Fluorinated ether polymer, the preparation method therefore and use thereof

Abstract

The embodiments herein relate to a fluorinated ether polymer which is capable of forming coatings with stain resistance, anti-fingerprint and anti-scratching properties. The polymer may be cured with multiple measures, therefore it has a variety of applications in coating and ink industry. The fluorinated ether polymers of the embodiments herein may be added into coating formulations to decrease the surface energy of resulting coatings. It is also feasible that the fluorinated ether polymers of the embodiments herein are used as the main resin component in coating formulations. The embodiments herein also relates to a method for manufacturing the polyester resin, and the use of the polyester resin in industries.

Claims

1. A fluorinated ether polymer comprising one of the following structures (I) to (VIII), ##STR00010## wherein A is a functional group comprising the following structure: ##STR00011## B is a functional group comprising one of the following structures: ##STR00012## n is an integer, on average, ranging from 1 to 50; R.sup.f is a functional group derived from a perfluoropolyether containing a carboxyl group at one end of its molecular chain, a perfluoropolyether containing carboxyl groups at both ends of its molecular chain, a perfluoropolyether containing a hydroxyl group at one end of its molecular chain, or a perfluoropolyether containing hydroxyl groups at both ends of its molecular chain, the average molecular weight of perfluoropolyether being from 500 to 4000.

2. The fluorinated ether polymer of claim 1, wherein n is an integer, on average, ranging from 10 to 30.

3. The fluorinated ether polymer of claim 1, wherein the number average molecular weight of R.sup.f is from 1000 to 3000.

4. The fluorinated ether polymer of claim 1, wherein R.sup.f is derived from F(CFCF.sub.3CF.sub.2O).sub.nCFCF.sub.3COOH, F(CFCF.sub.3CF.sub.2O).sub.nCFCF.sub.3CH.sub.2OH, HO(CH.sub.2CH.sub.2O).sub.mCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.p(CF.sub.2O).sub.qCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.mOH HOCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.p(CF.sub.2O).sub.nCF.sub.2CH.sub.2OH HOOCCF.sub.3FC(CFCF.sub.3CF.sub.2O).sub.nCFCF.sub.3COOH F(CF.sub.2CF.sub.2O).sub.nCFCF.sub.3COOH HOOCCFCF.sub.3(CF.sub.2CF.sub.2O).sub.nCFCF.sub.3COOH F(CF.sub.2CF.sub.2O).sub.nCF.sub.2COOH HOOCCF.sub.2(CF.sub.2CF.sub.2O).sub.nCF.sub.2COOH F(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2O).sub.nCF.sub.2COOH HOOCCF.sub.2(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2O).sub.nCF.sub.2COOH HOOCCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2COOH CF.sub.3O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2COOH HOOC(OCH.sub.2CH.sub.2).sub.nCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.nCOOH CF.sub.3O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.nCOOH F(CFCF.sub.3CF.sub.2O).sub.nCFCF.sub.3CH.sub.2OH HOCH.sub.2CF.sub.3FC(CFCF.sub.3CF.sub.2O).sub.nCFCF.sub.3CH.sub.2OH F(CF.sub.2CF.sub.2O).sub.nCFCF.sub.3CH.sub.2OH HOCH.sub.2CFCF.sub.3(CF.sub.2CF.sub.2O).sub.nCFCF.sub.3CH.sub.2OH F(CF.sub.2CF.sub.2O).sub.nCF.sub.2CH.sub.2OH HOCH.sub.2CF.sub.2(CF.sub.2CF.sub.2O).sub.nCF.sub.2CH.sub.2OH F(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2O).sub.nCF.sub.2CH.sub.2OH HOCH.sub.2CF.sub.2(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2O).sub.nCF.sub.2CH.sub.2OH HOCH.sub.2CH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2CH.sub.2OH CF.sub.3O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2CH.sub.2OH HOCH.sub.2(OCH.sub.2CH.sub.2).sub.nCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.nCH.sub.2OH, or CF.sub.3O(CF.sub.2CF.sub.2O).sub.m(CF.sub.2O).sub.nCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.nCH.sub.2OH wherein m, n, p, q are integers, and on average, independently ranging from 1 to 50.

5. The fluorinated ether polymer of claim 1, wherein the number average molecular weight of the fluorinated ether polymer is from 1000 to 100000.

6. The fluorinated ether polymer of claim 1, wherein the number average molecular weight of the fluorinated ether polymer is from 2000 to 5000.

7. A method for preparing the fluorinated ether polymer of claim 1, comprising: a) mixing a perfluoropolyether containing R.sub.f, monomers that are capable of forming structures A and B according to claim 1, and an inhibitor that stabilizes carbon double bonds; b) heating the mixture to a temperature ranging from 90 to 120° C., and c) maintaining the temperature for 2 to 5 hours.

8. The method of claim 7, wherein the molar ratio of perfluoropolyether containing R.sup.f, monomer that is capable of forming structure A, and monomer that is capable of forming structure B is 1:1-15:1-15.

9. The method of claim 8, wherein the molar ratio of perfluoropolyether containing R.sup.f, monomer that is capable of forming structure A, and monomer that is capable of forming structure B is 1:5-10:5-10.

10. A method of using a fluorinated ether polymer to form a coating onto a substrate, comprising applying and then curing the fluorinated ether polymer on the substrate.

11. A coating composition which contains a fluorinated ether polymer according to claim 1 or prepared by the method of claim 7.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) The above and other objectives, features and advantages of the embodiments herein will become more apparent to those of ordinary skill in the art by describing the embodiments thereof with reference to the accompanying drawings.

(2) FIG. 1 shows the GPC spectrum of obtained fluorinated polymers, wherein sample 1 and sample 2 are marked as lines (1) and (2), respectively;

(3) FIG. 2 shows FtIR of R.sup.f for comparison and sample 3, marked as lines (1) and (2), respectively;

(4) FIG. 3 shows FtIR of R.sup.f for comparison and sample 4, marked as lines (1) and (2), respectively;

(5) FIGS. 4a and 4b show NMR of sample 5 and sample 6, respectively;

(6) FIGS. 5a and 5b show stain repellence performance of coatings with and without fluorinated resin, respectively.

EXAMPLES

(7) The embodiments herein will be elucidated with reference to the following examples.

(8) Raw Material

(9) Perfluoropolyether (PFPE), glycidyl methacrylate (GMA), glycidyl acrylate (GA), phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride (THPA) and malic anhydride (MAH). PFPE with a carboxyl group at one end of its molecular chain is available from Chemours. PFPE with a hydroxyl group at one end of its molecular chain is available from Sinochem. PFPE with hydroxyl groups at both ends of its molecular chain is available from Solvay. The others are commonly available chemicals. Analytical grade or industrial grade chemicals can be used as materials according to the embodiments herein. Methyl isobutyl ketone (MIBK) is used as solvent.

Example 1

(10) 45.4 g R.sup.f with carboxyl group at one end of its molecular chain was mixed with 22.4 g PA, 32.2 g GMA, 60 g MIBK and 0.1% BHT in a 250 ml reactor and heated up to 100° C. within 60 minutes with stirring. The whole system was kept at 100° C. till the acid value of the resultant product decreased down to 10. The system was then cooled down to room temperature and diluted to an application solid content of 40 wt. % with solvent MIBK. The obtained fluorinated polymer is sample 1.

(11) Gel permeation chromatography (GPC) of the prepared fluorinated polymer was measured with a commercially available measuring apparatus named Agilent 1200. The fluorinated polymer was diluted in tetrahydrofuran (THF) solvent to 0.1 wt. % and passed through 0.5 μm filter. The molecular weight of the fluorinated polymer was measured accordingly.

(12) The GPC spectrum of sample 1 is shown as line (1) in FIG. 1.

Example 2

(13) 69.8 g R.sup.f with hydroxyl group at one end of its molecular chain was mixed with 10.3 g PA, 19.8 g GMA, 60 g MIBK and 0.1% BHT in a 250 ml reactor and heated up to 100° C. within 60 minutes with stirring. The whole system was kept at 100° C. till the acid value of the resultant product decreased down to 8. The system was then cooled down to room temperature and diluted to an application solid content of 40 wt. % with solvent MIBK. The obtained fluorinated polymer is sample 2.

(14) Gel permeation chromatography (GPC) of the prepared fluorinated polymer was measured with the same apparatus and method as described in example 1.

(15) The GPC spectrum of sample 2 is shown as line (2) in FIG. 1.

Example 3

(16) 16.2 g R.sup.f with carboxyl group at one end of its molecular chain was mixed with 41.6 g HHPA, 42.2 g GMA, 80 g MIBK and 0.1% BHT in a 250 ml reactor and heated up to 100° C. within 60 minutes with stirring. The whole system was kept at 100° C. till the acid value of the resultant product decreased down to 10. The system was then cooled down to room temperature and diluted to an application solid content of 35 wt. % with solvent MIBK. The obtained fluorinated polymer is sample 3.

(17) FtIR spectra of the prepared fluorinated polymer was obtained at a resolution of 4 cm.sup.−1 using a PerkinElmer Spectrum 100 FTIR Spectrometer with ATR sampling accessory. The wave-number range was set from 4000 to 450 cm.sup.−1. 32 scans were averaged to reduce noise.

(18) The FtIR spectrum of sample 3 is shown in FIG. 2, together with the spectrum of R.sup.f as a standard curve for comparison. It can be seen that most of the characteristic peaks from 1500 to 500 cm.sup.−1 are significantly overlapping between the curves of sample 3 and R.sup.f.

Example 4

(19) 25.3 g R.sup.f with hydroxyl group on both ends of its molecular chain was mixed with 38.9 g HHPA, 35.92 g GMA, 70 g MIBK and 0.1% BHT in a 250 ml reactor and heated up to 100° C. within 60 minutes with stirring. The whole system was kept at this temperature till the acid value of the resultant product decreased down to 10. The system was then cooled down to room temperature and diluted to an application solid content of 35 wt. % with solvent MIBK. The obtained fluorinated polymer is sample 4.

(20) FtIR spectra of the prepared fluorinated polymer was obtained using the same apparatus and method as described in example 3.

(21) The FtIR spectrum of sample 4 is shown in FIG. 3, together with the spectrum of R.sup.f as a standard curve for comparison. It can be seen that most of the characteristic peaks from 1500 to 500 cm.sup.−1 are significantly overlapping between the curves of sample 4 and R.sup.f.

Example 5

(22) 58.1 g R.sup.f with carboxyl group at one end of its molecular chain was mixed with 17.1 g MAH, 24.8 g GMA, 60 g MIBK and 0.1% BHT in a 250 ml reactor and heated up to 100° C. within 60 minutes with stirring. The whole system was kept at this temperature till the acid value of the resultant product decreased down to 20. The system was then cooled down to room temperature and diluted to an application solid content of 40 wt. % with solvent MIBK. The obtained fluorinated polymer is sample 5.

(23) The sample was dissolved in a mixture solvent of CDCl.sub.3 and DMSO, and measured with Nuclear Magnetic Resonance (NMR) spectroscopy. The NMR data was obtained in a 400 MHz NMR system using a 5 mm probe at room temperature. The sample was measured by means of 1D (1H, 13C) and 2D (COSY, HMQC) experiment.

(24) The NMR spectrum of sample 5 is shown in FIG. 4a. The intrinsic spectrum indicates that the synthesis of the resin was successful.

Example 6

(25) 53.4 g R.sup.f with carboxyl group on both ends of its molecular chain was mixed with 16.2 g THPA, 30.3 g GMA, 70 g MIBK and 0.1% BHT in a 250 ml reactor and heated up to 100° C. within 60 minutes with stirring. The whole system was kept at this temperature till the acid value of the resultant product decreased down to 10. The system was then cooled down to room temperature and diluted to an application solid content of 40 wt. % with solvent MIBK. The obtained fluorinated polymer is sample 6.

(26) NMR data of the sample was obtained with the same apparatus and method as described in example 5.

(27) The NMR spectrum of sample 6 is shown in FIG. 4b. The intrinsic spectrum indicates that the synthesis of the resin was successful.

Example 7—Formation of Hard Coatings

(28) In this example, fluorinated polymers according to the embodiments herein were cured by its own, and mixed with other resins, to form a hard coating film.

(29) The fluorinated polymer according to example 1 was applied onto a PC/ABS substrate, cured singly by being subject to a temperature above 150° C., and to ultraviolet light exposure, respectively. Clear coats were formed on the substrates accordingly.

Example 8—Liquid Contact Angle Test

(30) Liquid contact angle tests were conducted for the fluorinated polymers of the embodiments herein. The water and oil contact angles of coating film surface were measured with a commercially available apparatus named Dataphysics OCA20/6.

(31) Two samples of hard coating-forming polymers were prepared for comparison. One was a common UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD), and the other one was a mixture of the common UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD) and 1 wt. % of the fluorinated polymer of example 1. Both of the samples were applied onto PC/ABS substrates and cured by exposure to ultraviolet light.

(32) Water contact angle was measured on top of the cured hard coatings, respectively, with Sessile drop method. The droplets were set as 3 μl/droplet, and the measurement temperature was about 20° C. The test results are shown in the table 1 below.

(33) Oil contact angle tests were conducted similarly with the same method. The droplets were set as 2 μl/droplet, and the measurement temperature was about 20° C. The test results are shown in the table 1 below as well.

(34) TABLE-US-00001 TABLE 1 The liquid contact angle of cured samples Resin Water contact angle Hexadecane contact angle UV resin 64.4° <10°   UV resin + 1 wt % 111.1° 71.1° fluorinated resin

Example 9—Oil-Based Ink Repellence Test

(35) Oil-based ink repellence tests were conducted for the fluorinated polymers of the embodiments herein.

(36) Two samples of hard coating-forming polymers were prepared for comparison. One was common UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD), and the other one was a mixture of UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD) and 1 wt. % of the fluorinated polymer of example 1. Both of the samples were applied onto PC/ABS substrates and cured by exposure to ultraviolet light.

(37) Pens with different colors of oil-based inks were used to write and draw on top of the cured hard coatings, respectively. Pictures were taken to show the different appearance of the inks wrote onto the hard coatings, see FIGS. 5a and 5b. It was seen that the inks wrote on the hard coating of the common UV resin were well spread and shown as regular lines, and that the inks wrote on the hard coating of the mixture of UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD) and 1 wt. % of the fluorinated polymer were barely spread, while instead, shrank into small liquid beads, indicating that the latter coating surface has strong repellence to the oil-based inks. The oil-based inks wrote on the hard coating formed with the mixture of UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD) and 1 wt. % of the fluorinated polymer were easily wiped off, with substantially no stain remains (not shown in the picture).