CN107540777B - Modified polychlorotrifluoroethylene resin, and preparation method and application thereof - Google Patents
Modified polychlorotrifluoroethylene resin, and preparation method and application thereof Download PDFInfo
- Publication number
- CN107540777B CN107540777B CN201610479992.XA CN201610479992A CN107540777B CN 107540777 B CN107540777 B CN 107540777B CN 201610479992 A CN201610479992 A CN 201610479992A CN 107540777 B CN107540777 B CN 107540777B
- Authority
- CN
- China
- Prior art keywords
- modified polychlorotrifluoroethylene
- modified
- film
- membrane
- polychlorotrifluoroethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a modified polychlorotrifluoroethylene resin which is copolymerized by chlorotrifluoroethylene and a compound (structural formula is shown in the specification) shown in a structural formula (I). The modified polychlorotrifluoroethylene film prepared from the modified polychlorotrifluoroethylene resin provided by the invention has good barrier property to water vapor and/or oxygen, and is suitable for the fields of medical packaging, electronic and electrical element packaging, solar cell packaging and the like.
Description
Technical Field
The invention belongs to the field of fluorine-containing high polymer materials, and particularly relates to modified polychlorotrifluoroethylene resin.
Background
Polychlorotrifluoroethylene (PCTFE) was the earliest developed thermoplastic fluoroplastic for commercial production. The preparation of PCTFE was first reported by i.g. farben industrie, germany, 1937. In 1946, a PCTFE production device is formally built and put into production in the United states. In 1957, 3M, Inc. in the United states began selling PCTFE in large quantities under the trademark "Kel-F".
The PCTFE is polymerized by using Chlorotrifluoroethylene (CTFE) as a raw material, has excellent chemical stability, insulativity and weather resistance, can be used at the temperature of-196-125 ℃ 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 encapsulating film.
Among them, the sensitivity of modern drugs to water vapor and oxygen is becoming stronger in the field of medical materials and medicines, which puts higher demands on polymer films for packaging, which are desired to have both high water vapor barrier properties and high oxygen barrier properties. The conventional PCTFE film has excellent water vapor barrier property, but has slightly insufficient oxygen barrier property. Therefore, in the existing medicine packaging materials, the PCTFE film needs to be compounded with other materials in cooperation with an adhesive to meet the requirement of having both water vapor barrier property and oxygen barrier property.
In order to improve the oxygen barrier property of the PCTFE film, it is possible to increase the thickness of the film or to combine the film with other films in principle, but in practical applications, it is found that increasing the thickness of the PCTFE film does not necessarily improve the oxygen barrier property of the film, and the film is not economical in cost.
Therefore, there is a need for further improvement of polychlorotrifluoroethylene to enable films having better oxygen barrier properties and water vapor barrier properties.
Disclosure of Invention
The invention aims to provide a polychlorotrifluoroethylene resin which has better oxygen barrier property and water vapor barrier property when being prepared into a polychlorotrifluoroethylene film.
In order to realize the purpose of the invention, the functional group monomer is added to copolymerize with the chlorotrifluoroethylene, so that the main chain of the polychlorotrifluoroethylene resin has the functional group, and the polychlorotrifluoroethylene film can form stronger intermolecular force with the adhesive, thereby improving the bonding strength between the polychlorotrifluoroethylene film and other films and reducing the using amount of the adhesive in coating.
The invention provides the following technical scheme:
a modified polychlorotrifluoroethylene resin, the monomer used for preparing the modified polychlorotrifluoroethylene resin comprises chlorotrifluoroethylene and a compound represented by the structural formula (I),
wherein: rfA fluorine-containing alkyl group selected from C1 to C6;
the structural unit formed by the structural formula (I) accounts for 0.1-10% of the modified polychlorotrifluoroethylene resin chain segment structure by mass percentage.
The invention provides a compound shown in a structural formula (I), wherein RfSelected from C1-C6 fluoroalkyl groups. Preferably, R isfSelected from C1-C4 fluoroalkyl groups.
The modified polychlorotrifluoroethylene resin provided by the invention has the structural unit formed by the structural formula (I) in the chain segment structure of the modified polychlorotrifluoroethylene resin, wherein the mass percentage of the structural unit is 0.1-10%. Preferably, the mass percentage of the structural unit formed by the structural formula (I) in the chain segment structure of the modified polychlorotrifluoroethylene resin is 1-5%.
The invention also provides a preparation method of the modified polychlorotrifluoroethylene resin. The modified polychlorotrifluoroethylene resin is obtained by an emulsion polymerization method comprising:
in a mixed medium, under the existence of a fluorine-containing surfactant and an initiator, carrying out emulsion polymerization on chlorotrifluoroethylene and a compound shown in a structural formula (I) to obtain the modified polychlorotrifluoroethylene resin;
the mixed medium contains an organic solvent and water, and the mass percent of the organic solvent in the mixed medium is 5-25%.
In the emulsion polymerization method of the present invention, the mixed medium contains an organic solvent and water. The organic solvent may be an organic solvent commonly used in the art. Preferably, the organic solvent is at least one selected from the group consisting of xylene, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and n-hexane.
In the emulsion polymerization method of the present invention, the fluorosurfactant may be an organic solvent commonly used in the art. Preferably, the fluorosurfactant is selected from RFCOOM and RFSO3At least one of M, and RFIndependently selected from CnFn+1(n is 6 to 10) or F (CFCF)3CF2O)nCFCF3(n is 2 to 5), M is independently selected from H+、NH4 +、Na+Or K+。
The amount of the fluorine-containing surfactant is sufficient to allow the polymerization reaction to proceed smoothly. Preferably, the mass percentage concentration of the fluorine-containing surfactant in the water phase is 0.01-5%.
In the emulsion polymerization method of the present invention, the initiator may be an initiator commonly used in the art. Preferably, the initiator is at least one selected from azo-based and peroxydicarbonate-based oil-soluble initiators. More preferably, the azo initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, azobismethylbutyronitrile, azobisisooctonitrile, azobisisononannonitrile, and azobisisodecylonitrile. More preferably, the peroxydicarbonate-based initiator is at least one selected from the group consisting of dibutyl peroxydicarbonate, diisobutyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (2-ethylhexyl) 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 mixed medium is 0.01-2%.
In the emulsion polymerization method of the present invention, the polymerization temperature is satisfied to allow the polymerization reaction to proceed smoothly. Preferably, the polymerization temperature is 30 to 80 ℃.
In the emulsion polymerization method of the present invention, the polymerization pressure is satisfied to make the polymerization reaction proceed smoothly. Preferably, the polymerization pressure is 0.5 to 2.5 MPa.
The invention also provides a modified polychlorotrifluoroethylene membrane prepared from the modified polychlorotrifluoroethylene resin.
The hydroxyl value of the modified polychlorotrifluoroethylene membrane is 3-20 mgKOH/g. Preferably, the hydroxyl value is 5 to 15 mgKOH/g.
The initial adhesion force of the modified polychlorotrifluoroethylene membrane coated with the adhesive of 3 mu m and the PVC membrane is 3-15N/cm. Preferably, the initial adhesion force of the modified polychlorotrifluoroethylene membrane coated with a 3-micron adhesive and the PVC membrane is 5-10N/cm.
The invention also provides a preparation method of the modified polychlorotrifluoroethylene membrane, which comprises the following steps:
(1) carrying out melt processing on the modified polychlorotrifluoroethylene resin to obtain a membrane;
(2) and (3) putting the membrane into a methanol solution of sodium hydroxide, performing alcoholysis for 1-2 hours at the temperature of 30-50 ℃, and washing to obtain the modified polychlorotrifluoroethylene membrane.
The modified polychlorotrifluoroethylene membrane provided by the invention is suitable for blocking water vapor and/or oxygen.
The modified polychlorotrifluoroethylene membrane provided by the invention is suitable for medical packaging, electronic and electrical component packaging or solar cell packaging.
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 azobisisobutyronitrile (2.4 g) in ethyl acetate (240 g). Taking CF3(CF2)6COONH43.6g 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 together, the reaction kettle is vacuumized, filled with nitrogen and replaced 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 1200g of chlorotrifluoroethylene and CH into a reaction kettle through a metering device2＝C(CF3)OCOCH345g, stirring speed 500rpm, heating to 65 ℃, 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 1.68MPa, 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 in vacuo at 100 ℃ and 120 ℃ for 24 hours to obtain 1053g of a white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 35 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is 11.58 mgKOH/g.
Example 2
An initiator solution was prepared by dissolving 3.6g of azobisisoheptonitrile in 240g of butyl acetate. Taking CF3(CF2)7SO3NH43.6g 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 together, the reaction kettle is vacuumized, filled with nitrogen and replaced 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 1200g of chlorotrifluoroethylene and CH into a reaction kettle through a metering device2＝C(CF2CF3)OCOCH360g, stirring speed 500rpm, heating to 55 ℃, 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 1.32MPa, 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 982g of white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 35 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is tested to be 9.73 mgKOH/g.
Example 3
An initiator solution was prepared by dissolving 6g of diisopropyl peroxydicarbonate in 360g of n-hexane. Take F (CFCF)3CF2O)3CFCF3COONH4Adding 6g 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 1200g of chlorotrifluoroethylene and CH into a reaction kettle through a metering device2＝C(CF2CF2CF3)OCOCH390g, stirring speed 500rpm, heating to 55 ℃, 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 1.32MPa, 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 in vacuum at 100 ℃ and 120 ℃ for 24 hours to obtain 997g of a white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 35 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is tested to be 8.95 mgKOH/g.
Example 4
An initiator solution was prepared by dissolving 9g of bis (2-ethylhexyl) peroxydicarbonate in 390g of butyl acetate. Take F (CFCF)3CF2O)4CFCF3COONH46g 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 together, 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 1200g of chlorotrifluoroethylene and CH into a reaction kettle through a metering device2＝C(CF3CFCF3)OCOCH390g, stirring speed 500rpm, heating to 50 ℃, 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 1.17MPa, 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 936g of a white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 35 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is tested to be 8.31 mgKOH/g.
Example 5
An initiator solution was prepared by dissolving 12g of diisobutyl peroxydicarbonate in 510g of ethyl acetate. Taking CF3(CF2)6Adding COONa 6g and 3L 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 1200g of chlorotrifluoroethylene and CH into a reaction kettle through a metering device2＝C(CF2CF2CF2CF3)OCOCH3120g, stirring speed of 700rpm, 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 1.04MPa, and reacting for 12 hours. Washing the polymerized product with deionized water for multiple times until the conductivity is less than 10 muS/cm, and further vacuum-drying the product at 100-120 ℃ for 24 hours to obtain 882g of a white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 45 ℃, and stirring for 1.5 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is tested to be 7.35 mgKOH/g.
Example 6
An initiator solution was prepared by dissolving 15g of azobisisobutyronitrile in 540g of butyl acetate. Take F (CFCF)3CF2O)4CFCF3Adding 9g of COOH 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. 1200g of chlorotrifluoroethylene and CH2 ═ C (CF) were added to the reactor by means of a metering device3)3)OCOCH3120g, stirring speed of 700rpm, heating to 70 ℃, 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 1.87MPa, and reacting for 6.5 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 1093g of a white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 50 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is 7.65mgKOH/g by testing.
Example 7
An initiator solution was prepared by dissolving 12g of bis (2-ethylhexyl) peroxydicarbonate in 510g of n-hexane. Take F (CFCF)3CF2O)4CFCF3COONH4Adding 18g 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 CH into the reaction kettle through a metering device2＝C(CF3)OCOCH345g, stirring speed 500rpm, heating to 40 ℃, 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 0.91MPa, and reacting for 16 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 633g of white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 30 ℃, and stirring for 1 hour. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is tested to be 9.33 mgKOH/g.
Example 8:
an initiator solution was prepared by dissolving 9g of diisobutyl peroxydicarbonate in 480g of ethyl acetate. Take F (CFCF)3CF2O)3CFCF3COOH 75g 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 together, vacuumizing and nitrogen gas filling are carried out for three times, the measured oxygen content is below 10ppm, and vacuumizing is continued until the pressure in the reaction kettle is-0.1 MPa. Adding 900g of chlorotrifluoroethylene and CH into the reaction kettle through a metering device2＝C(CF2CF3)OCOCH360g, stirring speed 500rpm, heating to 50 ℃, 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 1.17MPa, 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.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 40 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is 10.37 mgKOH/g.
Example 9:
an initiator solution was prepared by dissolving 12g of azobisisoheptonitrile in 330g of butyl acetate. Taking CF3(CF2)9SO3NH47.5g 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 together, the reaction kettle is vacuumized, filled with nitrogen and replaced 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 1500g of chlorotrifluoroethylene and CH into a reaction kettle through a metering device2＝C(CF2CF2CF3)OCOCH390g, stirring speed of 700rpm, heating to 55 ℃, adding an initiator into the reaction kettle by using a metering pump after the temperature of the system is constantAnd (3) keeping the polymerization pressure in the reaction kettle at 1.32MPa, 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 vacuum-dried at 100 ℃ and 120 ℃ for 24 hours to obtain 1265g of a white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 40 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is 9.02mgKOH/g by testing.
Example 10:
an initiator solution was prepared by dissolving 12g of azobisisobutyronitrile in 510g of butyl acetate. Taking CF3(CF2)8COOK12g and 3L deionized water are added into a 5L reaction kettle with a mechanical stirring device, a temperature control device and a circulating heating/cooling device, vacuumizing and nitrogen gas filling are carried out for three times, the measured oxygen content is below 10ppm, and vacuumizing is continued until the pressure in the reaction kettle is-0.1 MPa. Adding 1500g of chlorotrifluoroethylene and CH into a reaction kettle through a metering device2＝C(CF2CF2CF2CF3)OCOCH3120g, stirring speed of 700rpm, heating to 70 ℃, 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 1.87MPa, 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 in vacuo at 100 ℃ and 120 ℃ for 24 hours to obtain 1402g of a white modified polychlorotrifluoroethylene resin.
The prepared modified polychlorotrifluoroethylene resin was prepared into a film having a thickness of 100 μm. A sodium hydroxide-methanol solution was prepared by dissolving 300g of sodium hydroxide in 3L of methanol. Adding the modified polychlorotrifluoroethylene membrane into a sodium hydroxide-methanol solution, controlling the temperature at 50 ℃, and stirring for 2 hours. And washing the modified polychlorotrifluoroethylene membrane subjected to surface alcoholization for multiple times by deionized water until the conductivity is less than 10 mu S/cm, and further drying the membrane in vacuum at 80-100 ℃ for 12 hours to obtain the modified polychlorotrifluoroethylene membrane.
The hydroxyl value of the prepared modified polychlorotrifluoroethylene membrane is tested to be 7.47 mgKOH/g.
Example 11
The modified polychlorotrifluoroethylene films prepared in examples 1 to 10 were coated with an adhesive (3 μm) and compounded with a PVC film, and the initial adhesion of the modified polychlorotrifluoroethylene films to the PVC film was tested. The results are given in table 1 below.
Meanwhile, an unmodified polychlorotrifluoroethylene membrane is coated with an adhesive (3 mu m) and compounded with a PVC membrane according to the same method, and the initial adhesion of the polychlorotrifluoroethylene membrane and the PVC membrane is tested. The results are also given in table 1 below, in comparative example.
TABLE 1
Claims (11)
1. A modified polychlorotrifluoroethylene resin characterized in that a monomer for preparing the modified polychlorotrifluoroethylene resin comprises chlorotrifluoroethylene and a compound represented by the formula (I),
wherein: rfA fluorine-containing alkyl group selected from C1 to C6;
the structural unit formed by the structural formula (I) accounts for 0.1-10% of the modified polychlorotrifluoroethylene resin chain segment structure by mass percentage.
2. The modified polychlorotrifluoroethylene resin according to claim 1, wherein R isfSelected from C1-C4 fluorine-containing alkyl, the structural unit formed by the structural formula (I) is modifiedThe mass percentage of the chain segment structure of the modified polychlorotrifluoroethylene resin is 1-5%.
3. The modified polychlorotrifluoroethylene resin according to claim 1, wherein the modified polychlorotrifluoroethylene resin is obtained by an emulsion polymerization process comprising:
in a mixed medium, under the existence of a fluorine-containing surfactant and an initiator, carrying out emulsion polymerization on chlorotrifluoroethylene and a compound shown in a structural formula (I) to obtain the modified polychlorotrifluoroethylene resin;
the mixed medium contains an organic solvent and water, and the mass percent of the organic solvent in the mixed medium is 5-25%.
4. The modified polychlorotrifluoroethylene resin according to claim 3, wherein:
the organic solvent is at least one selected from xylene, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and n-hexane;
the fluorosurfactant is selected from RFCOOM and RFSO3At least one of M, and RFIndependently selected from CnFn+1(n is 6 to 10) or F (CFCF)3CF2O)nCFCF3(n is 2 to 5), M is independently selected from H+、NH4 +、Na+Or K+And the mass percentage concentration of the fluorine-containing surfactant in the water phase is 0.01-5%;
the initiator is at least one of azo type and peroxydicarbonate type oil-soluble initiators, and the mass percentage concentration of the initiator in the mixed medium is 0.01-2%.
5. The modified polychlorotrifluoroethylene resin according to claim 4, wherein:
the azo initiator is selected from at least one of azodiisobutyronitrile, azodiisoheptonitrile, azodimethylbutanonitrile, azodiisooctylnitrile, azodiisonononitrile and azodiisodecyanate;
the peroxydicarbonate initiator is selected from at least one of dibutyl peroxydicarbonate, diisobutyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate and di (3-methoxybutyl) peroxydicarbonate;
the polymerization temperature is 30-80 ℃, and the polymerization pressure is 0.5-2.5 MPa.
6. A modified polychlorotrifluoroethylene film characterized in that it is prepared from the modified polychlorotrifluoroethylene resin according to any one of claims 1 to 5.
7. The modified polychlorotrifluoroethylene film of claim 6, wherein the hydroxyl value of the modified polychlorotrifluoroethylene film is 3 to 20mgKOH/g, and the initial adhesion between the film and the PVC film coated with the adhesive of 3 μm is 3 to 15N/cm.
8. The modified polychlorotrifluoroethylene film of claim 7, wherein the hydroxyl value of the modified polychlorotrifluoroethylene film is 5 to 15mgKOH/g, and the initial adhesion between the film and the PVC film coated with the adhesive of 3 μm is 5 to 10N/cm.
9. The modified polychlorotrifluoroethylene film according to claim 6, wherein the modified polychlorotrifluoroethylene resin is prepared by a process comprising:
(1) carrying out melt processing on the modified polychlorotrifluoroethylene resin to obtain a membrane;
(2) and (3) putting the membrane into a methanol solution of sodium hydroxide, performing alcoholysis for 1-2 hours at the temperature of 30-50 ℃, and washing to obtain the modified polychlorotrifluoroethylene membrane.
10. The modified polychlorotrifluoroethylene film of claim 6 wherein the modified polychlorotrifluoroethylene film is for a moisture and/or oxygen barrier.
11. The modified polychlorotrifluoroethylene film according to claim 10, wherein the modified polychlorotrifluoroethylene film is used for medical packaging, electronic and electrical component packaging or solar cell packaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610479992.XA CN107540777B (en) | 2016-06-23 | 2016-06-23 | Modified polychlorotrifluoroethylene resin, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610479992.XA CN107540777B (en) | 2016-06-23 | 2016-06-23 | Modified polychlorotrifluoroethylene resin, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107540777A CN107540777A (en) | 2018-01-05 |
| CN107540777B true CN107540777B (en) | 2020-06-09 |
Family
ID=60962337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610479992.XA Active CN107540777B (en) | 2016-06-23 | 2016-06-23 | Modified polychlorotrifluoroethylene resin, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107540777B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979857B (en) * | 2019-12-16 | 2022-09-02 | 浙江省化工研究院有限公司 | Modified polychlorotrifluoroethylene and preparation method thereof |
| CN114106622B (en) * | 2020-08-31 | 2022-09-06 | 浙江省化工研究院有限公司 | Aqueous dispersion coating |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050082713A1 (en) * | 2003-10-17 | 2005-04-21 | Altman Carl E. | Method of making oriented polychlorotrifluoethylene films |
| JP5582729B2 (en) * | 2008-06-19 | 2014-09-03 | ステラケミファ株式会社 | Modification method of fluororesin film |
| CN103304712A (en) * | 2013-05-07 | 2013-09-18 | 山东森福新材料有限公司 | Manufacturing method of beaded polytrifluorochloroethylene resins |
-
2016
- 2016-06-23 CN CN201610479992.XA patent/CN107540777B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107540777A (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107540777B (en) | Modified polychlorotrifluoroethylene resin, and preparation method and application thereof | |
| CN107408699B (en) | Electrode structure and method for manufacturing same | |
| CN107974221B (en) | Multi-response polymer adhesive glue material and application thereof | |
| JP2010513681A5 (en) | ||
| JP6413767B2 (en) | POLYMER, PROCESS FOR PRODUCING THE SAME, AND MOLDED BODY | |
| CN102766231B (en) | Synthesis method of hydroxylated polyvinyl chloride copolymer resin | |
| CN104610484A (en) | Preparation method for reactive polymer containing dangling double bonds | |
| CN103059212A (en) | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof | |
| CN104946124A (en) | High temperature wear resistance antistatic coating | |
| CN111825786A (en) | Self-plasticizing vinyl chloride-based copolymer, method of preparing the same, composition including the same, and resin article made from the composition | |
| CN103275260B (en) | Preparation method of acrylic plastic-plastic composite latex | |
| EP2897991A1 (en) | Fluoroelastomers | |
| JPH0455601B2 (en) | ||
| CN107383119B (en) | Method for synthesizing modified acrylate emulsion by adopting alkyl glucoside ester | |
| US20210171681A1 (en) | Flexible pvdf polymers | |
| CN103254375A (en) | Polymethyl hexafluorobutyl acrylate amphiphilic segmented copolymers and preparation method thereof | |
| JP2020526619A5 (en) | ||
| CN108242555A (en) | It can be from absorption flexible battery and preparation method thereof | |
| CN109762091B (en) | Tetrafluoroethylene-based copolymer and process for producing the same | |
| CN109485796B (en) | Water-soluble curing Teflon material coated on surface of rubber product and preparation method thereof | |
| CN103819907A (en) | Method for improving polypeptide membrane hydrophilicity by adopting polypropylene glycol and polyvinyl alcohol | |
| CN104311751A (en) | Method for preparing surface hydrophilic modifier for hydrophobic material | |
| CN104356289A (en) | Tetrafluoroethylene fluorocarbon coating resin special for solar backboard and preparation method thereof | |
| CN103524752A (en) | Fluorosiloxane-POSS acrylate block copolymers, blood-compatible coating thereof and preparation method of the fluorosiloxane-POSS acrylate block copolymers | |
| CN106496466A (en) | A kind of Green Chemistry preparation method of vinyl chloride/butyl acrylate copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A modified polytrifluoroethylene chloride resin, its preparation method and Application Effective date of registration: 20220628 Granted publication date: 20200609 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2022330001143 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230308 Granted publication date: 20200609 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2022330001143 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |