支化与交联型聚氨酯弹性体的合成与性能分析

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

摘要/Abstract

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

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

中图分类号:

TQ323.8

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.

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.

图/表 11

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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