Synthesis and Coating Properties of Carboxylated Fluorinated Poly（arylene ether）s

doi:10.7503/cjcu20210604

Abstract

Abstract:

In order to improve the adhesion of aromatic fluorocarbon coatings， tetraallyl biphenyl diphenol（TABP）， bisphenol A and decafluorobiphenyl were used as starting materials to prepare fluorinated poly（arylene ether）s（FPAEs） through room temperature polycondensation. After that， 3-mercaptopropionic acid was grafted to achieve carboxylated fluorinated poly（arylene ether）s（CFPAEs）. The carboxyl content of the products was adjusted by changing the loading amount of TABP. The CFPAE coatings were prepared by spraying the polymer solutions in 1-methyl-2-pyrrolidinone（NMP） onto tinplate. It has been found that the CFPAE coatings have excellent thermal stability and mechanical strength. The introduction of carboxyl groups could significantly improve the adhesion of the fluorocarbon coating. When the carboxyl content is 0.265 mmol/g， the adhesion level of the coating is 0， the pencil hardness is 6H， the minimum shaft rod diameter without coating damage is 0.5 mm， and the water contact angle is 103.9°. In addition， the CFPAE coatings also have excellent acid resistance， salt resistance， anti-ultraviolet aging and anti-corrosion properties. Therefore， the carboxylation is an effective way to expand the application of fluorinated poly（arylene ether）s to aromatic fluorocarbon coatings.

Key words: Fluorocarbon coating, Fluorinated poly（arylene ether）s, Carboxylation, Spraying, Adhesion force

CLC Number:

O631

TrendMD:

ZHANG Wenmeng, LI Mengqin, HOU Zhen, CHEN Dongyang. Synthesis and Coating Properties of Carboxylated Fluorinated Poly（arylene ether）s[J]. Chem. J. Chinese Universities, 2022, 43(2): 20210604.

Figures/Tables 16

Scheme 1 Synthesis of FPAEs and CFPAEs

Fig.1 1H NMR(A) and 19F NMR(B) spectra of CFPAE?10 and FPAE?10

Fig.2 FTIR spectra of FPAE?0, FPAE?10 and CFPAE?10

Fig.3 Digital photos of CFPAE?5 film(A) and CFPAE coatings(B)

Table 1 Carboxyl content and grafting ratio of CFPAEs

Sample	Theoretical carboxyl content/（mmol·g^-1）	Titrated carboxyl content/（mmol·g^-1）	Grafting ratio（%）
CFPAE?1	0.076	0.069	90.79
CFPAE?2	0.150	0.136	90.66
CFPAE?3	0.223	0.203	91.03
CFPAE?4	0.294	0.265	90.14
CFPAE?5	0.364	0.331	90.93
CFPAE?10	0.694	0.634	91.35

Fig.4 DSC curves of FEPAs(A) and TGA curves of FPAEs and CFPAEs(B)

Table 2 Basic properties of CFPAE coatings

Sample	Thickness/ $μ$ m	Crosshatch adhesion level	Hardness/H	Minimum shaft rod diameter/mm	Maximum falling height of heavy hammer/cm	Gloss/（°）	Contact angle/（°）
CFPAE?1	43	2	6	0.5	80	56.3	113.6
CFPAE?2	44	1	6	0.5	70	57.4	110.6
CFPAE?3	44	0	6	0.5	60	61.6	107.3
CFPAE?4	43	0	6	0.5	50	65.5	103.9
CFPAE?5	45	0	6	0.5	40	70.9	100.1
CFPAE?10	46	0	6	0.5	20	75.8	96.7

Table 2 Basic properties of CFPAE coatings

Sample	Thickness/ $μ$ m	Crosshatch adhesion level	Hardness/H	Minimum shaft rod diameter/mm	Maximum falling height of heavy hammer/cm	Gloss/（°）	Contact angle/（°）
CFPAE?1	43	2	6	0.5	80	56.3	113.6
CFPAE?2	44	1	6	0.5	70	57.4	110.6
CFPAE?3	44	0	6	0.5	60	61.6	107.3
CFPAE?4	43	0	6	0.5	50	65.5	103.9
CFPAE?5	45	0	6	0.5	40	70.9	100.1
CFPAE?10	46	0	6	0.5	20	75.8	96.7

Fig.5 Digital photos of water droplets on the surface of CFPAE?1(A), CFPAE?2(B), CFPAE?3(C), CFPAE?4(D), CFPAE?5(E) and CFPAE?10(F)

Table 3 Chemical resistance properties of CFPAE coatings

Sample	Time to get rust/h		Time to form bubble in 5% H₂SO₄solution/h	Severity of bubble formation after 3 d in 5% NaOH solution
Sample	In H₂O	In 3.5% NaCl solution	Time to form bubble in 5% H₂SO₄solution/h	Severity of bubble formation after 3 d in 5% NaOH solution
Tinplate	12	1	1	None
CFPAE?1	120	7	6	Slight
CFPAE?2	480	22	8	Slight
CFPAE?3	528	36	10	Middle
CFPAE?4	576	40	16	Middle
CFPAE?5	432	32	14	Middle
CFPAE?10	288	24	8	Severe

Fig.6 Surface SEM images of the bare tinplate(A1—E1, A2—E2) and CFPAE?4 coated tinplate(A3—E3, A4—E4) before(A1—A4) and after(B1—E1, B2—E2, B3—E3, B4—E4) immersed in different solutions with different time(B1—B4) H2O, 30 d; (C1—C4) 3.5% NaCl solution, 3d; (D1—D4) 5% H2SO4, 36 h; (E1—E4) 5% NaOH solution, 3 d.

Fig.7 Relationship between artificial UV?light aging gloss retention rate of CFPAE coatings and aging time

Fig.8 FTIR spectra of CFPAE?10 before and after UV?light aging for 720 h

Fig.9 Digital photos of CFPAE?4 coating before(A) and after UV?light aging(B) and SEM image of CFPAE?4 coating after UV?light aging(C)

Table 4 Properties of CFPAE coatings after 720 h of UV?light aging

Sample	Crosshatch adhesion	Hardness/H	Minimum shaft rod diameter/ mm	Gloss/（°）	Water contact angle（°）
CFPAE?1	1	6	0.5	37.5	80.52
CFPAE?2	0	6	0.5	36.0	77.90
CFPAE?3	0	6	0.5	35.6	74.22
CFPAE?4	0	6	0.5	35.5	71.77
CFPAE?5	0	6	0.5	34.5	69.70
CFPAE?10	0	6	0.5	32.8	65.85

Fig.10 Tafel curves of uncoated and CFPAE coated tinplates

Table 5 Ecorr, Icorr and Ic of tinplate and CFPAE coated tinplates

Sample	E_corr/V	I_corr/（A·cm^-2）	I_c/（mm·year^-1）	Sample	E_corr/V	I_corr/（A·cm^-2）	I_c/（mm·year^-1）
Tinplate	-0.677	1.804×10^-5	2.111×10^-1	CFPAE?4	-0.416	5.177×10^-8	9.163×10^-4
CFPAE?1	-0.360	3.788×10^-8	6.705×10^-4	CFPAE?5	-0.428	5.319×10^-8	9.415×10^-4
CFPAE?2	-0.402	1.873×10^-8	3.315×10^-4	CFPAE?10	-0.486	1.877×10^-7	3.322×10^-3
CFPAE?3	-0.401	4.891×10^-8	8.657×10^-4

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