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

doi:10.7503/cjcu20170698

Abstract

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

CLC Number:

O632

TrendMD:

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

Figures/Tables 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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