高替代率木质素酚醛树脂在胶合板中的应用性能比较

doi:10.3969/j.issn.0253-2417.2022.04.011

摘要/Abstract

摘要：

以云杉硫酸盐法制浆黑液中的碱木质素(UL)为原料，在改性得到脱甲基化木质素(DUL)和羟甲基化木质素(HUL)的基础上，合成了高替代率(≥70%)的木质素酚醛树脂(LPF)，并探讨了3种木质素羟基含量对LPF胶黏剂胶合强度和游离甲醛含量的影响。木质素的结构分析结果表明：相比原料UL，DUL和HUL的羟基比例分别提高了26.41%、72.35%。将UL、DUL和HUL替代苯酚制备LPF并将其用于杨木单板胶合实验中，实验结果显示：UL经脱甲基化改性后进一步提高了其耐热水胶合强度(σ_HWT)，在30%木质素替代率下，DUL的σ_HWT最大，达1.09 MPa，比PF(0.78 MPa)提高了39.39%。木质素替代率从30%(HUL)提高至70%(DUL)，同时胶合板中游离甲醛的质量浓度从0.33 mg/L(UL)降低至0.29 mg/L(DUL)，仍小于国标GB 9846.2—2004要求(< 0.5 mg/L)；UL经羟甲基化改性后，HUL制备LPF的胶合强度大幅提高，在30%木质素替代率下，干胶合强度(σ_dry)为2.55 MPa，与PF(1.43 MPa)相比提高了79.02%；湿胶合强度(σ_WST)为1.99 MPa，与PF(0.84 MPa)相比提高了135.31%。

关键词: 木质素, 木质素改性, 胶合强度, 游离甲醛含量

Abstract:

Lignin-based phenolic resin(LPF)with high phenol substitution rate(≥70%) were synthesized based on alkali lignin(UL)from black liquor of kraft pulping of spruce, or based on demethylated lignin(DUL) and hydroxymethylated lignin(HUL) obtained from the modification of UL. The effects of the hydroxyl content of three types of lignin on the adhesive strength and free formaldehyde content of LPF adhesives were compared and analyzed in this paper. The results of structure analysis of lignin showed that the hydroxyl ratios of DUL and HUL increased by 26.41% and 72.35%, respectively, while compared to raw UL. UL, DUL and HUL were separately used to replace phenol for the preparation of LPF that were applied in the bonding experiment of poplar veneer. The experimental results showed that demethylation of UL could further improve the heat-resistant water-based bonding strength((σ_HWT). At 30% lignin substitution rate, DUL showed the largest σ_HWT of 1.09 MPa, which was 39.39% higher than PF(0.78 MPa). The replacement rate of lignin increased from 30% to 70%. Meanwhile, the content of free formaldehyde in plywood decreased from 0.33 mg/L to 0.29 mg/L, which was still less than the requirement of national standard GB 9846.2—2004(< 0.5 mg/L). The bonding strength of LPF prepared from HUL was significantly improved after modification of UL by hydroxymethylation. At 30% lignin replacement rate, the dry bonding strength(σ_dry) and wet bonding strength(σ_WST) were 2.55 MPa and 1.99 MPa which increased by 79.02% and 135.31% respectively, while compared those with PF(1.43 MPa and 0.84 MPa).

Key words: lignin, lignin modification, bonding strength, free formaldehyde content

中图分类号:

TQ35

赵辉, 徐雁茹, 任浩. 高替代率木质素酚醛树脂在胶合板中的应用性能比较[J]. 林产化学与工业, 2022, 42(4): 75-80.

Hui ZHAO, Yanru XU, Hao REN. Application Performance Comparison of Lignin-based Phenolic Resin with High Phenol Substitution Rate in Plywood[J]. Chemistry and Industry of Forest Products, 2022, 42(4): 75-80.

图/表 6

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参考文献 17

1	刘纲勇, 葛虹, 郑公铭. 木质素酚醛树脂的固化动力学及机理研究[J]. 广州化工, 2011, 39 (11): 66- 68.
	LIU G Y , GE H , ZHENG G M . Kinetics and mechanism of curing reaction of LPF resin[J]. Guangzhou Chemical Industry, 2011, 39 (11): 66- 68.
2	QIAO W , LI S , GUO G , et al. Synthesis and characterization of phenol-formaldehyde resin using enzymatic hydrolysis lignin[J]. Journal of Industrial & Engineering Chemistry, 2015, 21:1417- 1422.
3	ZHANG W , MA Y , WANG C , et al. Preparation and properties of lignin-phenol-formaldehyde resins based on different biorefinery residues of agricultural biomass[J]. Industrial Crops and Products, 2013, 43:326- 333. doi: 10.1016/j.indcrop.2012.07.037
4	FLECKENSTEIN M , BIZIKS V , MAI C , et al. Modification of beech veneers with lignin phenol formaldehyde resins in the production of laminated veneer lumber(LVL)[J]. European Journal of Wood and Wood Products, 2018, 76:843- 851. doi: 10.1007/s00107-017-1275-7
5	ZHANG H N, REN H, ZHAI H M. Analysis of phenolation potential of spruce kraft lignin and construction of its molecular structure model[J]. Industrial Crops and Products, 2021, 167: 1-11[2020-12-10]. https://doi.org/10.1016/j.indcrop.2021.113506.
6	陈智糠. 木质素改性酚醛树脂胶粘剂的制备与性能研究[D]. 南宁: 广西大学, 2019.
	CHEN Z K. Preparation and properties of lignin modified phenolic resin adhesive[D]. Nanning: Guangxi University, 2019.
7	朱璐璐, 刘汗青, 钱爽, 等. 乙酰化前后木质素对甲酚与聚乳酸复合成膜性质影响的比较[J]. 中华纸业, 2017, 38 (4): 27- 31.
	ZHU L L , LIU H Q , QIAN S , et al. Comparison on properties of acetylated lignocresol-polylactic acid film before and after acetylation[J]. China Pulp and Paper Industry, 2017, 38 (4): 27- 31.
8	ZAWADZKI M , RAGAUSKAS A . N-Hydroxy compounds as new internal standards for the ³¹P-NMR determination of lignin hydroxy functional groups[J]. Holzforschung, 2001, 55:283- 285. doi: 10.1515/HF.2001.047
9	SPRINGER S D , HE J , CHUI M , et al. Peroxidative oxidation of lignin and a lignin model compound by a manganese SALEN derivative[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (6): 3212- 3219.
10	AHVAZI B , CLOUTIER E , WOJCIECHOWICZ O , et al. Lignin profiling: A guide for selecting appropriate lignin as precursors in biomaterials development[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (10): 5090- 5105.
11	HU L H , PAN H , ZHOU Y H , et al. Chemical groups and structural characterization of lignin via thiol-mediated demethylation[J]. Journal of Wood Chemistry and Technology, 2014, 34 (2): 122- 134. doi: 10.1080/02773813.2013.844165
12	XIE S , SUN Q , PU Y , et al. Advanced chemical design for efficient lignin bioconversion[J]. ACS Sustainable Chemistry & Engineering, 2017, 5 (3): 2215- 2223.
13	WANG H , EBERHARDT T L , WANG C , et al. Demethylation of alkali lignin with halogen acids and its application to phenolic resins[J]. Polymers, 2019, 11 (11): 1771- 1787. doi: 10.3390/polym11111771
14	CHEN Y , ZHANG H , ZHU Z , et al. High-value utilization of hydroxymethylated lignin in polyurethane adhesives[J]. International Journal of Biological Macromolecules, 2020, 152:775- 785. doi: 10.1016/j.ijbiomac.2020.02.321
15	TEODOR M , RALUCA N , POPA V I . Contribution to the study of hydroxymetylation reaction of alkali lignin[J]. Bioresources, 2007, 3 (1): 13- 20.
16	MOUBARIK A , GRIMI N , BOUSSETTA N , et al. Isolation and characterization of lignin from Moroccan sugar cane bagasse: Production of lignin-phenol-formaldehyde wood adhesive[J]. Industrial Crops and Products, 2013, 45:296- 302. doi: 10.1016/j.indcrop.2012.12.040
17	王冠华. 汽爆秸秆木质素分级及其材料的制备[D]. 北京: 中国科学院大学, 2015.
	WANG G H. Fractionation of lignin from steam-exploded corn stalk and lignin-based materials preparation[D]. Beijing: University of Chinese Academy of Sciences, 2015.

原料raw material	M_n	M_w	M_w/M_n(PDI)
碱木质素(UL)	1 631	6 348	3.89
脱甲基化木质素(DUL)	1 468	4 468	3.04
羟甲基化木质素(HUL)	3 266	27 332	8.36

样品 sample	脂肪族羟基 aliphatic hydroxyl	缩合酚羟基 condensed phenolic hydroxyl	愈创木基酚羟基 guaiacyl OH	对羟基苯基酚羟基 p-hydroxyphenyl OH	总酚羟基 total phenolic hydroxyl	羧基 carboxyl
UL	2.93	1.39	2.95	0.28	4.62	0.39
DUL	3.01	2.55	3.01	0.28	5.84	0.41
HUL	5.05	3.77	0.63	0.28	4.68	0.42

木质素替代率/% lignin substitution rate	σ_dry/MPa			σ_WST/MPa			σ_HWT/MPa
木质素替代率/% lignin substitution rate	UL	DUL	HUL	UL	DUL	HUL	UL	DUL	HUL
0	1.43	1.43	1.43	0.84	0.84	0.84	0.78	0.78	0.78
10	2.18	2.33	2.25	0.97	1.14	1.77	0.77	1.21	1.23
30	2.28	2.43	2.55	1.04	1.16	1.99	0.89	1.09	1.02
50	1.99	2.18		0.72	1.04		0.64	0.79
70	1.28	1.34		0.62	0.68		0.62	0.64

木质素 lignin	不同替代率下的游离甲醛/(mg·L^-1) free formaldehyde under different substitution rates
木质素 lignin	0	10%	30%	50%	70%
UL	0.13	0.15	0.16	0.25	0.33
DUL	0.13	0.14	0.15	0.17	0.29
HUL	0.13	0.16	0.17

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