腰果酚基不饱和树脂在木材增强改性中的应用

doi:10.16085/j.issn.1000-6613.2023-1581

摘要/Abstract

摘要：

人工林速生木材孔隙率较大，密度低，且具有渗透性，因此可通过化学浸渍将人工合成树脂浸渍到木材的内部，从而提升速生木材的抗吸水性、抗压强度等性能。本文用腰果酚合成不饱和树脂（UPR），并用于浸渍改性杨木、杉木、樟子松3种速生木材，效果最显著的是杉木，其平均密度从0.4g/cm³提高到1.04g/cm³，抗压强度从30.1MPa提升到90.4MPa，吸水率由167.3%降至7.9%。用傅里叶变换红外光谱仪（FTIR）证实了其化学结构，用凝胶渗透色谱（GPC）检测合成树脂各阶段产物的分子量分布，便于预测其结构式。X射线光电子能谱仪（XPS）分析表明，UPR浸渍以材料渗透性由外到内呈递减趋势的横向渗透为主。热重分析（TGA）表明UPR提高了改性木材的热稳定性。通过扫描电子显微镜（SEM）观察可以明显看到木材内部孔洞被树脂填充并交联固化，因此3种速生木材的抗吸水性、抗压强度和热稳定性都得到了不同程度的提升。

关键词: 腰果酚, 不饱和树脂, 复合材料, 聚合, 聚合物, 木材改性

Abstract:

Artificial forest fast-growing wood has a high porosity, low density, and permeability. Therefore, synthetic resin can be impregnated into the interior of the wood through chemical impregnation, thereby improving the water resistance, compressive strength and other properties of fast-growing wood. This study synthesized unsaturated resin (UPR) from cardanol and used it to impregnate and enhance three types of fast-growing wood, namely poplar, fir and camphor pine. The most significant effect was on fir, with an average density increased from 0.4g/cm³ to 1.04g/cm³, compressive strength increased from 30.1MPa to 90.4MPa and water absorption rate decreased from 167.3% to 7.9%. Its chemical structure was confirmed by FTIR spectrum. The molecular weight distribution of the products in each stage of the synthetic resin was detected by gel permeation chromatography (GPC), which was convenient for predicting its structural formula. X-ray photoelectron spectroscopy (XPS) analysis showed that the UPR impregnation method mainly exhibited a decreasing trend of lateral permeability from the outside to the inside. Thermogravimetric analysis (TGA) indicated that UPR improved the thermal stability of modified wood. Through scanning electron microscopy (SEM) observation, it can be clearly seen that the internal pores of the wood were filled with resin and crosslinked, resulting in varying degrees of improvement in water resistance, compressive strength and thermal stability of the three types of fast-growing wood.

Key words: cardanol, unsaturated resin, composites, polymerization, polymers, wood modification

中图分类号:

TQ31

向文丽, 唐辉, 许天乐, 张宝印. 腰果酚基不饱和树脂在木材增强改性中的应用[J]. 化工进展, 2024, 43(10): 5653-5662.

XIANG Wenli, TANG Hui, XU Tianle, ZHANG Baoyin. Application of cardanol-based unsaturated resin in wood enhanced modification[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5653-5662.

图/表 16

表1 实验试剂纯度及厂商

试剂名称	纯度	厂商
腰果酚	工业纯	浙江万盛股份有限公司
甲醛	37%	国药集团化学试剂有限公司
乙酸锌	99%	天津市风船化学试剂科技有限公司
环氧氯丙烷（ECH）	99.5%	上海麦克林生化科技股份有限公司
氢氧化钠	96%	上海麦克林生化科技股份有限公司
马来酸酐（MA）	99%	上海麦克林生化科技股份有限公司
对苯二酚	99%	国药集团化学试剂有限公司
苯乙烯（St，代号S）	99%	上海麦克林生化科技股份有限公司
二乙烯基苯（DVB，代号D）	80%	阿拉丁试剂（上海）有限公司
过氧化苯甲酰（BPO，代号B）	99%	上海麦克林生化科技股份有限公司
乙酸乙酯	99%	上海麦克林生化科技股份有限公司

表2 实验仪器型号及厂家

仪器名称	型号	生产厂家
旋转黏度计	NDJ-1	上海精密科学仪器有限公司
真空干燥箱	DZF-6020	上海东麓仪器设备有限公司
压力试验机	YAW-100D	济南中路昌试验机制造有限公司
傅里叶红外光谱仪（FTIR）	Spectrum Two	美国Perkin Elmer公司
凝胶色谱仪（GPC）	LC98IIRI	北京温分分析仪器技术开发有限公司
热重分析仪（TGA）	TGA-50	日本岛津公司
X射线光电子能谱（XPS）	Nexsa	赛默飞世尔科技（中国）有限公司
扫描电子显微镜（SEM）	GeminiSEM360	德国卡尔·蔡司股份公司

图1 腰果酚基不饱和树脂的合成路线[7]（ECF-UPR是本文预测结构）

图2 合成不饱和树脂的酸值变化

图3 腰果酚、CF、ECF、ECF-UPR及ECF-UPR（固化后）的红外光谱

图4 合成ECF-UPR各阶段产物的GPC谱图

表3 原木与改性木材的性质对比

木材试样代号	原木密度 /g·cm^-3	浸渍增重率 /%	改性木材密度 /g·cm^-3	剖面密度/g·cm^-3			密度增加率 /%	UPR在改性木材中的固化度/%
木材试样代号	原木密度 /g·cm^-3	浸渍增重率 /%	改性木材密度 /g·cm^-3	外	中	内	密度增加率 /%	UPR在改性木材中的固化度/%
M-S	0.40	156.35	1.04	1.10	1.06	1.01	160.00	98.04
M-Y	0.48	74.05	0.85	0.88	0.80	0.74	77.08	98.51
M-Z	0.40	121.76	0.92	0.98	0.94	0.89	130.00	94.01

图5 原木与改性木材的吸水率比较（S、Y、Z分别为原木杉木、杨木、樟子松；前缀“M-”表示改性木材）

图6 原木与改性木材的抗压强度比较

图7 原木、改性木材和ECF-UPR（固化后）的红外光谱

图8 原木、改性杉木与ECF-UPR（固化后）试样的TG、DTG曲线

表4 原木、改性杉木与ECF-UPR（固化后）试样的热重分析结果

样品代号	T_10%/℃	T_50%/℃	T_max/℃	残留率/%
S	282.2	352.2	356.1	17.4
M-S	286.8	394.6	402.6	8.6
ECF-UPR（固化后）	341.3	415.2	408.4	3.1

图9 杉木原木及ECF-UPR改性杉木样品XPS全谱图

图10 杉木原木及ECF-UPR改性杉木样品C 1s高分辨谱图

表5 杉木原木及改性杉木样品剖面密度及化学元素质量分数

样品代号	剖面密度/g·cm^-3	C—C/%	C—O/%	O—C—O/%	O—C $̿$ O/%	O/%	C/%	O/C/%
S	0.40^①	38.54	27.99	5.87	0.63	26.75	73.03	36.63
M-S-内	1.01	32.70	30.22	6.15	0.86	30.29	69.93	43.31
M-S-中	1.06	32.90	30.60	5.33	0.88	30.29	69.71	43.45
M-S-外	1.10	33.13	30.22	4.88	1.27	30.50	69.50	43.88

表5 杉木原木及改性杉木样品剖面密度及化学元素质量分数

样品代号	剖面密度/g·cm^-3	C—C/%	C—O/%	O—C—O/%	O—C $̿$ O/%	O/%	C/%	O/C/%
S	0.40^①	38.54	27.99	5.87	0.63	26.75	73.03	36.63
M-S-内	1.01	32.70	30.22	6.15	0.86	30.29	69.93	43.31
M-S-中	1.06	32.90	30.60	5.33	0.88	30.29	69.71	43.45
M-S-外	1.10	33.13	30.22	4.88	1.27	30.50	69.50	43.88

图11 原木及改性木材的内弦切面的扫描电镜图（S、Y、Z分别为原木杉木、杨木、樟子松；前缀“M-”表示改性木材）

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