Preparation and application of alcohol-soluble, multi-purpose polyurethane adhesives

doi:10.16085/j.issn.1000-6613.2025-0029

Abstract

Abstract:

Alcohol-soluble polyurethane adhesives (AS-PU) with hard segments containing different IPDI/HDI ratios were prepared using polytetrahydrofuran ether glycol (PTMEG), 1,4-butanediol (BDO), isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI). The effects of IPDI/HDI ratios on the structure, alcohol solubility, water resistance, thermal stability and adhesive properties of AS-PU were investigated by Fourier transform infrared spectroscopy (FTIR), UV-vis absorption spectroscopy, water contact angle analysis, thermo-gravimetric analyzer (TGA) and electronic universal testing machine. The results showed that with the increase of HDI content in the hard segments, the intensity of hydrogen bonding between the AS-PU molecular chains increased, and the transmittance of the adhesive decreased from 94.1% to 77.3% at a wavelength of 390nm, which implied a decrease in alcohol solubility. With the introduction of HDI, the water contact angle of AS-PU was increased from 83.61° to 95.05°, the water absorption after 24h of immersion was reduced from 5.31% to 1.37%, and the T_initial was increased from 285℃ to 298—308℃, which indicated the improvement of the water resistance and thermal stability of the adhesive. AS-PU indicated excellent adhesive properties to different substrates, in which the maximum shear strength of overlap could reach 2.78MPa, 2.33MPa, 2.08MPa and 0.51MPa for wood, glass, iron and polypropylene, respectively.

Key words: polyurethanes, adhesives, alcohol soluble, hard segment composition, multi-purpose

摘要：

采用聚四氢呋喃醚二醇（PTMEG）、1,4-丁二醇（BDO）、异佛尔酮二异氰酸酯（IPDI）和六亚甲基二异氰酸酯（HDI）等为主要原料，制备出硬段中含有不同IPDI/HDI配比的醇溶性聚氨酯胶黏剂（AS-PU）。采用傅里叶红外光谱（FTIR）、紫外-可见吸收光谱、水接触角分析仪、热重分析仪（TGA）、电子万能试验机等，研究了IPDI/HDI配比对AS-PU结构、醇溶性、耐水性、热稳定性及粘接性能的影响。结果表明，随着硬段中HDI含量的提高，AS-PU分子链间的氢键作用强度增加，胶液在波长390nm处的透光率由94.1%降低至77.3%，即醇溶性有所降低；随着HDI的引入，AS-PU的水接触角由83.61°升高至95.05°，浸泡24h的吸水率由5.31%降至1.37%，T_初始由285℃升高至298~308℃，提高了胶黏剂的耐水性和热稳定性；AS-PU对木材、玻璃、铁片、聚丙烯塑料的最大搭接剪切强度分别可达2.78MPa、2.33MPa、2.08MPa和0.51MPa，表现出对不同基材的优异粘接性能。

关键词: 聚氨酯, 胶黏剂, 醇溶性, 硬段组成, 多用途

CLC Number:

TQ43

WANG Yujie, CHEN Keyu, SUN Shiqi, XU Xiaoting, ZHAI Jiayi, NIE Huifang, WANG Fei. Preparation and application of alcohol-soluble, multi-purpose polyurethane adhesives[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4070-4077.

王玉杰, 陈科宇, 孙诗琪, 许小婷, 翟嘉怡, 聂慧芳, 王非. 醇溶性多用途聚氨酯胶黏剂的制备及应用[J]. 化工进展, 2025, 44(7): 4070-4077.

Figures/Tables 13

References 25

[1]	Adrián TENORIO-ALFONSO, Carmen SÁNCHEZ M, FRANCO José M. A review of the sustainable approaches in the production of bio-based polyurethanes and their applications in the adhesive field[J]. Journal of Polymers and the Environment, 2020, 28(3): 749-774.
[2]	GAMA Nuno, FERREIRA Artur, Ana BARROS-TIMMONS. Cure and performance of castor oil polyurethane adhesive[J]. International Journal of Adhesion and Adhesives, 2019, 95: 102413.
[3]	WANG Shuliang, LIU Zenghe, ZHANG Luzhi, et al. Strong, detachable, and self-healing dynamic crosslinked hot melt polyurethane adhesive[J]. Materials Chemistry Frontiers, 2019, 3(9): 1833-1839.
[4]	王学川, 王利红, 张思肖, 等. 聚氨酯交联改性工业明胶木材胶黏剂的制备与性能[J]. 高分子材料科学与工程, 2020, 36(2): 20-26.
	WANG Xuechuan, WANG Lihong, ZHANG Sixiao, et al. Preparation and properties of industrial gelatin wood adhesive modified by polyurethane[J]. Polymer Materials Science & Engineering, 2020, 36(2): 20-26.
[5]	张学敏, 龙来早, 马福波, 等. 聚氨酯木材胶粘剂的研究进展[J]. 中国胶粘剂, 2018, 27(6): 48-52.
	ZHANG Xuemin, LONG Laizao, MA Fubo, et al. Research progress of polyurethane wood adhesive[J]. China Adhesives, 2018, 27(6): 48-52.
[6]	张光涛, 刘亚琼, 张燕红, 等. 玻璃结构用双组分聚氨酯胶粘剂老化性能研究[J]. 中国胶粘剂, 2019, 28(11): 8-11.
	ZHANG Guangtao, LIU Yaqiong, ZHANG Yanhong, et al. Study on aging performance of two-component polyurethane adhesive for structural glazing[J]. China Adhesives, 2019, 28(11): 8-11.
[7]	钟强, 李绪宾, 陈爽, 等. 稻壳液化产物用于聚氨酯胶黏剂的制备与性能[J]. 化工进展, 2016, 35(3): 780-786.
	ZHONG Qiang, LI Xubin, CHEN Shuang, et al. Preparation and properties of polyurethane adhesive from liquefied rice husk polyols[J]. Chemical Industry and Engineering Progress, 2016, 35(3): 780-786.
[8]	刘野, 赵毅磊, 于国良, 等. 航空有机玻璃粘接用聚氨酯胶黏剂的研制[J]. 化学与黏合, 2016, 38(3): 197-198, 210.
	LIU Ye, ZHAO Yilei, YU Guoliang, et al. Study on a polyurethane adhesive for the aeronautical Perspex bonding[J]. Chemistry and Adhesion, 2016, 38(3): 197-198, 210.
[9]	叶留留, 张昕, 范浩军, 等. 不同阴离子亲水扩链剂合成的水性聚氨酯性能比较[J]. 中国皮革, 2018, 47(11): 15-23.
	YE Liuliu, ZHANG Xin, FAN Haojun, et al. Performance comparison of waterborne polyurethane synthesized by different anionic hydrophilic chain extenders[J]. China Leather, 2018, 47(11): 15-23.
[10]	夏雪婷, 杨建军, 吴庆云, 等. 交联型水性聚氨酯织物涂层剂的制备及防水透湿性能[J]. 高分子材料科学与工程, 2022, 38(12): 56-62.
	XIA Xueting, YANG Jianjun, WU Qingyun, et al. Preparation of crosslinked waterborne polyurethane fabric coating agents and their waterproof and moisture permeability[J]. Polymer Materials Science & Engineering, 2022, 38(12): 56-62.
[11]	李婷, 杜少辉, 崔锦峰, 等. 磷-硼杂化预聚物嵌段水性聚氨酯纸张施胶剂的制备和性能[J]. 化工进展, 2022, 41(10): 5549-5557.
	LI Ting, DU Shaohui, CUI Jinfeng, et al. Preparation and properties of waterborne polyurethane paper sizing agents with phosphorus-boron hybrid prepolymer blocks[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5549-5557.
[12]	徐欣欣, 孙坚, 纪尚超, 等. 环境友好型聚氨酯胶粘剂研究进展[J]. 中国胶粘剂, 2022, 31(11): 55-60, 68.
	XU Xinxin, SUN Jian, JI Shangchao, et al. Research progress on environmental-friendly polyurethane adhesive[J]. China Adhesives, 2022, 31(11): 55-60, 68.
[13]	邓威, 黄洪, 傅和青. 改性水性聚氨酯胶黏剂研究进展[J]. 化工进展, 2011, 30(6): 1341-1346.
	DENG Wei, HUANG Hong, FU Heqing. Progress of modification of waterborne polyurethane adhesive[J]. Chemical Industry and Engineering Progress, 2011, 30(6): 1341-1346.
[14]	ZHANG Yi, ZHANG Wenbo, WANG Xiao, et al. Waterborne polyurethanes from castor oil-based polyols for next generation of environmentally-friendly hair-styling agents[J]. Progress in Organic Coatings, 2020, 142: 105588.
[15]	OSPINA Anny C, OROZCO Víctor H, GIRALDO Luis F, et al. Study of waterborne polyurethane materials under aging treatments. Effect of the soft segment length[J]. Progress in Organic Coatings, 2020, 138: 105357.
[16]	YONG Qiwen, LIAO Bing, HUANG Jianheng, et al. Preparation and characterization of a novel low gloss waterborne polyurethane resin[J]. Surface and Coatings Technology, 2018, 341: 78-85.
[17]	REN Longfang, GUO Xudong, ZHAO Yongxia, et al. Synthesis and properties of waterborne polyurethane incorporated with phenolic acid grafted oligochitosan[J]. Progress in Organic Coatings, 2019, 135: 410-416.
[18]	赵鹏, 方宏远, 王磊, 等. 改性醇溶性聚氨酯制备及其性能评价[J]. 合成材料老化与应用, 2019, 48(6): 15-18.
	ZHAO Peng, FANG Hongyuan, WANG Lei, et al. Preparation and performance evaluation of modified alcohol-soluble polyurethane[J]. Synthetic Materials Aging and Application, 2019, 48(6): 15-18.
[19]	LIU Jingwen, CUI Tingting, XU Xiaowei, et al. Robust alcohol soluble polyurethane/chitosan/silk sericin (APU/CS/SS) nanofiber scaffolds toward artificial skin extracellular matrices via microfluidic blow-spinning[J]. Advanced Fiber Materials, 2023, 5(1): 349-361.
[20]	YANG Jianjun, JIN Zhilai, ZHANG Jianan, et al. Synthesis and characterization of alcohol soluble acrylate-polyurethane adhesive for low surface energy substrate[J]. Advanced Materials Research, 2013, 834/835/836: 169-174.
[21]	CHEN Xingbao, ZHAO Shiwei, YUAN Anqian, et al. Enabling high strength and toughness polyurethane through disordered-hydrogen bonds for printable, recyclable, ultra-fast responsive capacitive sensors[J]. Advanced Science, 2024, 11(45): 2405941.
[22]	王玉杰, 聂慧芳, 薛晓凯, 等. 醇溶性高性能聚氨酯基透明涂层的制备及应用研究[J]. 高分子学报, 2024, 55(11): 1586-1596.
	WANG Yujie, NIE Huifang, XUE Xiaokai, et al. Preparation and applied research of alcohol-soluble, high-performance polyurethane-based transparent coatings[J]. Acta Polymerica Sinica, 2024, 55(11): 1586-1596.
[23]	HEINZMANN Christian, WEDER Christoph, DE ESPINOSA Lucas Montero. Supramolecular polymer adhesives: Advanced materials inspired by nature[J]. Chemical Society Reviews, 2016, 45(2): 342-358.
[24]	ZHANG Qi, SHI Chenyu, QU Dahui, et al. Exploring a naturally tailored small molecule for stretchable, self-healing, and adhesive supramolecular polymers[J]. Science Advances, 2018, 4(7): eaat8192.
[25]	刘敬松, 沈一丁, 赖小娟. 丙烯酸酯改性水性聚氨酯胶黏剂的制备及性能[J]. 化工进展, 2010, 29(4): 699-703.
	LIU Jingsong, SHEN Yiding, LAI Xiaojuan. Synthesis and properties of waterborne polyurethane adhesive modified by acrylic ester[J]. Chemical Industry and Engineering Progress, 2010, 29(4): 699-703.

样品	PTMEG/mmol	IPDI^①/mmol	HDI^②/mmol	BDO/mmol	硬段质量分数/%
AS-PU-IPDI	7.5	37.50	0	30	42.4
AS-PU-I5H1	7.5	31.25	6.25	30	41.6
AS-PU-I4H1	7.5	30.00	7.50	30	41.5
AS-PU-I3H1	7.5	28.125	9.375	30	41.2
AS-PU-I2H1	7.5	25.00	12.50	30	40.8
AS-PU-I1H1	7.5	18.75	18.75	30	40.0

样品	PTMEG/mmol	IPDI^①/mmol	HDI^②/mmol	BDO/mmol	硬段质量分数/%
AS-PU-IPDI	7.5	37.50	0	30	42.4
AS-PU-I5H1	7.5	31.25	6.25	30	41.6
AS-PU-I4H1	7.5	30.00	7.50	30	41.5
AS-PU-I3H1	7.5	28.125	9.375	30	41.2
AS-PU-I2H1	7.5	25.00	12.50	30	40.8
AS-PU-I1H1	7.5	18.75	18.75	30	40.0

样品	T_初始/℃	T_1/2/℃	T_max1/℃	T_max2/℃	T_max3/℃
AS-PU-IPDI	285	385	325	/	414
AS-PU-I5H1	298	395	340	363	418
AS-PU-I4H1	303	404	331	360	422
AS-PU-I3H1	305	398	333	355	424
AS-PU-I2H1	308	401	335	365	427
AS-PU-I1H1	302	402	333	358	417

样品	T_初始/℃	T_1/2/℃	T_max1/℃	T_max2/℃	T_max3/℃
AS-PU-IPDI	285	385	325	/	414
AS-PU-I5H1	298	395	340	363	418
AS-PU-I4H1	303	404	331	360	422
AS-PU-I3H1	305	398	333	355	424
AS-PU-I2H1	308	401	335	365	427
AS-PU-I1H1	302	402	333	358	417