Synthesis and properties of phenylene-containing α,ω-hydroxy-terminated fluorosilicone polymers

doi:10.11949/0438-1157.20221455

Abstract

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

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

CLC Number:

TQ 333

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.

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.

Figures/Tables 16

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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