烯丙基改性生漆的合成及其光/氧固化特性研究

doi:10.3969/j.issn.0253-2417.2022.02.001

摘要/Abstract

摘要：

以生漆为原料，与烯丙基缩水甘油醚(AGE)反应制备了烯丙基醚改性生漆(AGE-L)，再与甲基丙烯酸酐(MAA)反应合成了烯丙基醚酯改性生漆(MAA-AGE-L)，采用FT-IR、¹H NMR和¹³C NMR等方法对其结构进行了表征，并测试其理化性能。进一步研究了生漆、AGE-L和MAA-AGE-L的紫外光和氧气(空气)固化过程，并测试了漆膜的机械性能及耐化学介质性能。研究结果表明：AGE-L和MAA-AGE-L已经成功合成，两者均为棕红色液体，其中AGE-L的羟值193 mg/g、碘值1.89 g/g、黏度400 mPa·s；MAA-AGE-L的羟值20 mg/g、碘值1.38 g/g、黏度2 000 mPa·s。与生漆相比，MAA-AGE-L漆膜在温度30℃、相对湿度80%的氧气(空气)环境下表干时间由2 h缩短至50 min，紫外光固化表干时间由50 s缩短至10 s；AGE-L经紫外光照射120 s时的漆膜铅笔硬度达到H，经温度30℃、相对湿度80%的氧气(空气)环境下固化一周的漆膜铅笔硬度达到2H，同时均具有较好的附着力、柔韧性和抗冲击强度；烯丙基改性生漆经2种固化方式形成的漆膜均具有较好的耐水、耐乙醇、耐盐水和耐酸性能。

关键词: 生漆, 漆酚, 烯丙基缩水甘油醚, 紫外光固化, 双固化

Abstract:

The allyl ether modified lacquer(AGE-L) was successfully prepared by the reaction of lacquer with allyl glycidyl ether(AGE), and subsequently reacted with methacrylic anhydride(MAA) to form a novel lacquer-based monomer with ether bond and ester bond(MAA-AGE-L). Their structures were then characterized by FT-IR, ¹H NMR and ¹³C NMR, and their physical and chemical properties were tested. Additionally, the UV and oxygen(air) curing processes of raw lacquer, AGE-L and MAA-AGE-L were investigated, and the mechanical properties as well as the resistances to chemical media of the cured films were also studied. The results confirmed the successful synthesis of AGE-L and MAA-AGE-L, which were all brownish red liquids. The hydroxyl value of AGE-L was 193 mg/g, the iodine value was 1.89 g/g and the viscosity was 400 mPa·s. The hydroxyl value of MAA-AGE-L was 20 mg/g, the iodine value was 1.39 g/g and the viscosity was 2 000 mPa·s. Compared with lacquer, the surface drying time of MAA-AGE-L was shortened from 2 h to 50 min in presence of the oxygen(air) environment at 30 ℃ with the relative humidity of 80%, and the UV curing surface drying time was shortened from 50 s to 10 s. The pencil hardness of the cured film was H when AGE-L was irradiated by ultraviolet light for 120 s, whereas the pencil hardness of the paint film cured under oxygen(air) for one week was 2H. Moreover, they exhibited good adhesion, flexibility and impact strength. Allyl-modified lacquer films obtained by two curing methods had good water resistance, ethanol resistance, salt water resistance and acid resistance.

Key words: lacquer, urushiol, allyl glycidyl ether, UV curing, dual curing

中图分类号:

TQ35

陈健, 吴国民, 霍淑平, 孔振武. 烯丙基改性生漆的合成及其光/氧固化特性研究[J]. 林产化学与工业, 2022, 42(2): 1-9.

Jian CHEN, Guomin WU, Shuping HUO, Zhenwu KONG. Synthesis of Allyl Modified Lacquer and Its Characteristics of UV/Oxygen Curing[J]. Chemistry and Industry of Forest Products, 2022, 42(2): 1-9.

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样品 sample	羟值/(mg·g^-1) hydroxyl value	碘值/(g·g^-1) iodine value	黏度/(mPa·s，25 ℃) viscosity	外观 appearance
烯丙基缩水甘油醚AGE	—	2.14	4	无色透明液体colorless transparent liquid
生漆lacquer	231	1.81	1600	棕灰色液体brown-grey liquid
烯丙基醚改性生漆AGE-L	193	1.89	400	棕红色液体brown-red liquid
烯丙基醚酯改性生漆MAA-AGE-L	20	1.38	2000	棕红色液体brown-red liquid

样品 sample	固化方式 curing method	铅笔硬度 pencil hardness	附着力/级 adhesion/ grade	柔韧性/mm flexibility	抗冲击强度/(kg·cm) impact strength
样品 sample	固化方式 curing method	铅笔硬度 pencil hardness	附着力/级 adhesion/ grade	柔韧性/mm flexibility	正冲 forward impact	反冲 back impact
生漆lacquer	氧oxygen(30 ℃，7 d)	H	7	10	10	5
	氧+热oxygen+hot(130 ℃，6 h)	4H	7	10	5	5
	UV	B	3	0.5	10	5
烯丙基醚改性生漆 AGE-L	氧oxygen(30 ℃，7 d)	2H	2	0.5	50	50
烯丙基醚改性生漆 AGE-L	UV	H	1	0.5	50	50
烯丙基醚酯改性生漆 MAA-AGE-L	氧oxygen(30 ℃，7 d)	2H	3	5	50	50
烯丙基醚酯改性生漆 MAA-AGE-L	UV	2H	5	10	5	5

样品 sample	固化方式 curing method	H₂O (7 d)	无水乙醇ethanol (7 d)	5% NaCl (7 d)	10% HCl (3 d)	10% H₂SO₄ (3 d)	10% NaOH (3 h)
生漆lacquer	氧oxygen(30 ℃，7 d)	+	+	+	+	+	-
生漆lacquer	UV(120 s)	+	+	+	+	+	-
烯丙基醚改性生漆 AGE-L	氧oxygen(30 ℃，7 d)	+	+	+	+	+	-
烯丙基醚改性生漆 AGE-L	UV(120 s)	+	+	+	+	+	-
烯丙基醚酯改性生漆 MAA-AGE-L	氧oxygen(30 ℃，7 d)	+	+	+	+	+	-
烯丙基醚酯改性生漆 MAA-AGE-L	UV(120 s)	+	+	+	+	+	-

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