Organic silicon modified perfluoropolyether UV anti-fingerprint agent and preparation method thereof

Abstract

The invention provides an organic silicon modified perfluoropolyether UV anti-fingerprint agent and a preparation method thereof. The method comprises the following steps: adding organic silicon modified perfluoropolyether into a fluorocarbon solvent, and adding an alcohol compound containing a propenyl terminal group and a catalyst for reaction to obtain a hydroxyl-containing organic silicon modified perfluoropolyether solution; the preparation method comprises the following steps: adding an acid-binding agent into a hydroxyl-containing organosilicon modified perfluoropolyether solution, and slowly dropwise adding acryloyloxy chloride for reaction to obtain a crude product; and adding an organic alcohol compound into the crude product for treatment, carrying out liquid separation and standing, taking out subnatant, and carrying out rotary evaporation to obtain the organic silicon modified perfluoropolyether UV anti-fingerprint agent. According to the method disclosed by the invention, the problem of compatibility of the perfluoropolyether-based anti-fingerprint agent and the UV coating is solved under the condition of reducing the fluorocarbon solvent through chemical synthesis. In the curing process, the perfluoropolyether-based anti-fingerprint agent part is quickly migrated to the surface of the UV coating, and in-situ curing and crosslinking are achieved.

Description

Technical Field

[0001] The invention relates to an organosilicon-modified perfluoropolyether UV anti-fingerprint agent and a preparation method thereof, and belongs to the field of coatings. Background Art

[0002] As perfluoropolyether (PFPE) anti-fingerprint oil is widely used in mobile phone screens, car screens, tablet screens, high-end lenses, glasses, etc., PFPE-based modified materials have become standard products in the electronics and coatings industries. The UV anti-fingerprint agent products currently on the market are a type of PFPE modifier containing acrylate groups, which are mainly used to improve the hydrophobicity and oleophobicity, anti-graffiti and anti-fingerprint effects of photocurable coatings. They are widely used in electronic packaging, ink printing, plastic coatings, metal surface coatings, flexible electronic skin and other fields. Such as Japan's Shin-Etsu KY-1203 and Italy's Solvay Fluorolink AD1700. Among them, KY-1203 contains silane segments on the molecular chain, which increases the flexibility of the molecular chain and improves the compatibility with UV resin. During the curing process, the molecular chain easily migrates to the surface of the UV resin for co-curing. Its friction resistance and anti-graffiti properties are better than current similar products, but the price is very expensive.

[0003] EP 4063406A1 discloses a method for preparing perfluoropolyether silane acrylate, but the synthesis process of the preparation method requires 5 steps, the reaction route is long, especially during the reaction process, acid and water need to be added, which easily makes siloxane self-crosslinked, resulting in low yield. The technical solution disclosed in CN 112574390A uses K-type perfluoropolyether alcohol and terminal hydroxyl silicone oil as raw materials, and isophorone diisocyanate as a bridging agent. This method leads to unclear product structure and affects the stability of product performance. The technical solution disclosed in CN 109679483A directly uses Y-type perfluoropolyether acrylate and other acrylate monomers for free radical polymerization as a perfluoropolyether modification auxiliary agent, but there is no acrylate group in the substance and it cannot be photocured with UV coating. Summary of the invention

[0004] In order to solve the above technical problems, the purpose of the present invention is to provide a silicone-modified perfluoropolyether UV anti-graffiti agent, which solves the compatibility problem with UV coatings while reducing or eliminating the use of fluorocarbon solvents, and does not affect the friction resistance and anti-graffiti properties of the final coating.

[0005] To achieve the above object, the present invention provides a method for preparing a silicone-modified perfluoropolyether UV anti-fingerprint agent, which comprises the following steps:

[0006] (a) adding an organosilicon-modified perfluoropolyether to a fluorocarbon solvent, and then adding an alcohol compound containing a terminal propylene group and a catalyst to react to obtain a hydroxyl-containing organosilicon-modified perfluoropolyether solution; wherein the molar ratio of the alcohol compound containing a terminal propylene group to the organosilicon-modified perfluoropolyether is 1.8-3:1;

[0007] (b) first adding an acid binding agent to the hydroxyl-containing organosilicon-modified perfluoropolyether solution obtained in step (a), and then slowly adding acryloyloxy chloride dropwise to react to obtain a crude product; wherein the molar ratio of the acid binding agent to the organosilicon-modified perfluoropolyether is 6-10:1, and the molar ratio of the acryloyloxy chloride to the organosilicon-modified perfluoropolyether is 6-12:1;

[0008] (c) adding an organic alcohol compound to the crude product of step (b) for treatment, separating the liquids and allowing them to stand, taking out the lower layer of liquid, and performing rotary evaporation to obtain the organosilicon-modified perfluoropolyether UV anti-fingerprint agent.

[0009] In the above preparation method, preferably, the structure of the organosilicon-modified perfluoropolyether is R f -bR;

[0010] Among them, R f R is polysiloxane.

[0011] In the above preparation method, preferably, the perfluoropolyether includes one or a combination of two or more of K-type perfluoropolyether, D-type perfluoropolyether, Y-type perfluoropolyether and Z-type perfluoropolyether. More preferably, the perfluoropolyether includes one or a combination of two or more of double-ended Z-type perfluoropolyether allyl ether, double-ended K-type perfluoropolyether allyl ether, double-ended Z-type perfluoropolyether acrylate, double-ended Z-type perfluoropolyether methacrylate, double-ended K-type perfluoropolyether acrylate, double-ended K-type perfluoropolyether methacrylate, double-ended D-type perfluoropolyether acrylate, and double-ended D-type perfluoropolyether methacrylate.

[0012] In the above preparation method, preferably, the polysiloxane comprises one or a combination of hydrogen-containing silicone oil and mercapto-containing silicone oil;

[0013] The hydrogen-containing silicone oil includes one or a combination of two or more of single-ended silicon hydrogen silicone oil, double-ended silicon hydrogen silicone oil, and side silicon hydrogen silicone oil;

[0014] The mercapto-containing silicone oil includes one or a combination of terminal mercapto silicone oil and pendant mercapto silicone oil.

[0015] In the above preparation method, preferably, the organosilicon-modified perfluoropolyether is:

[0016]

[0017] The molecular weight is 5100-30000.

[0018] In the above preparation method, preferably, the fluorocarbon solvent includes one or a combination of two or more of nonafluorobutyl ethyl ether, nonafluorobutyl methyl ether, trifluorotoluene, 1,3-di(trifluoromethyl)benzene, perfluorocyclic ether, and perfluorohexane.

[0019] In the above preparation method, preferably, the catalyst includes one or a combination of two or more of Custer's catalyst, Speier's catalyst, benzoyl peroxide, di-tert-butyl peroxide, and Pt / C.

[0020] In the above preparation method, preferably, the amount of the catalyst used is 0.01%-10% of the total mass of the reactants in step (a).

[0021] In the above preparation method, preferably, the alcohol compound containing a terminal propenyl group includes one or a combination of two or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate, pentaerythritol allyl ether, pentaerythritol dipropyl ether, 2,2-bis(hydroxymethyl)-1,3-propylene glycol allyl ether and trimethylolpropane allyl ether.

[0022] In the above preparation method, preferably, the reaction temperature in step (a) is 40-200° C., and the reaction time is 0.5-72 h.

[0023] In the above preparation method, preferably, the acid binding agent includes one or a combination of two or more of triethylamine, tripropylamine, tributylamine, pyridine, N,N-diisopropylethylamine, 4-methylimidazole, potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide.

[0024] In the above preparation method, preferably, the acryloyl chloride is methacryloyl chloride or acryloyl chloride.

[0025] In the above preparation method, preferably, the reaction temperature in step (b) is 0-90° C., and the reaction time is 0.3-24 h.

[0026] In the above preparation method, preferably, the organic alcohol compound includes one or a combination of two or more of methanol, ethanol, isopropanol, n-butanol, isobutanol and isopentanol.

[0027] The present invention also provides an organosilicon-modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the above-mentioned preparation method.

[0028] The preparation method of the organosilicon-modified perfluoropolyether UV anti-fingerprint agent provided by the present invention does not require a fluorocarbon solvent to dissolve the product obtained by chemical synthesis, while similar products on the market currently require a fluorocarbon solvent to dissolve. The present invention thus achieves the solution to the compatibility problem of the perfluoropolyether-based anti-fingerprint agent and the UV coating under the condition of reducing or not using a fluorocarbon solvent. At the same time, the present invention also achieves that during the curing process, the perfluoropolyether-based anti-fingerprint agent partially migrates to the surface of the UV coating and is cured and cross-linked in situ. Moreover, the preparation method is simple, highly operable, the perfluoropolyether-based anti-fingerprint agent has a clear structure, and the product yield is high, and it has immeasurable economic value in UV coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the infrared spectrum of double-terminal silicon hydrogen perfluoropolyether-b-polysiloxane.

[0030] Figure 2 This is the infrared spectrum of terminal hydroxyl silicone modified perfluoropolyether.

[0031] Figure 3 This is the infrared spectrum of terminal methacrylate silicone modified perfluoropolyether UV anti-fingerprint agent A.

[0032] Figure 4 This is the infrared spectrum of the terminal methacrylate silicone modified perfluoropolyether UV anti-fingerprint agent F. DETAILED DESCRIPTION

[0033] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0034] Raw materials of the embodiment:

[0035] Double-terminated silicon hydrogen perfluoropolyether-b-polysiloxane (models FES-1, FES-2 and FES-3): industrial grade, PetroChina (Shanghai) New Materials Research Institute Co., Ltd. The structural formula of FES is as follows, and the infrared spectrum is as follows Figure 1 As shown:

[0036]

[0037] m-Ditrifluorotoluene, methacryloyl chloride, acryloyl chloride, methacryloyloxypropyldimethylmethoxysilane, 2,2-bis(hydroxymethyl)-1,3-propylene glycol allyl ether, trimethylolpropane allyl ether, triethylamine, Custer's catalyst, tris(pentafluorophenyl)borane, methyl isoamyl ketone: reagent grade, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0038] Analysis and evaluation method: Refer to the international test standard GB / T 24368-2009 to test the water contact angle.

[0039] Wear resistance test: The polycarbonate sheet coated with UV coating and cured was fixed on the wear resistance tester (ZJ-339-GSR, Shenzhen Zhijia Instrument Equipment Co., Ltd.), with a contact head area of ​​2×2cm 2 , tie 0000# steel wool on the contact head friction probe; apply 1000g test load above the probe, test speed 40 times / min, stroke 3-4cm, reciprocating friction 3000 times.

[0040] Example 1

[0041] This embodiment provides a methacrylate-terminated silicone-modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the following steps:

[0042] 100 g of bifunctional silane-hydrogen perfluoropolyether-b-polysiloxane (FES-1, molecular weight of about 6800, HNMR test, PFPE segment is Z-type PFPE, molecular weight of about 1700, FNMR test), 20 mL of m-ditrifluorotoluene, 9 g of 2,2-bis(hydroxymethyl)-1,3-propylene glycol allyl ether and 20 μL of Custer catalyst (Pt, 300 ppm) were added into a three-necked flask and reacted at 85° C. for 7 h to obtain a crude product of hydroxyl-terminated organosilicon-modified perfluoropolyether, the infrared spectrum of which is shown in FIG. Figure 2 shown.

[0043]

[0044] Then cool to room temperature, add 10.8g triethylamine, and then drop 14.3g methacryloyl chloride; after the dropwise addition, heat to 40°C and stir for 5h; then cool to room temperature, add 30mL methanol, stir rapidly for 5min, stand to separate the upper liquid, and continue to wash the lower liquid with methanol repeatedly for 3 times; finally, reduce the pressure of the lower liquid to remove the solvent, and then dilute the product with methyl isoamyl ketone (MIBK) to a mass fraction of 30%, to obtain a terminal methacrylate organosilicon modified perfluoropolyether UV anti-fingerprint agent A, the infrared spectrum is as follows Figure 3 shown.

[0045]

[0046] Example 2

[0047] This embodiment provides a terminal acrylate silicone modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the following steps:

[0048] 100 g FES-1, 20 mL m-ditrifluorotoluene, 9 g 2,2-bis(hydroxymethyl)-1,3-propylene glycol allyl ether and 20 μL of Custer catalyst (Pt, 300 ppm) were added into a three-necked flask and reacted at 85° C. for 7 h;

[0049] Then cool to room temperature, add 10.8g triethylamine, and then drop 12.4g acryloyl chloride; after the dropwise addition, heat to 40°C and stir for 5h; then cool to room temperature, add 30mL methanol, stir rapidly for 5min, stand to separate the upper layer liquid, and continue to wash the lower layer liquid repeatedly with methanol for 3 times; finally, reduce the pressure of the lower layer liquid to remove the solvent, and then dilute the product with methyl isoamyl ketone (MIBK) to a mass fraction of 30%, to obtain the terminal acrylate organosilicon modified perfluoropolyether UV anti-fingerprint agent B, the infrared spectrum is as follows Figure 4 shown.

[0050]

[0051] Example 3

[0052] This embodiment provides a methacrylate-terminated silicone-modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the following steps:

[0053] 60 g FES-1, 15 mL m-ditrifluorotoluene, 3.6 g trimethylolpropane allyl ether and 20 μL Custer catalyst (Pt, 300 ppm) were added into a three-necked flask and reacted at 85 °C for 7 h;

[0054] Then cool to room temperature, add 4.0g triethylamine, and then drop 4.8g methacryloyl chloride; after the dropwise addition, heat to 40°C and stir for 3h; then cool to room temperature, add 30mL methanol, stir rapidly for 5min, stand to separate the upper liquid, and continue to wash the lower liquid repeatedly with methanol for 3 times; finally, reduce the pressure on the lower liquid to remove the solvent, and then dilute the product with MIBK to a mass fraction of 30%, to obtain terminal methacrylate silicone modified perfluoropolyether UV anti-fingerprint agent C.

[0055]

[0056] Example 4

[0057] This embodiment provides a methacrylate-terminated silicone-modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the following steps:

[0058] 100 g of FES-2 (molecular weight of about 7900, HNMR test, PFPE segment is Z-type PFPE, molecular weight of about 2500, FNMR test), 30 mL of m-ditrifluorotoluene, 8.0 g of 2,2-bis(hydroxymethyl)-1,3-propylene glycol allyl ether and 20 μL of Custer catalyst (Pt, 300 ppm) were added into a three-necked flask and reacted at 85° C. for 7 h;

[0059] Then cool to room temperature, add 8.5g of triethylamine, and then drop 10.3g of methacryloyl chloride; after the dropwise addition is completed, heat to 40°C and stir for 3.5h; then cool to room temperature, add 30mL of methanol, stir rapidly for 5min, stand to separate the upper liquid, and continue to wash the lower liquid repeatedly with methanol for 3 times; finally, reduce the pressure on the lower liquid to remove the solvent, and then dilute the product with MIBK to a mass fraction of 30%, to obtain terminal methacrylate silicone modified perfluoropolyether UV anti-fingerprint agent D.

[0060] Example 5

[0061] This embodiment provides a methacrylate-terminated silicone-modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the following steps:

[0062] 100 g of FES-3 (molecular weight of about 5100, HNMR test, PFPE segment is Z-type PFPE, molecular weight of about 1700, FNMR test), 30 mL of m-ditrifluorotoluene, 14.0 g of 2,2-bis(hydroxymethyl)-1,3-propylene glycol allyl ether and 40 μL of Custer catalyst (Pt, 300 ppm) were added into a three-necked flask and reacted at 85° C. for 7 h;

[0063] Then cool to room temperature, add 13.3g triethylamine, and then drop 16.0g methacryloyl chloride; after the dropwise addition, heat to 40°C and stir for 5.5h. Then cool to room temperature, add 50mL methanol, stir rapidly for 5min, stand to separate the upper liquid, and continue to wash the lower liquid with methanol repeatedly for 3 times; finally, reduce the pressure on the lower liquid to remove the solvent, and then dilute the product with MIBK to a mass fraction of 30%, and obtain the terminal methacrylate silicone modified perfluoropolyether UV anti-fingerprint agent E.

[0064] Example 6

[0065] This embodiment provides a methacrylate-terminated silicone-modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the following steps:

[0066] 30 g FES-1, 5 mL m-ditrifluorotoluene, 2.8 g methacryloyloxypropyldimethylmethoxysilane and 0.2 g tris(pentafluorophenyl)borane were added into a three-necked flask, first reacted at room temperature for 2 h, then heated to 60° C. for 5 h; cooled to room temperature, 100 mL methanol was added, rapidly stirred for 5 min, allowed to stand to separate the upper layer liquid, and the lower layer liquid was repeatedly washed with methanol for 3 times; finally, the lower layer liquid was decompressed to remove the solvent, and then the product was diluted with MIBK to a mass fraction of 30%, to obtain a terminal methacrylate silicone modified perfluoropolyether UV anti-fingerprint agent F.

[0067]

[0068] Example 7

[0069] The preparation was carried out according to the method of Example 6, wherein FES-1 was replaced by FES-2, to obtain terminal methacrylate silicone modified perfluoropolyether UV anti-fingerprint agent G.

[0070] Example 8

[0071] The preparation was carried out according to the method of Example 6, wherein FES-1 was replaced by FES-3, to obtain terminal methacrylate organosilicon modified perfluoropolyether UV anti-fingerprint agent H.

[0072] Comparative Example 1

[0073] Japan Shin-Etsu KY-1203.

[0074] Preparation of coatings and paint films

[0075] The basic UV coating was prepared according to the following formula: 100 parts by weight of 9-functionality polyurethane acrylate (CN9013NS, Sartomer, USA), 70 parts by weight of propylene glycol methyl ether acetate, 60 parts by weight of butyl acetate, 12 parts by weight of isopropyl alcohol, and 3 parts by weight of a photoinitiator (IRGACURE 184, BASF). The weight and content of the anti-fingerprint agent in the formula are shown in Table 1.

[0076] Table 1 Formulation of UV coating samples with anti-fingerprint agent

[0077]

[0078] The prepared coating was coated on a polycarbonate plastic sheet with a doctor blade to a coating thickness of 1-2 μm, and then placed in an 80°C forced air drying oven for 3 minutes; the baked plastic sheet was placed on a UV light curing machine for light curing, and the light source was a high-pressure mercury lamp with an output power of 80 W / cm and a cumulative brightness of 1600 mJ / cm 2 The samples were subjected to performance tests, and the test results are shown in Table 2.

[0079] Table 2 Performance test results of samples

[0080]

[0081] According to the test results shown in Table 2, it can be seen that the performance of the methacrylate-terminated silicone-modified perfluoropolyether anti-fingerprint agents A, C, D and E prepared in the present invention is close to that of Shin-Etsu KY-1203.

Claims

1. A method for preparing a silicone-modified perfluoropolyether UV anti-fingerprint agent, The following steps are involved: (a) adding an organosilicon-modified perfluoropolyether to a fluorocarbon solvent, and then adding an alcohol compound containing a terminal propylene group and a catalyst to react to obtain a hydroxyl-containing organosilicon-modified perfluoropolyether solution; wherein the molar ratio of the alcohol compound containing a terminal propylene group to the organosilicon-modified perfluoropolyether is 1.8-3:1; (b) first adding an acid binding agent to the hydroxyl-containing organosilicon-modified perfluoropolyether solution obtained in step (a), and then dropwise adding acryloyloxy chloride to react to obtain a crude product; wherein the molar ratio of the acid binding agent to the organosilicon-modified perfluoropolyether is 6-10:1, and the molar ratio of the acryloyloxy chloride to the organosilicon-modified perfluoropolyether is 6-12:1; (c) adding an organic alcohol compound to the crude product of step (b) for treatment, separating the liquids and allowing them to stand, taking out the lower layer of liquid, and performing rotary evaporation to obtain the organosilicon-modified perfluoropolyether UV anti-fingerprint agent.

2. The preparation method according to claim 1, in, The structure of the organosilicon-modified perfluoropolyether is R f -bR; Among them, R f R is polysiloxane.

3. The preparation method according to claim 2, in, The perfluoropolyether includes one or a combination of two or more of K-type perfluoropolyether, D-type perfluoropolyether, Y-type perfluoropolyether and Z-type perfluoropolyether.

4. The preparation method according to claim 3, in, The perfluoropolyether includes one or a combination of two or more of double-ended Z-type perfluoropolyether allyl ether, double-ended K-type perfluoropolyether allyl ether, double-ended Z-type perfluoropolyether acrylate, double-ended Z-type perfluoropolyether methacrylate, double-ended K-type perfluoropolyether acrylate, double-ended K-type perfluoropolyether methacrylate, double-ended D-type perfluoropolyether acrylate, and double-ended D-type perfluoropolyether methacrylate.

5. The preparation method according to claim 2, in, The polysiloxane comprises one or a combination of hydrogen-containing silicone oil and mercapto-containing silicone oil; The hydrogen-containing silicone oil includes one or a combination of two or more of single-ended silicon hydrogen silicone oil, double-ended silicon hydrogen silicone oil, and side silicon hydrogen silicone oil; The mercapto-containing silicone oil includes one or a combination of terminal mercapto silicone oil and pendant mercapto silicone oil.

6. The preparation method according to claim 2, in, The organosilicon-modified perfluoropolyether is: The molecular weight is 5100-30000.

7. The preparation method according to claim 1, in, The fluorocarbon solvent includes one or a combination of two or more of nonafluorobutyl ethyl ether, nonafluorobutyl methyl ether, trifluorotoluene, 1,3-di(trifluoromethyl)benzene, perfluorocyclic ether, and perfluorohexane.

8. The preparation method according to claim 1, in, The catalyst comprises one or a combination of two or more of Custer catalyst, Speier catalyst, benzoyl peroxide, di-tert-butyl peroxide and Pt / C.

9. The preparation method according to claim 1, in, The amount of the catalyst used is 0.01%-10% of the total mass of the reactants in step (a).

10. The preparation method according to claim 1, in, The alcohol compound containing a terminal propenyl group includes one or a combination of two or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate, pentaerythritol allyl ether, pentaerythritol dipropyl ether, 2,2-bis(hydroxymethyl)-1,3-propylene glycol allyl ether and trimethylolpropane allyl ether.

11. The preparation method according to claim 1, in, The reaction temperature in step (a) is 40-200° C., and the reaction time is 0.5-72 h.

12. The preparation method according to claim 1, in, The acid binding agent includes one or a combination of two or more of triethylamine, tripropylamine, tributylamine, pyridine, N,N-diisopropylethylamine, 4-methylimidazole, potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide.

13. The preparation method according to claim 1, in, The acryloyl chloride is methacryloyl chloride or acryloyl chloride.

14. The preparation method according to claim 1, in, The reaction temperature in step (b) is 0-90° C., and the reaction time is 0.3-24 h.

15. The preparation method according to claim 1, in, The organic alcohol compound includes one or a combination of two or more of methanol, ethanol, isopropanol, n-butanol, isobutanol and isopentanol.

16. An organosilicon-modified perfluoropolyether UV anti-fingerprint agent, which is prepared by the preparation method according to any one of claims 1 to 15.

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