Preparation method of perfluoropolyether modified anti-fouling additive

Abstract

The invention discloses a preparation method of a perfluoropolyether modified anti-fouling additive. The method mainly comprises the following steps: carrying out click reaction on a perfluoropolyether compound containing a plurality of double bonds at the tail end and a sulfhydryl compound, so that perfluoropolyether has a plurality of reaction groups; and then, the reaction group reacts with an isocyano acrylate compound to obtain the perfluoropolyether modified anti-fouling additive. The perfluoropolyether modified anti-fouling additive disclosed by the invention is applied to a UV curing coating, has good compatibility with the coating, can provide excellent water-proof, oil-proof, anti-fouling, anti-fingerprint and other properties for a hard coating after being subjected to UV curing to form a film, and also has the characteristics of friction resistance, long service life and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular fluorine material, in particular to a preparation method and application of a perfluoropolyether modified anti-fouling additive compound. BACKGROUND

[0002] Improving the anti-fouling performance of the coating surface after curing of the existing coating has always been a hot and difficult point of coating research. With the expansion of the application field of resin molded products and the trend of high value-added, the demand for high functionality of the cured coating is rising, and as one of them, the coating is required to have anti-fouling properties. However, the traditional UV light-cured coating has poor hydrophobic and oleophobic ability, thereby affecting the anti-fouling effect. Perfluoropolyether polymers have excellent hydrophobic and oleophobic, heat-resistant, low surface free energy and other properties. However, this substance is almost insoluble in organic solvents, which limits its application on the surface of the coating. Therefore, it is crucial to study a highly efficient perfluoropolyether anti-fouling additive and add it to ordinary solvents and existing coating formulations, so that the system remains uniform, and does not change the other properties of the original coating, and endows the coating with hydrophobic and oleophobic properties, high lubricity, self-cleaning properties and other properties. SUMMARY

[0003] In view of the above technical problems and the deficiencies existing in the art, the purpose of the present application is to provide a preparation method of a perfluoropolyether modified anti-fouling additive with good solubility.

[0004] To solve the above technical problems, the technical scheme adopted by the present application is as follows: A perfluoropolyether modified anti-fouling additive, the preparation method comprising the following steps: Step 1: adding a perfluoropolyether compound containing multiple double bonds at the end, an initiator and a mercapto compound into a flask, heating and reacting under nitrogen protection to obtain intermediate 1; Step 2: adding intermediate 1, an isocyanoacrylate compound and a catalyst into a flask, heating and reacting under nitrogen protection to obtain the perfluoropolyether modified anti-fouling additive.

[0005] Further, the perfluoropolyether compound containing multiple double bonds at the end in step 1 is any one or a combination of the following structures or a double end corresponding thereto, but is not limited to the following few: .

[0006] The Rf is a perfluoropolyether chain; wherein the perfluoropolyether chain is one of Z type, K type, Y type and D type, and the molecular weight is 300-20000. Further, the molecular weight of the perfluoropolyether chain is 4000.

[0007] The initiator is one of azobisisobutyronitrile, azobisisopentyl cyanide and azobisisoheptyl cyanide.

[0008] The mercapto compound has the following general formula: Wherein n is an integer from 0 to 40, X is O, N, C=O or other atoms, and R is one of hydroxyl or amino. (For example, mercaptoethanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, etc. straight-chain alkyl or branched-chain alkyl mercapto alcohol; or 2-mercaptoethoxyethanol, mercapto-triglycol, mercapto-tetraglycol, and other hydroxyl-polyglycol-mercapto, etc.; or mercaptoacetic acid, mercapto-propionic acid, etc. mercaptoalkyl acid reacted with diethanolamine to obtain mercapto diol with the following structure Wherein X is a polyalkyl or polyalkyloxy structure.

[0009] The mercapto compound in the present application reacts with the double bond to introduce a hydroxyl group with high reactivity to the overall structure, and the hydroxyl group can further introduce an acrylate with photocuring activity, thereby increasing the solubility of the anti-fouling additive in the coating system, enabling the additive to be cured together with other acrylate coatings, and thereby improving the anti-fouling performance of the coating.

[0010] The reaction temperature is 40-80℃, and the reaction time is 2-12 h.

[0011] The molar ratio of the perfluoropolyether compound containing multiple double bonds at the end, the mercapto compound, and the initiator is 1:(3-10):0.1.

[0012] Further, the molar ratio of the intermediate 1 and the isocyano acrylate compound in step 2 is 1:(3-10); and the amount of the catalyst is 5‰ of the intermediate 1.

[0013] The catalyst is selected from any one of dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dioctoate, dioctyl tin diacetate, dioctyl tin dilaurate, dioctyl tin dioctoate, stannous octoate, or any one of titanium ester or titanium chelate compounds such as tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra(2-ethylhexyloxy) titanium, dipropoxy bis(acetylacetone) titanium, isopropoxy octyldiol titanium, etc.

[0014] The isocyano-containing acrylate compound is selected from any one of isocyanoethyl methacrylate, isocyanate acrylate, and other compounds not listed.

[0015] The reaction temperature is 40-80℃, and the reaction time is 12-36 h.

[0016] Further, the reaction solvent in steps 1 and 2 is at least one of the following fluorinated solvents: perfluorohexane, perfluoromethylcyclohexane, perfluoro1,3-dimethylcyclohexane, bis(trifluoromethyl)benzene, 3,3-pentafluorobutane, HCFC-225, perfluoropropyl methyl ether, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluorohexyl methyl ether, or CF3CH2OCF2CHF2.

[0017] Furthermore, the anti-fouling additive is used in UV-curable coatings and coatings.

[0018] Furthermore, the antifouling additive is used in UV-curable coatings and coatings; the coating is at least one of acrylic coatings, epoxy coatings, phenolic coatings, alkyd coatings, polyurethane coatings, amino coatings, polysiloxane coatings, vinyl resin coatings, and UV-curable coatings. The amount of the antifouling additive added is 0.1-5% of the coating mass.

[0019] In this invention, all the raw materials described can be obtained by commercial purchase and / or by known means, and unless otherwise specified, they all meet the requirements of standard chemical products.

[0020] Another technical solution adopted by the present invention is: a coating containing the above-mentioned perfluoropolyether-based antifouling additive.

[0021] Compared with the prior art, the beneficial effects of this invention are as follows: The perfluoropolyether modified acrylate compound involved in this invention has a simple and easy preparation method, readily available raw materials, and mild, safe and environmentally friendly reaction conditions.

[0022] Secondly, when added to coatings as an antifouling additive, it overcomes the shortcomings of existing technologies, such as poor compatibility and reactivity of perfluoropolyether-based antifouling resins with polyurethane, alkyd, or epoxy coating formulations. The resulting cured product is less prone to unevenness or cloudiness. It imparts excellent waterproof, oil-proof, antifouling, and fingerprint-resistant properties to the substrate, with a water contact angle of over 110° and an oil contact angle of over 68° after curing. The additive prepared in this invention has good solubility with resins and exhibits excellent antifouling properties after curing. Attached Figure Description

[0023] Figure 1 The NMR spectroscopy of intermediate 1 in Example 1 1 NMR analysis spectrum.

[0024] Figure 2 The infrared spectrum of intermediate 1 in Example 1 is shown.

[0025] Figure 3 The NMR of UV-1 in Example 1 1 NMR analysis spectrum.

[0026] Figure 4 The image shows the infrared spectrum of UV-1 in Example 1. Detailed Implementation

[0027] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0028] The perfluoropolyether compound containing multiple double bonds at the end in this invention is any one or more of the following structures or their corresponding double ends, but is not limited to the following compounds; .

[0029] Example 1 Synthesis Example 1 40.1 g (10 mmol) of compound a and 2.38 g (30.5 mmol) of mercaptoethanol were added to 100 mL of m-difluorotoluene solvent, followed by the addition of 0.1 g of azobisisobutyronitrile (AIBN). The reaction was carried out under N2 and 75 °C for 6 h. After the reaction was completed by TLC monitoring, the solvent was evaporated. Then, methanol and perfluorohexane were added for extraction, and the lower fluorine phase was collected and distilled under reduced pressure to obtain 41.2 g of intermediate 1. Synthesis Example 2 41.2 g (10 mmol) of intermediate 1 and 4.8 g (31 mmol) of isocyanate methacrylate were added to 100 ml of m-difluorotoluene solvent, followed by the addition of 0.1 g of dibutyltin dilaurate. The mixture was reacted under N2 and 55°C for 24 h, and the solvent was evaporated to obtain the perfluoropolyether-modified acrylate compound. The resulting compound was diluted with methyl isobutyl ketone (MEK) to a solid content of 20% and designated as antifouling additive UV-1. The reaction equations for Synthetic Example 1-2 are as follows:

[0030] Example 2 In Example 1, the mercaptoethanol in Synthesis Example 1 was replaced with the same number of moles of 6-mercaptohexanol, while keeping the other conditions unchanged, to obtain the antifouling additive UV-2.

[0031] Example 3 In Example 1, the mercaptoethanol in Synthesis Example 1 was replaced with the same number of moles of 2-mercaptoethoxyethanol, while keeping the other conditions unchanged, to obtain the antifouling additive UV-3.

[0032] Example 4 By replacing compound a in Synthesis Example 1 with the same number of moles of compound b, while keeping all other conditions unchanged, the antifouling additive UV-4 was obtained.

[0033] Example 5 By replacing compound a in Synthesis Example 1 with the same number of moles of compound c, while keeping all other conditions unchanged, the antifouling additive UV-5 was obtained.

[0034] Example 6 By replacing compound a in Synthesis Example 1 with the same number of moles of compound d, while keeping all other conditions unchanged, the antifouling additive UV-6 was obtained.

[0035] Example 7 By replacing compound a in Synthesis Example 1 with the same number of moles of compound e, while keeping all other conditions unchanged, the antifouling additive UV-7 was obtained.

[0036] Comparative Example 1 The coatings were prepared according to the paint formulations shown in Table 1, without the addition of antifouling agents. (That is, as a blank control group, to demonstrate the difference between having and not having antifouling additives.) Comparative Example 2 0.32 g (2.06 mmol) of isocyanate methacrylate and 2 drops of dibutyltin dilaurate as a catalyst were added to a flask and 33.3 g of HFX was added. 8 g (2 mmol) of fluorohydrin was slowly added dropwise under N2 atmosphere. The mixture was then heated to 50 °C and reacted for 24 h to obtain the antifouling additive UV-8.

[0037] .

[0038] Comparative Example 3 4.0 g (1 mmol) of perfluoropolyether allyl ether was added to 30 g of HFX, along with 1.05 mmol of mercaptoethanol and 0.02 g of AIBN. The mixture was heated to 75 °C under N2 protection. After no double bond peak was observed during infrared monitoring, it was cooled to room temperature. Subsequently, 1 drop of DBTDL and 1.05 mmol of isocyanate methacrylate were added. The mixture was then heated to 55 °C under N2 protection and reacted for 24 h to obtain the antifouling additive UV-9. .

[0039] Comparative Example 4 Use the commercially available OPTOOL DAC-HP anti-fouling additive.

[0040] Performance testing The polyurethane coating was formulated according to the recipe shown in Table 1 (the amount of each component added is by weight). The coating was then sprayed onto a PET substrate to form a coating approximately 5 μm thick, and baked in an 80°C oven for 3 minutes. After the solvent dried, a 1600 mJ / cm² solution was applied. 2 The coating film is prepared by irradiating it with a UV lamp and curing it for 5-30 seconds. In the table, TMPTA represents trimethylolpropane triacrylate, EBECRYL 1290 is a hexafunctional aliphatic polyurethane acrylate produced by Cytec, BAC represents butyl acetate, and UV184 represents 1-hydroxycyclohexylphenyl ketone (photoinitiator, industrial grade).

[0041]

[0042] The performance of the hard coating film and low-reflection film prepared in the above examples and comparative examples was measured by the following methods, and the results are shown in Table 2 below.

[0043] (1) Contact angle test: The contact angle of the surface treatment layer with water and the contact angle of n-hexadecane were measured using a contact angle measuring instrument (XHS-CAZ1, Shenzhen Xinhengsen Instrument Equipment Co., Ltd.).

[0044] (2) Abrasion resistance test: The water contact angle of the surface treatment layer after abrasion was evaluated using a multi-functional abrasion tester (HG-9600, Dongguan Huaguo Precision Instruments Co., Ltd.) under the following conditions: steel wool: BONSTAR#0000; load: 1kg / cm 2 The coated surface was rubbed at a cycle speed of 25 times / minute, a rubbing length of 2.5 cm, and a rubbing count of 1000 times.

[0045] (3) Coating stain resistance: Draw lines on the coating surface using an oil-based black marker, wipe with a dry paper towel, and observe whether any stains remain on the surface. Classify and label according to the following standards: Level 1: Indicates that stains can be easily wiped off without leaving any coating residue; Level 2: This indicates that stains can be wiped off, but it requires some effort, and there is no residue left in the coating. Level 3: Indicates that stains can be wiped off, but ink residue on the coating will not; Level 4: Indicates that the stain cannot be removed.

[0046] Table 2 shows the properties of the films formed after curing in Examples 1-7 and Comparative Examples 1-4.

[0047] Table 2 shows that the anti-fouling additive for coatings of the present invention provides excellent waterproof, oil-proof, and abrasion-resistant properties after curing. able.

[0048] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and the present invention also intends to include these modifications and variations.

Claims

1. A process for the preparation of a perfluoropolyether modified antifouling additive characterized in that: The preparation method comprises the following steps: Step 1: the terminal containing a plurality of double bond perfluoropolyether compound, initiator and mercapto compound in a fluorine-containing solvent, under nitrogen protection at 40-80℃ for 2-12 hours to obtain intermediate 1; Step 2: the intermediate 1, isocyano acrylate compound and catalyst in a fluorine-containing solvent, under nitrogen protection at 40-80℃ for 12-36 hours to obtain the perfluoropolyether modified anti-fouling additive.

2. The method for preparing a perfluoropolyether modified antifouling additive according to claim 1, characterized in that, The terminal containing a plurality of double bond perfluoropolyether compound in step 1 is any one or more of the following structures or its corresponding double end, but not limited to the following several: ； The Rf is a perfluoropolyether chain; wherein the perfluoropolyether chain is one of Z type, K type, Y type, D type, and the molecular weight is 300 ~20000.

3. The preparation method of the perfluoropolyether modified anti-fouling additive according to claim 1, characterized in that, The mercapto compound has the following general formula: where n is an integer from 0 to 40, X is O, N, C=O or other atoms, and R is one of hydroxyl or amino.

4. The method for preparing a perfluoropolyether-modified antifouling additive according to claim 1, characterized in that, The initiator is one of azobisisobutyronitrile, azobisisopentyl nitrile, azobisisoheptyl nitrile; the molar ratio of the terminal containing a plurality of double bond perfluoropolyether compound, mercapto compound and initiator is 1:(3-10):0.1; The catalyst is selected from dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dioctoate, dioctyl tin diacetate, dioctyl tin dilaurate, dioctyl tin dioctoate, stannous octoate, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetrakis(2-ethylhexyloxy), titanium dipropoxide bis(acetylacetonate) or titanium isopropoxy octanediol; the amount of the catalyst is 0.1-0.5% of the mass of intermediate 1.

5. The method for preparing a perfluoropolyether modified antifouling additive according to claim 1, characterized in that, The reaction solvent is at least one of perfluorohexane, perfluoromethylcyclohexane, perfluoro 1, 3 dimethylcyclohexane, bis(trifluoromethyl)benzene, 3, 3 pentaf luorobutane, HCFC-225, perfluoropropyl methyl ether, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluorohexyl methyl ether or CF3CH2OCF2CHF2 fluorine-containing solvent; The isocyano-containing acrylate compound is selected from any one of isocyanoethyl methacrylate, isocyanate acrylate and other compounds not listed in the middle; the molar ratio of the intermediate 1, isocyano acrylate compound is 1:(3-10).

6. A perfluoropolyether-modified antifouling additive characterized in that, Prepared by the preparation method of any one of claims 1-5.

7. A coating composition characterized in that, The coating composition according to claim 7 or 8 is coated and cured to form a coating layer, wherein the water contact angle of the coating layer is ≥110°, and the oil contact angle is ≥68°.

8. The coating composition according to claim 7, characterized in that 10. Use of the perfluoropolyether modified anti-fouling additive according to claim 6 in the preparation of an anti-fouling coating, an optical coating, a touch screen surface coating or a flexible display coating.

9. A coating characterized in that, ​ ​

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