CN104693373A - Polyester modified water-based phosphorus-contained acrylic resin and preparation method and application thereof - Google Patents
Polyester modified water-based phosphorus-contained acrylic resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polyester modified acrylic resin, and particularly relates to polyester modified water-based phosphorus-contained acrylic resin and a preparation method and application thereof. The resin is obtained by a reaction of raw materials including, by mass, 5-10 parts of unsaturated polyester, 50-70 parts of acrylate monomer, 15-25 parts of hydroxyl-contained acrylate monomer and 5-7 parts of carboxyl-contained monomer, 1-5 parts of phosphorus-contained acrylate monomer, 1-3 parts of initiator and 55-75 parts of cosolvent. The resin is introduced into the phosphorus-contained acrylic monomer chain segment and the unsaturated polyester chain segment by using an ester group formed by alcohol acid condensation as a main chain, so that the adhesive force of a resin coating to a metal base material, particularly to Ni-Al, Mg-Si-Al, Mg-Al and other aluminum alloy and stainless steel base materials, is greatly improved; meanwhile, better adsorptivity and acting force to carbon black, titanium dioxide, aluminum powder and other pigments are achieved, wettability is more excellent, the resin can be used for metal coating primer, and the coating with rich colors is obtained.
Description
Technical field
The invention belongs to polyester modification acrylic resin technical field, particularly phosphorous acrylic resin of a kind of polyester modification water-based and its preparation method and application.
Background technology
Along with the development of building industry, the construction timber being applicable to door and window decoration also becomes more diversified, has natural materials (timber structure), metallic substance, high molecular synthetic material (engineering plastics polymeric amide, polyphenylene sulfide etc.) etc.Timber structure easily rots, and permanence is not high; High molecular synthetic material has creep behaviour, and after life-time service, material has contraction or expansion, limits widely using of they.Due to advantages such as metallic substance physical strength are high, high temperature resistant, texture is strong, more and more applied.But metal environmental corrosion resisting is poor, such as iron is oxidizable in atmosphere to get rusty, and not only affects beautiful decoration degree, also reduces mechanical strength.Therefore, investigation of materials person obtains alloy to the way that various metallic substance carries out studying also and other metal is mixing, not only physical strength is high, and good corrosion resistance, comprising various aluminium alloy (such as Ni-Al alloy, Mg-Si-Al alloy, Mg-Al alloy etc.), stainless steel, hot-galvanized steel etc.But, by the aluminium alloy after alloy modification, due to the introducing of the elements such as Si, Ni, cause the microphase-separated between metal crystalline region, make metallic surface paint film be difficult to attachment.Therefore, the attachment of coating on modified alloy is a great problem.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of polyester modification water-based phosphorous acrylic resin.
Another object of the present invention is the preparation method providing the phosphorous acrylic resin of a kind of above-mentioned polyester modification water-based.
Still a further object of the present invention is to provide the phosphorous acrylic resin of above-mentioned polyester modification water-based preparing the application in coating.Be particularly useful for making the coating for modified metal alloy.The phosphorous acrylic resin of polyester modification water-based of the present invention has excellent moisture dispersibility to color stuffing, utilizes the coating that it prepares, and has excellent adhesion effect to modified metal alloy base materials such as aluminium alloy, galvanized steel, stainless steels.
Object of the present invention is realized by following proposal:
The phosphorous acrylic resin of a kind of polyester modification water-based, is obtained by the raw material reaction of following mass parts:
Unsaturated polyester 5 ~ 10 parts; Acrylate monomer 50 ~ 70 parts; Hydroxy acryl acid ester monomer 15 ~ 25 parts; Carboxyl group-containing monomer 5 ~ 7 parts; Phosphoric acrylic ester monomer 1 ~ 5 part; Initiator 1 ~ 3 part; Solubility promoter 55 ~ 75 parts.
Described phosphoric acrylic ester monomer can be the phosphorous acrylated phosphate containing a double bond, is preferably at least one in (methyl) vinylformic acid (alkoxyl group) phosphoric acid ester and 2-hydroxyethyl (methyl) acrylate phosphate.
Described acrylate monomer can be at least two kinds in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) Isooctyl acrylate monomer and (methyl) glycidyl acrylate.
Described hydroxy acryl acid ester monomer can be at least one in (methyl) Hydroxyethyl acrylate and (methyl) Propylene glycol monoacrylate.
Described carboxyl group-containing monomer can be at least one in (methyl) vinylformic acid, methylene-succinic acid, maleic anhydride and fumaric acid.
Preferably, the solid content of unsaturated polyester used is 50 ~ 70%.Described unsaturated polyester is when solid content is 60%, liquid acid number is 10 ~ 30mg KOH/g, and the rotary viscosity at 25 DEG C is 2000 ~ 8000mPas, and second-order transition temperature is-20 DEG C ~ 20 DEG C, degree of unsaturation (representing by iodine number, in non-volatile part): 9.0 ~ 14.0.
Described initiator is preferably at least one in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, peroxidized t-butyl perbenzoate and the peroxidation 2 ethyl hexanoic acid tert-butyl ester.
Described solubility promoter is preferably at least one in ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propyl carbinol and isopropylcarbinol.
Preferably, the phosphorous acrylic resin of polyester modification water-based of the present invention is prepared by the method comprised the following steps: unsaturated polyester is added in solubility promoter and heats, after dripping acrylate monomer, hydroxy acryl acid ester monomer, carboxyl group-containing monomer, phosphoric acrylic ester monomer and initiator, insulation reaction, obtains the phosphorous acrylic resin of polyester modification water-based.
Described heating is preferably heated to 100 ~ 140 DEG C.
The described insulation reaction time is preferably 3 ~ 6h.
Described dropping monomer and initiator make preferably slowly to drip, and more preferably time for adding is 3 ~ 6h.
After described insulation reaction completes, can carry out lowering the temperature, neutralize and the subsequent disposal such as dilution.Neutralize the acid referring to add in alkaline neutraliser and in system, and the solid content that thin up system obtains being more suitable for using is about 40%, pH value is about the phosphorous acrylic resin of polyester modification water-based of 7.5 ~ 8.5.
Above-mentioned neutralization alkaline neutraliser used can be at least one in ammoniacal liquor, triethylamine, N, N-dimethylethanolamine, N-ethylmorpholine and 2-N, N-dimethylamino-2-methylpropanol.
Described unsaturated polyester can be prepared by following methods: Organic Alcohol, unsaturated acid (acid anhydride), organic acid (acid anhydride) esterifying polycondensation under catalyst action, obtain unsaturated polyester.
Described Organic Alcohol is preferably ethylene glycol, propylene glycol, 2-methyl isophthalic acid, at least one in ammediol, glycol ether, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol, TriMethylolPropane(TMP) and neopentyl glycol.When using multiple Organic Alcohol, should first mix to drop in reactor again and react.
Described unsaturated acid (acid anhydride) is preferably at least one in MALEIC ANHYDRIDE and fumaric acid.
Described organic acid (acid anhydride) is preferably at least one in m-phthalic acid, terephthalic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid, hexanodioic acid, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, HHPA and Succinic anhydried.
The total mass of organic acid used (acid anhydride) and the mass ratio of unsaturated acid (acid anhydride) are (9 ~ 15): 1, unsaturated acid (acid anhydride) account for Organic Alcohol, unsaturated acid (acid anhydride), organic acid (acid anhydride) total mass 3.5 ~ 6.0%.
Preferred elder generation mixes unsaturated acid (acid anhydride), organic acid (acid anhydride), then drop into reaction kettle for reaction.
Described catalyzer is conventional esterifying polycondensation catalyzer, as stannous octoate, dibutyl tin dilaurate or Mono-n-butyltin.The consumption of described catalyzer is catalytic amount.
The condition optimization of described esterification is 200 ~ 300 DEG C, and pressure is esterification 6 ~ 12h under 0 ~ 1MPa.
The condition optimization of described polycondensation is 180 ~ 200 DEG C, and pressure is 0 ~-0.1MPa polycondensation, 2 ~ 6h.
Preferably, described unsaturated polyester by Organic Alcohol, unsaturated acid (acid anhydride), organic acid (acid anhydride), catalyzer at 200 ~ 300 DEG C, esterification 6 ~ 12h under pressure 0 ~ 1MPa; After esterification completes, adjustment pressure is 0 ~-0.1MPa, obtains after polycondensation 2 ~ 6h.
In order to use better, the above-mentioned front solubility promoter of unsaturated polyester use prepared is diluted to 50 ~ 70% and admittedly contains.
The phosphorous acrylic resin of polyester modification water-based of the present invention has excellent color stuffing moisture dispersibility and metal base sticking power, can be used for preparing in coating, is particularly useful for making metal base primer base.
Mechanism of the present invention is:
The ester group that in the phosphorous acrylic resin of polyester modification water-based of the present invention, unsaturated polyester segment is formed with alkyd condensation is for main chain, compared to general carbon-carbon single bond main chain, there is larger polarity, powerful polar forces can be formed on metal alloy base surface, thus strengthen the sticking power of coating and metal base; Simultaneously, the phosphoric acrylic ester monomer segment introduced, can serve as metal alloy base surface and the bridge being coated with interlayer, the hydroxyl be connected with phosphorus can form chemical bond with the hydroxyl condensation on metal alloy base surface, thus strengthens the attachment of coating in metal alloy base further.Simultaneously, the strong polar ester groups main chain that the phosphorous acrylic resin of polyester modification water-based of the present invention has, have better adsorptivity and reactive force to color stuffings such as carbon black, titanium dioxide, aluminium powders, wettability is more excellent, can be used for metallic coating priming paint, prepare coloury coating.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) coating prepared of the phosphorous acrylic resin of polyester modification water-based of the present invention, has excellent sticking power to the aluminium alloys such as Ni-Al, Mg-Si-Al, Mg-Al, stainless steel substrate.
(2) coating prepared of the phosphorous acrylic resin of polyester modification water-based of the present invention, have excellent moisture dispersibility and adsorptivity to color stuffings such as carbon black, titanium dioxide, aluminium powders, the coating of preparation can obtain coloury outward appearance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: the preparation of the phosphorous acrylic resin of polyester modification water-based
By 150g ethylene glycol, 210g TriMethylolPropane(TMP), 1000g neopentyl glycol, 590g 1, 4-cyclohexane cyclohexanedimethanodibasic, 560g m-phthalic acid, 446g hexanodioic acid and 174g fumaric acid, 2.5g stannous octoate, input is equipped with agitator, thermometer, rectifying column, in the reactor of condenser and nitrogen inlet, temperature of reaction is 230 DEG C, pressure is 0.11MPa, rotating speed is 200rpm, control is heated up in a steamer a temperature and is no more than 105 DEG C, stir 10 hours, regulate pressure to-0.095MPa, temperature of reaction is 190 DEG C, stir 6 hours, sampling detecting acid number and viscosity, acid number testing method is as follows: get 12 grams of resins in Erlenmeyer flask, add 8g ethylene glycol monobutyl ether, shake Erlenmeyer flask makes sample dissolve completely, add 3 phenolphthalein indicators, being titrated to pink maintenance 30s colour-fast with potassium hydroxide-ethanol standardized solution is terminal.Reaction is to acid number 10mgKOH/g, cool to 120 DEG C, add the adjustment of 1600g ethylene glycol monobutyl ether admittedly to contain to 60 ± 2%, recording viscosity with rotational viscosimeter at 25 DEG C is 6000 ~ 8000mPa.s, degree of unsaturation (represents by iodine number, in non-volatile part) be 13.8, second-order transition temperature is-17 DEG C, and discharging obtains unsaturated polyester;
By the unsaturated polyester 50g synthesized above, 500g ethylene glycol monobutyl ether and 160g propyl carbinol are put in reactor, and temperature of reaction is 100 ~ 105 DEG C, 10g Diisopropyl azodicarboxylate, 300g methyl methacrylate, 200g butyl acrylate, 160g butyl methacrylate, 240g Rocryl 410, 50g vinylformic acid, 10g methacrylic acid phosphoric acid ester, mix at header tank, be added drop-wise in reactor, time for adding is 3 hours, rotating speed is 250rpm, during dropping, temperature controls at 100 ~ 105 DEG C, after monomer and initiator drip off, soaking time 5 hours, temperature 100 ~ 105 DEG C, cool to less than 50 DEG C, add after 692g deionized water and 97g ammoniacal liquor (25% effective part) stirs 30 minutes, filter to obtain the phosphorous acrylic resin of polyester modification water-based.
Embodiment 2: the preparation of the phosphorous acrylic resin of polyester modification water-based
By 100g propylene glycol, 200g TriMethylolPropane(TMP), 950g neopentyl glycol, 240g 1, 6-hexylene glycol, 290g terephthalic acid, 750g Tetra hydro Phthalic anhydride, 500g m-phthalic acid, 180g fumaric acid, 3g dibutyl tin dilaurate, input is equipped with agitator, thermometer, rectifying column, in the reactor of condenser and nitrogen inlet, temperature of reaction is 250 DEG C, pressure is 0.11MPa, rotating speed is 200rpm, control is heated up in a steamer a temperature and is no more than 105 DEG C, stir 10 hours, regulate pressure to-0.095MPa, temperature of reaction is 190 DEG C, stir 5 hours, sampling detecting acid number and viscosity, acid number is by the test of embodiment 1 method.Reaction is to acid number 20mgKOH/g, cool to 120 DEG C, add the adjustment of 1700g ethylene glycol monobutyl ether admittedly to contain to 60 ± 2%, recording viscosity with rotational viscosimeter at 25 DEG C is 4000 ~ 6000mPa.s, degree of unsaturation (represents by iodine number, in non-volatile part) be 11.5, second-order transition temperature is 18 DEG C, and discharging obtains unsaturated polyester;
By the unsaturated polyester 75g synthesized above, 300g propylene glycol monomethyl ether, 260g diethylene glycol monobutyl ether and 100g Virahol are put in reactor, and temperature of reaction is 115 ~ 120 DEG C, 10g peroxidized t-butyl perbenzoate and 15g benzoyl peroxide, 225g methyl methacrylate, 150g Isooctyl acrylate monomer, 100g β-dimethyl-aminoethylmethacrylate, 125g butyl methacrylate, 200g hydroxyethyl methylacrylate, 30g vinylformic acid, 40g methacrylic acid, 30g methacrylic phosphoric acid ester, mix at header tank, be added drop-wise in reactor, time for adding is 4 hours, rotating speed is 250rpm, during dropping, temperature controls at 115 ~ 120 DEG C, after monomer and initiator drip off, soaking time 4 hours, temperature 115 ~ 120 DEG C, cool to less than 50 DEG C, add 687g deionized water and 78.5g N, after N-dimethylethanolamine stirs 30 minutes, filter to obtain the phosphorous acrylic resin of polyester modification water-based.
Embodiment 3: the preparation of the phosphorous acrylic resin of polyester modification water-based
By 220g 2-methyl isophthalic acid, 3 propylene glycol, 150g TriMethylolPropane(TMP), 800g neopentyl glycol, 450g1, 4-cyclohexanedimethanol, 770g Tetra hydro Phthalic anhydride, 300g sebacic acid, 550g m-phthalic acid, 130g MALEIC ANHYDRIDE, 8g Mono-n-butyltin, input is equipped with agitator, thermometer, rectifying column, in the reactor of condenser and nitrogen inlet, temperature of reaction is 260 DEG C, pressure is 0.12MPa, rotating speed is 200rpm, control is heated up in a steamer a temperature and is no more than 105 DEG C, stir 6 hours, regulate pressure to-0.095MPa, temperature of reaction is 190 DEG C, stir 3 hours, sampling detecting acid number and viscosity, acid number is by the test of embodiment 1 method.Reaction is to acid number 30mgKOH/g, cool to 120 DEG C, add the adjustment of 1780g ethylene glycol monobutyl ether admittedly to contain to 60 ± 2%, recording viscosity with rotational viscosimeter at 25 DEG C is 2000 ~ 4000mPa.s, degree of unsaturation (represents by iodine number, in non-volatile part) be 9.2, second-order transition temperature is 1 DEG C, and discharging obtains unsaturated polyester;
By the unsaturated polyester 100g synthesized above, 320g propylene glycol monobutyl ether, 340g ethylene glycol monobutyl ether ether is put in reactor, and temperature of reaction is 135 ~ 140 DEG C, 15g peroxidized t-butyl perbenzoate and the 5g peroxidation 2 ethyl hexanoic acid tert-butyl ester, 250g methyl acrylate, 145g Isooctyl methacrylate, 120g ethyl propenoate, 100g glycidyl methacrylate, 160g Hydroxyethyl acrylate, 55g methylene-succinic acid, 50g 2-hydroxyethyl methacrylic acid phosphoric acid ester, mix at header tank, be added drop-wise in reactor, time for adding is 4 hours, rotating speed is 250rpm, during dropping, temperature controls at 135 ~ 140 DEG C, after monomer and initiator drip off, soaking time 3 hours, temperature 135 ~ 140 DEG C, cool to less than 50 DEG C, add after 655g deionized water and 85.6g triethylamine stir 30 minutes, filter to obtain the phosphorous acrylic resin of polyester modification water-based.
Comparative example 1
On the basis of embodiment 2, the phosphorous acrylic resin synthesis phase of polyester modification water-based does not add unsaturated polyester, and all the other are constant.
Comparative example 2
On the basis of embodiment 2, the phosphorous acrylic resin synthesis phase of polyester modification water-based does not add phosphoric acrylic ester monomer, and all the other are constant.
Comparative example 3
On the basis of embodiment 2, the phosphorous acrylic resin synthesis phase of polyester modification water-based does not add unsaturated polyester and phosphoric acrylic ester monomer, and all the other are constant.
Comparative example 4
By 100g propylene glycol, 200g TriMethylolPropane(TMP), 985g neopentyl glycol, 200g 1, 6-hexylene glycol, 663g terephthalic acid, 750g Tetra hydro Phthalic anhydride, 100g m-phthalic acid, 153g fumaric acid, 3g dibutyl tin dilaurate, input is equipped with agitator, thermometer, rectifying column, in the reactor of condenser and nitrogen inlet, temperature of reaction is 250 DEG C, pressure is 0.11MPa, rotating speed is 200rpm, control is heated up in a steamer a temperature and is no more than 105 DEG C, stir 10 hours, regulate pressure to-0.095MPa, temperature of reaction is 190 DEG C, stir 5 hours, sampling detecting acid number and viscosity, acid number is by the test of embodiment 1 method.Reaction is to acid number 20mgKOH/g, cool to 120 DEG C, add the adjustment of 1700g ethylene glycol monobutyl ether admittedly to contain to 60 ± 2%, recording viscosity with rotational viscosimeter at 25 DEG C is 4000 ~ 6000mPa.s, degree of unsaturation (represents by iodine number, in non-volatile part) be 11.5, second-order transition temperature is 28 DEG C, and discharging obtains unsaturated polyester;
The preparation process of the phosphorous acrylic resin of polyester modification water-based is with embodiment 2.
Comparative example 5
By 150g ethylene glycol, 210g TriMethylolPropane(TMP), 1000g neopentyl glycol, 590g 1, 4-cyclohexane cyclohexanedimethanodibasic, 360g m-phthalic acid, 652g hexanodioic acid and 145g fumaric acid, 3g dibutyl tin dilaurate, input is equipped with agitator, thermometer, rectifying column, in the reactor of condenser and nitrogen inlet, temperature of reaction is 250 DEG C, pressure is 0.11MPa, rotating speed is 200rpm, control is heated up in a steamer a temperature and is no more than 105 DEG C, stir 10 hours, regulate pressure to-0.095MPa, temperature of reaction is 190 DEG C, stir 5 hours, sampling detecting acid number and viscosity, acid number is by the test of embodiment 1 method.Reaction is to acid number 20mgKOH/g, cool to 120 DEG C, add the adjustment of 1700g ethylene glycol monobutyl ether admittedly to contain to 60 ± 2%, recording viscosity with rotational viscosimeter at 25 DEG C is 4000 ~ 6000mPa.s, degree of unsaturation (represents by iodine number, in non-volatile part) be 11.5, second-order transition temperature is-26 DEG C, and discharging obtains unsaturated polyester;
The preparation process of the phosphorous acrylic resin of polyester modification water-based is with embodiment 2.
Comparative example 6
On the basis of embodiment 2, unsaturated polyester synthesis phase, fumaric acid content changes 107g into, and the degree of unsaturation of the discord polyester obtained is 8.0, and all the other are constant.
Comparative example 7
On the basis of embodiment 2, unsaturated polyester synthesis phase, fumaric acid content changes 200g into, and the degree of unsaturation of the discord polyester obtained is 15.0, and all the other are constant.
Embodiment 4: the application of the phosphorous acrylic resin of polyester modification water-based
The phosphorous acrylic resin of polyester modification water-based that embodiment 1 ~ 3 and comparative example 1 ~ 7 prepare is made into priming paint, metal alloy base is formed film and evaluates and tests.For black primer, the preparation flow of priming paint: first carbon black 15.0g, deionized water 25.0g, dispersant B YK-1805.0g are placed in dispersion machine, put into 55.0g granulated glass sphere, disperses 5 hours, filters obtained black wash; Then, respectively by the resin that more than 50.0g embodiment and comparative example prepare, be put in dispersion cup, add 5.5g aminoresin, after stirring, add 0.2g Phenylsulfonic acid type catalyzer, after stirring, add 24.3g deionized water, 4.5g talcum powder and 15.0g black wash, stir, then disperse 20 minutes with 600r/min rotating speed, with 120 order filter-cloth filterings, obtain black primer.By basecoat paint in metal alloy base, 180 DEG C are toasted 15 minutes, and carry out correlated performance test and observation to coating, test result is as shown in table 1 below, testing standard: sticking power, GB/T 9286,5B.
From table 1, the phosphorous acrylic resin of polyester modification water-based of the present invention is to metal alloy base being had to excellent sticking power; Simultaneously good to the moisture dispersibility of pigment, when fillers such as disperse black carbon, titanium dioxide, aluminium powders, excellent adsorption, has good wetting and dispersing effect, obtains the color effect enriched, and can be applicable to metal base priming paint.
Table 1 black primer is coated with the test result installed in metal alloy base
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the phosphorous acrylic resin of polyester modification water-based, is characterized in that being obtained by the raw material reaction of following mass parts: unsaturated polyester 5 ~ 10 parts; Acrylate monomer 50 ~ 70 parts; Hydroxy acryl acid ester monomer 15 ~ 25 parts; Carboxyl group-containing monomer 5 ~ 7 parts; Phosphoric acrylic ester monomer 1 ~ 5 part; Initiator 1 ~ 3 part; Solubility promoter 55 ~ 75 parts.
2. the phosphorous acrylic resin of polyester modification water-based according to claim 1, it is characterized in that: described phosphoric acrylic ester monomer is the phosphorous acrylated phosphate containing a double bond, is at least one in (methyl) vinylformic acid (alkoxyl group) phosphoric acid ester and 2-hydroxyethyl (methyl) acrylate phosphate.
3. the phosphorous acrylic resin of polyester modification water-based according to claim 1, is characterized in that: described acrylate monomer is at least two kinds in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) Isooctyl acrylate monomer and (methyl) glycidyl acrylate;
Described hydroxy acryl acid ester monomer is (methyl) Hydroxyethyl acrylate and at least one in (methyl) Propylene glycol monoacrylate;
Described carboxyl group-containing monomer is at least one in (methyl) vinylformic acid, methylene-succinic acid, maleic anhydride and fumaric acid;
The solid content of unsaturated polyester used is 50 ~ 70%; Described unsaturated polyester is when solid content is 60%, and liquid acid number is 10 ~ 30mg KOH/g, and the rotary viscosity at 25 DEG C is 2000 ~ 8000mPas, and second-order transition temperature is-20 DEG C ~ 20 DEG C, degree of unsaturation: 9.0 ~ 14.0.
4. the phosphorous acrylic resin of polyester modification water-based according to claim 1, is characterized in that: described initiator is at least one in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, peroxidized t-butyl perbenzoate and the peroxidation 2 ethyl hexanoic acid tert-butyl ester;
Described solubility promoter is at least one in ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propyl carbinol and isopropylcarbinol.
5. the phosphorous acrylic resin of polyester modification water-based according to claim 1, it is characterized in that: described unsaturated polyester is prepared by following methods: Organic Alcohol, unsaturated acid (acid anhydride), organic acid (acid anhydride) esterifying polycondensation under catalyst action, obtain unsaturated polyester.
6. the phosphorous acrylic resin of polyester modification water-based according to claim 5, it is characterized in that: described Organic Alcohol is ethylene glycol, propylene glycol, 2-methyl isophthalic acid, ammediol, glycol ether, 1, at least one in 6-hexylene glycol, 1,4 cyclohexane dimethanol, TriMethylolPropane(TMP) and neopentyl glycol;
Described unsaturated acid (acid anhydride) is at least one in MALEIC ANHYDRIDE and fumaric acid;
Described organic acid (acid anhydride) is m-phthalic acid, at least one in terephthalic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid, hexanodioic acid, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, HHPA and Succinic anhydried.
7. the phosphorous acrylic resin of polyester modification water-based according to claim 5, is characterized in that: the total mass of organic acid used (acid anhydride) and the mass ratio of unsaturated acid (acid anhydride) are (9 ~ 15): 1; Described unsaturated acid (acid anhydride) account for Organic Alcohol, unsaturated acid (acid anhydride), organic acid (acid anhydride) total mass 3.5 ~ 6.0%.
8. the preparation method of the phosphorous acrylic resin of polyester modification water-based according to claim 1, it is characterized in that comprising the following steps: unsaturated polyester is added in solubility promoter and heats, after dripping acrylate monomer, hydroxy acryl acid ester monomer, carboxyl group-containing monomer, phosphoric acrylic ester monomer and initiator, insulation reaction, obtains the phosphorous acrylic resin of polyester modification water-based.
9. the preparation method of the phosphorous acrylic resin of polyester modification water-based according to claim 8, is characterized in that: described heating refers to be heated to 100 ~ 140 DEG C; The described insulation reaction time is 3 ~ 6h.
10. the phosphorous acrylic resin of polyester modification water-based according to any one of claim 1 ~ 7 is preparing the application in metal base primer base.
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| CN105111382A (en) * | 2015-08-20 | 2015-12-02 | 顾彩霞 | Polyester-modified waterborne phosphate-contained acrylic resin |
| CN106749945A (en) * | 2016-11-29 | 2017-05-31 | 广州慧谷化学有限公司 | A kind of polyester modification water-based acrylic resin and preparation and the application in varnish |
| CN112759720A (en) * | 2021-01-11 | 2021-05-07 | 广东锐涂精细化工有限公司 | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof |
| CN114773662A (en) * | 2022-05-05 | 2022-07-22 | 常州市宝丽胶粘剂有限公司 | Self-stripping reflective film surface resin and preparation method thereof |
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| CN112759720A (en) * | 2021-01-11 | 2021-05-07 | 广东锐涂精细化工有限公司 | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof |
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