CN108753013B - Water-soluble antifouling anti-doodling auxiliary agent and application thereof - Google Patents

Water-soluble antifouling anti-doodling auxiliary agent and application thereof Download PDF

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CN108753013B
CN108753013B CN201810384122.3A CN201810384122A CN108753013B CN 108753013 B CN108753013 B CN 108753013B CN 201810384122 A CN201810384122 A CN 201810384122A CN 108753013 B CN108753013 B CN 108753013B
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CN108753013A (en
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徐涛
艾显虎
周燚
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Sinochem Environmental Protection Chemicals Taicang Co Ltd
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    • 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
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Abstract

The invention discloses a water-soluble antifouling anti-doodling auxiliary agent and application thereof, wherein a polysiloxane chain segment, a water-soluble organic chain segment containing tertiary amino, a photocuring active group, a-CO-NH-and other groups are introduced into the auxiliary agent on the basis of a perfluoropolyether chain segment, so that the intermiscibility and the adhesive force of the auxiliary agent and a water-soluble UV paint film are improved, the perfluoropolyether chain segment can be more thoroughly migrated, and the paint film has good antifouling performance and wear resistance; the application comprises the following steps: the application of the anti-fouling and anti-doodling waterborne UV photocureable coating is provided.

Description

Water-soluble antifouling anti-doodling auxiliary agent and application thereof
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 water-soluble antifouling anti-doodling auxiliary agent and application thereof.
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 GDA0001711143690000011
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 example, patent CN2005800145739 discloses a perfluoropolyether modified acrylate with an anti-fouling effect, however, after the compound disclosed in this patent is applied to a coating, in the course of UV light curing of the coating, oxygen in the air can generate an oxygen inhibition effect on curing, and at the same time, the compound has poor adhesion and compatibility with a paint film, and further perfluoropolyether can continuously separate from the surface of the paint film in the course of using the product, and finally the durability of the antifouling function of the paint film is deteriorated, so that although a certain antifouling and wear resistance is realized, the effect is still not ideal, and the compound cannot be dissolved in an aqueous UV coating, that is, the antifouling and anti-graffiti performance of the aqueous UV coating cannot be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a water-soluble antifouling anti-doodling auxiliary agent which is suitable for a water-based UV (ultraviolet) photocureable coating, can realize a long-term stable antifouling anti-doodling effect and has good wear resistance.
The invention also provides an antifouling and anti-doodling waterborne UV photocureable coating.
In order to solve the above technical problems, the present invention adopts a technical scheme as follows:
a water-soluble antifouling anti-graffiti auxiliary agent, which has the following general structural formula:
Figure GDA0001711143690000021
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 an organic group containing a photocuring active group and-CO-NH-, the R isABy 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 GDA0001711143690000022
wherein d is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711143690000023
wherein e is more than or equal to 50 and more than or equal to 2;
Figure GDA0001711143690000031
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 GDA0001711143690000032
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-R1-NH-, wherein R1Is C1-20An alkylene group of (a). More preferably, R1Is C1-10An alkylene group of (a). Root of herbaceous plantAccording to some particular aspects of the invention, R1Can 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 GDA0001711143690000033
Wherein R is2Is 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, the photocurable active groups are unsubstituted acrylate functional groups and/or C1-10Alkyl-substituted acrylate functional groups of (a). The structural formula of the acrylate functional group is CH2The alkyl-substituted acrylate functional group may be CH ═ CHCOO2＝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 photocurable active group has 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 isAis-CO-NH-R3-NH-COO-R4Wherein, said R3Is composed of
Figure GDA0001711143690000034
R4Is- (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 and k are each independently selected from integers of 1 to 100.
R5、R6Are each independently-NH-CO-O-R7-O-CO-NH-，R7Is 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 GDA0001711143690000041
the positions shown indicate that other groups will be attached.
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 GDA0001711143690000042
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 GDA0001711143690000051
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 GDA0001711143690000052
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 GDA0001711143690000053
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 GDA0001711143690000061
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.
The invention provides another technical scheme that: the raw materials of the antifouling and anti-doodling water-based UV photocureable coating contain the water-soluble antifouling and anti-doodling auxiliary agent.
In the invention, the raw material formula of the antifouling anti-doodling water-based UV photocureable coating comprises the following components in parts by weight:
Figure GDA0001711143690000062
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.
In the invention, all the raw materials can be obtained by commercial purchase and/or known means, and meet the requirements of standard chemical products when not particularly stated.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the water-soluble antifouling and doodling-prevention auxiliary agent provided by the invention is good in raw material compatibility with a water-based UV (ultraviolet) 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 process of forming the paint film so as to achieve excellent antifouling and doodling-prevention effects, and capable of achieving stronger adhesion with the paint film and preventing the product from falling off in the using process, so that the long-term stable antifouling and doodling-prevention effects of the paint film are guaranteed, and the wear resistance is better.
Drawings
FIG. 1 shows nuclear magnetism H of PFPE-1 of example 11NMR spectrum analysis.
Detailed Description
The invention provides 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 a first 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 second 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.
The preparation method is simple, easy to operate, mild in reaction condition, safe in preparation process and environment-friendly.
According to some specific and preferred aspects of the present invention, the primary amino group-containing silane coupling agent 1 may be selected from the group consisting of γ -aminopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane, γ -aminopropylethyldimethoxysilane and γ -aminopropylethyldiethoxysilane in combination with one or more of these.
According to some specific and preferred aspects of the present invention, the secondary amino-containing silane coupling agent 2 may be selected from one or a combination of more of γ -piperazinylpropylmethyldimethoxysilane, γ -piperazinylpropylmethyldiethoxysilane, γ -piperazinylpropylethyldimethoxysilane, γ -piperazinylpropylethyldiethoxysilane, N- (N-butyl) - γ -aminopropylmethyldimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane and N- (N-butyl) - γ -aminopropylmethyldiethoxysilane.
Preferably, in step 1), the hydrolysis reaction and condensation reaction are carried out in desalted water.
Preferably, the first catalyst is a basic catalyst, and the basic catalyst is one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and the like.
Preferably, the siloxane ring body is a combination of one or more selected from the group consisting of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane and decamethylcyclopentasiloxane.
Preferably, the silicone blocking agent is a combination of one or more selected from hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.
Preferably, in the step 1), the hydrolysis reaction and the condensation reaction are carried out at 10-200 ℃, and the reaction time is 1-12 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.
Preferably, in the step 1), the polycondensation reaction is performed at 10-200 ℃ for 1-12 hours. More preferably, in the step 1), the polycondensation reaction is performed at 80-200 ℃ for 2-8 hours.
Preferably, the amidation reaction of step 2) is carried out in the presence of a protective gas (which may be, for example, nitrogen or the like).
Preferably, the structural general formula of the perfluoropolyether compound is RfOR8Wherein R is8Is C1-10 alkyl. According to some specific aspects of the invention, R8Can be-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH(CH3)CH3or-C (CH)3)2CH3。
Preferably, 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.
Preferably, the second catalyst may be a combination of one or more selected from triethylamine, tetrabutyl titanate, dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide and dibutyltin diacetate.
Preferably, 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.
Preferably, in 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.
Preferably, the isocyanate compound is a combination of one or more selected from isophorone diisocyanate and its trimer, toluene diisocyanate and its dimer, trimer, hexamethylene diisocyanate and its dimer, trimer, dicyclohexylmethane diisocyanate. The isocyanate may be a reaction product of the above isocyanate and a hydrophilic double-terminal hydroxyl compound, wherein the hydrophilic double-terminal hydroxyl compound is one or a combination of more selected from polytetrahydrofuran ether glycol, polyethylene glycol, polypropylene glycol and polyethylene glycol-polypropylene glycol copolymer. When the isocyanate compound is a reaction product of the above isocyanate and a hydrophilic double-terminal hydroxyl compound, the specific embodiment of step 3) is: 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.
Preferably, the hydroxy acrylate compound is selected from pentaerythritol triacrylate and/or dipentaerythritol tetraacrylate.
Preferably, in the step 3), the reaction is carried out at 20-150 ℃ for 1-12 hours.
Preferably, in the step 3), when the isocyanate compound is a reaction product of the isocyanate and a hydrophilic double-terminal hydroxyl compound, the step a is carried out at 60 to 150 ℃.
Preferably, in the step 3), when the isocyanate compound is a reaction product of the isocyanate and a hydrophilic double-terminal hydroxyl compound, the step b is carried out at 20-80 ℃.
Preferably, in the step 4), the reaction is carried out at 0-80 ℃ for 2-12 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.
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 starting materials are either commercially available or prepared by methods conventional in the art, unless otherwise specified in the following.
Example 1
This example provides a water-soluble antifouling anti-graffiti adjuvant # 1 sample (PFPE-1), the structural formula of PFPE-1 is shown below:
Figure GDA0001711143690000101
wherein, a is 1, b is 1, c is 8, d is 11, PEG represents polyethylene glycol molecular chain segment.
The preparation method comprises the following 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; the reaction system is cooled to 50 ℃, and polymerization inhibitor p-hydroxyanisole (0.25g) is added inSlowly adding pentaerythritol triacrylate (7.75g) under stirring, reacting for 4 hours to obtain an acrylic ester compound containing NCO, and supplementing a solvent of butyl acetate (188 g); 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 GDA0001711143690000102
wherein, d is 11;
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
This example provides a water-soluble antifouling anti-graffiti aid # 2 sample (PFPE-2).
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
This example provides a water-soluble antifouling anti-graffiti aid # 3 sample (PFPE-3).
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 polymerization inhibitor, slowly adding pentaerythritol triacrylate (15.50g) under stirring, reacting for 4 hours to obtain an acrylic ester compound containing NCO, and supplementing acetic acid serving as solventButyl ester (188 g); controlling the reaction temperature to be 10 ℃, slowly dripping the product into a pure product of the perfluoropolyether amido ethanol under the stirring condition, reacting for 4 hours, sampling, carrying out infrared spectroscopic analysis to eliminate an NCO peak, and decompressing the reaction product to remove the solvent to obtain the water-soluble antifouling anti-doodling assistant PFPE-4.
Figure GDA0001711143690000121
Wherein, a is 11 and q is 45.
Preparation of the coating
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 to prepare a UV coating, 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 transmission rate is 2.5 m/min. In the table, UV2282 stands for an aqueous UV-curable polyurethane dispersion
Figure GDA0001711143690000122
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 GDA0001711143690000131
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 provided by the invention has 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 (5)

1. The water-soluble antifouling anti-doodling auxiliary agent is characterized by having the following general structural formula:
Figure FDA0002657183940000011
wherein R isfIs a perfluoropolyether acyl group;
X1is-R1-NH-, wherein R1Is C1-20Alkylene group of (A), RfTo the nitrogen atom of said secondary amino group;
X2a tertiary amino group-containing water-soluble organic group represented by the following formula,
Figure FDA0002657183940000012
wherein R is2Is C1-20An alkylene group of (a);
RAis-CO-NH-R3-NH-COO-R4Wherein, said R3Is composed of
Figure FDA0002657183940000013
R4Is- (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;
R5、R6are each independently-NH-CO-O-R7-O-CO-NH-，R7Is 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 are different, and R is a hydrogen atomABy 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.
2. The water-soluble antifouling anti-graffiti aid of claim 1, wherein R isfIs one or more selected from the following groups:
Figure FDA0002657183940000014
wherein d is more than or equal to 50 and more than or equal to 2;
Figure FDA0002657183940000021
wherein e is more than or equal to 50 and more than or equal to 2;
Figure FDA0002657183940000022
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 FDA0002657183940000023
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.
3. The water-soluble antifouling anti-graffiti aid of claim 1, wherein R isCIs C1-10Alkyl groups of (a); and/or a and b are respectively independently selected from integers from 1 to 10, and c is selected from integers from 3 to 30.
4. The water-soluble antifouling anti-graffiti aid of claim 1, wherein the water-soluble antifouling anti-graffiti aid is one selected from the following structural formulae:
Figure FDA0002657183940000024
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 FDA0002657183940000025
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 FDA0002657183940000031
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 FDA0002657183940000032
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 FDA0002657183940000033
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.
5. An antifouling and anti-doodling water-based UV photocureable coating which is characterized in that the raw materials comprise the water-soluble antifouling and anti-doodling auxiliary agent as claimed in any one of claims 1 to 4.
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