CN103555120A - Polyacrylate grafted modified polyester water-based coating and preparation method thereof - Google Patents
Polyacrylate grafted modified polyester water-based coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a polyacrylate grafted modified polyester water-based coating. The preparation method is as follows: first, selecting a dihydric alcohol and a dibasic acid for a copolycondensation reaction at 240 DEG C for synthesis of a polyester with grafting activity, then adding the dibasic acid or a polybasic acid for polyester depolymerization and end capping for synthesis of water-dispersible polyester resin, then dissolving the water-dispersible polyester resin with a water soluble cosolvent, at 105 DEG C dropping a mixed liquid of a functional monomer, an acrylate monomer, a styrene monomer and an organic peroxide initiator for a free radical grafting copolymerization reaction for synthesis of a solution of water-dispersible-type polyacrylate grafted modified polyester resin with a water-dispersible main chain and a water-soluble graft chain, adding an amine neutralizer for neutralizing the solution of the water-dispersible-type polyacrylate grafted modified polyester resin, mixing the neutralized solution of the polyacrylate grafted modified polyester resin with an amino resin curing agent or an aziridine curing agent, a coating additive and deionized water for preparation of the polyacrylate grafted modified polyester water-based coating. The polyacrylate grafted modified polyester water-based coating has the advantages of a polyester coating and a polyacrylate coating, and is high in cured paint film glossiness and strong in water resistance.
Description
Technical field
The present invention relates to a kind of polyacrylate grafting modified poly ester water-borne coatings and preparation method thereof, belong to organic polymer material field.
Background technology
Due to the deterioration of the ecological environment, environment protection more and more comes into one's own.Solvent based coating contains a large amount of organic volatiles (VOC) composition, and not only contaminate environment, wastes resource, and also harm humans is healthy.The discharge that relevant laws and regulations strictly limit coating VOC has all been formulated in China and countries in the world.Oligosaprobic water-borne coatings, photo-cured coating, powder coating and high solid coating have become the developing direction of paint industry.Compare with other low Contamination Coatings, water-borne coatings due to have multiple synthetic method with technology of preparing, be widely used, the relative advantage such as simple of safety, construction becomes the kind that coating material production field is competitively developed.
Polyester coating is widely used in surface protection and the decoration of metal and woodenware; its cured paint film has that fullness ratio is high, wear resistance and the advantage such as petrol-resistance is good; but snappiness, impact resistance and workability are not good enough; more owing to containing a large amount of ester bonds on polyester molecule chain; easily hydrolysis chain rupture; water-fast, the light aging resisting, weather-resistant and the poor performance such as corrosion-resistant that cause its paint solidification paint film, the application of polyester coating is especially in the application in painting dressing automobiles field thereby be restricted.When the copolycondensation later stage of synthesizing polyester resin adds a kind of binary or polyprotonic acid to carry out depolymerization, two ends of polyester molecule chain are carried out to end capping, can give vibrin with water dispersible or claim self-emulsifying action, can be made into waterborne polyester coating.
It is high that polyacrylate coating cured paint film has glossiness, the advantage of the excellent property such as water-fast, corrosion-resistant, weather-resistant, heat-resisting deterioration by oxidation, but there is the shortcoming of the poor performance such as fullness ratio, hardness, bending.The monomeric unit of introducing with hydrophilic radicals such as carboxyl and hydroxyls in polyacrylic ester molecular chain can synthesize water-soluble polyacrylate resin, thereby can prepare water polyacrylic acid coating.
With vibrin and polyacrylate resin solution mixing system for composite coating, should obtain the cured paint film of mutual supplement with each other's advantages, be that this composite paint solidification paint film had both had advantages of polyester coating cured paint film, also there is polyacrylate coating cured paint film, thus the shortcoming that in the time of can overcoming independent use, cured paint film exists.But because the main chain of polyester macromolecule exists the ester bond of high polarity, and the macromolecular main chain of polyacrylic ester only consists of C-C, its polarity is low, causes the two consistency on thermodynamics poor and tend to be separated, and makes the remarkable variation of over-all properties of composite paint solidification paint film.
On aqueous dispersion type polyester molecule chain, connect water-soluble polyacrylate side chain, the good graft copolymer of vibrin and polyacrylate resin consistency be can obtain, thereby can prepare its cured paint film, polyester and water-borne coatings polyacrylic ester advantage thereby excellent property had concurrently.
Summary of the invention
The object of this invention is to provide a kind of polyacrylate grafting modified poly ester water-borne coatings and preparation method thereof.
The present invention is that the technical scheme that technical solution problem adopts is:
A preparation method for polyacrylate grafting modified poly ester water-borne coatings, comprises the steps:
(1) utilize the synthetic aqueous dispersion type polyester with graft reaction activity of dibasic alcohol, diprotic acid, acid anhydrides and epoxy monomer, then with water-soluble solubility promoter, dissolved and form polyester liquid;
(2) in above-mentioned solution, drip the mixed solution that function monomer, acrylic ester monomer, styrene monomer and organic peroxide evocating agent form, carry out graft copolymerization, make aqueous dispersion type polyacrylate grafting modified polyester resin lipoprotein solution;
(3) in polyacrylate grafting modified polyester resin lipoprotein solution, add neutralizing agent, solidifying agent, coatings additive(s) and deionized water to be mixed with water-borne coatings.
Preferably, the described aqueous dispersion type vibrin with graft reaction activity is with containing the dibasic alcohol of tertiary carbon hydrogen atom, diprotic acid, containing dibasic alcohol, diprotic acid and the acid anhydrides of methylene radical hydrogen atom, and the various of monomer mixtures such as the substituent epoxide of band aliphatic chain are made through copolycondensation; Described dibasic alcohol is 2-methyl isophthalic acid, ammediol, 1,4 cyclohexane dimethanol, 1, and two or more of 6-hexylene glycol, described diprotic acid is 1,6-hexanodioic acid; 1,4 cyclohexanedicarboxylic acid, two or more of nonane diacid, sebacic acid, described acid anhydrides is HHPA, the substituent epoxy monomer of described band aliphatic chain is tertiary carbonic acid glycidyl ester.
Preferably, in the reaction later stage of synthetic water decentralized polyester, add a kind of diprotic acid or polyprotonic acid, as depolymerization end-capping reagent, aqueous dispersion type polyester molecule chain is carried out to depolymerization reaction to reduce the molecular weight of polyester, and make two ends of the polyester molecule chain of synthesized respectively be with one or two carboxyl and there is water dispersible.Described depolymerization end-capping reagent be take trimellitic acid 1,2-anhydride as good.
Preferably, described dissolved polyester solubility promoter used is water-soluble and the polar solvent reactionless activity of linking agent, and in final synthetic aqueous dispersion type polyacrylate grafting modified poly ester solution, the mass percentage content of solubility promoter is 20%～50%.
Preferably, described solubility promoter is wherein one or more of ethylene glycol diethyl ether, diethylene glycol diethyl ether and pimelinketone.
Preferably, described acrylic ester monomer is one or more of methacrylic acid, vinylformic acid, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate, acetoacetoxyethyl methacrylate, methyl methacrylate, Tert-butyl Methacrylate, phenyl methacrylate, methacrylic acid benzyl ester, isobornyl methacrylate, butyl methacrylate, butyl acrylate and Isooctyl acrylate monomer, and described styrene monomer is vinylbenzene.
Preferably, described function monomer is wherein a kind of of methacrylic acid and vinylformic acid, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410 or Propylene glycol monoacrylate one or both and acetoacetoxyethyl methacrylate wherein.
Preferably, described in and polyacrylate grafting modified polyester resin lipoprotein solution neutralizing agent used be the amine neutralizing agent with the reactionless activity of linking agent, comprise one or more in Trimethylamine 99, triethylamine, xylidine, Diethyl Aniline, triphenylamine.
Preferably, described water-borne coatings solidifying agent used is amino resin curing agents or aziridine hardener.
A polyacrylate grafting modified poly ester water-borne coatings prepared by aforesaid method belongs to single-component water-based coating when making solidifying agent with aminoresin, belongs to double-component water paint when making solidifying agent with aziridine.
The free radical chain of polymkeric substance and vinyl monomer shifts the most important condition of graft modification, is to treat that grafting polymer molecular chain must have chain and shift graft reaction active site.Reactive behavior point generally has α-methyne hydrogen atom of carbon-to-carbon double bond, and its graft reaction activity is higher; Have tertiary carbon hydrogen atom, its graft reaction activity is taken second place, and also has methylene radical hydrogen atom, and its graft reaction activity is lower, and methyl hydrogen atom is difficult to occur chain and shifts graft reaction.For meeting the use properties of polyester coating cured paint film, as improve hardness and water tolerance etc., when synthesizing polyester, often to increase aromatic dicarboxylic or polycarboxylic acid and the binary or the ratio of polyvalent alcohol in copolycondensation monomer that lack tertiary carbon hydrogen atom and methylene radical hydrogen atom.Therefore traditional vibrin, its molecular chain is low because tertiary carbon hydrogen atom and the few and free radical chain of methylene radical hydrogen atom content shift graft reaction activity, is difficult to obtain desirable graft copolymer.In order to improve the graft reaction activity of polyester, the present invention passes through molecular designing, adopt the monomer containing tertiary carbon hydrogen atom to comprise 2-methyl isophthalic acid, ammediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexane cyclohexanedimethanodibasic, HHPA, with comprise 1 containing a fairly large number of monomer of methylene radical, 6-hexylene glycol, 1,6-hexanodioic acid, nonane diacid, sebacic acid, one or more dibasic alcohol such as tertiary carbonic acid glycidyl ester (E10P) and one or more diprotic acid carry out copolycondensation, to have the polyester of more graft reaction active site on synthetic molecules chain.In copolycondensation, an epoxy group(ing) is equivalent to 2 hydroxyls, and an anhydride group is equivalent to 2 carboxyls.Owing to existing acid anhydrides and the diprotic acid of carbon-to-carbon double bond structure to contain the active high α-methyne hydrogen atom of chain transfer reaction, on polyester molecule chain, suitably introduce this class monomeric unit as a kind of monomeric unit wherein such as itaconic anhydride, methylene-succinic acid, tetrahydrophthalic anhydride, can improve graft reaction activity.But when at high temperature carrying out copolycondensation, can cause the carbon-to-carbon double bond generation crosslinking reaction between polyester molecule chain.Slight crosslinked meeting improves the viscosity of polyester, is further cross-linked and can makes reaction system gelation, causes the polyester of synthesized to be difficult to and acrylic ester monomer generation graft copolymerization.Therefore, the present invention does not adopt the monomer participation copolycondensation of this class carbon-carbon double key to prepare vibrin.In copolycondensation process, because dibasic alcohol component can be lossy, so the charging capacity of alcohol component should be more.Research shows, the alcohol of copolycondensation system of the present invention: sour mol ratio is advisable with 1.3:1.2-methyl isophthalic acid in copolycondensation monomer, the percentage ratio that ammediol and tertiary carbonic acid glycidyl ester account for respectively monomer total mass is 15～25% and 0～4%.
Solubility promoter used is the water soluble polar solvent of not being with the group that can react with coating curing agent, and its boiling point is more than 110 ℃.According to this principle, dissolved polyester solubility promoter used adopts a kind of of ethylene glycol diethyl ether, diethylene glycol dimethyl ether and pimelinketone, wherein take ethylene glycol diethyl ether as optimum.The consumption of solubility promoter is equivalent to 20%～40% of graft product aqueous dispersion type polyacrylate grafting modified polyester resin.
In the copolycondensation later stage, add appropriate depolymerization end-capping reagent trimellitic acid 1,2-anhydride, diprotic acid or other acid anhydrides wherein a kind of, make polyester molecule chain that coalescence occur to separate end capping occurs simultaneously, with obtain acid number and molecular weight suitable, all there is the vibrin of one or two carboxy blocking at molecular chain two ends, thereby gives vibrin with good water dispersible or claim self-emulsifying action.Described depolymerization end-capping reagent is a kind of in trimellitic acid 1,2-anhydride, phthalic anhydride, terephthalic acid, succinic acid, wherein with trimellitic acid 1,2-anhydride for well, its consumption is equivalent to 1%～4% of copolycondensation monomer mass.
The present invention is used for improving the hardness of grafted chain for the vinylbenzene of methyl methacrylate, Tert-butyl Methacrylate, phenyl methacrylate, methacrylic acid benzyl ester, isobornyl methacrylate and the styrene monomer of the acrylic ester monomer of graft reaction, butyl acrylate and Isooctyl acrylate monomer are for improving the snappiness of grafted chain; Function monomer is used for improving the water-soluble of grafted chain and for solidifying agent provides curing reaction group, wherein acetoacetoxyethyl methacrylate also has the effect that reduces grafted chain viscosity, improves grafted chain water resistance.In acrylic ester monomer and styrene monomer, hard monomer: soft monomer: the batching mass ratio of function monomer is 30～50:30～40:20～40.And polyester: the batching mass ratio of grafted monomer is 30～60:70～40.
Acrylic ester monomer and styrene monomer and polyester graft reaction initiator used are organo-peroxides, wherein a kind of for peroxidized t-butyl perbenzoate, dibenzoyl peroxide, dicumyl peroxide, two t-amyl peroxy things, its consumption is equivalent to 1.5～2.5% of grafted monomer quality.
With the synthetic aqueous dispersion type polyacrylate grafting modified polyester resin of technology provided by the invention, its main chain is polyester, two ends of polyester molecule chain all have water dispersible or claim self-emulsifying with carboxyl, its grafted chain is with the acrylic ester monomer of a plurality of carboxyl side groups and styrene monomer multipolymer, thereby has water-soluble.Add amine neutralizing agent, by carboxyl and salify, polyacrylate grafting modified poly ester becomes and has the resin of water dispersible and dispersible in water.Neutralizing agent is advisable with triethylamine, and its consumption is equivalent to 6% left and right of aqueous dispersion type polyacrylate grafting modified polyester resin quality.
Polyacrylate grafting modified poly ester water-borne coatings provided by the invention solidifying agent used is that aminoresin is hexamethyl alcohol etherificate terpolycyantoamino-formaldehyde resin solidifying agent or trifunctional aziridine hardener.Aziridine hardener and carboxyl have strong reaction active, in acidic catalyst and hot environment can also with the hydroxyl generation cross-linking and curing reaction of acrylate resin.Aqueous dispersion type polyacrylate grafting modified poly ester molecular chain band carboxyl, with in amine neutralizing agent and form the amine salt of carboxylic acid, it is filmed amine neutralizing agent volatilization when high bake and separates out carboxyl, when making solidifying agent with aziridine, the carboxyl of separating out and aziridine generation crosslinking reaction, simultaneously also for catalysis aziridine and hydroxyl generation cross-linking and curing reaction provide an acidic catalyst; For amino resin curing agents, the carboxyl of separating out and aminoresin generation crosslinking reaction, the while also becomes an acidic catalyst of aminoresin and hydroxyl generation cross-linking and curing reaction.When preparation water-borne coatings, the consumption of amino resin curing agents and aziridine hardener is equivalent to respectively 35%～50% and 20%～40% of aqueous dispersion type polyacrylate grafting modified polyester resin quality.The polyacrylate grafting modified poly ester water-borne coatings of making solidifying agent with aminoresin belongs to single-component water-based coating, and belong to double-component water paint with the polyacrylate grafting modified poly ester water-borne coatings that aziridine is made solidifying agent, need in 6 hours after adding aziridine hardener, be finished.
The preparation technology of polyacrylate grafting modified poly ester water-borne coatings provided by the invention divides three steps to carry out.
The first step is the synthetic of aqueous dispersion type vibrin.To by molar ratio of alcohol to acid, be 1.3:1 batching by formula 2 kinds of consumption or multiple dibasic alcohol and 2 kinds or multiple diprotic acid, add reactor, under nitrogen protection, heat up, while reaching 120 ℃, material starts melting, start stirrer stirring at low speed, be warmed up to after 160 ℃, be incubated half an hour, after this heat up per half an hour 10 ℃, until temperature reaches 240 ℃, continue esterification to copolycondensation system and reach articulation point, stop passing into nitrogen, unlatching vacuum extractor slowly reduces the vacuum tightness of system, after half an hour, make be less than-0.098MPa of vacuum tightness, to remove the moisture content generating in copolycondensation, continue to vacuumize after 2 hours, stop vacuumizing, with nitrogen, recover normal pressure, and cool to 180 ℃, add trimellitic acid 1,2-anhydride, react sampling detecting acid number after 2 hours, when acid number reaches the scope of 12～46mg KOH/g, be cooled to 70 ℃ of left and right dischargings, obtain aqueous dispersion type vibrin.
Second step is with aqueous dispersion type vibrin and acrylic ester monomer and styrene monomer, to carry out solution graft copolymerization to prepare aqueous dispersion type polyacrylate grafting modified polyester resin.The aqueous dispersion type polyester and the solubility promoter that in reactor, add the consumption of filling a prescription, stir and heat up, and forms homogeneous solution.Polyester liquid is heated up and constant temperature in 110 ℃～120 ℃, start to drip acrylic ester monomer and the styrene monomer mixed solution that has dissolved initiator, in 4 hours, drip.After dripping monomer, add the initiator solution that is dissolved in solubility promoter, be incubated 2～4 hours, be then cooled to 70 ℃, drip neutralizing agent solution is neutralized, discharging, obtains aqueous dispersion type polyacrylate grafting modified poly ester solution.
The 3rd step is the preparation of water-borne coatings and cured paint film thereof.By formula consumption, aqueous dispersion type polyacrylate grafting modified poly ester solution, solidifying agent and coatings additive(s) are mixed, high-speed stirring is uniformly dispersed, and adds deionized water, being diluted to working viscosity is that 25s(is coated with-4 glasss, 25 ℃), filter discharging, obtain polyacrylic acid grafted modified poly ester water-borne coatings.This water paint spraying, on tinplate, after referring to do, is obtained to cured paint film with 130 ℃～160 ℃ baking 30min wait filming.
Below in conjunction with embodiment, the invention will be further described, but be not limited to this.
Embodiment
The preparation of polyacrylate grafting modified poly ester water-borne coatings divides three steps to carry out.The first step is synthetic water decentralized vibrin, second step is to carry out solution graft copolymerization with aqueous dispersion type vibrin and acrylic ester monomer and styrene monomer, with the acrylic ester grafted modified polyester resin of synthetic water decentralized, the 3rd step is the preparation of water-borne coatings and cured paint film thereof.
Table 1 is the raw materials used title of synthetic water decentralized vibrin and amount ranges thereof; Table 2 is the raw materials used title of synthetic water decentralized polyacrylate grafting modified polyester resin and amount ranges thereof.Table 3 and table 4 are respectively the basic recipes of synthetic water decentralized vibrin and synthetic water decentralized polyacrylate grafting modified polyester resin.In synthetic water decentralized vibrin monomer used, tertiary carbonic acid glycidyl ester is attributed to alcohols monomer.In the mix monomer of copolycondensation system (except depolymerizing agent), the molar ratio of alcohols monomer and acids monomer, i.e. alcohol: sour mol ratio is 1.3:1, and wherein alcohols monomer is excessive.
The raw material of table 1 synthetic water decentralized vibrin
The raw material of table 2 synthetic water decentralized polyacrylate grafting modified polyester resin
(1)solvent load calculates with solvent/(vibrin+grafted monomer+solvent) mass percent (Wt%) or solvent/(polyacrylate grafting modified polyester resin+solvent) mass percent.
The basic recipe of table 3 synthetic water decentralized vibrin
The basic recipe of table 4 synthetic water decentralized polyacrylate grafting modified polyester resin
(1)ethylene glycol diethyl ether consumption is with ethylene glycol diethyl ether/(polyester+grafted monomer+ethylene glycol diethyl ether) mass percent, or ethylene glycol diethyl ether/(polyacrylate grafting modified polyester resin+ethylene glycol diethyl ether) mass percent calculates.
In table 2 and table 4, solvent load calculates with solvent/(vibrin+grafted monomer+solvent) mass percent or solvent/(polyacrylate grafting modified polyester resin+solvent) mass percent.
Table 5 is raw material amount ranges and basic recipes of preparing polyacrylate grafting modified polyester resin water-borne coatings.
Table 5 is prepared the formula of polyacrylate grafting modified poly ester water-borne coatings
Embodiment 1
The present embodiment was to provide in the synthetic water decentralized vibrin stage, the impact of the consumption of depolymerizing agent trimellitic acid 1,2-anhydride on the performance of the performance of aqueous dispersion type vibrin, aqueous dispersion type polyacrylate grafting modified polyester resin and water-borne coatings and cured paint film.
The preparation process of aqueous dispersion type polyacrylate grafting modified poly ester water-borne coatings divides three steps to carry out.The first step is synthetic water decentralized vibrin, and second step is synthetic water decentralized polyacrylate grafting modified polyester resin, and the 3rd step is the preparation of water-borne coatings and cured paint film thereof.
Synthesizing of the first step aqueous dispersion type vibrin
Fix the consumption of monomer of the same race, in the later stage of copolycondensation, add the depolymerization end-capping reagent trimellitic acid 1,2-anhydride of different amounts, synthetic water decentralized polyester, the impact of the consumption of investigation trimellitic acid 1,2-anhydride on aqueous dispersion type vibrin performance.The formula of the aqueous dispersion type polyester that synthetic depolymerization end-capping reagent trimellitic acid 1,2-anhydride consumption is different is as shown in table 6.
The formula of the aqueous dispersion type polyester that the synthetic depolymerization end-capping reagent trimellitic acid 1,2-anhydride consumption of table 6 is different
(1)finger be take the mass fraction that feeds intake (together lower) of total mass umber (phr) trimellitic acid 1,2-anhydride during as 100phr of participating in copolycondensation monomer (except trimellitic acid 1,2-anhydride) in batching.
At one, be equipped with electric mixer, logical nitrogen device, mercurythermometer, water trap, in the 500ml four-hole glass flask of vacuum unit and oil bath thermostat, pass into nitrogen, add 2-methyl isophthalic acid, ammediol 51g, 1, 4-cyclohexanedimethanol 46.5g, 1, 6-hexylene glycol 16g, tertiary carbonic acid glycidyl ester (E10P) 6g, 1, 4-cyclohexane cyclohexanedimethanodibasic 55.5g, HHPA 49.8g, 1, 6-hexanodioic acid 11.7g, terephthalic acid 13.5g, be warmed up to 120 ℃, material starts melting, start agitator stirring at low speed, stop logical nitrogen, be warming up to 160 ℃ and be incubated half an hour, after this heat up per half an hour 10 ℃, until temperature reaches 240 ℃, continue esterification 3 hours to copolycondensation system and reach articulation point, stop passing into nitrogen, unlatching vacuum extractor slowly reduces the vacuum tightness of system, after half an hour, make be less than-0.098MPa of vacuum tightness, remove the moisture generating in copolycondensation, react after 2 hours, stop vacuumizing, with nitrogen, recover normal pressure, continue to pass into nitrogen and cool to 180 ℃, the trimellitic acid 1,2-anhydride that adds table 6 formula consumption, be that routine 1-1 is 2.5g, example 1-2 is 5g, example 1-3 is 7.5g, example 1-4 is 10.0g.React after 2 hours sampling detecting acid number.Cooling discharge, obtains aqueous dispersion type vibrin, measures its number-average molecular weight (Mn), weight-average molecular weight (Mw) and molecular weight distributing index (Mw/Mn) with gel permeation chromatography (GPC).
Take 10g vibrin, add 15g acetone to be dissolved, in high-speed stirring, adding neutralizing agent triethylamine that solution is neutralized to pH value is 7, then drip deionized water 15g, make polyester water dispersion, observe the outward appearance of polyester water dispersion, measure the stability in storage of polyester water dispersion.
Table 7 is the consumption of trimellitic acid 1,2-anhydride acid numbers to aqueous dispersion type vibrin, Mn, Mw and Mw/Mn, the outward appearance of polyester water dispersion and the impact of stability in storage thereof, the visible increase along with trimellitic acid 1,2-anhydride consumption, the acid number of polyester improves, Mn and Mw reduce, and Mw/Mn increases, and polyester water dispersion outward appearance and stability in storage improve.When trimellitic acid 1,2-anhydride consumption is 2～4phr, the aqueous dispersion type polyester of synthesized has suitable molecular weight and have good water dispersible, can guarantee to connect to have the polyacrylate grafting modified polyester resin forming after water miscible polyacrylate grafting chain and have good water dispersible.
The impact of table 7 trimellitic acid 1,2-anhydride consumption on polyester property
Synthesizing of second step aqueous dispersion type polyacrylate grafting modified polyester resin
The formula that carries out graft copolymerization with the synthetic aqueous dispersion type vibrin of the depolymerization end-capping reagent trimellitic acid 1,2-anhydride of different amounts and acrylic ester monomer and styrene monomer is as shown in table 8.
The synthesizing formula of table 8 aqueous dispersion type polyacrylate grafting modified polyester resin
At one, be equipped with electric mixer, logical nitrogen device, in the 1000ml four-hole glass flask of mercurythermometer and oil bath thermostat, pass into nitrogen, synthetic aqueous dispersion type vibrin 200g and ethylene glycol diethyl ether 214g be added in the first step under nitrogen protection in, stirring is warming up to 105 ℃, under this steady temperature, be added dropwise to methacrylic acid 21g, hydroxyethyl methylacrylate 30g, acetoacetoxyethyl methacrylate 30g, methyl methacrylate 90g, vinylbenzene 36g, the mixed solution of butyl acrylate 93g and initiator TBPB6g, in 3 hours, drip, be incubated after 1 hour, supplement and drip the solution being mixed with 3gTBPB and 30g ethylene glycol diethyl ether, be incubated 3 hours, obtain faint yellow translucent solution, be cooled to 60 ℃, dripping 21g triethylamine neutralizes solution, discharging, obtain the ethylene glycol diethyl ether solution of aqueous dispersion type polyacrylate grafting vibrin mass percent concentration approximately 70%.
The preparation of the 3rd step water-borne coatings and cured paint film thereof
Press table 3 basic recipe consumption, take solution, 40g aminoresin luwipal066 containing polyacrylate grafting modified polyester resin 100g, 0.24g curing catalysts BYK-450,1g flow agent BYK-333,1g defoamer BYK-028,, 10g diethylene glycol diethyl ether adds in stainless steel steel basin, high-speed stirring is uniformly dispersed, and adding deionized water dilution mixture to viscosity is that 23s(is coated with 4 glasss, 25 ℃), filter discharging, obtain polyacrylate grafting modified poly ester water-borne coatings.By this paint spay-coating in application in advance on the tinplate of curable epoxide paint film, at the temperature of 160 ℃, toast 30 minutes, obtain polyacrylate grafting modified poly ester water-borne coatings cured paint film, according to concerned countries standard, measure the glossiness of cured paint film, pencil hardness, sticking power, bending property, shock resistance and water tolerance, wherein water tolerance is to soak and measure in the warm water of 40 ℃.
Table 9 is the impacts on polyacrylic acid grafted modified poly ester water-borne coatings cured paint film performance of trimellitic acid 1,2-anhydride consumption, it is visible when trimellitic acid 1,2-anhydride consumption is 1%, the glossiness of the outward appearance of coating and stability in storage, cured paint film, shock resistance and water tolerance are all not good enough, reason is that the consumption of trimellitic acid 1,2-anhydride is incomplete to two of polyester molecule chain end-capped very little time, cause the water dispersible of polyester poor, not good enough with the water dispersible of its synthetic polyacrylate grafting modified polyester resin, the compactness of its water-borne coatings cured paint film is variation thereupon; When the consumption of trimellitic acid 1,2-anhydride is in 2～4% scopes, increase along with trimellitic acid 1,2-anhydride consumption, coating appearance and stability in storage improve, the glossiness of cured paint film improves and gradually all in higher level, water tolerance first improves afterwards and reduces, when the consumption of trimellitic acid 1,2-anhydride is 3%, the over-all properties of coating and cured paint film thereof especially water tolerance is best.The most suitable consumption of visible depolymerizing agent trimellitic acid 1,2-anhydride is 3%.
Table 9 trimellitic acid 1,2-anhydride consumption is to polyacrylate grafting modified poly ester water-borne coatings cured paint film
(1)the impact of performance
(1) solidification value is 160 ℃, set time 30min.
Embodiment 2
The present embodiment was to provide in the synthetic water decentralized vibrin stage, the impact of the consumption of tertiary carbonic acid glycidyl ester on aqueous dispersion type polyacrylate grafting modified poly ester water-borne coatings and cured paint film performance thereof.
Synthesizing of the first step aqueous dispersion type vibrin
Table 10 is to change the consumption of tertiary carbonic acid glycidyl ester, the formula of synthetic water decentralized polyester under the constant condition of the consumption that keeps other similar monomers to comprise trimellitic acid 1,2-anhydride.
Press table 10 formula batching, by the technological process of embodiment 1 the first step, carry out copolycondensation, synthetic water decentralized polyester.From table 10, tertiary carbonic acid glycidyl ester consumption in 0～3.6% scope, formed aqueous dispersion type vibrin outward appearance homogeneous transparent; But when consumption is increased to 4.8%, copolycondensation system generation gelation, formed product can not be for next step graft reaction.
The formula of the aqueous dispersion type vibrin that the synthetic tertiary carbonic acid glycidyl ester consumption of table 10 is different
(1)the quality of finger tertiary carbonic acid glycidyl fat and the per-cent (lower same) that participates in copolycondensation monomer (partially except phthalic acid) total mass.
Synthesizing of second step aqueous dispersion type polyacrylate grafting modified polyester resin
With the different aqueous dispersion type vibrin of tertiary carbonic acid glycidyl lipid structural unit content respectively the grafted monomer identical with kind and consumption carry out solution graft copolymerization reaction, with synthetic water decentralized polyacrylate grafting modified polyester resin, raw materials used kind and consumption are identical with embodiment 1 second step, and graft copolymerization condition is also identical with embodiment 1 second step with technological process.
The formula that carries out free-atom aqueous solution graft copolymerization synthetic water decentralized polyacrylate grafting modified polyester resin with the different aqueous dispersion type vibrin of tertiary carbonic acid glycidyl lipid structural unit content and grafted monomer is as shown in table 11.
The synthesizing formula of table 11 aqueous dispersion type polyacrylate grafting modified polyester resin
The 3rd step
The basic recipe providing according to table 3 and embodiment 1 the 3rd step provides joins paint and the preparation of spraying curing process and take the polyacrylate grafting modified poly ester water-borne coatings that aminoresin luwipal066 is solidifying agent, after spraying, at 160 ℃, solidifies.Table 12 is the impacts on polyacrylate grafting modified poly ester water-borne coatings and cured paint film performance thereof of the consumption of tertiary carbonic acid glycidyl fat.The consumption of visible tertiary carbonic acid glycidyl fat is in 0～3.6% scope, and prepared polyacrylate grafting modified poly ester water-borne coatings has good outward appearance and satisfactory stability; The glossiness of its cured paint film and water tolerance slightly reduce after first improving, and reach best water when consumption is 2.4%, illustrate that tertiary carbonic acid glycidyl fat can improve glossiness and the water tolerance of cured paint film, and its optimum amount is 2.4%.
Table 12 tertiary carbonic acid glycidyl fat consumption is to polyacrylate grafting modified poly ester water-borne coatings and cured paint film thereof
(1)the impact of performance
(1) solidification value is 160 ℃, set time 30min.
Embodiment 3
Embodiment 3 investigates the impact on its water-borne coatings cured paint film performance of polyacrylate grafting modified poly ester that aqueous dispersion type amount of polyester is different.Because the vibrin for graft modification is all same aqueous dispersion type vibrin, thus can be disposable the aqueous dispersion type vibrin of synthetic enough consumptions for the preparation of the different polyacrylate grafting modified polyester resin of aqueous dispersion type amount of polyester.
The first step, with one, be equipped with electric mixer, logical nitrogen device, mercurythermometer, water trap, the 2000ml there-necked flask of vacuum extractor and oil bath thermostat is made reactor synthetic water decentralized vibrin, the consumption of various monomers is as follows: 2-methyl isophthalic acid, ammediol 204g, 1, 4-cyclohexanedimethanol 186g, 1, 6-hexylene glycol 64g, tertiary carbonic acid glycidyl fat 24g, 1, 4-cyclohexane cyclohexanedimethanodibasic 222g, HHPA 199g, 1, 6-hexanodioic acid 47g, terephthalic acid 54g, depolymerization end-capping reagent trimellitic acid 1,2-anhydride (adding afterwards) 30g, technological process according to embodiment 1 the first step is carried out copolycondensation, synthesize aqueous dispersion type vibrin.
Second step is made reactor with a 1000ml four-hole boiling flask that has been equipped with electric mixer, logical nitrogen device, mercurythermometer and oil bath thermostat and is carried out graft copolymerization according to embodiment 1 second step technological process, the aqueous dispersion type polyacrylate grafting modified polyester resin that synthesizing polyester content is different, prepares its water-borne coatings and cured paint film with aminoresin luwipal066 as solidifying agent according to the technological process of embodiment 1 the 3rd step.Table 13 is synthesizing formulas of the aqueous dispersion type polyacrylate grafting modified polyester resin that amount of polyester is different.
The synthesizing formula of the aqueous dispersion type polyacrylate grafting modified polyester resin that table 13 amount of polyester is different
Table 14 is the impacts on polyacrylate grafting modified poly ester water-borne coatings and cured paint film performance thereof of the consumption of aqueous dispersion type vibrin, and solidifying agent used is aminoresin luwipal066.Visible paint film all has good performance, at polyester/grafted monomer mass ratio, is wherein 40/60 o'clock, and glossiness and the water tolerance of paint film are best.
Table 14 amount of polyester is to polyacrylate grafting modified poly ester paint solidification paint film
(1)the impact of performance
(1) solidification value is 160 ℃, set time 30min.
Embodiment 4
According to the aqueous dispersion type polyacrylate grafting modified polyester resin of the reaction conditions of the first step described in the basic recipe of table 3 and table 4 synthetic water decentralized vibrin and polyacrylate grafting modified polyester resin and embodiment 1 and second step and the synthetic enough consumptions of operating procedure, for the present embodiment and embodiment 5, prepare water-borne coatings and cured paint film thereof.The technological process of preparing water-borne coatings and cured paint film thereof is identical with embodiment 1 the 3rd step.
Table 15 is under aqueous dispersion type polyester/grafted monomer mass ratio is fixed as 40/60 condition, the impact of the consumption of amino resin curing agents luwipal066 on polyacrylate grafting modified poly ester water-borne coatings cured paint film performance, it is visible when consumption is 30phr, the performance of cured paint film especially water tolerance is not good enough, when consumption is 35phr～50phr, cured paint film has good performance, and especially glossiness and water tolerance are higher.When aminoresin consumption is 40phr, glossiness and the water tolerance of cured paint film reach optimum level.
The consumption of table 15 amino resin curing agents is to polyacrylate grafting modified poly ester water-borne coatings cured paint film
(1)the impact of performance
(1) solidification value is 160 ℃, set time 30min.
Table 16 is to make solidifying agent with aminoresin luwipal066, its consumption is while 40phr and set time being 30min, the impact of solidification value on polyacrylate grafting modified poly ester water-borne coatings cured paint film performance, it is visible when solidification value is 145 ℃, the poor performance of cured paint film, especially glossiness and water tolerance are relatively low, in solidification value, are within the scope of 150～165 ℃, cured paint film has good performance, and especially glossiness and water tolerance obviously improve; In the time of 160 ℃, the performance of cured paint film reaches optimum level.
Table 16 solidification value is to polyacrylate grafting modified poly ester water-borne coatings cured paint film
(1)the impact of performance
(1) set time 30min.
Embodiment 5
The embodiment 4 aqueous dispersion type polyacrylate grafting used modified polyester resin of take is raw material, take aziridine Sac-100 as solidifying agent, and the technological process of preparing water-borne coatings providing with table 3 prepares water-borne coatings and spraying is solidified.The water-borne coatings that the aziridine Sac-100 of take is solidifying agent preparation belongs to two-component coating, need in 6 hours after adding aziridine hardener, be finished, and long meeting storage period causes coating automatically to solidify and lost efficacy.
Table 17 and table 18 are respectively consumption and the impact of solidification value on polyacrylate grafting modified poly ester water-borne coatings cured paint film performance of aziridine Sac-100 solidifying agent.From table 17, when solidification value is 130 ℃, at aziridine Sac-100 consumption, be within the scope of 20phr～40phr, cured paint film has good performance, and when consumption is 25phr, glossiness and the water tolerance of cured paint film reach best level.From table 18, with aziridine, make solidifying agent, when its consumption is 25phr, solidification value is in the scope of 120-140 ℃, cured paint film all has good performance, and from saving the energy and guaranteeing that cured paint film has premium properties and weighs, solidification value is advisable with 130 ℃.Visible with table 16 contrast with table 18, the solidification value that aziridine Sac-100 can make cured paint film performance reach optimum level is starkly lower than aminoresin luwipal066, and aziridine Sac-100 consumption is also obviously lower simultaneously.
The consumption of table 17 aziridine hardener is to cured paint film
(1)the impact of performance
(1) solidification value is 130 ℃;
(2) in 100phr polyacrylate grafting modified poly ester, add the mass fraction of aziridine Sac-100 solidifying agent.
When table 18 is made solidifying agent with aziridine, solidification value is to cured paint film
(1)the impact of performance
(1) set time 30min.
Embodiment 6
The present embodiment was to provide in the synthetic water decentralized vibrin stage, the impact on aqueous dispersion type polyacrylate grafting modified poly ester water-borne coatings and cured paint film performance thereof of the kind of copolycondensation monomer and consumption.
Synthesizing of the first step aqueous dispersion type vibrin
At the alcohol that maintains copolycondensation monomer: under the condition that sour mol ratio is 1.3:1, progressively increase containing tertiary carbon hydrogen atom monomer 2-methyl isophthalic acid, the formula of the consumption of ammediol is shown in table 19; Reduce the kind containing tertiary carbon hydrogen atom monomer, the formula that adds the kind that is rich in methylene radical monomer is shown in table 20; Adopt containing tertiary carbon hydrogen atom monomer, and be rich in methylene radical monomeric species, only do not use hexanodioic acid, and the few formula of its consumption is shown in table 21.
The formula batching providing by table 19, table 20 and table 21, carries out copolycondensation by the technological process of embodiment 1 the first step, synthetic molecules chain structure and form altogether 9 kinds of different aqueous dispersion type vibrin.
Table 19 synthesizes 2-methyl isophthalic acid, the formula of the aqueous dispersion type vibrin that ammediol consumption is different
The formula of the aqueous dispersion type vibrin that the synthetic copolycondensation monomeric species of table 20 is different
The synthetic formula that does not contain the aqueous dispersion type vibrin of tertiary carbon hydrogen atom of table 21
Synthesizing of second step aqueous dispersion type polyacrylate grafting modified polyester resin
Press graft copolymerization condition and the technological process of embodiment 1 second step, with each aqueous dispersion type vibrin, carry out solution graft copolymerization with acrylic ester monomer, styrene monomer and the initiator TBPB of same formula and react synthetic water decentralized polyacrylate grafting modified polyester resin.Its synthesizing formula is: polyester/grafted monomer mass ratio 40/60, aqueous dispersion type polyester 200g, ethylene glycol diethyl ether 214g, methacrylic acid 21g, hydroxyethyl methylacrylate 30g, acetoacetoxyethyl methacrylate 30g, methyl methacrylate 90g, vinylbenzene 36g, butyl acrylate 93g, initiator TBPB6g, adds initiator TBPB3g and is dissolved in 30g ethylene glycol diethyl ether, neutralizing agent triethylamine 21g.
The preparation of the 3rd step water-borne coatings and cured paint film thereof
The basic recipe providing according to table 3 and embodiment 1 the 3rd step provides joins paint and the preparation of spraying curing process and take the polyacrylate grafting modified poly ester water-borne coatings that aminoresin Luwipal066 is solidifying agent, after spraying, with 160 ℃, solidifies.
Table 22, table 23 and table 24 are the impacts on water-borne coatings and cured paint film performance thereof of the different polyacrylate grafting modified polyester resin of polyester backbone structure and composition.The type of table 22, table 23 and table 24 aqueous dispersion type polyester used is corresponding with table 19, table 20 and table 21 successively.
Table 222-methyl isophthalic acid, the consumption of ammediol is to polyacrylate grafting modified poly ester water-borne coatings and cured paint film thereof
(1)the impact of performance
Note: 160 ℃ of (1) solidification values, set time 30min.
The kind of table 23 copolycondensation monomer is to polyacrylate grafting modified poly ester water-borne coatings and cured paint film thereof
1the impact of performance
Note: 160 ℃ of (1) solidification values, set time 30min.
Table 24 without the copolycondensation monomer of tertiary carbon hydrogen atom to polyacrylate grafting modified poly ester water-borne coatings and cured paint film thereof
1the impact of performance
Note: 160 ℃ of (1) solidification values, set time 30min.
In the copolycondensation monomer of table 19, table 20 and table 21, monomer containing tertiary carbon hydrogen atom has 2-methyl isophthalic acid, ammediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexane cyclohexanedimethanodibasic and HHPA, the monomer that is rich in methylene radical has 1,6-hexylene glycol, tertiary carbonic acid glycidyl ester, 1,6-hexanodioic acid, nonane diacid and sebacic acid; And neopentyl glycol, ethylene glycol, TriMethylolPropane(TMP), terephthalic acid, m-phthalic acid are neither containing tertiary carbon hydrogen atom, also containing methylene radical hydrogen atom.Visible with table 20 and table 21 contrast with table 19, when synthetic aqueous dispersion type vibrin molecular chain is rich in tertiary carbon hydrogen atom, its polyacrylate grafting modified poly ester water-borne coatings has good outward appearance and stability in storage, its cured paint film has good physical and mechanical properties, and especially glossiness and water tolerance reach higher level; When the tertiary carbon hydrogen atom of synthetic aqueous dispersion type vibrin molecular chain reduces and methylene radical while increasing, the outward appearance of its polyacrylate grafting modified poly ester water-borne coatings and stability in storage change little, but the physical and mechanical properties of its cured paint film decreases, glossiness and water tolerance obviously reduce; When synthetic aqueous dispersion type vibrin molecular chain is containing tertiary carbon hydrogen atom and methylene radical content also seldom time, the outward appearance of polyacrylate grafting modified poly ester water-borne coatings and the physical and mechanical properties of cured paint film thereof of synthesized are all not good enough, and glossiness and water tolerance significantly decline.Reason is that when polyester molecule chain is rich in tertiary carbon hydrogen atom, percentage of grafting is higher in polyester and acrylic ester monomer and styrene-grafted copolymerization system, causes the consistency of vibrin and formed acrylic styrene copolymer better; When the tertiary carbon hydrogen atom content of polyester molecule chain reduces and while increasing the content of methylene radical, the percentage of grafting of system declines, and causes the consistency decline of vibrin and formed acrylic styrene copolymer; When polyester molecule chain is not containing tertiary carbon hydrogen atom, and methylene radical content is also seldom time, the consistency of the formed acrylic styrene copolymer of vibrin is poor, macroface separation even occurs and the outward appearance of its water-borne coatings of grievous injury and the over-all properties of cured paint film thereof especially glossiness and water tolerance.
Embodiment 7
The aqueous dispersion type polyester synthesizing with embodiment 3 carries out solution graft copolymerization with different types of grafted monomer respectively and reacts, synthetic water decentralized polyacrylate grafting modified polyester resin, and the formula of its graft copolymerization system is as shown in Table 25.Paint and spraying curing process preparation are provided described in the basic recipe providing by table 5 and embodiment 1 the 3rd step and take the polyacrylate grafting modified poly ester water-borne coatings that aminoresin Luwipal066 is solidifying agent, after spraying, at 160 ℃, solidify.Table 26 is the impacts on polyacrylate grafting modified poly ester water-borne coatings cured paint film performance of different types of grafted monomer, visible each routine cured paint film all has good over-all properties, wherein, when adding methacrylic acid benzyl ester (routine 7-1) or isobornyl methacrylate (routine 7-2), the glossiness of cured paint film is higher.
Table 27 shows, the cured paint film of the polyacrylic acid grafted modified poly ester water-borne coatings of preparing with different types of grafted monomer while making solidifying agent with aziridine has good over-all properties equally.
The formula of different types of grafted monomer aqueous dispersion type polyacrylate grafting modified poly ester for table 25
When table 26 is made linking agent with aminoresin, different types of grafted monomer is to polyacrylate grafting modified poly ester water-borne coatings cured paint film
(1)the impact of performance
Note: 160 ℃ of (1) solidification values, set time 30min.
When table 27 is made solidifying agent with aziridine, different types of grafted monomer is to polyacrylate modified aqueous polyester paint solidification paint film
(1)the impact of performance
Note: 130 ℃ of (1) solidification values, set time 30min;
(2) in 100phr polyacrylate grafting modified polyester resin, add the mass fraction of aziridine Sac-100 solidifying agent.
Embodiment 8
In a 1000ml four-hole boiling flask that has been equipped with prolong and receptor, electric mixer and vacuum extractor, add the aqueous dispersion type vibrin 100g being synthesized by embodiment 3.Add 125g acetone by its dissolving and stir, then add neutralizing agent triethylamine 5g, slowly add deionized water 180g in stirring at normal temperature, polyester liquid is converted into emulsion, start vacuum extractor extract acetone to its less residue in quality of the emulsion 5%, obtain polyester water dispersion.In this polyester water dispersion, the dry solids content of polyester approximately 33%.In stirring, add 50g solidifying agent aminoresin Luwipal066,1g flow agent BYK-333,1g defoamer BYK-028,10g ethylene glycol monobutyl ether (BCS), adding deionized water that system is diluted to viscosity is that 24s(is coated with-4 glasss, 25 ℃), filter discharging, obtain waterborne polyester coating, with spray gun, coating is evenly sprayed on the dark paint film of tinplate, until moisture evaporation, to filming after sub-light, puts into baking oven, at 160 ℃ of temperature, toast 30min, obtain the waterborne polyester paint solidification paint film that polyester molecule chain is rich in tertiary carbon hydrogen atom.
The aqueous dispersion type polyester 100g synthesizing with the routine 6-8 of embodiment 6 table 21, prepares polyester molecule chain by above-mentioned batching and technological process and without tertiary carbon hydrogen atom exists, only contains waterborne polyester coating and the cured paint film thereof of a small amount of methylene radical.
Polyester molecule chain be rich in the waterborne polyester paint solidification paint film of tertiary carbon hydrogen atom and polyester molecule chain without tertiary carbon hydrogen atom exists only containing the performance of the waterborne polyester paint solidification paint film of a small amount of methylene radical respectively as shown in 8-1 as routine in table 28 and routine 8-2.Visible with the routine 6-8 contrast of the embodiment routine 1-3 of 1 table 9 and embodiment 6 table 23, lower and water tolerance is very poor without the glossiness of the waterborne polyester paint solidification paint film of graft modification.
The performance of table 28 waterborne polyester paint solidification paint film
Embodiment 9
The synthesizing formula of aqueous dispersion type polyacrylate resin is shown in table 29.In a four-hole boiling flask that is equipped with agitator, prolong, thermometer and oil bath heating unit, add solubility promoter; under nitrogen protection, be warming up to 110 ℃; monomer, Diisopropyl azodicarboxylate and the lauryl mercaptan mixed solution of formula consumption are splashed in four-hole boiling flask by constant pressure funnel; in 4h, drip off insulation 1h.With Virahol, dissolve Diisopropyl azodicarboxylate, added into four-hole boiling flask, insulation 3h, obtains colourless translucent copolymer solution.Be cooled to 60 ℃, dripping triethylamine, resin is neutralized to degree of neutralization is 80% to obtain water white water-dispersed acrylic ester resin.
The solution, 40g aminoresin Luwipal066,0.2g curing catalysts BYK-450,1g flow agent BYK-333,1g defoamer BYK-028, the 10g ethylene glycol monobutyl ether (BCS) that take moisture decentralized polyacrylate resin 100g add in stainless steel steel basin, high-speed stirring is even, adding deionized water that system is diluted to viscosity is that 23s(is coated with-4 glasss, 25 ℃), filter discharging, obtain polyacrylic ester water-borne coatings.This coating is sprayed on the dark paint film of tinplate by GB GB1727-92, films normal temperature levelling 15 minutes, then put into baking oven with 160 ℃ of bakings 30 minutes, obtain cured paint film.
The water-borne coatings of preparing with the synthetic aqueous dispersion type polyacrylate resin of different ingredients, the performance of its cured paint film is shown in table 30.Visible with the routine 1-3 of table 9 and the routine 6-8 contrast of table 21 respectively with the routine 9-1 of table 30 and routine 9-2, under the grafted monomer kind condition identical with proportioning, the glossiness of the glossiness of polyacrylic ester water-borne coatings cured paint film and polyacrylate grafting modified poly ester water-borne coatings cured paint film is suitable, and the former water tolerance is significantly lower than the latter.The routine 9-3 of table 29 is the synthesizing formula of common aqueous dispersion type polyacrylic ester, and the water-borne coatings cured paint film of being prepared with it as seen by the routine 9-3 of table 30 also has higher glossiness, but water tolerance is also very poor.As can be seen here, after using acrylic ester monomer and styrene monomer to the graft modification of aqueous dispersion type polyester, to improving the water tolerance of its water-borne coatings cured paint film, there is synergistic effect.
The formula that feeds intake of table 29 water polyacrylic acid resin
The performance of table 30 water polyacrylic acid paint solidification paint film
Claims (10)
1. a preparation method for polyacrylate grafting modified poly ester water-borne coatings, its feature comprises the steps:
(1) utilize the synthetic aqueous dispersion type polyester with graft reaction activity of dibasic alcohol, epoxy monomer, diprotic acid and acid anhydrides, then with water-soluble solubility promoter, dissolved and form polyester liquid;
(2) in above-mentioned solution, drip the mixed solution that function monomer, acrylic ester monomer, styrene monomer and organic peroxide evocating agent form, carry out copolyreaction, make aqueous dispersion type polyacrylate grafting modified polyester resin lipoprotein solution;
(3) in polyacrylate grafting modified polyester resin lipoprotein solution, add neutralizing agent, solidifying agent, coatings additive(s) and deionized water to be mixed with water-borne coatings.
2. a kind of preparation method of polyacrylate grafting modified poly ester water-borne coatings according to claim 1, the aqueous dispersion type vibrin described in it is characterized in that with graft reaction activity is with containing the dibasic alcohol of tertiary carbon hydrogen atom and diprotic acid, containing dibasic alcohol, diprotic acid and the acid anhydrides of methylene radical hydrogen atom, with the mix monomer of the substituent epoxide of aliphatic chain, through copolycondensation, makes; Described dibasic alcohol is 2-methyl isophthalic acid, ammediol, 1,4-cyclohexanedimethanol, 1, two or more of 6-hexylene glycol, described diprotic acid is 1,4-cyclohexane cyclohexanedimethanodibasic, 1,6-hexanodioic acid, two or more of nonane diacid, sebacic acid, described acid anhydrides is HHPA, and described epoxy monomer is the substituent tertiary carbonic acid glycidyl ester of band aliphatic chain.
3. a kind of preparation method of polyacrylate grafting modified poly ester water-borne coatings according to claim 1, it is characterized in that adding a kind of diprotic acid or polyprotonic acid to carry out depolymerization reaction to reduce the molecular weight of polyester to polyester molecule chain in the reaction later stage of synthesizing polyester, and make two ends of the polyester molecule chain of synthesized respectively be with one or two carboxyl and there is water dispersible.
4. a kind of preparation method of polyacrylic acid grafted modified poly ester water-borne coatings according to claim 1, it is characterized in that described dissolved polyester solubility promoter used is water-soluble and the polar solvent reactionless activity of linking agent, in final synthetic aqueous dispersion type polyacrylate grafting modified poly ester solution, the mass percentage content of solubility promoter is 20%～50%.
5. the preparation method of a kind of polyacrylic acid grafted modified poly ester water-borne coatings according to claim 4, is characterized in that described solubility promoter is wherein one or more of ethylene glycol diethyl ether, diethylene glycol diethyl ether and pimelinketone.
6. a kind of preparation method of polyacrylic acid grafted modified poly ester water-borne coatings according to claim 1, it is characterized in that described acrylic ester monomer is methacrylic acid, vinylformic acid, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate, acetoacetoxyethyl methacrylate, methyl methacrylate, Tert-butyl Methacrylate, phenyl methacrylate, methacrylic acid benzyl ester, isobornyl methacrylate, butyl methacrylate, one or more of butyl acrylate and Isooctyl acrylate monomer, described styrene monomer is vinylbenzene.
7. a kind of preparation method of polyacrylate grafting modified poly ester water-borne coatings according to claim 1, it is characterized in that described function monomer is one or both in methacrylic acid and vinylformic acid, one or more in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410 and Propylene glycol monoacrylate and acetoacetoxyethyl methacrylate.
8. a kind of preparation method of polyacrylate grafting modified poly ester water-borne coatings according to claim 1, it is characterized in that described in and polyacrylate grafting modified polyester resin lipoprotein solution neutralizing agent used be the amine neutralizing agent with the reactionless activity of linking agent, comprise one or more in Trimethylamine 99, triethylamine, xylidine, Diethyl Aniline, triphenylamine.
9. a kind of preparation method of polyacrylate grafting modified poly ester water-borne coatings according to claim 1, is characterized in that described water-borne coatings solidifying agent used is amino resin curing agents or aziridine hardener.
10. a polyacrylate grafting modified poly ester water-borne coatings of preparing according to the method described in any one in claim 1-9.
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