CN108624105B - Preparation method of water-soluble antifouling anti-doodling auxiliary agent - Google Patents

Preparation method of water-soluble antifouling anti-doodling auxiliary agent Download PDF

Info

Publication number
CN108624105B
CN108624105B CN201810384866.5A CN201810384866A CN108624105B CN 108624105 B CN108624105 B CN 108624105B CN 201810384866 A CN201810384866 A CN 201810384866A CN 108624105 B CN108624105 B CN 108624105B
Authority
CN
China
Prior art keywords
water
product
equal
reaction
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810384866.5A
Other languages
Chinese (zh)
Other versions
CN108624105A (en
Inventor
徐涛
周燚
盛磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinochem Environmental Protection Chemicals Taicang Co Ltd
Original Assignee
Sinochem Environmental Protection Chemicals Taicang Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinochem Environmental Protection Chemicals Taicang Co Ltd filed Critical Sinochem Environmental Protection Chemicals Taicang Co Ltd
Priority to CN201810384866.5A priority Critical patent/CN108624105B/en
Publication of CN108624105A publication Critical patent/CN108624105A/en
Application granted granted Critical
Publication of CN108624105B publication Critical patent/CN108624105B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Abstract

The invention discloses a preparation method of a water-soluble antifouling anti-doodling auxiliary agent, which comprises the following steps: 1) mixing a silane coupling agent 1 containing primary amino and a silane coupling agent 2 containing secondary amino, performing hydrolysis reaction and condensation reaction to obtain an initial product, and performing polycondensation reaction on the initial product, siloxane ring bodies and an organosilicon end-capping agent in the presence of an alkaline catalyst to obtain an amino silicone oil product 1; 2) carrying out amidation reaction on the amino silicone oil product 1 prepared in the step 1) and a perfluoropolyether compound to generate a product 2; 3) reacting an isocyanate compound and a hydroxyl acrylate compound in a solvent in the presence of a catalyst and a polymerization inhibitor to generate a product 3; 4) adding the product 3 prepared in the step 3) into the product 2 prepared in the step 2), and reacting to obtain the product; the preparation method of the water-soluble antifouling anti-doodling auxiliary agent is simple, easy to operate, mild in reaction condition, safe and environment-friendly.

Description

Preparation method of water-soluble antifouling anti-doodling auxiliary agent
Technical Field
The invention belongs to the field of high polymer materials, particularly relates to an auxiliary agent which is water-soluble and suitable for a water-based UV (ultraviolet) photocureable coating, and particularly relates to a preparation method of a water-soluble antifouling anti-doodling auxiliary agent.
Background
The water-based UV photocureable coating has the advantages of high curing speed, energy conservation, small environmental pollution, good performance of cured products, suitability for high-speed automatic production and the like, is a main substitute of the traditional coating (especially solvent-based coating), and is more and more emphasized by the coating industry. However, the paint film formed by the water-based UV paint contains a large amount of polar functional groups such as carbonyl, amino and the like, so that the antifouling and anti-graffiti performances of the paint film are poor. The improvement of antifouling, anti-sticking and anti-doodling performances of the surface of a paint film of the existing water-based UV paint is always a hotspot and a difficult point of paint research, and particularly relates to a 3C paint applied to the surfaces of computers, communications, consumer electronics and the like, a hardening paint applied to the surfaces of optical films of displays, touch screens and the like, and a low-surface-energy paint such as an anti-doodling paint used for preventing and treating urban psoriasis. From the technical point of view, two approaches are mainly used for realizing the hydrophobic and oleophobic functions of the material surface, namely adding low surface energy substances, mainly organic fluorine and organic silicon, on the material surface; secondly, a rough structure is constructed on the surface of the material. It is undoubtedly a fast, efficient and practical way to study the addition of an efficient antifouling adjuvant to existing coating formulations without changing other properties of the original coating.
The perfluoropolyether (PFPE) does not contain PFOA, PFCS and other environment-accumulative chemical components, and is a safe and environment-friendly fluorine source. The paint has poor intermiscibility with other hydrocarbon components in the paint, can float on the surface of a paint film in the film forming process, further reduces the surface energy of the paint film, and finally realizes the functions of oil resistance, water resistance, dust resistance and the like. The Chinese patent CN106220839A discloses a perfluoropolyether-based anti-doodling auxiliary agent and a preparation method thereof, and the structural formula is as follows:
Figure GDA0001711140520000011
wherein n is a natural number and is more than or equal to 2 and less than or equal to 30; x is R1N(R2) -or-HN-R2，R1、R2Respectively, the substituent group contains a polyurethane structure, and the tail end of X contains an alcoholic hydroxyl group. However, the compound mainly contains groups such as a polyurethane structure and the like, is difficult to apply to UV photocuring paint, has poor compatibility in the UV photocuring paint, and is difficult to exert the antifouling and anti-graffiti functions.
For another example, patent CN2005800145739 discloses a perfluoropolyether modified acrylate with anti-fouling effect, however, after the compound disclosed in this patent is applied to a coating, the coating is cured by UV light, oxygen in the air can generate oxygen inhibition effect on curing, and meanwhile, the compound has poor adhesion and compatibility with a paint film, further, the perfluoropolyether can continuously separate from the surface of the paint film in the using process of the product, finally the durability of the antifouling function of the paint film is deteriorated, therefore, although a certain antifouling and abrasion resistance is achieved, the effect is still not ideal, and the compound cannot be dissolved in the water-based UV coating, namely, the antifouling and anti-doodling performance of the aqueous UV coating cannot be improved, so that ordinary technicians in the field need to find a method for preparing the antifouling and anti-doodling auxiliary agent suitable for the aqueous UV coating, which is simple to operate, easily available in raw materials, mild in reaction conditions, safe and environment-friendly.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a water-soluble antifouling anti-doodling auxiliary agent, which is simple to operate, easy to obtain raw materials, mild in reaction conditions, safe and environment-friendly.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a water-soluble antifouling anti-doodling auxiliary agent comprises the following steps:
1) mixing a silane coupling agent 1 containing primary amino and a silane coupling agent 2 containing secondary amino, performing hydrolysis reaction and condensation reaction to obtain an initial product, and performing polycondensation reaction on the initial product, siloxane ring bodies and an organosilicon end-capping agent in the presence of an alkaline catalyst to obtain an amino silicone oil product 1;
2) carrying out amidation reaction on the amino silicone oil product 1 prepared in the step 1) and a perfluoropolyether compound to generate a product 2;
3) reacting an isocyanate compound and a hydroxyl acrylate compound in a solvent in the presence of a catalyst and a polymerization inhibitor to generate a product 3;
4) adding the product 3 prepared in the step 3) into the product 2 prepared in the step 2), and reacting to generate the water-soluble antifouling and anti-doodling auxiliary agent.
According to some preferred aspects of the present invention, the primary amino group-containing silane coupling agent 1 is a combination of one or more selected from the group consisting of γ -aminopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane, γ -aminopropylethyldimethoxysilane and γ -aminopropylethyldiethoxysilane.
According to some preferred aspects of the present invention, the secondary amino-containing silane coupling agent 2 is a combination of one or more selected from the group consisting of γ -piperazinylpropylmethyldimethoxysilane, γ -piperazinylpropylmethyldiethoxysilane, γ -piperazinylpropylethyldimethoxysilane, γ -piperazinylpropylethyldiethoxysilane, N- (N-butyl) - γ -aminopropylmethyldimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, and N- (N-butyl) - γ -aminopropylmethyldiethoxysilane.
According to some preferred aspects of the invention, the basic catalyst is selected from the group consisting of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, and the like, in combination with one or more of the foregoing catalysts.
According to some preferred aspects of the invention, the siloxane ring body is a combination of one or more selected from the group consisting of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, and decamethylcyclopentasiloxane.
According to some preferred aspects of the present invention, the silicone end-capping agent is a combination of one or more selected from hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.
According to some preferred aspects of the invention, in step 1), the hydrolysis reaction and the condensation reaction are carried out in desalted water.
According to some preferred aspects of the present invention, in the step 1), the hydrolysis reaction and the condensation reaction are performed at 10 ℃ to 200 ℃ for 1 to 12 hours. More preferably, in the step 1), the hydrolysis reaction and the condensation reaction are carried out at 10-100 ℃, and the reaction time is 2-8 hours.
According to some preferred aspects of the present invention, in the step 1), the polycondensation reaction is performed at 10 ℃ to 200 ℃ for 1 to 12 hours. More preferably, in the step 1), the polycondensation reaction is performed at 80-200 ℃ for 2-8 hours.
According to some preferred aspects of the present invention, the perfluoropolyether compound has the formula RfOR1Wherein R is1Is C1-10Alkyl of (a), said RfIs one or more selected from the following groups:
Figure GDA0001711140520000031
wherein d is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711140520000032
wherein e is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711140520000033
wherein f is more than or equal to 50 and more than or equal to 2, and g is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711140520000034
wherein, 50 is more than or equal to h and more than or equal to 2, and 50 is more than or equal to i and more than or equal to 2.
According to some specific aspects of the invention, R1Can be-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH(CH3)CH3or-C (CH)3)2CH3。
According to some preferred aspects of the invention, in step 2), the amidation reaction is carried out in the presence of a protective gas. Wherein, the protective gas can be nitrogen, argon, etc.
According to some preferred aspects of the present invention, in the step 2), the amidation reaction is performed at 50 ℃ to 200 ℃ for 1 to 12 hours. More preferably, in the step 2), the amidation reaction is performed at 50 to 150 ℃ for 3 to 12 hours. Further preferably, in the step 2), the amidation reaction is performed at 50 to 120 ℃ for 3 to 10 hours.
According to some preferred aspects of the invention, the catalyst is a combination of one or more selected from the group consisting of triethylamine, tetrabutyl titanate, dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecylthio) and dibutyltin diacetate.
According to some preferred aspects of the invention, the polymerization inhibitor is one or a combination of more selected from hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.
According to some preferred aspects of the present invention, in the step 3), the solvent is one or more selected from the group consisting of ethyl acetate, ethyl propyl ester, butyl acetate, amyl acetate, methyl ethyl ketone, methyl butyl ketone and methyl isobutyl ketone.
According to some preferred aspects of the present invention, the isocyanate compound is a combination of one or more selected from the group consisting of isophorone diisocyanate and its trimer, toluene diisocyanate and its dimer, trimer, hexamethylene diisocyanate and its dimer, trimer, dicyclohexylmethane diisocyanate; or the isocyanate compound is a reaction product of one or more of isophorone diisocyanate and tripolymer thereof, toluene diisocyanate and dipolymer and tripolymer thereof, hexamethylene diisocyanate and dipolymer and tripolymer thereof, and dicyclohexylmethane diisocyanate and a hydrophilic double-end hydroxyl compound.
According to some preferred aspects of the present invention, when the isocyanate compound is a reaction product of the above isocyanate and a hydrophilic double-terminal hydroxyl compound, specific embodiments of step 3) are: firstly, the isocyanate and a hydrophilic double-end hydroxyl compound react in the presence of a second catalyst to generate an NCO-terminated prepolymer product (which is called as step a for convenience of description), and then a polymerization inhibitor and a hydroxy acrylate compound are added to react (which is called as step b for convenience of description), so that a product 3 containing NCO and acrylate functional groups is generated.
According to some preferred aspects of the present invention, the hydrophilic double-terminal hydroxyl compound is one or more selected from the group consisting of polytetrahydrofuran ether glycol, polyethylene glycol, polypropylene glycol, and polyethylene-polypropylene glycol copolymer.
According to some preferred aspects of the present invention, the hydroxy acrylate compound is selected from pentaerythritol triacrylate and/or dipentaerythritol tetraacrylate.
According to some preferred aspects of the present invention, in the step 3), the reaction is carried out at 20 to 150 ℃ for 1 to 12 hours.
According to some preferred aspects of the present invention, in the step 3), when the isocyanate compound is a reaction product of the above isocyanate and a hydrophilic double-terminal hydroxyl compound, the step a is performed at 60 to 150 ℃.
According to some preferred aspects of the present invention, in the step 3), when the isocyanate compound is a reaction product of the above isocyanate and a hydrophilic double-terminal hydroxyl compound, the step b is performed at 20 to 80 ℃.
According to some preferred aspects of the invention, in the step 4), the reaction is carried out at 0 ℃ to 80 ℃ for 2 to 12 hours.
According to some specific aspects of the invention, step 4) is implemented as: slowly dripping the product 3 prepared in the step 3) into the product 2 prepared in the step 2) for reaction.
According to the invention, the water-soluble antifouling anti-doodling auxiliary agent prepared by the preparation method has the following structural general formula:
Figure GDA0001711140520000051
wherein R isfIs a perfluoropolyether acyl group;
X1being an organic radical containing a secondary amino group, RfTo the nitrogen atom of said secondary amino group;
X2is a water-soluble organic group containing a tertiary amino group;
RAis a compound containing unsubstituted acrylate functional groups and/or C1-10An alkyl-substituted acrylate functional group of-CO-NH-, said RABy the carbon atom of said-CO-NH-contained therein with said X2To the nitrogen atom of said tertiary amino group in (a);
RCis-CnH2n-1N is a positive integer;
a. b and c are respectively and independently selected from integers which are more than or equal to 1.
According to some preferred aspects of the invention, the R isfIs one or more selected from the following groups:
Figure GDA0001711140520000052
wherein d is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711140520000053
wherein e is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711140520000054
wherein f is more than or equal to 50 and more than or equal to 2, and g is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711140520000055
wherein, 50 is more than or equal to h and more than or equal to 2, and 50 is more than or equal to i and more than or equal to 2.
According to some preferred aspects of the invention, X is1is-R2-NH-, wherein R2Is C1-20An alkylene group of (a). More preferably, R2Is C1-10An alkylene group of (a). According to some specific aspects of the invention, R2Can be-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C(CH3)2CH2-。
According to some preferred aspects of the invention, X is2Is composed of
Figure GDA0001711140520000061
Wherein R is3Is C1-20An alkylene group of (a). More preferably, R3Is C1-10An alkylene group of (a). According to some specific aspects of the invention, R3Can be-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C(CH3)2CH2-。
According to some preferred aspects of the invention, the R isAis-CO-NH-R4-NH-COO-R5Wherein, said R4Is composed of
Figure GDA0001711140520000062
R5Is- (CH)2)j-C(CH2OOC-CH＝CH2)3Either, or,
-(CH2)k-C(CH2OOC-CH＝CH2)2-CH2-O-CH2-C(CH2OOC-CH＝CH2)3wherein j and k are each independently selected from positive integers; more preferably, j, k are each independently selected from integers from 1 to 100;
R6、R7are each independently-NH-CO-O-R8-O-CO-NH-，R8Is selected from C1-10Alkylene of (a) - (C)mH2mO)r1-CmH2m-、-(CpH2pO)r2-(CsH2sO)r3-CmH2m-one or more combinations of m, p, s, r1, r2 and r3 are each independently selected from positive integers, p and s being different. Specifically, m, p, s, r1, r2 and r3 are each independently selected from integers of 1 to 50. According to some specific aspects of the invention, C1-10The alkylene group of (A) may be-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C(CH3)2CH2-. According to still further specific aspects of the invention, m, p, s, r1, r2, and r3 are each independently selected from integers from 1-20.
In the present invention,
Figure GDA0001711140520000063
the positions shown indicate that other groups will be attached.
According to some preferred aspects of the invention, the unsubstituted acrylate functionality has the formula CH2＝CHCOO，C1-10The alkyl-substituted acrylate functional group may be CH2＝C(CH3)COO、CH2＝C(CH2CH3)COO、CH2＝C(CH2CH2CH3)COO、CH2＝C(CH2CH2CH2CH3) COO, and the like.
According to some specific and preferred aspects of the present invention, the unsubstituted acrylate functionality and/or C1-10Has at least three and is located at the RAThe ends of the structure.
According to some preferred aspects of the invention, the-CO-NH-has a plurality. Facilitating the introduction of other groups or being suitable for forming longer segments.
According to some preferred aspects of the invention, the R isCIs C1-10Alkyl group of (1). According to some specific aspects of the invention, RCCan be-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH(CH3)CH3or-C (CH)3)2CH3。
According to some preferred aspects of the invention, a, b are each independently selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.
According to some preferred aspects of the invention, c is an integer selected from 3 to 30. More preferably, c is an integer selected from 3 to 20. According to some specific aspects of the invention, c is an integer selected from 3 to 15.
According to some specific and preferred aspects of the present invention, the water-soluble antifouling anti-graffiti adjuvant is one selected from the following structural formulae:
Figure GDA0001711140520000071
formula I-1
Wherein d is more than or equal to 50 and more than or equal to 2, and a, b, c and t1 are respectively and independently positive integers;
Figure GDA0001711140520000072
formula I-2
Wherein d is more than or equal to 50 and more than or equal to 2, and a, b, c and t2 are respectively and independently positive integers;
Figure GDA0001711140520000081
formula I-3
Wherein d is more than or equal to 50 and more than or equal to 2, and a, b, c and t3 are respectively and independently positive integers;
Figure GDA0001711140520000082
formula I-4
Wherein d is more than or equal to 50 and more than or equal to 2, and a, b, c, t4 and t5 are respectively and independently positive integers;
Figure GDA0001711140520000083
formula I-5
Wherein d is more than or equal to 50 and more than or equal to 2, and a, b, c, t6 and t7 are respectively and independently positive integers.
According to some specific aspects of the invention, t1, t2, t3, t4, t5, t6, and t7 are each independently selected from integers from 1 to 50.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages: the method for preparing the water-soluble antifouling anti-doodling auxiliary agent has the advantages of simple operation, easily obtained raw materials, mild reaction conditions, safety, environmental protection and the like.
Meanwhile, the water-soluble antifouling and doodling-preventing auxiliary agent prepared by the method disclosed by the invention is good in compatibility with raw materials of the water-based UV photocuring paint, strong in mobility in a paint film, capable of enabling perfluoropolyether groups contained in the auxiliary agent to rapidly and thoroughly migrate to the surface of the paint film in the film forming process of the paint so as to achieve excellent antifouling and doodling-preventing effects, and capable of achieving stronger adhesion with the paint film and preventing the paint film from falling off in the using process of a product, further ensuring the long-term stable antifouling and doodling-preventing effects of the paint film, and being better in wear resistance.
Drawings
FIG. 1 shows nuclear magnetism H of PFPE-1 of example 11NMR spectrum analysis.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
All of the raw materials described below are commercially available and/or can be prepared by known means, and meet the requirements of standard chemical products unless otherwise specified.
Example 1
The embodiment provides a preparation method of a water-soluble antifouling doodling-prevention auxiliary agent 1# sample (PFPE-1), which comprises the following specific steps:
adding gamma-aminopropylmethyldimethoxysilane (5.25g), 3-piperazinylpropylmethyldimethoxysilane (5.8g) and 10g of desalted water into a 1L three-neck flask, stirring at 50 ℃ for hydrolysis reaction for 5 hours, slowly opening negative pressure and dehydrating to obtain a dry silane low-boiling-point substance; then adding potassium hydroxide powder (0.01g), octamethylcyclotetrasiloxane (15g) and hexamethyldisiloxane (4.05g), slowly heating to 130 ℃, stirring for reaction for 4 hours, and finally obtaining dry amino silicone oil by a process of removing low-boiling-point substances in vacuum; adding perfluoropolyether methanol ester (50g, structural formula shown as the following, wherein R is shown as the following) into the product under the protection of nitrogenfSelecting a hexafluoropropylene oxide polymerization unit provided by Taicang Zhonghua environmental protection chemical company), slowly heating to 80 ℃, and reacting for 8 hours to obtain the perfluoropolyether modified amino silicone oil.
In a 1L three-necked flask, dibutyltin dilaurate (2g), isophorone diisocyanate (11g), and polyethylene glycol (25g, molecular weight 1000g/mol, and polymerization unit CH were charged2CH2O) and butyl acetate (100g), slowly raising the temperature to 80 ℃ under the protection of nitrogen, and stirring for reacting for 2 hours to obtain an isocyanate prepolymer; cooling the reaction system to 50 ℃, adding p-hydroxyanisole (0.25g) serving as a polymerization inhibitor, slowly adding pentaerythritol triacrylate (7.75g) under stirring, reacting for 4 hours to obtain an acrylic ester compound containing NCO, and supplementing butyl acetate (188g) serving as a solvent; and controlling the reaction temperature to be 10 ℃, slowly dripping the product into the perfluoropolyether modified amino silicone oil under the stirring condition, reacting for 4 hours, sampling, carrying out infrared spectroscopy analysis to remove an NCO peak, and decompressing the reaction product to remove the solvent to obtain the water-soluble antifouling and anti-doodling assistant PFPE-1.
Raw material perfluoropolyether methanol ester R involved in preparation methodfOCH3In RfThe structure of (1) is as follows:
Figure GDA0001711140520000101
wherein, d is 11;
the structural formula of the product PFPE-1 is shown below:
Figure GDA0001711140520000102
wherein, a is 1, b is 1, c is 8, d is 11, PEG represents polyethylene glycol molecular chain segment.
Nuclear magnetic H of product PFPE-1 Compound1NMR analysis, H of PFPE-11The results of NMR analysis are shown in FIG. 1, and it is understood from FIG. 1 that: disordered chemical shift peaks in the range of 0ppm to 0.2ppm belong to absorption peaks of silicon methyl protons on the polydimethylsiloxane side groups; disordered chemical shift peaks in the range of 1.0ppm to 2.0ppm belong to proton absorption peaks on the silylene and isophorone molecule rings on the polydimethylsiloxane side groups; a chemical shift peak near 3.5ppm is attributed to methylene on the middle chain segment of the polyethylene glycol; other random chemical shift peaks in the range of 2.0ppm to 4.5ppm are assigned to piperazine, methylene groups attached to urea groups (or amide groups and urethane bonds) on the ring of isophorone molecule, and also absorption peaks for methylene groups on pentaerythritol; and a proton chemical shift peak on a double bond in an acrylate structure appears in the range of 5.5-6.5 ppm, which proves that the acrylate functional group is successfully introduced into a PFPE molecular chain.
Example 2
The embodiment provides a preparation method of a water-soluble antifouling doodling-prevention auxiliary agent 2# sample (PFPE-2), which comprises the following specific steps:
according to the procedure and process shown in example 1, 22g of isophorone diisocyanate, 50g of polyethylene glycol, 300g of a solvent butyl acetate supplement, 15.5g of pentaerythritol triacrylate and 11.6g of 3-piperazinylpropylmethyldimethoxysilane were used, and the other conditions and the quality were the same as those of example 1, to prepare a sample No. 2 water-soluble antifouling doodle-preventing aid (PFPE-2).
Example 3
The embodiment provides a preparation method of a water-soluble antifouling doodling-prevention auxiliary agent 3# sample (PFPE-3), which comprises the following specific steps:
according to the procedure and process shown in example 1, a water-soluble antifouling doodle-preventing assistant No. 3 sample (PFPE-3) was prepared by replacing 22g of isophorone diisocyanate, 2000g/mol of polyethylene glycol, 100g of polyethylene glycol, 425g of a butyl acetate supplement as a solvent, 15.5g of pentaerythritol triacrylate and 11.6g of 3-piperazinylmethyldimethoxysilane under the same conditions and by the same mass as in example 1.
Comparative example 1
The embodiment provides a preparation method of a water-soluble antifouling doodling-prevention auxiliary agent 4# sample (PFPE-4), which comprises the following specific steps:
A1L three-necked flask was charged with perfluoropolyether methanol ester (100g, specification same as in example 1) and aminoethanol (10g, specification same as in example 1), slowly heated to 80 ℃ for 8 hours, and sampled to analyze infrared absorption peak (1792 cm) of ester bond by infrared analysis-1) Disappearance, amide bond absorption peak (1712 cm)-1) (ii) occurs; and stirring and cleaning the crude product of the reaction product by using absolute methanol, standing, layering, taking the lower-layer liquid, repeating for 3 times, and performing reduced-pressure low-boiling-point removal and drying at 80 ℃ to obtain a pure product of the perfluoropolyether amido ethanol.
In a 1L three-necked flask, dibutyltin dilaurate (5g), isophorone diisocyanate (11g), and polyethylene glycol (200g, molecular weight 4000g/mol, polymerization unit CH were charged2CH2O) and butyl acetate (800g), slowly raising the temperature to 80 ℃ under the protection of nitrogen, and stirring for reacting for 2 hours to obtain an isocyanate prepolymer; cooling the reaction system to 50 ℃, adding p-hydroxyanisole (0.50g) serving as a polymerization inhibitor, slowly adding pentaerythritol triacrylate (15.50g) under stirring, reacting for 4 hours to obtain an acrylic ester compound containing NCO, and supplementing butyl acetate (188g) serving as a solvent; the reaction temperature is controlled to be 10 DEG CSlowly dripping the product into a pure product of perfluoropolyether amido ethanol under the condition of stirring, reacting for 4 hours, sampling, carrying out infrared spectroscopic analysis to remove an NCO peak, and decompressing the reaction product to remove the solvent to prepare the water-soluble antifouling and doodling-preventing assistant PFPE-4.
Figure GDA0001711140520000121
Wherein, a is 11 and q is 45.
Preparation of the coating
The water-soluble anti-fouling and anti-doodling auxiliary agent prepared by the preparation method is used for preparing the anti-fouling and anti-doodling water-based UV photocureable coating, and the raw material formula of the anti-fouling and anti-doodling water-based UV photocureable coating comprises the following components in parts by weight:
Figure GDA0001711140520000122
wherein, the UV active compound can be one or more of aqueous polyurethane acrylate, aqueous epoxy acrylate, aqueous polyester acrylate, 2-functional acrylate monomer, 3-functional acrylate monomer and the like.
The pH regulator can be one or more of triethylamine, ammonia water, diethanolamine, triethanolamine, methylethanolamine and the like.
The photoinitiator can be selected from one or more of Irgacure500, Irgacure819, Irgacure2959, Irgacure754, Irgacure819DW and the like.
Specifically, the UV coating is prepared by compounding according to a formula (the adding amount of each component is calculated by weight parts) shown in Table 1, dispersing at a high speed for 20 minutes, spraying the coating on a Polycarbonate (PC) plastic coating test board, leveling the coating film for 5 minutes at room temperature, baking the coating film in an oven at 50 ℃ for 30 minutes, and finally curing the coating film in a RW-UVA201-20 type UV curing machine under the curing condition that the light source power is 2kw, and the conveying speed is 2.5 m/min. In the table, UV2282 stands for an aqueous UV-curable polyurethane dispersion
Figure GDA0001711140520000123
UV2282 from Kesika, HDDA for 1, 6-hexanediol diacrylate (available from Bailingwei), Irgacure2959 for the photo-curing initiator basf;
performance testing of the paint films
Evaluation of scrawling resistance: and (3) adopting an oil-based black marking pen to scribble on the surface of the paint film, drying the paint film for 4 hours at room temperature, wiping stains on the surface of the paint film with a dry paper towel, and observing whether stains are left on the surface of the paint film. The hierarchical labeling was performed according to the following criteria:
level 1: means that stains can be easily wiped off and that no residue remains inside the paint film;
and 2, stage: indicating that the stain can be wiped off, but is laborious and has no residue inside the paint film;
and 3, level: indicating that stains can be wiped off, but there is ink bleeding inside the paint film;
4, level: indicating that the stain was not wiped off.
Contact angle test method: the test piece without any abrasion was placed on a contact angle meter (model: DSA30, supplied by kluyvers ltd, germany), a test drop volume of 4 μ L was measured using deionized water and dodecane as the test medium, contact angle values of 3 drops were recorded, and the arithmetic mean of the 3 test data was taken.
Evaluation of Friction durability: fixing the test piece on an abrasion resistance tester (ESIDA-NM-002, provided by Eichun instruments, Inc., Shenzhen), and binding a polypropylene non-woven fabric (model: B95, Jiangxi Haorui Industrial materials, Inc.) on a contact head friction probe; applying 500g of test load above the probe, wherein the test stroke is 20mm, and the sample speed is 10 times/min; after the abrasion test was performed for 20 minutes, the experiment was stopped and the contact angle of the surface was lost.
The results of the graffiti resistance, contact angle, and abrasion durability tests are shown in table 1.
Table 1 shows the formulations and performance test results of the coatings
Figure GDA0001711140520000141
Compared with the blank sample coating S7, the coating samples S1, S2, S3, S4, S5 and S6 show that the introduction of PFPE in the aqueous coating formula can obviously improve the anti-graffiti performance, the paint film without PFPE is not anti-fouling, oleic acid can be completely spread on the surface of the paint film, and the oil-based marking pen ink can pollute the paint film and cannot be erased; compared with S6, the paint film surfaces of S1, S2, S3, S4 and S5 have higher contact angles of water and oleic acid after being abraded, because a plurality of acrylate UV photocuring active functional groups and polysiloxane chain segments are introduced into the water-based paint S1, S2, S3, S4 and S5, and the water-based paint has higher compatibility and adhesion with a water-based paint body, so that the water-based paint has higher wear resistance, the perfluoropolyether chain segments are more thoroughly migrated, and the antifouling and anti-doodling performance is greatly improved; meanwhile, through comparison of water-based paint samples S1, S4 and S5, the increase of the content of the PFPE-based anti-fouling and anti-doodling assistant in a paint film is beneficial to the improvement of the anti-fouling performance, but the change of the improvement amplitude along with the content is not obvious, and the improvement of the anti-fouling performance is not obvious after the content of the PFPE-based anti-fouling and anti-doodling assistant in the water-based paint formula reaches a certain degree. The experimental results show that: the water-soluble antifouling and doodling-prevention auxiliary agent with water-solubility and UV photocuring activity prepared by the preparation method disclosed by the invention can have good intermiscibility and adhesive force with a water-soluble UV paint film, and can enable a perfluoropolyether chain segment to be more thoroughly migrated, so that the paint film added with the water-soluble antifouling and doodling-prevention auxiliary agent has good antifouling property and wear resistance.
The present invention is described in detail in order to make those skilled in the art understand the content and practice the invention, and the invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the invention should be covered by the scope of the invention.

Claims (8)

1. The preparation method of the water-soluble antifouling anti-doodling auxiliary agent is characterized by comprising the following steps:
1) mixing a silane coupling agent containing primary amino and a silane coupling agent containing secondary amino, carrying out hydrolysis reaction and condensation reaction to obtain an initial product, and carrying out polycondensation reaction on the initial product, siloxane ring bodies and an organosilicon end-capping agent in the presence of an alkaline catalyst to obtain an amino silicone oil product 1;
2) carrying out amidation reaction on the amino silicone oil product 1 prepared in the step 1) and a perfluoropolyether compound to generate a product 2;
3) reacting an isocyanate compound and a hydroxyl acrylate compound in a solvent in the presence of a catalyst and a polymerization inhibitor to generate a product 3; the isocyanate compound is a reaction product of one or more of isophorone diisocyanate and tripolymer thereof, toluene diisocyanate and dipolymer and tripolymer thereof, hexamethylene diisocyanate and dipolymer and tripolymer thereof, dicyclohexylmethane diisocyanate and hydrophilic double-end hydroxyl compound; the hydrophilic double-end hydroxyl compound is one or more of polytetrahydrofuran ether glycol, polyethylene glycol, polypropylene glycol and polyethylene glycol-polypropylene glycol copolymer;
4) adding the product 3 prepared in the step 3) into the product 2 prepared in the step 2), and reacting to generate the water-soluble antifouling and anti-doodling auxiliary agent;
wherein in the step 1), the hydrolysis reaction, the condensation reaction and the polycondensation reaction are respectively carried out at 10-200 ℃; in the step 2), the amidation reaction is carried out at 50-200 ℃; step 3), carrying out the reaction at 20-150 ℃; in the step 4), the reaction is carried out at 0-80 ℃.
2. The method for preparing the water-soluble antifouling doodle-preventing assistant according to claim 1, wherein the silane coupling agent containing primary amino group is one or more selected from the group consisting of γ -aminopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane, γ -aminopropylethyldimethoxysilane and γ -aminopropylethyldiethoxysilane; and/or the silane coupling agent containing the secondary amino group is one or more of gamma-piperazinylpropylmethyldimethoxysilane, gamma-piperazinylpropylmethyldiethoxysilane, gamma-piperazinylpropylethyldimethoxysilane, gamma-piperazinylpropylethyldiethoxysilane, N- (N-butyl) -gamma-aminopropylmethyldimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane and N- (N-butyl) -gamma-aminopropylmethyldiethoxysilane.
3. The method for preparing the water-soluble antifouling doodle-preventing assistant according to claim 1, wherein the basic catalyst is selected from one or more of potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide; and/or the siloxane ring body is one or more of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane and decamethylcyclopentasiloxane; and/or the organosilicon end-capping agent is one or more selected from hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane.
4. The method for preparing the water-soluble antifouling doodling-preventing assistant according to claim 1, wherein the structural formula of the perfluoropolyether compound is RfOR1Wherein R is1Is C1-10Alkyl of (a), said RfIs one or more selected from the following groups:
Figure 548024DEST_PATH_IMAGE001
wherein d is more than or equal to 50 and more than or equal to 2;
Figure 412075DEST_PATH_IMAGE002
wherein e is more than or equal to 50 and more than or equal to 2;
Figure 695289DEST_PATH_IMAGE003
wherein, f is more than or equal to 50 and more than or equal to 2, g is more than or equal to 50 and more than or equal to 2;
Figure 973211DEST_PATH_IMAGE004
wherein, 50 is more than or equal to h and more than or equal to 2, and 50 is more than or equal to i and more than or equal to 2.
5. The method for preparing the water-soluble antifouling doodle-preventing assistant according to claim 1, wherein in the step 2), the amidation reaction is carried out in the presence of a protective gas.
6. The preparation method of the water-soluble antifouling doodle-preventing auxiliary agent as claimed in claim 1, wherein the catalyst is one or more selected from triethylamine, tetrabutyl titanate, dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecylthio) and dibutyltin diacetate; and/or the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone.
7. The method for preparing the water-soluble antifouling doodle-preventing assistant according to claim 1, wherein the hydroxy acrylate compound is pentaerythritol triacrylate and/or dipentaerythritol tetraacrylate.
8. The preparation method of the water-soluble antifouling doodling prevention aid as claimed in any one of claims 1 to 7, wherein the water-soluble antifouling doodling prevention aid prepared by the preparation method has the following structural general formula:
Figure 709086DEST_PATH_IMAGE005
；
wherein R isfIs a perfluoropolyether acyl group;
X1being an organic radical containing a secondary amino group, RfTo the nitrogen atom of said secondary amino group;
X2is a water-soluble organic group containing a tertiary amino group;
RAis a compound containing unsubstituted acrylate functional groups and/or C1-10An alkyl-substituted acrylate functional group of-CO-NH-, said RABy the carbon atom of said-CO-NH-contained therein with said X2To the nitrogen atom of said tertiary amino group in (a);
RCis-CnH2n-1N is a positive integer; a. b and c are respectively and independently selected from integers which are more than or equal to 1.
CN201810384866.5A 2018-04-26 2018-04-26 Preparation method of water-soluble antifouling anti-doodling auxiliary agent Active CN108624105B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810384866.5A CN108624105B (en) 2018-04-26 2018-04-26 Preparation method of water-soluble antifouling anti-doodling auxiliary agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810384866.5A CN108624105B (en) 2018-04-26 2018-04-26 Preparation method of water-soluble antifouling anti-doodling auxiliary agent

Publications (2)

Publication Number Publication Date
CN108624105A CN108624105A (en) 2018-10-09
CN108624105B true CN108624105B (en) 2020-10-20

Family

ID=63694634

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810384866.5A Active CN108624105B (en) 2018-04-26 2018-04-26 Preparation method of water-soluble antifouling anti-doodling auxiliary agent

Country Status (1)

Country Link
CN (1) CN108624105B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109486280B (en) * 2018-11-14 2022-02-01 鳄鱼尼卡(上海)新材料有限公司 Two-component aqueous anti-graffiti coating containing water-soluble amino silicone oil for white board marker
CN109943227B (en) * 2019-03-07 2021-03-12 河北鼎炽道路标线工程有限公司 Low-density anti-fouling coating for surface of solid buoyancy material substrate
JP7369875B2 (en) * 2020-04-13 2023-10-26 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ Fluorinated alkoxysilyl-functional polymers for antifouling and anti-scratch coatings
CN117025075B (en) * 2023-09-11 2024-02-13 安徽科创美涂料科技股份有限公司 Anti-graffiti finishing paint and preparation method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3196621B2 (en) * 1995-04-20 2001-08-06 信越化学工業株式会社 Water-soluble surface treatment agent
JP3211656B2 (en) * 1996-03-18 2001-09-25 信越化学工業株式会社 Water-soluble fiber treating agent and method for producing the same
TWI250894B (en) * 2002-01-03 2006-03-11 Sipix Imaging Inc Functionalized halogenated polymers for microencapsulation
PL1651704T3 (en) * 2003-07-16 2012-01-31 Dow Corning Coating compositions containing aminofunctional silicone resins
JP4711080B2 (en) * 2006-07-25 2011-06-29 信越化学工業株式会社 Method for producing fluoroorganopolysiloxane resin for film forming composition
DE102007013262A1 (en) * 2007-03-15 2008-09-18 Basf Coatings Ag Coating compositions containing adducts with silane functionality and highly scratch-resistant coatings produced therefrom with improved crack resistance
WO2009113459A1 (en) * 2008-03-10 2009-09-17 旭化成イーマテリアルズ株式会社 Photosensitive polyorganosiloxane composition

Also Published As

Publication number Publication date
CN108624105A (en) 2018-10-09

Similar Documents

Publication Publication Date Title
CN108624105B (en) Preparation method of water-soluble antifouling anti-doodling auxiliary agent
CN108559087B (en) Preparation method of antifouling and doodling-preventing auxiliary agent with UV (ultraviolet) photocuring activity
CN107141867B (en) A kind of hard coat anti-fingerprint additive and preparation method thereof
CN112574390B (en) High-wear-resistance UV resin with anti-fingerprint function and preparation method thereof
CN108586699B (en) Antifouling and anti-doodling auxiliary agent and application thereof
CN101395191B (en) High energy ray-curable composition
US20060194707A1 (en) Curable coating compositions
CN113105605B (en) UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof
CN107603474B (en) Composition for antifouling coating of transparent optical device
CN109705382B (en) Self-repairing resin, coating, film preparation method and application
CN111434740A (en) Ultraviolet-cured fluorine-containing polyurethane acrylate coating
CN108753013B (en) Water-soluble antifouling anti-doodling auxiliary agent and application thereof
KR101821178B1 (en) Surface control additive for radiation curing system, preparation method therefor and application thereof
CN111875955B (en) UV-cured optical transparent flexible material and preparation method and application thereof
CN109722089B (en) Anti-fouling auxiliary agent for ultraviolet curing coating
CN109844004A (en) Radiation curable composition with anti-pollution
CN113321623B (en) Six-functionality-degree fluorine-containing photocuring anti-fouling additive and application thereof
KR100535873B1 (en) Fluorine Polyurethane Resin Having Excellent Pollution-Proof Property
CN115427474B (en) Fluorinated alkoxysilyl functional polymers for antifouling and scratch-resistant coatings
CN113387898B (en) Ten-functionality fluorine-containing photocuring anti-fouling additive and application thereof
CN109722088B (en) Anti-fouling auxiliary agent for photocureable coating and application thereof
CN112980309A (en) High-wear-resistance UV (ultraviolet) coating with fingerprint resistance function
CN116217916B (en) Y-type perfluoropolyether modified acrylic ester, antifouling paint, preparation method and application
CN107141440A (en) Aqueous oligomer of organosilicon polyurethane acrylate that a kind of stiffening ring is modified and preparation method thereof
CN112409912A (en) UV (ultraviolet) curing coating containing Y-type perfluoropolyether single-ended diol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant