CN103214662B - 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 two component matte white finish.
Background technology
Formaldehyde is a kind of colourless, gas of having intense stimulus smell, and relative molecular mass is 30.03, soluble in water, alcohol and ether.Mass concentration is 35% ~ 40%, be generally the formalin of 37% is otherwise known as " formalin " solution, and it is at room temperature highly volatile.Formaldehyde has good chemical reactivity and the cost performance of excellence, is a kind of important organic raw material be widely used, can plays an important role in industrial production and preservation process etc.But formaldehyde free in air is but a kind of serious pollutent.Formaldehyde belongs to 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, artificial interpolation and these five aspects of food own metabolism.Formaldehyde is all classified as potential carcinogens and important environmental pollutant by the World Health Organization and EPA, on April 16th, 1987, China national Environmental Protection Agency also announces that formaldehyde is human body suspect carcinogen.Regulation in the CNS GB-T16127-1995 hygienic standard of formaldehyde " in the indoor air ": in Indoor Air, formaldehyde hygienic standard (maximum allowable concentration) is 0.08mg/m
3.Because indoor are the resident for a long time places of people, remove Formaldehyde Pollution of Indoor Air, ensure that IAQ (indoor air quality) is particularly important to people.
At present, the technology that domestic civilian coating industry removes formaldehyde mainly contains physisorphtion, negative ion decomposition method, chitosan biological matter method and photocatalysis Decomposition method.Wherein, photocatalysis Decomposition method is a kind of novel improvement formaldehyde air pollution technologies, and be now applied in aqueous coating system, clear aldehyde speed is fast, effective; Through carrying out coating modification to its surface, as adopted dodecyltrimethoxysilane or KH-570 silane coupling agent to carry out modification, can lipophilicity be improved, thus can be applicable in oiliness wood lacquer.But this technology exists following two problems: one is under visible light, and photocatalysis efficiency is lower, two is that the free radical generated can by usual resins oxygenolysis and cause coating surface efflorescence easily.Therefore, this technical know-how is only applicable in the super ultraviolet resistance oil paint such as fluoro-resin and polysiloxane system, range of application is narrower.As shown in the above, the task of top priority that the exploitation of the clear aldehyde technology of the coating compound be more of practical significance and application have become in functional coatings industry.
The Synolac good film-forming property be widely used in paint field, rete after film-forming has gloss, toughness and stronger sticking power, and the feature such as good wear resistance, weathering resistance and insulativity, it is generally a class by the oily modified polyester resin of polyvalent alcohol, diprotic acid and lipid acid or grease condensation polymerization, as the Synolac by materials synthesis such as behenic acid, tetramethylolmethane and ethylene glycol, or by the Synolac of the materials synthesis such as glycerine, neopentyl glycol and orthoformic acid.Although above-mentioned existing Synolac is after being mixed with coating, in decoration and protection etc., performance is good, also cannot reach the Functional Requirement removing formaldehyde.Therefore, applicant considers, Synolac is carried out modification, has good removing effect of formaldehyde after making it be applied to coating.
Summary of the invention
In order to solve above technical problem, the invention provides the two component matte white finish of a kind of modified alkyd resin, its preparation method and one, this modified alkyd resin is applied in two component matte white finish, has good removing effect of formaldehyde.
The invention provides a kind of modified alkyd resin, be made up through reaction of alcohol acid mixture, described alcohol 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;
The oxidation inhibitor of losing lustre of 0.5 ~ 1 weight part;
The water entrainer of 15 ~ 20 weight parts;
The letdown solvent dun of 255 ~ 280 weight parts;
The antiaging agent of 0.5 ~ 1.5 weight part;
The compound shown in formula (I) of 60 ~ 76 weight parts:
In formula (I), 1≤n≤4.
Preferably, n is 2, and the compound shown in described formula (I), is obtained through transesterification reaction by the diethyl malonate of 50 ~ 60 weight parts and the ethylene glycol of 40 ~ 50 weight parts under the katalysis of the tetrabutyl titanate of 0.05 ~ 0.15 weight part.
Preferably, described water entrainer is selected from any one in dimethylbenzene, toluene and 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:
Reacted by alcohol acid mixture, obtain modified alkyd resin, described alcohol 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;
The oxidation inhibitor of losing lustre of 0.5 ~ 1 weight part;
The water entrainer of 15 ~ 20 weight parts;
The letdown solvent dun of 255 ~ 280 weight parts;
The antiaging agent of 0.5 ~ 1.5 weight part;
The compound shown in formula (I) of 60 ~ 76 weight parts:
In formula (I), 1≤n≤4.
Preferably, specifically comprise:
Diethyl malonate and ethylene glycol are carried out transesterification reaction under the katalysis of tetrabutyl titanate, obtains the compound shown in formula (I), n is 2;
Compound shown in described formula (I), behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, water entrainer are reacted after mixing with oxidation inhibitor of losing lustre, obtains crude product;
Described crude product, letdown solvent dun are mixed with antiaging agent, obtains modified alkyd resin.
Compared with prior art, the ageing-resistant alcohol acid mixture of the oxidation inhibitor of losing lustre of the tetramethylolmethane of the neopentyl glycol of the cis-butenedioic anhydride of the phthalic anhydride of the behenic acid of the compound shown in the formula (I) comprising 60 ~ 76 weight parts, 210 ~ 220 weight parts, 250 ~ 270 weight parts, 5 ~ 7 weight parts, 15 ~ 20 weight parts, 135 ~ 150 weight parts, 0.5 ~ 1 weight part, the water entrainer of 15 ~ 20 weight parts, the letdown solvent dun of 255 ~ 280 weight parts and 0.5 ~ 1.5 weight part reacts by the present invention, obtains modified alkyd resin.The present invention adopts the convenient source such as behenic acid, tetramethylolmethane, neopentyl glycol, phthalic anhydride and cis-butenedioic anhydride to prepare Synolac, adopts the compound shown in formula (I) to carry out modification simultaneously.Compound shown in described formula (I), with-OH functional group, can be grafted on resin segment; Further, because the molecule segment after grafting contains O=C-CH
2-C=O, it comprises active methylene group, can carry out nucleophilic reaction, thus obtain a kind of Synolac with function of removing formaldehyde clearly after film process or film forming with the formaldehyde molecule being adsorbed on its surface.
In addition, the present invention adopts the method for the compound modified Synolac shown in formula (I) simple to operate, and between batch, product is stablized.
The invention provides a kind of two component matte white finish, 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;
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;
The 1-Methoxy-2-propyl acetate of 2 ~ 4 weight parts.
Preferably, the dispersion agent of described dispersion agent to be model be BYK-110.
Preferably, described functional powder is negative ion powder.
Preferably, described first flow agent is polysiloxane polyether copolymer, and described second flow agent is aralkyl modified poly-methyl alkyl siloxane.
Compared with prior art, provided by the invention pair of component matte white finish mainly comprises modified alkyd resin mentioned above, and with the components matching such as dispersion agent, functional powder and flow agent, there is very excellent service performance.Detect being sprayed on glass after described pair of component matte white finish dilution, detected result shows, provided by the invention pair of component matte white finish can meet paint film requirement in gloss, hardness etc., and has excellent clear function of removing formaldehyde.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of modified alkyd resin, be made up through reaction of alcohol acid mixture, described alcohol 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;
The oxidation inhibitor of losing lustre of 0.5 ~ 1 weight part;
The water entrainer of 15 ~ 20 weight parts;
The letdown solvent dun of 255 ~ 280 weight parts;
The antiaging agent of 0.5 ~ 1.5 weight part;
The compound shown in formula (I) of 60 ~ 76 weight parts:
In formula (I), 1≤n≤4.
The present invention is that main raw material forms alcohol acid mixture, through being obtained by reacting modified alkyd resin with the compound shown in polyvalent alcohol, organic acid, auxiliary agent and a certain amount of formula (I).Described modified alkyd resin is applied in the coating such as two component matte white finish as filmogen, has the function removing formaldehyde.
In the present invention, the raw material as polyvalent alcohol has neopentyl glycol and tetramethylolmethane.Wherein, described alcohol acid mixture comprises the neopentyl glycol of 15 ~ 20 weight parts, preferably comprises the neopentyl glycol of 16 ~ 18 weight parts.Neopentyl glycol, owing to having two methyl branches, can bring Synolac molecule and other resin as polyurethane curing agent or the splendid consistency of solvent.
Described alcohol 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, is also a kind of polyvalent alcohol that synthetic alkyd resin is conventional.Because the functionality of tetramethylolmethane is larger, with its Synolac glyptal fast drying more of the same type for polyvalent alcohol synthesis, and the performances such as gloss, hardness, gloss retention and alkali resistance are also better, therefore tetramethylolmethane is a kind of rising Synolac raw material.The present invention is not particularly limited described tetramethylolmethane, preferably adopts monopentaerythritol content to be the tetramethylolmethane of 95%.
In the present invention, behenic acid, phthalic anhydride and cis-butenedioic anhydride is had as organic acid raw material.Wherein, described alcohol 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 (acid anhydride) of synthetic alkyd resin.
Described alcohol acid mixture comprises the cis-butenedioic anhydride of 5 ~ 7 weight parts, preferably comprises the cis-butenedioic anhydride of 5 ~ 6 weight parts.The full name MALEIC ANHYDRIDE of cis-butenedioic anhydride, also may be used for manufacturing Synolac.
Described alcohol 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 is more weak, applies comparatively extensive.
In the present invention, the compound shown in formula (I) is adopted to obtain modified alkyd resin.That is, described alcohol acid mixture comprises the compound shown in formula (I) of 60 ~ 76 weight parts, preferably comprises the compound shown in formula (I) of 68 ~ 72 weight parts.In formula (I), 1≤n≤4, preferred n is 2.
Compound shown in described formula (I), with-OH functional group, can be grafted on resin segment; Further, because the molecule segment after grafting contains O=C-CH
2-C=O, it comprises active methylene group, can carry out nucleophilic reaction, thus obtain a kind of Synolac with function of removing formaldehyde clearly after film process or film forming with the formaldehyde molecule being adsorbed on its surface.The molecular structural formula of described resin can as shown in the formula (II):
Because Synolac molecule is a kind of macromolecule mixture, R, R in formula (II) ' be uncertain structure, can for being grafted with the tetramethylolmethane remnants segment of behenic acid segment, also can be the remaining segment of neopentyl glycol, can also for being grafted with the remaining segment etc. that the remaining segment of phthalic anhydride or more described tetramethylolmethane, neopentyl glycol, behenic acid etc. is connected simultaneously.
The source of the present invention to the compound shown in described formula (I) is not particularly limited, and can buy from the market, also can prepare voluntarily.
When n is 2, the compound shown in described formula (I) preferably by the diethyl malonate of 50 ~ 60 weight parts and the ethylene glycol of 40 ~ 50 weight parts under the katalysis of the tetrabutyl titanate of 0.05 ~ 0.15 weight part, obtain through transesterification reaction.
In the present invention, described transesterification reaction take diethyl malonate as raw material, preferably adopts the diethyl malonate of 53 ~ 57 weight parts; Be another raw material with ethylene glycol, preferably adopt the ethylene glycol of 43 ~ 48 weight parts; Take tetrabutyl titanate as catalyzer, preferably adopt the tetrabutyl titanate of 0.08 ~ 0.12 weight part.In the present invention, described transesterification reaction and diethyl malonate and ethylene glycol under the catalysis of tetrabutyl titanate, the reaction of this new ester of the compound shown in production (I) and a new alcohol, wherein, tetrabutyl titanate is a kind of transesterification catalyst of excellence, and cost is lower; By product is ethanol, and it is 60 ~ 76 weight parts that the compound shown in target product formula (I) must be measured.
Described transesterification reaction preferably adopts atmospheric pressure device, and reaction whole process leads to rare gas element 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 DEG C ~ 165 DEG C by type of heating, heats up in a steamer temperature control≤78.4 DEG C, react after 3 hours ~ 5 hours, being warming up to 165 DEG C ~ 170 DEG C and reacting at least 10 minutes again, being terminal when distillating without overhead product, obtain the compound shown in formula (I-1);
The present invention adopts the transesterification reaction of diethyl malonate and ethylene glycol to prepare the compound shown in formula I, and is catalyzer with tetrabutyl titanate, and this is the reaction of a kind of normal pressure synthesis, and temperature of reaction is low, simple to operate, and between batch, product is stablized.
In order to obtain modified alkyd resin of good performance, the present invention also comprises a certain amount of auxiliary agent.Wherein, described alcohol acid mixture comprises the water entrainer of 15 ~ 20 weight parts, preferably comprises the water entrainer of 17 ~ 19 weight parts.Described water entrainer can reflux the micromolecular water sloughed in esterification process, Synolac reaction is carried out to esterifying polycondensation the Direction of Reaction.Further, the present invention controls the consumption of described water entrainer in above-mentioned scope, promotes that reaction is carried out further.Described water entrainer is preferably any one in dimethylbenzene, toluene and benzene, is more preferably dimethylbenzene, and when the present invention utilizes dimethylbenzene and water azeotropic, water accounts for the character that azeotrope ratio reaches 37.5%, adopts it to slough water, is beneficial to and obtains modified alkyd resin.
Described alcohol 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 by resin chemical solution, obtains modified alkyd resin.Described letdown solvent dun is preferably the mixture of dimethylbenzene and n-butyl acetate, easy and simple to handle, and products obtained therefrom quality is better.
Described alcohol 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.Described oxidation inhibitor of losing lustre can play antioxidant effect of losing lustre in Synolac building-up process, to improve appearance property and the application performance of Synolac.Described oxidation inhibitor of losing lustre can be the material such as Hypophosporous Acid, 50, triphenyl phosphite; From trade names, described in oxidation inhibitor of losing lustre include but not limited to lose lustre oxidation inhibitor SH-1, lose lustre oxidation inhibitor 3032 and oxidation inhibitor M070 of losing lustre, effectively can improve the color of resin.
Described alcohol 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 reduces the degree of aging of Synolac.Described antiaging agent can be phenolic compound, and can be also ester compound, 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 BHT.
Accordingly, the invention provides a kind of preparation method of modified alkyd resin, comprising:
Reacted by alcohol acid mixture, obtain modified alkyd resin, described alcohol 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;
The oxidation inhibitor of losing lustre of 0.5 ~ 1 weight part;
The water entrainer of 15 ~ 20 weight parts;
The letdown solvent dun of 255 ~ 280 weight parts;
The antiaging agent of 0.5 ~ 1.5 weight part;
The compound shown in formula (I) of 60 ~ 76 weight parts:
In formula (I), 1≤n≤4.
The present invention is that raw material reacts with the alcohol acid mixture comprising the compound shown in polyvalent alcohol, organic acid, auxiliary agent and formula (I), generate modified alkyd resin, make described modified alkyd resin as filmogen, be applied in the coating such as two component matte white finish, there is good performance, especially remove the excellent effect of formaldehyde.
In the present invention, the raw material as polyvalent alcohol has neopentyl glycol and tetramethylolmethane; Behenic acid, phthalic anhydride and cis-butenedioic anhydride is had as organic acid raw material.These convenient source are consistent with content mentioned above, and this is no longer going to repeat them.
The present invention adopts the compound shown in formula (I) to obtain modified alkyd resin.That is, described alcohol acid mixture comprises the compound shown in formula (I) of 60 ~ 76 weight parts, preferably comprises the compound shown in formula (I) of 68 ~ 72 weight parts.In formula (I), 1≤n≤4, preferred n is 2.Compound shown in described formula (I), with-OH functional group, can be grafted on resin segment; Further, because the molecule segment after grafting contains O=C-CH
2-C=O, it comprises active methylene group, can carry out nucleophilic reaction, thus obtain a kind of Synolac with function of removing formaldehyde clearly after film process or film forming with the formaldehyde molecule being adsorbed on its surface.
The present invention also adds a certain amount of auxiliary agent to obtain modified alkyd resin of good performance, mainly contains water entrainer, letdown solvent dun, lose lustre oxidation inhibitor and antiaging agent.The content of these auxiliary agents is consistent with content mentioned above, and this is no longer going to repeat them.
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, obtains the compound shown in formula (I), n is 2;
Compound shown in described formula (I), behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, water entrainer are reacted after mixing with oxidation inhibitor of losing lustre, obtains crude product;
Described crude product, letdown solvent dun are mixed with antiaging agent, obtains modified alkyd resin.
The embodiment of the present invention drops into the tetrabutyl titanate of the diethyl malonate of 50 ~ 60 weight parts, the ethylene glycol of 40 ~ 50 weight parts and 0.05 ~ 0.15 weight part to reactor; preferably under the condition stirred, carry out transesterification reaction after mixing; more preferably react after mixing under rare gas element is as nitrogen or carbon-dioxide protecting; most preferably react after mixing under continuous logical nitrogen protection, obtain the compound shown in formula (I).
In the present invention, described transesterification reaction take diethyl malonate as raw material, preferably adopts the diethyl malonate of 53 ~ 57 weight parts; Be another raw material with ethylene glycol, preferably adopt the ethylene glycol of 43 ~ 48 weight parts; Take tetrabutyl titanate as catalyzer, preferably adopt the tetrabutyl titanate of 0.08 ~ 0.12 weight part.In the present invention, described transesterification reaction and diethyl malonate and ethylene glycol under the catalysis of tetrabutyl titanate, the reaction of this new ester of the compound shown in production (I) and a new alcohol, wherein, tetrabutyl titanate is a kind of transesterification catalyst of excellence, and cost is lower; By product is ethanol, and it is 60 ~ 76 weight parts that the compound shown in target product formula (I) must be measured.
Described transesterification reaction preferably adopts atmospheric pressure device, is preferably specially:
Under whipped state, temperature of reaction kettle is remained on 150 DEG C ~ 165 DEG C by type of heating, heats up in a steamer temperature control≤78.4 DEG C, react after 3 hours ~ 5 hours, being warming up to 165 DEG C ~ 170 DEG C and reacting at least 10 minutes again, being terminal when distillating without overhead product, obtain the compound shown in formula (I).
The present invention adopts the compound shown in transesterification reaction preparation formula (I) of diethyl malonate and ethylene glycol, and is catalyzer with tetrabutyl titanate, and this is the reaction of a kind of normal pressure synthesis, and temperature of reaction is low, simple to operate, and between batch, product is stablized.
Then, the embodiment of the present invention then drops into behenic acid, the water entrainer of above-mentioned formulation weight number and oxidation inhibitor of losing lustre to aforesaid reaction vessel, and drop into the phthalic anhydride of above-mentioned formulation weight number, cis-butenedioic anhydride, neopentyl glycol and tetramethylolmethane by the special dog-house of powder, preferably mix under the condition stirred and react, obtain crude product.
In the present invention, described reaction is preferably carried out under rare gas element is as the protection of nitrogen, carbonic acid gas, not only can avoid side reaction, and be conducive to deviating from the low molecular weight volatile things such as water.That is, the present invention can lead to nitrogen or carbonic acid gas in a kettle. in advance, and the time controlling ventilation body is preferably 3 minutes ~ 8 minutes, is more preferably 5 minutes ~ 6 minutes; The flow controlling ventilation body is preferably 2m
3/ h ~ 5m
3/ h, is more preferably 3m
3/ h ~ 4m
3/ h, this flow is for 3M
3reactor.
Described reaction is preferably carried out in two-step approach heats up: be first warming up to 160 DEG C ~ 185 DEG C, and insulation backflow 1 hour ~ 2 hours, was then warming up to 200 DEG C ~ 220 DEG C in 3 hours ~ 5 hours.
After being warming up to 200 DEG C ~ 220 DEG C, the present invention is preferably incubated and lowers the temperature when acid number≤18mgKOH/g, viscosity are 16 seconds ~ 22 seconds/25 DEG C of form pipes, more preferably be incubated and lower the temperature when acid number≤15mgKOH/g, viscosity are 19 seconds ~ 20 seconds/25 DEG C of form pipes, be cooled to 180 DEG C ~ 200 DEG C, obtain crude product.It should be noted that, the testing method of this viscosity is: get solid resin and dimethylbenzene wiring solution-forming in reactor and test, the mass ratio of described solid resin and dimethylbenzene is 1:0.84, and namely solid resin accounting is about 53%.
After obtaining crude product, proceeded in thinning vessel to mix with letdown solvent dun, antiaging agent and carried out latting drown, obtained modified alkyd resin.
In the present invention, described latting drown preferably carries out under rare gas element is as the protection of nitrogen, carbonic acid gas.That is, the present invention can lead to nitrogen or carbonic acid gas in thinning vessel, and the flow controlling ventilation body is preferably 3m
3/ h ~ 9m
3/ h, is more preferably 4m
3/ h ~ 8m
3/ h, this flow is for 5M
3thinning vessel.Further, the present invention preferably opens the water coolant of the stirring of described thinning vessel, the cold oil of inner coil pipe and outer adjoining pipe.The time of described stirring, after being cooled to 100 DEG C ~ 130 DEG C, filter with the filter bag that specification is 20 μm, discharging barrelling, obtained modified alkyd resin preferably at more than 30min.
When the present invention adopts letdown solvent dun to carry out latting drown, by disposable for whole letdown solvent dun direct input thinning vessel, also first part letdown solvent dun can be dropped into thinning vessel, then drop into above-mentioned thinning vessel again by after another part letdown solvent dun cleaning reaction still.The letdown solvent dun of antiaging agent and 50% is preferably dropped into thinning vessel by the present invention, and carry out latting drown to the crude product proceeding to thinning vessel from reactor, still to be turned is complete, drops into thinning vessel again with after the letdown solvent dun cleaning reaction still of residue 50%.For the letdown solvent dun that dimethylbenzene mixes with n-butyl acetate, n-butyl acetate is preferably dropped into thinning vessel by the present invention in advance, after dimethylbenzene leaves cleaning reaction still, then drops into thinning vessel.
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, and the modified alkyd resin that the present invention obtains is yellow transparent thick liquid; When adopting the test of Fe-Co method, color and luster≤3; At 25 DEG C, viscosity is 8000mPas ~ 12000mPas; Acid number≤12.6mgKOH/g; Solid content (being called for short solid containing) is (70 ± 1.5) %.Show the functional of the modified alkyd resin that the present invention obtains, can form the film of different qualities, have very excellent service performance, Application Areas widely.
In addition, the present invention adopts the method for the compound modified Synolac shown in formula (I) simple to operate, and between batch, product is stablized.
Present invention also offers a kind of two component matte white finish, 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;
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;
The 1-Methoxy-2-propyl acetate of 2 ~ 4 weight parts.
Provided by the invention pair of component matte white finish mainly comprises modified alkyd resin mentioned above, and with the components matching such as dispersion agent, functional powder and flow agent, there is very excellent service performance, especially remove effect of formaldehyde good.
In the present invention, described pair of component matte white finish 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, as filmogen, is applied in coating, paint film can be made at gloss, levelling and remove many-sided performances with excellence such as formaldehyde, being beneficial to application.
The described pair of component matte white finish also comprises the 1-Methoxy-2-propyl acetate of 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, the first flow agent of 0.1 ~ 0.3 weight part, the second flow agent of 0.1 ~ 0.3 weight part and 2 ~ 4 weight parts, these compositions and described modified alkyd resin with the use of, obtain two component matte white finish of better performances.
Wherein, described titanium dioxide formal name used at school titanium dioxide, can strengthen physical strength and the sticking power of paint film, prevent crackle, prevent ultraviolet and moisture through, thus extend the paint film life-span; Described titanium dioxide is that this area is conventional, is the titanium dioxide of the R-706 of du pont company as the trade mark.It is specifically functional that described functional powder can give coating, is preferably negative ion powder, and this negative ion can generating negative ions effect when faint change occurs environment, has larger help to the improvement of human residential environment.Described polyethylene wax powder is in the process of the film forming of powder coating, and when film cooling, polyethylene wax is separated out from masking liquid, forms fine particle, floats over film coated surface, play the effects such as texture, delustring, smooth and anti-wiping scuffing; Described polyethylene wax powder is that this area is conventional.Described flatting silica can balancedly control film coated surface gloss, and has effects such as increasing the wear resistance of film and mar-resistance; Described flatting silica is that this area is conventional.
Described dispersion agent impels material particles to be dispersed in medium, and being preferably model is the dispersion agent of 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 that this area is conventional.
Described non-silicon defoamer can eliminate the unwanted bubbles in coating production process, and being preferably model is the defoamer of HX-2500.The organic solvents such as described 1-Methoxy-2-propyl acetate can play the effect of dilution coating.
Flow agent can impel coating in drying and forming-film process, form smooth, smooth, a uniform film, in the present invention, described first flow agent is preferably polysiloxane polyether copolymer, the model provided as Di Gao company is the flow agent of TEGO-410, described second flow agent is preferably aralkyl modified poly-methyl alkyl siloxane, as the HX-3130 flow agent of China's auxiliary agent, both with the use of, effect is better.
Accordingly, present invention also offers a kind of preparation method of two component matte white finish mentioned above, comprising:
The described modified alkyd resin of above-mentioned formulation weight number, dispersion agent, titanium dioxide, functional powder, polyethylene wax powder, defoamer, anti-settling agent, non-silicon defoamer, the first flow agent, the second flow agent and 1-Methoxy-2-propyl acetate are mixed, obtains two component matte white finish.
In the present invention, the preparation method of described pair of component matte white finish specifically comprises:
By the described modified alkyd resin of above-mentioned formulation weight number and dispersant, disperse 5 minutes ~ 10 minutes under the rotating speed of 300 revs/min ~ 500 revs/min, obtain the first mixture;
Described first mixture is mixed with the titanium dioxide of above-mentioned formulation weight number, functional powder, disperses 20 minutes ~ 25 minutes under the rotating speed of 1600 revs/min ~ 2000 revs/min, then be ground to fineness≤30 μm, obtain the second mixture;
The polyethylene wax powder of described second mixture and above-mentioned formulation weight number, flatting silica are mixed, disperses 15 minutes ~ 20 minutes under the rotating speed of 1600 revs/min ~ 2000 revs/min, obtain the 3rd mixture;
The anti-settling agent of described 3rd mixture and above-mentioned formulation weight number, non-silicon defoamer, the first flow agent, the second flow agent and 1-Methoxy-2-propyl acetate are mixed, disperse 4 minutes ~ 8 minutes under the rotating speed of 300 revs/min ~ 500 revs/min, obtain two component matte white finish.
During use, by described pair of component matte white finish: solidifying agent: thinner=1:(0.4 ~ 0.6): after the proportioning of (0.4 ~ 0.6), preferably=1:0.5:0.5 prepares and paints liquid, leave standstill 5min ~ 15min, after froth breaking, utilization has gas spray gun will paint liquid spraying on a glass, be 20 ± 2 DEG C in temperature, under relative humidity is the environment of 50 ± 10%, after maintenance 7d, carry out removings formaldehyde efficiency and persistence detection.Wherein, described solidifying agent and thinner adopt this area to commonly use, as solidifying agent can be with after n-butyl acetate latting drown solid containing for 40%, the L-75 solidifying agent of Bayer A.G, thinner can be made up of the dimethylbenzene of the 1-Methoxy-2-propyl acetate of the n-butyl acetate of 50 weight parts, 30 weight parts and 20 weight parts.
Purifying formaldehyde performance, the persistent detection method of purifying formaldehyde effect, with reference to national building material industry standard JC/T1074-2008 " function of purifying indoor air coating material purifying property " (I class), are below illustrating of detection method:
Test conditions
Testing circumstance is: temperature is 20 ± 2 DEG C, and relative humidity is 50 ± 10%.
Testing apparatus
Two 1m
3experimental cabin, be the glass manufacture of 8mm ~ 10mm by thickness, experimental cabin inner wall size length × wide × height is 1250mm × 800mm × 1000mm, one is placed sample is sample bin, another places blank glass plate for contrast cabin, cabin seam crossing adopts seal gum process, gas production mouth is experimental cabin sidewall central point, 30W fluorescent lamp 1 is placed in experimental cabin inner top central position, for to needing the photocatalyst material (II class) of illumination to test, in experimental cabin, a power is placed in Left-side center position is the fan of 15W, for air in even cabin.Experimental cabin length direction places four stainless steel specimen holders (outer diameter of steel pipes is 5mm), for placing sample panel, and makes model become 30 ° with bulkhead, model distance bilge portion 300mm.
For I class material (the invention belongs to this type of), the theory brushing amount provided according to product, and constructional method, sample is brushed to a surface of four pieces of 500mm × 500mm sheet glass (thickness 4mm ~ 6mm), temperature 20 ± 2 DEG C, in the testing circumstance of relative humidity 50 ± 10%, seasoning was tested after 7 days.
One glass planar ware is put into the bottom of experimental cabin, closed test, then by injection orifice, (3 ± 0.25) microlitre analytical pure formaldehyde is dropped in glass dish with microsyringe, airtight injection orifice.
Fluorescent lamp is not all opened in two cabins, and gather its concentration of gas test in cabin after airtight 1h, this concentration is starting point concentration (n
0); Gather gas in cabin after 24h and test its concentration, this concentration is for stopping 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 in contrast cabin
0) and stop concentration (n
1) compare the Natural Attenuation situation of objectionable impurities, formaldehyde decrement≤30%, test is set up.
Sample purification efficiency: r=(n
1-n
1 1)/n
1× 100%
In formula: r-purification efficiency, %
N
1-contrast gas that cabin is surveyed stops concentration, and unit is milligram every cubic metre (mg/m
3)
N
1 1gas that-sample chamber is surveyed stops concentration, and unit is milligram every cubic metre (mg/m
3)
Decontamination effect improving persistence
Saturation experiments: four pieces of test pieces of preparation are put into ready sample chamber, airtight sample chamber.Add formaldehyde analytical pure solution every day on time, continue 4d.
5d takes out the complete test piece of saturation testing, be placed on 24h under temperature 20 ± 2 DEG C, relative humidity 50 ± 10% envrionment conditions, then the model carrying out supersaturation test is tested according to clear aldehyde efficiency test step again, its decontamination effect improving endurance life test result method of calculation are sample purification efficiency calculation method above.
Detected result shows, the provided by the invention pair of component matte white finish meets the technical requirement that JC/T1074-2008 specifies in purifying formaldehyde performance and purifying formaldehyde effect persistence, has excellent removing effect of formaldehyde.
In order to understand the present invention further, below in conjunction with embodiment, modified alkyd resin provided by the invention, its preparation method and two component matte white finish are specifically described.
Embodiment of the present invention diethyl malonate, ethylene glycol, tetrabutyl titanate, behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, dimethylbenzene, n-butyl acetate used, lose lustre oxidation inhibitor and antiaging agent are industrial raw material, described tetramethylolmethane to be monopentaerythritol content be 95% technical grade pentaerythritol.
Following examples behenic acid used for the acid number index that Jiangmen Jia Li grease company provides be 195 ~ 205, iodine number index is the behenic acid of 122 ~ 130, the antiaging agent of antiaging agent to be marque be BHT-264, dispersion agent is 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, 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 auxiliary agent Chemical Co., Ltd. of Guangzhou China, first flow agent for the model that Di Gao company provides be the flow agent of TEGO-410, second flow agent is the HX-3130 flow agent of China's auxiliary agent, solidifying agent is for consolidating containing being 40% with after 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 1-Methoxy-2-propyl acetate of 30 weight parts and the dimethylbenzene composition of 20 weight parts.
Embodiment 1
In empty reactor, lead to nitrogen 8 minutes in advance, nitrogen flow is 2m
3/ h;
The tetrabutyl titanate dropping into the diethyl malonate of 50 weight parts, the ethylene glycol of 40 weight parts and 0.05 weight part to aforesaid reaction vessel successively carries out transesterification reaction, nitrogen protection is led in reaction whole process, under whipped state, described temperature of reaction kettle is remained on 150 DEG C by type of heating, heat up in a steamer temperature control≤78.4 DEG C, react after 5 hours, be warming up to 165 DEG C and react at least 10 minutes again, being terminal when distillating without overhead product, obtaining the compound shown in formula (I);
Close heating, the behenic acid of 210 weight parts is dropped into successively to aforesaid reaction vessel, the dimethylbenzene of 15 weight parts and the Hypophosporous Acid, 50 (commodity are called M070) of 0.5 weight part, and dropped into the phthalic anhydride of 250 weight parts successively to aforesaid reaction vessel by the special dog-house of powder, the cis-butenedioic anhydride of 5 weight parts, the neopentyl glycol of 15 weight parts and the tetramethylolmethane of 135 weight parts, under agitation heat up, be warming up to 160 DEG C, insulation backflow 2 hours, then in 3 hours, 220 DEG C are warming up to, insulation is to acid number≤18mgKOH/g, lower the temperature when viscosity is 16 seconds ~ 17 seconds/25 DEG C of grignard pipes, when temperature in described reactor is down to 180 DEG C, obtain crude product,
Open the nitrogen of thinning vessel and to control its flow be 3m
3/ h, opens the cold oil of thinning vessel inner coil pipe, the water coolant of outer adjoining pipe, opens and stir, drop into the n-butyl acetate of 135 weight parts and the antiaging agent of 0.5 weight part to described thinning vessel, and is proceeded in described thinning vessel by described crude product and carry out latting drown;
Still to be turned is complete, drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 120 weight parts, and by the material stirring cooling in described thinning vessel, after being cooled to 130 DEG C, filter with the filter bag that specification is 20 μm, discharging barrelling, obtains modified alkyd resin.
Carry out Performance Detection to the modified alkyd resin obtained, detected result is as shown in table 1, and table 1 is the performance index of the modified alkyd resin that the embodiment of the present invention 1 obtains.
The performance index of the modified alkyd resin that table 1 embodiment of the present invention 1 is obtained
As shown in Table 1, the modified alkyd resin that the present invention obtains functional, can form the film of different qualities, have very excellent service performance.
Embodiment 2
In empty reactor, lead to nitrogen 3 minutes in advance, nitrogen flow is 5m
3/ h;
The tetrabutyl titanate dropping into the diethyl malonate of 60 weight parts, the ethylene glycol of 50 weight parts and 1.5 weight parts to aforesaid reaction vessel successively carries out transesterification reaction, nitrogen protection is led in reaction whole process, under whipped state, described temperature of reaction kettle is remained on 165 DEG C by type of heating, heat up in a steamer temperature control≤78.4 DEG C, react after 3 hours, be warming up to 170 DEG C and react at least 10 minutes again, being terminal when distillating without overhead product, obtaining the compound shown in formula (I);
Close heating, the behenic acid of 220 weight parts is dropped into successively to aforesaid reaction vessel, the dimethylbenzene of 20 weight parts and the Hypophosporous Acid, 50 (commodity are called M070) of 1 weight part, and dropped into the phthalic anhydride of 270 weight parts successively to aforesaid reaction vessel by the special dog-house of powder, the cis-butenedioic anhydride of 7 weight parts, the neopentyl glycol of 20 weight parts and the tetramethylolmethane of 150 weight parts, under agitation heat up, be warming up to 180 DEG C, insulation backflow 2 hours, then in 4 hours, 220 DEG C are warming up to, insulation is to acid number≤18mgKOH/g, lower the temperature when viscosity is 21 seconds ~ 22 seconds/25 DEG C of grignard pipes, when temperature in described reactor is down to 180 DEG C, obtain crude product,
Open the nitrogen of thinning vessel and to control its flow be 9m
3/ h, opens the cold oil of thinning vessel inner coil pipe, the water coolant of outer adjoining pipe, opens and stir, drop into the n-butyl acetate of 150 weight parts and the antiaging agent of 1.5 weight parts to described thinning vessel, and is proceeded in described thinning vessel by described crude product and carry out latting drown;
Still to be turned is complete, drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 130 weight parts, and by the material stirring cooling in described thinning vessel, after being cooled to 130 DEG C, filter with the filter bag that specification is 20 μm, discharging barrelling, obtains modified alkyd resin.
Carry out Performance Detection to the modified alkyd resin obtained, detected result is as shown in table 2, and table 2 is the performance index of the modified alkyd resin that the embodiment of the present invention 2 obtains.
The performance index of the modified alkyd resin that table 2 embodiment of the present invention 2 is obtained
As shown in Table 2, the modified alkyd resin that the present invention obtains functional, can form the film of different qualities, have very excellent service performance.
Embodiment 3
In empty reactor, lead to nitrogen 5 minutes in advance, nitrogen flow is 5m
3/ h;
The tetrabutyl titanate dropping into the diethyl malonate of 55 weight parts, the ethylene glycol of 47 weight parts and 0.1 weight part to aforesaid reaction vessel successively carries out transesterification reaction, nitrogen protection is led in reaction whole process, under whipped state, described temperature of reaction kettle is remained on 160 DEG C by type of heating, heat up in a steamer temperature control≤78.4 DEG C, react after 4 hours, be warming up to 165 DEG C and react at least 10 minutes again, being terminal when distillating without overhead product, obtaining the compound shown in formula (I);
Close heating, the behenic acid of 216 weight parts is dropped into successively to aforesaid reaction vessel, the dimethylbenzene of 18 weight parts and the Hypophosporous Acid, 50 (commodity are called M070) of 0.7 weight part, and dropped into the phthalic anhydride of 261 weight parts successively to aforesaid reaction vessel by the special dog-house of powder, the cis-butenedioic anhydride of 6 weight parts, the neopentyl glycol of 17 weight parts and the tetramethylolmethane of 142 weight parts, under agitation heat up, be warming up to 178 DEG C, insulation backflow 2 hours, then in 4 hours, 215 DEG C are warming up to, insulation is to acid number≤18mgKOH/g, lower the temperature when viscosity is 19 seconds ~ 20 seconds/25 DEG C of grignard pipes, when temperature in described reactor is down to 180 DEG C, obtain crude product,
Open the nitrogen of thinning vessel and to control its flow be 5m
3/ h, opens the cold oil of thinning vessel inner coil pipe, the water coolant of outer adjoining pipe, opens and stir, drop into the n-butyl acetate of 140 weight parts and the antiaging agent of 0.8 weight part to described thinning vessel, and is proceeded in described thinning vessel by described crude product and carry out latting drown;
Still to be turned is complete, drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 125 weight parts, and by the material stirring cooling in described thinning vessel, after being cooled to 130 DEG C, filter with the filter bag that specification is 20 μm, discharging barrelling, obtains modified alkyd resin.
Carry out Performance Detection to the modified alkyd resin obtained, detected result is as shown in table 3, and table 3 is the performance index of the modified alkyd resin that the embodiment of the present invention 3 obtains.
The performance index of the modified alkyd resin that table 3 embodiment of the present invention 3 is obtained
As shown in Table 3, the modified alkyd resin that the present invention obtains functional, can form the film of different qualities, have very excellent service performance.
Embodiment 4
In empty reactor, lead to nitrogen 4.5 minutes in advance, nitrogen flow is 4m
3/ h;
The tetrabutyl titanate dropping into the diethyl malonate of 56 weight parts, the ethylene glycol of 48 weight parts and 0.11 weight part to aforesaid reaction vessel successively carries out transesterification reaction, nitrogen protection is led in reaction whole process, under whipped state, described temperature of reaction kettle is remained on 160 DEG C by type of heating, heat up in a steamer temperature control≤78.4 DEG C, react after 4 hours, be warming up to 165 DEG C and react at least 10 minutes again, being terminal when distillating without overhead product, obtaining the compound shown in formula (I);
Close heating, the behenic acid of 214 weight parts is dropped into successively to aforesaid reaction vessel, the dimethylbenzene of 18.5 weight parts and the Hypophosporous Acid, 50 (commodity are called M070) of 0.8 weight part, and dropped into the phthalic anhydride of 260 weight parts successively to aforesaid reaction vessel by the special dog-house of powder, the cis-butenedioic anhydride of 5.7 weight parts, the neopentyl glycol of 18 weight parts and the tetramethylolmethane of 145 weight parts, under agitation heat up, be warming up to 180 DEG C, insulation backflow 2 hours, then in 4 hours, 215 DEG C are warming up to, insulation is to acid number≤18mgKOH/g, lower the temperature when viscosity is 18 seconds ~ 19 seconds/25 DEG C of grignard pipes, when temperature in described reactor is down to 180 DEG C, obtain crude product,
Open the nitrogen of thinning vessel and to control its flow be 4.5m
3/ h, opens the cold oil of thinning vessel inner coil pipe, the water coolant of outer adjoining pipe, opens and stir, drop into the n-butyl acetate of 142 weight parts and the antiaging agent of 0.9 weight part to described thinning vessel, and is proceeded in described thinning vessel by described crude product and carry out latting drown;
Still to be turned is complete, drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 126 weight parts, and by the material stirring cooling in described thinning vessel, after being cooled to 130 DEG C, filter with the filter bag that specification is 20 μm, discharging barrelling, obtains modified alkyd resin.
Carry out Performance Detection to the modified alkyd resin obtained, detected result is as shown in table 4, and table 4 is the performance index of the modified alkyd resin that the embodiment of the present invention 4 obtains.
The performance index of the modified alkyd resin that table 4 embodiment of the present invention 4 is obtained
As shown in Table 4, the modified alkyd resin that the present invention obtains functional, can form the film of different qualities, have very excellent service performance.
Comparative example 1
In empty reactor, lead to nitrogen 5 minutes in advance, nitrogen flow is 3.5m
3/ h;
The behenic acid of 216 weight parts is dropped into successively to aforesaid reaction vessel, the dimethylbenzene of 18 weight parts and the Hypophosporous Acid, 50 (commodity are called M070) of 0.7 weight part, and dropped into the phthalic anhydride of 261 weight parts successively to aforesaid reaction vessel by the special dog-house of powder, the cis-butenedioic anhydride of 6 weight parts, the neopentyl glycol of 105 weight parts and the tetramethylolmethane of 142 weight parts, under agitation heat up, be warming up to 180 DEG C, insulation backflow 2 hours, then in 3 hours, 215 DEG C are warming up to, insulation is to acid number≤18mgKOH/g, lower the temperature when viscosity is 19 seconds/25 DEG C of grignard pipes, when temperature in described reactor is down to 180 DEG C, obtain crude product,
Open the nitrogen of thinning vessel and to control its flow be 3m
3/ h, opens the cold oil of thinning vessel inner coil pipe, the water coolant of outer adjoining pipe, opens and stir, drop into the n-butyl acetate of 145 weight parts and the antiaging agent of 0.8 weight part to described thinning vessel, and is proceeded in described thinning vessel by described crude product and carry out latting drown;
Still to be turned is complete, drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 130 weight parts, by the material stirring cooling in described thinning vessel, after being cooled to 130 DEG C, filter with the filter bag that specification is 20 μm, discharging barrelling, obtain the Synolac of the common modifications adopting behenic acid.
Carry out Performance Detection to the Synolac obtained, detected result is as shown in table 5, and table 5 is the performance index of the Synolac that comparative example 1 of the present invention obtains.
The performance index of the Synolac that table 5 comparative example of the present invention 1 is obtained
Comparative example 2
In empty reactor, lead to nitrogen 6 minutes in advance, nitrogen flow is 4.0m
3/ h;
The behenic acid of 220 weight parts is dropped into successively to aforesaid reaction vessel, the glycol ether of 54 weight parts, the dimethylbenzene of 18 weight parts and the Hypophosporous Acid, 50 (commodity are called M070) of 0.7 weight part, and dropped into the phthalic anhydride of 260 weight parts successively to aforesaid reaction vessel by the special dog-house of powder, the cis-butenedioic anhydride of 5 weight parts, the neopentyl glycol of 50 weight parts and the tetramethylolmethane of 144 weight parts, under agitation heat up, be warming up to 180 DEG C, insulation backflow 2 hours, then in 3 hours, 215 DEG C are warming up to, insulation is to acid number≤18mgKOH/g, lower the temperature when viscosity is 19 seconds/25 DEG C of grignard pipes, when temperature in described reactor is down to 180 DEG C, obtain crude product,
Open the nitrogen of thinning vessel and to control its flow be 3m
3/ h, opens the cold oil of thinning vessel inner coil pipe, the water coolant of outer adjoining pipe, opens and stir, drop into the n-butyl acetate of 145 weight parts and the antiaging agent of 0.8 weight part to described thinning vessel, and is proceeded in described thinning vessel by described crude product and carry out latting drown;
Still to be turned is complete, drops into described thinning vessel after cleaning described reactor with the dimethylbenzene of 130 weight parts, by the material stirring cooling in described thinning vessel, after being cooled to 130 DEG C, filter with the filter bag that specification is 20 μm, discharging barrelling, obtain the Synolac of the common modifications adopting behenic acid.
Carry out Performance Detection to the Synolac obtained, detected result is as shown in table 6, and table 6 is the performance index of the Synolac that comparative example 2 of the present invention obtains.
The performance index of the Synolac that table 6 comparative example of the present invention 2 is obtained
Embodiment 5
Successively the dispersion agent of modified alkyd resin obtained for the embodiment 1 of 50 weight parts and 1 weight part is dropped in pill tank, disperse 10 minutes under the rotating speed of 300 revs/min, make to be uniformly dispersed;
Then drop into the titanium dioxide of 28 weight parts and the functional powder of 1 weight part successively to described pill tank, disperse 25 minutes under the rotating speed of 1600 revs/min, then be ground to fineness≤30 μm;
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, disperse 20 minutes under the rotating speed of 1600 revs/min;
The most backward described pill tank drops into the 1-Methoxy-2-propyl acetate of the anti-settling agent of 1 weight part, the non-silicon defoamer of 0.05 weight part, the first flow agent of 0.1 weight part, the second flow agent of 0.1 weight part and 2 weight parts successively, disperse 8 minutes under the rotating speed of 300 revs/min, obtain two component matte white finish.
According to method mentioned above, removing formaldehyde efficiency and persistence detection are carried out to described pair of component matte white finish.Detected result is as shown in table 7, the clear aldehyde detected result of two component matte white finish that table 7 provides for the embodiment of the present invention 5 ~ 8 and comparative example 3,4.
Embodiment 6
Successively the dispersion agent of modified alkyd resin obtained for the embodiment 2 of 60 weight parts and 3 weight parts is dropped in pill tank, disperse 5 minutes under the rotating speed of 500 revs/min, make to be uniformly dispersed;
Then drop into the titanium dioxide of 32 weight parts and the functional powder of 3 weight parts successively to described pill tank, disperse 20 minutes under the rotating speed of 2000 revs/min, then be ground to fineness≤30 μm;
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, disperse 15 minutes under the rotating speed of 2000 revs/min;
The most backward described pill tank drops into the 1-Methoxy-2-propyl acetate of the anti-settling agent of 3 weight parts, the non-silicon defoamer of 0.15 weight part, the first flow agent of 0.3 weight part, the second flow agent of 0.3 weight part and 4 weight parts successively, disperse 4 minutes under the rotating speed of 500 revs/min, obtain two component matte white finish.
According to method mentioned above, carry out removing formaldehyde efficiency and persistence detection to described pair of component matte white finish, detected result is as shown in table 7.
Embodiment 7
Successively the dispersion agent of modified alkyd resin obtained for the embodiment 3 of 55.5 weight parts and 2 weight parts is dropped in pill tank, disperse 8 minutes under the rotating speed of 400 revs/min, make to be uniformly dispersed;
Then drop into the titanium dioxide of 30 weight parts and the functional powder of 2 weight parts successively to described pill tank, disperse 22 minutes under the rotating speed of 1800 revs/min, then be ground to fineness≤30 μm;
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, disperse 18 minutes under the rotating speed of 1800 revs/min;
The most backward described pill tank drops into the 1-Methoxy-2-propyl acetate of the anti-settling agent of 2 weight parts, the non-silicon defoamer of 0.1 weight part, the first flow agent of 0.2 weight part, the second flow agent of 0.2 weight part and 3 weight parts successively, disperse 6 minutes under the rotating speed of 400 revs/min, obtain two component matte white finish.
According to method mentioned above, carry out removing formaldehyde efficiency and persistence detection to described pair of component matte white finish, detected result is as shown in table 7.
Embodiment 8
Successively the dispersion agent of modified alkyd resin obtained for the embodiment 4 of 55 weight parts and 2 weight parts is dropped in pill tank, disperse 10 minutes under the rotating speed of 400 revs/min, make to be uniformly dispersed;
Then drop into the titanium dioxide of 29 weight parts and the functional powder of 2.5 weight parts successively to described pill tank, disperse 20 minutes under the rotating speed of 1800 revs/min, then be ground to fineness≤30 μm;
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, disperse 15 minutes under the rotating speed of 1800 revs/min;
The most backward described pill tank drops into the 1-Methoxy-2-propyl acetate of the anti-settling agent of 2 weight parts, the non-silicon defoamer of 0.12 weight part, the first flow agent of 0.2 weight part, the second flow agent of 0.2 weight part and 3 weight parts successively, disperse 5 minutes under the rotating speed of 500 revs/min, obtain two component matte white finish.
According to method mentioned above, carry out removing formaldehyde efficiency and persistence detection to described pair of component matte white finish, detected result is as shown in table 7.
Comparative example 3
With reference to embodiment 7, the Synolac that comparative example 1 obtains is made two component matte white finish, and according to method mentioned above, carry out removing formaldehyde efficiency and persistence detection to described pair of component matte white finish, detected result is as shown in table 7.
Comparative example 4
With reference to embodiment 8, the Synolac that comparative example 2 obtains is made two component matte white finish, and according to method mentioned above, carry out removing formaldehyde efficiency and persistence detection to described pair of component matte white finish, detected result is as shown in table 7.Two component matte white finish that table 7 embodiment of the present invention 5 ~ 8 and comparative example 3,4 provide clear
Aldehyde detected result
As shown in Table 7, two component matte white finish that the embodiment of the present invention provides removing, formaldehyde efficiency and persistence meet the technical requirement of relevant regulations, have excellent clear function of removing formaldehyde.
From above embodiment and comparative example, modified alkyd resin provided by the invention is applied in two component matte white finish, has good removing effect of formaldehyde.
In addition, the present invention adopts the method for the compound modified Synolac of formula (I) depicted simple to operate, and between batch, product is stablized.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (9)
1. a modified alkyd resin, be made up through reaction of alcohol acid mixture, described alcohol 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;
The oxidation inhibitor of losing lustre of 0.5 ~ 1 weight part;
The water entrainer of 15 ~ 20 weight parts;
The letdown solvent dun of 255 ~ 280 weight parts;
The antiaging agent of 0.5 ~ 1.5 weight part;
The compound shown in formula (I) of 60 ~ 76 weight parts:
In formula (I), 1≤n≤4.
2. modified alkyd resin according to claim 1, it is characterized in that, n is 2, compound shown in described formula (I), is obtained through transesterification reaction by the diethyl malonate of 50 ~ 60 weight parts and the ethylene glycol of 40 ~ 50 weight parts under the katalysis of the tetrabutyl titanate of 0.05 ~ 0.15 weight part.
3. modified alkyd resin according to claim 1, is characterized in that, described water entrainer is selected from any one in dimethylbenzene, toluene and 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. a preparation method for modified alkyd resin, comprising:
Reacted by alcohol acid mixture, obtain modified alkyd resin, described alcohol 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;
The oxidation inhibitor of losing lustre of 0.5 ~ 1 weight part;
The water entrainer of 15 ~ 20 weight parts;
The letdown solvent dun of 255 ~ 280 weight parts;
The antiaging agent of 0.5 ~ 1.5 weight part;
The compound shown in formula (I) of 60 ~ 76 weight parts:
In 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, obtains the compound shown in formula (I), n is 2;
Compound shown in described formula (I), behenic acid, phthalic anhydride, cis-butenedioic anhydride, neopentyl glycol, tetramethylolmethane, water entrainer are reacted after mixing with oxidation inhibitor of losing lustre, obtains crude product;
Described crude product, letdown solvent dun are mixed with antiaging agent, obtains modified alkyd resin.
7. a two component matte white finish, comprises:
The modified alkyd resin that the modified alkyd resin described in any one of Claims 1 to 4 of 50 ~ 60 weight parts or the preparation method of employing described in claim 5 or 6 obtain;
The dispersion agent of 1 ~ 3 weight part;
The titanium dioxide of 28 ~ 32 weight parts;
The negative ion 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;
The 1-Methoxy-2-propyl acetate of 2 ~ 4 weight parts.
8. according to claim 7 pair of component matte white finish, is characterized in that, the dispersion agent of described dispersion agent to be model be BYK-110.
9. according to claim 7 pair of component matte white finish, is characterized in that, described first flow agent is polysiloxane polyether copolymer, and described second flow agent is aralkyl modified poly-methyl alkyl siloxane.
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| 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 |
| CN114805774B (en) * | 2022-04-01 | 2023-04-04 | 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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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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