CN102627721A - High-solid hydroxyl fluorine-containing acrylic resin and preparation method thereof - Google Patents
High-solid hydroxyl fluorine-containing acrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to high-solid hydroxyl fluorine-containing acrylic resin and a preparation method thereof. The high-solid hydroxyl fluorine-containing acrylic resin comprises the following components in parts by weight: 10-25 parts of fluorine-containing acrylic ester monomer, 10-30 parts of hydroxyl group-containing acrylic ester monomer, 5-20 parts of methyl acrylic alkyl ester monomer, 5-15 parts of acrylic alkyl ester monomer, 0.3-6 parts of initiator, 0.2-4 parts of chain transfer and 30-50 parts of solvent. According to the hydroxyl fluorine-containing acrylic resin, the solid content reaches up to 75-90 percent, the viscosity is only 900-3,000 mPa.s, the number-average molecular weight is 1,200-6,000, and the molecular weight distribution index is 1.4-2.5; and the resin has the advantages of superior performance, high transparency, no odor of mercaptan, low VOC (Volatile Organic Compound) content, a fluorine carbon group included on a polymer chain and superior corrosion resistance of the resin and can be applied to the fields such as heavy anticorrosive coatings, marine antifouling coatings, aircraft surface coatings, anti-doodling coatings, exterior wall coatings of high weathering resistance and the like.
Description
Technical field
The present invention designs technical field of coatings, is specifically related to a kind of high solid fluorinated hydroxy vinyl resin and preparation method thereof.
Background technology
Fluorine is the maximum element of electronegativity, and with the fluoro-carbon bond that carbon atom forms, bond energy is up to 485.3KJ/mol, and is therefore very stable; In the fluoroacrylic resin in the shape of a spiral the fluorine atom arranged of shape carbon skeleton is played well " shielding protection " effect, make main chain inside avoid uviolizing and chemical reagent erosion, therefore, more common vinyl resin, its performance is more excellent, uses wider.The enhancing of Along with people's environmental consciousness, more and more stricter to the control of coating VOC content, research and development high solid, low viscous resin are the effective ways that obtains low VOC coatings.
Patent CN101619116B has reported a kind of thermoplastic fluorine-containing acrylic resin and preparation method thereof, adopts trifluoroethyl methacrylate or vinylformic acid trifluoro ethyl ester to obtain through radical polymerization.But owing to participate in not having the hydroxyl monomer in the monomer polymerized, the synthetic resin does not have crosslinkable group, process paint film after degree of crosslinking not enough.Patent CN100519603C has reported a kind of cross-linking type fluorine-containing acrylic resin; With trifluoroethyl methacrylate or vinylformic acid trifluoro ethyl ester is fluorochemical monomer, obtains through radical polymerization in organic solvent with TEB 3K, alkyl acrylate monomer, functional Acrylic Acid Monomer.Owing to have only 3 fluorine atoms on each (methyl) vinylformic acid trifluoro ethyl ester molecule; Obtain the fluorine resin of high fluorine content, must improve the fluorochemical monomer ratio, therefore; In this patent; The fluoro-acrylate monomer consumption is up to 50%, must cause other monomer ratio to descend, and the resin cost that synthesizes is higher; In addition, from the embodiment that announces, the amount of solid content of this resin has only 45 ~ 55%, the VOC too high levels.With regard to present disclosed patent and paper, as yet not relevant for the report that synthesizes high solid fluorinated hydroxy vinyl resin.
Summary of the invention
Technical problem:The purpose of this invention is to provide a kind of high solid fluorinated hydroxy vinyl resin and preparation method thereof.This high solid fluorinated hydroxy vinyl resin has following technical indicator: amount of solid content is 75 ~ 90 wt%, and viscosity is 900 ~ 3000 mPas, and number-average molecular weight is 1200 ~ 6000, and molecular weight distributing index is 1.4 ~ 2.5.
Technical scheme:High solid fluorinated hydroxy vinyl resin of the present invention passes through the free radical solution polymerization gained by fluorinated acrylate monomer, hydroxy acryl acid ester monomer, alkyl methacrylate monomer, alkyl acrylate monomer;
By weight; It is following to participate in each component of polymeric and consumption thereof: 10 ~ 25 parts of fluorinated acrylate monomers, 10 ~ 30 parts of hydroxy acryl acid ester monomers, 5 ~ 20 parts of alkyl methacrylate monomers; 5 ~ 15 parts of alkyl acrylate monomers; 0.3 ~ 6 part of initiator, 0.2 ~ 4 part of chain-transfer agent, 30 ~ 50 parts of solvents;
Said fluorinated acrylate monomer is one or both in vinylformic acid tetrafluoro propyl ester, tetrafluoropropyl propyl ester, vinylformic acid octafluoro pentyl ester, methylacrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, methylacrylic acid ten difluoro heptyl esters, vinylformic acid ten trifluoro monooctyl esters or the methylacrylic acid ten trifluoro monooctyl esters;
Said hydroxy acryl acid ester monomer is a kind of in methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, senecioate-hydroxyl ethyl ester or the senecioate-hydroxypropyl acrylate;
Said alkyl methacrylate monomer is one or both in TEB 3K, Jia Jibingxisuanyizhi, n-BMA, cyclohexyl methacrylate or the isobornyl methacrylate;
Said alkyl acrylate monomer is a kind of in ethyl propenoate, n-butyl acrylate or the vinylformic acid n-octyl;
Said initiator is a kind of in Diisopropyl azodicarboxylate, two t-amyl peroxy things or the ditertiary butyl peroxide;
Said chain-transfer agent is a kind of in 2 mercapto ethanol, n-butyl mercaptan, positive Dodecyl Mercaptan or the 3-Mercapto-1;
Said solvent is a kind of in vinyl acetic monomer, N-BUTYL ACETATE, toluene, o-Xylol, p-Xylol, m-xylene or the 2-butanone.
In described each component of participation polymeric and the consumption thereof, can also increase in 1-10 part vinylformic acid, methylacrylic acid, vinylbenzene or the vinyl acetate one or both.
The compound method of said high solid fluorinated hydroxy vinyl resin may further comprise the steps:
The first step: the solvent of total solvent amount 60 wt% is joined in the reactor drum, feed the nitrogen deoxygenation, be warming up to temperature of reaction;
Second step: will in 2 ~ 4 hours, join evenly in the reactor drum by 90 wt% of whole monomers, chain-transfer agent, initiator total amount, the mixing solutions that 30 wt% of solvent total amount form, and after adding, continue insulation reaction 1 ~ 2 hour;
The 3rd step: remaining initiator and solvent are joined in the reactor drum, continue insulation reaction and stopped in 1 ~ 2 hour, be cooled to room temperature;
The 4th step: the 3rd step product is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Beneficial effect:Synthetic fluorinated hydroxy vinyl resin amount of solid content is high as stated above, reaches 75 ~ 90 wt%, and viscosity is low, is merely 900 ~ 3000 mPas, and the number-average molecular weight scope is 1200 ~ 6000, and molecular weight distributing index is little, is merely 1.4 ~ 2.5; This high solid fluorinated hydroxy vinyl resin excellent property; The transparency is high; The stink of no mercaptan; VOC content is low, can cooperate polyisocyanate curing agent to be prepared into double-component polyurethane coating, is applicable to fields such as heavy-duty coating, marine antifouling coating, aircraft skin coating, anti-doodling paint, high-weatherability exterior coating.
Embodiment
Pass through specific embodiment below; The present invention is further specified, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in scope disclosed by the invention; The variation that can expect easily or replacement all should be encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the scope of claim protection.
Embodiment 1
(1) by weight, 24 parts of N-BUTYL ACETATEs are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 85 ℃;
(2) will in 3.5 hours, join in the reactor drum evenly by the mixing solutions that 19 parts of methylacrylic acid octafluoro pentyl esters, 13 parts of methylacrylic acid-β-hydroxypropyl acrylates, 11 parts of isobornyl methacrylates, 8 parts of n-butyl acrylates, 1.8 parts of Diisopropyl azodicarboxylates, 1 part of 2 mercapto ethanol, 12 parts of N-BUTYL ACETATEs are formed; After adding, continued insulation reaction 2 hours;
(3) 0.2 part of Diisopropyl azodicarboxylate, 4 parts of N-BUTYL ACETATEs are joined in the reactor drum, continued insulation reaction 1 hour, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 82.3 wt%, and viscosity is 2162 mPas, and number-average molecular weight is 4512, and molecular weight distributing index is 1.76.
Embodiment 2
(1) by weight, 18 parts of 2-butanone are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 80 ℃;
(2) will be by 13 parts of methylacrylic acids, ten difluoro heptyl esters, 18 parts of methylacrylic acid-beta-hydroxy ethyl esters, 15 parts of TEB 3Ks, 6 parts of ethyl propenoates, 1.6 parts of vinylformic acid; 2.7 part two t-amyl peroxy things, 2.1 parts of 3-sulfydryls-1; The mixing solutions of 2-Ucar 35,9 parts of 2-butanone compositions joined in the reactor drum in 4 hours evenly; After adding, continued insulation reaction 2 hours;
(3) 0.3 part of two t-amyl peroxy thing, 3 parts of 2-butanone are joined in the reactor drum, continued insulation reaction 1 hour, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 86.6 wt%, and viscosity is 2764 mPas, and number-average molecular weight is 5041, and molecular weight distributing index is 2.14.
Embodiment 3
(1) by weight, 27 parts of toluene are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 100 ℃;
(2) will be by 24 parts of vinylformic acid tetrafluoro propyl ester, 25 parts of senecioate-hydroxyl ethyl esters, 15 parts of cyclohexyl methacrylates, 5 parts of vinylformic acid n-octyls, 1 part of methylacrylic acid, 4 parts of vinylbenzene; 2.25 the mixing solutions of part Diisopropyl azodicarboxylate, 3.75 parts of positive Dodecyl Mercaptans, 13.5 parts of toluene compositions joined in the reactor drum in 4 hours evenly; After adding, continued insulation reaction 1.5 hours;
(3) 0.25 part of Diisopropyl azodicarboxylate, 4.5 parts of toluene are joined in the reactor drum, continued insulation reaction 2 hours, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 89.4 wt%, and viscosity is 1563 mPas, and number-average molecular weight is 3556, and molecular weight distributing index is 1.55.
Embodiment 4
(1) by weight, 30 parts of vinyl acetic monomers are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 76 ℃;
(2) will be by 12 parts of methylacrylic acids, ten trifluoro monooctyl esters, 21 parts of senecioate-hydroxyl ethyl esters, 15 parts of TEB 3Ks, 13 parts of n-butyl acrylates, 2 parts of vinyl acetates; 3.6 part ditertiary butyl peroxide, 3.5 parts of 3-sulfydryls-1; The mixing solutions of 2-Ucar 35,15 parts of vinyl acetic monomer compositions joined in the reactor drum in 2.5 hours evenly; After adding, continued insulation reaction 2 hours;
(3) 0.4 part of ditertiary butyl peroxide, 5 parts of vinyl acetic monomers are joined in the reactor drum, continued insulation reaction 2 hours, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 83.5 wt%, and viscosity is 1827 mPas, and number-average molecular weight is 4139, and molecular weight distributing index is 1.87.
Embodiment 5
(1) by weight, 24 parts of N-BUTYL ACETATEs are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 80 ℃;
(2) will be by 10 parts of dodecafluorhe-ptylacrylates, 30 parts of senecioate-hydroxypropyl acrylates, 20 parts of n-BMAs, 5 parts of n-butyl acrylates; 4.5 the mixing solutions of part two t-amyl peroxy things, 4 parts of tert-dodecyl mercaptans, 12 parts of N-BUTYL ACETATE compositions joined in the reactor drum in 3 hours evenly; After adding, continued insulation reaction 1 hour;
(3) 0.5 part of two t-amyl peroxy thing, 4 parts of N-BUTYL ACETATEs are joined in the reactor drum, continued insulation reaction 1 hour, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 76.5 wt%, and viscosity is 2712 mPas, and number-average molecular weight is 5185, and molecular weight distributing index is 1.51.
Embodiment 6
(1) by weight, 18 parts of p-Xylol are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 105 ℃;
(2) will be by 25 parts of tetrafluoropropyl propyl ester, 26 parts of methylacrylic acid-β-hydroxypropyl acrylates, 5 parts of Jia Jibingxisuanyizhis, 15 parts of ethyl propenoates, 7 parts of vinylformic acid, 3 parts of vinylbenzene; 1.35 the mixing solutions of part two t-amyl peroxy things, 1.5 parts of n-butyl mercaptans, 9 parts of p-Xylol compositions joined in the reactor drum in 2.5 hours evenly; After adding, continued insulation reaction 1.5 hours;
(3) 0.15 part of two t-amyl peroxy thing, 3 parts of p-Xylol are joined in the reactor drum, continued insulation reaction 2 hours, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 87.4 wt%, and viscosity is 1087 mPas, and number-average molecular weight is 3160, and molecular weight distributing index is 1.88.
Embodiment 7
(1) by weight, 27 parts of m-xylenes are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 110 ℃;
(2) will be by 20 parts of vinylformic acid, ten trifluoro monooctyl esters, 10 parts of senecioate-hydroxypropyl acrylates, 17 parts of isobornyl methacrylates, 11 parts of vinylformic acid n-octyls, 2 parts of methylacrylic acids; 0.54 the mixing solutions of part Diisopropyl azodicarboxylate, 0.5 part of positive Dodecyl Mercaptan, 13.5 parts of m-xylene compositions joined in the reactor drum in 3 hours evenly; After adding, continued insulation reaction 2 hours;
(3) 0.06 part of Diisopropyl azodicarboxylate, 4.5 parts of m-xylenes are joined in the reactor drum, continued insulation reaction 2 hours, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 85.3 wt%, and viscosity is 1226 mPas, and number-average molecular weight is 2531, and molecular weight distributing index is 2.39.
Embodiment 8
(1) by weight, 24 parts of N-BUTYL ACETATEs are put in the reactor drum, fed the nitrogen deoxygenation, be warming up to 85 ℃;
(2) will be by 25 parts of methylacrylic acids, ten difluoro heptyl esters, 15 parts of methylacrylic acid-beta-hydroxy ethyl esters, 7 parts of cyclohexyl methacrylates, 6 parts of n-butyl acrylates; 3.6 part Diisopropyl azodicarboxylate, 4 parts of 3-sulfydryls-1; The mixing solutions of 2-Ucar 35,12 parts of N-BUTYL ACETATE compositions joined in the reactor drum in 4 hours evenly; After adding, continued insulation reaction 1.5 hours;
(3) 0.4 part of Diisopropyl azodicarboxylate, 4 parts of N-BUTYL ACETATEs are joined in the reactor drum, continued insulation reaction 1.5 hours, be cooled to room temperature;
(4) reacted polymers soln is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
Its key technical indexes is following: amount of solid content is 80.7 wt%, and viscosity is 2462 mPas, and number-average molecular weight is 5725, and molecular weight distributing index is 1.45.
Claims (10)
1. high solid fluorinated hydroxy vinyl resin is characterized in that: it is through the free radical solution polymerization gained by fluorinated acrylate monomer, hydroxy acryl acid ester monomer, alkyl methacrylate monomer and alkyl acrylate monomer; By weight, participation each component of polymeric and consumption thereof are following:
10 ~ 25 parts of fluorinated acrylate monomers,
10 ~ 30 parts of hydroxy acryl acid ester monomers,
5 ~ 20 parts of alkyl methacrylate monomers,
5 ~ 15 parts of alkyl acrylate monomers,
0.3 ~ 6 part of initiator,
0.2 ~ 4 part of chain-transfer agent,
30 ~ 50 parts of solvents.
2. high solid fluorinated hydroxy vinyl resin as claimed in claim 1; It is characterized in that described fluorinated acrylate monomer is one or both in vinylformic acid tetrafluoro propyl ester, tetrafluoropropyl propyl ester, vinylformic acid octafluoro pentyl ester, methylacrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, methylacrylic acid ten difluoro heptyl esters, vinylformic acid ten trifluoro monooctyl esters or the methylacrylic acid ten trifluoro monooctyl esters.
3. high solid fluorinated hydroxy vinyl resin as claimed in claim 1; It is characterized in that described hydroxy acryl acid ester monomer is a kind of in methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, senecioate-hydroxyl ethyl ester or the senecioate-hydroxypropyl acrylate.
4. high solid fluorinated hydroxy vinyl resin as claimed in claim 1; It is characterized in that described alkyl methacrylate monomer is one or both in TEB 3K, Jia Jibingxisuanyizhi, n-BMA, cyclohexyl methacrylate or the isobornyl methacrylate.
5. high solid fluorinated hydroxy vinyl resin as claimed in claim 1 is characterized in that, described alkyl acrylate monomer is a kind of in ethyl propenoate, n-butyl acrylate or the vinylformic acid n-octyl.
6. high solid fluorinated hydroxy vinyl resin as claimed in claim 1 is characterized in that, described initiator is a kind of in Diisopropyl azodicarboxylate, two t-amyl peroxy things or the ditertiary butyl peroxide.
7. high solid fluorinated hydroxy vinyl resin as claimed in claim 1 is characterized in that, described chain-transfer agent is a kind of in 2 mercapto ethanol, n-butyl mercaptan, positive Dodecyl Mercaptan, tert-dodecyl mercaptan or the 3-Mercapto-1.
8. high solid fluorinated hydroxy vinyl resin as claimed in claim 1 is characterized in that, described solvent is a kind of in vinyl acetic monomer, N-BUTYL ACETATE, toluene, o-Xylol, p-Xylol, m-xylene or the 2-butanone.
9. high solid fluorinated hydroxy vinyl resin as claimed in claim 1 is characterized in that, in described each component of participation polymeric and the consumption thereof, and one or both in increase 1-10 part vinylformic acid, methylacrylic acid, vinylbenzene or the vinyl acetate.
10. the compound method of a high solid fluorinated hydroxy vinyl resin as claimed in claim 1 is characterized in that, this method may further comprise the steps:
The first step: the solvent that will account for total solvent amount 60 wt% joins in the reactor drum, feeds the nitrogen deoxygenation, is warming up to temperature of reaction;
Second step: will in 2 ~ 4 hours, join evenly in the reactor drum by 90 wt% of whole monomers, chain-transfer agent, initiator total amount, the mixing solutions that 30 wt% of solvent total amount form, and after adding, continue insulation reaction 1 ~ 2 hour;
The 3rd step: remaining initiator and solvent are joined in the reactor drum, continue insulation reaction and stopped in 1 ~ 2 hour, be cooled to room temperature;
The 4th step: the 3rd step product is poured in the hexanaphthene, separated out polymer precipitation, polymer precipitation is isolated the back in 25 ℃ of following vacuum-dryings 24 hours, be dissolved in again in the N-BUTYL ACETATE, obtain product.
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