CN103214662A - Modified alkyd resin as well as preparation method of alkyd resin and double-component matte white finish - Google Patents
Modified alkyd resin as well as preparation method of alkyd resin and double-component matte white finish Download PDFInfo
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Abstract
The invention provides a modified alkyd resin and a preparation method thereof. The preparation method of the modified alkyd resin comprises the following step of: enabling an alcohol acid mixture to react to obtain the modified alkyd resin, wherein the alcohol acid mixture comprises the following components in parts by weight: 210-220 parts of soya-bean oil acid, 250-270 parts of phthalic anhydride, 5-7 parts of maleic anhydride, 15-20 parts of neopentyl glycol, 135-150 parts of pentaerythritol, 0.5-1 part of color-reducing antioxidant, 15-20 parts of water-carrying agent, 255-280 parts of diluted solvent, 0.5-1.5 parts of anti-aging agent and 60-76 parts of a compound as shown in formula (I), wherein n is not less than 1 and not more than 4. The compound as shown in the formula (I) is used for modifying the alkyd resin, so that the alkyd resin with a formaldehyde removing function is obtained. The invention further provides double-component matte white finish with an excellent formaldehyde removing function.
Description
Technical field
The present invention relates to coating and coating Synolac technical field, particularly a kind of modified alkyd resin, its preparation method and the mute light white finish paint of two component.
Background technology
Formaldehyde is a kind of colourless, gas that the intense stimulus smell is arranged, and relative molecular mass is 30.03, soluble in water, pure and mild ether.Mass concentration is 35%～40%, be generally 37% formalin " formalin " solution that is otherwise known as, and it is at the room temperature highly volatile.Formaldehyde has good chemical reactivity and excellent cost performance, is a kind of important organic raw material that is widely used, and can play an important role at aspects such as industrial production and anticorrosion processes.Yet free formaldehyde but is a kind of serious pollutent in the air.Formaldehyde belongs to the protoplasma poisonous substance, can make the protein generation irreversible coagulation of cellular plasm, all can produce infringement to neural system, lung and liver, and it is mainly derived from environment, food, medicine, artificially adds and these five aspects of food self metabolism.The World Health Organization and EPA are all classified formaldehyde as potential carcinogens and important environmental pollutant, and China national Environmental Protection Agency also announces that on April 16th, 1987 formaldehyde is the human body suspect carcinogen.Regulation among the CNS GB-T16127-1995 " hygienic standard of formaldehyde in the indoor air ": occupy formaldehyde in indoor air hygienic standard (maximum allowable concentration) and be 0.08mg/m
3Because indoor is the long-term resident places of people, removes indoor formaldehyde and pollute, guarantee that IAQ (indoor air quality) is particularly important to people.
At present, the technology of domestic civilian coating industry removing formaldehyde mainly contains physisorphtion, negative ion decomposition method, chitosan biomass method and photocatalysis Decomposition method.Wherein, the photocatalysis Decomposition method is a kind of novel improvement formaldehyde atmospheric pollution technology, now is applied in the aqueous coating system, and clear aldehyde speed is fast, effective; Through coating modification is carried out on its surface, carry out modification as adopting dodecyl Trimethoxy silane or KH-570 silane coupling agent, can improve lipophilicity, thereby can be applicable in the oiliness wood lacquer.But there are following two problems in this technology: the one, and under visible light, photocatalysis efficiency is lower, and the 2nd, the free radical that generates can be with conventional resin oxygenolysis and cause the coating surface efflorescence easily.Therefore, be only applicable on this technical know-how in the super ultraviolet resistance oil paint systems such as fluoro-resin and polysiloxane, range of application is narrower.The exploitation of the compound clear aldehyde technology of the coating that more is of practical significance as shown in the above, and application have become the task of top priority in the functional coatings industry.
The Synolac good film-forming property that in paint field, is widely used, rete behind the film-forming has gloss, toughness and stronger sticking power, and characteristics such as good wear resistance, weathering resistance and insulativity, it generally is the oily modified polyester resin that a class is formed by polyvalent alcohol, diprotic acid and lipid acid or grease condensation polymerization, as by material synthetic Synolac such as behenic acid, tetramethylolmethane and ethylene glycol, perhaps by material synthetic Synolac such as glycerine, neopentyl glycol and orthoformic acids.Though above-mentioned existing Synolac after being mixed with coating, in the performance of aspects such as decoration and protection well, also can't reach the functional requirement of removing formaldehyde.Therefore, the applicant considers, Synolac is carried out modification, makes it be applied to have good removing formaldehyde effect behind the coating.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of modified alkyd resin, its preparation method and a kind of pair of mute light white finish paint of component, this modified alkyd resin is applied to have good removing formaldehyde effect in the mute light white finish paint of two components.
The invention provides a kind of modified alkyd resin, made through reaction by pure acid mixture, described pure acid mixture comprises:
The behenic acid of 210～220 weight parts;
The phthalic anhydride of 250～270 weight parts;
The cis-butenedioic anhydride of 5～7 weight parts;
The neopentyl glycol of 15～20 weight parts;
The tetramethylolmethane of 135～150 weight parts;
0.5 the oxidation inhibitor of losing lustre of～1 weight part;
The band aqua of 15～20 weight parts;
The letdown solvent dun of 255～280 weight parts;
0.5 the antiaging agent of～1.5 weight parts;
Compound shown in the formula of 60～76 weight parts (I):
In the formula (I), 1≤n≤4.
Preferably, n is 2, and the compound shown in the described formula (I), is made through transesterification reaction under the katalysis of the tetrabutyl titanate of 0.05～0.15 weight part by the ethylene glycol of the diethyl malonate of 50～60 weight parts and 40～50 weight parts.
Preferably, described band aqua is selected from any in dimethylbenzene, toluene and the benzene.
Preferably, described letdown solvent dun is the mixture of dimethylbenzene and n-butyl acetate.
The invention provides a kind of preparation method of modified alkyd resin, comprising:
Pure acid mixture is reacted, obtain modified alkyd resin, described pure acid mixture comprises:
The behenic acid of 210～220 weight parts;
The phthalic anhydride of 250～270 weight parts;
The cis-butenedioic anhydride of 5～7 weight parts;
The neopentyl glycol of 15～20 weight parts;
The tetramethylolmethane of 135～150 weight parts;
0.5 the oxidation inhibitor of losing lustre of～1 weight part;
The band aqua of 15～20 weight parts;
The letdown solvent dun of 255～280 weight parts;
0.5 the antiaging agent of～1.5 weight parts;
Compound shown in the formula of 60～76 weight parts (I):
In the formula (I), 1≤n≤4.
Preferably, specifically comprise:
Diethyl malonate and ethylene glycol are carried out transesterification reaction under the katalysis of tetrabutyl titanate, obtain the compound shown in the formula (I), n is 2;
React with compound, behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, the band aqua shown in the described formula (I) and after the oxidation inhibitor of losing lustre mixes, obtain crude product;
Described crude product, letdown solvent dun are mixed with antiaging agent, obtain modified alkyd resin.
Compared with prior art, the present invention will comprise compound, the behenic acid of 210～220 weight parts, the phthalic anhydride of 250～270 weight parts, the cis-butenedioic anhydride of 5～7 weight parts, the neopentyl glycol of 15～20 weight parts, the tetramethylolmethane of 135～150 weight parts, the oxidation inhibitor of losing lustre of 0.5～1 weight part, the band aqua of 15～20 weight parts, the letdown solvent dun of 255～280 weight parts and the ageing-resistant pure acid mixture of 0.5～1.5 weight part shown in the formula (I) of 60～76 weight parts and react, and obtain modified alkyd resin.The present invention adopts conventional feedstock production Synolac such as behenic acid, tetramethylolmethane, neopentyl glycol, phthalic anhydride and cis-butenedioic anhydride, adopts the compound shown in the formula (I) to carry out modification simultaneously.Compound shown in the described formula (I) has-OH functional group, can be grafted on the resin segment; And, because the molecule segment after the grafting contains O=C-CH
2-C=O, it comprises active methylene radical, after film process or film forming can be adsorbed on its surperficial formaldehyde molecule and carry out nucleophilic reaction, thereby obtain a kind of Synolac of removing the formaldehyde function that has.
In addition, the present invention adopts the method for the compound modified Synolac shown in the formula (I) simple to operate, and product is stable between batch.
The invention provides the mute light white finish paint of a kind of pair of component, comprise:
The modified alkyd resin mentioned above of 50～60 weight parts;
The dispersion agent of 1～3 weight part;
The titanium dioxide of 28～32 weight parts;
The functional powder of 1～3 weight part;
0.3 the polyethylene wax powder of～0.7 weight part;
The flatting silica of 4～5 weight parts;
The anti-settling agent of 1～3 weight part;
0.05 the non-silicon defoamer of～0.15 weight part;
0.1 first flow agent of～0.3 weight part;
0.1 second flow agent of～0.3 weight part;
The 1-Methoxy-2-propyl acetate of 2～4 weight parts.
Preferably, described dispersion agent is that model is the dispersion agent of BYK-110.
Preferably, described functional powder is a negative ion powder.
Preferably, described first flow agent is a polysiloxane polyether copolymer, and described second flow agent is the poly-methyl alkyl siloxane of aralkyl modification.
Compared with prior art, the mute light white finish paint of the provided by the invention pair of component mainly comprises modified alkyd resin mentioned above, and with components matching such as dispersion agent, functional powder and flow agent, have very excellent service performance.To be sprayed on glass the detection after the mute light white finish paint dilution of described pair of component, detected result shows that the provided by the invention pair of mute light white finish paint of component can satisfy the paint film requirement at aspects such as gloss, hardness, and has excellent removing formaldehyde function.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The invention provides a kind of modified alkyd resin, made through reaction by pure acid mixture, described pure acid mixture comprises:
The behenic acid of 210～220 weight parts;
The phthalic anhydride of 250～270 weight parts;
The cis-butenedioic anhydride of 5～7 weight parts;
The neopentyl glycol of 15～20 weight parts;
The tetramethylolmethane of 135～150 weight parts;
0.5 the oxidation inhibitor of losing lustre of～1 weight part;
The band aqua of 15～20 weight parts;
The letdown solvent dun of 255～280 weight parts;
0.5 the antiaging agent of～1.5 weight parts;
Compound shown in the formula of 60～76 weight parts (I):
In the formula (I), 1≤n≤4.
The present invention is that main raw material forms pure acid mixture with the compound shown in polyvalent alcohol, organic acid, auxiliary agent and a certain amount of formula (I), obtains modified alkyd resin through reaction.Described modified alkyd resin is applied to have the function of removing formaldehyde in the coating such as the mute light white finish paint of two components as filmogen.
In the present invention, the raw material as polyvalent alcohol has neopentyl glycol and tetramethylolmethane.Wherein, described pure acid mixture comprises the neopentyl glycol of 15～20 weight parts, preferably comprises the neopentyl glycol of 16～18 weight parts.Neopentyl glycol can bring Synolac molecule and other resin such as polyurethane curing agent or the splendid consistency of solvent owing to have two methyl branches.
Described pure acid mixture comprises the tetramethylolmethane of 135～150 weight parts, preferably comprises the tetramethylolmethane of 140～150 weight parts.The functionality of tetramethylolmethane is 4, also is synthetic alkyd resin a kind of polyvalent alcohol commonly used.Because the functionality of tetramethylolmethane is bigger, with it is polyvalent alcohol synthetic Synolac glyptal fast drying more of the same type, and performances such as gloss, hardness, gloss retention and alkali resistance are also better, so tetramethylolmethane is a kind of rising Synolac raw material.The present invention does not have particular restriction to described tetramethylolmethane, and preferably adopting monopentaerythritol content is 95% tetramethylolmethane.
In the present invention, as the organic acid raw material behenic acid, phthalic anhydride and cis-butenedioic anhydride are arranged.Wherein, described pure acid mixture comprises the phthalic anhydride of 250～270 weight parts, preferably comprises the phthalic anhydride of 255～265 weight parts.Phthalic anhydride has another name called Tetra hydro Phthalic anhydride, is one of the most frequently used diprotic acid of synthetic alkyd resin (acid anhydride).
Described pure acid mixture comprises the cis-butenedioic anhydride of 5～7 weight parts, preferably comprises the cis-butenedioic anhydride of 5～6 weight parts.Cis-butenedioic anhydride full name MALEIC ANHYDRIDE also can be used to make Synolac.
Described pure acid mixture comprises the behenic acid of 210～220 weight parts, preferably comprises the behenic acid of 213～218 weight parts.The xanthochromia of behenic acid a little less than, use comparatively extensive.
In the present invention, the compound shown in the employing formula (I) obtains modified alkyd resin.That is, described pure acid mixture comprises the compound shown in the formula (I) of 60～76 weight parts, preferably comprises the compound shown in the formula (I) of 68～72 weight parts.In the formula (I), 1≤n≤4, preferred n is 2.
Compound shown in the described formula (I) has-OH functional group, can be grafted on the resin segment; And, because the molecule segment after the grafting contains O=C-CH
2-C=O, it comprises active methylene radical, after film process or film forming can be adsorbed on its surperficial formaldehyde molecule and carry out nucleophilic reaction, thereby obtain a kind of Synolac of removing the formaldehyde function that has.The molecular structural formula of described resin can be suc as formula shown in (II):
Because the Synolac molecule is a kind of macromolecule mixture, R, R ' in the formula (II) is uncertain structure, can be for being grafted with the remaining segment of behenic acid segmental tetramethylolmethane, also can be the remaining segment of neopentyl glycol, can also be for being grafted with remaining segment that remaining segment of phthalic anhydride or above-described tetramethylolmethane, neopentyl glycol, behenic acid etc. are connected etc. simultaneously.
The present invention does not have particular restriction to the source of the compound shown in the described formula (I), can buy from the market, can prepare voluntarily yet.
When n is 2, the compound shown in the described formula (I) preferably by the ethylene glycol of the diethyl malonate of 50～60 weight parts and 40～50 weight parts under the katalysis of the tetrabutyl titanate of 0.05～0.15 weight part, make through transesterification reaction.
In the present invention, described transesterification reaction is raw material with the diethyl malonate, preferably adopts the diethyl malonate of 53～57 weight parts; With ethylene glycol is another raw material, preferably adopts the ethylene glycol of 43～48 weight parts; With the tetrabutyl titanate is catalyzer, preferably adopts the tetrabutyl titanate of 0.08～0.12 weight part.In the present invention, described transesterification reaction be diethyl malonate and ethylene glycol under the catalysis of tetrabutyl titanate, the reaction of this new ester of the compound shown in the production (I) and a new alcohol, wherein, tetrabutyl titanate is a kind of transesterification catalyst of excellence, and cost is lower; By product is an ethanol, and it is 60～76 weight parts that the compound shown in the target product formula (I) must be measured.
Described transesterification reaction preferably adopts normal pressure equipment, logical rare gas element of reaction whole process such as nitrogen (N
2) or carbonic acid gas (CO
2) protection.As preferably, described transesterification reaction specifically comprises:
Under whipped state, temperature of reaction kettle is remained on 150 ℃～165 ℃ by type of heating, heat up in a steamer temperature control≤78.4 ℃, react after 3 hours～5 hours, be warming up to 165 ℃～170 ℃ and reacted at least 10 minutes again, when no overhead product distillates, be terminal point, obtain the compound shown in the formula (I-1);
The present invention adopts the transesterification reaction of diethyl malonate and ethylene glycol to prepare the compound shown in the formula I, and is catalyzer with the tetrabutyl titanate, and this is a kind of normal pressure synthesis reaction, and temperature of reaction is low, and is simple to operate, and product is stable between batch.
In order to obtain well behaved modified alkyd resin, the present invention also comprises a certain amount of auxiliary agent.Wherein, described pure acid mixture comprises the band aqua of 15～20 weight parts, preferably comprises the band aqua of 17～19 weight parts.Described band aqua can reflux and slough micromolecular water in the esterification process, and the Synolac reaction is carried out to esterifying polycondensation the Direction of Reaction.And the present invention controls the consumption of described band aqua in above-mentioned scope, further promotes reaction to carry out.Described band aqua is preferably any in dimethylbenzene, toluene and the benzene, dimethylbenzene more preferably, and water accounted for the azeotrope ratio and reaches 37.5% character when the present invention utilized dimethylbenzene and water azeotropic, adopted it to slough water, was beneficial to and obtained modified alkyd resin.
Described pure acid mixture comprises the letdown solvent dun of 255～280 weight parts, preferably comprises the letdown solvent dun of 260～270 weight parts.The present invention adopts described letdown solvent dun with the resin chemical solution, obtains modified alkyd resin.Described letdown solvent dun is preferably the mixture of dimethylbenzene and n-butyl acetate, and is easy and simple to handle, and the products obtained therefrom quality is better.
Described pure acid mixture comprises the oxidation inhibitor of losing lustre of 0.5～1 weight part, preferably comprises the oxidation inhibitor of losing lustre of 0.6～0.8 weight part.The described oxidation inhibitor of losing lustre can play the antioxidant effect of losing lustre in the Synolac building-up process, with appearance property and the application performance that improves Synolac.The described oxidation inhibitor of losing lustre can be materials such as Hypophosporous Acid, 50, triphenyl phosphite; From trade names, the described oxidation inhibitor of losing lustre comprises but the oxidation inhibitor SH-1 that is not limited to lose lustre, the lose lustre oxidation inhibitor 3032 and the oxidation inhibitor M070 of losing lustre, and can effectively improve the color of resin.
Described pure acid mixture comprises the antiaging agent of 0.5～1.5 weight part, preferably comprises the antiaging agent of 0.5～0.9 weight part.In the present invention, described antiaging agent mainly is the degree of aging that reduces Synolac.Described antiaging agent can be phenolic compound, also can be ester compound, and the present invention there is no particular restriction to this.The model that described antiaging agent is preferably German Lanxess Corporation is the antiaging agent of BHT-264, and its chemical name is 2,6-di-t-butyl-4-cresols.
Accordingly, the invention provides a kind of preparation method of modified alkyd resin, comprising:
Pure acid mixture is reacted, obtain modified alkyd resin, described pure acid mixture comprises:
The behenic acid of 210～220 weight parts;
The phthalic anhydride of 250～270 weight parts;
The cis-butenedioic anhydride of 5～7 weight parts;
The neopentyl glycol of 15～20 weight parts;
The tetramethylolmethane of 135～150 weight parts;
0.5 the oxidation inhibitor of losing lustre of～1 weight part;
The band aqua of 15～20 weight parts;
The letdown solvent dun of 255～280 weight parts;
0.5 the antiaging agent of～1.5 weight parts;
Compound shown in the formula of 60～76 weight parts (I):
In the formula (I), 1≤n≤4.
The present invention is that raw material reacts with the pure acid mixture that comprises the compound shown in polyvalent alcohol, organic acid, auxiliary agent and the formula (I), generate modified alkyd resin, make described modified alkyd resin as filmogen, be applied in the coating such as the mute light white finish paint of two components, have good performance, especially remove the effect excellence of formaldehyde.
In the present invention, the raw material as polyvalent alcohol has neopentyl glycol and tetramethylolmethane; As the organic acid raw material behenic acid, phthalic anhydride and cis-butenedioic anhydride are arranged.These conventional raw materials are consistent with content mentioned above, give unnecessary details no longer one by one at this.
The present invention adopts the compound shown in the formula (I) to obtain modified alkyd resin.That is, described pure acid mixture comprises the compound shown in the formula (I) of 60～76 weight parts, preferably comprises the compound shown in the formula (I) of 68～72 weight parts.In the formula (I), 1≤n≤4, preferred n is 2.Compound shown in the described formula (I) has-OH functional group, can be grafted on the resin segment; And, because the molecule segment after the grafting contains O=C-CH
2-C=O, it comprises active methylene radical, after film process or film forming can be adsorbed on its surperficial formaldehyde molecule and carry out nucleophilic reaction, thereby obtain a kind of Synolac of removing the formaldehyde function that has.
The present invention has also added a certain amount of auxiliary agent in order to obtain well behaved modified alkyd resin, mainly contains band aqua, letdown solvent dun, lose lustre oxidation inhibitor and antiaging agent.The content of these auxiliary agents is consistent with content mentioned above, gives unnecessary details no longer one by one at this.
In the present invention, the preparation method of described modified alkyd resin specifically comprises:
Diethyl malonate and ethylene glycol are carried out transesterification reaction under the katalysis of tetrabutyl titanate, obtain the compound shown in the formula (I), n is 2;
React with compound, behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, the band aqua shown in the described formula (I) and after the oxidation inhibitor of losing lustre mixes, obtain crude product;
Described crude product, letdown solvent dun are mixed with antiaging agent, obtain modified alkyd resin.
The embodiment of the invention drops into diethyl malonate, the ethylene glycol of 40～50 weight parts and the tetrabutyl titanate of 0.05～0.15 weight part of 50～60 weight parts to reactor; carry out transesterification reaction after preferably under stirring condition, mixing; more preferably after mixing under rare gas element such as nitrogen or the carbon-dioxide protecting, react; most preferably after mixing under the continuously logical nitrogen protection, react, obtain the compound shown in the formula (I).
In the present invention, described transesterification reaction is raw material with the diethyl malonate, preferably adopts the diethyl malonate of 53～57 weight parts; With ethylene glycol is another raw material, preferably adopts the ethylene glycol of 43～48 weight parts; With the tetrabutyl titanate is catalyzer, preferably adopts the tetrabutyl titanate of 0.08～0.12 weight part.In the present invention, described transesterification reaction be diethyl malonate and ethylene glycol under the catalysis of tetrabutyl titanate, the reaction of this new ester of the compound shown in the production (I) and a new alcohol, wherein, tetrabutyl titanate is a kind of transesterification catalyst of excellence, and cost is lower; By product is an ethanol, and it is 60～76 weight parts that the compound shown in the target product formula (I) must be measured.
Described transesterification reaction preferably adopts normal pressure equipment, preferably is specially:
Under whipped state, temperature of reaction kettle is remained on 150 ℃～165 ℃ by type of heating, heat up in a steamer temperature control≤78.4 ℃, react after 3 hours～5 hours, be warming up to 165 ℃～170 ℃ and reacted at least 10 minutes again, when no overhead product distillates, be terminal point, obtain the compound shown in the formula (I).
The present invention adopts the compound shown in the transesterification reaction preparation formula (I) of diethyl malonate and ethylene glycol, and is catalyzer with the tetrabutyl titanate, and this is a kind of normal pressure synthesis reaction, and temperature of reaction is low, and is simple to operate, and product is stable between batch.
Then, the embodiment of the invention then to aforesaid reaction vessel drop into above-mentioned formulation weight umber behenic acid, be with aqua and the oxidation inhibitor of losing lustre, and drop into phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol and the tetramethylolmethane of above-mentioned formulation weight umber by the special-purpose dog-house of powder, preferably under stirring condition, mix and react, obtain crude product.
In the present invention, described reaction is preferably carried out under the protection of rare gas element such as nitrogen, carbonic acid gas, not only can avoid side reaction, and help deviating from low molecular weight volatile things such as water.That is, can be in reactor logical in advance nitrogen of the present invention or carbonic acid gas, the time of control ventilation body is preferably 3 minutes～and 8 minutes, more preferably 5 minutes～6 minutes; The flow of control ventilation body is preferably 2m
3/ h～5m
3/ h, more preferably 3m
3/ h～4m
3/ h, this flow is at 3M
3Reactor.
Described reaction is preferably carried out in two-step approach heats up: at first be warming up to 160 ℃～185 ℃, insulation refluxed 1 hour～2 hours, was warming up to 200 ℃～220 ℃ then in 3 hours～5 hours.
After being warming up to 200 ℃～220 ℃, the present invention preferably is incubated when acid number≤18mgKOH/g, viscosity are 16 seconds～22 seconds/25 ℃ form pipes and lowers the temperature, more preferably be incubated when acid number≤15mgKOH/g, viscosity are 19 seconds～20 seconds/25 ℃ form pipes and lower the temperature, be cooled to 180 ℃～200 ℃, obtain crude product.Need to prove that the testing method of this viscosity is: get interior solid resin of reactor and dimethylbenzene wiring solution-forming and test, the mass ratio of described solid resin and dimethylbenzene is 1:0.84, and promptly the solid resin accounting is about 53%.
After obtaining crude product, it is changed in the thinning vessel to mix with letdown solvent dun, antiaging agent carry out latting drown, obtain modified alkyd resin.
In the present invention, described latting drown preferably carries out under the protection of rare gas element such as nitrogen, carbonic acid gas.That is, the present invention can be led to nitrogen or carbonic acid gas in thinning vessel, and the flow of control ventilation body is preferably 3m
3/ h～9m
3/ h, more preferably 4m
3/ h～8m
3/ h, this flow is at 5M
3Thinning vessel.And, the present invention preferably open described thinning vessel stirring, inner coil pipe cold oil and accompany the water coolant of pipe outward.The time of described stirring preferably more than 30min, be cooled to 100 ℃～130 ℃ after, be that the filter bag of 20 μ m filters with specification, the discharging barrelling obtains modified alkyd resin.
When the present invention adopts letdown solvent dun to carry out latting drown, the disposable direct input thinning vessel of whole letdown solvent duns also can be dropped into thinning vessel with the part letdown solvent dun earlier, will drop into above-mentioned thinning vessel again behind another part letdown solvent dun cleaning reaction still then.The present invention preferably drops into thinning vessel with the letdown solvent dun of antiaging agent and 50%, and the crude product that changes thinning vessel from reactor over to is carried out latting drown, and still to be changeed finishes, and drops into thinning vessel again behind the letdown solvent dun cleaning reaction still with residue 50%.For dimethylbenzene and n-butyl acetate blended letdown solvent dun, the present invention preferably drops into thinning vessel in advance with n-butyl acetate, after dimethylbenzene stays the cleaning reaction still, drops into thinning vessel again.
After obtaining modified alkyd resin, the present invention carries out Performance Detection to it, and detection method is method well known to those skilled in the art.Detected result shows that the modified alkyd resin that the present invention makes is the yellow transparent thick liquid; When adopting the test of Fe-Co method, color and luster≤3; Under 25 ℃, viscosity is 8000mPas～12000mPas; Acid number≤12.6mgKOH/g; Solid content (be called for short and contain admittedly) is (70 ± 1.5) %.Show the functional of modified alkyd resin that the present invention makes, can form filming of different qualities, have very excellent service performance, Application Areas is very extensive.
In addition, the present invention adopts the method for the compound modified Synolac shown in the formula (I) simple to operate, and product is stable between batch.
The present invention also provides a kind of pair of component light white finish paint of making mute, comprises:
The modified alkyd resin mentioned above of 50～60 weight parts;
The dispersion agent of 1～3 weight part;
The titanium dioxide of 28～32 weight parts;
The functional powder of 1～3 weight part;
0.3 the polyethylene wax powder of～0.7 weight part;
The flatting silica of 4～5 weight parts;
The anti-settling agent of 1～3 weight part;
0.05 the non-silicon defoamer of～0.15 weight part;
0.1 first flow agent of～0.3 weight part;
0.1 second flow agent of～0.3 weight part;
The 1-Methoxy-2-propyl acetate of 2～4 weight parts.
The mute light white finish paint of the provided by the invention pair of component mainly comprises modified alkyd resin mentioned above, and with components matching such as dispersion agent, functional powder and flow agent, have very excellent service performance, it is respond well especially to remove formaldehyde.
In the present invention, the described pair of mute light white finish paint of component comprises the modified alkyd resin mentioned above of 50～60 weight parts, preferably comprises the modified alkyd resin mentioned above of 55～60 weight parts.Described modified alkyd resin is applied in the coating as filmogen, can make paint film have excellent performance in many-sides such as gloss, levelling and removing formaldehyde, is beneficial to application.
The described pair of mute light white finish paint of component also comprises the dispersion agent of 1～3 weight part, the titanium dioxide of 28～32 weight parts, the functional powder of 1～3 weight part, the polyethylene wax powder of 0.3～0.7 weight part, the flatting silica of 4～5 weight parts, the anti-settling agent of 1～3 weight part, the non-silicon defoamer of 0.05～0.15 weight part, first flow agent of 0.1～0.3 weight part, second flow agent of 0.1～0.3 weight part and the 1-Methoxy-2-propyl acetate of 2～4 weight parts, these compositions and described modified alkyd resin are used, and obtain the mute light white finish paint of two components of better performances.
Wherein, described titanium dioxide formal name used at school titanium dioxide can strengthen the physical strength and the sticking power of paint film, prevents crackle, prevents that ultraviolet ray and moisture from seeing through, thus the prolongation paint film life-span; Described titanium dioxide is commonly used the getting final product in this area, is the titanium dioxide of the R-706 of du pont company as the trade mark.Described functional powder can give coating specific functional, is preferably negative ion powder, but this negative ion element generating negative ions effect when faint variation takes place environment has bigger help to human residential environment's improvement.Described polyethylene wax powder is in the film forming process of powder coating, and when the cooling of filming, polyethylene wax is separated out from masking liquid, forms fine particle, floats over film coated surface, plays effects such as texture, delustring, smooth and anti-wiping scuffing; Described polyethylene wax powder is commonly used the getting final product in this area.Described flatting silica can balancedly be controlled film coated surface gloss, and has effects such as increasing the wear resistance film and mar-resistance; Described flatting silica is commonly used the getting final product in this area.
Described dispersion agent impels material particles to be dispersed in the medium, is preferably the dispersion agent that model is BYK-110.Described anti-settling agent makes coating have thixotropy, can play the anti-precipitating action of thickening in coating; Described anti-settling agent is commonly used the getting final product in this area.
Described non-silicon defoamer can be eliminated the harmful foam in the coating material production process, is preferably the defoamer that model is HX-2500.Organic solvents such as described 1-Methoxy-2-propyl acetate can play the effect of dilution coating.
Flow agent can impel coating in the drying and forming-film process, form one smooth, smooth, film uniformly, in the present invention, described first flow agent is preferably polysiloxane polyether copolymer, the model that provides as Di Gao company is the flow agent of TEGO-410, described second flow agent is preferably the poly-methyl alkyl siloxane of aralkyl modification, as the HX-3130 flow agent of China's auxiliary agent, both are used, and effect is better.
Accordingly, the preparation method that the present invention also provides a kind of two components mentioned above to make the light white finish paint mute comprises:
Described modified alkyd resin, dispersion agent, titanium dioxide, functional powder, polyethylene wax powder, defoamer, anti-settling agent, non-silicon defoamer, first flow agent, second flow agent and the 1-Methoxy-2-propyl acetate of above-mentioned formulation weight umber are mixed, obtain the mute light white finish paint of two components.
In the present invention, the preparation method of the described pair of mute light white finish paint of component specifically comprises:
With the described modified alkyd resin and the dispersant of above-mentioned formulation weight umber, under 300 rev/mins～500 rev/mins rotating speed, disperseed 5 minutes～10 minutes, obtain first mixture;
Described first mixture is mixed with the titanium dioxide of above-mentioned formulation weight umber, functional powder, under 1600 rev/mins～2000 rev/mins rotating speed, disperseed 20 minutes～25 minutes, be ground to fineness≤30 μ m again, obtain second mixture;
Described second mixture is mixed with polyethylene wax powder, the flatting silica of above-mentioned formulation weight umber, under 1600 rev/mins～2000 rev/mins rotating speed, disperseed 15 minutes～20 minutes, obtain the 3rd mixture;
Described the 3rd mixture is mixed with anti-settling agent, non-silicon defoamer, first flow agent, second flow agent and the 1-Methoxy-2-propyl acetate of above-mentioned formulation weight umber, under 300 rev/mins～500 rev/mins rotating speed, disperseed 4 minutes～8 minutes, obtain the mute light white finish paint of two components.
During use, by the mute light white finish paint of described pair of component: solidifying agent: thinner=1:(0.4～0.6): after the proportioning of (0.4～0.6), preferred=1:0.5:0.5 prepares lacquer liquid, leave standstill 5min～15min, after treating froth breaking, utilization has gas spray gun will coat with lacquer liquid to be sprayed on the sheet glass, in temperature is that 20 ± 2 ℃, relative humidity are under 50 ± 10% the environment, removes formaldehyde efficient behind the maintenance 7d and persistence detects.Wherein, described solidifying agent and thinner adopt commonly used the getting final product in this area, as solidifying agent can be 40% with containing admittedly behind the n-butyl acetate latting drown, the L-75 solidifying agent of Bayer A.G, thinner can be made up of the n-butyl acetate of 50 weight parts, the 1-Methoxy-2-propyl acetate of 30 weight parts and the dimethylbenzene of 20 weight parts.
Purifying formaldehyde performance, the persistent detection method of purifying formaldehyde effect below are specifying of detection method with reference to national building material industry standard JC/T1074-2008 " function of purifying indoor air coating material purifying property " (I class):
Test conditions
Testing circumstance is: temperature is 20 ± 2 ℃, and relative humidity is 50 ± 10%.
Testing apparatus
Two 1m
3Experimental cabin, by thickness is the glass manufacturing of 8mm～10mm, experimental cabin inwall size length * wide * height is 1250mm * 800mm * 1000mm, one is placed sample is sample bin, another is placed the blank glass plate and is the contrast cabin, the cabin seam crossing adopts seal gum to handle, the gas production mouth is an experimental cabin sidewall central point, 1 of 30W fluorescent lamp is placed in experimental cabin inner top central position, be used for photocatalyst material (II class) test to needing illumination, the fan that power is 15W is placed in the central position, left side in the experimental cabin, is used for air in the even cabin.The experimental cabin length direction is placed four stainless steel specimen holders (outer diameter of steel pipes is 5mm), is used to place sample panel, and makes model become 30 ° with bulkhead, and model is apart from the 300mm of bilge portion.
For I class material (the invention belongs to this type of), the theory brushing amount that provides according to product, and constructional method, sample is brushed to four 500mm * 500mm sheet glass (surface of thickness 4mm～6mm), 20 ± 2 ℃ of temperature, seasoning was tested after 7 days in the testing circumstance of relative humidity 50 ± 10%.
One glass planar ware is put into the bottom of experimental cabin, and airtight experimental cabin drops in (3 ± 0.25) microlitre analytical pure formaldehyde in the glass dish by injection orifice with microsyringe then, airtight injection orifice.
Fluorescent lamp is not all opened in two cabins, gathers its concentration of gas test in the cabin behind the airtight 1h, and this concentration is starting point concentration (n
0); Gather in the cabin gas behind the 24h and test its concentration, this concentration is termination concentration (n
1).Open fan 30min before gathering gas, close during sampling.
Natural decay rate: R=(n
0-n
1)/n
0* 100%
That is, with the initial concentration (n that contrasts the cabin
0) and stop concentration (n
1) the natural attenuation of objectionable impurities relatively, formaldehyde decrement≤30%, test is set up.
Sample purification efficient: r=(n
1-n
1 1)/n
1* 100%
In the formula: r-purification efficiency, %
n
1-contrast gas that the cabin is surveyed stops concentration, and unit is every cubic metre of (mg/m of milligram
3)
n
1 1Gas that-sample chamber is surveyed stops concentration, and unit is every cubic metre of (mg/m of milligram
3)
The decontamination effect improving persistence
Saturation experiments: four test pieces that will prepare are put into ready sample chamber, airtight sample chamber.Add formaldehyde analytical pure solution every day on time, continue 4d.
5d takes out the intact test piece of saturation testing, be placed on 24h under 20 ± 2 ℃ of temperature, relative humidity 50 ± 10% envrionment conditionss, then the model that carries out the supersaturation test is tested according to clear aldehyde efficiency test step again, its decontamination effect improving endurance life test method of calculation as a result is the sample purification efficiency calculation method of front.
Detected result shows that the provided by the invention pair of mute light white finish paint of component meets the technical requirement of JC/T1074-2008 regulation on purifying formaldehyde performance and purifying formaldehyde effect persistence, have excellent removing formaldehyde effect.
In order further to understand the present invention, the mute light white finish paint of modified alkyd resin provided by the invention, its preparation method and two component is specifically described below in conjunction with embodiment.
Used diethyl malonate, ethylene glycol, tetrabutyl titanate, behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, dimethylbenzene, the n-butyl acetate of the embodiment of the invention, lose lustre oxidation inhibitor and antiaging agent are industrial raw material, and described tetramethylolmethane is 95% technical grade pentaerythritol for monopentaerythritol content.
The used behenic acid of following examples is 195～205 for the acid number index that the good sharp grease in Jiangmen company provides, the iodine number index is 122～130 behenic acid, antiaging agent is that marque is the antiaging agent of BHT-264, dispersion agent is that the model of Bi Ke chemistry is the dispersion agent of BYK-110, titanium dioxide is the R-706 titanium dioxide of du pont company, the negative ion powder TL that functional powder provides for Beijing Lang Nuo company, the polyethylene wax powder is the 1400SF polyethylene wax powder of Lu Borun, flatting silica is the OK-500 flatting silica that moral is filled in admittedly, anti-settling agent is the HX-8820 polyoxygenated amide waxe anti-settling agent of China's auxiliary agent, defoamer is the HX-2500 defoamer of Guangzhou China auxiliary agent chemical industry company limited, the model that first flow agent provides for Di Gao company is the flow agent of TEGO-410, second flow agent is the HX-3130 flow agent of China's auxiliary agent, solidifying agent is for being 40% with containing admittedly behind the n-butyl acetate latting drown, the L75 solidifying agent of Bayer A.G, thinner is by the n-butyl acetate of 50 weight parts, the dimethylbenzene of the 1-Methoxy-2-propyl acetate of 30 weight parts and 20 weight parts is formed.
Embodiment 1
Logical in advance nitrogen is 8 minutes in empty reactor, and nitrogen flow is 2m
3/ h;
Drop into the diethyl malonate of 50 weight parts, the ethylene glycol of 40 weight parts and the tetrabutyl titanate of 0.05 weight part successively to aforesaid reaction vessel and carry out transesterification reaction, in the logical nitrogen protection of reaction whole process, under whipped state, described temperature of reaction kettle is remained on 150 ℃ by type of heating, heat up in a steamer temperature control≤78.4 ℃, react after 5 hours, be warming up to 165 ℃ of reactions at least 10 minutes again, when no overhead product distillates, be terminal point, obtain the compound shown in the formula (I);
Close heating, drop into the behenic acid of 210 weight parts successively to aforesaid reaction vessel, the Hypophosporous Acid, 50 of the dimethylbenzene of 15 weight parts and 0.5 weight part (commodity are called M070), and drop into the phthalic anhydride of 250 weight parts successively to aforesaid reaction vessel by the special-purpose dog-house of powder, the cis-butenedioic anhydride of 5 weight parts, the tetramethylolmethane of the neopentyl glycol of 15 weight parts and 135 weight parts, under agitation heat up, be warming up to 160 ℃, insulation refluxed 2 hours, in 3 hours, be warming up to 220 ℃ then, be incubated to acid number≤18mgKOH/g, cooling when viscosity is 16 seconds～17 seconds/25 ℃ Ge Shi pipes, when treating that the interior temperature of described reactor is reduced to 180 ℃, obtain crude product;
Opening the nitrogen of thinning vessel and controlling its flow is 3m
3/ h opens the cold oil of thinning vessel inner coil pipe, accompanies the water coolant of pipe outward, opens and stirs, and drops into the n-butyl acetate of 135 weight parts and the antiaging agent of 0.5 weight part to described thinning vessel, and described crude product changed over to carries out latting drown in the described thinning vessel;
Still to be changeed finishes, and drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 120 weight parts, and the material in the described thinning vessel is stirred cooling, be cooled to 130 ℃ after, be that the filter bag of 20 μ m filters with specification, the discharging barrelling obtains modified alkyd resin.
The modified alkyd resin that obtains is carried out Performance Detection, and detected result is as shown in table 1, the performance index of the modified alkyd resin that table 1 makes for the embodiment of the invention 1.
The performance index of the modified alkyd resin that table 1 embodiment of the invention 1 makes
As shown in Table 1, the modified alkyd resin that the present invention makes functional can form filming of different qualities, has very excellent service performance.
Embodiment 2
Logical in advance nitrogen is 3 minutes in empty reactor, and nitrogen flow is 5m
3/ h;
Drop into the diethyl malonate of 60 weight parts, the ethylene glycol of 50 weight parts and the tetrabutyl titanate of 1.5 weight parts successively to aforesaid reaction vessel and carry out transesterification reaction, in the logical nitrogen protection of reaction whole process, under whipped state, described temperature of reaction kettle is remained on 165 ℃ by type of heating, heat up in a steamer temperature control≤78.4 ℃, react after 3 hours, be warming up to 170 ℃ of reactions at least 10 minutes again, when no overhead product distillates, be terminal point, obtain the compound shown in the formula (I);
Close heating, drop into the behenic acid of 220 weight parts successively to aforesaid reaction vessel, the Hypophosporous Acid, 50 of the dimethylbenzene of 20 weight parts and 1 weight part (commodity are called M070), and drop into the phthalic anhydride of 270 weight parts successively to aforesaid reaction vessel by the special-purpose dog-house of powder, the cis-butenedioic anhydride of 7 weight parts, the tetramethylolmethane of the neopentyl glycol of 20 weight parts and 150 weight parts, under agitation heat up, be warming up to 180 ℃, insulation refluxed 2 hours, in 4 hours, be warming up to 220 ℃ then, be incubated to acid number≤18mgKOH/g, cooling when viscosity is 21 seconds～22 seconds/25 ℃ Ge Shi pipes, when treating that the interior temperature of described reactor is reduced to 180 ℃, obtain crude product;
Opening the nitrogen of thinning vessel and controlling its flow is 9m
3/ h opens the cold oil of thinning vessel inner coil pipe, accompanies the water coolant of pipe outward, opens and stirs, and drops into the n-butyl acetate of 150 weight parts and the antiaging agent of 1.5 weight parts to described thinning vessel, and described crude product changed over to carries out latting drown in the described thinning vessel;
Still to be changeed finishes, and drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 130 weight parts, and the material in the described thinning vessel is stirred cooling, be cooled to 130 ℃ after, be that the filter bag of 20 μ m filters with specification, the discharging barrelling obtains modified alkyd resin.
The modified alkyd resin that obtains is carried out Performance Detection, and detected result is as shown in table 2, the performance index of the modified alkyd resin that table 2 makes for the embodiment of the invention 2.
The performance index of the modified alkyd resin that table 2 embodiment of the invention 2 makes
As shown in Table 2, the modified alkyd resin that the present invention makes functional can form filming of different qualities, has very excellent service performance.
Embodiment 3
Logical in advance nitrogen is 5 minutes in empty reactor, and nitrogen flow is 5m
3/ h;
Drop into the diethyl malonate of 55 weight parts, the ethylene glycol of 47 weight parts and the tetrabutyl titanate of 0.1 weight part successively to aforesaid reaction vessel and carry out transesterification reaction, in the logical nitrogen protection of reaction whole process, under whipped state, described temperature of reaction kettle is remained on 160 ℃ by type of heating, heat up in a steamer temperature control≤78.4 ℃, react after 4 hours, be warming up to 165 ℃ of reactions at least 10 minutes again, when no overhead product distillates, be terminal point, obtain the compound shown in the formula (I);
Close heating, drop into the behenic acid of 216 weight parts successively to aforesaid reaction vessel, the Hypophosporous Acid, 50 of the dimethylbenzene of 18 weight parts and 0.7 weight part (commodity are called M070), and drop into the phthalic anhydride of 261 weight parts successively to aforesaid reaction vessel by the special-purpose dog-house of powder, the cis-butenedioic anhydride of 6 weight parts, the tetramethylolmethane of the neopentyl glycol of 17 weight parts and 142 weight parts, under agitation heat up, be warming up to 178 ℃, insulation refluxed 2 hours, in 4 hours, be warming up to 215 ℃ then, be incubated to acid number≤18mgKOH/g, cooling when viscosity is 19 seconds～20 seconds/25 ℃ Ge Shi pipes, when treating that the interior temperature of described reactor is reduced to 180 ℃, obtain crude product;
Opening the nitrogen of thinning vessel and controlling its flow is 5m
3/ h opens the cold oil of thinning vessel inner coil pipe, accompanies the water coolant of pipe outward, opens and stirs, and drops into the n-butyl acetate of 140 weight parts and the antiaging agent of 0.8 weight part to described thinning vessel, and described crude product changed over to carries out latting drown in the described thinning vessel;
Still to be changeed finishes, and drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 125 weight parts, and the material in the described thinning vessel is stirred cooling, be cooled to 130 ℃ after, be that the filter bag of 20 μ m filters with specification, the discharging barrelling obtains modified alkyd resin.
The modified alkyd resin that obtains is carried out Performance Detection, and detected result is as shown in table 3, the performance index of the modified alkyd resin that table 3 makes for the embodiment of the invention 3.
The performance index of the modified alkyd resin that table 3 embodiment of the invention 3 makes
As shown in Table 3, the modified alkyd resin that the present invention makes functional can form filming of different qualities, has very excellent service performance.
Embodiment 4
Logical in advance nitrogen is 4.5 minutes in empty reactor, and nitrogen flow is 4m
3/ h;
Drop into the diethyl malonate of 56 weight parts, the ethylene glycol of 48 weight parts and the tetrabutyl titanate of 0.11 weight part successively to aforesaid reaction vessel and carry out transesterification reaction, in the logical nitrogen protection of reaction whole process, under whipped state, described temperature of reaction kettle is remained on 160 ℃ by type of heating, heat up in a steamer temperature control≤78.4 ℃, react after 4 hours, be warming up to 165 ℃ of reactions at least 10 minutes again, when no overhead product distillates, be terminal point, obtain the compound shown in the formula (I);
Close heating, drop into the behenic acid of 214 weight parts successively to aforesaid reaction vessel, 18.5 the Hypophosporous Acid, 50 of the dimethylbenzene of weight part and 0.8 weight part (commodity are called M070), and drop into the phthalic anhydride of 260 weight parts successively to aforesaid reaction vessel by the special-purpose dog-house of powder, 5.7 the cis-butenedioic anhydride of weight part, the tetramethylolmethane of the neopentyl glycol of 18 weight parts and 145 weight parts, under agitation heat up, be warming up to 180 ℃, insulation refluxed 2 hours, in 4 hours, be warming up to 215 ℃ then, be incubated to acid number≤18mgKOH/g, cooling when viscosity is 18 seconds～19 seconds/25 ℃ Ge Shi pipes, when treating that the interior temperature of described reactor is reduced to 180 ℃, obtain crude product;
Opening the nitrogen of thinning vessel and controlling its flow is 4.5m
3/ h opens the cold oil of thinning vessel inner coil pipe, accompanies the water coolant of pipe outward, opens and stirs, and drops into the n-butyl acetate of 142 weight parts and the antiaging agent of 0.9 weight part to described thinning vessel, and described crude product changed over to carries out latting drown in the described thinning vessel;
Still to be changeed finishes, and drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 126 weight parts, and the material in the described thinning vessel is stirred cooling, be cooled to 130 ℃ after, be that the filter bag of 20 μ m filters with specification, the discharging barrelling obtains modified alkyd resin.
The modified alkyd resin that obtains is carried out Performance Detection, and detected result is as shown in table 4, the performance index of the modified alkyd resin that table 4 makes for the embodiment of the invention 4.
The performance index of the modified alkyd resin that table 4 embodiment of the invention 4 makes
As shown in Table 4, the modified alkyd resin that the present invention makes functional can form filming of different qualities, has very excellent service performance.
Comparative example 1
Logical in advance nitrogen is 5 minutes in empty reactor, and nitrogen flow is 3.5m
3/ h;
Drop into the behenic acid of 216 weight parts successively to aforesaid reaction vessel, the Hypophosporous Acid, 50 of the dimethylbenzene of 18 weight parts and 0.7 weight part (commodity are called M070), and drop into the phthalic anhydride of 261 weight parts successively to aforesaid reaction vessel by the special-purpose dog-house of powder, the cis-butenedioic anhydride of 6 weight parts, the tetramethylolmethane of the neopentyl glycol of 105 weight parts and 142 weight parts, under agitation heat up, be warming up to 180 ℃, insulation refluxed 2 hours, in 3 hours, be warming up to 215 ℃ then, be incubated to acid number≤18mgKOH/g, cooling when viscosity is 19 seconds/25 ℃ Ge Shi pipes, when treating that the interior temperature of described reactor is reduced to 180 ℃, obtain crude product;
Opening the nitrogen of thinning vessel and controlling its flow is 3m
3/ h opens the cold oil of thinning vessel inner coil pipe, accompanies the water coolant of pipe outward, opens and stirs, and drops into the n-butyl acetate of 145 weight parts and the antiaging agent of 0.8 weight part to described thinning vessel, and described crude product changed over to carries out latting drown in the described thinning vessel;
Still to be changeed finishes, and drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 130 weight parts, and the material in the described thinning vessel is stirred cooling, after being cooled to 130 ℃, with specification is that the filter bag of 20 μ m filters, and the discharging barrelling obtains adopting the Synolac of the common modification of behenic acid.
The Synolac that obtains is carried out Performance Detection, and detected result is as shown in table 5, the performance index of the Synolac that table 5 makes for comparative example 1 of the present invention.
The performance index of the Synolac that table 5 comparative example 1 of the present invention makes
Comparative example 2
Logical in advance nitrogen is 6 minutes in empty reactor, and nitrogen flow is 4.0m
3/ h;
Drop into the behenic acid of 220 weight parts successively to aforesaid reaction vessel, the glycol ether of 54 weight parts, the Hypophosporous Acid, 50 of the dimethylbenzene of 18 weight parts and 0.7 weight part (commodity are called M070), and drop into the phthalic anhydride of 260 weight parts successively to aforesaid reaction vessel by the special-purpose dog-house of powder, the cis-butenedioic anhydride of 5 weight parts, the tetramethylolmethane of the neopentyl glycol of 50 weight parts and 144 weight parts, under agitation heat up, be warming up to 180 ℃, insulation refluxed 2 hours, in 3 hours, be warming up to 215 ℃ then, be incubated to acid number≤18mgKOH/g, cooling when viscosity is 19 seconds/25 ℃ Ge Shi pipes, when treating that the interior temperature of described reactor is reduced to 180 ℃, obtain crude product;
Opening the nitrogen of thinning vessel and controlling its flow is 3m
3/ h opens the cold oil of thinning vessel inner coil pipe, accompanies the water coolant of pipe outward, opens and stirs, and drops into the n-butyl acetate of 145 weight parts and the antiaging agent of 0.8 weight part to described thinning vessel, and described crude product changed over to carries out latting drown in the described thinning vessel;
Still to be changeed finishes, and drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 130 weight parts, and the material in the described thinning vessel is stirred cooling, after being cooled to 130 ℃, with specification is that the filter bag of 20 μ m filters, and the discharging barrelling obtains adopting the Synolac of the common modification of behenic acid.
The Synolac that obtains is carried out Performance Detection, and detected result is as shown in table 6, the performance index of the Synolac that table 6 makes for comparative example 2 of the present invention.
The performance index of the Synolac that table 6 comparative example 2 of the present invention makes
Embodiment 5
The dispersion agent of modified alkyd resin that the embodiment 1 of 50 weight parts is made and 1 weight part drops in the pill tank successively, disperses 10 minutes under 300 rev/mins rotating speed, makes to be uniformly dispersed;
Drop into the titanium dioxide of 28 weight parts and the functional powder of 1 weight part successively to described pill tank then, under 1600 rev/mins rotating speed, disperseed 25 minutes, be ground to fineness≤30 μ m again;
Drop into the polyethylene wax powder of 0.3 weight part and the flatting silica of 4 weight parts successively to described pill tank again, under 1600 rev/mins rotating speed, disperseed 20 minutes;
At last drop into the anti-settling agent of 1 weight part, the non-silicon defoamer of 0.05 weight part, first flow agent of 0.1 weight part, second flow agent of 0.1 weight part and the 1-Methoxy-2-propyl acetate of 2 weight parts successively to described pill tank, under 300 rev/mins rotating speed, disperseed 8 minutes, obtain the mute light white finish paint of two components.
According to method mentioned above, the mute light white finish paint of described pair of component is removed formaldehyde efficient and persistence detection.Detected result is as shown in table 7, the clear aldehyde detected result of the mute light white finish paint of two components that table 7 provides for the embodiment of the invention 5～8 and comparative example 3,4.
Embodiment 6
The dispersion agent of modified alkyd resin that the embodiment 2 of 60 weight parts is made and 3 weight parts drops in the pill tank successively, disperses 5 minutes under 500 rev/mins rotating speed, makes to be uniformly dispersed;
Drop into the titanium dioxide of 32 weight parts and the functional powder of 3 weight parts successively to described pill tank then, under 2000 rev/mins rotating speed, disperseed 20 minutes, be ground to fineness≤30 μ m again;
Drop into the polyethylene wax powder of 0.7 weight part and the flatting silica of 5 weight parts successively to described pill tank again, under 2000 rev/mins rotating speed, disperseed 15 minutes;
At last drop into the anti-settling agent of 3 weight parts, the non-silicon defoamer of 0.15 weight part, first flow agent of 0.3 weight part, second flow agent of 0.3 weight part and the 1-Methoxy-2-propyl acetate of 4 weight parts successively to described pill tank, under 500 rev/mins rotating speed, disperseed 4 minutes, obtain the mute light white finish paint of two components.
According to method mentioned above, the mute light white finish paint of described pair of component is removed formaldehyde efficient and persistence detection, detected result is as shown in table 7.
Embodiment 7
The dispersion agent of modified alkyd resin that the embodiment 3 of 55.5 weight parts is made and 2 weight parts drops in the pill tank successively, disperses 8 minutes under 400 rev/mins rotating speed, makes to be uniformly dispersed;
Drop into the titanium dioxide of 30 weight parts and the functional powder of 2 weight parts successively to described pill tank then, under 1800 rev/mins rotating speed, disperseed 22 minutes, be ground to fineness≤30 μ m again;
Drop into the polyethylene wax powder of 0.5 weight part and the flatting silica of 4.5 weight parts successively to described pill tank again, under 1800 rev/mins rotating speed, disperseed 18 minutes;
At last drop into the anti-settling agent of 2 weight parts, the non-silicon defoamer of 0.1 weight part, first flow agent of 0.2 weight part, second flow agent of 0.2 weight part and the 1-Methoxy-2-propyl acetate of 3 weight parts successively to described pill tank, under 400 rev/mins rotating speed, disperseed 6 minutes, obtain the mute light white finish paint of two components.
According to method mentioned above, the mute light white finish paint of described pair of component is removed formaldehyde efficient and persistence detection, detected result is as shown in table 7.
Embodiment 8
The dispersion agent of modified alkyd resin that the embodiment 4 of 55 weight parts is made and 2 weight parts drops in the pill tank successively, disperses 10 minutes under 400 rev/mins rotating speed, makes to be uniformly dispersed;
Drop into the titanium dioxide of 29 weight parts and the functional powder of 2.5 weight parts successively to described pill tank then, under 1800 rev/mins rotating speed, disperseed 20 minutes, be ground to fineness≤30 μ m again;
Drop into the polyethylene wax powder of 0.5 weight part and the flatting silica of 4.5 weight parts successively to described pill tank again, under 1800 rev/mins rotating speed, disperseed 15 minutes;
At last drop into the anti-settling agent of 2 weight parts, the non-silicon defoamer of 0.12 weight part, first flow agent of 0.2 weight part, second flow agent of 0.2 weight part and the 1-Methoxy-2-propyl acetate of 3 weight parts successively to described pill tank, under 500 rev/mins rotating speed, disperseed 5 minutes, obtain the mute light white finish paint of two components.
According to method mentioned above, the mute light white finish paint of described pair of component is removed formaldehyde efficient and persistence detection, detected result is as shown in table 7.
Comparative example 3
With reference to embodiment 7, the Synolac that comparative example 1 obtains to be made the mute light white finish paint of two components, and, the mute light white finish paint of described pair of component is removed formaldehyde efficient and persistence detection according to method mentioned above, detected result is as shown in table 7.
Comparative example 4
With reference to embodiment 8, the Synolac that comparative example 2 obtains to be made the mute light white finish paint of two components, and, the mute light white finish paint of described pair of component is removed formaldehyde efficient and persistence detection according to method mentioned above, detected result is as shown in table 7.The mute light white finish paint of two components that table 7 embodiment of the invention 5～8 and comparative example 3,4 provide clear
The aldehyde detected result
As shown in Table 7, the mute light white finish paint of two components that the embodiment of the invention provides is being removed the technical requirement that meets relevant regulations on formaldehyde efficient and the persistence, has excellent removing formaldehyde function.
By above embodiment and comparative example as can be known, modified alkyd resin provided by the invention is applied to have good removing formaldehyde effect in the mute light white finish paint of two components.
In addition, the present invention adopts the method for compound modified Synolac of formula (I) institute formula simple to operate, and product is stable between batch.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a modified alkyd resin is made through reaction by pure acid mixture, and described pure acid mixture comprises:
The behenic acid of 210～220 weight parts;
The phthalic anhydride of 250～270 weight parts;
The cis-butenedioic anhydride of 5～7 weight parts;
The neopentyl glycol of 15～20 weight parts;
The tetramethylolmethane of 135～150 weight parts;
0.5 the oxidation inhibitor of losing lustre of～1 weight part;
The band aqua of 15～20 weight parts;
The letdown solvent dun of 255～280 weight parts;
0.5 the antiaging agent of～1.5 weight parts;
Compound shown in the formula of 60～76 weight parts (I):
In the formula (I), 1≤n≤4.
2. modified alkyd resin according to claim 1, it is characterized in that, n is 2, compound shown in the described formula (I), is made through transesterification reaction under the katalysis of the tetrabutyl titanate of 0.05～0.15 weight part by the ethylene glycol of the diethyl malonate of 50～60 weight parts and 40～50 weight parts.
3. modified alkyd resin according to claim 1 is characterized in that, described band aqua is selected from any in dimethylbenzene, toluene and the benzene.
4. modified alkyd resin according to claim 1 is characterized in that, described letdown solvent dun is the mixture of dimethylbenzene and n-butyl acetate.
5. the preparation method of a modified alkyd resin comprises:
Pure acid mixture is reacted, obtain modified alkyd resin, described pure acid mixture comprises:
The behenic acid of 210～220 weight parts;
The phthalic anhydride of 250～270 weight parts;
The cis-butenedioic anhydride of 5～7 weight parts;
The neopentyl glycol of 15～20 weight parts;
The tetramethylolmethane of 135～150 weight parts;
0.5 the oxidation inhibitor of losing lustre of～1 weight part;
The band aqua of 15～20 weight parts;
The letdown solvent dun of 255～280 weight parts;
0.5 the antiaging agent of～1.5 weight parts;
Compound shown in the formula of 60～76 weight parts (I):
In the formula (I), 1≤n≤4.
6. preparation method according to claim 5 is characterized in that, specifically comprises:
Diethyl malonate and ethylene glycol are carried out transesterification reaction under the katalysis of tetrabutyl titanate, obtain the compound shown in the formula (I), n is 2;
React with compound, behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, the band aqua shown in the described formula (I) and after the oxidation inhibitor of losing lustre mixes, obtain crude product;
Described crude product, letdown solvent dun are mixed with antiaging agent, obtain modified alkyd resin.
7. mute light white finish paint of two components comprises:
Each described modified alkyd resin of the claim 1～4 of 50～60 weight parts or the modified alkyd resin that adopts claim 5 or 6 described preparation methods to make;
The dispersion agent of 1～3 weight part;
The titanium dioxide of 28～32 weight parts;
The functional powder of 1～3 weight part;
0.3 the polyethylene wax powder of～0.7 weight part;
The flatting silica of 4～5 weight parts;
The anti-settling agent of 1～3 weight part;
0.05 the non-silicon defoamer of～0.15 weight part;
0.1 first flow agent of～0.3 weight part;
0.1 second flow agent of～0.3 weight part;
The 1-Methoxy-2-propyl acetate of 2～4 weight parts.
8. pair component according to claim 7 light white finish paint of making mute is characterized in that described dispersion agent is that model is the dispersion agent of BYK-110.
9. pair component according to claim 7 light white finish paint of making mute is characterized in that described functional powder is a negative ion powder.
10. pair component according to claim 7 light white finish paint of making mute is characterized in that described first flow agent is a polysiloxane polyether copolymer, and described second flow agent is the poly-methyl alkyl siloxane of aralkyl modification.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673066A (en) * | 2013-11-29 | 2015-06-03 | 立邦涂料（中国）有限公司 | Woodware varnish having function of removing formaldehyde and preparation method thereof |
| CN106669558A (en) * | 2016-12-09 | 2017-05-17 | 重庆健杰科技有限公司 | High-speed stirring reaction kettle |
| CN106700488A (en) * | 2016-12-20 | 2017-05-24 | 重庆市长寿区舒福食品有限公司 | Biodegradable food packing bag |
| CN112661646A (en) * | 2020-12-11 | 2021-04-16 | 江苏长能节能新材料科技有限公司 | Active methylene type aldehyde remover and application thereof |
| CN114805774A (en) * | 2022-04-01 | 2022-07-29 | 佛山市国化新材料科技有限公司 | Carboxylated nano chitin-based alkyd resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179170A (en) * | 2011-03-15 | 2011-09-14 | 上海格伦化学科技有限公司 | Formaldehyde-removing alkyd resin and preparation method thereof |
| CN103055465A (en) * | 2011-10-18 | 2013-04-24 | 上海格伦化学科技有限公司 | Formaldehyde scavenging agent with oil solubility and preparation method |
-
2013
- 2013-05-03 CN CN201310160681.3A patent/CN103214662B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179170A (en) * | 2011-03-15 | 2011-09-14 | 上海格伦化学科技有限公司 | Formaldehyde-removing alkyd resin and preparation method thereof |
| CN103055465A (en) * | 2011-10-18 | 2013-04-24 | 上海格伦化学科技有限公司 | Formaldehyde scavenging agent with oil solubility and preparation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673066A (en) * | 2013-11-29 | 2015-06-03 | 立邦涂料（中国）有限公司 | Woodware varnish having function of removing formaldehyde and preparation method thereof |
| CN106669558A (en) * | 2016-12-09 | 2017-05-17 | 重庆健杰科技有限公司 | High-speed stirring reaction kettle |
| CN106700488A (en) * | 2016-12-20 | 2017-05-24 | 重庆市长寿区舒福食品有限公司 | Biodegradable food packing bag |
| CN112661646A (en) * | 2020-12-11 | 2021-04-16 | 江苏长能节能新材料科技有限公司 | Active methylene type aldehyde remover and application thereof |
| CN114805774A (en) * | 2022-04-01 | 2022-07-29 | 佛山市国化新材料科技有限公司 | Carboxylated nano chitin-based alkyd resin and preparation method thereof |
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| CN103214662B (en) | 2015-04-01 |
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