Classifications

• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

• the present invention relates to a polyaryletherketone, a method for producing the same, and a resin composition. More specifically, the present invention relates to a novel polyaryletherketone having a specific structure, a method for producing the same, and a resin composition containing the polyaryletherketone and an oligomer.
• Fiber-reinforced composite materials obtained by combining reinforcing fiber materials such as carbon fiber, glass fiber, and aramid fiber with various matrix resins, are widely used in a variety of fields and applications.
• thermosetting resins such as unsaturated polyester resin, epoxy resin, and polyimide resin have been mainly used as matrix resins.
• thermosetting resins have the disadvantages of being brittle and having poor impact resistance. For this reason, particularly in the aerospace and aerospace fields, the use of thermoplastic resins as matrix resins is being considered from the standpoint of the impact resistance and molding costs of the resulting composite materials.
• PAEKs polyaryletherketones
• PEEK polyetheretherketone
• PEKK polyetherketoneketone
• polyaryletherketones have low versatility because their melting points and melt viscosities are too high, and they require molding at high temperatures. In addition, they can be difficult to handle because they need to be heated to a temperature close to the thermal decomposition temperature during molding.
• Patent Documents 1 and 2 disclose polyaryl ether ketones, but do not provide sufficient effects.
• polyaryl ether ketones composed of specific monomer units and having a specific degree of polymerization can solve the above problems, leading to the completion of the present invention. Furthermore, the inventors discovered that controlling the reaction order of the monomers during the production of polyaryl ether ketones can particularly improve crystallinity when the temperature is lowered, leading to the completion of the present invention. Furthermore, the inventors discovered that the above problems can be solved by using a specific oligomer having a bisphenol structure as a plasticizer in the polyaryl ether ketone, leading to the completion of the present invention.
• the reduced viscosity is 0.50 dL/g or more, and In differential scanning calorimetry, the crystallization enthalpy when the temperature is continuously decreased from a molten state of 400° C. at a rate of 90° C./min is greater than 0 J/g.
• the following formula (1) [In the formula (1), the Ar 1 portion is represented by the following formula (2): (In the formula (2), R 1 and R 2 are hydrogen atoms, or aliphatic hydrocarbons or aromatic hydrocarbons, which may have a substituent. R 1 and R 2 may be the same or different. R 1 and R 2 may be bonded to form a ring.
• R 3 to R 6 are hydrogen atoms, or aliphatic hydrocarbons or aromatic hydrocarbons, which may have a substituent.)
• the monomer unit is represented by
• the Ar2 moiety is a monomeric unit comprising a monomeric unit containing an aryl ketone structure.
• the Ar 1 portion is a monomer unit represented by the formula (2), The following formula (3) and/or the following formula (4)
• Y is any one of C ⁇ O, an alkylene group having 1 to 6 carbon atoms, —O—, —S—, and —SO 2 —.
• a monomer unit represented by The Ar2 portion is represented by the following formulas (5) to (7).
• polyaryl ether ketone which comprises one or more monomer units selected from those represented by the following formula:
• the Ar 1 portion of the formula (1) comprises a monomer unit represented by the formula (2) and a monomer unit represented by the formula (3)
• the formula (2) is a monomer unit derived from bisphenol A, The polyaryl ether ketone according to any one of [1] to [4], wherein a molar ratio of the monomer unit represented by the formula (2) to the monomer unit represented by the formula (3) in the Ar 1 portion of the formula (1) [formula (2)/formula (3)] is 10/90 to 60/40.
• the Ar2 portion of the formula (1) comprises a monomer unit represented by the formula (6) and a monomer unit represented by the formula (7),
• the polyaryl ether ketone according to any one of [1] to [5], wherein a molar ratio of the monomer unit represented by the formula (6) to the monomer unit represented by the formula (7) in the Ar2 portion of the formula (1), [formula (6)/formula (7)], is 60/40 to 90/10.
• the polyaryl ether ketone described in [1] above is a copolymer consisting of an Ar1 portion and an Ar2 portion, has a reduced viscosity, which is an index of the degree of polymerization, of 0.50 dL/g or more, and crystallizes when cooled under a specified condition.
• the index of crystallization is evaluated by the crystallization enthalpy when the temperature is continuously lowered from a molten state of 400°C at a rate of 90°C/min in differential scanning calorimetry.
• the crystallization enthalpy is greater than 0 J/g. That is, the exothermic peak due to crystallization is shown when the temperature is lowered under a specified condition.
• the polyaryl ether ketone described in [3] above has a high glass transition point of 150° C. or higher and a relatively low melting point of 380° C. or lower.
• the polyaryl ether ketones described in the above items [2], [4] to [6] have a predetermined monomer composition.
• the molar ratio [Formula (2)/Formula (3)] means the value obtained by dividing the number of moles of the monomer unit represented by Formula (2) by the number of moles of the monomer unit represented by Formula (3) (hereinafter the same).
• the oligomer is represented by the following formula (8):
• R a and R b are hydrogen atoms, aliphatic hydrocarbons, or aromatic hydrocarbons, and may have a substituent.
• R a and R b may be the same or different.
• R a and R b may be bonded to form a ring.
• a repeating unit B containing an aryl group In formula (8), R a and R b are hydrogen atoms, aliphatic hydrocarbons, or aromatic hydrocarbons, and may have a substituent.
• R a and R b may be the same or different. Furthermore, R a and R b may be bonded to form a ring.
• the resin composition described in [7] above contains an oligomer as a plasticizer, which comprises a repeating unit A containing a specific bisphenol structure and a repeating unit B containing an aryl group, in a base resin made of a polyaryl ether ketone described in any one of [1] to [6].
• R 1 and R 2 are hydrogen atoms, or aliphatic hydrocarbons, or aromatic hydrocarbons, which may have a substituent.
• R 1 and R 2 may be the same or different.
• R 1 and R 2 may be bonded to form a ring.
• R 3 to R 6 are hydrogen atoms, or aliphatic hydrocarbons, or aromatic hydrocarbons, which may have a substituent.
• each X is a halogen atom.
• each X is a halogen atom.
• a dihalogen monomer represented by the formula In a production method, the above-mentioned A diol monomer represented by the formula (9) is reacted with a dihalogen monomer represented by the formula (12) in a molar ratio [formula (9)/formula (12)] ⁇ 9/10 or a molar ratio [formula (9)/formula (12)] ⁇ 10/9, The diol monomer represented by the formula (10) and the dihalogen monomer represented by the formula (11) are reacted therewith, Next, the diol monomer represented by the formula (9) and/or the dihalogen monomer represented by the formula (12) are further reacted therewith.
• the method for producing a polyaryl ether ketone according to any one of [1] to [6].
• R 1 and R 2 are hydrogen atoms, or aliphatic hydrocarbons, or aromatic hydrocarbons, which may have a substituent.
• R 1 and R 2 may be the same or different.
• R 1 and R 2 may be bonded to form a ring.
• R 3 to R 6 are hydrogen atoms, or aliphatic hydrocarbons, or aromatic hydrocarbons, which may have a substituent.
• each X is a halogen atom.
• each X is a halogen atom.
• a dihalogen monomer represented by the formula: In a production method, the above-mentioned After reacting the diol monomer represented by the formula (10) with the dihalogen monomers represented by the formulas (11) and (12), A method for producing a polyaryl ether ketone according to any one of [1] to [6], characterized in that a diol monomer represented by the formula (9) is reacted with the polyaryl ether ketone.
• the production method described in the above [8] or [9] is a method for producing a polyaryl ether ketone by reacting monomers in a predetermined order.
• the polyaryletherketone of the present invention has a high glass transition point and therefore has high heat resistance.
• the polyaryletherketone of the present invention has an excellent balance between handleability and heat resistance because the melting point and glass transition point are adjusted within an appropriate range, and has high moldability because it crystallizes when cooled under specified conditions.
• the melt viscosity of the resin composition of the present invention is further reduced by the plasticizer, the decrease in performance caused by the plasticizer is small. According to the production method of the present invention, it is possible to produce a polyaryl ether ketone that has particularly excellent crystallinity when the temperature is lowered.
• the polyaryl ether ketone of the present invention is described below.
• the temperature is 25°C and the pressure is atmospheric pressure unless otherwise specified.
• Polyaryl ether ketone of the present invention has a structure represented by the following formula (1).
• the Ar1 portion contains a monomer unit represented by the following formula (2).
• the Ar1 portion is preferably composed of a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3) and/or a monomer unit represented by the following formula (4).
• R 1 and R 2 are hydrogen atoms, or aliphatic hydrocarbons, or aromatic hydrocarbons, which may have a substituent.
• R 1 and R 2 may be the same or different.
• R 1 and R 2 may be bonded to form a ring.
• R 3 to R 6 are hydrogen atoms, or aliphatic hydrocarbons, or aromatic hydrocarbons, which may have a substituent.
• R1 and R2 are preferably a hydrogen atom or an alkyl group, and more preferably a methyl group. Examples of R 3 to R 6 include a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, and a phenyl group.
• the monomer unit represented by formula (2) is preferably derived from a diol monomer represented by the following formula (9):
• R 1 to R 6 are as explained in formula (2).
• diol monomers represented by formula (9) examples include bisphenol A, bisphenol C, bisphenol E, and bisphenol F, with bisphenol A and bisphenol C being particularly preferred, and bisphenol A being even more preferred. Such bisphenols can also be obtained by depolymerizing polycarbonate when recycling the polycarbonate.
• the monomer unit represented by formula (3) is preferably a diol monomer represented by the following formula (10), i.e., biphenol.
• Y is any one of C ⁇ O, an alkylene group having 1 to 6 carbon atoms, —O—, —S—, and —SO 2 —.
• the monomer unit represented by formula (4) is preferably a monomer unit derived from a diol monomer such as 4,4'-dihydroxybenzophenone or dihydroxydiphenylmethane.
• the Ar 1 portion of formula (1) contains a monomer unit represented by formula (2), and the proportion of the monomer unit represented by formula (2) in the Ar 1 portion is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, and particularly preferably 20 to 50 mol%.
• the thermal properties and mechanical properties of the polyaryl ether ketone can be particularly improved. If it is less than 10 mol%, the melting point may be too high or the mechanical properties may not be sufficiently high. If it exceeds 60 mol%, the crystallinity during cooling may decrease.
• the proportion of the monomer unit represented by formula (3) in the Ar 1 portion of formula (1) is preferably 30 to 80 mol%, more preferably 40 to 75 mol%, and particularly preferably 50 to 70 mol%.
• the proportion of the monomer unit represented by formula (3) in the Ar 1 portion of formula (1) is preferably 30 to 80 mol%, more preferably 40 to 75 mol%, and particularly preferably 50 to 70 mol%.
• the proportion of the monomer unit represented by formula (4) in the Ar 1 portion of formula (1) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 30 mol%.
• the proportion of the monomer unit represented by formula (4) in the Ar 1 portion of formula (1) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 30 mol%.
• the total proportion of the monomer units represented by formulas (2) to (4) in the Ar 1 portion of formula (1) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 100 mol%.
• the thermal properties and mechanical properties of the polyaryl ether ketone can be particularly improved. If it is less than 90 mol%, the melting point and crystallinity during cooling may not be within the desired range.
• the Ar 1 moiety of formula (1) preferably consists of monomer units represented by formulas (2) and (3).
• the molar ratio of the monomer unit represented by formula (2) to the monomer unit represented by formula (3) in the Ar 1 portion of formula (1) [formula (2)/formula (3)] is preferably 10/90 to 60/40, more preferably 20/80 to 55/45, and particularly preferably 30/70 to 50/50.
• the thermal properties and mechanical properties of the polyaryl ether ketone can be particularly improved.
• the monomer unit represented by formula (2) is less than 10 mol%, the melting point may be too high or the mechanical properties may not be sufficiently high.
• the monomer unit represented by formula (2) is more than 60 mol%, the crystallinity during cooling may decrease.
• the Ar2 portion contains one or more monomer units selected from those represented by the following formulas (5) to (7).
• the monomer unit represented by formula (5) is preferably a monomer unit derived from a dihalogen monomer such as 4,4'-difluorobenzophenone.
• the monomer unit represented by formula (6) is preferably derived from a dihalogen monomer represented by the following formula (11):
• each X is a halogen atom, and is preferably a fluorine atom or a chlorine atom.
• the dihalogen monomer represented by formula (11) is preferably 1,4-bis(fluorobenzoyl)benzene or 1,4-bis(chlorobenzoyl)benzene.
• the monomer unit represented by formula (7) is preferably derived from a dihalogen monomer represented by the following formula (12):
• each X is a halogen atom, and preferably a fluorine atom or a chlorine atom.
• the dihalogen monomer represented by formula (12) is preferably 1,3-bis(fluorobenzoyl)benzene or 1,3-bis(chlorobenzoyl)benzene.
• the proportion of the monomer unit represented by formula (5) in the Ar 2 portion of formula (1) is preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less.
• the proportion of the monomer unit represented by formula (5) in the Ar 2 portion of formula (1) is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more.
• the thermal properties and mechanical properties of the polyaryl ether ketone can be particularly improved. If it is more than 30 mol% and less than 80 mol%, the crystallinity at the time of cooling may decrease.
• the proportion of the monomer unit represented by formula (6) in the Ar2 portion of formula (1) is preferably 50 to 90 mol%, more preferably 60 to 85 mol%, and particularly preferably 70 to 80 mol%.
• the proportion of the monomer unit represented by formula (6) in the Ar2 portion of formula (1) is preferably 50 to 90 mol%, more preferably 60 to 85 mol%, and particularly preferably 70 to 80 mol%.
• the proportion of the monomer unit represented by formula (7) in the Ar2 portion of formula (1) is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, and particularly preferably 20 to 30 mol%.
• the proportion of the monomer unit represented by formula (7) in the Ar2 portion of formula (1) is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, and particularly preferably 20 to 30 mol%.
• the total proportion of the monomer units represented by formulas (5) to (7) in the Ar2 portion of formula (1) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 100 mol%.
• the thermal properties and mechanical properties of the polyaryl ether ketone can be particularly improved. If it is less than 90 mol%, the melting point and crystallinity during cooling may not be within the desired range.
• the Ar2 moiety of formula (1) preferably consists of monomer units represented by formulas (6) and (7).
• the molar ratio of the monomer unit represented by formula (6) to the monomer unit represented by formula (7) in the Ar2 portion of formula (1) [formula (6)/formula (7)] is preferably 60/40 to 90/10, more preferably 65/35 to 85/15, and particularly preferably 70/30 to 80/20.
• the thermal properties and mechanical properties of the polyaryl ether ketone can be particularly improved. If the monomer unit represented by formula (6) is less than 60 mol%, the melting point may be too low, and the crystallinity may be reduced when the temperature is lowered. If the monomer unit represented by formula (6) is more than 90 mol%, the melting point may be too high, and the moldability may not be sufficiently high.
• the polyaryletherketone of the present invention has a reduced viscosity of 0.50 dL/g or more, preferably 0.55 dL/g or more, and more preferably 0.60 dL/g or more.
• the reduced viscosity is preferably 1.50 dL/g or less, more preferably 1.35 dL/g or less, and particularly preferably 1.20 dL/g or less.
• the reduced viscosity is less than 0.50 dL/g, the molecular weight (degree of polymerization) is low, and the thermal properties and mechanical properties of the polyaryletherketone are reduced. If the reduced viscosity exceeds 1.50 dL/g, the molecular weight (degree of polymerization) becomes too high, and the melt viscosity of the polyaryletherketone becomes too high, which may result in insufficient moldability and handleability.
• the reduced viscosity means a value ( ⁇ sp /c) obtained by dividing the specific viscosity ( ⁇ sp ) of the polyaryl ether ketone by the unit concentration (c) of the polyaryl ether ketone.
• the reduced viscosity in the present invention is a reduced viscosity obtained by measuring the viscosity of a solution obtained by dissolving 40 mg of the polyaryl ether ketone in 20 mL of p-chlorophenol under heating at a temperature of 60° C. using an Ostwald viscometer.
• the polyaryl ether ketone of the present invention is characterized in that, in differential scanning calorimetry, the crystallization enthalpy is greater than 0 J/g when the temperature is continuously lowered from a molten state of 400° C. at a rate of 90° C./min. That is, when the temperature is continuously lowered from a molten state of 400° C. at a rate of 90° C./min., an exothermic peak due to crystallization appears in the differential scanning calorimetry curve. The crystallization enthalpy is determined from the peak area of this exothermic peak.
• the crystallization enthalpy is preferably 3 J/g or more, more preferably 5 J/g or more, and particularly preferably 7 J/g or more.
• Polyaryletherketones with a crystallization enthalpy of more than 0 J/g crystallize when the temperature is lowered, so that the thermal properties and mechanical properties of the polyaryletherketones are excellent.
• the fast curing property during hot molding is excellent, the occupancy time of the mold can be shortened and the molding cycle can be increased, so that the productivity is improved.
• the polyaryl ether ketone of the present invention has an exothermic peak due to crystallization, and therefore naturally has a melting point, but in differential scanning calorimetry, this exothermic peak appears at a temperature lower than the melting point.
• the temperature at which the exothermic peak appears is preferably 190°C or higher, more preferably 210°C or higher, and particularly preferably 230°C or higher. The higher the temperature at which the exothermic peak appears, the more rapid the curing properties.
• the polyaryletherketone of the present invention has a melting point.
• the melting point is preferably 380°C or less, and more preferably 370°C or less.
• the lower limit of the melting point of the polyaryletherketone of the present invention is not particularly limited, but is preferably 250°C or more, more preferably 280°C or more, and particularly preferably 300°C or more.
• the melt viscosity of the polyaryletherketone is too high, and molding at high temperatures is required, which may reduce versatility.
• the glass transition point of the polyaryl ether ketone of the present invention is preferably 150°C or higher, more preferably 155°C or higher, and particularly preferably 160°C or higher. The higher the glass transition point, the better the heat resistance, so there is no particular upper limit.
• the melt viscosity of the polyaryletherketone of the present invention at 400°C is preferably 20,000 Pa ⁇ s or less, more preferably 15,000 Pa ⁇ s or less, and particularly preferably 10,000 Pa ⁇ s or less.
• the lower limit of the melt viscosity is preferably 100 Pa ⁇ s or more, more preferably 150 Pa ⁇ s or more, and particularly preferably 200 Pa ⁇ s or more. A melt viscosity in this range provides excellent handleability and moldability.
• the preferred polyaryletherketone of the present invention is clearly different from conventional polyaryletherketones in that it has crystallinity when cooled under specified conditions, and also has both a high glass transition point and a relatively low melting point as described above.
• the cured resin composition containing the polyaryl ether ketone of the present invention preferably has a flexural modulus of 2.4 GPa or more, more preferably 2.5 GPa or more, and particularly preferably 2.7 GPa or more, measured in accordance with JIS K7171.
• the cured resin composition containing the polyaryl ether ketone of the present invention preferably has a flexural strength of 60 MPa or more, more preferably 70 MPa or more, and particularly preferably 80 MPa or more, measured in accordance with JIS K7171.
• the polyaryletherketone of the present invention is produced by polymerizing various monomers that provide monomer units constituting the polyaryletherketone in a solvent in the presence of a metal compound (polymerization catalyst).
• the monomers used as raw materials are as described above.
• the composition of monomers charged during production is almost the same as the composition of monomer units in the resulting polymer, so that in order to obtain a polymer having the above-mentioned preferred molar ratio of monomer units, the composition of monomers charged during production may be adjusted as described above.
• the ratio of the monomers providing the monomer units represented by formula (2) to the total monomers is preferably 5 to 30 mol %, and more preferably 7.5 to 27.5 mol %.
• the ratio of the monomers providing the monomer units represented by formula (3) to the total monomers is preferably 15 to 40 mol%, and more preferably 20 to 37.5 mol%.
• the ratio of the monomers providing the monomer units represented by formula (4) to the total monomers is preferably 0 to 25 mol %, and more preferably 0 to 20 mol %.
• the ratio of the monomers providing the monomer units represented by formula (5) to the total monomers is preferably 15 mol% or less or 40 mol% or more, and more preferably 10 mol% or less or 45 mol% or more.
• the ratio of the monomers providing the monomer units represented by formula (6) to the total monomers is preferably 25 to 45 mol%, and more preferably 30 to 42.5 mol%.
• the ratio of the monomers providing the monomer units represented by formula (7) to the total monomers is preferably 5 to 25 mol %, and more preferably 7.5 to 20 mol %.
• Methods for polymerizing the monomers used in the present invention include solution polymerization and emulsion polymerization. Among these, solution polymerization is preferred because it is easy to adjust the degree of polymerization, etc.
• the solvent used during polymerization is not particularly limited as long as it is a high-boiling solvent that is easy to remove after polymerization is completed and allows easy temperature control during the polymerization reaction.
• solvents include diphenyl sulfone, sulfolane, dimethyl sulfoxide, N-methylpyrrolidone, N-cyclohexyl-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone. Of these, diphenyl sulfone and sulfolane are preferred.
• the total concentration of the monomers in the solvent is preferably 10 to 60% by mass.
• the various monomers may be dissolved all at once and polymerized, or may be added gradually during the polymerization reaction. As described below, adding the monomers gradually makes it easier to control the structure of the resulting polymer.
• Known polymerization initiation methods include methods in which polymerization is initiated by heating or electron beam irradiation, methods using various polymerization initiators, and methods using these in combination. Any polymerization initiation method may be used in the present invention, but a method in which polymerization is initiated by heating is preferred.
• the temperature during polymerization is preferably set appropriately within the range of 160 to 360°C.
• the polymerization can be substantially completed by maintaining the temperature at 320° C. for about 0.2 to 5 hours, for example.
• the polymerization catalyst carbonates or hydrogen carbonates of sodium, potassium, rubidium, and cesium are preferred, potassium carbonate and sodium carbonate are more preferred, and a combination of potassium carbonate and sodium carbonate is particularly preferred.
• the amount of polymerization catalyst added is not particularly limited, but 1.0 to 3.0 molar equivalents based on the total amount of diol monomers is preferred.
• the degree of polymerization and the ratio of the monomer components constituting each of the Ar1 portion and the Ar2 portion in the polymer of formula (1) i.e., the chain structure and the ratio of a specific chain structure to the entire polymer, can be adjusted by a known method, but can also be adjusted, for example, by sequentially adding monomers. An example of this is described below.
• the above-mentioned A diol monomer represented by the formula (9) is reacted with a dihalogen monomer represented by the formula (12) in a molar ratio [formula (9)/formula (12)] ⁇ 9/10 or a molar ratio [formula (9)/formula (12)] ⁇ 10/9
• the diol monomer represented by the formula (10) and the dihalogen monomer represented by the formula (11) are reacted therewith,
• a method of further reacting the diol monomer represented by the formula (9) and/or the dihalogen monomer represented by the formula (12) can be mentioned.
• the molecular chain formed by the alternating copolymerization of the formula (2) and the formula (7) is considered to be a chain structure that reduces crystallinity, and the diol monomer represented by the formula (9) and the dihalogen monomer represented by the formula (12) that provide these structures are reacted in advance at a molar ratio [formula (9)/formula (12)] ⁇ 9/10, or at a molar ratio [formula (9)/formula (12)] ⁇ 10/9, i.e., at a ratio far removed from 1/1, to control the length of the molecular chain formed by the alternating copolymerization of the formula (2) and the formula (7) not to be long.
• the diol monomer represented by the formula (10) and the dihalogen monomer represented by the formula (11) that provide a chain structure that increases crystallinity are reacted therewith, and finally the remaining diol monomer represented by the formula (9) and the dihalogen monomer represented by the formula (12) are added, thereby producing a polyaryl ether ketone that has higher crystallinity when cooled and does not have an excessively high melting point.
• the molar ratio [formula (9)/formula (12)] of the diol monomer represented by formula (9) and the dihalogen monomer represented by formula (12) to be reacted first is preferably [formula (9)/formula (12)] ⁇ 9/10, or [formula (9)/formula (12)] ⁇ 10/9, more preferably [formula (9)/formula (12)] ⁇ 4/5, or [formula (9)/formula (12)] ⁇ 5/4, and further preferably [formula (9)/formula (12)] ⁇ 2/3, or [formula (9)/formula (12)] ⁇ 3/2.
• a production method the above-mentioned After reacting the diol monomer represented by the formula (10) with the dihalogen monomers represented by the formulas (11) and (12),
• One example of such a method is to react a diol monomer represented by the above formula (9). By gradually adding the monomer in this manner, it is possible to further increase the crystallinity during the temperature decrease.
• the molecular chain containing the formula (2) is considered to be a structure that reduces crystallinity, and by reacting the monomers represented by the formulas (10) to (12) in advance without adding the diol monomer represented by the formula (9) that provides this structure, it is possible to control so that the molecular chain containing the formula (2) is not generated. Finally, by adding the diol monomer represented by the formula (9), it is possible to produce a polyaryl ether ketone that has higher crystallinity when cooled and does not have an excessively high melting point.
• the resin composition of the present invention is a resin composition comprising the polyaryl ether ketone of the present invention and a specified oligomer having a bisphenol structure.
• the amount of oligomer to be blended per 100 parts by mass of polyaryletherketone, which is the base resin is preferably 5 to 30 parts by mass, and more preferably 7 to 20 parts by mass. If it is less than 5 parts by mass, the effect of lowering the melt viscosity of polyaryletherketone is small. If it exceeds 30 parts by mass, the physical properties of the resin composition are likely to deteriorate.
• the resin composition obtained by adding an oligomer to a polyaryl ether ketone preferably has a melt viscosity at 400°C of 100 to 20,000 Pa ⁇ s, more preferably 150 to 15,000 Pa ⁇ s, and particularly preferably 200 to 10,000 Pa ⁇ s.
• melt viscosity at 400°C of a resin composition in which 15 parts by mass of oligomer are added to 100 parts by mass of polyaryletherketone is preferably reduced by 40 to 90%, and more preferably reduced by 40 to 80%, compared to the melt viscosity at 400°C of the same polyaryletherketone alone.
• the resin composition of the present invention contains the above-mentioned resin composition as an essential component and may contain other optional components, such as other thermoplastic resins, fillers, and colorants.
• the resin composition of the present invention preferably contains the above-mentioned resin composition in an amount of 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 99% by mass or more, and may of course contain 100% by mass of the resin composition as a whole.
• the melt viscosity of the resin composition of the present invention is a complex viscosity measured by using a rotational rheometer and subjecting a molten sample set on parallel plates in a nitrogen gas flow to the following evaluation conditions.
• Measurement mode Forced vibration method Measurement temperature: 400°C Gap distance: 1.000 mm Angular frequency: 10 rad/s
• the cured product of the resin composition of the present invention preferably has a flexural modulus of 2.4 GPa or more, more preferably 2.5 GPa or more, and particularly preferably 2.7 GPa or more, as measured in accordance with JIS K7171.
• the cured product of the resin composition of the present invention preferably has a flexural strength of 60 MPa or more, more preferably 70 MPa or more, and particularly preferably 80 MPa or more, as measured in accordance with JIS K7171.
• Oligomer (plasticizer) The oligomer used in the resin composition of the present invention has a bisphenol structure represented by the following formula (8):
• repeating unit A containing a structure represented by the formula: and repeating unit B containing an aryl group.
• R a and R b are hydrogen atoms, aliphatic hydrocarbons, or aromatic hydrocarbons, and may have a substituent.
• R a and R b may be the same or different.
• R a and R b may be bonded to form a ring.
• the substituent include a methyl group, an ethyl group, a cyclohexyl group, and a phenyl group.
• R a and R b are preferably an alkyl group, more preferably a methyl group.
• the aryl group constituting the repeating unit B is preferably an aryl group containing a ketone group, and is represented by the following chemical formula (13):
• the benzophenone structure is represented by the following formula:
• the mass average molecular weight (Mw) of the oligomer is preferably from 1,000 to 30,000, and more preferably from 1,000 to 25,000.
• Mw mass average molecular weight
• the resin physical properties are unlikely to deteriorate even if a plasticizer (oligomer) is added to the base resin. If the molecular weight is less than 1,000, the resin physical properties are likely to deteriorate when a plasticizer (oligomer) is added to the base resin. If the molecular weight exceeds 30,000, the compatibility with the base resin is likely to decrease.
• the oligomer used in the resin composition of the present invention preferably has a total ratio of repeating unit A having a structure represented by formula (8) and repeating unit B containing an aryl group of 70 to 100 mol %, more preferably 80 to 100 mol %, and particularly preferably 90 to 100 mol %.
• the ratio of repeating units A and B in the oligomer is preferably m/(m+n), where m is the number of moles of repeating units A and n is the number of moles of repeating units B, in a range of 0.1 to 0.9, and more preferably 0.2 to 0.8.
• oligomers examples include compounds represented by the following chemical formulas (14) to (16).
• the resin composition of the present invention can be produced by mixing the polyaryl ether ketone of the present invention, the oligomer, and, if necessary, other components. The order of mixing these components does not matter.
• the method of mixing the polyaryl ether ketone, the oligomer, and other components as necessary is not particularly limited, and conventionally known methods such as a powder mixing method, a solution method, a melt method, or a master batch method can be adopted.
• a powder mixing method such as a powder mixing method, a solution method, a melt method, or a master batch method.
• kneading kneading in a solution state or in a molten state is preferred from the viewpoint of uniformity.
• a conventionally known kneading device can be used for the mixing operation of the polyaryl ether ketone, the oligomer, and other components as necessary.
• the kneading device is not particularly limited, and conventionally known vertical reaction vessels, mixing tanks, kneading tanks, or single-shaft or multi-shaft horizontal kneading devices, such as single-shaft or multi-shaft extruders and kneaders, can be exemplified.
• the resin composition obtained by mixing in the present invention can be used after being pulverized as necessary.
• the pulverization method is not particularly limited, and a conventionally known method such as a freeze pulverization method, a cutting mill method, or a bowl mill method can be used.
• the melting temperature may be any temperature as long as it is equal to or higher than the melting point of the polyaryl ether ketone of the present invention.
• the polyaryletherketone or resin composition of the present invention can be composited with a fiber-reinforced substrate to form a fiber-reinforced composite material.
• the molding method of the fiber-reinforced composite material is not particularly limited, but examples thereof include molding methods with excellent productivity such as injection molding, autoclave molding, press molding, filament winding molding, and stamping molding, and these can be used in combination.
• Fiber-reinforced substrate The reinforcing fiber used as the fiber-reinforced substrate is not particularly limited, and examples thereof include carbon fiber, glass fiber, aramid fiber, silicon carbide fiber, polyester fiber, ceramic fiber, alumina fiber, boron fiber, metal fiber, mineral fiber, rock fiber, and slag fiber.
• carbon fiber is more preferred because it has good specific strength and specific elastic modulus, and can produce a lightweight, high-strength fiber-reinforced composite material.
• Polyacrylonitrile (PAN)-based carbon fiber is particularly preferred because it has excellent tensile strength.
• the tensile modulus is preferably 100 to 600 GPa, more preferably 200 to 500 GPa, and particularly preferably 230 to 450 GPa.
• the tensile strength is preferably 2000 MPa to 10000 MPa, and more preferably 3000 to 8000 MPa.
• the diameter of the carbon fibers is preferably 4 to 20 ⁇ m, and more preferably 5 to 10 ⁇ m.
• the reinforcing fiber substrate may be a reinforcing fiber bundle, or may be used as a reinforcing fiber sheet formed from reinforcing fibers in a sheet shape. It is more preferable to use a reinforcing fiber sheet formed from reinforcing fibers in a sheet shape.
• the reinforcing fiber sheet examples include a sheet (UD sheet) in which a large number of reinforcing fibers are aligned in one direction, a laminated sheet in which a plurality of UD sheets are laminated with the fiber direction aligned or changed, a bidirectional fabric such as a plain weave or twill weave, a multiaxial fabric, a nonwoven fabric, a mat, a knit, a braid, and a paper made from reinforcing fibers.
• a UD sheet, a laminated sheet, a bidirectional fabric, or a multiaxial fabric substrate formed from reinforcing fibers in a sheet shape as continuous fibers because a fiber-reinforced composite material with better mechanical properties can be obtained.
• the thickness of the sheet-shaped reinforcing fiber substrate is preferably 0.01 to 3 mm, more preferably 0.1 to 1.5 mm.
• the melt viscosity was measured using a rheometer, Discovery DHR-2, manufactured by TA Instruments, by setting a polymeric material sample on aluminum parallel plates at 400° C. in a nitrogen gas flow of 20 mL/min, holding the sample for 2 minutes, and then measuring the melt viscosity under the following evaluation conditions.
• Measurement mode forced vibration method Gap distance: 1.000 mm Angular frequency: 10 rad/s Distortion: 0.5
• the reduced viscosity was measured as follows. First, 40 mg of polyaryl ether ketone was added to 20 mL of p-chlorophenol, and the mixture was stirred and dissolved at 60° C. using a magnetic stirrer. If the mixture was difficult to dissolve, it was further heated up to an upper limit of 200° C., and the residue was removed using a glass filter. The reduced viscosity was calculated by measuring the viscosity of this solution at 60° C. using an Ostwald viscometer.
• the glass transition temperature was measured as follows. The measurements were performed using a differential scanning calorimeter, DSC Q2000, manufactured by TA Instruments, in a nitrogen gas flow rate of 50 ml/min using the following scan procedure. Step 1: The sample is heated from 30° C. to 400° C. at 10° C./min. Step 2: Hold for 3 minutes. Step 3: Decrease temperature to 30° C. at 90° C./min. Step 4: The temperature was increased from 30° C. to 400° C. at a rate of 10° C./min, and the inflection point in the transition process of the obtained curve was taken as the glass transition temperature (Tg).
• DSC Q2000 differential scanning calorimeter
• the melting points were measured as follows. A crystalline melting endothermic peak was detected from the curve obtained in step 1 of the above scanning procedure, and this temperature was taken as the melting point (Tm).
• the crystallization enthalpy was measured as follows. The exothermic peak due to crystallization was detected from the curve obtained in step 3 of the above scanning procedure, and this temperature was taken as the crystallization temperature (Tcd). The crystallization enthalpy ( ⁇ Hcd) was calculated from the area under this curve.
• the bending strength and bending modulus were measured according to JIS K 7171.
• Test pieces were prepared using an injection molding machine HAAKE MiniJet Pro manufactured by Thermo Fisher Scientific, Inc., and a mold for bending test pieces conforming to JIS K 7171 under the following conditions. Cylinder temperature: 380-400°C Mold temperature: 240°C Mold retention time: 60 seconds
• Example 1 Into a 300 mL separable flask equipped with a Dean-Stark tube, a nitrogen gas inlet tube, and a stirrer, 11.41 g (BisA: 0.0500 mol) of bisphenol A (2,2-bis(4-hydroxyphenyl)propane) (hereinafter sometimes abbreviated as BisA), 9.311 g (BP: 0.0500 mol) of 4,4'-dihydroxybiphenyl (hereinafter sometimes abbreviated as BP), 21.82 g (DFB: 0.1000 mol) of 4,4'-difluorobenzophenone (hereinafter sometimes abbreviated as DFB), and 60.00 g of diphenyl sulfone (melting point 127°C, boiling point 379°C) as a solvent were added, and the mixture was replaced with nitrogen and heated to 160°C with stirring to dissolve.
• BisA bisphenol A (2,2-bis(4-hydroxyphenyl)propane)
• BisA bisphenol
• the glass transition point (Tg) was 150° C.
• the melting point (Tm) was 331° C.
• the crystallization temperature (Tcd) during cooling was 265° C.
• the crystallization enthalpy ( ⁇ Hcd) was 19.8 J/g.
• Example 3 A polyaryl ether ketone was obtained in the same manner as in Example 1, except that the ratio of the monomers was changed as shown in Table 1. The results are shown in Table 1.
• 4,4'-dihydroxybenzophenone hereinafter sometimes abbreviated as DHB was used as the diol monomer in addition to BisA and BP.
• Example 4 Into a 100 mL separable flask equipped with a Dean-Stark tube, a nitrogen gas inlet tube, and a stirrer, 4.512 g (1,4-DFBB: 0.0140 mol) of 1,4-bis(fluorobenzoyl)benzene (hereinafter sometimes abbreviated as 1,4-DFBB), 1.934 g (1,3-DFBB: 0.0060 mol) of 1,3-bis(fluorobenzoyl)benzene (hereinafter sometimes abbreviated as 1,3-DFBB), 2.607 g (BP: 0.0140 mol) of 4,4'-dihydroxybiphenyl, and 30.00 g of diphenylsulfone (melting point 127°C, boiling point 379°C) as a solvent were added, and the mixture was replaced with nitrogen and heated to 160°C while stirring to dissolve.
• 1,4-DFBB 1,4-bis(fluorobenzoyl)benzene
• 1,3-DFBB 1,3
• Example 5 Into a 300 mL separable flask equipped with a Dean-Stark tube, a nitrogen gas inlet tube, and a stirrer, 17.40 g of 1,4-bis(fluorobenzoyl)benzene (1,4-DFBB: 0.0540 mol), 5.802 g of 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0180 mol), 9.385 g of 4,4'-dihydroxybiphenyl (BP: 0.0504 mol), 4.931 g of bisphenol A (2,2-bis(4-hydroxyphenyl)propane) (BisA: 0.0216 mol), and 108.0 g of diphenylsulfone as a solvent were added, and the mixture was replaced with nitrogen and heated to 160°C while stirring to dissolve.
• 1,4-bis(fluorobenzoyl)benzene 1,4-DFBB: 0.0540 mol
• Example 6 Polyaryl ether ketone was obtained in the same manner as in Example 5, except that the final polymerization temperature was changed to 315° C. The results are shown in Table 1.
• Example 7 Polyaryl ether ketone was obtained in the same manner as in Example 5, except that the final polymerization temperature was changed to 320° C. The results are shown in Table 1.
• Example 8 Into a 300 mL separable flask equipped with a Dean-Stark tube, a nitrogen gas inlet tube, and a stirrer, 18.57 g of 1,4-bis(fluorobenzoyl)benzene (1,4-DFBB: 0.0576 mol), 4.641 g of 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0144 mol), 8.044 g of 4,4'-dihydroxybiphenyl (BP: 0.0432 mol), 10.45 g (0.0756 mol) of potassium carbonate as a catalyst, and 108.0 g of diphenylsulfone as a solvent were added, and the mixture was replaced with nitrogen and heated to 160°C with stirring, maintained at 160°C for 60 minutes, and then heated to 200°C over approximately 40 minutes.
• Example 9 In a 300 mL separable flask equipped with a Dean-Stark tube, a nitrogen gas inlet tube, and a stirrer, 5.802 g of 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0180 mol), 2.055 g of 2,2-bis(4-hydroxyphenyl)propane (BisA: 0.0090 mol), and 108.0 g of diphenylsulfone (melting point 127°C, boiling point 379°C) as a solvent were added, and the mixture was replaced with nitrogen and heated to 160°C while stirring to dissolve.
• 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0180 mol)
• 2,2-bis(4-hydroxyphenyl)propane BisA: 0.0090 mol
• diphenylsulfone melting point 127°C, boiling point 379°C
• the mixture was heated to 250°C over about 30 minutes, and held at 250°C for 60 minutes.
• the mixture was further heated to 300°C over about 30 minutes, and held at 300°C for 60 minutes to complete the polymerization.
• the polymer was cooled, spread thinly on a tray, cooled and solidified, then pulverized, washed with acetone, water, and methanol, and dried to obtain polyaryl ether ketone.
• the structure of this polyaryl ether ketone was measured by NMR, and it was confirmed that the copolymer had substantially the same composition as the charged monomer composition. The results are shown in Table 1.
• Example 10 In a 300 mL separable flask equipped with a Dean-Stark tube, a nitrogen gas inlet tube, and a stirrer, 5.802 g of 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0180 mol), 2.055 g of 2,2-bis(4-hydroxyphenyl)propane (BisA: 0.0090 mol), and 108.0 g of diphenylsulfone (melting point 127°C, boiling point 379°C) as a solvent were added, and the mixture was replaced with nitrogen and heated to 160°C while stirring to dissolve.
• 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0180 mol)
• 2,2-bis(4-hydroxyphenyl)propane BisA: 0.0090 mol
• diphenylsulfone melting point 127°C, boiling point 379°C
• the mixture was further heated to 300°C over about 30 minutes, and held at 300°C for 60 minutes to complete the polymerization.
• the polymer was cooled, spread thinly on a tray, cooled and solidified, then pulverized, washed with acetone, water, and methanol, and dried to obtain polyaryl ether ketone.
• the structure of this polyaryl ether ketone was measured by NMR, and it was confirmed that the copolymer had substantially the same composition as the charged monomer composition. The results are shown in Table 1.
• Example 11 Polyaryl ether ketone was obtained in the same manner as in Example 10, except that the final polymerization temperature was changed to 310° C. The results are shown in Table 1.
• Example 12 100 parts by mass of the polyaryletherketone obtained in Example 11 was mixed with 15 parts by mass of the plasticizer (modBisA-PEEK) produced in Production Example 1, and kneaded at 380° C. using a Labo Plastomill to obtain a resin composition. The results are shown in Table 1.
• Example 13 Polyaryl ether ketone was obtained in the same manner as in Example 10, except that the final polymerization temperature was changed to 315° C. The results are shown in Table 1.
• Example 14 100 parts by mass of the polyaryletherketone obtained in Example 13 was mixed with 15 parts by mass of the plasticizer (modBisA-PEEK) produced in Production Example 1, and kneaded at 380° C. using a Labo Plastomill to obtain a resin composition. The results are shown in Table 1.
• Example 15 100 parts by mass of the polyaryl ether ketone obtained in Example 13 was mixed with 15 parts by mass of the plasticizer (BisA-PEEK) produced in Production Example 2, and kneaded at 380° C. using a Labo Plastomill to obtain a resin composition. The results are shown in Table 1.
• Example 16 Polyaryl ether ketone was obtained in the same manner as in Example 10, except that the final polymerization temperature was changed to 320° C. The results are shown in Table 1.
• Example 17 100 parts by mass of the polyaryl ether ketone obtained in Example 16 was mixed with 15 parts by mass of the plasticizer (BisA-PEEK) produced in Production Example 2, and kneaded at 380° C. using a Labo Plastomill to obtain a resin composition. The results are shown in Table 1.
• Example 18 Polyaryl ether ketone was obtained in the same manner as in Example 9, except that the final polymerization temperature was changed to 320° C. The results are shown in Table 1.
• Example 19 In a 300 mL separable flask equipped with a Dean-Stark tube, a nitrogen gas inlet tube, and a stirrer, 5.802 g of 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0180 mol), 2.055 g of 2,2-bis(4-hydroxyphenyl)propane (BisA: 0.0090 mol), and 108.0 g of diphenylsulfone (melting point 127°C, boiling point 379°C) as a solvent were added, and the mixture was replaced with nitrogen and heated to 160°C while stirring to dissolve.
• 1,3-bis(fluorobenzoyl)benzene (1,3-DFBB: 0.0180 mol)
• 2,2-bis(4-hydroxyphenyl)propane BisA: 0.0090 mol
• diphenylsulfone melting point 127°C, boiling point 379°C
• the mixture was heated to 250°C over about 30 minutes, and held at 250°C for 60 minutes.
• the mixture was further heated to 320°C over about 30 minutes, and held at 320°C for 60 minutes to complete the polymerization.
• the polymer was cooled, spread thinly on a tray, cooled and solidified, then pulverized, washed with acetone, water, and methanol, and dried to obtain polyaryl ether ketone.
• the structure of this polyaryl ether ketone was measured by NMR, and it was confirmed that the copolymer had substantially the same composition as the charged monomer composition. The results are shown in Table 1.
• Example 20 Polyaryl ether ketone was obtained in the same manner as in Example 10, except that the final temperature of the polymerization was set to 310° C. and the ratio of the monomers was changed as shown in Table 1. The results are shown in Table 1.
• Example 21 Polyaryl ether ketone was obtained in the same manner as in Example 10, except that the final temperature of the polymerization was set to 315° C. and the ratio of the monomers was changed as shown in Table 1. The results are shown in Table 1.

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