α，ω-端羟基亚苯基氟硅聚合物的合成及性能

doi:10.11949/0438-1157.20221455

摘要/Abstract

摘要：

在非平衡催化剂作用下，通过α,ω-端羟基聚甲基三氟丙基硅氧烷和亚苯基二硅醇单体的脱水缩聚反应，制得一系列α,ω-端羟基亚苯基氟硅聚合物，并研究了反应时间、催化剂用量、反应物浓度、单体比例等因素对所得聚合物的状态、特性黏度、分子量及分布、共聚组成的影响。采用红外、核磁、流变仪、热分析等手段对聚合物的结构、室温交联反应性、力学性能、耐高温性能和玻璃化转变进行了研究。结果表明，向主链中引入亚苯基在显著提高聚合物耐高温性能的同时，还有助于交联反应速率和力学性能的改善，并且当亚苯基含量低于30%(mol)时不会对聚合物的玻璃化温度(T_g)产生不利影响。分析原因，亚苯基的插入抑制了有机硅链的成环降解且提高了链的刚性(有利于耐高温性)，客观上隔开并降低了大体积三氟丙基侧基对端羟基的屏蔽效应(有利于交联反应性)，因而将聚合物制备成氟硅密封胶，具有较好的交联性能、力学性能和耐高低温性能。

关键词: 亚苯基, 氟硅, 聚合物, 合成, 催化, 非平衡催化剂, 热稳定性

Abstract:

A series of phenylene-containing α,ω-hydroxy-terminated fluorosilicone polymers were synthesized by dehydration polycondensation in the presence of non-equilibrium catalyst from α,ω-hydroxy-terminated poly(methyltrifluoropropyl) siloxanes and phenylene-containing disilanol monomers. The effects of reaction time, catalyst dosage, reactant concentration, and monomer ratio on the appearance, intrinsic viscosity, molecular weight and distribution, and copolymer composition of the obtained polymers were studied. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), rheometer and thermal analysis were utilized to study their chemical structure, room temperature crosslinking reactivity, mechanical property, thermal resistance, and glass transition. The results show that the introduction of phenylene into the main chain not only significantly improves the high temperature resistance of the polymer, but also contributes to the improvement of the crosslinking reaction rate and mechanical properties, and when the phenylene content is lower than 30%(mol), it does not adversely affect the glass transition temperature (T_g) of the polymer. It is reasonable that the insertion of phenylene inhibits the cyclization degradation and simultaneously improves the stiffness of the siloxane chain, which is beneficial to thermal resistance. Besides, the terminal silanol is separated from bulky trifluoropropyl side groups by the insertion of phenylene, and thus their shielding effect is reduced, which is helpful to the crosslinking reactivity. Therefore, the polymers can be utilized to prepare fluorosilicone sealants which show good crosslinking property, physical property, and high and low temperature resistance.

Key words: phenylene, fluorosilicone, polymer, synthesis, catalysis, non-equilibrium catalyst, thermal stability

中图分类号:

TQ 333

刘润竹, 储甜甜, 张孝阿, 王成忠, 张军营. α，ω-端羟基亚苯基氟硅聚合物的合成及性能[J]. 化工学报, 2023, 74(3): 1360-1369.

Runzhu LIU, Tiantian CHU, Xiaoa ZHANG, Chengzhong WANG, Junying ZHANG. Synthesis and properties of phenylene-containing α,ω-hydroxy-terminated fluorosilicone polymers[J]. CIESC Journal, 2023, 74(3): 1360-1369.

图/表 16

图1 α,ω-端羟基亚苯基氟硅聚合物（O1、O2、O3和O4）的合成路线

Fig.1 Synthetic route to α,ω-hydroxy-terminated phenylene-containing fluorosilicone polymers (O1, O2, O3, and O4)

表1 单体投料比对聚合物合成的影响

Table 1 Effect of monomer ratio on the synthesis of α，ω-hydroxy-terminated phenylene fluorosilicone polymers

序号	聚合物	氟硅原料	亚苯基单体	投料比^①	产率/%	聚合物形态	[η]/(ml/g)	M_n	PDI	含量/%(mol)^②
序号	聚合物	氟硅原料	亚苯基单体	投料比^①	产率/%	聚合物形态	[η]/(ml/g)	M_n	PDI	氟硅	亚苯基
1	O1	FMS-9921	BHSPE	2:1	94	黏稠液体	32	22700	1.84	89.30	21.40
2	O1	FMS-9921	BHSPE	1:1	92	半固体	87	36800	1.61	82.90	34.21
3	O1	FMS-9921	BHSPE	1:2	93	固体	132	33500	1.86	74.49	51.03
4	O1	FMS-9921	BHSPE	1:4	94	固体	158	46700	2.01	66.42	67.17
5	O1	FMS-9921	BHSPE	1:6	94	固体	184	60400	2.17	62.36	75.29
6	O2	FMS-9922	BHSPE	1:1	93	半固体	56	33000	1.71	83.48	33.05
7	O3	FMS-9921	BHSB	2:1	93	黏稠液体	30	15300	1.32	89.08	10.92
8	O3	FMS-9921	BHSB	1:1	94	黏稠液体	89	39100	1.56	72.89	27.11
9	O3	FMS-9921	BHSB	1:2	92	半固体	100	45300	1.68	61.69	38.31
10	O3	FMS-9921	BHSB	1:4	96	固体	158	50900	1.83	47.96	52.04
11	O3	FMS-9921	BHSB	1:6	95	固体	179	97800	2.22	37.60	62.40
12	O4	FMS-9922	BHSB	1:1	92	黏稠液体	69	24100	1.60	76.96	23.04

表2 反应时间对聚合物合成的影响

Table 2 Effect of reaction time on the synthesis of α，ω-hydroxy-terminated phenylene fluorosilicone polymers

序号	反应时间/h	产率/%	M_n^①	PDI^①	[η]/(ml/g)^②
1	4.5	88	9500	2.16	48
2	6.5	94	39100	1.56	89
3	8.5	95	77200	1.55	117
4	10.5	95	77500	1.68	121

表3 TMG用量对聚合物合成的影响

Table 3 Effect of TMG doasage on the synthesis of α，ω-hydroxy-terminated phenylene fluorosilicone polymers

序号	TMG∶Si—OH/ %(mol)	产率/%	M_n	PDI	[η] /(ml/g)
1	1	94	39100	1.56	89
2	2	95	76700	1.67	110
3	4	96	94700	1.66	132
4	6	96	102100	1.80	141

表4 反应物浓度对聚合物合成的影响

Table 4 Effect of reactant concentration on the synthesis of α，ω-hydroxy-terminated phenylene fluorosilicone polymers

序号	反应物浓度/ %(质量)	产率/%	M_n	PDI	[η] /(ml/g)
1	45	65	27300	1.46	62
2	55	76	32800	1.49	78
3	65	94	39100	1.56	89
4	75	85	3100	1.47	38
5^①	100	0	800	1.10	6

图2 聚合物O1（表1序号2）、O3（表1序号8、表4序号4和5）和FMS-9921的GPC曲线

Fig.2 GPC traces of polymer O1 (Table 1 No. 2), O3 (Table 1 No. 8, Table 4 No. 4 and 5), and FMS-9921

图3 聚合物O1（表1序号5）、O2（表1序号6）、O3（表1序号11）、O4（表1序号12）和FMS-9921的FTIR光谱

Fig.3 FTIR spectra of polymer O1 (Table 1 No. 5), O2 (Table 1 No. 6), O3 (Table 1 No. 11), O4 (Table 1 No. 12) and FMS-9921

图4 聚合物O1（表1序号5）、O3（表1序号11）和FMS-9921的1H NMR波谱

Fig.4 1H NMR spectra of polymer O1 (Table 1 No. 5), O3 (Table 1 No. 11) and FMS-9921

图5 聚合物O3（表1序号9）的29Si NMR波谱

Fig.5 29Si NMR spectrum of polymer O1 (Table 1 No. 9)

图6 O4及AFS-R-H1101在交联过程中G′和G″随时间的变化

Fig.6 G′ and G″ versus time during crosslinking of O4 and AFS-R-H1101

表5 AFS-R-H1101和O4硫化胶的硬度和拉伸性能

Table 5 Hardness and tensile properties of AFS-R-H1101 and O4 vulcanizates

基础聚合物	交联密度/ (10^-5 mol/ml)	邵A硬度	拉伸强度/ MPa	拉断伸长率/%
AFS-R-H1101	11.50	52±3	2.95±0.20	165±5
O4	7.29	59±3	3.34±0.20	199±2

图7 以AFS-R-H1101、O4为基础聚合物的密封胶的应力-应变曲线

Fig.7 Tensile curves of sealants with AFS-R-H1101 and O4 as base polymers

图8 聚合物O1（表1序号5）、O3（表1序号11）、O4（表1序号12）及AFS-R-H1101的热失重曲线

Fig.8 TGA curves of polymer O1 (Table 1 No. 5), O3 (Table 1 No. 11), O4 (Table 1 No. 12) and AFS-R-H1101

图9 聚合物O1（表1序号5）、O3（表1序号11）、O4（表1序号12）及AFS-R-H1101的微分失重曲线

Fig.9 DTG curves of polymer O1 (Table 1 No. 5), O3 (Table 1 No. 11), O4 (Table 1 No. 12) and AFS-R-H1101

图10 聚合物（表1序号1~12）的最大热失重温度（Tmax）和亚苯基含量的关系

Fig.10 Plots of Tmax of polymers (Table 1 No.1—12) with phenylene contents

图11 聚合物（表1序号1~12）的DSC曲线

Fig.11 DSC curves of polymers (Table 1 No.1—12)

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