KR101932801B1 - Polymerizable composition - Google Patents
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- KR101932801B1 KR101932801B1 KR1020150043452A KR20150043452A KR101932801B1 KR 101932801 B1 KR101932801 B1 KR 101932801B1 KR 1020150043452 A KR1020150043452 A KR 1020150043452A KR 20150043452 A KR20150043452 A KR 20150043452A KR 101932801 B1 KR101932801 B1 KR 101932801B1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/38—Polyamides prepared from aldehydes and polynitriles
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- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present application relates to a polymerizable composition, a prepolymer, a phthalonitrile resin, a composite, a method for producing the same, and a use thereof. The present application can provide a polymerizable composition comprising a curing agent that is excellent in heat resistance and does not cause defects that may adversely affect physical properties. The present application also allows the polymerizable composition to exhibit proper curability, processing temperature and process window, and to form a composite of excellent physical properties.
Description
The present application relates to a polymerizable composition, a prepolymer, a phthalonitrile resin, a composite, a method for producing the same, and a use thereof.
The phthalonitrile resin can be used in a variety of applications. For example, a composite formed by impregnating a phthalonitrile resin with a filler such as glass fiber or carbon fiber can be used as a material for an automobile, an airplane, or a ship. The process for producing the composite may include, for example, a process of mixing a prepolymer formed by the reaction of a mixture of phthalonitrile and a curing agent or a mixture thereof with a filler and then curing the mixture (see, for example,
When the curing agent is decomposed in the course of the reaction of the phthalonitrile compound with the curing agent, defects such as residual voids occur in the prepolymer, resin or composite, and such defects are factors that hinder the physical properties of the final product . Therefore, in order to solve the above problems, a method of controlling the ratio of the curing agent to a low level or adjusting the temperature to a low level during the curing reaction may be considered. However, such a method lowers the curing efficiency, Can be adversely affected.
The present application provides a polymerizable composition, a prepolymer, a phthalonitrile resin, a composite, a method for producing the same, and uses thereof. It is an object of the present application to provide a polymerizable composition comprising a curing agent which is excellent in heat resistance and does not cause defects such as voids which may adversely affect physical properties. In addition, the present application is also intended to enable the polymerizable composition to exhibit appropriate curing properties, processing temperatures and process windows, and to form a composite having excellent physical properties.
The present application is directed to a polymerizable composition. In one example, the polymerizable composition may be a composition capable of forming a so-called phthalonitrile resin through a polymerization reaction.
The polymerizable composition may include a phthalonitrile compound and a curing agent.
The kind of the phthalonitrile compound that can be used in the polymerizable composition is not particularly limited and may be, for example, two or more, two or more phthalonitrile structures capable of forming a phthalonitrile resin through reaction with a
The polymerizable composition further comprises a curing agent, and as the curing agent, a compound represented by the following formula (1) may be used. The curing agent of the following formula has an imide structure in the molecular structure and thereby exhibits excellent heat resistance and is contained in an excessive amount in the polymerizable composition or has an adverse effect on physical properties even when the polymerizable composition is processed or cured at a high temperature A polymerizable composition which does not generate voids or the like which can be given can be formed.
[Chemical Formula 1]
In Formula (1), M is a tetravalent radical, and X 1 and X 2 are each independently an alkylene group, an alkylidene group or an aromatic divalent radical.
In the present application, the radical n (n is an arbitrary number) in the present application may mean a quaternary residue derived from a predetermined compound, unless otherwise specified. For example, in the above formula (1), M may be a tetravalent radical derived from an aliphatic, alicyclic or aromatic compound. In such a case, for example, M may be an aliphatic, alicyclic or aromatic compound having four A radical in which a hydrogen atom is formed by leaving is connected to the carbon atom of the carbonyl group of the formula (1).
As the aliphatic compound in the above, straight-chain or branched alkane, alkene or alkyne may be exemplified. As the aliphatic compound, alkane, alkene or alkyne 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. In this case the alkane, alkene or alkyne may optionally be substituted by one or more substituents.
Examples of the alicyclic compounds include hydrocarbon compounds having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbon atoms, and 3 to 4 carbon atoms in the non-aromatic ring structure. Such an alicyclic hydrocarbon compound may contain 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.
The aromatic compound may be benzene, a compound containing benzene, or a derivative of any of the above. As used herein, the benzene-containing compound may mean a compound in which two or more benzene rings are condensed while sharing one or two carbon atoms, or a structure in which the benzene ring is directly linked or linked by an appropriate linker. The aromatic compound may, for example, comprise from 6 to 25, from 6 to 20 or from 6 to 12 carbon atoms and may be optionally substituted by one or more substituents.
In one example, the alicyclic or aromatic compound forming the tetravalent radical may be exemplified by a compound represented by any one of the following formulas (2) to (7).
(2)
In formula (2), R 1 to R 6 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group.
(3)
In formula (3), R 1 to R 8 each independently represents hydrogen, an alkyl group, an alkoxy group or an aryl group.
[Chemical Formula 4]
In the general formula 4 R 1 to R 10 are each independently hydrogen, an alkyl group or an aryl group, X is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, -A 1 -OC (= O) -A 2 -, -A 1 -C (= O) -OA 2 -, -S (= O) - or -S (= O) 2 -. In the above, A 1 and A 2 are each independently a single bond or an alkylene group.
In the present specification, the term "single bond" means a case where no additional atom exists at the corresponding site. For example, when X is a single bond in the general formula (4), it means that there is no additional atom , In which case the benzene rings on both sides of X may be directly connected to form a biphenyl structure.
[Chemical Formula 5]
In formula (5), R 1 to R 4 are each independently hydrogen, an alkyl group or an alkoxy group, and A is an alkylene group or an alkenylene group.
In formula (5), two of R 1 to R 4 may be connected to each other to form an alkylene group, and the alkylene group or alkenylene group of A may contain one or more oxygen atoms as a hetero atom.
[Chemical Formula 6]
In Formula (6), R 1 to R 4 are each independently hydrogen, an alkyl group or an alkoxy group, and A is an alkylene group.
(7)
In formula (7), R 1 to R 10 are each independently hydrogen, an alkyl group or an alkoxy group.
The alkyl group in the present application 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, where necessary, may be substituted by one or more substituents.
The term alkoxy group in the present application 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 groups may be linear, branched or cyclic and, where necessary, may be substituted by one or more substituents.
The term aryl group in the present application may mean a monovalent residue derived from the above-described aromatic compound unless otherwise specified. As used herein, the term " aryl group " may include not only a functional group commonly referred to as an aryl group but also an aralkyl group or an arylalkyl group.
The term alkylene group or alkylidene group in the present application means 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 do. The alkylene or alkylidene group may be linear, branched or cyclic. Also, the alkylene or alkylidene group may be optionally substituted with one or more substituents.
Examples of the substituent optionally substituted in the aliphatic compound, alicyclic compound, aromatic compound, alkyl group, alkoxy group, aryl group, alkylene group or alkylidene group in the present application include halogen such as chlorine or fluorine, glycidyl group, But are not limited to, epoxy groups such as epoxy alkyl groups, glycidoxyalkyl groups and alicyclic epoxy groups, acryloyl groups, methacryloyl groups, isocyanate groups, thiol groups, alkyl groups, alkoxy groups or aryl groups.
Examples of the compound of Formula 2 include, but are not limited to, benzene, alkylbenzene or dialkylbenzene.
Examples of the compound represented by the formula (4) include biphenyl and compounds represented by the following formulas (A) to (F), but the present invention is not limited thereto.
(A)
[Chemical Formula B]
≪ RTI ID = 0.0 &
[Chemical Formula D]
(E)
[Chemical Formula F]
Examples of the compound represented by the formula (5) include cyclohexane having 4 to 8 carbon atoms such as cyclohexane or cyclohexene which may be substituted with at least one alkyl group, and the like, , But are not limited thereto.
[Formula G]
[Formula H] <
(I)
As the compound of the formula (6), compounds represented by the following formula (J) which may be substituted with at least one alkyl group are exemplified, but are not limited thereto.
[Chemical Formula J]
In such a compound, for example, four hydrogen atoms may be released to form a radical, and the radical may be included in the structure of formula (1).
These radicals may be the same or different and are selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an alkylene group, or an alkenylene group, which is a substituent that R 1 to R 10 in the above Chemical Formulas 2 to 7 are directly displaced or may exist in R 1 to R 10 Hydrogen atoms may be separated from each other.
For example, when the radical is derived from the compound of formula (2), at least one, more than two, at least three or four of R 1 to R 6 of formula (2) form radicals, or R 1 to R The hydrogen atom of the alkyl group, the alkoxy group, or the aryl group present in R < 6 > may be removed to form the radical. The formation of a radical in the above may mean that the moiety is linked to the carbon atom of the carbonyl group of formula (1) as described above. For example, when R 2 , R 3 , R 5 and R 6 in the general formula (2) form radicals connected to the general formula (1), a core structure similar to the
In one example, the tetravalent radical of formula (1) may be a tetravalent radical derived from a compound represented by any one of formulas (2) to (4). Formula 2 of R 1 to in which case R 6, formula 3 of R 1 to R 8) or (4, R 1 to R 11 each independently represent a hydrogen, an alkyl group or an aryl Kii are, each of said four or more Can form radicals linked to formula (1). Each of which does not form radicals may be hydrogen, an alkyl group or an alkoxy group, or may be hydrogen or an alkyl group. In one example, R 2 , R 3 , R 5 and R 6 may form the radicals in formula (2), R 1 and R 4 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group, An alkyl group or an alkoxy group, or hydrogen or an alkyl group. In
In Formula 4, X may be an alkylene group, an alkylidene group, an oxygen atom, or a sulfur atom. In another example, X in Formula 4 may be an alkylene group, an alkylidene group, an oxygen atom, or an oxygen atom.
In formula (1), X 1 and X 2 are each independently an alkylene group, an alkylidene group or an aromatic divalent radical, and in another example, the same or different aromatic divalent radicals may be mentioned. In the above, the aromatic divalent radical may be a divalent radical derived from the above-mentioned aromatic compound.
In one example, X 1 and X 2 in
[Chemical Formula 8]
In formula (8), R 1 to R 6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or a carboxyl group.
[Chemical Formula 9]
Formula in 9 R 1 to R 10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group or an aryl group, X is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, -NR 11 -, -S (= O) - or -S (= O) 2 -, wherein R 11 is hydrogen, an alkyl group, an alkoxy group or an aryl group.
The meaning of the single bond in the above is the same as defined in formula (4).
[Chemical formula 10]
In formula (10), R 1 to R 10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group or an aryl group.
As the compound of the formula (8), benzene which may be substituted with at least one hydroxy group or a carboxyl group is exemplified, but is not limited thereto.
The compound represented by the formula (9) may be a biphenyl which may be substituted with at least one hydroxy group or a carboxyl group, or a compound represented by any one of the above formulas (A) to (F) or at least one hydroxy group Or a compound which may be substituted with a carboxyl group or a compound represented by the following formula (K) to (N), or a compound which may be substituted with at least one hydroxyl group or a carboxyl group represented by the following formulas (K) to (N) It is not.
[Chemical formula K]
[Chemical formula L]
[Formula M]
[Chemical formula N]
Examples of the compound represented by the formula (10) include a compound represented by the following formula (O) or a compound represented by the formula (O) that may be substituted with at least one hydroxy group or a carboxyl group.
[Chemical formula O]
In one example, the aromatic divalent radical may be a radical derived from the compound of formula (8), for example, phenylene, but is not limited thereto. In the case where the divalent radical is phenylene, the substitution position of the amine group based on the moiety connected to N in X 1 of formula (1) may be an ortho, meta or para position, The substitution position of the amine group based on the moiety connected to N in X 2 of formula (1) may also be an ortho, meta or para position.
The compound of the formula (1) can be synthesized according to the synthesis method of a known organic compound, and the specific method thereof is not particularly limited. For example, the compound of formula (1) can be formed by a dehydration condensation reaction of a dianhydride compound and a diamine compound.
The compound of the formula (1) has a high boiling point and is not volatilized or decomposed at a high temperature, so that the curing property of the polymerizable composition can be stably maintained, and the voids can be adversely affected in the process of high temperature processing or curing void. Thus, in one example, the compound may have a decomposition temperature of 300 ° C or higher, 350 ° C or higher, 400 ° C or higher, or 500 ° C or higher. The term decomposition temperature in the present application may mean a temperature at which the decomposition rate of the compound of the formula (1) is maintained in the range of 10% or less, 5% or less or 1% or less. The upper limit of the decomposition temperature is not particularly limited, and may be, for example, about 1,000 DEG C or less.
In addition, the compounds of formula (1) of the core of the M or linker, X 1 or naejineun reactive by the selection of X 2 polymerizable composition itself, the process window, that is the melting temperature of the polymeric composition or a prepolymer formed therefrom, and curing temperature The difference can be easily controlled, so that it can act as a curing agent having various physical properties depending on the application.
The proportion of the curing agent in the polymerizable composition is not particularly limited. The ratio can be adjusted so that the desired curability can be ensured in consideration of, for example, the ratio or type of the curable component such as the phthalonitrile compound contained in the composition. For example, the curing agent may be included in an amount of about 0.02 to 1.5 moles per mole of the phthalonitrile compound contained in the polymerizable composition. However, the above ratios are only examples of the present application. Usually, the proportion of the curing agent in the polymerizable composition tends to be high, but the process window tends to become narrow. When the proportion of the curing agent is low, the curability tends to become insufficient. have.
The polymerizable composition of the present application is a polymerizable composition capable of forming a complex of excellent physical properties that exhibits appropriate curability, melting temperature and process window through the use of the compound of formula (1) The composition and the prepolymer can be provided.
Thus, in one example, the processing temperature of the polymerizable composition may be in the range of from 150 캜 to 350 캜. The term processing temperature in the present application may mean the temperature at which the compound, the following polymerizable composition or prepolymer containing it, etc. are present in a processable state. Such a processing temperature may be, for example, a melting temperature (Tm) or a glass transition temperature (Tg). In this case, the absolute value of the difference (Tc-Tp) between the processing temperature (Tp) of the polymerizable composition and the curing temperature (Tc) of the phthalonitrile compound and the compound of Formula , 50 ° C or higher, or 100 ° C or higher. In one example, the curing temperature Tc may be higher than the processing temperature Tp. Such a range may be advantageous for securing proper processability in the process of producing a complex to be described later, for example, using a polymerizable composition. The upper limit of the process window is not particularly limited. For example, the absolute value of the difference (Tc-Tp) between the processing temperature Tp and the curing temperature Tc may be 400 ° C or lower or 300 ° C or lower.
The polymerizable composition may further comprise various additives. Examples of such additives include various fillers. The kind of the material that can be used as the filler is not particularly limited, and any known filler suitable for the intended use may be used. Exemplary fillers include, but are not limited to, metal materials, ceramic materials, glass, metal oxides, metal nitrides or carbon-based materials. The form of the filler is not particularly limited, and may be a fibrous material such as aramid fiber, glass fiber or ceramic fiber, or a woven fabric, nonwoven fabric, string or string formed by the material, particulate, polygonal or other amorphous And the like. Examples of the carbon-based material include graphite, graphene, carbon nanotubes, derivatives thereof such as oxides thereof, and isomers thereof. However, the components that the polymerizable composition may further contain are not limited to the above, and various monomers known to be applicable to the production of so-called engineering plastics such as polyimide, polyamide or polystyrene, Additives may also be included without limitation depending on the purpose.
The present application is also directed to a prepolymer formed by the reaction of the polymerizable composition, that is, the polymerizable composition comprising the phthalonitrile compound and the compound of formula (1).
The term " prepolymer state " in the present application means a state in which the reaction of the phthalonitrile compound with the compound of the formula (1) occurs in the polymerizable composition to some extent (for example, It does not reach the fully polymerized state and exhibits appropriate fluidity, and can mean, for example, a state in which the composite body as described below can be processed. In one example, the prepolymer state is a state in which the polymerization of the polymerizable composition proceeds to some extent, and a melt viscosity of the composition measured at any temperature within the range of about 150 캜 to 250 캜 is from 100 cP to 10,000 cP , From 100 cP to 5,000 cP, or from 100 cP to 3,000 cP.
The prepolymer may also exhibit excellent curability, a low melting temperature and a wide process window.
For example, the processing temperature of the prepolymer may be in the range of 150 캜 to 350 캜. In this case, the absolute value of the difference (Tc-Tp) between the processing temperature Tp of the prepolymer and the curing temperature Tc of the prepolymer may be 30 ° C or more, 50 ° C or more, or 100 ° C or more. In one example, the curing temperature Tc may be higher than the processing temperature Tp. Such a range may be advantageous for securing appropriate processability in the process of preparing a complex to be described later, for example, using a prepolymer. The upper limit of the process window is not particularly limited. For example, the absolute value of the difference (Tc-Tp) between the processing temperature Tp and the curing temperature Tc may be 400 ° C or lower or 300 ° C or lower.
The prepolymer may further contain any known additives in addition to the above components. Examples of such additives include, but are not limited to, the above-mentioned fillers and the like.
The present application is also directed to a phthalonitrile resin which is a polymer of said polymerizable composition. Such a resin can be formed, for example, by polymerizing the above-mentioned polymerizable composition or prepolymer.
The present application is also directed to a composite. The composite may include the above-described phthalonitrile resin and filler. As described above, the use of the polymerizable composition of the present application makes it possible to achieve an appropriate curing property, a melting temperature and a process window, and can adversely affect physical properties even at a high temperature applied during the formation of the composite or resin Voids and the like which are contained in the reinforced polymer composite can be prevented. Thus, a so-called reinforced polymer composite having excellent physical properties can be easily formed. The composite thus formed may contain the phthalonitrile resin and filler and may be applied to various uses including durables for automobiles, airplanes or ships, and the like.
The kind of the filler is not particularly limited and may be suitably selected in consideration of the intended use. Fillers that may be used include fibrous materials such as carbon fibers, aramid fibers, glass fibers or ceramic fibers, or carbon nanomaterials such as woven, non-woven, string or string formed by the materials, or carbon nanotubes or grapheme And the like, but the present invention is not limited thereto.
The proportion of the filler is not particularly limited, and may be set in an appropriate range depending on the intended use.
The present application is also directed to a precursor for making the composite, which may comprise, for example, the polymeric composition described above and the filler, or the prepolymer described above and the filler.
The complex can be prepared in a known manner using the precursor. For example, the composite can be formed by curing the precursor.
In one example, the precursor may be prepared by blending a polymerizable composition prepared by compounding the phthalonitrile compound with the compound of
The present application can provide a polymerizable composition comprising a curing agent that is excellent in heat resistance and does not cause defects such as voids that can adversely affect physical properties. The present application also allows the polymerizable composition to exhibit proper curability, processing temperature and process window, and to form a composite of excellent physical properties.
1 to 10 are NMR analysis results of the compound prepared in Production Example.
11 shows FT-IR analysis results of the polymerizable compositions of Examples and Comparative Examples.
Hereinafter, the polymerizable composition or the like of the present application will be specifically described by way of examples and comparative examples, but the scope of the polymerizable composition and the like is not limited to the following examples.
1. TGA ( Thermogravimetric Analysis )
TGA analysis was performed using a Mettler-Toledo TGA e850 instrument. Analysis was carried out in an atmosphere of N 2 flow while raising the temperature from about 25 ° C. to 800 ° C. at a rate of 10 ° C./min.
2. FT - IR ( Fourier - transform infrared spectroscopy )
The FT-IR analysis was performed using ATR (Attenuated Total Reflectance) method using Varian's equipment. As a sample, the prepolymer of Example or Comparative Example was thermally cured, pulverized and pulverized, and the FT-IR peak was measured at an absorption wavelength ranging from 400 cm -1 to 4000 cm -1 wavelength.
Manufacturing example 1. Compound ( PN1 ) Synthesis of
The following compounds of formula (I) were synthesized in the following manner. 27.9 g of a compound represented by the following formula (II) and 100 g of DMF (Dimethyl Formamide) were put into a 3 neck round bottom flask (RBF) and dissolved by stirring at room temperature. Subsequently, 51.9 g of the compound of the following formula (III) was added thereto, and 50 g of DMF was added, followed by stirring to dissolve. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 DEG C with stirring. After reacting for about 5 hours in the above state, it was cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring into a 0.2N aqueous hydrochloric acid solution, followed by filtration and washing with water. The filtered reaction was then dried in a vacuum oven at 100 ° C for 1 day, and after removal of water and residual solvent, a compound of formula (I) was obtained in a yield of about 83% by weight. The NMR results for the compound of formula (I) are shown in FIG.
(I)
≪ RTI ID = 0.0 &
(III)
Manufacturing example 2. Compound ( PN2 ) Synthesis of
50.4 g of the compound of the following formula (IV) and 150 g of DMF (Dimethyl Formamide) were added to a 3 neck round bottom flask (RBF) and dissolved by stirring at room temperature. Then, 51.9 g of the compound of the formula (III) in Production Example 1 was added, and 50 g of DMF was added and dissolved by stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 DEG C with stirring. After reacting for about 5 hours in the above state, it was cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring into a 0.2N aqueous hydrochloric acid solution, followed by filtration and washing with water. The filtered reaction was then dried in a vacuum oven at 100 캜 for 1 day and after removal of water and residual solvent, a compound of formula V (PN2) was obtained in a yield of about 87% by weight. The NMR results for the compound of formula V are shown in FIG.
(IV)
(V)
Manufacturing example 3. Compound ( CA1 ) Synthesis of
The following compounds of formula (IIX) were synthesized in the following manner. First, 24 g of the compound of the following formula (VI) and 45 g of NMP (N-methyl-pyrrolidone) were added to a 3 neck round bottom flask (RBF) and dissolved by stirring at room temperature. The above was cooled with a water bath, and 12.4 g of the compound of the formula (VII) was gradually added in 3 portions and added with 45 g of NMP. When all of the added compounds were dissolved, 18 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was extracted with methanol to remove residual reactants and dried in a vacuum oven to yield the compound of formula IIX in a yield of about 81% by weight. The NMR results for the compound of formula (IIX) are shown in FIG.
(VI)
(VII)
(IIX)
Manufacturing example 4. Compound ( CA2 ) Synthesis of
The following compounds of formula (X) were synthesized in the following manner. 13 g of the compound of the formula (IX) and 33 g of NMP (N-methyl-pyrrolidone) were added to a 3 neck round bottom flask (RBF) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 12.4 g of compound VII of Preparation Example 3 was slowly added to the mixture in three portions, followed by 30 g of NMP. When all the charged compound was dissolved, 13 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was extracted with methanol to remove residual reactants and dried in a vacuum oven to yield a compound of formula X in a yield of about 78% by weight. The NMR results for the compound of formula X are shown in FIG.
(IX)
(X)
Manufacturing example 5. Compound ( CA3 ) Synthesis of
The following compounds of formula (XII) were synthesized in the following manner. 13 g of the compound of the following formula (XI) and 33 g of NMP (N-methyl-pyrrolidone) were added to a 3 neck round bottom flask (RBF) and dissolved by stirring at room temperature. The above solution was cooled with a water bath, and 12.4 g of compound VII of Preparation Example 3 was slowly added to the mixture in three portions, followed by 30 g of NMP. When all the charged compound was dissolved, 13 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was extracted with methanol to remove residual reactants and dried in a vacuum oven to yield a compound of formula XII in a yield of about 80% by weight. The NMR results for the compound of formula (XII) are shown in FIG.
(XI)
(XII)
Manufacturing example 6. Compound ( CA4 ) Synthesis of
The compound of the following formula (14) was synthesized by dehydration condensation of diamine and dianhydride. 24 g of the compound represented by the formula (VI) (4,4'-oxydianiline) of Production Example 3 and 40 g of NMP (N-methyl-pyrrolidone) were put into a 3 neck round bottom flask and dissolved by stirring at room temperature . The above solution was cooled with a water bath, and 8.7 g of the compound of the following formula (13) was slowly added to the solution in three portions, and the solution was added with 40 g of NMP. When all the added compounds were dissolved, 16 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was extracted with methanol to remove residual reactants and dried in a vacuum oven to yield the compound of formula 14 in a yield of about 85% by weight. The NMR results for the compound of Formula 14 are shown in FIG.
[Chemical Formula 13]
[Chemical Formula 14]
Manufacturing example 7. Compound ( CA5 ) Synthesis of
The compound of formula (16) was synthesized by dehydration condensation of diamine and dianhydride. 24 g of the compound represented by the formula (VI) (4,4'-oxydianiline) of Production Example 3 and 45 g of NMP (N-methyl-pyrrolidone) were put into a 3 neck round bottom flask and dissolved by stirring at room temperature . The above solution was cooled with a water bath, and 11.8 g of the compound of the following formula (15) was slowly added to the mixture in three portions and added with 45 g of NMP. When all of the added compounds were dissolved, 18 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was extracted by soxhlet with methanol to remove residual reaction and dried in a vacuum oven to obtain a compound of formula 16 in a yield of about 77% by weight. The NMR results for the compound of Formula 16 are shown in FIG.
[Chemical Formula 15]
[Chemical Formula 16]
Manufacturing example 8. Compound ( CA6 ) Synthesis of
The compound of the following formula (18) was synthesized by dehydration condensation of diamine and dianhydride. 24 g of the compound represented by the formula (VI) (4,4'-oxydianiline) of Production Example 3 and 45 g of NMP (N-methyl-pyrrolidone) were put into a 3 neck round bottom flask and dissolved by stirring at room temperature . The above solution was cooled with a water bath, and 11.8 g of a compound represented by the following formula (17) was slowly added to the mixture in three portions and added with 45 g of NMP. When all of the added compounds were dissolved, 18 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was extracted by soxhlet with methanol to remove residual reaction and dried in a vacuum oven to obtain a compound of formula 18 in a yield of about 87% by weight. The NMR results for the compound of Formula 18 are shown in FIG.
[Chemical Formula 17]
[Chemical Formula 18]
Manufacturing example 9. Compound ( CA7 ) Synthesis of
The compound of the following formula (20) was synthesized by dehydration condensation of diamine and dianhydride. 24 g of the compound represented by the formula (VI) (4,4'-oxydianiline) of Production Example 3 and 45 g of NMP (N-methyl-pyrrolidone) were put into a 3 neck round bottom flask and dissolved by stirring at room temperature . The above solution was cooled with a water bath, and 9 g of the compound of the following formula (19) was slowly added to the mixture in three portions, followed by the addition of 41 g of NMP. When all of the added compounds were dissolved, 18 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove residual reaction, and dried in a vacuum oven to obtain a compound of
[Chemical Formula 19]
[Chemical Formula 20]
Manufacturing example 10. Compound ( CA8 ) Synthesis of
The compound of formula (22) was synthesized by dehydration condensation of diamine and dianhydride. 24 g of the compound represented by the formula (VI) (4,4'-oxydianiline) of Production Example 3 and 60 g of NMP (N-methyl-pyrrolidone) were put in a 3 neck round bottom flask and dissolved by stirring at room temperature . The above solution was cooled with a water bath, and 12.3 g of the compound of the following formula (21) was slowly added to the mixture in three portions and added with 60 g of NMP. When all the charged compounds were dissolved, 24 g of toluene was added to the reaction for azeotrope. A Dean-Stark device and a reflux condenser were installed, and the Dean-Stark device was charged with toluene. 4.2 mL of pyridine was added as a dehydration condensation catalyst, the temperature was raised to 170 DEG C, and the mixture was stirred for 3 hours. The water generated as the imide ring was formed was further stirred for 2 hours while removing with Dean Stark apparatus, and residual toluene and pyridine were removed. The reaction product was cooled to room temperature, precipitated in methanol and recovered. The recovered precipitate was subjected to soxhlet extraction with methanol to remove residual reactants, and dried in a vacuum oven to obtain a compound of Formula 22 in a yield of about 87% by weight. The NMR results for the compound of Formula 22 are shown in FIG.
[Chemical Formula 21]
[Chemical Formula 22]
Manufacturing example 11. Compound ( CA9 ) Synthesis of
A compound (CA9) of the following formula (23) was obtained from TCI (Tokyo Chemical Industry Co., Ltd.) and used without further purification.
(23)
The results of TGA analysis of the compounds of Production Examples 3 to 11 are summarized in Table 1 below. From Table 1, it can be confirmed that the compounds (CA1 to CA8) of Production Examples 3 to 10 exhibit excellent heat resistance characteristics as compared with the compound (CA9) of Production Example 11. CA9 compounds are all decomposed at around 330 ° C, whereas CA1 to CA8 compounds show almost no decomposition by heat even at high temperature calcination of
Example One.
About 6 mol% of the compound (CA1) of Production Example 3 relative to the amount of the compound (PN1) used in Production Example 1 (PN1) was added and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition are shown in FIG. When the polymerizable composition is melted at 240 캜 and stirred for 5 minutes, prepolymer production is possible. As shown in FIG. 11, it was confirmed by FT-IR analysis that the imide stretching peak of the polymerizable composition was observed at 1720 cm -1 and 1770 cm -1 , indicating excellent heat resistance and the like 1 is a second graph at the top of FIG. 11).
Example 2.
About 6 mol% of the compound (CA1) of Preparation Example 3 relative to the amount of the compound (PN2) used in Production Example 2 (PN2) was added and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition are shown in FIG. When the polymerizable composition is melted at 240 캜 and stirred for 5 minutes, prepolymer production is possible. As shown in FIG. 11, it was confirmed by FT-IR analysis that the imide stretching peak of the polymerizable composition was observed at 1720 cm -1 and 1770 cm -1 , indicating excellent heat resistance and the like 2 is the uppermost graph in Fig. 11).
Example 3
A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA2) of Production Example 4 was used in place of the compound (CA1) of Production Example 3. In the case of Example 3, imide stretching peaks can be observed at 1720 cm -1 and 1770 cm -1 in the FT-IR analysis.
Example 4
A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA3) of Production Example 5 was used in place of the compound (CA1) of Production Example 3. In the case of Example 4, imide stretching peaks can be observed at 1720 cm -1 and 1770 cm -1 in the FT-IR analysis.
Example 5
A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA4) of Production Example 6 was used in place of the compound (CA1) of Production Example 3. In the case of Example 5, imide stretching peaks can be observed at 1720 cm -1 and 1770 cm -1 in the FT-IR analysis.
Example 6
A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA5) of Preparation Example 7 was used in place of the compound (CA1) of Production Example 3. In the case of Example 6, imide stretching peaks can be observed at 1720 cm -1 and 1770 cm -1 in the FT-IR analysis.
Example 7
A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA6) of Production Example 8 was used in place of the compound (CA1) of Production Example 3. In the case of Example 7, imide stretching peaks can be observed at 1720 cm -1 and 1770 cm -1 in the FT-IR analysis.
Example 8
A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA7) in Production Example 9 was used in place of the compound (CA1) in Production Example 3. Also in the case of Example 8, imide stretching peaks can be observed at 1720 cm -1 and 1770 cm -1 in the FT-IR analysis.
Example 10
A polymerizable composition and a prepolymer were prepared in the same manner as in Example 1, except that the compound (CA8) of Production Example 10 was used in place of the compound (CA1) in Production Example 3. In the case of Example 10, imide stretching peaks can be observed at 1720 cm -1 and 1770 cm -1 in the FT-IR analysis.
Comparative Example One.
About 6 mol% of the compound (CA9) of Production Example 11 relative to the amount of the compound (PN1) used in Production Example 1 (PN1) was added and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition are shown in FIG. When the polymerizable composition is melted at 240 캜 and stirred for 5 minutes, prepolymer production is possible. As shown in FIG. 11, the FT-IR analysis of the polymerizable composition showed no imide stretching peaks observed, indicating that the physical properties such as heat resistance were lower than those of the examples (Comparative Example 1, Graph Is the fourth graph from the top in Fig. 11).
Comparative Example 2.
About 6 mol% of the compound (CA9) of Production Example 11 relative to the amount of the compound (PN2) used in Production Example 2 (PN2) was added and mixed well to prepare a polymerizable composition. The results of performing the FT-IR analysis on the composition are shown in FIG. When the polymerizable composition is melted at 240 캜 and stirred for 5 minutes, prepolymer production is possible. As shown in FIG. 11, the FT-IR analysis of the polymerizable composition showed no imide stretching peaks observed, indicating that the physical properties such as heat resistance were lower than those of the examples (Comparative Example 1, Graph Is the third graph at the top in Fig. 11).
Claims (17)
[Chemical Formula 1]
In Formula (1), M is a tetravalent radical, and X 1 and X 2 are each independently an alkylene group, an alkylidene group or an aromatic divalent radical.
(2)
In formula (2), R 1 to R 6 are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group:
(3)
In Formula (3), R 1 to R 8 are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group.
[Chemical Formula 4]
In the general formula 4 R 1 to R 10 are each independently hydrogen, an alkyl group or an aryl group, X is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, -A 1 -OC (= O) -A 2 -, -A 1 -C (═O) -OA 2 -, -S (═O) - or -S (═O) 2 - in which A 1 and A 2 are Independently are a single bond or an alkylene group:
[Chemical Formula 5]
In formula (5), R 1 to R 4 are each independently hydrogen, an alkyl group or an alkoxy group, and A is an alkylene group or an alkenylene group (provided that two of R 1 to R 4 are connected to form an alkylene group And the alkylene group or alkenylene group of A may contain one or more oxygen atoms as a hetero atom):
[Chemical Formula 6]
In Formula (6), R 1 to R 4 are each independently hydrogen, an alkyl group or an alkoxy group, and A is an alkylene group.
(7)
In formula (7), R 1 to R 10 are each independently hydrogen, an alkyl group or an alkoxy group.
[Chemical Formula 8]
In Formula (8), R 1 to R 6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, or a carboxyl group.
[Chemical Formula 9]
Formula in 9 R 1 to R 10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group or an aryl group, X is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, -A 1 -OC (= O) -A 2 -, -A 1 -C (= O) -OA 2 - or -NR 11 - is, in the R 11 is hydrogen, an alkyl group, an alkoxy group or an aryl group, A 1 and A 2 are each independently a single bond or an alkylene group:
[Chemical formula 10]
In formula (10), R 1 to R 10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group or an aryl group.
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KR102071909B1 (en) * | 2016-11-29 | 2020-01-31 | 주식회사 엘지화학 | Polymerizable composition |
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KR102380727B1 (en) * | 2018-01-03 | 2022-03-29 | 주식회사 엘지화학 | Phthalonitrile resin |
KR102202060B1 (en) | 2018-08-17 | 2021-01-12 | 주식회사 엘지화학 | Low friction resin composites |
WO2020036443A1 (en) * | 2018-08-17 | 2020-02-20 | 주식회사 엘지화학 | Low-friction resin composite |
KR102218559B1 (en) * | 2018-08-28 | 2021-02-22 | 주식회사 엘지화학 | Phthalonitrile-based resin with improved impact strength |
WO2020045897A1 (en) * | 2018-08-28 | 2020-03-05 | 주식회사 엘지화학 | Phthalonitrile-based resin having improved impact strength |
KR102409436B1 (en) * | 2018-09-20 | 2022-06-14 | 주식회사 엘지화학 | A resin composition for metallic surface coating having high heat resistance and low friction property and a metallic substrate coated with the resin composition |
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