磺酸/羧酸型水性聚氨酯乳液的可控合成与性能研究
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摘要
以聚己二酸1,4-丁二醇酯二醇(PBA)为软段、异佛尔酮二异氰酸酯(IPDI)、2,2-二羟甲基丙酸(DMPA)和乙二胺基乙磺酸钠(A95)为硬段,合成了一系列水性聚氨酯乳液。用激光光散射粒度仪(LSPSA)、傅里叶变换红外光谱(FTIR)、X-射线光电子能谱仪(XPS)、X-射线衍射仪(XRD)、原子力显微镜(AFM)、热重分析仪(TG)和动态力学分析仪(DMA)对水性聚氨酯乳液的分子结构和相关性能进行了表征。乳液测试结果表明:随着分子链中磺酸基团含量的不断提高,乳液粒径不断减小,Zeta电位由-46.2 mV降至-55.6 mV,稳定性进一步增强;同时随着分子链中磺酸基团含量的不断提高,硬段和软段出现了微弱的相分离结构,使得水性聚氨酯胶膜热稳定和动态力学性能有了明显提高。
A series of sulfonic/carboxylic waterborne polyurethane emulsions were synthesized based on poly-l,4-butanediol-adipateglycolas soft segments, isophorone diisocyanate(IPDI), 2, 2-dimethoxtol propionic acid(DMPA) and N-(2-aminoethyl)-amino ethane sulphonated sodium(A95) as hard segments. The molecular structure and mechanical properties of waterborne polyurethane emulsion were characterized by laser-scattering particle size analyzer(LSPSA), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), X-ray diffractometer(XRD), atomic force microscope(AFM), thermogravimetric analyzer(TG) and dynamic mechanical analyzer(DMA). The characterization results showed that, with the increase of sulfonic group content in the molecular chain, the particle size decreased and the Zeta potential decreased from-46.2 mV to-55.6 mV, indicating that the stability of the emulsion further enhanced. Meanwhile, with the continuous increase of the content of the sulfonic group in the molecular chain, weak phase separation between the hard segment and the soft segment appeared, and the thermal stability and dynamic mechanical properties of the waterborne polyurethane film were improved significantly.
A series of sulfonic/carboxylic waterborne polyurethane emulsions were synthesized based on poly-l,4-butanediol-adipateglycolas soft segments, isophorone diisocyanate(IPDI), 2, 2-dimethoxtol propionic acid(DMPA) and N-(2-aminoethyl)-amino ethane sulphonated sodium(A95) as hard segments. The molecular structure and mechanical properties of waterborne polyurethane emulsion were characterized by laser-scattering particle size analyzer(LSPSA), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), X-ray diffractometer(XRD), atomic force microscope(AFM), thermogravimetric analyzer(TG) and dynamic mechanical analyzer(DMA). The characterization results showed that, with the increase of sulfonic group content in the molecular chain, the particle size decreased and the Zeta potential decreased from-46.2 mV to-55.6 mV, indicating that the stability of the emulsion further enhanced. Meanwhile, with the continuous increase of the content of the sulfonic group in the molecular chain, weak phase separation between the hard segment and the soft segment appeared, and the thermal stability and dynamic mechanical properties of the waterborne polyurethane film were improved significantly.
引文
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[26] YONG Q W,NIAN F W,LIAO B,et al. Synthesis and characterization of solvent-free waterborne polyurethane dispersion with both sulfonic and carboxylic hydrophilic chain-extending agents for matt coating applications[J]. RSC Advances, 2015,130 (5):107413-107420.
[27] 袁腾,杨卓鸿,周显宏,等. 羧酸盐/磺酸盐复合型WPU胶黏剂的制备与表征[J]. 化工学报, 2015, 66 (10):4258-4267.
[28] XIAO Y,FU X,ZHANG Y,et al. Preparation of waterborne polyurethanes based on the organic solvent-free process[J]. Green Chemistry, 2016, 18 (2):412-416.
[29] MA L,SONG L,WANG H, et al. Synthesis and characterization of poly(propylene carbonate) glycol-based waterborne polyurethane with a high solid content[J]. Progress in Organic Coatings, 2018(122):38-44.
[30] ZHANG Z L, SI T T, LIU J, et al. Controllable assembly of a hierarchical multiscale architecture based on silver nanoparticle grids/nanowires for flexible organic solar cells[J]. Nanotechnology, 2018, 29 (41):415603.
[31] ZHANG Z L, SI T T, LIU J, et al. Controllable synthesis of AgNWs@PDA@AgNPs core-shell nanocobs based on a mussel-inspired polydopamine for highly sensitive SERS detection[J]. RSC Advances, 2018, 8 (48):27349-27358.
[2] WANG Y L,JIN L Q. Preparation and characterization of self-colored waterborne polyurethane and its application in eco-friendly manufacturing of microfiber synthetic leather base[J]. Polymers, 2018, 10 (3):289.
[3] 杨建军,陈春俊,吴庆云,等. 水性聚氨酯树脂在工业水性涂料中的应用进展[J]. 化学推进剂与高分子材料, 2017, 15 (1):1-7.
[4] 陈旭,韩玉红,夏海渤,等. 水性涂料在轨道车辆上的应用及影响要素[J]. 涂料技术与文摘, 2017(3):18-23.
[5] XU Y,YANG Y,YAN D X,et al. Gradient structure design of flexible waterborne polyurethane conductive films for ultraefficient electromagnetic shielding with low reflection characteristic[J]. ACS Applied Materials & Interfaces, 2018, 10 (22):19143-19152.
[6] 贾红圣,程炜,刘尚莲. 阳离子型荧光水性聚氨酯的制备及性能[J]. 精细化工, 2015, 32 (12):1421-1425.
[7] 刘若望,钟凯,袁继新,等.以N,N-(2-羟乙基)-2-氨基乙磺酸钠为亲水扩链剂的水性聚氨酯的制备及性能[J]. 材料科学与工程学报, 2012, 30 (6):884-888.
[8] SANTAMARIA-ECHART A,UGARTE L,ARBELAIZ A, et al. Modulating the microstructure of waterborne polyurethanes for preparation of environmentally friendly nanocomposites by incorporating cellulose nanocrystals[J]. Cellulose, 2017, 24 (2):823-834.
[9] 胡杨飞,王德海,杜治波,等. 非离子型水性聚氨酯的制备及其涂膜表面性质研究[J]. 涂料工业, 2014, 44 (9):37-43.
[10] 鲍俊杰,张海龙,刘都宝,等. 磺酸盐型水性聚氨酯的合成与性能研究[J]. 中国胶粘剂, 2008, 17 (12):32-35.
[11] WAN T,CHEN D. Synthesis and properties of self-healing waterborne polyurethanes containing disulfide bonds in the main chain[J]. Journal of Materials Science, 2017, 52 (1):197-207.
[12] 孙东成,周伟乾. 聚氨酯预聚体分散体胶粒的形成与扩链[J]. 高分子材料科学与工程, 2009,25 (12):26-30.
[13] 徐恒志,王焕,鲍俊杰,等. 水性聚氨酯硬段含量对其氢键相互作用及性能的影响[J]. 应用化学, 2011,28 (7):770-776.
[14] LAI Y,KUANG X,ZHU P, et al. Colorless, transparent, robust, and fast scratch-self-healing elastomers via a phase-locked dynamic bonds design[J]. Advanced Materials, 2018,30(38):1802556.
[15] 孙东成,董德全. 双峰粒径分布的高固含量聚氨酯分散体的研究[J]. 高校化学工程学报, 2011,25 (2):248-253.
[16] 陶灿,王继印,鲍俊杰,等. 高硬度磺酸型水性聚氨酯涂料的合成及性能研究[J]. 涂料工业, 2014, 44(11):58-63.
[17] 黄书,孙东成. 1,4-二羟基丁烷-2-磺酸钠基磺酸型PUD膜性能研究[J]. 中国胶粘剂, 2012(7):16-18.
[18] CAO X,GE X,CHEN H,et al. Effects of trimethylol propane and AAS salt on properties of waterborne polyurethane with low gloss[J]. Progress in Organic Coatings, 2017, 107:5-13.
[19] HOU L J,DING Y T,ZHANG Z L, et al.Synergistic effect of anionic and nonionic monomers on the synthesis of high solid content waterborne polyurethane[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2015, 467:46-56.
[20] 夏宇正,寇红叶,石淑先,等. 磺酸/羧酸型水性聚氨酯分散体粒径的影响因素[J]. 北京化工大学学报(自然科学版), 2015 (3):62-66.
[21] 韩飞龙,陶灿,鲍俊杰,等. 混合磺酸型水性聚氨酯胶粘剂的制备及性能研究[J]. 应用化工, 2015,44 (3):515-519.
[22] 曹高华,夏正斌,张燕红,等. AAS/DMPA对水性聚氨酯胶膜结晶性能的影响[J]. 化工学报, 2013,64(7):2672-2678.
[23] LIU N,ZHAO Y,KANG M,et al. The effects of the molecular weight and structure of polycarbonatediols on the properties of waterborne polyurethanes[J]. Progress in Organic Coatings, 2015, 82:46-56.
[24] SANTAMARIA-ECHART A,UGARTE L,ARBELAIZ A, et al. Two different incorporation routes of cellulose nanocrystals in waterborne polyurethane nanocomposites[J]. European Polymer Journal, 2016, 76:99-109.
[25] 强涛涛,李小宁,唐华,等. 磺酸/羧酸型高固含量水性聚氨酯的制备及其性能[J]. 精细化工, 2016,33 (2):121-126.
[26] YONG Q W,NIAN F W,LIAO B,et al. Synthesis and characterization of solvent-free waterborne polyurethane dispersion with both sulfonic and carboxylic hydrophilic chain-extending agents for matt coating applications[J]. RSC Advances, 2015,130 (5):107413-107420.
[27] 袁腾,杨卓鸿,周显宏,等. 羧酸盐/磺酸盐复合型WPU胶黏剂的制备与表征[J]. 化工学报, 2015, 66 (10):4258-4267.
[28] XIAO Y,FU X,ZHANG Y,et al. Preparation of waterborne polyurethanes based on the organic solvent-free process[J]. Green Chemistry, 2016, 18 (2):412-416.
[29] MA L,SONG L,WANG H, et al. Synthesis and characterization of poly(propylene carbonate) glycol-based waterborne polyurethane with a high solid content[J]. Progress in Organic Coatings, 2018(122):38-44.
[30] ZHANG Z L, SI T T, LIU J, et al. Controllable assembly of a hierarchical multiscale architecture based on silver nanoparticle grids/nanowires for flexible organic solar cells[J]. Nanotechnology, 2018, 29 (41):415603.
[31] ZHANG Z L, SI T T, LIU J, et al. Controllable synthesis of AgNWs@PDA@AgNPs core-shell nanocobs based on a mussel-inspired polydopamine for highly sensitive SERS detection[J]. RSC Advances, 2018, 8 (48):27349-27358.