CN101407568A - High solid low viscosity acrylic resin and preparation thereof - Google Patents
High solid low viscosity acrylic resin and preparation thereof Download PDFInfo
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Abstract
The invention provides a preparation method of acrylic resin with high solid content and low viscosity, which aims at overcoming the defects of large viscosity, low solid content (Wt percent is less than or equal to 60 percent), and the like of the acrylic resin prepared by the traditional technology, which causes large amount of waste of organic solvent and environmental pollution in application. The technical point is as follows: in a solvent system, the acrylic resin is prepared by radical polymerization; a complex initiator system and a chain transfer agent are used; reaction temperature range is controlled within 145 DEG C to 170 DEG C; the acrylic resin with solid content of wt percent more than or equal to 70 percent and viscosity range of 1000 to 4000 MPa.s; and the method largely reduces VOC content in the application of the products. The acrylic resin can be applied to high-solid coatings and paintings.
Description
Technical field
The present invention relates to a kind of high solid low viscosity acrylic resin and preparation method thereof.In particular, the present invention relates to a kind of paint vehicle that is used to produce high solid coating.
Background technology
At present, the Hydroxylated acrylic resin in the market is general prepares acroleic acid polyurethane coating with the solidifying agent collocation that contains isocyano; Or with aminoresin collocation preparation acrylic-amino baking vanish, more than the coating of two kinds of systems all have the light of guarantor tint retention can be good, advantage such as weathering resistance is excellent is widely used in automotive industry, mechanical implement and industrial circle.
Traditional acrylic resin is because the viscosity height, molecular weight is big and molecular weight distribution is inhomogeneous, and (wt% 〉=60%) its viscosity is excessive when solid content is high.Therefore, the high solid coating of traditional acrylic resin preparation in order to obtain suitable working viscosity, has only and uses a large amount of organic solvent dilutings, causes a large amount of volatilizations of organic solvent, and atmospheric environment is caused serious pollution.In recent years, various countries were more and more stricter to environmental protection requirement, especially the cry that reduces coating VOC raise day by day, and high solid coating arises at the historic moment, and the application of high solid low viscosity resin is to reduce one of coating VOC effective means.
Patent CN1228442A describes a kind of high solid, low-viscosity acrylic resin, is by the mixture of neodecanoic acid glycidyl ester, vinyl monomer, chain-transfer agent, makes by radical polymerization.
What patent CN1492885A described is a kind of acrylic copolymer, by the ester bond and the low hydroxyl value (being no more than the hydroxyl value of about 135mgKOH/g) of control of a repeating side groups part of stretching out at main polymer chain, reaches the purpose of high solids content and low volatility.
It is the synthetic article of High-Solids Hydroxyl Acrylic Resins that Lu Jun, Yu Huiqun and Xiao Chaobo have delivered exercise question at Wuhan University's journal (version of science), mention in the literary composition: with benzoyl peroxide (BPO)/dicumyl peroxide (DCP) (mass ratio is 2: 3) is composite initiator, introducing tertiary carbonic acid glycidyl ester (CE-10) is comonomer, with dimethylbenzene is solvent, synthesized molecular weight and be lower than 6000, the High-Solids Hydroxyl Acrylic Resins of dispersed index D＜2.
Preceding two pieces of patents are not described the preparation method of high solid low viscosity acrylic resin described herein, that is to say, use the method for composite initiator system.Used composite initiator in synthetic this piece article of High-Solids Hydroxyl Acrylic Resins, done reaction solvent with dimethylbenzene, the number-average molecular weight of synthetic High-Solids Hydroxyl Acrylic Resins is lower than 6000.But above synthetic acrylic resin does not reach a kind of ideal high solid low viscosity resin yet, uses tertiary carbonic acid glycidyl ester (CE-10) to cause shortcomings such as raw materials cost height or process complications.
By improvement, use composite initiator system in this article, improve temperature of reaction, the synthetic high solid low viscosity acrylic resin that obtains about 1000-5000 of number-average molecular weight and viscosity 1000-4000mPas to about 145 ℃-170 ℃ to traditional synthesis technique.
Summary of the invention
Purpose of the present invention just provides a kind of high solid low viscosity acrylic resin and preparation method thereof.This high solid low viscosity acrylic resin can prepare high solid coating and lacquer, reaches the purpose that reduces coating and lacquer VOC content.High solid low viscosity acrylic resin of the present invention has used composite initiator system and chain-transfer agent in preparation process.It is a kind of such as the weathering resistance of high gloss, high fullness ratio, excellence and the finish paint that performances such as hardness and sticking power are enough to be used in automobile, machinery and industrial circle that high solid low viscosity acrylic resin of the present invention can provide.
The objective of the invention is by realizing by the following technical solutions: in the preparation acrylic resin, use composite initiator system, introduce chain-transfer agent, 145 ℃-170 ℃ of range of reaction temperature, obtain acrylic resin by radical polymerization in reactor, prepared acrylic resin has the characteristic of high solid and low-viscosity.
The preparation method of acrylic resin of the present invention is as follows:
Reactor adopts the round-bottomed flask that mechanical stirring and thermometer and nitrogen ingress pipe and reflux exchanger and dropping funnel are housed.
The first step, the solvent of adding total solvent amount 60wt% in the reactor, logical nitrogen protection is warmed up to temperature of reaction;
Second step, the common mixed solution of forming of the solvent of the 95-99wt% of the 90-99wt% of all reaction monomers and chain-transfer agent total amount and composite initiator system total amount and total solvent amount 35wt% is added Dropping feeder, in 3-4 hour, dropwise, kept temperature of reaction 1-2 hour with uniform velocity;
In the 3rd step, the remaining dissolution with solvents of 1-5wt% of the 1-10wt% of chain-transfer agent total amount and composite initiator total amount at the uniform velocity added in 0.5 hour in the reactor, kept temperature of reaction 1-2 hour, got acrylic resin of the present invention.
Used composite initiator system when characteristics of the present invention are the synthesizing propylene acid resin, its consumption is about 1-10wt% of reaction monomers total amount, preferably about 2-5wt%; Introduced chain-transfer agent, its consumption is about 0-5wt% of reaction monomers, preferably about 1-3wt%.
Acrylic resin of the present invention is a kind of multipolymer of radical polymerization, is made of following component: (1) (methyl) acrylic acid hydroxy alkyl ester is made the function monomer; (2) (methyl) alkyl acrylate and vinyl aromatic compounds are made comonomer; (3) has carboxylic functional Acrylic Acid Monomer.When in conjunction with application of the present invention, the hydroxyl on (methyl) acrylic acid hydroxy alkyl ester can react with the linking agent such as containing isocyanic ester and amino.The ratio between (methyl) acrylic acid hydroxy alkyl ester and other monomers adjusted can effectively provide a kind of hydroxyl value between at least about 20mgKOH/g, but be not more than about 100mgKOH/g, and an importance, hydroxyl value is between the acrylic resin of about 25-60mgKOH/g; Selection by temperature of reaction, composite initiator system and chain-transfer agent etc. the acrylic resin that is provided is provided is not more than 5000, at least 1000, on the one hand, and between the number-average molecular weight of about 2000-4000; And be not more than about 2.5, on the one hand, between the dispersed index of 1.0-2.0.The low hydroxyl value of acrylic resin of the present invention helps obtaining the multipolymer of low-viscosity; In addition, in application, use the linking agent of low quantity, help reducing the volatile quantity of unreacted isocyano in the solidifying agent.The low dispersed index of acrylic resin of the present invention helps to reduce acrylic resin viscosity of the present invention, reaches the purpose that reduces VOC content.
The weight proportion of the reaction monomers that acrylic resin of the present invention is used: hydroxyalkyl methacrylate, consumption are 5-25 part; Acrylic acid hydroxy alkyl ester, consumption are 5-25 part; Unsaturated carboxylic acid, consumption are 1-10 part; Alkyl methacrylate, consumption are 10-45 part; Alkyl acrylate, consumption are 10-45 part; Vinyl aromatic compounds, consumption are 0-10 part.
(methyl) alkyl acrylate is meant (methyl) methyl acrylate or (methyl) ethyl propenoate or (methyl) butyl acrylate or (methyl) isobutyl acrylate or (methyl) vinylformic acid n-pentyl ester or (methyl) vinylformic acid isopentyl ester or the just own ester of (methyl) vinylformic acid or (methyl) Isohexyl acrylate or (methyl) vinylformic acid 2-ethyl dissident's ester or (methyl) cyclohexyl acrylate or (methyl) lauryl acrylate, is preferably (methyl) methyl acrylate or (methyl) ethyl propenoate or (methyl) butyl acrylate.
(methyl) acrylic acid hydroxy alkyl ester is meant (methyl) vinylformic acid hydroxyl methyl esters or (methyl) Propylene glycol monoacrylate or (methyl) vinylformic acid hydroxy butyl ester.
Unsaturated carboxylic acid can be (methyl) vinylformic acid or methylene-succinic acid.
Vinyl aromatic compounds, for example vinylbenzene or alpha-methyl styrene or vinyl cyanide or (methyl) acrylamide.
High solid low viscosity acrylic resin of the present invention uses composite initiator system in preparation process.Generally in Raolical polymerizable, adopt initiator can select multiple material for use, as superoxide, azo initiator.According to the use temperature scope of initiator, can be divided into four classes to initiator: high temperature (more than 100 ℃) class, as alkyl peroxide or alkyl peroxide thing or peroxyester etc.; Middle temperature (30～100 ℃) class is as Diisopropyl azodicarboxylate or peroxidation two acyls or persulphate etc.; Lower temperature (0～30 ℃) class is as redox initiation system; Utmost point low temperature (below 0 ℃) class is as superoxide-metal alkylide.The initiator that is applicable to the preparation high solid low viscosity acrylic resin has only two classes, promptly a class is middle temperature initiator, mainly comprise Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) or dioctanoyl peroxide or peroxidation two (2, the 4-dichloro-benzoyl) or diacetyl peroxide or dilauroyl peroxide and benzoyl peroxide or peroxidation-2 ethyl hexanoic acid tert-pentyl ester or peroxide-2-ethyl hexanoic acid tert-butyl, preferably benzoyl peroxide or peroxidation-2 ethyl hexanoic acid tert-pentyl ester or peroxide-2-ethyl hexanoic acid tert-butyl; One class is a high-temperature initiator, mainly comprise dicumyl peroxide or di-t-butyl peroxide or peroxidation phenylformic acid tertiary butyl ester or peroxidation two tert-pentyls or tertbutyl peroxide or isopropyl benzene hydroperoxide or methylethyl ketone peroxide, preferably dicumyl peroxide or di-t-butyl peroxide or peroxidation phenylformic acid tertiary butyl ester or peroxidation two tert-pentyls or tertbutyl peroxide or methylethyl ketone peroxide.In the acrylic resin of the present invention preparation employed composite initiator system be meant at least a in warm initiator and at least a high-temperature initiator, be preferably a kind of in warm initiator and a kind of high-temperature initiator, its weight proportion is 0.1-10: 1, and optimum 0.5-5: 1.For example, the initiator system that benzoyl peroxide and dicumyl peroxide are formed utilizes both transformation period different with decomposition rate, helps making acrylic resin of the present invention to obtain the high conversion of low-viscosity and reaction monomers.
The common consumption of composite initiator system (by total monomer) is about 1-10wt%, preferably about 2-5wt%; Above percentage ratio is to be benchmark with all monomeric gross weights.Composite initiator system generally is added dropwise to reactor after all reaction monomers and chain-transfer agent mix.Composite initiator can once add, also can be at twice or repeatedly the different steps in reaction process add, twice adding mode of general employing, promptly add with reaction monomers for the first time, be about 95-99wt% of composite initiator total amount, add about 1-5wt% of composite initiator total amount for the second time.
The chain-transfer agent that high solid low viscosity acrylic resin of the present invention uses in preparation process comprises that mercaptoethanol, Thiovanic acid, thiohydracrylic acid, uncle's lauryl mercaptan, thioglycolic acid, allyl sulfide are for thing, vinylbenzene ether.The consumption of chain-transfer agent is the 0-5wt% of reaction monomers total amount, preferably about 1-3wt%.
About 145 ℃-170 ℃ of the temperature of reaction of high solid low viscosity acrylic resin of the present invention.Utilize the boiling point difference of each solvent, select for use proper solvent system to keep temperature of reaction.Preparing the solvent that acrylic resin of the present invention is suitable for includes: at least a in dimethylbenzene and methyl amylketone and pimelinketone and N-BUTYL ACETATE and amyl acetate-n and ethylene glycol ether acetate and 2-Butoxyethyl acetate and Diethylene Glycol monobutyl ether acetate and the 1-Methoxy-2-propyl acetate, be preferably a kind of and ethylene glycol ether acetate in dimethylbenzene and the N-BUTYL ACETATE and a kind of composition mixed solvent system in the 2-Butoxyethyl acetate, its weight proportion 1: 0.1-5; Optimum solvent system dimethylbenzene: ethylene glycol ether acetate=1: 0.5-2 (weight ratio) or N-BUTYL ACETATE: 2-Butoxyethyl acetate=1: 0.5-2 (weight ratio).Higher temperature of reaction can be controlled the dispersed exponential sum number-average molecular weight of resin, obtains the narrow and less acrylic resin of number-average molecular weight of dispersed index, helps to obtain high solid low viscosity acrylic resin.
The feature of synthetic acrylic resin has the about 20-100mgKOH/g of hydroxyl value as stated above, and dispersed index is not more than about 2.5 and the number-average molecular weight of about 1000-5000, solids content wt% 〉=70%, viscosity 1000-4000mPas.
Acrylic resin of the present invention is to adopt a kind of novel process preparation, and it is simple to have a synthesis technique, and raw materials cost is cheap, and reaction process is easy to characteristics such as control; Prepared high solid coating organic solvent content obviously reduces, and can effectively protect atmospheric environment; Coating possesses excellent performance, as high gloss, high fullness ratio, sticking power is good and hardness is high, is applicable to fields such as automotive industry, mechanical implement and industry.
Description of drawings
Fig. 1 is the gel chromatography spectrogram of 1 synthetic high solid low viscosity acrylic resin of embodiment embodiment in the patent of the present invention.
Fig. 2 is the gel chromatography spectrogram of 2 synthetic high solid low viscosity acrylic resins of embodiment embodiment in the patent of the present invention.
Fig. 3 is the gel chromatography spectrogram of embodiment Comparative Examples institute synthetic High solids Acrylic Resin in the patent of the present invention.
Embodiment
Following examples are to further specify of the present invention, but the invention is not restricted to this.
Embodiment 1
In the reactor that thermometer, stirrer, reflux exchanger, water trap, dropping funnel and nitrogen conduit are housed, add 80 parts of dimethylbenzene, 40 parts of ethylene glycol ether acetates, import nitrogen, be warmed up to 150 ℃, with 145 parts of methyl methacrylates, 95 parts of butyl acrylates, 65 parts of ethyl propenoates, 40 parts of Propylene glycol monoacrylates, 5 parts in vinylformic acid, composite initiator (benzoyl peroxide/di-t-butyl peroxide=1.2/1.0) 13.5 parts, the mixture that lauryl mercaptan is 4.2 parts dripped in 3.5 hours, and insulation is 1 hour under the temperature of reaction; Get 0.5 part of composite initiator again, 0.3 part of lauryl mercaptan, 15 parts of xylene soluble dripped off in 0.5 hour, and insulation is 2 hours under the temperature of reaction, promptly gets resin.
Its key technical indexes is as follows:
1. hydroxyl value (mgKOH/g) 48.6
2. acid number (mgKOH/g) 12.2
3. amount of solid content (%) 70.6
4. viscosity (mPas) 3620
The gel chromatography of above product (GPC) spectrogram is seen Figure of description Fig. 1, by the number-average molecular weight Mn=3220 of this resin as can be known in the spectrogram, weight-average molecular weight Mw=4969, dispersed index D=1.54.
Embodiment 2
In the reactor that thermometer, stirrer, reflux exchanger, water trap, dropping funnel and nitrogen conduit are housed, add 60 parts of N-BUTYL ACETATEs, 55 parts of 2-Butoxyethyl acetates, import nitrogen, be warmed up to 155 ℃, with 145 parts of methyl methacrylates, 110 parts of butyl acrylates, 50 parts of ethyl propenoates, 55 parts of Hydroxyethyl acrylates, 5 parts in vinylformic acid, composite initiator (benzoyl peroxide/peroxidation two tert-pentyls=1.5/1.0) 14.5 parts, the mixture that lauryl mercaptan is 5.8 parts dripped off in 4 hours, and insulation is 1 hour under the temperature of reaction; Get 0.5 part of composite initiator again, 0.2 part of lauryl mercaptan, 15 parts of N-BUTYL ACETATE dissolvings dripped off in 0.5 hour, and insulation is 2 hours under the temperature of reaction, promptly gets resin.
Its key technical indexes is as follows:
1. hydroxyl (mgKOH/g) 55.2
2. acid number (mgKOH/g) 11.4
3. amount of solid content (%) 70.8
4. viscosity (mPas) 2860
The gel chromatography of above product (GPC) spectrogram is seen Figure of description Fig. 2, by the number-average molecular weight Mn=2488 of this resin as can be known in the spectrogram, weight-average molecular weight Mw=3073, dispersed index D=1.24.。
Comparative Examples
By above-mentioned same equipment and preparation technology, add 120 parts of dimethylbenzene, feed nitrogen, be warmed up to 144 ℃, with 145 parts of methyl methacrylates, 85 parts of butyl acrylates, 45 parts of ethyl propenoates, 75 parts of Propylene glycol monoacrylates, 5 parts in vinylformic acid, the mixture that benzoyl peroxide is 15.6 parts dripped in 4 hours, and insulation is 1 hour under the temperature of reaction; Get 0.4 part of benzoyl peroxide again, 15 parts of xylene soluble dripped off in 0.5 hour, and insulation is 2 hours under the temperature of reaction; Distill out 25 parts of dimethylbenzene, add 25 parts of N-BUTYL ACETATEs, promptly get resin.
Its key technical indexes is as follows:
1. hydroxyl (mgKOH/g) 99.2
2. acid number (mgKOH/g) 11.4
3. amount of solid content (%) 70.8
4. viscosity (mPas) 12600
The gel chromatography of above product (GPC) spectrogram is seen Figure of description Fig. 3, by the number-average molecular weight Mn=8239 of this resin as can be known in the spectrogram, weight-average molecular weight Mw=24140, dispersed index D=2.93.
The test example:
Respectively resin is made high solid coating according to same recipe, arrange in pairs or groups-NCO with the polyisocyanate curing agent (model HI-100, NCO content 22%) of BASF AG respectively then :-OH=1.01: 1.00 (mol ratios).
Reference formulation:
Name of product per-cent %
Acrylic resin (70%) 60
Rutile type Titanium Dioxide (R-930) 25
Wetting agent 0.3
Dispersion agent 0.5
Flow agent 0.1
Table 1 coating property detects table
| Detect index | Embodiment 1 | Embodiment 2 | Comparative Examples |
| Paint viscosity (mPas) | 6350 | 5680 | 13540 |
| Fineness, micron ,≤ | 7 | 8 | 6 |
| Paint film appearance | Smooth smooth | Smooth smooth | Smooth smooth |
| Film thickness, (μ m) | 14 | 16 | 15 |
| Gloss, % | 100 | 98 | 96 |
| Snappiness (mm) | 1 | 1 | 2 |
| Sticking power, cross cut test, level≤ | 1 | 1 | 2 |
| Shock strength, Kgcm | 50 | 50 | 50 |
| Hardness (pencil cut) | 3H | 3H | 2H |
Application by embodiment and comparative example contrasts as can be known: the high solid coating of acrylic resin preparation of the present invention obviously reduces at the product viscosity, and every performance is better than Comparative Examples.
Claims (10)
1. high solid low viscosity acrylic resin is characterized in that: acrylic resin hydroxyl value 20-100mgKOH/g, dispersed index are not more than 2.5 and the number-average molecular weight of 1000-5000.
2. high solid low viscosity acrylic resin according to claim 1 is characterized in that: acrylic resin solids content wt% 〉=70%, viscosity scope 1000-4000mPas.
3. high solid low viscosity acrylic resin according to claim 1 is characterized in that: the initiator that is adopted in the preparation acrylic resin is: composite initiator system; The functional monomer who is adopted is: hydroxyalkyl methacrylate and acrylic acid hydroxy alkyl ester and unsaturated carboxylic acid; The comonomer that is adopted is: alkyl methacrylate and alkyl acrylate and vinyl aromatic compounds.
4. high solid low viscosity acrylic resin according to claim 1 is characterized in that: the weight proportion of each reaction monomers of preparation acrylic resin is:
Hydroxyalkyl methacrylate, consumption are 5-25 part;
Acrylic acid hydroxy alkyl ester, consumption are 5-25 part;
Unsaturated carboxylic acid, consumption are 1-10 part;
Alkyl methacrylate, consumption are 10-45 part;
Alkyl acrylate, consumption are 10-45 part;
Vinyl aromatic compounds, consumption are 0-10 part.
5. synthetic method for preparing the described high solid low viscosity acrylic resin of claim 1 is characterized in that reactions steps is as follows:
The first step, the solvent of adding total solvent amount 60wt% in the reactor, logical nitrogen protection is warmed up to temperature of reaction;
Second step, the common mixed solution of forming of the solvent of the 95-99wt% of the 90-99wt% of all reaction monomers and chain-transfer agent total amount and composite initiator system total amount and total solvent amount 35wt% is added Dropping feeder, in 3-4 hour, dropwise, kept temperature of reaction 1-2 hour with uniform velocity;
In the 3rd step, the remaining dissolution with solvents of 1-5wt% of the 1-10wt% of chain-transfer agent total amount and composite initiator total amount at the uniform velocity added in 0.5 hour in the reactor, kept temperature of reaction 1-2 hour, got acrylic resin of the present invention.
6. high solid low viscosity acrylic resin synthetic method according to claim 5, it is characterized in that composite initiator system refer at least a in warm initiator and at least a high-temperature initiator carry out composite.
In warm initiator comprise Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) or dioctanoyl peroxide or peroxidation two (2,4 dichloro benzene formyl) or diacetyl peroxide or dilauroyl peroxide or benzoyl peroxide or peroxidation-2 ethyl hexanoic acid tert-pentyl ester or peroxide-2-ethyl hexanoic acid tert-butyl;
High-temperature initiator comprises dicumyl peroxide or di-t-butyl peroxide or peroxidation two tert-pentyls or tertbutyl peroxide or isopropyl benzene hydroperoxide or methylethyl ketone peroxide or peroxidation phenylformic acid tertiary butyl ester.
7. high solid low viscosity acrylic resin synthetic method according to claim 5 is characterized in that the composite initiator system consumption is generally the 1-10wt% of reaction monomers total amount.
8. high solid low viscosity acrylic resin synthetic method according to claim 5, it is characterized in that the chain-transfer agent that uses as mercaptoethanol or Thiovanic acid or thiohydracrylic acid or uncle's lauryl mercaptan or thioglycolic acid or allyl sulfide for thing or vinylbenzene ether.
9. high solid low viscosity acrylic resin synthetic method according to claim 5 is characterized in that the chain-transfer agent consumption that the uses 0-5wt% as the reaction monomers total amount.
10. high solid low viscosity acrylic resin preparation method according to claim 5 is characterized in that 145 ℃-170 ℃ of the range of reaction temperature of acrylic resin.
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| CN106009454A (en) * | 2016-05-25 | 2016-10-12 | 华南理工大学 | High-solid low-viscosity hydroxy acrylic resin as well as preparation method and application thereof |
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