CN109942772B - Preparation method of ultraviolet curing water-based resin with adjustable functionality - Google Patents
Preparation method of ultraviolet curing water-based resin with adjustable functionality Download PDFInfo
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Abstract
The invention provides a preparation method of ultraviolet curing water-based resin with adjustable functionality, which comprises the following steps: synthesizing polyacrylate chain segments with side chains containing hydroxyl; synthesizing a polyurethane acrylate chain segment with-NCO groups at one end, wherein the polyurethane acrylate chain segment contains carboxylic acid groups capable of being hydrated; reacting the obtained polyacrylate chain segment with a side chain containing hydroxyl with a polyurethane acrylate chain segment with-NCO group at one end to obtain polyurethane acrylate modified polyacrylate resin capable of being hydrated; adding an alkali solution for neutralization to obtain the anionic ultraviolet curing water-based resin. By adopting the technical scheme of the invention, the mutual balance of multiple properties is realized through one resin, the viscosity is low, the water-solubility is realized, a diluent is not required, and the environment is more environment-friendly; the obtained resin side chain has multiple functionality, the resin crosslinking degree is greatly improved in the curing process, and various performances of the curing film are improved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of ultraviolet curing water-based resin with adjustable functionality.
Background
The Ultraviolet (UV) curing technology is an environment-friendly curing technology, and after the liquid coating is irradiated by UV light, it can produce photochemical reaction to produce polymerization and cross-linking, so that the liquid coating can be changed into solid film in short time. The coating is expected to replace the traditional solvent-based coating, adhesive, 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 ultraviolet curing system generally comprises photoactive resin, monofunctional group or polyfunctional group diluting monomer, photoinitiator, auxiliary agent and the like. The photoactive resin forms a three-dimensional network structure of a 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. The photoinitiator is used to initiate the UV free radical cure in small amounts and the auxiliaries are added to impart specific properties to the coating. The properties of coatings, inks, adhesives using UV curing are largely dependent on the nature of the photoactive resin used in the formulation. Most UV curing systems are based on acrylate-functional oligomers, the types of resins used being mainly acrylated epoxies, polyesters, polyurethanes and silicones, which are obtained by reacting acrylic with epoxies, polyesters, polyurethanes.
The photoactive resin with relatively high molecular weight has larger viscosity, generally speaking, the resin has large molecular weight and small volume shrinkage rate during curing, but has high molecular weight and high viscosity, more monomer dilution is needed, the diluent can react with the photoactive resin finally, but the low molecular weight reactive diluent has toxicity and irritation to human bodies, and when the photoactive resin is used on some porous substrates, such as wood, cement and paper, the diluent is easy to diffuse into pores and can not be cured, so that coated objects have long-term odor, and the physical and chemical properties of a cured film, such as cured gel fraction, cured film wear resistance and the like, can be obviously reduced by adding more reactive diluent.
In order to solve this problem, one approach is to develop a photoactive resin with low viscosity, and in recent years, a star-shaped hyperbranched polymer having a three-dimensional spherical structure has become a hot point of research. Unlike traditional linear polymer, star polymer and hyperbranched branched polymer have high functionality, no entanglement between molecules and other structural features, so that the polymer has low viscosity, high solubility, high activity, easy modification of surface functional group, high glass transition temperature and excellent intermingling performance. However, the reaction process of the star hyperbranched polymer is relatively difficult to control, and the large-scale industrial production process is difficult to realize.
Another method to solve this problem is to prepare the resin into water-soluble or water-emulsion resin, so that water can be used as solvent when preparing the photo-curing system, and the water-based photo-curing system has the following characteristics compared with the traditional oil-based photo-curing system: the viscosity and rheological property of the paint can be adjusted by adding water or traditional thickening agents and leveling agents; the toxicity and the irritation of the system are reduced, the coating is suitable for various existing coating devices, and the coating devices are easy to clean so as to obtain an ultrathin cured film; the paint does not contain volatile organic compounds, reduces the inflammability of the paint, is safe to produce and is particularly more meaningful for spraying.
At present, many researchers carry out the research of photocuring water-based resins, many of the early researches use an emulsifier to dissolve an oligomer in water, the resins can be hydrated only by adding the emulsifier, and the addition of the emulsifier has a great influence on the performance of a cured film, so that water-soluble photocuring resins are developed at present, and hydrophilic functional groups are introduced into the resin structure to realize the purpose, wherein water-soluble epoxy acrylate and water-soluble urethane acrylate are researched more, but the resins are mostly in linear structures, only have one main chain and have single performance, and if the epoxy acrylate has high hardness and poor flexibility; the polyurethane acrylate has the defects of good flexibility and wear resistance, low hardness and the like, and in order to obtain a cured film with good comprehensive performance, a plurality of resins must be compounded for use, so that the performance is difficult to control. In addition, the waterborne ultraviolet curing resin generally only has acrylate double bonds at two ends, and most of the waterborne ultraviolet curing resin has bifunctionality, the overall crosslinking degree in the subsequent ultraviolet curing process is not high due to the fact that the functionality is not high, the physical and chemical properties of a cured film such as hardness, wear resistance, alcohol resistance and the like are not high, the requirement of the industry for the performance of an ultraviolet curing coating to be higher and higher is difficult to meet, and the existing waterborne ultraviolet curing resin is difficult to use in a large scale in the industry.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of ultraviolet curing water-based resin with adjustable functionality, the obtained resin structure comprises a polyacrylate main chain and a water-based polyurethane acrylate side chain, wherein the resin has higher glass transition temperature and better hardness and other properties by controlling the proportion of monomers in the synthesis process of polyacrylate, and meanwhile, the polyurethane acrylate of the side chain can endow the resin with better flexibility and wear resistance, so that the mutual balance of multiple properties of one resin is realized, and the problems that most of the traditional water-based resin has single structural property and is single and the like are solved.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of a UV-curable water-based resin with adjustable functionality comprises the following steps:
step S1, synthesizing polyacrylate chain segments with side chains containing hydroxyl;
step S2, synthesizing a polyurethane acrylate chain segment with-NCO group at one end, wherein the polyurethane acrylate chain segment contains carboxylic acid group capable of being hydrated;
step S3, reacting the polyacrylate chain segment with the side chain containing hydroxyl obtained in the step S1 with the polyurethane acrylate chain segment with-NCO group at one end obtained in the step S2, wherein the molar ratio of-NCO group to polyacrylate chain segment side chain OH group is 0.2-1: 1 (namely grafting modification is 20-100 percent) to obtain polyurethane acrylate modified polyacrylate resin capable of being hydrated, wherein a side chain in the molecular structure of the resin simultaneously contains a plurality of acrylate double bonds;
and step S4, adding an alkali solution into the polyurethane acrylate modified polyacrylate resin which is obtained by the reaction in the step S3 and can be hydrated to neutralize, so as to obtain the anionic ultraviolet curing water-based resin.
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 by controlling the proportion of reaction monomers in the process of preparing the polyacrylate main chain, and the specific content of the hydroxyl groups can be adjusted according to the requirement; then, a plurality of polyurethane acrylates capable of being subjected to water-based polymerization are grafted on the side chain by utilizing hydroxyl groups, the obtained comb-like resin structure can enable the resin to have lower viscosity, the prepared water-based ultraviolet curing resin is water-soluble, the negative influence caused by the addition of an emulsifier in 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 a reactive diluent is avoided, and the problems that the reactive diluent influences the physical and chemical properties of a curing film and has residual odor and the like can be thoroughly solved.
In addition, according to the requirements of water-based property and final performance of resin, the molar ratio of-NCO groups to polyacrylate chain segment side chain OH groups can be adjusted according to the requirements, namely the grafting proportion of the side chain urethane acrylate is adjusted to be 20-100%, so that the resin side chain has multiple functionality (multiple acrylate double bonds), the resin crosslinking degree is improved in the subsequent ultraviolet curing process, 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 two properties are not currently available with many aqueous photocurable resins.
In a further improvement of the present invention, in step S1, the mass percentage of the hydroxyl acrylate in the polyacrylate segment having hydroxyl groups in the side chains is 20 to 50%. The hydroxy acrylate may be at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate, but is not limited thereto.
As a further improvement of the present invention, step S1 includes the steps of:
adding a solvent and a reaction monomer with double bonds into a reaction container, wherein the mass percent of the solvent is 5-30%, and the mass percent of the reaction monomer with double bonds is 70-95%; wherein the double-bond reaction monomer comprises a hydroxyl acrylate monomer; adding a catalyst accounting for 0.1-1.5% of the total mass of the monomers, stirring and heating to 50-95 ℃, and reacting for 1-4 hours to obtain a polyacrylate chain segment with a side chain containing hydroxyl.
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 reaction monomer with double bonds comprises at least one acrylic hydroxyl ester monomer and at least one of butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic acid, acrylamide and styrene; the content of the acrylic hydroxyl ester monomer is 5-50% of the total mass of the solvent and the reaction monomer with double bonds;
the catalyst is at least one of azodiisobutyronitrile, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
Further, the hydroxyl acrylate monomer 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 and styrene.
As a further improvement of the present invention, step S2 includes the steps of:
adding diisocyanate and a solvent into a reaction container, and heating to 50-90 ℃; adding a dihydroxy carboxylic acid and dibutyl tin dilaurate in an amount such that the molar ratio of diisocyanate to dihydroxy carboxylic acid is 2: 1; after reacting for 1-5h, adding hydroxyl acrylate and a polymerization inhibitor into a 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 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; wherein the addition amount of the dibutyl tin dilaurate is 0.1-0.8% of the total mass of substances in the reaction vessel; the polymerization inhibitor is p-hydroxyanisole or hydroquinone, and the addition amount of the polymerization inhibitor is 0.1-0.8% of the total mass.
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:
adding the polyacrylate chain segment obtained in the step S1 and the waterborne polyurethane acrylate chain segment which is obtained in the step S2 and has-NCO groups at one end into a reaction vessel, and adjusting the side chain grafting proportion and the number of acrylate double bonds according to requirements; and then 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 waterborne polyurethane acrylate modified polyacrylate resin, wherein a side chain in a molecular structure of the resin simultaneously contains a plurality of acrylate double bonds.
Further, 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 being neutralized by adding an alkali solution is 8-10.
Further, the concentration of the alkali solution is 0.01-1 mol/L
Further, the alkali is one of ammonia, sodium hydroxide, potassium hydroxide, dimethylamine, diethylamine, dipropylamine, dibutylamine and diethanolamine.
The invention also discloses an anionic ultraviolet curing water-based resin which is prepared by adopting the preparation method of the ultraviolet curing water-based resin with adjustable functionality, the anionic ultraviolet curing water-based resin comprises a polyacrylate main chain and a polyurethane acrylate side chain capable of being hydrated, and the side chain of the anionic ultraviolet curing water-based resin simultaneously contains a plurality of acrylate double bonds and carboxylate groups.
Further, the solid content of the anionic ultraviolet curing water-based resin is 60-68%, and the viscosity is 1100-1800 mPa.s.
Furthermore, the solid content of the anionic ultraviolet curing water-based resin is 62-66%, and the viscosity is 1300-1600 mPa.s.
The resin structure in the technical scheme comprises a polyacrylate main chain and a polyurethane acrylate side chain capable of being hydrated, and a plurality of polyurethane acrylate side chains capable of being hydrated can be grafted on the same polyacrylate main chain as required to form a comb-shaped structure, so that the number of ultraviolet-curable acrylate double bonds in the resin structure can be adjusted. The obtained resin has 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 multifunctional acrylate double bond grafted by the side chain can improve the crosslinking degree in the photocuring process, and can effectively improve the performances of the cured film such as hardness, adhesive force, wear resistance, solvent resistance, salt mist resistance and the like.
The solid content of the water-based resin is more than 62 percent, the hardness of a cured film can reach more than 3H, the adhesive force is more than grade 1, the RCA wear resistance test (applying 175g of load) is more than 2300 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and 500g of load) is more than 1200 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 120 hours.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the ultraviolet curing water-based resin structure with adjustable functionality obtained by adopting the technical scheme of the invention comprises a polyacrylate main chain and a polyurethane acrylate side chain capable of being hydrated, 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, and the main chain with certain rigidity can be obtained; the water-soluble urethane acrylate side chain can provide carboxylic acid groups capable of being water-based, and the water-soluble urethane acrylate side chain can enable the resin to have certain flexibility and wear resistance, so that the mutual balance of multiple properties of one resin is realized. The technical scheme avoids the problem of single performance caused by the single structure of the traditional water-based resin, such as water-soluble epoxy acrylate and water-soluble polyurethane acrylate, but the resin is mostly in a linear structure and only has one main chain, and the performance is single, such as high hardness and poor flexibility of the epoxy acrylate; the polyurethane acrylate has the defects of good flexibility and wear resistance, low hardness and the like, and in order to obtain a cured film with good comprehensive performance, a plurality of resins must be compounded for use, but the compounding of the two resins makes the performance difficult to control. The anionic ultraviolet curing water-based resin disclosed by the invention has multiple structures (a polyacrylate main chain and a polyurethane acrylate side chain capable of being hydrated), and a single resin can obtain better comprehensive and reasonable performance, so that the problems of water solubility mismatching, poor curing film forming effect, limited improvement on physical and chemical properties and the like caused by traditional multiple resin compounding are solved.
Secondly, the preparation method of the invention obtains the ultraviolet curing resin with multiple functionality and water-solubility characteristic, the resin has a main chain and a side chain structure, the main chain is provided with a plurality of hydroxyl groups by controlling the proportion of reaction monomers in the process of preparing the polyacrylate main chain, then a plurality of polyurethane acrylate capable of being water-based is 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 acrylate can be adjusted according to the requirements of water-based and subsequent performances, the resin side chain has multiple functionality (a plurality of acrylate double bonds), the prepared water-based ultraviolet curing resin is water-soluble, the negative influence caused by adding an emulsifier additionally in the common water emulsion resin is avoided, water can be used as a solvent in the subsequent process of preparing paint and adhesive, and the use of an active diluent is avoided, 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.
Thirdly, the side chain of the resin obtained by the preparation method has multiple functionality (a plurality of acrylate double bonds), so that the crosslinking degree of the resin is greatly improved in the ultraviolet curing process, and the hardness, adhesive force, wear resistance, solvent resistance, salt mist resistance and other properties of the cured film are improved. These several properties are currently not available with many aqueous photocurable resins.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
Firstly, adding 20g of propylene glycol monomethyl ether acetate, 40g of methyl methacrylate, 20g of butyl methacrylate, 40g of methyl acrylate, 10g of butyl acrylate, 60g 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 percent of the total mass of the monomers, heating to 67 ℃ while stirring, and reacting for 3 hours to obtain a polyacrylate chain segment I with hydroxyl on a side chain, wherein the mass percent content of the hydroxyethyl methacrylate in the polyacrylate chain segment is 30 percent.
Secondly, adding 1mol of Toluene Diisocyanate (TDI) and 18g of propylene glycol methyl ether acetate solvent into a 1000mL three-neck flask, heating to 68 ℃, adding 0.5 percent of dibutyl tin dilaurate by the total mass into 0.5mol of 2, 3-dihydroxypropionic acid, gradually adding the mixture into Toluene Diisocyanate (TDI) solution, continuing to react for 2.5 hours after dripping, adding 0.4 percent of p-hydroxyanisole into 1mol of hydroxyethyl methacrylate, adding the reaction system, heating to 80 ℃ 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, and then adding metered polyurethane acrylate chain segment (II) synthesized in the second step and capable of being hydrated, wherein one end of the polyurethane acrylate chain segment is provided with an-NCO group, and the adding amount of the polyurethane acrylate chain segment capable of being hydrated, wherein one end of the polyurethane acrylate chain segment is provided with the-NCO group, so 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 hydroquinone accounting for 0.6 percent of the total mass, stirring uniformly, heating to 75 ℃ 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 0.12mol/L ammonia water solution while stirring until the pH value of the solution is between 8 and 10 to obtain the water-soluble anionic ultraviolet curing resin.
The solid content of the obtained water-based resin is 64.1 percent, the viscosity of the resin is 1500mPa.s, 96 percent of water-based resin is taken as a basic raw material, 4 percent of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) is directly added, a light curing system is prepared, and the performance of a curing film is tested. After film coating, the film is dried by flash evaporation, and then is cured by ultraviolet light, the hardness of a cured film (pencil) is 4H, the adhesive force (GB/T9286-1998) is grade 1, the RCA abrasion resistance test (applying 175g of load) is more than 2600 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and applying 500g of load) is more than 1400 times, and the salt spray resistance (the 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 150 hours.
Example 2
Firstly, 20g of solvent ethylene glycol butyl ether acetate, 40g of butyl acrylate, 60g of methyl methacrylate, 40g of butyl 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 66 ℃ while being stirred, and the reaction is carried out for 3 hours, so as to obtain a polyacrylate chain segment I with hydroxyl on a side chain, wherein the mass percent content of the hydroxyethyl acrylate in the polyacrylate chain segment is 20 percent.
Secondly, adding 1mol of dicyclohexyl methane diisocyanate (HMDI) and 16g of ethylene glycol butyl ether acetate serving as a solvent into a 1000mL three-neck flask, heating to 66 ℃, adding 0.4 percent of dibutyl tin dilaurate in the total mass into 0.5mol of 2, 2-dimethylolbutyric acid, gradually adding the mixture into a dicyclohexyl methane diisocyanate (HMDI) solution, continuing to react for 2.5 hours after finishing dripping, adding 0.6 percent of p-hydroxyanisole into 1mol of hydroxyethyl acrylate, adding the reaction system, heating to 83 ℃ 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, 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 p-hydroxyanisole accounting for 0.6 percent of the total mass, stirring uniformly, heating to 86 ℃ 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 anionic ultraviolet curing resin.
The solid content of the obtained water-based resin is 65.3%, the viscosity of the resin is 1400mPa.s, 96% of the water-based resin is taken as a basic raw material, 4% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) is directly added, a light curing system is prepared, and the performance of a curing film is tested. After film coating, the film is dried by flash evaporation, and then is cured by ultraviolet light, the hardness of a cured film (pencil) is 3H, the adhesive force (GB/T9286-1998) is 0 grade, the RCA abrasion resistance test (applying 175g of load) is more than 2400 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and applying 500g of load) is more than 1300 times, and the salt spray resistance (the salt water concentration is 5 percent, the temperature is 35 ℃ plus or minus 1 ℃, and the humidity is more than 80 percent) is unchanged after being placed for 130 hours.
Example 3
Firstly, 20g of propylene glycol diacetate solvent, 30g of butyl methacrylate, 40g of methyl acrylate, 40g of hydroxypropyl methacrylate, 40g of hydroxypropyl acrylate, 20g of hydroxyethyl methacrylate, 10g of styrene and 20g of acrylamide are added into a 500mL three-neck flask, uniformly stirred, added with benzoyl peroxide catalyst accounting for 0.8 percent of the total mass of the monomers, heated to 73 ℃ while stirring, and reacted for 2.5 hours to obtain a polyacrylate chain segment I with hydroxyl on a side chain, wherein the sum of the mass percentages of the hydroxypropyl methacrylate, the hydroxypropyl acrylate and the hydroxyethyl methacrylate in the polyacrylate chain segment is 50 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 65 ℃, adding 0.6 percent of dibutyl tin dilaurate in the total mass into 0.5mol of 2, 4-dihydroxybutyric 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 90 ℃ 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, 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 0.2: 1 (20 percent of hydroxyl on the side chain of the 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 0.3 percent of the total mass, stirring uniformly, heating to 80 ℃ 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 anionic ultraviolet curing resin.
The solid content of the obtained water-based resin is 62.1%, the viscosity of the resin is 1200mPa.s, 96% of the water-based resin is taken as a basic raw material, 4% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) is directly added, a light curing system is prepared, and the performance of a curing film is tested. After film coating, the film is dried by flash evaporation, and then is cured by ultraviolet light, the hardness of a cured film (pencil) is 3H, the adhesive force (GB/T9286-1998) is grade 1, the RCA abrasion resistance test (applying 175g of load) is more than 2300 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and applying 500g of load) is more than 1200 times, and the salt spray resistance (the 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 120 hours.
Example 4
Firstly, 20g of solvent ethylene glycol ethyl ether acetate, 50g of butyl methacrylate, 30g of butyl acrylate, 30g of hydroxyethyl methacrylate, 30g of hydroxypropyl methacrylate, 20g of hydroxyethyl acrylate, 20g of styrene and 20g of acrylonitrile 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 75 ℃ while being stirred, and the reaction is carried out for 2.5 hours, so as to obtain a polyacrylate chain segment I with hydroxyl on a side chain, wherein the sum of the mass percentages of the hydroxyethyl methacrylate, the hydroxypropyl methacrylate and the hydroxyethyl acrylate in the polyacrylate chain segment is 40 percent.
Secondly, adding 1mol of Hexamethylene Diisocyanate (HDI) and 15g of solvent ethylene glycol monoethyl ether acetate into a 1000mL three-neck flask, heating to 66 ℃, adding dibutyl tin dilaurate into 0.5mol of 2, 3-dihydroxypropionic acid according to 0.6 percent of the total mass, gradually adding the mixture into a Hexamethylene Diisocyanate (HDI) solution, continuing to react for 3 hours after dripping, adding 0.7 percent of p-hydroxyanisole into 1mol of hydroxypropyl acrylate, adding the reaction system, heating to 80 ℃ and reacting for 3 hours to obtain the waterborne polyurethane acrylate chain segment with-NCO groups 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 0.8: 1 (80 percent of hydroxyl on the side chain of the polyacrylate chain segment is grafted and modified), then adding dibutyl tin dilaurate accounting for 0.6 percent of the total mass and polymerization inhibitor p-hydroxyanisole accounting for 0.5 percent of the total mass, stirring uniformly, heating to 83 ℃ 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 0.14mol/L diethylamine solution while stirring until the pH value of the solution is between 8 and 10 to obtain the water-soluble anionic ultraviolet curing resin.
The solid content of the obtained water-based resin is 65.6%, the viscosity of the resin is 1600mPa.s, 96% of water-based resin is taken as a basic raw material, 4% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) is directly added, a light curing system is prepared, and the performance of a curing film is tested. After coating, the film is dried by flash evaporation, and then is cured by ultraviolet light, the hardness of the cured film (pencil) is 4H, the adhesive force (GB/T9286-1998) is grade 1, the RCA abrasion resistance test (applying 175g load) is more than 2800 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and applying 500g load) is more than 1500 times, and the salt spray resistance (the salt water concentration is 5%, the temperature is 35 ℃ plus or minus 1 ℃, and the humidity is more than 80%) is not changed after being placed for 150 hours.
Comparative example 1
A common oily 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 (applying 175g of load) 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 2
A comparison test is carried out on an ultraviolet curing system compounded by two kinds of water-based resin, and the formula comprises the following components:
48 percent of waterborne epoxy resin acrylate
48 percent of waterborne polyurethane acrylate
Photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone) 4%
The viscosity of the prepared system is 2600 mPa.s, the ultraviolet curing is carried out, the performance of the cured film is tested, the hardness of the cured film is 3H, the adhesive force (GB/T9286-1998) is grade 1, the RCA abrasion resistance test (175 g of load is applied) is more than 1100 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and 500g of load is applied) is more than 600 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 70 hours.
Compared with the comparative examples, the resin of the invention has the following outstanding advantages: (1) the water-based resin of the embodiment has low viscosity, can be dissolved in water, does not need to additionally add a monofunctional or polyfunctional reactive diluent when preparing a photocuring system, and avoids the problems of reduced physical and chemical properties of a cured film or residual odor and the like caused by the reactive diluent. (2) The resin has multiple functionality, one resin molecule has multiple light-curable acrylate double bonds, and after ultraviolet light curing, the cured film has high crosslinking degree, and can effectively improve the cured hardness, adhesive force, wear resistance, solvent resistance, salt mist resistance and other properties. According to the data of the embodiment, the hardness of the cured film of the resin provided by the embodiment of the invention can reach more than 3H, the adhesion is more than grade 1, the RCA wear resistance test (applying 175g of load) is more than 2300 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and 500g of load is applied) is more than 1200 times, and the salt spray resistance (salt water concentration is 5%, temperature is 35 ℃ plus or minus 1 ℃, and humidity is more than 80%) is unchanged after being placed for more than 120 hours. The performances are obviously higher than those of a comparative example (an oil-soluble single ultraviolet curing system or a water-based compound ultraviolet 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 (8)
1. A preparation method of ultraviolet curing water-based resin with adjustable functionality is characterized in that: which comprises the following steps:
step S1, synthesizing polyacrylate chain segments with side chains containing hydroxyl; in the polyacrylate chain segment with the side chain containing hydroxyl, the mass percentage content of the acrylic hydroxyl ester is 20-50%;
step S2, synthesizing a polyurethane acrylate chain segment with-NCO group at one end, wherein the polyurethane acrylate chain segment contains carboxylic acid group capable of being hydrated;
step S3, reacting the polyacrylate chain segment with the side chain containing hydroxyl obtained in the step S1 with the polyurethane acrylate chain segment with-NCO group at one end obtained in the step S2, wherein the molar ratio of-NCO group to polyacrylate chain segment side chain OH group is 0.2-1: 1, obtaining polyurethane acrylate modified polyacrylate resin capable of being hydrated, wherein a side chain in a molecular structure of the resin simultaneously contains a plurality of acrylate double bonds;
step S4, adding an alkali solution into the polyurethane acrylate modified polyacrylate resin which can be hydrated and is obtained by the reaction in the step S3 for neutralization to obtain an anionic ultraviolet light curing water-based resin;
step S1 includes the following steps:
adding a solvent and a reaction monomer with double bonds into a reaction container, wherein the mass percent of the solvent is 5-30%, and the mass percent of the reaction monomer with double bonds is 70-95%; wherein the double-bond reaction monomer comprises a hydroxyl acrylate monomer; 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 containing hydroxyl;
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 reaction monomer with double bonds comprises acrylic hydroxyl ester monomers and at least one of butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic acid, acrylamide and styrene; the content of the acrylic hydroxyl ester monomer is 5-50% of the total mass of the double-bond reaction monomers.
2. The method for preparing ultraviolet curable water-based resin with adjustable functionality according to claim 1, wherein:
the acrylic hydroxyl ester monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate;
the catalyst is at least one of azodiisobutyronitrile, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
3. The method for preparing ultraviolet curable water-based resin with adjustable functionality according to claim 1, wherein: step S2 includes the following steps:
adding diisocyanate and a solvent into a reaction container, and heating to 50-90 ℃; adding a dihydroxy carboxylic acid and dibutyl tin dilaurate in an amount such that the molar ratio of diisocyanate to dihydroxy carboxylic acid is 2: 1; after reacting for 1-5h, adding hydroxyl acrylate and a polymerization inhibitor into a 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 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; wherein the addition amount of the dibutyl tin dilaurate is 0.1-0.8% of the total mass of substances in the reaction vessel; the polymerization inhibitor is p-hydroxyanisole or hydroquinone, and the addition amount of the polymerization inhibitor is 0.1-0.8% of the total mass.
4. The method for preparing ultraviolet curable water-based resin with adjustable functionality according to claim 3, wherein: 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.
5. The method for preparing ultraviolet curable water-based resin with adjustable functionality according to claim 3, wherein: step S3 includes the following steps:
adding the polyacrylate chain segment obtained in the step S1 and the waterborne polyurethane acrylate chain segment which is obtained in the step S2 and has-NCO groups at one end into a reaction vessel, and adjusting the side chain grafting proportion and the number of acrylate double bonds according to requirements; and then 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 waterborne polyurethane acrylate modified polyacrylate resin, wherein a side chain in a molecular structure of the resin simultaneously contains a plurality of acrylate double bonds.
6. The method for preparing ultraviolet curable water-based resin with adjustable functionality according to claim 5, wherein: in the step S4, adding an alkali solution to neutralize the solution, wherein the pH value of the neutralized solution is 8-10.
7. An anionic ultraviolet light curing water-based resin is characterized in that: the ultraviolet curing water-based resin with adjustable functionality is prepared by the method for preparing the ultraviolet curing water-based resin with adjustable functionality according to any one of claims 1 to 6, wherein the anionic ultraviolet curing water-based resin comprises a polyacrylate main chain and a water-based polyurethane acrylate side chain, and the side chain of the anionic ultraviolet curing water-based resin simultaneously contains a plurality of acrylate double bonds and carboxylate groups.
8. The anionic ultraviolet-curable aqueous resin according to claim 7, characterized in that: the solid content of the anionic ultraviolet curing water-based resin is 60-68%, and the viscosity is 1100-1800 mPa.s.
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