合成工艺对热解油改性酚醛树脂老化性能影响

doi:10.16085/j.issn.1000-6613.2018-1181

摘要/Abstract

摘要：

利用热解油部分替代苯酚改性酚醛（PF）树脂，旨在改善树脂韧性和耐水性，从而提高树脂老化性能。b本文利用紫外光老化仪，研究了热解油替代苯酚比例、氢氧化钠（NaOH）添加量（占苯酚质量比）和反应温度对热解油改性酚醛（BPF）树脂老化性能的影响，考察了不同合成工艺制备的BPF树脂胶合板和胶膜随老化时间的胶合强度和表观构造变化，利用傅里叶红外光谱（FTIR）和固体核磁共振（NMR）分析了BPF树脂的老化行为。研究结果表明，胶合强度损失率和树脂胶膜表观结构老化程度，随着热解油替代苯酚比例和反应温度的增大而减小；随着NaOH添加量的增多，胶合强度损失率变化不大，但胶膜表观结构老化程度先减小后增大。FTIR和¹³C NMR分析得出，老化960h后树脂的亚甲基和醚键峰强减小，醛、酮和羧酸等含氧官能团的峰强增大。

关键词: 合成工艺, 热解油, 酚醛树脂, 老化性能

Abstract:

Bio-oil was added as a substitute of phenol for phenol-formaldehyde (PF) resin to enhance the toughness and water resistance, thus improving the aging performance. The effects of the substitute rate of bio-oil to phenol, addition of sodium hydroxide (NaOH) and reaction temperature on the aging performance of bio-oil phenol-formaldehyde (BPF) resin were examined using UV weathering. The variations on bonding strength of plywood and microstructure of cured resin were measured. The changes in the chemical structure of cured BPF resin were analyzed by the Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (NMR) to understand the aging behavior of BPF resin. Results showed that the decrease rate of bonding strength of plywood and aging degree of cured resin were reduced with the increase of the substitute rate of bio-oil to phenol and reaction temperature. As the growing addition of NaOH, the decrease rate of bonding strength changed little, but the aging degree of cured resin decreased first then increased. After aging 960h, the peak strength of methylene and ether bonds decreased, while the peak strength of aldehyde, ketone and carboxyl acids increased.

Key words: synthesis technology, bio-oil, phenol-formaldehyde resin, aging performance

中图分类号:

TQ322

虞宇翔,徐平平,邢靖晨,常建民. 合成工艺对热解油改性酚醛树脂老化性能影响[J]. 化工进展, 2019, 38(03): 1530-1537.

Yuxiang YU,Pingping XU,Jingchen XING,Jianmin CHANG. Effects of synthesis technology on aging performance of phenol-formaldehyde resin modified by bio-oil[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1530-1537.

图/表 8

表1 不同合成工艺制备的BPF树脂基本性能

命名	合成工艺参数			树脂性能
命名	热解油替代苯酚比例/%	NaOH添加量（占苯酚质量）/%	温度 /℃	pH （25℃）	黏度（25℃）/ mPa·s	固体含量 /%	吸水率（25℃，24h）/%
PF	0	20	90	10.92±0.17	122±29	47.26±0.22	30.75±2.82
BPF1	10	20	90	10.67±0.10	185±32	46.22±0.31	27.62±2.08
BPF2	20	20	90	10.47±0.14	293±43	45.31±0.24	24.93±1.73
BPF3	30	20	90	10.25±0.21	696±67	42.89±0.19	22.13±1.36
BPF4	20	15	90	9.81±0.19	569±49	44.11±0.12	29.35±1.62
BPF5	20	25	90	10.84±0.33	100±29	43.08±0.21	33.84±1.30
BPF6	20	20	85	10.42±0.08	55±33	44.49±0.13	31.71±1.87
BPF7	20	20	95	10.56±0.15	729±65	44.20±0.29	23.31±2.83

图1 合成工艺对不同老化时间胶合板胶合强度的影响

图2 合成工艺对不同老化时间树脂胶膜表面构造的影响

图3 不同制备工艺BPF树脂老化前后FTIR谱图

表2 BPF树脂FTIR特征峰归属

波数/cm^-1	吸收峰归属
3423	酚羟基和烷羟基的伸缩振动
2921, 2859	CH₂伸缩振动
1643	芳香酮和芳香醛的C $?$ O伸缩振动
1604，1471，1402	苯环骨架的伸缩振动
1040	芳香醚中与烷基相连的C—O伸缩振动
877	苯环（1,2,4,6）取代时C—H面外弯曲振动
854	苯环（1,2,4或1,4）取代时C—H面外弯曲振动
765	苯环（1,2）取代时C—H面外弯曲振动

表2 BPF树脂FTIR特征峰归属

波数/cm^-1	吸收峰归属
3423	酚羟基和烷羟基的伸缩振动
2921, 2859	CH₂伸缩振动
1643	芳香酮和芳香醛的C $?$ O伸缩振动
1604，1471，1402	苯环骨架的伸缩振动
1040	芳香醚中与烷基相连的C—O伸缩振动
877	苯环（1,2,4,6）取代时C—H面外弯曲振动
854	苯环（1,2,4或1,4）取代时C—H面外弯曲振动
765	苯环（1,2）取代时C—H面外弯曲振动

图4 热固性酚醛树能结构式

图5 BPF2树脂和PF树脂老化前后固体13C NMR谱图

表3 BPF树脂和PF树脂固体13C NMR化学位移

官能团	化学位移	表示
醛或酮C $?$ O	220～200	a
羧酸C $?$ O	186～176	b
羧酸酯C $?$ O	176～168	c
苯环上连接酚羟基的碳	160～148	d
苯环上邻位或对位被取代的碳	137～123	e
—CH₂—O—CH₂—	75～65	f
—CH₂OH	63～58	g
—CH—	58～45	h
—CH₂—	45～29	j

表3 BPF树脂和PF树脂固体13C NMR化学位移

官能团	化学位移	表示
醛或酮C $?$ O	220～200	a
羧酸C $?$ O	186～176	b
羧酸酯C $?$ O	176～168	c
苯环上连接酚羟基的碳	160～148	d
苯环上邻位或对位被取代的碳	137～123	e
—CH₂—O—CH₂—	75～65	f
—CH₂OH	63～58	g
—CH—	58～45	h
—CH₂—	45～29	j

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