Please wait a minute...
材料研究学报  2021, Vol. 35 Issue (9): 651-656    DOI: 10.11901/1005.3093.2020.420
  研究论文 本期目录 | 过刊浏览 |
有机硅油改性水性酚醛的制备及其性能
鄢俊1,2, 杨进1,2(), 王涛1,2, 徐桂龙1,2, 李朝晖3
1.华南理工大学轻工科学与工程学院 制浆造纸国家重点实验室 广州 510640
2.华南理工大学 造纸与污染控制国家工程研究中心 广州 510640
3.南方海洋科学与工程广东省实验室(珠海) 珠海 519082
Preparation and Properties of Aqueous Phenolic Resin Modified by Organosilicone Oil
YAN Jun1,2, YANG Jin1,2(), WANG Tao1,2, XU Guilong1,2, LI Zhaohui3
1.School of Light Industry and Engineer, State Key Lab of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
2.National Engineering Research Center of Papermaking and Pollution Control, South China University of Technology, Guangzhou 510640, China
3.Guangdong Laboratory of South Ocean Science and Engineering (Zhuhai), Zhuhai 519082, China
引用本文:

鄢俊, 杨进, 王涛, 徐桂龙, 李朝晖. 有机硅油改性水性酚醛的制备及其性能[J]. 材料研究学报, 2021, 35(9): 651-656.
Jun YAN, Jin YANG, Tao WANG, Guilong XU, Zhaohui LI. Preparation and Properties of Aqueous Phenolic Resin Modified by Organosilicone Oil[J]. Chinese Journal of Materials Research, 2021, 35(9): 651-656.

全文: PDF(1456 KB)   HTML
摘要: 

以烯丙基聚氧化乙烯醚(PEO)和烯丙基缩水甘油醚(AGE)为原料,进行硅氢加成反应对有机硅油进行接枝改性,使其在水中具有分散性并引入了具有反应活性的环氧基团。使用红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征其结构,用示差扫描量热分析(DSC)和热重分析(TGA)表征改性硅油与水性酚醛树脂共混的稳定性和耐热性能。将有机硅改性酚醛树脂应用于机油滤纸,用扫描电镜(SEM)分析其微观形貌并探究其力学性能、耐油和耐高温性能。结果表明,PEO与AGE的摩尔比为3:1时共接枝有机硅在水中具有良好的分散性能,以5%的质量比与水性酚醛树脂共混复配后形成三维网络结构,具有良好的共混稳定性。通过浸渍增强的机油滤纸,其力学性能均有较大的提高。经过高温机油浸泡后的滤纸保持较高的力学性能,其挺度保持率、耐破度保持率和抗张强度保持率分别为55%、63%和87%。

关键词 有机高分子材料机油滤纸硅氢加成接枝改性酚醛有机硅油共混    
Abstract

Silicone oil was grafted and modified with allyl polyoxyethylene ether (PEO) and allyl glycidyl ether (AGE) via hydrosilylation reactions to enhance the dispersibility in water of the silicone oil, while proper amount of reactive epoxy groups were introduced in order to prepare aqueous phenolic resin. The structures, as well as the stability and heat resistance of the blends of modified silicone oil and aqueous phenolic resin were characterized by FT-IR, 1H-NMR, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) respectively. In addition, silicone-modified phenolic resin was applied to oil filter paper, of which the micro-morphology, mechanical properties, oil resistance and high temperature resistance were examined. The results show that after being co-grafted with PEO and AGE (3:1 in molar ratio) the silicone has good dispersibility in water, and then, the bland complex of aqueous phenolic resin with 5% (mass fraction) of the co-grafted silicone can forms a three-dimensional network structure with good stability. After being reinforced through impregnation of the above bland complex, the oil filter paper presents greatly enhanced mechanical properties. What is more, the reinforced oil filter paper shows high retention rate of mechanical properties even after soaking in high temperature oil, namely, retention rate of 55%, 63%, and 87% for stiffness, burst strength and tensile strength respectively.

Key wordsorganic polymer materials    oil filter paper    hydrosilylation    graft modification    phenolic    silicone oil    blending
收稿日期: 2020-10-10     
ZTFLH:  TB332  
基金资助:广东省自然资源厅广东省海洋经济发展(海洋六大产业)专项资金(粤自然资合2021-33)
作者简介: 鄢俊,男,1995年生,硕士生
图1  有机硅油的硅氢加成反应
图2  g-PHMS的核磁共振氢谱图

PEO / AGE

(mol ratio)

1∶12∶12.5∶13∶14∶1
12 hWater solubilitySedimentLayeredLayeredMiscibleMiscible
Centrifugal stabilitySedimentSedimentEmulsionMiscibleMiscible
72 hWater solubilitySedimentLayeredLayeredMiscibleMiscible
Centrifugal stabilitySedimentSedimentEmulsionMiscibleMiscible
表1  g-PHMS的稳定性
g-PHMS/PF (mass ratio)5%10%15%
0 hTransparentTransparentTurbid liquid
12 hTransparentTransparentMore precipitation
48 hTransparentLess precipitationMore precipitation
表2  PF/g-PHMS的稳定性
图3  PF、g-PHMS及PF/g-PHMS的红外光谱
图4  PF、g-PHMS以及PF/g-PHMS的DSC谱
图5  酚醛及共混树脂的TGA曲线
图6  机油滤纸的SEM照片

Bending stiffness

/mN

Bursting strength

/kPa

Tensile strength

/kN·m-2

Elongation at break/%
Original filter paper70.00103.001.001.51
PF-enhanced filter paper189.10322.005.743.36
PF/g-PHMS-enhanced filter paper250.33389.007.354.17
表3  机油滤纸的力学性能
Bending stiffnessBursting strengthTensile strength
PF-enhanced filter paper52%58%80%
PF/g-PHMS-enhanced filter paper55%63%87%
表4  机油滤纸的耐油性能
1 Aziz T, Fan H, Khan F U, et al. Modified silicone oil types, mechanical properties and applications [J]. Polym. Bull., 2019, 76: 2129
2 Ge T J, Hu X Q, Tang K H, et al. The preparation and properties of Terephthalyl-alcohol-modified phenolic foam with high heat aging resistance [J]. Polymers, 2019, 11(8): 1267
3 Choi J, Hui C M, Schmitt M, et al. Effect of polymer-graft modification on the order formation in particle assembly structures [J]. Langmuir, 2013, 29: 6452
4 Galhenage T P, Hoffman D, Silbert S D, et al. Fouling-release performance of silicone oil-modified siloxane-polyurethane coatings [J]. ACS Appl. Mater. Interfaces, 2016, 8: 29025
5 Yong Q W, Nian F W, Liao B, et al. Synthesis and surface analysis of self-matt coating based on waterborne polyurethane resin and study on the matt mechanism [J]. Polym. Bull., 2016, 74: 1061
6 Xu C S, Ouyang L, Liu H Y, et al. Synthesis of blocking polyether silicone oil and silicone blocking waterborne polyurethane and application to cashmere knitted fabric finishing [J]. Text. Res. J., 2015, 85: 2040
7 Chen H R, Shen Y F, Lin H M, et al. Synthesis of modified silicone with long chain acylate [J]. J. Zhejiang Inst. Sci. Technol., 2009, 26: 211
7 陈洪瑞, 沈一峰, 林鹤鸣等. 长链烷基酯改性硅油的合成研究 [J]. 浙江理工大学学报, 2009, 26: 211
8 Pan C Q, Zheng X W, Li D G, et al. Study on synthesis of polyether modified polysiloxane [J]. China Elastom., 2012, 22(4): 37
8 潘朝群, 郑先伟, 李德贵等. 聚醚改性硅油的合成研究 [J]. 弹性体, 2012, 22(4): 37
9 Gao M, Wu W H, Wang Y H, et al. Phenolic foam modified with dicyandiamide as toughening agent [J]. J. Therm. Anal. Calorim., 2016, 124: 189
10 Jalil S N A, Wang D K, Yacou C, et al. Vacuum-assisted tailoring of pore structures of phenolic resin derived carbon membranes [J]. J. Membr. Sci., 2017, 525: 240
11 Ren P L, Yang J, Fu Y Y, et al. Preparation of modified silicone oil and its application in oil filter paper reinforced with phenolic resin [J]. J. Jinan Univ. (Nat. Sci. Med. Ed.), 2017, 38: 457
11 任盼玲, 杨进, 付艳艳等. 改性硅油的制备及其在酚醛增强机油滤纸中的应用 [J]. 暨南大学学报(自然科学与医学版), 2017, 38: 457
12 Hong H Y, Yang J, Deng J H, et al. Preparation of silicone modified styrene-acrylate emulsion and application of enhanced air filter paper [J]. Polym. Mater. Sci. Eng., 2019, 35(6): 130
12 洪浩源, 杨进, 邓钧豪等. 有机硅改性苯丙乳液的制备及增强空滤纸的应用 [J]. 高分子材料科学与工程, 2019, 35(6): 130
13 Eren M, Akbulut G, Senler S, et al. Synthesis of core–shell-type styrene acrylic latexes with low NMA content and their application in pigment printing pastes [J]. J. Coat. Technol. Res., 2018, 15: 121
14 Wu S Z, Zeng F, Li F X. Synthesis and characterization of electro-optic polysiloxane [J]. Chin. J. Mater. Res., 2001, 15: 257
14 吴水珠, 曾钫, 李凤仙. 电光型有机硅聚合物的合成与表征 [J]. 材料研究学报, 2001, 15: 257
15 Barde M, Celikbag Y, Via B, et al. Semi-interpenetrating novolac-epoxy thermoset polymer networks derived from plant biomass [J]. J. Renew. Mater., 2018, 6: 724
16 Sangthumchai T, Kamjornsupamitr T, Saengsaen S, et al. Composite polymer electrolyte membranes from semi-interpenetrating networks of poly(vinyl alcohol) and silica nanoparticles containing poly(2-acrylamido-2-methyl-1-propanesulfonic acid) [J]. Polymer, 2020, 207: 122910
17 Fu Y Y, Yang J, Ren P L, et al. Preparation of modified phenolic resin and its application in oil filter paper [J]. Paper Sci. Technol., 2017, 36(3): 45
17 付艳艳, 杨进, 任盼玲等. 改性硅氧烷增韧酚醛树脂的制备及其在机油滤纸中的应用 [J]. 造纸科学与技术, 2017, 36(3): 45
18 Xiao J J, Qiu Z M, Yang W R, et al. Organosilicone modification of allyl methacrylate with speier's catalyst for waterborne self-matting styrene-acrylic emulsion [J]. Prog. Org. Coat., 2018, 116: 1
[1] 叶姣凤, 王飞, 左洋, 张钧翔, 罗晓晓, 冯利邦. 兼具高强度、高韧性和自修复性能的环氧树脂改性热可逆聚氨酯[J]. 材料研究学报, 2023, 37(4): 257-263.
[2] 李瀚楼, 焦晓光, 朱欢欢, 赵晓欢, 矫庆泽, 冯彩虹, 赵芸. 支链含氟聚酯的合成和性能[J]. 材料研究学报, 2023, 37(4): 315-320.
[3] 马逸舟, 赵秋莹, 杨路, 裘进浩. 热塑型聚酰亚胺/聚偏氟乙烯全有机复合薄膜的制备及其介电储能[J]. 材料研究学报, 2023, 37(2): 89-94.
[4] 殷洁, 胡云涛, 刘慧, 杨逸霏, 王艺峰. 基于电沉积技术构建聚苯胺/海藻酸膜及电化学性能研究[J]. 材料研究学报, 2022, 36(4): 314-320.
[5] 申延龙, 李北罡. 磁性氨基酸功能化海藻酸铝凝胶聚合物的制备及对偶氮染料的超强吸附[J]. 材料研究学报, 2022, 36(3): 220-230.
[6] 龙庆, 王传洋. 不同碳黑含量PMMA的热降解行为和动力学分析[J]. 材料研究学报, 2022, 36(11): 837-844.
[7] 蒋平, 吴丽华, 吕太勇, José Pérez-Rigueiro, 王安萍. 蜘蛛大壶状腺丝的反复拉伸力学行为和性能[J]. 材料研究学报, 2022, 36(10): 747-759.
[8] 张昊, 李帆, 常娜, 王海涛, 程博闻, 王攀磊. 羧酸型接枝淀粉吸附树脂的制备和对染料的去除性能[J]. 材料研究学报, 2021, 35(6): 419-432.
[9] 孙丽颖, 钱建华, 赵永芳. AgNWs-TPU/PVDF柔性薄膜电容传感器的制备和性能[J]. 材料研究学报, 2021, 35(6): 441-448.
[10] 唐开元, 黄洋, 黄湘舟, 葛颖, 李娉婷, 袁凡舒, 张威威, 孙东平. 碳化细菌纤维素的理化性质及其在甲醇电催化中的应用[J]. 材料研究学报, 2021, 35(4): 259-270.
[11] 苏晨文, 张婷玥, 郭丽伟, 李乐, 杨苹, 刘艳秋. 用于模拟细胞外基质的硫醇-烯水凝胶的制备[J]. 材料研究学报, 2021, 35(12): 903-910.
[12] 张向阳, 章奇羊, 汤涛, 郑涛, 柳浩, 刘国金, 朱海霖, 朱海峰. 基于MOFs的复合材料制备及其对亚甲基蓝染料的吸附性能[J]. 材料研究学报, 2021, 35(11): 866-872.
[13] 万里鹰, 肖洋, 张伦亮. 基于热可逆Diels-Alder动态共价键PU-DA体系的制备和性能[J]. 材料研究学报, 2021, 35(10): 752-760.
[14] 张翠歌, 胡良, 卢祖新, 周佳慧. 基于海藻酸自组装胶体粒子的制备及其乳化性能[J]. 材料研究学报, 2021, 35(10): 761-768.
[15] 黄健, 林春香, 陈瑞英, 熊万永, 温小乐, 罗鑫. 离子液体辅助纳米纤维素吸附剂的制备及其吸附性能[J]. 材料研究学报, 2020, 34(9): 674-682.