The effects of soft segments on microphase separation of solvent-free polyurethane resin

doi:10.19398/j.att.202111026

Abstract

Abstract: Four kinds of solvent-free polyurethanes(SFPU) resin films were prepared by two-component prepolymer in-situ blending polymerization,in which modified diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BDO) acted as hard segments and Polycaprolactone diol(PCL), polycarbonates of 1,6-hexanediol (PCDL), poly (tetramethylene oxide glycol) (PTMEG) and polyoxypropylene glycol (PPG) acted as soft segments, respectively.The effects of soft segment structure on the microphase separation, crystallinity, thermal and mechanical properties of SFPU were investigated by Fourier transforminfrared,X-ray diffraction, differential scanning calorimetry, tensile test and dynamic mechanical property analysis.The results show that PTMEG-SFPU with weak polarity and unbranched chain has high degree of microphase separation, crystallinity and thermal stability.Besides, its glass transition temperatureis as low as -58.6 ℃ and the elongation at break is as high as 371.1%.The highly polar PCDL-SFPU has a weak degree of microphase separation, good compatibility between soft and hard segments, and a higher glass transition temperature. The tensile strength of PCDL-SFPU reaches 32.7 MPa and modulus reaches 23.3 MPa.

Key words: solvent-free polyurethane, soft segment structure, polarity, thermal properties, microphase separation

摘要： 分别以聚己内酯二醇(PCL)、聚碳酸酯二醇(PCDL)、聚四氢呋喃二醇(PTMEG)、聚氧化丙烯二醇(PPG)为软段,改性二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇(BDO)为硬段,采用双组份预聚物原位共混聚合法制备了4种无溶剂聚氨酯(SFPU)树脂膜。通过傅里叶红外、X射线衍射、差示扫描量热、拉伸试验、动态力学性能分析等方法,考察了软段结构对SFPU膜微相分离及其结晶性、热性能和机械性能的影响。结果表明:弱极性软段且无侧基的PTMEG-SFPU具有高的微相分离程度、结晶性和热稳定性,并且其玻璃化温度低至 -58.6 ℃,断裂伸长率高达371.1%;强极性软段的PCDL-SFPU具有低的微相分离程度,软硬段相容性好,玻璃化温度较高,拉伸强度达到32.7 MPa,模量达23.3 MPa。

关键词: 无溶剂聚氨酯, 软段结构, 极性, 热性能, 微相分离

CLC Number:

YANG Hao, TIAN Qianjun, SHI Lei, WANG Lin, HUANG Zhichao, QI Dongming. The effects of soft segments on microphase separation of solvent-free polyurethane resin[J]. Advanced Textile Technology, 2022, 30(5): 74-81.

杨浩, 田千俊, 石磊, 王淋, 黄志超, 戚栋明. 软段结构对无溶剂聚氨酯树脂微相分离的影响[J]. 现代纺织技术, 2022, 30(5): 74-81.

References

[1] BAGDI K, MOLNAR K, SAJO I, et al. Specific interactions, structure and properties in segmented polyurethane elastomers[J]. Express Polymer Letters, 2011, 5(5): 417-427.
[2] STRAWHECKER K E, HSIEH A J, CHANTAWAHSRI T L, et al. Influence of microstructure on micro-/nano-mechanical measurements of select model transparent poly(urethane urea) elastomers[J]. Polymer, 2013, 54(2): 901-908.
[3] KROL P. Synthesis methods, chemical structures and phase structures of linear polyurethanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers[J]. Progress in Materials Science, 2007, 52(6): 915-1015.
[4] 刘厚钧.聚氨酯弹性体手册[M].2版,北京:化学工业出版社,2012.
LIU Houjun. Handbook of Polyurethane Elastomers[M]. 2nd edition, Beijing:Chemical Industry Press, 2012.
[5] 武浩浩,谢昊圃,田新欣,等.聚酯-聚醚型聚氨酯的制备及性能[J].工程塑料应用,2019,47(9):17-21.
WU Haohao, XIE Haopu, TIAN Xinxin, et al. Preparation and properties of polyester-polyether polyurethane[J].Engineering Plastics Application, 2019, 47(9):17-21.
[6] 张家祖,徐康,袁少飞,等.水性聚氨酯漆料干燥速率及漆膜性能影响规律研究[J].中南林业科技大学学报,2019,39(1):134-140.
ZHANG Jiazu, XU Kang, YUAN Shaofei, et al. Study on drying rate and film properties of waterborne polyurethane coatings[J].Journal of Central South University of Forestry & Technology, 2019, 39(1):134-140.
[7] 冯见艳,王学川,张哲.聚氨酯合成革绿色清洁化生产发展趋势分析与探讨[J].皮革科学与工程,2018,28(1):25-29,45.
FENG Jianyan, WANG Xuechuan, ZHANG Zhe.Analysis and discussion on the development trend of green clean production of polyurethane synthetic leather[J].Leather Science And Engineering, 2018, 28(1): 25-29, 45.
[8] 刘帅,马兴元.封闭型无溶剂聚氨酯的研究进展[J].材料导报,2019,33(23):3892-3899.
LIU Shuai, MA Xingyuan.Research progress of blocked solvent-free polyurethane[J]. Materials Reports, 2018, 28(1): 25-29.
[9] YUMIAO S, TING W, YULIN D, et al. Preparation technology of solvent-free polyurethane: Amini-review[J].Chinese Journal of Structural Chemistry, 2020, 39(12):2057-2067.
[10] THOMAS J, SINGH V, JAIN R. Synthesis and characterization of solvent free acrylic copolymer for polyurethane coatings[J]. Progress in Organic Coatings, 2020, 145: 105677.
[11] 马兴元,冯见艳,张韬琳. 合成革化学及工艺学[M].北京:中国轻工业出版社,2015.
MA Xingyuan, FENG Jianyan, ZHANG Taolin. Synthetic Leather Chemistry and Technology[M]. Beijing:China Light Industry Press, 2015.
[12] 吴泽.无溶剂聚氨酯合成革的制备工艺与性能研究[D].西安:陕西科技大学,2014.
WU Ze.Preparation Process and Properties of Solvent-free Polyurethane Synthetic Leather[D]. Xi′an:Shaanxi University of Science and Technology, 2014.
[13] 温文宪,刘旭,杜春毅.PU延迟性催化剂的合成与应用[J].新余学院学报,2012,17(5):95-97.
WEN Wenxian, LIU Xu, DU Chunyi. Synthesization and application PU ductile catalyst[J]. Journal of Xinyu University, 2012, 17(5):95-97.
[14] 何远鑫,马兴元,丁博,等.封闭型无溶剂聚氨酯超细纤维合成革基布的制备及性能[J].复合材料学报,2021,38(2):389-397.
HE Yuanxin, MA Xingyuan, DING Bo, et al. Preparation and properties of blocked solvent-free polyurethaneultrafine synthetic leather base cloth[J].Acta Materiae Compositae Sinica, 2021, 38(2):389-397.
[15] 顾佳佳,蒋红梅.二胺固化剂对无溶剂封闭型聚氨酯树脂性能的影响[J].聚氨酯工业,2020,35(4):35-38.
GU Jiajia, JIANG Hongmei.Effects of diamine curing agent on the properties ofsolvent-free blocked polyurethane resin[J].Polyurethane Industry, 2020, 35(4):35-38.
[16] 陈晓东,周南桥,张海,等.聚氨酯弹性体微相分离及其结构的研究方法(Ⅰ)热分析技术的应用[J].弹性体,2008,18(5):58-65.
CHEN Xiaodong, ZHOU Nanqiao, ZHANG Hai, et al. Characterization methods for polyurethan elastomermicro-phase separated structure (I):application of thermal analysis technique[J].Elastomer, 2008, 18(5):58-65.
[17] 区洁,田立颖,王新灵.软硬段对聚氨酯弹性体结构性能的影响[J].功能高分子学报,2010,23(2):160-165.
QU Jie, TIAN Liying, WANG Xinling.Effect of hard and soft segment on structure-property ofthermoplastic polyurethane elastomer[J].Journal of Functional Polymers, 2010, 23(2):160-165.
[18] 靳昊,罗建勋,毛立新,等.聚醚多元醇和醇类扩链交联剂并用对聚氨酯弹性体性能的影响[J].北京化工大学学报(自然科学版),2011,38(4):94-98.
JIN Hao, LUO Jianxun, MAO Lixin, et al. The effect of polyether polyols, alcohol chain extenders and crosslinkers on the properties of polyurethane elastomers[J].Journal of Beijing University of Chemical Technology (Natural Science), 2011, 38(4):94-98.
[19] 沈照羽,崔盛恺,吕小健,等.多元醇种类对微孔聚氨酯弹性体性能的影响[J].塑料工业,2020,48(10):146-149.
SHEN Zhaoxu, CUI Shengkai, Lü Xiaojian, et al. Effect of polyol type on properties of microcellular polyurethane elastomer[J].China Plastics Industry, 2020, 48(10):146-149.
[20] STEFANOVIC, I S, DZUNUZOVIC, J V, DZUNU-ZOVIC, E S, et al. Composition-property relationship of polyurethane networks based on polycaprolactone diol. Polym, 2020.
[21] 倪铭键,倪梯铜,谭鹏飞,等.不同软链段对水性聚氨酯性能的影响[J].中国胶粘剂,2019,28(1):20-24.
NI Mingjian, NI Titong, TAN Pengfei, et al. Effect of different soft segments on properties of waterborne polyurethane[J].China Adhesives, 2019, 28(1):20-24.
[22] 张聪聪,郑梦凯,李伯耿.软段结构对聚氨酯弹性体性能的影响[J].化工学报,2019,70(10):4043-4051.
ZHANG Congcong, ZHENG Mengkai, LI Bogeng.Effect of soft segment structure on properties of polyurethane elastomers[J].CIESC Journal, 2019, 70(10):4043-4051.
[23] 刘娜,赵雨花,冯月兰,等.软段结构对水性聚氨酯微相分离的影响[J].聚氨酯工业,2015,30(2):15-19.
LIU Na, ZHAO Yuhua, FENG Yuelan, et al. Effect of soft segments on phase separation of waterborne polyurethanes[J]. Polyurethane Industry, 2015, 30(2):15-19.
[24] WAN Y, LU X, DALAI S, et al. Thermophysical properties of polycaprolactone/chitosan blend membranes[J]. Thermochimica Acta, 2009, 487(1-2): 33-38.
[25] GHASEMI-MOBARAKEH L, PRABHAKARAN M P, MORSHED M, et al. Bio-functionalized PCL nanofibrous scaffolds for nerve tissue engineering[J]. Materials Science and Engineering C, 2010, 30(8): 1129-1136.
[26] KWAK Y S, KIM E Y, YOO B H, et al. Preparation and properties of waterborne poly(urethane urea)s for adhesives: The effects of the 2,2-bis(hydroxylmethyl)propionic acid content on the properties[J]. Journal of Applied Polymer Science, 2004, 94(4): 1743-1751.
[27] TROVATI G, SANCHES E A, NETO S C, CHIERICE G O. Characterization of polyurethane resins by FTIR, TGA, and XRD[J]. Journal of Applied Polymer Science. 2010, 115(1): 263-268.
[28] SHI J, ZHENG T, GUO B, et al. Solvent-free thermo-reversible and self-healable crosslinked polyurethane with dynamic covalent networks based on phenol-carbamate bonds[J]. Polymer, 2019, 181: 121788.
[29] DIEZ-GARCIA I, SANTAMARIA-ECHART A, ECRIZA A, et al. Synthesis and characterization of environmentally-friendly waterborne poly(urethane-urea)s[J]. European Polymer Journal, 2018, 99: 240-249.