Reactive oligomers, additive manufacturing methods, and articles thereof

Abstract

To provide reactive oligomers. [Solution] The reactive oligomer has a skeleton derived from at least one of polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole, or polybenzimidazole, and is functionalized with at least one unreacted functional group that can undergo heat chain extension and crosslinking after the formation of the reactive oligomer, and the reactive oligomer has a molecular weight of about 250 to about 10,000 g / mol calculated using Carothers' equation. n It has.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of U.S. Provisional Application No. 62 / 932,892, filed on 8 November 2019, and U.S. Provisional Application No. 63 / 075,610, filed on 8 September 2020, both of which are incorporated herein by reference in their entirety. [Background technology]

[0002] All-aromatic polyamide-imides (PAIs) are high-performance polymers with alternating cyclic imide and amide bonds in their polymer backbone, first commercialized in the early 1970s. High molecular weight PAIs possess excellent high-temperature strength, low-temperature toughness, and impact strength, as well as outstanding chemical resistance and dimensional stability. High molecular weight PAIs can have amidic acid groups in the unimidized polymer backbone. The amidic acid groups provide some flexibility to the polymer backbone, making PAIs somewhat melt-processable, though not easily. However, several challenges remain associated with the melt processing of high molecular weight PAIs. Melt viscosity is highly sensitive to temperature and shear rate, and PAIs have a narrow processing width requiring processing temperatures above 600°F (316°C). The amidic acid is thermally converted to imide by dehydration cyclization, and the conversion of amidic acid groups to cyclic imide groups results in a rapid increase in the rigidity of the polymer backbone, and therefore a rapid increase in melt viscosity. If this occurs during extrusion, there is a risk that the polymer molten material will solidify in the extruder. Due to the presence of non-imidized amic acid groups, PAIs are highly sensitive to moisture and must be completely dried before melting and maintained dryness during processing to prevent degradation of molecular weight and thermal / mechanical properties. Furthermore, to obtain optimal properties, imidization and removal of imidized moisture may be required for 20 days or more at 500°F (260°C). These difficulties limit the use of high molecular weight PAIs to the production of simple stock shapes such as rods, plates, tubes, and other external forms. Therefore, these stock shapes can be mechanically processed by steps such as swirling, drilling, and milling to parts that are inaccessible by injection molding.

[0003] Given the processing limitations of high molecular weight PAIs, low viscosity injection molding grades have been developed. These grades can be used to manufacture injection-molded, filled and unfilled parts and stock shapes, but this is challenging. Injection molding grades are mixtures of amine-terminated low molecular weight (oligomeric) polyamides with dianhydride chain extenders such as pyromellitic anhydride (PMDA), which are thought to construct the molecular weight at its position. The oligomeric nature of the polyamide reduces the melt viscosity, which facilitates the melt processing step, and the amine-terminated polyamide oligomers react with the dianhydride to form high molecular weight polyamidoamic acid intermediates through chain extension. After processing, the manufactured parts and stock shapes need to be post-cured. During post-curing, the amidic acid groups undergo dehydration cyclization to form PAIs. A major drawback of this pathway to PAIs is the need to remove large amounts of water from the final parts. Two sources of such water are i) physicoadsorbed water associated with the hygroscopic residual amidic acid moieties in the chain-extended PAIs, and ii) water generated in the dehydration cyclization step. Removing moisture from parts and stock shapes is a time-consuming process that can take days to weeks under programmed heating protocols, depending on the part thickness and end-use. There is a need in the art for all-aromatic PAIs that do not require extended post-curing steps and time-consuming demolysis steps.

[0004] While injection-molded PAI represents an improvement over high molecular weight PAI, melt processing still presents many challenges. As mentioned above, the amidic acid groups are still present in chain-extended PAI and must be completely dried before use. A post-heat treatment step is still required to complete polymerization (chain extension) and / or imidize the amidic acid groups. As mentioned above, moisture is generated in these post-treatment steps and must be removed to avoid foaming, microbubble formation, and part embrittlement. Injection-molded grade PAI has other drawbacks as well. Residence times must be optimized, as excessive residence times result in flow loss and increased viscosity due to chain extension. Molds must be filled quickly, and pressure must be optimized for each mold size and shape. Injection molding of combination designs does not work well. The viscosity of injection-molded grade PAI is still very shear-sensitive. Therefore, injection speed, injection pressure, back pressure, screw speed, barrel temperature, cycle time, and mold heating must all be optimized for each specific mold shape and size.

[0005] Post-heat treatment remains crucial in injection-molded grade PAI. While such molded parts may appear finished, they are actually weak, brittle, poorly resistant to chemicals and abrasion, and have suboptimal heat resistance. To achieve optimal properties, molded parts must be heated in a forced-air oven with a curing schedule of progressively increasing temperatures at time intervals, which must be optimized for each part type and size. A common curing schedule recommended by manufacturers is 375°F (191°C) for one day, 425°F (218°C) for one day, 475°F (246°C) for one day, and 500°F (260°C) for five days, totaling eight days. For the reaction to proceed, the water in the reaction must diffuse from the part, and thicker parts may take longer to cure. Therefore, the reaction rate decreases as the diffusion path lengthens. Furthermore, certain parts, such as those with very thin walls and / or delicate shapes, may require fixing during post-curing to meet strict dimensional tolerances.

[0006] In light of the above issues, there remains a need in the art for readily melt-workable and curable PAIs that do not require extensive drying before processing and extensive post-heat treatment to remove water resulting from the dehydration cyclization of amidic acid functional groups. There also remains a need for PAIs suitable for various manufacturing processes, including fusion deposition (FDM) using filaments or rods, selective laser sintering (SLS) for powder bed printing, directed energy deposition (DED), laser-operated net molding (LENS), and composite additive manufacturing (CBAM).

[0007] These challenges are not limited to PAI. Furthermore, other engineering polymers and high-performance polymers are needed in the art to provide articles that are not only easily melt-processable and curable, but also possess excellent thermal and mechanical properties. Such improvements are particularly desirable in polyimides, polyetherimides, polyaryletherketones, polyethersulfones, polyphenylene sulfides, polyamides, polyesters, polyarylates, polyesteramides, polycarbonates, polybenzoxazoles, and polybenzimidazoles, as well as polyamideimides.

[0008] The subject matter described herein addresses these shortcomings in the relevant art. [Overview of the project] [Means for solving the problem]

[0009] Simple explanation The reactive oligomer is derived from at least one of polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole, or polybenzimidazole, and comprises a skeleton functionalized with at least one unreacted functional group that allows for thermal chain extension and crosslinking after the formation of the reactive oligomer, and the reactive oligomer has a number average molecular weight (M) of about 250 to about 10,000 g / mol, calculated using Carothers' equation. n ) has.

[0010] A composition containing a reactive oligomer may contain at least one other component. A method for formulating a reactive oligomer involves mixing the reactive oligomer with at least one other component at a temperature and time sufficient to form a homogeneous molten mixture but without crosslinking unreacted functional groups. The at least one other component may be at least one of a second reactive oligomer, an oligomer lacking unreacted functional groups that can be thermally extended and crosslinked, a thermoplastic polymer, a thermoplastic polymer having the same skeletal repeating units as the reactive oligomer, a filler, or an additive.

[0011] A method for manufacturing an article includes heating a composition containing a reactive oligomer at a temperature and time sufficient to shape and crosslink the reactive oligomer. The manufacturing method may be an addition process. Articles manufactured from a composition containing a reactive oligomer include addition-processed articles. In embodiments of the present invention, for example, the following items are provided. (Item 1) A reactive oligomer comprising a skeleton derived from at least one of polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole, or polybenzimidazole, and functionalized with at least one unreacted functional group that is capable of thermal chain extension and crosslinking after the formation of the reactive oligomer, wherein the reactive oligomer has a number average molecular weight (M) of about 250 to about 10,000 g / mol, calculated using Carothers' equation. n A reactive oligomer having ). (Item 2) The reactive oligomer according to item 1, wherein the at least one unreacted functional group is maleimide, 5-norbornene-2,3-dicarboximide, phthalonitrile, benzocyclobutene, biphenylene, cyanate ester, ketoethin, ethin, methylethin, phenylethin, propargyl ether, benzoxazine, or a combination thereof. (Item 3) The reactive oligomer according to item 1 or 2, wherein the reactive oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after its formation, the first unreacted functional group being self-reactive within a first temperature range, the second unreacted functional group being self-reactive within a second temperature range, and the second temperature range being higher than the first temperature range. (Item 4) The reactive oligomer according to any one of items 1 to 3, wherein the aforementioned skeleton is linear or branched. (Item 5) The reactive oligomer according to any one of items 1 to 4, wherein the aforementioned skeleton is derived from polyamide-imide. (Item 6) The aforementioned at least one unreacted functional group [Table 1] A reactive oligomer according to item 5, derived from a monomer or end capper selected from the group consisting of the following. (Item 7) A reactive oligomer according to item 6, comprising a unit derived from at least one anhydride selected from the group consisting of trimellitic anhydride and 4-chloroformylphthalic anhydride, at least one aromatic diamine selected from the group consisting of 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, and at least one endocapper selected from the group consisting of 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride. (Item 8) A reactive oligomer according to item 6, comprising a unit derived from at least one dianhydride selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, at least one bifunctional aromatic compound selected from the group consisting of isophthalic acid and isophthaloyl chloride, at least one aromatic diamine selected from the group consisting of 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, and at least one endocapper selected from the group consisting of 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride. (Item 9) A reactive oligomer according to item 6, comprising a unit derived from at least one dianhydride selected from the group consisting of pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(ethyn-1,2-diyl)diphthalic anhydride; at least one bifunctional aromatic compound selected from the group consisting of isophthalic acid and isophthaloyl chloride; at least one aromatic diamine selected from the group consisting of 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline; and at least one anhydride selected from the group consisting of phthalic anhydride, 4-methylethynylphthalic anhydride, and 4-phenylethynylphthalic anhydride. (Item 10) The aforementioned skeleton is derived from polyimide, and is a reactive oligomer according to any one of items 1 to 4. (Item 11) Equation (I): [ka] It has, in the formula, Ar 1 The tetravalent aryl group represented by [ka] At least one of the following, Ar 2 The divalent aryl group represented by [ka] At least one of Y 1 and Z 1 However, each is independent of the others. [Table 2] Derived from an end capper selected from the group consisting of, where n is calculated in the range of approximately 250 to approximately 10,000 g / mol. n The reactive oligomers described in item 10 are selected to provide the following: (Item 12) Y and Z are different reactive oligomers as described in item 11. (Item 13) The reactive oligomer according to any one of items 10 to 12, wherein the polyimide is a polyetherimide. (Item 14) The reactive oligomer according to item 13, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide. (Item 15) The reactive oligomer according to item 13, wherein the unreacted functional group is derived from at least one of 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4,4'-(ethyn-1,2-diyl)diphthalic dianhydride, or N-(4-aminophenyl)maleimide. (Item 16) The reactive oligomer according to item 13, comprising units derived from 4,4'-(4,4'-isopropylidenediphenoxy) bis(phthalic anhydride) (CAS 38103-06-9), 1,3-phenylenediamine, 4-methylethynylphthalic anhydride, and N-(4-aminophenyl) maleimide. (Item 17) The reactive oligomer according to item 13, comprising units derived from 2,3,3',4'-biphenyltetracarboxylic dianhydride, at least one aromatic diamine selected from the group consisting of 1,3-benzenediamine, 3,4'-oxydianiline, and 4,4'-oxydianiline, and at least one end-capper selected from the group consisting of 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride. (Item 18) The reactive oligomer according to any one of items 1 to 4, wherein the backbone is derived from polyaryletherketone. (Item 19) Formula (II):

Chemical formula

Chemical formula

Chemical formula

[0012] Now, let's refer to the drawings.

[0013] [Figure 1] The concepts of diffusion across interfaces, as well as entanglement and crosslinking of chains across interfaces, are illustrated. Figures 1A and 1B show diffusion and entanglement of high molecular weight, high-performance thermoplastic resins. Figures 1C and 1D show diffusion, entanglement, and chain elongation and crosslinking of reactive oligomers. [Figure 2] This graph shows the axial force (N) versus time (min) during melt polymerization of 1,3-phenylenediamine, 4,4'-oxydianiline, trimellitic anhydride, and 4-(phenylethynyl)phthalic anhydride in a twin-screw extruder. [Modes for carrying out the invention]

[0014] A reactive oligomer comprising a skeleton functionalized with at least one unreacted functional group that is heat-chain elongation and crosslinkable after the formation of the reactive oligomer, derived from at least one of polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole, or polybenzimidazole, wherein the reactive oligomer has a number average molecular weight (M) of 250 to 10,000 g / mol calculated using Carothers' equation. n A reactive oligomer having ). At least one unreacted functional group may be at least one of maleimide, 5-norbornene-2,3-dicarboximide, phthalonitrile, benzocyclobutene, biphenylene, cyanate ester, ketoethin, ethin, methylethin, phenylethin, propargyl ether, or benzoxazine.

[0015] Reactive oligomers may be desirable to be curable in stages over different temperature ranges, i.e., partially cured in a first temperature range and further cured in a second, higher temperature range. Therefore, in some embodiments, the reactive oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the formation of the reactive oligomer, the first unreacted functional group being self-reactive within a first temperature range, and the second unreacted functional group being self-reactive within a second temperature range, the second temperature range being higher than the first temperature range.

[0016] The reactive oligomer has a skeleton derived from at least one of the following: polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole, or polybenzimidazole. The skeleton can be linear or branched.

[0017] x-PAI In some embodiments, the reactive oligomers have a backbone derived from polyamide-imide and are defined herein as reactive polyamide-imide oligomers. Also disclosed herein are reactive polyamide-amic acid oligomers, reactive ammonium carboxylate salts, methods for producing reactive oligomers and reactive ammonium carboxylate salts, methods for processing reactive oligomers and reactive ammonium carboxylate salts, and articles produced from reactive oligomers and reactive ammonium carboxylate salts. The routes to polyamide-imide articles described herein eliminate the need for extended post-curing and time-consuming water removal steps. This is achieved by designing fully imidized reactive polyamide-imide oligomers that can be melt-processed and then subjected to short (at most a few hours) post-curing to obtain high molecular weight polyamide-imide via chain elongation / crosslinking. The latter reaction is carried out by carefully incorporating selected functional groups into the reactive polyamide-imide oligomer. These functional groups remain unreacted throughout the oligomerization process and are therefore available for post-curing. During post-curing, these functional groups can polymerize (chain elongation / crosslinking) via addition reactions without producing small molecule byproducts such as water.

[0018] The reactive polyamide-imide oligomers having unreacted functional groups described herein enable the production of stock shapes, injection-molded complex parts, 3D-printed parts, and fiber- or mineral-reinforced composites without any thickness limitations, as a water removal step from the final product is no longer required. These routes to polyamide-imide not only offer processing advantages (e.g., low viscosity, no residual water, no generated water) but also enable the design and manufacture of PAI articles that were previously impossible to produce.

[0019] M nHaving a molecular weight in the range of approximately 1,000 to 10,000 g / mol provides a lower melt viscosity and a lower processing temperature, thereby allowing melt processing to be carried out using conventional melt processing equipment. However, it is known that low molecular weight polymers (oligomers) have poor mechanical properties because they lack entanglement of polymer chains. By using crosslinkable monomers and / or crosslinkable end cappers in the preparation of reactive oligomers, the molecular weight can be increased either during insight thermal polymerization (e.g., during reaction injection molding) or during a post-heat treatment step (e.g., when preparing fiber-reinforced composites).

[0020] Reactive polyamide-imide oligomers with thermosetting groups offer several advantages. They are readily melt-processable, do not require extensive drying before processing, and do not require extensive post-heat treatment. Complex parts can be fabricated in a single step from reactive polyamide-imide oligomers. Curing can be performed at approximately 160 to 450°C, depending on the thermosetting groups. In some embodiments, curing is performed at approximately 300 to 450°C and can be completed in just 1 to 60 minutes, compared to several days for currently available grades of PAI. If the reactive polyamide-imide oligomer is fully imidized before melt processing, the difficult step of removing water from the stock shape or injection-molded part is not required. Advantageously, reactive polyamide-imide oligomers can be used for one-step injection molding of complex parts under conditions where the reactive oligomer cures instantaneously. Alternatively, the parts can be readily thermo-cured in approximately 1 to 60 minutes. Furthermore, the cured reactive polyamide-imide oligomer has a T g Furthermore, the elongation at fracture, strength at fracture, and toughness can be far superior to those of currently available PAIs.

[0021] The reactive polyamide-imide oligomer comprises a unit derived from at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end-capper, wherein the crosslinkable monomer or crosslinkable end-capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamide-imide oligomer, and the reactive polyamide-imide oligomer has an average molecular weight (M) of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol, calculated using Carothers' equation. n ) has.

[0022] The reactive polyamide-imide oligomer contains units derived from at least one aromatic diamine. The at least one aromatic diamine may have one of the following chemical structures. [ka] In some embodiments, at least one diamine is at least one of 1,3-phenylenediamine, 4,4'-oxydianiline, or 3,4'-oxydianiline.

[0023] Reactive polyamide-imide oligomers also contain at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent. A functional equivalent of a carboxylic acid is a functional group in which the carboxyl carbon atoms are in the same oxidation state, such as carboxylic acid esters, carboxylic acid halides, and carboxylic acid anhydrides. For example, a functional equivalent of trimellitic anhydride is a compound in which the substituted carbon atoms at positions 1, 2, and 4 of the benzene ring are in the same oxidation state. A functional equivalent of trimellitic anhydride is 4-chloroformylphthalic anhydride. At least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent contains at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent having a nearby (ortho) carboxylic acid or functional equivalent group, such as a phthalic anhydride group, thereby enabling the formation of a five-membered phthalimide ring within the reactive oligomer skeleton. At least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent may have one of the following chemical structures. The "functional equivalents" of carboxylic acids include compounds in which the carbon atoms of the carboxylic acid group are in the same oxidation state, and these include esters, acid chlorides, and their anhydrides. [ka] In some embodiments, at least one aromatic di-, tri-, or tetrafunctional carboxylic acid or its functional equivalent is at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthaloyl chloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride.

[0024] The reactive polyamide-imide oligomer also comprises at least one crosslinkable monomer or crosslinkable end capper having at least one unreacted functional group that is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, and which is capable of chain elongation and crosslinking after the formation of the reactive polyamide-imide oligomer. This functional group remains unreacted after the formation of the reactive polyamide-imide oligomer and is therefore available to participate in subsequent chain elongation, branching, and crosslinking reactions. The chain elongation, branching, and crosslinking that occur after the formation of the reactive polyamide-imide oligomer are known collectively as “curing.” As used herein, “crosslinking” is also a shorthand notation for any combination of chain elongation, branching, and crosslinking. Curing or crosslinking can be initiated by heat, chemical beam (electromagnetic) irradiation, and electron beam irradiation. In some embodiments, curing is initiated thermally. The unreacted functional groups involved in the subsequent chain elongation, branching, and crosslinking reactions are at least one of ethyne, methylethyne, phenylethyne, ketoethyne, propargyl ether, norbornene, maleimide, cyanate ester, phthalonitrile, benzocyclobutene, biphenylene, or benzoxazine. These unreacted functional groups are shown in Table 1 along with their chemical formulas, chemical names, and curing temperature ranges. At least one crosslinkable monomer or crosslinkable end capper may be two crosslinkable monomers or crosslinkable end cappers that are reactive over different temperature ranges. [Table 1]

[0025] In some embodiments, at least one unreacted functional group is derived from a monomer or end capper selected from the group consisting of the following: [Table 2] 1,2-diphenylethyne is a crosslinkable monomer. All other compounds are crosslinkable end cappers. In some embodiments, the crosslinkable monomer or crosslinkable end capper is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA), or 4,4'-(ethyn-1,2-diyl)diphthalic anhydride.

[0026] The reactive polyamide-imide oligomer may further comprise units derived from at least one non-crosslinkable end-capper, the non-crosslinkable end-capper being reactive with at least one aromatic diamine, or at least one di, tri, or tetrafunctional aromatic carboxylic acid, or its functional equivalent, but without unreacted functional groups that allow for chain elongation and crosslinking after the formation of the reactive polyamide-imide oligomer. The non-crosslinkable end-capper may be at least one of benzoic acid, benzoyl chloride, phthalic anhydride, or aniline.

[0027] Reactive polyamide-imide oligomers can be linear or branched. In some embodiments, reactive polyamide-imide oligomers are branched. Branching is obtained by using trifunctional monomers. Thus, in some embodiments, reactive polyamide-imide oligomers further comprise units derived from at least one of aromatic triamines, aromatic tricarboxylic acids, or aromatic tricarboxylic acid chlorides. An example of an aromatic triamine is 1,3,5-triaminobenzene, an example of an aromatic tricarboxylic acid is 1,3,5-benzenetricarboxylic acid, and an example of an aromatic tricarboxylic acid chloride is 1,3,5-benzenetricarboxylic acid chloride.

[0028] Number average molecular weight (M) used herein n) is a target value, not a measured value. The amounts of monomer and crosslinkable end capper used to prepare the reactive oligomer are calculated using Carothers' equation, Eq.(2). Using Eq.(1), the target

number

number

number

number

number

number

number

number

[0029] Polyamidoamidic acids are intermediates in the synthesis of polyamidoimides. As shown in Scheme 1 below, polyamidoimides are produced by the dehydration and cyclization of the intermediate polyamidoamidic acid (upper right structure). Scheme 1 [ka] Since polyamidomic acids are intermediates in the preparation of polyamidomides, reactive polyamidomide oligomers can have varying degrees of imidization, i.e., conversion of the polyamidomic acid intermediate to polyamidomide. Therefore, in some embodiments, reactive polyamidomide oligomers are derived from reactive polyamidomic acid oligomer intermediates by dehydration cyclization, resulting in imidization of approximately 80% to 100% of the amide acid groups in the reactive polyamidomic acid intermediate. When the degree of imidization falls within this range, the reactive polyamidomide oligomer is considered "fully imidized." Within this range, imidization can occur at 85%, 90%, 95%, 96%, 97%, 98%, and 99% or more and 100% or less of the polyamidomic acid groups.

[0030] Reactive polyamide-imide oligomers with less than 80% imidization may be useful in several applications. Therefore, in some embodiments, reactive polyamide-imide oligomers are derived from reactive polyamide-amic acid oligomer intermediates by dehydration cyclization, with approximately 20% to 80% of the amide acid groups in the reactive polyamide-amic acid intermediate being imidized. Imidization can be achieved within the ranges of 30%, 40%, 50%, 60%, and 70% to 80% of the amide acid groups.

[0031] Advantageously, the reactive polyamide-imide oligomer has a melt complex viscosity of about 1,000 to about 100,000 Pa·s at 360°C, measured by vibrational shear rheology between parallel plates at a heating rate of 10°C / min under N2, a frequency of 2 radians / second, and a strain of 0.03% to 1.0%. Within this range, the melt complex viscosity is due to the use of at least one diamine, at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, as well as crosslinkable or non-crosslinkable monomers and end cappers M used to produce the reactive polyamide oligomer. n It is also a function of type and relative quantity. Therefore, the molten complex viscosity as a function of shear rate, time, temperature, and heating rate can be adjusted by the selection of monomers and reactive and non-reactive end cappers, as well as their relative quantities. For example, the molten complex viscosity can be 2,000, 3,000, 4,000, or 5,000 Pa·s or higher and 90,000, 70,000, 50,000, or 30,000 Pa·s or lower. In some embodiments, the molten complex viscosity is about 5,000 to about 30,000 Pa·s at 360°C. In contrast, currently available PAIs have been reported to have a molten complex viscosity of 100,000 Pa·s at 2 radians / second.

[0032] Certain reactive polyamide-imide oligomers are disclosed herein. For example, the reactive polyamide-imide oligomers may include units derived from at least one anhydride selected from trimellitic anhydride and 4-chloroformylphthalic anhydride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4-methylethynylphthalic anhydride, and optionally 4-phenylethynylphthalic anhydride. Reactive polyamide-imide oligomers may also include units derived from at least one dianhydride selected from pyromellitic dihydrate and 4,4'-oxydiphthalic anhydride, at least one bifunctional aromatic compound selected from isophthalic acid and isophthaloyl chloride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4-methylethynylphthalic anhydride, and optionally 4-phenylethynylphthalic anhydride. Reactive polyamide-imide oligomers may also include units derived from at least one dianhydride selected from pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, at least one bifunctional aromatic compound selected from isophthalic acid and isophthaloyl chloride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4,4'-(ethyn-1,2-diyl)diphthalic anhydride, and at least one anhydride selected from phthalic anhydride, 4-methylethynylphthalic anhydride, or 4-phenylethynylphthalic anhydride.

[0033] x-PAI manufacturing method Reactive polyamide-imide oligomers can be produced by a method comprising copolymerizing at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper in the presence of a polar solvent to form a reactive polyamide-amic acid, and heating the reactive polyamide-amic acid oligomer at a temperature and time sufficient to produce a reactive polyamide-imide oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamide-imide oligomer. An exemplary production of a reactive polyamide-imide oligomer is provided in Scheme 2. Scheme 2 [ka] A- Synthesis of reactive polyamide-imide oligomers having only one type of crosslinkable end capper. B-Synthesis of reactive polyamide-imide oligomers having two different crosslinkable end cappers. C-Synthesis of reactive polyamide-imide oligomers from dihydrates (tetrafunctional) and diacid / diacid chlorides (bifunctional) having only one type of crosslinkable end capper. Synthesis of reactive polyamide-imide oligomers from D-crosslinkable monomers and non-crosslinkable end cappers, and Synthesis of reactive polyamide-imide oligomers from E-crosslinkable monomers and crosslinkable end cappers.

[0034] The temperature and time sufficient to produce reactive polyamide-imide oligomers are approximately 140°C to 220°C for approximately 1 minute to 120 minutes. As described above, reactive polyamide-imide oligomers are produced via the formation of reactive polyamide-amic acid oligomer intermediates. The temperature and time required to imidize the reactive polyamide-amic acid oligomer intermediate in this method depend on the presence or absence of a polar solvent, the specific reactive polyamide-imide oligomer being produced, and the desired degree of imidization. If imidization is carried out in the absence of a solvent, i.e., in the solid state with a pure reactive polyamide-imide acid oligomer, the temperature and time sufficient to produce the reactive polyamide-imide oligomers are approximately 220°C to 300°C for approximately 1 minute to 120 minutes. If imidization is carried out in the presence of a polar solvent, the temperature and time sufficient to produce the reactive polyamide-imide oligomers are approximately 140°C to 220°C for approximately 1 minute to 120 minutes.

[0035] Reactive polyamide-imide oligomers are prepared in the presence of a polar solvent that reduces the temperature range sufficient to produce the reactive oligomer. The polar solvent should have a boiling point of at least 150°C at 1 atm. The polar solvent can be at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, or sulfolane. In some embodiments, the polar solvent is N-methyl-2-pyrrolidone. The preparation method may further include removing the polar solvent from the polyamide-amic acid oligomer before heating the reactive polyamide-amic acid oligomer to a temperature and time sufficient to produce the reactive polyamide-imide oligomer.

[0036] There are different methods for imidizing reactive polyamide-imide oligomers. Reactive polyamide-imide oligomers can be prepared by adding toluene to a reactive polyamide-imide oligomer, as well as by azeotropic distillation of toluene and water. Reactive polyamide-imide oligomers can also be prepared by microwave irradiation of a reactive polyamide-imide oligomer. The imidizing agent can be acetic anhydride. The acidic byproduct produced by imidization is, for example, acetic anhydride when used. Therefore, a base, such as a tertiary amine, can be used. The tertiary amine can be, for example, pyridine or triethylamine. Thus, in some embodiments, reactive polyamide-imide oligomers are prepared by heating a reactive polyamide-imide oligomer in the presence of acetic anhydride and a catalytic amount of a tertiary amine.

[0037] Another method for producing reactive polyamide-imide oligomers is copolymerization in the presence of a phosphorylating agent and a catalytic amount of salt. In this method, the di, tri, or tetrafunctional carboxylic acid or its functional equivalent does not contain acid halides such as acid chlorides. The advantage of this method is that expensive acid chlorides are not required as starting materials. As an example, copolymerization is carried out in the presence of triphenylphosphite, a polar solvent such as NMP as the solvent, and a catalytic amount of salt such as LiCl or CaCl2. Heating at up to 120°C for 1.5–2 hours under nitrogen results in the formation of a reactive polyamide-amic acid oligomer and partial imidation to the corresponding reactive polyamide-imide oligomer. Further heating at up to 150°C for up to 5 hours under nitrogen with additional pyridine provides complete imidation.

[0038] Reactive polyamide-imide oligomers can also be produced by reactive extrusion. Therefore, a method for producing a reactive polyamide-imide oligomer involves reactive extruding at least one aromatic diamine or its activated derivative (e.g., diacetylated diamine), at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper at a temperature and time sufficient to produce a reactive polyamide-imide oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamide-imide oligomer.

[0039] Reactive extrusion can be carried out in the presence of a polar solvent. The polar solvent can be at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, or sulfolane. In some embodiments, the polar solvent is N-methyl-2-pyrrolidone. The polar solvent can dissolve the monomer, or partially dissolve the monomer, to form a fluid suspension or slurry of the monomer together with the oligomers and intermediates formed during reactive extrusion.

[0040] Reactive extrusion can be carried out in the presence of an acid catalyst to promote the imidation (dehydration cyclization) of amidic acid intermediates. If the acid catalyst is liquid under reactive extrusion conditions, it can also partially dissolve the monomer, forming a fluid suspension or slurry of monomers together with the oligomers and intermediates formed during reactive extrusion. If the acid catalyst is liquid, it can be removed by distillation through a vent port during reactive extrusion. In some embodiments, the acid catalyst is acetic acid, which is removed by distillation during reactive extrusion. Reactive extrusion can also be carried out in the presence of acetic anhydride, which is removed by distillation during reactive extrusion. To facilitate the removal of any of the water, HCl, polar solvents, acid catalysts, and acetic anhydride that are present or produced, reactive extrusion can be carried out in a melt extruder having multiple preset heating zones with vent ports or other means for removing these volatile substances.

[0041] Reactive polyamide-imide oligomers can also be produced by the "ammonium carboxylate salt" method. The ammonium carboxylate salt method involves mixing at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper with water or C 1-4 Heating in the presence of at least one alcohol for a temperature and time sufficient to form at least one reactive ammonium carboxylate salt, and excess water and C 1-4 The method comprises removing an alcohol and heating a reactive ammonium carboxylate salt at a temperature and for a time sufficient to form a reactive polyamide-imide oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine, or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamide-imide oligomer. 1-4The alcohol can be, for example, at least one of methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-butanol, or tert-butanol. In some embodiments, C 1-4 The alcohol is at least one of methanol or ethanol. The production of exemplary reactive polyamide-imide oligomers by the ammonium carboxylate salt method is described in Scheme 3 below. Scheme 3 [ka]

[0042] Anhydrides and diamines are dissolved in water or C 1-4 Heat at 70°C for 1 hour in at least one of alcohols, such as methanol or ethanol. This opens the ring of the anhydride and produces the corresponding alkyl dicarboxylate half-ester, such as methyl or ethyl half-ester. Then add water or C 1-4 At least one of the alcohols is removed by vacuum distillation. Thus, the reactive ammonium carboxylate salt is Ar-COO - and + A mixture of all possible combinations of H3N-Ar, where Ar represents an aryl group, and Ar-COO - is C 1-4It is an alkyl half-ester. Ammonium carboxylate salts (similar to nylon salts) can be converted to reactive polyamide-imide oligomers by polymerization and imidation, which can be achieved in various ways. Polymerization and imidation can be carried out by heating anhydrous reactive ammonium carboxylate salt in an inert atmosphere, preferably under pressure (0-300 MPa), to a maximum of 300°C to obtain reactive polyamide-imide oligomers. (Option 1 of Scheme 3) Heating can be carried out in a sealed container (Option 1 of Scheme 3), and / or in an extruder having aeration capacity for the removal of water and methanol or ethanol vapor. (Option 2 of Scheme 3) For example, reactive ammonium carboxylate salt can be heated stepwise in an inert atmosphere in a sealed container at 60, 100, and 200°C for 1 hour each, then cooled to 25°C, and then oligomerized in an extruder at 320-360°C to obtain reactive polyamide-imide oligomers. Thus, in some embodiments, the method involves reactive extrusion of reactive ammonium carboxylate salt at temperatures and times sufficient to form reactive polyamide-imide oligomers. Polymerization and imidation can also be carried out by dissolving the reactive ammonium carboxylate salt in at least one polar solvent such as water, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, or sulfolane, followed by heating to 160°C. (Option 3 of Scheme 3) Thus, in some embodiments, the method involves dissolving the reactive ammonium carboxylate salt in a polar solvent and then heating it for a temperature, pressure, and time sufficient to form a reactive polyamide-imide oligomer.

[0043] Alternatively, at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper can be mixed with water, methanol, ethanol, a methanol / water mixture, or an ethanol / water mixture, and then heated to 220°C in a pressure vessel (cylinder calorimeter or autoclave) to polymerize and imide the reactive ammonium carboxylic acid salt.

[0044] Advantageously, reactive ammonium carboxylate salts have a melt complex viscosity ranging from about 1 to about 100 Pa·s in a temperature range of about 80 to about 120°C, and their solubility in polar solvents such as NMP is up to 70–80% by weight at 60°C. The low melt complex viscosity and high solubility of reactive ammonium carboxylate salts enable high yields for the production of reactive polyamide-imide oligomers.

[0045] Polyamide acid As described above, reactive polyamidomide oligomers are intermediates in the production of reactive polyamidomide oligomers. Therefore, reactive polyamidomide oligomers contain units derived from at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, and have at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamidomide oligomer, and the reactive polyamidomide oligomer has an average molecular weight (M) of about 1,000 to about 10,000 g / mol, calculated using Carothers' equation. nReactive polyamide-imide oligomers and reactive polyamide-amic acid oligomers are closely related in that the reactive polyamide-amic acid oligomer is an intermediate in the formation of the corresponding reactive polyamide-imide oligomer. They differ only in the degree of imidization. The reactive polyamide-imide oligomers as defined herein may have more than 20% and less than 100% amide acid groups in the imidized reactive polyamide-amic acid intermediate, while 0% to about 20% of the amide acid groups are imidized in the reactive polyamide-amic acid oligomers as defined herein.

[0046] The descriptions of compositions applicable to the reactive polyamide-imide oligomers disclosed herein also apply to reactive polyamide-amic acid oligomers. Thus, the aromatic diamine may be at least one of 1,3-phenylenediamine, 4,4'-oxydianiline, or 3,4'-oxydianiline, and the difunctional, trifunctional, or tetrafunctional aromatic carboxylic acid, or its functional equivalent, may be at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthaloyl chloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride. Unreacted functional groups involved in subsequent chain elongation, branching, and crosslinking reactions may be at least one of ethyne, methylethyne, phenylethyne, ketoethyne, propargyl ether, norbornene, maleimide, cyanate ester, phthalonitrile, benzocyclobutene, biphenylene, or benzoxazine. These unreacted functional groups are shown in Table 1 along with their chemical formulas, chemical names, and curing temperature ranges. At least one crosslinkable monomer or crosslinkable end capper can be two crosslinkable monomers or crosslinkable end cappers that are reactive over different temperature ranges. In some embodiments, the crosslinkable monomer or crosslinkable end capper is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA), or 4,4'-(ethyn-1,2-diyl)diphthalic anhydride.

[0047] The reactive polyamidomidoic acid oligomer may further comprise units derived from at least one non-crosslinkable end-capper, the non-crosslinkable end-capper being reactive with at least one aromatic diamine, or at least one di, tri, or tetrafunctional aromatic carboxylic acid, or its functional equivalent, but without unreacted functional groups that allow for chain elongation and crosslinking after the formation of the reactive polyamidomidoic oligomer. The non-crosslinkable end-capper may be at least one of benzoic acid, benzoyl chloride, phthalic anhydride, or aniline.

[0048] Reactive polyamidoamic acid oligomers can be produced by a method comprising copolymerizing at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper in the presence of a polar solvent to form a reactive polyamidoamic acid oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamidoamic acid oligomer.

[0049] Reactive polyamidoamic acid oligomers are prepared in the presence of a polar solvent that reduces the temperature range sufficiently for the production of the reactive oligomers. The polar solvent should have a boiling point of at least 150°C at 1 atm. The polar solvent can be at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, or sulfolane. In some embodiments, the polar solvent is N-methyl-2-pyrrolidone. In some embodiments, the method further includes isolating the reactive polyamidoamic acid oligomer from the polar solvent.

[0050] Other skeletal structures Reactive oligomers may have a backbone derived from polymers other than polyamide-imides. In some embodiments, reactive oligomers have a backbone derived from polyimides and are defined herein as reactive polyimide oligomers. Reactive polyimide oligomers are given by formula (I): [ka] It can have, in the formula, Ar 1 The tetravalent aryl group represented by [ka] At least one of the following, Ar 2 The divalent aryl group represented by [ka] At least one of Y 1 and Z 1 However, each is independent of the others. [Table 3] Selected from the group consisting of, n is calculated in the range of approximately 250 to approximately 10,000 g / mol, preferably approximately 1,000 to approximately 10,000 g / mol. n It is selected to provide.

[0051] The molar ratio of monomers can be selected such that there is an excess of amine-functional end groups or carboxylic acid anhydride-functional end groups in the polyimide oligomer skeleton; that is, an amine-terminated or carboxylic acid anhydride-terminated polyimide oligomer skeleton can exist. If there is an excess of amine-terminated groups, an acid chloride-functional end capper (X=-COCl) or an anhydride end capper is selected. If there is an excess of anhydride-terminated groups, an amine-functional end capper (X=-NH2) is selected.

[0052] Reactive polyimide oligomers can be cured stepwise over different temperature ranges, i.e., it may be desirable for them to be partially cured in a first temperature range and further cured in a second, higher temperature range. Therefore, in some embodiments, the reactive polyimide oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the formation of the reactive oligomer, the first unreacted functional group being self-reactive in a first temperature range, and the second unreacted functional group being self-reactive in a second temperature range, the second temperature range being higher than the first temperature range. Thus, the reactive polyimide oligomer of formula (I) is Y 1 and Z 1 If the conditions are different, curing can be performed gradually over different temperature ranges.

[0053] In some embodiments, Ar 1 or Ar 2 At least one of these oligomers has an ether bond between the aryl groups, i.e., the reactive oligomer is a reactive polyetherimide oligomer. The unreacted functional group in the reactive polyetherimide oligomer can be at least one of methylethynyl, phenylethynyl, or maleimide. In particular, the unreacted functional group can be derived from at least one of 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4,4'-(ethyn-1,2-diyl)diphthalic dianhydride, or N-(4-aminophenyl)maleimide.

[0054] Exemplary reactive polyetherimide oligomers are disclosed herein. For example, the reactive polyetherimide oligomers can include units derived from 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (CAS 38103-06-9), 1,3-phenylenediamine, 4-methylethynylphthalic anhydride, and N-(4-aminophenyl)maleimide. The reactive polyetherimide oligomers can also include units derived from 2,3,3',4'-biphenyltetracarboxylic dianhydride, at least one aromatic diamine selected from 1,3-benzenediamine, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4-methylethynylphthalic anhydride, and optionally 4-phenylethynylphthalic anhydride.

[0055] The reactive oligomers can also have a backbone derived from polyaryl ether ketone and are referred to herein as reactive polyaryl ether ketone (PAEK) oligomers. For example, the reactive PAEK oligomers can be reactive polyether ether ketone oligomers or reactive polyether ketone oligomers. The reactive PAEK oligomers can have the formula (II):

Chemical formula

Chemical formula

Chemical formula

[0056] The molar ratio of the monomers can be selected such that there are excess fluorine functional end groups or phenol end groups in the PAEK oligomer backbone, i.e., fluorine-terminated or phenol-terminated PAEK oligomer backbones can be present. When there are excess fluorine functional end groups, a phenol functional end capper is selected. When there are excess phenol end groups, a fluorine functional end capper is selected. The unreacted functional groups in the reactive PAEK oligomer can be at least one of methyl ethynyl, phenyl ethynyl, or maleimide.

[0057] The reactive PAEK oligomer can be cured stepwise in different temperature ranges, i.e., it can be desirably partially cured in the first temperature range and further cured in the second, higher temperature range. Thus, in some embodiments, the reactive PAEK oligomer is functionalized with first and second unreacted functional groups that allow for thermal chain extension and crosslinking after formation of the reactive oligomer, the first unreacted functional group being self-reactive within the first temperature range, the second unreacted functional group being self-reactive within the second temperature range, and the second temperature range being higher than the first temperature range. Thus, the reactive PAEK oligomer of formula (II) is Y 2 and Z 2 are capable of stepwise curing in different temperature ranges when different.

[0058] The reactive oligomer can also have a backbone derived from polyethersulfone and is referred to herein as a reactive polyethersulfone oligomer. In some embodiments, the backbone is derived from polysulfone (PSU), polyphenylsulfone (PPSU), or polyethersulfone (PES) and is referred to herein as a reactive polysulfone oligomer, a reactive polyphenylsulfone oligomer, or a reactive polyethersulfone oligomer, respectively. The reactive polyethersulfone oligomer has the formula (III):

Chemical formula

Chemical formula

Chemical formula

[0059] The reactive polyethersulfone oligomer can be cured stepwise in different temperature ranges, i.e., it can be desirable to be partially cured in a first temperature range and further cured in a second, higher temperature range. Thus, in some embodiments, the reactive polyethersulfone oligomer is functionalized with first and second unreacted functional groups capable of thermal chain extension and crosslinking after the formation of the reactive oligomer, the first unreacted functional group is self-reactive within the first temperature range, the second unreacted functional group is self-reactive within the second temperature range, and the second temperature range is higher than the first temperature range. Thus, the reactive polyethersulfone oligomer of formula (III) is Y 3 and Z 3 can be cured stepwise in different temperature ranges when they are different.

[0060] The molar ratio of the monomers can be selected such that there are excess fluorine functional end groups or phenol end groups in the polyethersulfone oligomer backbone, i.e., a fluorine-terminated or phenol-terminated polyethersulfone oligomer backbone can be present. When there are excess fluorine functional end groups, a phenol functional endcapper is selected. When there are excess phenol end groups, a fluorine functional endcapper is selected. The unreacted functional groups in the reactive polyethersulfone oligomer can be at least one of methylethynyl, phenylethynyl, or maleimide.

[0061] Reactive oligomers may also have a skeleton derived from polyphenylene sulfide and are referred to herein as reactive polyphenylene sulfide oligomers. Reactive polyphenylene sulfide oligomers are given by formula (IV): [ka] It can have, where the divalent aryl group represented by Ar, [ka] And in the formula, W is [ka] And Y and Z are independent of each other. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] M is calculated such that n is in the range of approximately 250 to approximately 10,000 g / mol, preferably approximately 1,000 to approximately 10,000 g / mol. n It is selected to provide.

[0062] Reactive polyphenylene sulfide oligomers can be cured stepwise over different temperature ranges, i.e., they may be partially cured in a first temperature range and then further cured in a second, higher temperature range. Therefore, in some embodiments, the reactive polyphenylene sulfide oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the formation of the reactive oligomer, the first unreacted functional group being self-reactive within a first temperature range, and the second unreacted functional group being self-reactive within a second temperature range, the second temperature range being higher than the first temperature range. Thus, the reactive polyphenylene sulfide oligomer of formula (IV) can be cured stepwise over different temperature ranges when Y and Z are different.

[0063] The molar ratio of monomers can be selected such that the polyphenylene sulfide oligomer skeleton has an excess of fluorine-functional or phenol-terminal groups, i.e., a fluorine-terminated or phenol-terminated polyphenylene sulfide oligomer skeleton may exist. If an excess of fluorine-functional groups is present, a phenol-functional end capper is selected. If an excess of phenol-terminal groups is present, a fluorine-functional end capper is selected. The unreacted functional group in the reactive polyphenylene sulfide oligomer may be at least one of methylethynyl, phenylethynyl, or maleimide.

[0064] Reactive oligomers may also have a skeleton derived from polyamides and are referred to herein as reactive polyamide oligomers. Reactive polyamide oligomers are given by formula (Va) or (Vb): [ka] It can have, in the formula, A 1 and A 2 The divalent groups represented by are, independently, C4-C 12Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, or 1,2-, 1,3-, or 1,4-xylylene, Y 4 and Z 4 However, each is independent of the others. [Table 4] M is derived from an end capper selected from the group consisting of the following, and is calculated in the range of approximately 250 to approximately 10,000 g / mol, preferably approximately 1,000 to approximately 10,000 g / mol. n It is selected to provide.

[0065] The molar ratio of monomers can be selected such that there is an excess of amine-functional end groups or carboxylic acid anhydride-functional end groups in the polyamide oligomer skeleton; that is, an amine-terminated or carboxylic acid anhydride-terminated polyamide oligomer skeleton may exist. If there is an excess of amine-terminated groups, an acid chloride-functional end capper (X=-COCl) or an anhydride end capper is selected. If there is an excess of anhydride-terminated groups, an amine-functional end capper (X=-NH2) is selected.

[0066] Reactive polyamide oligomers can be cured stepwise over different temperature ranges, i.e., it may be desirable for them to be partially cured in a first temperature range and further cured in a second, higher temperature range. Therefore, in some embodiments, the reactive polyamide oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the formation of the reactive polyamide oligomer, the first unreacted functional group being self-reactive in a first temperature range, and the second unreacted functional group being self-reactive in a second temperature range, the second temperature range being higher than the first temperature range. Thus, the reactive polyamide oligomer of formula (Va) or (Vb) is Y 4 and Z 4If the properties differ, it is possible to cure it stepwise over different temperature ranges. The unreacted functional group in the reactive polyamide oligomer can be at least one of methylethynyl, phenylethynyl, or maleimide.

[0067] Reactive oligomers may also have a backbone derived from polyester and are referred to herein as reactive polyester oligomers. Reactive polyester oligomers are given by formula (VIa) or (VIb): [ka] It can have, in the formula, B 1 and B 2 The divalent groups represented by are, independently, C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, [ka] Y 5 and Z 5 However, each is independent of the others. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] Here, X is -OH, -NH2, -COOH, or -COCl, and n is calculated in the range of approximately 250 to approximately 10,000 g / mol, preferably approximately 1,000 to approximately 10,000 g / mol. n It is selected to provide.

[0068] The molar ratio of monomers can be selected such that the polyester oligomer skeleton has an excess of hydroxyl-functional end groups or either carboxylic acid or acid chloride-functional end groups; that is, a hydroxy-terminated or carboxylic acid or acid chloride-terminated polyester oligomer skeleton may exist. If an excess of hydroxyl-terminated groups is present, a carboxylic acid-(X=-COOH) or acid chloride-(X=-COCl) functional end capper is selected. If an excess of carboxylic acid-terminated groups is present, a hydroxyl-functional (X=-OH) or amine-functional (X=-NH2) end capper is selected.

[0069] Reactive polyester oligomers can be cured stepwise over different temperature ranges, i.e., they may be partially cured in a first temperature range and then further cured in a second, higher temperature range. Therefore, in some embodiments, the reactive polyester oligomer is functionalized with first and second unreacted functional groups that are capable of heat chain extension and crosslinking after the formation of the reactive polyester oligomer, the first unreacted functional group being self-reactive within a first temperature range, and the second unreacted functional group being self-reactive within a second temperature range, the second temperature range being higher than the first temperature range. Thus, the reactive polyester oligomer of formula (VIa) or (VIb) is Y 5 and Z 5 If the properties differ, it is possible to cure stepwise over different temperature ranges. The unreacted functional group in the reactive polyester oligomer can be at least one of methylethynyl, phenylethynyl, or maleimide.

[0070] Reactive oligomers may also have a backbone derived from polyesteramides and are referred to herein as reactive polyesteramide oligomers. Reactive polyesteramide oligomers are represented by formula (VIIa) or (VIIb): [ka] It can have, in the formula, D 1and D 2 The divalent groups represented by are, independently, C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, [ka] Y 6 and Z 6 However, each is independent of the others. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] Here, X is -OH, -NH2, -COOH, or -COCl, and n is calculated in the range of approximately 250 to approximately 10,000 g / mol, preferably approximately 1,000 to approximately 10,000 g / mol. n It is selected to provide.

[0071] The molar ratio of monomers can be selected such that the polyesteramide oligomer skeleton has an excess of hydroxyl-functional end groups or either carboxylic acid or acid chloride-functional end groups; that is, a hydroxy-terminated or carboxylic acid or acid chloride-terminated polyesteramide oligomer skeleton may exist. If an excess of hydroxyl-terminated groups is present, a carboxylic acid-(X=-COOH) or acid chloride-(X=-COCl) functional end capper is selected. If an excess of carboxylic acid-terminated groups is present, a hydroxyl-functional (X=-OH) or amine-functional (X=-NH2) end capper is selected.

[0072] Reactive polyesteramide oligomers can be cured stepwise over different temperature ranges, i.e., it may be desirable for them to be partially cured in a first temperature range and further cured in a second, higher temperature range. Therefore, in some embodiments, the reactive polyesteramide oligomer is functionalized with first and second unreacted functional groups that are capable of heat chain extension and crosslinking after the formation of the reactive polyesteramide oligomer, the first unreacted functional group being self-reactive in a first temperature range, and the second unreacted functional group being self-reactive in a second temperature range, the second temperature range being higher than the first temperature range. Thus, the reactive polyesteramide oligomer of formula (VIIa) or (VIIb) is Y 6 and Z 6 If the properties differ, it is possible to cure it stepwise over different temperature ranges. The unreacted functional group in the reactive polyesteramide oligomer can be at least one of methylethynyl, phenylethynyl, or maleimide.

[0073] composition Also disclosed are compositions comprising at least one reactive oligomer, including a mixture of reactive oligomers. In some embodiments, the composition comprises first and second reactive aromatic oligomers, wherein the first reactive oligomer is functionalized with a first unreacted functional group that is heat-chain extendable and crosslinkable after the formation of the first reactive oligomer, and the second reactive oligomer is functionalized with a second unreacted functional group that is heat-chain extendable and crosslinkable after the formation of the second reactive oligomer, wherein the first unreacted functional group is self-reactive within a first temperature range, and the second unreacted functional group is self-reactive within a second temperature range, the second temperature range being higher than the first temperature range. The use of combinations of first and second reactive oligomers having different unreacted functional groups provides a method for controlling the overall thermosetting range of a composition, for example, in a composition for additive manufacturing.

[0074] The composition may also contain a first and a second reactive oligomer, the first reactive oligomer having a first number average molecular weight (M nThe second reactive oligomer has a second number average molecular weight (M n ) has. For example, the composition has 3,000 g / mol M n A first reactive oligomer having and 8,000 g / mol M n The material comprises a second reactive oligomer having the same properties as both the first and second reactive oligomers, thereby obtaining different physical properties from both.

[0075] The composition may also include a reactive oligomer and a thermoplastic polymer. In some embodiments of the mixture of the reactive oligomer and thermoplastic polymer, the thermoplastic polymer may contain the same skeletal repeating units as at least one of the reactive oligomers. In these mixtures, for example, the reactive oligomer may be a reactive polyamide-imide oligomer, and the thermoplastic polymer may be a polyamide-imide polymer having the same skeletal repeating units but with a higher molecular weight. Thus, the reactive oligomer provides a useful method for modifying the physical properties of the thermoplastic polymer.

[0076] The composition may also include a reactive oligomer and an oligomer lacking unreacted functional groups that can be hot-chain extended. The oligomer lacking unreacted functional groups that can be hot-chain extended may also be present in concentrations of approximately 250 to 10,000 g / mol. n Preferably, M is about 1,000 to 10,000 g / mol. n It can have.

[0077] The composition may also contain at least one of the fillers or additives. Examples of fillers include carbon black, ceramic powder, mica, talc, silica, silicates, metal powders (Al, Cu, Ni, Fe), and chip fibers such as carbon, glass, paraamide, meta-aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), silicon carbide, boron, and alumina, as well as graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, and clay tablets.

[0078] It may be desirable to coat a layer of reactive oligomers onto an article containing a thermoplastic polymer, for example, a thermoplastic polymer having the same skeletal repeating units as the reactive oligomers. For example, the article may be a powder or filament for additive manufacturing containing a thermoplastic polymer. Thus, in some embodiments, the composition comprises a reactive oligomer coating on thermoplastic particles or filaments, optionally having the same skeletal repeating units as the thermoplastic polymer.

[0079] combination To improve thermomechanical properties, it may be desirable to compound reactive oligomers with other materials. Therefore, a method for compounding reactive oligomers involves mixing the reactive oligomer with at least one other component at a temperature and time sufficient to form a homogeneous molten mixture without crosslinking unreacted functional groups. The other component may be at least one of the following: a second reactive oligomer, an oligomer lacking unreacted functional groups that can undergo thermal chain extension and crosslinking, a thermoplastic polymer, a thermoplastic polymer having the same skeletal repeating units as the reactive oligomer, a filler, or an additive.

[0080] Manufacturing method Reactive oligomers and compositions containing reactive oligomers can be used to manufacture a variety of articles or components having useful properties. Therefore, a method for manufacturing an article involves heating the reactive aromatic oligomer at a temperature and time sufficient to shape and crosslink it. The temperature and time sufficient to shape and crosslink the reactive oligomer depends on the curing temperature range of the unreacted functional groups in the reactive oligomer that are capable of thermal chain extension, branching, and crosslinking. As can be seen from Table 1, a sufficient temperature is in the range of about 160 to about 450°C. It may be desirable to select a temperature such that the unreacted groups crosslink and the reactive oligomer cures in about 1 to about 60 minutes. Thus, a sufficient temperature and time is about 160 to about 450°C for about 1 to about 60 minutes. In some embodiments, a sufficient temperature and time is about 300 to about 450°C for about 1 to about 60 minutes, preferably about 350 to about 400°C for about 30 to about 60 minutes, for example, about 360°C for about 45 minutes. Articles manufactured by this method are also disclosed.

[0081] Methods for manufacturing reactive oligomers and compositions containing reactive oligomers may be additive manufacturing. Articles manufactured from reactive oligomers and compositions by additive manufacturing are also disclosed. Reactive oligomers and compositions are suitable for several additive manufacturing methods, including fused filament manufacturing (FFF), selective laser sintering (SLS), directed energy deposition (DED), laser-operated net forming (LENS), and composite additive manufacturing (CBAM).

[0082] In some embodiments of additive manufacturing, the method is molten filament manufacturing. Molten filament manufacturing comprises extruding a reactive oligomer or a composition thereof into adjacent horizontal layers such that interfaces exist between each layer, and exposing the layers to heat for a temperature and time sufficient to crosslink the reactive oligomers and form an article. In this method, the reactive oligomers migrate across the interfaces and covalently bond together, thereby forming an integrated article. Articles produced by molten filament manufacturing are also disclosed. Articles produced from reactive oligomers or compositions by molten filament manufacturing are also disclosed.

[0083] Fusible filament manufacturing uses material extrusion to print items, with the raw material being extruded through an extruder. In most fusible filament manufacturing 3D printers, the raw material is in the form of filament wound on a spool. The 3D printer liquefaction unit is the main component used in this type of printing. Extruders for these prints have a hot end and a cold end. The "cold" end is cooler than the hot end, but can still be in the temperature range of 100-250°C. The cold end uses gear or roller-based torque to pull the material from the spool and uses a stepping motor to control the feed rate. The cold end pushes the raw material into the hot end. The hot end consists of a heating chamber and a nozzle. The heating chamber receives the liquefaction unit and melts the raw material, converting it into a molten state. The molten material exits through a small nozzle, allowing it to form thin, sticky plastic beads that adhere to the material it is placed on. The nozzle typically has a diameter of 0.3mm to 1.0mm. Different types of nozzles and heating methods are used depending on the material being printed.

[0084] The filament can be in the form of a thin filament wound on a spool. In a variation of this method, the raw material is in the form of a rod instead of a filament. Because the rod is thicker than the filament, it can be pushed towards the hot end by means of a piston or roller, applying greater force and / or speed compared to conventional molten filament manufacturing.

[0085] A weld line is defined as the planar interface between adjacent layers of extruded material. Reactive polyamide-imide oligomers diffuse across the interface and react to rapidly increase polymer chain entanglement and network formation across the interface, thereby fusing the adjacent layers together. The weld line (interface) is further strengthened by chain elongation and / or crosslinking of the reactive aromatic oligomers entangled across the interface, resulting in improved z-axis strength.

[0086] In some embodiments of additive manufacturing, the method is selective laser sintering. Selective laser sintering involves selectively sintering and crosslinking particles of a reactive aromatic oligomer or a composition thereof with a laser to form an article. Similar to molten filament manufacturing, the reactive aromatic oligomers migrate across particle interfaces and covalently bond together, thereby forming a unified article. Articles produced by selective laser sintering are also disclosed. Selective laser sintering (SLS) involves the use of a high-power laser (e.g., a carbon dioxide laser) to fuse small particles of plastic, metal, ceramic, or glass powder into a mass having a desired three-dimensional shape. The laser selectively fuses the powder material by scanning cross-sections generated from a 3D digital description of the part (e.g., from a CAD file or scan data) on the surface of the powder bed. After scanning each cross-section, the powder bed is lowered by a layer thickness, a new layer of material is added on top, and the process is repeated until the part is complete. The SLS machine preheats the bulk powder material in the powder bed to a temperature below the powder's pour point, making it easier for the laser to raise the temperature of a selected region to the point where the powder softens and fuses together. Articles produced from reactive aromatic oligomers by selective laser sintering are also disclosed.

[0087] In contrast to several other additive manufacturing processes such as stereolithography (SLA) and fused filament fabrication (FFF), which often require special support structures to assemble overhang designs, SLS does not require a separate feeder for support material because the part being constructed is always surrounded by unsintered powder, thereby enabling the construction of shapes that were previously impossible. Also, because the machine's chamber is always filled with powder material, assembling multiple parts can be done by arranging multiple parts to fit within the machine's boundaries through a technique known as "nesting," which has the effect of significantly lowering the overall difficulty and cost of the design.

[0088] In addition processes such as FFF and SLS that use reactive oligomers as raw materials, the reactive oligomers rapidly diffuse across particle or filament interfaces, thereby increasing polymer chain entanglement and chain-chain interactions across the interface, fusing adjacent particles or filaments together. The interface is further strengthened by chain elongation and crosslinking of the reactive oligomers entangled across the interface.

[0089] The concepts of diffusion across the interface, as well as entanglement and crosslinking across the interface, are further illustrated by Figures 1A-1D. In Figures 1A and 1D, the oligomer or polymer on the left is in a solid state, and the oligomer or polymer on the right is in a molten state. Figure 1A shows a high molecular weight high-performance thermoplastic material on both sides of the interface. The high molecular weight polymer can diffuse across the interface in both directions and can form the entanglement shown in Figure 1B. However, T g It exceeds T m A long annealing period (several hours) at temperatures below a certain level is required.

[0090] Figure 1C shows the reactive oligomers on both sides of the interface. Low molecular weight reactive oligomers are T g It exceeds T mBelow this point, the material diffuses very rapidly across the interface in both directions, forming the chain entanglement shown in Figure 1D. This rapid diffusion results in a reduced annealing time. Chain elongation and crosslinking can also occur through unreacted functional groups. The net effect of faster diffusion, chain entanglement, and chain elongation and crosslinking is improved interlaminar strength, i.e., improved z-axis strength in FFF and SLS.

[0091] The processes of cross-interface entanglement, network formation, chain elongation, and crosslinking in the additive manufacturing described above can be optimized by using a reactive oligomer having two different reactive end groups in the same oligomer. The first unreacted functional group is self-reactive within a first temperature range, and the second unreacted functional group is self-reactive within a second temperature range, the second temperature range being higher than the first. For these reactive oligomers, the additive manufacturing method includes the steps of curing the first unreacted functional group within a first temperature range and curing the second unreacted functional group within a second temperature range. The first unreacted functional group, which is self-reactive over the first curing temperature range, can fix the initially crosslinked and printed structure in place. The partially crosslinked oligomer, which still has the second unreacted functional group, which is self-reactive over the second temperature range higher than the first temperature range, can diffuse across the interface and cure within the second curing temperature range, thereby constructing the molecular weight, crosslink density, and strength of the part. The interface can be between adjacent filaments, as in molten filament manufacturing, or between adjacent particles, as in selective laser sintering. Articles produced by addition manufacturing from a reactive oligomer having a first unreacted functional group that is self-reactive within a first temperature range and a second unreacted functional group that is self-reactive within a second temperature range are also disclosed.

[0092] The processes of cross-interface chain entanglement, network formation, chain elongation, and crosslinking in additive manufacturing can also be optimized by using two different reactive oligomers, each having a different reactive end group, such that the first unreacted functional group is self-reactive within a first temperature range and the second unreacted functional group is self-reactive within a second temperature range, where the second temperature range is higher than the first. For these reactive oligomers, the additive manufacturing method includes curing a first reactive oligomer functionalized with the first unreacted functional group within a first temperature range, and curing a second reactive oligomer functionalized with the second unreacted functional group within a second temperature range, where the second temperature range is higher than the second temperature range. The oligomer chain having the first unreacted functional group having a first curing temperature can be crosslinked first to fix the printed structure in place. An oligomer chain having a second unreacted functional group having a second curing temperature higher than a first curing temperature can diffuse across the interface and cure at the second curing temperature, thereby constructing the molecular weight, crosslink density, and strength of the part. The interface can be between adjacent filaments, as in molten filament manufacturing, or between adjacent particles, as in selective laser sintering. Also disclosed are articles produced by addition manufacturing from a first reactive oligomer having a first unreacted functional group that is self-reactive within a first temperature range, and a second reactive aromatic oligomer having a second unreacted functional group that is self-reactive within a second temperature range.

[0093] Reactive polyamide-imide oligomers and reactive polyamide-amic acid oligomers, manufacturing methods using reactive oligomers, and articles made from reactive oligomers have several advantageous properties. High molecular weight PAIs currently available can have relatively high levels of amidic acid groups because they have a sufficiently low complex viscosity to be melt-workable. The presence of amidic acid groups can make PAIs extremely hygroscopic; therefore, pre-treatment drying is also required. Manufacturing and processing of currently available PAIs, configured as shown in Figure 1, involves imidization of polyamide-amic acid stock forms or injection-molded parts, requiring prolonged heat post-treatment to remove water resulting from the conversion of amidic acid groups to imide groups. Machined PAI parts are also subjected to multi-day heat treatment protocols after machining. A typical curing schedule recommended by manufacturers is 1 day at 375°F (191°C), 1 day at 425°F (218°C), 1 day at 475°F (246°C), and 5 days at 500°F (260°C) for a total of 8 days. In contrast, curing of reactive polyamide-imide oligomers at approximately 300–450°C can be completed in as little as 1–60 minutes. Advantageously, this reduction in post-heat treatment time results in a significant decrease in manufacturing cycle time and cost.

[0094] M nReactive polyamide-imide oligomers having a compound phosphate structure (PAI) are advantageous in that they exhibit a melt complex viscosity of approximately 1,000 to 100,000 Pa·s at 360°C, and in particular, approximately 5,000 to 30,000 Pa·s at 360°C. In contrast, currently available PAIs have been reported to have a melt complex viscosity of approximately 1,000,000 Pa·s at 2 radians / second. Compared to currently available PAIs, the low melt complex viscosity of fully imidized reactive polyamide-imide oligomers is unexpected. In contrast to the low melt complex viscosity obtained, the alternating combination of rigid phthalimide skeletal units and aromatic amide units, which are expected to have strong hydrogen bonding like polyaramids, is expected to result in a high melting point and high melt complex viscosity, even in reactive polyamide-imide oligomers. Advantageously, with a melt complex viscosity in the range of approximately 1,000 to 100,000 Pa·s at 360°C, melt processing can be carried out using conventional melt processing equipment, and ready-to-use injection-molded parts, films, fibers, and melt-processable high-temperature adhesives can be produced. Furthermore, compared to polyamidoamic acid polymers, fully imidized reactive polyamidoimide oligomers are less hygroscopic and may be insoluble in polar solvents such as DMF, NMP, and DMAc, depending on the monomer used and the reactive and non-reactive end cappers.

[0095] Advantageously, the thermosetting temperature range and post-curing thermomechanical properties can be controlled by the selection of the skeletal monomer, crosslinkable monomer, crosslinkable end capper, and non-crosslinkable end capper. Furthermore, improved thermomechanical properties can be obtained using the reactive polyamide-imide oligomer of the present invention. This is referred to in Example 1C below, which uses 5,000 g / mol M, where both reactive end groups are phenylethine. n It is a reactive polyamide-imide oligomer having [a specific characteristic]. A film made from the reactive polyamide-imide oligomer and cured at 370°C for 1 hour is [a specific characteristic]. g It has the T of PAI film currently available. g It is approximately 46°C higher than that. As will be mentioned in Example 2 below, this is with 5,000 g / mol Mn and a reactive polyamide-imide oligomer having mixed reactive end groups (50 / 50 methylethine / phenylethine). A film made from the reactive polyamide-imide oligomer and cured at 370°C for 1 hour was 301°C T g It had 94.3 MJ / m². 3 It possessed toughness. In contrast, currently available PAI is approximately 10 MJ / m 3 It possesses only the toughness of [unspecified material]. Therefore, the toughness of PAI films made from this reactive polyamide-imide oligomer can be almost 10 times higher than that of PAI made from currently available PAI. Compared to currently commercially available PAI, T g Furthermore, both the strength at fracture and the elongation at fracture have increased.

[0096] Advantageously, the low melt complex viscosity of reactive polyamide-imide oligomers compared to high molecular weight polyamide-imide polymers makes them ideal for preparing fiber-reinforced composites such as glass, carbon, and aramid fiber-reinforced composites. Solution-based prepreg methods, melt impregnation methods, and melt drawing methods can all be used. High molecular weight polyamide-imide acids have been used to prepare fire / resin prepregs and composites. However, obtaining sufficient melt flow to melt and solidify the polyamide-imide acid prepreg into a composite panel would be difficult. Also, removing water from the composite panel during the imidation of the polyamide-imide acid can be difficult. This means that achieving voids of less than 2%, which is considered acceptable, would be difficult. Alternatively, high molecular weight polyamide-imide acids can be converted to high molecular weight polyamide-imides at the prepreg stage, and the polyamide-imide prepreg can be cemented into the composite. The even higher melt complex viscosity of high molecular weight polyamide-imides can make it difficult to obtain sufficient melt flow under pressure to cement the prepreg into a composite panel of acceptable quality. Therefore, the relatively low melt complex viscosity of reactive polyamide-imide oligomers offers advantages over both high molecular weight polyamide-imides and high molecular weight polyamide-amic acids in the production of fiber-reinforced composites.

[0097] In contrast to high molecular weight polyamide-imide polymers, the low melt complex viscosity of reactive polyamide-imide oligomers also makes them ideal for 3D printing applications. Reactive polyamide-imide oligomers can be available in filament, rod, or powder form.

[0098] This disclosure is further illustrated by the following aspects of this disclosure, which are not intended to limit the scope of the claims.

[0099] Embodiments based on these claims Embodiment 1. A reactive oligomer comprising a skeleton derived from at least one of polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole, or polybenzimidazole, and functionalized with at least one unreacted functional group that allows for thermal chain extension and crosslinking after the formation of the reactive oligomer, wherein the reactive oligomer has a number average molecular weight (M) of about 250 to about 10,000 g / mol, calculated using Carothers' equation. n A reactive oligomer having ).

[0100] Embodiment 2. The reactive oligomer of Embodiment 1, wherein at least one unreacted functional group is at least one of maleimide, 5-norbornene-2,3-dicarboximide, phthalonitrile, benzocyclobutene, biphenylene, cyanate ester, ketoethin, ethin, methylethin, phenylethin, propargyl ether, or benzoxazine.

[0101] Embodiment 3. A reactive oligomer according to Embodiment 1 or 2, which is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the formation of the reactive oligomer, wherein the first unreacted functional group is self-reactive within a first temperature range, the second unreacted functional group is self-reactive within a second temperature range, and the second temperature range is higher than the first temperature range.

[0102] Embodiment 4. A reactive oligomer according to any of Embodiments 1 to 3, wherein the skeleton is linear or branched.

[0103] Embodiment 5. A reactive oligomer from any of Embodiments 1 to 4, wherein the skeleton is derived from a polyamide-imide.

[0104] Embodiment 6. At least one unreacted functional group, [Table 5] A reactive oligomer according to embodiment 5, derived from a monomer or end capper selected from the group consisting of the following.

[0105] Embodiment 7. A reactive oligomer of Embodiment 5, comprising a unit derived from at least one anhydride selected from trimellitic anhydride and 4-chloroformylphthalic anhydride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4-methylethynylphthalic anhydride, and optionally 4-phenylethynylphthalic anhydride.

[0106] Embodiment 8. A reactive oligomer of Embodiment 5, comprising a unit derived from at least one dianhydride selected from pyromellitic dihydrate and 4,4'-oxydiphthalic anhydride, at least one bifunctional aromatic compound selected from isophthalic acid and isophthaloyl chloride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4-methylethynylphthalic anhydride, and optionally 4-phenylethynylphthalic anhydride.

[0107] Embodiment 9. A reactive oligomer of Embodiment 5, comprising units derived from at least one dianhydride selected from pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, at least one bifunctional aromatic compound selected from isophthalic acid and isophthaloyl chloride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4,4'-(ethyn-1,2-diyl)diphthalic anhydride, and at least one anhydride selected from phthalic anhydride, 4-methylethynylphthalic anhydride, and 4-phenylethynylphthalic anhydride.

[0108] Embodiment 10. A reactive oligomer according to any of Embodiments 1 to 4, wherein the skeleton is derived from polyimide.

[0109] Appearance 11. Formula (I): [ka] It has, in the formula, Ar 1 The tetravalent aryl group represented by [ka] At least one of the following, Ar 2 The divalent aryl group represented by [ka] At least one of Y 1 and Z 1 However, each is independent of the others. [Table 6] Derived from an end capper selected from the group consisting of, where n is calculated in the range of approximately 250 to approximately 10,000 g / mol. n A reactive oligomer of embodiment 10, selected to provide.

[0110] Embodiment 12. Y and Z are different reactive oligomers of Embodiment 11.

[0111] Embodiment 13. A reactive oligomer from any of Embodiments 10 to 12, wherein the polyimide is a polyetherimide.

[0112] Embodiment 14. The reactive oligomer of Embodiment 13, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide.

[0113] Embodiment 15. A reactive oligomer of Embodiment 13, wherein the unreacted functional group is derived from at least one of 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4,4'-(ethyn-1,2-diyl)diphthalic dianhydride, or N-(4-aminophenyl)maleimide.

[0114] Aspect 16. A reactive oligomer of Aspect 13 comprising units derived from 4,4'-(4,4'-isopropylidene diphenoxy)bis(phthalic anhydride) (CAS 38103-06-9), 1,3-phenylenediamine, 4-methylethynylphthalic anhydride, and N-(4-aminophenyl)maleimide.

[0115] Aspect 17. A reactive oligomer of Aspect 13 comprising a unit derived from 2,3,3',4'-biphenyltetracarboxylic dianhydride, at least one aromatic diamine selected from 1,3-benzenediamine, 3,4'-oxydianiline, and 4,4'-oxydianiline, 4-methylethynylphthalic anhydride, and optionally 4-phenylethynylphthalic anhydride.

[0116] Embodiment 18. A reactive oligomer according to any of Embodiments 1 to 4, wherein the skeleton is derived from a polyaryl ether ketone.

[0117] Appearance 19. Formula (II): [ka] It has, in the formula, Ar 3 The divalent aryl group represented by [ka] At least one of the following, in the formula, S 1 S 2 S 3 , and S 4 However, each is independent of H, F, Cl, Br, and C. 1-6 Selected from the group consisting of linear or branched alkyls and phenyls, W is [ka] And Ar 4 The divalent aryl group represented by [ka] At least one of Y 2 and Z 2 However, each is independent of the others. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] And A is, [ka] And M is calculated when n is in the range of approximately 250 to approximately 10,000 g / mol. n A reactive oligomer of embodiment 18, selected to provide.

[0118] Appearance 20.Y 3 and Z 3However, a different reactive oligomer of embodiment 19.

[0119] Embodiment 21. A reactive oligomer of Embodiment 19 or 20, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide.

[0120] Embodiment 22. A reactive oligomer from any of Embodiments 1 to 4, wherein the skeleton is derived from a polyethersulfone.

[0121] Embodiment 23. The reactive oligomer of Embodiment 22, wherein the skeleton is derived from polysulfone (PSU), polyphenylsulfone (PPSU), or polyethersulfone (PES).

[0122] Appearance 24. Formula (III): [ka] It has, in the formula, Ar 5 The divalent aryl group represented by [ka] And Ar 6 The divalent aryl group represented by formula (IIIa): [ka] It has Y 3 and Z 3 However, each is independent of the others. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] And M is calculated when n is in the range of approximately 250 to approximately 10,000 g / mol. nA reactive oligomer of embodiment 22, selected to provide.

[0123] Appearance 25.Y 3 and Z 3 However, a different reactive oligomer of embodiment 24.

[0124] Embodiment 26. A reactive oligomer of Embodiment 22 or 23, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide.

[0125] Embodiment 27. A reactive oligomer from any of Embodiments 1 to 4, wherein the skeleton is derived from a polyphenylene sulfide.

[0126] Apparatus 28. Equation (IV): [ka] It has a divalent aryl group represented by Ar in the formula, [ka] And in the formula, W is [ka] And Y and Z are independent of each other. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] And M is calculated when n is in the range of approximately 250 to approximately 10,000 g / mol. n A reactive oligomer of embodiment 27, selected to provide.

[0127] Embodiment 29. Y and Z are different reactive oligomers of Embodiment 28.

[0128] Embodiment 30. The reactive oligomer of Embodiment 27, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide.

[0129] Embodiment 31. A reactive oligomer from any of Embodiments 1 to 4, wherein the skeleton is derived from a polyamide.

[0130] Appearance 32. Equation (Va) or (Vb): [ka] It has, in the formula, A 1 and A 2 The divalent groups represented by are, independently, C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, or 1,2-, 1,3-, or 1,4-xylylene, Y 4 and Z 4 However, each is independent of the others. [Table 7] Derived from an end capper selected from the group consisting of, where n is calculated in the range of approximately 250 to approximately 10,000 g / mol. n A reactive oligomer of embodiment 31, selected to provide.

[0131] Appearance 33.Y 4 and Z 4 Reactive oligomers of embodiment 32, which differ from the other.

[0132] Embodiment 34. The reactive oligomer of Embodiment 31, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide.

[0133] Embodiment 35. A reactive oligomer from any of Embodiments 1 to 4, wherein the skeleton is derived from polyester.

[0134] Appearance 36. Formula (VIa) or (VIb): [ka] It has, in the formula, B 1 and B 2 The divalent groups represented by are, independently, C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, [ka] Y 5 and Z 5 However, each is independent of the others. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] And X is -OH, -NH2, -COOH, or -COCl, n is calculated in the range of approximately 250 to approximately 10,000 g / mol. n A reactive oligomer of embodiment 35, selected to provide.

[0135] Appearance 37.Y 5 and Z 5 However, a different reactive oligomer of embodiment 36.

[0136] Embodiment 38. The reactive oligomer of Embodiment 35, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide.

[0137] Embodiment 39. A reactive oligomer from any of Embodiments 1 to 4, wherein the skeleton is derived from a polyesteramide.

[0138] Appearance 40. Formula (VIIa) or (VIIb): [ka] It has, in the formula, D 1 and D 2 The divalent groups represented by are, independently, C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, [ka] Y 6 and Z 6 However, each is independent of the others. [ka] Derived from an end capper selected from the group consisting of, where D is [ka] And X is -OH, -NH2, -COOH, or -COCl, n is calculated in the range of approximately 250 to approximately 10,000 g / mol. n A reactive oligomer of embodiment 39, selected to provide.

[0139] Appearance 41.Y 6 and Z 6 However, a different reactive oligomer of embodiment 40.

[0140] Embodiment 42. The reactive oligomer of Embodiment 40, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl, or maleimide.

[0141] Embodiment 43. A composition comprising at least one reactive oligomer from any of Embodiments 1 to 42.

[0142] Embodiment 44. The composition of Embodiment 43, comprising a first and a second reactive oligomer, wherein the first reactive oligomer is functionalized with a first unreacted functional group that can undergo heat chain extension and crosslinking after the formation of the first reactive oligomer, the second reactive oligomer is functionalized with a second unreacted functional group that can undergo heat chain extension and crosslinking after the formation of the second reactive oligomer, the first unreacted functional group is self-reactive within a first temperature range, the second unreacted functional group is self-reactive within a second temperature range, and the second temperature range is higher than the first temperature range.

[0143] Embodiment 45. A first and second reactive oligomer comprising a first reactive oligomer having a first number average molecular weight (M n ) has a second reactive oligomer, and the second number average molecular weight (M n A composition according to embodiment 43, having )

[0144] Embodiment 46. A composition from any of Embodiments 43 to 45, further comprising a thermoplastic polymer.

[0145] Embodiment 47. The composition of Embodiment 46, wherein the thermoplastic polymer comprises at least one reactive oligomer and the same skeletal repeating units.

[0146] Embodiment 48. The composition of Embodiment 43 or 47, further comprising an oligomer lacking unreacted functional groups that is capable of thermal chain extension and crosslinking.

[0147] Embodiment 49. A composition from any of Embodiments 43 to 48, further comprising at least one filler or additive.

[0148] Embodiment 50. A composition comprising a reactive oligomer from any of Embodiments 1 to 42 coated on thermoplastic polymer particles or filaments.

[0149] Embodiment 51. The composition of Embodiment 50, wherein the thermoplastic polymer contains the same skeletal repeating units as the reactive oligomer.

[0150] Embodiment 52. A method for formulating any of the compositions from Embodiments 43 to 51, comprising mixing the components of the composition at a sufficient temperature and time to form a homogeneous molten mixture without crosslinking unreacted functional groups.

[0151] Embodiment 53. A method for manufacturing an article, comprising heating any composition from Embodiments 43 to 51 at a temperature and for a time sufficient to shape and crosslink a reactive oligomer.

[0152] Embodiment 54. The manufacturing method of Embodiment 53, wherein the method is additive manufacturing.

[0153] Embodiment 55. An additive manufacturing method according to Embodiment 54, wherein the method is fused filament manufacturing (FFF), selective laser sintering (SLS), directed energy deposition (DED) laser-operated net forming (LENS), or composite additive manufacturing (CBAM).

[0154] Embodiment 56. An addition method using the reactive oligomer of Embodiment 3, comprising the steps of curing a first unreacted functional group within a first temperature range and curing a second unreacted functional group within a second temperature range.

[0155] Embodiment 57. An addition manufacturing method using the composition of Embodiment 44, comprising the steps of curing a first reactive oligomer functionalized with a first unreacted functional group within a first temperature range, and curing a second reactive oligomer functionalized with a second unreacted functional group within a second temperature range.

[0156] Embodiment 58. The manufacturing method of Embodiment 54, wherein the method is a molten filament manufacturing method, and the method comprises extruding a composition into adjacent horizontal layers such that interfaces exist between each layer, and crosslinking reactive oligomers by exposing the layers to heat for a sufficient temperature and time to form an article.

[0157] Embodiment 59. The manufacturing method of Embodiment 54, wherein the method is selective laser sintering, and the method comprises selectively sintering and crosslinking particles of a composition with a laser to form an article.

[0158] Appearance 60. An article manufactured by any of the methods described in Appearances 53 to 58.

[0159] Embodiment 101. A reactive polyamide-imide oligomer comprising a unit derived from at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end-capper, wherein the crosslinkable monomer or crosslinkable end-capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamide-imide oligomer, and the reactive polyamide-imide oligomer has an average molecular weight (M) of about 1,000 to about 10,000 g / mol, calculated using Carothers' equation. n A reactive polyamide-imide oligomer having )

[0160] Embodiment 102. The reactive polyamideimide oligomer of Embodiment 101, wherein the reactive polyamideimide oligomer is derived from a reactive polyamideamic acid oligomer intermediate by dehydration cyclization, and approximately 80% to 100% of the amide acid groups in the reactive polyamideamic acid intermediate are imidized.

[0161] Embodiment 103. The reactive polyamideimide oligomer of Embodiment 101, wherein the reactive polyamideimide oligomer is derived from a reactive polyamideamic acid oligomer intermediate by dehydration cyclization, and approximately 20% or more and 80% or less of the amide acid groups in the reactive polyamideamic acid intermediate are imidized.

[0162] Embodiment 104. A reactive polyamide-imide oligomer from any of Embodiments 101 to 103, wherein the crosslinkable monomer or crosslinkable end capper has one unreacted functional group that can undergo hot chain extension and crosslinking after the formation of the reactive polyamide-imide oligomer.

[0163] Embodiment 105. A reactive polyamide-imide oligomer from any of Embodiments 101 to 104, wherein at least one crosslinkable monomer or crosslinkable end capper is at least one crosslinkable end capper.

[0164] Embodiment 106. A reactive polyamide-imide oligomer from any of Embodiments 101 to 105, wherein at least one aromatic diamine is two aromatic diamines.

[0165] Embodiment 107. A reactive polyamide-imide oligomer from any of Embodiments 101 to 106, wherein at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent is two aromatic di, tri, or tetrafunctional carboxylic acids or their functional equivalents.

[0166] Embodiment 108. A reactive polyamide-imide oligomer from any of Embodiments 101 to 107, prepared by a process comprising the simultaneous stepwise growth polymerization of at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper.

[0167] Embodiment 109. Aromatic diamines, [ka] A reactive polyamide-imide oligomer in any of embodiments 101 to 108, which is at least one of the above.

[0168] Embodiment 110. A reactive polyamide-imide oligomer from any of Embodiments 101 to 109, wherein the aromatic diamine is at least one of 1,3-phenylenediamine, 4,4'-oxydianiline, or 3,4'-oxydianiline.

[0169] Embodiment 111. A bifunctional, tertifunctional, or tetrafunctional aromatic carboxylic acid, or its functional equivalent, [ka] A reactive polyamide-imide oligomer in any of embodiments 101 to 110, which is at least one of the above.

[0170] Embodiment 112. A reactive polyamide-imide oligomer from any of Embodiments 101 to 111, wherein the aromatic difunctional, trifunctional, or tetrafunctional carboxylic acid or its functional equivalent is at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthaloyl chloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride.

[0171] Embodiment 113. A reactive polyamide-imide oligomer from any of Embodiments 101 to 112, wherein the unreacted functional group is at least one of ethyne, methylethyne, phenylethyne, ketoethyne, propargyl ether, norbornene, maleimide, cyanate ester, phthalonitrile, benzocyclobutene, biphenylene, or benzoxazine.

[0172] Appearance 114. A crosslinkable monomer or crosslinkable end capper, [Table 8] A reactive polyamide-imide oligomer in any of embodiments 101 to 113, which is at least one of the above.

[0173] Embodiment 115. A reactive polyamide-imide oligomer from any of Embodiments 101 to 114, wherein the crosslinkable monomer or crosslinkable end capper is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA), or 4,4'-(ethyn-1,2-diyl)diphthalic anhydride.

[0174] Embodiment 116. A reactive polyamide-imide oligomer from any of Embodiments 101 to 115, comprising two crosslinkable monomers or crosslinkable end cappers that are reactive in different temperature ranges.

[0175] Embodiment 117. A reactive polyamide-imide oligomer from any of Embodiments 101 to 116, further comprising a unit derived from at least one non-crosslinkable end-capper, wherein the non-crosslinkable end-capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent.

[0176] Embodiment 118. The reactive polyamide-imide oligomer of Embodiment 117, wherein the non-crosslinkable end capper is at least one of benzoic acid, benzoyl chloride, phthalic anhydride, or aniline.

[0177] Embodiment 119. A reactive polyamide-imide oligomer from any of Embodiments 101 to 118, further comprising a unit derived from at least one of an aromatic triamine, an aromatic tricarboxylic acid, or an aromatic tricarboxylic acid chloride.

[0178] Embodiment 120. A reactive polyamide-imide oligomer from any of Embodiments 101 to 119, wherein the reactive polyamide-imide oligomer has a melt complex viscosity of about 1,000 to about 100,000 Pa·s at 360°C, as measured by vibrational shear rheology between parallel plates at a heating rate of 10°C / min under N2, a frequency of 2 radians / second, and a strain of 0.03% to 1.0%.

[0179] Embodiment 121. A reactive polyamide-imide oligomer, [ka] An aromatic diamine selected from at least one of the following, [ka] A difunctional, trifunctional, or tetrafunctional aromatic carboxylic acid or its functional equivalent, selected from at least one of the following, [Table 9] A reactive polyamide-imide oligomer comprising a crosslinkable monomer or crosslinkable end capper selected from at least one of the following, and a unit derived from there.

[0180] Embodiment 122. A reactive polyamide-imide oligomer comprising a unit derived from an aromatic diamine selected from at least one of 1,3-phenylenediamine, 4,4'-oxydianiline, or 3,4'-oxydianiline; a difunctional, trifunctional, or tetrafunctional aromatic carboxylic acid or its functional equivalent selected from at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthaloyl chloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride; and a crosslinkable monomer or crosslinkable end capper selected from at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA), or 4,4'-(ethyn-1,2-diyl)diphthalic anhydride.

[0181] Embodiment 123. A method for producing a reactive polyamide-imide oligomer, one of Embodiments 101 to 122, comprising: copolymerizing at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper in the presence of a polar solvent to form a reactive polyamide-imide acid oligomer; and heating the reactive polyamide-imide acid oligomer at a temperature and time sufficient to produce a reactive polyamide-imide oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine, or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamide-imide oligomer.

[0182] Embodiment 124. The manufacturing method of Embodiment 123, wherein the temperature and time sufficient to produce the reactive polyamide-imide oligomer are approximately 140°C to approximately 220°C for approximately 1 minute to approximately 120 minutes.

[0183] Embodiment 125. A method for producing the product according to Embodiment 123 or 124, wherein the polar solvent is at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, or sulfolane.

[0184] Embodiment 126. A method of production from any one of Embodiments 123 to 125, further comprising removing a polar solvent from the polyamidoami acid oligomer before heating the reactive polyamidoimide oligomer to a temperature and time sufficient to produce a reactive polyamidoimide oligomer.

[0185] Embodiment 127. The method for producing the reactive polyamide-imide oligomer, wherein the temperature and time sufficient to produce the reactive polyamide-imide oligomer are approximately 220°C to approximately 300°C for approximately 1 minute to approximately 120 minutes.

[0186] Embodiment 128. A method for producing a product from any of Embodiments 123 to 127, wherein the method further comprises adding toluene to a reactive polyamidoamic acid oligomer, and azeotropic distillation of toluene and water.

[0187] Embodiment 129. A method for producing a reactive polyamidoamic acid oligomer in the presence of acetic anhydride and a catalytic amount of a tertiary amine, the method comprising any one of Embodiments 123 to 127.

[0188] Embodiment 130. A method for producing a reactive polyamidoamic acid oligomer, any one of Embodiments 123 to 127, wherein the method further comprises microwave irradiation of the reactive polyamidoamic acid oligomer.

[0189] Embodiment 131. A method for producing copolymerization in any of Embodiments 123 to 127, wherein copolymerization is carried out in the presence of a phosphorylating agent and a catalytic amount of salt.

[0190] Aspect 132. A method for producing a reactive polyamide-imide oligomer from any of Aspects 1 to 16, wherein the method comprises: at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper, with water or C 1-4 Heating in the presence of at least one alcohol for a temperature and time sufficient to form at least one reactive ammonium carboxylate salt, and optionally adding excess water or C 1-4 A method for producing a reactive polyamide-imide oligomer, comprising: removing an alcohol; and heating a reactive ammonium carboxylate salt at a temperature and for a time sufficient to form a reactive polyamide-imide oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine, or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamide-imide oligomer.

[0191] Embodiment 133. The method of Embodiment 132, wherein the method comprises reactive extrusion of a reactive ammonium carboxylate salt at a temperature and time sufficient to form a reactive polyamide-imide oligomer.

[0192] Embodiment 134. The method of Embodiment 26, wherein the method comprises dissolving a reactive ammonium carboxylate salt in a polar solvent before heating to a temperature, pressure, and time sufficient to form a reactive polyamide-imide oligomer.

[0193] Embodiment 135. A method for producing a reactive polyamide-imide oligomer, one of Embodiments 101 to 122, comprising reactively extruding at least one aromatic diamine or its activated derivative, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper at a temperature and time sufficient to produce a reactive polyamide-imide oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and has at least one unreacted functional group that allows for chain elongation and crosslinking after the formation of the reactive polyamide-imide oligomer.

[0194] Embodiment 136. The manufacturing method of Embodiment 135, wherein reactive extrusion is carried out in the presence of a polar solvent, and the polar solvent is removed by distillation during reactive extrusion.

[0195] Embodiment 137. The method for producing the method according to Embodiment 135 or 136, wherein reactive extrusion is carried out in the presence of an acid catalyst.

[0196] Embodiment 138. The method for producing the product according to Embodiment 137, wherein the acid catalyst is acetic acid, and the acetic acid is removed by distillation during reactive extrusion.

[0197] Embodiment 139. A method of production from any of Embodiments 135 to 138, wherein reactive extrusion is carried out in the presence of acetic anhydride, and the acetic anhydride is removed by distillation during reactive extrusion molding.

[0198] Embodiment 140. A manufacturing method according to any one of Embodiments 135 to 139, wherein reactive extrusion is performed in a melt extruder having a plurality of preset heating zones equipped with vent ports.

[0199] Embodiment 141. A blended composition comprising a reactive polyamide-imide oligomer and a thermoplastic polymer, one of the embodiments 101 to 122.

[0200] Embodiment 142. A method for formulating a reactive polyamide-imide oligomer from any of Embodiments 101 to 122, comprising mixing the reactive polyamide-imide oligomer with at least one other material at a sufficient temperature and time to melt the reactive polyamide-imide oligomer but without crosslinking.

[0201] Embodiment 143. A method for manufacturing an article, comprising heating a reactive polyamide-imide oligomer from any of Embodiments 101 to 122 at a temperature and for a time sufficient to shape and crosslink the reactive oligomer.

[0202] Embodiment 144. The manufacturing method of Embodiment 143, wherein the sufficient temperature and time is approximately 160 to approximately 450°C for approximately 1 to approximately 60 minutes.

[0203] Appearance 145. An article manufactured by the method of Appearance 143 or 144.

[0204] Embodiment 146. An article comprising a reactive polyamide-imide oligomer from any of Embodiments 101 to 122.

[0205] Embodiment 147. The article according to Embodiment 146, wherein a reactive polyamide-imide oligomer is crosslinked.

[0206] Embodiment 148. A manufacturing method according to Embodiment 143 or 144, wherein the method is additive manufacturing.

[0207] Embodiment 149. A method for manufacturing according to Embodiment 148, wherein the method is a molten filament manufacturing method, and the method comprises extruding reactive polyamide-imide oligomers into adjacent horizontal layers such that interfaces exist between each layer of polyamide-imide oligomers, and exposing the layers to heat for a temperature and time sufficient to crosslink the reactive polyamide-imide oligomers and form an article.

[0208] Embodiment 150. The manufacturing method of Embodiment 148, wherein the method is selective laser sintering, and the method comprises selectively sintering and crosslinking particles of a reactive polyamide-imide oligomer with a laser to form an article.

[0209] Embodiment 151. The manufacturing method of Embodiment 148, wherein the method is directed energy deposition (DED) or laser-operated net forming (LENS).

[0210] Appearance 152. An article manufactured by any of the methods described in Appearances 148 to 151.

[0211] Embodiment 153. An addition product comprising a reactive polyamide-imide oligomer from any of Embodiments 101 to 122.

[0212] Embodiment 154. An additive manufacturing article of Embodiment 153, wherein a reactive polyamide-imide oligomer is crosslinked.

[0213] Embodiment 155. A reactive polyamidoamicoic acid oligomer comprising a unit derived from at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of the reactive polyamidoamicoic acid oligomer, and the reactive polyamidoamicoic acid oligomer has an average molecular weight (M) of about 1,000 to about 10,000 g / mol, calculated using Carothers' equation. n A reactive polyamidomic acid oligomer having )

[0214] A reactive polyamidoamitic acid oligomer of Aspect 155, wherein 6.0% to approximately 20% of the amide acid groups are imidized.

[0215] Embodiment 157. A reactive polyamide acid oligomer according to Embodiment 155 or 156, wherein the crosslinkable monomer or crosslinkable end capper has one unreacted functional group that can be hot-chain extended and crosslinked after the formation of the reactive polyamide imide oligomer.

[0216] Embodiment 158. A reactive polyamidoamic acid oligomer from any of Embodiments 155 to 157, wherein at least one crosslinkable monomer or crosslinkable end capper is at least one crosslinkable end capper.

[0217] Embodiment 159. A reactive polyamidomic acid oligomer from any of Embodiments 155 to 158, wherein at least one aromatic diamine is two aromatic diamines.

[0218] Embodiment 160. A reactive polyamidoamitic acid oligomer from any of Embodiments 155 to 159, wherein at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent is two aromatic di, tri, or tetrafunctional carboxylic acids or their functional equivalents.

[0219] Embodiment 161. A reactive polyamidoamic acid oligomer from any of Embodiments 155 to 160, prepared by a process comprising the simultaneous stepwise growth polymerization of at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper.

[0220] Embodiment 162. Aromatic diamines [ka] A reactive polyamidomic acid oligomer selected from at least one of embodiments 155 to 161.

[0221] Embodiment 163. A reactive polyamidomic acid oligomer from any of Embodiments 155 to 162, wherein the aromatic diamine is at least one of 1,3-phenylenediamine, 4,4'-oxydianiline, or 3,4'-oxydianiline.

[0222] Appearance 164. A bifunctional, tertifunctional, or tetrafunctional aromatic carboxylic acid, or its functional equivalent, [ka] A reactive polyamidomic acid oligomer selected from at least one of embodiments 155 to 163.

[0223] Appearance 165. A reactive polyamidomic acid oligomer from any of Appearances 155 to 62a, wherein the two-, three-, or four-functional aromatic carboxylic acid or its functional equivalent is at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthaloyl chloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride.

[0224] Embodiment 166. A reactive polyamidomic acid oligomer from any of Embodiments 155 to 165, wherein at least one unreacted functional group is at least one of ethyne, methylethyne, phenylethyne, ketoethyne, propargyl ether, norbornene, maleimide, cyanate ester, phthalonitrile, benzocyclobutene, biphenylene, or benzoxazine.

[0225] Appearance 167. A crosslinkable monomer or a crosslinkable end capper, [Table 10] A reactive polyamidomic acid oligomer in any of embodiments 155 to 166, which is at least one of the above.

[0226] Embodiment 168. A reactive polyamidomic acid oligomer from any of Embodiments 155 to 167, wherein the crosslinkable monomer or crosslinkable end capper is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA), or 4,4'-(ethyn-1,2-diyl)diphthalic anhydride.

[0227] Embodiment 169. A reactive polyamidoamic acid oligomer from any of Embodiments 155 to 168, comprising two crosslinkable monomers or crosslinkable end cappers that are reactive in different temperature ranges.

[0228] Embodiment 170. A reactive polyamidoamic acid oligomer from any of Embodiments 155 to 169, further comprising a unit derived from at least one non-crosslinkable end capper, wherein the non-crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent.

[0229] Embodiment 171. A reactive polyamidomic acid oligomer of Embodiment 170, wherein the non-crosslinkable end capper is at least one of benzoic acid, benzoyl chloride, phthalic anhydride, or aniline.

[0230] Embodiment 172. A reactive polyamidomic acid oligomer, [ka] ; A compound diamine selected from at least one of the following, [ka] A difunctional, trifunctional, or tetrafunctional aromatic carboxylic acid or its functional equivalent selected from at least one of the following: [Table 11] A reactive polyamidoamic acid oligomer comprising a crosslinkable monomer or crosslinkable end capper selected from at least one of the following, and a unit derived from there.

[0231] Embodiment 173. A reactive polyamidomic acid oligomer comprising a unit derived from an aromatic diamine selected from at least one of 1,3-phenylenediamine, 4,4'-oxydianiline, or 3,4'-oxydianiline; a difunctional, trifunctional, or tetrafunctional aromatic carboxylic acid or its functional equivalent selected from at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthaloyl chloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride; and a crosslinkable monomer or crosslinkable end capper selected from at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA), or 4,4'-(ethyn-1,2-diyl)diphthalic anhydride.

[0232] Embodiment 174. A method for producing a reactive polyamidoamic acid oligomer from any of Embodiments 155 to 173, the method comprising copolymerizing at least one aromatic diamine, at least one aromatic di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end capper in the presence of a polar solvent to form a reactive polyamidoamic acid oligomer, wherein the crosslinkable monomer or crosslinkable end capper is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional carboxylic acid or its functional equivalent, and after the formation of the reactive polyamidoamic acid oligomer, it has at least one unreacted functional group that can be chain-extended and crosslinked.

[0233] Embodiment 175. The method for producing Embodiment 174, wherein the polar solvent is at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, or sulfolane.

[0234] Embodiment 176. A method for producing the reactive polyamidoamic acid oligomer from a polar solvent, further comprising isolating the reactive polyamidoamic acid oligomer from a polar solvent.

[0235] Embodiment 177. A blended composition comprising a reactive polyamidomic acid oligomer and a thermoplastic polymer, as selected from Embodiments 155 to 173.

[0236] Embodiment 178. A method for formulating a reactive polyamidoami acid oligomer from any of Embodiments 155 to 173, comprising mixing the reactive polyamidoami acid oligomer with at least one other material at a sufficient temperature and time, imidizing the reactive polyamidoami acid oligomer but without crosslinking.

[0237] Embodiment 179. A method for producing an article, comprising heating a reactive polyamidoami acid oligomer from any of Embodiments 155 to 173 at a temperature and time sufficient to imidize, shape, and crosslink the reactive polyamidoami acid oligomer.

[0238] Embodiment 180. The manufacturing method of Embodiment 179, wherein the sufficient temperature and time is approximately 160 to approximately 400°C for approximately 10 to approximately 60 minutes.

[0239] Appearance 181. An article manufactured by the method of Appearance 179 or 180.

[0240] Embodiment 182. An article comprising a reactive polyamidomic acid oligomer from any of Embodiments 155 to 173.

[0241] Embodiment 183. The manufacturing method of Embodiment 179 or 180, wherein the method is additive manufacturing.

[0242] Embodiment 184. A method for manufacturing a molten filament, comprising extruding reactive polyamidoami acid oligomers into adjacent horizontal layers such that interfaces exist between each layer of polyamidoami acid oligomers, and exposing the layers to heat for a temperature and time sufficient to imidize and crosslink the reactive polyamidoami acid oligomers to form an article, the method for manufacturing an article according to Embodiment 183.

[0243] Embodiment 185. The manufacturing method of Embodiment 183, wherein the method is selective laser sintering, and the method comprises selectively sintering, imidizing, and crosslinking particles of reactive polyamidoamic acid oligomer with a laser to form an article.

[0244] Embodiment 186. The manufacturing method of Embodiment 183, wherein the method is directed energy deposition (DED) or laser-operated net forming (LENS).

[0245] Appearance 187. An article manufactured by any of the methods described in Appearances 183 to 186.

[0246] Embodiment 188. An addition product comprising a reactive polyamidoamic acid oligomer from any of Embodiments 155 to 173. [Examples]

[0247] material and method Abbreviations for materials used or referred to herein are defined in Table 2. Sources for these materials used in the examples are provided. A list of other abbreviations used herein is provided in Table 3. [Table 12] [Table 13]

[0248] Rheology. Melt complex viscosity was measured by vibrational shear rheology under N2 conditions with a heating rate of 10°C / min, a frequency of 2 radians / second, and a strain of 0.03% to 1.0%. A 13 mm diameter sample was placed in the center between parallel 25 mm diameter plates for measurement.

[0249] Thermogravimetric analysis (TGA). T d、5%重量損失 To determine: TA instrument TGA5500, Pt pan, 10℃ / min, N2, 10 mg sample.

[0250] Differential scanning calorimetry (DSC). g To determine: TA instrument DSC2500, T zero pan with sealed lid, 10°C / min, N2, approximately 7 mg sample. In this method, T g This is determined from the inflection point.

[0251] Dynamic mechanical thermal analysis (DMTA). The TA instrument RSA G2 was used in tension mode, at 2°C / min from 25°C to 400°C, in an N2 atmosphere, with sample dimensions of 0.030 mm × 2 mm × 10 mm. In this method, T g This is determined from the maximum value of the loss modulus peak.

[0252] Stress-strain measurement. TA apparatus RSA G2 (32N load cell), strain rate 1 mm / min, sample dimensions = approximately 0.030 mm × approximately 2 mm × 10 mm. Young's modulus was determined by linear fitting of the stress-strain curve in the elastic region: 0.1~0.3% strain.

[0253] Gel permeation chromatography (GPC). Shimadzu Prominence ultrafast liquid chromatography (UFLC) system equipped with an LC20AD pump, SIL-20A HT autosampler, CTO-20A column oven at 60°C, and RID-20A refractive index detector. The column used for the measurements was SHODEX® LF-804. The eluent used for the measurements was NMP containing 0.05 M LiBr and 0.05 M H3PO4, operated at a constant flow rate of 0.5 mL / min. Relative molecular weight was obtained by comparison with SHODEX® polystyrene standards.

[0254] Example 1 The preparation of reactive polyamide-imide oligomers is shown below in Scheme 5. The molecular weight of the oligomer affects the thermal properties, (thermo-)mechanical properties, and melt properties of the reactive polyamide-imide oligomer. In this example, phenylethynyl end capper (PEPA) is used to prepare oligomers at molecular weights of 5,000 g / mol (Ex. 1B~1E), 3,000 g / mol (Ex. 1F~1G), and 8,000 g / mol (Ex. 1H~1I). n A reactive polyamide-imide oligomer with a value was prepared. Using Carothers' equation (Eq. 2), the desired M was obtained. n The amount of monomer required to prepare a reactive polyamide-imide oligomer with a specific value was calculated. n When using two or more diamine monomers while maintaining a constant ratio, the relative molar amounts of the diamine monomers affect the rigidity of the oligomer skeleton. Therefore, the thermal properties, (thermo-)mechanical properties, and melting properties of the reactive polyamide-imide oligomer can be changed by varying the ratio of diamine monomers. In Example 1A, the M of the reactive polyamide-imide oligomer n The molecular weight was 5,000 g / mol, and the skeleton was composed of two diamines, 4,4'-ODA and 1,3-PD, in a molar ratio of 0.72:0.28. Varying the molar ratio of the two diamines leads to changes in the oligomeric properties. The molar ratio of 4,4'-ODA to 1,3-PD was 0.72:0.28 in Examples 1A to 1I, 0.62:0.32 in Examples 1J to 1K, and 0.813:0.197 in Examples 1L to 1M. [ka] Scheme 5. Synthesis of reactive polyamide-imide oligomers having phenylethynyl reactive terminal groups.

[0255] Example 1A - Reactive polyamidomic acid oligomer solution, M n = 5,000 g / mol In a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube, 1,3-phenylenediamine (6.38 mmol, 0.69 g), 4,4'-oxydianiline (16.33 mmol, 3.27 g), and 37 g of NMP were added. The mixture was stirred until a homogeneous solution was obtained. The solution was cooled to 0°C. Trimellitus anhydride chloride (21.28 mmol, 4.48 g) and 4-(phenylethynyl)phthalic anhydride (2.9 mmol, 0.72 g) were added all at once. The reaction mixture was stirred under a nitrogen atmosphere at 0°C for 1-2 hours, then the ice bath was removed, the reaction mixture was stirred, and the mixture was heated to 25°C overnight (approximately 16 hours) to provide a solution of the reactive polyamidomic acid oligomer in NMP.

[0256] Example 1B - Reactive polyamide-imide oligomer film, M n = 5,000 g / mol This is an example of preparing a self-supporting reactive polyamide-imide oligomer film without curing of the phenylethynyl terminal group. The reactive polyamide-amic acid oligomer solution (10 mL) prepared in Example 1A was cast onto a glass plate and dried under vacuum at 60°C. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C, 200°C, and 300°C over 1 hour, yielding a reactive polyamide-imide oligomer with unreacted phenylethynyl terminal groups. The film was brittle and difficult to handle, a direct result of its low molecular weight. g The temperature was measured at 248°C using differential scanning calorimetry (N2, 10°C / min).

[0257] Example 1C - Cured polyamide-imide oligomer film, M n = 5,000 g / mol This is an example of preparing a flexible, self-supporting film with curing of phenylethynyl terminal groups. A reactive polyamidoami acid oligomer solution (10 mL), as prepared in Example 1A, was cast onto a glass plate and dried under vacuum at 60°C. The reactive polyamidoami acid oligomer was dehydrated by gradually increasing the temperature to 100°C over 1 hour, 200°C over 1 hour, and 300°C over 1 hour to obtain a reactive polyamidoimide oligomer with unreacted phenylethynyl terminal groups. The temperature was increased to 370°C, and the film was held at this temperature for 1 hour. After cooling the film to 25°C, a flexible and robust film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 483°C. Differential scanning calorimetry (N2, 10°C / min) showed a T at 301°C. g This is shown. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) revealed storage modulus (E') of 3.2 GPa at 33°C, 0.81 GPa at 300°C, and T at 306.8°C. g The following is demonstrated. Stress-strain experiments (25°C) show that the film exhibits a Young's modulus of 3.4 GPa, a strength at break of 134 MPa, and a strain at break of 17%. The film properties exceed those expected for high molecular weight polymer films.

[0258] Example 1D - Isolated reactive polyamideimide oligomer powder, M n = 5,000 g / mol The imidized reactive polyamide-imide oligomer powder was obtained by precipitation of the reactive polyamide-amic acid solution in NMP in Example 1A in MeOH. The polyamide-amic acid was precipitated by pouring 50 mL of the polyamide-amic acid solution from Example 1A into 200 mL of MeOH while mixing in a Warring blender for 1-3 minutes. The precipitate was collected by filtration using a Buchner funnel and washed with an additional 200 mL of MeOH. The washed polyamide-amic acid powder was dried in an oven under vacuum at 60°C for 2 hours. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 260°C in 1 hour to obtain a reactive polyamide-imide oligomer with unreacted phenylethynyl-terminated groups. The parallel plate rheology (N2, 10°C / min) of the fully imidized reactive polyamide-imide oligomer showed a melt complex viscosity of 19,000 Pa·s at 361°C.

[0259] Example 1E - Cured polyamide-imide oligomer film, M n = 5,000 g / mol This is another example of the preparation of a flexible, self-supporting film with curing of phenylethynyl terminal groups. The reactive polyamidomidoic acid oligomer solution of Example 1A was imidized as follows: Anhydrous toluene was added to the reaction flask. Water produced during the dehydration cyclization (of the amide acid to the imide) was removed by azeotropic distillation. After 2 hours, the reactive polyamidomidoic acid oligomer was 98% imidized, and the remaining toluene was removed by distillation. The resulting NMP solution of the reactive polyamidomidoimide oligomer (30 wt% solids) (10 mL) was cast onto a glass plate and dried under vacuum at 60°C. After cooling to room temperature, the temperature was gradually increased to 40°C in 2 hours, 60°C in 2 hours, 100°C in 30 minutes, 200°C, 300°C, and 370°C in 1 hour. After cooling the film to 25°C, a flexible and robust film was obtained. Differential scanning calorimetry (N2, 10°C / min) was performed at 326°C. g This shows that the T of PAI film currently available g This is about 46°C higher than (280°C).

[0260] Example 1F, Cured polyamide-imide oligomer film, M n = 3,000 g / mol M n A reactive polyamide-imide oligomer with a concentration of 3,000 g / mol was prepared using 4-phenylethynylphthalic anhydride end capper. In a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube, 1,3-phenylenediamine (22.84 mmol, 2.47 g), 4,4'-oxydianiline (62.07 mmol, 12.43 g), and 82 g of NMP were added. The mixture was stirred until a homogeneous solution was obtained. The solution was cooled to 0°C. Trimellitus anhydride chloride (76.08 mmol, 16.02 g) and 4-(phenylethynyl)phthalic anhydride (17.64 mmol, 4.38 g) were added all at once. The reaction mixture was stirred at 0°C for 1-2 hours under a nitrogen atmosphere. Afterward, the ice bath was removed, the reaction mixture was stirred, and the mixture was heated to 25°C overnight (approximately 16 hours) to provide a solution of the reactive polyamidomide oligomer in NMP. 10 mL of the reactive polyamidomide oligomer solution was cast onto a glass plate and dried under vacuum at 60°C. The reactive polyamidomide oligomer was dehydrated by gradually increasing the temperature to 100°C over 1 hour, 200°C over 1 hour, and 300°C over 1 hour to obtain a reactive polyamidomide oligomer with unreacted phenylethynyl terminal groups. The temperature was increased to 370°C, and the film was held at this temperature for 1 hour. After cooling the film to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 500°C. Differential scanning calorimetry (N2, 10°C / min) was performed at 291°C T g This shows that the storage modulus (E') was 1.71 GPa at 35°C, 0.25 GPa at 300°C, and T at 292°C. g The stress-strain experiment (25°C) shows that the film exhibits a Young's modulus of 3.0 GPa, a strength at break of 110 MPa, and a strain at break of 16.4%.

[0261] Example 1G - Isolated reactive polyamide-imide oligomer powder, M n = 3,000 g / mol The imidized reactive polyamide-imide oligomer powder was obtained by precipitation of the reactive polyamide-amic acid solution in NMP of Example 1D in MeOH. The polyamide-amic acid was precipitated by pouring 50 mL of the polyamide-amic acid solution of Example 1D into 200 mL of MeOH while mixing in a Warring blender for 1–3 minutes. The precipitate was collected by filtration using a Buchner funnel and washed with an additional 200 mL of MeOH. The washed polyamide-amic acid powder was dried in an oven under vacuum at 60°C for 2 hours. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 260°C in 1 hour to obtain a reactive polyamide-imide oligomer with unreacted phenylethynyl-terminated groups. The parallel plate rheology (N2, 10°C / min) of the fully imidized reactive polyamide-imide oligomer showed a melt complex viscosity of 5450 Pa·s at 361°C.

[0262] Example 1H-Cured polyamide-imide oligomer film, M n = 8,000 g / mol M nA reactive polyamide-imide oligomer having 8,000 g / mol was prepared using a reactive end group of 4-phenylethynylphthalic anhydride. In a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube, 1,3-phenylenediamine (22.84 mmol, 2.47 g), 4,4'-oxydianiline (56.43 mmol, 11.30 g), and 73 g of NMP were added. The mixture was stirred until a homogeneous solution was obtained. The solution was cooled to 0°C. Trimellitus anhydride chloride (76.08 mmol, 16.02 g) and 4-(phenylethynyl)phthalic anhydride (6.04 mmol, 1.5 g) were added all at once. The reaction mixture was stirred at 0°C for 1-2 hours under a nitrogen atmosphere. After removing the ice bath, the reaction mixture was stirred and heated to 25°C overnight (approximately 16 hours) to provide a solution of the reactive polyamidomide oligomer in NMP. 10 mL of the reactive polyamidomide oligomer solution was cast onto a glass plate and dried under vacuum at 40°C for 2 hours and then at 60°C for 2 hours. The reactive polyamidomide oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 300°C in 1 hour to obtain a reactive polyamidomide oligomer with unreacted phenylethynyl terminal groups. The temperature was increased to 370°C, and the film was held at this temperature for 1 hour. After cooling to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 490°C. Differential scanning calorimetry (N2, 10°C / min) was performed at 287°C T g The following was shown. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) revealed storage modulus (E') of 3.0 GPa at 35°C and 0.75 GPa at 300°C, and T at 300°C. g The following was demonstrated: Stress-strain experiments (25°C) showed that the film exhibited a Young's modulus of 3.1 GPa, a fracture strength of 139 MPa, and a fracture strain of 57.4%.

[0263] Example 1I - Isolated reactive polyamideimide oligomer powder, M n = 8,000 g / mol The imidized reactive polyamide-imide oligomer powder was obtained by precipitation of the reactive polyamide-amic acid solution in NMP in Example 1F in MeOH. The polyamide-amic acid was precipitated by pouring 50 mL of the polyamide-amic acid solution into 200 mL of MeOH while mixing in a Warring blender for 1–3 minutes. The precipitate was collected by filtration using a Buchner funnel and washed with an additional 200 mL of MeOH. The washed polyamide-amic acid powder was dried in a tam oven under vacuum at 60°C for 2 hours. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 260°C in 1 hour to obtain a reactive polyamide-imide oligomer with unreacted phenylethynyl-terminated groups. The parallel plate rheology (N2, 10°C / min) of the fully imidized reactive polyamide-imide oligomer showed a melt complex viscosity of 49,902 Pa·s at 333°C.

[0264] Example 1: J-Cured oligomeric polyamide-imide oligomeric film, 4,4'-ODA:1,3-PD ratio = 0.62:0.32, M n = 5,000 g / mol In this example, the molar ratio of the two diamines, 4,4'-ODA and 1,3-PD, was 0.62:0.32. 1,3-phenylenediamine (37.54 mmol, 4.06 g), 4,4'-oxydianiline (62.52 mmol, 12.52 g), and 92 g of NMP were added to a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube. The mixture was stirred until a homogeneous solution was obtained. The solution was cooled to 0°C. Trimellitus anhydride chloride (93.89 mmol, 19.77 g) and 4-(phenylethynyl)phthalic anhydride (12.41 mmol, 3.08 g) were added all at once. The reaction mixture was stirred at 0°C for 1-2 hours under a nitrogen atmosphere. Afterward, the ice bath was removed, the reaction mixture was stirred, and the mixture was heated to 25°C overnight (approximately 16 hours) to provide a solution of the reactive polyamidomide oligomer in NMP. 10 mL of the reactive polyamidomide oligomer solution was cast onto a glass plate and dried under vacuum at 40°C for 2 hours and then at 60°C for 2 hours. The reactive polyamidomide oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 300°C in 1 hour to obtain a reactive polyamidomide oligomer with unreacted phenylethynyl terminal groups. The temperature was increased to 370°C, and the film was held at this temperature for 1 hour. After cooling to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 478°C. Differential scanning calorimetry (N2, 10°C / min) was performed at 283°C T g The following was shown. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) revealed storage modulus (E') of 2.0 GPa at 35°C and 0.24 GPa at 300°C, and T at 291.3°C. g The following was demonstrated: Stress-strain experiments (25°C) showed that the film exhibited a Young's modulus of 2.5 GPa, a fracture strength of 82.5 MPa, and a fracture strain of 10.1%.

[0265] Example 1K - Isolated reactive polyamideimide oligomer powder, 4,4'-ODA:1,3-PD ratio = 0.62:0.32, M n = 5,000 g / mol The imidized reactive polyamide-imide oligomer powder was obtained by precipitation of the reactive polyamide-amic acid solution in NMP in Example 1I in MeOH. The reactive polyamide-amic acid oligomer was precipitated by pouring 50 mL of the reactive polyamide-amic acid oligomer solution into 200 mL of MeOH while mixing in a Waring blender for 1-3 minutes. The precipitate was collected by filtration using a Buchner funnel and washed with an additional 200 mL of MeOH. The washed reactive polyamide-amic acid oligomer powder was dried in an oven under vacuum at 60°C for 2 hours. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 260°C in 1 hour to obtain reactive polyamide-imide oligomers having unreacted phenylethynyl terminal groups. The parallel plate rheology (N2, 10°C / min) of fully imidized reactive polyamide-imide oligomers exhibits a melt complex viscosity of 40,339 Pa·s at 370°C.

[0266] Example 1 L - Cured oligomeric polyamide-imide oligomeric film, 4,4'-ODA:1,3-PD ratio = 0.813:0.197, M n = 5,000 g / mol In this example, the molar ratio of the two diamines, 4,4'-ODA and 1,3-PD, was 0.813:0.187. 1,3-phenylenediamine (18.77 mmol, 2.03 g), 4,4'-oxydianiline (81.70 mmol, 16.36 g), and 96 g of NMP were added to a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube. The mixture was stirred until a homogeneous solution was obtained. The solution was cooled to 0°C. Trimellitus anhydride chloride (93.89 mmol, 19.77 g) and 4-(phenylethynyl)phthalic anhydride (12.41 mmol, 3.08 g) were added all at once. The reaction mixture was stirred at 0°C for 1-2 hours under a nitrogen atmosphere. Afterward, the ice bath was removed, the reaction mixture was stirred, and the mixture was heated to 25°C overnight (approximately 16 hours) to provide a solution of the reactive polyamidomide oligomer in NMP. 10 mL of the reactive polyamidomide oligomer solution was cast onto a glass plate and dried under vacuum at 40°C for 2 hours and then at 60°C for 2 hours. The reactive polyamidomide oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 300°C in 1 hour to obtain a reactive polyamidomide oligomer with unreacted phenylethynyl terminal groups. The temperature was increased to 370°C, and the film was held at this temperature for 1 hour. After cooling to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 496°C. Differential scanning calorimetry (N2, 10°C / min) was performed at 308°C. g The results showed that the storage modulus (E') was 2.5 GPa at 35°C, 1.0 GPa at 300°C, and T at 322°C. g The following was demonstrated: Stress-strain experiments (25°C) showed that the film exhibited a Young's modulus of 3.7 GPa, a fracture strength of 132 MPa, and a fracture strain of 12.6%.

[0267] Example 1M - Isolated reactive polyamideimide oligo powder, 4,4'-ODA:1,3-PD ratio = 0.813:0.197, M n = 5,000 g / mol Imidized reactive polyamide-imide oligomer powder was obtained by precipitation of a reactive polyamide-amic acid solution in NMP in MeOH. The reactive polyamide-amic acid oligomer was precipitated by pouring 50 mL of the reactive polyamide-amic acid solution into 200 mL of MeOH in a Warring blender and mixing for 1-3 minutes. The mixture was washed in a Warring blender for 1-3 minutes. The precipitate was collected by filtration using a Buchner funnel and washed with an additional 200 mL of MeOH. The washed reactive polyamide-amic acid oligomer powder was dried in an oven under vacuum at 60°C for 2 hours. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 260°C in 1 hour to obtain reactive polyamide-imide oligomers with unreacted phenylethynyl terminal groups. The parallel plate rheology (N2, 10°C / min) of fully imidized reactive polyamide-imide exhibits a melt complex viscosity of 49502 Pa·s at 359°C.

[0268] Example 2 Using two different end cappers, 5,000 g / mol M n The preparation of a reactive polyamide-imide (PAI) oligomer having the following is shown in Scheme 6. The two different end cappers are 4-(phenylethynyl)phthalic anhydride and 4-(methylethynyl)phthalic anhydride. [ka] Scheme 6. M having two different reactive terminal groups n Synthesis of 5,000 g / mol of total aromatic reactive polyamide-imide oligomers. 50 / 50 4-(phenylethynyl)phthalic anhydride / 4-(methylethynyl)phthalic anhydride.

[0269] In a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube, 1,3-phenylenediamine (6.38 mmol, 0.69 g), 4,4'-oxydianiline (16.33 mmol, 3.27 g), and 36 g of NMP were added. The mixture was stirred until a homogeneous solution was obtained. The solution was cooled to 0°C. Trimellitus anhydride chloride (21.28 mmol, 4.48 g), 4-(phenylethynyl)phthalic anhydride (1.45 mmol, 0.36 g), and 4-(methylethynyl)phthalic anhydride (1.45 mmol, 0.27 g) were all added at once. The reaction mixture was stirred at 0°C for 1-2 hours under a nitrogen atmosphere, then the ice bath was removed, the reaction mixture was stirred, and the mixture was heated to 25°C overnight (approximately 16 hours). The prepared reactive polyamidoamic acid oligomer solution (10 mL) was cast onto a glass plate and dried under vacuum at 60°C. The reactive polyamidoamic acid oligomer was dehydrated by gradually increasing the temperature to 100°C, 200°C, and 300°C over 1 hour, yielding a reactive polyamidoimide oligomer with unreacted phenylethynyl terminal groups. The temperature was then increased to 370°C, and the film was held at this temperature for 1 hour. After cooling the film to 25°C, a flexible and robust film was obtained.

[0270] Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 466°C. Differential scanning calorimetry (N2, 10°C / min) showed a T at 298°C. g The following was shown. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) revealed storage modulus (E') of 2.6 GPa at 33°C, 0.64 GPa at 300°C, and T at 301°C. g The parallel plate rheology (N2, 10°C / min) showed a viscosity of 98,560 Pa·s at 301°C. Stress-strain experiments at 25°C showed the film had a Young's modulus of 3.6 GPa, a strength at break of 155 MPa, an elongation at break of 75%, and 94.3 MJ / m². 3 This demonstrated that it represents toughness. In contrast, a review of available literature showed that currently available PAIs are at best about 10 MJ / m 3It has been shown to have toughness, strength at 140 MPa, and elongation at 10-15%. Therefore, PAI films made from reactive polyamide-imide oligomers can have nearly 10 times higher toughness, about 5 times higher elongation at rupture, and about 10% higher strength at rupture than currently available PAIs, respectively. Generally, crosslinking of polymers results in a decrease in elongation at rupture. Surprisingly, crosslinking of reactive polyamide-imide oligomers increases both strength and elongation at rupture, resulting in a significant increase in toughness.

[0271] In addition manufacturing methods such as molten filament manufacturing and selective laser sintering, the low molecular weight of reactive polyamide-imide oligomers facilitates rapid diffusion across interfaces between two filaments or two particles. Furthermore, reactive functional groups can be selected to polymerize (chain elongation / crosslinking) over a wide temperature range. In this example, the reactive polyamide-imide oligomer can be cured in two steps at different temperatures. Methylethynyl groups cure over a temperature range of 280–330°C, and phenylethynyl groups cure over a temperature range of 330–400°C. In addition manufacturing methods, the low-temperature curable methylethynyl groups ensure rapid structural fixation, while the high-temperature curable phenylethynyl groups allow for additional chain diffusion and chain elongation / crosslinking after curing of the low-temperature groups without compromising structural integrity.

[0272] Example 3 The preparation of another reactive polyamide-imide oligomer is shown below in Scheme 7. Since TMACl is expensive, it is desirable to minimize its use in the preparation of reactive polyamide-imide oligomers. TMACl has one acid chloride group and one carboxylic acid anhydride group. Instead of using 1 equivalent of TMACl, 1 / 2 equivalent of pyromellitic dianhydride (PMDA) and 1 / 2 equivalent of isophthaloyl chloride (IPC) were used. The reactive oligomer had a 4-(phenylethynyl)phthalic anhydride reactive end group and was prepared at 5,000 g / mol M n It was prepared using [method / tool]. [ka] Scheme 7.4-(phenylethynyl)phthalic anhydride with reactive terminal groups M n Synthesis of 5,000 g / mol total aromatic reactive polyamide-imide oligomers. In Ex. 2, trimellitic anhydride chloride is replaced by pyromellitic dianhydride and isophthaloyl chloride.

[0273] In a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube, pyromellitic dianhydride (10.64 mmol, 2.32 g), isophthaloyl chloride (10.64 mmol, 2.16 g), 4-(phenylethynyl)phthalic anhydride (2.9 mmol, 0.72 g), and 37 g of NMP were added. This suspension was stirred for 15 minutes and cooled to 0°C. Both diamines, 1,3-phenylenediamine (6.38 mmol, 0.69 g) and 4,4'-oxydianiline (16.33 mmol, 3.27 g), were added all at once. The reaction mixture was stirred at 0°C for 1 hour under a nitrogen atmosphere, then the ice bath was removed, the reaction mixture was stirred, and it was incubated at 25°C overnight (approximately 16 hours). The prepared reactive polyamidoamic acid oligomer solution (10 mL) was cast onto a glass plate and dried under vacuum at 60°C. The reactive polyamidoamic acid oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 300°C in 1 hour to obtain a reactive polyamidoimide oligomer with unreacted phenylethynyl terminal groups. The temperature was increased to 370°C and the film was held at this temperature for 1 hour. After cooling the film to 25°C, a flexible and robust film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 476°C. Differential scanning calorimetry (N2, 10°C / min) showed a T at 315°C. g The following was shown. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) revealed storage modulus (E') of 2.8 GPa at 33°C, 0.93 GPa at 300°C, and T at 299°C. gThe results showed that the film exhibited a Young's modulus of 3.2 GPa, a fracture strength of 121 MPa, and an elongation of 25% at fracture.

[0274] Example 4 The preparation of another reactive polyamide-imide oligomer is shown below in Scheme 8. A crosslinkable dianhydride monomer (4,4'-(ethyn-1,2-diyl)diphthalic acid dianhydride or EBPA) was incorporated into the reactive oligomer skeleton. Molecular weight (M n To limit the concentration to 5,000 g / mol, a phthalic anhydride (non-reactive) end capper was used. [ka] Scheme 8. M having a crosslinkable acetylene-based dianhydride monomer (4,4'-(ethyn-1,2-diyl)diphthalic acid dianhydride or EBPA) in the skeleton. n Synthesis of a 5,000 g / mol total aromatic reactive polyamide-imide oligomer. Molecular weight (M n The concentration is limited to 5,000 g / mol by using a non-reactive phthalic anhydride end capper.

[0275] In a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube, 4,4'-oxydiphthalic anhydride (ODPA) (7.98 mmol, 2.48 g), isophthaloyl chloride (10.64 mmol, 2.16 g), EBPA (2.66 mmol, 0.85 g), phthalic anhydride (2.9 mmol, 0.43 g), and 42 g of NMP were added. This suspension was stirred for 15 minutes and cooled to 0°C. The diamine 4,4'-oxydianiline (22.71 mmol, 4.55 g) was added all at once. The reaction mixture was stirred under a nitrogen atmosphere at 0°C for 1 hour, then the ice bath was removed, the reaction mixture was stirred, and the mixture was heated to 25°C overnight (approximately 16 hours). The prepared reactive polyamidoamic acid oligomer solution (10 mL) was cast onto a glass plate and dried under vacuum at 60°C to form a film. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C, 200°C, and 300°C over 1 hour, yielding a reactive polyamide-imide oligomer with unreacted phenylethynyl terminal groups. The temperature was then increased to 370°C, and the film was held at this temperature for 1 hour. After cooling the film to 25°C, a flexible and robust film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 463°C. Differential scanning calorimetry (N2, 10°C / min) showed a 5% weight loss at 268°C. g This was shown.

[0276] Another film was formed in the same manner, except that the reactive polyamide-imide oligomer film was cured at 400°C for 1 hour instead of 370°C. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 459°C. Dynamic mechanical thermal analysis (N2, 10°C / min, 1 Hz) showed storage modulus (E') of 2.0 GPa at 33°C, 0.16 GPa at 300°C, and T at 282°C. g The results showed that the film exhibited a Young's modulus of 2.1 GPa, a fracture strength of 56 MPa, and an elongation of 3% at fracture.

[0277] Example 5 The preparation of another reactive polyamide-imide oligomer is shown below in Scheme 9. A crosslinkable dianhydride monomer (4,4'-(ethyn-1,2-diyl)diphthalic acid dianhydride or EBPA) was incorporated into the reactive oligomer skeleton. Molecular weight (M n To limit the concentration to 5,000 g / mol, a reactive endocapper of 4-(phenylethynyl)phthalic anhydride was used. [ka] Scheme 9. M having a crosslinkable acetylene-based dianhydride monomer (4,4'-(ethyn-1,2-diyl)diphthalic acid dianhydride or EBPA) in its skeleton. n Synthesis of a total aromatic reactive polyamide-imide oligomer with a molecular weight of 5,000 g / mol. By using reactive 4-(phenylethynyl)phthalic anhydride end capper, molecular weight (M n Limit the amount to 5,000 g / mol.

[0278] In a 150 mL two-necked round-bottom flask equipped with a stirring bar and a nitrogen inlet tube, 4,4'-oxydiphthalic anhydride (ODPA) (7.98 mmol, 2.48 g), isophthaloyl chloride (10.64 mmol, 2.16 g), EBPA (2.66 mmol, 0.85 g), 4-(phenylethynyl)phthalic anhydride (2.9 mmol, 0.72 g), and 42 g of NMP were added. This suspension was stirred for 15 minutes and cooled to 0°C. The diamine 4,4'-oxydianiline (22.71 mmol, 4.55 g) was added all at once. The reaction mixture was stirred under a nitrogen atmosphere at 0°C for 1 hour, then the ice bath was removed, the reaction mixture was stirred, and it was incubated at 25°C overnight (approximately 16 hours).

[0279] Example 5A This is an example of preparing a self-supporting polyamide-imide film obtained by selectively curing the phenylethynyl terminal groups while leaving the ethynyl skeleton groups uncured. A reactive polyamide-amic acid oligomer solution (10 mL), as prepared in Example 5, was cast onto a glass plate and dried under vacuum at 60°C. The reactive polyamide-amic acid oligomer was dehydrated by gradually increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 300°C in 1 hour to obtain a reactive polyamide-imide oligomer having unreacted phenylethynyl terminal groups and 1,2-diphenylethynyl skeleton groups. The temperature was increased to 370°C and the film was held at this temperature for 1 hour. At this temperature, the phenylethynyl terminal groups cured, but the 1,2-diphenylethynyl skeleton groups did not. After cooling the film to 25°C, a flexible and robust film was obtained. Differential scanning calorimetry (N2, 10°C / min) was performed at 298°C T g This was shown. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) revealed a storage modulus (E') of 2.3 GPa at 33°C and T at 302°C. g This was shown.

[0280] Example 5B This is an example of the preparation of a self-supporting polyamide-imide film with curing of both the phenylethynyl terminal group and the 1,2-diphenylethynyl backbone group. A reactive polyamide-amic acid oligomer solution (10 mL), as prepared in Example 5, was cast onto a glass plate and dried under vacuum at 60°C. The reactive polyamide-amic acid oligomer was dehydrated by stepwise increasing the temperature to 100°C in 1 hour, 200°C in 1 hour, and 300°C in 1 hour to obtain a reactive polyamide-imide oligomer with unreacted phenylethynyl terminal groups. The temperature was increased to 400°C and the film was held at this temperature for 1 hour. At this temperature, both the phenylethynyl terminal group and the 1,2-diphenylethynyl backbone group cured. After cooling the film to 25°C, a flexible and robust film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 453°C. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) revealed a storage modulus (E') of 2.7 GPa at 33°C and T at 324°C. gThe results showed that the film exhibited a Young's modulus of 2.6 GPa, a fracture strength of 78 MPa, and an elongation of 4% at fracture.

[0281] Example 6 Using the ammonium carboxylate salt pathway, M n The preparation of another reactive polyamide-imide oligomer having a concentration of 5000 g / mol is shown below in Scheme 10. [ka] Scheme 10. M via the ammonium carboxylate salt pathway n Synthesis of 5,000 g / mol total aromatic reactive polyamide-imide oligomers.

[0282] 0.2556 moles (49.11 g) of trimellitic anhydride, 0.036 moles (8.94 g) of 4-(phenylethynyl)phthalic anhydride, and 85 g of MeOH were added to a flame-dried, three-necked, 500 mL round-bottom flask equipped with a reflux condenser and a nitrogen inlet adapter. The mixture was refluxed under nitrogen at 70°C for 2 hours. 0.2730 moles (54.67 g) of 4,4'-oxydianiline were added to the mixture in a single addition. The mixture was refluxed for 24 hours, and methanol was removed by evaporation. The resulting ammonium carboxylate salt was dried under vacuum at 70°C. The salt was heated under nitrogen at 10°C / min to 300°C, and then kept isothermal at 300°C for 1 hour under 3 atm to obtain a reactive polyamide-imide oligomer.

[0283] Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 510°C. Differential scanning calorimetry (N2, 10°C / min) showed that the oligomer before crosslinking was 226°C. g This shows that after thermal crosslinking of the reactive oligomer (at 370°C for 1 hour), T g The temperature rose from 226°C to 287°C. (Fourier transform infrared spectroscopy (FTIR) using Perkin Elmer Spectrum, ATR mode: 1718 cm⁻¹) -1 (Imide C=O), 1660cm -1(Amide C=O), and 1374 cm -1 (Imido CN).

[0284] Example 7 The production of reactive polyamide-imide (PAI) oligomers by reactive extrusion is illustrated below in Scheme 11. Using phenylethynyl end capper (PEPA), 5,000 g / mol M n A reactive oligomer having the following properties was prepared. [ka] Scheme 11. M having a phenylethynyl reactive end group by melt polymerization. n Synthesis of 5,000 g / mol total aromatic reactive polyamide-imide oligomers.

[0285] In a 500 mL two-necked round-bottom flask equipped with an overhead stirrer and a nitrogen inlet tube, 1,3-phenylenediamine (63.8 mmol, 6.9 g), 4,4'-oxydianiline (163.3 mmol, 32.7 g), trimellitic anhydride (212.8 mmol, 40.9 g), 4-(phenylethynyl)phthalic anhydride (29 mmol, 7.2 g), and 200 mL of glacial acetic acid were added. The resulting reaction mixture was heated under reflux for 2 hours, then 20 mL of acetic anhydride was added, and the reaction was refluxed for a further 1 hour. Acetic acid, residual acetic anhydride, and water produced during the reaction were removed by vacuum distillation. The resulting yellow monomer mixture was fed into an aerated Xplore twin-screw extruder at 290°C. The molten material was circulated in the extruder at 50 rpm for 55 minutes at 290°C to allow polymerization to occur. Polymerization was monitored by measuring axial force (N) versus time (minutes), as shown in Figure 2. Polymerization was deemed complete when an axial force of 5000 N was reached (55 minutes). At this point, the reactive PAI oligomer was extruded as a continuous amber filament and analyzed.

[0286] To confirm that a reactive oligomer was obtained and that it was not a crosslinking agent, a small sample was dissolved in NMP. GPC analysis against a polystyrene standard was performed at 4500 M n The TGA was obtained from the filament and performed under nitrogen at 10°C / min, showing a mass loss of 1% at 395°C and a mass loss of 5% at 448°C. The powdered sample was compressed in a 13 mm pellet press die and subjected to an oscillating shear temperature gradient from 30°C to 350°C with a strain of 0.03% at a gradient rate of 10°C / min and 2 rad / s. The minimum viscosity recorded was 33,000 Pa·s.

[0287] The filament sample was ground into a powder, dissolved overnight in 20% by weight of NMP, and then cast as a film approximately 40 μm thick. The film was cured under vacuum at 40°C for 2 hours, 60°C for 1.5 hours, and 100°C, 200°C, 300°C, and 350°C for 1 hour each. The cured film was subjected to uniaxial deformation and exhibited an elastic modulus of 3 GPa and best stress at fracture at 115 MPa with 17% strain. The sample was subjected to uniaxial vibration temperature gradient at 0.03% strain and 2 rad / s with a gradient rate of 2°C / min from 30°C to 400°C. The sample exhibited an elastic modulus of 3 GPa and T at 290°C. g This was shown.

[0288] Example 8 5,000 g / mol of Mn, T at approximately 200°C g The following examples illustrate reactive polyetherimide (PEI) oligomers having two different end cappers. The two different end cappers are 4-(methylethynyl)phthalic anhydride and N-arylmaleimide. In this example, the reactive polyetherimide oligomer is capable of two-step curing at different temperatures. The N-arylmaleimide group cures over a temperature range of 200-250°C, and the methylethynyl group cures over a temperature range of 280-330°C. In the addition method, the low-temperature curable N-arylmaleimide group ensures rapid fixation of the structure, while the high-temperature curable methylethynyl group allows for additional chain diffusion and chain extension / crosslinking after curing of the low-temperature group without loss of structural integrity. [ka]

[0289] Example 9 Using two different end cappers, 5,000 g / mol M n The production of a reactive polyetherimide (PEI) oligomer having the following is shown in Scheme 12. The two different end cappers are 4-(phenylethynyl)phthalic anhydride and 4-(methylethynyl)phthalic anhydride. In this example, the reactive polyetherimide oligomer can also be cured in two steps at different temperatures. The methylethynyl group is cured over a temperature range of 280-330°C, and the phenylethynyl group is cured over a temperature range of 330-400°C. In the addition method, the low-temperature curable methylethynyl ensures rapid fixation of the structure, while the high-temperature curable phenylethynyl group allows for additional chain diffusion and chain extension / crosslinking after curing of the low-temperature group without compromising structural integrity. [ka] Scheme 12. M having two different reactive terminal groups n Synthesis of a 5,000 g / mol total aromatic reactive polyetherimide oligomer. 50 / 50 4-(phenylethynyl)phthalic anhydride / 4-(methylethynyl)phthalic anhydride.

[0290] The reactive oligomers described herein, such as reactive polyamide-imide oligomers and reactive polyamide-amic acid oligomers, may also be referred to as "macromonomers."

[0291] As used herein, "crosslinkable monomer" refers to a monomer that is reactive with at least one aromatic diamine, or at least one di, tri, or tetrafunctional aromatic carboxylic acid, or a functional equivalent thereof, and has unreacted functional groups that can be chain-extended and crosslinked after the formation of a reactive polyamide-imide oligomer.

[0292] As used herein, “crosslinkable end capper” refers to an end capper that is reactive with at least one aromatic diamine or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after the formation of a reactive polyamide-imide oligomer.

[0293] As used herein, “non-crosslinkable end capper” refers to an end capper that is reactive with at least one aromatic diamine, or at least one di, tri, or tetrafunctional aromatic carboxylic acid or its functional equivalent, but does not have unreacted functional groups that can be chain-extended and / or crosslinked after the formation of a reactive polyamide-imide oligomer.

[0294] The "functional equivalents" of carboxylic acids include compounds in which the carbon atoms of the carboxylic acid group are in the same oxidation state, and include esters, acid chlorides, and their anhydrides.

[0295] As used herein, curing refers collectively to any combination of chain extension, branching, and crosslinking that leads to improved thermomechanical properties. Curing can be initiated by heat, chemical (electromagnetic) irradiation, or electron beam irradiation. The terms “thermosetting,” “thermopost-treatment,” and “postthermosetting” are used interchangeably for curing initiated by heat.

[0296] The terms "acetylene" and "alkyne" are used interchangeably herein.

[0297] The terms “additive manufacturing” and “3D printing” are used interchangeably herein.

[0298] The terms "molten filament manufacturing" and "molten deposition molding" are used interchangeably herein.

[0299] As used herein in relation to enumeration, “at least one of” means that an enumeration is the inclusion of each element individually, as well as combinations of two or more elements of the enumeration, and combinations of at least one element of the enumeration with similar elements that are not named.

[0300] Compositions, methods, and articles may, alternatively, include, consist of, or essentially consist of any suitable materials, steps, or components disclosed herein. Compositions and methods may, additionally or alternatively, be formulated to exclude, or substantially exclude, any materials (or species), steps, or components not otherwise required for achieving the function or purpose of the composition and method.

[0301] All scopes disclosed herein encompass endpoints, which can be combined independently of each other (for example, the range “25% by weight or less, or more specifically 5% to 20% by weight” includes, for example, “5% to 25% by weight,” the endpoints of the range and all intermediate values). References to “about” values ​​or parameters herein include (and are described) embodiments indicated by the value or parameter itself. In certain embodiments, the term “about” includes ±50% of the indicated amount. In certain embodiments, the term “about” includes ±20% of the indicated amount. In certain embodiments, the term “about” includes ±10% of the indicated amount. In other embodiments, the term “about” includes ±5% of the indicated amount. In certain embodiments, the term “about” includes ±1% of the indicated amount. In certain other embodiments, the term “about” includes ±0.5% of the indicated amount, and in some certain other embodiments, 0.1%. Such variations are appropriate for performing the disclosed method or using the disclosed composition. The term “about x” also includes the description of “x.”

[0302] "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "a," "an," and "the" do not indicate a limit on quantity and should be interpreted as encompassing both singular and plural unless otherwise indicated herein or the context clearly contradicts this. "Or" means "and / or" unless otherwise specified.

[0303] Throughout this specification, any reference to “several embodiments,” “embodiments,” etc., means that certain elements described in relation to an embodiment are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the elements described can be combined by any preferred means in various embodiments.

[0304] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to whom this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology in this application conflicts with or is inconsistent with any terminology in an incorporated reference, the terminology from this application shall prevail over the conflicting terminology from the incorporated reference.

[0305] While specific embodiments are described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently anticipated or cannot be anticipated may arise for the applicant or those skilled in the art. Therefore, the applied appendices are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents, insofar as they can be modified.

Claims

1. A method for producing an article, the method comprising heating a composition comprising at least one reactive oligomer at a temperature and time sufficient to shape and crosslink the reactive oligomer, The above method is additive manufacturing. The reactive oligomer comprises a skeleton derived from at least one of polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole, or polybenzimidazole, and is functionalized with at least one unreacted functional group that can undergo thermal chain extension and crosslinking after the formation of the reactive oligomer. The reactive oligomer has a number-average molecular weight (Mn) of 250 to 10,000 g / mol, calculated using Carothers' equation. Manufacturing method.

2. The manufacturing method according to claim 1, wherein the method is a molten filament manufacturing method, the method comprising extruding the composition into adjacent horizontal layers such that interfaces exist between each layer, and exposing the layers to heat for a temperature and time sufficient to crosslink the reactive oligomer and form an article.

3. The manufacturing method according to claim 1, wherein the method is selective laser sintering, and the method comprises selectively sintering and crosslinking particles of the composition with a laser to form an article.

4. The method according to any one of claims 1 to 3, wherein the at least one unreacted functional group is at least one of maleimide, 5-norbornene-2,3-dicarboximide, phthalonitrile, benzocyclobutene, biphenylene, cyanate ester, ketoethin, ethin, methylethin, phenylethin, propargyl ether, or benzoxazine.

5. The at least one unreacted functional group 【Chemistry 1】 The method according to any one of claims 1 to 4, derived from a monomer or end capper selected from the group consisting of the following.

6. The method according to any one of claims 1 to 5, wherein the reactive oligomer comprises a skeleton derived from polyimide.

7. The reactive oligomer is of formula (I): 【Chemistry 2】 It has, in the formula, the tetravalent aryl group represented by Ar 1, 【Transformation 3】 At least one of the divalent aryl group represented by Ar2 is 【Chemistry 4】 At least one of the above, where Y1 and Z1 are independently, 【Transformation 5】 Induced from an end capper selected from the group consisting of, n is selected to provide a calculated Mn in the range of 250 to 10,000 g / mol. The method according to claim 6.

8. The method according to claim 7, wherein Y1 and Z1 are different.

9. The method according to any one of claims 1 to 7, wherein the composition comprises a first and a second reactive oligomer, the first reactive oligomer being functionalized with a first unreacted functional group that can undergo heat chain extension and crosslinking after the formation of the first reactive oligomer, the second reactive oligomer being functionalized with a second unreacted functional group that can undergo heat chain extension and crosslinking after the formation of the second reactive oligomer, the first unreacted functional group being self-reactive within a first temperature range, the second unreacted functional group being self-reactive within a second temperature range, and the second temperature range being higher than the first temperature range.

10. The method according to claim 7, wherein the reactive oligomer further comprises a non-crosslinkable end capper.

11. An article manufactured by the method described in any one of Claims 1 to 10.

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