CN110003480B - Preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect - Google Patents
Preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect Download PDFInfo
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Abstract
The invention provides a preparation method of a cationic ultraviolet curing resin with synergistic water-solubility effect, which comprises the following steps: synthesizing a polyacrylate chain segment with a side chain containing hydroxyl and epoxy groups as a main chain; synthesizing a polyurethane acrylate chain segment with an-NCO group at one end as a side chain; reacting the two chain segments to obtain polyurethane acrylate modified polyacrylate resin with a side chain containing a plurality of acrylate double bonds and epoxy groups; and (3) uniformly stirring the obtained resin, heating, dropwise adding amine, reacting, cooling, adding acid, adding water, and uniformly stirring. By adopting the technical scheme of the invention, the obtained resin is comb-shaped and has lower viscosity and water solubility; wherein the grafted urethane acrylate side chain has a synergistic effect on the water solubility of the whole resin; the multiple functionality greatly improves the resin crosslinking degree in the curing process, and effectively improves the performance of the curing film.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a cationic ultraviolet curing resin with a synergistic water-soluble effect.
Background
Ultraviolet (UV) curing technology is an environment-friendly curing technology, and a liquid coating is irradiated by ultraviolet light and then undergoes photochemical reaction, so that polymerization and crosslinking are caused, and the liquid coating is changed into a solid film in a short time. Because the curing agent has the advantages of high curing speed, less environmental pollution, automatic production, suitability for thermosensitive substrates and the like, the curing agent 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 10s), 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.
Compared with the photoactive resin with higher molecular weight, the photoactive resin has higher viscosity, generally speaking, the resin has larger molecular weight and small volume shrinkage rate during curing, but has higher 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 is toxic, some human bodies have irritation, 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 peculiar smell for a long time, and the physical and chemical properties of a cured film, such as cured gel rate, cured film wear resistance and the like, can be obviously reduced by adding more reactive diluent. The most straightforward way to solve this problem is to prepare the resin as a water-soluble or water-emulsifiable resin, so that water can be the solvent in formulating the photocurable system.
Currently, many researchers have studied photo-curable water-based resins, and many of the early studies have conducted the purpose of dissolving oligomers in water by adding emulsifiers, and such resins require the addition of emulsifiers to achieve the water-based resin, but the addition of emulsifiers has a great influence on the properties of the cured film. Therefore, water-soluble light-cured resin is mostly developed at present, hydrophilic functional groups are introduced into the resin structure to realize the purpose, the resin is mostly of a linear structure and only has one main chain, and the performance is single, for example, epoxy acrylate has high hardness but 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, and different waterborne resins have inconsistent waterborne ions, so that the compounding of the resins is difficult to use, and the curing performance and the physical and chemical properties are difficult to control.
In addition, the water-based ultraviolet curing resin generally only has acrylate double bonds at two ends, and is mostly bifunctionality, the integral crosslinking degree in the subsequent ultraviolet curing process is not high due to the low functionality, the physicochemical properties of a cured film, such as hardness, wear resistance, alcohol resistance and the like, are not high, and in addition, the number of water-based functional groups in the molecular structure of the cured film is limited, so that the water solubility of the cured film is limited, and the cured film is difficult to dilute by a large amount of water in the application of spraying and the like. The defects of the waterborne resin cause that the waterborne resin is difficult to meet the increasingly high requirements of the industry on the performance of the ultraviolet curing coating, and the waterborne ultraviolet curing resin is difficult to be used in the industry at present on a large scale. However, from the viewpoint of environmental protection, aqueous uv curable resins are certainly an important direction for future development.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect, and the obtained resin is comb-shaped, so that the resin has lower viscosity; the water-soluble quaternary ammonium salt cationic waterborne polyurethane resin has a main chain and a side chain structure, wherein the main chain is provided with a plurality of hydroxyl groups and epoxy groups, and the epoxy groups are reacted with amine to form quaternary ammonium salt cationic waterborne groups through acid neutralization, so that the water-soluble quaternary ammonium salt cationic waterborne polyurethane resin has water solubility; in addition, the grafted urethane acrylate side chains synergistically contribute to the water solubility of the overall resin.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect 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 polyurethane acrylate chain segment with-NCO group at one end as a side chain;
step S3, synthesizing a side chain urethane acrylate modified main chain polyacrylate resin, and reacting the polyacrylate chain segment with the side chain having hydroxyl and epoxy groups obtained in the step S1 with the urethane acrylate chain segment with an-NCO group at one end obtained in the step S2, wherein the molar ratio of the-NCO group to the side chain OH group of the polyacrylate chain segment is 0.4-1: 1 (grafting ratio is 40-100%), and obtaining polyurethane acrylate modified polyacrylate resin with a side chain containing a plurality of acrylate double bonds and epoxy groups;
and S4, uniformly stirring the polyurethane acrylate modified polyacrylate resin obtained in the step S3, heating to 50-90 ℃, dropwise adding amine, reacting for 2-5 hours, cooling, adding acid with the same molar amount as the amino, adding water, and uniformly stirring to obtain the cationic ultraviolet curing water-based resin.
By adopting the technical scheme, the obtained 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 in the process of preparing the polyacrylate main chain, then a plurality of polyurethane acrylates are grafted on the side chain by utilizing the hydroxyl groups, the comb-like resin structure can enable the resin to have lower viscosity, and then the epoxy groups are reacted with amine to form quaternary ammonium salt cationic waterborne groups through acid neutralization, so that the water solubility of the resin is effectively improved. And wherein the grafted urethane acrylate side chains synergistically contribute to the water solubility of the overall resin. If the water-solubility effect of the resin is changed, the number of the quaternary ammonium salt cationic water-solubilizing groups in the resin structure can be easily adjusted and changed.
The cationic water-based ultraviolet curing resin prepared by the preparation method has good water solubility, avoids the negative influence caused by the addition of an emulsifier in common water emulsion resin, can use water as a solvent in the subsequent process of preparing a coating and an adhesive, avoids using an active diluent, can thoroughly solve the problems of influence of the active diluent on the physical and chemical properties of a cured film, residual smell and the like, can be diluted by more water in the fields of spraying and the like, and has very special significance on the processes of spraying and the like.
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 10-30% and 70-95%; wherein the double-bond reaction monomer comprises monomers of acrylic hydroxyl ester and acrylic glycidyl ester; adding a catalyst, stirring and heating to 50-95 ℃, and reacting for 1-4h to obtain a polyacrylate chain segment with a side chain having hydroxyl and an epoxy group.
As a further improvement of the invention, the double-bond reactive monomer comprises at least one of glycidyl acrylate and glycidyl methacrylate, at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate, 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 catalyst is at least one of azodiisobutyronitrile, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide. Furthermore, the dosage of the catalyst is 0.1-1.5% of the total mass of the monomers.
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 double-bond reaction monomer, the percentage of the acrylate hydroxyl ester monomer in the total mass of the double-bond reaction monomer is 5-40%; the percentage of the monomers of glycidyl acrylate in the total mass of the reaction monomers with double bonds is 5-40%.
In a further improvement of the present invention, in step S1, in the polyacrylate segment having hydroxyl and epoxy groups in its side chains, the mass percentage of the hydroxyl acrylate is 15% to 40%, and the mass percentage of the glycidyl acrylate is 15% to 30%. Furthermore, the sum of the mass percentages of the hydroxyl acrylate and the glycidyl acrylate is 30-65%.
As a further improvement of the present invention, the step S2 of synthesizing a urethane acrylate segment having an-NCO group at one end thereof comprises the steps of: adding diisocyanate into a reaction vessel, heating to 50-90 ℃, adding dihydric alcohol and dibutyl tin dilaurate into the diisocyanate, wherein the adding amount of the dihydric alcohol meets the condition that the molar ratio of the diisocyanate to the dihydric alcohol is 2: 1; after reacting for 1-4h, 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 the reaction system to 70-105 ℃, and reacting for 2-4 hours to obtain a polyurethane acrylate chain segment with an-NCO group at one end. 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 present invention, the diisocyanate is at least one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), p-phenylene diisocyanate (PPDI);
the dihydric alcohol is at least one of polyether dihydric alcohol, polyester dihydric alcohol, propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol and polyethylene glycol with the molecular weight of 200-4000;
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 invention, the dihydric alcohol is one of polyethylene glycols with molecular weight of more than 600.
As a further improvement of the present invention, step S3 includes the steps of: and adding the polyacrylate chain segment synthesized in the step S1 and the polyurethane acrylate chain segment synthesized in the step S2 and provided with an-NCO group at one end, adding dibutyl tin dilaurate accounting for 0.1-0.5% 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 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. Further, the polymerization inhibitor is p-hydroxyanisole or hydroquinone.
As a further improvement of the present invention, in step S4, the amine is added in an amount such that the molar ratio of the epoxy group to the amine group is 1: 1; the amine is at least one of dimethylamine, diethylamine, dipropylamine, dibutylamine and diethanolamine; the acid is at least one of lactic acid, acetic acid, formic acid, oxalic acid, propionic acid, butyric acid, malonic acid and succinic acid.
Further, the cationic ultraviolet curing resin with the synergistic water-soluble effect obtained by the preparation method has the viscosity of 1500-3000 mPas; furthermore, the cationic ultraviolet curing resin with the synergistic water-soluble effect obtained by the preparation method has the viscosity of 1800-2800 mPas.
Compared with the prior art, the invention has the beneficial effects that:
firstly, by adopting the technical scheme of the invention, the resin structure comprises a polyacrylate main chain and a polyurethane acrylate side chain, 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, the main chain with certain rigidity can be obtained, and the polyurethane 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 traditional water-based resin is avoided to be mostly of a single structure, such as water-soluble epoxy acrylate and water-soluble polyurethane acrylate, but the resin is mostly of a linear structure and only has one main chain, and the performance is relatively single, such as high hardness but 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, so that the performance of the cured film is difficult to control.
The cationic ultraviolet-curing water-based resin disclosed by the invention has multiple structures (a polyacrylate main chain and a polyurethane acrylate side chain) at the same time, and a single resin can obtain better comprehensive and reasonable performance, so that the problems of mismatching of water solubility, poor curing film-forming effect, limited improvement of physical and chemical properties and the like caused by the traditional compounding of multiple water-soluble resins are avoided.
Secondly, by adopting the technical scheme of the invention, the grafted polyurethane acrylate side chain has a synergistic promotion effect on the water solubility of the whole resin. Specifically, on the basis of having the same number of quaternary ammonium salt cationic waterborne groups, the polyurethane acrylate side chain prepared by grafting polyethylene glycol with the molecular weight of more than 600 can effectively improve the water solubility of the resin, and mainly the C-O-C functional group in the polyethylene glycol can form a hydrogen bond effect with water, so that the improvement of the water solubility of the resin is favorably promoted.
The cationic aqueous ultraviolet curing resin prepared by the invention has good water solubility, avoids the negative influence caused by adding an emulsifier in common aqueous emulsion resin, can use water as a solvent in the subsequent process of preparing coating and adhesive, avoids using an active diluent, can thoroughly solve the problems of influence of the active diluent on the physical and chemical properties of the cured film, residual odor and the like, can be diluted by more water in the fields of spraying and the like, and has very special significance for the processes of spraying and the like.
Thirdly, by adopting the technical scheme of the invention, the obtained ultraviolet curing resin has multiple functionality and water solubility, 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 then a plurality of polyurethane acrylates are grafted on the side chain by utilizing the hydroxyl groups, and the comb-like resin structure can enable the resin to have lower viscosity. Moreover, the grafting proportion of the urethane acrylate can be adjusted according to the requirements of subsequent performance, so that the side chain of the resin has multiple functionality (multiple acrylate double bonds), and the resin crosslinking degree can be greatly improved in the ultraviolet curing process due to the multiple functionality of the resin, thereby effectively improving the performances of the cured film such as hardness, adhesive force, wear resistance, solvent resistance, salt mist resistance and the like. 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
A preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect comprises the following steps:
firstly, adding 30g of propylene glycol monomethyl ether acetate, 40g of methyl methacrylate, 40g of methyl acrylate, 30g of glycidyl methacrylate, 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% 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 hydroxyl and epoxy groups on side chains, wherein in the polyacrylate chain segment, the mass percentage of the hydroxyethyl methacrylate (the hydroxyl source) is 30% and the mass percentage of the glycidyl methacrylate (the epoxy group source) is 15%.
Secondly, adding 1mol of Toluene Diisocyanate (TDI) into a 1000mL three-neck flask, heating to 63 ℃, adding 0.5 percent of dibutyl tin dilaurate into 0.5mol of polyethylene glycol (molecular weight 200) according to the total mass, dropwise adding the Toluene Diisocyanate (TDI) solution, continuing to react for 2.5 hours after the dropwise addition, adding 0.5 percent of p-hydroxyanisole according to the total mass of a reaction system into 1mol of hydroxyethyl acrylate, adding the reaction system, heating to 80 ℃, and reacting for 3.5 hours to obtain a polyurethane acrylate chain segment with an-NCO group at one end.
Thirdly, 115g (resin content 100g) of polyacrylate chain segment (I) synthesized in the first step is added into a 500mL three-neck flask, then a metered polyurethane acrylate chain segment (II) synthesized in the second step and provided with-NCO groups at one end is added, and the adding amount of the polyurethane acrylate chain segment provided with-NCO groups at one end meets the condition that the molar ratio of NCO groups to polyacrylate chain segment side chain OH groups 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 0.5 percent of the total mass and polymerization inhibitor hydroquinone accounting for 0.4 percent of the total mass, stirring uniformly, heating to 75 ℃ and reacting for 4.5 hours to obtain the polyurethane acrylate modified polyacrylate resin.
And fourthly, adding 100g of the polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, stirring, heating to 62 ℃, and dropwise adding diethanolamine, wherein the adding amount of the amine meets the condition that the molar ratio of an epoxy group to an amino group is 1: 1, reacting for 4 hours, cooling, adding acetic acid with the same mole as the amido, then gradually adding a proper amount of water, and uniformly stirring to obtain the cationic ultraviolet curing water-based resin.
In order to investigate the synergistic effect of the urethane acrylate side chains on the water solubility of the resin, the other synthesis processes are not changed, the cationic content of quaternary ammonium salt formed by epoxy is fixed, namely the mass percentage of the monomer containing epoxy group in the polyacrylate chain segment is 15%, the molecular weight of polyethylene glycol (PEG) in the second step is changed (specifically from 200, 400, 600, 800, 1000 and 2000), a series of urethane acrylate side chains with different lengths are synthesized, and then a limit hydration experiment is carried out, wherein the specific hydration results are shown in the following table 1:
TABLE 1 Limited Water solubility test results for polyurethane acrylate side chains of varying lengths
From experimental results, under the condition that the quantity of the cations of the water-based quaternary ammonium salt is consistent, the water solubility of the resin is obviously increased along with the increase of PEG chain segments in the side chains of the urethane acrylate, and under the condition of continuously adding water, the self-emulsifying effect is realized, the formed emulsion can stably exist even under the condition of being placed for a long time, and the layering phenomenon does not occur, so that the resin has good water solubility. However, as the urethane acrylate side chain grows, the flexibility of the resin increases but the hardness decreases, so the length of the urethane acrylate side chain is appropriately selected according to the use requirements.
The resin prepared based on PEG600 is used for testing the performance, the viscosity of the obtained water-based resin is 1800mPa.s, the water-based resin is used as a base raw material, the mass percent of the water-based resin is 96%, a photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) is directly added, the mass percent of the initiator is 4%, a light curing system is prepared, and the performance of a cured 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 2200 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 130 hours.
The resin prepared on the basis of PEG2000 was tested for properties and the resulting aqueous resin had a viscosity of 2800 mPa.s. The method comprises the steps of taking water-based resin as a base raw material, directly adding a photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) with the mass percent of 96%, preparing a photocuring system with the initiator content of 4%, and testing the performance of a cured film. 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 2H, the adhesive force (GB/T9286-1998) is grade 1, 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%, the temperature is 35 ℃ plus or minus 1 ℃, and the humidity is more than 80%) is not changed after being placed for 140 hours.
Example 2
A preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect comprises the following steps:
firstly, adding 30g of solvent ethylene glycol butyl ether acetate, 20g of butyl methacrylate, 40g of methyl methacrylate, 40g of hydroxyethyl acrylate, 30g of hydroxyethyl methacrylate, 50g of glycidyl methacrylate, 10g of styrene and 10g of acrylonitrile into a 500mL three-neck flask, uniformly stirring, adding a catalyst benzoyl peroxide tert-butyl ester accounting for 1.1% of the total mass of the monomer, heating to 68 ℃ while stirring, and reacting for 3 hours to obtain a polyacrylate chain segment (i) with hydroxyl and epoxy groups on side chains, wherein in the polyacrylate chain segment, the mass percentage of the hydroxyl acrylate (the source of the hydroxyl) is 35% and the mass percentage of the glycidyl acrylate (the source of the epoxy) is 25%.
Secondly, adding 1mol of Hexamethylene Diisocyanate (HDI) into a 1000mL three-neck flask, heating to 70 ℃, adding 0.6 percent of dibutyl tin dilaurate by total mass into 0.5mol of polyethylene glycol (molecular weight 200), dropwise adding into a Hexamethylene Diisocyanate (HDI) solution, continuing to react for 2.5h after dropwise adding, adding 0.6 percent of p-hydroxyanisole by total mass of a reaction system into 1mol of hydroxypropyl methacrylate, adding the reaction system, heating to 88 ℃ and reacting for 3h to obtain a polyurethane acrylate chain segment with an-NCO group at one end.
Thirdly, 115g (resin content 100g) of polyacrylate chain segment (I) synthesized in the first step is added into a 500mL three-neck flask, then a metered polyurethane acrylate chain segment (II) synthesized in the second step and provided with-NCO groups at one end is added, and the adding amount of the polyurethane acrylate chain segment provided with-NCO groups at one end meets the condition that the molar ratio of NCO groups to polyacrylate chain segment side chain OH groups is 0.8: 1 (80 percent of hydroxyl on a side chain of a polyacrylate chain segment is grafted and modified), then adding dibutyl tin dilaurate accounting for 0.5 percent of the total mass and a 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 the polyacrylate resin modified by polyurethane acrylate.
And fourthly, adding 100g of the polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, stirring, heating to 65 ℃, and dropwise adding diethylamine, wherein the adding amount of the amine meets the condition that the molar ratio of an epoxy group to an amino group is 1: 1, reacting for 4 hours, cooling, adding formic acid with the same mole as the amido, then gradually adding a proper amount of water, and uniformly stirring to obtain the cationic ultraviolet curing water-based resin.
In order to investigate the synergistic effect of the urethane acrylate side chains on the water solubility of the resin, the other synthesis processes do not change and fix the cationic content of the quaternary ammonium salt formed by epoxy, i.e. the mass percentage of the monomer containing epoxy groups to the polyacrylate chain segment is 25%, the molecular weight of polyethylene glycol (PEG) in the second step is changed (specifically from 200, 400, 600, 800, 1000, 2000) to synthesize a series of urethane acrylate side chains with different lengths, and then a limit hydration experiment is carried out, and the specific hydration results are shown in the following table 2:
TABLE 2 limiting Water-based Experimental results for polyurethane acrylate side chains of varying lengths
From the experimental results, similar to example 1, in the case of consistent amount of the water-based quaternary ammonium salt cations, the water solubility of the resin is obviously increased along with the increase of the PEG chain segment in the side chain of the urethane acrylate, and in the case of continuously adding water, the self-emulsifying effect is achieved, and the formed emulsion can stably exist even if being placed for a long time, and the layering phenomenon does not occur, which indicates that the resin has good water solubility. In addition, in example 2, due to the increase (25%) of the cation amount of the quaternary ammonium salt and the increase of the amount of the side chain grafted urethane acrylate, the water solubility is also significantly increased compared to example 1. Also as the urethane acrylate side chains grow, the flexibility of the resin increases, but the hardness decreases, so more use requires a reasonable choice of the length of the urethane acrylate side chains.
The resin prepared based on PEG600 is used for testing the performance, the viscosity of the obtained water-based resin is 1700mPa.s, 96 percent of water-based resin is used as a base 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 cured 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 2H, 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 140 hours.
The resin prepared by taking PEG2000 as a base tests performance, the viscosity of the obtained water-based resin is 2300mPa.s, 96% of water-based resin is taken as a base raw material, 4% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-acetone) is directly added, a photocuring system is prepared, and the performance of a cured 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 1H, the adhesive force (GB/T9286-1998) is grade 1, the RCA abrasion resistance test (applying 175g load) is more than 2500 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and applying 500g load) is more than 1400 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 150 hours.
Compared with the example 1, the side chain grafted urethane acrylate is increased, the water solubility promotion effect is more obvious, the flexibility of the resin is increased, the hardness is reduced, but the performances of the resin such as wear resistance, alcohol resistance and the like are slightly increased due to the increase of the crosslinking degree.
Comparative example 1
A preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect comprises the following steps:
firstly, adding 30g of solvent ethylene glycol butyl ether acetate, 50g of butyl acrylate, 40g of methyl methacrylate, 8g of hydroxyethyl methacrylate, 10g of glycidyl methacrylate, 50g of styrene and 42g of acrylonitrile into a 500mL three-neck flask, uniformly stirring, adding a catalyst benzoyl peroxide tert-butyl ester accounting for 1.0% 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 hydroxyl and epoxy groups on side chains, wherein in the polyacrylate chain segment, the mass percentage of the hydroxyl acrylate (the hydroxyl source) is 4%, and the mass percentage of the glycidyl acrylate (the epoxy group source) is 5%.
Secondly, adding 1mol of Hexamethylene Diisocyanate (HDI) into a 1000mL three-neck flask, heating to 70 ℃, adding 0.6 percent of dibutyl tin dilaurate by total mass into 0.5mol of polyethylene glycol (molecular weight 200), dropwise adding into a Hexamethylene Diisocyanate (HDI) solution, continuing to react for 2.5h after dropwise adding, adding 0.6 percent of p-hydroxyanisole by total mass of a reaction system into 1mol of hydroxypropyl methacrylate, adding the reaction system, heating to 88 ℃ and reacting for 3h to obtain a polyurethane acrylate chain segment with an-NCO group at one end.
Thirdly, 115g (resin content 100g) of polyacrylate chain segment (I) synthesized in the first step is added into a 500mL three-neck flask, then a metered polyurethane acrylate chain segment (II) synthesized in the second step and provided with-NCO groups at one end is added, and the adding amount of the polyurethane acrylate chain segment provided with-NCO groups at one end meets the condition that the molar ratio of NCO groups to polyacrylate chain segment side chain OH groups 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 83 ℃ and reacting for 2.5 hours to obtain the polyurethane acrylate modified polyacrylate resin.
And fourthly, adding 100g of the polyurethane acrylate modified polyacrylate resin synthesized in the third step into a 500mL three-neck flask, stirring, heating to 65 ℃, and dropwise adding diethanolamine, wherein the adding amount of the amine meets the condition that the molar ratio of an epoxy group to an amino group is 1: 1, reacting for 2.5h, cooling, adding formic acid with the same mole as the amido, then gradually adding a proper amount of water, and uniformly stirring to obtain the cationic ultraviolet curing water-based resin.
The experimental result shows that the resin is semitransparent after a small amount of water (accounting for 2 percent of the total mass of the resin) is added into the resin, then the resin is quickly emulsion-shaped, the water-based degree of the resin is not high due to the fact that the water-based functional groups are few, the viscosity of the obtained water-based resin is 1400mPa.s, 96 percent of the water-based resin is taken as a base 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 cured film is tested. After film coating, the film is dried by flash evaporation, and then is cured by ultraviolet light, the hardness HB and the adhesive force (GB/T9286-1998) of the cured film (pencil) are grade 1, the RCA abrasion resistance test (applying 175g load) is more than 400 times, the alcohol resistance (pure cotton cloth is dipped in absolute alcohol and 500g load is applied) is more than 200 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 20 hours.
Comparative example 2
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 prepared system has the viscosity of 9800mPa.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 grade 2, 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 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 2600mPa.s, the performance of the cured film is tested after ultraviolet curing, 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 standing for 70 hours.
Compared with the comparative example, the resin of the embodiment of the invention has the following outstanding advantages:
(1) the waterborne resin has low viscosity and can be dissolved in water, and a monofunctional group or polyfunctional group reactive diluent does not need to be additionally added when an ultraviolet 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 urethane acrylate chain segment of the resin side chain has a very good water solubility promoting effect on the water solubility of the resin, so that the resin can be added with more water to form water-based resin or stable emulsion (wherein PEG2000 modified resin can be added with more than 50% of water to form transparent water-soluble resin at most), and the construction process is very favorable for the subsequent spraying and other processes needing more water.
(3) 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 embodiment, the hardness of the cured film of the resin can reach more than 1H, the adhesive force is more than grade 1, the RCA abrasion resistance test (applying 175g of load) is more than 2200 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 when the resin is placed for more than 130 hours. All are obviously higher than the performances of the comparative examples (oil-soluble single ultraviolet curing system or aqueous 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 cationic ultraviolet curing resin with synergistic water-soluble effect is characterized in that: 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 polyurethane acrylate chain segment with-NCO group at one end as a side chain;
step S3, synthesizing a side chain urethane acrylate modified main chain polyacrylate resin, and reacting the polyacrylate chain segment with the side chain having hydroxyl and epoxy groups obtained in the step S1 with the urethane acrylate chain segment with an-NCO group at one end obtained in the step S2, wherein the molar ratio of the-NCO group to the side chain OH group of the polyacrylate chain segment is 0.4-1: 1, obtaining polyurethane acrylate modified polyacrylate resin with a side chain containing a plurality of acrylate double bonds and epoxy groups;
step S4, uniformly stirring the polyurethane acrylate modified polyacrylate resin obtained in the step S3, heating to 50-90 ℃, dropwise adding amine, reacting for 2-5 hours, cooling, adding acid with the same molar amount as the amino, adding water, and uniformly stirring to obtain the cationic ultraviolet curing water-based 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 10-30% and 70-95%; wherein the double-bond reaction monomer comprises monomers of acrylic hydroxyl ester and acrylic glycidyl ester; adding a catalyst, stirring and heating to 50-95 ℃, and reacting for 1-4h to obtain a polyacrylate chain segment with a side chain having hydroxyl and an epoxy group;
in the reaction monomer with the double bond, the percentage of the monomer of the acrylic hydroxyl ester in the total mass of the reaction monomer with the double bond is 5-40%; the percentage of the monomers of the glycidyl acrylate in the total mass of the reaction monomers with double bonds is 5-40%; the reaction monomer with double bonds comprises glycidyl acrylate monomers, hydroxyl acrylate monomers and other monomers with double bonds, and the other monomers with double bonds are at least one of butyl acrylate, butyl methacrylate, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic acid, acrylamide and styrene;
the step S2 of synthesizing the urethane acrylate chain segment with an-NCO group at one end comprises the following steps: adding diisocyanate into a reaction vessel, heating to 50-90 ℃, adding dihydric alcohol and dibutyl tin dilaurate into the diisocyanate, and reacting to obtain the product; the dihydric alcohol is at least one of polyether dihydric alcohol, polyester dihydric alcohol, propylene glycol, neopentyl glycol, 1, 4-butanediol and 1, 6-hexanediol.
2. The method for preparing the cationic ultraviolet-curable resin with synergistic water-soluble effect according to claim 1, wherein:
the monomer of the acrylic acid hydroxyl ester comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate;
the monomer of the glycidyl acrylate comprises at least one of glycidyl acrylate and glycidyl methacrylate;
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 catalyst is at least one of azodiisobutyronitrile, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
3. The method for preparing the cationic ultraviolet-curable resin with synergistic water-soluble effect according to claim 2, wherein: 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 15-30%.
4. The method for preparing the cationic ultraviolet-curable resin with synergistic water-soluble effect according to claim 2, wherein: in the step of synthesizing the urethane acrylate chain segment with an-NCO group at one end in step S2, the addition amount of the dihydric alcohol is such that the molar ratio of the diisocyanate to the dihydric alcohol is 2: 1; after reacting for 1-4h, 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 the reaction system to 70-105 ℃, and reacting for 2-4 hours to obtain a polyurethane acrylate chain segment with an-NCO group at one end.
5. The method for preparing the cationic UV-curable resin with synergistic water-soluble effect according to claim 4, wherein: the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and p-phenylene diisocyanate;
the hydroxy acrylic ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
6. The method for preparing cationic UV-curable resin with synergistic water-soluble effect according to claim 5, wherein: the dihydric alcohol is one of polyethylene glycols with molecular weight of more than 600.
7. The method for preparing the cationic ultraviolet-curable resin with synergistic water-soluble effect according to any one of claims 1 to 6, characterized in that: step S3 includes the following steps: and adding the polyacrylate chain segment synthesized in the step S1 and the polyurethane acrylate chain segment synthesized in the step S2 and provided with an-NCO group at one end, adding dibutyl tin dilaurate accounting for 0.1-0.5% 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 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.
8. The method for preparing the cationic ultraviolet-curable resin with synergistic water-soluble effect according to any one of claims 1 to 6, characterized in that: in step S4, the amine is added in an amount such that the molar ratio of the epoxy group to the amine group is 1: 1; the amine is at least one of dimethylamine, diethylamine, dipropylamine, dibutylamine and diethanolamine; the acid is at least one of lactic acid, acetic acid, formic acid, oxalic acid, propionic acid, butyric acid, malonic acid and succinic acid.
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