论文总字数：18650字

摘 要

随着国家有关部门对环境问题越来越重视，环保成为人们密切关注的话题，在涂料油墨行业，UV固化由于具有环保节能高效的技术特点而被广泛的应用和推广，在3C塑料、家装面漆、汽车漆、光盘和信用卡等很多方面已经开发出了不可替代的产品，已开始慢慢取代传统的溶剂型涂料的霸主地位。本文以价格低廉的双环戊二烯（DCPD）与三羟甲基丙烷（TMP）、顺酐（MA）、苯酐（PA）、二甘醇（DEG）为原料来合成双环戊二烯改性不饱和聚酯多元醇（DUPP），再用异佛尔酮二异氰酸酯（IPDI）、季戊四醇三丙烯酸酯（PET3A）与DUPP进行反应制备出可进行UV固化的双环基聚氨酯丙烯酸酯（DPUA）。

首先合成了双环基不饱和聚酯多元醇。最佳条件为合成DUPP时选择反应温度为210℃，反应时间5h较为适宜，选择0.04 wt%钛酸四丁酯（TBT）作为催化剂较为合适。考察了醇酸比对DUPP羟值和粘度的影响，最终选择了较适宜的醇酸比4:3，即原料摩尔比为HOR¹OH:DEG:MA:PA=4:4:3:3。对产物DUPP作了红外剖析，能够明显看到羟基和酯基的吸收峰，证明了羟基和酯基的存在，并且也证实有利于后期光固化的碳碳不饱和双键的吸收峰存在，能判断此反应产物与目标产物相同。

合成了双环改性聚氨酯丙烯酸酯。实验表明，第1步反应中反应条件为45 ℃、2.5 h为佳、催化剂DBTDL用量0.04 %；第2步反应利用PET3A对树脂体系封端，反应条件为75 ℃、2.5 h、催化剂DBTDL用量0.06%较好；阻聚剂对苯二酚用量为0.2 %。DPUA和DUPP红外谱图相比，在3493 cm^-1处羟基峰消失，而在3312 cm^-1处出现了仲氨基（NR¹R²H）的伸缩振动吸收峰；同时，在810 cm^-1、1635 cm^-1处出现丙烯酸酯碳碳不饱和双键的特征吸收峰，证明合成了DPUA树脂。

关键词：双环戊二烯 不饱和聚酯多元醇 聚氨酯丙烯酸酯 UV固化

Synthesis of terpene-based UV-curable epoxy acrylate

Abstract

With the relevant departments of the state more and more attention to environmental issues, surroundings protection is the very topic which people keeps a close eye on, in the paint ink industry, UV curing due to environmental protection and energy saving and efficient technical features have been widely used and promotion, in 3C plastic, Paint, car paint, CD-ROM and credit card, and many other aspects have been developed an irreplaceable product, has begun to slowly replace the traditional solvent-based coatings dominance. In this paper, the synthesis of dicyclopentadiene with dicyclopentadiene (DCPD) and trimethylol propane (TMP), maleic anhydride (MA), phthalic anhydride (PA) and diethylene glycol (DEG) (DPUA) can be prepared by reacting DUPP with isophorone diisocyanate (IPDI) and pentaerythritol triacrylate (PET3A) to prepare UV-curable polyether polyol (DUPP). The synthesized DPUA was used as matrix resin to adjust the formulation and UV curing, and its performance was tested and characterized. Specific work as follows:

First, bicyclic amino unsaturated polyols were synthesized. The optimum reaction conditions were as follows: the reaction temperature was 210 ℃, the reaction time was 5h, and the optimum conditions were as follows: 0.04 wt% tetrabutyl titanate (TBT) was used to study the effect of reaction temperature Finally, the coating formulation. ) As a catalyst is more appropriate. The effect of alkyd ratio on the hydroxyl value and viscosity of DUPP was investigated. The optimum molar ratio of alkyd to alcohol was 4: 3, that is, the molar ratio of raw material was HOR1OH: DEG: MA: PA = 4: 4: 3: 3. The absorption peaks of the hydroxyl groups and ester groups were confirmed by infrared analysis of the product DUPP, demonstrating the presence of hydroxyl groups and ester groups, and also confirming the presence of the absorption peaks of carbon-unsaturated double bonds that favored photoluminescence The reaction product was judged to be the same as the target product.

Followed by the synthesis of double-ring modified polyurethane acrylate. The effects of reaction temperature, time, amount of catalyst and amount of polymerization inhibitor on the synthesis of two steps were investigated. In the first step, the reaction conditions were 45 ℃ and 2.5 h, and the dosage of DBTDL was 0.04%. The reaction was terminated with PET3A on the resin system. The reaction conditions were 75 ℃ and 2.5 h. The amount of catalyst DBTDL was 0.06% ; The amount of polymerization inhibitor hydroquinone was 0.2%. At the same time, at 810 cm-1, 1635 cm- 1, the characteristic absorption peak of acrylate carbon-carbon unsaturated double bond appeared, and it was proved that DPUA resin was synthesized.

KEYWORDS:dicyclopentadiene ;unsaturated polyester polyol; polyurethane acrylate ;UV curing

目 录

摘 要 I

Abstract II

第一章 绪论 1

1.1 前言 1

1.2 紫外光固化技术 2

1.2.1 紫外光固化机理 2

1.2.2 紫外光固化设备 3

1.2.3 紫外光固化技术的特点 4

1.2.4 紫外光固化技术的应用 4

1.3 双环戊二烯的研究进展 5

1.3.1 双环戊二烯的简介 5

1.3.2 双环戊二烯的应用 5

第二章 双环基聚氨酯丙烯酸酯的合成 7

2.1 前言 7

2.2 实验部分 7

2.2.1 主要原料与仪器 7

2.2.2 双环基聚氨酯丙烯酸酯（DPUA）的合成 8

2.2.3 产物分析及测试 9

2.3 结果与讨论 11

2.3.1 反应温度和时间对体系-NCO含量的影响 11

2.3.2 催化剂用量对DPUA合成的影响 13

2.3.3 阻聚剂用量对DPUA合成的影响 15

2.3.4 DPUA的红外光谱图分析 15

2.4 本章小结 16

第三章 结论与展望 18

3.1 结论 18

3.2 展望 19

参考文献 20

致 谢 23

第一章 绪论

1.1 前言

涂料作为一种高分子材料，通过工艺技术涂覆在物体表面，它能与被涂物通过物理或者化学手段形成一层薄膜，并且能牢固附着于其表面，能够起到保护、装饰、绝缘、防锈、防霉或耐热等一系列功能，在工业界一直有着“工业外衣”的美誉，在全世界的发达国家中，涂料的生产根据统计已经占化学工业的年产值的10 %，具有重要的地位，加强其开发意义重大^[1]。以二甲苯等高挥发性有机溶剂作为分散介质，再混以树脂、流平剂、消泡剂等施工的称为传统型的溶剂型涂料，其虽然可以在延展性、丰满度和手感度等性能上具有一定优势，但其含30% - 70% 的挥发性有机化合物（VOC），非常容易释放到大气中，会造成环境污染，从而危害身心健康^[2]。

随人们环保意识的提高和国家对环保要求越来越严格，对高性能、高清洁无污染涂料的需求越来越多，特别是家居木器、3C 塑料等与人密切相关的领域，对低VOC含量甚至是无VOC含量的涂料需求与日俱增。因此，紫外光（UV）固化涂料应运而生，UV涂料的特点是环保、高效和节能，一般UV固化所需要消耗资源能耗为热固化的五分之一，固化时间缩短至为十几秒甚至几秒，而远小于传统热固化所需要的极长的几小时甚至几天，符合经济（Economy）、生态（Ecology）、能源（Energy）、高效（Efficiency）、适用性（Enabling）的“5E”原则^[3,4]。该技术经过七十年左右的发展，已成为较成熟的技术。为了降粘，其涂料使用TPGDA、NPGDA、HDDA、PET3A、DPHA等丙烯酸酯类活性单体作为稀释剂，其既能参与反应，也能增加涂膜性能，譬如柔韧性、刚性、交联密度等，在UV固化涂料中使用甚广^[5]。

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