UV light-curable acrylate organic fluorosilicone polymer, coating and preparation method of UV light-curable acrylate organic fluorosilicone polymer

Abstract

The invention relates to the field of organic silicon and fluorosilicone high-molecular polymers, in particular to a preparation method of a UV photocuring fluorosilicone material with good alkali resistance. The acrylate organic fluorosilicone polymer is composed of a fluorinated alkoxy silane compound, an acrylate alkoxy silane compound, deionized water, a polymerization inhibitor, a solvent, an acid catalyst and a neutralizer. The composition is simple, the preparation process is simple, and the problems that high-temperature curing operation is tedious, low-temperature curing performance is poor and alkali corrosion resistance is poor can be solved.

Description

Technical Field

[0001] The invention relates to the field of organic silicon and fluorosilicone macromolecular polymers, and in particular to a method for preparing a UV light-curing fluorosilicone material with good alkali resistance. Background Art

[0002] UV light curing technology is widely used and studied due to its "5E" characteristics. At present, there are many types of UV light curing products on the market, such as UV light curing coatings, UV light curing oil films, UV light curing adhesives, photoresists, etc.

[0003] At present, there are three main curing methods for organic fluorosilicone materials: condensation curing, hydrosilylation and thermal crosslinking. These three traditional curing methods have some defects to a greater or lesser extent, such as the long cycle of condensation curing, the high curing temperature required for thermal curing, and the use of relatively expensive transition metals and the catalysts are easily deactivated in hydrosilylation curing, which results in that organic fluorosilicone polymers cannot be applied to some specific fields, such as substrates that require a short operating cycle or are sensitive to temperature. UV light curing can be cured at room temperature and only takes tens of seconds. These advantages of UV light curing technology make it have great potential application value in the field of organic silicon / fluorosilicone. If UV light curing technology is introduced into organic fluorosilicone coatings, its application field can be greatly expanded. In addition, fluorosilicone materials not only have excellent low temperature and high temperature resistance like polysiloxanes, but also have good oil resistance and solvent resistance like organic fluoropolymers. However, due to the silicon-oxygen bond structure characteristics of fluorosilicone materials, fluorosilicone materials have poor alkali corrosion resistance, resulting in certain restrictions on their application fields.

[0004] Therefore, it is urgent to propose a UV light-curable acrylate organic fluorosilicone polymer and coating and a preparation method to solve the above technical problems. Summary of the invention

[0005] The purpose of the present invention is to solve the problem of poor alkali corrosion resistance formed by conventional technology. A brief summary of the present invention is given below to provide a basic understanding of certain aspects of the present invention. It should be understood that this summary is not an exhaustive summary of the present invention. It is not intended to determine the key or important parts of the present invention, nor is it intended to limit the scope of the present invention.

[0006] The technical solution of the present invention:

[0007] A UV-curable acrylate organofluorosilicone polymer, wherein the acrylate organofluorosilicone polymer is composed of a fluorinated alkoxysilane compound, an acrylate alkoxysilane compound, deionized water, an inhibitor, a solvent, an acid catalyst, and a neutralizer;

[0008] The mass component of the fluorinated alkoxysilane compound is 10-80 parts, the mass component of the acrylate alkoxysilane compound is 0-80 parts, the mass component of deionized water is 0-20 parts, the mass component of the inhibitor is 0-10 parts, the mass component of the solvent is 0-50 parts, the mass component of the acid catalyst is 0.0001-0.005 parts, and the mass component of the neutralizer is 0.001-0.5 parts.

[0009] Preferred fluorinated alkoxysilane compounds are one or more of trifluoropropylmethyldimethoxysilane, trifluoropropylmethyltrimethoxysilane, nonafluorohexylmethyldimethoxysilane and tridecafluorooctylmethyldimethoxysilane.

[0010] Preferably, the acrylate alkoxysilane compound is one or more of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane and γ-methacryloxypropylmethyldiethoxysilane.

[0011] Preferably, the polymerization inhibitor is one or more of hydroquinone and p-benzoquinone.

[0012] Preferably, the solvent is one or more of methanol, ethanol, acetone, butanone, methyl ethyl ketone and ethyl acetate.

[0013] Preferably, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid and trifluoromethanesulfonic acid, and the neutralizing agent is one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate.

[0014] Preferably, the photoinitiator is one or more of 2,2-dimethyl-2-phenylacetophenone and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

[0015] A method for preparing a UV-curable acrylate organic fluorine silicon polymer comprises the following steps:

[0016] Step 1: Add the fluorinated alkoxysilane compound and the acrylate alkoxysilane compound into a reactor, then add water, a polymerization inhibitor and a solvent, add trifluoromethanesulfonic acid at 25-70° C., and react for 0.5-72 hours;

[0017] Step 2: After the reaction is completed, add a neutralizing agent, neutralize for 1-72 hours, then filter and collect the filtrate;

[0018] Step 3: The collected filtrate is decompressed at 70-120°C to -0.09MPa, and the low boiling point is removed for 1-3h to prepare an organic fluorosilicone polymer containing acrylate.

[0019] A UV light-curable acrylate organic fluorine silicon polymer coating, the acrylate organic fluorine silicon polymer coating is composed of an organic fluorine silicon polymer containing acrylate, a photoinitiator, and a fluorine-containing compound;

[0020] The mass component of the organic fluorine silicon polymer containing acrylate is 10-80 parts, the mass component of the photoinitiator is 0.1-10 parts, and the mass component of the fluorine-containing compound is 0-50 parts.

[0021] A method for preparing a UV-curable acrylate organic fluorosilicone polymer coating comprises the following steps:

[0022] Step 1: Evenly mix the organic fluorine silicon polymer containing acrylate, the photoinitiator and the fluorine-containing compound until a stable uniform solution is formed;

[0023] Step 2: coating the mixed solution on the substrate, and then curing it by UV light for 45 seconds to obtain an acrylate organic fluorosilicone polymer coating.

[0024] The present invention has the following beneficial effects:

[0025] The invention has simple components and a simple preparation process, and can solve the problems of complicated high-temperature curing operation, poor low-temperature curing performance and poor alkali corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of the structure of an organic fluorine-silicon polymer containing acrylate;

[0027] Figure 2 is the infrared spectrum of the fluorine-containing polysiloxane containing acrylate prepared in Example 1;

[0028] Figure 3 Schematic diagram of acid, alkali and salt corrosion of tinplate after the fluorosilicone coating prepared in Example 1 is coated at different times;

[0029] Figure 4 Schematic diagram of acid, alkali and salt corrosion at different times after the fluorosilicone coating prepared in Example 2 is coated on tinplate;

[0030] Figure 5 Schematic diagram of acid, alkali and salt corrosion of tinplate after the fluorosilicone coating prepared in Example 3 is coated at different times;

[0031] Figure 6 It is a schematic diagram of acid, alkali and salt corrosion of tinplate coated with the fluorosilicone coating prepared in Example 4 at different times. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is described below by the specific embodiments shown in the accompanying drawings. However, it should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0033] Specific implementation method 1: Combination Figure 1-Figure 6 This embodiment is described. This embodiment is a UV light-curable acrylate organofluorosilicone polymer, wherein the acrylate organofluorosilicone polymer is composed of a fluorinated alkoxysilane compound, an acrylate alkoxysilane compound, deionized water, an inhibitor, a solvent, an acid catalyst, and a neutralizer;

[0034] The mass component of the fluorinated alkoxysilane compound is 10-80 parts, the mass component of the acrylate alkoxysilane compound is 0-80 parts, the mass component of deionized water is 0-20 parts, the mass component of the inhibitor is 0-10 parts, the mass component of the solvent is 0-50 parts, the mass component of the acid catalyst is 0.0001-0.005 parts, and the mass component of the neutralizer is 0.001-0.5 parts.

[0035] Specific implementation method 2: Combination Figure 1-Figure 6 The present embodiment is described as a UV light-curable acrylate organic fluorosilicone polymer, wherein the fluorinated alkoxysilane compound is one or more of trifluoropropylmethyldimethoxysilane, trifluoropropylmethyltrimethoxysilane, nonafluorohexylmethyldimethoxysilane and tridecafluorooctylmethyldimethoxysilane.

[0036] Specific implementation method three: Combination Figure 1-Figure 6 The present embodiment is described as a UV light-curable acrylate organic fluorosilicone polymer, wherein the acrylate alkoxysilane compound is one or more of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropylmethyldiethoxysilane.

[0037] Specific implementation method four: Combination Figure 1-Figure 6 The present embodiment is described as follows. The present embodiment is a UV light-curable acrylic organic fluorosilicone polymer, and the polymerization inhibitor is one or more of hydroquinone and p-benzoquinone.

[0038] Specific implementation method five: Combination Figure 1-Figure 6 The present embodiment is described as a UV light-curable acrylic organic fluorosilicone polymer, wherein the solvent is one or more of methanol, ethanol, acetone, butanone, methyl ethyl ketone, and ethyl acetate.

[0039] Specific implementation method six: Combination Figure 1-Figure 6 The present embodiment is described. The present embodiment is a UV light-curable acrylate organic fluorosilicone polymer, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid and trifluoromethanesulfonic acid, and the neutralizer is one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate.

[0040] Specific implementation method seven: Combination Figure 1-Figure 6 This embodiment is described. This embodiment is a UV light-curable acrylate organic fluorine silicon polymer, and the photoinitiator is one or more of 2,2-dimethyl-2-phenylacetophenone and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

[0041] Specific implementation method eight: Combination Figure 1-Figure 6 This embodiment is described. A method for preparing a UV-curable acrylate organic fluorosilicone polymer in this embodiment comprises the following steps:

[0042] Step 1: Add the fluorinated alkoxysilane compound and the acrylate alkoxysilane compound into a reactor, then add water, a polymerization inhibitor and a solvent, add trifluoromethanesulfonic acid at 25-70° C., and react for 0.5-72 hours;

[0043] Step 2: After the reaction is completed, add a neutralizing agent, neutralize for 1-72 hours, then filter and collect the filtrate;

[0044] Step 3: The collected filtrate is decompressed at 70-120°C to -0.09MPa, and the low boiling point is removed for 1-3h to prepare an organic fluorosilicone polymer containing acrylate.

[0045] Specific implementation method nine: Combination Figure 1-Figure 6 The present embodiment is described. The present embodiment is a UV light-curable acrylate organic fluorosilicone polymer coating, wherein the acrylate organic fluorosilicone polymer coating is composed of an organic fluorosilicone polymer containing acrylate, a photoinitiator, and a fluorine-containing compound;

[0046] The mass component of the organic fluorine silicon polymer containing acrylate is 10-80 parts, the mass component of the photoinitiator is 0.1-10 parts, and the mass component of the fluorine-containing compound is 0-50 parts.

[0047] Specific implementation method ten: Combination Figure 1-Figure 6 This embodiment is described. A method for preparing a UV light-curable acrylate organic fluorosilicone polymer coating comprises the following steps:

[0048] Step 1: Evenly mix the organic fluorine silicon polymer containing acrylate, the photoinitiator and the fluorine-containing compound until a stable uniform solution is formed;

[0049] Step 2: coating the mixed solution on the substrate, and then curing it by UV light for 45 seconds to obtain an acrylate organic fluorosilicone polymer coating.

[0050] Example 1

[0051] 0.05 mol of trifluoropropylmethyldimethoxysilane and 0.03 mol of acrylate methyldimethoxysilane compound are added to the reactor, and then 0.0005 mol of hydroquinone, 0.2 mol of deionized water and 0.21 mol of ethanol are added, and 0.0035 mol of trifluoromethanesulfonic acid is added at 40°C, and then the temperature is raised to 70°C and reacted for 2 hours; then 0.30 mol of sodium carbonate is added, neutralized for 2 hours, and then filtered, the filtrate is collected, and then the filtrate is decompressed at 70°C to above -0.09 MPa, and the low boiling is removed for 1-3 hours to obtain an organic fluorine silicon polymer containing acrylate;

[0052] 100 phr of the prepared acrylate-containing organic fluorosilicone polymer and 11732 phr of a photoinitiator were mixed, stirred evenly until a stable and uniform mixed liquid was formed, the mixture was coated on tinplate, and photocured for 45 seconds using a UV light curing machine to obtain an organic fluorosilicone coating.

[0053] Example 2

[0054] 0.05 mol of trifluoropropylmethyldimethoxysilane and 0.03 mol of acrylate methyldimethoxysilane compound were added to the reactor, followed by 0.0005 mol of hydroquinone, 0.2 mol of deionized water and 0.21 mol of ethanol, and 0.0035 mol of trifluoromethanesulfonic acid was added at 40°C, followed by heating to 70°C and reacting for 2 hours; followed by adding 0.30 mol of sodium carbonate and neutralizing for 2 hours. The mixture was then filtered and the filtrate was collected, and then the filtrate was decompressed at 70°C to above -0.09 MPa, and the low boiling temperature was removed for 1-3 hours to obtain an organic fluorine silicon polymer containing acrylate;

[0055] The prepared organic fluorosilicone polymer containing acrylate 100phr, photoinitiator 11732phr and 2,2,3,4,4,4-hexafluorobutyl methacrylate 3phr, 6phr, 9phr and 12phr were mixed and stirred evenly until a stable and uniform mixed liquid was formed. The mixture was coated on tinplate and photocured for 45s in a UV light curing machine to obtain an organic fluorosilicone coating.

[0056] Example 3

[0057] 0.05 mol of trifluoropropylmethyldimethoxysilane and 0.03 mol of acrylate methyldimethoxysilane compound are added to the reactor, and then 0.0005 mol of hydroquinone, 0.2 mol of deionized water and 0.21 mol of ethanol are added, and 0.0035 mol of trifluoromethanesulfonic acid is added at 40°C, and then the temperature is raised to 70°C and reacted for 2 hours; then 0.30 mol of sodium carbonate is added, neutralized for 2 hours, and then filtered, the filtrate is collected, and then the filtrate is decompressed at 70°C to above -0.09 MPa, and the low boiling is removed for 1-3 hours to obtain an organic fluorine silicon polymer containing acrylate;

[0058] Then, 100 phr of the prepared organic fluorosilicone polymer containing acrylate, 11732 phr of a photoinitiator, and 3 phr, 6 phr, 9 phr, and 12 phr of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate were mixed and stirred evenly until a stable and uniform mixed liquid was formed. The mixture was coated on tinplate and photocured for 45 seconds using a UV light curing machine to obtain an organic fluorosilicone coating.

[0059] Example 4

[0060] 0.05 mol of trifluoropropylmethyldimethoxysilane and 0.03 mol of acrylate methyldimethoxysilane compound were added to the reactor, followed by 0.0005 mol of hydroquinone, 0.2 mol of deionized water and 0.21 mol of ethanol, and 0.0035 mol of trifluoromethanesulfonic acid was added at 40°C, followed by heating to 70°C and reacting for 2 hours; followed by adding 0.30 mol of sodium carbonate and neutralizing for 2 hours. The mixture was then filtered and the filtrate was collected, and then the filtrate was decompressed at 70°C to above -0.09 MPa, and the low boiling temperature was removed for 1-3 hours to obtain an organic fluorine silicon polymer containing acrylate;

[0061] Then, 100 phr of the prepared acrylate-containing organic fluorosilicone polymer, 11732 phr of photoinitiator, and 3 phr, 6 phr, 9 phr, and 12 phr of 2-(perfluorooctyl)ethyl methacrylate were mixed and stirred evenly until a stable and uniform mixed liquid was formed. The mixture was coated on tinplate and photocured for 45 seconds using a UV light curing machine to obtain an organic fluorosilicone coating.

[0062] Comparative Example 1

[0063] 0.05 mol of trifluoropropylmethyldimethoxysilane was added to the reactor, followed by 0.0005 mol of hydroquinone, 0.2 mol of deionized water and 0.21 mol of ethanol, and 0.0035 mol of trifluoromethanesulfonic acid was added at 40°C, followed by heating to 70°C and reacting for 2 hours; followed by adding 0.30 mol of sodium carbonate, neutralizing for 2 hours, and then filtering and collecting the filtrate, and then decompressing the filtrate at 70°C to above -0.09 MPa, and removing the low boiling point for 1-3 hours to obtain an organic fluorine-silicon polymer;

[0064] Then, 100 phr of the prepared organic fluorosilicone polymer and 11732 phr of the photoinitiator were mixed and stirred evenly until a stable and uniform mixed liquid was formed. The mixture was coated on the tinplate and photocured for 45 seconds using a UV light curing machine to obtain an organic fluorosilicone coating.

[0065] Test standard: Hardness test standard: GB / T 6379-1996; Adhesion test standard: GB / T1720-79 (89); Corrosion resistance test: First, the UV-curable fluorosilicone coating prepared in the embodiment is coated on the tinplate, and then UV-cured for 45 seconds. Then, two drops of 5wt% hydrochloric acid, 5wt% sodium hydroxide and 5wt% sodium chloride aqueous solution are taken and dropped on the tinplate area not coated with the fluorosilicone coating and the tinplate area coated with the light-cured fluorosilicone coating, respectively, and the corrosion resistance of the prepared fluorosilicone coating is evaluated by observing the corrosion state of the tinplate at different times.

[0066] The test results are as follows:

[0067]

[0068] It should be noted that in the above embodiments, as long as the technical solutions are not contradictory, they can be arranged and combined, and those skilled in the art can exhaust all possibilities based on the mathematical knowledge of arrangement and combination. Therefore, the present invention will no longer describe the technical solutions after arrangement and combination one by one, but it should be understood that the technical solutions after arrangement and combination have been disclosed by the present invention.

[0069] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A UV light-curable acrylate organic fluorine silicon polymer, characterized in that: The acrylate organic fluorine silicon polymer is composed of a fluorinated alkoxysilane compound, an acrylate alkoxysilane compound, deionized water, an inhibitor, a solvent, an acid catalyst, and a neutralizer; The mass component of the fluorinated alkoxysilane compound is 10-80 parts, the mass component of the acrylate alkoxysilane compound is 0-80 parts, the mass component of deionized water is 0-20 parts, the mass component of the inhibitor is 0-10 parts, the mass component of the solvent is 0-50 parts, the mass component of the acid catalyst is 0.0001-0.005 parts, and the mass component of the neutralizer is 0.001-0.5 parts.

2. The UV-curable acrylate organic fluorosilicone polymer according to claim 1, characterized in that: The fluorinated alkoxysilane compound is one or more of trifluoropropylmethyldimethoxysilane, trifluoropropylmethyltrimethoxysilane, nonafluorohexylmethyldimethoxysilane and tridecafluorooctylmethyldimethoxysilane.

3. The UV-curable acrylate organic fluorosilicone polymer according to claim 1, characterized in that: The acrylate alkoxysilane compound is one or more of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane and γ-methacryloxypropylmethyldiethoxysilane.

4. The UV-curable acrylate organic fluorosilicone polymer according to claim 1, characterized in that: The polymerization inhibitor is one or more of hydroquinone and p-benzoquinone.

5. The UV light-curable acrylate organic fluorosilicone polymer according to claim 1, characterized in that: The solvent is one or more of methanol, ethanol, acetone, butanone, methyl ethyl ketone and ethyl acetate.

6. The UV-curable acrylate organic fluorosilicone polymer according to claim 1, characterized in that: The acid catalyst is one or more of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid and trifluoromethanesulfonic acid, and the neutralizing agent is one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate.

7. The UV light-curable acrylate organic fluorosilicone polymer according to claim 1, wherein the photoinitiator is one or more of 2,2-dimethyl-2-phenylacetophenone and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide.

8. A method for preparing a UV-curable acrylate organic fluorine silicon polymer, characterized in that: The steps include: Step 1: Add the fluorinated alkoxysilane compound and the acrylate alkoxysilane compound into a reactor, then add water, a polymerization inhibitor and a solvent, add trifluoromethanesulfonic acid at 25-70° C., and react for 0.5-72 hours; Step 2: After the reaction is completed, add a neutralizing agent, neutralize for 1-72 hours, then filter and collect the filtrate; Step 3: The collected filtrate is decompressed at 70-120°C to -0.09MPa, and the low boiling point is removed for 1-3h to prepare an organic fluorosilicone polymer containing acrylate.

9. A UV-curable acrylate organic fluorine-silicon polymer coating, characterized in that: The acrylate organic fluorine silicon polymer coating is composed of an organic fluorine silicon polymer containing acrylate, a photoinitiator, and a fluorine-containing compound; The mass component of the organic fluorine silicon polymer containing acrylate is 10-80 parts, the mass component of the photoinitiator is 0.1-10 parts, and the mass component of the fluorine-containing compound is 0-50 parts.

10. A method for preparing a UV-curable acrylate organic fluorosilicone polymer coating, characterized in that: The steps include: Step 1: Evenly mix the organic fluorine silicon polymer containing acrylate, the photoinitiator and the fluorine-containing compound until a stable uniform solution is formed; Step 2: coating the mixed solution on the substrate, and then curing it by UV light for 45 seconds to obtain an acrylate organic fluorosilicone polymer coating.

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