ZHAO Xin, WANG Liang, GAO Shuzhen, CHI Wenrui

( College of Light Industry and Textile Technology, Qiqihar University, Qiqihar 161006, China )

Synthesis and application of DMDHEU resin modified with glycerol

ZHAO Xin, WANG Liang, GAO Shuzhen, CHI Wenrui

( College of Light Industry and Textile Technology, Qiqihar University, Qiqihar 161006, China )

After DMDHEU resin was synthesized by one-step process, the effects of etherification temperature and glycerol dosage on the properties of the modified DMDHEU resin in weakly acidic conditions were studied. The optimal process was glycerol dosage of 40%, pH 4.0-5.0, reaction at 50 ℃ for 4 h. The result showed that the fabric crease recovery angle was 114.96° and the released formaldehyde was 13.5 mg/kg after modified, meeting the requirements of low formaldehyde resin finishing agent.

glycerol; modified DMDHEU resin; linen fabric; low formaldehyde resin

0 Introduction

Linen fabric has good ability of moisture absorption with neat appearance[1-2]. and natural antibacterial performance which is beneficial to human’s health[3]. However, due to the low elongation at break of pure linen (about 3%), the elastic recovery of pure linen fabric is poor and easily wrinkled[4]. To obtain better linen textile products, anti-crease finishing is necessary for linen textile products[5]. At present, the main kinds of fabric crease resistant finishing agents are N-hydroxymethyl amide resin finishing agent, non-formaldehyde resin finishing agent and reactive cross-linking agent[6]. N-hydroxymethyl amide resin is the dominant crease resistant finishing agent currently, especially the modified DMDHEU resin. It is due to that the textile after the processing by the modified DMDHEU resin has good anti-crease property and low formaldehyde emission during processing and taking process[7]. For example, the formaldehyde emission of the fabric finished by DMDHEU resin modified by methanol, diethylene glycol, ethylene glycol or mixed alcohol were 38.37, 30.96, 33.18, 37.60 mg/kg, respectively.

In order to further produce the resin finishing agent with super low formaldehyde, the DMDHEU resin was modified and its glycerol etherification conditions of were explored.

1 Experiment

1.1 Materials

Desizing linen, homemade, an areal weight of 215 g/m2; 40% glyoxal, 37% formaldehyde, glycerol, magnesium chloride, hydrochloric acid. All of the reagents are analytical reagent.

YG(B)541E intelligent woven fabric crease recovery tester, Wenzhou Darong Textile Instrument Company Limited; 721 spectrophotometer meter, Shandong Gaomi analysis instrument factory; Specdrum100 infrared spectrometer, American PE Company.

1.2 Experimental methods

1.2.1 One-step synthesis of DMDHEU resin

A certain number of glyoxal, formaldehyde and urea were used and pH was adjusted to 6.0-6.5 with 20% sodium carbonate. The urea was added when the temperature increased to 30-40 ℃. When the temperature increased to 50 ℃, the solution was mixed for 1.5 h, then pH was adjusted to 6.0-6.5 with 20% sodium carbonate for 3 h. At the end of the reaction, the temperature was reduced to below 48 ℃, and pH was adjusted to neutral with 20% sodium carbonate.

1.2.2 The process of glycerol modified DMDHEU resin

A certain amount of DMDHEU resin and etherification agent were added into the reaction kettle mixed evenly. pH was adjusted to 4.0-5.0 with glacial acetic acid and the reaction temperature was controlled at 40 to 60 ℃ for 4 h. At the end of the reaction, the temperature was reduced to below 48 ℃, pH was adjusted to 4.4-5.0 with 25% sodium hydroxide.

1.2.3 Crease resistant finishing process

Two dip two rolling (25 ℃, liquid hold up 90%-95%)→dry (80 ℃, 3 min)→cure (160 ℃, 3 min).

Process recipe: resin finishing agent 80 g/L, magnesium chloride 16 g/L, soaking agent (JFC) 2 g/L.

1.3 Properties tests

The content of free formaldehyde in resin was tested according to GB/T 5543—2006. The content of free and hydrolyzed formaldehyde on the fabric was tested according to GB/T 2912.1—2009, and the crease recovery angle was tested according to GB/T 3819—1997.

2 Results and discussion

2.1 The experimental process of glycerol modified DMDHEU resin

According to a large number of related literatures, DMDHEU resin under acidic conditions can be modified by some etherification agent to become lower formaldehyde anti-crease finishing agent. To obtain better performance of the modified DMDHEU resin, the preferable conditions were proposed as follows: the reaction time 4 h, pH 4.0-5.0. The effects of etherification temperature, glycerol content, and different etherifying agent on the properties of the modified DMDHEU resin were studied.

2.2 Effect of temperature on the properties of modified DMDHEU resin

The synthesis conditions were as follows: 40% glycerol (the amount of DMDHEU resin), pH 4.0-5.0, the reaction temperature of 40 to 60 ℃, the reaction time of 4 h. The effect of reaction temperature on the properties of modified DMDHEU resin was shown in Tab. 1.

Tab.1 Effect of temperature on the properties of modified DMDHEU resin

The results in Tab. 1 showed that the fabric released lower formaldehyde, and the crease recovery angle was relatively higher when the temperatures was 50 ℃ after DMDHEU resin modified. If the reaction temperature was too low, the formaldehyde release amount was relatively high, and could not meet the requirements of the resin finishing agent with super low formaldehyde (lower than 20 mg/kg); but if the reaction temperature was too high, the formation of the ether bond would break and the comprehensive performance of the modified resin would decrease[11]. Under comprehensive consideration, the proper temperature of etherification glycerol modified DMDHEU resin was 50 ℃.

2.3 Effect of glycerol content on the properties of modified DMDHEU resin

The synthesis conditions were as follows: pH 4.0-5.0, reaction temperature 50 ℃, the mass fraction of glycerol 20%-45% (the amount of DMDHEU resin), the reaction time 4 h. Effects of glycerol contents on the influence of synthetic properties of modified DMDHEU resin were shown in Tab. 2.

Tab.2 Effects of glycerol contents on the properties of modified DMDHEU resin

The results in Tab. 2 showed that the fabric released less amount of formaldehyde after the DMDHEU resin modified. When the dosage of glycerol was 40%, the fabric formaldehyde released decreased to 13.5 mg/kg and the wrinkle recovery angle reduced to 114.96°, which could meet the standard of resin finished agent with super low formaldehyde (lower than 20 mg/kg). With the increasing of glycerin amount, the change of formaldehyde released amount was not obvious, but the loss of crease resistance was obvious; therefore, in order to ensure the optimal crease resistance and low formaldehyde released amount, the optimal mass fraction of glycerin was 40%[11]. To ensure the anti-crease performance indicators and to meet the requirements of reducing formaldehyde emission, preferably glycerin dosage was 40% (the amount of DMDHEU resin).

2.4 DMDHEU resin and modified DMDHEU resin properties

The one-step synthesis conditions were as follows: the molar ratio of glyoxal, formaldehyde and urea of 0.95∶1.70∶1.00, the reaction pH, temperature, time of 6.0-6.5, 50 ℃, 3 h respectively. The properties of DMDHEU resin were shown in Tab. 3.

Tab.3 Effects of glycerol on the properties of modified DMDHEU resin

The synthesis conditions of modified DMDHEU resin were as follows: pH 4.0-5.0, the reaction temperature 50 ℃, 40% glycerol (the amount of DMDHEU resin), the reaction time 4 h. The effect of glycerol synthesis on properties of modified DMDHEU resin were shown in Tab. 3. The results in Tab. 3 showed that under the optimal conditions, the fabric crease recovery angle and formaldehyde emission reduced to 114.96° and 13.5 mg/kg respectively after modified. Linen fabric released less amount of formaldehyde but the wrinkle recovery angle reduced after modified.

2.5 Characterization of glycerol modified DMDHEU resin

The infrared spectroscopy of the homemade and modified DMDHEU resin was shown in Fig. 1. In Fig. 1, the absorption peaks at 2 963 and 2 885 cm-1were significantly enhanced, because the new methylene formed when the DMDHEU etherified. The C—O absorption peak at 1 050-1 000 cm-1exhibits blue shift, for the bonding between the hydroxyl may be weakened during the etherification. There was a strong stretching vibration peak at 1 270-1 010 cm-1attributed to the C—O—C bond. There was a strong and wide C—O stretching vibration peak at 1 150-1 060 cm-1, attributed to the forming of alkyl ether compounds, which was the only way to identify the feature of ethers. The above results showed that DMDHEU had been etherified.

Fig.1 FT-IR spectra of DMDHEU resin before and after modified

3 Conclusion

One-step synthesis of DMDHEU resin, the released formaldehyde of the fabric was 278 mg/kg after DP. The crease recovery angle, solid content and the content of free formaldehyde were 184.85°, 69.72% and 5.02%, respectively.

The optimal process of glycerol modified DMDHEU resin were as follows: pH 4.0-5.0, reaction temperature 50 ℃, reaction time 4 h, the etherification agent content 40% (the amount of DMDHEU resin). The linen fabric modified by the etherification DMDHEU resin was with the crease recovery angle of 114.96°, the released formaldehyde of 13.5 mg/kg, solid content of 69.89%, and the free formaldehyde content of 0.88%. All the properties of modified DMDHEU resin could meet the requirements of resin finishing agent with super low formaldehyde.

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亞麻用丙三醇改性DMDHEU樹脂的合成與應(yīng)用

趙 欣， 汪 亮， 高 樹 珍， 遲 文 銳

( 齊齊哈爾大學(xué) 輕工與紡織學(xué)院， 黑龍江 齊齊哈爾 161006 )

采用一步法工藝合成DMDHEU樹脂，通過丙三醇對(duì)DMDHEU樹脂進(jìn)行醚化改性，研究在較低酸性條件下，醚化溫度、丙三醇用量對(duì)改性DMDHEU樹脂性能的影響。結(jié)果表明，優(yōu)化改性工藝為pH 4.0～5.0，反應(yīng)溫度50 ℃，反應(yīng)時(shí)間為4 h，醚化劑用量為40%，所得改性DMDHEU樹脂的固含量為60.02%，游離甲醛量為0.59%。亞麻織物經(jīng)改性DMDHEU樹脂整理后的折皺回復(fù)角為114.96°，釋放甲醛量為13.5 mg/kg，滿足低甲醛樹脂整理劑的要求。

丙三醇；改性DMDHEU樹脂；亞麻織物；低甲醛樹脂

TS195.2

A

1674-1404(2017)03-0210-04

by: 2015-10-15.

ZHAO Xin(1963-), Male, Professor, E-mail:zx427213@sina.com.

趙欣,汪亮,高樹珍,遲文銳.亞麻用丙三醇改性DMDHEU樹脂的合成與應(yīng)用(英文)[J].大連工業(yè)大學(xué)學(xué)報(bào),2017,36(3):210-213.

ZHAO Xin, WANG Liang, GAO Shuzhen, CHI Wenrui. Synthesis and application of DMDHEU resin modified with glycerol (In English)[J]. Journal of Dalian Polytechnic University, 2017, 36(3): 210-213.

Supported by: Heilongjiang Provincial Natural Science Foundation(B201112); Heilongjiang Provincial Education Department Revitalize the Northeast Old Industrial Base of Major Scientific and Technological Projects (1152GZB09).