WO2020045897A1 - Résine à base de phtalonitrile présentant une résistance aux chocs améliorée - Google Patents

Résine à base de phtalonitrile présentant une résistance aux chocs améliorée Download PDF

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WO2020045897A1
WO2020045897A1 PCT/KR2019/010708 KR2019010708W WO2020045897A1 WO 2020045897 A1 WO2020045897 A1 WO 2020045897A1 KR 2019010708 W KR2019010708 W KR 2019010708W WO 2020045897 A1 WO2020045897 A1 WO 2020045897A1
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group
formula
compound
phthalonitrile
independently
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PCT/KR2019/010708
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English (en)
Korean (ko)
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이승희
김상우
김영대
고은호
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주식회사 엘지화학
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Priority claimed from KR1020190102574A external-priority patent/KR102218559B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/977,379 priority Critical patent/US11932727B2/en
Priority to CN201980017402.3A priority patent/CN111819221B/zh
Priority to EP19855813.2A priority patent/EP3741791B1/fr
Priority to JP2020545659A priority patent/JP6935119B2/ja
Publication of WO2020045897A1 publication Critical patent/WO2020045897A1/fr

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the present invention relates to a phthalonitrile resin.
  • Phtharonitrile-based resins are known as thermosetting resins excellent in heat resistance and flame retardancy.
  • the resin composition in which phthalonitrile-based resins and additives such as glass fibers and carbon fibers are mixed may be used as a durable material for airplanes, ships, automobiles, and the like.
  • Phtharonitrile-based resins are generally formed by polymerization and high temperature curing by applying a phthalonitrile compound having two or more phthalonitrile groups and a curing agent thereof.
  • the phthalonitrile compound has many aromatic groups and has high rigidity and large molecular weight.
  • the prepolymer formed by the mixture of the phthalonitrile compound and the curing agent or by reaction of the mixture has a very narrow process window.
  • the process window is a measure of the processability of the resin, the processing temperature (T p ) and the temperature at which the prepolymer formed by the reaction of the mixture of the phthalonitrile monomer and the curing agent or the mixture is present in a processable state and curing It may be expressed as an absolute value of the difference T c -T p of the temperature T c .
  • the phthalonitrile resin has a disadvantage that the mechanical properties such as impact strength are very weak because the phthalonitrile resin has a hardened structure by the triazine produced through high temperature curing.
  • the present invention is to provide a phthalonitrile-based resin having excellent workability and improved impact strength.
  • the phthalonitrile compound is 4,4'-bis (3,4-dicyanophenoxy) diphenyl oxide (4,4'-bis (3,4-dicyanophenoxy) diphenyloxide) represented by the formula (1)
  • 4,4'-bis (3,4-dicyanophenoxy) biphenyl represented by 2 comprises 4,4'-bis (3,4-dicyanophenoxy) biphenyl in a weight ratio of 30:70 to 90:10 doing,
  • Phtharonitrile-based resins are provided:
  • the phthalonitrile compound is 4,4'-bis (3,4-dicyanophenoxy) diphenyl oxide (4,4'-bis (3,4-dicyanophenoxy) diphenyloxide) represented by the formula (1)
  • 4,4'-bis (3,4-dicyanophenoxy) biphenyl represented by 2 comprises 4,4'-bis (3,4-dicyanophenoxy) biphenyl in a weight ratio of 30:70 to 90:10 doing,
  • Phtharonitrile-based resins are provided:
  • the phthalonitrile-based resin formed by applying the phthalonitrile compounds represented by the formulas (1) and (2) in a weight ratio of 30:70 to 90:10 exhibits excellent workability and improved impact strength. It was confirmed that.
  • the phthalonitrile-based resin having the above characteristics makes it possible to provide a durable agent that can be more suitably used in airplanes, ships, automobiles and the like.
  • the phthalonitrile-based resin may be provided from a polymerizable composition comprising a phthalonitrile compound and a curing agent.
  • PN1 4,4'-bis (3,4-dicyanophenoxy) diphenyl oxide represented by Chemical Formula 1 (4,4'-bis (3,4-dicyanophenoxy) diphenyloxide, hereinafter " PN1 ") and 4,4'-bis (3,4-dicyanophenoxy) biphenyl represented by Chemical Formula 2 (4,4'-bis (3,4-dicyanophenoxy) biphenyl, hereinafter referred to as "PN2"
  • PN2 4,4'-bis (3,4-dicyanophenoxy) biphenyl
  • the weight ratio (PN1: PN2) of PN1 and PN2 is 30:70 to 90:10, or 35:65 to 90:10, or 30:70 to 85:15, or 40:60 to 90:10. Or 30:70 to 75:25, or 50:50 to 90:10, or 30:70 to 60:40, or 40:60 to 85:15, or 40:60 to 75:25.
  • the weight ratio (PN1: PN2) of PN1 and PN2 is 30:70, or 35:65, or 40:60, or 45:55, or 50:50, or 55:45, or 60:40, or 65:35, or 70:30, or 75:25, or 80:20, or 85:15, or 90:10.
  • the PN1 is preferably contained in 30% by weight or more of the phthalonitrile compound.
  • the PN 2 is preferably contained in 10% by weight or more of the phthalonitrile compound.
  • the curing agent is not particularly limited as long as it can react with the phthalonitrile compound to form a phthalonitrile resin.
  • one or more compounds selected from the group consisting of amine compounds, hydroxy compounds and imide compounds may be used as the curing agent.
  • the amine compound, the hydroxy compound, and the imide compound mean each compound including at least one amino group, hydroxy group, and imide group in a molecule.
  • the curing agent may be an imide compound represented by Formula 3 below:
  • M is a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound
  • X 1 and X 2 are each independently a divalent radical derived from an alkylene group, an alkylidene group, or an aromatic compound,
  • n is a number of 1 or more.
  • the imide-based compound represented by the formula (3) has an imide structure in the molecule, thereby exhibiting excellent heat resistance, so that it is excessively contained in the polymerizable composition or adversely affects physical properties even when the polymerizable composition is processed or cured at a high temperature. Do not cause defects such as voids that may be caused.
  • M may be a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound.
  • radicals formed by leaving four hydrogen atoms in a molecule may each have a structure in which a carbon atom of the carbonyl group of Formula 3 is connected.
  • alkanes, alkenes, or alkynes straight or branched alkanes, alkenes, or alkynes can be exemplified.
  • alkanes, alkenes, or alkynes having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms may be used.
  • the alkanes, alkenes, or alkynes may be optionally substituted by one or more substituents.
  • Examples of the alicyclic compound include hydrocarbon compounds having a non-aromatic ring structure having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbon atoms, or 3 to 4 carbon atoms.
  • Such an alicyclic hydrocarbon compound may include at least one hetero atom, such as oxygen or nitrogen, as a ring constituent atom, and may be optionally substituted with one or more substituents if necessary.
  • aromatic compound benzene, the compound containing benzene, or derivatives thereof can be illustrated.
  • compound including the benzene a compound having a structure in which two or more benzene rings are condensed while sharing one or two carbon atoms, or connected by a directly linked structure or an appropriate linker.
  • L 1 to L 8 may be each independently a single bond, —O—, an alkylene group, or an alkylidene group, and Ar 1 and Ar 2 may each independently be an arylene group.
  • the aromatic compound may include, for example, 6 to 30, 6 to 28, 6 to 27, 6 to 25, 6 to 20 or 6 to 12 carbon atoms. It may be substituted by one or more substituents if necessary.
  • the number of carbon atoms of the said aromatic compound is the number including the carbon atom which exists in the linker, when the compound contains the above-mentioned linker.
  • M may be a tetravalent radical derived from alkanes, alkenes, or alkynes, or may be a tetravalent radical derived from a compound represented by one of the following Formulas 4 to 9.
  • R 40 to R 45 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
  • R 50 to R 57 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
  • R 60 to R 69 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group,
  • a single bond means a case where an atom is not present in a portion thereof. Therefore, when X in Formula 12 is a single bond, it means a case where an atom is not present in the moiety represented by X. In this case, the benzene rings on both sides of X may be directly connected to form a biphenyl structure.
  • L 5 - in L 1 to L 5 are each independently, having 1 to 12 carbon atoms, having 1 to 8 carbon atoms, or carbon atoms can be an 1 alkylene group or alkylidene of 1 to 4, wherein the alkylene group or alkylidene group is a substituted or unsubstituted It may be.
  • L 6 and L 8 may be -O-
  • L 7 has 1 to 12 carbon atoms, and 1 to 1 carbon atoms.
  • Ar 1 and Ar 2 may be a phenylene group, in which case L 6 and L 8 based on L 7 may be connected to the ortho, meta or para position of the phenylene, respectively.
  • R 70 to R 73 are each independently hydrogen, an alkyl group, or an alkoxy group, two of R 70 to R 73 may be connected to each other to form an alkylene group,
  • A is an alkylene group or alkenylene group, wherein the alkylene group or alkenylene group of A may contain one or more oxygen atoms as a hetero atom.
  • R 80 to R 83 are each independently hydrogen, an alkyl group, or an alkoxy group, and A is an alkylene group.
  • R 90 to R 99 are each independently hydrogen, an alkyl group, or an alkoxy group.
  • the tetravalent radical derived from the compound represented by the above formulas (4) to (9) is formed by directly leaving the substituents of the above formulas (4) to (9), or in the examples of the substituents, an alkyl group, an alkoxy group, an aryl group, an alkylene group or an alkenylene group
  • the hydrogen atom to which it belongs may leave and formed.
  • the tetravalent radical when the tetravalent radical is derived from a compound of Formula 4, at least one, at least two, at least three or four of R 40 to R 45 of Formula 4 form a radical or R 40
  • R 40 to R 45 of Formula 4 To a hydrogen atom of the alkyl group, alkoxy group, or aryl group present in R 45 may be released to form a radical.
  • Forming a radical in the above may mean that the site is connected to the carbon atom of the carbonyl group of Formula 4 as described above.
  • R 60 to R 69 of formula 6 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, at least one, at least two, at least three Or more than four may form a radical linked to formula (3).
  • Each of which does not form a radical in the above may be hydrogen, an alkyl group or an alkoxy group, or may be hydrogen or an alkyl group.
  • any two of R 67 to R 69 and any two of R 62 to R 64 may form the radical, and the other substituents are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group, It may be a hydrogen, an alkyl group or an alkoxy group, or may be a hydrogen or an alkyl group.
  • the compound represented by Formula 4 may be benzene or 1,2,4,5-tetraalkylbenzene.
  • the compound represented by Chemical Formula 6 may be biphenyl, or a compound represented by any one of the following Chemical Formulas A to F:
  • the compound represented by Formula 7 may be a cycloalkane having 4 to 8 carbon atoms such as cyclohexane, a cycloalkene having 4 to 8 carbon atoms such as cyclohexene which may be substituted with one or more alkyl groups, or any one of the following Formulas G to I It may be a compound represented by the formula:
  • the compound represented by Chemical Formula 8 may be represented by Chemical Formula J or a compound in which at least one hydrogen of the compound represented by Chemical Formula J is substituted with an alkyl group:
  • X 1 and X 2 may each independently be a divalent radical derived from an aromatic compound.
  • X 1 and X 2 may each independently be a divalent radical derived from an aromatic compound having 6 to 40 carbon atoms. The divalent radical derived from the said aromatic compound is replaced by the content mentioned above.
  • X 1 and X 2 may each independently be a divalent radical derived from a compound represented by any one of Formulas 10 to 12:
  • R 100 to R 105 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group;
  • R 110 to R 119 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group,
  • R 120 to R 129 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group.
  • the divalent radical derived from the compound represented by the formulas (10) to (12) is formed by directly leaving the substituents of the formulas (10) to (12), or in the examples of the substituents, an alkyl group, an alkoxy group, an aryl group, an alkylene group or an alkenylene group
  • the hydrogen atom to which it belongs may leave and formed.
  • the substitution position of the amine group based on the site linked to N in X 1 of Chemical Formula 3 may be represented by ortho ( ortho, meta or para position, and the substitution position of the amine group based on the site linked to N in X 2 of Formula 3 is also ortho, meta or para. (para) location.
  • any one of R 117 to R 119 of Formula 11 and R 112 to R 114 of Formula 11 is connected to the nitrogen atom of Formula 3 To form radicals.
  • Other substituents other than the substituents forming the radicals may each independently be hydrogen, an alkyl group, an alkoxy group or an aryl group, a hydrogen, an alkyl group or an alkoxy group, or may be a hydrogen or an alkyl group.
  • the compound represented by Formula 10 is benzene which may be substituted with at least one hydroxy group or carboxyl group.
  • the compound represented by Formula 11 may be a biphenyl which may be substituted with at least one hydroxy group or a carboxyl group, a compound which may be substituted with at least one hydroxy group or a carboxyl group while being represented by any one of Formulas A to F, or the following Formula A compound which may be substituted with at least one hydroxyl group or carboxyl group, represented by K or M:
  • the compound represented by Chemical Formula 12 is a compound represented by the following Chemical Formula N, or at least one of hydrogen of the compound represented by the following Chemical Formula N is substituted with a hydroxyl group or a carboxyl group:
  • the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified.
  • the alkyl group may be linear, branched, or cyclic and may be substituted by one or more substituents if necessary.
  • the alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified.
  • the alkoxy group may be linear, branched, or cyclic and may be substituted by one or more substituents if necessary.
  • an aryl group may mean a monovalent moiety derived from the aforementioned aromatic compound, unless otherwise specified.
  • an alkylene group or an alkylidene group is an alkylene group or an alkylidene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. Can mean.
  • the alkylene group or alkylidene group may be linear, branched, or cyclic.
  • the alkylene group or alkylidene group may be optionally substituted with one or more substituents.
  • substituent which may be optionally substituted with an aliphatic compound, an alicyclic compound, an aromatic compound, an alkyl group, an alkoxy group, an aryl group, an alkylene group, or an alkylidene group, halogen, glycine such as chlorine or fluorine Epoxy groups, such as a dill group, an epoxy alkyl group, a glycidoxy alkyl group, or an alicyclic epoxy group, an acryloyl group, a methacryloyl group, an isocyanate group, a thiol group, an alkyl group, an alkoxy group, an aryl group, etc. can be illustrated.
  • n means the number of imide repeating units and is one or more. Specifically, n is 1 to 200, 1 to 150, 1 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, Or a number in the range of 1 to 10.
  • the curing agent may be a compound represented by Formula C1 or Formula C2:
  • L 1 to L 8 are each independently a direct bond, -O-, or a C 1-5 alkylene group
  • Ar 1 and Ar 2 are each independently a C 6-30 arylene group
  • R 90 to R 99 each independently is hydrogen, an alkoxy group, an aryl group, a hydroxy group of a C 6-30 alkyl group, C 1-5 of C 1-5, or a carboxyl group.
  • the compound represented by Chemical Formula 3 may be synthesized according to a known method for synthesizing an organic compound, and the specific manner thereof is not particularly limited.
  • the compound represented by Formula 3 may be formed by a dehydration condensation reaction between a dianhydride compound and a diamine compound.
  • Compound represented by the formula (3) has a high boiling point, does not volatilize or decompose at high temperature, thereby maintaining a stable curability of the polymerizable composition, voids that may adversely affect the physical properties during high temperature processing or curing ( void).
  • the compound represented by Chemical Formula 3 may have a decomposition temperature of 300 ° C. or higher, 350 ° C. or higher, 400 ° C. or higher, or 500 ° C. or higher.
  • the decomposition temperature may mean a temperature at which the decomposition rate of the compound represented by Formula 3 is maintained in a range of 10% or less, 5% or less, or 1% or less.
  • the upper limit of the decomposition temperature is not particularly limited, but may be, for example, about 1000 ° C. or less.
  • the compound represented by the formula (3) is a process window of the reactive or polymerizable composition itself, i.e., melting of the polymerizable composition or the prepolymer formed therefrom by the selection of X 1 or X 2 which is M or a linker of the core. Since the difference between temperature and hardening temperature can be adjusted easily, it can act as a hardening
  • the amount of the curing agent may be adjusted in a range that can ensure the curability to be imparted to the polymerizable composition for providing the phthalonitrile-based resin.
  • the curing agent may be included in a molar ratio of 0.01 to 1.5 moles per mole of the phthalonitrile compound.
  • the process window may be narrowed, resulting in poor processability or high temperature curing conditions. And, when the molar ratio of the curing agent is lowered, the curing property may be insufficient.
  • the polymerizable composition for providing the phthalonitrile-based resin may further include an additive depending on the application field and use of the phthalonitrile-based resin.
  • the kind of the additive is not particularly limited.
  • the content of the additive may be adjusted within a range that does not inhibit the physical properties of the phthalonitrile-based resin.
  • the additives include reinforcing fibers such as metal fibers, carbon fibers, glass fibers, aramid fibers, potassium titanate fibers, celluloid fibers, sepiolite fibers, ceramic fibers, and acrylic fibers; Inorganic fillers such as barium sulfate, calcium carbonate, zirconia, alumina, zirconium silicate, and silicon carbide; Lubricants such as graphite, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, milled carbon fiber, and the like may be applied.
  • reinforcing fibers such as metal fibers, carbon fibers, glass fibers, aramid fibers, potassium titanate fibers, celluloid fibers, sepiolite fibers, ceramic fibers, and acrylic fibers
  • Inorganic fillers such as barium sulfate, calcium carbonate, zirconia, alumina, zirconium silicate, and silicon carbide
  • Lubricants such as graphit
  • the phthalonitrile-based resin has a repeating unit formed by the reaction of the phthalonitrile compound and the curing agent of the above-described characteristics, it may exhibit improved impact strength while having excellent workability.
  • the phthalonitrile-based resin may have an impact strength of 350 MPa or more according to ASTM D256 (23 ° C.) test method.
  • the phthalonitrile-based resin is 350 MPa or more, or 350 MPa to 500 MPa, or 400 MPa to 500 MPa, or 400 MPa to 490 MPa, or 420 MPa to 490 according to ASTM D256 (23 °C) test method MPa, or 420 MPa to 480 MPa, or 430 MPa to 480 MPa, or 430 MPa to 480 MPa.
  • the phthalonitrile-based resin may have a process window of 50 ° C. or more.
  • the process window of the phthalonitrile-based resin may be 50 ° C or more, or 50 ° C to 210 ° C, or 55 ° C to 205 ° C.
  • the process window is a measure of the processability of the resin, the difference between the processing temperature (T p ) and the curing temperature (T c ) (T c -T p ), which is the temperature at which the phthalonitrile resin exists in a processable state. It can be expressed as the absolute value of.
  • the processing temperature (T p ) means a temperature at which the phthalonitrile-based resin exists in a processable state, and may be exemplified as a glass transition temperature (T g ) or a melting temperature (T m ).
  • the curing temperature (T c ) may be exemplified as an exothermic onset temp. (T o ) of the phthalonitrile-based resin.
  • a molded article manufactured using the phthalonitrile-based resin is provided.
  • the phthalonitrile-based resin makes it possible to provide a molded article having excellent impact strength.
  • Examples of the molded article include durable materials such as airplanes, ships, and automobiles.
  • the molded article may be prepared by heating a prepolymer containing the phthalonitrile-based resin to form a desired formation and then curing it. Processing and curing methods for the production of the molded article can be carried out in a known manner.
  • the phthalonitrile-based resin according to the present invention has excellent processability and improved impact strength, and thus can be more suitably used as a durable material for airplanes, ships, automobiles, and the like.
  • PN1 compound (4,4'-bis (3,4-dicyanophenoxy) diphenyloxide) represented by the following formula (1) was obtained in a yield of 91% by weight.
  • PN2 compound (4,4'-bis (3,4-dicyanophenoxy) biphenyl) represented by the following Chemical Formula 2 was obtained in a yield of 90% by weight.
  • a mixture of 75 wt% of the PN1 compound of Preparation Example 1 and 25 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 60 wt% of the PN1 compound of Preparation Example 1 and 40 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 50 wt% of the PN1 compound of Preparation Example 1 and 50 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 40 wt% of the PN1 compound of Preparation Example 1 and 60 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 30 wt% of the PN1 compound of Preparation Example 1 and 70 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 90 wt% of the PN1 compound of Preparation Example 1 and 10 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • PN1 compound of Preparation Example 1 was prepared as a phthalonitrile compound.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • the PN2 compound of Preparation Example 2 was prepared as a phthalonitrile compound.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 10 wt% of the PN1 compound of Preparation Example 1 and 90 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 25 wt% of the PN1 compound of Preparation Example 1 and 75 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • a mixture of 95 wt% of the PN1 compound of Preparation Example 1 and 5 wt% of the PN2 compound of Preparation Example 2 was prepared.
  • the CA1 compound of Preparation Example 3 was mixed to be 0.15 mol per mol of the phthalonitrile compound to prepare a polymerizable composition.
  • the polymerizable composition was cured by heating in an oven at a temperature of 220 ° C., 250 ° C., 280 ° C., and 310 ° C. for a total of 3 hours to prepare a phthalonitrile-based resin.
  • Test Example 1 One Nuclear magnetic resonance (H-NMR) analysis
  • Test Example 2 Differential scanning calorimetry (DSC) analysis
  • the DSC analysis was carried out in an N 2 flow atmosphere using a TA instrument company's Q20 system while heating up at a rate of temperature rise of 10 ° C./minute from 35 ° C. to 450 ° C.
  • the impact strength (IS) of the phthalonitrile-based resin was measured according to the ASTM D256 (23 °C) test method using a digital impact tester (QM (700A)). .
  • the results are shown in Table 1 below.
  • the phthalonitrile-based resin according to the embodiments it is confirmed that the process window is wide but excellent impact strength and there is no void in the resin.

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Abstract

La présente invention concerne une résine à base de phtalonitrile. La résine à base de phtalonitrile, selon la présente invention, présente une excellente aptitude au traitement et une résistance aux chocs améliorée, et peut ainsi être utilisée de manière plus adéquate en tant que matériau durable pour des avions, des navires, des automobiles, etc.
PCT/KR2019/010708 2018-08-28 2019-08-22 Résine à base de phtalonitrile présentant une résistance aux chocs améliorée WO2020045897A1 (fr)

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US16/977,379 US11932727B2 (en) 2018-08-28 2019-08-22 Phthalonitrile-based resin with improved impact strength
CN201980017402.3A CN111819221B (zh) 2018-08-28 2019-08-22 具有改善的冲击强度的基于邻苯二甲腈的树脂
EP19855813.2A EP3741791B1 (fr) 2018-08-28 2019-08-22 Résine à base de phtalonitrile présentant une résistance aux chocs améliorée
JP2020545659A JP6935119B2 (ja) 2018-08-28 2019-08-22 向上した衝撃強度を有するフタロニトリル系樹脂

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KR1020190102574A KR102218559B1 (ko) 2018-08-28 2019-08-21 향상된 충격 강도를 갖는 프탈로니트릴계 수지
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CN102936340A (zh) * 2012-11-30 2013-02-20 吉林大学 一种双邻苯二甲腈树脂/芳香胺有机化蒙脱土纳米复合材料及其制备方法
KR20160115543A (ko) * 2015-03-27 2016-10-06 주식회사 엘지화학 중합성 조성물
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