Preparation and properties of branched polyurethane elastomer via bulk prepolymerization

doi:10.16085/j.issn.1000-6613.2020-1295

Abstract

Abstract:

To improve the mechanical properties and thermal-deformation stability of polyurethane elastomer, the branched or crosslinked polyurethanes were synthesized by bulk prepolymerization from polydiethylene glycol adipate, two phenyl methane diisocyanate and 1,4-butanediol with the different additive amounts of branched monomers, i.e., poly-propylene glycerol (PPG-3) or glycerol. All the branched polyurethanes showed better mechanical properties and thermal-deformation stability than the linear polyurethane. Compared with the linear polyurethane, the tensile strength of the branched polyurethane containing 3% PPG-3 was increased by 170% (33.9MPa), the tear strength was increased by 36% (90.7 MPa), and the Vicat softening temperature was raised to 95.1 ℃. When the content of glycerin was 5%, the crosslinked polyurethane was obtained. Its tensile strength increased by 154% (31.8MPa), tear strength enhanced by 26% (84.4MPa) and Vicat softening temperature increased up to 150.6℃. Moreover, the microphase separation of polyurethane between hard and soft segments was decreased because the structure of PPG-3 or glycerol played a role of compatilizer. The elasticity modulus and complex viscosity of branched polyurethane elastomer and crosslinked polyurethane elastomer were higher than those of the linear polyurethane elastomer.

Key words: branched polyurethane, crosslinked polyurethane, elastomer, mechanical properties, heat resistance

摘要：

为提高聚氨酯弹性体力学性能和耐热性，本文以聚己二酸二乙二醇酯二醇、二苯基甲烷二异氰酸酯和 1,4-丁二醇为原料，以聚氧化丙烯三醇（PPG-3）或丙三醇为支化单体，并通过调控其添加量（1%、3%和5%，相对于PDGA-2000的摩尔分数），采用本体预聚物法合成支化或交联型聚氨酯弹性体。与线型聚氨酯相比，支化聚氨酯具有较高机械强度和耐热性。添加3% PPG-3所制备支化聚氨酯的拉伸强度提高170%（33.9MPa），撕裂强度提高36%（90.7MPa），维卡软化点温度为95.1℃；然而，5%的丙三醇引发交联结构的形成，交联型聚氨酯的拉伸强度提高154%（31.8MPa），撕裂强度提高26%（84.4MPa），维卡软化点温度为150.6℃。此外，PPG-3和丙三醇发挥聚氨酯软段和硬段相容剂的作用，抑制微相分离，使聚氨酯弹性体的橡胶平台增大。动态流变行为测试结果表明，支化和交联型聚氨酯弹性体具有更高的弹性模量和复数黏度。

关键词: 支化聚氨酯, 交联型聚氨酯, 弹性体, 机械性能, 耐热性

CLC Number:

TQ323.8

DANG Haichun, LIU Zhanzhou, LEI Chunxing, XU Zhaozan, LI Zhenzhong. Preparation and properties of branched polyurethane elastomer via bulk prepolymerization[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3380-3388.

党海春, 刘占洲, 雷春兴, 许召赞, 李振中. 支化与交联型聚氨酯弹性体的合成与性能分析[J]. 化工进展, 2021, 40(6): 3380-3388.

Figures/Tables 11

References 38

1	KROL Piotr. 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.
2	杨舒逸, 金怀洋, 高山俊, 等. 热塑性聚氨酯弹性体改性研究进展[J]. 工程塑料应用, 2018, 46 (6): 138-142.
	YANG Shuyi, JIN Huaiyang, GAO Shanjun, et al. Research progress on modification of thermoplastic polyurethane elastomer[J]. Engineering Plastics Application, 2018, 46(6): 138-142.
3	山西省化工研究所. 聚氨酯弹性体手册 [M]. 北京：化学工业出版社, 2001.
	Shanxi Provincial Institute of Chemical Industry. Polyurethane elastomers manual[M]. Beijing: Chemical Industry Press, China, 2001.
4	XIE Fengwei, ZHANG Tianlong, BRYANT Peter, et al. Degradation and stabilization of polyurethane elastomers[J]. Progress in Polymer Science, 2019, 90: 211-268.
5	ENGELS Hans Wilhelm, PIRKL Hans Georg, ALBERS Reinhard, et al. Polyurethanes: versatile materials and sustainable problem solvers for today’s challenges[J]. Angewandte Chemie: International Edition, 2013, 52(36): 9422-9441.
6	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 Baigeng. Effect of soft segment structure on properties of polyurethane elastomers[J]. CIESC Journal, 2019, 70(10): 4043-4051.
7	HU Jinlian, YANG Zhuohong, YEUNG Lapyan, et al. Crosslinked polyurethanes with shape memory properties[J]. Polymer International, 2005, 54(5): 854-859.
8	LI Mei, ZHANG Rongchun, LI Xiaohui, et al. High-performance recyclable cross-linked polyurethane with orthogonal dynamic bonds: the molecular design, microstructures, and macroscopic properties[J]. Polymer, 2018, 148: 127-137.
9	李翰模, 杨一林, 李志鹏, 等. 基于网络结构设计制备宽温域高阻尼聚氨酯弹性体[J]. 高分子材料科学与工程, 2017, 3(6): 146-151.
	LI Hanmo, YANG Yilin, LI Zhipeng, et al. Preparation of high damping polyurethane with wide temperature range based on network structure designing[J]. Polymer Materials Science & Engineering, 2017, 33(6): 146-151.
10	BRONDI Cosimo, DI CAPRIO Maria Rosaria, SCHERILLO Giuseppe, et al. Thermosetting polyurethane foams by physical blowing agents: chasing the synthesis reaction with the pressure[J]. Journal of Supercritical Fluids, 2019, 154:104630.
11	郑建伟, 夏修炀, 王惟, 等. 气相甲醛对聚氨酯硬段晶区的化学改性[J]. 高分子材料科学与工程, 2007, 23(5): 227-229.
	ZHENG Jianwei, XIA Xiuyang, WANG Wei, et al. Study on the chemical modification of hard segments of polyurethane elastomer by formaldehyde[J]. Polymer Materials Science & Engineering，2007, 23(5): 227-229.
12	INOUE K. Functional dendrimers, hyperbranched and star polymers[J]. Progress in Polymer Science, 2000, 25(4): 453-571.
13	LIU Tuo, LI Jing, PAN Yi, et al. A new approach to shape memory polymer: design and preparation of poly(methyl methacrylate) composites in the presence of star poly(ethylene glycol) [J]. Soft Matter, 2011, 7(5): 1641-1643.
14	WANG Ling, DING Wei, SONG Kaoping, et al. Synthesis of a branched star copolymer by aqueous SET-LRP and its thermo-stimuli response[J]. Journal of Macromolecular Science, A, 2020, 57(4): 266-273.
15	CAO Xiaodong, HABIBI Yousself, LUCIA Lucian A. One-pot polymerization, surface grafting, and processing of waterborne polyurethane-cellulose nanocrystal nanocomposites[J]. Journal of Materials Chemistry, 2009, 19(38): 7137-7145.
16	XUE Liang, DAI Shiyao, LI Zhi. Biodegradable shape-memory block co-polymers for fast self-expandable stents[J]. Biomaterials, 2010, 31(32): 8132-8140.
17	祝仰文.微支化微交联聚丙烯酰胺的合成及性能研究[J].西南石油大学学报(自然科学版), 2017, 39(2): 179-184.
	ZHU Yangwen. Synthesis and performance of partially branched and partially crosslinked polyacrylamides[J]. Journal of Southwest Petroleum University (Science & Technology Edition), 2017, 39(2): 179-184.
18	ZHANG Junle, FU Peng, ZHAO Qingxiang, et al. Progress in the synthesis of amphiphilic branched polymers[J]. Polymer Materials Science & Engineering, 2010, 26(8): 154-156.
19	Khine Yi MYA, GOSE Halima Binte, PREYSCH Thorsten, et al. Star-shaped POSS-polycaprolactone polyurethanes and their shape memory performance[J]. Journal of Materials Chemistry, 2011, 21(13): 4827-4836.
20	BOTHE Martin, Khine Yi MYA, LIN Esther Marie JIE, et al. Triple-shape properties of branched POSS-polycaprolactone polyurethane networks[J]. Soft Matter， 2012, 8(4): 965-972.
21	YANG Xifeng, WANG Lin, WANG Wenxi, et al. Triple shape memory effect of branched polyurethane[J]. ACS Applied Materials & Interfaces， 2014, 6(9): 6545-6554.
22	陈政, 张帆, 黄美松，等. 支化结构阴/非离子聚氨酯丙烯酸酯的制备与性能[J].精细化工, 2011, 28(8): 791-796.
	CHEN Zheng, ZHANG Fan, HANG Meisong, et al. Preparation and performance of star-shape anionic/non-ionic polyurethane-acrylate[J]. Fine Chemicals, 2011, 28(8): 791-796.
23	张彬. 聚醚多元醇的合成及其聚氨酯弹性体制备研究[D]. 太原：中北大学, 2015.
	ZHANG Bin. Research on the synthesis of polyether polyols and its application in preparation of polyurethane elastomer[D]. Taiyuan: Zhongbei University, 2015.
24	张美杰, 赵秀丽. 多代超支化聚氨酯的合成与表征[J]. 材料保护, 2013, 46(S1): 8-11.
	ZHANG Meijie, ZHAO Xiuli. Synthesis and characterization of multigenerations hyperbranched polyurethanes [J]. Materials Protection, 2013, 46(S1): 8-11.
25	Miriam SAENZ-PEREZ, LIZUNDIA Erlantz, LAZA Jose Manuel, et al. Methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI) based polyurethanes: thermal, shape-memory and mechanical behavior[J]. RSC Advances, 2016, 6(73): 69094-69102.
26	张士玉. 交联型聚氨酯的合成及其室温自修复性能的研究[D]. 青岛: 青岛科技大学, 2017.
	ZHANG Shiyu. Synthesis and room temperature self-healing performance of crosslinked polyurethane[D]. Qingdao: Qingdao University of Science & Technology, 2017.
27	TANG Qiheng, GAO Kezheng. Structure analysis of polyether-based thermoplastic polyurethane elastomers by FTIR, ¹H NMR and ¹³C NMR[J]. International Journal of Polymer Analysis and Characterization, 2017, 22(7): 569-574.
28	STERN Theodor. Conclusive chemical deciphering of the consistently occurring double-peak carbonyl-stretching FTIR absorbance in polyurethanes[J]. Polymers for Advanced Technologies, 2019, 30(3): 675-687.
29	LIU Jin, MA Dezhu, LI Zhen. FTIR studies on the compatibility of hard-soft segments for polyurethane-imide copolymers with different soft segments[J]. European Polymer Journal, 2002, 38(4): 661-665.
30	XU Zhaozan, CUI Yangli, LI Tingting, et al. Enhanced mechanical and shape memory properties of poly(propylene glycol)-based star-shaped polyurethane[J]. Macromolecular Chemistry and Physics, 2020, 221(13): 2000082.
31	李月婷. 聚醚型聚氨酯及其复合材料的控制制备与形状记忆性[D]. 北京: 北京化工大学, 2017.
	LI Yueting. Preparation and shape memory properties of polyether polyurethane and its composites [D]. Beijing: Beijing University of Chemical Technology, 2017.
32	BARRETO LUNA Carlos Bruno, SIQUEIRA Danilo Diniz, BARBOSA FERREIRA Eduardo da Silva, et al. Reactive compatilization of PCL/WP upon addition of PCL-MA. Smart option for recycling industry[J]. Materials Research Express, 2019, 6(12): 125317-125317.
33	丁琳, 杨建军, 吴庆云, 等. 内交联水性聚氨酯自消光树脂的制备及表征[J].精细化工, 2017, 34(12): 1334-1339.
	DING Lin, YANG Jianjun, WU Qingyun, et al. Synthesis and characterization of internal crosslinking waterborne polyurethane self-matting resin[J]. Fine Chemicals. 2017, 34(12): 1334-1339.
34	朱广超, 王贵友, 胡春圃. 交联密度对脂肪族聚氨酯弹性体结构与性能的影响[J]. 高分子学报, 2011(3): 274-280.
	ZHU Guangchao, WANG Guiyou, HU Chunpu. Effect of crosslinking desnsity on the structures and properties of aliphatic polyurethane elastomer. [J]. Acta Polymerica Sinica, 2011(3): 274-280.
35	CHEN S, MO F, YANG Y, et al. Development of zwitterionic polyurethanes with multi-shape memory effects and self-healing properties[J]. Journal of Materials Chemistry A. 2015, 3(6): 2924-2933.
36	朱聪, 杜瑞春, 张秋红等. 交联型聚氨酯阻尼材料性能研究[J]. 南京大学学报(自然科学版), 2019, 55(5): 825-831.
	ZHU Cong, DU Ruichun, ZHANG Qiuhong, et al. Study on the damping properties of cross-linking polyurethanes[J]. Journal of Nanjing University (Natural Sciences), 2019, 55(5): 825-831.
37	肖建华, 陈思维. 医用级热塑性聚氨酯的流变性能[J]. 高分子材料科学与工程, 2016, 32(12): 87-90.
	XIAO Jianhua, CHEN Siwei. Rheological properties of medical grade thermoplastic polyurethane[J]. Polymer Materials Science & Engineering, 2016, 32(12): 87-90.
38	徐晓梅, 郑晓婷, 刘晶如, 等.支链长度及支化程度对聚苯乙烯流变行为的影响[J].高分子材料科学与工程, 2015, 31(4): 78-82.
	XU Xiaomei, ZHENG Xiaoting, LIU Jingru, et al. Influence of branch length and branching level on rheological behaviors of branching polystyrene[J]. Polymer Materials Science & Engineering, 2015, 31(4): 78-82.

样品	PPG-3或丙三醇	PPG-3（丙三醇）/PDGA/MDI/BDO	M_n/×10⁴	M_w/×10⁴	M_w/M_n	［η］	HS/%
PU	0	0/1/3/2	3.55	5.77	1.63	0.52	31.8
BPU1	1% PPG-3	0.01/0.985/3/2	3.72	6.06	1.62	0.55	32.3
BPU2	3% PPG-3	0.03/0.955/3/2	4.76	8.14	1.71	0.69	32.7
BPU3	5% PPG-3	0.05/0.925/3/2	4.52	10.20	2.26	0.85	33.3
BPU4	1% 丙三醇	0.01/0.985/3/2	4.54	8.82	1.94	0.67	32.1
BPU5	3% 丙三醇	0.03/0.955/3/2	6.11	13.16	2.15	0.69	32.7

样品	PPG-3或丙三醇	PPG-3（丙三醇）/PDGA/MDI/BDO	M_n/×10⁴	M_w/×10⁴	M_w/M_n	［η］	HS/%
PU	0	0/1/3/2	3.55	5.77	1.63	0.52	31.8
BPU1	1% PPG-3	0.01/0.985/3/2	3.72	6.06	1.62	0.55	32.3
BPU2	3% PPG-3	0.03/0.955/3/2	4.76	8.14	1.71	0.69	32.7
BPU3	5% PPG-3	0.05/0.925/3/2	4.52	10.20	2.26	0.85	33.3
BPU4	1% 丙三醇	0.01/0.985/3/2	4.54	8.82	1.94	0.67	32.1
BPU5	3% 丙三醇	0.03/0.955/3/2	6.11	13.16	2.15	0.69	32.7

样品	T_g，s/℃	T_g，h/℃	T_m/℃	ΔH_m1/J·g^-1	T_m/℃	ΔH_m2/J·g^-1
PU	-29.8	58.1	124.4	2.03	156.5	2.34
BPU1	-30.2	58.0	123.3	1.44	154.6	3.85
BPU2	-27.8	49.6	129.8	1.06	165.1	3.51
BPU3	-27.9	57.3	128.4	0.80	161.5	3.09
BPU4	-27.9	58.0	128.9	1.19	154.4	0.82
BPU5	-28.1	58.5	128.7	1.64	160.9	1.30
CPU	-24.6	57.3	145.9	0.88	175.3	3.60

样品	T_g，s/℃	T_g，h/℃	T_m/℃	ΔH_m1/J·g^-1	T_m/℃	ΔH_m2/J·g^-1
PU	-29.8	58.1	124.4	2.03	156.5	2.34
BPU1	-30.2	58.0	123.3	1.44	154.6	3.85
BPU2	-27.8	49.6	129.8	1.06	165.1	3.51
BPU3	-27.9	57.3	128.4	0.80	161.5	3.09
BPU4	-27.9	58.0	128.9	1.19	154.4	0.82
BPU5	-28.1	58.5	128.7	1.64	160.9	1.30
CPU	-24.6	57.3	145.9	0.88	175.3	3.60

样品	拉伸强度/MPa	断裂伸长率/%	撕裂强度/MPa	邵氏A硬度
PU	12.5±0.4	819.4±41.1	66.5±2.4	76
BPU1	18.8±0.4	627.6±60.3	84.2±2.8	77
BPU2	33.9±1.2	585.2±12.2	90.7±1.6	76
BPU3	19.4±2.1	517.2±27.2	81.1±5.6	79
BPU4	13.6±1.4	551.6±43.4	79.3±3.5	75
BPU5	20.7±1.8	540.7±21.7	84.1±2.2	75
CPU	31.8±2.1	409.2±21.8	84.4±2.8	82