多胺型纤维素基螯合纤维的合成工艺与结构表征

doi:10.3969/j.issn.0253-2417.2023.04.012

摘要/Abstract

摘要：

将环氧活化的纤维素纤维(CPGMA)分别在水介质和二甲基酰胺(DMF)介质体系中进行多胺化有机合成反应，考察反应介质、胺浓度、反应时间、温度、液比和初始环氧基含量等对胺化反应的影响。研究结果表明：DMF作为反应介质、温度为60 ℃时最有利于胺化反应进行，纤维增重与胺浓度之间符合线性关系。在DMF介质中，胺化反应在1 h之内达到饱和，反应液比增大不利于胺化反应的进行，CPGMA的环氧基含量越高越有利于胺化反应进行。600 ℃时，CPGMA(接枝率198%)的残余量为5.1%，而胺化改性后的CPGMA-EDA残余量为16.8%，纤维热稳定性提高。固体核磁¹³C CP/MAS NMR谱图中5′环氧基上的叔碳峰的消失及2′季碳和6′环氧基上亚甲基碳峰强度的减弱，均验证了胺化反应的成功进行。

关键词: 漂白化学浆, 胺化, 螯合纤维, 合成工艺

Abstract:

The epoxy-activated cellulose fibers(CPGMA) were subjected to polyamination organic synthesis in water medium and in dimethylamide(DMF) medium, respectively. The effects of reaction medium, amine concentration, reaction time, temperature, liquid ratio and initial epoxy group content on the amination reaction were investigated. The results showed that DMF as the reaction medium and the temperature of 60 ℃ were the most favorable to reaction, and there was a linear relationship between fiber weight gain and amine concentration. In DMF medium, the amination reaction reached saturation within 1 h, and the increase of reaction liquid ratio was not conducive to the amination reaction. The higher epoxy group content of CPGMA, the better amination reaction. At 600 ℃, the residual amount of CPGMA(grafting rate was 198%) was 5.1%, while the residual amount of amine-modified CPGMA-EDA was 16.8%, and the thermal stability of the fiber increased. The disappearance of the tertiary carbon peak on the 5′ epoxide group and the reduction in the intensity of the methylene carbon peaks on the 2′-quaternary carbon and 6′ epoxide groups in the solid-state ¹³C CP/MAS NMR spectrum confirmed the success of amination reaction.

Key words: bleaching chemical pulp, amination, chelated fiber, synthesis process

中图分类号:

TQ35
TS7

王宇, 黄军, 翟华敏, 任浩. 多胺型纤维素基螯合纤维的合成工艺与结构表征[J]. 林产化学与工业, 2023, 43(4): 81-89.

Yu WANG, Jun HUANG, Huamin ZHAI, Hao REN. Synthesis Process and Structural Characterization of Polyamine Cellulose Based Chelated Fibers[J]. Chemistry and Industry of Forest Products, 2023, 43(4): 81-89.

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胺amine	介质medium	a	b	R²	-b/a	x=exp(-b/a)	x_H₂O/x_DMF
EDA	DMF	0.021 7	0.112 5	0.986 0	-5.184 3	0.005 6	3.83
EDA	H₂O	0.012 6	0.048 4	0.997 9	-3.841 3	0.021 5	3.83
DETA	DMF	0.027 5	0.153 4	0.995 1	-5.578 2	0.003 8	13.73
DETA	H₂O	0.014 4	0.042 6	0.974 8	-2.958 3	0.051 9	13.73

介质 medium	含氮量nitrogen content/%		△m/m_CPGMA/(g·g^-1)
介质 medium	EDA	DETA	EDA	DETA
H₂O	2.12	1.98	0.041 9	0.031 7
二甲基甲酰胺DMF	4.09	5.05	0.095 0	0.137 0
二甲亚砜DMSO	3.64	4.54	0.066 4	0.118 9
V(H₂O)∶V(DMF)=3∶1	2.09	2.35	0.058 2	0.073 5
V(H₂O)∶V(DMF)=1∶1	2.58	2.98	0.056 3	0.081 0
V(H₂O)∶V(DMF)=1∶3	3.04	3.61	0.065 3	0.107 1

试样¹⁾ sample	不同失重率时的分解温度/℃ decomposition temperatures under different weight loss rates
试样¹⁾ sample	2%	5%	15%	30%	50%	70%	85%	98%
桉木浆eucalyptus pulp	41.7	82.9	302.3	328.3	346.9	364.8	522	>600
CPGMA(198%)	48.1	248.4	297.4	319.1	337.8	362.1	393.6	>600
CPGMA(83%)	40.3	80.6	299.4	327.5	344.1	398.8	>600	>600
CPGMA-EDA	34.3	51.8	283.5	326.6	354.8	411.4	>600	>600

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