CN100372882C - Quick-drying alkide resin and preparation method thereof - Google Patents
Quick-drying alkide resin and preparation method thereof Download PDFInfo
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- CN100372882C CN100372882C CNB2005101230533A CN200510123053A CN100372882C CN 100372882 C CN100372882 C CN 100372882C CN B2005101230533 A CNB2005101230533 A CN B2005101230533A CN 200510123053 A CN200510123053 A CN 200510123053A CN 100372882 C CN100372882 C CN 100372882C
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Abstract
The present invention relates to a quick-drying alkyd resin having the advantages of quick dryness, good water resistance and good corrosion resistance and a preparation method thereof. The present invention is characterized in that the quick-drying alkyd resin prepared from 32 to 50%wt of fatty acid without conjugated double bonds, 0.5 to 1.5%wt of maleic anhydride, 12.5 to 16.5%wt of benzoic anhydride, 11 to 14%wt of pentaerythritol or glycerol of equivalent weight and 28 to 50%wt of vinyl toluene by addition, esterification and copolymerization. The present invention has the advantages that production cost is reduced, compared with that of an elaeostearic acid containing the conjugated double bonds and xylene viscous solvent, the cost can be reduced by about 5 to 8%, modification is better, and product molecular weight distribution is more uniform. The obtained resin has the advantages of quick drying, good water resistance and high corrosion resistance, and can be diluted by an aliphatic hydrocarbon solvent with low price. The obtained resin conforms to the requirement of environmental protection, which can be combined with unmodified alkyd resin for use, and the use range of the alkyd resin is greatly enlarged.
Description
Technical field
The present invention relates to a kind of Synolac and preparation method of improvement, it is lower to relate in particular to a kind of employing price, and it is synthetic and through Vinyl toluene (VT) modification not contain conjugated double bond lipid acid, has when dried fast, water-tolerant, the quick-drying alkide resin of good corrosion resistance and preparation method.
Background technology
Synolac, the wider medium-to-high grade coating synthetic resins of a kind of purposes that obtains through esterification by 6.5-9%wt polyvalent alcohol (glycerine of tetramethylolmethane or equivalent), 12-16%wt polyprotonic acid (phthalic anhydride), 22-40%wt lipid acid usually.It can do priming paint, finish paint, varnish; Also can be with other resin such as aminoresin, urethane resin mixes into baking vanish or two component coats with lacquer; And can carry out modification to perchloropolyvinyl paint, pyroxylin(e)finish etc., to improve its performance.Its deficiency is: when often feeling when doing self-drying paint to do slow (the about 6-8 of surface drying hour), and poor water resistance, corrosion-resistant.People carry out Synolac are carried out modification for this reason, to obtain desired properties.
As during the higher phthalic resin coating of fast when requiring to do, water-tolerant, non-corrosibility, a kind of common method is to adopt vinylbenzene to the Synolac modification, obtains having styryl Synolac multipolymer or styryl Synolac.Phenylethene modified have higher molecular weight and a higher Tg value, therefore water tolerance, alkali resistance, do rate, hardness is all more unmodified improves a lot, can cooperate with pigment, make fast dried, moistureproof, bright, attractive in appearance indoor protection and decorate enamel paint, agricultural machinery lacquer etc.Yet the Synolac after phenylethene modified has reduced hydrocarbon resistant solvent, is easily stung the end by strong solvent such as dimethylbenzene slightly in brushing during second road, therefore requires the brushing twice very short pitch time, has reduced use properties, and snappiness and weather resisteant; Especially the Synolac after phenylethene modified can only be transferred stickingly with aromatic solvents such as toluene and/or dimethylbenzene, does not meet the environmental requirement that improves day by day; Besides, it and unmodified Synolac can not fuse, so can not piece together use mutually, use and are placed restrictions on.
Chinese patent 90108360.7,97105337.5 disclosed employing deposed polystyrenes are through the dissolving of aromatic solvents such as toluene and/or dimethylbenzene, again with the cold assembly modification of Synolac.But not only still need use aromatic solvents such as toluene and/or dimethylbenzene after the modification; And because of cold assembly modification, molecular weight is inhomogeneous, and performance will be worse than styrene alkyd resin, and paint film is crisp, and is aging fast; Besides, fused poor with pigment, paint film easily grows dim, so can only do some low-grade ready-mixed paint or hard floor paint.
Chinese patent 95192452.4,00812016.1,00810902.8 disclosed employing acrylic acid modified alkyd resin, cost height not only, more phenylethene modified increase cost about 10%, and modification synthesis technique complexity.
Therefore still having is worth improved place.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, a kind of fast doing that both had is provided, the aliphatic solvents that available rates is cheap is again transferred sticking, uses more environmental protection, and can with the fused quick-drying alkide resin that uses of piecing together mutually of unmodified Synolac.
Another object of the present invention is to provide a kind of preparation method of above-mentioned quick-drying alkide resin.
The present invention's first purpose realizes, through a large amount of tests, adopt MALEIC ANHYDRIDE (hereinafter to be referred as cis-butenedioic anhydride), carry out addition reaction with the unsaturated fatty acids that does not contain conjugated double bond, make it to become the cis-butenedioic anhydride affixture that contains conjugated double bond, affixture carries out conventional alcoholic acid esterification reaction with phthalic anhydride, tetramethylolmethane again, and the Synolac that obtains carries out copolymerization with Vinyl toluene (being called for short VT).Specifically, quick-drying alkide resin of the present invention is characterized in that being formed by the unsaturated fatty acids that does not contain conjugated double bond of 32～41%wt, the MALEIC ANHYDRIDE of 0.5～1.5%wt, the phthalic anhydride of 12.5～16.5%wt, the tetramethylolmethane of 11～14%wt or glycerine, the Vinyl toluene addition of 28～44%wt, esterification, the copolymerization of equivalent.
Because tetramethylolmethane quality and qualities of glycerin are inequality,, then should adopt equivalent to substitute if substitute tetramethylolmethane with glycerine.
The reaction principle that the present invention does not contain the unsaturated fatty acids of conjugated double bond and cis-butenedioic anhydride is as follows:
Cis-butenedioic anhydride and the unsaturated fatty acids (for example linolenic acid, soy(a)-bean oil fatty acid, Trisun Oil R 80 lipid acid) that does not contain conjugated double bond carry out addition reaction, make the lipid acid that does not contain conjugated double bond originally become the lipid acid that contains conjugated double bond.Cis-butenedioic anhydrideization, the transformation efficiency when helping improving follow-up and VT copolymerization.The cis-butenedioic anhydride amount is crossed and can be caused two key amounts not enough at least, can influence the transformation efficiency of follow-up VT; Cross easy gel control difficulty when polymerization at most.The glycerine consumption of tetramethylolmethane or equivalent is excessive, in the time of then can influencing the coating paint film and do, water tolerance is descended; Consumption is too small, and then acid number decline is difficult, and easily causes gel.But test shows between aforementioned zones to be not to refer to the limit of accuracy value, more a spot of increase and decrease, and performance impact is not fairly obvious, and is any departing from a small quantity for obtaining above-mentioned performance in view of the above, belongs to the scope of the invention equally.
The unsaturated fatty acids that does not contain conjugated double bond of the present invention is excellent with behenic acid especially, and not only price is cheap than linolenic acid for it, and color is more shallow suitable does light-colored resin, and when paint film is done behind the lacquering, hardness is all good.
Feature of quick-drying alkide resin of the present invention is:
Because with VT (CH=CH
2) Synolac is carried out the vinylation copolymerization,
So contain following molecule knot in the Synolac
Feature.
This is the important difference that quick-drying alkide resin of the present invention is different from other Synolac or styrene alkyd resin, and this molecular structure can detect its existence by test example such as spectrophotometer or kaleidophon.
Quick-drying alkide resin of the present invention is synthetic, earlier obtain cis-butenedioic anhydrideization and have conjugated double bond lipid acid by unsaturated fatty acids that does not contain conjugated double bond and MALEIC ANHYDRIDE addition reaction, vinylation method before can adopting then, even after gained lipid acid and the VT copolyreaction, glycerine, the phthalic anhydride with tetramethylolmethane or equivalent carries out esterification again; Also can adopt back vinylation method, even the glycerine of gained lipid acid and tetramethylolmethane or equivalent, phthalic anhydride carry out esterification and obtains Synolac, again with the VT copolyreaction.Specifically, the preparation method of quick-drying alkide resin of the present invention, it is characterized in that at first making the unsaturated fatty acids and the MALEIC ANHYDRIDE addition reaction that do not contain conjugated double bond to obtain containing conjugated double bond lipid acid, make the glycerine esterification reaction of gained lipid acid and phthalic anhydride, tetramethylolmethane or equivalent obtain Synolac then, add Vinyl toluene again and carry out copolyreaction; Or after making gained conjugated double bond lipid acid and Vinyl toluene carry out copolyreaction, the glycerine with phthalic anhydride, tetramethylolmethane or equivalent carries out esterification again.
Experiment shows: preceding vinylation method, control is comparatively complicated, the production difficulty is big, and gained molecular resin amount is difficult for evenly, wherein contain more small molecular weight resin, can influence resin water tolerance and when dried, therefore, the present invention prepares preferred employing back vinylation method, even gained contains the glycerine of conjugated double bond lipid acid and tetramethylolmethane or equivalent, phthalic anhydride carries out esterification and obtains Synolac, again with the VT copolyreaction, back vinylation method, the VT transformation efficiency is higher, and product molecular weight distribution is more even, drying is faster when making the paint film forming with it, and the paint film water tolerance is better.
The glycerine of adduct of the present invention and tetramethylolmethane or equivalent, the esterification of phthalic anhydride, reaction principle and condition have no special requirements with the Synolac esterification is identical usually, no longer carefully state.
Be convenient preparation, described addition, esterification, copolyreaction can be carried out in same reactor.But carry out for helping the back vinylation, can reaction be carried out according to the order of sequence, be that the addition reaction temperature should be low than esterification reaction temperature, can at first carry out addition reaction like this, and then temperature raise, carry out esterification, cooling at last adds VT and carries out copolyreaction.Addition, esterification, copolyreaction temperature should be controlled at respectively: 140-160 ℃, and 190-230 ℃, 120-145 ℃.
Quick-drying alkide resin of the present invention, owing to adopt the unsaturated fatty acids that does not contain conjugated double bond, MALEIC ANHYDRIDE, phthalic anhydride, the glycerine of tetramethylolmethane or equivalent, the Vinyl toluene addition, esterification, copolymerization, the gained Synolac, not only reduced production cost, and the eleostearic acid that contains conjugated double bond, the about 5-8% of cost falls in the Synolac that dimethylbenzene makes, and modification is better, product molecular weight distribution is more even, fast during the gained resin dry, water-tolerant, good corrosion resistance, and the cheap aliphatic solvents (for example 200# paint solvent) of available rates is transferred sticking, compliance with environmental protection requirements more, also can with unmodified Synolac (trade mark 389-8 for example, 389-9) piece together use mutually, enlarged the Synolac use range greatly.For example modified alkyd resin is equally as antifouling paste, the film-forming resin of insullac and enamel paint, and film forming has drying rate fast (surface drying 15 minutes was done solid work 45 minutes), water tolerance is excellent, gloss of film good, hardness is high, has better use properties.Especially adopt behenic acid to make raw material, can obtain the Synolac of light colour.
Quick-drying alkide resin of the present invention and prepared paint and styrene alkyd resin and contain that conjugated double bond raw material of fatty acid gained resin property contrast sees Table one, table two.
Below in conjunction with five specific embodiments, further specify the present invention, but the embodiment of the invention should not be construed as to concrete qualification of the present invention.
Embodiment
Embodiment 1: get 41% linolenic acid, and 1% cis-butenedioic anhydride, 16% phthalic anhydride, 14% tetramethylolmethane drops in the stainless steel cauldron, seals dog-house, opens blow-off valve, logical CO
2Behind the gas 15min, begin to stir.Be warming up to 160 ℃, behind the insulation 30-60min, be warming up to 220 ℃ of insulations again after 6 hours, control in the sampling, qualified until middle control.Logical immediately nitrogen or CO after middle control is qualified
2, be cooled to 160 ℃ and add part 200
#Solvent oil after stirring evenly, begins to drip 28% VT, and temperature is controlled at 140 ± 2 ℃, after 3 hours, controls in the sampling, and is qualified until middle control, and sampling is transferred sticking, suitable after, the press filtration packing.Concrete technical parameter sees the following form.22 hours total times of reaction.
Embodiment 2: soy(a)-bean oil fatty acid 36%, cis-butenedioic anhydride 0.8%, phthalic anhydride 14.5%, tetramethylolmethane 13%, operation be with embodiment 1 addition, esterification, reach requirement after, the VT of beginning Dropwise 35 .7%, operation is with embodiment 1, the gained resin removes color than embodiment 1 shallow 3
#Outward, all the other indexs are identical.
Embodiment 3: soy(a)-bean oil fatty acid 32%, cis-butenedioic anhydride 0.6%, phthalic anhydride 12.4%, tetramethylolmethane 11%, operation with embodiment 1 addition, esterification instead, reach requirement after, begin to drip 44% VT, operation is with embodiment 1, the gained resin removes color than embodiment 1 shallow 3
#Outward, all the other indexs are identical.
Embodiment 4: use-case 2 batchings, and make soy(a)-bean oil fatty acid and cis-butenedioic anhydride 160 ℃ of addition reactions earlier, middle control is qualified, adds VT 140 ± 2 ℃ of copolymerization 6 hours, adds phthalic anhydride, tetramethylolmethane at last, is warming up to 210-220 ℃ and carries out esterification.Total reaction time 28 hours.
Embodiment 5: use-case 1 proportioning, adopt preceding vinylation production technique as embodiment 4.
Reference examples: get 41% eleostearic acid, linolenic acid mixture, 16% phthalic anhydride, 14% tetramethylolmethane drops in the stainless steel cauldron, seals dog-house, opens blow-off valve, logical CO
2Behind the gas 15min, begin to stir, be warming up to 180 ℃ of insulation 30min after, be warming up to 210 ± 2 ℃ of insulations 6 hours again, after control required in reaching, cooling began to drip 29% VT, operation is with embodiment 1.
VT modified alkyd resin of the present invention and styrene alkyd resin and lacquering technical indicator contrast table.
Table one Synolac of the present invention and prior art parameter comparison table
| Sequence number | Project | Synolac of the present invention | Styrene alkyd resin | Reference examples |
| 1 | Outward appearance (range estimation) | Light yellow transparent liquid | Light yellow transparent liquid | Brown transparent liquid |
| 2 | Non-volatile part of % | 50±2 | 50±2 | 50±2 |
| 3 | Color and luster (Fe-Co) number≤ | 6 | 6 | 9 |
| 4 | S/25 ℃ of viscosity (being coated with-4 glasss) | 200-400 | 200-400 | 200-400 |
| 5 | Solvent for use | 200 #Solvent oil | Dimethylbenzene | Dimethylbenzene |
| 6 | Material cost (unit/ton) | 9200 | 9100 | 9920 |
Table two resin of the present invention and existing resin are as black car chassis paint performance comparison table
| Sequence number | Project | Priming paint of the present invention | Phenylethene modified priming paint | Reference examples priming paint |
| 1 | Fineness (scraper plate fineness) μ m≤ | 30 | 30 | 30 |
| 2 | Show time of drying in | 15min | 15min | 15min |
| Do solid work | 45min | 45min | 45min | |
| 3 | Shock-resistant 50kg.cm | By | By | By |
| 4 | Hardness (pencil) | HB + | HB | H |
| 5 | Snappiness mm | 1 | 1 | 1 |
| 6 | Sticking power (drawing the circle method) level | 1-2 | 1-2 | 1 |
| 7 | Anti-3%NaCL hour | 96 | 72 | 120 |
| 8 | Film thickness μ m | 20 | 20 | 20 |
Claims (7)
1. quick-drying alkide resin is characterized in that being formed by the unsaturated fatty acids that does not contain conjugated double bond of 32～41%wt, the MALEIC ANHYDRIDE of 0.5～1.5%wt, the phthalic anhydride of 12.5～16.5%wt, the tetramethylolmethane of 11～14%wt or glycerine, the Vinyl toluene addition of 28～44%wt, esterification, the copolymerization of equivalent.
2. according to the described quick-drying alkide resin of claim 1, it is characterized in that the said unsaturated fatty acids that does not contain conjugated double bond is a behenic acid.
3. according to the preparation method of claim 1 or 2 described quick-drying alkide resins, it is characterized in that at first making according to claim 1, the unsaturated fatty acids that does not contain conjugated double bond and the MALEIC ANHYDRIDE addition reaction of ratio obtain containing conjugated double bond lipid acid, make the glycerine esterification reaction of gained lipid acid and phthalic anhydride, tetramethylolmethane or equivalent obtain Synolac then, add Vinyl toluene again and carry out copolyreaction; Or after making gained conjugated double bond lipid acid and Vinyl toluene carry out copolyreaction, the glycerine with phthalic anhydride, tetramethylolmethane or equivalent carries out esterification again.
4. according to the preparation method of the described quick-drying alkide resin of claim 3, it is characterized in that addition, esterification, copolyreaction carry out in same reactor.
5. according to the preparation method of claim 3 or 4 described quick-drying alkide resins, it is characterized in that making earlier according to claim 1, the unsaturated fatty acids that does not contain conjugated double bond and the MALEIC ANHYDRIDE addition reaction of ratio obtain containing conjugated double bond lipid acid, make the glycerine esterification reaction of gained lipid acid and phthalic anhydride, tetramethylolmethane or equivalent obtain Synolac then, add Vinyl toluene again and carry out copolyreaction.
6. according to the preparation method of the described quick-drying alkide resin of claim 5, it is characterized in that reaction being carried out according to the order of sequence by controlled temperature is low, high and low.
7. according to the preparation method of the described quick-drying alkide resin of claim 6, it is characterized in that addition, esterification, copolyreaction temperature are respectively: 140-160 ℃, 190-230 ℃, 120-145 ℃.
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| CN101280055B (en) * | 2008-04-30 | 2012-04-18 | 杭州油漆有限公司 | High-solid low-viscosity environment-friendly alkyd resin and preparation method thereof |
| CN101602848B (en) * | 2009-06-25 | 2013-03-27 | 江苏三木化工股份有限公司 | Alkyd resin for metal coiled material back paint |
| CN102746464A (en) * | 2012-05-29 | 2012-10-24 | 兰州理工大学 | Alkyd acrylic graft copolymer and preparation method thereof |
| CN103833948B (en) * | 2014-03-12 | 2016-03-30 | 中钞油墨有限公司 | A kind of phenylethene modified polyurethane alkyd resin and method for making |
| CN104262595A (en) * | 2014-09-16 | 2015-01-07 | 田清峰 | Water-based alkyd resin synthesis technique |
| CN106634484A (en) * | 2015-10-29 | 2017-05-10 | 丹阳市海信涂料化工厂 | Novel quick-dry alkyd ready mixed paint |
| CN108129964A (en) * | 2017-12-13 | 2018-06-08 | 成都拜迪新材料有限公司 | The preparation method of halogenated polyethylene modified water-based alkyd resin and coating |
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