低醛三聚氰胺树脂湿强剂的研究
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摘要
随着科学技术的突飞猛进以及生活水平的不断提高,人们对居住环境品质的要求越来越高。采用不同的浸渍纸和不同的垫板贴面,木质地板可产生逼真的纹理效果和柔和的光麻面,受到家具行业及室内装饰业的普遍认可和广泛应用。其中以三聚氰胺甲醛树脂浸渍纸饰面的木质地板发展最为迅速,已成为我国木地板市场中份额最大的主力产品。但其存在着弹性差、固含量低、贮存稳定性差等缺点,特别是游离甲醛含量高限制了它的发展。因此研究低醛三聚氰胺树脂,同时改善树脂的性能,具有重要的经济价值和环保意义。
通过对MF树脂外观、反应时间、固含量、游离甲醛含量、储存稳定性及其浸渍纸力学性能的测定,探讨了三聚氰胺甲醛湿强剂的较佳合成工艺,并使用现代仪器分析技术对产物进行了分析。
研究结果表明：
(1)确定较佳合成工艺为：n(甲醛)：n(三聚氰胺)=2.5：1,n(乙二醇)：n(三聚氰胺)=2.0：1,以三乙醇胺为催化剂,pH=8～9,反应温度为80～90℃,采用三次加三聚氰胺的方法(50%-40%-10%),反应终点控制在水数为2-3。
(2)己内酰胺与H2O2配合作为甲醛吸收剂,比单一的甲醛吸收剂更能有效降低树脂中游离甲醛含量,同时提高树脂储存稳定性和浸渍纸力学性能。
(3)FTIR证实了MF树脂中乙二醇单体单元的存在,实验成功制的了乙二醇增韧MF树脂。通过对固化前后树脂的FTIR研究证明了三聚氰胺树脂的固化是通过亚甲基或者二亚甲基醚键相互交联实现的。
(4)DSC研究表明乙二醇的加入使得MF树脂固化温度升高,而己内酰胺与H2O2改性MF树脂则使固化温度降低,避免了因固化温度过高导致树脂降解,影响树脂性能。
With the rapid progress of science and technology and the continuous improvement of living standards,people have a higher requirement about the quality of their living conditions.Using different impregnated paper and veneers plate,can produce realistic texture and soft smooth pockmarked face,the laminate floor generally recognized and widely used by the furniture industry and interior decoration industry, one of which is the laminate floor covering decorated with melamine-formaldehyde resin impregnated paper,which has developed fastest and become the main product of Chinese wooding floor market.But it has many shortcomings,such as poor flexibility,low solid content and poor storage stability,especially the high content of free formaldehyde limit its development.Therefore,the study of low formaldehyde resins,while improving the performance of resin,has important economic value and environmental significance.
By the determination of the appearance,reaction time,solid content,free formaldehyde content,storage stability and mechanical properties of impregnated paper of MF resins,We explore the better synthesis process of melamine-formaldehyde wet strength agent and use modern instrumental to analysis the products.
The main results are shown as follows:
(l)The better reaction conditions of solution polymerization are described as below: n(formaldehyde):n(melarnine)=2.5:1,n(ethylene glycol):n(melamine)=2.0:1,triethanolamine as the catalyst,pH=8-9,the reaction temperature is 80～90℃, melamine using three feeding method (50%-40%-10%),the Water dilution of reaction end point should be controlled in 2～3.
(2)Compared with the single formaldehyde absorber,caprolactam collaboration with H2O2 as formaldehyde absorbent,can reduce the free formaldehyde content of MF resins more effectively,while increasing the storage stability and impregnated paper mechanical properties.
(3)FTIR indicates the exist of the ethylene glycol monomer in the MF resins.Ethylene glycol toughened MF resin is successfully prepared. By the FTIR study of cured and uncured MF resins,proved that the melamine resin curing by methylene or dimethylene cross-linked with each other in the form of ether bond.
(4)DSC study shows the addition of ethylene glycol makes the curing temperature of MF resins rise, but MF resin modified with caprolactam and H2O2 has a lower curing temperature.Successfully avoided the degradation and decreased in performance of MF resins because of high temperature.
通过对MF树脂外观、反应时间、固含量、游离甲醛含量、储存稳定性及其浸渍纸力学性能的测定,探讨了三聚氰胺甲醛湿强剂的较佳合成工艺,并使用现代仪器分析技术对产物进行了分析。
研究结果表明：
(1)确定较佳合成工艺为：n(甲醛)：n(三聚氰胺)=2.5：1,n(乙二醇)：n(三聚氰胺)=2.0：1,以三乙醇胺为催化剂,pH=8～9,反应温度为80～90℃,采用三次加三聚氰胺的方法(50%-40%-10%),反应终点控制在水数为2-3。
(2)己内酰胺与H2O2配合作为甲醛吸收剂,比单一的甲醛吸收剂更能有效降低树脂中游离甲醛含量,同时提高树脂储存稳定性和浸渍纸力学性能。
(3)FTIR证实了MF树脂中乙二醇单体单元的存在,实验成功制的了乙二醇增韧MF树脂。通过对固化前后树脂的FTIR研究证明了三聚氰胺树脂的固化是通过亚甲基或者二亚甲基醚键相互交联实现的。
(4)DSC研究表明乙二醇的加入使得MF树脂固化温度升高,而己内酰胺与H2O2改性MF树脂则使固化温度降低,避免了因固化温度过高导致树脂降解,影响树脂性能。
With the rapid progress of science and technology and the continuous improvement of living standards,people have a higher requirement about the quality of their living conditions.Using different impregnated paper and veneers plate,can produce realistic texture and soft smooth pockmarked face,the laminate floor generally recognized and widely used by the furniture industry and interior decoration industry, one of which is the laminate floor covering decorated with melamine-formaldehyde resin impregnated paper,which has developed fastest and become the main product of Chinese wooding floor market.But it has many shortcomings,such as poor flexibility,low solid content and poor storage stability,especially the high content of free formaldehyde limit its development.Therefore,the study of low formaldehyde resins,while improving the performance of resin,has important economic value and environmental significance.
By the determination of the appearance,reaction time,solid content,free formaldehyde content,storage stability and mechanical properties of impregnated paper of MF resins,We explore the better synthesis process of melamine-formaldehyde wet strength agent and use modern instrumental to analysis the products.
The main results are shown as follows:
(l)The better reaction conditions of solution polymerization are described as below: n(formaldehyde):n(melarnine)=2.5:1,n(ethylene glycol):n(melamine)=2.0:1,triethanolamine as the catalyst,pH=8-9,the reaction temperature is 80～90℃, melamine using three feeding method (50%-40%-10%),the Water dilution of reaction end point should be controlled in 2～3.
(2)Compared with the single formaldehyde absorber,caprolactam collaboration with H2O2 as formaldehyde absorbent,can reduce the free formaldehyde content of MF resins more effectively,while increasing the storage stability and impregnated paper mechanical properties.
(3)FTIR indicates the exist of the ethylene glycol monomer in the MF resins.Ethylene glycol toughened MF resin is successfully prepared. By the FTIR study of cured and uncured MF resins,proved that the melamine resin curing by methylene or dimethylene cross-linked with each other in the form of ether bond.
(4)DSC study shows the addition of ethylene glycol makes the curing temperature of MF resins rise, but MF resin modified with caprolactam and H2O2 has a lower curing temperature.Successfully avoided the degradation and decreased in performance of MF resins because of high temperature.
引文
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