Polyamide-imide polymer and its manufacturing method

Abstract

The present invention relates to compounds of formula (I) and (II): [Formula 1] TIFF2022546854000025.tif89170(in the formula: Z is an alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 18 carbon atoms; R is a divalent alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 20 carbon atoms; and m and n are, independently of each other, integers of 0 to 10.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 897,476, filed September 9, 2019, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to polyamide-imide (PAI) polymers and methods for making same. [Background technology]

[0003] Polyamide-imides (PAIs) are high-performance polymers with outstanding thermal, chemical, and mechanical properties, making them suitable for demanding applications where high mechanical strength, stiffness, and low friction are required in combination with high temperature, corrosion, and wear resistance. For these reasons, they are widely used in the aerospace and automotive industries, insulators, coatings, solvent-resistant films, and electronic devices.

[0004] PAIs are polymers containing both amide and imide functionality in the backbone. Therefore, PAI polymers tend to exhibit hybrid properties between polyamides and polyimides. The increased rigidity of the imide groups confers better hydrolytic, chemical, and thermal stability to the polymer, as well as superior mechanical properties, particularly for aromatic monomer-based polymers. Most commercially available PAI polymers are indeed aromatic, typically based on trimellitic acid, trimellitic anhydride, or trimellitic acid halide, and aromatic diamines.

[0005] During the PAI preparation process, imides are formed from the reaction between two adjacent carboxylic acid groups (or their derivatives, such as acid halides, acid anhydrides, esters, etc.) and a primary amine-containing molecule. An amide acid is first formed, which closes into an imide ring upon further elimination of a molecule of water.

[0006] The imidization reaction generally requires high temperatures, especially for PAI polymers based on aromatic monomers. However, the use of high temperatures can lead to crosslinking side reactions, which can result in PAI polymers with limited processability or even thermoset-like structures. Although the PAI polymers are chemically stable, their poor flowability during melt processing, thermal resistance (i.e., poor melt-processability) and poor solubility in conventional processing methods limit their use in certain applications.

[0007] Several attempts have been made to improve these properties of the PAI polymers while simultaneously maintaining their good thermal and mechanical performance, particularly by grafting the polymers, blending them with other types of polymers, and forming composites with additives and inorganic fibers.

[0008] Other attempts to improve the solubility and processability of PAI polymers have included incorporating flexible linkages and alicyclic units into their polymer chains. For example, Journal of Polymer Science, Part A: Polymer Chemistry 2018, 56, 1782-1786 discloses polyamide-imides based on CTA and bis-(trifluoromethyl)benzidine. While the polyamide-imides exhibit improved solubility in some solvents, they have glass transition temperatures (Tg) above 300°C, making the polymers difficult to melt-process.

[0009] US Patent Application Publication No. 2011 / 160407 discloses PAI polymers obtained by reacting at least one aromatic organic compound having a carboxyl group with at least one diamine compound and, optionally, at least one diacid compound. The diamine compound may be aromatic, arylaliphatic, aliphatic, or cycloaliphatic. This document more precisely describes PAI polymers based on hexamethylenediamine (HMD) as the diamine compound and trimellitic acid, pyromellitic acid, or trimellitic anhydride as the aromatic organic compound. However, being aromatic, the imide bonds of the PAI impart color (yellow to orange to red) to the polymer.

[0010] None of the above listed documents describe PAI polymers based on cycloaliphatic acid components, such as cycloaliphatic tricarboxylic acids, and cycloaliphatic diamines. Summary of the Invention

[0011] In a first aspect, the present invention provides compounds of formula (I) and (II): [ka] (In the formula: - Z is an alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 18 carbon atoms; - R is a divalent alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 20 carbon atoms; m and n are each independently an integer of 0 to 10, preferably 1 to 5, and more preferably 1 to 3. The present invention relates to polyamide-imide (PAI) polymers comprising repeat units according to any of the following:

[0012] In a second aspect, the present invention provides a method for preparing a PAI polymer as specified above, the method comprising: a) Formulas (IX) and (X): [ka] (In the formula: - Z is an alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 18 carbon atoms; - Y is OR a and R a is H or alkyl, preferably alkyl having 1 to 5 carbon atoms; - at least two Y(C=O) are bonded to two adjacent carbon atoms of Z in formula (X) and at least one alicyclic acid component according to any one of the preceding claims. b) Formula (XI): H2N-(CH2) m -R-(CH2) n -NH2(XI) (In the formula: - R is a divalent alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 20 carbon atoms; m and n are each independently an integer of 0 to 10, preferably 1 to 5, and more preferably 1 to 3. and at least one alicyclic diamine according to The present invention relates to a method comprising the step of reacting

[0013] In a third aspect, the present invention relates to a polymer composition comprising a PAI polymer as identified above.

[0014] In a fourth aspect, the present invention relates to an article comprising said PAI polymer or said polymer composition.

[0015] Applicants have surprisingly found that PAI polymers according to the present invention exhibit an interesting set of properties, including low and controlled branching. The PAI polymers according to the present invention exhibit enhanced solubility, melt processability, and moldability, while maintaining good thermal and mechanical properties, such as a high glass transition temperature (Tg). In particular, the PAI polymers according to the present invention can be readily processed using conventional polymer processing techniques, such as extrusion and injection molding. Furthermore, the PAI polymers according to the present invention can be readily converted into films and other articles.

[0016] Applicants have also interestingly found that articles comprising PAI polymers or polymer compositions according to the present invention are transparent and colorless and exhibit a low yellowness index. DETAILED DESCRIPTION OF THE INVENTION

[0017] As used herein, unless otherwise specified, the following terms shall have the following meanings:

[0018] The term "alicyclic moiety" means an organic group that contains at least one aliphatic ring and no aromatic rings. The alicyclic moiety can be substituted with one or more linear or branched alkyl or alkoxy groups and / or halogen atoms, and / or can contain one or more heteroatoms, such as nitrogen, oxygen, and sulfur, in the ring.

[0019] The terms "alkyl," as well as derivative terms such as "alkoxy," include within their scope straight-chain, branched-chain, and cyclic moieties. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclopropyl. Unless otherwise specifically stated, each alkyl group may be unsubstituted or substituted with one or more substituents selected from, but not limited to, hydroxy, sulfo, C1-C6 alkoxy, and C1-C6 alkylthio, provided that the substituents are sterically compatible and chemical bonding and strain energy rules are satisfied.

[0020] The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine, with fluorine being preferred.

[0021] Polyamide-imide (PAI) polymer The object of the present invention is to provide a compound of formula (I) and (II): [ka] (In the formula: Z is an alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 18 carbon atoms; R is a divalent alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 20 carbon atoms; m and n are each independently an integer of 0 to 10, preferably 1 to 5, more preferably 1 to 3. The PAI polymer comprises repeat units according to any of the following:

[0022] Preferably, Z is an alicyclic moiety containing 1 to 4 aliphatic rings. When Z contains more than one aliphatic ring, i.e., two or more aliphatic rings, the aliphatic rings may be fused or may be directly or bridged by one of the following: -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -(CF2) q -, (q is an integer from 1 to 5). The term "directly" means that the aliphatic rings are linked together by a bond.

[0023] Preferably, Z is represented by the formula (III-A) to (III-D): [ka] and the corresponding substituted structural moieties, and X is -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -(CF2)q-, where q is an integer from 1 to 5.

[0024] Preferably, R is an alicyclic moiety containing 1 to 4 aliphatic rings. When R contains more than one aliphatic ring, i.e., two or more aliphatic rings, the aliphatic rings may be fused together or may be directly or bridged by one of the following: -O-, -S-, -SO2-, -CH2-, -C(CF3)2-, -(CF2) q -, (q is an integer from 1 to 5). The term "directly" means that the aliphatic rings are linked together by a bond.

[0025] Preferably, R is represented by formula (IV-A) to (IV-C): [ka] and the corresponding substituted structural moieties, and A is -O-, -S-, -SO2-, -CH2-, -C(CF3)2-, -(CF2) q -, (q is an integer from 1 to 5).

[0026] The PAI polymers of the present invention preferably comprise at least 5 mole %, more preferably at least 20 mole %, even more preferably at least 40 mole %, and most preferably at least 60 mole % of repeat units of formula (I), based on the total number of moles of repeat units in the PAI polymer.

[0027] The PAI polymers of the present invention preferably contain at most 10 mole %, more preferably at most 5 mole %, and even more preferably at most 1 mole % of repeat units of formula (II), based on the total number of moles of repeat units in the PAI polymer.

[0028] According to some embodiments, in addition to the recurring units of formulae (I) and (II), the PAI polymers of the present invention may also contain recurring units of formulae (V) and (VI): [ka] (In the formula, R 1is a divalent aliphatic hydrocarbon group preferably containing 2 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aliphatic hydrocarbon group includes linear and branched chains, preferably linear hydrocarbon chains.

[0029] Preferably, the PAI polymer comprises at most 50 mole %, more preferably at most 40 mole %, and even more preferably at most 35 mole %, of repeat units according to either of formulas (V) and (VI), based on the total number of moles of repeat units according to formulas (I), (II), (V) and (VI) in the PAI polymer.

[0030] According to some embodiments, in addition to the recurring units of formulae (I) and (II), the PAI polymers of the present invention may also contain recurring units of formulae (VII) and (VIII): [ka] (In the formula, R, R 1 , m and n are as defined above, and R 2 The polyamide further comprises repeating units according to any of the following groups: (wherein R is a divalent hydrocarbon group, particularly a divalent aliphatic, alicyclic, or aromatic hydrocarbon group, preferably containing 4 to 18 carbon atoms). Preferred examples of aliphatic groups are alkylene groups having 4 to 16 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. Preferred examples of alicyclic groups are 1,4- and 1,3-cyclohexylene groups. Preferred examples of aromatic groups are benzene and naphthalene groups, which may be substituted or unsubstituted.

[0031] Preferably, the PAI polymer comprises at most 20 mole %, more preferably at most 10 mole %, and even more preferably at most 5 mole %, of repeat units according to either of formulas (VII) and (VIII), based on the total number of moles of repeat units in the PAI polymer.

[0032] According to a preferred embodiment of the present invention, the PAI polymer consists of or consists essentially of repeat units of formula (I) and repeat units of formula (II). The expression "consisting essentially of" means that the PAI polymer contains repeat units of formula (I) and repeat units of formula (II) and less than 10 mol %, preferably less than 5 mol %, more preferably less than 3 mol %, and even more preferably less than 1 mol %, based on the total number of moles of repeat units in the PAI polymer, of other repeat units different from the repeat units of formulas (I) and (II).

[0033] According to an even more preferred embodiment, the PAI polymer consists of or consists essentially of repeat units of formula (I). The expression "consisting essentially of" means that the PAI polymer contains repeat units of formula (I) and less than 10 mol %, preferably less than 5 mol %, more preferably less than 3 mol %, and even more preferably less than 1 mol %, based on the total number of moles of repeat units in the PAI polymer, of other repeat units different from repeat units of formula (I).

[0034] In a preferred embodiment, the repeat unit according to formula (I) is of formula (Ia): [ka] It has.

[0035] In a preferred embodiment, the repeat unit according to formula (II) is of formula (IIa): [ka] It has.

[0036] Preferably, the PAI polymer has a glass transition temperature (Tg) of at least 100°C, more preferably at least 120°C, even more preferably at least 140°C, and most preferably at least 150°C, as measured by DSC according to ASTM D3418.

[0037] Preferably, the PAI polymer has a glass transition temperature, as measured by DSC according to ASTM D3418, of at most 250°C, more preferably at most 240°C, even more preferably at most 230°C, and most preferably at most 220°C.

[0038] Preferably, the PAI polymer has a number average molecular weight (Mn) of at least 5,000 g / mol, more preferably at least about 10,000 g / mol, and even more preferably at least 15,000 g / mol, as measured by gel permeation chromatography (GPC) using a fluorinated solvent, a 2HFIP gel column, and a UV-visible / refractive index detector.

[0039] Preferably, the PAI polymer has a number average molecular weight (Mn) of at most 50,000 g / mol, more preferably at most 45,000 g / mol, and even more preferably at most 40,000 g / mol, as measured by gel permeation chromatography (GPC) using a fluorinated solvent, a 2HFIP gel column, and a UV-visible / refractive index detector.

[0040] Advantageously, the PAI polymer is soluble in a variety of solvents, especially hexafluoro-2-propanol, o-cresol, sulfuric acid 98% and dimethylformamide.

[0041] The PAI polymers according to the present invention can be processed using conventional polymer processing techniques such as extrusion and injection molding for subsequent shaping after melting.

[0042] Furthermore, the PAI polymers of the present invention can be easily converted into films and other articles. The PAI polymers of the present invention are soluble in a variety of organic solvents, and films can be advantageously produced by casting a solution containing the PAI polymer and then evaporating the solvent, according to standard processes known to those skilled in the art. In particular, the films can be produced by dissolving the PAI polymer in a solvent to obtain a solution, casting the solution onto a substrate, and finally evaporating the solvent.

[0043] The PAI polymer can be used in a number of applications, particularly in the production of yarns, fibers or filaments, or films, or in the formation of articles by injection molding, extrusion, or extrusion / blow molding, and it can be used in particular in engineering plastic compositions.

[0044] Method for preparing the polyamide-imide polymer Another object of the present invention is a method for preparing a PAI polymer as defined above, said method comprising the steps of: a) Formulas (IX) and (X): [ka] (In the formula: Z is an alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 18 carbon atoms; Y is for OR a and R a is H or alkyl, preferably alkyl having 1 to 5 carbon atoms; At least two Y(C=O) are bonded to two adjacent carbon atoms of Z in formula (X). and at least one alicyclic acid component according to any one of the preceding claims. b) Formula (XI): H2N-(CH2) m -R-(CH2) n -NH2(XI) (In the formula: R is a divalent alicyclic moiety selected from the group consisting of substituted or unsubstituted, monocyclic or polycyclic groups having 5 to 50 carbon atoms, preferably 6 to 20 carbon atoms; m and n are each independently an integer of 0 to 10, preferably 1 to 5, more preferably 1 to 3. and at least one alicyclic diamine according to The method includes the step of reacting

[0045] Preferred examples of Z and R are as defined above for the PAI polymers of formulas (I) and (II).

[0046] In a preferred embodiment, the alicyclic acid component is represented by formulas (IXa) and (Xa): [ka] Follow one of the following.

[0047] According to this embodiment, the method of the present invention comprises: - reacting a cycloaliphatic acid component according to formula (IXa) with at least one cycloaliphatic diamine, - reacting an alicyclic acid component according to formula (Xa) with at least one alicyclic diamine; or - reacting a mixture of cycloaliphatic acid components according to formulas (IXa) and (Xa) with at least one cycloaliphatic diamine. Includes:

[0048] The alicyclic diamine is preferably selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and 4,4'-methylenebis(2-methylcyclohexylamine).

[0049] According to one embodiment, the reaction mixture comprises a compound of formula (XII): H2N-R 1-NH2(XII) (In the formula, R 1 is as defined above) The compound further comprises at least one aliphatic diamine of the formula:

[0050] The aliphatic diamine is preferably selected from the group consisting of putrescine, cadaverine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, and dodecamethylenediamine.

[0051] For simplicity, the term "diamino component" as used below includes both cycloaliphatic and aliphatic diamines.

[0052] Preferably, the diamine component comprises at least 50 mole %, more preferably at least 65 mole %, and even more preferably at least 80 mole % of cycloaliphatic diamines, based on the total number of moles of diamine components involved in the process. Even more preferably, the diamine component consists of or consists essentially of cycloaliphatic diamines. The expression "consisting essentially of" means that the diamine component comprises cycloaliphatic diamines and less than 10 mole %, preferably less than 5 mole %, more preferably less than 3 mole %, and even more preferably less than 1 mole %, of aliphatic diamines, based on the total number of moles of diamines in the reaction mixture.

[0053] According to certain embodiments, the reaction mixture further comprises at least one diacid component or derivative thereof.

[0054] The expression "derivatives thereof" is intended to mean any derivative that is susceptible to reacting under polycondensation conditions to form an amide bond. Examples of amide-forming derivatives include acyl groups, such as substituted or unsubstituted aliphatic acyl and aromatic acyl groups. Examples of these acyl groups are formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, benzoyl, toluoyl, and xyloyl.

[0055] This additional diacid component may be aliphatic, alicyclic or aromatic, and comprises at least two carboxylic acid moieties -COOH, and optionally one or several heteroatoms, preferably selected from N, S and O.

[0056] The diacid component preferably has the following formula (XII): HOOC-R 2 -COOH (XII) (In the formula, R 2 represents a divalent hydrocarbon group, particularly a divalent aliphatic, alicyclic, or aromatic hydrocarbon group, preferably containing 4 to 18 carbon atoms. Preferred examples of aliphatic groups are alkylene groups having 4 to 16 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. Preferred examples of alicyclic groups are 1,4- and 1,3-cyclohexylene groups. Preferred examples of aromatic groups are benzene and naphthalene groups, which may be substituted or unsubstituted.

[0057] The diacid component is preferably selected from the group consisting of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dibenzoic acid, 5-hydroxyisophthalic acid, 5-sulfophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof.

[0058] A chain limiter or endcapping agent can be added to the reaction mixture to control the molecular weight. A chain limiter or endcapping agent is a molecule that has only one reaction site with an amine and / or a carboxylic acid. Examples of endcapping agents are monoamines, such as benzylamine and 1-hexaneamine, and monocarboxylic acids, such as acetic acid, propionic acid, benzoic acid, phthalic acid, or anhydride.

[0059] According to a preferred embodiment, the method comprises reacting the at least one cycloaliphatic acid component, the at least one cycloaliphatic diamine, optionally the at least one aliphatic diamine, and optionally the at least one diacid component by melt polymerization, and further comprises maintaining the reaction mixture in a homogeneous liquid state throughout the melt polymerization at a temperature of at least 200°C.

[0060] The term "melt polymerization" means that the reaction mixture is maintained in a homogeneous liquid state throughout the polymerization at a temperature of at least 200°C.

[0061] In the context of the present invention, the term "homogeneous liquid state" means that the reaction mixture remains in a fluid state without any solidification and / or precipitation of the resulting PAI polymer.

[0062] During melt polymerization, the reaction mixture is continuously heated to increasing temperatures so that the PAI polymer being prepared remains in a molten state. The minimum temperature to which the reaction mixture should be heated can generally be determined based on the melting or softening point of the PAI polymer being prepared. The melting or softening point of the PAI polymer being prepared can vary over the polymerization time based on the amounts of reactants involved in the reaction, particularly the amount of limiting reactant, for example, if one of the reactants is added gradually to the reaction mixture. In this case, the melting or softening point of the PAI polymer being prepared can be determined based on complete conversion of the limiting reactant monomer. Because the limiting reactant can be added sequentially to the reaction mixture, several temperature increases / increments may be necessary to prepare the PAI polymers of the present invention. Each step of the polymerization process is then carried out at a temperature above the melting or softening point of the PAI polymer being produced.

[0063] The melt polymerization process is advantageously carried out in the absence of organic solvents. In other words, the process is advantageously free of organic solvents, meaning that the polymerization medium is free of organic solvents or contains an amount of organic solvent that is less than 1% by weight, less than 0.5% by weight, or even less than 0.2% by weight, based on the total weight of the reaction mixture. However, the process may use water.

[0064] According to different embodiments, said process of melt polymerization is carried out in the absence of added water or in the presence of added water in an amount of less than 50% by weight, preferably less than 40% by weight, more preferably less than 30% by weight, even more preferably less than 15% by weight, and most preferably less than 5% by weight, based on the total weight of the reaction mixture.

[0065] Thus, the polymerization medium can be an aqueous solution comprising the above-identified components (i.e., the at least one cycloaliphatic acid component, the at least one cycloaliphatic diamine, optionally the at least one aliphatic diamine, and optionally the at least one diacid component), or a liquid comprising said components. Preferably, the polymerization medium comprises water as a solvent, as this facilitates agitation of the medium and thus its homogeneity.

[0066] According to various embodiments, either the alicyclic acid component or the diamine component is added sequentially, gradually, or continuously to the reaction mixture.

[0067] Preferably, the reaction mixture contains the alicyclic acid component and the diamine component in an equivalent ratio in the range of 0.8 to 1.2, preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and even more preferably 0.97 to 1.03.

[0068] When the process of the present invention employs a diacid component, the diacid component and the diamine component may be introduced, at least in part, in the form of a salt of the diacid and the diamine component.

[0069] PAI polymers are generally obtained by polycondensation of a cycloaliphatic acid component, a cycloaliphatic diamine, optionally an aliphatic diamine, and optionally a diacid component to form polyamide-imide chains with the formation of elimination products, especially water. Preferably, the water generated during the process is evaporated, for example by fractional distillation using a condenser, at a pressure of 1 mbar to 30 bar.

[0070] The reaction mixture is preferably maintained in a homogeneous liquid state throughout the melt polymerization at a temperature of at least 200°C, preferably 215°C to 300°C, to evaporate elimination products, particularly water (originally present in the polymerization medium and / or formed during polycondensation), while preventing any formation of a solid phase to prevent the mixture from solidifying.

[0071] The melt polymerization process can be carried out under pressure for at least some parts of the process. In these cases, a maximum pressure of 20 bar, preferably a maximum pressure of 10 bar, more preferably a maximum pressure of 3 bar is used. In order to drive the reaction to completion and to more easily remove the water formed during the reaction, the end of the process is in any case preferably carried out at low pressure (vacuum or atmospheric pressure).

[0072] The melt polymerization process can be carried out in equipment made of materials inert to the above-identified components (i.e., the at least one alicyclic acid component, the at least one alicyclic diamine, optionally the at least one aliphatic diamine, and optionally the at least one diacid component). In this case, the equipment is selected to provide sufficient contact between the components and to allow for the removal of volatile reaction products, especially water. Suitable equipment includes stirred reactors, extruders, and kneaders. The reaction vessel is preferably equipped with a stirring means, such as a rotating shaft.

[0073] Preferably, the order of introduction of the components into the reaction vessel during the process is as follows: water is added first, then the diamine component is charged, and lastly the alicyclic acid component and the diacid component are added.

[0074] Preferably, an inert gas, such as nitrogen gas, is introduced into the reaction vessel to replace the atmosphere in the vessel. Preferably, the reaction vessel is purged with said inert gas both before and after charging all of the above-identified components. Preferably, a flow of inert gas is maintained throughout the process.

[0075] polymer composition Another object of the present invention is a polymer composition comprising a PAI polymer as defined above.

[0076] Preferably, the PAI polymer is present in the polymer composition in an amount of at least 10 wt. %, more preferably at least 15 wt. %, even more preferably at least 20 wt. %, and most preferably at least 25 wt. %, based on the total weight of the polymer composition.

[0077] Preferably, the PAI polymer is present in the polymer composition in an amount of at most 99 wt. %, more preferably at most 95 wt. %, even more preferably at most 80 wt. %, and most preferably at most 60 wt. %, based on the total weight of the polymer composition.

[0078] According to one embodiment of the present invention, the PAI polymer is present in the polymer composition in an amount ranging from 10 to 70 wt %, preferably from 20 to 60 wt %, based on the total weight of the polymer composition.

[0079] According to one embodiment of the present invention, the polymer composition comprises at least one additional additive selected from the group consisting of reinforcing agents, colorants, dyes, pigments, lubricants, plasticizers, flame retardants, nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, electromagnetic absorbers, and combinations thereof.

[0080] The reinforcing agent, also referred to as a reinforcing filler or fiber, may be selected from the group consisting of fibrous reinforcing fillers, particulate reinforcing fillers, and mixtures thereof. Fibrous reinforcing fillers are herein considered to be materials having a length, width, and thickness in which the average length is significantly greater than both the width and thickness. Generally, fibrous reinforcing fillers have an aspect ratio, defined as the average ratio between the length and the maximum width and thickness, of at least 5, at least 10, at least 20, or at least 50.

[0081] Fibrous reinforcing fillers include glass fibers, carbon or graphite fibers, and fibers formed from silicon carbide, alumina, titania, boron, etc., and may include mixtures containing two or more such fibers. According to one embodiment, the fibers are flat fibers. Non-fibrous reinforcing fillers include talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, mineral fillers, etc., among others.

[0082] According to this embodiment, the PAI polymer is advantageously mixed with said at least one additional additive. Preferably, the mixing of the PAI polymer with said at least one additional additive is carried out by dry blending and / or melt compounding. More preferably, the mixing of the polyamide (PA) with said at least one additional additive is carried out by melt compounding, especially in a continuous or batch device. Such devices are well known to those skilled in the art. An example of a suitable continuous device is a screw extruder. Preferably, the melt compounding is carried out in a twin-screw extruder.

[0083] Goods The present invention also relates to articles comprising said PAI polymer or said polymer composition.

[0084] The article according to the present invention is preferably a molded article, preferably molded from a PAI polymer or a polymer composition comprising said PAI polymer using methods well known in the art, including, but not limited to, injection molding, blow molding, rotational molding, compression molding, or extrusion.

[0085] If the disclosure of any patent, patent application, and publication incorporated herein by reference contradicts the statement of this application to the extent that it may render a term unclear, the statement shall control.

[0086] The present invention will now be described with reference to the following examples, the purposes of which are illustrative only and are not intended to limit the scope of the invention.

[0087] Experimental section raw materials Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (CTA), available from Mitsubishi Gas Chemical.

[0088] 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), available from Mitsubishi Gas Chemical.

[0089] Hexamethylenediamine (HMDA), available from Ascend Performance Materials.

[0090] 4,4'-methylenebis(cyclohexylamine) (PACM), available from Sigma-Aldrich.

[0091] Phosphorous acid, available from Sigma-Aldrich.

[0092] method thermal analysis Thermal properties were measured using differential scanning calorimetry (DSC). DSC analysis was performed on a DSC Q200-5293 TA Instrument according to ASTM. Three scans were used for each DSC test: a first heating cycle at 20.00°C / min to 300°C; a first cooling cycle at 20.00°C / min to 300°C; and a second heating cycle at 20.00°C / min to 300°C. The glass transition temperature (Tg) was determined from the transition midpoint during the second heating cycle.

[0093] GPC Mn was measured by gel permeation chromatography (GPC).

[0094] solubility A 5 mg sample of PAI polymer was added to 5 ml of solvent. The resulting mixture was stirred at room temperature for 24-48 hours, and any dissolution or softening of the sample was noted. If the sample dissolved completely, it was considered soluble. If the sample did not show any change in appearance after 48 hours, it was considered insoluble. Solubility was tested in hexafluoro-2-propanol (HFIP), o-cresol, sulfuric acid 98%, and dimethylformamide (DMF).

[0095] Yellowness Test Films having a thickness of 0.1-0.2 mm were prepared in a hot press (280°C, 2000 lbf). The yellowness index was measured for the films using an X-Rite Ci7800 spectrophotometer.

[0096] Mechanical testing PAI 1 polymer, synthesized as described below, was ground in a mortar and dried overnight under vacuum at 120°C. It was then injection molded into Type V tensile bars according to ASTM D3641 using a mold temperature of 140°C, a melt temperature of 290°C, and an injection pressure of 6 bar. Mechanical testing was performed on injection-molded test specimens with a 0.3-inch gauge length according to ASTM D638 at 23.2°C and 54.7% humidity using an Instron 5569 machine. Notched Izod impact strength was measured according to ASTM D256 using injection-molded test specimens.

[0097] Synthesis method Polyamide-imide 1 (PAI 1) CTA (53.9 g), 1,3-BAC (39.1 g), phosphorous acid (0.032 g), and deionized water (42 g) were charged into a 300 ml reactor. The reactor was then purged with nitrogen for 5 minutes, stirred, and heated to 280°C within 2 hours to carry out the polymerization reaction. The generated steam was released when the target temperature was reached. The reactor was then depressurized, and the resulting molten polymer was held at this condition for another hour. Upon cooling, the polymer was removed from the reactor and used for analysis.

[0098] Polyamide-imide 2 (PAI 2) CTA (55.6 g), 1,3-BAC (25.9 g), HMDA (11.7 g), phosphorous acid (0.032 g), and deionized water (42 g) were charged into a 300 ml reactor. The reactor was then purged with nitrogen for 5 minutes, stirred, and heated to 280°C within 2 hours to carry out the polymerization reaction. The generated steam was released when the target temperature was reached. The reactor was then depressurized, and the resulting molten polymer was held at this condition for another hour. Upon cooling, the polymer was removed from the reactor and used for analysis.

[0099] Polyamide-imide 3 (PAI 3) CTA (50.7 g), PACM (27.1 g), HMDA (15.0 g), phosphorous acid (0.032 g), and deionized water (42 g) were charged into a 300 ml reactor. The reactor was then purged with nitrogen for 5 minutes, stirred, and heated to 280°C within 2 hours to carry out the polymerization reaction. The generated steam was released when the target temperature was reached. The reactor was then depressurized, and the resulting molten polymer was held at this condition for another hour. Upon cooling, the polymer was removed from the reactor and used for analysis.

[0100] result Table 1 shows the glass transition temperature (Tg), number average molecular weight (Mn), yellowness index and solubility results for PAI 1, PAI 2 and PAI 3 polymers prepared according to the present invention.

[0101] Table 2 shows the mechanical properties of PAI 1.

[0102] [Table 1]

[0103] [Table 2]

[0104] As evidenced in Table 1 above, high molecular weight PAI polymers based on CTA and various diamines (1,3-BAC, HMDA, and PACM) were successfully prepared. The PAI polymers exhibited glass transition temperatures (Tg) ranging from 150 to 176°C; Tg could be easily adjusted by varying the nature and amount of the diamine component.

[0105] The PAI polymers also exhibit a very low yellowness index.

[0106] Furthermore, these PAI polymers have been shown to be soluble in several organic solvents, which indicates that they have low and controlled branching.

[0107] As evidenced in Table 2, PAI 1 was melt processed and parts were produced by injection molding, demonstrating that PAI 1 also exhibits melt processability and moldability. PAI 1 also exhibits excellent mechanical properties combined with high tensile modulus and strength.

Claims

1. Formulas (Ia) and (IIa): A polyamide-imide (PAI) polymer comprising repeat units according to any of the following: Formulas (V) and (VI): (In the formula: Z is of formula (III-A): and -R １ is a divalent aliphatic hydrocarbon group derived from at least one aliphatic diamine selected from the group consisting of putrescine, cadaverine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, and dodecamethylenediamine. and further comprising a repeat unit according to any of the following: A polyamide-imide (PAI) polymer, wherein the PAI polymer comprises at most 50 mole % of repeat units according to either formula (V) and (VI), based on the total number of moles of repeat units according to formulas (Ia), (IIa), (V), and (VI) in the PAI polymer.

2. 2. The PAI polymer of claim 1, comprising at least 5 mol % of repeat units of formula (Ia) and / or at most 10 mol % of repeat units of formula (IIa), based on the total number of moles of repeat units in the PAI polymer.

3. As measured by DSC according to ASTM D3418 at least 140°C, and - Maximum 220°C 3. The PAI polymer of claim 1, having a glass transition temperature (Tg) of

4. The PAI polymer according to any one of claims 1 to 3, which is soluble in hexafluoro-2-propanol, o-cresol, 98% sulfuric acid, and dimethylformamide.

5. A method for preparing a polyamide-imide (PAI) polymer, said method comprising: a) Formulas (IX) and (X): (In the formula: Z is of formula (III-A): and - Y is OR ａ and R ａ is H or alkyl, - at least two Y(C=O) are bonded to two adjacent carbon atoms of Z in formula (X) at least one alicyclic acid component according to any one of the preceding claims; b) Formula (XI): H ２ N-(CH ２ ) ｍ -R-(CH ２ ) ｎ -NH ２ (XI) (Wherein R represents a group represented by formula (IV-A) to (IV-C): and A is selected from the group consisting of -O-, -S-, -SO 2 -, -CH 2 -, -C(CF 3 ) 2 -, -(CF 2 ) q -, where q is an integer from 1 to 5; m and n are, independently of one another, integers from 0 to 10. and at least one cycloaliphatic diamine according to c) Formula (XII): H ２ N−R １ −NH ２ (XII) (wherein R 1 is a divalent aliphatic hydrocarbon group derived from at least one aliphatic diamine selected from the group consisting of putrescine, cadaverine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, and dodecamethylenediamine) and at least one aliphatic diamine of The method comprises reacting

6. The at least one alicyclic acid component may be represented by formula (IXa) and / or (Xa): The method according to claim 5,

7. 7. The method of claim 5 or 6, comprising reacting the at least one alicyclic acid component and the at least one alicyclic diamine by melt polymerization, the method further comprising maintaining the reaction mixture in a homogeneous liquid state throughout the melt polymerization at a temperature of at least 200°C.

8. 8. The method of claim 7, wherein the method is carried out in the absence of added water or in the presence of added water in an amount of less than 50% by weight, based on the total weight of the reaction mixture.

9. A polymer composition comprising the PAI polymer of any one of claims 1 to 4.

10. An article comprising the PAI polymer of any one of claims 1 to 4 or the polymer composition of claim 9.

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