CN115477719B - Chlorotrifluoroethylene-vinyl ether powder resin and preparation method thereof - Google Patents
Chlorotrifluoroethylene-vinyl ether powder resin and preparation method thereof Download PDFInfo
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- CN115477719B CN115477719B CN202211181064.7A CN202211181064A CN115477719B CN 115477719 B CN115477719 B CN 115477719B CN 202211181064 A CN202211181064 A CN 202211181064A CN 115477719 B CN115477719 B CN 115477719B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
- C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
- C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/165—Carbocyclic compounds
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
- C08F216/20—Monomers containing three or more carbon atoms in the unsaturated aliphatic radical
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Abstract
A chlorotrifluoroethylene-vinyl ether powder resin and a preparation method thereof belong to the technical field of FEVE fluorocarbon resin. The powder resin effectively prevents Huang Bianhei of the resin powder during falling film evaporation by adding a color retention agent to the formulation, while maintaining the thermal stability of the resin polymer. By adding the hydroxyl protecting agent, the loss of hydroxyl in the falling film evaporation process is effectively prevented. In addition, by adding the auxiliary agent, the melt index of the polymer is improved, and by the cooperation of the color retention agent and the auxiliary agent, the yellowing index can be further reduced, and the ageing resistance of the powder FEVE resin is remarkably improved. The powder resin has low polymerization temperature, adopts volatile solvent, is simple and efficient to recycle, and realizes zero emission of VOC; the glass transition temperature is higher, and the storage is stable without pressure; the weather resistance is excellent and stable, and the weather resistance is far superior to that of the existing powder resin.
Description
Technical Field
The invention belongs to the technical field of FEVE fluorocarbon resin, and particularly relates to powder resin obtained by copolymerizing chlorotrifluoroethylene and vinyl ether and a preparation method thereof.
Background
The fluorine-containing high molecular polymer is commonly called fluorocarbon resin, and has wide application in various high-requirement industrial fields, especially the outdoor building field, due to the excellent weather resistance, corrosion resistance and chemical resistance stability. With the continuous development of decades, the annual fluororesin yield of China breaks through tens of thousands of tons, and the market value breaks through billions. However, with the development of technology, environmental problems facing the world are more and more prominent, and the environmental requirements of China are more stringent in recent years. The traditional solvent type fluororesin usually discharges a large amount of VOC, and the common resin-derived paint needs relatively frequent construction, thus having great consumption and waste of energy. Many developed countries have prohibited or highly restricted the import and use of such non-environment-friendly products, and under such a large environment, development of fluorine-containing powder resins which are more environmentally friendly, consume less energy, and have more excellent properties has become necessary.
Disclosure of Invention
The invention provides a powder type FEVE resin and a preparation method thereof, which are used for solving the problems existing in the prior art.
The technical scheme of the invention is as follows: a powder FEVE resin is prepared by reacting non-fluorine monomer, trifluorochloroethylene, initiator, first auxiliary agent and second auxiliary agent in solvent;
the molar ratio of the non-fluorine monomer to the trifluorochloroethylene is 1:1-1.2, and the non-fluorine monomer is at least two selected from isobutyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether and 2-ethyleneoxy ethanol;
the dosage of the initiator is 0.5-1% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the first auxiliary agent is 0.5% -1% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the second auxiliary agent is 0.5% -2% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the solvent is 90% -110% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the initiator is an initiator for FEVE resin, and specifically the initiator is at least one selected from tert-butyl peroxyneodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxypivalate, dilauroyl peroxide, didecanoyl peroxide, 2-azobisisobutyronitrile, dibenzoyl peroxide, 2-azobis (2-methylbutyronitrile), tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylacetate, tert-butyl peroxy-3, 5-trimethylhexanoate, 2-bis (tert-butylperoxy) butane, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1, 4-bis (tert-butylperoxyformate) cyclohexane, 1-bis (tert-butylperoxy) cyclohexane and dicumyl peroxide.
The first auxiliary agent is selected from potassium hydroxide, sodium hydroxide, calcium hydroxide, anhydrous sodium carbonate, 10-water sodium carbonate, triethylamine, ethanolamine, diethanolamine, hydroquinone, poly (4-hydroxyethyl-2, 6-tetramethyl-1-piperidylethanol) succinate, bis (1, 2, 6-pentamethyl-4-piperidyl) sebacate, at least one of 1- (methyl) -8- (1, 2, 6-pentamethyl-4-piperidine) sebacate.
The second auxiliary agent comprises a color retention agent and a hydroxyl protective agent.
The color retention agent is selected from at least one of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, di [3- (1, 1-dimethylethyl) -4-hydroxy-5-methylbenzoic acid ] tri-polyethylene glycol, thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and 2-methyl-4, 6-bis [ (N-octylthio) methyl ] phenol.
The hydroxyl protecting agent is at least one selected from ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether and propenyl polyether glycidyl ether.
The auxiliary agent is selected from at least one of 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane.
The second auxiliary agent also comprises an auxiliary agent.
The auxiliary agent is at least one selected from 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane and 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane.
The usage amount of the hydroxyl protecting agent is not more than 1.5% of the total mass of the monomers (non-fluorine monomer and chlorotrifluoroethylene), the total amount of the color protecting agent and the auxiliary agent is not more than 1% of the total mass of the monomers (non-fluorine monomer and chlorotrifluoroethylene), and the weight ratio of the color protecting agent to the auxiliary agent is 1:1-2:1.
In some embodiments, the non-fluorinated monomer in the starting material of the powdered FEVE resin comprises at least one hydroxyl group-containing monomer and at least one non-hydroxyl group-containing monomer, wherein the molar ratio of the hydroxyl group-containing monomer to the non-hydroxyl group-containing monomer is 1:1.5-6.
A preparation method of powder FEVE resin comprises the following steps:
1) Mixing all materials except the initiator, the chlorotrifluoroethylene and the second auxiliary agent, stirring at 20 ℃ for 15-25 minutes, filtering out impurities and taking supernatant.
2) And (3) uniformly mixing the clear solution obtained in the step (1) with an initiator, then putting the mixture into a reaction kettle, discharging oxygen, adding chlorotrifluoroethylene, and stirring and reacting for 5-8 hours at 50-55 ℃.
3) The temperature is reduced to 45-48 ℃ and the reaction is continued for 12-16 hours.
4) And (3) taking out the product of the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
5) And (3) putting the product obtained in the step (4) into a falling film evaporator, adjusting the temperature according to the boiling point of the solvent, and evaporating the solvent for one hour under the conditions of 150-200 ℃ and 1000-5000 Pa in vacuum, thereby completely recovering the solvent.
6) And (5) cooling, tabletting and crushing the product in the step (5) to obtain a final product.
The solid hydroxyl value of the obtained powder resin is 33-105mgKOH/g, the acid value is 0-5mgKOH/g, the glass transition temperature is 48-60 ℃, the softening point is 105-125 ℃ and the fluorine content is 25% -26%.
The invention has the beneficial effects that:
(1) The polymerization temperature is lower, the product is 100%, and the zero emission of VOC is realized.
(2) The product adopts volatile solvent, the recovery is simple and efficient, and the solvent is reused without pollution.
(3) The solid glass transition temperature of the product is higher, and the product is stable in storage without pressure.
(4) The weather resistance is excellent and stable, the fluorine content is higher, and the weather resistance is far higher than that of the existing powder resin.
The powder FEVE resin of the invention effectively prevents Huang Bianhei of FEVE resin powder during falling film evaporation by adding a color retention agent to the formulation, while maintaining the thermal stability of the resin polymer. The powder FEVE resin contains active hydroxyl as a group for preparing the paint and reacting with a curing agent, and in the high-temperature desolvation process, the hydroxyl or part of residual active monomer is reacted to cause secondary reaction of the resin in the desolvation link, so that the hydroxyl of the resin is lost, and the original curing performance is affected. In addition, the auxiliary agent is added in the formula of the invention, so that the melt index of the polymer is improved, and meanwhile, the yellowing index can be further reduced through the cooperation of the color retention agent and the auxiliary agent, and the ageing resistance of the powder FEVE resin is obviously improved. The first auxiliary agent in the formula of the invention is a decelerator added in the polymerization reaction process to prevent the rapid reaction from causing safety accidents, and in the polymerization reaction of the system, if the whole reaction environment presents acidity, the reaction speed is multiplied, so the protectant mostly consists of alkaline substances or polymerization inhibiting substances.
Detailed Description
The technical scheme of the present invention will be specifically described by examples, but the present invention is not limited to the following examples.
Example 1
The amount of each substance of the FEVE powder resin of this example is as follows:
0.375mol ethyl vinyl ether
1.6mol of cyclohexyl vinyl ether
0.2mol of 4-hydroxybutyl vinyl ether
0.3mol of 2-ethyleneoxyethanol
2.75mol of chlorotrifluoroethylene
2, 2-azobis (2-methylbutyric acid) in an amount of 1% by mass of the total monomers
Triethylamine of 0.5% of the total mass of the monomers
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate in an amount of 0.5% by weight based on the total mass of the monomers
3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane in an amount of 0.4% by weight based on the total mass of the monomers
Diethylene glycol diglycidyl ether having a total mass of 1% of the monomers
Part of xylene in an amount of 85% by mass of the total monomer
Butyl acetate in an amount of 15% by mass based on the total mass of the monomers.
The specific preparation steps of the FEVE powder resin of this example are:
(1) All materials except the polymerization initiator, the chlorotrifluoroethylene and the second auxiliary agent are mixed, stirred at 20 ℃ for 15 minutes, and impurities are filtered out to obtain supernatant.
(2) And (3) uniformly mixing the clear solution obtained in the step (1) with a polymerization initiator, putting the mixture into a high-pressure reaction kettle, carrying out vacuum deoxidation, carrying out high-purity nitrogen substitution to discharge oxygen, adding chlorotrifluoroethylene, slowly raising the temperature to 55 ℃, and stirring and reacting for 5 hours.
(3) The temperature was reduced to 46℃and the reaction was continued for 15 hours.
(4) And (3) taking out the product of the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) Slowly adding the product obtained in the step 4 into a falling film evaporator, heating the falling film evaporator to 200 ℃, evaporating the falling film evaporator for one hour under the condition of vacuum 1500 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product in the step (5) to obtain a final product.
Example 2
The amount of each substance of the FEVE powder resin of this example is as follows:
0.3mol of isobutyl vinyl ether
1.7mol of cyclohexyl vinyl ether
0.5mol of 2-ethyleneoxyethanol
2.75mol of chlorotrifluoroethylene
Bis (4-tert-butylcyclohexyl) peroxydicarbonate in an amount of 1% by mass of the total monomer
Anhydrous sodium carbonate with total monomer mass of 0.5%
Thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] in an amount of 0.5% by weight based on the total mass of the monomers
3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane in an amount of 0.5% by weight based on the total mass of the monomers
Diethylene glycol diglycidyl ether having a total monomer mass of 0.8%
Xylene in an amount of 90% by mass of the total monomer.
The specific preparation steps of the FEVE powder resin of this example are:
(1) All materials except the polymerization initiator, the chlorotrifluoroethylene and the second auxiliary agent are mixed, stirred at 20 ℃ for 15 minutes, and impurities are filtered out to obtain supernatant.
(2) And (3) uniformly mixing the clear solution obtained in the step (1) with a polymerization initiator, putting the mixture into a high-pressure reaction kettle, carrying out vacuum deoxidation, carrying out high-purity nitrogen substitution to discharge oxygen, adding chlorotrifluoroethylene, slowly raising the temperature to 50 ℃, and stirring and reacting for 20 hours.
(3) And (3) taking out the product of the step (2), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(4) Slowly adding the product obtained in the step 3 into a falling film evaporator, heating the falling film evaporator to 200 ℃, evaporating the falling film evaporator for one hour under the condition of vacuum 1000 Pa, and completely recovering the solvent.
(5) And (3) cooling, tabletting and crushing the product obtained in the step (4) to obtain a final product.
Example 3
The amount of each substance of the FEVE powder resin of this example is as follows:
0.4mol of ethyl vinyl ether
1.6mol of cyclohexyl vinyl ether
0.5mol of 2-ethyleneoxyethanol
2.85mol of chlorotrifluoroethylene
Tertbutyl peroxy-2-ethylhexanoate with 1% of total monomer mass
Potassium hydroxide of 0.5% of total monomer mass
2-methyl-4, 6-bis [ (N-octylthio) methyl ] phenol in an amount of 0.6% by weight based on the total mass of the monomers
3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane in an amount of 0.3% by weight based on the total mass of the monomers
Carbon tridecyl glycidyl ether with 1.1 percent of total monomer mass
Xylene at 104% of the total mass of the monomer.
The specific preparation steps of the FEVE powder resin of this example are:
(1) All materials except the polymerization initiator, the chlorotrifluoroethylene and the second auxiliary agent are mixed, stirred at 20 ℃ for 15 minutes, and impurities are filtered out to obtain supernatant.
(2) And (3) uniformly mixing the clear solution obtained in the step (1) with a polymerization initiator, putting the mixture into a high-pressure reaction kettle, carrying out vacuum deoxidation, carrying out high-purity nitrogen substitution to discharge oxygen, adding chlorotrifluoroethylene, slowly raising the temperature to 52 ℃, and stirring and reacting for 6 hours.
(3) The temperature was reduced to 47℃and the reaction was continued for 14 hours.
(4) And (3) taking out the product of the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) Slowly adding the product obtained in the step 4 into a falling film evaporator, heating the falling film evaporator to 200 ℃, evaporating the falling film evaporator for one hour under the condition of vacuum 1000 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product in the step (5) to obtain a final product.
Example 4
The amount of each substance of the FEVE resin of this example was as follows:
0.5mol of ethyl vinyl ether
1.5mol of cyclohexyl vinyl ether
0.5mol of 4-hydroxybutyl vinyl ether
2.75mol of chlorotrifluoroethylene
2, 2-azobis (2-methylbutyric acid) in an amount of 1% by mass of the total monomers
10 sodium carbonate hydrate with total monomer mass of 0.5%
Thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] in an amount of 0.4% by weight based on the total mass of the monomers
3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane in an amount of 0.3% by weight based on the total mass of the monomers
Dipropylene glycol diglycidyl ether having a total monomer mass of 0.6%
Xylene in an amount of 100% by mass of the total monomer.
The specific preparation steps of the FEVE powder resin are as follows:
(1) All materials except the polymerization initiator and the trifluorochloroethylene and the second auxiliary agent are mixed, stirred at 20 ℃ for 15 minutes, and impurities are filtered out to obtain supernatant.
(2) And (3) uniformly mixing the clear solution obtained in the step (1) with a polymerization initiator, putting the mixture into a high-pressure reaction kettle, carrying out vacuum deoxidation, carrying out high-purity nitrogen substitution to discharge oxygen, adding chlorotrifluoroethylene, slowly raising the temperature to 55 ℃, and stirring and reacting for 4 hours.
(3) The temperature was reduced to 69 ℃ and the reaction was continued for 5 hours.
(4) And (3) taking out the product of the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) Slowly adding the product obtained in the step 4 into a falling film evaporator, heating the falling film evaporator to 200 ℃, evaporating the falling film evaporator for one hour under the condition of vacuum 1000 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product in the step (5) to obtain a final product.
Example 5
The amount of each substance of the FEVE resin of this example was as follows:
0.15mol of ethyl vinyl ether
1.35mol of cyclohexyl vinyl ether
1.0mol of 2-ethyleneoxyethanol
2.5mol of chlorotrifluoroethylene
Dilauryl peroxide in an amount of 1% by mass of the total monomer
Potassium hydroxide of 0.5% of total monomer mass
3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane in an amount of 0.3% by weight of the total monomer
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate in an amount of 0.2% by weight based on the total mass of the monomers
Allyl polyether glycidyl ether with total monomer mass of 1.1%
Xylene in an amount of 105% by mass of the total monomer.
The specific preparation steps of the FEVE powder resin are as follows:
(1) All materials except the polymerization initiator and the trifluorochloroethylene and the second auxiliary agent are mixed, stirred at 20 ℃ for 15 minutes, and impurities are filtered out to obtain supernatant.
(2) And (3) uniformly mixing the clear solution obtained in the step (1) with a polymerization initiator, putting the mixture into a high-pressure reaction kettle, carrying out vacuum deoxidation, carrying out high-purity nitrogen substitution to discharge oxygen, adding chlorotrifluoroethylene, slowly raising the temperature to 52 ℃, and stirring and reacting for 5 hours.
(3) The temperature was reduced to 47℃and the reaction was continued for 15 hours.
(4) And (3) taking out the product of the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) Slowly adding the product obtained in the step 4 into a falling film evaporator, heating the falling film evaporator to 200 ℃, evaporating the falling film evaporator for one hour under the condition of vacuum 1000 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product in the step (5) to obtain a final product.
Example 6
The amount of each substance of the FEVE resin of this example was as follows:
0.45mol of ethyl vinyl ether
1.45mol of cyclohexyl vinyl ether
0.6mol of 2-ethyleneoxyethanol
2.5mol of chlorotrifluoroethylene
Dilauryl peroxide in an amount of 1% by mass of the total monomer
Potassium hydroxide of 0.5% of total monomer mass
3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane in an amount of 0.1% by weight of the total monomer
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate in an amount of 0.1% by weight based on the total mass of the monomers
Allyl polyether glycidyl ether with total monomer mass of 1.1%
Xylene in an amount of 105% by mass of the total monomer.
Specific preparation procedure of the present example FEVE powder resin was as described in example 5.
Example 7
The amounts of each substance of the FEVE resin of this comparative example were as follows:
1.05mol of ethyl vinyl ether
0.95mol of cyclohexyl vinyl ether
0.5mol of 4-hydroxybutyl vinyl ether
2.75mol of chlorotrifluoroethylene
Dilauryl peroxide in an amount of 1% by mass of the total monomer
Potassium hydroxide of 0.5% of total monomer mass
3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane in an amount of 0.6% by weight of the total monomer
Allyl polyether glycidyl ether with total monomer mass of 0.9%
Xylene at 105% of total monomer mass
Specific preparation procedure of the present example FEVE powder resin was as described in example 5.
Example 8
The amounts of each substance of the FEVE resin of this comparative example were as follows:
0.6mol of ethyl vinyl ether
1.55mol of cyclohexyl vinyl ether
0.35mol of 2-ethyleneoxyethanol
2.5mol of chlorotrifluoroethylene
Dilauryl peroxide in an amount of 1% by mass of the total monomer
Potassium hydroxide of 0.5% of total monomer mass
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate in an amount of 0.2% by weight based on the total mass of the monomers
Allyl polyether glycidyl ether with total monomer mass of 0.3%
Xylene at 105% of total monomer mass
Specific preparation procedure of the present example FEVE powder resin was as described in example 5.
Example 9
The amounts of each substance of the FEVE resin of this comparative example were as follows:
0.2mol of ethyl vinyl ether
1.3mol of cyclohexyl vinyl ether
0.5mol of 2-ethyleneoxyethanol
0.5mol of 4-hydroxybutyl vinyl ether
2.75mol of chlorotrifluoroethylene
Dilauryl peroxide in an amount of 1% by mass of the total monomer
Potassium hydroxide of 0.5% of total monomer mass
Allyl polyether glycidyl ether with total monomer mass of 1.1%
Xylene at 105% of total monomer mass
Specific preparation procedure of the present example FEVE powder resin was as described in example 5.
Example 10
The amounts of each substance of the FEVE resin of this comparative example were as follows:
0.65mol parts of ethyl vinyl ether
1.35mol of cyclohexyl vinyl ether
0.5mol of 2-ethyleneoxyethanol
2.6mol of chlorotrifluoroethylene
Dilauryl peroxide in an amount of 1% by mass of the total monomer
Potassium hydroxide of 0.5% of total monomer mass
Xylene at 105% of total monomer mass
Specific preparation procedure of the present example FEVE powder resin was as described in example 5.
Example 11
The main technical indexes of the powder FEVE fluororesins prepared in examples 1-10, such as hydroxyl value, acid value, glass transition temperature, softening point, fluorine content, 40 ℃ balance weight storage, etc., were measured by the conventional methods in the art, and specific indexes are shown in the following table.
TABLE 1 examples 1-10FEVE fluororesin powder resin main technical index
Experimental example 12
The FEVE fluoropowder resins prepared in examples 1-10 were subjected to physical and chemical property test of coating templates, and the required amount of isocyanate curing agent (B1540), leveling agent (BYK 360P), benzoin, titanium pigment, necessary auxiliary agent for precipitated barium sulfate and filler were added according to the calculation, and fully mixed for two minutes in a premix tank, and then melt-extruded at 105-125 ℃ by a twin screw extruder, crushed and sieved through a 200 mesh square sieve to obtain the fluororesin powder coating. The powder coating is sprayed and constructed through an electrostatic spraying device, and is put into an oven for baking at 200 ℃ for 20 minutes after being sprayed, and then all physical and chemical properties are detected according to building aluminum profile standards (GB 5237.1-2017), and meanwhile ultraviolet artificial accelerated ageing tests (UVB 313) are carried out, wherein all the property detection data are shown in Table 2.
TABLE 2 physical and chemical Properties of examples 1-10FEVE fluororesin powder coating templates
As shown in the table, after the resin related in the examples 1-10 of the invention is prepared into the coating, the coating completely accords with the national standard building aluminum profile standard, has excellent performance, particularly has outstanding ultraviolet manual accelerated aging data, and is obviously superior to the existing polyester powder resin, polyurethane powder resin and acrylic resin.
Claims (4)
1. A powder FEVE resin is characterized in that the FEVE resin is obtained by reacting a non-fluorine monomer, chlorotrifluoroethylene, an initiator, a first auxiliary agent and a second auxiliary agent in a solvent;
the molar ratio of the non-fluorine monomer to the trifluorochloroethylene is 1:1-1.2, and the non-fluorine monomer is at least two selected from isobutyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether and 2-ethyleneoxy ethanol;
the dosage of the initiator is 0.5-1% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the first auxiliary agent is 0.5% -1% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the second auxiliary agent is 0.5% -2% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the solvent is 90% -110% of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the first auxiliary agent is selected from potassium hydroxide, sodium hydroxide, calcium hydroxide, anhydrous sodium carbonate, sodium carbonate decahydrate, triethylamine, ethanolamine, diethanolamine, hydroquinone, poly (4-hydroxyethyl-2, 6-tetramethyl-1-piperidylethanol) succinate, bis (1, 2, 6-pentamethyl-4-piperidyl) sebacate, at least one of 1- (methyl) -8- (1, 2, 6-pentamethyl-4-piperidine) sebacate;
the second auxiliary agent comprises a color retention agent and a hydroxyl protective agent;
the color retention agent is at least one selected from 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, bis [3- (1, 1-dimethylethyl) -4-hydroxy-5-methylbenzoic acid ] triethylene glycol, thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and 2-methyl-4, 6-bis [ (N-octylthio) methyl ] phenol;
the hydroxyl protecting agent is at least one selected from ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether and propenyl polyether glycidyl ether.
2. A powdered FEVE resin according to claim 1, wherein the second auxiliary agent further comprises an auxiliary agent;
the auxiliary agent is selected from at least one of 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane.
3. A powdered FEVE resin according to claim 2, wherein the non-fluorinated monomer comprises at least one hydroxyl-containing monomer and at least one non-hydroxyl-containing monomer, the molar ratio of hydroxyl-containing monomer to non-hydroxyl-containing monomer being 1:1.5-6.
4. A method for preparing a powder FEVE resin according to any one of claims 1-3, comprising the steps of:
1) Mixing all substances except the initiator, the chlorotrifluoroethylene and the second auxiliary agent, stirring at 20 ℃ for 15-25 minutes, filtering out impurities and taking supernatant;
uniformly mixing the clear solution obtained in the step 1 with an initiator, then putting the mixture into a reaction kettle, discharging oxygen, adding chlorotrifluoroethylene, and stirring and reacting for 5-8 hours at 50-55 ℃;
the temperature is reduced to 45-48 ℃ to continue the reaction for 12-16 hours;
taking out the product of the step 3, adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃;
putting the product obtained in the step 4 into a falling film evaporator, adjusting the temperature according to the boiling point of the solvent, and evaporating the solvent for one hour under the conditions of 150-200 ℃ and 1000-5000 Pa in vacuum, so as to fully recover the solvent;
and (5) cooling, tabletting and crushing the product in the step (5) to obtain a final product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743392A (en) * | 2005-10-08 | 2006-03-08 | 大连振邦氟涂料股份有限公司 | Thermosetting fluoro powder coating resin and its preparing method |
| CN101791526A (en) * | 2009-12-09 | 2010-08-04 | 山东东岳高分子材料有限公司 | Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof |
| CN104031199A (en) * | 2014-05-22 | 2014-09-10 | 巨化集团技术中心 | Method of preparing fluororesin for electrostatic spraying by dispersion polymerization and coating application of resin |
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| US6806304B2 (en) * | 2001-09-27 | 2004-10-19 | Cytec Technology Corp. | Process for improving the shelf life of a hindered phenol antioxidant |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743392A (en) * | 2005-10-08 | 2006-03-08 | 大连振邦氟涂料股份有限公司 | Thermosetting fluoro powder coating resin and its preparing method |
| CN101791526A (en) * | 2009-12-09 | 2010-08-04 | 山东东岳高分子材料有限公司 | Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof |
| CN104031199A (en) * | 2014-05-22 | 2014-09-10 | 巨化集团技术中心 | Method of preparing fluororesin for electrostatic spraying by dispersion polymerization and coating application of resin |
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