Polyaryletherketone composition and preparation method therefor

Abstract

The present disclosure relates to a polyaryletherketone composition and a preparation method therefor. The polyaryletherketone composition comprises a polyaryletherketone, which includes a repeating unit represented by the following chemical formula 5, and a residual compound, which includes an unreacted monomer containing a silyl group, a monomer decomposition product containing a silyl group, or a combination thereof, wherein the residual compound is included in an amount of 0-0.005 wt% on the basis of 100 wt% of the polyaryletherketone composition. [Chemical formula 5] In chemical formula 5, each of R111 to R224 is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, a halogenated alkyl group, an aldehyde group, a nitro group, a nitroso group or a nitrile group, each of X11 and X21 is independently a single bond, -O-, -S- or a divalent organic group, provided that X11 and / or X21 is a ketone group (-CO-), Z51 is oxygen, and each of n1, n2 and n3 is independently an integer of 0 to 5, provided that at least any one of n1, n2 and n3 is 1 or more.

Description

Polyaryl ether ketone composition and method for preparing the same

[0001] The present disclosure relates to a polyaryletherketone composition and a method for preparing the same, and more specifically, to a polyaryletherketone composition with improved purity and thermal stability through a two-step solvent-free polymerization of a first solvent-free polymerization and a second solvent-free polymerization, and a method for preparing the same.

[0002] Polyaryletherketone has excellent heat resistance, chemical resistance, moldability, mechanical properties, and electrical properties, and is widely used in electronic components, semiconductor process jigs, mechanical parts for automobiles, and OA equipment.

[0003] Regarding the methods for preparing polyaryletherketone compositions, there are broadly two polymerization methods. One is an aromatic globular substitution reaction, and the other is an aromatic globular substitution reaction.

[0004] Examples of aromatic electron substitution reactions include a method for obtaining polyaryletherketones by using nitrobenzene as a solvent (see U.S. Patent No. 3,065,205) and a report that the molecular weight increased slightly by using dichloromethane as a solvent (see UK Patent No. 971,227). However, in all cases, the molecular weight was very low.

[0005] In addition, U.S. Patent No. 3,442,857 describes that high molecular weight polyaryletherketones were obtained by an aromatic covalent electron substitution reaction in an HF / BF3 system using liquid hydrogen fluoride as the solvent. However, the method of producing polyaryletherketones by these aromatic covalent electron substitution reactions is not industrially desirable because it is difficult to obtain high molecular weights and it is difficult to limit the reaction positions in the aromatic ring, making it difficult to obtain linear polymers, which results in poor thermal properties, and even when obtained, it is necessary to use highly toxic strong acidic solvents, making processes such as neutralization / deacidification treatment unavoidable.

[0006] In addition, it is known that low molecular weight polyaryletherketones can be obtained by direct dehydration polycondensation by an aromatic electron substitution reaction using polyphosphoric acid as a solvent (see J. Polym. Sci. A-1, 6, 3345 (1968)). However, in this system, since polyphosphoric acid is used, phosphorus remains as an impurity in the polyaryletherketone obtained, which is undesirable.

[0007] British Patent No. 1,387,303 describes that high molecular weight polymers were obtained in the same way when HF / BF3 was used in a direct dehydration polycondensation method. However, this is also not industrially desirable because it requires the use of a highly toxic strong acidic solvent.

[0008] Meanwhile, it is known that the polymerization of polyaryletherketones by aromatic nucleus substitution reaction can be achieved by generating an alkali metal salt of an aromatic diol monomer using an alkali metal compound as a catalyst, followed by a polycondensation reaction with a benzophenone halide compound (see J. Polym. Sci. A-1, 5, 2375 (1967)). The aforementioned aromatic nucleus substitution reaction is called the desalination polycondensation method because the alkali metal halide salt is removed during polycondensation.

[0009] Typically, in this method, polymerization proceeds by reacting with the polymer dissolved in a solvent. However, polymers with low solubility in solvents, such as polyaryletherketone, precipitate at a low molecular weight stage, and since subsequent polymerization reactions do not proceed, high molecular weight polymers could not be obtained.

[0010] In addition, in the desalination polycondensation method, it is considered important to sufficiently remove water that is produced as a byproduct when an alkali salt of an aromatic diol monomer is generated from the reaction system. For example, Japanese Patent No. 42-7799 states that it is essential to maintain the solvent in an anhydrous state before and during the polymerization reaction, and to remove water from the system, methods are taken such as using benzene or toluene as an azeotropic solvent for water to remove it by distillation and removing the effluent water by adsorption with a molecular sieve.

[0011] Polyaryletherketones, which have low solubility in solvents, are reacted at very high temperatures to maintain the polymer in a constantly dissolved state, thereby obtaining high molecular weight products. However, this method requires carrying out the polymerization reaction at very high temperatures and necessitates a very cumbersome purification process. The literature [Macromolecules, 23, 4029 (1990)] states that when diphenylsulfone is used as a solvent in the production of polyaryletherketones, the molecular weight does not increase at polymerization temperatures below 280°C, where the resulting polymer precipitates. Additionally, there are cases where diphenylsulfone is similarly used as a polymerization solvent and the temperature is gradually increased to maintain the resulting polymer in a dissolved state, with the reaction finally carried out at 320°C (see Japanese Registered Patent No. 60-32642).

[0012] Although a method for producing polyaryletherketone by solvent-free polymerization without using high-boiling point solvents such as diphenylsulfone is known, there is a problem in that it is difficult to remove unreacted residual monomers and monomer decomposition products generated during the reaction process, which leads to a decrease in purity and thermal stability.

[0013] According to one embodiment, a polyaryletherketone composition with improved purity and thermal stability through a two-step solvent-free polymerization process and a method for preparing the same are provided.

[0014] One embodiment provides a polyaryletherketone composition comprising a polyaryletherketone having repeating units represented by the following chemical formula 5, and a residual compound comprising an unreacted monomer having a silyl group, a monomer decomposition product having a silyl group, or a combination thereof, wherein the residual compound is included in an amount of 0% to 0.005% by weight with respect to 100% by weight of the polyaryletherketone composition.

[0015] [Chemical Formula 5]

[0016]

[0017] In the above chemical formula 5, the R 111 to R 224 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group, and X 11 and X 21 Each is independently a single bond, -O-, -S-, or a divalent organic group, and only X 11 and X 21 At least one of them is a ketone group (-CO-), and the above Z 51 is oxygen, and the above n 1 , n 2 , and n 3 are each independently integers from 0 to 5, where n 1 , n 2 , and n 3 At least one of them is 1 or more.

[0018] Another embodiment provides a method for preparing a polyaryletherketone composition comprising: a step of preparing an intermediate polymer by primary solvent-free polymerization of a monomer represented by the following chemical formula 1 and a monomer represented by the following chemical formula 2 under a catalyst; and a step of preparing a polyaryletherketone by secondary solvent-free polymerization of the intermediate polymer under an inert gas or vacuum at a temperature of 20°C to 340°C for 1 hour to 80 hours.

[0019] [Chemical Formula 1]

[0020]

[0021] [Chemical Formula 2]

[0022]

[0023] In Chemical Formula 1 and Chemical Formula 2, R 111 to R 224 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group, and X 11 and X 21 Each is independently a single bond, -O-, -S-, or a divalent organic group, and only X 11 and X 21 At least one of them is a ketone group (-CO-), and X 12 and X 13 Each is independently a halogen atom, and X 22 and X 23 Each is independently a trialkylsiloxy group, and n 1 and n 2 are each independently integers from 0 to 5, where n 1 and n 2 At least one of them is 1 or more.

[0024] The polyaryletherketone composition and the method for preparing the same according to one embodiment can improve purity and thermal stability through a total of two stages of solvent-free polymerization, including a first solvent-free polymerization and a second solvent-free polymerization.

[0025] Hereinafter, embodiments of the present disclosure are described in detail so that those skilled in the art to which the present disclosure pertains can easily implement them. However, the present disclosure may be embodied in various different forms and is not limited to the embodiments described herein.

[0026] Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Furthermore, the singular form includes the plural form unless specifically stated otherwise in the text.

[0027] As used herein, the term "alkyl" refers, unless otherwise noted, to saturated monovalent aliphatic hydrocarbon radicals, including straight-chain and branched-chains, having a specific number of carbon atoms. An alkyl group typically has 1 to 20 carbon atoms ("C1-C 20 alkyl"), preferably 1 to 12 carbon atoms ("C1-C 12It contains alkyl (*)*, more preferably 1 to 8 carbon atoms (*C1-C8 alkyl*), 1 to 6 carbon atoms (*C1-C6 alkyl*), or 1 to 4 carbon atoms (*C1-C4 alkyl*). Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, etc. The alkyl group may be substituted or unsubstituted. In particular, unless otherwise specified, the alkyl group may be substituted with one or more halogens up to the total number of hydrogen atoms present on the alkyl residue. Thus, the C1-C4 alkyl includes a halogenated alkyl group, for example, a fluorinated alkyl group having 1 to 4 carbon atoms, such as trifluoromethyl (-CF3) or difluoroethyl (-CH2CHF2).

[0028] An alkyl group described herein as optionally substituted may be substituted with one or more substituents, and the substituents are selected independently unless otherwise described. The total number of substituents is equal to the total number of hydrogen atoms on the alkyl residue to the extent that such substitution satisfies chemical sense. The optionally substituted alkyl group may typically contain 1 to 6 optional substituents, often 1 to 5 optional substituents, preferably 1 to 4 optional substituents, more preferably 1 to 3 optional substituents.

[0029] Optional substituents suitable for the alkyl group are, but are not limited to, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3 to 12 heterocyclyl, C6-C 12 Aryl and 5- to 12-membered heteroaryls, halo, =O (oxo), =S (thiono), =N-CN, =N-OR x , =NR x , -CN, -C(O)R x , -CO2R x, -C(O)NR x R y , -SR x , -SOR x , -SO2R x , -SO2NR x R y , -NO2, -NR x R y , -NR x C(O)R y , -NR x C(O)NR x R y , -NR x C(O)OR x , -NR x SO2R y , -NR x SO2NR x R y , -OR x , -OC(O)R x and -OC(O)NR x R y Includes, and each R x and R y is independently hydrogen (H), C1-C8 alkyl, C1-C8 acyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3 to 12 heterocyclyl, C6-C 12 It is an aryl or a 5- to 12-membered heteroaryl, or R x and R y They can form 3 to 12-membered heterocyclile or 5 to 12-membered heteroaryl rings with the N atom to which they are attached, each optionally O, N, and S(O) q It may contain 1, 2, or 3 additional heteroatoms selected from (wherein q is 0 to 2), and each R x and R yis optionally substituted with one to three substituents independently selected from the group consisting of halo, =O, =S, =N-CN, =N-OR', =NR', -CN, -C(O)R', -CO2R', -C(O)NR'2, -SOR', -SO2R', -SO2NR'2, -NO2, -NR'2, -NR'C(O)R', -NR'C(O)NR'2, -NR'C(O)OR', -NR'SO2R', -NR'SO2NR'2, -OR', -OC(O)R', and -OC(O)NR'2, wherein each R' is independently hydrogen (H), C1-C8 alkyl, C1-C8 acyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3 to 12 heterocyclyl, C6-C 12 Aryl or C5-C 12 They are heteroaryls, and each C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, 3 to 12 heterocyclyl, C6-C 12 Aryl and 5- to 12-membered heteroaryls may be optionally substituted as further defined herein.

[0030] As used herein, the term “divalent aliphatic hydrocarbon (i.e., alkylene)” refers, unless otherwise noted, to a divalent hydrocarbyl group having a specific number of carbon atoms capable of linking two different groups together. Often, alkylenes are -(CH2) n-(wherein n is 1 to 8, preferably n is 1 to 4) refers to. Where specified, the alkylene may also be substituted with other groups and may include at least 1 degree of unsubstitution (i.e., an alkenylene or alkenylene residue) or a ring. The open valence of the alkylene does not need to be at opposite ends of the chain. Thus, branched alkylene groups, e.g. -CH(Me)-, -CH2CH(Me)-, and -C(Me)2- are also included in the category of the term "alkylene," as are cyclic groups, e.g. cyclopropane-1,1-diyl, and unsaturated groups, e.g. ethylene (-CH=CH-) or propylene (-CH2-CH=CH-). The alkylene group is substituted or unsubstituted by the same groups as described herein as suitable for alkyl.

[0031] As used herein, the terms “halo” or “halogen” refer to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) unless otherwise noted.

[0032] As used in this specification, the term "hydroxy" refers to an -OH group unless otherwise noted.

[0033] Unless otherwise noted, the term “alkoxy” as used herein refers to a monovalent -O-alkyl group having a specific number of carbon atoms in the alkyl portion. The alkoxy group typically has 1 to 8 carbon atoms (“C1-C8 alkoxy”), 1 to 6 carbon atoms (“C1-C6 alkoxy”), or 1 to 4 carbon atoms (“C1-C4 alkoxy”). For example, C1-C4 alkoxy groups include methoxy (-OCH3), ethoxy (-OCH2CH3), isopropoxy (-OCH(CH3)2), tert-butyloxy (-OC(CH3)3), etc. The alkoxy group is substituted or unsubstituted on the alkyl portion by the same groups described herein as suitable for alkyl. In particular, the alkoxy group may optionally be substituted with one or more halo atoms, particularly one or more fluoro atoms, up to the total number of hydrogen atoms present on the alkyl portion. These groups are referred to as "haloalkoxy" groups having a specific number of carbon atoms and substituted with one or more halo substituents, e.g., when fluorinated, more specifically as "fluoroalkoxy" groups, and typically these groups contain 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, often 1 or 2 carbon atoms, and 1, 2 or 3 halo atoms (i.e., "C1-C6 haloalkoxy", "C1-C4 haloalkoxy", or "C1-C2 haloalkoxy"). More specifically, the fluorinated alkyl group may be specifically referred to as a fluoroalkoxy group typically substituted with 1, 2 or 3 fluoro atoms, e.g., a C1-C6, C1-C4, or C1-C2 fluoroalkoxy group. Therefore, C1-C4 fluoroalkoxy includes trifluoromethyloxy (-OCF3), difluoromethyloxy (-OCF2H), fluoromethyloxy (-OCFH2), difluoroethyloxy (-OCH2CF2H), etc.

[0034] As used herein, the terms “optionally substituted” and “substituted or unsubstituted” are used interchangeably to indicate that a particular group described may have no non-hydrogen substituents (i.e., unsubstituted) at all, or that the group may have one or more non-hydrogen substituents (i.e., substituted). Unless otherwise specified, the total number of possible substituents is equal to the number of H atoms present on the unsubstituted form of the group described. If an optional substituent is attached via a double bond (e.g., an oxo (=O) substituent), the group occupies the available valence, and the total number of other substituents included is reduced by 2. If an optional substituent is selected independently from a list of substitutes, the selected group is the same or different. Throughout this specification, it will be understood that the number and nature of optional substituents will be limited to the extent that such substitutions satisfy chemical sense.

[0035] In this specification, * at both ends of a chemical formula indicates that it is connected to an adjacent chemical formula.

[0036] In this specification, a polymer comprising a repeating unit represented by a single general formula means not only comprising a repeating unit represented by a chemical formula of any one type included in the general formula, but also comprising repeating units represented by several types of chemical formulas included in the general formula.

[0037] Polyaryl ether ketone composition

[0038] According to one embodiment, a polyaryletherketone composition comprising a polyaryletherketone having repeating units represented by the following chemical formula 5 is provided.

[0039] [Chemical Formula 5]

[0040]

[0041] In the above chemical formula 5, the R 111 to R 224Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group.

[0042] The above X 11 and X 21 Each is independently a single bond, -O-, -S-, or a divalent organic group, and only X 11 and X 21 At least one of them is a ketone group (-CO-).

[0043] Here, the divalent organic group is a divalent organic group that attracts or gives up electrons, e.g., -CO-, -SO2-, -CONH-, -COO-, -CR'2-, -C(CH3)2-, -C(CF3)2-, or -(CH2) n - may include. In this case, R' includes a hydrogen atom, a halogen atom, an alkyl group, or an alkyl halide group, and n may be an integer from 1 to 10.

[0044] The above Z 51 is oxygen, and the above n 1 , n 2 , and n 3 are each independently integers from 0 to 5, where n 1 , n 2 , and n 3 At least one of them is 1 or more.

[0045] For example, a polyaryl ether ketone containing repeating units represented by chemical formula 5 may be polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone (PEK), polyether ether ether ketone (PEEEK), polyether ketone ether ketone (PEKEK), or polyether ether ether ether ketone (PEEEEK), etc.

[0046] For example, polyaryletherketone can be produced using a solvent-free polymerization method in which an aromatic diol monomer is reacted with hexamethyldisilazane to produce a silylated monomer, which is then reacted with an aromatic dihalogen monomer. Specifically, when the aromatic diol monomer is silylated and then reacted, there is no need to use a high-boiling point solvent such as diphenylsulfone to dissolve the polymer during the polymerization reaction, and metal halides are not formed as polymerization byproducts, so there is no need for a process of grinding or extracting the polymer to remove the solvent and polymerization byproducts, which has the advantage of simplifying the post-polymerization process.

[0047] However, even in this case, there is a problem in that it is difficult to remove unreacted residual monomers and monomer decomposition products generated during the reaction from the synthesized polyaryletherketone because the polymerization method used to obtain a polymer material by applying only heat to the material—that is, a solvent-free polymerization reaction—is used to raise the temperature only to the final polymerization temperature.

[0048] A polyaryletherketone composition according to one embodiment is prepared through a two-step solvent-free polymerization reaction and may contain residual compounds including unreacted monomers containing silyl groups, monomer decomposition products containing silyl groups, or a combination thereof. The residual compounds can be mostly removed by performing a second solvent-free polymerization stepwise after the first solvent-free polymerization described below. For example, the residual compounds may be included in an amount of 0% to 0.005% by weight relative to 100% by weight of the polyaryletherketone composition. A polyaryletherketone composition according to one embodiment can largely remove residual compounds generated during solvent-free polymerization by preparing an intermediate polymer through solvent-free polymerization and then further performing solvent-free polymerization using the intermediate polymer, thereby improving purity and thermal stability.

[0049] The unreacted monomer containing the above silyl group may include a compound represented by the following chemical formula 2.

[0050] [Chemical Formula 2]

[0051]

[0052] In Chemical Formula 2, R 211 to R 224 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group.

[0053] X 21 is a single bond, -O-, -S-, or a divalent organic group, and since the description of the divalent organic group is the same as previously described, a repetitive description is omitted.

[0054] X 21 If this is a single bond, X 21 This means that the phenyl groups on both sides are directly connected, and a typical example of this is the biphenyl group.

[0055] X 22 and X 23 Each is independently a trialkylsiloxy group, and n 2 is an integer from 0 to 5.

[0056] The compound represented by the above chemical formula 2 is identical to the reactant of the monomer represented by chemical formula 2 when preparing the polyaryletherketone composition described later, and is an unreacted monomer that remains after not being synthesized into polyaryletherketone.

[0057] The above residual compound may also include an unreacted monomer represented by the following chemical formula 1 in addition to the unreacted monomer containing a silyl group.

[0058] [Chemical Formula 1]

[0059]

[0060] In Chemical Formula 1, R111 to R 124 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group.

[0061] X 11 ... is a single bond or a divalent organic group, and since the description of the divalent organic group is the same as previously described, a repetitive description is omitted. As an example, the divalent organic group may be a ketone group (-CO-).

[0062] X 12 and X 13 Each is independently a halogen atom, and the halogen atom may be any one selected from the group consisting of, for example, bromine, fluorine, and chlorine.

[0063] n 1 is an integer from 1 to 5.

[0064] The unreacted monomer represented by the above chemical formula 1 is identical to the reactant of the monomer represented by chemical formula 1 when preparing the polyaryletherketone composition described later, and is an unreacted monomer that remains after not being synthesized into polyaryletherketone.

[0065] The monomer decomposition product containing the above silyl group may include a compound represented by the following chemical formula 6, a compound represented by the following chemical formula 7, or a combination thereof. Here, the compound represented by the following chemical formula 6 is a silyl halogenated compound and may be a byproduct generated by a polymerization reaction, and the compound represented by the following chemical formula 7 may also be a monomer decomposition product generated during a thermal decomposition process.

[0066] [Chemical Formula 6]

[0067] X 61 -Si-(R 61 )3

[0068] In the above chemical formula 6, the X 61is a halogen group or a hydroxyl group, and the above R 61 is independently an alkyl group.

[0069] In the above chemical formula 6, the X 61 is a hydroxyl group, and the above R 61 can be an alkyl group having 1 to 10 carbon atoms. For example, the above R 61 It may be an alkyl group having 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 2 carbon atoms, or 1 carbon atom.

[0070] [Chemical Formula 7]

[0071] R 71 -OR 72

[0072] In Chemical Formula 7, R 71 and R 72 Each is independently a trialkylsilyl group.

[0073] The above residual compound may also include, in addition to the monomer decomposition product containing a silyl group, a monomer decomposition product represented by the following chemical formula 8. This may be a monomer decomposition product generated during hydrolysis by moisture or thermal decomposition.

[0074] [Chemical Formula 8]

[0075]

[0076] In chemical formula 8, R 81 and R 82 Each is independently a hydroxyl group or a trialkylsiloxy group. The above R 81 and R 82 Each may independently be a trialkylsilyl group having 1 to 10 carbon atoms, and may be, for example, a trialkylsilyl group having 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 2 carbon atoms, or 1 carbon atom.

[0077] For example, the monomer hydrolysate represented by the above chemical formula 8 may include the monomer hydrolysate represented by the following chemical formula 8-1, the monomer hydrolysate represented by the following chemical formula 8-2, or a combination thereof.

[0078] [Chemical Formula 8-1]

[0079]

[0080] [Chemical Formula 8-2]

[0081]

[0082] In chemical formula 8-2, R 83 is a trialkylsilyl group. The above R 83 It may be a trialkylsilyl group having 1 to 10 carbon atoms, for example, a trialkylsilyl group having 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 2 carbon atoms, or 1 carbon atom.

[0083] As the polyaryletherketone resin composition according to one embodiment is manufactured by the manufacturing method described below, the reaction time can be extended, and accordingly, the molecular weight can be increased while most of the residual compounds are removed, thereby improving purity.

[0084] The Mw-R (molecular weight) of the above polyaryletherketone resin composition may be 34,000 Da to 90,000 Da, for example, 35,000 Da to 90,000 Da, 36,000 Da to 90,000 Da, 37,000 Da to 90,000 Da, 38,000 Da to 90,000 Da, 39,000 Da to 90,000 Da, 40,000 Da to 90,000 Da, or 45,000 Da to 90,000 Da. The Mw-R of the above polyaryletherketone composition can be measured using Dynamic Light Scattering (DLS). Specifically, the polyaryletherketone composition can be dispersed in a sulfuric acid solvent, injected into a DLS device, and measured under a temperature condition of 25°C. The hydration radius (R) of the particles is calculated using the Strokes-Einstein equation, and the average molecular weight (Mw-R) can be calculated based on the measured scattering intensity of the particles. The Mw-R (molecular weight) of the polyaryletherketone composition may be greater than the Mw-R (molecular weight) of the intermediate polymer prepared according to the primary solvent-free polymerization described below. The Mw-R of the intermediate polymer is as described below. Temperature and time, etc., can be appropriately controlled during the polymerization process so that the Mw-R (molecular weight) of the polyaryletherketone composition satisfies the above range. As the solvent-free polymerization time increases, the molecular weight may increase, but at the same time, the content of residual compounds increases. However, the polyaryletherketone composition prepared according to the manufacturing method of one embodiment may have high purity, as it has a high molecular weight while simultaneously having a low content of residual compounds.

[0085] The above residual compound is included in an amount of 0% to 0.005% by weight with respect to 100% by weight of the polyaryletherketone composition. For example, the above residual compound may be included in an amount greater than 0% by weight and less than or equal to 0.005% by weight, greater than 0% by weight and less than or equal to 0.004% by weight, greater than 0% by weight and less than or equal to 0.003% by weight, or greater than 0% by weight and less than or equal to 0.002% by weight with respect to 100% by weight of the polyaryletherketone composition. To extract the residual compound from the polyaryletherketone composition, the above residual compound may be dissolved in a tetrahydrofuran (THF) solvent, filtered, and the obtained filtrate may be used as a sample, and 1 μL may be injected at a temperature of 300°C for analysis. In the polyaryletherketone composition according to one embodiment, the above-mentioned residual compound may be present in a very small amount at an amount that is detectable but immeasurable, or present in a small amount that is measurable. A polyaryletherketone composition according to one embodiment is prepared through a two-step solvent-free polymerization reaction, and by removing residual compounds generated in the first solvent-free polymerization step during the second solvent-free polymerization step, the content of residual compounds can be reduced compared to a conventional polyaryletherketone composition prepared through a one-step solvent-free polymerization reaction.

[0086] As described above, the polyaryletherketone composition according to one embodiment has a high molecular weight and minimizes the content of residual compounds, thereby improving thermal stability. Thermal stability can be measured through thermogravimetric analysis (TGA).

[0087] The higher the 5 wt% reduction temperature (Td5), the better the thermal stability. For example, the 5 wt% reduction temperature (Td5) according to thermogravimetric analysis (TGA) of the polyaryletherketone resin composition may be 300°C to 650°C, 350°C to 650°C, 400°C to 650°C, 450°C to 650°C, 500°C to 650°C, 500°C to 600°C, 500°C to 580°C, 500°C to 560°C, 520°C to 560°C, or 540°C to 560°C. The 5 wt% reduction temperature (Td5) of the above polyaryletherketone resin composition may refer to the temperature at which a 5 wt% reduction occurs when the polyaryletherketone resin composition is analyzed using a thermal analyzer, such as a METTLER instrument, by introducing it at a rate of 50 ml / min and increasing the temperature at a rate of 10℃ / min from 30℃ to 950℃ under a nitrogen atmosphere. The Td5 of the polyaryletherketone composition according to one embodiment may satisfy the above range, thereby having excellent thermal stability.

[0088] The higher the 10 wt% reduction temperature (Td10), the better the thermal stability. The 10 wt% reduction temperature (Td10) of the polyaryletherketone resin composition according to thermogravimetric analysis (TGA) may be 400°C to 650°C, for example, 450°C to 650°C, 500°C to 650°C, 500°C to 600°C, 500°C to 580°C, 500°C to 560°C, 520°C to 560°C, or 530°C to 560°C. The 10 wt% reduction temperature (Td10) of the polyaryletherketone resin composition may be measured as the same as the 5 wt% reduction temperature (Td5) and may mean the temperature at which a 10 wt% reduction occurs. The Td10 of the polyaryletherketone composition according to one embodiment satisfies the above range, so that the thermal stability may be excellent.

[0089] The lower the weight loss rate, the better the thermal stability. For example, under a temperature of 400°C and a nitrogen atmosphere, the weight loss rate of the polyaryletherketone resin composition may be 0.9 wt% or less, and for example, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, 0.3 wt% or less, or 0.25 wt% or less, and the lower limit is not specifically limited but may be, for example, 0 wt% or more, 0.05 wt% or more, or 0.1 wt% or more. For example, the weight loss rate of the polyaryletherketone resin composition may be 0 wt% to 0.9 wt%, 0 wt% to 0.8 wt%, 0 wt% to 0.7 wt%, 0 wt% to 0.6 wt%, 0 wt% to 0.5 wt%, 0.05 wt% to 0.5 wt%, or 0.1 wt% to 0.5 wt%. The weight loss rate of the polyaryletherketone resin composition may be measured through thermogravimetric analysis in the same manner as the aforementioned method for the temperature (Td5) at which a 5 wt% reduction occurs and the temperature (Td10) at which a 10 wt% reduction occurs. The weight loss rate of the polyaryletherketone composition according to one embodiment may satisfy the above range, thereby providing excellent thermal stability.

[0090] The higher the melting point, the better the thermal stability. For example, the melting point (Tm) of the polyaryletherketone composition may be 300°C to 400°C, for example, 300°C to 380°C, 300°C to 360°C, or 320°C to 360°C. The melting point was measured using a differential scanning calorimeter (DSC 1) from Mettler Toledo. The sample can be measured by placing about 5 to 10 mg of powder into an aluminum pan and heating it from room temperature (25°C) to 380°C at a rate of 20°C / min under a nitrogen atmosphere (N2, 50 ml / min). The melting point of the polyaryletherketone composition according to one embodiment may satisfy the above range, thereby demonstrating excellent thermal stability.

[0091] The above polyaryletherketone composition may be manufactured by the manufacturing method described below, and accordingly, thermal stability and purity may be improved.

[0092] Method for preparing a polyaryl ether ketone composition

[0093] According to another embodiment, a method for preparing a polyaryletherketone composition is provided, comprising the steps of: preparing an intermediate polymer by primary solvent-free polymerization of a monomer represented by the following chemical formula 1 and a monomer represented by the following chemical formula 2 under a catalyst; and preparing a polyaryletherketone by secondary solvent-free polymerization of the intermediate polymer under an inert gas or vacuum at a temperature of 20°C to 340°C for 1 hour to 80 hours. The polyaryletherketone composition may be prepared according to the method for preparing a polyaryletherketone composition.

[0094] First, an intermediate polymer is prepared by primary solvent-free polymerization of a monomer represented by Chemical Formula 1 below and a monomer represented by Chemical Formula 2 below under a catalyst. At this time, the step of preparing the intermediate polymer is carried out according to primary solvent-free polymerization, that is, a method of polymerization in which heat is applied to the monomer and catalyst without the use of a solvent. The primary solvent-free polymerization may include bulk polymerization, melt polymerization, solid-state polymerization, fluidized bed polymerization, or a combination thereof. Since high-boiling point solvents such as diphenylsulfone, which are used in conventional commercial solution polymerization methods for polyaryletherketone, are not used, it is an environmentally friendly process with low wastewater, and process costs can be reduced because the process is simple. Here, the intermediate polymer is intended to indicate that it is in a prepolymer state prior to the secondary solvent-free polymerization stage in order to distinguish it from polyaryletherketone prepared by primary solvent-free polymerization alone.

[0095] [Chemical Formula 1]

[0096]

[0097] [Chemical Formula 2]

[0098]

[0099] In Chemical Formula 1 and Chemical Formula 2, R 111 to R 224 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group.

[0100] X 11 and X 21 Each is independently a single bond, -O-, -S-, or a divalent organic group, and only X 11 and X 21At least one of them is a ketone group (-CO-). The description of the above divalent organic group is the same as previously described, so a repetitive description is omitted.

[0101] X 11 or X 21 In the case of this single bond, X 11 or X 21 This means that the phenyl groups on both sides are directly connected, and a typical example of this is the biphenyl group.

[0102] X 12 and X 13 Each is independently a halogen atom, and since the description of the halogen atom is the same as previously described, a repetitive description is omitted.

[0103] For example, the monomer represented by Chemical Formula 1 may be 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, or 4-chloro-4'-fluorobenzophenone.

[0104] X 22 and X 23 Each is independently a trialkylsiloxy group and may include, for example, trimethylsiloxy group, triethylsiloxy group, tripropylsiloxy group, tributylsiloxy group, triisobutylsiloxy group, dimethylethylsiloxy group, or methyldiethylsiloxy group.

[0105] Meanwhile, in Chemical Formula 1 and Chemical Formula 2, n 1 and n 2 are each independently integers from 0 to 5, where n 1 and n 2 At least one of them is 1 or greater. In this case, X 11 and X 21 Among them, n repeating units containing a ketone group (-CO-). 1 or n 2 It can be 1 or more.

[0106] The molar ratio of the monomer represented by Chemical Formula 1 and the monomer represented by Chemical Formula 2 is an important factor in determining the degree of polymerization, for example, the molar ratio of the monomer represented by Chemical Formula 2 and the monomer represented by Chemical Formula 1 may be 0.8 : 1.2 to 1.2 : 0.8, and for example, the molar ratio of the monomer represented by Chemical Formula 2 and the monomer represented by Chemical Formula 1 may be 0.9 : 1.1 to 1.1 : 0.9.

[0107] Before preparing the intermediate polymer above, the method may further include a step of reacting the monomer represented by Chemical Formula 3 below with hexaalkyldisilazane to silylate it and produce the monomer represented by Chemical Formula 2 above. If the monomer represented by Chemical Formula 3 below is silylated as described above and then reacted with Chemical Formula 1 above, there is an advantage in that the post-polymerization process is simple. For example, if the monomer represented by Chemical Formula 3 is reacted with Chemical Formula 1 without silylating, a high-boiling point solvent such as diphenylsulfone must be used to dissolve the polymer, and metal halides (e.g., NaF, KF, NaCl, etc.) are formed as polymerization by-products, so there is a disadvantage in that a separate process of grinding the polymer and multiple solvent and by-product extraction processes are required to remove the solvent and polymerization by-products. In one embodiment, an intermediate polymer can be prepared through solvent-free polymerization in which heat is applied to the monomer and catalyst to polymerize them without the use of a solvent, as the monomer represented by Formula 2, which is silylated from the monomer represented by Formula 3, contains a trialkylsiloxy group.

[0108] [Chemical Formula 3]

[0109]

[0110] In Chemical Formula 3, R 311 to R 324Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group.

[0111] X 31 The group is a single bond, -O-, -S-, or a divalent organic group, and as an example, the divalent organic group may be a ketone group (-CO-).

[0112] X 32 and X 33 Each is independently a hydroxyl group, and n 3 is an integer from 0 to 5.

[0113] The step of reacting the monomer represented by Chemical Formula 3 with hexaalkyldisilazane to silylate it can be carried out by refluxing for 7 to 12 hours. If the refluxing time is less than 7 hours, incomplete silylation may occur, and if it exceeds 12 hours, thermal decomposition of the monomer may occur.

[0114] The solvent used in the silylation reaction may be benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, or tetrahydrofuran.

[0115] The above first solvent-free polymerization can be carried out at a temperature of 20°C to 420°C for 1 hour to 12 hours, for example, at a temperature of 50°C to 420°C, 100°C to 420°C, 150°C to 420°C, 200°C to 420°C, or 240°C to 370°C, and can also be carried out for 1 hour to 10 hours. If the temperature of the first solvent-free polymerization is less than 20°C or the time is less than 1 hour, the polymerization may not proceed, and if the temperature of the first solvent-free polymerization exceeds 420°C or the time exceeds 12 hours, carbonized material is produced due to thermal decomposition and the molecular weight decreases, so a high molecular weight resin may not be obtained.

[0116] The above catalyst may be an alkali metal halide, and for example, the alkali metal halide may include CsF, CsCl, CsBr, CsI, KF, KCl, KBr, RbF, RbCl, RbI, RbBr, or a mixture thereof.

[0117] The content of the catalyst may be 0.0001 to 4 moles per 1 mole of the monomer represented by Chemical Formula 1, for example, 0.0005 to 0.002 moles. When the content of the catalyst is within this range, sufficient alkali metal salts of the monomer represented by Chemical Formula 1 are produced to increase the degree of polymerization, and the degree of polymerization may not be lowered by preventing the excess alkali metal compound from hydrolyzing the produced polymer.

[0118] The above intermediate polymer is a prepolymer of the final product, the polyaryletherketone composition, and has the same structure as the final product, the polyaryletherketone composition, but may differ only in molecular weight. The molecular weight at this time may be, for example, Mw-R. For example, the Mw-R of the intermediate polymer may differ from the Mw-R of the aforementioned final product, the polyaryletherketone composition, and as described above, the Mw-R of the intermediate polymer may be smaller than the Mw-R of the polyaryletherketone composition. The Mw-R of the intermediate polymer is measured using the same method as the Mw-R of the polyaryletherketone composition, and for example, the Mw-R may be measured using an intermediate polymer prepared through primary solvent-free polymerization.

[0119] The Mw-R of the above intermediate polymer may be less than 34,000 Da, and, for example, may be 10,000 Da or more and 34,000 Da or less, 15,000 Da to 33,000 Da, 16,000 Da to 35,000 Da, 17,000 Da to 35,000 Da, 18,000 Da to 35,000 Da, 19,000 Da to 35,000 Da, 20,000 Da to 35,000 Da, 21,000 Da to 34,000 Da, or 22,000 Da to 34,000 Da. In order to perform the secondary solvent-free polymerization described below, the weight-average molecular weight of the intermediate polymer prepared according to the primary solvent-free polymerization may be adjusted to satisfy the above range.

[0120] The above intermediate polymer may have a 5 wt% reduction temperature (Td5) according to thermogravimetric analysis (TGA) analysis of 300°C to 650°C, 350°C to 650°C, 400°C to 650°C, 450°C to 650°C, 500°C to 650°C, 500°C to 600°C, 500°C to 580°C, 500°C to 560°C, or 500°C to 540°C. The 5 wt% reduction temperature of the above intermediate polymer may be lower than the 5 wt% reduction temperature of the polyaryletherketone composition prepared by secondary solvent-free polymerization, and the thermal stability of the polyaryletherketone composition may be further improved by undergoing the secondary solvent-free polymerization described below. The temperature range for a 5 weight% reduction of the polyaryletherketone composition is as described above, so it is omitted below.

[0121] The above intermediate polymer may have a 10 wt% reduction temperature (Td10) according to thermogravimetric analysis (TGA) of 400°C to 650°C, 450°C to 650°C, 500°C to 650°C, 500°C to 600°C, 500°C to 580°C, 500°C to 560°C, 500°C to 550°C, or 510°C to 550°C. The 10 wt% reduction temperature of the above intermediate polymer may be lower than the 10 wt% reduction temperature of the polyaryletherketone composition prepared by secondary solvent-free polymerization, and the thermal stability of the polyaryletherketone composition may be further improved by undergoing the secondary solvent-free polymerization described below. Since the 10 wt% reduction temperature range of the polyaryletherketone composition is as described above, it is omitted below.

[0122] Under a temperature of 400°C and a nitrogen atmosphere, the weight loss rate of the intermediate polymer may be 1% to 2% by weight, for example, 1% to 1.8% by weight, 1% to 1.6% by weight, or 1.2% to 1.6% by weight. Under a temperature of 400°C and a nitrogen atmosphere, the weight loss rate of the intermediate polymer may be higher than the weight loss rate of the polyaryletherketone composition prepared through a secondary solvent-free polymerization reaction. Thermal stability may be improved when prepared according to the method for preparing polyaryletherketone according to one embodiment.

[0123] The melting point (Tm) of the above intermediate polymer may be 300°C to 380°C, for example, 300°C to 360°C, 300°C to 340°C, or 320°C to 340°C.

[0124] The weight loss rate and melting point of the above intermediate polymer at a 5 wt% reduction temperature, a 10 wt% reduction temperature, a temperature of 400°C, and under a nitrogen atmosphere, respectively, can be measured in the same way as the weight loss rate and melting point measurement method of the above-described polyaryletherketone composition at a 5 wt% reduction temperature, a 10 wt% reduction temperature, a temperature of 400°C, and under a nitrogen atmosphere.

[0125] Next, the method includes the step of producing polyaryletherketone by performing a secondary solvent-free polymerization of the intermediate polymer. In a method for producing a polyaryletherketone composition according to one embodiment, a secondary solvent-free polymerization is performed following a primary solvent-free polymerization to improve purity and thermal properties. Here, the primary solvent-free polymerization is the same as the solvent-free polymerization when producing polyaryletherketone by a conventional solvent-free single process.

[0126] Specifically, when polyaryletherketone is manufactured by a conventional solvent-free polymerization single process, that is, by the primary solvent-free polymerization described in this specification, it is difficult to remove unreacted monomers remaining and monomer decomposition products generated during the reaction from the final product, polyaryletherketone, which results in a decrease in thermal stability. However, when polyaryletherketone is manufactured by a two-step polymerization process in which an intermediate polymer is manufactured by primary solvent-free polymerization as in one embodiment and the polymer is subjected to secondary solvent-free polymerization, residual compounds such as unreacted monomers or monomer decomposition products can be removed to improve purity, and thermal properties can be improved by preventing deterioration during the polymerization process as the temperature conditions of the secondary solvent-free polymerization are relatively mild. For example, the secondary solvent-free polymerization may be of the same type as described above in the primary solvent-free polymerization, and for example, it may be solid-state polymerization.

[0127] The above secondary solvent-free polymerization step is carried out under an inert gas or vacuum at a temperature of 20°C to 340°C for 1 hour to 80 hours. Through the above secondary solvent-free polymerization step, the molecular weight can be further increased, and residual compounds such as unreacted monomers remaining after the melting reaction or monomer decomposition products generated during the reaction can be removed.

[0128] For example, the inert gas may be nitrogen, carbon dioxide, argon, helium, or neon, and the vacuum may mean a pressure reduction condition of -1 bar to 1 bar, or -0.95 bar to 0.7 bar.

[0129] For example, the solid-state polymerization can be performed at a temperature of 50°C to 340°C, 100°C to 340°C, 150°C to 340°C, 200°C to 340°C, 250°C to 340°C, or 300°C to 320°C, and can also be performed for 1 hour to 70 hours, 1 hour to 60 hours, 1 hour to 40 hours, or 2 hours to 25 hours.

[0130] After preparing the intermediate polymer, before performing the secondary solvent-free polymerization step, the method may further include a step of crystallizing the intermediate polymer.

[0131] Prior to the crystallization step, the intermediate polymer may be discharged out of the reactor and granulated. The granulation method may use a strand cutting method in which the polymer is extruded in a strand form, solidified in a cooling liquid, and then cut with a cutter, or an underwater cutting method in which the die hole is immersed in a cooling liquid, the polymer is extruded directly into the cooling liquid, and then cut with a cutter; however, the method is not limited to these methods and any known method may be used.

[0132] The granulated intermediate polymer may undergo a crystallization step to prevent fusion during the solid-state polymerization reaction. The crystallization step may be performed for 30 minutes to 30 hours at a temperature of 150°C to 200°C under an inert gas or vacuum. Here, the inert gas is as described above, and the vacuum may refer to a reduced pressure condition of -0.1 bar to 1 bar. When the above temperature and time ranges are satisfied, the rate at which particle crystals are formed can be appropriately controlled during the crystallization step, and the particles can be prevented from sticking together and fusing. The crystallization step may be divided into several stages and carried out by increasing the temperature step by step.

[0133] Example 1

[0134] A monomer represented by the following chemical formula 11 (4,4'-Difluorobenzophenone (DFBP)) and a monomer represented by the following chemical formula 21 (1,4-Bis((trimethylsilyl)oxy)benzene (TMSB)) were mixed in a molar ratio of 1:1.02, and a solvent-free polymerization was performed at 370 °C for 2 hours in the presence of CsF (0.001 mole per 1 mole of the monomer represented by chemical formula 11) to prepare a pre-polymer.

[0135] A polyaryletherketone composition (PAEK comp.) was prepared by solid-state polymerization using the above intermediate polymer at a temperature of 320 ℃ and under vacuum for 2 hours.

[0136] [Chemical Formula 11]

[0137]

[0138] [Chemical Formula 21]

[0139]

[0140]

[0141] Example 2

[0142] An intermediate polymer (pre-polymer) and a polyaryletherketone composition (PAEK comp.) were prepared in substantially the same manner as in Example 1, except that the solvent-free polymerization time was changed to 2 hours and 30 minutes and the solid-state polymerization time to 4 hours.

[0143]

[0144] Example 3

[0145] An intermediate polymer (pre-polymer) and a polyaryletherketone composition (PAEK comp.) were prepared in substantially the same manner as in Example 1, except that the solvent-free polymerization time was changed to 3 hours and the solid-state polymerization time to 8 hours.

[0146]

[0147] Example 4

[0148] An intermediate polymer (pre-polymer) and a polyaryletherketone composition (PAEK comp.) were prepared in substantially the same manner as in Example 1, except that the solvent-free polymerization time was changed to 4 hours and the solid-state polymerization time to 16 hours.

[0149]

[0150] Example 5

[0151] An intermediate polymer (pre-polymer) and a polyaryletherketone composition (PAEK comp.) were prepared in substantially the same manner as in Example 1, except that the solvent-free polymerization time was changed to 5 hours and the solid-state polymerization time to 24 hours.

[0152]

[0153] Comparative Example 1

[0154] A polyaryletherketone composition was prepared in substantially the same manner as in Example 1, except that in the method for preparing the polyaryletherketone composition of Example 1, only the solvent-free polymerization step was performed without performing the solid-state polymerization step, and the solvent-free polymerization temperature and time were performed for 390°C and 4 hours, respectively.

[0155]

[0156] Comparative Example 2

[0157] A polyaryletherketone composition was prepared in substantially the same manner as Comparative Example 1, except that the solvent-free polymerization time in Comparative Example 1 was changed from 4 hours to 6 hours.

[0158]

[0159] Comparative Example 3

[0160] A polyaryletherketone composition was prepared in substantially the same manner as Comparative Example 1, except that the solvent-free polymerization time in Comparative Example 1 was changed from 4 hours to 8 hours.

[0161]

[0162] Evaluation Example 1: Dynamic Light Scattering (DLS)

[0163] The hydration radius (R) and Mw-R of the polyaryletherketone compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3, as well as the intermediate polymers of Examples 1 to 5, were measured using the dynamic light scattering method. Each sample was prepared by dissolving it in 98 wt% sulfuric acid to a concentration of 0.40 mg / L and filtered through a 0.45 μm PTFE filter before use. Measurements were performed using a DLS device at a laser wavelength of 661 nm, a scattering angle of 90°, and a temperature of 20°C. The refractive index of the solvent n = 1.423 and the viscosity η = 25 mPa·s were input into the device. Each sample was measured 12 times after 10 minutes of equilibrium, and the hydration radius (R) was calculated using the cumulants (secondary) method. Data were reported on an intensity-weighted basis, and the Stokes-Einstein equation was used for calculations. The measurement results are shown in Table 1 below.

[0164] Evaluation Example 2: Measurement of Purity and Thermal Stability

[0165] (1) Measurement of residual compound content

[0166] The residual compounds contained in the polyaryletherketone compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were measured according to the following. First, to extract residual compounds from the polyaryletherketone composition, the sample (polyaryletherketone composition) was dissolved in a tetrahydrofuran (THF) solvent and then filtered. The obtained filtrate was used as a sample, and 1 μL was injected at a temperature of 300 °C for analysis, and the content of residual compounds was calculated from the analysis results. The residual compounds were classified into (i) 1,4-bis((trimethylsilyl)oxy)benzene (TMSB) and TMSB-derived degradation products and (ii) 4,4'-difluorobenzophenone (DFBP) and DFBP-derived degradation products. The total content of each was calculated in ppm units and then converted to weight% based on 100 wt% of the polyaryletherketone composition. At this time, the content of the residual compounds was rounded from the fifth decimal place to the fourth decimal place. The measurement results are shown in Table 1 below.

[0167] In the polyaryletherketone compositions of Examples 1 to 5, (i) compounds represented by the following chemical formulas A to E were detected as TMSB and TMSB-derived degrading products, and (ii) compounds represented by the following chemical formula F were detected as DFBP and DFBP-derived degrading products. Additionally, in the polyaryletherketone compositions of Comparative Examples 1 to 3, (i) compounds represented by the same chemical formulas A to E as in Examples 1 to 5, and compounds represented by chemical formulas G and H, which were not detected in Examples 1 to 5, were additionally detected as TMSB and TMSB-derived degrading products, and (ii) compounds represented by the same chemical formula F as in Examples 1 to 5 were detected as DFBP and DFBP-derived degrading products.

[0168] [Chemical Formula A: Trimethylsilanol]

[0169]

[0170] [Chemical Formula B: Hexamethyldisiloxane]

[0171]

[0172] [Chemical Formula C: Hydroquinone]

[0173]

[0174] [Chemical Formula D: 4-(trimethylsilyloxy)phenol]

[0175]

[0176] [Chemical Formula E: Trimethylsilylhydroquinone]

[0177]

[0178] [Chemical formula F: 4,4'-difluorobenzophenone]

[0179]

[0180] [Chemical Formula G: Octamethyltrisiloxane]

[0181]

[0182] [Chemical formula H: p-benzoquinone]

[0183]

[0184] (2) Thermogravimetric analysis

[0185] Thermogravimetric analysis (TGA) of the polyaryletherketone compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 was performed using a METTLER TGA / DSC1. Approximately 5 mg of polyaryletherketone powder was placed in an aluminum pan and analyzed under a nitrogen atmosphere (N2, 50 ml / min) at a heating rate of 10°C / min from 30°C to 950°C. Td5 and Td10 were defined as the temperatures at which a 5% and 10% reduction from the initial mass occurred, respectively. Additionally, the weight loss (%) at 400°C was calculated as the mass loss rate measured at 400°C under the same conditions. The measurement results are shown in Table 1 below.

[0186] (3) Melting point (Tm) measurement

[0187] The melting point (Tm) of the polyaryletherketone compositions prepared in Example 1 and Comparative Example 1 was measured using a differential scanning calorimeter (DSC 1) from Mettler Toledo. Approximately 5 mg of the powder was placed in an aluminum pan, and measurements were taken while increasing the temperature from room temperature (25°C) to 380°C at a rate of 20°C / min under a nitrogen atmosphere (N2, 50 ml / min). Tm was defined as the maximum endothermic peak temperature on the DSC curve. The measurement results are shown in Table 1 below.

[0188] Molecular Weight Residual Compound Thermogravimetric Analysis Tm(°C) Mw-RTMSB and TMSB Induced Degradation Products (Wt%) DFBP and DFBP Induced Degradation Products (Wt%) Total Content (Wt%) Td5(°C) Td10(°C) 400°C Weight Loss (%) Example 1 Pre-polymer2 2765 0.01 160.000 30.01 1950 3.55 17.5 1.545 732 6.02 PAEK comp.45320 0.000 90.000 20.00 1154 0.254 90.244 633 9.60 Example 2 Pre-polymer2 409 10.01 08 0.000 30.01 115 25.75 33.2 1.50 6232 8.57 PAEK comp.529240.00020.00020.0004545.8559.70.2110342.18 Example 3 Pre-polymer273280.01090.00030.0112526.1533.41.4992326.04PAEK comp.636710 * 0 * 0 * 551.2560.80.1530338.05 Example 4 Pre-polymer 301100.01060.00030.0109536.6544.11.4862331.90PAEK comp.781190 * 0 * 0 * 548.3555.00.1470336.13 Example 5 Pre-polymer 334740.010780.00020.108536.9546.71.4857329.89 PAEK comp.812760 * 0 * 0 * 549.3558.70.1310338.85 Comparative Example 1450700.00560.00020.0058541.0550.10.9180339.94 Comparative Example 2488220.00590.00020.0061538.0549.70.9254338.22 Comparative Example 3513420.00650.00020.0067502.0520.71.0685340.42

[0189] In Table 1 above, 0 * It means cases where it is detected but contained at a concentration below the detection limit.

[0190] Referring to Table 1 above, it can be confirmed that in Examples 1 to 5, an intermediate polymer is prepared by solvent-free polymerization, and a polyaryletherketone composition is prepared by solid-state polymerization using this. Consequently, compared to Comparative Examples 1 to 3, the molecular weight (Mw-R) of the polyaryletherketone composition is higher, and the content of residual compounds gradually decreases to a level of almost none or none. Furthermore, it can be confirmed that the polyaryletherketone compositions of Examples 1 to 5 exhibit improved thermal properties, such as a 5 wt% weight reduction temperature and a 10 wt% weight reduction temperature, a lower weight reduction rate at 400°C, and a higher melting point, due to the increase in molecular weight (Mw-R) and the decrease in residual compound content compared to the intermediate polymers of Examples 1 to 5 as well as Comparative Examples 1 to 3.

[0191] On the other hand, in the case of the polyaryletherketone compositions of Comparative Examples 1 to 3, it can be seen that the molecular weight increases as the polymerization time increases, but due to the harsh temperature conditions (390°C) compared to Examples 1 to 5 (320°C), it can be seen that the content of residual compounds increases and thermal properties deteriorate as the polymerization time increases.

[0192] Through this, according to the method for preparing a polyaryletherketone composition according to one embodiment, polymerization can be carried out for a long period at a relatively mild polymerization temperature, so that the molecular weight increases while the content of residual compounds is simultaneously reduced, and as a result, thermal properties can be improved.

[0193]

[0194] Hereinafter, embodiments are described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

Claims

A polyaryletherketone comprising repeating units represented by the following chemical formula 5, and It comprises a residual compound comprising an unreacted monomer containing a silyl group, a monomer decomposition product containing a silyl group, or a combination thereof, and The above residual compound is included in an amount of 0% to 0.005% by weight based on 100% by weight of the polyaryletherketone composition, Composition of polyaryletherketone: [Chemical Formula 5] In the above chemical formula 5, The above R 111 to R 224 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group, and The above X 11 and X 21 Each is independently a single bond, -O-, -S-, or a divalent organic group, and only X 11 and X 21 At least one of them is a ketone group (-CO-), and The above Z 51 It is oxygen, and The above n 1 , n 2 , and n 3 are each independently integers from 0 to 5, where n 1 , n 2 , and n 3 At least one of them is 1 or more. In Paragraph 1, The unreacted monomer containing the silyl group comprises a compound represented by the following chemical formula 2, Polyaryl etherketone composition: [Chemical Formula 2] In Chemical Formula 2, R 211 to R 224 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group, and X 21 is a single bond, -O-, -S-, or a divalent organic group, and X 22 and X 23 Each is independently a trialkylsiloxy group, and n 2 is an integer from 0 to 5. In Paragraph 1, The monomer hydrolysate containing the silyl group comprises a compound represented by the following chemical formula 6, a compound represented by the following chemical formula 7, or a combination thereof. Polyaryl etherketone composition: [Chemical Formula 6] X 61 -Si-(R 61 )3 In the above chemical formula 6, The above X 61 is a hydroxyl group, and The above R 61 is independently an alkyl group, and [Chemical Formula 7] R 71 -O-R 72 In Chemical Formula 7, R 71 and R 72 Each is independently a trialkylsilyl group. In paragraph 1, The above residual compound further comprises an unreacted monomer represented by the following chemical formula 1, Polyaryl etherketone composition: [Chemical Formula 1] In Chemical Formula 1, R 111 to R 124 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group, and X 11 is a single bond or a divalent organic group, and X 12 and X 13 Each is independently a halogen atom, and n 1 is an integer from 1 to 5. In Paragraph 1, The above residual compound further comprises a monomer decomposition product represented by the following chemical formula 8, Polyaryl etherketone composition: [Chemical Formula 8] In chemical formula 8, R 81 and R 82 Each is independently a hydroxyl group or a trialkylsiloxy group. In paragraph 1, The Mw-R of the above polyaryletherketone resin composition is 34,000 Da to 90,000 Da, Polyaryl ether ketone resin composition. In paragraph 1, The above polyaryletherketone resin composition has a 5 wt% reduction temperature (Td5) of 300°C or higher according to thermogravimetric analysis (TGA), Polyaryl ether ketone resin composition. In paragraph 1, The above polyaryletherketone resin composition has a 10 wt% reduction temperature (Td10) according to thermogravimetric analysis (TGA) of 400°C to 650°C, Polyaryl ether ketone resin composition. In paragraph 1, The above polyaryletherketone resin composition has a weight loss rate of 0.9 weight% or less at 400°C, Polyaryl ether ketone resin composition. A step of preparing an intermediate polymer by primary solvent-free polymerization of a monomer represented by the following chemical formula 1 and a monomer represented by the following chemical formula 2 under a catalyst; and A step of preparing polyaryletherketone by secondary solvent-free polymerization of the above intermediate polymer under an inert gas or vacuum at a temperature of 20°C to 340°C for 1 hour to 80 hours; comprising Method for preparing a polyaryl ether ketone composition: [Chemical Formula 1] [Chemical Formula 2] In Chemical Formula 1 and Chemical Formula 2, R 111 to R 224 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group, and X 11 and X 21 Each is independently a single bond, -O-, -S-, or a divalent organic group, and only X 11 and X 21 At least one of them is a ketone group (-CO-), and X 12 and X 13 Each is independently a halogen atom, and X 22 and X 23 Each is independently a trialkylsiloxy group, and n 1 and n 2 are each independently integers from 0 to 5, where n 1 and n 2 At least one of them is 1 or more. In Paragraph 10, Before manufacturing the above intermediate polymer, The method further comprises the step of preparing a monomer represented by the chemical formula 2 by reacting the monomer represented by the chemical formula 3 below with hexaalkyldisilazane to silylate it. Method for preparing a polyaryl ether ketone composition: [Chemical Formula 3] In Chemical Formula 3, R 311 to R 324 Each is independently a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, an alkyl sulfonyl group, an acyl group, an alkyl halide group, an aldehyde group, a nitro group, a nitroso group, or a nitrile group, and X 31 is a single bond, -O-, -S-, or a divalent organic group, and X 32 and X 33 Each is independently a hydroxyl group, and n 3 is an integer from 0 to 5. In Paragraph 10, The above primary solvent-free polymerization is carried out at a temperature of 20°C to 420°C for 1 to 12 hours, Method for preparing a polyaryl ether ketone composition. In Paragraph 10, The above catalyst includes an alkali metal halide, Method for preparing a polyaryl ether ketone composition. In Paragraph 13, The above alkali metal halide comprises CsF, CsCl, CsBr, CsI, KF, KCl, KBr, RbF, RbCl, RbI, RbBr, or a mixture thereof. Method for preparing a polyaryl ether ketone composition. In Paragraph 10, The Mw-R of the above intermediate polymer is 10,000 Da or more and less than 34,000 Da, Method for preparing a polyaryl ether ketone composition.

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