CN110734525B - Fluorine-containing cage type silsesquioxane modified polychlorotrifluoroethylene resin - Google Patents
Fluorine-containing cage type silsesquioxane modified polychlorotrifluoroethylene resin Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Abstract
The invention discloses a modified polychlorotrifluoroethylene resin which is prepared by taking a compound shown in a structural formula (I) as a modified monomer. The invention also provides a method for preparing the modified polychlorotrifluoroethylene resin by suspension polymerization. The modified polychlorotrifluoroethylene resin prepared by the method has good thermal stability, and can overcome the defects of narrow forming temperature range and easy decomposition in PCTFE processing.
Description
Technical Field
The invention belongs to the field of fluorine-containing high polymer materials, relates to a modified polychlorotrifluoroethylene resin, and particularly relates to a modified polychlorotrifluoroethylene resin with high thermal stability.
Background
Polychlorotrifluoroethylene (PCTFE) is a thermoplastic fluoroplastic which is developed to be industrially produced at the earliest, is polymerized by using Chlorotrifluoroethylene (CTFE) as a raw material, has excellent chemical stability, insulation property and weather resistance, can be used at the temperature of-196 to 125 ℃ for a long time, has better mechanical strength and hardness than polytetrafluoroethylene, is prepared into a film with better transparency and excellent water vapor barrier property, and is widely applied to the fields of electroluminescent electronic elements, electrical components, electronic components, medical materials, medicaments and the like as an encapsulation film.
Compared with common thermoplastic polymers, the PCTFE has slow heat transfer efficiency, and the melt viscosity of the PCTFE is still higher at 230 ℃ although the melt temperature is 210-215 ℃, so that the PCTFE needs to obtain enough fluidity at higher temperature for molding processing. At the same time, however, the PCTFE has a very narrow molding temperature range, the molding processing temperature is only 250 ℃ and 320 ℃, and the PCTFE is thermally decomposed at 300 ℃, so that the processing of the PCTFE is difficult, and the product performance is influenced.
To improve the thermal stability of PCTFE, the prior art has made the following efforts:
(1) US patents 2751376 and US3045000 report treatment of PCTFE with ozone pyro-chlorine to improve the thermal stability of PCTFE;
(2) chinese patent CN102020737 reports that treatment of PCTFE by cobalt fluoride can obtain high temperature degradation resistant PCTFE resin;
(3) chinese patent CN103172773 reports the adoption of F2/N2And treating the PCTFE by the mixed gas to obtain the PCTFE resin resistant to high-temperature degradation.
All of the above methods for improving the thermal stability of PCTFE resin are modification after the synthesis of PCTFE resin is completed, and not only new equipment investment is required to be added, but also new impurities are introduced, thereby increasing the difficulty in industrialization of PCTFE resin.
Therefore, further technical improvements to PCTFE resins having higher thermal stability are needed.
Disclosure of Invention
The invention aims to provide a modified polychlorotrifluoroethylene resin which has good thermal stability and can overcome the defects of narrow molding temperature range and easy decomposition in PCTFE processing.
The invention achieves the aim by introducing the fluorine-containing cage type silsesquioxane structural unit into a PCTFE main chain.
The invention provides a fluorine-containing polyhedral oligomeric silsesquioxane modified polychlorotrifluoroethylene resin with high thermal stability, wherein monomers for preparing the modified polychlorotrifluoroethylene resin comprise chlorotrifluoroethylene and a compound shown in a structural formula (I),
wherein: r is selected from-CH2CH2CF3Rf is selected from-R1-O-CF＝CF2，R1Is selected from C1 to C6 alkyl.
The compound shown in the structural formula (I) used in the invention can be abbreviated as POSS, and is an organic-inorganic hybrid molecule, the cage-shaped center consisting of silicon and oxygen elements endows the POSS with strong rigidity and thermal stability, and the organic R group helps the POSS to obtain chemical reaction activity. POSS is used as a polymerization monomer, cage type silsesquioxane of trifluorovinyl ether groups is copolymerized with chlorotrifluoroethylene, and a polytrifluorochloroethylene resin chain segment contains a cage type silsesquioxane structure, so that the polytrifluorochloroethylene resin has the effect of improving the thermal stability of polytrifluorochloroethylene, and the polytrifluorochloroethylene after being modified is easy to process and form.
The compound of formula (I) used in the invention has the substituent Rf selected from-R1-O-CF＝CF2，R1Is selected from alkyl of C1-C6.
The R is1The alkyl group selected from C1-C6 may be a straight-chain alkyl group selected from C1-C6, a branched-chain alkyl group selected from C1-C6, or a cyclic alkyl group selected from C3-C6.
In a preferred mode, the R1 group is selected from C1-C3 alkyl.
According to the fluorine-containing polyhedral oligomeric silsesquioxane modified polychlorotrifluoroethylene resin with high thermal stability, provided by the invention, the modified monomer is a structural unit formed by a compound shown in a structural formula (I), and the mass percentage of the modified monomer in the chain segment structure of the modified polychlorotrifluoroethylene resin meets the requirement that the modified polychlorotrifluoroethylene resin has high thermal stability.
Preferably, the mass percentage of the structural unit composed of the compound shown in the structural formula (I) in the chain segment structure of the modified polychlorotrifluoroethylene resin is 0.1-10%.
More preferably, the mass percentage of the structural unit composed of the compound represented by the structural formula (I) in the chain segment structure of the modified polychlorotrifluoroethylene resin is 1 to 5%.
The invention provides a modified polychlorotrifluoroethylene resin of which the content is 1% N2The decomposition temperature is 360-390 ℃, and even 370-390 ℃.
The yellowing index of the modified polychlorotrifluoroethylene resin provided by the invention is 1.5-5.0, and even can be 1.5-3.5.
The modified polychlorotrifluoroethylene resin provided by the present invention can be prepared by an emulsion polymerization method, a suspension polymerization method, a solution polymerization method or a bulk polymerization method.
When the modified polychlorotrifluoroethylene resin is prepared by a suspension polymerization method, the suspension polymerization method comprises:
in a polymerization medium, under the existence of a dispersant and an initiator, carrying out suspension polymerization on chlorotrifluoroethylene and a compound shown in a structural formula (I) to obtain the modified polychlorotrifluoroethylene resin;
the mass ratio of the chlorotrifluoroethylene to the compound shown in the structural formula (I) is 10: 1-100: 1. More preferably, the mass ratio of the chlorotrifluoroethylene to the compound shown in the structural formula (I) is 20: 1-50: 1.
The polymerization medium comprises deionized water, a fluorine-containing organic solvent and a non-fluorine-containing organic solvent, and the mass percentage of the fluorine-containing organic solvent and the non-fluorine-containing organic solvent in the polymerization medium is 0.01-10%.
In the method for preparing the modified polychlorotrifluoroethylene resin by suspension polymerization, the polymerization medium used comprises deionized water, a fluorine-containing organic solvent and a non-fluorine-containing organic solvent.
The fluorine-containing organic solvent may be one that can be used as a polymerization medium in the suspension polymerization method in the art. Preferably, the fluorine-containing organic solvent is selected from CF3CClHCF2Cl、CF2ClCFClCH2CH2Cl、CF3CH2CH2CH2Cl、CF2ClCFCl2、CF3CCl3、CF3CFClCFClCF3、CF3CH2CF2CH3、CF2HCF2CF2CF2H、CF3CF2CF2CF2CF2H. Perfluorocyclohexane, CF2HCF2OCH2CF3、CF2HCF2OCH2CF2CF2H and CF2HCF2OCH2CH3At least one of (1).
The non-fluorine-containing organic solvent may be a non-fluorine-containing organic solvent which can be used as a polymerization medium in the suspension polymerization method in the art. Preferably, the non-fluorine-containing organic solvent is at least one selected from the group consisting of toluene, n-hexane, chloroform, ethyl acetate and butyl acetate.
The fluorine-containing organic solvent and the non-fluorine-containing organic solvent in the polymerization medium may be mixed in any ratio. Preferably, the mass ratio of the fluorine-containing organic solvent to the non-fluorine-containing organic solvent is 1: 3-3: 1. More preferably, the mass ratio of the fluorine-containing organic solvent to the non-fluorine-containing organic solvent is 1:1 to 2: 1.
The contents of the fluorine-containing organic solvent and the non-fluorine-containing organic solvent in the polymerization medium are sufficient to allow the reaction to proceed smoothly. Preferably, the mass percent of the fluorine-containing organic solvent and the non-fluorine-containing organic solvent in the polymerization medium is 0.01-10%. More preferably, the mass percentage of the fluorine-containing organic solvent and the non-fluorine-containing organic solvent in the polymerization medium is 0.1-5%.
In the method for preparing the modified polychlorotrifluoroethylene resin by suspension polymerization, the used dispersing agent comprises a main dispersing agent and an auxiliary dispersing agent.
The primary dispersant may be a dispersant commonly used in the art for suspension polymerization. Preferably, the primary dispersant is at least one selected from the group consisting of polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and polyvinylpyrrolidone.
The auxiliary dispersant is preferably selected from R2COOM and R2SO3M, wherein: r2Is independently selected from-CnFn+1 or-F (CFCF)3CF2O)mCFCF3N is an integer of 6 to 10, M is an integer of 2 to 5, and M is independently H+、NH4 +、Na+Or K+。
The proportion of the main dispersant and the auxiliary dispersant is satisfied to ensure that the reaction is smoothly carried out. Preferably, the mass ratio of the main dispersant to the auxiliary dispersant is 5: 1-10: 1.
In the method for preparing the modified polychlorotrifluoroethylene resin by suspension polymerization provided by the present invention, the initiator used may be an initiator commonly used in the art. Preferably, the initiator is at least one selected from the group consisting of a dialkyl peroxide, a diacyl peroxide, a peroxycarboxylic ester, and a peroxydicarbonate-based compound.
The peroxydicarbonate compound is preferably at least one selected from the group consisting of dibutyl peroxydicarbonate, diisobutyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, and bis (3-methoxybutyl) peroxydicarbonate.
The amount of the initiator is sufficient to allow the polymerization reaction to proceed smoothly. Preferably, the mass percentage concentration of the initiator in the polymerization medium is 0.05-1%.
In the method for preparing the modified polychlorotrifluoroethylene resin by suspension polymerization, the polymerization temperature can meet the requirement of smoothly carrying out the reaction. Preferably, the polymerization temperature is 30 to 60 ℃.
In the method for preparing the modified polychlorotrifluoroethylene resin by suspension polymerization provided by the present invention, the polymerization pressure is satisfied to make the reaction smoothly proceed. Preferably, the polymerization pressure is 0.5 to 1.3 MPa.
Compared with the prior art, the modified polychlorotrifluoroethylene resin and the preparation method thereof provided by the invention have the following advantages:
(1) the modified polychlorotrifluoroethylene resin has good thermal stability, and is not easy to degrade and discolor under the processing condition of 230-320 ℃;
(2) by using a mixed reaction medium containing deionized water, a fluorine-containing organic solvent and a non-fluorine-containing organic solvent to respectively dissolve the monomer, the initiator and the dispersing agent, the heat released by polymerization can be effectively conducted, and the dispersing effect of the monomer/auxiliary agent can be improved;
(3) by using a composite dispersant system consisting of a main dispersant and an auxiliary dispersant, the interfacial tension can be further reduced, the loose degree of resin can be improved, the difficulty of the post-treatment of resin washing can be reduced, and the yield of wastewater can be reduced;
(4) the organic initiator is used for initiating polymerization, so that the problems of degradation, yellowing, melt viscosity increase and the like of the polymer in the processing process caused by the fact that the traditional inorganic initiator initiates polymerization and the polymer has unstable terminal groups can be avoided, and equipment investment and introduction of other impurities caused by unstable terminal group treatment are avoided.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
An initiator solution was prepared by dissolving 6g of bis (2-ethylhexyl) peroxydicarbonate in 39.45g of ethyl acetate. Reacting 45g of POSS-Rf, wherein Rf is-CH2-O-CF＝CF2And dissolved in 39.45g of chloroform to prepare a POSS-Rf chloroform solution.
25g of hydroxypropylmethylcellulose, 5g of CF3(CF2)6COONH4、78.9g CF2ClCFCl2Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times for replacement, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 900g of chlorotrifluoroethylene and POSS-Rf chloroform solution into a reaction kettle by a metering device, stirring at 500rpm, heating to 45 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.05MPa, and reacting for 10 hours. Washing the polymerization product for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the product for 24 hours in vacuum at 100-120 ℃ to obtain the polymer739g of a white modified polychlorotrifluoroethylene resin.
Example 2
An initiator solution was prepared by dissolving 6g of bis (2-ethylhexyl) peroxydicarbonate in 23.1g of ethyl acetate. 45g of POSS-Rf, wherein Rf is- (CH)2)2-O-CF＝CF2And dissolved in 23.1g of chloroform to prepare a POSS-Rf chloroform solution.
25g of hydroxypropylmethylcellulose, 5g of CF3(CF2)7SO3NH4、46.2g CF2ClCFCl2Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 900g of chlorotrifluoroethylene and POSS-Rf chloroform solution into a reaction kettle by a metering device, stirring at 500rpm, heating to 45 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.03MPa, and reacting for 10 hours. The polymerization product was washed with deionized water several times until the conductivity became less than 10. mu.S/cm, and further dried in vacuo at 100 ℃ and 120 ℃ for 24 hours to obtain 721g of a white modified polychlorotrifluoroethylene resin.
Example 3
An initiator solution was prepared by dissolving 9g of bis (2-ethylhexyl) peroxydicarbonate in 39.45g of ethyl acetate. 45g of POSS-Rf, wherein Rf is- (CH)2)3-O-CF＝CF2And dissolved in 39.45g of chloroform to prepare a POSS-Rf chloroform solution.
25g of hydroxypropylmethylcellulose, 5g F (CFCF)3CF2O)3CFCF3COONH4、78.9g CF2ClCFCl2Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times for replacement, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. 900g of chlorotrifluoroethylene and POSS-Rf chloroform solution are added into a reaction kettle by a metering device, the stirring speed is 500rpm,and (3) heating to 45 ℃, adding an initiator solution into the reaction kettle by using a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.05MPa, and reacting for 10 hours. The polymerization product is washed for a plurality of times by deionized water until the conductivity is less than 10 mu S/cm, and the product is further dried in vacuum at the temperature of 100 ℃ and 120 ℃ for 24 hours to obtain 717g of white modified polychlorotrifluoroethylene resin.
Example 4
6g of diisopropyl peroxydicarbonate was dissolved in 8.5g of butyl acetate to prepare an initiator solution. 12.2g of POSS-Rf, wherein Rf is-CH2-O-CF＝CF2And dissolved in 3.6g of chloroform to prepare a POSS-Rf chloroform solution.
13g of polyvinyl alcohol, 2g F (CFCF)3CF2O)4CFCF3COONH4、18.2g CF2HCF2OCH2CH3Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times for replacement, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 600g of chlorotrifluoroethylene and POSS-Rf chloroform solution into a reaction kettle by a metering device, stirring at the speed of 500rpm, heating to 50 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.13MPa, and reacting for 10 hours. The polymerization product was washed with deionized water several times until the conductivity became less than 10. mu.S/cm, and further dried in vacuo at 100 ℃ and 120 ℃ for 24 hours to obtain 778g of a white modified polychlorotrifluoroethylene resin.
Example 5
An initiator solution was prepared by dissolving 3g of dicyclohexyl peroxydicarbonate in 3.7g of butyl acetate. 3.1g of POSS-Rf, wherein Rf is-CH2-O-CF＝CF2And dissolved in 1.58g of chloroform to prepare a POSS-Rf chloroform solution.
2.6g of polyvinyl alcohol, 0.4g of CF3(CF2)6COONa, 9.82g of perfluorocyclohexane and 3L of deionized water are added into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, and the reaction kettle is vacuumized and filled with nitrogenReplacing for three times, measuring the oxygen content below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 300g of chlorotrifluoroethylene and POSS-Rf chloroform solution into a reaction kettle by a metering device, stirring at the speed of 400rpm, heating to 50 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.12MPa, and reacting for 8 hours. The polymerization product is washed for a plurality of times by deionized water until the conductivity is less than 10 mu S/cm, and the product is further dried in vacuum at the temperature of 100 ℃ and 120 ℃ for 24 hours to obtain 752g of white modified polychlorotrifluoroethylene resin.
Example 6
6g of diisopropyl peroxydicarbonate was dissolved in 14.68g of ethyl acetate to prepare an initiator solution. 18.6g of POSS-Rf, wherein Rf is- (CH)2)2-O-CF＝CF2And dissolved in 9.8g of n-hexane to prepare a POSS-Rf chloroform solution.
8.1g of polyvinylpyrrolidone, 0.9g F (CFCF)3CF2O)4CFCF3COOH、36.72g CF2HCF2OCH2CF3Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 600g of chlorotrifluoroethylene and POSS-Rf normal hexane solution into a reaction kettle through a metering device, stirring at a speed of 400rpm, heating to 50 ℃, adding an initiator solution into the reaction kettle through a metering pump after the temperature of a system is constant, keeping the polymerization pressure in the reaction kettle at 1.12MPa, and reacting for 10 hours. The polymerization product was washed with deionized water several times until the conductivity became less than 10. mu.S/cm, and further dried under vacuum at 100 ℃ and 120 ℃ for 24 hours to obtain 763g of white modified polychlorotrifluoroethylene resin.
Example 7
An initiator solution was prepared by dissolving 3g of dicyclohexyl peroxydicarbonate in 2.64g of butyl acetate. 6.1g of POSS-Rf, wherein Rf is- (CH)2)2-O-CF＝CF2And dissolved in 2.64g of toluene to prepare a POSS-Rf chloroform solution.
2.5g of polyvinyl alcohol, 0.5g F (CFCF)3CF2O)4CFCF3COONH4、9.82g CF2HCF2OCH2CH3Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times for replacement, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 300g of chlorotrifluoroethylene and POSS-Rf toluene solution into a reaction kettle by a metering device, stirring at the speed of 400rpm, heating to 50 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.12MPa, and reacting for 8 hours. The polymerization product was washed with deionized water several times until the conductivity became less than 10. mu.S/cm, and further dried under vacuum at 100 ℃ and 120 ℃ for 24 hours to obtain 726g of a white modified polychlorotrifluoroethylene resin.
Example 8
An initiator solution was prepared by dissolving 12g of bis (3-methoxybutyl) peroxydicarbonate in 32.5g of ethyl acetate. 25g of POSS-Rf, wherein Rf is- (CH)2)3-O-CF＝CF2And dissolved in 13.9g of chloroform to prepare a POSS-Rf chloroform solution.
13.2g of hydroxypropylmethylcellulose, 1.8g F (CFCF)3CF2O)3CFCF3COOH、46.4g CF2ClCFCl2Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 600g of chlorotrifluoroethylene and POSS-Rf chloroform solution into a reaction kettle by a metering device, stirring at the speed of 500rpm, heating to 40 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 0.88MPa, and reacting for 15 hours. The polymerization product is washed for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and the product is further dried in vacuum at the temperature of 100 ℃ and 120 ℃ for 24 hours to obtain 682g of white modified polychlorotrifluoroethylene resin.
Example 9
An initiator solution was prepared by dissolving 6g of bis (4-t-butylcyclohexyl) peroxydicarbonate in 16.52g of butyl acetate. 27.8g of POSS-Rf, wherein Rf is-CH2-O-CF＝CF2And dissolved in 11.02g of n-hexane to prepare a POSS-Rf chloroform solution.
12.8g of hydroxypropyl cellulose, 2.2g of CF3(CF2)9SO3NH433.66g of perfluorocyclohexane and 3L of deionized water are added into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, the reaction kettle is vacuumized and filled with nitrogen for three times, the measured oxygen content is below 10ppm, and the reaction kettle is continuously vacuumized until the pressure is-0.1 MPa. Adding 900g of chlorotrifluoroethylene and POSS-Rf normal hexane solution into a reaction kettle by a metering device, stirring at a speed of 600rpm, heating to 48 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.08MPa, and reacting for 10 hours. The polymerization product was washed with deionized water several times until the conductivity became less than 10. mu.S/cm, and further dried under vacuum at 100 ℃ and 120 ℃ for 24 hours to obtain 749g of a white modified polychlorotrifluoroethylene resin.
Example 10
An initiator solution was prepared by dissolving 3g of diisopropyl peroxydicarbonate in 17.12g of ethyl acetate. 18.4g of POSS-Rf, wherein Rf is-CH2-O-CF＝CF2And dissolved in 7.36g of toluene to prepare a POSS-Rf chloroform solution.
12.5g of polyvinylpyrrolidone, 2.5g of CF3(CF2)8COOK、36.72g CF2ClCFCl2Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times for replacement, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 900g of chlorotrifluoroethylene and POSS-Rf toluene solution into a reaction kettle by a metering device, stirring at the speed of 600rpm, heating to 45 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.02MPa, and reacting for 15 DEG CAnd (4) hours. The polymerization product was washed with deionized water several times until the conductivity became less than 10. mu.S/cm, and further dried in vacuo at 100 ℃ and 120 ℃ for 24 hours to obtain 795g of a white modified polychlorotrifluoroethylene resin.
Comparative example 1
An initiator solution was prepared by dissolving 6g of bis (2-ethylhexyl) peroxydicarbonate in 39.45g of ethyl acetate.
25g of hydroxypropylmethylcellulose, 5g of CF3(CF2)6COONH4、78.9g CF2ClCFCl2Adding the mixture and 3L of deionized water into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and filling nitrogen for three times for replacement, measuring the oxygen content to be below 10ppm, and continuously vacuumizing until the pressure in the reaction kettle is-0.1 MPa. Adding 900g of chlorotrifluoroethylene into a reaction kettle by a metering device, stirring at the speed of 500rpm, heating to 45 ℃, adding an initiator solution into the reaction kettle by a metering pump after the temperature of the system is constant, keeping the polymerization pressure in the reaction kettle at 1.04MPa, and reacting for 10 hours. The polymerization product is washed for a plurality of times by deionized water until the conductivity is less than 10 mu S/cm, and the product is further dried in vacuum at the temperature of 100 ℃ and 120 ℃ for 24 hours to obtain 754g of white modified polychlorotrifluoroethylene resin.
The modified polychlorotrifluoroethylene resins and polychlorotrifluoroethylene resins prepared in the above examples and comparative examples were subjected to heat stability and Yellowness (YI) tests in which:
(1) the thermal stability test method comprises the following steps: n is a radical of2Temperature rise rate of atmosphere 80 ml/min: temperature rise interval of 10 ℃/min: 50-800 ℃;
(2) the yellowness test method comprises the following steps: ASTM E313 thickness 1 mm.
The test results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the modified polychlorotrifluoroethylene resin prepared by the present invention has significantly improved thermal stability.
Claims (12)
1. A fluorine-containing cage type silsesquioxane modified polychlorotrifluoroethylene resin with high thermal stability is characterized in that: the monomer for preparing the modified polychlorotrifluoroethylene resin comprises chlorotrifluoroethylene and a compound represented by the structural formula (I),
wherein: r is selected from-CH2CH2CF3Rf is selected from-R1-O-CF＝CF2，R1An alkylene group selected from C1 to C6;
and the mass percentage of the structural unit formed by the compound shown in the structural formula (I) in the chain segment structure of the modified polychlorotrifluoroethylene resin is 0.1-10%.
2. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 1, wherein: the R is1Is selected from C1-C3 alkylene.
3. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 1, wherein: the mass percentage of the structural unit formed by the compound shown in the structural formula (I) in the chain segment structure of the modified polychlorotrifluoroethylene resin is 1-5%.
4. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 1, wherein: the modified polychlorotrifluoroethylene resin, 1% N thereof2The decomposition temperature is 360-390 ℃, and the yellowing index is 1.5-5.0.
5. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 4, wherein: 1% N of the modified polychlorotrifluoroethylene resin2The decomposition temperature is 370-390 ℃, and the yellowing index is 1.5-3.5.
6. The fluorine-containing cage type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 1, wherein: the modified polychlorotrifluoroethylene resin is prepared by a suspension polymerization method comprising:
in a polymerization medium, under the existence of a dispersant and an initiator, carrying out suspension polymerization on chlorotrifluoroethylene and a compound shown in a structural formula (I) to obtain the modified polychlorotrifluoroethylene resin;
the mass ratio of the chlorotrifluoroethylene to the compound shown in the structural formula (I) is 10: 1-100: 1;
the polymerization medium comprises deionized water, a fluorine-containing organic solvent and a non-fluorine-containing organic solvent, and the mass percentage of the fluorine-containing organic solvent and the non-fluorine-containing organic solvent in the polymerization medium is 0.01-10%.
7. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 6, wherein:
the mass ratio of the chlorotrifluoroethylene to the compound shown in the structural formula (I) is 20: 1-50: 1;
in the polymerization medium, the fluorine-containing organic solvent is selected from CF3CClHCF2Cl、CF2ClCFClCH2CH2Cl、CF3CH2CH2CH2Cl、CF2ClCFCl2、CF3CCl3、CF3CFClCFClCF3、CF3CH2CF2CH3、CF2HCF2CF2CF2H、CF3CF2CF2CF2CF2H. Full fluorine ringHexane, CF2HCF2OCH2CF3、CF2HCF2OCH2CF2CF2H and CF2HCF2OCH2CH3At least one of the fluorine-containing organic solvents, wherein the fluorine-free organic solvent is selected from at least one of toluene, n-hexane, chloroform, ethyl acetate and butyl acetate, and the mass percentage of the fluorine-containing organic solvent and the fluorine-free organic solvent in a polymerization medium is 0.1-5%.
8. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 7, wherein:
in the polymerization medium, the mass ratio of the fluorine-containing organic solvent to the non-fluorine-containing organic solvent is 1: 3-3: 1.
9. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 8, wherein:
in the polymerization medium, the mass ratio of the fluorine-containing organic solvent to the non-fluorine-containing organic solvent is 1: 1-2: 1.
10. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 6, wherein:
the dispersant comprises a main dispersant and an auxiliary dispersant;
the main dispersing agent is at least one selected from polyvinyl alcohol, methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose and polyvinylpyrrolidone;
the auxiliary dispersant is selected from R2COOM and R2SO3M, wherein: r2Is independently selected from-CnF2n+1Or F (CFCF)3CF2O)mCF(CF3) N is an integer of 6 to 10, M is an integer of 2 to 5, and M is independently H+、NH4 +、Na+Or K+；
The mass ratio of the main dispersant to the auxiliary dispersant is 5: 1-10: 1.
11. The fluorine-containing cage type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 6, wherein:
the initiator is at least one of dialkyl peroxide, diacyl peroxide, peroxycarboxylic ester and peroxydicarbonate compounds;
the peroxydicarbonate compound is selected from at least one of dibutyl peroxydicarbonate, diisobutyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate and di (3-methoxybutyl) peroxydicarbonate;
the mass percentage concentration of the initiator in the mixed medium is 0.05-1%.
12. The fluorine-containing cage-type silsesquioxane modified polychlorotrifluoroethylene resin having high thermal stability according to claim 6, wherein: the polymerization temperature is 30-60 ℃, and the polymerization pressure is 0.5-1.3 MPa.
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| CN1938342A (en) * | 2004-03-29 | 2007-03-28 | 通用电气公司 | Compound for optical materials and methods of fabrication |
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| WO2016044880A1 (en) * | 2014-09-25 | 2016-03-31 | Deakin University | Liquid repellent article and process for the preparation of the article |
| CN106188377A (en) * | 2015-05-08 | 2016-12-07 | 浙江省化工研究院有限公司 | The fluoroelastomer of a kind of modification, its preparation method and application |
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| US20140234579A1 (en) * | 2013-02-15 | 2014-08-21 | Liang Wang | Composite Preventing Ice Adhesion |
| WO2017180264A2 (en) * | 2016-03-08 | 2017-10-19 | Giner, Inc. | Separator for use in electrochemical cells and method of fabrication thereof |
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| CN1938342A (en) * | 2004-03-29 | 2007-03-28 | 通用电气公司 | Compound for optical materials and methods of fabrication |
| CN104218111A (en) * | 2014-08-19 | 2014-12-17 | 乐凯胶片股份有限公司 | Environment-friendly solar cell backing film excellent in flame retardation |
| WO2016044880A1 (en) * | 2014-09-25 | 2016-03-31 | Deakin University | Liquid repellent article and process for the preparation of the article |
| CN106188377A (en) * | 2015-05-08 | 2016-12-07 | 浙江省化工研究院有限公司 | The fluoroelastomer of a kind of modification, its preparation method and application |
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Denomination of invention: A Fluorinated Cage Type Silsesquioxane Modified Polytrifluoroethylene Resin Effective date of registration: 20230331 Granted publication date: 20220701 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2023330000634 |
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