新型三聚氰胺-尿素-甲醛树脂的制备*—用高浓度甲醛和大豆蛋白降解液制备MUF

doi:10.11901/1005.3093.2015.148

材料研究学报

2015, Vol. 29

Issue (11): 814-820 DOI: 10.11901/1005.3093.2015.148

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新型三聚氰胺-尿素-甲醛树脂的制备*—用高浓度甲醛和大豆蛋白降解液制备MUF

吴志刚^1,²,席雪冬²,曹明³,王辉²,雷洪²,张本刚²,杜官本²(

)

1. 北京林业大学材料科学与技术学院北京 100083
2. 西南林业大学云南省木材胶黏剂及胶合制品重点实验室昆明 650224
3. 南京林业大学材料科学与工程学院南京 210037

Synthesis of a New Melamine-urea-formaldehyde Resin —Preparation of MUF with Degradated Liquid of Soy-Protein and Concentrated Formaldehyde

Zhigang WU^1,²,Xuedong XI²,Ming CAO³,Hui WANG²,Hong LEI²,Bengang ZHANG²,Guanben DU^2,^**(

)

1. College of Matericals Science and Technology, Beijing Forestry University, Beijing 650224, China
2. Wood Adhesives and Glued Products Key Laboratory of Yunnan Province, Southwest Forestry University, Kunming 650224, China
3. College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China

引用本文:

吴志刚,席雪冬,曹明,王辉,雷洪,张本刚,杜官本. 新型三聚氰胺-尿素-甲醛树脂的制备*—用高浓度甲醛和大豆蛋白降解液制备MUF[J]. 材料研究学报, 2015, 29(11): 814-820.
Zhigang WU, Xuedong XI, Ming CAO, Hui WANG, Hong LEI, Bengang ZHANG, Guanben DU. Synthesis of a New Melamine-urea-formaldehyde Resin —Preparation of MUF with Degradated Liquid of Soy-Protein and Concentrated Formaldehyde[J]. Chinese Journal of Materials Research, 2015, 29(11): 814-820.

全文: PDF(1322 KB) HTML

摘要:

以三聚氰胺、高浓度甲醛、尿素和大豆蛋白(SPI)降解液为原料, 合成了三聚氰胺-尿素-甲醛树脂(MUF)。对比改性后MUF的性能, 并借助核磁共振(¹³C-NMR)、红外光谱(FT-IR)和动态热机械性能(DMA)分析了改性后MUF的结构变化和热机械性能。结果表明, 用高浓度甲醛合成的MUF游离甲醛降低了52%, 制备的刨花板内结合强度和静曲强度分别提高了25%和64%。用高浓度甲醛和SPI降解液合成的MUF游离甲醛降低了56%, 制备的刨花板内结合强度和静曲强度分别提高了48%和97%。FT-IR分析结果表明, 蛋白质降解液与MUF树脂发生了交联反应。¹³C-NMR和DMA测试结果表明, 用高浓度甲醛制备的MUF树脂亚甲基醚键含量较高, 树脂体系缩聚度高, 树脂具有很高的初始强度, 但是热稳定性较差。用高浓度甲醛和SPI降解液制备的MUF树脂, 树脂体系具有较高的缩聚度, 亚甲基桥键含量明显升高, 能部分抵消醚键在高温下断裂重排带来的不稳定性, 使树脂具有较高的热机械性能、热稳定性和较低的游离甲醛。

关键词 ：有机高分子材料, 三聚氰胺-尿素-甲醛树脂, 高浓度甲醛, 大豆蛋白, 结构特征, 热性能

Abstract：

A new melamine-urea-formaldehyde (MUF) resin was prepared with concentrated formaldehyde and degradated liquid of soy-protein as raw materials . The molecular structure and thermal mechanical properties of MUF resin were characterized by ¹³C-NMR, FT-IR and DMA. The prepared MUF resins were used as bonding material to fabricate particleboards and then their bonding strength and modulus of rupture(MOR)as well as free formaldehyde content were also examined. The results show that with the MUF resin synthesized merely with concentrated formaldehyde (hereinafter named MUF resin-F), the bonding strength and MOR of the fabricated particleboard increased by 25% and 64%, and the free formaldehyde content decreased by 52%; however, with the MUF resin synthesized jointly with concentrated formaldehyde and degradated liquid of soy-protein (herinafter named MUF resin-FP), the bonding strength and MOR of the fabricated particleboard increased by 48% and 97% respectively, and the free formaldehyde content decreased by 56%. The FT-IR results indicated that the degradated liquid of soy-protein did react with MUF. ¹³C-NMR and DMA results indicated that the MUF resin-F has high amount of ether bond and high condensation degree, high initial strength and low thermal stability; in the contrast, the MUF resin-FP has high condensation degree and high amount of methylene bridge bond, which can offset the instability induced by the fracture and rearrangement of ether bonds. In sum, the newly synthesized MUF resin-FP possesses good thermal mechanical properties, high strength and low free formaldehyde content.

Key words： organic polymer materials MUF high concentration formaldehyde soy-protein structure characteristics thermal mechanical properties

收稿日期: 2015-03-22

基金资助:* “十二五”国家科技支撑计划2012BAD24B03; 云南省教育厅项目2004Y318; 林业公益性行业科研专项201304505资助。

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https://www.cjmr.org/CN/10.11901/1005.3093.2015.148 或 https://www.cjmr.org/CN/Y2015/V29/I11/814

表1 三聚氰胺-尿素-甲醛树脂的性能

图1 MUF0 13C-NMR谱图

图2 HMUF0 13C-NMR谱图

表2 三聚氰胺-尿素-甲醛树脂13C-NMR主要谱峰归属和定量分析结果

图3 S2HMUF 13C-NMR 谱图

图4 胶黏剂的红外谱图

图5 胶黏剂的DMA曲线

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