CN105693999A - Ultraviolet-curing waterborne cationic resin and preparation method thereof - Google Patents
Ultraviolet-curing waterborne cationic resin and preparation method thereof Download PDFInfo
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- CN105693999A CN105693999A CN201610243978.XA CN201610243978A CN105693999A CN 105693999 A CN105693999 A CN 105693999A CN 201610243978 A CN201610243978 A CN 201610243978A CN 105693999 A CN105693999 A CN 105693999A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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Abstract
The invention provides ultraviolet-curing waterborne cationic resin and a preparation method thereof. The formula of the ultraviolet-curing waterborne cationic resin is as shown in formula (1), wherein R1 is CH3, CH2CH3, CH2CH2OH, CH2CH2CH3 or CH2CH2CH2CH3; R2 is CH3, CH2CH3, CH2CH2OH, CH2CH2CH3 or CH2CH2CH2CH3. By the arrangement, the ultraviolet-curing waterborne cationic resin has the advantages that the molecules of the resin contain acrylate double bonds and ammonium salt positive ions at the same time, ultraviolet-cured products can be prepared by using water the solvent, diluent use amount is reduced, environment protection is achieved, and the performance of the cured products is unaffected; the whole resin synthesizing process is simple, easy structure control is achieved, subsequent use performance can be guaranteed, and product stability and consistency can be well guaranteed during batch production.
Description
Technical field
The invention belongs to organic polymer synthesis technical field, particularly relate to a kind of UV-curable water-borne cationic resin and preparation method thereof。
Background technology
Ultraviolet light (UV) curing technology is a kind of environment-friendly type curing technology of the twentieth century exploitation forties, it is after being subject to irradiation under ultraviolet ray, there is photochemical reaction, thus causing polymerization, crosslinking, liquid coating moment is made to become solid film, it have the advantage that the saving energy, power consumption is about the 1/5-1/10 of heat curing coating；Solvent-free discharge, not only safe but also free from environmental pollution；Curing rate fast (0.1-10s), production efficiency is high, is suitable for production line balance；Can application to heat sensitive base material；Coating performance is excellent, has the performances such as good rub resistance, solvent resistance and polluting proofing property。UV-curing technology has broad application prospects in coating, ink, binding agent。
Most UV cured article or UV curing system are by photoactive oligomers, simple function group or polyfunctional group dilution property monomer, and light trigger and auxiliary agent etc. form。Photoactive oligomers forms the three-dimensional net structure of polymer after hardening, and the physicochemical property of cured film is played conclusive effect。Simple function group or polyfunctional group dilution property monomer are mainly used to the viscosity of regulation system, so as to be suitable for industrial coating needs。Light trigger is used for causing UV to solidify, and consumption is less, and auxiliary agent is then add to give some special performances of coating。
Adopting the coating of UV solidification, ink, binding agent, its performance depends primarily on the character of oligomer used in formula。Most of UV curing systems are all by with based on the oligomer of acrylate-functional groups, and resinous type used is mainly the epoxy of acroleic acid esterification, polyester, polyurethane or organosilicon, and they are obtained by acrylic acid and epoxy, polyester, polyurethane or organosilicon reaction。The oligomer viscosities that relative molecular mass is higher is relatively big, and in general, oligomer molecules quality is big, and during solidification, cubical contraction is little, but the big viscosity of molecular mass is high, it is necessary to more monomer dilution, finally can affect condensate performance。
But, in current ultraviolet light polymerization product, in order to ensure uniformity, generally can use substantial amounts of low-molecular-weight reactive diluent, so, following problem can be caused: some diluent is harmful, even if the droplet that harmless diluent is formed in spraying process also pollutes the environment, stimulate the skin of people；At some porous substrates, during as used photocureable coating on timber, cement, paper, diluent readily diffuses in hole and can not solidify, and makes coated article have abnormal flavour for a long time；Diluent can be strong the character affecting cured film。
It addition, the structure of the final resin that some UV-curable water-borne cationic resin obtain in synthesis should not control at present, have impact on the performance of product, what have even can affect use；In batch production, have impact on product stability and concordance。
Summary of the invention
For above technical problem, the invention discloses a kind of UV-curable water-borne cationic resin and preparation method thereof, this molecular resin has acrylic double bond and ammonium salt cation simultaneously, ultraviolet light polymerization product can be prepared for solvent with water, and the easy control of structure of resin, it is ensured that product stability and concordance。
To this, the technical solution used in the present invention is:
A kind of UV-curable water-borne cationic resin, shown in the structure such as formula (1) of described UV-curable water-borne cationic resin:
Wherein, R1 is CH3、CH2CH3、CH2CH2OH、CH2CH2CH3Or CH2CH2CH2CH3；
R2 is CH3、CH2CH3、CH2CH2OH、CH2CH2CH3Or CH2CH2CH2CH3。
In order to reduce the use of reactive diluent in preparation ultraviolet light polymerization product, light-cured resin is made aqueous by a good way, so can make solvent with water when preparing ultraviolet light polymerization product。Many purposes making oligomer reach to be dissolved in water by additional emulsifying agent of waterborne ultraviolet curing resin early stage research, recent study then biases toward introducing hydrophilic group in oligomer, it is achieved self emulsifying。The introducing hydrophilic radical of urethane acrylate is easier to, and therefore studies relatively fully, and introducing hydrophilic group in urethane acrylate mainly has three kinds: cationic, anionic and non-ionic。Anionic mainly introduces carboxyl in strand, then neutralizes into salt with amine (such as triethylamine), so as to have bigger hydrophilic。Cationic acrylic polyurethane is typically in main chain to draw tertiary amine group, then quaternization so that it is have water solublity, has the report of the cationic acrylic polyurethane being Material synthesis with IPDI, PTMG, N methyldiethanol amine and HEMA。Non-ionic general with PEG for hydrophilic group, there is the research to poly ethyldiol modified acroleic acid polyurethane self-emulsifying systems to report。Technical scheme is then different from the studies above system, adopts this technical scheme, has acrylic double bond and ammonium salt cation in this molecular resin simultaneously, ultraviolet light polymerization product can be prepared for solvent with water, decrease the consumption of diluent, more environmentally-friendly, and do not affect condensate performance。
As a further improvement on the present invention, described UV-curable water-borne cationic resin adopts following steps to prepare:
Step S1: add epoxy resin in reaction vessel, in 70～120 DEG C of oil baths；Being subsequently adding catalyst and MEHQ, wherein, the mass percent shared by described catalyst is 0.1～1.0%, and the mass percent shared by described MEHQ is 0.1～0.8%；Adding acrylic acid, it is 2:1 that described acrylic acid addition meets epoxide group with acrylic acid mol ratio；Acid number≤the 3mgKOH/g of regulation system, obtains the acrylic acid epoxy monoesters segment that structural formula is formula (2)；
Step S2: add the acrylic acid epoxy monoesters of step S1 synthesis in reaction vessel, add the solvent of equal in quality, after stirring, it is warming up to 50-90 DEG C, drips amine, it is 1:1 that the addition of described amine meets the mol ratio of epoxide group and amido, after reaction 2-5h, cooling, add and the equimolar acid of amido, add the water of above-mentioned gross mass 1-2 times of quality of resin, stir and obtain the UV-curable water-borne cationic resin that structural formula is formula (1)。
In this technical scheme, with epoxy acrylate for a kind of novel ultraviolet light curable water-borne cationic resin of main chain preparation, this molecular resin has acrylic double bond and ammonium salt cation simultaneously, ultraviolet light polymerization product can be prepared with water for solvent, reduce the use of low-molecular-weight reactive diluent in existing ultraviolet light polymerization product。And in this resin synthesis process, first step reaction can be passed through titrimetry and strictly monitor the esterification of acrylic acid and epoxy, owing to epoxide group is excessive, it is possible to controls acrylic acid and is esterified completely；The aminating reaction of second step can also pass through titrimetry and monitor the reaction of epoxide group and amine in real time, it is ensured that the course of reaction of epoxide group and amino carries out completely。Whole resin synthesis process is relatively simple, and structure is easily controlled, and can ensure that subsequent use performance, when batch production, can well ensure that product stability and concordance。
As a further improvement on the present invention, described epoxy resin is the one in bisphenol A epoxide resin and homologue, novolac epoxy resin, bisphenol F epoxy resin, tetrabromo bisphenol-a epoxy resin, diepoxide polypropylene oxide, naphthalene system epoxy, aliphatic epoxy or alicyclic epoxy。
As a further improvement on the present invention, described catalyst is four butyl bromation amine, triethyl benzyl ammonia chloride, chromium trichloride, triphenylphosphine, N, N-dimethyl benzylamine (BDMA), N, N-diethyl benzylamine, triethylamine, triethanolamine, tri acetylacetonato network aluminum (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), four (acetylacetone,2,4-pentanedione) network zirconium, tri acetylacetonato network ferrum (III), two (acetylacetone,2,4-pentanedione) network copper (II), two (acetylacetone,2,4-pentanedione) network cobalt (II), dichloride two (acetylacetone,2,4-pentanedione) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network manganese (III), two (acetylacetone,2,4-pentanedione) network nickel (II), tri acetylacetonato network vanadium (III), two (acetylacetone,2,4-pentanedione) network vanadyl (IV), two (acetylacetone,2,4-pentanedione) network beryllium (II), one in two (acetylacetone,2,4-pentanedione) network zinc (II)。
As a further improvement on the present invention, described amine is the one in dimethylamine, diethylamine, di-n-propylamine, dibutyl amine or diethanolamine。
As a further improvement on the present invention, described acid is at least one in lactic acid, acetic acid, formic acid, ethanedioic acid, propanoic acid, butanoic acid, malonic acid, succinic acid。
As a further improvement on the present invention, described solvent is the one in acetone, butanone or alcohol ether solvents。
The preparation method that the invention also discloses a kind of UV-curable water-borne cationic resin as above, it comprises the following steps:
Step S1: the synthesis that acrylic acid is esterified with epoxy moieties；
Reaction vessel adds epoxy resin, in 70～120 DEG C of oil baths；Being subsequently adding catalyst and MEHQ, wherein, the mass percent shared by described catalyst is 0.1～1.0%, and the mass percent shared by described MEHQ is 0.1～0.8%；Adding acrylic acid, it is 2:1 that described acrylic acid addition meets epoxide group with acrylic acid mol ratio；Acid number≤the 3mgKOH/g of regulation system, obtains the acrylic acid epoxy monoesters segment that structural formula is formula (2)；
Step S2: the synthesis of UV-curable water-borne cationic resin；
Reaction vessel adds the acrylic acid epoxy monoesters of step S1 synthesis, add the solvent of equal in quality, after stirring, it is warming up to 50-90 DEG C, drips amine, it is 1:1 that the addition of described amine meets the mol ratio of epoxide group and amido, after reaction 2-5h, cooling, add and the equimolar acid of amido, add the water of above-mentioned gross mass 1-2 times of quality of resin, stir and obtain the UV-curable water-borne cationic resin that structural formula is formula (1)；
Wherein, described epoxy resin is the one in bisphenol A epoxide resin and homologue, novolac epoxy resin, bisphenol F epoxy resin, tetrabromo bisphenol-a epoxy resin, diepoxide polypropylene oxide, naphthalene system epoxy, aliphatic epoxy or alicyclic epoxy；
Described catalyst is four butyl bromation amine, triethyl benzyl ammonia chloride, chromium trichloride, triphenylphosphine, N, N-dimethyl benzylamine (BDMA), N, N-diethyl benzylamine, triethylamine, triethanolamine, tri acetylacetonato network aluminum (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), four (acetylacetone,2,4-pentanedione) network zirconium, tri acetylacetonato network ferrum (III), two (acetylacetone,2,4-pentanedione) network copper (II), two (acetylacetone,2,4-pentanedione) network cobalt (II), dichloride two (acetylacetone,2,4-pentanedione) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network manganese (III), two (acetylacetone,2,4-pentanedione) network nickel (II), tri acetylacetonato network vanadium (III), two (acetylacetone,2,4-pentanedione) network vanadyl (IV), two (acetylacetone,2,4-pentanedione) network beryllium (II), one in two (acetylacetone,2,4-pentanedione) network zinc (II)；
Described amine is the one in dimethylamine, diethylamine, di-n-propylamine, dibutyl amine or diethanolamine；
Described acid is at least one in lactic acid, acetic acid, formic acid, ethanedioic acid, propanoic acid, butanoic acid, malonic acid, succinic acid；
Described solvent is the one in acetone, butanone or alcohol ether solvents。
The invention have the benefit that
First, adopt technical scheme, this molecular resin has acrylic double bond and ammonium salt cation simultaneously, it is possible to prepare ultraviolet light polymerization product with water for solvent, decrease the consumption of diluent, more environmentally-friendly, and do not affect condensate performance。
Second, adopt technical scheme, whole resin synthesis process is relatively simple, and structure is easily controlled, and can ensure that subsequent use performance, when batch production, can well ensure that product stability and concordance。
Detailed description of the invention
Below the preferably embodiment of the present invention is described in further detail。
Embodiment 1
A kind of UV-curable water-borne cationic resin, it is characterised in that: shown in the structure such as formula (1) of described UV-curable water-borne cationic resin:
Wherein, R1 and R1 is CH2CH3。
It adopts following steps to prepare:
Step S1: add 180g bisphenol-A epoxy (epoxy E44) in 500mL there-necked flask, oil bath to 110 DEG C, stirring, additionally in the acrylic acid of metering, add catalyst triethyl benzyl ammonia chloride and MEHQ, being added dropwise in epoxy resin, wherein, epoxide group and acrylic acid mol ratio are 2:1, mass percent shared by catalyst triethyl benzyl ammonia chloride is 0.5%, and the mass percent shared by MEHQ is 0.4%；After reaction 4h, by alkalimetric titration regulation system acid number less than 3mgKOH/g, namely obtain epoxy monoacrylate。
Step S2: add the 200g step S1 epoxy monoacrylate prepared in the there-necked flask of 1000mL, it is subsequently adding 200g alcohol ether solvents, it is heated with stirring to 70 DEG C, dropping diethylamine, wherein the addition of amine meets the mol ratio of epoxide group and amido is 1:1, reacts 4h, cooling, add acetic acid equimolar with amido, add 300g water, stir and obtain UV-curable water-borne cationic resin。
Embodiment 2
A kind of UV-curable water-borne cationic resin, it is characterised in that: shown in the structure such as formula (1) of described UV-curable water-borne cationic resin, wherein, R1 and R1 is CH2CH2OH。
It adopts following steps to prepare:
Step S1: add 600g tetrabromo bisphenol-a epoxy resin in 1000mL there-necked flask, oil bath to 100 DEG C, stirring, additionally in the acrylic acid of metering, add catalyst tri acetylacetonato network lanthanum (III) and MEHQ, it is added dropwise in epoxy resin, wherein, epoxide group and acrylic acid mol ratio are 2:1, mass percent shared by described catalyst tri acetylacetonato network lanthanum (III) is 0.8%, and the mass percent shared by MEHQ is 0.3%；After reaction 3.5h, by alkalimetric titration regulation system acid number less than 3mgKOH/g, namely obtain epoxy monoacrylate。
Step S2: add the 220g step S1 epoxy monoacrylate prepared in the there-necked flask of 1000mL, add 220g acetone solvent, it is heated with stirring to 55 DEG C, dropping diethanolamine, it is 1:1 that the addition of amine meets the mol ratio of epoxide group and amido, reacts 5h, cooling, add lactic acid equimolar with amido, add 350g water, stir and obtain UV-curable water-borne cationic resin。
Embodiment 3
A kind of UV-curable water-borne cationic resin, it is characterised in that: shown in the structure such as formula (1) of described UV-curable water-borne cationic resin, wherein, R1 and R1 is CH2CH2CH3。
It adopts following steps to prepare:
Step S1: add 260g bisphenol-A epoxy (epoxy E51) in 500mL there-necked flask, oil bath to 90 DEG C, stirring, additionally in the acrylic acid of metering, add gross mass 1.0% catalyst n, N-dimethyl benzylamine (BDMA) and 0.3% MEHQ, it is added dropwise in epoxy resin, wherein, epoxide group and acrylic acid mol ratio are 2:1, catalyst n, mass percent shared by N-dimethyl benzylamine (BDMA) is 1.0%, and the mass percent shared by MEHQ is 0.3%；After reaction 6h, by alkalimetric titration regulation system acid number less than 3mgKOH/g, namely obtain epoxy monoacrylate。
Step S2: add the 150g step S1 epoxy monoacrylate prepared in the there-necked flask of 1000mL, it is subsequently adding 150g butanone solvent, it is heated with stirring to 65 DEG C, dropping di-n-propylamine, it is 1:1 that the addition of amine meets the mol ratio of epoxide group and amido, reacts 3h, cooling, add and the equimolar butanoic acid of amido, add 250g water, stir and obtain UV-curable water-borne cationic resin。
Embodiment 4
A kind of UV-curable water-borne cationic resin, it is characterised in that: shown in the structure such as formula (1) of described UV-curable water-borne cationic resin, wherein, R1 and R1 is CH2CH2CH2CH3。
It adopts following steps to prepare:
Step S1: add 220g novolac epoxy resin in 500mL there-necked flask, oil bath to 115 DEG C, stirring, the another MEHQ adding gross mass 0.8% catalyst triethanolamine and 0.8% in the acrylic acid of metering, it is added dropwise in epoxy resin, wherein, epoxide group and acrylic acid mol ratio are 2:1, mass percent shared by catalyst triethanolamine is 0.8%, mass percent shared by MEHQ is 0.8%, after reaction 3.0h, by alkalimetric titration regulation system acid number less than 3mgKOH/g, namely obtain epoxy monoacrylate。
Step S2: add the 180g step S1 epoxy monoacrylate prepared in the there-necked flask of 1000mL, it is subsequently adding 180g alcohol ether solvents, it is heated with stirring to 70 DEG C, dropping dibutyl amine, it is 1:1 that the addition of amine meets the mol ratio of epoxide group and amido, reacts 2.5h, cooling, add and the equimolar ethanedioic acid of amido, add 300g water, stir and obtain UV-curable water-borne cationic resin。
Embodiment 5
A kind of UV-curable water-borne cationic resin, it is characterised in that: shown in the structure such as formula (1) of described UV-curable water-borne cationic resin, wherein, R1 and R1 is CH2CH2OH。
It adopts following steps to prepare:
Step S1: add 320g bisphenol F epoxy resin in 1000mL there-necked flask, oil bath to 100 DEG C, stirring, the another MEHQ adding gross mass 0.9% catalyst two (acetylacetone,2,4-pentanedione) network vanadyl (IV) and 0.6% in the acrylic acid of metering, it is added dropwise in epoxy resin, wherein, epoxide group and acrylic acid mol ratio are 2:1, mass percent shared by catalyst two (acetylacetone,2,4-pentanedione) network vanadyl (IV) is 0.9%, mass percent shared by MEHQ is 0.6%, after reaction 4.5h, by alkalimetric titration regulation system acid number less than 3mgKOH/g, namely epoxy monoacrylate is obtained。
Step S2: add the 250g step S1 epoxy monoacrylate prepared in the there-necked flask of 1000mL, it is subsequently adding 250g alcohol ether solvents, it is heated with stirring to 80 DEG C, dropping diethanolamine, it is 1:1 that the addition of amine meets the mol ratio of epoxide group and amido, reacts 2.5h, cooling, it is subsequently adding lactic acid equimolar with amido, adds 320g water, stir and obtain UV-curable water-borne cationic resin。
Above content is in conjunction with concrete preferred implementation further description made for the present invention, it is impossible to assert that specific embodiment of the invention is confined to these explanations。For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, it is also possible to make some simple deduction or replace, protection scope of the present invention all should be considered as belonging to。
Claims (8)
1. a UV-curable water-borne cationic resin, it is characterised in that: shown in the structure such as formula (1) of described UV-curable water-borne cationic resin:
Wherein, R1 is CH3、CH2CH3、CH2CH2OH、CH2CH2CH3Or CH2CH2CH2CH3；
R2 is CH3、CH2CH3、CH2CH2OH、CH2CH2CH3Or CH2CH2CH2CH3。
2. UV-curable water-borne cationic resin according to claim 1, it is characterised in that: described UV-curable water-borne cationic resin adopts following steps to prepare:
Step S1: add epoxy resin in reaction vessel, in 70～120 DEG C of oil baths；Being subsequently adding catalyst and MEHQ, wherein, the mass percent shared by described catalyst is 0.1～1.0%, and the mass percent shared by described MEHQ is 0.1～0.8%；Adding acrylic acid, it is 2:1 that described acrylic acid addition meets epoxide group with acrylic acid mol ratio；Acid number≤the 3mgKOH/g of regulation system, obtains the acrylic acid epoxy monoesters segment that structural formula is formula (2)；
Step S2: add the acrylic acid epoxy monoesters of step S1 synthesis in reaction vessel, add the solvent of equal in quality, after stirring, it is warming up to 50-90 DEG C, drips amine, it is 1:1 that the addition of described amine meets the mol ratio of epoxide group and amido, after reaction 2-5h, cooling, add and the equimolar acid of amido, add the water of above-mentioned gross mass 1-2 times of quality of resin, stir and obtain the UV-curable water-borne cationic resin that structural formula is formula (1)。
3. UV-curable water-borne cationic resin according to claim 2, it is characterised in that: described epoxy resin is the one in bisphenol A epoxide resin and homologue, novolac epoxy resin, bisphenol F epoxy resin, tetrabromo bisphenol-a epoxy resin, diepoxide polypropylene oxide, naphthalene system epoxy, aliphatic epoxy or alicyclic epoxy。
4. UV-curable water-borne cationic resin according to claim 2, it is characterised in that: described catalyst is four butyl bromation amine, triethyl benzyl ammonia chloride, chromium trichloride, triphenylphosphine, N, N-dimethyl benzylamine, N, N-diethyl benzylamine, triethylamine, triethanolamine, tri acetylacetonato network aluminum (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), four (acetylacetone,2,4-pentanedione) network zirconium, tri acetylacetonato network ferrum (III), two (acetylacetone,2,4-pentanedione) network copper (II), two (acetylacetone,2,4-pentanedione) network cobalt (II), dichloride two (acetylacetone,2,4-pentanedione) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network manganese (III), two (acetylacetone,2,4-pentanedione) network nickel (II), tri acetylacetonato network vanadium (III), two (acetylacetone,2,4-pentanedione) network vanadyl (IV), two (acetylacetone,2,4-pentanedione) network beryllium (II), one in two (acetylacetone,2,4-pentanedione) network zinc (II)。
5. UV-curable water-borne cationic resin according to claim 2, it is characterised in that: described amine is the one in dimethylamine, diethylamine, di-n-propylamine, dibutyl amine or diethanolamine。
6. UV-curable water-borne cationic resin according to claim 2, it is characterised in that: described acid is at least one in lactic acid, acetic acid, formic acid, ethanedioic acid, propanoic acid, butanoic acid, malonic acid, succinic acid。
7. UV-curable water-borne cationic resin according to claim 2, it is characterised in that: described solvent is the one in acetone, butanone or alcohol ether solvents。
8. the preparation method of a UV-curable water-borne cationic resin as claimed in claim 1, it is characterised in that comprise the following steps:
Step S1: add epoxy resin in reaction vessel, in 70～120 DEG C of oil baths；Being subsequently adding catalyst and MEHQ, wherein, the mass percent shared by described catalyst is 0.1～1.0%, and the mass percent shared by described MEHQ is 0.1～0.8%；Adding acrylic acid, it is 2:1 that described acrylic acid addition meets epoxide group with acrylic acid mol ratio；Acid number≤the 3mgKOH/g of regulation system, obtains the acrylic acid epoxy monoesters segment that structural formula is formula (2)；
Step S2: add the acrylic acid epoxy monoesters of step S1 synthesis in reaction vessel, add the solvent of equal in quality, after stirring, it is warming up to 50-90 DEG C, drips amine, it is 1:1 that the addition of described amine meets the mol ratio of epoxide group and amido, after reaction 2-5h, cooling, add and the equimolar acid of amido, add the water of above-mentioned gross mass 1-2 times of quality of resin, stir and obtain the UV-curable water-borne cationic resin that structural formula is formula (1)；
Wherein, described epoxy resin is the one in bisphenol A epoxide resin and homologue, novolac epoxy resin, bisphenol F epoxy resin, tetrabromo bisphenol-a epoxy resin, diepoxide polypropylene oxide, naphthalene system epoxy, aliphatic epoxy or alicyclic epoxy；
Described catalyst is four butyl bromation amine, triethyl benzyl ammonia chloride, chromium trichloride, triphenylphosphine, N, N-dimethyl benzylamine (BDMA), N, N-diethyl benzylamine, triethylamine, triethanolamine, tri acetylacetonato network aluminum (III), tri acetylacetonato network lanthanum (III), tri acetylacetonato network chromium (III), four (acetylacetone,2,4-pentanedione) network zirconium, tri acetylacetonato network ferrum (III), two (acetylacetone,2,4-pentanedione) network copper (II), two (acetylacetone,2,4-pentanedione) network cobalt (II), dichloride two (acetylacetone,2,4-pentanedione) network titanium (IV), tri acetylacetonato network cobalt (III), tri acetylacetonato network manganese (III), two (acetylacetone,2,4-pentanedione) network nickel (II), tri acetylacetonato network vanadium (III), two (acetylacetone,2,4-pentanedione) network vanadyl (IV), two (acetylacetone,2,4-pentanedione) network beryllium (II), one in two (acetylacetone,2,4-pentanedione) network zinc (II)；
Described amine is the one in dimethylamine, diethylamine, di-n-propylamine, dibutyl amine or diethanolamine；
Described acid is at least one in lactic acid, acetic acid, formic acid, ethanedioic acid, propanoic acid, butanoic acid, malonic acid, succinic acid；
Described solvent is the one in acetone, butanone or alcohol ether solvents。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853982A (en) * | 2022-04-29 | 2022-08-05 | 广东柯力森树脂有限公司 | Water-based UV-cured epoxy acrylate resin and preparation method and application thereof |
| CN114853982B (en) * | 2022-04-29 | 2024-02-27 | 广东柯力森树脂有限公司 | Water-based UV (ultraviolet) curing epoxy acrylate resin as well as preparation method and application thereof |
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