CN115477719A - 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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- 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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- 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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- 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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- 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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- 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, belonging to the technical field of FEVE fluorocarbon resin. The powder resin effectively prevents the resin powder from yellowing and blackening in the falling film evaporation process by adding a color retention agent into the formula, and simultaneously maintains the thermal stability of the resin polymer. By adding the hydroxyl protective agent, hydroxyl loss in the falling film evaporation process is effectively prevented. In addition, the auxiliary agent is added, so that the melting index of the polymer is improved, 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 polymerization temperature of the powder resin is low, the volatile solvent is adopted, the recovery is simple and efficient, and the zero emission of VOC is realized; the glass transition temperature is high, and the storage is stable without pressure; the weather resistance is superior and stable, far surpassing the prior powder resin.
Description
Technical Field
The invention belongs to the technical field of FEVE fluorocarbon resin, and particularly relates to chlorotrifluoroethylene and vinyl ether copolymerized powder resin 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, particularly the field of outdoor buildings due to excellent weather resistance, corrosion resistance and excellent chemical resistance stability. With the continuous development of decades, the annual fluororesin yield of China breaks through ten thousand tons, and the market value breaks through billions. However, with the development of technology, environmental problems all over the world are more prominent, and the requirements of China on environmental protection become more strict in recent years. The traditional solvent-type fluororesin usually discharges a large amount of VOC, and the common resin-derived coating needs relatively frequent construction, so that the energy is greatly consumed and wasted. In many developed countries, the import and application of such environmentally unfriendly products have been prohibited or highly restricted, and under such large circumstances, it has become necessary to develop fluorine-containing powder resins that are more environmentally friendly, consume less energy, and have more excellent properties.
Disclosure of Invention
The invention provides a powder type FEVE resin and a preparation method thereof, aiming at solving the problems in the prior art.
The technical scheme of the invention is as follows: a powder type 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 mol ratio of the non-fluorine monomer to the chlorotrifluoroethylene is 1-1.2, and the non-fluorine monomer is selected from at least two of isobutyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether and 2-vinyloxyethanol;
the amount of the initiator is 0.5 to 1 percent 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 used for FEVE resin, and is specifically selected from at least one of 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-tert-butyl ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylacetate, tert-butyl peroxy-3, 5-trimethylhexanoate, 2-bis (tert-butylperoxy) butane, tert-butyl peroxycarbonate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1, 4-bis (tert-butyl peroxyformate) 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 and hydroquinone, poly (4-hydroxyethyl-2, 6-tetramethyl-1-piperidineethanol) 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-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, di [3- (1, 1-dimethylethyl) -4-hydroxy-5-methylpropanoic acid ] triethylene glycol, thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-methyl-4, 6-bis [ (N-octylthio) methyl ] phenol.
The hydroxyl protective agent is selected from at least one of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether and propenyl polyether glycidyl ether.
The auxiliary agent is at least one selected from 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
The second auxiliary agent also comprises an auxiliary table.
The adjuvant is selected from at least one of 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
The dosage of the hydroxyl protective agent is not more than 1.5 percent of the total mass of the monomers (non-fluorine monomers and chlorotrifluoroethylene), the total amount of the color retention agent and the auxiliary agent is not more than 1 percent of the total mass of the monomers (non-fluorine monomers and chlorotrifluoroethylene), and the weight ratio of the color retention agent to the auxiliary agent is 1-2.
In some embodiments, the non-fluorine-containing monomers in the feedstock of the powder type FEVE resin comprise at least one hydroxyl-containing monomer and at least one non-hydroxyl-containing monomer, and the molar ratio of the hydroxyl-containing monomer to the non-hydroxyl-containing monomer is 1.5 to 6.
A method of preparing a powdered FEVE resin, comprising the steps of:
1) Mixing all the materials except the initiator, the chlorotrifluoroethylene and the second auxiliary agent, stirring for 15-25 minutes at 20 ℃, filtering out impurities, and taking supernatant.
2) And (3) uniformly mixing the clear liquid obtained in the step (1) with an initiator, putting the mixture into a reaction kettle, discharging oxygen, adding chlorotrifluoroethylene, and stirring and reacting at 50-55 ℃ for 5-8 hours.
3) The temperature is reduced to 45-48 ℃ and the reaction is continued for 12-16 hours.
4) And (4) taking out the product in the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
5) Putting the product in the step 4 into a falling film evaporator, adjusting the temperature according to the boiling point of the solvent, generally 150-200 ℃, reducing the film evaporation for one hour under the condition of vacuum 1000-5000 Pa, and completely recovering the solvent.
6) And (5) cooling, tabletting and crushing the product in the step 5 to obtain the final product.
The obtained powdered resin has a solid hydroxyl value of 33-105mgKOH/g, an acid value of 0-5mgKOH/g, a glass transition temperature of 48-60 ℃, a softening point of 105-125 ℃ and a fluorine content of 25-26%.
The invention has the beneficial effects that:
(1) The polymerization temperature is lower, the product is 100 percent, and the zero emission of VOC is realized.
(2) The product adopts a volatile solvent, the recovery is simple and efficient, and the solvent is recycled without pollution.
(3) The product has high solid vitrification point and stable 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 effectively prevents the FEVE resin powder from yellowing and blackening in the falling film evaporation process by adding the color retention agent in the formula, and simultaneously maintains the thermal stability of the resin polymer. The powder FEVE resin contains active hydroxyl as a group for making a coating and reacting with a curing agent, and hydroxyl or partial residual active monomers are often reacted in the process of high-temperature desolventizing, so that the resin is subjected to secondary reaction in the desolventizing link, and the hydroxyl of the resin is lost, thereby affecting the original curing performance. In addition, the auxiliary agent is added into the formula of the invention, so that the melting 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, so that the ageing resistance of the powder FEVE resin is obviously improved. The first auxiliary agent in the formula is a speed reducer which is added in the polymerization reaction process and prevents safety accidents caused by too fast reaction, and in the polymerization reaction of the system, if the whole reaction environment is acidic, the reaction speed can be doubled, so that the protective agent is mostly composed of alkaline substances or polymerization inhibitor substances.
Detailed Description
The technical solution of the present invention is specifically described below by way of examples, but the present invention is not limited to the following examples.
Example 1
The FEVE powder resin of this example was used in the following amounts:
0.375mol of ethyl vinyl ether
1.6mol of cyclohexyl vinyl ether
0.2mol of 4-hydroxybutyl vinyl ether
0.3mol of 2-vinyloxyethanol
2.75mol of chlorotrifluoroethylene
1 percent of 2, 2-azo bis (2-methyl butyronitrile) by the total mass of the monomers
Triethylamine with 0.5 percent of total mass of monomer
1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid with the total mass of the monomer of 0.5 percent
3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane with a total monomer mass of 0.4%
Diethylene glycol diglycidyl ether with the total mass of the monomers being 1%
Xylene fraction of 85% of the total mass of the monomers
Butyl acetate 15% of the total mass of the monomers.
The specific preparation steps of the FEVE powder resin in this example are:
(1) All the materials except the polymerization initiator, chlorotrifluoroethylene and the second aid were mixed, stirred at 20 ℃ for 15 minutes, and the supernatant was obtained by filtering off impurities.
(2) And (2) uniformly mixing the clear liquid 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 replacement to discharge oxygen, adding chlorotrifluoroethylene, slowly heating to 55 ℃, and stirring to react for 5 hours.
(3) The temperature was lowered to 46 ℃ and the reaction was continued for 15 hours.
(4) And (4) taking out the product in the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) And (4) slowly adding the product in the step (4) into a falling-film evaporator, heating the falling-film evaporator to 200 ℃, evaporating the falling-film for one hour under the vacuum condition of 1500 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product obtained in the step (5) to obtain the final product.
Example 2
The FEVE powder resin of this example was used in the following amounts:
0.3mol of isobutyl vinyl ether
1.7mol of cyclohexyl vinyl ether
0.5mol of 2-ethyleneoxyethanol
2.75mol of chlorotrifluoroethylene
1% of the total mass of the monomers of bis (4-tert-butylcyclohexyl) peroxydicarbonate
Anhydrous sodium carbonate with 0.5% of total monomer mass
Thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] in an amount of 0.5% by mass based on the total amount of the monomers
0.5% of 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane by total mass of monomer
Diethylene glycol diglycidyl ether with the total mass of the monomers being 0.8%
Xylene in an amount of 90% by mass of the total monomer.
The specific preparation steps of the FEVE powder resin in this example are:
(1) All the substances except the polymerization initiator, chlorotrifluoroethylene and the second aid were mixed, stirred at 20 ℃ for 15 minutes, and the supernatant liquid was obtained by filtering off impurities.
(2) And (2) uniformly mixing the clear liquid 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 replacement to discharge oxygen, adding chlorotrifluoroethylene, slowly heating to 50 ℃, and stirring to react for 20 hours.
(3) And (3) taking out the product in the step (2), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(4) And (4) slowly adding the product in the step (3) into a falling-film evaporator, heating the falling-film evaporator to 200 ℃, evaporating the falling-film for one hour under the vacuum condition of 1000 Pa, and completely recovering the solvent.
(5) And (4) cooling, tabletting and crushing the product obtained in the step (4) to obtain a final product.
Example 3
The FEVE powder resin of this example was used in the following amounts:
0.4mol of ethyl vinyl ether
1.6mol of cyclohexyl vinyl ether
0.5mol of 2-ethyleneoxyethanol
2.85mol of chlorotrifluoroethylene
Tert-butyl peroxy-2-ethylhexanoate at 1% of the total mass of the monomers
Potassium hydroxide of 0.5% of the total mass of the monomers
0.6 percent of 2-methyl-4, 6-bis [ (N-octylthio) methyl ] phenol 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 mass based on the total mass of the monomers
Carbon tridecyl glycidyl ether accounting for 1.1 percent of the total mass of the monomers
104% xylene of the total mass of the monomers.
The specific preparation steps of the FEVE powder resin in the embodiment are as follows:
(1) All the materials except the polymerization initiator, chlorotrifluoroethylene and the second aid were mixed, stirred at 20 ℃ for 15 minutes, and the supernatant was obtained by filtering off impurities.
(2) And (2) uniformly mixing the clear liquid 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 replacement to discharge oxygen, adding chlorotrifluoroethylene, slowly heating to 52 ℃, and stirring to react for 6 hours.
(3) The temperature was lowered to 47 ℃ and the reaction was continued for 14 hours.
(4) And (4) taking out the product in the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) And (4) slowly adding the product in the step (4) into a falling-film evaporator, heating the falling-film evaporator to 200 ℃, evaporating the falling-film for one hour under the vacuum condition of 1000 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product obtained in the step (5) to obtain a final product.
Example 4
The FEVE resin of this example was used in the following amounts:
0.5mol of ethyl vinyl ether
1.5mol of cyclohexyl vinyl ether
0.5mol of 4-hydroxybutyl vinyl ether
2.75mol of chlorotrifluoroethylene
1 percent of 2, 2-azo bis (2-methyl butyronitrile) by the total mass of the monomers
10 parts of sodium carbonate hydrate accounting for 0.5 percent of the total mass of the monomers
Thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] in an amount of 0.4% by mass 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 mass based on the total mass of the monomers
0.6 percent of dipropylene glycol diglycidyl ether by total mass of monomers
Xylene in an amount of 100% by mass of the total monomer.
Examples the specific preparation steps of the FEVE powder resin were:
(1) All the materials except the polymerization initiator, chlorotrifluoroethylene and a second aid were mixed, and stirred at 20 ℃ for 15 minutes to filter out impurities and take the supernatant.
(2) And (2) uniformly mixing the clear liquid 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 replacement to discharge oxygen, adding chlorotrifluoroethylene, slowly heating to 55 ℃, and stirring to react for 4 hours.
(3) The temperature was lowered to 69 ℃ and the reaction was continued for 5 hours.
(4) And (4) taking out the product in the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) And (4) slowly adding the product in the step (4) into a falling-film evaporator, heating the falling-film evaporator to 200 ℃, evaporating the falling-film for one hour under the vacuum condition of 1000 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product obtained in the step (5) to obtain a final product.
Example 5
The amounts of the materials of the FEVE resin of this example were as follows:
0.15mol of ethyl vinyl ether
1.35mol of cyclohexyl vinyl ether
1.0mol 2-ethyleneoxy ethanol
2.5mol of chlorotrifluoroethylene
Dilauroyl peroxide accounting for 1 percent of the total mass of the monomer
Potassium hydroxide with a total monomer mass of 0.5%
0.3% of 3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane by total mass of the monomers
0.2 percent of 1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid in the total mass of the monomers
1.1% of propylene-based polyether glycidyl ether by mass of the total monomer
Xylene in a total monomer mass of 105%.
Examples the specific preparation steps of the FEVE powder resin were:
(1) All the materials except the polymerization initiator, chlorotrifluoroethylene and the second aid were mixed, stirred at 20 ℃ for 15 minutes, and the supernatant was obtained by filtering off impurities.
(2) And (2) uniformly mixing the clear liquid 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 replacement to discharge oxygen, adding chlorotrifluoroethylene, slowly heating to 52 ℃, and stirring for reaction for 5 hours.
(3) The temperature was lowered to 47 ℃ and the reaction was continued for 15 hours.
(4) And (4) taking out the product in the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃.
(5) And (4) slowly adding the product in the step (4) into a falling-film evaporator, heating the falling-film evaporator to 200 ℃, evaporating the falling-film for one hour under the vacuum condition of 1000 Pa, and completely recovering the solvent.
(6) And (5) cooling, tabletting and crushing the product obtained in the step (5) to obtain the final product.
Example 6
The FEVE resin of this example was used in the following amounts:
0.45mol of ethyl vinyl ether
1.45mol of cyclohexyl vinyl ether
0.6mol of 2-ethyleneoxyethanol
2.5mol of chlorotrifluoroethylene
Dilauroyl peroxide accounting for 1 percent of the total mass of the monomer
Potassium hydroxide with a total monomer mass of 0.5%
0.1% by mass of 3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane
1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid with the total mass of the monomer of 0.1 percent
1.1% of propylene-based polyether glycidyl ether by mass of the total monomer
Xylene in a total monomer mass of 105%.
This example refers to example 5 for the specific preparation procedure of FEVE powder resin.
Example 7
The amounts of the materials 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
Dilauroyl peroxide accounting for 1 percent of the total mass of the monomer
Potassium hydroxide with a total monomer mass of 0.5%
0.6% of 3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane by total mass of the monomers
Allyl polyether glycidyl ether with the total mass of the monomers being 0.9 percent
Xylene in a total of 105% by mass of the monomers
The specific procedure for the preparation of FEVE powder resin of this example refers to example 5.
Example 8
The FEVE resin of this comparative example was used in the following amounts of materials:
0.6mol of ethyl vinyl ether
1.55mol of cyclohexyl vinyl ether
0.35mol of 2-ethyleneoxyethanol
2.5mol of chlorotrifluoroethylene
Dilauroyl peroxide with the total mass of the monomer being 1%
Potassium hydroxide of 0.5% of the total mass of the monomers
1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid with the total monomer mass of 0.2 percent
Allyl polyether glycidyl ether with the total mass of the monomers being 0.3 percent
Xylene in a total mass of 105% of the monomers
This example refers to example 5 for the specific preparation procedure of FEVE powder resin.
Example 9
The amounts of the materials 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
Dilauroyl peroxide accounting for 1 percent of the total mass of the monomer
Potassium hydroxide with a total monomer mass of 0.5%
1.1% of propylene-based polyether glycidyl ether by mass of the total monomer
Xylene in a total mass of 105% of the monomers
The specific procedure for the preparation of FEVE powder resin of this example refers to example 5.
Example 10
The FEVE resin of this comparative example was used in the following amounts of materials:
0.65mol part of ethyl vinyl ether
1.35mol of cyclohexyl vinyl ether
0.5mol of 2-ethyleneoxyethanol
2.6mol of chlorotrifluoroethylene
Dilauroyl peroxide with the total mass of the monomer being 1%
Potassium hydroxide with a total monomer mass of 0.5%
Xylene in a total of 105% by mass of the monomers
This example refers to example 5 for the specific preparation procedure of FEVE powder resin.
Example 11
The hydroxyl number, acid number, glass transition temperature, softening point, fluorine content, weight storage at 40 ℃ and other major technical indices of the powdered FEVE fluororesins prepared in examples 1-10 were measured by methods conventional in the art, and the specific indices are shown in the following table.
TABLE 1 examples 1-10FEVE fluororesin powder resins Main technical indices
Experimental example 12
The FEVE fluorine powder resin prepared in examples 1 to 10 was subjected to a coating sample physical and chemical property test, and the isocyanate curing agent (B1540), the leveling agent (BYK 360P), benzoin, titanium dioxide, the necessary auxiliary agent for precipitating barium sulfate and the filler were added in the required amounts according to the calculation, and were fully mixed for two minutes in a premix tank, and then melt-extruded at 105 to 125 ℃ by a twin-screw extruder, and after the sheeting and crushing, the powder was pulverized and sieved with a 200-mesh sieve, to obtain a fluorine resin powder coating. The powder coating is sprayed and constructed by an electrostatic spraying device, the powder coating is put into an oven to be baked for 20 minutes at 200 ℃ after being sprayed, various physical and chemical properties are detected according to the building aluminum profile standard (GB 5237.1-2017), meanwhile, an ultraviolet artificial accelerated aging test (UVB 313) is carried out for testing, and various property detection data are shown in table 2.
TABLE 2 examples 1-10FEVE fluororesin powder resin coating panels physicochemical Properties
The data in the table show that the resin disclosed by the embodiments 1-10 of the invention completely accords with the standard of national building aluminum profiles after being prepared into the coating, has excellent performance, particularly has outstanding ultraviolet artificial accelerated aging data, and is obviously superior to the existing polyester powder resin, polyurethane powder resin and acrylic resin.
Claims (4)
1. A powder type 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 mol ratio of the non-fluorine monomer to the chlorotrifluoroethylene is 1-1.2, and the non-fluorine monomer is selected from at least two of isobutyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether and 2-vinyloxyethanol;
the amount of the initiator is 0.5 to 1 percent of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the first auxiliary agent is 0.5 to 1 percent of the total mass of the non-fluorine monomer and the chlorotrifluoroethylene;
the dosage of the second auxiliary agent is 0.5 to 2 percent 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, 10-water sodium carbonate, triethylamine, ethanolamine, diethanolamine and hydroquinone, poly (4-hydroxyethyl-2, 6-tetramethyl-1-piperidineethanol) 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-methylpropanoic acid ] triethylene glycol, thiobis (ethane-2, 1-diyl) bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-methyl-4, 6-bis [ (N-octylthio) methyl ] phenol;
the hydroxyl protective 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 powder type FEVE resin according to claim 1, wherein the second aid further comprises an adjuvant;
the auxiliary agent is at least one selected from 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
3. A powder type FEVE resin according to claim 2, wherein the non-fluorine containing monomers comprise at least one hydroxyl containing monomer and at least one non-hydroxyl containing monomer, and the molar ratio of the hydroxyl containing monomer to the non-hydroxyl containing monomer is 1.5 to 6.
4. A method for preparing powder FEVE resin comprises the following steps:
1) Mixing all the substances except the initiator, the chlorotrifluoroethylene and the second auxiliary agent, stirring for 15-25 minutes at 20 ℃, filtering out impurities, and taking supernatant liquor;
uniformly mixing the clear liquid obtained in the step (1) with an initiator, putting the mixture into a reaction kettle, discharging oxygen, adding chlorotrifluoroethylene, and stirring and reacting at 50-55 ℃ for 5-8 hours;
the temperature is reduced to 45 to 48 ℃ and the reaction is continued for 12 to 16 hours;
taking out the product obtained in the step (3), adding a second auxiliary agent, and stirring for 30 minutes at 20 ℃;
putting the product in the step 4 into a falling film evaporator, adjusting the temperature according to the boiling point of the solvent, generally 150-200 ℃, falling film evaporating for one hour under the vacuum condition of 1000-5000 Pa, and completely recovering the solvent;
and (5) cooling, tabletting and crushing the product in the step 5 to obtain a final product.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030073771A1 (en) * | 2001-09-27 | 2003-04-17 | Sanders Brent M. | Process for improving the shelf life of a hindered phenol antioxidant |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030073771A1 (en) * | 2001-09-27 | 2003-04-17 | Sanders Brent M. | Process for improving the shelf life of a hindered phenol antioxidant |
| 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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