烯丙基腰果酚单体光固化反应特性研究

doi:10.3969/j.issn.0253-2417.2021.02.008

摘要/Abstract

摘要：

以腰果酚为原料制备氢化腰果酚（HC），再与烯丙基缩水甘油醚（AGE）反应合成烯丙基醚型氢化腰果酚（AGE-HC），进一步与甲基丙烯酸酐（MAA）反应合成烯丙基醚酯型氢化腰果酚（MAA-AGE-HC）。以烯丙基醚型腰果酚（AGE-C）和烯丙基醚酯型腰果酚（MAA-AGE-C）为对照样，采用红外光谱、凝胶渗透色谱研究了烯丙基腰果酚单体的紫外光固化反应特性。研究结果表明：烯丙基腰果酚单体的最佳光固化反应条件为无极灯光源（铁灯，主波长365 nm），功率1 500 W，辐照距离40 mm，辐照时间60 s，引发剂2-羟基-2-甲基-1-苯基-1-丙酮（1173）用量为单体质量的3%；烯丙基腰果酚的光固化反应活性由高到低依次为MAA-AGE-C > MAA-AGE-HC > AGE-C > AGE-HC≈腰果酚；腰果酚在有氧或光引发剂条件下可紫外光固化，紫外光固化过程温度升高可协同加速固化反应，使腰果酚快速固化；烯丙基酯、烯丙基醚和烯丙基烷基在紫外光固化过程中，依据基团反应活性高低分步固化，主要通过光、热引发自由基聚合反应实现烯丙基单体的固化。

关键词: 腰果酚, 氢化腰果酚, 烯丙基腰果酚, 紫外光固化反应, 反应活性

Abstract:

The hydrogenated cardanol(HC) was prepared from cardanol, and then reacted with allyl glycidyl ether(AGE) to synthesize allyl ether type hydrogenated cardanol(AGE-HC). The AGE-HC reacted with methacrylic anhydride(MAA) to form allyl hydrogenated cardanol with ether bond and ester bond(MAA-AGE-HC).The characteristics of UV curing reaction of allyl cardanol monomers were studied by Fourier transform infrared spectroscopy(FT-IR) and gel permeation chromatography(GPC), with allyl ether type cardanol(AGE-C) and allyl cardanol with ether bond and ester bond(MAA-AGE-C) as contrast.The results showed that the optimal UV curing reaction conditions of allyl cardanol monomers were as follows: electrodeless lamp (iron lamp, main wavelength 365 nm) as UV source, power 1 500 W, irradiation distance 40 mm, irradiation time 60 s, 2-hydroxy-2-methyl-1-phenyl-1-acetone(1173) as initiator with the dosage of 3% of the monomer by weight. The UV curing activities of allyl cardanols were MAA-AGE-C > MAA-AGE-HC > AGE-C > AGE-HC≈cardanol. Cardanol could be cured by UV light under the condition of oxygen or photoinitiator. The curing reaction rate could be accelerated by the combination of UV and high temperature. Furthermore, the allyl ester, allyl ether and allyl alkyl were gradually cured according to the activity of functional groupsby the photoinitiated radical polymerization and thermal initiated oxygen radical polymerization.

Key words: cardanol, hydrogenated cardanol, allyl cardanol, UV curing reaction, reaction activity

中图分类号:

TQ35

陈健, 吴国民, 霍淑平, 孔振武. 烯丙基腰果酚单体光固化反应特性研究[J]. 林产化学与工业, 2021, 41(2): 55-64.

Jian CHEN, Guomin WU, Shuping HUO, Zhenwu KONG. Characteristics of UV Curing Reaction of Allyl Cardanol Monomers[J]. Chemistry and Industry of Forest Products, 2021, 41(2): 55-64.

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样品samples	羟值/(mg·g^-1)hydroxyl value	碘值/(g·g^-1)iodine value	黏度(25 ℃)/(mPa·s)viscosity
HC	180	1.27	—
AGE-HC	135	0.78	130
MAA-AGE-HC	16	0.95	190

辐照时间/sirradiation time	保留时间/minretention time	腰果酚cardanol			AGE-HC			AGE-C			MAA-AGE-HC			MAA-AGE-C
辐照时间/sirradiation time	保留时间/minretention time	M_w	M_n	p/%	M_w	M_n	p/%	M_w	M_n	p/%	M_w	M_n	p/%	M_w	M_n	p/%
	0~12.5	—	—	—	—	—	—	—	—	—	30964	25544	8.18	26185	20921	12.63
10	12.5~14.5	1739	1361	16.69	2222	1898	11.12	2069	1806	14.86	1901	1724	20.46	2091	1869	18.70
	14.5~16	300	283	83.31	557	525	88.88	540	507	85.14	621	575	71.35	609	565	68.67
	0~12.5	—	—	—	—	—	—	6517	6185	2.18	31350	26683	15.45	30087	22499	16.76
20	12.5~14.5	3067	1697	28.15	2154	1808	17.00	2252	1947	20.97	2085	1889	22.65	2331	1984	26.47
	14.5~16	297	279	71.85	499	453	83.00	545	516	76.85	624	594	61.90	590	550	56.77
	0~12.5	—	—	—	—	—	—	18246	15022	5.48	34530	24324	18.35	56344	23751	21.18
30	12.5~14.5	3113	1730	31.31	2478	2029	24.57	3167	2443	31.53	2563	2217	31.02	2625	2131	31.50
	14.5~16	294	275	68.69	514	469	75.43	528	506	62.99	622	583	50.63	588	548	47.31
	0~12.5	—	—	—	—	—	—	24044	18245	7.58	45813	24882	22.63
40	12.5~14.5	3110	1738	21.64	2977	2237	30.58	3261	2519	30.55	2758	2146	41.20
	14.5~16	295	276	78.36	519	478	69.42	515	496	61.87	624	590	36.17

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