至60℃后过滤包装，即得到所述3D打印用双重固化树脂。
2.如权利要求1所述的一种3D打印用双重固化树脂的制备方法，其特征在于，步骤1）中，所述酯化催化剂为单丁基氧化锡。
3.如权利要求1所述的一种3D打印用双重固化树脂的制备方法，其特征在于，步骤1）中，所述干性油醇酸树脂A：油度45-55%、羟值112-128mgKOH/g、分子量为2500-3000。
4.如权利要求1或2所述的一种3D打印用双重固化树脂的制备方法，其特征在于，步骤2）中，半加成物B中NCO含量为12-14%wt。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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