以缩水甘油醚为核的星形羟基聚酯的合成及其涂膜性能

doi:10.11949/j.issn.0438-1157.20160460

化工学报 ›› 2016, Vol. 67 ›› Issue (11): 4878-4884.DOI: 10.11949/j.issn.0438-1157.20160460

• 材料化学工程与纳米技术 • 上一篇下一篇

以缩水甘油醚为核的星形羟基聚酯的合成及其涂膜性能

黄山¹, 朱延安², 陈荣华², 瞿金清¹

1 华南理工大学化学与化工学院, 广东广州 510641;
2 嘉宝莉化工集团股份有限公司, 广东江门 529085

收稿日期:2016-04-08 修回日期:2016-07-20 出版日期:2016-11-05 发布日期:2016-11-05
通讯作者: 瞿金清,cejqqu@scut.edu.cn
基金资助:
广东省科技计划项目（2012A090300004，2014B090903010，2015A010105010，2015B090925006）。

Synthesis and film properties of star hydroxyl polyesters

HUANG Shan¹, ZHU Yan'an², CHEN Ronghua², QU Jinqing¹

1 School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, Guangdong, China;
2 Carpoly Chemical Group Co. Ltd., Jiangmen 529085, Guangdong, China

Received:2016-04-08 Revised:2016-07-20 Online:2016-11-05 Published:2016-11-05
Supported by:
supported by the Science and Technology Program of Guangdong Province (2012A090300004, 2014B090903010, 2015A010105010, 2015B090925006).

摘要/Abstract

摘要：

以三羟甲基丙烷三缩水甘油醚（TMPGE）为核分子，利用AB₂型单体2，2-二羟甲基丙酸与ε-己内酯开环反应产物及一元羧酸的羧基与TMPGE的环氧基反应，合成了系列星形羟基聚酯（SHPs），研究了一元羧酸种类及原料配比对SHPs性能的影响。采用FTIR、¹H NMR对SHPs的分子结构进行表征，用GPC对其相对分子质量及分布进行了测试，并考察了其溶液黏度和特性黏度。测试了以甲苯二异氰酸酯/三羟甲基丙烷（TDI/TMP）加成物为固化剂制备的SHPs漆膜性能。SHP-2的溶液黏度低至220 mPa·s（80%固含），用其制备的高固含涂料VOC低于320 g·L^-1，其漆膜具有优异的附着力、柔韧性和较高的硬度。

关键词: 三羟甲基丙烷三缩水甘油醚, 星形羟基聚酯, 双组分聚氨酯, 高固含涂料, 涂膜性能

Abstract:

Using trimethylolpropane triglycidyl ether (TMPGE) as a core molecule, star hydroxyl polyesters (SHPs) were synthesized via the ring-opening reaction of epoxy groups and carboxyl groups. The influence of the categories and molar ratios of raw materials on the properties of SHPs were investigated. The structures and molecular weights of SHPs were characterized with Fourier transform infrared spectrometer (FTIR), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The results showed that the SHPs prepared from oleic acid had the lowest viscosity. IR and ¹H NMR spectra indicated that the target SHPs were successfully prepared and possessed similar molecular skeleton structures. The GPC curves displyed that the measured molecular weights of SHPs approached to the theoretical values, and the polydispersity indexes (PDI) of SHPs were in the range of 1.10 to 1.28. The film properties of SHPs cured by the toluene diisocyanate adduct were tested and found that the cured films exhibited excellent adhesion, flexibility and high hardness. Especially, the solution viscosity of SHP-2 was less than 220 mPa·s at 80% solid content and the VOC contents of 2K-PU from SHP-2 was low to 320 g·L^-1.

Key words: trimethylolpropane triglycidyl ether, star hydroxyl polyester, two component polyurethane, high solid coatings, film properties

中图分类号:

O633.14

黄山, 朱延安, 陈荣华, 瞿金清. 以缩水甘油醚为核的星形羟基聚酯的合成及其涂膜性能[J]. 化工学报, 2016, 67(11): 4878-4884.

HUANG Shan, ZHU Yan'an, CHEN Ronghua, QU Jinqing. Synthesis and film properties of star hydroxyl polyesters[J]. CIESC Journal, 2016, 67(11): 4878-4884.

参考文献 27

[1]	YAN D Y, GAO C, FREY H. Hyperbranched Polymers:Synthesis, Properties, and Applications[M]. Hoboken:John Wiley & Sons, 2011.
[2]	DEKA H, KARAK N. Bio-based hyperbranched polyurethanes for surface coating applications[J]. Progress in Organic Coatings, 2009, 66(3):192-198.
[3]	KANTHETI S, NARAYAN R, RAJU K V S N. Development of moisture cure polyurethane-urea coatings using 1,2,3-triazole core hyperbranched polyesters[J]. Journal of Coatings Technology & Research, 2013, 10(5):609-619.
[4]	BAT E, GÜNDÜZ G, KISAKÜREK D, et al. Synthesis and characterization of hyperbranched and air drying fatty acid based resins[J]. Progress in Organic Coatings, 2006, 55(4):330-336.
[5]	IKLADIOUS N E, MANSOUR S H, ASAAD J N, et al. Synthesis and evaluation of new hyperbranched alkyds for coatings[J]. Progress in Organic Coatings, 2015, 89:252-259.
[6]	NAIK R B, RATNA D, SINGH S K. Synthesis and characterization of novel hyperbranched alkyd and isocyanate trimer based high solid polyurethane coatings[J]. Progress in Organic Coatings, 2014, 77(2):369-379.
[7]	任强, 黄春燕, 周琳楠, 等. 高固体分涂料用含羟基星形丙烯酸酯树脂的制备及性能[J]. 化工学报, 2015, 66(6):2336-2342. REN Q, HUANG C Y, ZHOU L N, et al. Preparation and properties of hydroxyl functionalized star acrylic resin for high solid coating[J]. CIESC Journal, 2015, 66(6):2336-2342.
[8]	WANG X C, FU Y Q, GUO P Y, et al. Synthesis, characterization, and properties of PCDL aliphatic hyperbranched polyurethane coatings[J]. Journal of Applied Polymer Science, 2013, 130(4):2671-2679.
[9]	KANTHETI S, NARAYAN R, RAJU K V S N. Click chemistry engineered hyperbranched polyurethane-urea for functional coating applications[J]. Industrial & Engineering Chemistry Research, 2014, 53(20):8357-8365.
[10]	SATO E, UEHARA I, HORIBE H, et al. One-step synthesis of thermally curable hyperbranched polymers by addition-fragmentation chain transfer using divinyl monomers[J]. Macromolecules, 2014, 47(3):937-943.
[11]	MURILLO E A, LOPEZ B L, BROSTOW W. Synthesis and characterization of novel alkyd-silicone hyperbranched nanoresins with high solid contents[J]. Progress in Organic Coatings, 2011, 72(3):292-298.
[12]	NAIK R B, RATNA D. Synthesis of silver nanoparticles embedded novel hyperbranched urethane alkyd-based nanocomposite for high solid antimicrobial coating application[J]. Journal of Coatings Technology & Research, 2015, 12(6):1073-1083.
[13]	SIMI? S, DUNJI? B, TASI? S, et al. Synthesis and characterization of interpenetrating polymer networks with hyperbranched polymers through thermal-UV dual curing[J]. Progress in Organic Coatings, 2008, 63(1):43-48.
[14]	CHENG G, GREENLAND B W, LAMPARD C, et al. Hyperbranched polymers containing oxazoline monomers and succinic anhydride:applications in fast drying, low solvent coating formulations[J]. Progress in Organic Coatings, 2014, 77(10):1516-1522.
[15]	MEHTA P N. Hyperbranched polymers:unique design tool for coatings[J]. Surface Coatings International Part B:Coatings Transactions, 2006, 89(4):333-342.
[16]	王勇, 朱延安, 瞿金清. 超支化聚酯的端基改性及其涂膜性能[J]. 化工学报, 2013, 64(6):2240-2246. WANG Y, ZHU Y A, QU J Q. Modification of end groups of hyperbranched polyester and its film properties[J]. CIESC Journal, 2013, 64(6):2240-2245.
[17]	王勇, 孔霞, 朱延安, 等. 涂料用超支化聚酯的合成及改性[J]. 高分子材料科学与工程, 2013, 29(3):14-18. WANG Y, KONG X, ZHU Y A, et al. Synthesis and modification of hyperbranched polyester used as coatings[J]. Polymer Materials Science and Engineering, 2013, 29(3):14-18.
[18]	王勇, 朱延安, 孔霞, 等. 二元醇为核单体的超支化聚酯的合成与性能[J]. 高校化学工程学报, 2013, 27(3):482-487. WANG Y, ZHU Y A, KONG X, et al. Synthesis and properties of hyperbranched polyesters with diol as a core monomer[J]. Journal of Chemical Engineering of Chinese Universities, 2013, 27(3):482-487.
[19]	解德良, 姜标, 杨昌正. 羟基酸引发ε-己内酯开环聚合的研究[J]. 高分子学报, 2000, (5):532-537. XIE D L, JIANG B, YANG C Z. Study on the ring-opening polymerization of ε-caprolactone initiated by hydroxyl acids[J]. Acta Polymerica Sinica, 2000, (5):532-537.
[20]	SANDA F, SANADA H, SHIBASAKI Y, et al. Star polymer synthesis from ε-caprolactone utilizing polyol/protonic acid initiator[J]. Macromolecules, 2002, 35(3):680-683.
[21]	MURILLO E A, VALLEJO P P, LÓPEZ B L. Effect of tall oil fatty acids content on the properties of novel hyperbranched alkyd resins[J]. Journal of Applied Polymer Science, 2011, 120(6):3151-3158.
[22]	邢凤兰, 王清滨, 王则臻, 等. 三羟甲基丙烷/环氧氯丙烷的合成及其光谱分析[J]. 齐齐哈尔大学学报(自然科学版), 2004, 20(1):8-10. XING F L, WANG Q B, WANG Z Z, et al. Synthesis of trimethylolporpane/epoxychloroporpane and spectral analysis[J]. Joumal of Qiqihar University, 2004, 20(1):8-10.
[23]	SUTTER M, DAYOUB W, MÉTAY E, et al. 1-O-Alkyl (di)glycerol ethers synthesis from methyl esters and triglycerides by two pathways:catalytic reductive alkylation and transesterification/reduction[J]. Green Chemistry, 2013, 15(3):786-797.
[24]	张娅, 许涌深, 邱守季, 等. 乙二醇二缩水甘油醚的合成及表征[J]. 化学工业与工程, 2014, 31(5):31-36. ZHANG Y, XU Y S, QIU S J, et al. Preparation and characterization of glycol diglycidyl ether[J]. Chemical Industry and Engineering, 2014, 31(5):31-36.
[25]	HUA C, PENG S M, DONG C M. Synthesis and characterization of linear-dendron-like poly(ε-caprolactone)-b-poly(ethylene oxide) copolymers via the combination of ring-opening polymerization and click chemistry[J]. Macromolecules, 2008, 41(18):6686-6695.
[26]	瞿金清, 陈焕钦. 高固含量丙烯酸涂料的进展[J]. 高分子材料科学与工程, 2001, 17(6):1-5. QU J Q, CHEN H Q. Development of high solid content acrylic coatings[J]. Polymer Materials Science and Engineering, 2001, 17(6):1-5.
[27]	FRIDRIHSONE-GIRONE A, STIRNA U, MISāNE M, et al. Spray-applied 100% volatile organic compounds free two component polyurethane coatings based on rapeseed oil polyols[J]. Progress in Organic Coatings, 2016, 94:90-97.

以缩水甘油醚为核的星形羟基聚酯的合成及其涂膜性能

Synthesis and film properties of star hydroxyl polyesters

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 27

相关文章 1

编辑推荐

Metrics

本文评价