叔胺铜离子络合物的表征及在铜离子缓释防污涂料中的应用

doi:10.7503/cjcu20170698

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (7): 1602.doi: 10.7503/cjcu20170698

叔胺铜离子络合物的表征及在铜离子缓释防污涂料中的应用

丛非¹, 孙秀花¹(), 王科², 桂泰江², 高昌录¹()

1. 哈尔滨工业大学(威海)海洋科学与技术学院, 威海 264209
2. 海洋化工研究院有限公司海洋涂料国家重点实验室, 青岛 266071

收稿日期:2017-11-06 出版日期:2018-07-10 发布日期:2018-06-13
作者简介:联系人简介: 高昌录, 男, 博士, 教授, 博士生导师, 主要从事防污材料及聚酰亚胺材料研究. E-mail: clgao@hitwh.edu.cn; 孙秀花, 女, 博士, 教授, 主要从事界面材料的防污改性研究. E-mail: sunxh@hitwh.edu.cn
基金资助:
国家自然科学基金(批准号: 51573033, 21405028)、山东省自然科学基金(批准号: ZR2014EMM007)和山东省重点研发计划(批准号: 2017JHZ011)资助.

Characterization of Tertiary Amine-Cu Complex and Application in Copper Ion Slow-release Coatings^†

CONG Fei¹, SUN Xiuhua^1,^*(), WANG Ke², GUI Taijiang², GAO Changlu^1,^*()

1. Harbin Institute of Technology at Weihai, School of Marine Science and Technology, Weihai 264209, China
2. State Key Lab of Marine Coatings, Marine Chemical Research Institute Co., Ltd., Qingdao 266071, China

Received:2017-11-06 Online:2018-07-10 Published:2018-06-13
Contact: SUN Xiuhua,GAO Changlu E-mail:sunxh@hitwh.edu.cn;clgao@hitwh.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51573033, 21405028), the Natural Science Foundation of Shandong Province, China(No.ZR2014EMM007) and the Key Research and Development Plan of Shandong Province, China(No.2017JHZ011).

摘要/Abstract

摘要：

以五水合硫酸铜和甲基丙烯酸N,N-二甲基氨基乙酯为原料得到络合物, 并利用傅里叶红外光谱及核磁共振谱对络合物进行表征. 结果表明, 铜离子与叔胺基发生配位, 测定甲醇溶液中的电导率验证其最大配位数为4. 形成的络合物对金属离子的释放具有缓释作用. 合成了一系列甲基丙烯酸N,N-二甲基氨基乙酯无规共聚物涂料, 结果表明, 加入甲基丙烯酸N,N-二甲基氨基乙酯使涂料具有更好的抗菌性能且有助于延长其防污性能.

关键词: 缓释作用, 铜离子络合物, 防污涂料, 甲基丙烯酸N, N-二甲基氨基乙酯

Abstract:

Controlling the release rate of biocides in antifouling coatings is beneficial to marine environment and economy. One of the promising approaches to achieve the controllable release is to complex the metal ions with polymers. We reported a new type of complex by coordinating copper sulfate(CuSO₄) with N,N-dimethylaminoethyl methacrylate(DMAEMA). The complex was characterized by Fourier transform infrared(FTIR) spectroscopy and nuclear magnetic resonance(NMR) spectroscopy. The results confirmed that the copper ions coordinate to tertiary amino groups of DMAEMA. A maximum coordination number of four was determined by measuring the conductivity of complex via a designed experiment. Conductivity and antimicrobial results revealed that the formation of complex slows the release rate of copper ions. Coatings with different contents of PDMAEMA were prepared, the antibacterial test and field test indicated that higher content of PDMAEMA in a coating demonstrated better antifouling ability.

Key words: Slow-release, Copper ion complex, Antifouling coating, N, N-Dimethylaminoethyl methacrylate

中图分类号:

O632

TrendMD:

丛非, 孙秀花, 王科, 桂泰江, 高昌录. 叔胺铜离子络合物的表征及在铜离子缓释防污涂料中的应用. 高等学校化学学报, 2018, 39(7): 1602.

CONG Fei, SUN Xiuhua, WANG Ke, GUI Taijiang, GAO Changlu. Characterization of Tertiary Amine-Cu Complex and Application in Copper Ion Slow-release Coatings^†. Chem. J. Chinese Universities, 2018, 39(7): 1602.

图/表 14

Table 1 Composition of the solutions in methanol

No.	c(Cu)/(mmol·L^-1)	c(DMAEMA)/(mmol·L^-1)	No.	c(Cu)/(mmol·L^-1)	c(DMAEMA)/(mmol·L^-1)
1	1.00	—	14	1.00	5.00
2	2.00	—	15	1.25	5.00
3	3.00	—	16	1.50	5.00
4	4.00	—	17	1.75	5.00
5	5.00	—	18	2.00	5.00
6	—	1.00	19	2.25	5.00
7	—	2.00	20	2.50	5.00
8	—	3.00	21	2.75	5.00
9	—	4.00	22	3.00	5.00
10	—	5.00	23	3.50	5.00
11	0.25	5.00	24	4.00	5.00
12	0.50	5.00	25	4.50	5.00
13	0.75	5.00	26	5.00	5.00

Table 2 Composition of the coatings

Resin	Molar fraction(%)				M_n	PDI
Resin	AIBN	DMAEMA	TIPSA	MMA	M_n	PDI
PDMAEMA	1	100	0	0	21140	2.54
C0	1	—	30.0	70.0	24350	2.64
C1	1	10.0	10.0	80.0	22750	2.53
C2	1	12.5	7.5	80.0	21630	2.60
C3	1	15.0	5.0	80.0	22010	2.56
C4	1	17.5	2.5	80.0	21200	2.51
C5	1	20.0	—	80.0	20100	2.43

Fig.1 1H NMR spectra of DMAEMA(a) and CuSO4 complex(b)

Fig.2 13C NMR spectra of DMAEMA(a) and CuSO4 complex(b)

Fig.3 FTIR spectra of DMAEMA(a), CuSO4·5H2O(b) and CuSO4 complex(c)

Fig.4 Conductivity of CuSO4·5H2O and DMAEMA in methanol(A) and mixed solutions in methanol(B)^Molar ratio of DMAEMA to CuSO4·5H2O: a. 20∶1; b. 10∶1; c. 6.67∶1; d. 5∶1; e. 4∶1; f. 3.33∶1; g. 2.86∶1; h. 2.5∶1; i. 2.22∶1; j. 2∶1; k. 1.82∶1; l. 1.67∶1; m. 1.43∶1; n. 1.25∶1; o. 1.11∶1; p. 1∶1.

Fig.5 Relation ship between q and molar ratio of DMAEMA to CuSO4·5H2O^Molar ratio of DMAEMA to CuSO4·5H2O: a. 10∶1; b. 6.67∶1; c. 5∶1; d. 4∶1; e. 3.33∶1; f. 2.86∶1; g. 2.5∶1; h. 2.22∶1; i. 2∶1; j. 1.82∶1; k. 1.67∶1; l. 1.43∶1; m. 1.25∶1; n. 1.11∶1; o. 1∶1.

Fig.6 1H NMR spectrum of coating C1 resin

Fig.7 Absorption of CuSO4·5H2O in methanol

Fig.8 Standard curve of CuSO4·5H2O in methanol

Fig.9 Conductivity of water with released CuSO4(a), CuSO4 complex(b) and PDMAEMA(c) in 8 d

Fig.10 Antibacterial property of the sterile nutrient agar plates prepared with PDMAEMA(A), CuSO4 complex(B) and CuSO4 after releasing in water(C) for 8 d

Fig.11 Antibacterial property of coatings with(B0—B5) and without(C0—C5) copper ions in 24 h

Fig.12 Results of field test in 14—84 d at Weihai

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叔胺铜离子络合物的表征及在铜离子缓释防污涂料中的应用

Characterization of Tertiary Amine-Cu Complex and Application in Copper Ion Slow-release Coatings^†

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叔胺铜离子络合物的表征及在铜离子缓释防污涂料中的应用

Characterization of Tertiary Amine-Cu Complex and Application in Copper Ion Slow-release Coatings†

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Characterization of Tertiary Amine-Cu Complex and Application in Copper Ion Slow-release Coatings^†