Study on measurement method of gas evolution of foaming agent ADC based on thermogravimetric analysis

doi:10.19491/j.issn.1001-9278.2022.01.021

Abstract

Abstract:

According to the decomposition equation of the first stage of azodicarbon amide（ADC） thermal decomposition in the temperature range of 200 ~ 240 ℃， the functional relationship between ADC decomposition process and gas generation process was established， and the thermal weight loss curve of ADC was transformed into TG gas?generation curve. The results indicated that by comparing the TG gas?generation curve of foaming agent ADC and the gas?generation curve measured by the drainage gas?gathering method， the data of starting temperature， maximum gas?generation?rate temperature， and ending gas?generation temperature of ADC measured by the two methods were very close with each other. The comparison adjusted R?squares between the two curves and the fitting curve were 0.993 7 and 0.915 43， respectively， In the first stage of ADC thermal decomposition， the TG gas?generation curve of ADC can be calculated using a TG gas?generation curve formula， which can replace the gas?generation curve measured by traditional drainage gas?gathering methods.

Key words: foaming agent, azodicarbon amide, gas volume, thermogravimetric analysis, gas evolution curve

CLC Number:

TQ314.259

WANG Xiaodong, HUA Lei, DONG Aijuan, LUO Lihua. Study on measurement method of gas evolution of foaming agent ADC based on thermogravimetric analysis[J]. China Plastics, 2022, 36(1): 142-147.

Figures/Tables 7

Fig.1. Device for measuring gas evolution by drainage gas collecting method

阶段	温度区间/℃	主要气体产物
1	200~225	N₂
2	225~260	NH₃、HNCO
3	260~285	NH₃

Tab. 1. ADC thermal decomposition process

Fig.2. TG and DTG curves of ADC

Fig.3. Gas evolution curve and derivative gas volume of ADC by drainage gas collecting method

Fig.4. Gas evolution curve of ADC by drainage gas collecting method and TG method

Fig.5. Comparison of the gas evolution curve of ADC by TG method and drainage gas collecting method with fit curve

测试方法	拟合公式	Adjusted R?Square数值
TG数据	$y = ? 270 - 270 1 + (x 230) 45$	0.993 7
排水集气法	$y = ? 270 - 270 1 + (x 230) 45$	0.915 43

测试方法	拟合公式	Adjusted R?Square数值
TG数据	$y = ? 270 - 270 1 + (x 230) 45$	0.993 7
排水集气法	$y = ? 270 - 270 1 + (x 230) 45$	0.915 43

Tab. 2. Correlation coefficient between ADC fitting formula and TG method， and the correlation coefficient between ADC fitting formula and drainage gas collecting method

References 19

1	HECK R L. A review of commercially used chemical foaming agents for thermoplastic foams［J］. Journal of Vinyl & Additive Technology， 1998， 4（2）： 113⁃116.
2	ROBLEDO⁃ORTIZ J R， ZEPEDA C， GOMEZ C， et al. Non⁃isothermal decomposition kinetics of azodicarbonamide in high density polyethylene using a capillary rheometer［J］. Polymer Testing， 2008， 27（6）： 730⁃735.
3	SIMS G L A， JAAFAR H A S. A chemical blowing agent system （CBAS） based on azodicarbonamide［J］. Journal of Cellular Plastics， 1994， 30（2）： 175⁃188.
4	MARCILLA A， GARCíA⁃QUESADA J C， BELTRAN M I， et al. Study of the formulations and process conditions in the crosslinking of polyethylene foams at atmospheric pressure［J］. Journal of Applied Polymer Science， 2008， 107（3）： 2 028⁃2 037.
5	陈立军，孙曰圣，刘燕燕，等. 偶氮二甲酰胺的改性探讨［J］. 江西化工， 2002（4）： 61⁃65.
	CHEN L J， SUN Y S， LIU Y Y， et al. Discussion on modification of azodicarbonamide ［J］. Jiangxi Chemical Industry， 2002（4）： 61⁃65.
6	周琼，王甲坤，吴俊涛，等. AC发泡剂的分解活化机理及其突发性的表征［J］. 中国塑料， 1999， 13（5）： 78⁃83.
	ZHOU Q， WANG J K， WU J T， et al. Activation mechanism of azodicarbamide and characterization of its burst ［J］. China Plastics， 1999， 13（5）： 78⁃83.
7	上海向阳化工厂. 偶氮二甲酰胺（发泡剂ADC）：［S］. 北京：化工部标准化研究所， 1991.
8	宜宾天原集团股份有限公司. 发泡剂ADC：［S］. 北京：化学工业出版社， 2008.
9	江苏索普（集团）有限公司，江西世龙实业股份有限公司. 发泡剂偶氮二甲酰胺（ADC）：［S］. 北京：化学工业出版社， 2017.
10	黎继群，吴英瑜. ADC发泡剂发气量测定方法的改进［J］. 中国氯碱， 2001 （2）： 33⁃35.
	LI J Q， WU Y Y. Improvement of the determination method about blowing in ADC foaming agent gas volume ［J］. China Chlor⁃Alkali， 2001（2）： 33⁃35.
11	曹沛，梁坤，王雪丽，等. TGA和DSC分析发泡剂对NBR橡胶发泡性能的影响［J］. 弹性体， 2012， 22（1）： 29⁃34.
	CAO P， LIANG K， WANG X L， et al. The effect of foaming agent on the foaming properties of NBR rubber analyzed by TGA and DSC ［J］. China Elastomerics， 2012， 22（1）： 29⁃34.
12	谢志强，黄金明，陈宪宏. 硬质聚氯乙烯用复合发泡剂的研究［J］. 功能材料， 2012， 43（7）： 936⁃939.
	XIE Z Q， HUANG J M， CHEN X H. Study of the composite foaming agent for rigid polyvinyl chloride ［J］. Journal of Functional Materials， 2012， 43（7）： 936⁃939.
13	RYCHLA L， RYCHLY J， SVOBODA J， et al. DSC study of the decomposition of azodicarbonamide in different media.1. decomposition of pure azodicarbonamide ⁃ the search for the kinetic⁃model［J］. Journal of Thermal Analysis and Calorimetry， 1984， 29（1）： 77⁃85.
14	REYES⁃LABARTA J A， MARCILLA A. Differential scanning calorimetry analysis of the thermal treatment of ternary mixtures of ethylene vinyl acetate， polyethylene， and azodicarbonamide［J］. Journal of Applied Polymer Science， 2008， 110（5）： 3 217⁃3 224.
15	张婕，史翎，张军营. 偶氮二甲酰胺热分解机理及氧化锌对其分解的影响［J］. 北京化工大学学报（自然科学版）， 2011， 38（3）： 39⁃43.
	ZHANG J， SHI L， ZHANG J Y. The mechanism of thermal decomposition of azodicarbonamide and the influence of zinc oxide ［J］. Journal of Beijing University of Chemical Technology（Natural Science Edition）， 2011， 38（3）： 39⁃43.
16	REYES⁃LABARTA J A， MARCILLA A. Kinetic study of the decompositions involved in the thermal degradation of commercial azodicarbonamide［J］. Journal of Applied Polymer Science， 2008， 107（1）： 339⁃346.
17	BHATTI A S， DOLLIMORE D， GODDARD R J， et al. The thermal⁃decomposition of azodicarbonamide［J］. Thermochimica Acta， 1984， 76（1/2）： 63⁃77.
18	王晓东，罗李华，俞卫丰. 塑料发泡剂在固定体积密闭容器下发气量的研究［J］. 中国塑料， 2020， 34（1）： 83⁃86.
	WANG X D， LUO L H， YU W F. Research on the Gas Volume of Plastic Foaming Agent in a Fixed Volume Closed Container ［J］. China Plastics， 2020， 34（1）： 83⁃86.
19	桂观群，李文刚. AC发泡剂分解活化机理的红外光谱分析［J］. 塑料科技， 2012， 40（2）： 86⁃88.
	GUI G Q， LI W G. The Activation Mechanism of Foa⁃ming Agent AC during Decomposition by Infrared Spectrum Analysis ［J］. Plastics Science and Technology， 2012， 40（2）： 86⁃88.

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