十三氟辛醇接枝改性三聚氰胺树脂的合成及其疏水性能

doi:10.3969/j.issn.1001-1803.2022.05.006

日用化学工业 ›› 2022, Vol. 52 ›› Issue (5): 499-505.doi: 10.3969/j.issn.1001-1803.2022.05.006

十三氟辛醇接枝改性三聚氰胺树脂的合成及其疏水性能

高于洋¹,刘绍英²,王庆印²,王公应^2,^3,^*()

1.中国核动力研究设计院反应堆燃料及材料重点实验室,四川成都 610213
2.中国科学院成都有机化学研究所,四川成都 610041
3.中国科学院大学挥发性有机物污染控制材料与技术国家工程实验室,北京 101408

收稿日期:2022-01-07 修回日期:2022-04-26 出版日期:2022-05-22 发布日期:2022-05-24
通讯作者: 王公应
基金资助:
四川省重点研发项目(2020YFG0159)

Preparation and hydrophobic properties of melamine-formaldehyde resin grafted by 1H,1H,2H,2H-Perfluoro-1-octanol

Gao Yuyang¹,Liu Shaoying²,Wang Qingyin²,Wang Gongying^2,^3,^*()

1. Science and Technology on Reactor Fuel and Materials Laboratory, Nuclear Power Institute of China, Chengdu, Sichuan 610213, China
2. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041, China
3. National Engineering Laboratory for VOCs Pollution Control Material & Technology, University of Chinese Academy of Sciences, Beijing 101408, China

Received:2022-01-07 Revised:2022-04-26 Online:2022-05-22 Published:2022-05-24
Contact: Gongying Wang

摘要/Abstract

摘要：

以1H,1H,2H,2H-十三氟-1-辛醇（PF-OH）为改性剂,三聚氰胺和多聚甲醛为原料,二甲基乙酰胺为反应介质,合成了一系列PF-OH接枝改性三聚氰胺树脂（MF-F）。FT-IR和固体¹³C NMR结果表明PF-OH与三聚氰胺树脂（MF树脂）成功接枝。采用XPS、接触角测定仪和TG对材料进行测定,结果表明：PF-OH的接枝提升MF-F材料的疏水性能,氟元素向材料的表面迁移并发生富集;当PF-OH的摩尔分数为3.0%（以三聚氰胺物质的量计）,其水接触角由67.83°增至103.50°,表面自由能由44.5 mN/m降至21.1 mN/m。PF-OH的引入提高MF-F材料的热稳定性,其T_{d, 5%}（失重5%温度）、T_{d, 80%}（失重80%温度）和790 ℃时的残留率均提高。

关键词: 三聚氰胺甲醛树脂, 接枝, 十三氟辛醇, 疏水性能, 表面富集

Abstract:

An anhydrous method was developed for the polymerization of 1H,1H,2H,2H-Perfluoro-1-octanol （PF-OH） grafted melamine-formaldehyde （MF-F） resin aiming at improving the hydrophobic performance of MF material and widening its downstream application. The MF-F resins were characterized by FT-IR and solid state ¹³C NMR, and it is found that PF-OH is grafted in MF resin matrix. From the results of XPS, the migration and enrichment of the fluorine moieties toward the surface of the MF-F film are verified. The hydrophobicity and thermal stability of MF-F materials were investigated by contact angle and TG analysis. Due to the grafting of PF-OH, the water contact angles of MF-F films increase from 67.83° to 103.50° and the surface free energy reduce from 44.5 to 21.1 mN/m. Furthermore, the TG results show that MF-F materials still exhibit excellent thermal stabilities.

Key words: melamine-formaldehyde, graft, 1H,1H,2H,2H-Perfluoro-1-octanol, hydrophobicity, surface enrichment

中图分类号:

TQ322.4

高于洋,刘绍英,王庆印,王公应. 十三氟辛醇接枝改性三聚氰胺树脂的合成及其疏水性能[J]. 日用化学工业, 2022, 52(5): 499-505.

Gao Yuyang,Liu Shaoying,Wang Qingyin,Wang Gongying. Preparation and hydrophobic properties of melamine-formaldehyde resin grafted by 1H,1H,2H,2H-Perfluoro-1-octanol[J]. China Surfactant Detergent & Cosmetics, 2022, 52(5): 499-505.

图/表 12

图1

表1

表2

图2

图3

图4

图5

表3

图6

图7

图8

表4

参考文献 22

[1]	Fink J K. Chapter 6-melamine resins, in reactive polymers fundamentals and applications (Second Edition)[M]. Oxford: William Andrew Publishing, 2013: 193-201.
[2]	Magina S, Ferra J, Cruz P, et al. Fluorinated polyhedral oligomeric silsesquioxane nanoparticles to boost the dirt repellence of high pressure laminates[J]. Chemical Engineering Journal, 2016, 301: 362-370. doi: 10.1016/j.cej.2016.05.028
[3]	Sha Min, Zhang Ding, Pan Renming, et al. Synthesis and surface properties study of novel fluorine-containing homopolymer and copolymers for coating applications[J]. Applied Surface Science, 2015, 349: 496-502. doi: 10.1016/j.apsusc.2015.04.219
[4]	Xiong Mian. Six fluorine butanol modified melamine formaldehyde resin[D]. Zhengzhou: Zhengzhou University, 2014.
[5]	Chang Jinxin, Feng Yuzhi, Tang Xudong. Preparation and properties of fluorine trimethylol melamine resin[J]. Paint & Coatings Industry, 2017, 47 (1): 12-15, 21.
[6]	Badila M, Kohlmayr M, Zikulnig-Rusch E M, et al. Improving the cleanability of melamine-formaldehyde-based decorative laminates[J]. Journal of Applied Polymer Science, 2014, 131 (21): 40964-40972.
[7]	Owens D K, Wendt R C. Estimation of the surface free energy of polymers[J]. Journal of Applied Polymer Science, 1969, 13 (8): 1741-1747. doi: 10.1002/app.1969.070130815
[8]	Berrueco C, Alvarez P, Venditti S, et al. Sample contamination with NMP-oxidation products and byproduct-free NMP removal from sample solutions[J]. Energy & Fuels, 2009, 23 (3): 3008-3015. doi: 10.1021/ef900036m
[9]	Henriques A, Paiva N, Bastos M, et al. Improvement of storage stability and physicochemical properties by addition of benzoguanamine in melamine-formaldehyde resin synthesis[J]. Journal of Applied Polymer Science, 2017, 134 (32): 45185-45195. doi: 10.1002/app.45185
[10]	Ajinkya S, Siddhesh M, Deepak P, et al. Synthesis of melamine formaldehyde cured castor oil based hydroxyl functional alkyd for coating application[J]. Progress in Organic Coatings, 2019, 131: 165-175. doi: 10.1016/j.porgcoat.2019.01.044
[11]	Zhou Yingsong, Yu Junrong, Shen Yan, et al. Structure and properties of benzoguanamine modified melamine formaldehyde/polyvinyl alcohol fibers[J]. Polymer Materials Science and Engneering, 2017, 33 (2): 50-55.
[12]	Zhu Chunfang, Yang Haitao, Liang Hongbo, et al. A novel synthetic UV-curable fluorinated siloxane resin for low surface energy coating[J]. Polymers, 2018, 10 (9): 979-992. doi: 10.3390/polym10090979
[13]	Gottlieb H E, Kotlyar V, Nudelman A. NMR chemical shifts of common laboratory solvents as trace impurities[J]. The Journal of Organic Chemistry, 1997, 62 (21): 7512-7515. doi: 10.1021/jo971176v
[14]	Urdl K, Weiss S, Karpa A, et al. Furan-functionalised melamine-formaldehyde particles performing Diels-Alder reactions[J]. European Polymer Journal, 2018, 108: 225-234. doi: 10.1016/j.eurpolymj.2018.08.023
[15]	Weiss S, Urdl K, Hermann A M, et al. IR spectroscopy: suitable method for determination of curing degree and crosslinking type in melamine-formaldehyde resins[J]. Journal of Applied Polymer Science, 2019, 136 (25): 47691-47700. doi: 10.1002/app.47691
[16]	Hyeon-Deuk H, Hyun-Joong K. UV-curable low surface energy fluorinated polycarbonate-based polyurethane dispersion[J]. Journal of Colloid and Interface Science, 2011, 362 (2): 274-284. doi: 10.1016/j.jcis.2011.06.044 pmid: 21788027
[17]	Coullerez G, Léonard D, Lundmark S, et al. XPS and ToF-SIMS study of freeze-dried and thermally cured melamine-formaldehyde resins of different molar ratios[J]. Surface and Interface Analysis, 2000, 29 (7): 431-443. doi: 10.1002/1096-9918(200007)29:7<431::AID-SIA886>3.0.CO;2-1
[18]	Deryło-Marczewska A, Goworek J, Pikus S, et al. Characterization of melamine-formaldehyde resins by XPS, SAXS, and Sorption Techniques[J]. Langmuir, 2002, 18 (20): 7538-7543. doi: 10.1021/la0202172
[19]	Xiong Jinsu, Xia Lei, Shentu Baoqing, et al. Synthesis of fluoroalkyl-modified polyester and its application in improving the hydrophobicity and oleophobicity of cured polyester coatings[J]. Journal of Applied Polymer Science, 2014, 131 (2): 39812-39820.
[20]	Merline D J, Vukusic S, Abdala A A. Melamine formaldehyde: curing studies and reaction mechanism[J]. Polymer Journal, 2013, 45 (4): 413-419. doi: 10.1038/pj.2012.162
[21]	Devallencourt C, Saiter J M, Fafet A, et al. Thermogravimetry/Fourier transform infrared coupling investigations to study the thermal stability of melamine formaldehyde resin[J]. Thermochimica Acta, 1995, 259 (1): 143-151. doi: 10.1016/0040-6031(95)02262-Z
[22]	Dong Yueben, Pei Kemei. Study on properties of hydroxy-terminated polydimethylsilane modified with melamine-formaldehyde[J]. Journal of Zhejiang Sci-Tech University, 2019, 41 (4): 532-536.

溶剂	固含量/%	黏度/（mPa·s）	外观	储存期/天
DMF	60.31	2 517.6	白色粘稠液体（有分层）	>30
DMAc	60.59	3 602.8	白色粘稠液体	>30
DMSO	60.98	5 780.2	白色粘稠液体（有分层）	>21
NMP	60.77	15 624.0	白色粘稠液体	>14

样品	固含量/%	黏度/（mPa·s）	储存期/天
MF	58.5	3 868	>14
MF-F-1	61.0	3 401	>45
MF-F-2	63.0	3 023	>45
MF-F-3	67.7	2 901	>45
MF-F-4^①	59.6	2 850	>30
MF-F-5^①	58.9	2 801	>30

样品	元素含量/%				n（F）:n（C）	n（F）:n（C） ^②
样品	C	N	O	F	n（F）:n（C）	n（F）:n（C） ^②
MF	50.14	38.39	11.48	—	—	—
MF-F-1	47.74	34.33	11.62	6.31	0.13:1	0.02:1
MF-F-2	45.33	32.17	10.63	11.87	0.26:1	0.04:1
MF-F-3	43.22	22.25	10.85	23.68	0.55:1	0.06:1

样品	特定失重温度/℃			790 ℃时残留率/%
样品	T_{d, 5%}	T_dmax	T_{d, 80%}	790 ℃时残留率/%
MF	277.8	370.7	658.7	10.4
MF-F-1	269.7	366.5	675.3	12.4
MF-F-2	283.8	370.6	741.8	16.9
MF-F-3	278.5	374.7	766.5	18.9

十三氟辛醇接枝改性三聚氰胺树脂的合成及其疏水性能

Preparation and hydrophobic properties of melamine-formaldehyde resin grafted by 1H,1H,2H,2H-Perfluoro-1-octanol

RichHTML

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 22

相关文章 6

Metrics

本文评价

推荐阅读 10

[1]	周春晓,张天春,李铁军,邢铁玲,陈国强. 基于漆酶催化的没食子酸酯接枝真丝疏水改性[J]. 日用化学工业, 2022, 52(8): 827-832.
[2]	黄旭娟,王婷,丁正青,杨欣欣,蔡照胜,商士斌. 脱氢枞氧基聚氧乙烯缩水甘油醚接枝羟乙基壳聚糖制备及其表面活性[J]. 日用化学工业, 2022, 52(6): 594-600.
[3]	冯美西, 颜慧琼, 陈秀琼, 林良泉, 杨正, 林强. 苄基接枝海藻酸衍生物对TiO₂纳米粒分散稳定性的影响[J]. 日用化学工业, 2018, 48(6): 341-347.
[4]	任冬寅, 尚志新, 王启宝. 壳聚糖的接枝改性及其CO₂/N₂响应乳化性能研究[J]. 日用化学工业, 2018, 48(5): 260-265.
[5]	李韶隆, 曹光群, 杨成, 孙培冬. 烷基改性有机硅弹性体凝胶的合成及表征[J]. 日用化学工业, 2014, 44(6): 324-327.
[6]	程春风, 李嘉诚, 颜慧琼, 刘若林, 王春修, 林强. 海藻酸衍生物活化二氧化硅纳米粒制备Pickering乳液[J]. 日用化学工业, 2014, 44(5): 241-246.