交联型特辛基酚醛树脂酚羟基间位的溴化改性

doi:10.16085/j.issn.1000-6613.2022-0021

摘要/Abstract

摘要：

以交联型特辛基酚醛树脂为原料进行改性，得到了一种交联型酚羟基间位溴化特辛基酚醛树脂，采用红外光谱（FTIR）、核磁碳谱（NMR）对树脂的结构进行了表征，结果表明成功地在酚羟基的间位上取代上了溴。采用莫尔法滴定反应测定剩余溴含量，计算得到苯环上的溴化率为84.7%。采用凝胶渗透色谱（GPC）对改性前后的酚醛树脂进行表征，结果表明经过溴化改性的酚醛树脂的数均分子量、重均分子量有所降低，分子量分布变窄。根据交联型特辛基酚醛树脂的交联机理，分别对交联型特辛基酚醛树脂、交联型链端溴化特辛基酚醛树脂树脂和交联型酚羟基间位溴化特辛基酚醛树脂交联橡胶的硫化历程和物理力学性能进行测试，结果表明改性后的酚羟基间位溴化特辛基酚醛树脂交联橡胶的硫化程度、硫化速度、力学性能都有明显提升。

关键词: 交联型特辛基酚醛树脂, 酚羟基间位溴化, 交联机理, 力学性能

Abstract:

A crosslinked teroctyl phenolic resin with brominated phenol hydroxyl group was obtained by modifying the crosslinked teroctyl phenolic resin. The structure of the resin was characterized by FTIR and NMR. The results showed that bromine was successfully substituted on the phenol hydroxyl group. The residual bromine content was determined by Mohr titration reaction. The bromination rate on the benzene ring was calculated to be 84.7%. GPC was used to characterize the phenolic resin before and after modification. The results indicated that the number average molecular weight and weight average molecular weight of the brominated phenolic resin decreased, and the molecular weight distribution narrowed. According to the crosslinking mechanism of crosslinked teoctyl phenolic resin, the vulcanization process and physical and mechanical properties of rubber coordination systems of crosslinked teoctyl phenolic resin, crosslinked chain end brominated teoctyl phenolic resin and crosslinked phenolic hydroxyl meta brominated teoctyl phenolic resin were tested respectively. The results showed that the vulcanization degree, vulcanization speed and physical and mechanical properties of the modified phenolic hydroxyl meta brominated teoctyl phenolic resin were significantly improved.

Key words: p-teroctyl phenolic resin, phenol hydroxyl meta bromination, crosslinking mechanism, physical and mechanical properties

中图分类号:

刘大晨, 杜明慧, 王衡. 交联型特辛基酚醛树脂酚羟基间位的溴化改性[J]. 化工进展, 2022, 41(S1): 382-388.

LIU Dachen, DU Minghui, WANG Heng. Bromination modification of phenolic hydroxyl sites of crosslinked teroctyl phenolic resin[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 382-388.

图/表 16

图1 201酚醛树脂

图2 交联型酚羟基间位溴化特辛基酚醛树脂

图3 交联型酚羟基间位溴化特辛基酚醛树脂制备方案

表1 配合不同酚醛树脂交联的橡胶基本配方

配方编号	1	2	3
IR	100	100	100
交联型特辛基酚醛树脂	10	—	—
交联型链端溴化特辛基酚醛树脂	—	10	—
交联型酚羟基间位溴化特辛基酚醛树脂	—	—	10
ZnO	5	5	5
白炭黑	20	20	20
轻质碳酸钙	30	30	30
硬脂酸	1	1	1

图4 三种树脂的红外光谱图a—交联型特辛基酚醛树脂；b—交联型链端溴化特辛基酚醛树脂；c—交联型酚羟基间位溴化取代特辛基酚醛树脂

图5 交联型特辛基酚醛树脂的碳谱谱图

图6 交联型链端溴化特辛基酚醛树脂的碳谱谱图

图7 交联型苯酚羟基间位溴化特辛基酚醛树脂的碳谱谱图

表2 交联型辛基酚醛树脂溴化前后分子量对比

样品	M_n	M_w	M_v	PD
交联型特辛基酚醛树脂	2639	4870	4441	1.8454
交联型酚羟基间位溴化取代特辛基酚醛树脂	1742	2363	2247	1.35649

图8 酚醛树脂交联机理第一步

图9 酚醛树脂交联机理第二步

图10 交联型链端溴化特辛基酚醛树脂交联机理

图11 交联型酚羟基间位溴化取代特辛基酚醛树脂电子偏移原理

图12 交联型酚羟基间位溴化取代特辛基酚醛树脂交联机理

图13 配合不同交联型酚醛树脂硫化橡胶的硫化特性曲线a—改性前的交联型特辛基酚醛树脂；b—传统交联型链端省化特辛基酚醛树脂；c—改性后的交联型酚羟基间位溴化取代特辛基酚醛树脂

表3 配合不同交联型酚醛树脂硫化胶的力学性能对比

配方

编号

拉伸强度

/MPa

断裂

伸长率/%

300%定伸

应力/MPa

撕裂强度

/N·mm^-1

邵氏A

硬度/HA

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