KR102380727B1 - Phthalonitrile resin - Google Patents

Abstract

In the present invention, there is provided a phthalonitrile resin capable of exhibiting excellent mechanical strength characteristics with a wide window process by including the repeating unit derived from a mixture of two or more types of cyanide monomers in an optimal content ratio.

Description

Phthalonitrile resin {PHTHALONITRILE RESIN}

The present invention relates to a phthalonitrile resin that exhibits excellent mechanical strength properties with a wide process window.

Phthalonitrile resin (PNR) is a thermosetting resin with excellent heat resistance and flame retardancy. It forms a composite with glass fiber or carbon fiber, and is used as a durable material for airplanes, ships, and automobiles. The manufacturing process of the composite may include, for example, a process of mixing a mixture of phthalonitrile and a curing agent or a prepolymer formed by the reaction of the mixture and a filler and curing the mixture.

Since phthalonitrile resin has a solid hardening structure by triazine generated through high temperature curing, it has a disadvantage in that mechanical properties such as impact strength are very weak due to strong brittleness.

In order to effectively produce a resin or composite, it is required that the monomer phthalonitrile or a polymerizable composition or prepolymer formed therefrom have appropriate meltability and fluidity, and that the so-called process window is wide.

In addition, when the mixture or prepolymer of the phthalonitrile and the curing agent contains voids or creates voids during processing or curing, deterioration of physical properties, particularly mechanical properties, of the composite may occur, so this problem is also should be considered.

Korean Patent No. 0558158

Accordingly, the present invention is to solve the problems of the prior art, and to provide a phthalonitrile resin exhibiting excellent mechanical strength characteristics with a wide process window, a method for manufacturing the same, and a polymerizable composition comprising the phthalonitrile resin do.

In order to solve the above problems, according to an embodiment of the present invention,

A first repeating unit derived from a compound of Formula 1; and

Provided is a phthalonitrile resin comprising a second repeating unit derived from at least one compound selected from the group consisting of compounds of Formulas 2 to 4 in a weight ratio of 20:80 to 99:1:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,

L ₁₁ , L ₁₂ , L ₂₁ , L ₂₂ , L ₃₁ , and L ₄₁ to L ₄₄ are each independently a functional group represented by the following Chemical Formula 5;

[Formula 5]

In Formula 5, X is an oxygen atom or a sulfur atom,

R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group, wherein at least two of R ₁ to R ₅ are a cyano group,

R _a to R _i are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group and an aryl group,

m1, m2, n1, n2, and q1 to q4 are each independently an integer of 0 to 4,

p is an integer from 0 to 3.

In addition, according to another embodiment of the present invention, the compound of Formula 1; and at least one compound selected from the group consisting of compounds of Formulas 2 to 4 in an amount of 20:80 to 99:1 by weight, and a polymerizable composition further comprising a curing agent, and a prepolymer as a reactant thereof, respectively do.

According to another embodiment of the present invention, there is provided a method for producing a phthalonitrile resin, comprising the step of curing the above-described polymerizable composition or prepolymer.

The phthalonitrile resin according to the present invention may exhibit a remarkably wide process window and mechanical strength characteristics.

1 to 4 are graphs showing the results of nuclear magnetic resonance (NMR) analysis of the compounds prepared in Preparation Examples 1 to 4, respectively.

The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprises", "comprising" or "have" are intended to designate the presence of an embodied feature, step, element, or a combination thereof, but one or more other features or steps; It should be understood that the possibility of the presence or addition of components, or combinations thereof, is not precluded in advance.

Since the present invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Hereinafter, the phthalonitrile resin of the present invention, a polymerizable composition and prepolymer comprising the same, and a method for producing the same will be described in detail.

The phthalonitrile resin according to an embodiment of the present invention is

a first repeating unit derived from a compound of Formula 1; and

The second repeating unit derived from at least one compound selected from the group consisting of compounds of Formulas 2 to 4 is included in a weight ratio of 20:80 to 99:1:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,

L ₁₁ , L ₁₂ , L ₂₁ , L ₂₂ , L ₃₁ , and L ₄₁ to L ₄₄ are each independently a functional group represented by the following Chemical Formula 5;

[Formula 5]

In Formula 5, X is an oxygen atom or a sulfur atom,

R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group, wherein at least two of R ₁ to R ₅ are a cyano group,

R _a to R _i are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group and an aryl group,

m1, m2, n1, n2, and q1 to q4 are each independently an integer of 0 to 4,

p is an integer from 0 to 3.

As described above, the present invention provides a monomer compound having an excellent effect of improving the mechanical properties of the phthalonitrile resin, but having a limit in processability due to a very narrow process window due to a high melting point, a monomer compound of Formula 1 having a low melting point, and By mixing and using at an optimal mixing ratio, the process window of the phthalonitrile resin to be produced can be widened, and mechanical properties such as tensile strength or impact strength can be improved in a well-balanced manner. In particular, the compounds of Formulas 3 and 4 are polyfunctional monomers containing five or more cyano groups as reactive functional groups in the compound, and can exhibit excellent curing efficiency and heat resistance properties by increasing the curing density during thermal curing, but have high melting points and high Voids are likely to occur during processing or curing due to melt viscosity. As described above, processability is improved by mixing the monomer compound of Chemical Formula 1, which shows a low melting point and low viscosity, with respect to the monomer compounds having difficulty in securing processability, and mechanical properties can be simultaneously secured by suppressing the occurrence of voids in the prepared resin. .

Meanwhile, in the present specification, the term “repeating unit” derived from a given compound may mean a skeleton of a polymer formed by polymerization or curing of the compound. For example, the polymerization unit derived from the compound of Formula 1 may have a structure in which a cyano group of the compound of Formula 1 reacts with a functional group present in a curing agent such as an amino group or a hydroxyl group.

In addition, in this specification, a halogen group means fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

In addition, in the present specification, the alkyl group may be straight-chain or branched, and may be substituted by one or more substituents as necessary. In addition, the number of carbon atoms in the alkyl group is not particularly limited, but may be 1 to 40, or 1 to 20, or 1 to 12, or 1 to 8, or 1 to 4. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

In addition, in the present specification, alkoxy may be represented by a -ORa group, wherein Ra is an alkyl group as previously defined. Specific examples include, but are not limited to, methoxy, ethoxy, phenyloxy or cyclohexyloxy.

In addition, in the present specification, the aryl group may mean a monovalent residue derived from a benzene ring, a compound containing a benzene ring, or a derivative of any one of the above. As used herein, the compound containing a benzene ring may refer to a compound having a structure in which two or more benzene rings are condensed while sharing one or two carbon atoms, or are directly connected or connected by an appropriate linker. Biphenyl, naphthalene, etc. may be exemplified as the above compound. The aryl group may contain 6 to 30, or 6 to 20, or 6 to 12 carbon atoms. Specific examples of the aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, and the like.

In the present specification, unless otherwise specified, an alkylene group or an alkylidene group means an alkylene group or alkylidene group having 1 to 20 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 4 carbon atoms. can The alkylene group or alkylidene group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

In the present specification, the description of the above-described aryl group may be applied except that arylene is an aromatic divalent radical.

In addition, in the present specification, unless otherwise specified, the alkyl group, alkoxy group, aryl group, alkylene group or alkylidene group is an epoxy group such as a halogen group, a glycidyl group, an epoxyalkyl group, a glycidoxyalkyl group or an alicyclic epoxy group, It may be substituted with one or more substituents such as an acryloyl group, a methacryloyl group, an isocyanate group, a thiol group, an alkyl group, an alkoxy group, or an aryl group.

Specifically, in the phthalonitrile-based resin according to the embodiment, the first repeating unit may have a structure derived from the compound of Formula 1a:

[Formula 1a]

In Formula 1a,

X ₁₁ and X ₁₂ are each independently an oxygen atom or a sulfur atom,

R ₁₁ to R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyano group, at least two of R ₁₁ to R ₁₅ , And at least two of R ₁₆ to R ₂₀ are cyano groups,

R _a and R _b are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,

m1 and m2 are each independently an integer of 0 to 4.

More specifically, in Formula 1a, X ₁₁ and X ₁₂ are each independently an oxygen atom,

R ₁₁ to R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group, wherein at least two of R ₁₁ to R ₁₅ and at least two of R ₁₆ to R ₂₀ are cyano groups, more specifically , at least two of R ₁₁ to R ₁₅ , and at least two of R ₁₆ to R ₂₀ are cyano groups, and the remaining functional groups are hydrogen,

R _a and R _b are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

m1 and m2 are each an integer of 0 or 1.

More specifically, the compound of Formula 1 may be a compound represented by Formula 1a-1 below.

[Formula 1a-1]

Since the compound of Formula 1 having the above structure has a low melting point and has a very wide process window, it is possible to greatly improve processability in the preparation of phthalonitrile resin, and also to prepare a prepreg of phthalonitrile resin at a temperature of less than 240° C. is easy In addition, the compound of Formula 1 has excellent reactivity with a curing agent.

On the other hand, in the phthalonitrile resin according to an embodiment of the present invention, the compounds of Formulas 2 to 4 forming the second repeating unit include two or more reactive functional groups (CN) in the molecule, and have a highly crystalline structure. It has a high melting point or softening point. However, due to such a high melting point, the resin is not sufficiently melted at a processing temperature and exhibits a high viscosity, so the use of a curing agent is limited. In addition, the process window is very narrow (less than 50℃), and the curing speed is fast, so it is very difficult to control voids in the resin.

Specifically, the compound of Formula 2 is a structural isomer of the compound of Formula 1, and has a higher melting point than the compound of Formula 1 due to a structural difference. However, when the phthalonitrile resin is prepared by mixing with the compound of Formula 1, processability is improved by reducing the melting point of the mixture, and a molded article exhibiting excellent mechanical properties without voids can be manufactured.

Specifically, the compound of Formula 2 may be a compound represented by the following Formula 2a:

[Formula 2a]

In Formula 2a,

X ₂₁ and X ₂₂ are each independently an oxygen atom or a sulfur atom,

R ₂₁ to R ₃₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyano group, at least two of R ₂₁ to R ₂₅ ; And at least two of R ₂₆ to R ₃₀ are cyano groups,

R _c and R _d are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,

n1 and n2 are each independently an integer of 0 to 4.

Among the compounds satisfying the above structure, when the linking group and the substituent of the central biphenylene structure and the reactive functional group in Formula 2 are optimized, the effect of using the compound of Formula 2 may be further increased. Specifically, The compound of Formula 2 is in Formula 2a,

X ₂₁ and X ₂₂ are each independently an oxygen atom,

R ₂₁ to R ₃₀ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group, wherein at least two of R ₂₁ to R ₂₅ and at least two of R ₂₆ to R ₃₀ are cyano groups, more specifically , at least two of R ₂₁ to R ₂₅ , and at least two of R ₂₆ to R ₃₀ are cyano groups, and the remaining functional groups are hydrogen,

R _c and R _d are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

Since n1 and n2 each have a structure that is an integer of 0 or 1, a more excellent effect may be exhibited.

More specifically, the compound of Formula 2a may be a compound represented by Formula 2a-1 below.

[Formula 2a-1]

In addition, the compound of Formula 3 includes a benzene ring as a central structure, but includes 6 or more reactive functional groups, so that the curing density can be greatly reduced when mixing with the compound of Formula 1 to prepare a phthalonitrile resin, As a result, the mechanical properties of the phthalonitrile resin can be improved.

The effect of the compound of Formula 3 as described above can be further improved by optimizing the bonding position of the reactive functional group to the benzene ring. Specifically, the compound of Formula 3 has a structure represented by the following Formula 3a, thereby exhibiting a better effect. can:

[Formula 3a]

In Formula 3a,

L _31a to L _31c are each independently a functional group represented by the following formula (5),

[Formula 5]

In Formula 5, X is an oxygen atom or a sulfur atom,

R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyano group, wherein at least two of R ₁ to R ₅ are cyano group is anger,

Re is each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,

p is an integer from 0 to 3.

In addition, the effect of the compound of Formula 3 can be further improved by optimizing the position of the reactive functional group, the linking group and the substituent. Specifically, in Formula 3a, L _31a to L _31c are each independently represented by Formula 5 is the indicated functional group,

In Formula 5, X is an oxygen atom,

R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group, wherein at least two of R ₁ to R ₅ are cyano groups, more specifically, at least 2 of R ₁ to R ₅ dog is a cyano group, the remaining functional groups are hydrogen,

Re is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

p may be a compound that is an integer of 0 or 1.

More specifically, the compound of Formula 3 may be a compound of Formula 3a-1 below:

[Formula 3a-1]

In addition, the compound of Formula 4 includes, as a central structure, a symmetric structure in which carbons at positions 1 and 2 of ethane are substituted with two phenyl groups, respectively, and may include 8 or more reactive functional groups (CN) in the molecule there is. Accordingly, when the phthalonitrile resin is prepared by mixing with the compound of Formula 1, the process window is widened, and mechanical properties can be greatly improved through void control.

Among them, this effect can be further increased by optimizing the bonding position of the reactive functional group with respect to the central structure. Specifically, the compound of Formula 4 may exhibit a better effect by having a structure represented by Formula 4a below. :

[Formula 4a]

In Formula 4a,

L ₄₁ to L ₄₄ are each independently a functional group represented by the following formula (5),

[Formula 5]

In Formula 5, X is an oxygen atom or a sulfur atom,

R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyano group, wherein at least two of R ₁ to R ₅ are cyano group is anger,

R _f to R _i are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,

q1 to q4 are each independently an integer of 0 to 4.

In addition, the improvement effect can be further increased by optimizing the linking group and the substituent together with the bonding position of the reactive functional group. Specifically, in the compound of Formula 4, in Formula 4a, L ₄₁ to L ₄₄ are each independently Formula 5 is a functional group represented by

In Formula 5, X is an oxygen atom,

R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group, wherein at least two of R ₁ to R ₅ are cyano groups, and more specifically, at least 2 of R ₁ to R ₅ dog is a cyano group, the remaining functional groups are hydrogen,

R _f to R _i are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

q1 to q4 are each independently an integer of 0 or 1, and may exhibit a better effect by having a structure.

More specifically, the compound of Formula 4 may be a compound of Formula 4a-1 below.

[Formula 4a-1]

The first repeating unit derived from the compound of Formula 1 and the second repeating unit derived from one or more of the compounds of Formulas 2 to 4 are used in the phthalonitrile resin to be prepared in order to realize excellent mechanical properties with a wide process window. The mixing ratio needs to be optimized.

Specifically, in the phthalonitrile resin according to the embodiment, the first repeating unit and the second repeating unit may be included in a weight ratio of 20:80 to 99:1. If the weight ratio of the first repeating unit to the second repeating unit is out of 20:80 and the content of the second repeating unit is too high, there is a risk of deterioration in workability, and the weight ratio of the first repeating unit to the second repeating unit is 99: When the content of the first repeating unit is excessively high and the content of the second repeating unit is excessively low outside 1, the improvement effect due to the inclusion of the second repeating unit, such as heat resistance and curability, is insignificant. In addition, considering the effect of improving the balance of workability and mechanical properties while maintaining the excellent effect derived from the structure of each of the first and second repeating units, the first repeating unit and the second repeating unit are 20:80 to 90:10, More specifically, it may be included in a weight ratio of 25:75 to 75:25.

More specifically, when the second repeating unit includes a repeating unit derived from the compound of Formula 2, the first repeating unit and the second repeating unit are 25:75 to 50:50, or 25:75 to 40:60 may be included in the weight ratio of When included in the above content ratio, it is possible to significantly improve mechanical properties while exhibiting excellent processability.

In addition, when the second repeating unit includes a repeating unit derived from a compound of Chemical Formula 3 or Chemical Formula 4, the first repeating unit and the second repeating unit are 50:50 to 75:25, or 60:40 to 75:25. It may be included as a weight ratio. When included in the above content ratio, processability and mechanical properties may be improved in good balance.

On the other hand, in the phthalonitrile resin according to an embodiment of the present invention, the first and second repeating units are formed by the reaction of the compound of Formula 1 and at least one compound among the compounds of Formulas 2 to 4 with a curing agent. It is a polymerization unit that becomes Accordingly, the phthalonitrile resin may further include a curing agent-derived repeating unit as a polymerization unit.

In this case, the curing agent is particularly limited if it can react with the monomer compound for forming the first and second repeating units to form a phthalonitrile resin, such as an aromatic amine compound, a phenol compound, an inorganic acid, an organic acid, a metal, or a metal salt. Although it can be used without it, according to an embodiment of the present invention, a compound of Formula 6 below may be used as the curing agent. Accordingly, the phthalonitrile resin according to an embodiment of the present invention may further include a repeating unit derived from the compound of Formula 6 below:

[Formula 6]

In Formula 6, N is a nitrogen atom,

M is a tetravalent radical,

Z ₁ and Z ₂ are each independently an alkylene group, an alkylidene group, or an aromatic divalent radical.

The compound of Formula 6 does not volatilize or decompose at high temperature because it has a high boiling point. As a result, it is possible to stably maintain the curability of the polymerizable composition, and to prevent the formation of voids that may adversely affect the mechanical properties of the composite during processing and curing at high temperatures. The compound of Formula 6 facilitates the process window of the polymerizable composition itself, that is, the difference between the melting point and the curing temperature of the polymerizable composition or the prepolymer formed therefrom, by selecting the central element M or the linker Z ₁ or Z ₂ Since it can be adjusted to a certain degree, it can act as a curing agent with various physical properties depending on the use.

In particular, in the case of the compound of Formula 4 used to form the second repeating unit in the preparation of the phthalonitrile resin in the present invention, a high temperature of 270° C. or higher is required during the preparation of the prepreg, but the curing agent used together at such a high temperature is usually easy to decompose However, since the compound of Chemical Formula 6 has a high boiling point, it is possible to prepare a prepreg without concern about decomposition when the compound of Chemical Formula 4 is used to perform the reaction at a high temperature.

However, in the case of the compound of Chemical Formula 2 used in the present invention, there is a problem in that the state of the resin is deteriorated because the curing reaction proceeds simultaneously with melting when the phthalonitrile resin is manufactured using the compound of Chemical Formula 6 as a curing agent. However, by mixing and using the compound of Formula 1 together, the compound of Formula 1 serves as a solvent so that the compound of Formula 2 and the curing agent of Formula 6 can be easily dissolved at a lower temperature.

Specifically, in the compound of Formula 6, M may be a tetravalent radical derived from a substituted or unsubstituted, aliphatic, alicyclic or aromatic compound, and more specifically, from the group consisting of compounds of the following Formulas 7a to 7f It may be a tetravalent radical from a selected compound:

[Formula 7a]

In Formula 7a, R _a1 to R _a6 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.

[Formula 7b]

In Formula 7b, R _b1 to R _b8 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.

[Formula 7c]

In Formula 7c, R _c1 to R _c10 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, W ₁ is a single bond, an alkylene group, a haloalkylene group, an alkylidene group, an oxygen atom, a sulfur atom, or a carbonyl group (-C(=O)-), -A ₁ -OC(=O)- A ₂ -, - A ₁ -C(=O)-O- A ₂ -, -S(=O)- or -S (=O) ₂ -, wherein A ₁ and A ₂ may each independently be a single bond or an alkylene group.

[Formula 7d]

In Formula 7d, R _d1 to R _d4 are each independently hydrogen, an alkyl group, or an alkoxy group, or two adjacent groups may be connected to each other to form an alicyclic ring structure, and W ₂ is one or more oxygen atoms, or It is an alkylene group or an alkenylene group that does not contain it.

[Formula 7e]

In Formula 7e, R _e1 to R _e4 are each independently hydrogen, an alkyl group, or an alkoxy group, and W ₃ is an alkylene group.

[Formula 7f]

In Formula 7f, R _f1 to R _f10 are each independently hydrogen, an alkyl group, or an alkoxy group.

In addition, specifically, in the compound of Formula 6, Z ₁ and Z ₂ may each independently be a divalent radical derived from a compound selected from the group consisting of compounds of Formulas 8a to 8c:

[Formula 8a]

In Formula 8a, R _g1 to R _g6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group.

[Formula 8b]

In Formula 8b, R _h1 to R _h10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group or an aryl group, and W ₄ is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, and a carbo group. a nyl group, -NR-, -S(=O)-, or -S(=O) ₂ -, wherein R is hydrogen, an alkyl group, an alkoxy group or an aryl group.

[Formula 8c]

In Formula 8c, R _i1 to R _i10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, or an aryl group.

More specifically, the curing agent may be a compound in which Z ₁ and Z ₂ in Formula 6 are each independently a divalent radical derived from the compound of Formula 8a, wherein Z ₁ and Z ₂ of Formula 6 are connected to N at a site The substitution position of the amino group with respect to may be an ortho, meta, or para position, respectively.

In addition, the compound of Formula 6 may have a decomposition temperature of 300° C. or more, 400° C. or more, or 500° C. or more, and 1,000° C. or less. In the present specification, the decomposition temperature means a temperature at which the decomposition rate of the compound of Formula 6 is maintained in the range of 10% or less, 5% or less, or 1% or less.

As a specific example, as the compound of Formula 6, compounds of the following Formulas 6a to 6h may be mentioned, and any one or a mixture of two or more thereof may be used.

(6a)

(6b)

(6c)

(6d)

(6e)

(6f)

(6g)

(6h)

On the other hand, the content of the curing agent-derived repeating unit in the phthalonitrile resin according to an embodiment of the present invention is not particularly limited. However, if the ratio of the curing agent in the polymerizable composition is high, the process window tends to be narrow, and when the ratio of the curing agent is low, the curability tends to be insufficient. It can be appropriately determined taking into account. According to one embodiment of the invention, in consideration of the good balance of processability and mechanical properties of the finally manufactured phthalonitrile resin, the curing agent-derived repeating unit is based on 1 mole of the total of the first repeating unit and the second repeating unit It may be included in a molar ratio of 0.02 to 1.5 moles, or 0.02 to 0.7 moles.

The phthalonitrile resin according to one embodiment as described above has a wide process window and excellent In addition to mechanical properties, processability can be expressed in a good balance.

On the other hand, the phthalonitrile resin according to an embodiment of the present invention, at least one of the compounds of Formula 1 for providing the first repeating unit, and the compounds of Chemical Formulas 2 to 4 for providing the second repeating unit, and It can be prepared by curing a polymerizable composition including a curing agent for curing after polymerization, or a prepolymer that is a reactant thereof. Accordingly, according to another embodiment of the present invention, a method for preparing the phthalonitrile resin, a polymerizable composition useful for preparing the phthalonitrile resin, and a prepolymer are provided.

Specifically, the processing temperature (Tp) of the polymerizable composition comprising one or more of the compounds of Formulas 2 to 4 together with the compound of Formula 1 may be 50° C. to 300° C., or 65° C. to 250° C. . As used herein, the term "processing temperature" refers to the temperature at which the compound of Formula 1 and the polymerizable composition or prepolymer including at least one of the compounds of Formulas 2 to 4 exist in a processable state, and specific Examples include softening point (Tg), or melting point (Tm). The processing temperature in the above range ensures a wide process window, and through this, it is possible to implement a polymerizable composition or prepolymer capable of forming a composite with excellent physical properties.

In addition, the polymerizable composition according to an embodiment of the present invention initiates a curing reaction between a monomer compound such as the compound of Formula 1 and a curing agent with a process window, that is, a processing temperature (Tp), under conditions satisfying the above-described processing temperature range. The absolute value of the difference (To - Tp) of the temperature To may be 50° C. or more, or 70° C. or more, or 100° C. or more. As used herein, the term “curing reaction initiation temperature” refers to a temperature at which polymerization or curing of a polymerizable composition or a prepolymer to be described later starts. For example, the curing reaction initiation temperature (To) is higher than the processing temperature, and the greater the difference, the better the processability may be. In addition, the absolute value of the difference (To - Tp) between the processing temperature (Tp) and the curing reaction initiation temperature (To) may be 600° C. or less, or 300° C. or less, or 250° C. or less. When the above temperature conditions are satisfied, it is possible to produce a phthalonitrile resin having adequate fluidity and processability, securing a wide process window, and having excellent mechanical properties.

In the polymerizable composition, the compound of Formula 1 is the same as described above, and may be prepared using a known organic synthesis reaction. For example, the compound of Formula 1 may be prepared through a nitro substitution reaction, and specifically, it may be prepared by reacting a compound containing a hydroxyl group and a compound containing a nitrile group in the presence of a basic catalyst.

In addition, the compounds of Chemical Formulas 2 to 4, and the type and content of the curing agent are also the same as described above, and are manufactured using a known chemical reaction or are commercially available.

In addition, the polymerizable composition may further include one or more additives depending on the purpose in order to improve physical properties.

The additive may specifically be a filler, and the filler is not particularly limited, and any suitable filler may be used depending on the intended use. Specifically, the filler may include a metal material, a ceramic material, glass, a metal oxide, a metal nitride, or a carbon-based material, and any one or a mixture of two or more thereof may be used. In addition, as the carbon-based material, graphite, graphene, carbon nanotubes, and the like, derivatives such as oxides thereof, or isomers may be used.

The polymerizable composition may further include various monomers or other additives known to be applicable to the production of so-called engineering plastics such as polyimide, polyamide or polystyrene, depending on the purpose.

According to another embodiment of the present invention, there is provided a prepolymer formed by the reaction of the above-described polymerizable composition.

The prepolymer is in a state in which a certain degree of reaction between the compound of Formula 1, at least one of the compounds of Formulas 2 to 4, and a curing agent has occurred in the polymerizable composition (eg, so-called A or B stage). It means a state in which the polymerization step has occurred) or a state in which it does not reach a completely polymerized state, and exhibits appropriate fluidity, so that, for example, processing of the composite as described below is possible. For example, the prepolymer is a state in which polymerization of the polymerizable composition has progressed to a certain extent, and the melt viscosity measured at any one temperature within the range of about 150° C. to 250° C. for the composition is 100 cP to 10,000 cP, 100 cP It may mean a state in the range of to 5,000 cP or 100 cP to 3,000 cP.

The prepolymer may also exhibit excellent hardenability, a low melting point, and a wide process window, along with low curing density and excellent impact strength properties. For example, the processing temperature (Tp) of the prepolymer may be in the range of 60°C to 350°C, more specifically, 65 to 300°C. In this case, the absolute value of the difference (To-Tp) between the process window of the prepolymer, that is, the processing temperature (Tp) and the curing start temperature (To) of the prepolymer, is 50°C or more, or 70°C or more, or 100°C or more. and 600°C or less, or 300°C or less, or 250°C or less. For example, when the curing initiation temperature (To) is higher than the processing temperature (Tp) and is within the above range, better processability may be exhibited.

Meanwhile, the prepolymer may optionally further include known additives in addition to the above-described components. Examples of such additives may include, but are not limited to, the aforementioned fillers.

According to another embodiment of the invention, a composite including the phthalonitrile resin, more specifically, a reinforced polymer composite is provided.

The composite may include a phthalonitrile resin and a filler, and may exhibit excellent mechanical properties through the compounds of Chemical Formulas 1 and 2, and the like. Accordingly, it can be applied to various uses including durable goods such as automobiles, airplanes or ships.

The composite may include the polymerizable composition and the filler, or may be prepared by curing a precursor including the prepolymer and the filler. The precursor is a polymerizable composition comprising a compound of Formula 1, at least one of the compounds of Formulas 2 to 4, and a curing agent, or a state in which the prepolymer formed by pre-curing the polymerizable composition is melted by heating, etc. In, if necessary, it can be prepared by mixing with the filler. For example, it is possible to manufacture the above-described composite by curing the precursor prepared as described above after molding it into a desired shape.

The material as described above may be used as the filler, and additionally, a fibrous material, or a woven fabric, non-woven fabric, string or string, or carbon nanomaterial formed therefrom may be used as the filler. In addition, examples of the fibrous material include glass fiber, carbon fiber, aramid fiber, or ceramic fiber, and examples of the carbon nanomaterial include graphene or carbon nanotubes. The proportion of the filler to be included is not particularly limited, and may be set in an appropriate range depending on the intended use.

The polymerizable composition or prepolymer has an appropriate processing temperature and a wide process temperature, and has excellent curability, so that molding and curing can be efficiently performed in the process. In addition, a method of forming a prepolymer or the like in the above process, a method of preparing a composite by mixing, processing, and curing the prepolymer and the like with a filler may be carried out according to a known method.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and thus the content of the present invention is not limited thereto.

production example 1: Synthesis of compound (1a-1) (PN1)

A compound of Formula 1a-1 below was synthesized in the following manner.

(1a-1)

(1a-1)

First, 27 g of 2,2'-dihydroxybiphenyl and 150 g of DMF (dimethyl formamide) were put into 500 mL of 3 neck round-bottom flast (RBF), and dissolved by stirring at room temperature. 50.2 g of 4-nitrophthalonitrile was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve. Then, after adding 60.1 g of potassium carbonate and 50 g of DMF together, the temperature was raised to 85° C. while stirring. After reacting for about 5 hours, it was cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution for neutralization and precipitation. After filtering, it was washed with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100° C. for one day, and after removing water and residual solvent, the compound of Formula 1a-1 was obtained in a yield of about 91% by weight.

The results of NMR analysis of the prepared compound of Formula 1a-1 are shown in FIG. 1 . At this time, NMR analysis was performed according to the manufacturer's manual using Agilent's 500 MHz NMR equipment. A sample for NMR measurement was prepared by dissolving the compound in DMSO (dimethyl sulfoxide)-d6.

production example 2: compound (2a- 1) of Synthesis (PN2)

(2a-1)

(2a-1)

27 g of 4,4'-dihydroxybiphenyl and 150 g of DMF (dimethyl formamide) were put into 500 mL of 3 neck round-bottom flast (RBF), and dissolved by stirring at room temperature. 50.2 g of 4-nitrophthalonitrile was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve. Then, after adding 60.1 g of potassium carbonate and 50 g of DMF together, the temperature was raised to 85° C. while stirring. After reacting for about 5 hours, it is cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution for neutralization and precipitation. After filtering, it was washed with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100° C. for one day, and after removing water and residual solvent, the compound of Formula 2a-1 was obtained in a yield of about 90% by weight.

The results of NMR analysis of the prepared compound of Formula 2a-1 are shown in FIG. 2 .

production example 3: compound (3a- 1) of Synthesis (PN3)

(3a-1)

(3a-1)

1,3,5-Trihydroxybenzene (1,3,5-Trihydroxybenzene) 13.5 g and 150 g of DMF (Dimethyl Formamide) were put into a 3-neck round bottom flask (RBF), and dissolved by stirring at room temperature. 55.1 g of 4-nitrophthalonitrile was added thereto, and 50 g of dimethyl formamide (DMF) was added thereto, followed by stirring to dissolve. Subsequently, 65.9 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85° C. while stirring. After reacting in the above state for about 5 hours, it was cooled to room temperature. The cooled reaction solution was poured into an aqueous hydrochloric acid solution having a concentration of 0.2N for neutralization and precipitation, followed by filtering and washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100° C. for one day, and after removing water and residual solvent, the compound of 3a-1 was obtained in a yield of about 85% by weight.

The results of NMR analysis of the prepared compound of Formula 3a-1 are shown in FIG. 3 .

production example 4: compound (4a- 1) of Synthesis (PN4)

(4a-1)

(4a-1)

28 g of 1,1,2,2-Tetrakis(4-hydroxyphenyl)-ethane and 150 g of DMF (Dimethyl Formamide) were put into a 3 neck round bottom flask (RBF), and dissolved by stirring at room temperature. 48.8 g of 4-nitrophthalonitrile was added thereto, and 50 g of dimethyl formamide (DMF) was added thereto, followed by stirring to dissolve. Then, 58.4 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85° C. while stirring. After reacting in the above state for about 5 hours, it was cooled to room temperature. The cooled reaction solution was poured into an aqueous hydrochloric acid solution having a concentration of 0.2N for neutralization and precipitation, followed by filtering and washing with water. Thereafter, the filtered reactant was dried in a vacuum oven at 100° C. for one day, and after removing water and residual solvent, the compound of 4a-1 was obtained in a yield of about 85% by weight.

The results of NMR analysis of the prepared compound of Formula 4a-1 are shown in FIG. 4 .

production example 5. Synthesis of compound (6a)

A compound of Formula 6a was synthesized in the following manner.

(6a)

(6a)

4,4'-oxydiphthalic anhydride and 4,4'-oxydianiline having a solid content of 15wt% were added to the NMP solvent in 1:4 equivalents and dissolved. After dissolution, r-valerolactone, pyridine, and toluene were added and reacted at 185 °C for 3 hours, followed by cooling to room temperature. After cooling, the reaction solution was poured into methanol to precipitate, and then filtered to obtain compound 6a in a solid state.

Example One

With respect to 1 mole of the composition in which the compound of Formula 1a-1 prepared in Preparation Example 1 (PN1) and the compound of Formula 2a-1 prepared in Preparation Example 2 (PN2) were mixed in a weight ratio of 25:75, About 0.2 mol of the compound of Formula 6a prepared in Preparation Example 5 was mixed to prepare a polymerizable composition.

The composition was melted at 240° C. and stirred for 5 minutes to prepare a prepolymer, and then heated at 220° C., 250° C., 275° C., and 300° C. for a total of 3 hours and cured in an oven to prepare a phthalonitrile resin.

Example 2

In Example 1, the same method as in Example 1 was performed except that the ratio of the compound of 1a-1 (PN1) to the compound of Formula 2a-1 (PN2) was used in a weight ratio of 50:50. A polymerizable composition, a prepolymer, and a phthalonitrile resin were prepared.

Example 3

In Example 1, the same method as in Example 1 was performed except that the ratio of the compound of 1a-1 (PN1) to the compound of Formula 2a-1 (PN2) was used in a weight ratio of 75:25. to prepare a polymerizable composition, a prepolymer, and a phthalonitrile resin.

Example 4

In Example 2, it was carried out in the same manner as in Example 2, except that the compound of Formula 3a-1 prepared in Preparation Example 3 (PN3) was used instead of the compound of Formula 2a-1 (PN2). to prepare a polymerizable composition, a prepolymer, and a phthalonitrile resin.

Example 5

In Example 2, the same method as in Example 2 was performed, except that the compound of Formula 4a-1 prepared in Preparation Example 4 (PN4) was used instead of the compound of Formula 2a-1 (PN2). to prepare a polymerizable composition, a prepolymer, and a phthalonitrile resin.

Example 6 to 10

A polymerizable composition, a prepolymer, and a phthalonitrile resin were prepared in the same manner as in Example 1, except that the monomer compounds were mixed in the base weight ratio as shown in Table 1 below.

comparative example One

With respect to 1 mole of the compound (PN2) of Formula 2a-1 prepared in Preparation Example 2, 0.2 mole of the compound of Formula 6a prepared in Preparation Example 5 was added and mixed to prepare a polymerizable composition.

The composition was melted at 240° C. and stirred for 5 minutes to prepare a prepolymer, and then heated at 220° C., 250° C., 275° C., and 300° C. for a total of 3 hours and cured in an oven to prepare a phthalonitrile resin.

comparative example 2

A polymerizable composition in the same manner as in Comparative Example 1 except that the compound (PN3) of the formula 3a-1 prepared in Preparation Example 3 was used instead of the compound of the formula 2a-1 (PN2); A prepolymer and a phthalonitrile resin were prepared.

comparative example 3

The polymerizable composition, the prepolymer, and the phthalonitrile were carried out in the same manner as in Comparative Example 1, except that the compound of the formula 4a-1 (PN4) was used instead of the compound of the formula 2a-1 (PN2). A resin was prepared.

comparative example 4

Polymerizable composition, prepolymer, and phthalonitrile were carried out in the same manner as in Comparative Example 1, except that the compound of Formula 1a-1 (PN1) was used instead of the compound of Formula 2a-1 (PN2). A resin was prepared.

comparative example 5

A polymerizable composition, a prepolymer, and a phthalonitrile resin were prepared in the same manner as in Example 1, except that the monomer compounds were mixed in the base weight ratio as shown in Table 1 below.

test example

Processability and mechanical properties of the prepolymers and phthalonitrile resins prepared in Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 1 below.

1) Softening point (Tg), melting temperature (Tm), curing reaction initiation temperature (Exothermal onset temp.: To), exothermic energy and process window:

The prepolymers prepared in Examples and Comparative Examples were analyzed using a Differential Scanning Calorimeter (DSC), and Tg, Tm, To, exothermic energy and process window were measured, respectively. In the analysis, the differential scanning calorimeter Q20 system of TA Instruments was used, and the DSC analysis was performed in an N ₂ flow atmosphere while the temperature was increased from 35° C. to 450° C. at a temperature increase rate of 10° C./min.

2) Impact strength:

For the phthalonitrile resins prepared in Examples and Comparative Examples, unnotched specimens according to ASTM D256 were prepared, respectively, and impact strength was measured according to ASTM D256.

3) Resin state after curing: After curing, the presence of voids in the phthalonitrile resins prepared in Examples and Comparative Examples was visually observed and evaluated according to the following criteria.

<Evaluation criteria>

○: No voids observed

△: Voids were not observed only under pressure conditions

X: Voids are visually confirmed

Monomer mix
(weight ratio) Tg
(℃) Tm
(℃) To
(℃) process window
(℃) heat energy
(J/g)
impact strength
(J/m)
after curing
resin state Example 1 PN1+PN2
(25/75) 73 217 272 199 74 460 ○ Example 2 PN1+PN2
(50/50) 70 203 280 210 73 320 ○ Example 3 PN1+PN2
(75/25) 70 does not exist 278 208 66 253 ○ Example 4 PN1+PN3
(50/50) 80 242 274 194 107 195 ○ Example 5 PN1+PN4
(50/50) 89 does not exist 234 145 89 103 ○ Example 6 PN1+PN2
(40/60) 72 210 281 209 70 360 ○ Example 7 PN1+PN4
(75/25) 77 does not exist 276 199 88 200 ○ Example 8 PN1+PN4 (25/75) 101 does not exist 260 159 119 75 ○ Example 9 PN1+PN2
(90/10) 68 does not exist 284 216 62 - ○ Example 10 PN1+PN4
(90/10) 70 does not exist 278 208 83 - ○ Comparative Example 1 PN2
(100) does not exist 206 228 22 58 232 △ Comparative Example 2 PN3
(100) does not exist 270 273 3 130 <10 X Comparative Example 3 PN4
(100) does not exist 265 294 29 100 <10 X Comparative Example 4 PN1
(100) 66 does not exist 279 213 78 240 ○ Comparative Example 5 PN1+PN4
(10/90) 116 does not exist 251 135 88 <10 X

In Table 1, "-" means no measurement.

As a result of the experiment, by mixing PN1 with PN2, PN3 or PN4, which is a monomer compound exhibiting a high melting point due to its crystalline structure, to lower crystallinity, the prepolymers of Examples 1 to 10 not only exhibit a low Tg of 101 ° C. or less, When Tm was present, Tg was exhibited at a temperature lower than Tm. In addition, the prepolymers of Examples 1 to 10 exhibited a wide process window by exhibiting a processing temperature, specifically, To of 150° C. or higher compared to Tg, or 30° C. or higher compared to Tm, and improved the processability of the resin. A void-free resin could be produced without applying pressure during the curing process. In addition, the phthalonitrile resins of Examples 1 to 10 exhibited high impact strength, thereby exhibiting the effect of simultaneously improving the above-described processability and mechanical properties.

More specifically, the prepolymers of Examples 1 to 3, 6, and 9 prepared by mixing PN1 and PN2 had a significantly wider process window compared to Comparative Example 1 using PN2 alone, and after curing, pressurized during resin production No voids were observed even if no conditions were applied, and the impact strength was also increased. In addition, compared to Comparative Example 4 in which PN1 was used alone, the prepolymers of Examples 1 to 3, 6, and 9 exhibited improved effects in terms of impact strength while maintaining excellent processability. In particular, when the content of PN2 in the mixing ratio of PN1 and PN2 was greater than the content of PN1, the effect of improvement in impact strength was more remarkable.

In addition, in the case of Example 4 in which PN1 and PN3 were mixed, compared with Comparative Example 2 in which PN3 was used alone, improved effects were exhibited in terms of process window, impact strength, and resin state after curing. In addition, it can be seen that compared with Comparative Example 4 in which PN1 was used alone, the inclusion of the PN3-derived repeating unit showed more improved heat resistance due to an increase in softening point and exothermic energy.

In addition, the prepolymers of Examples 5, 7, 8 and 10 in which PN1 and PN4 were mixed also showed improved effects in terms of process window, impact strength, and resin state after curing compared to Comparative Example 3 using PN4 alone. , in particular, as the content of PN1 in the mixing ratio of PN1 and PN4 was greater than that of PN4, the mechanical strength and workability were improved in a well-balanced manner. On the other hand, when the mixing ratio of PN1 and PN4 was out of the optimal range in the present invention and PN4 was used in an excessive amount, the impact strength and properties after curing were greatly reduced (refer to Comparative Example 5).

From the above results, by including the first repeating unit and the second repeating unit in an optimal content ratio, the process window can be widened, void formation in the produced resin can be suppressed, and mechanical properties such as impact strength can be significantly improved. can confirm.

Claims (18)

a first repeating unit derived from a compound of Formula 1; and
A phthalonitrile resin comprising the second repeating unit derived from the compound of Formula 2 in a weight ratio of 25:75 to 40:60:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
L ₁₁ , L ₁₂ , L ₂₁ , and L ₂₂ are each independently a functional group represented by the following Chemical Formula 5;
[Formula 5]

In Formula 5, X is an oxygen atom or a sulfur atom,
R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group, wherein at least two of R ₁ to R ₅ are a cyano group,
R _a to R _d are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group and an aryl group,
m1, m2, n1, and n2 are each independently an integer from 0 to 4.
According to claim 1,
The compound of Formula 1 is a compound represented by the following Formula 1a, a phthalonitrile resin:
[Formula 1a]

In Formula 1a,
X ₁₁ and X ₁₂ are each independently an oxygen atom,
R ₁₁ to R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group, wherein at least two of R ₁₁ to R ₁₅ and at least two of R ₁₆ to R ₂₀ are cyano groups,
R _a and R _b are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
m1 and m2 are respectively 0 or 1.
According to claim 1,
The compound of Formula 1 is a compound represented by the following Formula 1a-1, a phthalonitrile resin.
[Formula 1a-1]

According to claim 1,
The compound of Formula 2 is a compound represented by the following Formula 2a, a phthalonitrile resin:
[Formula 2a]

In Formula 2a,
X ₂₁ and X ₂₂ are each independently an oxygen atom,
R ₂₁ to R ₃₀ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group, wherein at least two of R ₂₁ to R ₂₅ and at least two of R ₂₆ to R ₃₀ are cyano groups,
R _c and R _d are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n1 and n2 are respectively 0 or 1.
According to claim 1,
The compound of Formula 2 is a compound represented by the following Formula 2a-1, a phthalonitrile resin.
[Formula 2a-1]

delete delete delete delete delete delete According to claim 1,
A phthalonitrile resin further comprising a repeating unit derived from a compound of formula (6):
[Formula 6]

In Formula 6,
M is a tetravalent radical,
Z ₁ and Z ₂ are each independently an alkylene group, an alkylidene group, or an aromatic divalent radical.
A compound of Formula 1, and
The compound of Formula 2 is included in a weight ratio of 25:75 to 40:60,
A polymerizable composition further comprising a curing agent:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
L ₁₁ , L ₁₂ , L ₂₁ , and L ₂₂ are each independently a functional group represented by the following Chemical Formula 5;
[Formula 5]

In Formula 5, X is an oxygen atom or a sulfur atom,
R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a cyano group, wherein at least two of R ₁ to R ₅ are a cyano group,
R _a to R _d are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group and an aryl group,
m1, m2, n1, and n2 are each independently an integer from 0 to 4.
14. The method of claim 13,
The curing agent comprises a compound of formula (6), a polymerizable composition:
[Formula 6]

In Formula 6, M is a tetravalent radical,
Z ₁ and Z ₂ are each independently an alkylene group, an alkylidene group, or an aromatic divalent radical.
15. The method of claim 14,
Wherein M is a tetravalent radical derived from a compound selected from the group consisting of compounds of formulas 7a to 7f,
Wherein Z ₁ and Z ₂ are each independently a divalent radical derived from a compound selected from the group consisting of compounds of the following formulas 8a to 8c, a polymerizable composition:
[Formula 7a]

In Formula 7a, R _a1 to R _a6 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
[Formula 7b]

In Formula 7b, R _b1 to R _b8 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
[Formula 7c]

In Formula 7c, R _c1 to R _c10 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, W ₁ is a single bond, an alkylene group, a haloalkylene group, an alkylidene group, an oxygen atom, a sulfur atom, or a carbonyl group (-C(=O)-), -A ₁ -OC(=O)- A ₂ -, - A ₁ -C(=O)-O- A ₂ -, -S(=O)- or -S (=O) ₂ -, wherein A ₁ and A ₂ are each independently a single bond or an alkylene group.
[Formula 7d]

In Formula 7d, R _d1 to R _d4 are each independently hydrogen, an alkyl group, or an alkoxy group, or two adjacent groups are connected to each other to form an alicyclic ring structure, and W ₂ contains or contains one or more oxygen atoms It is not an alkylene group or an alkenylene group.
[Formula 7e]

In Formula 7e, R _e1 to R _e4 are each independently hydrogen, an alkyl group, or an alkoxy group, and W ₃ is an alkylene group.
[Formula 7f]

In Formula 7f, R _f1 to R _f10 are each independently hydrogen, an alkyl group, or an alkoxy group.
[Formula 8a]

In Formula 8a, R _g1 to R _g6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, or a carboxyl group.
[Formula 8b]

In Formula 8b, R _h1 to R _h10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group or an aryl group, and W ₄ is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, or a carbonyl group. , -NR-, -S(=O)- or -S(=O) ₂ -, wherein R is hydrogen, an alkyl group, an alkoxy group or an aryl group.
[Formula 8c]

In Formula 8c, R _i1 to R _i10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, or an aryl group.
14. The method of claim 13,
The curing agent, a polymerizable composition comprising any one or two or more selected from the group consisting of compounds of the following formulas 6a to 6h:

(6a)

(6b)

(6c)

(6d)

(6e)

(6f)

(6g)

(6h)
A prepolymer that is a reactant of the polymerizable composition of claim 13 .
A method for producing a phthalonitrile resin, comprising the step of curing the polymerizable composition of claim 13 or the prepolymer of claim 17 .

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