Effects of synthesis technology on aging performance of phenol-formaldehyde resin modified by bio-oil

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

Abstract

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

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

CLC Number:

TQ322

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.

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.

Figures/Tables 8

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

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 $\overset{}{?}$ 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

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 $\overset{}{?}$ 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

官能团	化学位移	表示
醛或酮C $\overset{}{?}$ O	220～200	a
羧酸C $\overset{}{?}$ O	186～176	b
羧酸酯C $\overset{}{?}$ 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

官能团	化学位移	表示
醛或酮C $\overset{}{?}$ O	220～200	a
羧酸C $\overset{}{?}$ O	186～176	b
羧酸酯C $\overset{}{?}$ 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

References 26

1	HIRANO K , ASAMI M . Phenolic resins——100 years of progress and their future[J]. Reactive and Functional Polymers, 2013, 73（2）：256-269.
2	EFFENDI A , GERHAUSER H , BRIDGWATER A V . Production of renewable phenolic resins by thermochemical conversion of biomass: a review[J]. Renewable and Sustainable Energy Reviews, 2008, 12(8): 2092-2116.
3	STRZEMIECKA B , ZIEBA0 PALUS J , VOELKEL A , et al . Examination of the chemical changes in cured phenol-formaldehyde resins during storage[J]. Journal of Chromatography A, 2016, 1441: 106-115.
4	PETHRICK R A . Design and ageing of adhesives for structural adhesive bonding——a reviews[J]. Proceedings of the Institution of Mechanical Engineers， Part L: Journal of Materials Design and Applications, 2014, 229(5): 1-31.
5	YU Y X , XU P P , XING J C , et al . Investigation of aging performance of bio-oil phenol-formaldehyde resin with the treatment of artificial accelerated aging method[J]. Polymer Engineering and Science, 2018, 58(10): 1810-1816.
6	GUO D , ZHAN M , WANG K . Microstructure evolution of ammonia-catalyzed phenolic resin during thermooxidative aging[J]. Journal of Applied Polymer Science, 2012, 126(6): 2010-2016.
7	SPEEKALA M S , KUMARAN M G , GEETHAKUMARIAMMA M L , et al . Environmental effects in oil palm fiber reinforced phenol formaldehyde composites: studies on thermal, biological, moisture and high energy radiation effects[J]. Advanced Composite Materials, 2004, 13(3-4): 171-197.
8	YUE K , CHEN Z , LU W , et al . Evaluating the mechanical and fire-resistance properties of modified fast-growing Chinese fir timber with boric-phenol-formaldehyde resin[J]. Construction and Building Materials, 2017, 154：956-962.
9	张西莹, 刘育红 . 酚醛树脂/碳化硼/聚硼氮烷复合物的固化行为及其热解性能[J]. 化工学报, 2014, 65(8): 3268-3276．
	ZHANG Xiyin , LIU Yuhong . Curing and pyrolysis behavior of PF/B4C/PBZ composite[J]. CIESC Journal, 2014, 65(8): 3268-3276．
10	欧阳兆辉, 伍林, 易德莲, 等 . 钼改性酚醛树脂胶黏剂的研究[J]. 化工进展, 2005, 24(8): 901-904．
	OUYANG Zhaohui , WU Lin , YI Delian , et al . Study on Mo-PF used as bonding agent[J]. Chemical Industry and Engineering Progress, 2005, 24(8): 901-904．
11	FANG Q , CUI H , DU G . Montmorillonite reinforced phenol formaldehyde resin: preparation, characterization, and application in wood bonding[J]. International Journal of Adhesion and Adhesives, 2014, 49(4): 33-37.
12	GAO W . ¹³C CP/MAS NMR analysis of cure characteristics of phenol formaldehyde resin in the presence of wood composite preservatives and wood: effect of ammonium pentaborate and copper compounds[J]. Iranian Polymer Journal, 2012, 21(5): 283-288.
13	LUBCZAK R . Thermally resistant carbazole-modified phenol-formaldehyde resins[J]. Polymer International, 2015, 64(9): 1163-1171.
14	PAPADOPOULOU E , CHRISSAFIS K . Thermal study of phenol-formaldehyde resin modified with cashew nut shell liquid[J]. Thermochimica Acta, 2011, 512(1): 105-109．
15	WANG W , LI X , YE D , et al . Catalytic pyrolysis of larch sawdust for phenol-rich bio-oil using different catalysts[J]. Renewable Energy, 2018, 121： 146-152.
16	KIM J . Production, separation and applications of phenolic-rich bio-oil——a review[J]. Bioresource Technology, 2015, 178： 90-98.
17	虞宇翔, 王文亮, 常建民, 等 . 生物质与废轮胎共热解液化技术研究现状[J] 化工进展, 2013, 32(s1): 70-75.
	YU Yuxiang , WANG Wenliang , CHANG Jianmin , et al . Research status of the co-pyrolysis liquefaction of biomass and waste tyre[J]. Chemical Industry and Engineering Progress, 2013, 32(s1): 70-75.
18	张伟, 赵增立, 郑安庆, 等 . 生物油储存稳定性的研究进展[J] 化工进展, 2011, 30(5): 973-982.
	ZHANG Wei , ZHAO Zengli , ZHENG Anqing , et al . Storage stability of bio-oil[J]. Chemical Industry and Engineering Progress, 2011, 30(5): 973-982.
19	ASLAN M , ÖZBAY G , AYRILMIS N . Adhesive characteristics and bonding performance of phenol formaldehyde modified with phenol-rich fraction of crude bio-oil[J]. Journal of Adhesion Science and Technology, 2015, 29(24): 2679-2691.
20	CHAOUM M , DIOUF P N , LAGHDIR A , et al . Bio-oil from whole-tree feedstock in resol-type phenolic resins[J]. Journal of Applied Polymer Science, 2014, 131(6): 596-602
21	CHENG S , D’CRU I , YUAN Z , et al . Use of biocrude derived from woody biomass to substitute phenol at a high‐substitution level for the production of biobased phenolic resol resins[J]. Journal of Applied Polymer Science, 2011, 121(5): 2473-2751.
22	ÖZBAY G , AYRILMIS N . Bonding performance of wood bonded with adhesive mixtures composed of phenol-formaldehyde and bio-oil[J]. Industrial Crops and Products, 2015, 66: 68-72.
23	MONNI J , ALVILA L , RAINIO J , et al . Effects of silane and the lowering of pH on the properties of phenol-formaldehyde resol resins and resin coatings[J]. Journal of Applied Polymer Science, 2007, 104(3): 1933-1941.
24	FAN D , LI G , QIN T , et al . Synthesis and structure characterization of phenol-urea-formaldehyde resins in the presence of magnesium oxide as catalyst[J]. Polymers, 2014, 6(8): 2221-2231.
25	HU X , ZHAO Y , CHENG W , et al . Synthesis and characterization of phenol-urea-formaldehyde foaming resin used to block air leakage in mining[J]. Polymer Composites, 2014, 35(10): 2056-2066.
26	CHEN Y , CHEN Z , XIAO S , et al . A novel thermal degradation mechanism of phenol-formaldehyde type resins[J]. Thermochimica Acta, 2008, 476(1): 39-43.

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