Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
  • C08G65/4031—(I) or (II) containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols

Definitions

• the present invention relates to a polyethernitrile film and a method for producing a polyethernitrile film.
• Polyether nitrile is a type of super engineering plastic that has excellent heat resistance, chemical resistance, and flame retardancy, as well as excellent mechanical properties such as abrasion resistance and abrasion resistance.
• a stretched film of polyether nitrile has high heat resistance and mechanical properties (see, for example, Patent Document 1).
• the polymer shown in Patent Document 1 has the above-mentioned excellent properties, it also has a high melting point compared to other thermoplastic resins, so the processing temperature during processing is high. Furthermore, the polymer shown in Patent Document 1 has high crystallinity and therefore has poor stretchability. Furthermore, the polymer shown in Patent Document 1 crystallizes during stretching, resulting in poor stretching, so the stretching speed needs to be slowed down, resulting in poor productivity.
• the present invention is a polyether nitrile film that has excellent processability and high heat resistance, which has excellent stretchability before stretching and has high crystallinity after stretching.
• the purpose of the present invention is to provide a polyether nitrile film having the following properties.
• the present inventors have conducted extensive studies and found that the above object can be achieved by using polyether nitrile with a controlled polymer skeleton structure. That is, the present invention has the following configuration. (1) It has N repeating units represented by formula (I) and M repeating units represented by formula (II), where N and M are 0.80 ⁇ [N/(N+M)] ⁇ 1
• a polyethernitrile film which is a film molded body made of polyethernitrile having an integer that satisfies the relationship of .00, and whose heat of fusion is observed.
• Ar 1 has one skeleton selected from the units represented by formulas (a) to (e), and X is a hydrogen atom, a methyl group, or a trifluoromethyl group.
• R is any one of a linear organic group having 1 to 6 carbon atoms, a branched organic group having 3 to 6 carbon atoms, and a cyclic organic group having 3 to 6 carbon atoms; may contain one or more, R may be equal to or different from each other, and a represents the number of substituents of R and is an integer of 0 to 4.
• Step (1) N repeating units represented by formula (I) and M repeating units represented by formula (II), where N and M are 0.80 ⁇ [N/(N+M)] ⁇
• Step (2) Step of cooling the molded product obtained in step (1) to 180°C or less
• Ar 1 has one skeleton selected from the units represented by formulas (a) to (e), and X is a hydrogen atom, a methyl group, or a trifluoromethyl group.
• R is any one of a linear organic group having 1 to 6 carbon atoms, a branched organic group having 3 to 6 carbon atoms, and a cyclic organic group having 3 to 6 carbon atoms, and includes an oxygen atom, a nitrogen atom, It may contain one or more sulfur atoms, R may be equal to or different from each other, and a indicates the number of substituents of R and is an integer from 0 to 4.
• Step (3) Stretching the molded product obtained in step (2) at 180 to 250°C
• Step (4) Heating the molded product obtained in step (3) at 220 to 320°C
• a polyethernitrile film that has excellent processability and high heat resistance, has excellent stretchability before stretching, and has high crystallinity after stretching.
• polyethernitrile has N repeating units represented by formula (I) and M repeating units represented by formula (II), where N and M are 0 It is an integer that satisfies the relationship: .80 ⁇ [N/(N+M)] ⁇ 1.00.
• Ar 1 has one skeleton selected from the units represented by formulas (a) to (e), and X is a hydrogen atom, a methyl group, or a trifluoromethyl group.
• R is any one of a linear organic group having 1 to 6 carbon atoms, a branched organic group having 3 to 6 carbon atoms, and a cyclic organic group having 3 to 6 carbon atoms; may contain one or more, R may be equal to or different from each other, and a represents the number of substituents of R and is an integer of 0 to 4.
• the polyether nitrile has N repeating units represented by formula (I) and M repeating units represented by formula (II), where N and M are 0.80 ⁇ It is an integer that satisfies the relationship [N/(N+M)] ⁇ 1.00.
• the upper limit of [N/(N+M)] is not particularly limited as long as it is less than 1.00, but the closer it gets to 1.00, the higher the melting point, so it is preferably 0.99 or less, more preferably 0.97 or less.
• the lower limit of [N/(N+M)] is not particularly limited as long as it is 0.80 or more, but if it is less than 0.80, the crystallinity decreases and becomes amorphous, which is not suitable.
• N and M are preferably integers that satisfy the relationship 0.80 ⁇ [N/(N+M)] ⁇ 0.99, more preferably 0.85 ⁇ [N/( N+M)] ⁇ 0.97, more preferably an integer satisfying the relationship 0.90 ⁇ [N/(N+M)] ⁇ 0.97.
• N and M is not particularly limited, but can be exemplified in the range of 5 to 10,000, preferably in the range of 5 to 5,000, more preferably in the range of 5 to 1,000, even more preferably in the range of 5 to 500.
• the repeating unit represented by the formula (I) is a structural unit represented by the following formula (III), and the structural unit represented by the formula (II) is represented by the following formula (IV). It is more preferable that the structural unit is
• Ar 1 has one skeleton selected from the units represented by the formula (a) to the formula (e), and is represented by the formula (a) to the formula (e).
• a is 0, and X is a hydrogen atom, a methyl group, or a trifluoromethyl group.
• Ar 1 has a skeleton represented by the formula (a), the formula (c), the formula (d), or the formula (e), and a in each of the formulas is More preferably, it is 0, and even more preferably, it has a skeleton represented by the formula (d), and all a's in the formula (d) are 0.
• the polyether nitrile in the present invention is preferably a polymer with excellent stretchability. Therefore, if the difference between the crystallization temperature when the temperature is raised from the amorphous state, that is, the cold crystallization temperature and the glass transition temperature is small, the drawability will deteriorate, so it is preferable that the difference is higher to some extent.
• the difference between the cold crystallization temperature and the glass transition temperature is preferably 40 to 130°C. By setting the temperature to 40° C. or higher, the crystallization rate becomes slow and the stretchability is easily improved. Further, by setting the temperature to 130° C. or lower, the glass transition temperature and melting point become sufficiently distant, and crystallinity tends to improve.
• the difference between the cold crystallization temperature and the glass transition temperature is more preferably 50 to 110°C.
• the polyether nitrile in the present invention is preferably a crystalline polymer with excellent processability. Therefore, it is preferable that the crystallization temperature when the temperature is lowered from the molten state, that is, the difference between the cooling crystallization temperature and the melting point, be small to some extent, but if it is too small, the moldability will deteriorate.
• the difference between the melting point and the cooling crystallization temperature is preferably 40 to 100°C. By setting the temperature to 100°C or less, crystallinity can be easily improved. Further, by setting the temperature to 40° C. or higher, the solidification rate of the molten polymer becomes slow, and the processability is easily improved.
• the difference between the melting point and the cooling crystallization temperature is more preferably 50 to 90°C.
• the melting point of the polyether nitrile in the present invention is preferably 280 to 360°C from the viewpoint of processability, and more preferably 300 to 360°C from the viewpoint of mechanical properties.
• the terminal groups of the polyether nitrile in the present invention include a hydroxyl group, a metal salt of a hydroxyl group, a halogeno group, a linear organic group having 1 to 16 carbon atoms, a branched organic group having 3 to 16 carbon atoms, and a branched organic group having 3 to 16 carbon atoms. is a cyclic organic group.
• the structure of the terminal group may affect the thermal stability.
• the thermal stability of the polyether nitrile in the present invention can be evaluated by thermogravimetric analysis (TG).
• TG thermogravimetric analysis
• the weight reduction rate is preferably 5% or less, more preferably 4% or less, even more preferably 3% or less. Note that the weight loss rate is calculated based on the weight after being held at 50° C. for 1 minute.
• the terminal structure of the polyether nitrile in the present invention can be quantified by nuclear magnetic resonance (NMR) analysis.
• NMR nuclear magnetic resonance
• the terminal end of the polyether nitrile in the present invention preferably satisfies the above-mentioned thermal stability, and more preferably a halogeno group or a cyclic organic group.
• the method for producing the polyethernitrile used in the present invention is not particularly limited as long as it can synthesize polyethernitrile that satisfies the requirements of (1) above, and any production method may be used.
• an aromatic compound substituted with two hydroxyl groups (M1) used in a preferred embodiment of the present invention an aromatic compound substituted with two hydroxyl groups different from the aromatic compound (M1)
• the compound (M2), the aromatic compound (M3) having a benzonitrile skeleton substituted with two halogeno groups, the base, the organic polar solvent, and the reaction conditions will be described.
• Examples of the aromatic compound (M1) substituted with two hydroxyl groups in a preferred embodiment of the method for producing polyethernitrile in the present invention include a compound represented by the following formula (k). Further, as the aromatic compound (M2) substituted with two hydroxyl groups, compounds represented by the following formulas (l) to (p) can be exemplified.
• R is any one of a linear organic group having 1 to 6 carbon atoms, a branched organic group having 3 to 6 carbon atoms, and a cyclic organic group having 3 to 6 carbon atoms. and may contain one or more oxygen atoms, nitrogen atoms, and sulfur atoms.
• a represents the number of substituents in R, and is an integer of 0 to 4. Note that when a plurality of R's exist, the R's may be equal to or different from each other.
• X is a hydrogen atom, a methyl group, or a trifluoromethyl group.
• the compound (M1) substituted with two hydroxyl groups includes hydroquinone, methylhydroquinone, methoxyhydroquinone, 2,6-dimethylhydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, 2, Examples include 5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, and 2-acetylhydroquinone. Among them, hydroquinone is preferred from the viewpoint of economy and physical properties.
• the compound (M2) substituted with two hydroxyl groups includes resorcinol, 5-methoxyresorcinol, 2-methylresorcinol, 5-methylresorcinol, 2,4-dihydroxybenzaldehyde, 4-ethylresorcinol, 3, 5-dihydroxyacetophenone, 4-butylresorcinol, 2-acetylresorcinol, 4-hexylresorcinol, 4-acetylresorcinol, 3,5-dihydroxybenzoic acid, 4-benzoylresorcinol, 4,6-diacetylresorcinol, 2,6-dihydroxy Benzoic acid, 2,4-dihydroxybenzoic acid, 4-propionylresorcinol, 3,5-dihydroxybenzamide, 3,5-dihydroxy-4-methylbenzoic acid, 2-nitroresorcinol, 2,6-dihydroxy-4-methylbenzoic acid Acid, 2,4-dihydroxybenzamide, 1,4-dihydroxybenz
• resorcinol, catechol, 4,4'-dihydroxybiphenyl, 2,7-dihydroxynaphthalene, 2,2'-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, 1,1'-bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane are preferred, and resorcinol, catechol, 4,4'-dihydroxybiphenyl, 2,2'-bis( More preferred are 4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, and 2,2-bis(4-hydroxyphenyl)hexafluoropropane, and even more preferred is 4,4'-dihydroxybiphenyl.
• the arrangement of the copolymer may be random or block, but is preferably random from the viewpoint of crystallinity. Further, it is preferable that the compound (M1) substituted with two hydroxyl groups and the compound (M2) are mixed in advance and then reacted.
• the compound (M3) having a benzonitrile skeleton substituted with two halogeno groups is, for example, a compound represented by the following formula (q). can.
• R is any one of a linear organic group having 1 to 6 carbon atoms, a branched organic group having 3 to 6 carbon atoms, and a cyclic organic group having 3 to 6 carbon atoms, and an oxygen atom, It may contain one or more nitrogen atoms and sulfur atoms.
• a represents the number of substituents in R, and is an integer of 0 to 3.
• X 1 and X 2 each independently represent a halogen atom, and may be the same or different. When there is a plurality of R's, the R's may be equal to or different from each other.
• the compound (M3) having a benzonitrile skeleton substituted with two halogeno groups includes 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2-chloro-6-fluorobenzo Nitrile, 2,5-dichlorobenzonitrile, 2-chloro-5-fluorobenzonitrile, 2,5-difluorobenzonitrile, 3,5-dichlorobenzonitrile, 3,5-difluorobenzonitrile, 2,3-dichlorobenzo Nitrile, 2,3-difluorobenzonitrile, 3-chloro-2-fluorobenzonitrile, 3,4-dichlorobenzonitrile, 3,4-difluorobenzonitrile, 4-chloro-3-fluorobenzonitrile, 3-chloro- Examples include 4-fluorobenzonitrile. Among them, from the viewpoint of economy, 2,6-dichlorobenzonitrile and 2,6-difluororobenzo
• the amounts of compounds (M1), (M2), and (M3) used are as follows: compound (M1) per 1.00 mol of compound (M3);
• the sum of and (M2) is preferably in the range of 0.90 to 1.10 mol, from the viewpoint of polymer physical properties, is preferably in the range of 0.95 to 1.05 mol, and in the range of 0.95 to 1.00 mol. is more preferable.
• the usage amounts of compounds (M1) and (M2) the relationship is 0.80 ⁇ [(M1) usage amount (mol)/Total usage amount (mol) of (M1) and (M2)] ⁇ 1.00.
• examples of the base include organic bases and inorganic bases. Specifically, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, 7-methyl-1,5,7-tria organic bases such as zabicyclo[4.4.0]dec-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, lithium carbonate, sodium carbonate, potassium carbonate, Alkali metal carbonates such as rubidium carbonate and cesium carbonate, alkaline earth metal carbonates such as calcium carbonate, strontium carbonate, and barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, etc.
• alkaline metal bicarbonates such as calcium bicarbonate, strontium bicarbonate, barium bicarbonate, or alkaline earth metal bicarbonates, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide.
• Alkaline metal hydroxides such as calcium hydroxide, strontium hydroxide, barium hydroxide and other alkaline earth metal hydroxides can be mentioned.
• carbonates such as potassium carbonate, and bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate are preferred, sodium carbonate and potassium carbonate are more preferred, and sodium carbonate is even more preferably used. These may be used alone or in combination of two or more without any problem.
• aqueous mixture here refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component.
• the amount of base depends on the sum of the aromatic compound (M1) and the aromatic compound (M2).
• the molar ratio of the base to the total number of moles of hydroxyl groups in the compounds (M1) and (M2) is at least 1.0, and from the viewpoint of reactivity, it is preferably 1.2 or more.
• the base in the present invention can be produced without problems even when used in excess, so the upper limit is not particularly limited, but a practical upper limit is 100 based on the total number of moles of hydroxyl groups in (M1) and (M2).
• the molar ratio of the base to the total number of moles of hydroxyl groups in (M1) and (M2) is from 1.2 to 10.
• the organic polar solvent is not particularly limited as long as it does not inhibit the reaction.
• organic polar solvents include N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1, Nitrogen-containing polar solvents such as 3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide, and tetramethylurea; sulfoxide/sulfone solvents such as dimethylsulfoxide (DMSO), dimethylsulfone, diphenylsulfone, and sulfolane; Examples include nitrile solvents such as benzonitrile, diaryl ethers such as diphenyl ether, ketones such as benzophenone and acetophenone, and mixtures thereof.
• the amount of the organic polar solvent is preferably such that the total amount of organic solvents contained in the mixture is 0.50 liter or more per 1.0 mol of the total benzene ring components contained in the mixture, and more preferably is 1.00 liters or more, more preferably 2.00 liters or more. Further, there is no particular restriction on the upper limit of the amount of organic polar solvent in the mixture, but it is preferably 100 liters or less, more preferably 50 liters or less, per 1.0 mol of the total benzene ring component in the mixture. preferable.
• the amount of organic polar solvent here is based on the volume of the solvent at room temperature and normal pressure, and the amount of organic polar solvent used in the mixture is determined by the amount of organic polar solvent introduced into the reaction system by dehydration etc.
• the benzene ring component in the mixture here refers to the benzene ring component contained in the raw materials that can become a constituent component of the repeating unit in polyethernitrile through reaction, and the "number of moles" of the benzene ring component in these raw materials is represents "the number of benzene rings constituting the compound”.
• a molecular weight regulator can be added here, if necessary.
• the molecular weight regulator for example, a compound represented by the following formula (r), a compound represented by the following formula (s), etc. can be used.
• Q is any one of a linear organic group having 1 to 10 carbon atoms, a branched organic group having 3 to 10 carbon atoms, and a cyclic organic group having 3 to 10 carbon atoms. , oxygen atom, nitrogen atom, or sulfur atom. Note that Q may be equal to or different from each other.
• b indicates the number of substituents in Q, and is an integer from 0 to 5.
• phenol, 4-phenylphenol, 4-tert-butylphenol, 4-cumylphenol, 4-phenoxyphenol, 4-ethylphenol, 4-methoxyphenol, 4-tert-octylphenol, 1-naphthol, 2 - Examples include naphthol. Among these, 4-phenylphenol, 4-phenoxyphenol, 1-naphthol, and 2-naphthol are preferred from the viewpoint of manufacturability.
• water is produced as a by-product as the reaction progresses.
• an organic compound that forms an azeotrope with water may be added, if necessary.
• Such an organic compound is not particularly limited as long as it forms an azeotrope with water, but a nonpolar organic solvent having a boiling point lower than that of the reaction solvent is preferred, and a specific example is toluene.
• the amount of the organic compound is not particularly limited as long as it does not inhibit the reaction, but it is preferably in the range of 0 to 50% by volume, more preferably in the range of 0 to 20%, based on the amount of the organic polar solvent.
• a range of 0 to 10% is more preferable.
• a preferred embodiment of the method for producing polyethernitrile in the present invention is carried out under heating under a nitrogen atmosphere or reduced pressure.
• the reaction temperature can vary over a wide range, but is carried out at a temperature of at least 80°C, preferably at least 150°C, at most 400°C, and from a manufacturability point of view preferably at a maximum of 350°C. It is better. Taking into account the sublimability and reactivity of the compound used, it is preferable to carry out the reaction in a temperature range of 150°C to 350°C, more preferably in a range of 150°C to 200°C, while increasing the temperature in stages. Furthermore, for the purpose of improving reactivity, it is more preferable to carry out the reaction with stirring.
• the reaction time can vary widely depending to some extent on the reaction temperature, the nature of the reagents used and the presence of solvent, but from 0.1 hours to 100 hours, Preferably, from the viewpoint of manufacturability, the time is 0.5 to 50 hours.
• the reaction container is not particularly limited as long as it can withstand the above reaction temperature, but for example, a glass container, a stainless steel container, etc. can be used. .
• the pressure applied to the reaction is sufficient to maintain the reactant in the liquid phase in the reaction medium, and a pressure in the range of 1 atm to 10 atm can be used. From the viewpoint of manufacturability, the pressure is preferably 1 atm to 2 atm.
• the produced polyethernitrile can be obtained by separating and recovering from the reaction mixture obtained by the above-mentioned production method.
• the reaction mixture obtained by the above production method contains at least polyethernitrile, and may contain other components such as unreacted raw materials, by-product salts, and unreacted bases.
• There are no particular limitations on the method for recovering polyethernitrile from such a reaction mixture for example, a method of recovering polyethernitrile by contacting it with a solvent that is soluble in by-product salts, if necessary, under heating, if necessary. Examples include a method in which by-product salts and unreacted organic bases are removed under reduced pressure.
• the solvent used is generally a relatively highly polar solvent.
• Preferred solvents vary depending on the type of base and by-product salt used, but examples include water, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and hexanol, acetone, ketones such as methyl ethyl ketone, and acetic acid.
• Acetate esters such as ethyl and butyl acetate, N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1 , 3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide, nitrogen-containing polar solvents such as tetramethylurea, sulfoxide/sulfone solvents such as dimethylsulfoxide (DMSO), dimethylsulfone, diphenylsulfone, sulfolane, etc.
• acids such as acetic acid, hydrochloric acid, sulfuric acid, and nitric acid.
• water, methanol, acetone, acetic acid, hydrochloric acid, sulfuric acid, and NMP are preferred, and water, acetic acid, hydrochloric acid, and NMP are more preferred, from the viewpoint of availability and economic efficiency.
• the reaction may be carried out under heating in the range of 0.001 atm to 1 atm after the completion of the reaction, if necessary.
• the structure of the polyether nitrile in the present invention can be confirmed by infrared spectroscopy or nuclear magnetic resonance spectroscopy.
• Step (1) N repeating units represented by formula (I) and M repeating units represented by formula (II), where N and M are 0.80 ⁇ [N/(N+M)] ⁇
• Step (2) Step of cooling the molded product obtained in step (1) to 180°C or less
• Ar 1 has one skeleton selected from the units represented by formulas (a) to (e), and X is a hydrogen atom, a methyl group, or a trifluoromethyl group.
• R is any one of a linear organic group having 1 to 6 carbon atoms, a branched organic group having 3 to 6 carbon atoms, and a cyclic organic group having 3 to 6 carbon atoms, and includes an oxygen atom, a nitrogen atom, It may contain one or more sulfur atoms, R may be equal to or different from each other, and a indicates the number of substituents of R and is an integer from 0 to 4.
• Step (1) has N repeating units represented by formula (I) and M repeating units represented by formula (II), where N and M are 0.80 ⁇ [N/(N+M) ] ⁇ 1.00 is a process in which polyether nitrile, an integer satisfying the relationship, is melt-molded at 310 to 400°C.
• step (1) polyether nitrile can be produced, for example, by the method described in (2) above.
• polyethernitrile is formed into a film.
• This step can be carried out by applying a conventional method, such as a press molding method or an extrusion molding method.
• a conventional method such as a press molding method or an extrusion molding method.
• the processability becomes poor and there is deterioration due to oxidation, which is not preferable.
• the film forming properties are poor and non-uniform, which is not preferable.
• the preferred processing temperature is from 10°C to 80°C above the melting point, specifically from 310°C to 400°C, preferably from 320°C to 400°C, and more preferably from 340°C to 380°C.
• step (2) the step of cooling the molded article obtained in step (1) of step (2) to 180° C. or lower will be described.
• the formed film is cooled.
• the temperature during cooling is not particularly limited as long as it is below the glass transition temperature, but temperatures near the glass transition temperature are not preferred because crystallization progresses and drawability decreases.
• the temperature during cooling is preferably 180°C or lower, more preferably 150°C or lower.
• the method for producing a polyether nitrile film of the present invention further includes the following step (3) and step (4).
• Step (3) Stretching the molded body obtained in step (2) at 180 to 250°C.
• Step (4) Heating the molded body obtained in step (3) at 220 to 320°C.
• the stretching ratio is preferably 1.01 times or more, more preferably 1.5 times or more, and even more preferably 2 times or more. More specifically, in the case of uniaxial stretching, the length magnification in the stretching direction is 1.01 times or more, and in the case of simultaneous biaxial stretching and sequential biaxial stretching, the area magnification is 1.01 times or more. It is more preferable. When the stretching ratio is 1.01 times or more, more preferably 1.5 times or more, still more preferably 2 times or more, sufficient orientation can be easily obtained.
• the upper limit of the stretching ratio is not particularly limited, but is usually about 10 times.
• the stretching temperature in step (3) is 180° C. to 250° C., preferably 200° C. to 240° C., since the stretching is performed at a temperature higher than the glass transition temperature and lower than the cold crystallization temperature.
• step (4) is a step of heating the molded product obtained in step (3) at 220 to 320°C.
• the stretched film can be heat-set and stabilized.
• Heat setting can be performed with the film stretched at a temperature above the stretching temperature and below the melting point of the polymer.
• the heat setting temperature is 220° C. to 320° C., preferably 240° C. to 300° C., since the heat setting temperature is higher than the stretching temperature and lower than the melting point of the polymer.
• the heat fixing time is not particularly limited, but is preferably 1 second to 10 minutes.
• the stretching speed is not particularly limited as long as it can be stretched, but from the viewpoint of productivity, a speed of 10 mm/min or more is preferable.
• the polyethernitrile film of the present invention has N repeating units represented by formula (I) and M repeating units represented by formula (II), where N and M are It is a film molded article made of polyethernitrile, an integer satisfying the relationship of 0.80 ⁇ [N/(N+M)] ⁇ 1.00, and the heat of fusion is observed.
• Ar 1 has one skeleton selected from the units represented by formulas (a) to (e), and X is a hydrogen atom, a methyl group, or a trifluoromethyl group.
• R is any one of a linear organic group having 1 to 6 carbon atoms, a branched organic group having 3 to 6 carbon atoms, and a cyclic organic group having 3 to 6 carbon atoms; may contain one or more, R may be equal to or different from each other, and a represents the number of substituents of R and is an integer of 0 to 4.
• Preferred embodiments of the polyether nitrile in the polyether nitrile film of the present invention are as described in (1) above.
• the heat of fusion of the polyether nitrile film of the present invention is observed.
• the observation of heat of fusion means that an endothermic peak due to melting is observed when the temperature is increased in differential scanning calorimetry (DSC) measurement.
• the lower limit of the heat of fusion is not particularly limited as long as it can be observed, and is, for example, 1 J/g.
• the upper limit of the heat of fusion is not particularly limited, but if it is too large, the crystallinity may increase and the drawability may decrease, so it is, for example, 60 J/g.
• Examples of the form of the polyether nitrile film of the present invention include a melt-pressed film pressed in a molten state, an extrusion-molded film or extrusion-molded sheet, and a stretched stretched film.
• Melt-pressed films and extruded films can be heat-treated after molding to increase their crystallinity and improve their mechanical properties.
• the temperature of the heat treatment is not particularly limited as long as it is above the glass transition temperature and below the melting point, but is preferably 200 to 300°C, more preferably 250 to 300°C.
• the polyether nitrile film of the present invention is preferably a stretched film.
• a stretched film By being a stretched film, excellent transparency and dielectric properties can be easily obtained. Moreover, by being a stretched film, heat resistance, chemical resistance, transparency, flame retardance, dielectric properties, and mechanical properties are likely to be improved.
• a stretched film refers to a film whose degree of crystal orientation can be observed by wide-angle X-ray diffraction.
• the stretched film may be a uniaxially stretched film or a biaxially stretched film.
• the biaxially stretched film may be a biaxially simultaneously stretched film or a sequentially biaxially stretched film.
• the stretching ratio is preferably 1.01 times or more, more preferably 1.5 times or more, and even more preferably 2 times or more.
• the upper limit of the stretching ratio is not particularly limited, but is usually about 10 times.
• the degree of crystal orientation of the polyether nitrile film of the present invention is preferably 50% or more, more preferably 70% or more, and even more preferably 85% or more.
• the upper limit of the degree of crystal orientation of the polyether nitrile film of the present invention is not particularly limited, but is 100%.
• chemical resistance can be easily improved. Examples of methods for bringing the degree of crystal orientation within the above range include a method of heat-treating a melt-pressed film or an extrusion-molded film after molding, and a method of heat-treating a film after stretching.
• the degree of crystal orientation can be measured by the wide-angle X-ray diffraction method described in ⁇ Measurement of degree of crystal orientation> in Examples below.
• the melting point of the polyether nitrile film of the present invention is preferably as high as possible from the viewpoint of heat resistance.
• the melting point of the polyether nitrile film is preferably 280 to 400°C, more preferably 300 to 400°C, and even more preferably 320 to 400°C.
• the melting point can sometimes be improved by heat-treating a melt-pressed film or an extruded film.
• the polyether nitrile film of the present invention preferably has a total light transmittance of 80% or more and a haze of 10% or less when the thickness is 20 micrometers.
• transparency is expressed by total light transmittance and haze.
• the total light transmittance is preferably 80% or more, more preferably 85% or more.
• the total light transmittance is less than 100% because transparency increases as the total light transmittance approaches 100%.
• the haze is preferably 10% or less, more preferably 5% or less.
• the haze is greater than 0% because transparency increases as the haze approaches 0%. Total light transmittance and haze can be measured with a spectroscopic haze meter.
• a method for making the total light transmittance of the polyether nitrile film 80% or more and the haze 10% or less includes, for example, a method in which the polyether nitrile film is made into a stretched film.
• the dielectric constant at a frequency of 5.8 GHz is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less. If the dielectric constant is low, that is, if the dielectric properties are excellent, it can be used for a wide range of applications such as communication equipment and circuit boards.
• the lower limit of the dielectric constant is not particularly limited, but the smaller the dielectric constant is, the more preferable it is, and the closer the dielectric constant is to 0, the more preferable it is.
• a method for reducing the dielectric constant of the polyether nitrile film to 4.0 or less for example, a method of forming a polyether film into a stretched film can be mentioned.
• the dielectric loss tangent at a frequency of 5.8 GHz is It is preferably less than 0.008, more preferably 0.007 or less.
• the lower limit of the dielectric loss tangent is not particularly limited, it is preferably smaller, and the closer the dielectric loss tangent is to 0, the more preferable it is.
• An example of a method for adjusting the dielectric loss tangent within the above range is a method in which a polyether film is made into a stretched film.
• the polyether nitrile film of the present invention has a nitrile group which is a polar group, it may have excellent adhesion to resin materials other than polyether nitrile or different materials.
• resin materials other than polyethernitrile include polyamide, polyester, polyetherimide, polyetherketone, polyetheretherketone, liquid crystal polymer, polyamideimide, polyimide, polyacetal, polycarbonate, polyarylate, polyphenylene sulfide, and polyether.
• examples include sulfone, polysulfone, polyvinyl alcohol, polyethylene-vinyl alcohol copolymer, polyurethane, norbornene resin, and fluororesin.
• different materials include fibrous reinforcing materials such as glass fiber, carbon fiber, cellulose nanofiber, and alumina fiber, and metal materials such as aluminum, silver, gold, and copper.
• the polyether nitrile film of the present invention Since the polyether nitrile film of the present invention has good mechanical properties, it also has excellent radiation resistance. Specifically, in the polyether nitrile film of the present invention, the tensile elongation retention after gamma ray irradiation is preferably 50 to 100%. The tensile elongation retention after gamma ray irradiation is measured by the method described in ⁇ Radiation resistance evaluation> below.
• Suitable uses for the polyether nitrile film of the present invention include displays, electrical/electronic parts, communication parts, circuit board parts, household/office electrical appliance parts, optical equipment/precision machinery parts, plumbing parts, automobiles/vehicles. Examples include related parts, aircraft/rocket/satellite parts, power plant related parts, and other industrial uses.
• the melting point and heat of fusion of polyethernitrile and polyethernitrile film were determined by differential scanning calorimetry (DSC) measurement. DSC measurement was performed using Q20 manufactured by TA Instruments. Using a cooled press film (3 to 10 mg), the temperature was raised from 50° C. to 400° C. at a rate of 10° C./min. From the results, the difference between the melting point, heat of fusion, cold crystallization temperature, and glass transition temperature was calculated.
• ⁇ Crystal orientation measurement> The degree of crystal orientation of the polyether nitrile film was measured using Bruker's D8 DISCOVER ⁇ HR Hybrid. A polyether nitrile film was cut to a width of 1 mm, and one pressed film and 10 stretched films were stacked together as measurement samples. X-rays were incident perpendicularly to the cross section of the film, and wide-angle X-ray diffraction was measured. Regarding the main peak of the obtained two-dimensional wide-angle X-ray diffraction image, the diffraction intensity was cut out in the circumferential direction to create an orientation profile.
• Crystal orientation degree [(180-H)/180]*100 ⁇ Total light transmittance/haze measurement>
• the total light transmittance and haze measurement of the polyether nitrile film was performed using a 20 micrometer thick polyether nitrile film using a Nippon Denshoku Sha spectral haze meter 300A.
• the dielectric constant of the polyether nitrile film was measured at a frequency of 5.8 GHz using a cavity resonator CP521 manufactured by Kanto Denshi Application Development Co., Ltd.
• the dielectric constant and dielectric loss tangent were measured using a sample obtained by rolling a polyether nitrile film (60 mm x 60 mm) with a thickness of 5 to 40 micrometers into a PTFE tube and heat-shrinking it, and using an empty PTFE tube as a reference.
• Adhesion evaluation of the polyether nitrile film was conducted using Imada's MX-500N and ZTA-500N. A polyether nitrile press film was produced on aluminum foil, a 180 degree peel test was performed, and the peel stress was calculated.
• the radiation resistance of the polyether nitrile film was evaluated using a polyether nitrile film having a thickness of 200 micrometers by measuring the tensile elongation retention before and after irradiation with 1000 kGy of gamma rays at 27°C.
• the tensile elongation retention was measured using Imada's MX-500N and ZTA-500N.
• the tensile elongation retention rate was determined by the following formula, where the tensile elongation before gamma ray irradiation is A 0 (%) and the tensile elongation after gamma ray irradiation is A 1 (%).
• the polyether nitrile stretched film was produced using an automatic biaxial stretching device IMC-11A9 manufactured by Imoto Seisakusho Co., Ltd.
• the stretched film was produced using a press film with length and width of 50 mm*50 mm at 220°C, stretching speed of 10 to 100 mm/min, and 3x*3x.
• the quality of stretchability is judged as "Stretchability: OK” if it can be stretched without tearing when stretched at a stretching speed of 10 mm/min, and "Stretchability: NG” if it can be stretched without tearing. And so.
• Aromatic compound substituted with two hydroxyl groups (M1) (M1-1) Hydroquinone (Fujifilm Wako Pure Chemical Industries, Ltd.) Aromatic compound substituted with two hydroxyl groups (M2) (M2-1) Resorcinol (Fujifilm Wako Pure Chemical Industries, Ltd.) (M2-2) 4,4'-dihydroxybiphenyl (Tokyo Kasei Kogyo Co., Ltd.) (M2-3) 2,2-bis(4-hydroxyphenyl)propane (Tokyo Kasei Kogyo Co., Ltd.) (M2-4) Catechol (Tokyo Kasei Kogyo Co., Ltd.) (M2-5) 2,2-bis(4-hydroxyphenyl)hexafluoropropane (Tokyo Kasei Kogyo Co., Ltd.) Compound with benzonitrile skeleton substituted with two halogeno groups (M3) (M3-1) 2,6-dichlor
• Example 1 After drying the polyether nitrile obtained in Reference Example 1 under vacuum at 80°C for 12 hours, a press film was prepared at 360°C and cooled at 20°C to a thickness of 0.2 mm and a length and width of 50 mm. A press film was obtained. As a result of measuring the melting point and heat of fusion of the obtained press film, the melting point was 345° C. and the heat of fusion was 38 J/g. Further, the difference between the cold crystallization temperature and the glass transition temperature was 74°C. The peel stress for aluminum was 12N.
• Example 2 After producing a press film using the same method as in Example 1, a heat-treated press film was produced by heating to 250° C. and heat-treating for 30 minutes. As a result of measuring the melting point and heat of fusion of the obtained heat-treated press film, the melting point was 351° C. and the heat of fusion was 48 J/g. The tensile elongation of the obtained heat-treated press film was 30%. After this heat-treated press film was irradiated with gamma rays at a total dose of 1000 kGy, the tensile elongation was 30%, and the tensile elongation retention was 100%.
• Example 10 Using the press film obtained in Example 1, the stretching temperature was 220°C, the stretching speed was 100 mm/min, the stretching ratio was 3 times in both the longitudinal and transverse directions, and after simultaneous biaxial stretching, it was heat-set at 250°C for 1 minute. . The degree of crystal orientation of the obtained film was 89%.
• Examples 11 to 17 The press films obtained in Examples 3 to 9 were stretched in the same manner as in Example 10.
• the amount of aromatic compounds (M1) and (M2) used was determined to be 0.80 ⁇ [Amount of (M1) used (mol)/total amount of (M1) and (M2) used ( mole)] ⁇ 1.00, [N/(N+M)] becomes a range of 0.80 ⁇ [N/(N+M)] ⁇ 1.00, and the melting point of the press film
• the film can be stretched at 350°C or less and the heat of fusion is 10 J/g or more, and the obtained stretched film has a total light transmittance of 80% or more, a haze of 10% or less, and a dielectric film with a frequency of 5.8 GHz.
• the ratio was 3.5 or less, and the degree of crystal orientation was 89%.
• Comparative Example 1 the melting point of the polyethernitrile obtained in Reference Example 9 was as high as 388°C, and it could not be produced at 360°C as in Example 1, and the press film had to be produced at 410°C. Poor workability. Furthermore, from the results of Comparative Examples 3 and 4, when the range of [N/(N+M)] was outside the above range, stretching was not possible and a stretched film was not obtained, so no melting point or heat of fusion was observed.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Polyethers (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (4)

Applications Claiming Priority (4)

Publications (1)

Family

ID=88200893

Family Applications (1)

Country Status (5)

Citations (7)

Family Cites Families (3)

• 2023
  • 2023-02-08 JP JP2023511559A patent/JPWO2023188842A1/ja active Pending
  • 2023-02-08 EP EP23778878.1A patent/EP4502020A4/en active Pending
  • 2023-02-08 US US18/729,319 patent/US20250092208A1/en active Pending
  • 2023-02-08 WO PCT/JP2023/004095 patent/WO2023188842A1/ja not_active Ceased
  • 2023-02-16 TW TW112105480A patent/TW202344564A/zh unknown

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events