CN101870844A - Preparation method of nano particle/polyester composite coating and composite coating prepared by same - Google Patents
Preparation method of nano particle/polyester composite coating and composite coating prepared by same Download PDFInfo
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- CN101870844A CN101870844A CN200910134122A CN200910134122A CN101870844A CN 101870844 A CN101870844 A CN 101870844A CN 200910134122 A CN200910134122 A CN 200910134122A CN 200910134122 A CN200910134122 A CN 200910134122A CN 101870844 A CN101870844 A CN 101870844A
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Abstract
The invention relates to a preparation method of nano particle/polyester composite coating and composite coating obtained by the preparation method. The method is as follows: firstly preparing nano particle powder, a first resin and the nano particle slurry of the good solvent of the first resin; then mixing the nano particle slurry and a second monomer to carry out direct esterification polycondensation or interesterification polycondensation so as to obtain a nano particle/polyester compound; finally using xylene/butyl acetate complex solvent to prepare the compound into a coating product the solid content of which is 30-70wt%.The coating film prepared by the composite coating of the invention has good UV absorption property and good hardness; in the method of the invention, additional dispersant does not need to be added for the preparation of nano particle slurry, thus reducing the production cost, having simple operation and being suitable for nano particles with organically modified surfaces or surfaces which are not organically modified. The method of the invention can be widely applied to the preparation filed of organic/inorganic composite coatings.
Description
Technical field
The present invention relates to a kind of preparation method of nano particle/polyester composite coating and the composite coating for preparing by this method.The surface of nanoparticle is coated with polyester molecule in the composite coating of the present invention.
Background technology
Prior art document CN1637091A has reported nano composite polyester resin coated material of a kind of high-solid lower-viscosity and preparation method thereof, but its silicon dioxide gel that just will have hydroxyl directly mixes aftercondensated with polyvalent alcohol, diprotic acid, and the consistency and the stability of the coating products that obtains make moderate progress.
The open CN1583880A of Chinese patent application discloses a kind of method for preparing polyester/phyllosilicate nano-composite material, this method is included in layered silicate and exists down, make each monomer of polyester carry out the direct esterification polycondensation or carry out ester exchange polycondensation, thereby obtain polyester/phyllosilicate nano-composite material.In the method, monomer as polyester, must use and have sulfonic aromatic dicarboxylate, make polyester and silicate plate interlayer have special interaction by introducing this ionic group of sulfonic group, thereby increase the consistency of the two, make the silicate lamella in polyester matrix, peel off better and dispersion equably.
The present invention is in the preparation nano particle/polyester composite coating, by nanoparticle is carried out the reactivity coating with polyester monocase before, earlier the nanoparticle powder is utilized first resin and good solvent thereof to make the nanoparticle slurry, in the presence of this nanoparticle slurry, make the second polyester monocase polymerization then, obtain the nano particle/polyester complex body, thereby make nanoparticle in nano particle/polyester composite coating, disperse equably, and have outstanding dispersion stabilization, this method has extensive applicability more to various nanoparticles and polyester system.
Summary of the invention
Therefore, the present invention provides a kind of method for preparing nano particle/polyester composite coating in first aspect, and this method comprises:
(a) mixture with the good solvent of nanoparticle powder, first resin and first resin is uniformly dispersed, and makes the nanoparticle slurry;
(b) the nanoparticle slurry that step (a) is obtained mixes with second polyester monocase, carries out polyreaction under normal pressure, obtains the nano particle/polyester complex body; And
(c) the nano particle/polyester complex body that step (b) is obtained is mixed with the coating products that solids content is 30-70 weight % with dimethylbenzene/butylacetate double solvents.
The present invention provides a kind of nano particle/polyester composite coating by method for preparing on the other hand, and wherein the surface of nanoparticle is coated with polyester molecule.This nano particle/polyester composite particles homodisperse in the good solvent of polyester.
These and other purposes of the present invention and advantage will become cheer and bright after the reference accompanying drawing reads whole specification sheets.
Description of drawings
Fig. 1 is the powder that obtained by the embodiment of the invention 3 gained titanium dioxide/polyester composite coatings and the infrared spectrogram of blank polyester coating sample powder;
The sem photograph of filming of Fig. 2 for obtaining by gained titanium dioxide/polyester composite coating in the embodiment of the invention 1 and 3 respectively; With
Fig. 3 is filming to ultraviolet shielding rate of being obtained by the embodiment of the invention 1 and Comparative Examples 1 gained titanium dioxide/polyester composite coating and blank polyester sample coating.
Detailed Description Of The Invention
Owing to adopted in the methods of the invention the step for preparing first nanometer particle slurry, can be so that the nanometer particle disperses more evenly in coating system, and the structure of the nano particle/polyester composite particles that the method obtains is more stable, thereby so that the gained nano particle/polyester composite coating has higher rate of ultraviolet shield.
Dispersed better in order to obtain, more stable coating products, the mixture of the good solvent of nanometer particle powder, the first resin and the first resin high speed shear 0.5～6 hour and/or ultrasonic oscillation under 3000rpm～5000rpm rotating speed can be processed 0.5～30 minute in the step (a), be uniformly dispersed. The product that step (a) obtains also can grind further dispersion.
The operation of step (a) is preferably carried out under protective atmosphere, and the gas of this protective atmosphere can also use the gas that the operation of step (a) is not had the significant adverse impact, for example nitrogen except inert gas.
The nanometer particle is the inorganic and/or organic nano particle that is usually comprised in the coating among the present invention, and preferred inorganic nano-particle is particularly preferably and is selected from least a in the group that is comprised of titanium dioxide, silica and aluminium oxide. These nanometer particles can be surface organic modification or without organically-modified, particle diameter is between 10～500nm, between the preferred 10-100nm, more preferably between the 10-50nm. In addition, these nanometer particles can also be that the surface coats through sial. These modified Nano particles or surface can the Hombitec trade name be provided by Sachtleben company through the nanometer particle that sial coats.
In the method for the invention, the good solvent of used the first resin is not participate in the solvent that reacts in the preparation process of nano particle/polyester complex in the step (a), the boiling point of this solvent should be lower than 170 ℃, and example comprises and is selected from least a in the group that is comprised of acetone, chloroform and dimethylbenzene (comprising ortho-xylene, meta-xylene and paraxylene).
In the method for the invention, the part by weight of the good solvent of the first resin and the first resin can change in wide scope in the step (a), and usually, this weight ratio is between 0.1: 100 to 10: 100, preferably between 0.5: 100 to 3: 100.
In the method for the invention, nanoparticle powder concentration in the gained nanoparticle slurry in step (a) can change in wide region, and usually, this concentration is 1-250g/L, preferred 5-50g/L.In addition, the content of nanoparticle powder is conventional for whole coating, usually, depends on the purposes that is intended to of coating, and the nanoparticle powder accounts for 0.1-25wt% in whole coating, preferred 0.1-5wt%, more preferably 1-2wt%.Preferably, the mass ratio of the nanoparticle powder and first resin is between 5: 1 to 1: 5.
In step (a), the mixture of the good solvent of nanoparticle powder, first resin and first resin at room temperature can be uniformly dispersed, make the nanoparticle slurry.
In the method for the invention, first resin is the resin that is used as base-material or matrix in the coating usually, and this resin is preferably the polymkeric substance that contains ester group in the repeating unit.This first resin can be selected from contain ester group in the repeating unit acrylic resin (promptly, the polymkeric substance of the ester that acrylic acid series unsaturated acid (comprising vinylformic acid, methacrylic acid and ethylacrylic acid etc.) and alcohol form), first polyester or its mixture, and this first polyester is preferably Synolac or other vibrin, and can be identical or different with second polyester hereinafter described.
In the step (b) of the inventive method, relate to the nanoparticle slurry that step (a) is obtained and mix to react with second polyester monocase.This second polyester monocase is used for final polymerization and forms second polyester.Second polyester and first polyester mentioned above can be identical or different.
Operable second polyester (or first polyester) is the polymerisate that at least a binary/polyvalent alcohol and at least a diprotic acid obtain through polycondensation, perhaps, this second polyester (or first polyester) can be the polymerisate that the ester of at least a binary/polyvalent alcohol, at least a diprotic acid and at least a diprotic acid obtains by transesterify and polycondensation.
Therefore, in order to obtain the nano particle/polyester complex body in the step (b), can adopt two kinds of methods of direct esterification-polycondensation process or ester exchange polycondensation method to prepare.
Direct esterification-polycondensation process:
In the method, in order to obtain the nano particle/polyester complex body in the step (b), be second polyester monocase with at least a binary/polyvalent alcohol and at least a diprotic acid, in the presence of polycondensation catalyst, carry out polyreaction.This polycondensation is conventional alkyd polycondensation, usually, this polycondensation is 100-260 ℃, preferred 130-230 ℃, more preferably carries out (referring to " Methoden der Organischen Chemie (organic chemistry method) " under 220-230 ℃ and raw materials melt or the ebullient condition in temperature in inert atmosphere, Houben-weyl, Georg Thieme Verlag, Stuttgart, 1963, the 14/2nd volume, 1-5 page or leaf, 21-23 page or leaf and 40-44 page or leaf).Polycondensation catalyst usually adopts and is selected from least a in the group of being made up of zinc acetate, Cobaltous diacetate, aluminum alkoxide, dibutyltin oxide, toxilic acid dibutyl tin and tetrabutyl titanate, and its consumption is a convention amount, is generally about the 0.01wt% of total monomer weight.It can be equimolar amount that the consumption of binary/polyvalent alcohol and diprotic acid should make the contained carboxyl of contained hydroxyl of binary/polyvalent alcohol and diprotic acid compare usually, also can surpass or not as good as equimolar amount; Advantageously, the mol ratio of hydroxyl that binary/polyvalent alcohol is contained and the contained carboxyl of diprotic acid is between 5: 3 to 1: 1, and preferred molar ratio is 4: 3.
The ester exchange polycondensation method:
In the method, in order to obtain the nano particle/polyester complex body in the step (b), ester with at least a binary/polyvalent alcohol, at least a diprotic acid and at least a diprotic acid is second polyester monocase, earlier in the presence of transesterification catalyst, carry out transesterify, in the presence of polycondensation catalyst, carry out polycondensation then.This transesterify and polycondensation all are conventional, usually, be 100-260 ℃, preferred 130-230 ℃, more preferably carry out (referring to " Methoden der Organischen Chemie (organic chemistry method) " under 220-230 ℃ and raw materials melt or the ebullient condition in temperature in this transesterification reaction and each comfortable inert atmosphere of this polycondensation, Houben-weyl, Georg Thieme Verlag, Stuttgart, 1963, the 14/2nd volume, 1-5 page or leaf, 21-23 page or leaf and 40-44 page or leaf).Transesterification catalyst adopts the acetate of Zn, Mn, Mg, Ca or Co usually, polycondensation catalyst usually adopts and is selected from least a in the group of being made up of zinc acetate, Cobaltous diacetate, aluminum alkoxide, dibutyltin oxide, toxilic acid dibutyl tin and tetrabutyl titanate, and each plant demand of these catalyzer is a convention amount.Certainly, when the catalyzer that uses not only can be used as transesterification catalyst but also can be used as polycondensation catalyst, this transesterification reaction and polycondensation can combine, for example when use zinc acetate, dibutyltin oxide, tetrabutyl titanate etc. during as catalyzer.The ester of diprotic acid is equivalent to diprotic acid in transesterification reaction and polycondensation.Thereby, it can be equimolar amount that the consumption of the ester of binary/polyvalent alcohol, diprotic acid and diprotic acid should make the contained carboxyl of contained hydroxyl of binary/polyvalent alcohol and diprotic acid compare with the contained ester group sum of diester usually, also can surpass or too late equimolar amount, advantageously, the mol ratio of the ester group sum that carboxyl that hydroxyl that binary/polyvalent alcohol is contained and diprotic acid are contained and diester are contained is between 5: 3 to 1: 1, and preferred molar ratio is 4: 3.
The diprotic acid that is applicable to the inventive method can be: aliphatic diacid, alicyclic diacid, aromatic diacid and/or heterocycle family diacid.Preferred these diprotic acid can be that the part halogen replaces and/or undersaturated, and halogen herein comprises fluorine, chlorine, bromine and iodine, preferred fluorine and chlorine.The example of suitable diprotic acid comprises: Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, phthalic acid, m-phthalic acid, terephthalic acid, hexahydrophthalic acid, six hydrogen terephthalic acids, two chloro-o-phthalic acids, tetrachlorophthalic acid, endo-methylene group tetrahydrophthalic acid and 1,4-cyclohexane diacid; Wherein be preferably selected from the group of forming by terephthalic acid, m-phthalic acid, Succinic Acid, pentanedioic acid and hexanodioic acid one or more.
Be applicable to the inventive method binary/polyvalent alcohol can for be selected from down the group in one or more: ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, glycerol, 2,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, decanediol, dodecanol, neopentyl glycol, cyclohexanediol, 3 (4), 8 (9)-two (methylol) three ring [5.2.1.0
2,6] decanediol, 1, the two methylol hexanaphthenes of 4-, 2, two (4-hydroxyl-cyclohexyl) propane of 2-, 2, two [4-(the 2-hydroxy ethoxy)-phenyl] propane of 2-, the 2-methyl isophthalic acid, 3-dihydroxyl-propane, the 2-methyl isophthalic acid, 5-dihydroxyl-pentane, 2,2,4-trimethylammonium-1,6-hexylene glycol, TriMethylolPropane(TMP), trimethylolethane, 1,2, the 6-hexanetriol, 1,2, the 4-trihydroxybutane, three-2-hydroxyethyl isocyanuric acid ester, tetramethylolmethane, N.F,USP MANNITOL, sorbyl alcohol, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, the pure and mild hydroxyl new pentane diacid of terephthaldehyde DOPCP; Preferred ethylene glycol, 1, ammediol, 1,4-butyleneglycol, glycerol, neopentyl glycol, 1,6-hexylene glycol, TriMethylolPropane(TMP) or their any mixture.
Be applicable to and be generally the lower alkyl esters of di-carboxylic acid by the ester of the diprotic acid of the inventive method (alkyl in this lower alkyl esters refers to the straight or branched alkyl with 1-4 carbon atom, especially the alkyl that has 1-2 carbon atom, for example methyl, ethyl), for example the ester of this diprotic acid can be for being selected from down in the group one or more: dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl phthalate, diethyl terephthalate, dimethyl isophthalate, diethyl phthalate, dimethyl adipate and Methyl glutarate.
The hydroxyl value that the degree that reaction is carried out in the step (b) should make the whole polymeric system that obtains is between 90-100mg KOH/g, and acid number is between 8-12mg KOH/g.
Certainly, in the method for the invention, can also comprise additive in the reaction of step (b), this additive mainly is a stablizer commonly used, comprises the phosphoric acid ester or the phosphonate ester compound of triphenylphosphate, triphenyl phosphite.These additives or stablizer exist with convention amount.
In the preferred embodiment of the inventive method, when step (b) adopted the ester exchange polycondensation method to prepare the nano particle/polyester complex body, step (b) can be decomposed into for two steps again carried out,
First kind of decomposition method:
(b-1) make the ester of at least a diprotic acid and at least a binary/polyvalent alcohol monomer under normal pressure, carry out transesterification reaction under the state of raw materials melt; With
(b-2) the nanoparticle slurry and at least a dicarboxylic acid monomer that obtain in reactant that step (b-1) is obtained and the step (a) are carrying out polycondensation under normal pressure under the state of raw materials melt, thereby obtain the nano particle/polyester complex body,
Perhaps, second kind of decomposition method:
(b-1 ') make the nanoparticle slurry that obtains in ester, at least a binary/polyvalent alcohol monomer and the step (a) of at least a diprotic acid under normal pressure, carry out transesterification reaction under the state of raw materials melt; With
(b-2 ') carrying out polycondensation with reactant and at least a dicarboxylic acid monomer that step (b-1 ') obtains under normal pressure under the state of raw materials melt, thereby obtain the nano particle/polyester complex body.
The operation of step (b) is preferably carried out under protective atmosphere, and the gas of this protective atmosphere can also use the gas that the operation of step (b) is not had the significant adverse influence, for example nitrogen except rare gas element.
In the methods of the invention, after the nano particle/polyester complex body in making step (b), can be by this nano particle/polyester complex body be prepared as the solvent of base-material with the conventional polyester that is suitable for that uses in the coating, make that solids content is 30-70 weight %, promptly obtains nano particle/polyester composite coating of the present invention.Described solvent is preferably dimethylbenzene/butylacetate double solvents, and further preferably, this double solvents is that the weight ratio of dimethylbenzene and butylacetate is 1: 1 a double solvents.
By the inventive method, make a kind of nano particle/polyester composite coating, wherein the surface of nanoparticle is coated with polyester molecule.This nano particle/polyester composite particles is homodisperse in the good solvent (as above-mentioned dimethylbenzene/butylacetate double solvents) of polyester.Certainly, can also comprise other conventional additives in this composite coating, for example the conventional coatings additive(s) of pigment, Ricinate, emulsifying agent, anti-sludging agent, anti-skinning agent, sanitas, sterilant, mould inhibitor, auxiliary rheological agents, anti-sag agent, membrane-forming agent, non-blushing thinner, flow agent, defoamer, softening agent, anti-zoned trace agent, fire retardant, static inhibitor, matting agent, inhibiter or the like.The consumption of these auxiliary agents is conventional, they can be in step (c) in the solvent preparation or add afterwards, can certainly add on other opportunity, as long as its interpolation does not influence the preparation of nano particle/polyester complex body of the present invention opportunity.
Preparing nano particle/polyester composite coating by the inventive method has the following advantages:
1, the surface is passed through organically-modified or all is applicable to the present invention without organically-modified nanoparticle, therefore need not nanoparticle is carried out special surface organic modification; In nanoparticle slurry preparation process, can not add dispersion agent simultaneously, simple to operate, need not aftertreatment, not only avoided the influence of properties-correcting agent and dispersion agent, and greatly reduced cost the finished product.
2, the good solvent that the preparation nanoparticle is starched the first required resin in the inventive method can reclaim by the cut form when the preparation nano particle/polyester composite coating, and recycle has reduced cost.
3, method provided by the invention is not only applicable to the preparation of polyester composite coating, is applicable to the compound coating of other serial organic-inorganics of preparation yet.
4. the inventive method is by before carrying out the coating of second polyester to nanoparticle, earlier the nanoparticle powder is made the nanoparticle slurry with the good solvent of first resin and this first resin, make the gained nano particle/polyester composite coating have better dispersion stabilization, nanoparticle disperses more even.
Embodiment:
Three kinds of used in the following example of the present invention nanometer products are provided by Sachtleben company with the Hombitec trade(brand)name, and its character sees the following form:
| Color/particle diameter | |
| ??1 #Nano-TiO 2 | Yellow, surface organic modification, sial coats, 10～20nm |
| ??2 #Nanometer SiO 2 | White, surface organic modification, sial coats, 300～400nm |
| ??3 #Nano-TiO 2 | White, sial coats, 10～20nm |
The acid number of being mentioned in following examples of the present invention obtains according to standard DIN EN ISO 2114_E; Hydroxyl value obtains according to standard DIN 53240-2_E.
Embodiment 1:
(1) at first, with 32g nano titanium oxide powder 1
#With 64ml first Resin A (be 1.43mol dimethyl terephthalate (DMT) and 6.15mol neopentyl glycol, 1.22mol TriMethylolPropane(TMP), 2.3mol m-phthalic acid and 2.00mol hexanodioic acid under 200～220 ℃ temperature with zinc acetate as 8 hours product of catalyzer synthesis under normal pressure; The polymerization degree and molecular weight are because of existing crosslinked can't accurately measuring, and acid number is 8mg KOH/g, and hydroxyl value is 90mg KOH/g) at room temperature mix with the 3.2L chloroform, high speed shear is 6 hours under the 3000rpm rotating speed; Ultra-sonic dispersion is 6 minutes again, is uniformly dispersed, and makes the TiO that nano titanium oxide powder content is about 10g/L
2Slurry.
(2) dimethyl terephthalate (DMT) 278.5g, neopentyl glycol 640.8g, TriMethylolPropane(TMP) 163.2g and zinc acetate catalyst 0.1912g are added in the glass reactor again, slowly be warming up to 200～220 ℃, synthesis under normal pressure is cooled to 80 ℃ after 3 hours.
(3) in the mixture that above-mentioned steps (2) makes, drip the TiO of step (1) preparation
2Slurry adds m-phthalic acid 381.2g and hexanodioic acid 287.6g subsequently successively, stirs.Slowly be warming up to 220～230 ℃, steam chloroform, react after 6 hours, often measure system acid number and hydroxyl value, acid number reaches when 8mg KOH/g and hydroxyl value reach 90mg KOH/g and is cooled to 130 ℃.
(4) in the product that above-mentioned steps (3) makes, add dimethylbenzene and butylacetate (weight ratio 1: 1) mixed solvent, be mixed with the product that solid content is 50wt%.
All carry out under nitrogen protection above-mentioned steps (1)-(3).
Comparative Examples 1
(1) at first, 64ml such as embodiment 1 described first Resin A are at room temperature mixed with the 3.2L chloroform, obtain first resin dispersion.
(2) dimethyl terephthalate (DMT) 278.5g, neopentyl glycol 640.8g, TriMethylolPropane(TMP) 163.2g and zinc acetate catalyst 0.1912g are added in the glass reactor again, slowly be warming up to 200～220 ℃, synthesis under normal pressure is cooled to 80 ℃ after 3 hours.
(3) in the mixture that above-mentioned steps (2) makes, add first resin dispersion of step (1) preparation, and 32g nano titanium oxide powder 1
#, adding m-phthalic acid 381.2g and hexanodioic acid 287.6g subsequently successively, high speed shear is 6 hours under the 3000rpm rotating speed, and ultra-sonic dispersion is 6 minutes again, is uniformly dispersed.Slowly be warming up to 220～230 ℃, steam chloroform, react after 6 hours, often measure system acid number and hydroxyl value, acid number reaches when 8mg KOH/g and hydroxyl value reach 90mg KOH/g and is cooled to 130 ℃.
(4) in the product that above-mentioned steps (3) makes, add dimethylbenzene and butylacetate (weight ratio 1: 1) mixed solvent, be mixed with the product that solid content is 50wt%.
All carry out under nitrogen protection above-mentioned steps (1)-(3).
Embodiment 2:
(1) at first, with 48g silicon dioxide powder 2
#With 24ml first resin B (be 4mol butyleneglycol, 2mol dimethyl terephthalate (DMT) and 1mol m-phthalic acid under 200～220 ℃ temperature with dibutyltin oxide as 10 hours product of catalyzer synthesis under normal pressure; Acid number is 10mg KOH/g, and hydroxyl value is 90mg KOH/g) at room temperature mix with 2.4L acetone, high speed shear is 3 hours under the 3000rpm rotating speed; Ultra-sonic dispersion is 9 minutes again, is uniformly dispersed, and makes the nanometer SiO that silicon dioxide powder content is about 20g/L
2Slurry.
(2) the nanometer SiO that dimethyl terephthalate (DMT) 557g, dimethyl isophthalate 557g, hexylene glycol 1602g, TriMethylolPropane(TMP) 306g, dibutyltin oxide 0.734g and step (1) are prepared
2Slurry adds in the glass reactor, slowly is warming up to 200～220 ℃, steams acetone, reacts to be cooled to 80 ℃ after 3 hours.
(3) in the product of step (2), add m-phthalic acid 381.2g and pentanedioic acid 260.0g successively, stir.Slowly be warming up to 220～230 ℃, react after 6 hours, often measure system acid number and hydroxyl value, acid number reaches when 12mg KOH/g and hydroxyl value reach 100mg KOH/g and is cooled to 130 ℃.
(4) in the product that above-mentioned steps (3) makes, add dimethylbenzene and butylacetate (weight ratio 1: 1) mixed solvent, be mixed with the product that solid content is 30wt%.
All carry out under nitrogen protection above-mentioned steps (1)-(3).
Embodiment 3:
(1) at first, with 16g nano titanium oxide powder 3
#With the 16ml first resin C (be acrylic resin, by 40wt% n-butyl acrylate, 40wt% methyl methacrylate, 13wt% vinylformic acid and 5wt% butylacetate, be the product that initiator obtained in 80 ℃ of synthesis under normal pressure in 8 hours with the 2wt% benzoyl peroxide; Acid number is 8mg KOH/g, and hydroxyl value is 90mg KOH/g) at room temperature mix with the 1.6L chloroform, ultra-sonic dispersion 6 minutes is uniformly dispersed, and makes the nano-TiO that titanium dioxide powder content is about 10g/L
2Slurry.
(2) dimethyl terephthalate (DMT) 278.5g, neopentyl glycol 640.8g, TriMethylolPropane(TMP) 163.2g and zinc acetate 0.1912g are added in the glass reactor, slowly be warming up to 200～220 ℃, react and be cooled to 80 ℃ after 3 hours.
(3) in the mixture that above-mentioned steps (2) makes, drip the TiO for preparing in advance
2Slurry adds m-phthalic acid 381.2g and hexanodioic acid 287.6g afterwards successively, mixes.Slowly be warming up to 220～230 ℃, steam chloroform, react after 5 hours, often measure system acid number and hydroxyl value, acid number reaches when 12mg KOH/g and hydroxyl value reach 100mg KOH/g and is cooled to 130 ℃.
(4) in the product that above-mentioned steps (3) makes, add dimethylbenzene and butylacetate (weight ratio 1: 1) mixed solvent, be mixed with the product that solid content is 50wt%.
All carry out under nitrogen protection above-mentioned steps (1)-(3).
Embodiment 4:
(1) at first, with the alumina powder of 90g median size about 13nm (with AEROXIDEAlu C trade(brand)name available from Evonik Degussa company) and the 30ml first resin D (be Synolac, the product that under 200 ℃ temperature, obtained in 10 hours as the catalyzer synthesis under normal pressure by 1.5mol hexanodioic acid, 0.25mol hexylene glycol, 0.25mol neopentyl glycol and 1mol TriMethylolPropane(TMP) with tetrabutyl titanate; The polymerization degree and molecular weight are because of existing crosslinked can't accurately measuring, and acid number is 12mg KOH/g, and hydroxyl value is 100mg KOH/g) at room temperature mix with 3L acetone, high speed shear is 3 hours under the 5000rpm rotating speed; Ultra-sonic dispersion is 3 minutes again, is uniformly dispersed, and makes the nanometer Al that alumina powder content is about 30g/L
2O
3Slurry.
(2) dimethyl isophthalate 1114g, hexylene glycol 1602g, TriMethylolPropane(TMP) 306g and tetrabutyl titanate catalyzer 0.878g are added in the glass reactor, slowly be warming up to 200～210 ℃, react and be cooled to 80 ℃ after 3 hours.
(3) in the mixture of step (2) preparation, drip the nanometer Al that the concentration for preparing in advance is about 30g/L
2O
3Slurry adds terephthalic acid 381.2g and pentanedioic acid 260.0g afterwards successively.Slowly be warming up to 220～230 ℃, steam acetone, react after 6 hours, often measure system acid number and hydroxyl value, acid number reaches when 8mg KOH/g and hydroxyl value reach 90mg KOH/g and is cooled to 60 ℃.
(4) in the product that above-mentioned steps (3) makes, add dimethylbenzene and butylacetate (weight ratio 1: 1) mixed solvent, be mixed with the product that solid content is 70wt%.
All carry out under nitrogen protection above-mentioned steps (1)-(3).
Embodiment 5:
(1) at first, with 16g nano titanium oxide powder 1
#At room temperature mix with the 1.6L chloroform with 32ml such as embodiment 1 described first Resin A, high speed shear is 3 hours under the 5000rpm rotating speed; Ultra-sonic dispersion is 6 minutes again, is uniformly dispersed, and makes the TiO that nano titanium oxide powder content is about 10g/L
2Slurry.
(2) again dimethyl terephthalate (DMT) 278.5g, neopentyl glycol 640.8g, TriMethylolPropane(TMP) 163.2g and zinc acetate catalyst 0.1912g are added in the glass reactor, slowly be warming up to 200～220 ℃, react and be cooled to 80 ℃ after 3 hours.
(3) in the product of above-mentioned steps (2) preparation, drip the nano-TiO for preparing in advance
2Slurry adds m-phthalic acid 381.2g and hexanodioic acid 287.6g subsequently successively.Slowly be warming up to 220～230 ℃, steam chloroform, react after 6 hours, often measure system acid number and hydroxyl value, acid number reaches when 8mg KOH/g and hydroxyl value reach 90mg KOH/g and is cooled to 130 ℃.
(4) in the product that above-mentioned steps (3) makes, add dimethylbenzene and butylacetate (weight ratio 1: 1) mixed solvent, be mixed with the product that solid content is 50wt%.
All carry out under nitrogen protection above-mentioned steps (1)-(3).
Embodiment 6:
(1) at first, with 8g nano titanium oxide powder 1
#At room temperature mix with the 0.8L chloroform with 16ml such as embodiment 1 described first Resin A, high speed shear is 6 hours under the 5000rpm rotating speed; Ultra-sonic dispersion is 6 minutes again, is uniformly dispersed, and makes the TiO that nano titanium oxide powder content is about 10g/L
2Slurry.
(2) again dimethyl terephthalate (DMT) 278.5g, neopentyl glycol 640.8g, TriMethylolPropane(TMP) 163.2g and zinc acetate catalyst 0.1912g are added in the glass reactor, slowly be warming up to 200～220 ℃, react and be cooled to 80 ℃ after 3 hours.
(3) in the mixture that above-mentioned steps (2) makes, drip the TiO for preparing in advance
2Slurry adds m-phthalic acid 381.2g and hexanodioic acid 287.6g subsequently successively, mixes.Slowly be warming up to 220～230 ℃, steam chloroform, react after 6 hours, often measure system acid number and hydroxyl value, acid number reaches when 12mg KOH/g and hydroxyl value reach 100mg KOH/g and is cooled to 130 ℃.
(4) in the product that above-mentioned steps (3) makes, add dimethylbenzene and butylacetate (weight ratio 1: 1) mixed solvent, be mixed with the product that solid content is 50wt%.
All carry out under nitrogen protection above-mentioned steps (1)-(3).
Test and sign:
1. structural characterization
In order to investigate the structure of the coating that nano particle/polyester composite coating that the inventive method obtains obtains, it has been carried out infrared spectra (FTIR) analyzed: sample is selected the TiO of embodiment 3 preparations for use
2/ polyester composite coating product, (the sample preparation: the TiO that gets part embodiment 3 preparations of preparation coated substrate powdered sample
2The seasoning in uncovered bottle of/polyester composite coating product is got dried bulk sample grinding and is made the coated substrate powdered sample); Instrument uses Nicolet-20sx-B type infrared spectrometer (U.S. Buddhist nun's high-tensile strength instrument company), and sweep limit is 400～4000cm
-1, resolving power is 4cm
-1, useful range from 0.02 μ m to 2000 μ m.Test result as shown in Figure 1.
The preparation of the blank polyester coating sample among Fig. 1 and embodiment 3 steps (1)-(4) are basic identical, and difference is not use TiO
2Nanoparticle makes not comprise TiO in the blank polyester coating sample
2Particle.
As seen from Figure 1, TiO
2The molecular structure of/polyester compound coating matrix and blank polyester do not have to change more substantially, and this illustrates the good solvent of employed first resin and has neither part nor lot in reaction, and the nanoparticle that adds does not exert an influence to the chemical structure of polyester yet.
2. scanning electron microscope (SEM) test:
The composite coating of embodiment 1 and embodiment 3 is made its performance of back test of filming.Concrete grammar is: add the nano titanium oxide/polyester composite coating of embodiment 1 or 3 preparations in there-necked flask, add HMMM (CYMEL 303) and catalyzer tosic acid.Add the back and stir 1h, according to GB3186-1988 (sampling of coating products) and GB 1727-92 (the general preparation method of paint film), the gained mixture is coated on the clean sheet glass (120mm*90mm), slowly be warming up to 160 ℃ and in convection oven, be heating and curing then, make and film (referring to: military favorable to the people, the coating technology basis, Beijing: Chemical Industry Press, 1999:40-41; Zeno W. Weeks, Frank N. Jones, the organic coating Science and Technology, Beijing: Chemical Industry Press, 2003:267-269).
According to the method described above behind the composite coating difference curing of coating with embodiment 1 and 3, with the configuration of surface that JSM-5600LV (JEOL Jeol Ltd.) scanning electron microscopic observation is filmed, acceleration voltage 10kv, electric current 5mA.Fig. 2 (a) is the product of embodiment 1, and Fig. 2 (b) is the product of embodiment 3.
As shown in Figure 2, can be clear that TiO in the drawings
2Particle is random shape, but has excellent dispersion and epigranular in polyester matrix.
3. the test of rate of ultraviolet shield:
(preparation of this blank polyester coating is substantially the same manner as Example 1, and difference is not use TiO for nano titanium oxide/polyester composite coating that embodiment 1 and Comparative Examples 1 are prepared respectively and blank polyester coating
2Nanoparticle makes not comprise TiO in the blank polyester coating
2Particle), according to the method described above adopt TU1901 type ultraviolet-visible spectroscopic instruments (Beijing Puxi General Instrument Co., Ltd) to test it behind (that is method described in above-mentioned scanning electron microscope (SEM) test) curing of coating to ultraviolet shielding rate.
As seen from Figure 3, the compound coating matrix of embodiment 1 preparation is to the product of ultraviolet shielding rate significantly better than Comparative Examples 1, and this should be owing to nano-TiO in the compound coating matrix of embodiment 1 preparation
2Disperse more even, the cause that the aggregate median size is less.The step that description of step (a) prepares nanoparticle slurry in advance can make prepared coating have better dispersion stabilization about wherein nanoparticle, thereby makes coating have higher rate of ultraviolet shield.
Claims (13)
1. method for preparing nano particle/polyester composite coating comprises:
(a) mixture with the good solvent of nanoparticle powder, first resin and first resin is uniformly dispersed, and makes the nanoparticle slurry;
(b) the nanoparticle slurry that step (a) is obtained mixes with second polyester monocase, carries out polyreaction under normal pressure, obtains the nano particle/polyester complex body; And
(c) the nano particle/polyester complex body that step (b) is obtained is mixed with the coating products that solids content is 30-70 weight % with dimethylbenzene/butylacetate double solvents.
2. the method for claim 1, it is characterized in that in the step (a) that mixture with the good solvent of nanoparticle powder, first resin and first resin high speed shear 0.5～6 hour and/or ultrasonic oscillation under 3000rpm～5000rpm rotating speed handled 0.5～30 minute, be uniformly dispersed.
3. method as claimed in claim 1 or 2, it is characterized in that nanoparticle is to be selected from least a in the group of being made up of titanium dioxide, silicon-dioxide and aluminum oxide, these nanoparticles be surface organic modification or without organically-modified, particle diameter is between 10～500nm, preferably between 10～100nm, more preferably between 10～50nm.
4. as each described method among the claim 1-3, it is characterized in that the nanoparticle powder accounts for the 0.1-25wt% of whole coating, preferred 0.1-5wt%, more preferably 1-2wt%.
5. as each described method among the claim 1-4, the ratio that it is characterized in that the good solvent of first resin and first resin in the step (a) is between 0.1: 100 to 10: 100, preferably between 0.5: 100 to 3: 100.
6. as each described method among the claim 1-5, it is characterized in that the concentration of the middle nanoparticle of step (a) in the nanoparticle slurry between 1～250g/L, preferred 5～50g/L.
7. as each described method among the claim 1-6, it is characterized in that first resin is the polymkeric substance that contains ester group in the repeating unit, this first resin be preferably selected from contain ester group in the repeating unit acrylic resin (promptly, the polymkeric substance of the ester that acrylic acid series unsaturated acid (comprising vinylformic acid, methacrylic acid and ethylacrylic acid etc.) and alcohol form), first polyester or its mixture, and this first polyester is preferably Synolac, and wherein first polyester is identical or different with second polyester.
8. as each described method among the claim 1-7, it is characterized in that described second polyester is the polymerisate that at least a binary/polyvalent alcohol and at least a diprotic acid obtain through polycondensation, or the polymerisate that obtains by transesterify and polycondensation of the ester of at least a binary/polyvalent alcohol, at least a diprotic acid and at least a diprotic acid, wherein
Described diprotic acid be preferably be selected from down the group in one or more: Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, phthalic acid, m-phthalic acid, terephthalic acid, hexahydrophthalic acid, six hydrogen terephthalic acids, two chloro-o-phthalic acids, tetrachlorophthalic acid, endo-methylene group tetrahydrophthalic acid and 1,4-cyclohexane diacid;
Described binary/polyvalent alcohol be preferably be selected from down the group in one or more: ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, glycerol, 2,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, decanediol, dodecanol, neopentyl glycol, cyclohexanediol, 3 (4), 8 (9)-two (methylol) three ring [5.2.1.0
2,6] decanediol, 1, the two methylol hexanaphthenes of 4-, 2, two (4-hydroxyl-cyclohexyl) propane of 2-, 2, two [4-(the 2-hydroxy ethoxy)-phenyl] propane of 2-, the 2-methyl isophthalic acid, 3-dihydroxyl-propane, the 2-methyl isophthalic acid, 5-dihydroxyl-pentane, 2,2,4-trimethylammonium-1,6-hexylene glycol, TriMethylolPropane(TMP), trimethylolethane, 1,2, the 6-hexanetriol, 1,2, the 4-trihydroxybutane, three-2-hydroxyethyl isocyanuric acid ester, tetramethylolmethane, N.F,USP MANNITOL, sorbyl alcohol, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, the pure and mild hydroxyl new pentane diacid of terephthaldehyde DOPCP; And
The ester of described diprotic acid be preferably be selected from down the group in one or more: dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl phthalate, diethyl terephthalate, dimethyl isophthalate, diethyl phthalate, dimethyl adipate and Methyl glutarate.
9. method as claimed in claim 8 is characterized in that step (b) is decomposed into following two steps again when step (b) adopts the ester exchange polycondensation method to prepare the nano particle/polyester complex body:
(b-1) make the ester of at least a diprotic acid and at least a binary/polyvalent alcohol monomer under normal pressure, carry out transesterification reaction under the state of raw materials melt; With
(b-2) the nanoparticle slurry and at least a dicarboxylic acid monomer that obtain in reactant that step (b-1) is obtained and the step (a) are carrying out polycondensation under normal pressure under the state of raw materials melt, thereby obtain the nano particle/polyester complex body,
Perhaps step (b) is decomposed into following two steps again:
(b-1 ') make the nanoparticle slurry that obtains in ester, at least a binary/polyvalent alcohol monomer and the step (a) of at least a diprotic acid under normal pressure, carry out transesterification reaction under the state of raw materials melt; With
(b-2 ') carrying out polycondensation with reactant and at least a dicarboxylic acid monomer that step (b-1 ') obtains under normal pressure under the state of raw materials melt, thereby obtain the nano particle/polyester complex body.
10. as each described method among the claim 1-9, it is characterized in that hydroxyl value that reaction is carried out in the step (b) degree should make the whole polymeric system that obtains between 90-100mg KOH/g, and acid number is between 8-12mg KOH/g.
11. as each described method among the claim 1-10, the good solvent that it is characterized in that first resin in the step (a) is to be selected from least a in the group of being made up of acetone, chloroform and dimethylbenzene.
12. as each described method among the claim 8-11, it is characterized in that polycondensation in the step (b) is at least a in being selected from the group of being made up of zinc acetate, Cobaltous diacetate, aluminum alkoxide, dibutyltin oxide, toxilic acid dibutyl tin and tetrabutyl titanate carries out in the presence of as catalyzer, and the transesterification reaction in the step (b) is carried out as in the presence of the catalyzer at the acetate of Zn, Mn, Mg, Ca or Co.
13. according to the nano particle/polyester composite coating as each described method preparation among the claim 1-12, wherein the surface of nanoparticle is coated with polyester molecule.
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| CN102311673A (en) * | 2011-07-26 | 2012-01-11 | 昆山市大地化工新技术开发有限公司 | Ultraviolet (UV) coating capable of forming porcelain lines automatically and production method thereof |
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| CN113813796B (en) * | 2021-08-27 | 2022-11-29 | 浙江大学 | Nano composite dispersion liquid, high-gas-barrier nano composite film and preparation method thereof |
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