CN116867817A - Copolymer, molded article, extrusion molded article, and transfer molded article - Google Patents

Copolymer, molded article, extrusion molded article, and transfer molded article Download PDF

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Publication number
CN116867817A
CN116867817A CN202280016136.4A CN202280016136A CN116867817A CN 116867817 A CN116867817 A CN 116867817A CN 202280016136 A CN202280016136 A CN 202280016136A CN 116867817 A CN116867817 A CN 116867817A
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China
Prior art keywords
copolymer
molded article
present
permeability
test piece
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CN202280016136.4A
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Inventor
井坂忠晴
善家佑美
山本有香里
津田早登
山口安行
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority claimed from PCT/JP2022/003647 external-priority patent/WO2022181232A1/en
Publication of CN116867817A publication Critical patent/CN116867817A/en
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Abstract

The present invention provides a copolymer comprising tetrafluoroethylene units and perfluoro (propyl vinyl ether) units, wherein the content of the perfluoro (propyl vinyl ether) units is 4.9 to 7.0% by mass relative to the total monomer units, the melt flow rate at 372 ℃ is 0.5 to 1.5g/10 min, and the number of functional groups is per 10 6 The number of carbon atoms of the main chain is 20 or less.

Description

Copolymer, molded article, extrusion molded article, and transfer molded article
Technical Field
The present invention relates to a copolymer, a molded body, an extrusion molded body and a transfer molded body.
Background
Patent document 1 describes a material for OA equipment comprising a tetrafluoroethylene copolymer as a constituent, wherein the tetrafluoroethylene copolymer has tetrafluoroethylene units derived from tetrafluoroethylene and perfluoro (alkyl vinyl ether) units derived from perfluoro (alkyl vinyl ether), the perfluoro (alkyl vinyl ether) units being 4.5 to 6.6 mass% of the total monomer units, and unstable terminal groups being 1×10 per 1×10 6 The number of carbon atoms is 20 or less.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-042478
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a copolymer which is not easily deformed even in a molten state, can easily obtain a thick sheet having a uniform thickness by an extrusion molding method, and can obtain a molded article which is extremely excellent in transparency, has a small compression set, has high tensile strength at high temperatures, has low air permeability, low reagent permeability, has excellent rigidity at a high temperature of 110 ℃, has excellent creep resistance, wear resistance and low carbon dioxide permeability, and is less likely to dissolve in a reagent such as hydrogen peroxide.
Means for solving the problems
According to the present invention, there is provided a copolymer comprising tetrafluoroethylene units and perfluoro (propyl vinyl ether) units, wherein the content of perfluoro (propyl vinyl ether) units is 4.9 to 7.0% by mass relative to the total monomer units, and the melt flow rate at 372 ℃ is 0.5g/10 minClock 1.5g/10 min, the number of functional groups relative to every 10 6 The number of carbon atoms of the main chain is 20 or less.
In the copolymer of the present invention, the melt flow rate at 372℃is preferably 0.7g/10 min to 1.3g/10 min.
Further, according to the present invention, there is provided an extrusion molded article or a transfer molded article comprising the copolymer.
Further, according to the present invention, there is provided a coated wire comprising a coating layer containing the copolymer.
Further, according to the present invention, there is provided a molded article comprising the copolymer, wherein the molded article is a sheet or a tube.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a copolymer which is hardly deformed even in a molten state, can easily obtain a thick sheet having a uniform thickness by an extrusion molding method, and can obtain a molded article which is extremely excellent in transparency, has a small compression set, has a high tensile strength at a high temperature, has a low air permeability, a low reagent permeability, has excellent rigidity at a high temperature of 110 ℃, has excellent creep resistance, has excellent abrasion resistance, has excellent low carbon dioxide permeability, and is hardly soluble in a reagent such as hydrogen peroxide.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.
The copolymers of the present invention contain Tetrafluoroethylene (TFE) units and perfluoro (propyl vinyl ether) (PPVE) units.
Copolymers (PFA) containing TFE units and PPVE units are used as the material to form the slabs. Thick sheets tend to have superior tensile strength compared to thin sheets, but the thicker the sheet, the lower the transparency, and therefore, in order to form thick and high-transparency sheets, copolymers having extremely small haze values are required. In addition, such slabs are generally produced by extrusion molding a copolymer using an extrusion molding machine. Since the copolymer in a molten state discharged from the extrusion molding machine is easily deformed by its own weight before being cooled and solidified, there is a problem in that it is not easy to manufacture a sheet having a desired thickness if a thick sheet is to be manufactured. Further, such slabs have a problem of being easily deformed or worn under a long-term continuous load.
Patent document 1 describes: the OA equipment material having the above characteristics is a material exhibiting excellent flexibility, toner releasability, a balance between heat resistance and crack resistance, and melt extrusion moldability. However, when this OA equipment material is used as a material for a thick sheet, it is not easy to obtain a thick sheet having a uniform thickness, and the obtained thick sheet has problems of insufficient transparency, abrasion resistance, compression set resistance and tensile strength at high temperature.
The discovery is as follows: by appropriately adjusting the content of PPVE units, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE units and PPVE units, the following copolymer can be obtained: a thick sheet having a uniform thickness can be easily obtained by an extrusion molding method, and a molded article having extremely excellent transparency, a small compression set, a high tensile strength at high temperature, a low air permeability, a low reagent permeability, a high rigidity at 110 ℃, a high creep resistance, an excellent abrasion resistance, a high carbon dioxide low permeability, and a low tendency to dissolve out fluoride ions into a reagent such as hydrogen peroxide can be obtained.
Further, by using the copolymer of the present invention, a large-diameter tube having high dimensional accuracy can be produced by extrusion molding. Thus, the copolymer of the present invention can be used not only as a sheet material but also for a wide range of applications such as a tube material.
The copolymer of the present invention is a melt-processible fluororesin. Melt processability means that a polymer can be melted and processed using a conventional processing equipment such as an extruder.
The content of PPVE unit in the copolymer is 4.9 to 7.0 mass% relative to the total monomer units. The content of PPVE unit in the copolymer is preferably 5.0% by mass or more, more preferably 5.1% by mass or more, still more preferably 5.2% by mass or more, still more preferably 5.3% by mass or more, particularly preferably 5.4% by mass or more, most preferably 5.5% by mass or more, preferably 6.9% by mass or less, more preferably 6.8% by mass or less, still more preferably 6.7% by mass or less, still more preferably 6.6% by mass or less, particularly preferably 6.5% by mass or less, and most preferably 6.4% by mass or less. When the content of the PPVE unit in the copolymer is within the above range, a copolymer which can give a molded article excellent in transparency, small compression set, high tensile strength at high temperature, low air permeability, low reagent permeability, rigidity at high temperature of 110 ℃, creep resistance, abrasion resistance and low carbon dioxide permeability can be obtained. If the content of PPVE units in the copolymer is too small, the haze value becomes large, or the tensile strength at high temperature becomes low, or the abrasion resistance is poor.
The TFE unit content of the copolymer is preferably 93.0 mass% to 95.1 mass%, more preferably 93.1 mass% or more, still more preferably 93.2 mass% or more, still more preferably 93.3 mass% or more, still more preferably 93.4 mass% or more, particularly preferably 93.5 mass% or more, most preferably 93.6 mass% or more, more preferably 95.0 mass% or less, still more preferably 94.9 mass% or less, still more preferably 94.8 mass% or less, still more preferably 94.7 mass% or less, particularly preferably 94.6 mass% or less, and most preferably 94.5 mass% or less, relative to the total monomer units. When the TFE unit content of the copolymer is in the above range, a copolymer which is extremely excellent in transparency, has a smaller compression set, has a higher tensile strength at high temperature, has low air permeability, has low reagent permeability, and has excellent rigidity at high temperature of 110 ℃, creep resistance, abrasion resistance, and carbon dioxide low permeability can be obtained. If the TFE unit content of the copolymer is too large, the haze value may be large, the tensile strength at high temperature may be low, or the abrasion resistance may be poor.
In the present invention, the content of each monomer unit in the copolymer is determined by 19 F-NMR measurement.
The copolymer may also contain monomer units derived from monomers copolymerizable with TFE and FAVE. In this case, the content of the monomer unit copolymerizable with TFE and PPVE is preferably 0 to 2.1 mass%, more preferably 0.05 to 1.5 mass%, and even more preferably 0.1 to 0.9 mass%, based on the total monomer units of the copolymer.
Examples of monomers copolymerizable with TFE and PPVE include Hexafluoropropylene (HFP) and CZ 1 Z 2 ＝CZ 3 (CF 2 ) n Z 4 (wherein Z is 1 、Z 2 And Z 3 Identical or different, H or F, Z 4 H, F or Cl, n represents an integer of 2 to 10), and CF) 2 ＝CF-ORf 1 (wherein Rf 1 Perfluoro (alkyl vinyl ether) [ PAVE ] represented by perfluoroalkyl group having 1 to 8 carbon atoms](except PPVE), and CF 2 ＝CF-OCH 2 -Rf 1 (wherein Rf 1 A perfluoroalkyl group having 1 to 5 carbon atoms. ) Alkyl perfluorovinyl ether derivatives shown and the like. Among them, HFP is preferable.
The copolymer is preferably at least one selected from the group consisting of a copolymer composed of only TFE units and PPVE units, and a TFE/HFP/PPVE copolymer, and more preferably a copolymer composed of only TFE units and PPVE units.
The Melt Flow Rate (MFR) of the copolymer is 0.5g/10 min to 1.5g/10 min. The MFR of the copolymer is preferably 0.6g/10 min or more, more preferably 0.7g/10 min or more, still more preferably 0.8g/10 min or more, particularly preferably 0.9g/10 min or more, preferably 1.4g/10 min or less, still more preferably 1.3g/10 min or less, and still more preferably 1.1g/10 min or less. When the MFR of the copolymer is within the above range, the copolymer is not easily deformed even in a molten state, and a thick material having a uniform thickness can be easily obtained by an extrusion molding method. Further, by using such a copolymer, a molded article having extremely excellent transparency, a small compression set, high tensile strength at high temperature, excellent rigidity at high temperature, excellent abrasion resistance, and excellent carbon dioxide low permeability can be obtained. If the MFR of the copolymer is too high, it is difficult to produce a thick sheet having a uniform thickness, and the obtained molded article is poor in transparency, abrasion resistance, compression set resistance and tensile strength at high temperature. If the MFR of the copolymer is too low, the extrusion pressure at the time of molding becomes high, the moldability becomes poor, or the air permeability, rigidity at a high temperature of 110 ℃ and carbon dioxide permeability of the obtained molded article become poor.
In the present invention, MFR is a value obtained as a mass (g/10 min) of a polymer flowing out from a nozzle having an inner diameter of 2.1mm and a length of 8mm at 372℃under a 5kg load every 10 minutes using a melt index meter according to ASTM D1238.
The MFR can be adjusted by adjusting the kind and amount of a polymerization initiator used in polymerizing the monomers, the kind and amount of a chain transfer agent, and the like.
In the present invention, every 10 of the copolymer 6 The number of functional groups having the number of main chain carbon atoms is 20 or less. Every 10 of the copolymer 6 The number of functional groups having the number of main chain carbon atoms is preferably 15 or less, more preferably 10 or less, and further preferably less than 6. By setting the number of functional groups of the copolymer in the above range, a molded article having excellent carbon dioxide low permeability, air low permeability, reagent low permeability and creep resistance and being less likely to cause elution of fluorine ions into a reagent such as hydrogen peroxide can be obtained.
The identification of the kind of the functional group and the measurement of the number of functional groups may be performed by infrared spectroscopic analysis.
Specifically, the number of functional groups was measured by the following method. First, the copolymer was cold-molded to prepare a film having a thickness of 0.25mm to 0.3 mm. The film was analyzed by fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of the above copolymer, and to obtain a differential spectrum from the fully fluorinated background spectrum without functional groups. The specific absorption peak of the specific functional group in the copolymer was calculated for every 1X 10 based on the following formula (A) 6 Number of functional groups N of carbon atoms.
N＝I×K/t (A)
I: absorbance of light
K: correction coefficient
t: film thickness (mm)
For reference, the absorption frequency, molar absorptivity, and correction factor are shown in table 1 for some functional groups. The molar absorptivity was determined from FT-IR measurement data of the low molecular weight model compound.
TABLE 1
TABLE 1
-CH 2 CF 2 H、-CH 2 COF、-CH 2 COOH、-CH 2 COOCH 3 、-CH 2 CONH 2 The absorption frequency ratios of (C) are shown in the tables respectively for-CF 2 H. -COF, free-COOH and bonded-COOH, -COOCH 3 、-CONH 2 Is tens of kesse (cm) -1 )。
For example, the functional group number of-COF means the number of functional groups derived from-CF 2 Absorption frequency of COF 1883cm -1 The number of functional groups obtained from the absorption peak at the site and the number of functional groups obtained from the absorption peak derived from-CH 2 Absorption frequency of COF 1840cm -1 The total number of functional groups obtained from the absorption peak at the position.
The functional groups are functional groups present at the main chain end or side chain end of the copolymer and functional groups present in the main chain or side chain. The number of functional groups may be-cf=cf 2 、-CF 2 H、-COF、-COOH、-COOCH 3 、-CONH 2 and-CH 2 Total number of OH.
The functional group is introduced into the copolymer, for example, by a chain transfer agent or a polymerization initiator used in producing the copolymer. For example, using alcohols as chain transfer agents, or using compounds having-CH 2 In the case of peroxides of OH structure as polymerization initiators, -CH 2 OH is introduced into the backbone end of the copolymer. In addition, the functional group is introduced into the terminal of the side chain of the copolymer by polymerizing a monomer having the functional group.
By subjecting the copolymer having such a functional group to fluorination treatment, a copolymer having the number of functional groups in the above range can be obtained. That is, the copolymer of the present invention is preferably a fluorinated copolymer. The copolymers of the invention also preferably have-CF 3 End groups.
The melting point of the copolymer is preferably 290℃to 310℃and more preferably 296℃to 304 ℃. By having the melting point within the above range, the copolymer is more difficult to deform even in a molten state. In addition, a copolymer which provides a molded article having a smaller compression set and a higher tensile strength at high temperature can be obtained.
In the present invention, the melting point can be measured using a differential scanning calorimeter [ DSC ].
The haze value of the copolymer of the present invention is preferably 4.5% or less, more preferably 4.0% or less. When the haze value is within the above range, it is easy to observe the inside of the molded article by visual observation, a camera or the like, and to confirm the flow rate and the residual amount of the content when the molded article such as a sheet, a pipe, a joint, a flowmeter case, a bottle, a nut or the like is obtained by using the fluorocopolymer of the invention. The haze value can be reduced by adjusting the PPVE unit content and Melt Flow Rate (MFR) of the copolymer. In the present invention, the haze value can be measured according to JIS K7136.
The copolymer of the present invention preferably has a compression set of 45% to 77% as measured at 65℃for 72 hours under a compression ratio of 50%. By setting the compression set at 65℃within the above range, a molded article which is less likely to deform under a long-term continuous load can be obtained.
In the present invention, the compression set may be according to ASTM D395 or JIS K6262: the method described in 2013.
The copolymer of the present invention preferably has a tensile strength of 20.5MPa or more at 150 ℃. By making the tensile strength at 150 ℃ within the above range, the obtained molded body can exhibit high durability even at high temperature and high pressure. The tensile strength at 150℃can be increased by adjusting the PPVE unit content and the Melt Flow Rate (MFR) of the copolymer. In the present invention, the tensile strength at 150℃can be measured according to ASTM D638.
The copolymer preferably has a carbon dioxide permeability coefficient of 2300cm 3 ·mm/(m 2 24 h.atm) or less, more preferably 2250cm 3 ·mm/(m 2 24 h.atm) or less. The copolymer of the present invention has excellent low permeability to carbon dioxide because the content of PPVE units, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE units and PPVE units are appropriately adjusted. Therefore, for example, a molded article obtained using the copolymer of the present invention can be suitably used as a sealing member for preventing leakage of a carbon dioxide refrigerant.
In the present invention, the carbon dioxide permeability coefficient can be measured under the conditions of a test temperature of 70℃and a test humidity of 0% RH. The specific measurement of the carbon dioxide permeation coefficient can be performed by the method described in examples.
The copolymer preferably has an air permeability coefficient of 620cm 3 ·mm/(m 2 24 h.atm) or less, more preferably 600cm 3 ·mm/(m 2 24 h.atm) or less. The copolymer of the present invention has excellent low air permeability because the content of PPVE unit, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE unit and PPVE unit are appropriately adjusted.
In the present invention, the air permeability coefficient can be measured under the conditions of a test temperature of 70℃and a test humidity of 0% RH. Specific measurement of the air permeability coefficient can be performed by the method described in examples.
The copolymer preferably has an ethyl acetate permeability of 7.8 g.cm/m 2 Hereinafter, it is more preferably 7.2 g.cm/m 2 The following is given. The copolymer of the present invention has excellent ethyl acetate low permeability because the content of PPVE unit, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE unit and PPVE unit are appropriately adjusted. That is, by using the copolymer of the present invention, a molded article which is hard to permeate a reagent such as ethyl acetate can be obtained.
In the present invention, ethyl acetate permeability can be measured at a temperature of 60℃for 45 days. Specific measurement of ethyl acetate permeability can be performed by the method described in examples.
The copolymer of the present invention can be produced by a polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization, or bulk polymerization. As the polymerization method, emulsion polymerization or suspension polymerization is preferable. In these polymerizations, the conditions such as temperature and pressure, polymerization initiator, and other additives may be appropriately set according to the composition and amount of the copolymer.
As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.
The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, and the following are exemplified as typical examples:
dialkyl peroxycarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and di-2-ethoxyethyl peroxydicarbonate;
peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate;
dialkyl peroxides such as di-t-butyl peroxide;
Di [ fluoro (or fluoro chloro) acyl ] peroxides; etc.
As bis [ fluoro (or fluoro chloro) acyl groups]The peroxides include [ (RfCOO) & lt- & gt ]] 2 (Rf is perfluoroalkyl, omega-hydroperfluoroalkyl or fluorochloroalkyl).
Examples of the di [ fluoro (or fluorochloroacyl ] peroxides include di (ω -hydro-dodecafluoroheptanoyl) peroxide, di (ω -hydro-hexadecanoyl) peroxide, di (perfluoropropionyl) peroxide, di (perfluorobutanoyl) peroxide, di (perfluoropentanoyl) peroxide, di (perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (ω -chloro-hexafluorobutanoyl) peroxide, di (ω -chloro-dodecafluoroheptanoyl) peroxide, di (ω -chloro-dodecafluorooctanoyl) peroxide, ω -hydro-dodecafluoroheptanoyl-peroxide, ω -chloro-hexafluorobutanoyl-peroxide, ω -hydrododecafluoroheptanoyl-perfluorobutanoyl-peroxide, di (perfluoroheptanoyl) peroxide, di (dichloro-heptanoyl) peroxide, di (dichloro-dodecanoyl) peroxide, and di (dichloro-dodecanoyl) dodecanoyl peroxide.
The water-soluble radical polymerization initiator may be a known water-soluble peroxide, and examples thereof include ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, and percarbonic acid, potassium salts, sodium salts, disuccinic acid peroxide, and organic peroxides such as dipentaerythritol peroxide, t-butyl peroxymaleate, and t-butyl hydroperoxide. The reducing agent such as sulfite may be used in combination with the peroxide in an amount of 0.1 to 20 times the amount of the peroxide.
In the polymerization, a surfactant, a chain transfer agent and a solvent may be used, and conventionally known ones may be used, respectively.
As the surfactant, a known surfactant can be used, and for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, and the like can be used. Among them, the fluorinated anionic surfactant is preferable, and the fluorinated anionic surfactant having 4 to 20 carbon atoms, which may be linear or branched, and which may or may not contain ether-bonded oxygen (i.e., may have an oxygen atom interposed between carbon atoms), is more preferable. The amount of the surfactant to be added (relative to the polymerization water) is preferably 50ppm to 5000ppm.
Examples of the chain transfer agent include: hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatic compounds such as toluene and xylene; ketones such as acetone; acetate esters such as ethyl acetate and butyl acetate; alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and methyl chloride; etc. The amount of the chain transfer agent to be added may vary depending on the amount of the chain transfer constant of the compound to be used, and is usually in the range of 0.01 to 20% by mass relative to the polymerization solvent.
Examples of the solvent include water, a mixed solvent of water and alcohol, and the like.
In the suspension polymerization, a fluorine-based solvent may be used in addition to water. As the fluorine-based solvent, there may be mentionedTo give CH 3 CClF 2 、CH 3 CCl 2 F、CF 3 CF 2 CCl 2 H、CF 2 ClCF 2 Hydrochlorofluoroalkanes such as CFHCl; CF (compact flash) 2 ClCFClCF 2 CF 3 、CF 3 CFClCFClCF 3 Isophlorofluoroalkanes; CF (compact flash) 3 CFHCFHCF 2 CF 2 CF 3 、CF 2 HCF 2 CF 2 CF 2 CF 2 H、CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 Hydrofluoroalkanes such as H; CH (CH) 3 OC 2 F 5 、CH 3 OC 3 F 5 CF 3 CF 2 CH 2 OCHF 2 、CF 3 CHFCF 2 OCH 3 、CHF 2 CF 2 OCH 2 F、(CF 3 ) 2 CHCF 2 OCH 3 、CF 3 CF 2 CH 2 OCH 2 CHF 2 、CF 3 CHFCF 2 OCH 2 CF 3 Isohydrofluoroethers; perfluorocyclobutane, CF 3 CF 2 CF 2 CF 3 、CF 3 CF 2 CF 2 CF 2 CF 3 、CF 3 CF 2 CF 2 CF 2 CF 2 CF 3 Among them, perfluoroalkanes are preferable. The amount of the fluorine-based solvent to be used is preferably 10 to 100% by mass based on the aqueous medium in view of suspension property and economy.
The polymerization temperature is not particularly limited, and may be 0 to 100 ℃. The polymerization pressure is appropriately determined depending on the kind and amount of the solvent used, the vapor pressure, the polymerization temperature, and other polymerization conditions, and may be generally 0 to 9.8MPaG.
When an aqueous dispersion containing a copolymer is obtained by polymerization, the copolymer contained in the aqueous dispersion can be precipitated, washed, and dried to recover the copolymer. In addition, in the case where the copolymer is obtained as a slurry by polymerization, the copolymer can be recovered by taking out the slurry from the reaction vessel, washing it, and drying it. The copolymer can be recovered in the form of a powder by drying.
The copolymer obtained by polymerization may be molded into pellets. The molding method for molding the pellets is not particularly limited, and conventionally known methods can be used. For example, a method of melt-extruding a copolymer using a single screw extruder, a twin screw extruder, or a tandem extruder, cutting the copolymer into a predetermined length, and molding the copolymer into pellets, and the like can be mentioned. The extrusion temperature at the time of melt extrusion is required to be changed depending on the melt viscosity of the copolymer and the production method, and is preferably from +20℃to +140℃of the melting point of the copolymer. The method of cutting the copolymer is not particularly limited, and conventionally known methods such as a wire cutting method, a thermal cutting method, an underwater cutting method, and a sheet cutting method can be employed. The volatile components in the pellets may also be removed by heating the resulting pellets (degassing treatment). The obtained pellets may be treated by contacting them with warm water at 30 to 200 ℃, steam at 100 to 200 ℃ or hot air at 40 to 200 ℃.
The copolymer obtained by polymerization may also be subjected to a fluorination treatment. The fluorination treatment may be performed by contacting the copolymer that has not been subjected to the fluorination treatment with a fluorine-containing compound. By fluorination treatment, the-COOH, -COOCH-of the copolymer can be obtained 3 、-CH 2 OH、-COF、-CF＝CF 2 、-CONH 2 Isothermally labile functional groups and relatively thermally stable-CF 2 Conversion of functional groups such as H to extremely thermally stable-CF 3 . As a result, the-COOH, -COOCH-of the copolymer can be used 3 、-CH 2 OH、-COF、-CF＝CF 2 、-CONH 2 and-CF 2 The total number of H (the number of functional groups) is easily adjusted to be within the above-mentioned range.
The fluorine-containing compound is not particularly limited, and examples thereof include a fluorine radical source that generates a fluorine radical under the fluorination treatment conditions. As the fluorine radical source, F may be mentioned 2 Gas, coF 3 、AgF 2 、UF 6 、OF 2 、N 2 F 2 、CF 3 OF, fluorinated halogens (e.g. IF 5 、ClF 3 ) Etc.
F 2 Gas and its preparation methodThe concentration of the iso-fluorine radical source may be 100%, but from the viewpoint of safety, it is preferably used by mixing with an inert gas and diluting it to 5 to 50% by mass, more preferably 15 to 30% by mass. The inert gas may be nitrogen, helium, argon, or the like, and nitrogen is preferable from the viewpoint of economy.
The conditions of the fluorination treatment are not particularly limited, and the copolymer in a molten state may be brought into contact with the fluorine-containing compound, but may be usually conducted at a temperature of 20 to 240℃and more preferably 100 to 220℃below the melting point of the copolymer. The fluorination treatment is generally carried out for 1 to 30 hours, preferably 5 to 25 hours. The fluorination treatment preferably involves reacting the copolymer which has not been subjected to the fluorination treatment with fluorine gas (F 2 Gas) contact.
The copolymer of the present invention may be mixed with other components as needed to obtain a composition. Examples of the other components include fillers, plasticizers, processing aids, mold release agents, pigments, flame retardants, lubricants, light stabilizers, weather stabilizers, conductive agents, antistatic agents, ultraviolet absorbers, antioxidants, foaming agents, perfumes, oils, softeners, dehydrofluorination agents, and the like.
Examples of the filler include silica, kaolin, clay, organized clay, talc, mica, alumina, calcium carbonate, calcium terephthalate, titanium oxide, calcium phosphate, calcium fluoride, lithium fluoride, crosslinked polystyrene, potassium titanate, carbon, boron nitride, carbon nanotubes, and glass fibers. Examples of the conductive agent include carbon black. Examples of the plasticizer include dioctyl phthalate and pentaerythritol. Examples of the processing aid include carnauba wax, sulfone compound, low molecular weight polyethylene, and fluorine-based aid. Examples of the dehydrofluorination agent include organic onium and amidines.
As the other components, other polymers than the above copolymers may be used. Examples of the other polymer include a fluororesin other than the above copolymer, a fluororubber, a nonfluorinated polymer, and the like.
The method for producing the composition includes: a method of dry-mixing the copolymer with other components; a method in which the copolymer and other components are mixed in advance by a mixer, and then melt-kneaded by a kneader, a melt extruder, or the like; etc.
The copolymer or the composition of the present invention can be used as a processing aid, a molding material, or the like, and is preferably used as a molding material. Aqueous dispersions, solutions, suspensions, and copolymer/solvent systems of the copolymers of the present invention may also be utilized, which may be applied as coatings or used for encapsulation, impregnation, film casting. However, the copolymer of the present invention is preferably used as the molding material because it has the above-mentioned characteristics.
The copolymer of the present invention or the above composition may be molded to obtain a molded article.
The method for molding the copolymer or the composition is not particularly limited, and examples thereof include injection molding, extrusion molding, compression molding, blow molding, transfer molding, rotational molding, and roll lining molding. Among the molding methods, extrusion molding, compression molding or transfer molding is preferable, extrusion molding or transfer molding is more preferable, and extrusion molding is further preferable, since a molded article can be produced with high productivity. That is, the molded article is preferably an extrusion molded article, a compression molded article, an injection molded article or a transfer molded article, and more preferably an extrusion molded article or a transfer molded article, and even more preferably an extrusion molded article, because it can be produced at high productivity. The copolymer of the present invention can be molded by extrusion molding or transfer molding to obtain a beautiful molded article.
Examples of molded articles containing the copolymer of the present invention include nuts, bolts, joints, films, bottles, gaskets, wire coatings, pipes, hoses, pipes, valves, sheets, seals, gaskets, tanks, rolls, containers, taps, connectors, filter housings, filter covers, flow meters, pumps, wafer carriers, wafer cassettes, and the like.
The copolymer, the composition or the molded article of the present invention can be used for the following purposes, for example.
A film for packaging food, a lining material for a fluid transfer line used in a food manufacturing process, a gasket, a sealing material, a fluid transfer member for a food manufacturing apparatus such as a sheet;
reagent delivery members such as plugs for chemicals, packaging films, liners for fluid delivery lines used in chemical manufacturing processes, gaskets, seals, sheets, etc.;
inner lining members of reagent tanks and piping of chemical equipment and semiconductor factories;
fuel delivery members such as hoses and sealing materials used in AT devices of automobiles such as O (square) rings/tubes/gaskets, valve core materials, hoses and sealing materials used in fuel systems and peripheral devices of automobiles;
flange gaskets, shaft seals, stem seals, sealing materials, brake hoses for automobiles such as hoses, air conditioning hoses, radiator hoses, wire coating materials, and other automobile components used in engines and peripheral devices of automobiles;
A reagent transporting member for a semiconductor device, such as an O-ring, a tube, a gasket, a valve body material, a hose, a sealing material, a roller, a gasket, a diaphragm, and a joint of a semiconductor manufacturing apparatus;
coating and ink members such as coating rolls, hoses, tubes, ink containers for coating equipment;
pipes such as pipes for food and drink, hoses, belts, gaskets, joints, and other food and drink conveying members, food packaging materials, and glass cooking devices;
a waste liquid transporting member such as a tube or a hose for transporting waste liquid;
high-temperature liquid transmission members such as pipes and hoses for high-temperature liquid transmission;
a member for steam piping such as a pipe or a hose for steam piping;
a corrosion-resistant belt for piping such as a belt wound around piping such as a deck of a ship;
various coating materials such as a wire coating material, an optical fiber coating material, a transparent surface coating material provided on a light incidence side surface of a photovoltaic element of a solar cell, and a back surface agent;
sliding components such as diaphragms and various gaskets of the diaphragm pump;
weather resistant covers for agricultural films, various roofing materials, sidewalls, and the like;
glass-like coating materials such as interior materials and incombustible fire-resistant safety glass used in the construction field;
Lining materials such as laminated steel sheets used in the field of home appliances and the like.
Further examples of the fuel delivery member used in the fuel system of the automobile include a fuel hose, a filler hose, and an evaporator hose. The fuel delivery member can be used as a fuel delivery member for acid-resistant gasoline, alcohol-resistant fuel, and fuel to which a gasoline additive such as methyl t-butyl ether or amine-resistant additive is added.
The above-mentioned chemical stopper and packaging film have excellent chemical resistance to acids and the like. The reagent transporting member may be an anti-corrosive tape wound around a piping of a chemical apparatus.
Examples of the molded article include radiator chambers, reagent tanks, bellows, separators, rolls, gasoline tanks, waste liquid transport containers, high-temperature liquid transport containers, fishery and fish farming tanks, and the like of automobiles.
Further, examples of the molded article include a bumper, a door trim, an instrument panel, a food processing device, a cooking machine, water/oil resistant glass, a lighting-related instrument, an indication board and a housing for OA instruments, an electric lighting sign, a display screen, a liquid crystal display, a cellular phone, a printer chassis, electric and electronic parts, sundries, a dustbin, a bathtub, an entire bathroom, a ventilator, a lighting frame, and the like.
The molded article containing the copolymer of the present invention is extremely excellent in transparency, small in compression set, high in tensile strength at high temperature, low in air permeability, low in reagent permeability, excellent in rigidity at high temperature of 110 ℃, creep resistance, abrasion resistance and low in carbon dioxide permeability, and is not liable to dissolve out fluorine ions into a reagent such as hydrogen peroxide, and therefore can be suitably used for nuts, bolts, joints, gaskets, valves, taps, connectors, filter housings, filter covers, flow meters, pumps, and the like. Among them, the present invention can be suitably used as a piping member (in particular, a valve or a joint) used for transporting a reagent or a flowmeter case having a flow path for a reagent in a flowmeter. The piping member and the flowmeter case of the present invention are extremely excellent in transparency, have a small compression set, and have high tensile strength at high temperatures. Therefore, the piping member and the flowmeter case of the present invention are excellent in visibility, and particularly in the flowmeter case, the float inside can be easily observed by visual observation, a camera, or the like, and even if the stress is repeatedly applied according to the start of the flow of the reagent, the stop of the flow, or the flow rate change, the flow rate is not easily damaged.
The molded article containing the copolymer of the present invention is extremely excellent in transparency, small in compression set, high in tensile strength at high temperature, low in air permeability, low in reagent permeability, excellent in rigidity at high temperature of 110 ℃, creep resistance, abrasion resistance and low in carbon dioxide permeability, and is not liable to dissolve out fluorine ions into a reagent such as hydrogen peroxide, and therefore can be suitably used as a compressed member such as a gasket or a gasket. The compressed member of the present invention may be a gasket or a seal. The gasket or the sealing gasket of the invention has extremely excellent transparency, small compression set, high tensile strength at high temperature, low air permeability, low reagent permeability, excellent rigidity at high temperature of 110 ℃, excellent creep resistance, excellent wear resistance and excellent carbon dioxide low permeability, and is not easy to dissolve out fluoride ions into reagents such as hydrogen peroxide. Further, the compressed member of the present invention is excellent in low permeability of carbon dioxide, and therefore can be suitably used as a sealing member for preventing leakage of a carbon dioxide refrigerant.
The compressed member of the present invention exhibits excellent compression set resistance even when deformed at a high compression set rate. The compressed member of the present invention can be used in a state of being compressed and deformed at a compression deformation rate of 10% or more, and can be used in a state of being compressed and deformed at a compression deformation rate of 20% or more or 25% or more. By deforming the compressed member of the present invention at such a high compression set, a certain rebound resilience can be maintained for a long period of time, and sealing properties and insulating properties can be maintained for a long period of time.
The compression set is the compression set at the portion where the compression set is the largest when the compressed member is compressed. For example, when a flat compressed member is used in a state compressed in the thickness direction, the compression set is the compression set in the thickness direction. For example, when the member is used in a state where only a part of the member is compressed, the member is a part having the highest compression set among compression sets of the compressed part.
The size and shape of the compressed member of the present invention may be appropriately set according to the application, and are not particularly limited. The compressed member of the present invention may be annular in shape, for example. The compressed member of the present invention may have a circular shape, an elliptical shape, a quadrangular shape with rounded corners, or the like in a plan view, and may have a through hole in a central portion thereof.
The compressed member of the present invention is preferably used as a member for constituting a nonaqueous electrolyte battery. The compressed member of the present invention is particularly suitable as a member used in a state of being in contact with a nonaqueous electrolyte in a nonaqueous electrolyte battery. That is, the compressed member of the present invention may have a liquid receiving surface of the nonaqueous electrolyte in the nonaqueous electrolyte battery.
The nonaqueous electrolyte battery is not particularly limited as long as it is a battery provided with a nonaqueous electrolyte, and examples thereof include a lithium ion secondary battery and a lithium ion capacitor. Further, as a member constituting the nonaqueous electrolyte battery, a sealing member, an insulating member, and the like can be given.
The nonaqueous electrolyte is not particularly limited, and 1 or 2 or more of known solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, dimethyl carbonate, diethyl carbonate, and methylethyl carbonate may be used. The nonaqueous electrolyte battery may further include an electrolyte. The electrolyte is not particularly limited, and LiClO may be used 4 、LiAsF 6 、LiPF 6 、LiBF 4 、LiCl、LiBr、CH 3 SO 3 Li、CF 3 SO 3 Li, cesium carbonate, and the like.
The compressed member of the present invention can be preferably used as a sealing member such as a gasket or a packing, or an insulating member such as an insulating gasket or an insulating packing, for example. The sealing member is used to prevent leakage of liquid or gas or intrusion of liquid or gas from the outside. The insulating member is a member used for electrical insulation. The compressed member of the present invention may be a member used for both sealing and insulation purposes.
The compressed member of the present invention has a small compression set and high tensile strength at high temperature, and therefore can be suitably used as a sealing member for a nonaqueous electrolyte battery or an insulating member for a nonaqueous electrolyte battery. For example, in the case of charging a battery such as a nonaqueous electrolyte secondary battery, the temperature of the battery may be temporarily 40 ℃ or higher, in particular, temporarily 150 ℃ or higher. The compressed member of the present invention is used in a battery such as a nonaqueous electrolyte secondary battery by deforming at a high compression deformation rate even at a high temperature, and does not deteriorate high rebound resilience even when it is in contact with a nonaqueous electrolyte at a high temperature. Therefore, in the case where the compressed member of the present invention is used as a sealing member, it has excellent sealing properties and can maintain the sealing properties for a long period of time even at high temperatures. In addition, the compressed member of the present invention has excellent insulating properties because it contains the copolymer. Therefore, when the compressed member of the present invention is used as an insulating member, the compressed member is firmly adhered to 2 or more conductive members, and short-circuiting can be prevented for a long period of time.
The copolymer of the present invention can be suitably used as a material for forming an electric wire coating.
The coated wire comprises a core wire and a coating layer provided around the core wire and containing the copolymer of the present invention. For example, an extrusion molded article obtained by melt-extruding the copolymer of the present invention on a core wire may be used as the coating layer. The covered wire is suitable for a LAN Cable (ethernet Cable), a high-frequency transmission Cable, a flat Cable, a heat-resistant Cable, and the like, and is suitable for a transmission Cable such as a LAN Cable (ethernet Cable), a high-frequency transmission Cable, and the like.
As the material of the core wire, for example, a metal conductor material such as copper or aluminum can be used. The core wire preferably has a diameter of 0.02mm to 3mm. The diameter of the core wire is more preferably 0.04mm or more, still more preferably 0.05mm or more, and particularly preferably 0.1mm or more. The diameter of the core wire is more preferably 2mm or less.
Specific examples of the core wire include AWG (American wire gauge) -46 (solid copper wire with a diameter of 40 μm), AWG-26 (solid copper wire with a diameter of 404 μm), AWG-24 (solid copper wire with a diameter of 510 μm), AWG-22 (solid copper wire with a diameter of 635 μm), and the like.
The thickness of the coating layer is preferably 0.1mm to 3.0mm. The thickness of the coating layer is also preferably 2.0mm or less.
As the high-frequency transmission cable, a coaxial cable may be mentioned. The coaxial cable generally has a structure in which an inner conductor, an insulating coating layer, an outer conductor layer, and a protective coating layer are laminated in this order from a core portion to an outer peripheral portion. The molded article containing the copolymer of the present invention can be suitably used as an insulating coating layer containing the copolymer. The thickness of each layer in the above-described structure is not particularly limited, and in general, the diameter of the inner conductor is about 0.1mm to 3mm, the thickness of the insulating coating layer is about 0.3mm to 3mm, the thickness of the outer conductor layer is about 0.5mm to 10mm, and the thickness of the protective coating layer is about 0.5mm to 2mm.
The coating may contain bubbles, which are preferably uniformly distributed in the coating.
The average cell diameter of the bubbles is not limited, and is, for example, preferably 60 μm or less, more preferably 45 μm or less, further preferably 35 μm or less, further preferably 30 μm or less, particularly preferably 25 μm or less, and particularly preferably 23 μm or less. The average cell diameter is preferably 0.1 μm or more, more preferably 1 μm or more. The average bubble diameter can be obtained by obtaining an electron microscope image of a wire cross section, calculating the diameter of each bubble by image processing, and averaging.
The foaming ratio of the coating layer may be 20% or more. More preferably 30% or more, still more preferably 33% or more, still more preferably 35% or more. The upper limit is not particularly limited, and is, for example, 80%. The upper limit of the foaming ratio may be 60%. The foaming ratio was obtained as ((specific gravity of wire coating material-specific gravity of coating layer)/specific gravity of wire coating material) ×100. The foaming ratio can be appropriately adjusted according to the application by, for example, adjusting the amount of gas inserted into an extruder to be described later, or by selecting the type of dissolved gas.
The coated wire may further include a different layer (outer layer) around the coating layer, and a different layer may be provided between the core wire and the coating layer. When the coating layer contains bubbles, the electric wire of the present invention may have a 2-layer structure (skin-foam) in which a non-foam layer is interposed between the core wire and the coating layer; a 2-layer structure (foam-skin) having a non-foam layer coated on the outer layer; further, the outer layer of the skin-foam was covered with a 3-layer structure (skin-foam-skin) of a non-foam layer. The non-expanded layer is not particularly limited, and may be a resin layer composed of a polyolefin resin such as TFE/HFP copolymer, TFE/PAVE copolymer, TFE/ethylene copolymer, vinylidene fluoride polymer, polyethylene [ PE ], or a resin such as polyvinyl chloride [ PVC ].
The coated wire can be produced, for example, by heating the copolymer using an extruder, extruding the copolymer onto the core wire in a molten state, and forming a coating layer.
In forming the coating layer, the gas may be introduced into the copolymer in a molten state by heating the copolymer, thereby forming the coating layer containing bubbles. As the gas, for example, a gas such as difluoromethane, nitrogen, carbon dioxide, or the like, or a mixture of the above gases can be used. The gas may be introduced into the heated copolymer as a pressurized gas or may be produced by mixing a chemical blowing agent into the copolymer. The gas is dissolved in the copolymer in a molten state.
In addition, the copolymer of the present invention can be suitably used as a material for a product for high-frequency signal transmission.
The product for transmitting a high-frequency signal is not particularly limited as long as it is a product for transmitting a high-frequency signal, and examples thereof include (1) a molded plate such as an insulating plate for a high-frequency circuit, an insulating material for a connecting member, and a printed wiring board, (2) a molded body such as a base or a radome for a high-frequency vacuum tube, and (3) a covered wire such as a coaxial cable or a LAN cable. The high-frequency signal transmission product can be suitably used for satellite communication equipment, mobile telephone base stations, and other equipment utilizing microwaves, particularly microwaves of 3GHz to 30 GHz.
In the above-mentioned high-frequency signal transmission product, the copolymer of the present invention is suitable for use as an insulator in view of low dielectric loss tangent.
The molded plate (1) is preferably a printed wiring board in terms of obtaining good electrical characteristics. The printed wiring board is not particularly limited, and examples thereof include printed wiring boards for electronic circuits of mobile phones, various computers, communication devices, and the like. As the molded article (2), a radome is preferable in terms of low dielectric loss.
The copolymer of the present invention is not easily deformed even in a molten state, can easily obtain a thick sheet having a uniform thickness, and further, the obtained molded article is excellent in transparency, is not easily deformed even at a high temperature, is excellent in tensile strength at a high temperature, is excellent in air low permeability, reagent low permeability, rigidity at a high temperature of 110 ℃, creep resistance, abrasion resistance and carbon dioxide low permeability, and is not easily eluted with fluorine ions into a reagent such as hydrogen peroxide, and therefore, can be suitably used as a film or sheet.
The film of the present invention is useful as a release film. The release film can be produced by molding the copolymer of the present invention by melt extrusion molding, calender molding, press molding, casting molding, or the like. From the viewpoint of obtaining a uniform film, a release film can be produced by melt extrusion molding.
The film of the present invention can be applied to the surface of a roll used in an OA apparatus. The copolymer of the present invention can be molded into a desired shape by extrusion molding, compression molding, press molding, etc., and formed into a sheet, film, tube shape, etc., for use as a surface material for OA equipment rolls, OA equipment belts, etc. In particular, a thick sheet and a large pipe can be produced by a melt extrusion molding method.
The copolymer of the present invention is not easily deformed even in a molten state, and therefore a large-diameter tube with high dimensional accuracy can be easily obtained by an extrusion molding method. Further, the obtained molded article is extremely excellent in transparency, small in compression set, high in tensile strength at high temperature, low in air permeability, low in reagent permeability, excellent in rigidity at high temperature of 110 ℃, creep resistance, abrasion resistance and low in carbon dioxide permeability, and is not liable to dissolve out fluorine ions into a reagent such as hydrogen peroxide. Thus, the fluorocopolymer of the invention can be suitably used for a tube (tube) or a pipe (pipe). The fluorocopolymer-containing tube of the present invention can be produced with high productivity even when the diameter is large, and also has a beautiful shape even when the thickness is large, and is extremely excellent in transparency, small in compression set, high in tensile strength at high temperature, low in air permeability, low in reagent permeability, excellent in rigidity at high temperature of 110 ℃, creep resistance, abrasion resistance and low in carbon dioxide permeability, and is not liable to dissolve out fluorine ions into a reagent such as hydrogen peroxide.
The molded article containing the copolymer of the present invention is extremely excellent in transparency, small in compression set, high in tensile strength at high temperature, low in air permeability, low in reagent permeability, excellent in rigidity at high temperature of 110 ℃, creep resistance, abrasion resistance and low in carbon dioxide permeability, and is not liable to dissolve out fluorine ions into a reagent such as hydrogen peroxide, and therefore can be suitably used as a bottle. The bottle of the present invention can easily visually confirm the content, and is not easily damaged in use.
While the embodiments have been described above, it will be understood that various changes in form and details may be made therein without departing from the spirit and scope of the claims.
Examples
Next, embodiments of the present invention will be described with reference to examples, but the present invention is not limited to the examples.
The values of the examples were measured by the following methods.
(content of monomer units)
The content of each monomer unit was measured by an NMR analyzer (for example, AVANCE300 high temperature probe manufactured by Bruker Biospin Co.).
(melt flow Rate (MFR))
The mass (G/10 minutes) of the polymer flowing out from a nozzle having an inner diameter of 2.1mm and a length of 8mm per 10 minutes was determined by using a melt index analyzer G-01 (manufactured by Toyo Seisakusho-Sho Co., ltd.) at 372℃under a 5kg load in accordance with ASTM D1238.
(number of functional groups)
The pellets of the copolymer were cold-molded to prepare a film having a thickness of 0.25mm to 0.3 mm. The film was scanned 40 times by a fourier transform infrared Spectrum analyzer [ FT-IR (Spectrum One, manufactured by PerkinElmer corporation) ] to obtain an infrared absorption Spectrum, and a differential Spectrum from the fully fluorinated background Spectrum having no functional group was obtained. The number N of functional groups per 1×106 carbon atoms in the sample is calculated from the absorption peak of the specific functional group shown by the differential spectrum according to the following formula (a).
N＝I×K/t(A)
I: absorbance of light
K: correction coefficient
t: film thickness (mm)
For reference, regarding the functional groups in the present invention, the absorption frequency, molar absorptivity, and correction coefficient are shown in table 2. The molar absorptivity was determined from FT-IR measurement data of the low molecular weight model compound.
TABLE 2
TABLE 2
(melting point)
The melting point was determined from the melting curve peak generated during the 2 nd heating process by performing the 1 st heating from 200℃to 350℃at a heating rate of 10℃per minute using a differential scanning calorimeter (trade name: X-DSC7000, manufactured by Hitachi High-Tech Science Co., ltd.), then cooling from 350℃to 200℃at a cooling rate of 10℃per minute, and performing the 2 nd heating from 200℃to 350℃again at a heating rate of 10℃per minute.
Example 1
After adding 26.6L of pure water to a 174L-volume autoclave and sufficiently performing nitrogen substitution, 30.4kg of perfluorocyclobutane and 1.76kg of perfluoro (propyl vinyl ether) (PPVE) were added, and the temperature in the system was kept at 35℃and the stirring speed was kept at 200rpm. Subsequently, tetrafluoroethylene (TFE) was introduced under pressure to 0.58MPa, and then 0.010kg of a 50% methanol solution of di-n-propyl peroxydicarbonate was introduced to start polymerization. Since the pressure in the system decreased as polymerization proceeded, TFE was continuously fed so that the pressure became constant, and 0.058kg of PPVE was added per 1kg of TFE fed, and polymerization was continued for 6 hours. TFE was discharged, and after the autoclave was allowed to return to atmospheric pressure, the obtained reaction product was washed with water and dried to obtain 15kg of powder.
The obtained powder was melt-extruded at 360℃by a screw extruder (trade name: PCM46, manufactured by Mitsui Co., ltd.) to obtain pellets of TFE/PPVE copolymer. Using the pellets obtained, the PPVE content was determined by the method described above. The results are shown in Table 3.
The obtained pellets were placed in a vacuum vibration type reaction apparatus VVD-30 (manufactured by Dachuan origin Co., ltd.) and heated to 210 ℃. After evacuation, N for introduction 2 F gas dilution to 20 vol% 2 The gas is brought to atmospheric pressure. From F 2 After 0.5 hour from the time of gas introduction, the mixture was once evacuated and F was introduced again 2 And (3) gas. After 0.5 hour, the mixture was again evacuated and F was introduced again 2 And (3) gas. Thereafter, F is as described above 2 The gas introduction and evacuation operations were continued for 1 time within 1 hour, and the reaction was carried out at 210℃for 10 hours. After the reaction, the inside of the reactor was fully replaced with N 2 And (3) ending the fluorination reaction by using the gas. Using the fluorinated pellets, various physical properties were measured by the above-described method. The results are shown in Table 3.
Example 2
Fluorinated pellets were obtained in the same manner as in example 1 except that PPVE was changed to 2.12kg, PPVE was changed to 0.068kg added per 1kg of TFE supplied, and the polymerization time was changed to 7 hours. The results are shown in Table 3.
Example 3
After filling a 174L autoclave with 51.8L of pure water and sufficiently replacing the pure water with nitrogen, 40.9kg of perfluorocyclobutane, 3.01kg of perfluoro (propyl vinyl ether) (PPVE) and 0.92kg of methanol were charged, the temperature in the system was kept at 35℃and the stirring speed was kept at 200rpm. Subsequently, tetrafluoroethylene (TFE) was introduced under pressure to 0.64MPa, and then 0.013kg of a 50% methanol solution of di-n-propyl peroxydicarbonate was introduced to start polymerization. Since the pressure in the system decreased as polymerization proceeded, TFE was continuously fed so that the pressure became constant, and 0.063kg of PPVE was additionally fed per 1kg of TFE fed. When the additional amount of TFE fed reached 40.9kg, polymerization was terminated. Unreacted TFE was discharged, the pressure in the autoclave was returned to the atmospheric pressure, and the obtained reaction product was washed with water and dried to obtain 43.5kg of a powder.
Using the obtained powder, a fluorination reaction was performed in the same manner as in example 1 to obtain fluorinated pellets. The results are shown in Table 3.
Comparative example 1
After adding 26.6L of pure water to a 174L-volume autoclave and sufficiently performing nitrogen substitution, 30.4kg of perfluorocyclobutane, 1.32kg of perfluoro (propyl vinyl ether) (PPVE) and 0.06kg of methanol were added, and the temperature in the system was kept at 35℃and the stirring speed was kept at 200rpm. Subsequently, tetrafluoroethylene (TFE) was introduced under pressure to 0.58MPa, and then 0.010kg of a 50% methanol solution of di-n-propyl peroxydicarbonate was introduced to start polymerization. Since the pressure in the system decreased as polymerization proceeded, TFE was continuously fed so that the pressure became constant, and 0.046kg of PPVE was added to each 1kg of TFE fed, and polymerization was continued for 5.5 hours. TFE was discharged, and after the autoclave was allowed to return to atmospheric pressure, the obtained reaction product was washed with water and dried to obtain 15kg of powder.
The obtained powder was melt-extruded at 360℃by a screw extruder (trade name: PCM46, manufactured by Mitsui Co., ltd.) to obtain pellets of TFE/PPVE copolymer. Using the pellets obtained, the PPVE content was determined by the method described above. The results are shown in Table 3.
The obtained pellets were placed in a vacuum vibration type reaction apparatus VVD-30 (manufactured by Dachuan origin Co., ltd.) and heated to 210 ℃. After the vacuum is pumped out, the vacuum pump is connected with the vacuum pump, N for introduction 2 F gas dilution to 20 vol% 2 The gas is brought to atmospheric pressure. From F 2 After 0.5 hour from the time of gas introduction, the mixture was once evacuated and F was introduced again 2 And (3) gas. After 0.5 hour, the mixture was again evacuated and F was introduced again 2 And (3) gas. Thereafter, F is as described above 2 The gas introduction and evacuation operations were continued for 1 time within 1 hour, and the reaction was carried out at 210℃for 10 hours. After the reaction, the inside of the reactor was fully replaced with N 2 And (3) ending the fluorination reaction by using the gas. Using the fluorinated pellets, various physical properties were measured by the above-described method. The results are shown in Table 3.
Comparative example 2
Fluorinated pellets were obtained in the same manner as in comparative example 1, except that PPVE was changed to 1.72kg, methanol was changed to 0.08kg, PPVE was changed to 0.057kg added per 1kg of TFE supplied, and the polymerization time was changed to 6.5 hours. The results are shown in Table 3.
Comparative example 3
Fluorinated pellets were obtained in the same manner as in comparative example 1, except that PPVE was changed to 2.12kg, methanol was changed to 0.03kg, PPVE was changed to 0.068kg added per 1kg of TFE supplied, and the polymerization time was changed to 7 hours. The results are shown in Table 3.
Comparative example 4
An unfluorinated pellet was obtained in the same manner as in example 1, except that PPVE was changed to 2.08kg, PPVE was changed to 0.067kg added per 1kg of TFE fed, and the polymerization time was changed to 7 hours. The results are shown in Table 3.
Comparative example 5
After filling a 174L-volume autoclave with 51.8L of pure water and sufficiently replacing the pure water with nitrogen, 40.9kg of perfluorocyclobutane and 3.33kg of perfluoro (propyl vinyl ether) (PPVE) were charged, the temperature in the system was kept at 35℃and the stirring speed was kept at 200rpm. Subsequently, tetrafluoroethylene (TFE) was introduced under pressure to 0.64MPa, and then 0.004kg of a 50% methanol solution of di-n-propyl peroxydicarbonate was introduced to start polymerization. Since the pressure in the system decreased as polymerization proceeded, TFE was continuously fed so that the pressure became constant, and 0.068kg of PPVE was additionally fed per 1kg of TFE fed. When the additional amount of TFE fed reached 40.9kg, polymerization was terminated. Unreacted TFE was discharged, and after the autoclave was allowed to return to atmospheric pressure, the obtained reaction product was washed with water and dried to obtain 41.0kg of powder.
Using the obtained powder, a fluorination reaction was performed in the same manner as in example 1 to obtain fluorinated pellets. The results are shown in Table 3.
TABLE 3
TABLE 3 Table 3
The expression "< 6" in Table 3 means that the number of functional groups is less than 6.
Next, using the obtained pellets, the following characteristics were evaluated. The results are shown in Table 4.
(haze value)
Using the pellets and the hot press molding machine, a sheet having a thickness of about 1.0mm was produced. The sheet was immersed in a quartz dish containing pure water according to JIS K7136 using a haze meter (trade name: NDH7000SP, manufactured by Nippon electric color industry Co., ltd.), and the haze value was measured.
(compression set (CS))
Compression set was measured according to ASTM D395 or JIS K6262: 2013.
About 2g of the pellets were put into a mold (inner diameter: 13mm, height: 38 mm), melted at 370℃for 30 minutes by a hot plate press, and then water-cooled while being pressurized with a pressure of 0.2MPa (resin pressure), to prepare a molded article having a height of about 8 mm. Thereafter, the obtained molded article was cut to prepare a test piece having an outer diameter of 13mm and a height of 6 mm. The test piece thus produced was compressed to a compression set of 50% at normal temperature (i.e., a test piece having a height of 6mm was compressed to a height of 3 mm) using a compression device.
Then, the compressed test piece was left standing in an electric furnace at 65℃for 72 hours while being fixed to a compression device. The compression device was taken out of the electric furnace, cooled to room temperature, and then the test piece was taken out. After the recovered test piece was left at room temperature for 30 minutes, the height of the recovered test piece was measured, and the compression set was determined by the following formula.
Compression set (%) = (t) 0 －t 2 )/(t 0 －t 1 )×100
t 0 : original height (mm) of test piece
t 1 : height of spacer (mm)
t 2 : height (mm) of test piece removed from compression device
In the above test, t 0 ＝6mm，t 1 ＝3mm。
(tensile Strength at 150 ℃ C. (TS))
Tensile strength at 150℃was measured according to ASTM D638.
The molded article having a high tensile strength at 150℃is excellent in pressure resistance.
(sheet formability)
UsingThe pellets were molded into pellets by an extruder (manufactured by the well manufacturing company) and a T-die. Extrusion molding conditions were as follows.
a) Coiling speed: 0.1 m/min
b) Roller temperature: 120 DEG C
c) Film width: 70mm of
d) Thickness: 1.00mm
e) Extrusion conditions:
single screw extrusion moulding machine with cylinder axis diameter=14 mm and L/d=20
Set temperature of extruder: barrel C-1 (330 ℃ C.), barrel C-2 (350 ℃ C.), barrel C-3 (370 ℃ C.), T-die head (380 ℃ C.)
Extrusion of the copolymer was continued until the copolymer was stably extruded from the molding machine. Subsequently, the copolymer was extrusion molded to prepare a sheet (width: 70 mm) having a length of 3m or more so as to have a thickness of 1.00 mm. From the end of the obtained sheet, a portion of 2 to 3m was cut, and a test piece (length 1m, width 70 mm) for measuring the thickness fluctuation was produced. The thickness of the center point in the width direction of the end portion of the produced sheet and the total of 3 points of 2 points separated from the center point by 25mm in the width direction were measured. Further, the thickness of a total of 9 points, which were 3 center points arranged at an interval of 25cm from the center point in the width direction of the end portion of the sheet toward the other end portion and 2 points separated from each center point by 25mm in the width direction, was measured. Of the total of 12 measured values, the case where the number of measured values out of the range of ±10% of 1.00mm is 1 or less was defined as o, and the case where the number of measured values out of the range of ±10% of 1.00mm was 2 or more was defined as x.
(tube formability)
UsingThe pellets were extruded by an extruder (field plastic machine), and a pipe having an outer diameter of 10.0mm and a wall thickness of 1.0mm was obtained. Extrusion molding conditions were as follows.
a) Die inside diameter: 25mm of
b) Mandrel outside diameter: 13mm of
c) Sizing die inner diameter: 10.5mm
d) Traction speed: 0.4 m/min
e) Outer diameter: 10.0mm
f) Wall thickness: 1.0mm
g) Extrusion conditions:
single screw extrusion moulding machine with cylinder shaft diameter=30 mm, L/d=22
Set temperature of extruder: barrel section C-1 (350 ℃ C.), barrel section C-2 (370 ℃ C.), barrel section C-3 (380 ℃ C.), head section H-1 (390 ℃ C.), die section D-2 (390 ℃ C.)
The obtained tube was observed and evaluated according to the following criteria. The appearance of the tube was visually confirmed.
O: good appearance
X: the cross section was not circular, and the appearance was poor due to flattening, uneven thickness, and the like.
(self-weight deformation test at melting)
A molded article having a diameter of 13mm and a height of about 6.5mm was produced using the pellets and a hot press molding machine. The obtained molded article was cut to prepare a test piece having a height of 6.3 mm. The test piece thus prepared was placed in a SUS dish, heated at 330℃for 30 minutes by an electric furnace, and then water-cooled together with the dish in which the test piece was placed. The diameter of the surface (bottom surface) of the test piece taken out in contact with the dish was measured with a vernier caliper, and the bottom area increase rate was calculated by the following formula.
Base area increase rate (%) = { test piece base area after heating (mm) 2 ) Test piece bottom area before heating (mm) 2 ) Bottom area of test piece before heat (mm) 2 )×100
The lower the base area increase rate means that the molded body is less likely to be deformed by its own weight when melted. The copolymer which provides a molded article having a low increase in the base area is excellent in the following aspects: even when a thick sheet or a large pipe is produced by molding the copolymer by extrusion molding, the molded article in a molten state is not easily deformed, and a molded article having a desired shape is obtained after cooling and solidification.
(abrasion test)
Using the pellets and a hot press molding machine, a sheet-like test piece having a thickness of about 0.2mm was produced, from which a 10 cm. Times.10 cm test piece was cut. The test piece thus prepared was fixed to a test stand of a taber abrasion tester (taber abrasion tester, model No.101, manufactured by An Tian refiner manufacturing company), and abrasion test was performed using the taber abrasion tester under conditions of a load of 500g, abrasion wheel CS-10 (20 revolutions ground with grinding paper # 240), and a rotation speed of 60 rpm. The weight of the test piece after 1000 revolutions was measured, and the test piece weight was further measured after 10000 revolutions with the same test piece. The abrasion loss was determined by the following formula.
Abrasion loss (mg) =m1-M2
M1: test piece weight after 1000 revolutions (mg)
M2: test piece weight after 10000 revolutions (mg)
(carbon dioxide permeability coefficient)
A sheet-like test piece having a thickness of about 0.1mm was produced using the pellets and a hot press molding machine. Using the obtained test piece, the test piece was prepared according to JIS K7126-1:2006, a differential pressure type gas permeameter (L100-5000 type gas permeameter),Manufactured by sysetch ilinois company), and carbon dioxide permeability was measured. Obtaining a permeation area of 50.24cm 2 The carbon dioxide permeability at a test temperature of 70℃and a test humidity of 0% RH. Using the obtained carbon dioxide permeation rate and the thickness of the test piece, the carbon dioxide permeation coefficient was calculated by the following formula.
Carbon dioxide permeability coefficient (cm) 3 ·mm/(m 2 ·24h·atm))＝GTR×d
GTR: carbon dioxide permeability (cm) 3 /(m 2 ·24h·atm))
d: test piece thickness (mm)
(air permeability coefficient)
A sheet-like test piece having a thickness of about 0.1mm was produced using the pellets and a hot press molding machine. Using the obtained test piece, the test piece was prepared according to JIS K7126-1:2006, air permeability was measured using a differential pressure type gas permeability meter (L100-5000 type gas permeability meter, manufactured by Systemech ilinois Co.). Obtaining a permeation area of 50.24cm 2 The air permeability at a test temperature of 70℃and a test humidity of 0% RH. Using the obtained air permeability and the test piece thickness, the air permeability coefficient was calculated by the following formula.
Air permeability coefficient (cm) 3 ·mm/(m 2 ·24h·atm))＝GTR×d
GTR: air permeability (cm) 3 /(m 2 ·24h·atm))
d: test piece thickness (mm)
(ethyl acetate permeability)
A sheet-like test piece having a thickness of about 0.1mm was produced using the pellets and a hot press molding machine. In a test cup (permeation area 12.56 cm) 2 ) 10g of ethyl acetate was added thereto, and the mixture was covered with a sheet-like test piece, and fastened and sealed with a PTFE gasket interposed therebetween. The sheet-like test piece was brought into contact with ethyl acetate, kept at a temperature of 60℃for 45 days, taken out, left at room temperature for 1 hour, and then the mass reduction was measured. The ethyl acetate permeability (g.cm/m) was determined by 2 )。
Ethyl acetate (g.cm/m) 2 ) =mass reduction (g) ×thickness (cm)/penetration of sheet test pieceArea of passage (m) 2 )
(110 ℃ C. Load deflection rate)
Using the pellets and a hot press molding machine, a sheet-like test piece having a thickness of about 4.2mm was produced, from which a test piece having a thickness of 80X 10mm was cut, and heated at 100℃for 20 hours by an electric furnace. The test was carried out using a thermal deformation tester (manufactured by An Tian refiner) according to the method described in JIS K-K7191, except for the test piece obtained, under conditions of a test temperature of 30 to 150 ℃, a temperature rising rate of 120 ℃/hr, a bending stress of 1.8MPa, and a flat-bed (flat-bed) method. The load deflection was obtained by the following method. The sheet having a small flexural modulus under load at 110 ℃ has excellent rigidity at a high temperature of 110 ℃.
Load deflection (%) =a2/a1×100
a1: thickness of test piece before test (mm)
a2: deflection (mm) at 110 DEG C
(evaluation of creep resistance)
Determination of creep resistance according to ASTM D395 or JIS K6262: 2013. A molded article having an outer diameter of 13mm and a height of 8mm was produced using pellets and a hot press molding machine. The obtained molded article was cut to prepare a test piece having an outer diameter of 13mm and a height of 6 mm. The test piece produced was compressed to a compression set of 25% at normal temperature using a compression device. The compressed test piece was left standing in an electric furnace at 80℃for 72 hours in a state of being fixed to a compression device. The compression device was taken out of the electric furnace, cooled to room temperature, and then the test piece was taken out. After the recovered test piece was left at room temperature for 30 minutes, the height of the recovered test piece was measured, and the recovery ratio was determined by the following formula.
Recovery ratio (%) = (t) 2 －t 1 )/t 3 ×100
t 1 : height of spacer (mm)
t 2 : height (mm) of test piece removed from compression device
t 3 : height after compression deformation (mm)
In the above test, t 1 ＝4.5mm，t 3 ＝1.5mm。
(Hydrogen peroxide impregnation test)
25g of the pellets were immersed in 50g of a 3 wt% hydrogen peroxide solution, heated at 90℃for 20 hours in an electric furnace, and then heated at 121℃for 1 hour in a sterilizer, followed by cooling to room temperature. The pellet was taken out of the aqueous solution, and a TISAB solution (10) (manufactured by kanto chemical company) was added to the remaining aqueous solution, and the concentration of fluorine ions in the obtained aqueous solution was measured by a fluorine ion meter. From the obtained measurement values, the fluoride ion concentration (eluted fluoride ion amount) per weight of the pellet was calculated.
Dissolved fluoride ion amount (mass ppm) =measurement value (mass ppm) ×aqueous solution amount (g)/pellet weight (g)
(extrusion pressure)
Extrusion pressure was measured using a double capillary rheometer RHEGRAPH 25 (manufactured by Goettfert Co.). The main die inner diameter of 1mm, L/D=16, the auxiliary die inner diameter of 1mm and L/D < 1 are used for measuring the temperature of 390 ℃ and the residual heat time after the pellet is put into is 10 minutes and the shearing speed is 20sec -1 The barrel internal pressure value after 10 minutes of lower extrusion was subjected to Bagley correction, thereby serving as extrusion pressure. The copolymer having a low extrusion pressure is excellent in moldability such as extrusion moldability and injection moldability.
(dielectric loss tangent)
The pellets were melt-molded to prepare a cylindrical test piece having a diameter of 2 mm. The test piece thus fabricated was set in a cavity resonator for 6GHz manufactured by kanto electronics application development company, and measured by a network analyzer manufactured by agilent technologies. The measurement result was analyzed by analysis software "CPMA" manufactured by Kanto electronic application development Co., ltd. On a personal computer connected to the network analyzer, to thereby determine the dielectric loss tangent (tan. Delta.) at 20℃and 6 GHz.

Claims (6)

1. A copolymer comprising tetrafluoroethylene units and perfluoro (propyl vinyl ether) units,
The content of perfluoro (propyl vinyl ether) unit is 4.9 to 7.0 mass% relative to the total monomer units,
the melt flow rate at 372 ℃ is 0.5g/10 min-1.5 g/10 min,
the number of functional groups per 10 6 The number of carbon atoms of the main chain is 20 or less.
2. The copolymer of claim 1, wherein the melt flow rate at 372 ℃ is from 0.7g/10 min to 1.3g/10 min.
3. An extrusion molded body comprising the copolymer according to claim 1 or 2.
4. A transfer molded article comprising the copolymer according to claim 1 or 2.
5. A coated wire comprising a coating layer comprising the copolymer according to claim 1 or 2.
6. A molded body which is a molded body containing the copolymer according to claim 1 or 2, wherein the molded body is a sheet or a tube.
CN202280016136.4A 2021-02-26 2022-01-31 Copolymer, molded article, extrusion molded article, and transfer molded article Pending CN116867817A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021-031113 2021-02-26
JP2021162080 2021-09-30
JP2021-162080 2021-09-30
PCT/JP2022/003647 WO2022181232A1 (en) 2021-02-26 2022-01-31 Copolymer, molded body, extruded body, and transfer molded body

Publications (1)

Publication Number Publication Date
CN116867817A true CN116867817A (en) 2023-10-10

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ID=88223868

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280016136.4A Pending CN116867817A (en) 2021-02-26 2022-01-31 Copolymer, molded article, extrusion molded article, and transfer molded article

Country Status (1)

Country Link
CN (1) CN116867817A (en)

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