CN101974143B - Organic silicon modified epoxy acrylate aqueous dispersion and preparation method thereof - Google Patents
Organic silicon modified epoxy acrylate aqueous dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic silicon modified epoxy acrylate aqueous dispersion and a preparation method thereof. The method comprises the following steps of: mixing a polyether epoxy diluent and epoxy resin, and reacting the mixture with a crylic acid monomer to obtain low-viscosity epoxy acrylate prepolymer; performing grafting modification on the low-viscosity epoxy acrylate prepolymer by using maleic anhydride and introducing a hydrophilic group on a molecular chain; mixing micro-molecular amino silicone oil and organic alkali to obtain a neutralizer; and neutralizing the system, adding water for dilution and dispersion, and regulating solid content and viscosity to obtain the UV-curable organic silicon modified epoxy acrylate aqueous dispersion. The organic silicon modified epoxy acrylate aqueous dispersion has high solid content of over 60 percent and low viscosity of between 1,500 and 5,500 mPa.s. A UV cured film has high hardness of between 4H and 6H, high flexibility and water resistance and low water absorption of below 5.0 percent, and can be applied to the fields of furniture, buildings, household appliances, papermaking and printing, and the like.
Description
Technical field
The present invention relates to a kind of organic-silicon-modified propylene oxide acid esters water dispersion, particularly relate to a kind ofly highly contain admittedly, low viscous ultraviolet curing organic silicon modified epoxy acrylic ester aqueous dispersion and preparation method thereof.
Background technology
UV-light (UV) curing technology is because it is efficient, environmental protection and save energy and be widely used in a plurality of fields such as paint, coating, printing ink and tackiness agent.Along with people's limits and reduces the formulation and the enforcement of volatile organic matter (VOC) Abgasgesetz to the concern of environment, and ultraviolet-curing paint replaces traditional solvent based coating just gradually.The general prescription of ultraviolet-curing paint comprises light trigger, reactive monomer and photosensitive prepolymer, i.e. epoxy acrylate, urethane acrylate, propenoate (polyethers or polyester) and unsaturated polyester.Wherein the epoxy acrylic resin raw material sources are extensive; Low price; And contain stable C-C key, phenyl ring and ehter bond in the main chain, have good chemical proofing, tensile modulus, mechanical property etc., therefore become the main matrix resin of preparation UV-curable waterborne coatings.But often there are shortcomings such as viscosity is excessive, film forming is hard and crisp, snappiness is not good enough in conventional epoxy acrylic ester prepolymer, need add a certain amount of reactive monomer when therefore using, and the volatility of reactive monomer makes it become the potential environomental pollution source.Therefore, in the process of preparation ultraviolet-curing paint, begin to attempt replacing reactive monomer, aquosity ultraviolet light (UV) curing technology from then on occurred with environmentally friendly solvent " water ".This technology has combined the advantage of traditional U V curing technology and water-borne coatings technology, becomes a main direction of ultraviolet-curing paint development.But; Along with the adding of the hydrophilic modifying and the environmentally friendly solvent of photosensitive resin, some negative impact appears in the performance of filming, as adds too much environmentally friendly solvent and will influence drying and curing speed; The existence of hydrophilic radical causes problems such as water tolerance is relatively poor, has limited its application in a lot of industries.Along with the increase day by day of resource and environment pressure, need constantly to improve the performance of environment-friendly type aqueous light-cured epoxy acrylate resin, to expand its Application Areas.
Summary of the invention
It is big that the object of the invention is to overcome the viscosity that prior art exists; Fragility is high; The shortcoming of poor in flexibility and poor water resistance provides a kind of and highly contains admittedly, LV, ultraviolet cured epoxy acrylic water dispersion that mechanical property and water resistance are good and preparation method thereof.
The object of the invention is realized through following technical scheme:
A kind of preparation method of organic-silicon-modified propylene oxide acid esters water dispersion comprises the steps:
(1) preparation of low viscosity epoxy acrylic ester prepolymer: in container, add epoxy resin, polyether-type epoxide diluent and stopper; Stirring is warming up to 70～75 ℃, dropwise addition of acrylic acid and catalyzer, and 0.5～1h dropwises; Be warming up to 80 ℃～90 ℃ subsequently, reaction 3～5h measures the system acid number and is lower than the 5mgKOH/g stopped reaction, obtains the epoxy acrylic ester prepolymer through the modification of polyether-type epoxide diluent viscosity reduction;
Described epoxy resin is bisphenol A type epoxy resin E-51, E-54 or E-44; The polyethyleneglycol diglycidylether that described polyether-type epoxide diluent is a number-average molecular weight 550～650, the polypropylene glycol diglycidyl ether of number-average molecular weight 550～750 and in the trihydroxymethylpropanyltri diglycidyl ether one or both; The epoxy group(ing) in epoxy resin and the polyether-type epoxide diluent and the mol ratio of acrylic acid carboxyl are 1: 1; The epoxy group(ing) mol ratio of epoxy resin and polyether-type epoxide diluent is 2: 1～1: 2; The stopper consumption is 0.2%～0.4% of epoxy resin, polyether-type epoxide diluent and a vinylformic acid total mass; Catalyst levels is 0.5%～0.8% of epoxy resin, epoxide diluent and a vinylformic acid total mass;
(2) preparation of MALEIC ANHYDRIDE grafting epoxy acrylic ester prepolymer: step (1) reaction system is cooled to 50～60 ℃, adds MALEIC ANHYDRIDE, catalyzer and stopper, stir; Adopt sectional heating method, 50～60 ℃ of reaction 0.5～1h are warming up to 70～80 ℃ of reaction 0.5～1h subsequently, and reaction stops when reaching theoretical acid number, obtains the cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer that side chain has carboxyl; The mole dosage of said MALEIC ANHYDRIDE be in the epoxy acrylic ester prepolymer of step (1) gained the pendant hydroxyl group molar content 40%～60%;
Said catalyzer and stopper consumption are respectively 0.5%～0.8% and 0.2%～0.4% of the middle epoxy acrylic ester prepolymer total mass of step (1);
(3) preparation of organic-silicon-modified propylene oxide acid esters water dispersion: the reaction system of step (2) is cooled to 40～50 ℃, adds stopper, continue to stir; With organic bases and the composite neutralizing agent of processing of small molecules amido silicon oil, the cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer that the side chain that step (2) is made has carboxyl neutralizes, and degree of neutralization is 60%～100%; Add deionized water, dilution under agitation and emulsification dispersion obtain solid content at 60%～90% organic-silicon-modified propylene oxide acid esters water dispersion;
Said organic bases is dimethylaminoethanol or triethylamine; The number-average molecular weight of said amido silicon oil is 100～400; The organic bases consumption is 60%～100% of a MALEIC ANHYDRIDE mole dosage; Amido silicon oil and stopper consumption are respectively 1.0%～2.0% and 0.1～0.4% of the middle cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass of step (2);
The stopper of said step (1)～(3) is p methoxy phenol, Resorcinol or DBPC 2,6 ditertiary butyl p cresol; The catalyzer of said step (1) and step (2) is tetraethylammonium bromide or N, the N-dimethyl benzylamine.
For realizing that further the object of the invention, said theoretical acid value defined are the system acid number when keeping a carboxyl behind the MALEIC ANHYDRIDE molecule esterification by ring opening.
The consumption of said deionized water is preferably and makes the solid content of organic-silicon-modified propylene oxide acid esters water dispersion control to 60%～80%.
The epoxy group(ing) mol ratio of said epoxy resin and epoxide diluent is preferably 1: 1.
A kind of organic-silicon-modified propylene oxide acid esters water dispersion is by method for preparing.
Said organic-silicon-modified propylene oxide acid esters water dispersion solid content is higher than 60%, and viscosity is 1,500～5,500mPa.s.
The solid content of said water dispersion may be defined as the quality percentage composition of non-water section in the water dispersion.
Preparing method of the present invention is with polyether-type epoxide diluent and the composite viscosity reduction of epoxy resin; Carry out the epoxy addition esterification with Acrylic Acid Monomer again; Thereby in the prepolymer molecule, introduce the low modulus polyether segment, improve molecular activity, thereby reach viscosity reduction and toughening modifying purpose; Acrylic acid esterification can be introduced two keys in molecular chain, give prepolymer with photosensitivity; Utilize the pendant hydroxyl group that generates after MALEIC ANHYDRIDE and the epoxy resin open loop to carry out the half ester reaction again, the wetting ability carboxyl is introduced molecular chain, increased the double bond content in the prepolymer simultaneously; With small molecules amido silicon oil and the composite neutralizing agent that makes of organic bases, the carboxyl in the prepolymer is neutralized then, obtain low viscous ultraviolet curing organic silicon modified epoxy acrylic ester prepolymer; After the neutralization reaction, drip deionized water and further regulate solid content and viscosity, and stir, obtain that transparent or semitransparent height contains admittedly, low-viscosity UV-cured organic-silicon-modified propylene oxide acid esters water dispersion.
The present invention adopts the polyether-type epoxide diluent that bisphenol-a epoxy acrylate prepolymer and water dispersion thereof are carried out viscosity reduction and toughening modifying, can obtain higher solid content and lower working viscosity simultaneously, and has improved the snappiness of cured film.
The dilution of deionized water is relevant with the consumption of carboxyl-content, degree of neutralization and the deionized water of cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer with the emulsification degree of scatter; The carboxyl-content of prepolymer is high more; Degree of neutralization is big more; Good more with the intermiscibility of deionized water, water dispersion is just transparent more than low-solid content the time.
The viscosity of water dispersion is relevant with solid content with the preliminary drying time, and solid content is more little, and viscosity is more little, and the preliminary drying time is just long more.
The organic-silicon-modified propylene oxide acid esters of gained of the present invention water dispersion has the uV curable characteristic, and cured product has excellent mechanical property and water tolerance.
Compared with prior art, the present invention has following advantage:
(1) the present invention is directed to that conventional epoxy acrylic ester prepolymer viscosity is big, film forming is hard and crisp and shortcoming such as poor in flexibility, adopt the polyether-type epoxide diluent that it is carried out viscosity reduction and toughening modifying.After adding the polyether-type epoxide diluent of suitable proportion, the initial viscosity of epoxy resin compound system, the viscosity of epoxy acrylic ester prepolymer and cis-butenedioic anhydride grafting and the prepolymer system viscosity after neutralization all decline to a great extent, and viscosity break ratio can be up to 90%～99%.Snappiness through polyether-modified UV cured film can be brought up to 1～2mm more than bending diameter 10mm.
(2) the present invention is directed to defectives such as photosensitive resin water tolerance after the viscosity reduction modification is relatively poor, mechanical property is not good; Adopt small molecules amido silicon oil and the composite neutralizing agent of processing of organic bases; During carboxy-modified photosensitive prepolymer carried out and modification; Thereby in resin structure, introduce the organosilicon segment, obviously improved the water tolerance of resin cured film, water-intake rate can be reduced to below 5.0%.
(3) preparation method of the present invention has advantages such as technology is simple and convenient, pollution-free, environmental friendliness, film quality is high, application prospect is extensive; Be new generation of green environment-friendly and high-performance Chemicals, can be applicable to field and environmentally friendly coating, printing ink and tackiness agent industries such as green furniture, construction and decoration, household electrical appliance, papermaking printing.
The practical implementation method
Below in conjunction with embodiment the present invention is further described, but embodiment does not constitute the restriction that the present invention is required protection domain.
Embodiment 1
(1) is 550～750 polypropylene glycol diglycidyl ether and the hydroquinone of polymerization retarder of 0.32g with 46.26g epoxy resin E-51,77.86g number-average molecular weight, adds and have in the four-hole reaction flask of stirring rake, TM, constant pressure funnel and prolong; 35.26g vinylformic acid is packed in the constant pressure funnel.Wherein, the epoxide group mol ratio in epoxy resin E-51 and the polypropylene glycol diglycidyl ether is 1: 1, and the epoxy group(ing) mol ratio of acrylic acid carboxyl and epoxy resin compound system is 1: 1.When the system of treating is warming up to 75 ℃, add the catalyzer tetraethylammonium bromide of 1.28g, and the beginning dropwise addition of acrylic acid, 0.5h dropwises.Continue to be warming up to 85 ℃, finish when reacting to system acid number＜5mgKOH/g, cooling obtains the epoxy acrylic ester prepolymer of viscosity reduction modification.The stopper consumption is 0.2% of epoxy resin E-51, polypropylene glycol diglycidyl ether and a vinylformic acid total mass; Catalyst levels is 0.8% of epoxy resin E-51, polypropylene glycol diglycidyl ether and a vinylformic acid total mass.
(2) treat that system is cooled to 60 ℃; Add 23.67g cis-butenedioic anhydride (MALEIC ANHYDRIDE), 1.46g catalyzer tetraethylammonium bromide and 0.36g hydroquinone of polymerization retarder, stirring reaction 0.5h is warming up to 75 ℃ then; When reaching theoretical acid number 75.80mgKOH/g, reaction lowers the temperature termination reaction.Wherein, The mole dosage of cis-butenedioic anhydride be epoxy acrylic ester prepolymer the pendant hydroxyl group molar content 50%; Catalyst levels is 0.8% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass; The stopper consumption is 0.2% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass, and theoretical acid number is the system acid number after cis-butenedioic anhydride and the epoxy acrylic ester prepolymer generation half esterization.
(3) treat that system is cooled to 50 ℃, add 0.36g hydroquinone of polymerization retarder and 15.00g organic bases neutralizing agent dimethylaminoethanol, carry out neutralization reaction.Stir and to add the 21.22g deionized water behind the 30min and regulate solid content and system viscosity, obtain that height contains admittedly, low viscous ultraviolet cured epoxy acrylic water dispersion, outward appearance is the tawny hyalomucoid.Wherein, the degree of neutralization of system is 70%, and solid content is 90%, and the stopper consumption is 0.2% of a cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass.
(4) in the epoxy acrylic ester aqueous dispersion of step (3) gained, add the reactive thinner tripropylene glycol diacrylate; Light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone (light trigger 1173); Film after stirring; And in 60 ℃ of baking ovens preliminary drying 20min, use the ultra violet lamp 5s of 2KW then, obtain the epoxy acrylate cured film.Wherein, the light trigger consumption is 4% of epoxy acrylic ester aqueous dispersion and a reactive thinner total mass, and the mass ratio of reactive thinner and cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer is 2: 8.
Through detecting, the composite back of epoxide diluent polypropylene glycol diglycidyl ether and epoxy resin E-51 system is from initial viscosity 6, and 220mPas reduces to 114mPas, and viscosity break ratio is 98.17%; The system viscosity of the epoxy acrylic ester prepolymer of process viscosity reduction modification is from 35, and 080mPas reduces to 1,340mPas, and viscosity break ratio is 96.16%; System viscosity after maleic anhydride modified is 10 again, 840mPas, and without the corresponding prepolymer system viscosity of viscosity reduction modification up to 100, more than the 000mPas.During thin up to 90% solid content, the viscosity drop to 6 of water dispersion, 410mPa.s shows that the adding of epoxide diluent greatly reduces system viscosity.The pencil hardness that UV films after solidifying is 4H, and sticking power is 2 grades, and impact property is 30Kgcm, and bending property is 2mm, shows that cured film has higher hardness and good snappiness.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 11.30%.
Embodiment 2
(1) is 550～750 polypropylene glycol diglycidyl ether and the stopper p methoxy phenol of 0.48g with 46.26g epoxy resin E-51,77.86g number-average molecular weight, adds and have in the four-hole reaction flask of stirring rake, TM, constant pressure funnel and prolong; 35.26g vinylformic acid is packed in the constant pressure funnel.Wherein, the epoxide group mol ratio in epoxy resin E-51 and the polypropylene glycol diglycidyl ether is 1: 1, and the epoxy group(ing) mol ratio of acrylic acid carboxyl and epoxy resin compound system is 1: 1.When the system of treating is warming up to 75 ℃, add the catalyst n of 0.80g, N-dimethyl benzylamine, and beginning dropwise addition of acrylic acid, 0.5h dropwises.Continue to be warming up to 85 ℃, finish when reacting to system acid number＜5mgKOH/g, cooling obtains the epoxy acrylic ester prepolymer of viscosity reduction modification.The stopper consumption is 0.3% of epoxy resin E-51, polypropylene glycol diglycidyl ether and a vinylformic acid total mass; Catalyst levels is 0.5% of epoxy resin E-51, polypropylene glycol diglycidyl ether and a vinylformic acid total mass.
(2) treat that system is cooled to 60 ℃, add 23.67g cis-butenedioic anhydride, 0.91g catalyst n, N-dimethyl benzylamine and 0.54g stopper p methoxy phenol, stirring reaction 0.5h is warming up to 75 ℃ then, reacts when reaching theoretical acid number 75.80mgKOH/g and lowers the temperature termination reaction.Wherein, The mole dosage of cis-butenedioic anhydride be epoxy acrylic ester prepolymer the pendant hydroxyl group molar content 50%; Catalyst levels is 0.5% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass; The stopper consumption is 0.3% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass, and theoretical acid number is the system acid number after cis-butenedioic anhydride and the epoxy acrylic ester prepolymer generation half esterization.
(3) treat that system is cooled to 50 ℃, add 0.36g stopper p methoxy phenol and 15.00g organic bases neutralizing agent dimethylaminoethanol, carry out neutralization reaction.Stir and to add the 21.22g deionized water behind the 30min and regulate solid content and system viscosity, obtain that height contains admittedly, low viscous ultraviolet cured epoxy acrylic water dispersion, outward appearance is light yellow hyalomucoid.Wherein, the degree of neutralization of system is 70%, and solid content is 90%, and the stopper consumption is 0.2% of a cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass.
(4) in the epoxy acrylic ester aqueous dispersion of step (3) gained, add reactive thinner tripropylene glycol diacrylate and Viscoat 295; Light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone (light trigger 1173); Film after stirring; And in 60 ℃ of baking ovens preliminary drying 30min, use the ultra violet lamp 5s of 2KW then, obtain the epoxy acrylate cured film.Wherein, The light trigger consumption is 4% of epoxy acrylic ester aqueous dispersion and a reactive thinner total mass, and the mass ratio of reactive thinner tripropylene glycol diacrylate and Viscoat 295 and cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer is 1: 1: 8.
Compare with embodiment 1, the curing speed of photosensitive prepolymer is accelerated in this example, and degree of crosslinking increases; The pencil hardness that UV films after solidifying is 5H, and sticking power is 2 grades, and impact property is 35Kgcm; Bending property is 3mm, shows that cured film has higher hardness and good snappiness.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 9.15%.
Embodiment 3
(1) is 550～650 polyethyleneglycol diglycidylether and the stopper p methoxy phenol of 0.31g with 46.26g epoxy resin E-51,72.47g number-average molecular weight, adds and have in the four-hole reaction flask of stirring rake, TM, constant pressure funnel and prolong; 35.26g vinylformic acid is packed in the constant pressure funnel.Wherein, the epoxide group mol ratio in epoxy resin E-51 and the polypropylene glycol diglycidyl ether is 1: 1, and the epoxy group(ing) mol ratio of acrylic acid carboxyl and epoxy resin compound system is 1: 1.When the system of treating is warming up to 75 ℃, add the catalyst n of 1.23g, N-dimethyl benzylamine, and beginning dropwise addition of acrylic acid, 0.5h dropwises.Continue to be warming up to 85 ℃, finish when reacting to system acid number＜5mgKOH/g, cooling obtains the epoxy acrylic ester prepolymer of viscosity reduction modification.The stopper consumption is 0.2% of epoxy resin E-51, polyethyleneglycol diglycidylether and a vinylformic acid total mass; Catalyst levels is 0.8% of epoxy resin E-51, polyethyleneglycol diglycidylether and a vinylformic acid total mass.
(2) treat that system is cooled to 60 ℃, add 23.67g cis-butenedioic anhydride, 1.42g catalyst n, N-dimethyl benzylamine and 0.36g stopper p methoxy phenol, stirring reaction 0.5h is warming up to 75 ℃ then, reacts when reaching theoretical acid number 77.25mgKOH/g and lowers the temperature termination reaction.Wherein, The mole dosage of cis-butenedioic anhydride be epoxy acrylic ester prepolymer the pendant hydroxyl group molar content 50%; Catalyst levels is 0.8% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass; The stopper consumption is 0.2% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass, and theoretical acid number is the system acid number after cis-butenedioic anhydride and the epoxy acrylic ester prepolymer generation half esterization.
(3) treat that system is cooled to 50 ℃, add 0.36g stopper p methoxy phenol and 15.00g organic bases neutralizing agent dimethylaminoethanol, carry out neutralization reaction.Stir and to add the 42.08g deionized water behind the 30min and regulate solid content and system viscosity, obtain that height contains admittedly, low viscous ultraviolet cured epoxy acrylic water dispersion, outward appearance is light yellow hyalomucoid.Wherein, the degree of neutralization of system is 70%, and solid content is 80%, and the stopper consumption is 0.2% of a cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass.
(4) in the epoxy acrylic ester aqueous dispersion of step (3) gained, add reactive thinner tripropylene glycol diacrylate and Viscoat 295; Light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone (light trigger 1173); Film after stirring; And in 60 ℃ of baking ovens preliminary drying 30min, use the ultra violet lamp 5s of 2KW then, obtain the epoxy acrylate cured film.Wherein, The light trigger consumption is 4% of epoxy acrylic ester aqueous dispersion and a reactive thinner total mass, and the mass ratio of reactive thinner tripropylene glycol diacrylate and Viscoat 295 and cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer is 1: 1: 8.
Through detecting, the composite back of epoxide diluent polyethyleneglycol diglycidylether and epoxy resin E-51 system is from initial viscosity 6, and 220mPas reduces to 65mPas, and viscosity break ratio is 98.88%; The system viscosity of the epoxy acrylic ester prepolymer of process viscosity reduction modification is from 35, and 080mPas reduces to 780mPas, and viscosity break ratio is 97.76%; System viscosity after maleic anhydride modified is 7 again, 150mPas, and without the corresponding prepolymer system viscosity of viscosity reduction modification up to 100, more than the 000mPas.During thin up to 80% solid content, the viscosity drop to 2 of water dispersion, 650mPa.s shows that the adding of epoxide diluent and portion water greatly reduces system viscosity.The pencil hardness that UV films after solidifying is 4H, and sticking power is 1 grade, and impact property is 42Kgcm, and bending property is 2mm, shows that cured film has higher hardness and good flexible.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 12.70%.
Embodiment 4
(1) is the stopper p methoxy phenol of 550～750 polypropylene glycol diglycidyl ether, 24.82g trihydroxymethylpropanyltri diglycidyl ether and 0.44g with 46.26g epoxy resin E-51,38.95g number-average molecular weight, adds and have in the four-hole reaction flask of stirring rake, TM, constant pressure funnel and prolong; 35.26g vinylformic acid is packed in the constant pressure funnel.Wherein, the epoxide group mol ratio in epoxy resin E-51 and polypropylene glycol diglycidyl ether and the trihydroxymethylpropanyltri diglycidyl ether is 1: 0.5: 0.5, and the epoxy group(ing) mol ratio of acrylic acid carboxyl and epoxy resin compound system is 1: 1.When the system of treating is warming up to 75 ℃, add the catalyst n of 0.73g, N-dimethyl benzylamine, and beginning dropwise addition of acrylic acid, 0.5h dropwises.Continue to be warming up to 85 ℃, finish when reacting to system acid number＜5mgKOH/g, cooling obtains the epoxy acrylic ester prepolymer of viscosity reduction modification.The stopper consumption is 0.3% of epoxy resin E-51, polypropylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether and a vinylformic acid total mass; Catalyst levels is 0.5% of epoxy resin E-51, polypropylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether and a vinylformic acid total mass.
(2) treat that system is cooled to 60 ℃, add 28.40g cis-butenedioic anhydride, 0.87g catalyst n, N-dimethyl benzylamine and 0.52g stopper p methoxy phenol, stirring reaction 0.5h is warming up to 75 ℃ then, reacts when reaching theoretical acid number 94.50mgKOH/g and lowers the temperature termination reaction.Wherein, The mole dosage of cis-butenedioic anhydride be epoxy acrylic ester prepolymer the pendant hydroxyl group molar content 60%; Catalyst levels is 0.5% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass; The stopper consumption is 0.3% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass, and theoretical acid number is the system acid number after cis-butenedioic anhydride and the epoxy acrylic ester prepolymer generation half esterization.
(3) treat that system is cooled to 50 ℃, add 0.35g stopper p methoxy phenol and 15.50g organic bases neutralizing agent dimethylaminoethanol, carry out neutralization reaction.Stir and to add the 126.13g deionized water behind the 30min and regulate solid content and system viscosity, obtain that height contains admittedly, low viscous ultraviolet cured epoxy acrylic water dispersion, outward appearance is light yellow translucent colloid.Wherein, the degree of neutralization of system is 60%, and solid content is 60%, and the stopper consumption is 0.2% of a cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass.
(4) in the epoxy acrylic ester aqueous dispersion of step (3) gained, add reactive thinner tripropylene glycol diacrylate and Viscoat 295; Light trigger 1-hydroxyl-cyclohexyl-phenyl ketone (light trigger 184); Film after stirring; And in 60 ℃ of baking ovens preliminary drying 40min, use the ultra violet lamp 5s of 2KW then, obtain the epoxy acrylate cured film.Wherein, The light trigger consumption is 4% of epoxy acrylic ester aqueous dispersion and a reactive thinner total mass, and the mass ratio of reactive thinner tripropylene glycol diacrylate and Viscoat 295 and cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer is 1: 1: 8.
Through detecting, the composite back of epoxide diluent polypropylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether and epoxy resin E-51 system is from initial viscosity 6, and 220mPas reduces to 350mPas, and viscosity break ratio is 94.37%; The system viscosity of the epoxy acrylic ester prepolymer of process viscosity reduction modification is from 35, and 080mPas reduces to 3,120mPas, and viscosity break ratio is 91.11%; System viscosity after maleic anhydride modified is 32 again, 610mPas, and without the corresponding prepolymer system viscosity of viscosity reduction modification up to 100, more than the 000mPas.During thin up to 60% solid content, the viscosity drop to 2 of water dispersion, 950mPa.s.It is thus clear that, though add the viscosity that the epoxide diluent trihydroxymethylpropanyltri diglycidyl ether of three-functionality-degree can improve prepolymer system, be diluted to more low-solid content after, still can be to 3000mPa.s with viscosity drop.The pencil hardness of filming after UV solidifies is 6H, and sticking power is 2 grades, and impact property is 33Kgcm, and bending property is 4mm, shows that cured film has very high hardness and snappiness preferably.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 8.90%.
Embodiment 5
(1) be 550～750 polypropylene glycol diglycidyl ether and the stopper 2 of 0.48g with 46.26g epoxy resin E-51,77.86g number-average molecular weight; The 6-ditertbutylparacresol, adding has in the four-hole reaction flask of stirring rake, TM, constant pressure funnel and prolong; 35.26g vinylformic acid is packed in the constant pressure funnel.Wherein, the epoxide group mol ratio in epoxy resin E-51 and the polypropylene glycol diglycidyl ether is 1: 1, and the epoxy group(ing) mol ratio of acrylic acid carboxyl and epoxy resin compound system is 1: 1.When the system of treating is warming up to 75 ℃, add the catalyst n of 0.80g, N-dimethyl benzylamine, and beginning dropwise addition of acrylic acid, 0.5h dropwises.Continue to be warming up to 85 ℃, finish when reacting to system acid number＜5mgKOH/g, cooling obtains the epoxy acrylic ester prepolymer of viscosity reduction modification.The stopper consumption is 0.3% of epoxy resin E-51, polypropylene glycol diglycidyl ether and a vinylformic acid total mass; Catalyst levels is 0.5% of epoxy resin E-51, polypropylene glycol diglycidyl ether and a vinylformic acid total mass.
(2) treat that system is cooled to 60 ℃, add 18.94g cis-butenedioic anhydride, 0.89g catalyst n, N-dimethyl benzylamine and 0.53g stopper 2; The 6-ditertbutylparacresol, stirring reaction 0.5h is warming up to 75 ℃ then; When reaching theoretical acid number 75.80mgKOH/g, reaction lowers the temperature termination reaction.Wherein, The mole dosage of cis-butenedioic anhydride be epoxy acrylic ester prepolymer the pendant hydroxyl group molar content 40%; Catalyst levels is 0.5% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass; The stopper consumption is 0.3% of epoxy acrylic ester prepolymer and a cis-butenedioic anhydride total mass, and theoretical acid number is the system acid number after cis-butenedioic anhydride and the epoxy acrylic ester prepolymer generation half esterization.
(3) treat that system is cooled to 50 ℃; Add 0.36g stopper 2; The 6-ditertbutylparacresol is that 100 amido silicon oil mixes and processes neutralizing agent with 15.65g organic bases triethylamine and 3.56g number-average molecular weight, adds in the cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer and carries out neutralization reaction.Add the 49.38g deionized water after stirring 30min, regulate solid content and system viscosity, obtain that height contains admittedly, low viscous ultraviolet cured epoxy acrylic water dispersion, outward appearance is light yellow translucent colloid.Wherein solid content is 80%, and the organic bases degree of neutralization of system is 80%, and amido silicon oil accounts for 2.0% of cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass, and the stopper consumption is 0.2% of a cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass.
(4) in the organic-silicon-modified propylene oxide acid esters prepolymer of step (3) gained, add reactive thinner tripropylene glycol diacrylate and Viscoat 295; Light trigger 1-hydroxyl-cyclohexyl-phenyl ketone (light trigger 184); Film after stirring; And in 60 ℃ of baking ovens preliminary drying 30min, use the ultra violet lamp 5s of 2KW then, obtain the epoxy acrylate cured film.Wherein, The light trigger consumption is 4% of organic-silicon-modified propylene oxide acid esters prepolymer and a reactive thinner total mass, and the mass ratio of reactive thinner tripropylene glycol diacrylate and Viscoat 295 and cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer is 1: 1: 8.
Compare with 2 with embodiment 1, system viscosity is from 10 after organic-silicon-modified for the epoxy acrylic ester prepolymer in this example, and 840mPas is increased to 18,540mPas.During thin up to 80% solid content, the viscosity of water dispersion reduces to 5 again, and 270mPa.s shows that the adding of epoxide diluent greatly reduces system viscosity.The pencil hardness that UV films after solidifying is 5H, and sticking power is 2 grades, and impact property is 38Kgcm, and bending property is 3mm, shows that cured film has higher hardness and good snappiness.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 3.05%, demonstrates excellent in water resistance.
Embodiment 6
Basic identical with embodiment 5 reaction process.Wherein, 15.65g organic bases triethylamine in the step (3) and 3.56g number-average molecular weight are that to use 17.60g organic bases triethylamine and 1.78g number-average molecular weight instead be 100 amido silicon oil for 100 amido silicon oil; The corresponding proportioning of other raw materials remains unchanged, and consumption is done corresponding adjustment.
Compare with embodiment 5, system viscosity is from 10 after organic-silicon-modified for the epoxy acrylic ester prepolymer in this example, and 840mPas increases to 13,100mPas.During thin up to 80% solid content, the viscosity drop to 3 of water dispersion, 250mPa.s.The pencil hardness that UV films after solidifying is 5H, and sticking power is 1 grade, and impact property is 43Kgcm, and bending property is 2mm, shows that cured film has higher hardness and good snappiness.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 3.90%, demonstrates excellent in water resistance.
Embodiment 7
Basic identical with embodiment 6 reaction process.Wherein, the 46.26g epoxy resin E-51 in the step (1) uses 44.69g epoxy resin E-54 instead, and the corresponding proportioning of other raw materials remains unchanged, and consumption is done corresponding adjustment.
Compare with embodiment 6, system viscosity is from 7 after organic-silicon-modified for the epoxy acrylic ester prepolymer in this example, and 350mPas increases to 8,620mPas.During thin up to 80% solid content, the viscosity drop to 2 of water dispersion, 100mPa.s shows that the initial viscosity of epoxy resin E-54 is lower, the viscosity of the final organic-silicon-modified propylene oxide acid esters of synthetic water dispersion can be low to moderate 2, about 000mPa.s.The pencil hardness that UV films after solidifying is 6H, and sticking power is 2 grades, and impact property is 40Kgcm, and bending property is 3mm, shows that cured film has higher hardness and good snappiness.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 3.30%, demonstrates excellent in water resistance.
Embodiment 8
Basic identical with embodiment 6 reaction process.Wherein, the 46.26g epoxy resin E-51 in the step (1) uses the 54.96g epoxy resin E-44 instead, and the corresponding proportioning of other raw materials remains unchanged, and consumption is done corresponding adjustment.
Compare with embodiment 6, system viscosity is from 21 after organic-silicon-modified for the epoxy acrylic ester prepolymer in this example, and 540mPas increases to 25,060mPas.During thin up to 80% solid content, the viscosity drop to 9 of water dispersion, 850mPa.s shows that the initial viscosity of epoxy resin E-44 is higher, the viscosity of the final organic-silicon-modified propylene oxide acid esters of synthetic water dispersion is still near 10, about 000mPa.s.During thin up to 60% solid content, the viscosity of water dispersion can reduce to 4,120mPa.s.The pencil hardness that UV films after solidifying is 4H, and sticking power is 1 grade, and impact property is 48Kgcm, and bending property is 1mm, shows that cured film has higher hardness and good snappiness.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 4.60%, demonstrates excellent in water resistance.
Embodiment 9
Identical with embodiment 8 reaction process.Wherein, 54.96g epoxy resin E-44 in the step (1) and 77.86g number-average molecular weight are that to use 36.39g epoxy resin E-44 and 103.59g number-average molecular weight instead be 550～750 polypropylene glycol diglycidyl ether for 550～750 polypropylene glycol diglycidyl ether; Be that epoxide group mol ratio in epoxy resin E-44 and the polypropylene glycol diglycidyl ether changed 1: 2 into by 1: 1; The corresponding proportioning of other raw materials remains unchanged, and consumption is done corresponding adjustment.
Compare with embodiment 8, the system viscosity of the organic-silicon-modified propylene oxide acid esters prepolymer in this example is from 25, and 060mPas is reduced to 12,160mPas.During thin up to 80% solid content, the viscosity drop to 3 of water dispersion, 510mPa.s shows that the consumption that increases polypropylene glycol diglycidyl ether can significantly reduce the viscosity of organic-silicon-modified propylene oxide acid esters water dispersion.The pencil hardness that UV films after solidifying is 4H, and sticking power is 1 grade, and impact property is 50Kgcm, and bending property is 1mm, shows that cured film has higher hardness and good snappiness.Cured film is soaked no change behind the 24h (nondiscoloration, non-foaming, do not come off) in 25 ℃ of zero(ppm) water, water-intake rate is 4.85%, still has excellent in water resistance.
Claims (5)
1. the preparation method of an organic-silicon-modified propylene oxide acid esters water dispersion is characterized in that comprising the steps:
(1) preparation of low viscosity epoxy acrylic ester prepolymer: in container, add epoxy resin, polyether-type epoxide diluent and stopper; Stirring is warming up to 70～75 ℃, dropwise addition of acrylic acid and catalyzer, and 0.5～1h dropwises; Be warming up to 80 ℃～90 ℃ subsequently, reaction 3～5h measures the system acid number and is lower than the 5mgKOH/g stopped reaction, obtains the epoxy acrylic ester prepolymer through the modification of polyether-type epoxide diluent viscosity reduction;
Described epoxy resin is bisphenol A type epoxy resin E-51, E-54 or E-44; The polyethyleneglycol diglycidylether that described polyether-type epoxide diluent is a number-average molecular weight 550～650, the polypropylene glycol diglycidyl ether of number-average molecular weight 550～750 and in the trihydroxymethylpropanyltri diglycidyl ether one or both; The epoxy group(ing) in epoxy resin and the polyether-type epoxide diluent and the mol ratio of acrylic acid carboxyl are 1: 1; The epoxy group(ing) mol ratio of epoxy resin and polyether-type epoxide diluent is 2: 1～1: 2; The stopper consumption is 0.2%～0.4% of epoxy resin, polyether-type epoxide diluent and a vinylformic acid total mass; Catalyst levels is 0.5%～0.8% of epoxy resin, epoxide diluent and a vinylformic acid total mass;
(2) preparation of MALEIC ANHYDRIDE grafting epoxy acrylic ester prepolymer: step (1) reaction system is cooled to 50～60 ℃, adds MALEIC ANHYDRIDE, catalyzer and stopper, stir; Adopt sectional heating method, 50～60 ℃ of reaction 0.5～1h are warming up to 70～80 ℃ of reaction 0.5～1h subsequently, and reaction stops when reaching theoretical acid number, obtains the cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer that side chain has carboxyl; The mole dosage of said MALEIC ANHYDRIDE be in the epoxy acrylic ester prepolymer of step (1) gained the pendant hydroxyl group molar content 40%～60%;
Said catalyzer and stopper consumption are respectively 0.5%～0.8% and 0.2%～0.4% of the middle epoxy acrylic ester prepolymer total mass of step (1);
(3) preparation of organic-silicon-modified propylene oxide acid esters water dispersion: the reaction system of step (2) is cooled to 40～50 ℃, adds stopper, continue to stir; With organic bases and the composite neutralizing agent of processing of small molecules amido silicon oil, the cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer that the side chain that step (2) is made has carboxyl neutralizes, and degree of neutralization is 60%～100%; Add deionized water, dilution under agitation and emulsification dispersion obtain solid content at 60%～90% organic-silicon-modified propylene oxide acid esters water dispersion;
Said organic bases is dimethylaminoethanol or triethylamine; The number-average molecular weight of said amido silicon oil is 100～400; The organic bases consumption is 60%～100% of a MALEIC ANHYDRIDE mole dosage; Amido silicon oil and stopper consumption are respectively 1.0%～2.0% and 0.1～0.4% of the middle cis-butenedioic anhydride grafting epoxy acrylic ester prepolymer total mass of step (2);
The stopper of said step (1)～(3) is p methoxy phenol, Resorcinol or DBPC 2,6 ditertiary butyl p cresol; The catalyzer of said step (1) and step (2) is tetraethylammonium bromide or N, the N-dimethyl benzylamine;
Said theoretical acid number is the system acid number when keeping a carboxyl behind the MALEIC ANHYDRIDE molecule esterification by ring opening.
2. the preparation method of organic-silicon-modified propylene oxide acid esters water dispersion according to claim 1 is characterized in that: the consumption of said deionized water is to make the solid content of organic-silicon-modified propylene oxide acid esters water dispersion control to 60%～80%.
3. the preparation method of organic-silicon-modified propylene oxide acid esters water dispersion according to claim 1 is characterized in that: the epoxy group(ing) mol ratio of said epoxy resin and epoxide diluent is 1: 1.
4. an organic-silicon-modified propylene oxide acid esters water dispersion is characterized in that by the said method preparation of claim 1.
5. organic-silicon-modified propylene oxide acid esters water dispersion according to claim 4 is characterized in that: said organic-silicon-modified propylene oxide acid esters water dispersion solid content is higher than 60%, and viscosity is 1,500～5,500 mPas.
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| CN109096500B (en) * | 2018-07-06 | 2021-04-13 | 福建拓烯新材料科技有限公司 | Organic silicon resin microemulsion and preparation method thereof |
| US11236244B2 (en) | 2018-09-10 | 2022-02-01 | Sun Chemical Corporation | Energy curable compositions comprising partially acrylated polyols |
| CN110003441B (en) * | 2019-04-22 | 2021-06-22 | 广州大学 | Preparation method of UV-cured waterborne isocyanate-grafted fluorosilicone modified epoxy acrylic resin |
| CN111690151A (en) * | 2020-06-10 | 2020-09-22 | 华南理工大学 | Preparation method of water-based UV (ultraviolet) curing epoxy acrylate emulsion |
| CN112048233A (en) * | 2020-09-11 | 2020-12-08 | 广州市白云化工实业有限公司 | Primer coating liquid for sealant and preparation method thereof |
| CN112538156B (en) * | 2020-12-11 | 2023-06-16 | 南雄市沃太化工有限公司 | Cigarette end scalding-resistant stain-resistant flame-retardant photo-cured resin and photo-cured coating |
| CN113372796A (en) * | 2021-06-21 | 2021-09-10 | 中铁上海工程局集团有限公司 | Ultraviolet-curing bisphenol F-type epoxy acrylate resin and preparation method thereof |
| CN114921180B (en) * | 2022-02-09 | 2023-04-07 | 广东绿色大地化工有限公司 | Organic silicon modified epoxy resin gloss oil and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560106A (en) * | 2004-03-10 | 2005-01-05 | 中国科学院广州化学研究所 | Modified epoxy resin by organic silicon and its electronic packag material and preparation process thereof |
-
2010
- 2010-10-14 CN CN 201010508740 patent/CN101974143B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560106A (en) * | 2004-03-10 | 2005-01-05 | 中国科学院广州化学研究所 | Modified epoxy resin by organic silicon and its electronic packag material and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| 杨伟平等.小分子氨基硅油改性水性聚氨酯的合成及性能探究.《中国涂料》.2010,第25卷(第3期), * |
| 陈尊等.高固低黏水性紫外光固化环氧丙烯酸酯的合成及性能.《化工新型材料》.2010,第38卷(第2期), * |
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