CN110016144B - Water-soluble polyfunctional resin and preparation method thereof - Google Patents
Water-soluble polyfunctional resin and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
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- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
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- 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
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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Abstract
The invention provides a water-soluble multifunctional resin and a preparation method thereof, wherein the water-soluble multifunctional resin comprises a polyacrylate main chain and a polyurethane acrylate side chain capable of being hydrated, and the side chain of the water-soluble multifunctional resin comprises two or more acrylate double bonds and epoxy groups. By adopting the technical scheme of the invention, the resin has good water solubility and polyfunctional group, does not need to use the traditional reactive diluent, and is more environment-friendly; the ultraviolet free radical-heat mixed curing or the ultraviolet free radical-cation mixed curing can be realized, the crosslinking degree is improved in the curing process due to the multiple functionality, and the hardness, the adhesive force, the wear resistance, the solvent resistance, the salt mist resistance and other properties of the cured film are improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a water-soluble polyfunctional resin and a preparation method thereof.
Background
The Ultraviolet (UV) curing technology is a green environment-friendly curing technology, has the advantages of high curing speed, less environmental pollution, automatic production, suitability for thermosensitive substrates and the like, is expected to replace the traditional solvent-based coatings, adhesives, printing ink and the like in industry, and has good application prospect in multiple fields. There are two types of radical curing and cationic curing according to the photo-curing mechanism.
The free radical photocuring system has the advantages of high curing speed (less than or equal to 10 s), easy performance adjustment, moisture resistance, multiple types of initiators and the like, but also has the problems of difficult surface drying, large polymerization volume shrinkage, poor adhesion, no post-curing effect and the like. The cationic photocuring system has the advantages of small volume shrinkage, strong adhesive force, post-curing, wear resistance, high hardness and the like, but also has the defects of low curing speed, few types of oligomers and reactive diluents and the like, so that the practical application of the cationic photocuring system is limited, and the cationic photocuring system is mainly applied to a dark coating or ink system. In order to exert the advantages of various curing systems and avoid the defects thereof, the research of various mixed ultraviolet curing systems is more and more widely regarded at present, and various mixed ultraviolet curing systems are developed and have wide application prospects in the aspects of special coatings, adhesives, printing ink and the like.
At present, the research on the hybrid ultraviolet curing system mainly includes the following types: a free radical-cation mixed ultraviolet curing system, an ultraviolet-heat curing mixed curing system, an ultraviolet-air-mixed curing system, an ultraviolet-moisture mixed curing system and the like. The mixed ultraviolet curing system generally comprises light curing resin, other curing resin (thermosetting or moisture curing resin and the like), monofunctional or polyfunctional diluting monomer, photoinitiator, auxiliary agent and the like. The resin forms a three-dimensional network structure of the polymer after being cured, and plays a decisive role in the physical and chemical properties of a cured film. The mono-functional or multi-functional diluted monomer is mainly used for adjusting the viscosity of the system, so that the system is suitable for industrial coating requirements.
At present, in the preparation and research of various mixed ultraviolet curing systems, oil-soluble systems are basically researched, most of researches adopt the mixing of several resins with different curing groups, so that the problems of local curing unevenness or poor compatibility among the resins exist in the use, and few researchers carry out the synthesis research of the resins with various functional groups capable of being cured by mixing.
In addition, when the oil-soluble mixed light curing system is prepared conventionally, the adopted resin has high viscosity, the formulation of hybrid curing systems requires the addition of relatively large amounts of reactive diluents which, although ultimately react with the resin, are somewhat toxic and somewhat irritating to humans, and when used on some porous substrates, such as wood, cement, paper, the diluent easily diffuses into the pores and cannot be cured, the coated object has peculiar smell for a long time, and the physicochemical property of the cured film can be obviously reduced by adding more reactive diluent, such as curing gel rate, wear resistance of a cured film and the like, the method for better solving the problem is to prepare the resin into water-soluble or water-emulsion resin, therefore, water can be used as a solvent when a mixed curing system is prepared, and the problems of residual smell, reduction of the physical and chemical properties of a cured film and the like can be solved. At present, many researchers research single light-cured water-based resins, but the research field of ultraviolet light mixed curing water-based resins is still in a blank state basically, and the defects of mainly lack of resins capable of being mixed and cured simultaneously, high resin viscosity, need of using more reactive diluents and the like prevent the mixed ultraviolet light curing system from being applied to the industrial field.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a water-soluble polyfunctional group resin and a preparation method thereof, the resin has good water solubility and polyfunctionality, does not use the traditional reactive diluent, avoids the influence of the reactive diluent on the performance of a curing film, can realize ultraviolet free radical-heat mixed curing or ultraviolet free radical-cation mixed curing, and the polyfunctionality can improve the crosslinking degree in the curing process and has better physical and chemical properties.
In contrast, the technical scheme adopted by the invention is as follows:
a water-soluble multifunctional resin comprises a polyacrylate main chain and a polyurethane acrylate side chain which can be hydrated, wherein the molecular chain of the water-soluble multifunctional resin is of a comb-shaped structure, and the side chain of the water-soluble multifunctional resin respectively comprises two or more acrylate double bonds, an epoxy group and carboxylate. Further, the side chains of the water-soluble multi-functional resin respectively include a plurality of acrylate double bonds, epoxy groups, and carboxylates.
The resin adopting the technical scheme has the unique properties of good water solubility and multiple functionality, the water-soluble resin can use water as a solvent in subsequent use, the environment is protected, the traditional reactive diluent is not used, and the influence of the reactive diluent on the performance of a cured film is avoided; the side chain has acrylic ester double bond and epoxy group with multiple functionality, which can realize ultraviolet free radical-heat mixed curing or ultraviolet free radical-cation mixed curing, the multiple functionality can improve the crosslinking degree in the curing process, and can effectively improve the properties of the curing film such as hardness, adhesive force, wear resistance, solvent resistance, salt mist resistance and the like, which are not possessed by many resins at present.
Because two curing groups (acrylate double bond and epoxy group) exist in the same resin molecular structure, the problem caused by compounding two different resins in the conventional mixed curing system can be solved. And a plurality of urethane acrylate side chains can be grafted according to the requirement, and the resin has better water solubility on the basis of having multiple functionality. The water-soluble resin can use water as a solvent in subsequent use, is green and environment-friendly, does not use the traditional reactive diluent, and avoids the influence of the reactive diluent on the performance of a cured film.
Further, the viscosity of the water-soluble polyfunctional resin is 1000-2000 mPa.s, and the solid content is 60-68%; further, the viscosity is 1200-1600 mPa.s, and the solid content is 61-66%.
The hardness of a cured film of the resin can reach more than 5H, the adhesive force is 0 grade, an RCA (Rolling circle) abrasion test (applying a load of 175 g) is more than 3100 times, the alcohol resistance (pure cotton cloth is fully dipped in absolute alcohol and a load of 500 g) is more than 1600 times, and the salt spray resistance (the salt water concentration is 5 percent, the temperature is 35 +/-1 ℃, and the humidity is more than 80 percent) is not changed after being placed for more than 160 hours.
The invention also discloses a preparation method of the water-soluble multifunctional resin, which comprises the following steps:
step S1, synthesizing a polyacrylate chain segment with a side chain having hydroxyl and epoxy groups as a main chain;
step S2, synthesizing a water-soluble polyurethane acrylate chain segment serving as a side chain, wherein one end of the water-soluble polyurethane acrylate side chain is provided with an-NCO group, and the water-soluble polyurethane acrylate side chain contains carboxylic acid groups;
step S3, synthesizing multifunctional resin, and reacting the polyacrylate chain segment with hydroxyl and epoxy groups on the side chain obtained in the step S1 with the waterborne urethane acrylate chain segment obtained in the step S2, wherein the molar ratio of-NCO groups to side chain OH groups of the polyacrylate chain segment is 0.4-1: 1, obtaining waterborne polyurethane acrylate modified polyacrylate resin with a side chain containing a plurality of acrylate double bonds and epoxy groups;
step S4, adding an alkali solution into the waterborne polyurethane acrylate modified polyacrylate resin obtained in step S3 for neutralization to obtain a water-soluble multifunctional resin.
In step S1, in the polyacrylate segment having hydroxyl and epoxy groups on its side chain, the mass percentage of the hydroxyl acrylate is 5-40%, and the mass percentage of the glycidyl acrylate is 5-40%.
In step S1, in the polyacrylate segment having hydroxyl and epoxy groups on its side chain, the mass percentage of the monomer of acrylic hydroxy esters is 15-40%, and the mass percentage of the monomer of glycidyl acrylates is 15-40%. Furthermore, the sum of the mass percent of the two components is 40-60%.
By adopting the technical scheme, the resin has a main chain and a side chain structure, the main chain is provided with a plurality of hydroxyl groups and epoxy groups by controlling the proportion of reaction monomers according to needs in the process of preparing the polyacrylate main chain, then a plurality of polyurethane acrylates capable of being subjected to water-based treatment are grafted on the side chain by utilizing the hydroxyl groups, the comb-like resin structure can ensure that the resin has lower viscosity, the grafting proportion of the polyurethane acrylates can be adjusted according to the water-based treatment requirement, the prepared water-based multi-functional group resin is water-soluble, the negative influence caused by the additional addition of an emulsifier in the common water emulsion resin is avoided, water can be used as a solvent in the subsequent process of preparing a coating and an adhesive, the use of an active diluent is avoided, and the problems of influence of the active diluent on the physical and chemical properties of a cured film, residual odor and the like can be thoroughly solved.
As a further improvement of the present invention, the step S1 of synthesizing a polyacrylate segment having hydroxyl and epoxy groups in its side chains comprises the steps of: adding a solvent and a reaction monomer with double bonds into a reaction container, wherein the mass percentages of the solvent and the reaction monomer are respectively 5-30% and 70-95%; wherein the reaction monomer with double bonds comprises a monomer of acrylic hydroxyl ester and a monomer of acrylic glycidyl ester; adding a catalyst, stirring and heating to 50-95 ℃, and reacting for 1-4 h to obtain a polyacrylate chain segment with a side chain having hydroxyl and an epoxy group. Further, the adding amount of the catalyst is 0.1-1.5% of the total mass of the reaction monomer with the double bonds;
as a further improvement of the invention, the double-bond reaction monomer comprises a hydroxyl acrylate monomer, a glycidyl acrylate monomer and at least one of butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic acid, acrylamide and styrene;
further, the solvent is one or a mixture of more of propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and dipropylene glycol dimethyl ether;
further, the catalyst is at least one of azobisisobutyronitrile, benzoyl peroxide, benzoyl tert-butyl peroxide and methyl ethyl ketone peroxide.
Further, the monomer of the glycidyl acrylate is at least one of glycidyl acrylate and glycidyl methacrylate.
Further, the monomer of the hydroxyl acrylate is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
Further, the double-bond-containing reactive monomer comprises three or more monomers.
Further, the double-bond reaction monomer is three or more monomers of butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic acid, acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, glycidyl methacrylate and styrene.
As a further improvement of the invention, in the reaction monomer with double bonds, the percentage of the monomer of glycidyl acrylate in the total mass of the reaction monomer with double bonds is 5-40%; the percentage of the monomer of acrylic hydroxyl ester accounts for 5-40% of the total mass of the reaction monomer with double bonds.
As a further improvement of the invention, the step S2 of synthesizing the waterborne polyurethane acrylate segment comprises the following steps: adding diisocyanate and a solvent into a reaction vessel, heating to 50-90 ℃, and adding dihydroxy carboxylic acid and dibutyl tin dilaurate into the diisocyanate, wherein the adding amount of the dihydroxy carboxylic acid is that the molar ratio of the diisocyanate to the dihydroxy carboxylic acid is 2: 1; after reacting for 1-5h, adding hydroxyl acrylate and a polymerization inhibitor into the reaction system, wherein the adding amount of the hydroxyl acrylate meets the condition that the molar ratio of the hydroxyl acrylate to diisocyanate is 0.5-0.55: 1, adding p-hydroxyanisole or hydroquinone into the hydroxyl acrylate; heating the reaction system to 65-100 ℃, and reacting for 1.5-4 h to obtain a polyurethane acrylate chain segment with an-NCO group at one end, wherein the polyurethane acrylate chain segment contains a carboxylic acid group capable of being hydrated. Further, the polymerization inhibitor is p-hydroxyanisole or hydroquinone. The dosage of the polymerization inhibitor is 0.1-0.8% of the total mass of the reaction system. The dosage of the dibutyl tin dilaurate is 0.1-0.5% of the total mass of the reaction system.
As a further improvement of the invention, the solvent is one or a mixture of more of propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and dipropylene glycol dimethyl ether;
the diisocyanate is at least one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI) and p-phenylene diisocyanate (PPDI);
the dihydroxy carboxylic acid is at least one of 2, 3-dihydroxy propionic acid, 2, 2-dimethylolpropionic acid, 2, 3-dihydroxy benzoic acid, 2, 4-dihydroxy benzoic acid, 2, 5-dihydroxy benzoic acid, 2, 6-dihydroxy benzoic acid, 3, 5-dihydroxy benzoic acid, 2, 2-dimethylolbutyric acid, 2, 4-dihydroxy butyric acid and 2, 3-dihydroxy butyric acid;
the hydroxy acrylic ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
As a further improvement of the present invention, step S3 includes the steps of: and (2) adding the polyacrylate chain segment synthesized in the step S1 and the water-soluble polyurethane acrylate chain segment synthesized in the step S2 and provided with an-NCO group at one end, adding dibutyl tin dilaurate accounting for 0.1-0.8% of the total mass and a polymerization inhibitor accounting for 0.1-0.8%, uniformly stirring, heating to 60-100 ℃, and reacting for 2-5 hours to obtain the water-soluble polyurethane acrylate modified polyacrylate resin, wherein a side chain in the molecular structure of the resin simultaneously contains a plurality of acrylate double bonds and epoxy groups. The polymerization inhibitor is p-hydroxyanisole or hydroquinone.
As a further improvement of the invention, in step S4, the pH value of the solution after adding alkali solution for neutralization is 8-10.
As a further improvement of the invention, in the step S4, the concentration of the added alkali solution is 0.01-1 mol/L.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the water-soluble multifunctional resin comprises a polyacrylate main chain and a water-soluble polyurethane acrylate side chain in a resin structure, wherein the polyacrylate main chain with different glass transition temperatures can be obtained by adjusting the proportion of various monomers in the synthesis process of the polyacrylate main chain, so that a main chain with certain rigidity can be obtained, the water-soluble polyurethane acrylate side chain can provide a carboxylic acid group capable of being water-soluble, and the resin can have certain flexibility; because the side chain has multiple functionality, namely has a plurality of acrylate double bonds and a plurality of epoxy groups, the resin crosslinking degree of the whole resin molecular chain in the mixed curing process is improved, and the performances of the cured film such as hardness, adhesive force, wear resistance, solvent resistance, salt mist resistance and the like can also be effectively improved. These several properties are currently not available with many resins.
Secondly, the water-soluble multi-functional group resin can graft a plurality of flexible water-based urethane acrylate side chains on the side chain of the rigid polyacrylate main chain, so that the molecular structure of the resin contains a plurality of acrylate double bonds and epoxy groups at the same time, and ultraviolet free radical-heat mixed curing or ultraviolet free radical-cation mixed curing can be realized. The double bonds of the acrylate are rapidly cured in a free radical mode under the irradiation of ultraviolet light, so that the viscosity of a curing system is rapidly increased, the effect of primary bonding is achieved, meanwhile, the bonding strength is further improved by initiating cationic polymerization or thermosetting of an epoxy group, the curing volume shrinkage rate is reduced due to the reduction of the density of the double bonds in the system, and the ring-opening polymerization curing of the epoxy group has some volume compensation effect. Meanwhile, because the two curing modes are generated on the same molecule, a polymerization whole combined by strong chemical bonds is formed after curing, and the volume complementation is transmitted through the chemical bonds, the volume shrinkage rate of the system is greatly reduced after curing, the bonding performance is enhanced, and the problems of large shrinkage rate, large brittleness, poor flexibility and the like of a single acrylate free radical curing system can be solved. Because two curing groups (acrylate double bond and epoxy group) exist in the same resin molecular structure, the resin of the invention can also solve the problem caused by the compounding of two different resins used in the existing mixed curing system.
Thirdly, the resin of the invention can obtain mixed curing resin with multifunctionality and water-solubility, the resin has main chain and side chain structure, during the preparation of the polyacrylate main chain, the proportion of the reaction monomers can be controlled to ensure that the main chain is provided with a plurality of hydroxyl groups and epoxy groups, then a plurality of polyurethane acrylates capable of being hydrated are grafted on a side chain by utilizing hydroxyl, the comb-like resin structure can enable the resin to have lower viscosity, and the grafting proportion of the urethane acrylate can be adjusted according to the requirement of aquosity, the prepared water-based polyfunctional resin is water-soluble, the negative influence caused by adding an emulsifier in the common water-emulsion resin is avoided, in the subsequent process of preparing the coating and the adhesive, water can be used as a solvent, so that an active diluent is not used, can thoroughly solve the problems of influence of the reactive diluent on the physical and chemical properties of the cured film, residual odor and the like.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
A water-soluble polyfunctional resin is prepared by the following steps:
firstly, adding 20g of propylene glycol monomethyl ether acetate, 30g of methyl methacrylate, 30g of methyl acrylate, 30g of glycidyl methacrylate, 80g of hydroxyethyl methacrylate and 30g of styrene into a 500mL three-neck flask, uniformly stirring, adding azodiisobutyronitrile serving as a catalyst accounting for 0.8% of the total mass of the monomers, heating to 68 ℃ while stirring, and reacting for 3 hours to obtain a polyacrylate chain segment (i) with a side chain containing hydroxyl and epoxy groups, wherein in the polyacrylate chain segment, the mass percentage of the hydroxyethyl methacrylate (the hydroxyl source) is 40% and the mass percentage of the glycidyl methacrylate (the epoxy group source) is 15%.
Secondly, adding 1mol of dicyclohexyl methane diisocyanate (HMDI) and 15g of propylene glycol methyl ether acetate solvent into a 1000mL three-neck flask, heating to 70 ℃, adding 0.4 percent of dibutyl tin dilaurate by the total mass into 0.5mol of 2, 3-dihydroxy propionic acid, gradually adding the mixture into a dicyclohexyl methane diisocyanate (HMDI) solution, continuing to react for 2.5h after dripping, adding 0.4 percent of p-hydroxyanisole into 1mol of hydroxyethyl methacrylate, adding the reaction system, heating to 78 ℃ and reacting for 3.5h to obtain the waterborne polyurethane acrylate chain segment (II) with an NCO group at one end.
And thirdly, adding 110g (resin content is 100 g) of polyacrylate chain segment (I) synthesized in the first step into a 500mL three-neck flask, then adding metered polyurethane acrylate chain segment (II) capable of being hydrated and synthesized in the second step, wherein one end of the polyurethane acrylate chain segment capable of being hydrated is provided with an-NCO group, and the adding amount of the polyurethane acrylate chain segment capable of being hydrated and provided with the-NCO group meets the condition that the molar ratio of the NCO group to the side chain OH group of the polyacrylate chain segment is 0.6: 1 (60 percent of hydroxyl on a side chain of a polyacrylate chain segment is grafted and modified), then adding dibutyl tin dilaurate accounting for 0.4 percent of the total mass and polymerization inhibitor hydroquinone accounting for 0.5 percent of the total mass, stirring uniformly, heating to 72 ℃ and reacting for 4.5 hours to obtain side chain water-soluble polyurethane acrylate modified polyacrylate resin.
And fourthly, adding 100g of the side chain water-soluble polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, and dropwise adding 0.10mol/L ammonia water solution while stirring until the pH value of the solution is between 8 and 10 to obtain the water-soluble multifunctional resin.
The solid content of the obtained waterborne resin is 65.2%, the viscosity is 1600mPa.s, the waterborne resin is taken as a basic raw material 90%, 3% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) and 7% of waterborne closed type thermal curing agent are directly added to prepare a mixed curing system, and the performance of the cured film is tested. After coating, the film is dried by flash evaporation, and then cured by ultraviolet-heat mixing, the hardness of the cured film (pencil) is 5H, the adhesive force (GB/T9286-1998) is 0 grade, the RCA abrasion resistance test (applying 175g load) is more than 3300 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol, applying 500g load) is more than 1700 times, and the salt spray resistance (salt water concentration is 5%, the temperature is 35 ℃ plus or minus 1 ℃, and the humidity is more than 80%) is unchanged after being placed for 180 hours.
Example 2
A water-soluble polyfunctional resin is prepared by the following steps:
firstly, 20g of solvent ethylene glycol butyl ether acetate, 40g of butyl acrylate, 60g of methyl methacrylate, 40g of glycidyl methacrylate, 40g of hydroxyethyl acrylate and 20g of acrylonitrile are added into a 500mL three-neck flask, the mixture is uniformly stirred, a catalyst benzoyl peroxide tert-butyl ester accounting for 1.0 percent of the total mass of the monomers is added, the mixture is heated to 65 ℃ while being stirred, and the reaction is carried out for 3 hours, so as to obtain a polyacrylate chain segment (i) with a side chain having hydroxyl and an epoxy group, wherein the mass percent of the hydroxyethyl acrylate (a hydroxyl source) and the mass percent of the glycidyl methacrylate (an epoxy group source) are 20 percent.
Secondly, adding 1mol of Toluene Diisocyanate (TDI) and 20g of ethylene glycol monobutyl ether acetate solvent into a 1000mL three-neck flask, heating to 65 ℃, adding 0.4 percent of dibutyl tin dilaurate by total mass into 0.5mol of 2, 2-dimethylolbutyric acid, gradually adding the mixture into Toluene Diisocyanate (TDI) solution, continuing to react for 2.5 hours after dripping, adding 0.5 percent of p-hydroxyanisole into 1mol of hydroxyethyl acrylate, adding the reaction system, heating to 85 ℃ and reacting for 3 hours to obtain the waterborne polyurethane acrylate chain segment (II) with an-NCO group at one end.
And thirdly, adding 110g (resin content is 100 g) of polyacrylate chain segment (I) synthesized in the first step into a 500mL three-neck flask, then adding metered polyurethane acrylate chain segment (II) capable of being hydrated and synthesized in the second step, wherein one end of the polyurethane acrylate chain segment capable of being hydrated is provided with an-NCO group, and the adding amount of the polyurethane acrylate chain segment capable of being hydrated and provided with the-NCO group meets the condition that the molar ratio of the NCO group to the side chain OH group of the polyacrylate chain segment is 0.9: 1 (90 percent of hydroxyl on the side chain of the polyacrylate chain segment is grafted and modified), then adding dibutyl tin dilaurate accounting for 0.5 percent of the total mass and 0.6 percent of polymerization inhibitor p-hydroxyanisole, stirring uniformly, heating to 88 ℃ and reacting for 3 hours to obtain side chain water-soluble polyurethane acrylate modified polyacrylate resin.
And fourthly, adding 100g of the side chain water-soluble polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, and dropwise adding 0.12mol/L dimethylamine solution while stirring until the pH value of the solution is between 8 and 10 to obtain the water-soluble multifunctional resin.
The solid content of the obtained waterborne resin is 63.6%, the viscosity is 1500mPa.s, the waterborne resin is taken as a basic raw material 90%, 3% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) and 7% of waterborne closed type thermal curing agent are directly added to prepare a mixed curing system, and the performance of the cured film is tested. After coating, the film is dried by flash evaporation, and then cured by ultraviolet-heat mixing, the hardness of the cured film (pencil) is 5H, the adhesive force (GB/T9286-1998) is 0 grade, the RCA abrasion resistance test (applying 175g load) is more than 3400 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol, applying 500g load) is more than 1800 times, and the salt spray resistance (salt water concentration is 5%, the temperature is 35 ℃ plus or minus 1 ℃, and the humidity is more than 80%) is unchanged after being placed for 190 hours.
Example 3
A water-soluble polyfunctional resin is prepared by the following steps:
firstly, 20g of propylene glycol diacetate solvent, 20g of butyl methacrylate, 20g of methyl acrylate, 80g of glycidyl acrylate, 20g of hydroxyethyl acrylate, 10g of hydroxypropyl methacrylate, 30g of styrene and 20g of acrylamide are added into a 500mL three-neck flask, uniformly stirred, added with benzoyl peroxide catalyst accounting for 0.6 percent of the total mass of the monomers, and heated to 73 ℃ while stirring for reaction for 2.5 hours to obtain a polyacrylate chain segment (i) with hydroxyl and epoxy groups on side chains, wherein in the polyacrylate chain segment, the sum of the mass percent of the hydroxyethyl acrylate and the hydroxypropyl methacrylate (the source of the hydroxyl) is 15 percent, and the mass percent of the glycidyl acrylate (the source of the epoxy) is 40 percent.
Secondly, adding 1mol of phenyl Methane Diisocyanate (MDI) and 15g of propylene glycol diacetate serving as a solvent into a 1000mL three-neck flask, heating to 66 ℃, adding 0.7 percent of dibutyl tin dilaurate in the total mass into 0.5mol of 2, 3-dihydroxypropionic acid, gradually adding into a phenyl Methane Diisocyanate (MDI) solution, continuing to react for 2.5 hours after finishing dripping, adding 0.7 percent of p-hydroxyanisole into 1mol of hydroxypropyl methacrylate, adding into the reaction system, heating to 92 ℃ and reacting for 2.5 hours to obtain the waterborne polyurethane acrylate chain segment with an-NCO group at one end.
And thirdly, adding 110g (resin content is 100 g) of polyacrylate chain segment (I) synthesized in the first step into a 500mL three-neck flask, adding metered polyurethane acrylate chain segment (II) capable of being hydrated and synthesized in the second step, wherein one end of the polyurethane acrylate chain segment capable of being hydrated is provided with an-NCO group, and the adding amount of the polyurethane acrylate chain segment capable of being hydrated and provided with the-NCO group meets the condition that the molar ratio of the NCO group to the side chain OH group of the polyacrylate chain segment is 1: 1 (100 percent of hydroxyl on the side chain of the polyacrylate chain segment is grafted and modified), then adding dibutyl tin dilaurate accounting for 0.5 percent of the total mass and polymerization inhibitor hydroquinone accounting for 0.5 percent of the total mass, stirring uniformly, heating to 82 ℃ and reacting for 4 hours to obtain side chain water-soluble polyurethane acrylate modified polyacrylate resin.
And fourthly, adding 100g of the side chain water-soluble polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, and dropwise adding 0.15mol/L of diethanolamine solution while stirring until the pH value of the solution is between 8 and 10 to obtain the water-soluble polyfunctional group resin.
The obtained water-based resin has the solid content of 61.6 percent and the viscosity of 1400mPa.s, the water-based resin is taken as a basic raw material of 90 percent, 3 percent of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) and 7 percent of water-based closed thermal curing agent are directly added to prepare a mixed curing system, and the performance of a cured film is tested. After coating, the film is dried by flash evaporation, and then cured by ultraviolet-heat mixing, the hardness of the cured film (pencil) is 5H, the adhesive force (GB/T9286-1998) is 0 grade, the RCA abrasion resistance test (applying 175g load) is more than 3500 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol, applying 500g load) is more than 1900 times, and the salt spray resistance (salt water concentration is 5%, the temperature is 35 ℃ plus or minus 1 ℃, the humidity is more than 80%) is unchanged after being placed for 200 hours.
Example 4
A water-soluble polyfunctional resin is prepared by the following steps:
firstly, 20g of solvent ethylene glycol ethyl ether acetate, 30g of butyl methacrylate, 40g of methyl acrylate, 30g of glycidyl methacrylate, 30g of glycidyl acrylate, 20g of hydroxyethyl acrylate, 30g of hydroxypropyl methacrylate and 20g of styrene are added into a 500mL three-neck flask, the mixture is uniformly stirred, a catalyst methyl ethyl ketone peroxide accounting for 1.2 percent of the total mass of the monomers is added, the mixture is heated to 78 ℃ while being stirred, and the reaction is carried out for 2 hours, so that a polyacrylate chain segment (i) with hydroxyl and epoxy groups on side chains is obtained, wherein in the polyacrylate chain segment, the sum of the mass percentages of the hydroxyethyl acrylate and the hydroxypropyl methacrylate (the sources of the hydroxyl groups) is 25 percent, and the sum of the mass percentages of the glycidyl methacrylate and the glycidyl acrylate (the sources of the epoxy groups) is 30 percent.
Secondly, adding 1mol of Hexamethylene Diisocyanate (HDI) and 15g of solvent ethylene glycol ethyl ether acetate into a 1000mL three-neck flask, heating to 66 ℃, adding dibutyl tin dilaurate into 0.5mol of 2, 2-dimethylolbutyric acid according to 0.5% of the total mass, gradually adding the mixture into a Hexamethylene Diisocyanate (HDI) solution, continuing to react for 3 hours after dripping, adding 0.8% of p-hydroxyanisole into 1mol of hydroxypropyl acrylate, adding the reaction system, heating to 82 ℃ and reacting for 3 hours to obtain a waterborne polyurethane acrylate chain segment with an-NCO group at one end.
And thirdly, adding 110g (resin content is 100 g) of polyacrylate chain segment (I) synthesized in the first step into a 500mL three-neck flask, then adding metered polyurethane acrylate chain segment (II) capable of being hydrated and synthesized in the second step, wherein one end of the polyurethane acrylate chain segment capable of being hydrated is provided with an-NCO group, and the adding amount of the polyurethane acrylate chain segment capable of being hydrated and provided with the-NCO group meets the condition that the molar ratio of the NCO group to the side chain OH group of the polyacrylate chain segment is 0.7: 1 (70 percent of hydroxyl on the side chain of the polyacrylate chain segment is grafted and modified), then adding dibutyl tin dilaurate accounting for 0.5 percent of the total mass and polymerization inhibitor p-hydroxyanisole accounting for 0.5 percent of the total mass, stirring uniformly, heating to 85 ℃, and reacting for 3 hours to obtain side chain water-soluble polyurethane acrylate modified polyacrylate resin.
And fourthly, adding 100g of the side chain water-soluble polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, and dropwise adding 0.13mol/L diethylamine solution while stirring until the pH value of the solution is between 8 and 10 to obtain the water-soluble polyfunctional group resin.
The solid content of the obtained waterborne resin is 63.2%, the viscosity is 1500mPa.s, the waterborne resin is taken as a basic raw material 90%, 3% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) and 7% of waterborne closed type thermal curing agent are directly added to prepare a mixed curing system, and the performance of the cured film is tested. After coating, the film is dried by flash evaporation, and then cured by ultraviolet-heat mixing, the hardness of the cured film (pencil) is 5H, the adhesive force (GB/T9286-1998) is 0 grade, the RCA abrasion resistance test (applying 175g load) is more than 3400 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol, applying 500g load) is more than 1700 times, and the salt spray resistance (salt water concentration is 5%, the temperature is 35 ℃ plus or minus 1 ℃, and the humidity is more than 80%) is unchanged after being placed for 180 hours.
Comparative example 1
Firstly, 20g of solvent ethylene glycol butyl ether acetate, 40g of butyl acrylate, 60g of methyl methacrylate, 40g of styrene, 8g of glycidyl acrylate, 8g of hydroxypropyl acrylate and 44g of acrylonitrile are added into a 500mL three-neck flask, the mixture is uniformly stirred, a catalyst benzoyl peroxide tert-butyl ester accounting for 1.0 percent of the total mass of the monomer is added, the mixture is heated to 65 ℃ while being stirred, and the reaction is carried out for 3 hours, so as to obtain a polyacrylate chain segment I with hydroxyl and epoxy groups on side chains, wherein the mass percent of hydroxypropyl acrylate (a hydroxyl source) and the mass percent of glycidyl acrylate (an epoxy group source) in the polyacrylate chain segment are respectively 4 percent and 4 percent.
Secondly, adding 1mol of Toluene Diisocyanate (TDI) and 20g of ethylene glycol monobutyl ether acetate solvent into a 1000mL three-neck flask, heating to 65 ℃, adding 0.4 percent of dibutyl tin dilaurate by total mass into 0.5mol of 2, 2-dimethylolbutyric acid, gradually adding the mixture into Toluene Diisocyanate (TDI) solution, continuing to react for 2.5 hours after dripping, adding 0.5 percent of p-hydroxyanisole into 1mol of hydroxyethyl acrylate, adding the reaction system, heating to 85 ℃ and reacting for 3 hours to obtain the waterborne polyurethane acrylate chain segment (II) with an-NCO group at one end.
And thirdly, adding 110g (resin content is 100 g) of polyacrylate chain segment (I) synthesized in the first step into a 500mL three-neck flask, then adding metered polyurethane acrylate chain segment (II) capable of being hydrated and synthesized in the second step, wherein one end of the polyurethane acrylate chain segment capable of being hydrated is provided with an-NCO group, and the adding amount of the polyurethane acrylate chain segment capable of being hydrated and provided with the-NCO group meets the condition that the molar ratio of the NCO group to the side chain OH group of the polyacrylate chain segment is 0.1: 1 (100 percent of hydroxyl on the side chain of the polyacrylate chain segment is grafted and modified), then adding dibutyl tin dilaurate accounting for 0.5 percent of the total mass and polymerization inhibitor p-hydroxyanisole accounting for 0.6 percent of the total mass, stirring uniformly, heating to 88 ℃ and reacting for 3 hours to obtain side chain water-soluble polyurethane acrylate modified polyacrylate resin.
And fourthly, adding 100g of the side chain water-soluble polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, and dropwise adding 0.12mol/L diethylamine solution while stirring until the pH value of the solution is between 8 and 10 to obtain the water-soluble polyfunctional group resin.
The solid content of the obtained waterborne resin is 73.7%, the viscosity is 2200mPa.s, the waterborne resin is taken as a basic raw material of 90%, 3% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) and 7% of waterborne closed type thermal curing agent are directly added to prepare a mixed curing system, and the performance of a cured film is tested. After coating, the film is dried by flash evaporation, and then cured by ultraviolet-heat mixing, the hardness of the cured film (pencil) is 1H, the adhesive force (GB/T9286-1998) is 0 grade, RCA abrasion resistance test (applying 175g load) is more than 600 times, alcohol resistance (pure cotton cloth is dipped in absolute alcohol, applying 500g load) is more than 300 times, and the salt spray resistance (salt water concentration is 5%, temperature is 35 ℃ plus or minus 1 ℃, humidity is more than 80%) is unchanged after being placed for 30 hours.
The resin has few double bonds and epoxy groups which can be cured, the crosslinking is insufficient, and various properties of a cured film are seriously reduced.
Comparative example 2
A common oily single ultraviolet curing system on the market at present is used for a comparison test, and the formula is as follows:
35 percent of epoxy acrylate
35 percent of urethane acrylate
The content of the diluent is 27 percent (8 percent of dipropylene glycol diacrylate, 8 percent of 1, 6-hexanediol diacrylate and 11 percent of hydroxyethyl acrylate)
Photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone) 3%
The viscosity of the prepared system is 9800 mPa.s, the performance of the cured film is tested after photocuring, the hardness of the cured film is 2H, the adhesive force (GB/T9286-1998) is 2 grade, the RCA abrasion resistance test (175 g of load is applied) is more than 1000 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and 500g of load is applied) is more than 500 times, and the salt spray resistance (the salt water concentration is 5%, the temperature is 35 +/-1 ℃, and the humidity is more than 80%) is not changed after standing for 50 hours.
Comparative example 3
A mixed curing system compounded by two resins is used for a comparison test, and the formula is as follows:
35 percent of epoxy resin
35 percent of urethane acrylate
The content of the diluent is 22 percent (8 percent of dipropylene glycol diacrylate, 8 percent of 1, 6-hexanediol diacrylate and 5 percent of glycidyl acrylate)
Photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone) 3%
Thermal curing agent aliphatic modified amine 5%
The viscosity of the prepared system is 9100 mPa.s, the performance of the cured film is tested after ultraviolet-heat mixed curing, the hardness of the cured film is 3H, the adhesive force (GB/T9286-1998) is grade 1, the RCA abrasion resistance test (applying 175g of load) is more than 1400 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and applying 500g of load) is more than 700 times, and the salt spray resistance (the salt water concentration is 5%, the temperature is 35 +/-1 ℃, and the humidity is more than 80%) is unchanged after being placed for 80 hours.
Compared with the comparative example, the resin of the embodiment 1-4 of the invention has the following outstanding advantages: (1) the waterborne multifunctional resin has low viscosity and can be dissolved in water, and a monofunctional or multifunctional reactive diluent does not need to be additionally added when a mixed curing system is prepared, so that the problems of reduced physical and chemical properties of a cured film or residual odor and the like caused by the reactive diluent are avoided. (2) The resin has multiple functionality, one resin molecule has a plurality of light-curable acrylate double bonds and a plurality of epoxy groups capable of being cured by thermosetting or cationic light, and after mixing and curing, the cured film has high crosslinking degree, and can effectively improve the properties of curing such as hardness, adhesive force, wear resistance, solvent resistance, salt mist resistance and the like.
As can be seen from the comparison of the properties of the examples and the comparative examples, the hardness of the cured film of the resin of the invention can reach more than 5H, the adhesion is 0 grade, the RCA abrasion resistance test (applying 175g of load) is more than 3300 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and 500g of load is applied) is more than 1700 times, and the salt spray resistance (salt water concentration is 5%, temperature is 35 ℃ plus or minus 1 ℃, humidity is more than 80%) is unchanged for more than 180 hours. Are obviously higher than those of comparative examples (oil-soluble single ultraviolet curing system or oil-soluble compound ultraviolet-thermal mixed curing system).
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (7)
1. A water-soluble polyfunctional resin characterized in that: the molecular chain of the water-soluble multifunctional resin is of a comb-shaped structure and comprises a polyacrylate main chain and a polyurethane acrylate side chain which can be hydrated, wherein the side chain of the water-soluble multifunctional resin respectively comprises two or more acrylate double bonds, an epoxy group and carboxylate;
which comprises the following steps:
step S1, synthesizing a polyacrylate chain segment with a side chain containing hydroxyl and epoxy groups as a main chain;
step S2, synthesizing a water-soluble polyurethane acrylate chain segment serving as a side chain, wherein one end of the water-soluble polyurethane acrylate side chain is provided with an-NCO group, and the water-soluble polyurethane acrylate side chain contains carboxylic acid groups;
step S3, synthesizing multifunctional resin, and reacting the polyacrylate chain segment with hydroxyl and epoxy groups on the side chain obtained in the step S1 with the waterborne urethane acrylate chain segment obtained in the step S2, wherein the molar ratio of-NCO groups to side chain OH groups of the polyacrylate chain segment is 0.4-1: 1, obtaining waterborne polyurethane acrylate modified polyacrylate resin with a side chain containing a plurality of acrylate double bonds and epoxy groups;
step S4, adding an alkali solution into the waterborne polyurethane acrylate modified polyacrylate resin obtained in step S3 for neutralization to obtain a water-soluble multifunctional resin;
the step S1 of synthesizing a polyacrylate segment with a side chain having hydroxyl and epoxy groups comprises the following steps: adding a solvent and a reaction monomer with double bonds into a reaction container, wherein the mass percentages of the solvent and the reaction monomer are respectively 5-30% and 70-95%; wherein the reaction monomer with double bonds comprises a monomer of acrylic hydroxyl ester and a monomer of acrylic glycidyl ester; adding a catalyst, stirring and heating to 50-95 ℃, and reacting for 1-4 h to obtain a polyacrylate chain segment with a side chain having hydroxyl and an epoxy group;
in the step S1, in the polyacrylate chain segment with the side chain containing hydroxyl and epoxy groups, the mass percentage of the hydroxyl acrylate is 15-40%, and the mass percentage of the glycidyl acrylate is 15-40%.
2. The water-soluble multifunctional resin according to claim 1, characterized in that: the viscosity of the water-soluble polyfunctional resin is 1000-2000 mPa.s, and the solid content is 60-68%.
3. The water-soluble multifunctional resin according to claim 1, characterized in that: the reaction monomer with double bonds comprises a monomer of acrylic hydroxyl ester, a monomer of acrylic glycidyl ester and at least one of butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic acid, acrylamide and styrene;
the solvent is one or a mixture of more of propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and dipropylene glycol dimethyl ether;
the monomer of the acrylic hydroxyl ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate;
the monomer of the glycidyl acrylate is at least one of glycidyl acrylate and glycidyl methacrylate;
the catalyst is at least one of azodiisobutyronitrile, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
4. The water-soluble multifunctional resin according to claim 3, characterized in that: in the reaction monomer with the double bonds, the percentage of the monomer of the glycidyl acrylate in the total mass of the reaction monomer with the double bonds is 5-40%; the percentage of the monomer of acrylic hydroxyl ester accounts for 5-40% of the total mass of the reaction monomer with double bonds.
5. The water-soluble multifunctional resin according to any one of claims 1 to 4, wherein: step S2 synthesizing a waterborne urethane acrylate segment includes the steps of: adding diisocyanate and a solvent into a reaction vessel, heating to 50-90 ℃, and adding dihydroxy carboxylic acid and dibutyl tin dilaurate into the diisocyanate, wherein the adding amount of the dihydroxy carboxylic acid is that the molar ratio of the diisocyanate to the dihydroxy carboxylic acid is 2: 1; after reacting for 1-5h, adding hydroxyl acrylate and a polymerization inhibitor into the reaction system, wherein the adding amount of the hydroxyl acrylate meets the condition that the molar ratio of the hydroxyl acrylate to diisocyanate is 0.5-0.55: 1; heating the reaction system to 65-100 ℃, and reacting for 1.5-4 h to obtain a polyurethane acrylate chain segment with an-NCO group at one end, wherein the polyurethane acrylate chain segment contains a carboxylic acid group capable of being hydrated.
6. The water-soluble multifunctional resin according to claim 5, characterized in that: the solvent is one or a mixture of more of propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and dipropylene glycol dimethyl ether;
the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and p-phenylene diisocyanate;
the dihydroxy carboxylic acid is at least one of 2, 3-dihydroxy propionic acid, 2, 2-dimethylolpropionic acid, 2, 3-dihydroxy benzoic acid, 2, 4-dihydroxy benzoic acid, 2, 5-dihydroxy benzoic acid, 2, 6-dihydroxy benzoic acid, 3, 5-dihydroxy benzoic acid, 2, 2-dimethylolbutyric acid, 2, 4-dihydroxy butyric acid and 2, 3-dihydroxy butyric acid;
the hydroxy acrylic ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
7. The water-soluble multifunctional resin according to any one of claims 1 to 4, wherein: step S3 includes the following steps: and (2) adding the polyacrylate chain segment synthesized in the step S1 and the water-soluble polyurethane acrylate chain segment synthesized in the step S2 and provided with an-NCO group at one end, adding dibutyl tin dilaurate accounting for 0.1-0.8% of the total mass and a polymerization inhibitor accounting for 0.1-0.8%, uniformly stirring, heating to 60-100 ℃, and reacting for 2-5 hours to obtain the water-soluble polyurethane acrylate modified polyacrylate resin, wherein a side chain in the molecular structure of the resin simultaneously contains a plurality of acrylate double bonds and epoxy groups.
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