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1、.工程硕士学位论文47 / 47.摘要.紫外光固化涂料因优异的性能和绿色环保取得了高速的增长和广泛的应用。本文通过聚氨酯丙烯酸酯的合成及其在紫外光固化皮革涂料方面的应用,探索了PUA 树脂合成的最佳工艺条件和影响 PUA 树脂粘度的主要因素,通过配方试验和工艺优化,最终研制出性能优异的紫外光固化皮革涂料。该涂料通过了XX省科技厅主持的成果鉴定。经专家鉴定,该产品填补了国内相关应用领域的空白,属国内首创,该技术达到了国际先进水平。通过选用不同类型和不同分子量的二元醇预聚物作为中间体,合成一系列双官能团的 PUA 树脂。从合成路线、催化剂、加料方式、反应温度等方面对 PUA合成的工艺条件进行了探索
2、,从分子结构和反应条件分析了影响 PUA 树脂粘度的因素。总结了合成 PUA 的最佳工艺条件：第一步,多元醇与 TDI 在 50-60温度下反应生成带 NCO 基团的预聚体；第二步,以总量的 0.05%的二月桂酸二丁基锡做催化剂,在 60-70条件下IPDI 比 TDI 的反应温度低 10,以恒定的速度加入 HEA 并反应至终点。当投料摩尔比多元醇：TDI：HEA为 1：2.05：2.15 时,合成的 PUA 树脂具有最理想的贮存稳定性和光反应活性。从分子结构和工艺条件两方面探讨了影响 PUA 树脂粘度的因素。最重要的因素是设计的 PUA 分子聚合度,树脂的粘度随着分子聚合度的增加而显著增大。
3、对相同聚合度的树脂,中间体分子量对粘度有一定的影响：一般地,多元醇的分子量越大,PUA 树脂粘度越低；但是用 PTMG 合成的 PUA 树脂粘度却随着分子量的增加而增大。此外,合成线路和加料方式等对 PUA 树脂的粘度也有一定程度的影响。多元醇结构决定了 PUA 树脂的主要性能。同类型 PUA 的光固化速度随着树脂的相对分子质量的增加而下降,对不同类型的 PUA,聚醚型 PUA 的固化速度相对聚酯型 PUA 的固化速度要快,在聚醚型 PUA 中,以 PPG 合成的树脂具有相对较慢的固化速度。在 UV 皮革涂料的应用中,以聚丁二烯二元醇和聚四亚甲基醚二醇为骨架的 PUA 具有极佳的柔韧性和优异的
4、低温耐曲折性能,而且,HTPB 改性的聚氨酯具有极好的弹性和优异的附着力,以及非常快的固化速度。但是,极高的粘度和很差的相容性,只适合于高粘度的 UV 涂料的配制。以 PTMG 改性的 PUA 树脂为基础,从单体、光引发剂、光增感剂、助剂和施工工艺等多个方面研究了紫外光固化皮革涂料的性能,最终研制出一种性价比高的 UV 皮革涂料。关键词：皮革涂料;紫外光固化；聚氨酯丙烯酸酯；聚丁二烯二元醇；聚丙二醇；聚四亚甲基醚二醇；聚酯多元醇；低温耐曲折性；I.工程硕士学位论文AbstractUltraviolet cured coatings have made large growth and exte
5、nsive applicationbecause of their excellent performance and green environmental protection . This paperstudies the process conditions on synthesis of polyurethane acrylate resin and thefactors which influence the viscosity of PUA resin through synthesis of polyurethaneacrylate and application on the
6、 ultraviolet cured leather coating. We attain a kind ofultraviolet cured leather coating with excellent performance finally through trial offormulation and optimizing process. The appraisal of the UV leather coating weregained in charge of office of scientific and technological of Hunan Province. Th
7、eexperts thought that the product filled in blank of the domestic relevant application,belonged to domestic initiation and the technology had reached the internationaladvanced level.This paper studies the synthesis of a series ofPUA resin with two functional.group by selecting the different polyols
8、kinds and the different molecular weight polyols.The process conditions on synthesis of PUA are researched from all aspects by theexperiment, such as the route, catalyst, reinforced way, response temperature, etc. Wediscuss the factor which influenced the viscosity of the PUA resin from molecularstr
9、ucture and process conditions. The best process conditions of the synthesis of PUA issummarized : First, polyols and TDI react and turn into the prepolymer with NCO groupunder 50- 60 Centigrade of temperature; Second, the reaction will be ended at 60-70Centigrade, adding HEA at a certain speed, whil
10、e the catalyst is ditin n-butyl dilauratewhich use 0.05% of the whole quantity . PUA resin is the best in storing stabilityand speed on UV reaction while the mol rate of polyol : TDI: HEA is 1:2. 05:2.15. The.influential factors on theviscosity of PUA resin are discussed from molecular.structure and
11、 process conditions. The important factor influencing on the viscosity isdegree of polymerization while PUA resin molecule designed, the viscosity of resinincreases notably with the polymerization degree of molecule increasing. When thedegree of polymerization of resin is same, the molecular weight
12、of intermedia influenceon the viscosity of PUA. Generally, the viscosity of PUA resin is lower while themolecular weight of the polyols is higher. But the viscosity of PUA resin of PTMG ishigher while the molecular weight of the polyols is bigger. In addition, the route ofII.工程硕士学位论文synthesis and re
13、inforced way will influence the viscosity of PUA resin.The polyols determine the main performance of PUA resin. The curing rate of PUAcomposed of the same type polyols is lower while the molecular weight of the polyols isbigger. Comparing different kinds of PUA , polyether type PUA cure faster thanp
14、olyester. The rate of PUA which was synthesized by PPG is lowest among thepolyether type PUA resins. We find that the polyurethane acrylate resin with hydroxylterminated polybutadiene or polytetramethylene glycol as skeletonhave good flexibility and excellent low-temperature zigzag resistance throug
15、h theapplication of UV cured leather coating. And the polyurethane acrylate which ismodified by HTPB has extremely elasticity ,excellent adhesive and fast speed. however,it is only suitable for the manufacture of high viscosity UV cured coatings because oflarge viscosity and bad dissolved ability. Based on the polyurethane acrylate modifiedby PTMG, the performance of ultraviolet cured leather coating is researched from a lotof respects, such as mononer, photointiator, co-initiator,addition
