CN103333285A - UV-curing side-chain fluorine-containing water-based polyurethane paint and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of paints, particularly to a UV-curing side-chain fluorine-containing water-based polyurethane paint and a preparation method thereof. The preparation method comprises the following steps: by using handy fluorine-containing acrylate monomer and/or fluorine-free acrylic monomer and chain transfer diol as raw materials, carrying out free-radical polymerization to obtain fluorine-containing alkyl diol; polymerizing side-chain fluorine-containing alkyl diol monomer to a water-based polyurethane hard section, and meanwhile, introducing photosensitive reactive group to the tail end of the polyurethane chain to prepare a UV-curing side-chain fluorine-containing water-based polyurethane resin; and blending with assistants to obtain the UV-curing water-based paint. The water-based paint provided by the invention has the characteristics of environmental protection and UV quick curing, has the advantages of excellent solvent property, excellent weatherability, high glossiness, excellent anti-staining property, excellent self-cleaning property and the like, can be used as a waterproof anticorrosive paint for building external walls, automobiles, ships and the like.

Description

A kind of UV-curable side chain fluorine-containing waterborne polyurethane coating and preparation method thereof

technical field

The invention relates to the technical field of coatings, in particular to a UV-curable side chain fluorine-containing aqueous polyurethane coating and a preparation method thereof.

Background technique

In response to the requirements of environmental regulations, water-based coatings are developing rapidly. In advanced countries, the production of water-based coatings accounts for more than half of the total coatings. Polyurethane materials are widely used because of their excellent properties such as wear resistance, chemical corrosion resistance, high elasticity and strength. There are many varieties of polyurethane, and the theoretical research and production technology are mature. In the 1960s, there were a lot of research and reports on waterborne polyurethane, but there were some problems in the performance of waterborne polyurethane, such as the decline of water resistance and solvent resistance. Therefore, the theoretical research, product development and modification of waterborne polyurethane are the development of waterborne coatings. direction.

Fluoropolymers have excellent solvent resistance, heat resistance, low surface free energy and other properties, and produce fluorine enrichment effect on the surface of materials. Using fluoropolymers to improve the surface properties of materials is a research hotspot. There have been many reports on the modification of water-based polyurethane with fluorine-containing polymers. Hyejin Lim et al. synthesized macromolecular fluorine-containing diols, introduced them into polyurethane chains as chain extenders, and synthesized side-chain fluorine-containing water-based polyurethanes; Hong Tan et al. Fluorine-containing side chains were introduced into polyurethane, and the migration of fluorine chain segments on the surface was studied. UV curing technology has the characteristics of fast curing, environmental protection and high efficiency, and has entered people's field of vision. The research on UV curing water-based fluorine-containing polyurethane has been favored by people. Chinese patent CN: 201210565342.9 discloses a trimerization method using The reaction between the body and the fluorine-containing alcohol to form an adduct to prepare UV light-curable water-based fluorine-containing polyurethane latex film and its preparation method; Hyeon-Deuk Hwang et al. used perfluoroether diol as the soft segment to synthesize the soft-segment main chain fluorine-containing UV-curable polyurethane emulsion , but at present, the preparation cost of fluorine-containing bifunctional monomers is high, the purification process is cumbersome, and perfluoroalkyl glycols are rare in China, which limits the research on UV-curable waterborne fluorine-containing polyurethanes.

Contents of the invention

The technical problem to be solved by the present invention is to provide a fluorine-containing alkyl glycol for the shortcomings of the above-mentioned existing products.

Another technical problem to be solved by the present invention is to provide a UV-curable side chain fluorine-containing aqueous polyurethane resin.

Another technical problem to be solved by the present invention is to provide a UV-curable side chain fluorine-containing aqueous polyurethane coating.

Another technical problem to be solved by the present invention is to provide a method for preparing a UV-curable side chain fluorine-containing waterborne polyurethane coating.

In order to achieve the above object, the present invention is achieved through the following technical solutions :

A fluorine-containing alkyl glycol, the fluorine-containing alkyl glycol has the structure shown in formula (I):

Formula (I);

Wherein R _f is a fluorine-containing group, and the fluorine-containing group is a perfluoroalkyl group with 1 to 20 carbon atoms; R ₁ =H, Me, CF3 or halogen, m≥0; R ₂ =H or Me; p ≥0; n>0;

The preparation method of described fluorine-containing alkyl glycol is as follows:

In parts by weight, 1 to 90 parts of fluorine-containing acrylate monomer, 0 to 90 parts of acrylate monomer or methacrylate monomer, 0.1 to 15 parts of chain transfer diol, 0.01 to 2 parts Initiator and 10-80 parts of solvent are reacted in a nitrogen atmosphere at 50°C-90°C for 6-24 hours by semi-titration solution polymerization, and purified by n-hexane or petroleum ether precipitation to obtain fluorine-containing alkyl glycol.

The fluorine-containing acrylate monomer can be expressed as R _f (CH ₂ ) _m OC(O)CR ₁ =CH ₂ , wherein R _f is a fluorine-containing group, and most of them are all 1-20 carbon atoms. Fluoroalkyl; R ₁ =H, Me, CF ₃ or halogen, m≥0. Preferably, the fluorine-containing acrylate monomers are perfluoroalkyl (meth)acrylates, perfluoroalkyl (meth)acrylates containing sulfur heteroatoms, perfluoronitrogen-containing fluoroalkane (meth)acrylates base ester or perfluorosulfonamide (meth)acrylate.

The acrylate monomer or methacrylate monomer is methyl methacrylate, ethyl methacrylate, butyl methacrylate or methyl acrylate; the chain transfer diol is 1- Thioglycerol; the initiator is benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile or azobisisoheptanonitrile, etc., preferably azobisisobutyronitrile; the solvent It is a low-boiling inert solvent such as toluene and tetrahydrofuran, preferably tetrahydrofuran.

A UV-curable side chain fluorine-containing water-based polyurethane coating, in parts by weight, the coating is composed of the following components: 20-50 parts of UV-curable side-chain fluorine-containing water-based polyurethane resin, 40-80 parts of Ionized water, 0.5-4.0 parts of photoinitiator, 0.5-2.0 parts of film-forming aid, 0.1-1.0 part of defoamer, 0.1-1.0 part of leveling agent, 0.1-1.0 part of anti-corrosion and anti-mold agent and 0.1 ~1.0 part of thickener;

Preferably, the UV-curable side chain fluorine-containing water-based polyurethane coating is composed of the following components in parts by mass: 30 parts of water-soluble UV-curable fluorine-containing acrylate resin, 65.5 parts of deionized water , 2.0 parts of photoinitiator, 1.0 part of film-forming aid, 0.5 part of defoamer, 0.5 part of leveling agent, 0.2 part of anti-corrosion and anti-mold agent and 0.3 part of thickener;

Preferably, described photoinitiator is aqueous photoinitiator such as Darocur 2959, Darocur 1173 or UV-500.

Preferably, the film-forming aid is propylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, or propylene glycol phenyl ether. The defoaming agent is water-soluble silicone oil, modified organopolysiloxane mixture or amino silicone oil, etc.; the leveling agent is polyether modified polysiloxane copolymer or polyether modified acrylic functional group Dimethyl siloxane, etc.; the anti-corrosion and anti-fungal agents are isothiazolinone derivatives, benzimidazole compounds, substituted aromatic compounds, triazine compounds, etc.; the thickener is cellulose ether and Its derivatives, alkali-swellable thickeners, polyurethane thickeners, hydrophobically modified non-polyurethane thickeners, etc.

The preparation method of described UV-curable side chain fluorine-containing waterborne polyurethane resin may further comprise the steps:

S1. In parts by weight, react 5 to 50 parts of diisocyanate monomer, 5 to 80 parts of polyether diol and/or polyester diol, and 0.01 to 2 parts of catalyst at 60 to 100°C for 1 to 3 hours ;

S2. Cool down to below 70°C, add 0-15 parts of low molecular weight diol or diamine chain extender, 0.1-50 parts of self-made fluorine-containing alkyl glycol, keep the temperature at 50-70°C, and react for 1~ 3h;

S3. Add 0.1-15 parts of hydrophilic chain extender to continue the reaction for 1-3 hours, add 0.1-30 parts of methacrylate hydroxy ester monomer or acrylate hydroxy ester monomer and 0.01-2 parts of polymerization inhibitor to continue React for 1 to 3 hours, during the reaction, solvent can be added to adjust the viscosity;

S4. Cool down to 30-60°C, add 0.1-2 parts of neutralizing agent to carry out salt-forming reaction for 0.5-1.5 hours, and then obtain UV-curable side chain fluorine-containing water-based polyurethane resin.

The diisocyanate monomer described in step S1 is an aliphatic diisocyanate such as isophorone diisocyanate, hexamethylene diisocyanate trimer, 2,4- or 2,6-toluene diisocyanate or diphenylmethane diisocyanate. Isocyanates and aromatic diisocyanates.

The polyether glycol and/or polyester glycol described in step S1 is polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, poly(1,4-butylene glycol carbonate ) diol, poly(1,6-hexanediol carbonate) diol, etc., the molecular weight is 500-3000, preferably 500-2000.

The catalyst described in step S1 is dibutyltin laurate, stannous octoate, cobalt octoate, lead octoate, triethanolamine and the like.

The fluorine-containing alkyl diol described in step S2 is used as a side chain fluorine-containing alkyl diol chain extender, and the molecular weight of the fluorine-containing alkyl diol is 800-5000, preferably 800-3000.

The low-molecular-weight diol or diamine chain extender described in step S2 is 1,4-butanediol, 1,6-hexanediol, ethylenediamine or 1,4-butanediamine, etc., and the number of carbon atoms is 2 to 10 aliphatic dihydric alcohols or aliphatic dibasic amines;

The hydrophilic chain extender described in step S3 is an anionic chain extender such as 2,2-bis(hydroxymethyl)propionic acid, amino acid, diaminobenzoic acid, sodium ethylenediaminoethanesulfonate or N-formazan cationic chain extender such as phenyldiethanolamine, preferably 2,2-bis(hydroxymethyl)propionic acid or N-methyldiethanolamine.

The acrylate hydroxy ester monomer or methacrylate hydroxy ester monomer described in step S3 is used as a blocking agent for polyisocyanate, so that the prepared coating can be cured by UV light, and the reaction temperature is slightly higher than room temperature, shortening the The production cycle reduces the preparation cost; preferably, the hydroxyethyl methacrylate monomer is hydroxyethyl methacrylate or hydroxypropyl methacrylate; the hydroxy acrylate monomer is hydroxyethyl acrylate, Hydroxypropyl acrylate, trihydroxypropane diacrylate or pentaerythritol triacrylate, etc.

The polymerization inhibitor described in step S3 is hydroquinone or p-hydroxyanisole etc.

The neutralizing agent described in step S4 is ammonia water, triethylamine, triethanolamine, acetic acid and the like.

The UV-curable side chain fluorine-containing aqueous polyurethane resin obtained in step S4 is a block polymer with a molecular weight of 3000-20000.

The present invention also provides a method for preparing a UV-curable side chain fluorine-containing water-based polyurethane coating. The specific steps are as follows: in parts by weight, 20-50 parts of UV-curable side-chain fluorine-containing water-based polyurethane resin, 40-80 parts 0.5-4.0 parts of deionized water, 0.5-4.0 parts of photoinitiator, 0.5-2.0 parts of film-forming aid, 0.1-1.0 parts of defoamer, 0.1-1.0 parts of leveling agent, 0.1-1.0 parts of anti-corrosion and anti-mildew agent and 0.1-1.0 parts of thickener are stirred and mixed at 10-40° C. for 0.5-2 hours to obtain the coating.

Compared with the prior art, the present invention has the following advantages:

1. The present invention utilizes readily available fluorine-containing acrylate monomer raw materials to synthesize a fluorine-containing alkyl macromolecule containing diol at one end, and the preparation and purification process is simple; it is combined with diisocyanate, polyglycol, chain extender, (Meth) hydroxyethyl acrylate monomers are polymerized to produce UV-curable side chain fluorine-containing water-based polyurethane resins. It has the characteristics of rapid light curing and is a green coating that meets the protection of the environment.

2. The UV-curable side chain fluorine-containing water-based polyurethane coating prepared by the present invention has good stability, high gloss of the coating film, excellent surface hydrophobic and antifouling performance, heat resistance, water resistance, solvent resistance, and scrubbing resistance of the coating film Excellent mechanical properties.

Detailed ways

The present invention will be further described in detail below in conjunction with specific examples. Unless otherwise specified, the reagents, equipment and methods used in the present invention are commercially available reagents, equipment and routinely used methods in this technical field.

Example 1

The preparation method of UV curable side chain fluorine-containing waterborne polyurethane resin is as follows:

S1. In parts by weight, 10 parts of dodecafluoroheptyl acrylate, 20 parts of methyl methacrylate, 2.5 parts of 1-thioglycerol, 0.2 parts of azobisisobutyronitrile, and 67.3 parts of tetrahydrofuran were heated at 60°C under nitrogen Under the atmosphere, react for 24 hours by semi-titration solution polymerization method, and obtain fluorine-containing alkyl glycol by precipitation and purification with n-hexane or petroleum ether;

S2. In parts by weight, react 32 parts of isophorone diisocyanate, 36 parts of polypropylene glycol 1000, and 0.05 parts of dibutyltin laurate at 80-90°C for 2.5 hours, cool down to below 70°C, and add 1.8 parts of 1 , 4-butanediol, 13.6 parts of fluorine-containing alkyl glycol described in S1, keep the temperature at 60-70°C, react for 2.5 hours, add 5.0 parts of 2,2-bis(hydroxymethyl)propionic acid to continue the reaction After 2.5 hours, add 7.5 parts of hydroxyethyl methacrylate and 0.05 parts of p-hydroxyanisole, and continue the reaction for 2 hours. During the reaction, acetone solvent can be added to adjust the viscosity. Lower the temperature to 45-50°C, add 4 parts of triethylamine to carry out a salt-forming reaction for 1 hour, and obtain the UV-curable side chain fluorine-containing waterborne polyurethane resin.

Take 30g of the above-mentioned UV-curable side chain fluorine-containing water-based polyurethane resin, 65g of deionized water, 2.5g of photoinitiator Darocur 2959, 1.0g of propylene glycol methyl ether, 0.5g of amino silicone oil, and 0.5g of polyether-modified polysiloxane , 0.2g 2-methyl-4-isothiazolin-3-one and 0.3g hydroxyethyl cellulose; Stir and mix at room temperature for 0.5 hour to obtain the coating.

Example 2

The preparation method of UV curable side chain fluorine-containing waterborne polyurethane resin is as follows:

S1. In parts by weight, put 15 parts of decafluoroheptyl acrylate, 15 parts of methyl methacrylate, 2.5 parts of 1-thioglycerol, 0.2 parts of azobisisobutyronitrile, and 67.3 parts of tetrahydrofuran in a nitrogen atmosphere at 60 ° C. Under the condition of semi-titration solution polymerization reaction for 24h, the fluorine-containing alkyl glycol was prepared by precipitation and purification of n-hexane or petroleum ether;

S2. In parts by weight, react 25 parts of isophorone diisocyanate, 25 parts of polytetrahydrofuran ether glycol 1000, and 0.05 part of dibutyltin laurate at 80-90°C for 2.5h, cool to below 70°C, and add 1.4 parts of 1,4-butanediol, 34 parts of fluorine-containing alkyl glycol described in S1, keep the temperature at 60-70°C, react for 2.5 hours, add 4.8 parts of 2,2-bis(hydroxymethyl) propane The acid continued to react for 2.5 hours, and 5.8 parts of hydroxyethyl methacrylate and 0.05 parts of p-hydroxyanisole were added to continue the reaction for 2 hours. During the reaction, acetone solvent could be added to adjust the viscosity. Cool down to 45-50°C, add 3.9 parts of triethylamine to carry out salt-forming reaction for 1 hour, and obtain the UV-curable side chain fluorine-containing waterborne polyurethane resin.

Take 28g of the above-mentioned UV curable side chain fluorine-containing water-based polyurethane resin, 67g of deionized water, 2.5g of photoinitiator Darocur 2959, 1.0g of propylene glycol n-butyl ether, 0.5g of amino silicone oil, and 0.5g of polyether modified polysiloxane Alkanes copolymer, 0.2g 2-methyl-4-isothiazolin-3-one, 0.3g methyl hydroxyethyl cellulose; Stir and mix at room temperature for 0.5 hours to obtain the coating.

Example 3

The preparation method of UV curable side chain fluorine-containing waterborne polyurethane resin is as follows:

S1. In parts by weight, 25 parts of trifluorooctyl acrylate, 1.0 part of 1-thiodiol, 0.1 part of azobisisobutyronitrile, and 73.9 parts of tetrahydrofuran were half-titrated at 60°C under a nitrogen atmosphere. Polymerization reaction for 24 hours, and precipitation and purification of n-hexane or petroleum ether to obtain fluorine-containing alkyl glycol;

S2. In parts by weight, react 29.8 parts of isophorone diisocyanate, 26.8 parts of polypropylene glycol 1000, and 0.1 part of dibutyltin laurate at 80-90°C for 2.5 hours, cool down to below 70°C, and add 1.8 parts of 1 , 4-butanediol, 16.8 parts of fluorine-containing alkyl glycol described in S1, keep the temperature at 60-70°C, react for 2.5 hours, add 4.9 parts of 2,2-bis(hydroxymethyl)propionic acid to continue the reaction After 2.5 hours, add 16 parts of pentaerythritol triacrylate and 0.1 part of polymerization inhibitor to continue the reaction for 2 hours. During the reaction, acetone solvent can be added to adjust the viscosity. Cool down to 45-50°C, add 3.7 parts of triethylamine to carry out salt-forming reaction for 1 hour, and obtain the UV-curable side chain fluorine-containing waterborne polyurethane resin.

Take 30g of the above-mentioned UV curable side chain fluorine-containing waterborne polyurethane resin, 65.5g of deionized water, 2.0g of photoinitiator Darocur 1173, 1.0g of propylene glycol monomethyl ether, 0.5g of amino silicone oil, and 0.5g of polyether modified silicone , 0.2g 2-methyl-4-isothiazolin-3-one and 0.3g hydroxyethyl cellulose; Stir and mix at room temperature for 0.5 hour to obtain the coating.

Example 4

The preparation method of UV curable side chain fluorine-containing waterborne polyurethane resin is as follows:

S1. In parts by weight, 15 parts of trifluorooctyl acrylate, 10 parts of methyl methacrylate, 2.8 parts of thioglycol, 0.2 parts of azobisisobutyronitrile, and 67.3 parts of tetrahydrofuran were placed under a nitrogen atmosphere at 60 ° C. , by semi-titration solution polymerization reaction for 24h, and then purified by n-hexane or petroleum ether precipitation to obtain fluorine-containing alkyl glycol;

S2. In parts by weight, react 23.4 parts of toluene diisocyanate, 26.9 parts of polytetrahydrofuran ether glycol 1000, and 0.05 parts of diisobutyronitrile laurate at 80-90°C for 2.5 hours, cool down to below 70°C, and add 1.8 1,4-butanediamine, 25.2 parts of the fluorine-containing alkyl glycol described in S1, keep the temperature at 60-70°C, react for 2.5 hours, add 4.4 parts of methyldiethanolamine to continue the reaction for 2.5 hours, add 16 parts Pentaerythritol triacrylate and 0.05 parts of p-hydroxyanisole continue to react for 2 hours, and acetone solvent can be added to adjust the viscosity during the reaction. Lower the temperature to 45-50°C, add 2.2 parts of acetic acid to carry out a salt-forming reaction for 1 hour, and obtain the UV-curable side chain fluorine-containing waterborne polyurethane resin.

Take 28g of the above-mentioned UV curable side chain fluorine-containing waterborne polyurethane resin, 67.5g of deionized water, 2.0g of photoinitiator Darocur 1173, 1.0g of propylene glycol methyl ether acetate, 0.5g of amino silicone oil, 0.5g of polyether modified organic Silicon, 0.2g 2-(4-thiazolyl)benzimidazole and 0.3g methyl hydroxyethyl cellulose ether; stir and mix at room temperature for 0.5 hour to obtain the coating.

Example 5

The preparation method of UV curable side chain fluorine-containing waterborne polyurethane resin is as follows:

S1. In parts by weight, mix 15 parts of dodecafluoroheptyl methacrylate, 15 parts of butyl methacrylate, 2.5 parts of 1-thioglycerol, 0.2 parts of azobisisobutyronitrile, and 67.3 parts of tetrahydrofuran in 60 Under a nitrogen atmosphere at ℃, react for 24 hours by semi-titration solution polymerization method, and obtain fluorine-containing alkyl glycol by precipitation and purification with n-hexane or petroleum ether;

S2. In parts by weight, react 26 parts of isophorone diisocyanate, 22 parts of polypropylene glycol 1000, and 0.05 part of diisobutyltin laurate at 80-90°C for 2.5h, cool to below 70°C, add 1.8 One part of 1,4-butanediol, 30 parts of fluorine-containing alkyl glycol described in S1, keep the temperature at 60-70°C, react for 2.5 hours, add 4.8 parts of 2,2-bis(hydroxymethyl)propionic acid Continue the reaction for 2.5 hours, add 12.6 parts of pentaerythritol triacrylate and 0.05 parts of p-hydroxyanisole, continue the reaction for 2 hours, and add acetone solvent during the reaction to adjust the viscosity. Cool down to 45-50°C, add 3.9 parts of triethylamine to carry out salt-forming reaction for 1 hour, and obtain the UV-curable side chain fluorine-containing waterborne polyurethane resin.

Take 30g of the above-mentioned UV-curable side chain fluorine-containing waterborne polyurethane resin, 65g of deionized water, 2.0g of photoinitiator Darocur 1173, 1.0g of dipropylene glycol n-butyl ether, 0.5g of amino silicone oil, and 0.5g of polyether modified silicone , 0.2g 2-(4-thiazolyl)benzimidazole and 0.3g methyl hydroxyethyl cellulose ether; stir and mix at room temperature for 0.5 hour to obtain the coating.

Example 6

The preparation method of UV curable side chain fluorine-containing waterborne polyurethane resin is as follows:

S1. In parts by weight, 15 parts of hexafluorobutyl acrylate, 15 parts of methyl methacrylate, 2.85 parts of chain transfer diol, 0.15 parts of initiator, and 67 parts of tetrahydrofuran were half-titrated under a nitrogen atmosphere at 60°C. Solution polymerization reaction for 24 hours, and precipitation and purification of n-hexane or petroleum ether to obtain fluorine-containing alkyl glycol;

S2. In parts by weight, react 27.5 parts of isophorone diisocyanate, 24.8 parts of polypropylene glycol 1000, and 0.05 parts of dibutyltin laurate at 80-90°C for 2.5 hours, cool down to below 70°C, and add 1.67 parts of 1 , 4-butanediol, 23.2 parts of the fluorine-containing alkyl glycol described in S1, keep the temperature at 60-70°C, react for 2.5 hours, add 4.85 parts of 2,2-bis(hydroxymethyl)propionic acid to continue the reaction After 2.5 hours, add 14.20 parts of pentaerythritol triacrylate and 0.05 parts of p-hydroxyanisole to continue the reaction for 2 hours. During the reaction, acetone solvent can be added to adjust the viscosity. Cool down to 45-50°C, add 3.68 parts of triethylamine to carry out salt-forming reaction for 1 hour, and obtain the UV-curable side chain fluorine-containing waterborne polyurethane resin.

Take 32g of the above-mentioned UV curable side chain fluorine-containing waterborne polyurethane resin, 63g of deionized water, 2.0g of photoinitiator Darocur 2959, 1.0g of dipropylene glycol n-butyl ether, 0.5g of amino silicone oil, 0.5g of polyether modified silicone, 0.2g 2-(4-thiazolyl)benzimidazole and 0.3g methyl hydroxyethyl cellulose ether; stir and mix at room temperature for 0.5 hour to obtain the coating.

Table 1 The main properties of the coatings prepared in Examples 1 to 6

project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Construction Barrier-free painting Barrier-free painting Barrier-free painting Barrier-free painting Barrier-free painting Barrier-free painting Coating Appearance normal normal normal normal normal normal Fluorine content 1～3% 7～11.2% 7～10% 7～9% 6～8.5% 3～5.5% Surface water contact angle (°) 85～90 100～112 100～108 100～105 95～100 90～95 low temperature stability no deterioration no deterioration no deterioration no deterioration no deterioration no deterioration Coating resistance to temperature denaturation (5 cycles) No abnormality No abnormality No abnormality No abnormality No abnormality No abnormality Drying time (surface dry h) ≤1 ≤1 ≤1 ≤1 ≤1 ≤1 Washing resistance ≥10000 ≥10000 ≥10000 ≥10000 ≥10000 ≥10000 water resistance good good good good good good Alkali resistance 7d pass pass pass pass pass pass Acid resistance 7d pass pass pass pass pass pass pencil hardness 3H 3H 4H 4H 4H 4H Impact resistance (cm) ≥100 ≥100 ≥100 ≥100 ≥100 ≥100 Adhesion (level) 1 1 2 1 1 1

As can be seen from Table 1, the comprehensive properties of the coatings prepared in Examples 1 to 6 are good. In addition to excellent mechanical properties and good acid and alkali resistance and water resistance, there are also good coating properties due to the presence of perfluoroalkyl groups. Hydrophobic properties, the contact angle with water can reach 112°, at the same time, because of the shielding effect of the fluorine-containing alkyl group on the carbon chain, the thermal stability of the coating film is improved.

Claims (10)

1. a fluorine-containing alkyl diol is characterized in that, fluorine-containing alkyl diol has structure shown in the formula I:

Formula I;

R wherein _fBe fluoro-containing group, fluoro-containing group is that carbonatoms is 1～20 perfluoroalkyl; R ₁=H, Me, CF ₃Or halogen, m 〉=0; R ₂=H or Me; P 〉=0; N＞0;

The preparation method of described fluorine-containing alkyl diol is as follows:

Count by weight, 1～90 part of acrylate containing fluorine monomer, 0～90 part of acrylic ester monomer or methyl acrylic ester monomer, 0.1～15 part of chain are shifted glycol, 0.01～2 part of initiator, 10～80 parts of solvents under 50～90 ℃ of nitrogen atmospheres, with half volumetric soiutions polymerization reaction, 6～24h, make fluorine-containing alkyl diol through normal hexane or petroleum ether precipitation purification.

2. according to the described fluorine-containing alkyl diol of claim 1, it is characterized in that described fluorine-containing alkyl diol molecular weight is 800 ~ 5000.

3. according to the described fluorine-containing alkyl diol of claim 1, it is characterized in that described acrylate containing fluorine monomer molecule formula is R _f(CH ₂) _mOC (O) CR ₁=CH ₂, R wherein _fBe fluoro-containing group, fluoro-containing group is that carbonatoms is 1～20 perfluoroalkyl; R ₁=H, Me, CF ₃Or halogen, m 〉=0.

4. according to the described fluorine-containing alkyl diol of claim 3, it is characterized in that described acrylate containing fluorine monomer is that perfluoroalkyl acrylate, perfluoroalkyl methacrylate, vinylformic acid contain the sulfur heteroatom perfluoroalkyl ester, methacrylic acid contains sulfur heteroatom perfluoroalkyl ester, the nitrogenous fluoroalkyl ester of vinylformic acid perfluor, the nitrogenous fluoroalkyl ester of methacrylic acid perfluor, vinylformic acid perfluor sulfonyl amine ester or methacrylic acid perfluor sulfonyl amine ester.

5. according to the described fluorine-containing alkyl diol of claim 1, it is characterized in that described methyl acrylic ester monomer is methyl methacrylate, Jia Jibingxisuanyizhi or butyl methacrylate; Acrylic ester monomer is methyl acrylate, ethyl propenoate or butyl acrylate; It is the 1-thioglycerin that described chain shifts glycol.

6. UV-curable lateral chain fluorine-containing waterborne polyurethane coating, it is characterized in that, count by weight, described coating is composed of the following components: 20～50 parts UV-curable lateral chain fluorine-containing waterborne polyurethane resin, 40～80 parts deionized water, 0.5～4.0 part light trigger, 0.5～2.0 part film coalescence aid, 0.1～1.0 part defoamer, 0.1～1.0 part flow agent, 0.1～1.0 part of Antisepticize and mildew preventive, 0.1～1.0 part of thickening material;

Described UV-curable lateral chain fluorine-containing waterborne polyurethane resin prepares by following steps:

S1. meter by weight, with 5～50 parts of diisocyanate monomers, 5～80 parts of polyether Glycols and/or polyester diol, 0.01～2 part of catalyzer at 60～100 ℃ of reaction 1～3h down;

S2. be cooled to below 70 ℃, add 0～15 part of low-molecular-weight diol or diamine chain extenders, 0.1～50 part of each described fluorine-containing alkyl diol of claim 1 to 5, maintain the temperature at 50～70 ℃, reaction 1～3h;

S3. add 0.1～15 part of wetting ability chainextender and continue reaction 1～3h, add 0.1～30 part of methacrylic ester hydroxyl esters monomer or acrylate hydroxyl esters monomer and 0.01～2 part of stopper continuation reaction 1～3h;

S4. be cooled to 30～60 ℃, add 0.1～2 part of neutralizing agent and carry out salt-forming reaction 0.5～1.5h, namely get UV-curable lateral chain fluorine-containing waterborne polyurethane resin.

7. according to the described UV-curable lateral chain fluorine-containing waterborne polyurethane of claim 6 coating, it is characterized in that step S3 described methacrylic ester hydroxyl esters monomer or acrylate hydroxyl esters monomer are hydroxyethyl methylacrylate, Rocryl 410, acrylate hydroxyl ethyl ester, acrylate hydroxypropyl acrylate, trihydroxy-propane diacrylate ester or pentaerythritol triacrylate.

8. according to the described UV-curable lateral chain fluorine-containing waterborne polyurethane of claim 6 coating, it is characterized in that, the described wetting ability chainextender of step S3 is anionic chainextender or cationic chainextender, described anionic chainextender is that two (methylol) propionic acid of 2,2-, amino acid, diaminobenzoic acid or the described cationic chainextender of quadrol base ethyl sulfonic acid sodium are N methyldiethanol amine.

9. described UV-curable lateral chain fluorine-containing waterborne polyurethane coating according to Claim 8 is characterized in that, described wetting ability chainextender is two (methylol) propionic acid of 2,2-or N methyldiethanol amine.

10. the preparation method of each described UV-curable lateral chain fluorine-containing waterborne polyurethane coating of claim ~ 9, it is characterized in that, in parts by weight, 20～50 parts UV-curable lateral chain fluorine-containing waterborne polyurethanes, 40～80 parts deionized water, 0.5～4.0 part light trigger, 0.5～2.0 part film coalescence aid, 0.1～1.0 part defoamer, 0.1～1.0 part flow agent, 0.1～1.0 part of Antisepticize and mildew preventive, 0.1～1.0 part of thickening material were mixed under 10～40 ℃ 0.5～2 hour, namely get described coating.