丙烯酸酯用量对溶胀-嵌段型水性聚氨酯性能的影响

doi:10.11949/j.issn.0438-1157.20180481

摘要/Abstract

摘要：

以甲基丙烯酸甲酯（MMA）、丙烯酸正丁酯（BA）为单体，通过巯基乙醇链转移自由基无规共聚合成端羟基聚丙烯酸酯（PA-OH），采用嵌段共聚法将PA-OH与水性聚氨酯（WPU）嵌段，通过预聚体分散法制得聚丙烯酸酯嵌段水性聚氨酯乳液（WPUA），进而通过乳液聚合法制备了一系列以MMA/BA为单体的聚丙烯酸酯嵌段-溶胀水性聚氨酯复合乳液（WPUA-PA），结果表明WPUA-PA中丙烯酸酯量最多可达到WPUA的240%，当丙烯酸酯量为WPUA的120%时WPUA-PA的性能最佳，此时乳液平均粒径为68 nm、粒径分布指数为0.174，胶膜拉伸强度为13.88 MPa、断裂伸长率为558.3%、吸水率为4.94%，且具有优异的乳液稳定性。

关键词: 水性聚氨酯, 端羟基聚丙烯酸酯, 嵌段聚合物, 乳液聚合

Abstract:

Hydroxyl-terminated polyacrylate (PA-OH) was synthesized by free radical copolymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) using mercaptoethanol as chain transfer. PA-OH was blocked with waterborne polyurethane (WPU) by block polymerization, and then prepared polyacrylate block waterborne polyurethane emulsion (WPUA) by prepolymer dispersion. A series of polyacrylate swelling-block waterborne polyurethane composite emulsions with MMA/BA as the monomer were prepared by emulsion polymerization. The results showed that the dosage of acrylates in WPUA-PA can reach 240% of WPUA. WPUA-PA has the best performance when the dosage of acrylates is 120% of WPUA. The average emulsion particle size is 68 nm, the particle distribution index is 0.174, the tensile strength of the film is 13.88 MPa, the elongation at break is 558.3%, the water absorption is 4.94%, and the emulsion stability is excellent.

Key words: waterborne polyurethanes, hydroxy-terminated polyacrylate, block polymer, emulsion polymerization

中图分类号:

TQ436.5

杨东杰, 施一鸣, 单国荣. 丙烯酸酯用量对溶胀-嵌段型水性聚氨酯性能的影响[J]. 化工学报, 2018, 69(11): 4856-4861.

YANG Dongjie, SHI Yiming, SHAN Guorong. Effect of acrylate amount on properties of swelling-block waterborne polyurethane[J]. CIESC Journal, 2018, 69(11): 4856-4861.

参考文献 30

[1]	ZHOU X, LI Y, FANG C Q, et al. Recent advances in synthesis of waterborne polyurethane and their application in water-based ink:a review[J]. J. Mater. Sci. Tech., 2015, 31(7):708-722.
[2]	LEI L, XIA Z B, OU C B, et al. Effects of crosslinking on adhesion behavior of waterborne polyurethane ink binder[J]. Prog. Org. Coat., 2015, 88:155-163.
[3]	WU D M, QIU F X, XU H P, et al. Preparation, characterization, and properties of environmentally friendly waterborne poly(urethane acrylate)/silica hybrids[J]. J. Appl. Polym. Sci., 2011, 119(3):1683-1695.
[4]	GURUNATHAN T, MOHANTY S, NAYAK S K. Isocyanate terminated castor oil-based polyurethane prepolymer:synthesis and characterization[J]. Prog. Org. Coat., 2015, 80(1):39-48.
[5]	PARK D H, OH J K, KIM S B, et al. Synthesis and characterization of sulfonated polyol-based waterborne polyurethane-polyacrylate hybrid emulsions[J]. Macromol. Res., 2013, 21(11):1247-1253.
[6]	LEE J M, KIM J S, CHEONG I W, et al. Synthesis, characterization, and mechanical property of poly(urethane-glycidyl methacrylate-methyl methacrylate) hybrid polymers[J]. J. Appl. Polym. Sci., 2011, 121(6):3111-3121.
[7]	ZHU G Q. Properties of polyurethane-poly(2,2,3,3-tetrafluoropropyl acrylate) triblock copolymer aqueous dispersion and its film cast from the dispersion[J]. Fibers Polym., 2007, 8(3):243-248.
[8]	HIROSE M, ZHOU J H, NAGAI K. The structure and properties of acrylic-polyurethane hybrid emulsions[J]. Prog. Org. Coat., 2000, 38(1):27-34.
[9]	UDAGAMA R, DEGRANDI-CONTRAIRES E, CRETON C, et al. Synthesis of acrylic-polyurethane hybrid latexes by miniemulsion polymerization and their pressure-sensitive adhesive applications[J]. Macromolecules, 2011, 44(8):2632-2642.
[10]	SULTAN M, ISLAM A, GULL N, et al. Structural variation in soft segment of waterborne polyurethane acrylate nanoemulsions[J]. J. Appl. Polym. Sci., 2015, 132(12):1-10.
[11]	LEE S W, LEE Y H, PARK H, et al. Effect of total acrylic/fluorinated acrylic monomer contents on the properties of waterborne polyurethane/acrylic hybrid emulsions[J]. Macromol. Res., 2013, 21(6):709-718.
[12]	PERUZZO P J, ANBINDER P S, PARDINI O R, et al. Waterborne polyurethane/acrylate:comparison of hybrid and blend systems[J]. Prog. Org. Coat., 2011, 72(3):429-437.
[13]	GUO Y H, LI S C, WANG G S, et al. Waterborne polyurethane/poly(n-butyl acrylate-styrene) hybrid emulsions:particle formation, film properties, and application[J]. Prog. Org. Coat., 2012, 74(1):248-256.
[14]	WANG X R, SHEN Y D, LAI X J. Micromorphology and mechanism of polyurethane/polyacrylate membranes modified with epoxide group[J]. Prog. Org. Coat., 2014, 77(1):268-276.
[15]	WANG C, LI X R, DU B, et al. Preparation and properties of a novel waterborne fluorinated polyurethane-acrylate hybrid emulsion[J]. Colloid Polym. Sci., 2014, 292(3):579-587.
[16]	WANG X R, SHEN Y D, LAI X J, et al. Micromorphology and thermal properties of polyurethane/polyacrylate soap-free emulsion in the presence of functional monomers[J]. J. Polym. Res., 2014, 21(3):1-8.
[17]	MA G Y, SHEN Y D, GAO R M, et al. Micromorphology and adhesive properties of sulfonated polyurethane/polyacrylate emulsions prepared by surfactant-free polymerization[J]. J. Polym. Res., 2017, 24(3):1-11.
[18]	FEI G, YAN T, WANG H, et al. Micromorphology, phase behavior, and properties of environmental, multi-cross-linked polyurethane/polyacrylate microemulsions based on in situ surfactant-free polymerization[J]. Colloid Polym. Sci., 2017, 295(10):1743-1755.
[19]	YUAN C D, WANG J P, CUI M T, et al. Aqueous PUA emulsion prepared by dispersing polyurethane prepolymer in polyacrylate emulsion[J]. J. Appl. Polym. Sci., 2016, 133(11):1-9.
[20]	LI X R, WANG X R, SHEN Y D, et al. Synthesis and characterization of self-crosslinked polyurethane/polyacrylate composite emulsion based on carbonyl-hydrazide reaction[J]. J. Polym. Res., 2013, 20(11):1-9.
[21]	YI T F, MA G Z, HOU C Y, et al. Polyurethane-acrylic hybrid emulsions with high acrylic/polyurethane ratios:synthesis, characterization, and properties[J]. J. Appl. Polym. Sci., 2016, 134(8):44488.
[22]	DEGRANDI-CONTRAIRES E, UDAGAMA R, MCKENNA T, et al. Influence of composition on the morphology of polyurethane/acrylic latex particles and adhesive films[J]. Int. J. Adh. Adh., 2014, 50(4):176-182.
[23]	HWANG H D, KIM H J. Enhanced thermal and surface properties of waterborne UV-curable polycarbonate-based polyurethane (meth)acrylate dispersion by incorporation of polydimethylsiloxane[J]. React. Funct. Polym., 2011, 71(6):655-665.
[24]	黄毅萍, 许戈文. 水性聚氨酯及应用[M]. 北京:化学工业出版社, 2015:6-7. HUANG Y P, XU G W. Waterborne Polyurethane and Its Application[M]. Beijing:Chemical Industry Press, 2015:6-7.
[25]	XU W, AN Q F, HAO L F, et al. Synthesis and characterization of self-crosslinking fluorinated polyacrylate soap-free latices with core-shell structure[J]. Appl. Surf. Sci., 2013, 268(3):373-380.
[26]	WANG L, SHEN Y D, LAI X J, et al. Synthesis and properties of crosslinked waterborne polyurethane[J]. J. Polym. Res., 2011, 18(3):469-476.
[27]	LAI X J, SHEN Y D, WANG L. Preparation and properties of self-crosslinkable polyurethane/silane hybrid emulsion[J]. J. Polym. Res., 2011, 18(6):2425-2433.
[28]	CHAI S L, JIN M M, TAN H M. Comparative study between core-shell and interpenetrating network structure polyurethane/polyacrylate composite emulsions[J]. Eur. Polym. J., 2008, 44(10):3306-3313.
[29]	GUO A, CHO Y, PETROVI? Z S. Structure and properties of halogenated and nonhalogenated soy-based polyols[J]. J. Polym. Sci. Part A-Polym. Chem., 2000, 38(21):3900-3910.
[30]	WANG Y Q, LI Y P, ZHANG R Y, et al. Synthesis and characterization of nanosilica/polyacrylate composite latex[J]. Polym. Comp., 2006, 27(3):282-288.