Reactive oligomers, additive manufacturing methods, and articles thereof

Abstract

The invention relates to a reactive oligomer, an additive manufacturing method and an article thereof. The invention discloses a reactive oligomer. The composition is derived from polyamide-imide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylester, polyesteramide and polycarbonate. And a backbone functionalized with at least one of a polybenzoxazole or a polybenzimidazole and functionalized with at least one unreacted functional group capable of thermal chain extension and cross-linking upon formation of the reactive oligomer, wherein the Mn of the reactive oligomer is from about 250 to about 10000 g / mol as calculated by the Carrothers equation. A composition comprising the reactive oligomer has at least one further component including a second reactive oligomer, an oligomer lacking unreactive functional groups capable of undergoing thermal chain extension and crosslinking, a thermoplastic polymer, a thermoplastic polymer having the same backbone repeat units as the reactive oligomer, a filler or an additive. A method of making an article includes heating a composition comprising a reactive oligomer at a sufficient temperature and time to shape and cross-link the reactive oligomer, including additive manufacturing.

Description

Technical Field

[0001] This application claims the benefit of U.S. Provisional Application No. 62 / 932,892, filed on November 8, 2019, and U.S. Provisional Application No. 63 / 075,610, filed on September 8, 2020, the disclosures of which are incorporated herein by reference in their entireties. Background Art

[0002] Fully aromatic polyamide-imide (PAI) is a high-performance polymer with alternating cyclic imide and amide bonds in the polymer backbone, which was first commercialized in the early 1970s. High molecular weight PAI has excellent high temperature strength, low temperature toughness and impact strength, as well as outstanding chemical resistance and dimensional stability. High molecular weight PAI can have unimidized amic acid groups in the polymer backbone. The amic acid groups impart some flexibility to the polymer backbone, which makes PAI melt-processable to some extent, but not easily. However, there are still several challenges associated with the melt processing of high molecular weight PAI. Melt viscosity is highly sensitive to temperature and shear rate, and the processing window of PAI is narrow, requiring processing temperatures above 600°F (316°C). Amic acid is thermally converted to imide by cyclodehydration, and the conversion of amic 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 happens during extrusion, there is a risk that the polymer melt may solidify in the extruder. Due to the presence of unimidized amic acid groups, PAI is highly sensitive to moisture and must be thoroughly dried before melt processing and kept dry during melt processing to prevent molecular weight and thermal / mechanical property degradation. In addition, imidization and removal of imidized water at 500°F (260°C) for 20 days or more may be required to obtain optimal properties. These difficulties limit the use of high molecular weight PAI to the manufacture of simple stock shapes, such as rods, plates, tubes, and other profiles. These stock shapes can then be processed into parts that cannot be achieved by injection molding, such as turning, drilling, and milling steps.

[0003] In view of the processing limitations of high molecular weight PAI, injection molding grades with lower viscosity have been developed. These grades can be used to produce injection molded, filled and unfilled parts and profiles, but with great difficulty. Injection molding grades are considered to be mixtures of amine-terminated low molecular weight (oligo) polyamides with dianhydride chain extenders such as pyromellitic anhydride (PMDA) to build molecular weight in situ. The oligomeric nature of the polyamide reduces the melt viscosity, which aids the melt processing step, and the amine-terminated polyamide oligomer reacts with the dianhydride to form a high molecular weight polyamide amic acid intermediate through chain extension. After processing, the resulting parts and profiles require post-curing. In the post-curing, the amic acid groups cyclodehydrate to form PAI. A major disadvantage of this route to PAI is the need to remove a large amount of water from the final part. This water has two sources: i) physically adsorbed water associated with the hygroscopic residual amic acid moiety in the chain-extended PAI; ii) water generated in the cyclodehydration step. Removing water from parts and profiles is a time consuming process requiring programmed heating regimens from days to weeks, depending on the thickness of the part and its ultimate application. There is a need in the art for fully aromatic PAIs that do not require extended thermal post-curing and time consuming water removal steps.

[0004] Although injection molding grade PAI is an improvement over high molecular weight PAI, it still presents several challenges in melt processing. As mentioned above, the amic acid groups are still present in the chain-extended PAI, so it must be thoroughly dried before use. A thermal post-processing step is also required to complete the polymerization (chain extension) and / or imidization of the amic acid groups. As mentioned above, water is generated during these post-processing steps and must be removed to avoid foaming, microbubble formation, and part embrittlement. Injection molding grade PAI also presents other difficulties. Residence time must be optimized, as too long residence time will cause flow loss due to chain extension and increased viscosity. The mold must be filled quickly, and the pressure must be optimized for each mold size and shape. Injection molding with a family mold design does not work well. The viscosity of injection molding grade PAI is still highly shear sensitive. Therefore, injection speed, injection pressure, back pressure, screw speed, barrel temperature, cycle time, and mold heating must be optimized for each specific mold shape and size.

[0005] Post-heat treatment remains critical for injection-molded grade PAI. Although molded parts may appear finished, they are actually weak, brittle, have poor chemical and abrasion resistance, and suboptimal heat resistance. To achieve optimal properties, molded parts must be heated in a forced-air oven according to a curing schedule with a series of incremental temperature increases at certain intervals, which must be optimized for each type and size of part. The general curing schedule recommended by manufacturers is: 375℉(191℃) 1 day, 425℉(218℃) 1 day, 475℉(246℃) 1 day, and 500℉(260℃) 5 days, for a total of 8 days. Thicker parts may take longer to cure because the reacting water must diffuse out of the part to react. Therefore, the reaction rate decreases as the diffusion path is extended. In addition, some parts, such as those with very thin walls and / or delicate features, may need to be fixed during post-cure to meet tight dimensional tolerances.

[0006] In view of the above problems, there is still a need in the art for PAIs that are easily melt-processable and curable, which do not require extensive drying before processing and do not require extensive thermal post-treatment to remove water produced by the cyclodehydration of the amide acid functional groups. There is also a need for PAIs that are suitable for various article manufacturing processes, including additive manufacturing, such as fused deposition modeling (FDM) using filaments or rods, selective laser sintering (SLS) for powder bed printing, directed energy deposition (DED) laser engineered net shaping (LENS), and composite-based additive manufacturing (CBAM).

[0007] These challenges are not limited to PAI. There is also a need in the art for other engineering polymers and high performance polymers that are not only easily melt processed and solidified, but also provide articles with excellent thermal and mechanical properties. In particular, such improvements are also highly desirable for polyimides, polyetherimides, polyaryletherketones, polyethersulfones, polyphenylene sulfides, polyamides, polyesters, polyarylates, polyesteramides, polycarbonates, polybenzoxazoles and polybenzimidazoles, and polyamideimides.

[0008] The subject matter described herein addresses these shortcomings in the art and more. Summary of the invention

[0009] A reactive oligomer comprises a backbone derived from at least one of polyamideimide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole or polybenzimidazole and functionalized with at least one unreacted functional group capable of thermal chain extension and crosslinking after formation of the reactive oligomer, wherein the number average molecular weight (M) of the reactive oligomer is n ) is calculated using the Carothers equation to be about 250 to about 10,000 g / mol.

[0010] The composition comprising the reactive oligomer may comprise at least one other component. A method of compounding a reactive oligomer comprises mixing the reactive oligomer with at least one other component at a sufficient temperature and time to form a uniform molten mixture, but without crosslinking unreacted functional groups. The at least one other component may be at least one of the following: a second reactive oligomer, an oligomer lacking unreacted functional groups capable of thermal chain extension and crosslinking, a thermoplastic polymer, a thermoplastic polymer having the same backbone repeating unit as the reactive oligomer, a filler, or an additive.

[0011] A method of manufacturing an article comprises heating a composition comprising the reactive oligomer at a sufficient temperature and time to shape and crosslink the reactive oligomer. The manufacturing method can be additive manufacturing. Articles manufactured from a composition comprising the reactive oligomer include additively manufactured articles. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Now refer to the accompanying drawings:

[0013] Figure 1 A to 1D illustrate the concepts of cross-interface diffusion and chain entanglement and cross-linking across the interface. Figure 1 A and 1B depict the diffusion and entanglement of high molecular weight high performance thermoplastics. Figure 1 C and 1D depict the diffusion, entanglement, chain extension, and cross-linking of reactive oligomers.

[0014] Figure 2 This is a graph showing the relationship between the axial force (N) and time (min) during the melt polymerization of 1,3-phenylenediamine, 4,4'-oxydiphenylamine, trimellitic anhydride and 4-(phenylethynyl)phthalic anhydride in a twin-screw extruder. DETAILED DESCRIPTION

[0015] A reactive oligomer comprises a backbone derived from at least one of polyamideimide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole or polybenzimidazole and functionalized with at least one unreacted functional group capable of thermal chain extension and crosslinking after formation of the reactive oligomer, wherein the number average molecular weight (M) of the reactive oligomer is n ) is calculated using the Carothers equation to be about 250 to about 10,000 g / mol. The at least one unreacted functional group may be at least one of maleimide, 5-norbornene-2,3-dicarboxylic acid imide, phthalonitrile, benzocyclobutene, biphenylene, cyanate, ketoacetylene, acetylene, methylacetylene, phenylacetylene, propargyl ether, or benzoxazine.

[0016] It may be desirable that the reactive oligomer be cured in stages at different temperature ranges, i.e. partially cured at a first temperature range and further cured at a higher second temperature range. Thus, in some embodiments, the reactive oligomer is functionalized with first and second unreacted functional groups capable of thermal chain extension and crosslinking after the reactive oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range.

[0017] The reactive oligomer has a backbone derived from at least one of polyamideimide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole or polybenzimidazole. The backbone may be linear or branched.

[0018] x-PAI

[0019] In some embodiments, the reactive oligomer has a skeleton derived from polyamideimide and is defined as a reactive polyamideimide oligomer herein. Also disclosed herein are reactive polyamide amic acid oligomers, reactive carboxylic acid ammonium salts, methods for making reactive oligomers and reactive carboxylic acid ammonium salts, methods for processing reactive oligomers and reactive carboxylic acid ammonium salts, and products made of reactive oligomers and reactive carboxylic acid ammonium salts. The approach to obtaining polyamideimide products described herein eliminates the need for extended thermal post-curing and time-consuming water removal steps. This is achieved by designing a fully imidized reactive polyamideimide oligomer, which can be melt processed, then subjected to short-term (up to several hours) thermal post-curing, and high molecular weight polyamideimide is produced by chain extension / cross-linking. The reaction behind occurs by incorporating carefully selected functional groups into reactive polyamideimide oligomers. These functional groups remain unreacted during the oligomerization process and can then be used for thermal post-curing. During thermal post-curing, these functional groups can be polymerized (chain extension / cross-linking) via addition reactions without generating small molecule byproducts like water.

[0020] The reactive polyamideimide oligomers with unreacted functional groups described herein allow the production of profiles, complex parts for injection molding, 3D printed parts, and fiber or mineral reinforced composites without any thickness restrictions, because the step of removing water from the final product is no longer required. These routes to polyamideimide not only provide processing advantages (e.g., low viscosity, no residual water, no generated water), but also allow the design and manufacture of PAI articles that were previously impossible to manufacture.

[0021] With M in the range of about 1000 to about 10000 g / mol nProvides lower melt viscosity and lower processing temperature, thereby can use conventional melt processing equipment for melt processing. However, low molecular weight polymers (oligomers) are known to have poor mechanical properties because they lack polymer chain entanglement. The use of crosslinkable monomers and / or crosslinkable end-capping agents in the preparation of reactive oligomers can increase the molecular weight by in situ thermal polymerization (e.g. during reaction injection molding) or during a thermal post-treatment step (e.g. when preparing fiber reinforced composites).

[0022] Reactive polyamideimide oligomers with heat-curable groups have several advantages. Reactive polyamideimide oligomers are easily melt-processed, do not require extensive drying before processing, and do not require extensive thermal post-treatment. Complex parts can be made from reactive polyamideimide oligomers in one step. Depending on the heat-curable group, curing can be carried out at about 160 to about 450°C. In some embodiments, curing is carried out at about 300 to about 450°C and can be completed in as little as about 1 to about 60 minutes, compared to several days for currently available grades of PAI. When the reactive polyamideimide oligomer is fully imidized before melt processing, there is no need for the difficult step of removing water from the profile or injection molded part. Advantageously, the reactive polyamideimide oligomer can be used for one-step injection molding of complex parts under conditions where the reactive oligomer cures instantaneously. Alternatively, the part can be easily thermally cured for about 1 to about 60 minutes. In addition, the T of the cured reactive polyamideimide oligomer is g , elongation at break, breaking strength and toughness can be far superior to currently available PAI.

[0023] The reactive polyamideimide oligomer comprises units derived from at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end-capping agent; wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed; and the number average molecular weight (M) of the reactive polyamideimide oligomer is n ) is calculated using the Carothers equation to be about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol.

[0024] The reactive polyamideimide oligomer comprises units derived from at least one aromatic diamine.The at least one aromatic diamine may have any chemical structure described below.

[0025]

[0026] In some aspects, the at least one diamine is at least one of 1,3-phenylenediamine, 4,4'-oxydiphenylamine, or 3,4'-oxydiphenylamine.

[0027] The reactive polyamide-imide oligomer also comprises at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent. The functional equivalent of carboxylic acid is a functional group in which the carboxyl carbon atom is in the same oxidation state, such as carboxylate, carboxylic acid halide and carboxylic anhydride. For example, the functional equivalent of trimellitic anhydride is a compound in which the substituent carbon atoms at 1-, 2- and 4-positions on the benzene ring are in the same oxidation state. The functional equivalent of trimellitic anhydride is 4-chloroformyl phthalic anhydride. At least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent includes at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent with ortho (ortho) carboxylic acid or functional equivalent group (such as phthalic anhydride group), so that a 5-membered phthalimide ring can be formed in the reactive oligomer skeleton. At least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent can have any chemical structure described below. "Functional equivalents" of carboxylic acids include compounds in which the carbon atom of the carboxylic acid group is in the same oxidation state, and include esters, chlorides, and anhydrides thereof.

[0028]

[0029] In some embodiments, the at least one aromatic di-, tri-, or tetra-functional carboxylic acid or a functional equivalent thereof is at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthalic dichloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride.

[0030] The reactive polyamideimide oligomer also comprises at least one crosslinkable monomer or crosslinkable end-capping agent, which is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed. This functional group remains unreacted after the reactive polyamideimide oligomer is formed, and therefore can be used to participate in subsequent chain extension, branching and crosslinking reactions. Chain extension, branching and crosslinking occurring after the reactive polyamideimide oligomer is formed are collectively referred to as "curing". As used herein, "crosslinking" is also a shorthand for any combination of chain extension, branching and crosslinking. Curing or crosslinking can be initiated by heat, actinic (electromagnetic) radiation and electron beam radiation. In some embodiments, curing is thermally initiated. The unreacted functional groups participating in the subsequent chain extension, branching and crosslinking reactions are at least one of acetylene, methylacetylene, phenylacetylene, ketoacetylene, propargyl ether, norbornene, maleimide, cyanate, phthalonitrile, benzocyclobutene, biphenylene or benzoxazine. These unreacted functional groups are described in Table 1 by chemical formula, chemical name and curing temperature range. At least one crosslinkable monomer or crosslinkable end-capping agent can be two crosslinkable monomers or crosslinkable end-capping agents that react at different temperature ranges.

[0031] Table 1. Functional groups capable of thermal chain extension, branching, and crosslinking and cure temperature range.

[0032]

[0033]

[0034]

[0035] In some embodiments, the at least one unreacted functional group is derived from a monomer or a capping agent selected from the group consisting of:

[0036]

[0037]

[0038] 1,2-Diphenylacetylene is a crosslinkable monomer. All other compounds are crosslinkable end-capping agents. In some embodiments, the crosslinkable monomer or crosslinkable end-capping agent is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA) or 4,4'-(ethynyl-1,2-diyl) diphthalic anhydride.

[0039] The reactive polyamideimide oligomer may also contain units derived from at least one non-crosslinkable end-capping agent, wherein the non-crosslinkable end-capping agent is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent, but has no unreacted functional groups capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed. The non-crosslinkable end-capping agent may be at least one of benzoic acid, benzoyl chloride, phthalic anhydride or aniline.

[0040] The reactive polyamideimide oligomer can be linear or branched. In some embodiments, the reactive polyamideimide oligomer is branched. Branching is obtained by using a trifunctional monomer. Therefore, in some embodiments, the reactive polyamideimide oligomer also includes units derived from at least one of an aromatic triamine, an aromatic tricarboxylic acid, or an aromatic tricarboxylic acid chloride. 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.

[0041] As used herein, the number average molecular weight M n is a target value, not a measured value. Using the Carothers equation, Eq. (2) calculates the amount of monomer and cross-linkable end-capping agent used to prepare the reactive oligomer. Eq. (1) is used to calculate the target Required degree of polymerization

[0042]

[0043] (Also referred to as M n ) is a target number average molecular weight selected from the range of about 250 to about 10000 g / mol, preferably about 1000 to about 10000 g / mol) and is the average molecular weight of the repeating unit of the oligomer. and In the case of and substitute into Eq.2. Assuming the reaction is complete, so p = 1, this simplifies Eq.2 to an equation with one unknown r, which is the ratio of the reactants, and provides the required amount of energy to prepare the target The desired stoichiometric shift of the reactive oligomer.

[0044] Polyamide amic acid is an intermediate in the synthesis of polyamide imide. As shown in Scheme 1 below, polyamide imide is produced by cyclodehydration of the intermediate polyamide amic acid (upper right structure).

[0045] Solution 1

[0046]

[0047] Since polyamide amic acid is an intermediate for preparing polyamideimide, reactive polyamideimide oligomers can have different degrees of imidization, that is, polyamide amic acid intermediates are converted into polyamideimide. Therefore, in some embodiments, reactive polyamideimide oligomers are derived from reactive polyamide amic acid oligomer intermediates by dehydration cyclization, and the amic acid groups greater than about 80% and less than or equal to 100% in the reactive polyamide amic acid intermediate are imidized. When the imidization degree is within this range, reactive polyamideimide oligomers are considered to be "completely imidized". Within this range, polyamide amic acid groups greater than or equal to 85%, 90%, 95%, 96%, 97%, 98% and 99% and less than or equal to 100% can be imidized.

[0048] In some applications, less than 80% of the reactive polyamide-imide oligomers imidized may be useful. Therefore, in some embodiments, the reactive polyamide-imide oligomer is derived from the reactive polyamide amic acid oligomer intermediate by dehydration cyclization, and the amic acid groups greater than or equal to 20% and less than or equal to 80% in the reactive polyamide amic acid intermediate are imidized. Within this range, greater than or equal to 30%, 40%, 50%, 60% and 70% and less than or equal to 80% of the amic acid groups can be imidized.

[0049] Advantageously, the reactive polyamideimide oligomer has a melt complex viscosity of about 1000 to about 100000 Pa·s at 360°C, as measured by oscillatory shear rheology between parallel plates at a heating rate of 10°C / min, a frequency of 2 rad / sec, and a strain of 0.03% to 1.0% under N2. In this range, the melt complex viscosity is M n and at least one diamine, at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent and a function of the type and relative amount of crosslinkable or non-crosslinkable monomers and end-capping agents used to make reactive polyamide oligomers. Therefore, the melt complex viscosity as a function of shear rate, time, temperature and heating rate can be adjusted by selecting monomers and reactive and non-reactive end-capping agents and their relative amounts. For example, the melt complex viscosity may be greater than or equal to 2000, 3000, 4000 or 5000 Pa s and less than or equal to 90000, 70000, 50000 or 30000 Pa s. In some embodiments, the melt complex viscosity is from about 5000 to about 30000 Pa s at 360 ° C. In contrast, it is reported that currently available PAI has a melt complex viscosity of 100000 Pa s at 2 radians / second.

[0050] Specific reactive polyamideimide oligomers are disclosed herein. For example, the reactive polyamideimide oligomer may comprise 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'-oxydiphenylamine and 4,4'-oxydiphenylamine, 4-methylethynylphthalic anhydride and optionally 4-phenylethynylphthalic anhydride. The reactive polyamideimide oligomer may also comprise units derived from at least one dianhydride selected from pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, at least one difunctional aromatic compound selected from isophthalic acid and isophthaloyl chloride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydiphenylamine and 4,4'-oxydiphenylamine, 4-methylethynylphthalic anhydride and optionally 4-phenylethynylphthalic anhydride. The reactive polyamideimide oligomer may also comprise units derived from at least one dianhydride selected from pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, at least one difunctional aromatic compound selected from isophthalic acid and isophthaloyl chloride, at least one aromatic diamine selected from 1,3-diaminobenzene, 3,4'-oxydiphenylamine and 4,4'-oxydiphenylamine, 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride and at least one anhydride selected from phthalic anhydride, 4-methylethynylphthalic anhydride or 4-phenylethynylphthalic anhydride.

[0051] x-PAI production method

[0052] The reactive polyamideimide oligomer can be made by a method comprising: copolymerizing at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent and at least one crosslinkable monomer or crosslinkable end-capping agent in the presence of a polar solvent to form a reactive polyamide amic acid; heating the reactive polyamide amic acid oligomer at a sufficient temperature and time to prepare the reactive polyamideimide oligomer; wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed. The preparation of an exemplary reactive polyamideimide oligomer is provided in Scheme 2.

[0053] Solution 2

[0054]

[0055]

[0056] A – Synthesis of reactive polyamideimide oligomers with only one cross-linkable end-capping agent;

[0057] B – Synthesis of reactive polyamideimide oligomers with two different cross-linkable end-capping agents;

[0058] C – Synthesis of reactive polyamideimide oligomers from dianhydrides (tetrafunctional) and diacids / diacid chlorides (difunctional) with only one crosslinkable end-capping agent;

[0059] D - Synthesis of reactive polyamideimide oligomers from crosslinkable monomers and non-crosslinkable end-capping agents; and

[0060] E - Synthesis of reactive polyamideimide oligomers from crosslinkable monomers and crosslinkable endcapping agents.

[0061] The sufficient temperature and time for preparing the reactive polyamideimide oligomer is about 140°C to about 220°C for about 1 minute to about 120 minutes. As described above, the reactive polyamideimide oligomer is manufactured by forming a reactive polyamide amic acid oligomer intermediate. The temperature and time required for imidizing the reactive polyamide amic acid oligomer intermediate in this method depend on whether there is a polar solvent, the specific reactive polyamideimide oligomer prepared, and the desired degree of imidization. When imidization is carried out in the absence of a solvent, that is, using a pure solid reactive polyamide amic acid oligomer, the sufficient temperature and time for preparing the reactive polyamideimide oligomer is about 220°C to about 300°C for about 1 minute to about 120 minutes. When imidization is carried out in the presence of a polar solvent, the sufficient temperature and time for preparing the reactive polyamideimide oligomer is about 140°C to about 220°C for about 1 minute to about 120 minutes.

[0062] The reactive polyamide-imide oligomer is manufactured in the presence of a polar solvent, which reduces the temperature range sufficient to prepare the reactive oligomer. The boiling point of the polar solvent at one atmosphere should be at least 150°C. 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 cyclopentane. In some embodiments, the polar solvent is N-methyl-2-pyrrolidone. The manufacturing method may also 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 prepare the reactive polyamide-imide oligomer.

[0063] There are different methods for the imidization of reactive polyamide amic acid oligomers. Reactive polyamide imide oligomers can be prepared by adding toluene to the reactive polyamide amic acid oligomers and azeotropically distilling toluene with water. Reactive polyamide imide oligomers can also be prepared by microwave irradiation of reactive polyamide amic acid oligomers. The imidization agent can be acetic anhydride. Acidic byproducts are produced by imidization, such as acetic acid when acetic anhydride is used. Therefore, a base, such as a tertiary amine, can be used. The tertiary amine can be, for example, pyridine or triethylamine. Therefore, in some embodiments, reactive polyamide imide oligomers are prepared by heating reactive polyamide amic acid oligomers in the presence of acetic anhydride and a catalytic amount of a tertiary amine.

[0064] Another method of making reactive polyamideimide oligomers is to copolymerize in the presence of a phosphorylating agent and a catalytic amount of a salt. In this method, di-, tri- or tetra-functional carboxylic acids or their functional equivalents do not include acyl halides, such as acyl chlorides. The advantage of this method is that expensive acyl chlorides are not required as starting materials. For example, copolymerization is carried out in the presence of triphenyl phosphite, polar solvents such as NMP as solvents and catalytic amounts of salts such as LiCl or CaCl2. Heating to 120°C for 1.5 to 2 hours under nitrogen results in the formation of reactive polyamide amic acid oligomers and partial imidization to the corresponding reactive polyamideimide oligomers. Further heating to 150°C for up to 5 hours with additional pyridine under nitrogen can provide complete imidization.

[0065] Reactive polyamideimide oligomers can also be prepared by reactive extrusion. Thus, the method of making reactive polyamideimide oligomers comprises reactively extruding at least one aromatic diamine or an activated derivative thereof (e.g., diacetylated diamine), at least one aromatic di-, tri-, or tetra-functional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end-capping agent at a temperature and time sufficient to prepare the reactive polyamideimide oligomer; wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with at least one aromatic diamine or at least one di-, tri-, or tetra-functional aromatic carboxylic acid or its functional equivalent and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0066] 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 it can partially dissolve the monomer and form a fluid suspension or slurry of the monomer together with the oligomers and intermediates formed during the reactive extrusion.

[0067] Reactive extrusion can be carried out in the presence of an acid catalyst to promote the imidization (cyclodehydration) of the amide acid intermediate. When in liquid state under the reaction extrusion conditions, the acid catalyst can also partially dissolve the monomer and form a fluid suspension or slurry of the monomer together with the oligomers and intermediates formed during the reaction extrusion. When the acid catalyst is liquid, it can be removed by distillation through the vent during the reaction extrusion. In some embodiments, the acid catalyst is acetic acid, and it is removed by distillation during the reaction extrusion. Reactive extrusion can also be carried out in the presence of acetic anhydride, wherein acetic anhydride is removed by distillation during the reaction extrusion. In order to promote the removal of any water, HCl, polar solvents, acid catalysts and acetic anhydride present or produced, the reaction extrusion can be carried out in a melt extruder, and the melt extruder has a plurality of preset heating zones equipped with vents or other devices for removing these volatiles.

[0068] The reactive polyamideimide oligomer can also be made by the "ammonium carboxylate" method. The ammonium carboxylate method comprises: reacting a polyamideimide oligomer in water or C at a temperature and time sufficient to form at least one reactive ammonium carboxylate. 1-4 heating at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end-capping agent in the presence of at least one of 1-4 alcohol; and heating the reactive carboxylic acid ammonium salt at a temperature and for a time sufficient to form a reactive polyamideimide oligomer; wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed. 1-4 The alcohol may be, for example, at least one of methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-butanol, or tert-butanol. 1-4 The alcohol is at least one of methanol or ethanol. The preparation of an exemplary reactive polyamideimide oligomer by the ammonium carboxylate salt method is described in Scheme 3 below.

[0069] Solution 3

[0070]

[0071] Mix the anhydride and diamine in water or C 1-4 The mixture is heated in at least one of the following alcohols (e.g., methanol or ethanol) at 70°C for 1 hour. This will cause the anhydride to ring-open and form the corresponding dicarboxylic acid alkyl half ester, such as methyl or ethyl half ester. Water or C is then removed by vacuum distillation. 1-4 Therefore, the reactive carboxylic acid ammonium salt is Ar-COO - and +A mixture of all possible combinations of H3N-Ar, where Ar represents an aromatic group, and where Ar-COO - It is C 1-4 Alkyl half esters. Ammonium carboxylate salts (similar to nylon salts) can be converted into reactive polyamideimide oligomers by polymerization and imidization, which can be accomplished in a variety of ways. Polymerization and imidization can be carried out by heating the dried reactive ammonium carboxylate salt in an inert atmosphere, preferably heated to 300°C under pressure (0 to 300 MPa) to obtain reactive polyamideimide oligomers. (Option 1 in Scheme 3) The heating can be carried out in a sealed container (Option 1 in Scheme 3) and / or in an extruder with exhaust capability for removing water and methanol or ethanol vapor. (Option 2 in Scheme 3) For example, the reactive ammonium carboxylate salt can be gradually heated at 60, 100 and 200°C in a sealed container under an inert atmosphere for 1 hour, then cooled to 25°C, and then oligomerized at 320 to 360°C in an extruder to obtain a reactive polyamideimide oligomer. Therefore, in some embodiments, the method includes reactively extruding a reactive ammonium carboxylate salt at a temperature and time sufficient to form a reactive polyamideimide oligomer. Polymerization and imidization can also be carried out by dissolving the reactive carboxylic acid ammonium 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, and then heating to 160° C. (Option 3 in Scheme 3) Therefore, in some embodiments, the method includes dissolving the reactive carboxylic acid ammonium salt in a polar solvent and then heating at a temperature, pressure, and time sufficient to form a reactive polyamideimide oligomer.

[0072] Alternatively, at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or a functional equivalent thereof, and at least one crosslinkable monomer or crosslinkable endcapping agent may 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 (bomb calorimeter or autoclave) to polymerize and imidize the reactive carboxylic acid ammonium salt.

[0073] Advantageously, the reactive carboxylic acid ammonium salt has a melt complex viscosity of about 1 to about 100 Pa.s in a temperature range of about 80 to about 120° C., and a solubility of up to 70 to 80 wt % in a polar solvent such as NMP at 60° C. The low melt complex viscosity and high solubility of the reactive carboxylic acid ammonium salt allow for high yield production of reactive polyamideimide oligomers.

[0074] Polyamide Acid

[0075] As mentioned above, reactive polyamide amic acid oligomer is an intermediate for making reactive polyamide imide oligomer. Therefore, reactive polyamide amic acid oligomer comprises a unit derived from at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable end-capping agent, wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with the at least one aromatic diamine or the at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group that can be chain-extended and crosslinked after reactive polyamide amic acid oligomer is formed; and wherein the number average molecular weight (M) of reactive polyamide amic acid oligomer is less than 1.0; n ) is calculated using the Carothers equation to be about 1000 to about 10000 g / mol. Reactive polyamideimide oligomers and reactive polyamide amic acid oligomers are closely related in that reactive polyamide amic acid oligomers are intermediates that form corresponding reactive polyamideimide oligomers. They differ only in the degree of imidization. Although reactive polyamideimide oligomers as defined herein can have amic acid groups greater than 20% and less than or equal to 100% imidized in reactive polyamide amic acid intermediates, 0% to about 20% amic acid groups are imidized in reactive polyamide amic acid oligomers as defined herein.

[0076] The composition description applicable to the reactive polyamideimide oligomer disclosed herein is also applicable to the reactive polyamide amic acid oligomer. Therefore, the aromatic diamine can be at least one of 1,3-phenylenediamine, 4,4'-oxydiphenylamine or 3,4'-oxydiphenylamine, and the di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent can be at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthalic chloride, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride. The unreacted functional groups involved in the subsequent chain extension, branching and cross-linking reactions can be at least one of acetylene, methylacetylene, phenylacetylene, ketoacetylene, propargyl ether, norbornene, maleimide, cyanate, phthalonitrile, benzocyclobutene, biphenylene or benzoxazine. These unreacted functional groups are described in Table 1 with chemical formula, chemical name and curing temperature range. At least one crosslinkable monomer or crosslinkable end-capping agent can be two crosslinkable monomers or crosslinkable end-capping agents that react at different temperature ranges. In some embodiments, the crosslinkable monomer or crosslinkable end-capping agent is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA) or 4,4'-(ethynyl-1,2-diyl) diphthalic anhydride.

[0077] The reactive polyamide amic acid oligomer may also contain units derived from at least one non-crosslinkable end-capping agent, wherein the non-crosslinkable end-capping agent is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent, but does not have unreacted functional groups capable of chain extension and crosslinking after the reactive polyamide imide oligomer is formed. The non-crosslinkable end-capping agent may be at least one of benzoic acid, benzoyl chloride, phthalic anhydride or aniline.

[0078] The reactive polyamide amic acid oligomer can be made by a method comprising: copolymerizing at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent and at least one crosslinkable monomer or crosslinkable end-capping agent in the presence of a polar solvent to form a reactive polyamide amic acid; wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamide imide oligomer is formed.

[0079] The reactive polyamide amic acid oligomer is manufactured in the presence of a polar solvent, which reduces the temperature range sufficient to prepare the reactive oligomer. The boiling point of the polar solvent at one atmosphere should be at least 150°C. The polar solvent may be at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene or cyclopentane. In some embodiments, the polar solvent is N-methyl-2-pyrrolidone. In some embodiments, the method further comprises separating the reactive polyamide amic acid oligomer from the polar solvent.

[0080] Other skeleton structures

[0081] The reactive oligomer may have a backbone derived from a polymer other than polyamideimide. In some embodiments, the reactive oligomer has a backbone derived from polyimide and is defined herein as a reactive polyimide oligomer. The reactive polyimide oligomer may have formula (I):

[0082]

[0083] Among them, Ar 1 The tetravalent aromatic group represented by is at least one of the following:

[0084]

[0085] By Ar 2 The divalent aromatic group represented by is at least one of the following:

[0086]

[0087] Y 1 and Z 1 Each is independently derived from a capping agent selected from the group consisting of:

[0088]

[0089] and

[0090] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol. n .

[0091] The molar ratio of the monomers can be selected so that there is an excess of amine functional end groups or carboxylic anhydride functional end groups in the polyimide oligomer backbone, that is, there can be an amine-terminated or carboxylic anhydride-terminated polyimide oligomer backbone. When the amine end groups are excessive, an acyl chloride functional end-capping agent (X = -COCl) or an anhydride end-capping agent is selected. When the anhydride end groups are excessive, an amine functional end-capping agent (X = -NH2) is selected.

[0092] It may be desirable that the reactive polyimide oligomer be cured in stages at different temperature ranges, i.e., partially cured in a first temperature range and further cured in a second higher temperature range. Thus, 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 reactive oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range. Thus, when Y 1 and Z 1 At the same time, the reactive polyimide oligomer of formula (I) can be cured in stages at different temperature ranges.

[0093] In some embodiments, Ar 1 or Ar 2 At least one of the reactive oligomers has an ether bond between the aromatic groups, i.e., the reactive oligomer is a reactive polyetherimide oligomer. The unreacted functional group in the reactive polyetherimide oligomer may be at least one of a methylethynyl group, a phenylethynyl group, or a maleimide. Specifically, the unreacted functional group may be derived from at least one of 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4,4'-(acetylene-1,2-diyl) diphthalic anhydride, or N-(4-aminophenyl) maleimide.

[0094] Exemplary reactive polyetherimide oligomers are disclosed herein. For example, the reactive polyetherimide oligomer may include units derived from 4,4'-(4,4'-isopropylidene diphenyloxy)bis(phthalic anhydride) (CAS 38103-06-9), 1,3-phenylenediamine, 4-methylethynylphthalic anhydride, and N-(4-aminophenyl)maleimide. The reactive polyetherimide oligomer may also include units derived from 2,3,3',4'-biphenyltetracarboxylic dianhydride, at least one aromatic diamine selected from 1,3-phenylenediamine, 3,4'-oxydiphenylamine, and 4,4'-oxydiphenylamine, 4-methylethynylphthalic anhydride, and optionally 4-phenylethynylphthalic anhydride.

[0095] The reactive oligomer may also have a backbone derived from a polyaryletherketone and is referred to herein as a reactive polyaryletherketone (PAEK) oligomer. For example, the reactive PAEK oligomer may be a reactive polyetheretherketone oligomer or a reactive polyetherketone oligomer. The reactive PAEK oligomer may have formula (II):

[0096]

[0097] Among them, Ar 3 The divalent aromatic group represented by is at least one of the following:

[0098]

[0099] Where S 1 , S 2 , S 3 and S 4 Each independently selected from H, F, Cl, Br, C 1-6 The group consisting of a straight chain or branched chain alkyl group, and a phenyl group; and

[0100] W is:

[0101]

[0102] By Ar 4 The divalent aromatic group represented by is at least one of the following:

[0103]

[0104] Y 2 and Z 2 Each is independently derived from a capping agent selected from the group consisting of:

[0105]

[0106] Where D is:

[0107] and

[0108] A is:

[0109] and

[0110] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol. n .

[0111] The molar ratio of the monomers can be selected so that there is an excess of fluorine functional end groups or phenolic end groups in the PAEK oligomer backbone, i.e., there can be a fluorine-terminated or phenolic end-capped PAEK oligomer backbone. When the fluorine functional end groups are in excess, a phenolic end-capping agent is selected. When the phenolic end groups are in excess, a fluorine functional end-capping agent is selected. The unreacted functional group in the reactive PAEK oligomer can be at least one of methylethynyl, phenylethynyl, or maleimide.

[0112] It may be desirable that the reactive PAEK oligomer be curable in stages at different temperature ranges, i.e., partially cured in a first temperature range and further cured in a second higher temperature range. Thus, in some embodiments, the reactive PAEK oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the reactive oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, and the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range. Thus, when Y 2 and Z 2 At the same time, the reactive PAEK oligomer of formula (II) can be cured in stages within different temperature ranges.

[0113] 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 can have formula (III):

[0114]

[0115] Among them, Ar 5 The divalent aromatic group represented by is:

[0116]

[0117] By Ar 6 The divalent aromatic group represented by has the formula (IIIa):

[0118]

[0119] Y 3 and Z 3 Each is independently derived from a capping agent selected from the group consisting of:

[0120]

[0121] Where D is:

[0122] and

[0123] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol. n .

[0124] It may be desirable to cure the reactive polyethersulfone oligomer in stages at different temperature ranges, i.e., partially cure in a first temperature range and further cure in a higher second temperature range. Therefore, 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 reactive oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range. Therefore, when Y 3 and Z 3 At the same time, the reactive polyethersulfone oligomer of formula (III) can be cured in stages at different temperature ranges.

[0125] The molar ratio of the monomers can be selected so that there is an excess of fluorine-functional end groups or phenolic end groups in the polyethersulfone oligomer backbone, i.e., a fluorine-terminated or phenolic-terminated polyethersulfone oligomer backbone can be present. When the fluorine-functional end groups are excessive, a phenolic-functional end-capping agent is selected. When the phenolic end groups are excessive, a fluorine-functional end-capping agent is selected. The unreacted functional groups in the reactive polyethersulfone oligomer can be at least one of methylethynyl, phenylethynyl or maleimide.

[0126] The reactive oligomer may also have a backbone derived from polyphenylene sulfide and is referred to herein as a reactive polyphenylene sulfide oligomer. The reactive polyphenylene sulfide oligomer may have formula (IV):

[0127]

[0128] The divalent aromatic group represented by Ar is:

[0129]

[0130] Where W is:

[0131]

[0132] Y and Z are each independently derived from a capping agent selected from the group consisting of:

[0133]

[0134] Where D is:

[0135] and

[0136] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol. n .

[0137] It may be desirable that the reactive polyphenylene sulfide oligomer can be cured in stages at different temperature ranges, i.e., partially cured at a first temperature range and further cured at a higher second temperature range. Therefore, in some embodiments, the reactive polyphenylene sulfide oligomer is functionalized with first and second unreacted functional groups that can be thermally extended and crosslinked after the reactive oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range. Therefore, when Y and Z are different, the reactive polyphenylene sulfide oligomer of formula (IV) can be cured in stages at different temperature ranges.

[0138] The molar ratio of the monomers can be selected so that there is an excess of fluorine-functional end groups or phenolic end groups in the polyphenylene sulfide oligomer backbone, that is, there can be a fluorine-terminated or phenolic end-capped poly-oligomer backbone. When the fluorine-functional end groups are excessive, a phenolic end-capping agent is selected. When the phenolic end groups are excessive, a fluorine-functional end-capping agent is selected. The unreacted functional group in the reactive polyphenylene sulfide oligomer can be at least one of methylethynyl, phenylethynyl or maleimide.

[0139] The reactive oligomer may also have a backbone derived from a polyamide and is referred to herein as a reactive polyamide oligomer. The reactive polyamide oligomer may have formula (Va) or (Vb):

[0140]

[0141] Among them, A 1 and A 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene or 1,2-, 1,3- or 1,4-xylylene;

[0142] Y 4 and Z 4 Each is independently derived from a capping agent selected from the group consisting of:

[0143] and

[0144] n is selected to provide a calculated Mn in the range of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol.

[0145] The molar ratio of the monomers can be selected so that there is an excess of amine functional end groups or carboxylic anhydride functional end groups in the polyamide oligomer backbone, that is, there can be an amine-terminated or carboxylic anhydride-terminated polyamide oligomer backbone. When the amine end groups are in excess, an acyl chloride functional end-capping agent (X = -COCl) or an anhydride end-capping agent is selected. When the anhydride end groups are in excess, an amine functional end-capping agent (X = -NH2) is selected.

[0146] It may be desirable that the reactive polyamide oligomer can be cured in stages at different temperature ranges, i.e., partially cured at a first temperature range and further cured at a higher second temperature range. Thus, 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 reactive polyamide oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range. Thus, when Y 4 and Z 4 At the same time, the reactive polyamide oligomer of formula (Va) or (Vb) can be cured in stages at different temperature ranges. The unreacted functional group in the reactive polyamide oligomer can be at least one of methylethynyl, phenylethynyl or maleimide.

[0147] The reactive oligomer may also have a backbone derived from a polyester and is referred to herein as a reactive polyester oligomer. The reactive polyester oligomer may have formula (VIa) or (VIb):

[0148]

[0149] Among them, B 1 and B 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene,

[0150]

[0151] Y 5 and Z 5 Each is independently derived from a capping agent selected from the group consisting of:

[0152]

[0153] Where D is:

[0154] and

[0155] X is -OH, -NH2, -COOH or -COCl; and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol. n .

[0156] The molar ratio of the monomers can be selected so that there is an excess of hydroxyl functional end groups, or carboxylic acid or acyl chloride functional end groups in the polyester oligomer backbone, i.e., there can be a hydroxyl-terminated, or carboxylic acid- or acyl chloride-terminated polyester oligomer backbone. When the hydroxyl end groups are in excess, a carboxylic acid- (X = -COOH) or acyl chloride- (X = -COCl) functional end-capping agent is selected. When the carboxylic acid end groups are in excess, a hydroxyl functional (X = -OH) or amine functional end-capping agent (X = -NH2) is selected.

[0157] It may be desirable that the reactive polyester oligomer be cured in stages at different temperature ranges, i.e., partially cured at a first temperature range and further cured at a higher second temperature range. Thus, in some embodiments, the reactive polyester oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the reactive polyester oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range. Thus, when Y 5 and Z 5 At the same time, the reactive polyester oligomer of formula (VIa) or (VIb) can be cured in stages at different temperature ranges. The unreacted functional group in the reactive polyester oligomer can be at least one of methylethynyl, phenylethynyl or maleimide.

[0158] The reactive oligomer may also have a backbone derived from a polyester amide and is referred to herein as a reactive polyester amide oligomer. The reactive polyester amide oligomer may have formula (VIIa) or (VIIb):

[0159]

[0160] Among them, D 1 and D 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene,

[0161]

[0162] Y 6 and Z 6Each is independently derived from a capping agent selected from the group consisting of:

[0163]

[0164] Where D is:

[0165]

[0166] X is -OH, -NH2, -COOH or -COCl; and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol, preferably about 1,000 to about 10,000 g / mol. n .

[0167] The molar ratio of the monomers can be selected so that there is an excess of hydroxyl functional end groups, or carboxylic acid or acyl chloride functional end groups in the polyester amide oligomer backbone, i.e., there can be a hydroxyl-terminated, or carboxylic acid- or acyl chloride-terminated polyester amide oligomer backbone. When the hydroxyl end groups are in excess, carboxylic acid- (X = -COOH) or acyl chloride- (X = -COCl) functional end capping agents are selected. When the carboxylic acid end groups are in excess, hydroxyl functional (X = -OH) or amine functional end capping agents (X = -NH2) are selected.

[0168] It may be desirable that the reactive polyester amide oligomer can be cured in stages at different temperature ranges, i.e., partially cured in a first temperature range and further cured in a higher second temperature range. Therefore, in some embodiments, the reactive polyester amide oligomer is functionalized with first and second unreacted functional groups that are capable of thermal chain extension and crosslinking after the reactive polyester amide oligomer is formed, wherein the first unreacted functional group is self-reactive in the first temperature range, and the second unreacted functional group is self-reactive in the second temperature range, and the second temperature range is higher than the first temperature range. Therefore, when Y 6 and Z 6 At the same time, the reactive polyester amide oligomer of formula (VIIa) or (VIIb) can be cured in stages at different temperature ranges. The unreacted functional group in the reactive polyester amide oligomer can be at least one of methyl ethynyl, phenyl ethynyl or maleimide.

[0169] Composition

[0170] Also disclosed are compositions comprising at least one reactive oligomer, including mixtures of reactive oligomers. In some embodiments, the composition comprises a first and a second reactive aromatic oligomer, wherein the first reactive oligomer is functionalized with a first unreacted functional group capable of thermal chain extension and crosslinking after the first reactive aromatic oligomer is formed, the second reactive oligomer is functionalized with a second unreacted functional group capable of thermal chain extension and crosslinking after the second reactive oligomer is formed, 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. For example, using a combination of first and second reactive oligomers having different unreacted functional groups in a composition for additive manufacturing provides a method for controlling the overall thermal curing range of the composition.

[0171] The composition may further comprise first and second reactive oligomers, wherein the first reactive oligomer has a first number average molecular weight (M n ), the second reactive oligomer has a second number average molecular weight (M n ). For example, the composition may include M n The first reactive oligomer is 3000 g / mol and M n The second reactive oligomer is 8000 g / mol to obtain physical properties different from the physical properties of the first and second reactive oligomers.

[0172] The composition can also include a reactive oligomer and a thermoplastic polymer. In some embodiments of a mixture of a reactive oligomer and a thermoplastic polymer, the thermoplastic polymer can include a backbone repeating unit identical to at least one reactive oligomer. In these mixtures, for example, the reactive oligomer can be a reactive polyamideimide oligomer and the thermoplastic polymer can be a polyamideimide polymer having the same backbone repeating unit but with a higher molecular weight. Therefore, reactive oligomers provide a useful method for changing the physical properties of thermoplastic polymers.

[0173] The composition may also include a reactive oligomer and an oligomer lacking unreacted functional groups capable of thermal chain extension. The oligomer lacking unreacted functional groups capable of thermal chain extension may also have an M of about 250 to 10,000 g / mol. n , preferably about 1000 to 10000 g / mol M n .

[0174] The composition may further comprise at least one of a filler or an additive. Examples of fillers include carbon black, ceramic powders, mica, talc, silica, silicates, metal powders (Al, Cu, Ni, Fe) and chopped fibers such as carbon, glass, para-amid, meta-aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), silicon carbide, boron and aluminum oxide, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes and clay flakes.

[0175] It may be desirable to apply a layer of a reactive oligomer to an article comprising a thermoplastic polymer, such as a thermoplastic polymer having the same backbone repeating unit as the reactive oligomer. For example, the article may be a powder or filament for additive manufacturing comprising a thermoplastic polymer. Thus, in some embodiments, the composition comprises a reactive oligomer coating on thermoplastic particles or filaments, optionally wherein the thermoplastic polymer has the same backbone repeating unit as them.

[0176] Mixing

[0177] It may be desirable to compound the reactive oligomer with other materials to improve thermomechanical properties. Thus, the method of compounding the reactive oligomer comprises mixing the reactive oligomer with at least one other component at a temperature and for a time sufficient to form a uniform molten mixture without crosslinking the unreacted functional groups. The other component may be, for example, at least one of a second reactive oligomer, an oligomer lacking unreacted functional groups capable of thermal chain extension and crosslinking, a thermoplastic polymer, a thermoplastic polymer having the same backbone repeating unit as the reactive oligomer, a filler, or an additive.

[0178] Manufacturing method

[0179] Reactive oligomers and compositions containing reactive oligomers can be used to manufacture a variety of articles or parts with useful properties. Therefore, the method of manufacturing an article includes heating the reactive oligomer at a temperature and time sufficient to form and crosslink the reactive aromatic oligomer. The temperature and time sufficient to form and crosslink the reactive oligomer depend on the curing temperature range of the unreacted functional groups in the reactive oligomer that can be thermally extended, branched and crosslinked. As can be seen from Table 1, the sufficient temperature is in the range of about 160 to about 450°C. It may be necessary to select a temperature so that the unreacted groups are crosslinked and the reactive oligomer is cured within about 1 to about 60 minutes. Therefore, the sufficient temperature and time are about 160 to about 450°C for about 1 to about 60 minutes. In some embodiments, the sufficient temperature and time are 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.

[0180] The manufacturing method using the reactive oligomer and the composition containing the reactive oligomer can be additive manufacturing. Also disclosed are articles made by the reactive oligomer and the composition thereof by additive manufacturing. The reactive oligomer and the composition thereof are suitable for a variety of additive manufacturing methods, including fused filament fabrication (FFF), selective laser sintering (SLS), directed energy deposition (DED), laser engineered net shaping (LENS) and composite-based additive manufacturing (CBAM).

[0181] In some embodiments of additive manufacturing, the method is fused filament fabrication. Fused filament fabrication comprises extruding reactive oligomers or a composition thereof in adjacent horizontal layers such that there are interfaces between the layers, and exposing the layers to heat at a temperature and for a time sufficient to crosslink the reactive oligomers and form an article. In this method, the reactive oligomers migrate and covalently bond across the interface to form an integral article. Also disclosed are articles manufactured by fused filament fabrication. Also disclosed are articles manufactured by fused filament fabrication from reactive oligomers or compositions.

[0182] Fused filament fabrication uses material extrusion to print objects, where the feedstock is pushed through an extruder. In most fused filament fabrication 3D printers, the feedstock comes in the form of a filament wound on a spool. The 3D printer liquefier is the main component used in this type of printing. The extruders of these printers 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 to 250°C. The cold end pulls the material from the spool using gear- or roller-based torque applied to the material and controlling the feed rate via a stepper motor. The cold end pushes the feedstock into the hot end. The hot end consists of a heating chamber and a nozzle. The heating chamber houses the liquefier, which melts the feedstock to convert it into a molten state. It allows the molten material to exit from a small nozzle, forming a thin, sticky bead of plastic that adheres to the material it is laying on. The diameter of the nozzle is usually between 0.3 mm and 1.0 mm. Different types of nozzles and heating methods are used depending on the material to be printed.

[0183] The filament can be in the form of a thin wire wound on a spool. In a variation of this method, the feedstock is in the form of a rod rather than a filament. Since the rod is thicker than the filament, it can be pushed toward the hot end by a piston or drum, exerting greater force and / or speed than conventional fused wire manufacturing.

[0184] The weld line is defined as the planar interface between adjacent extruded material layers. The reactive polyamideimide oligomer diffuses across the interface and reacts to rapidly increase polymer chain entanglement and network formation across the interface, fusing the adjacent layers together. The weld line (interface) is further strengthened by chain extension and / or crosslinking of the reactive aromatic oligomer entangled across the interface, thereby increasing z-axis strength.

[0185] In some embodiments of additive manufacturing, the method is selective laser sintering. Selective laser sintering includes selectively sintering and cross-linking particles of reactive aromatic oligomers or compositions thereof with a laser to form an article. Similar to fused filament manufacturing, reactive aromatic oligomers migrate across particle interfaces and covalently bond to form an integral article. Articles manufactured by selective laser sintering are also disclosed. Selective laser sintering (SLS) involves using a high-power laser (e.g., a carbon dioxide laser) to melt small particles of plastic, metal, ceramic, or glass powder into a substance having a desired three-dimensional shape. The laser selectively melts the powdered material by scanning a cross section generated by a 3D digital description of the part on the surface of the powder bed (e.g., from a CAD file or scanned data). After scanning each cross section, the powder bed is lowered by one layer of thickness, and then a layer of new material is applied on top, and the process is repeated until the part is completed. The SLS machine preheats the bulk powder material in the powder bed to a temperature below the flow point of the powder so that the laser can more easily raise the temperature of the selected area to a temperature at which the powder softens and melts together. Articles manufactured by reactive aromatic oligomers by selective laser sintering are also disclosed.

[0186] Compared to some other additive manufacturing processes such as stereolithography (SLA) and fused filament fabrication (FFF), which most often require special support structures to manufacture overhanging designs, SLS does not require a separate feeder for support material because the part being built is always surrounded by unsintered powder, which allows the construction of previously impossible geometries. In addition, because the machine's chamber is always full of powder material, the manufacture of multiple parts has a much smaller impact on the overall difficulty and price of the design, because through a technique called "nesting", multiple parts can be positioned to fit within the boundaries of the machine.

[0187] In additive manufacturing methods such as FFF and SLS that use reactive oligomers as raw materials, the reactive oligomers diffuse rapidly through the particle or filament interface, thereby increasing polymer chain entanglement and chain-chain interactions across the particle or filament interface and fusing adjacent particles or filaments together. The interface is further strengthened by chain extension and cross-linking of the reactive oligomers entangled across the interface.

[0188] Figure 1 A to 1D further illustrate the concepts of cross-interface diffusion and cross-interface chain entanglement and cross-linking. Figure 1 In each of A 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 1 A depicts high molecular weight, high performance thermoplastics on either side of the interface. High molecular weight polymers can diffuse through the interface in both directions and form Figure 1 The chains are entangled as depicted in B. However, above T g But lower than T mA longer thermal annealing time (hours) is required at a temperature.

[0189] Figure 1 C depicts the reactive oligomers on either side of the interface. Low molecular weight reactive oligomers are g But lower than T m The diffusion across the interface is faster in both directions and forms Figure 1 Chain entanglement depicted in D. This rapid diffusion leads to a reduction in thermal annealing time. Chain extension and cross-linking can also occur through unreacted functional groups. The net effect of faster diffusion, chain entanglement, and chain extension and cross-linking is an increase in interlayer strength, i.e., an increase in z-axis strength in FFF and SLS.

[0190] The processes of cross-interface chain entanglement, network formation, chain extension and cross-linking in the above-mentioned additive manufacturing can be optimized by using reactive oligomers with two different reactive end groups in the same oligomer. The first unreacted functional group is self-reactive in a first temperature range, the second unreacted functional group is self-reactive in a second temperature range, and the second temperature range is higher than the first temperature range. For these reactive oligomers, an additive manufacturing method includes the following steps: curing the first unreacted functional group in a first temperature range; and curing the second unreacted functional group in a second temperature range. The first unreacted functional group that self-reacts in the first curing temperature range can first be cross-linked to fix the printed structure in place. The partially cross-linked oligomer that still has the second unreacted functional group that self-reacts in the second temperature range higher than the first temperature range can diffuse through the interface and cure in the second curing temperature range, thereby establishing the molecular weight, cross-linking density and strength of the part. The interface can be between adjacent filaments, such as in fused filament manufacturing, or between adjacent particles, such as in selective laser sintering. Also disclosed are articles made by additive manufacturing from a reactive oligomer having a first unreacted functional group that self-reacts within a first temperature range and a second unreacted functional group that self-reacts within a second temperature range.

[0191] The processes of cross-interface chain entanglement, network formation, chain extension and cross-linking in additive manufacturing can also be optimized by using two different reactive oligomers, each having a different reactive end group, wherein the first unreacted functional group is self-reactive in a first temperature range, the second unreacted functional group is self-reactive in a second temperature range, and the second temperature range is higher than the first temperature range. For these reactive oligomers, the additive manufacturing method includes the following steps: curing the first reactive oligomer functionalized with the first unreacted functional group in the first temperature range; and curing the second reactive oligomer functionalized with the second unreacted functional group in the second temperature range, wherein the second temperature range is higher than the second temperature range. The oligomer chains with the first unreacted functional group having the first curing temperature can first be cross-linked to fix the printed structure in place. The oligomer chains with the second unreacted functional group having the second curing temperature higher than the first curing temperature can diffuse through the interface and cure at the second curing temperature, thereby establishing the molecular weight, cross-linking density and strength of the part. The interface can be between adjacent filaments, as in fused filament fabrication, or between adjacent particles, as in selective laser sintering. Also disclosed is an article made by additive manufacturing from a first reactive oligomer having a first unreacted functional group that self-reacts within a first temperature range and a second reactive aromatic oligomer having a second unreacted functional group that self-reacts within a second temperature range.

[0192] Reactive polyamideimide oligomers and reactive polyamide amic acid oligomers, methods of making using reactive oligomers, and articles made from reactive oligomers have several advantageous properties. Currently available high molecular weight PAIs can have relatively high levels of amic acid groups in order to have sufficiently low complex viscosities to be melt processable. The presence of amic acid groups can make PAIs extremely hygroscopic. Therefore, pre-processing drying is also required. For example, Figure 1 The manufacture and processing of currently available PAI of the illustrated construction involves imidization of polyamide amic acid profiles or injection molded parts, requiring a long thermal post-treatment to remove water generated from the conversion of amic acid groups to imide groups. Processed PAI parts are also exposed to a multi-day thermal treatment regimen after processing. The general curing schedule recommended by the manufacturer is: 375℉ (191℃) 1 day, 425℉ (218℃) 1 day, 475℉ (246℃) 1 day and 500℉ (260℃) 5 days, for a total of 8 days. In contrast, the curing of reactive polyamideimide oligomers at about 300 to about 450℃ can be completed in as little as about 1 to about 60 minutes. Advantageously, this reduction in thermal post-treatment time results in a significant reduction in manufacturing cycle time and cost.

[0193] With an M of about 1000 to about 10000 g / mol nThe reactive polyamideimide oligomer advantageously exhibits a melt complex viscosity of about 1000 to about 100000 Pa.s at 360°C, particularly about 5000 to about 30000 Pa.s at 360°C. In contrast, currently available PAI is reported to have a melt complex viscosity of about 1000000 Pa.s at 2 rad / sec. The low melt complex viscosity of the fully imidized reactive polyamideimide oligomer relative to the currently available PAI is unexpected. In contrast to the low melt complex viscosity obtained, the alternating combination of rigid backbone phthalimide units and aromatic amide units that are expected to be strongly hydrogen-bonded as in polyaramids is expected to result in a high melting point and a high melt complex viscosity even for reactive polyamideimide oligomers. Advantageously, with a melt complex viscosity in the range of about 1000 to about 100,000 Pa·s at 360° C., conventional melt processing equipment can be used for melt processing and ready-to-use injection molded parts, films, fibers, and melt-processable high temperature adhesives can be made. In addition, compared to polyamide amic acid polymers, fully imidized reactive polyamideimide oligomers are less hygroscopic than polyamide amic acid polymers and are insoluble in polar solvents such as DMF, NMP, and DMAc, depending on the monomers and reactive and non-reactive end-capping agents used.

[0194] Advantageously, the thermal curing temperature range and the post-curing thermomechanical properties can be controlled by selecting the backbone monomer, the crosslinkable monomer, the crosslinkable end-capping agent, and the non-crosslinkable end-capping agent. In addition, improved thermomechanical properties are obtained using the reactive polyamideimide oligomers of the present invention. Referring to Example 1C below, which is M n The T of the film made of the reactive polyamideimide oligomer and cured at 370°C for 1 hour is 5000 g / mol, wherein both reactive end groups are phenylacetylene. g The T of currently available PAI films is 326°C. g High about 46 ° C. Also refer to Example 2 below, which is a 5000 g / mol M n Reactive polyamideimide oligomer with mixed reactive end groups (50 / 50 methylacetylene / phenylacetylene). T of films made from reactive polyamideimide oligomer and cured at 370°C for 1 hour g The toughness of the film is 94.3MJ / m 3 In comparison, the toughness of currently available PAI is only about 10 MJ / m 3 Therefore, the toughness of the PAI film made from this reactive polyamideimide oligomer is almost 10 times that of the PAI made from currently available PAI. g , breaking strength and breaking elongation are also improved.

[0195] Advantageously, the low melt complex viscosity of the reactive polyamideimide oligomers relative to high molecular weight polyamideimide polymers makes the reactive polyamideimide oligomers ideally suited for use in preparing fiber reinforced composites, such as glass, carbon and aramid fiber reinforced composites.

[0196] Solution-based prepreg, melt infusion and melt pultrusion methods can all be used. High molecular weight polyamide amic acid can be used to prepare fiber / resin prepregs and composite materials. However, it is difficult to obtain sufficient melt flow to melt and consolidate the polyamide amic acid prepreg into a composite board. In addition, during the imidization process of polyamide amic acid, it may be difficult to remove water from the composite board. This means that it is difficult to achieve a void of less than 2%, which is considered acceptable. Alternatively, the high molecular weight polyamide amic acid can be converted into a high molecular weight polyamide-imide in the prepreg stage, and the polyamide-imide prepreg can be consolidated into a composite material. The even higher melt complex viscosity of high molecular weight polyamide-imide makes it difficult to obtain sufficient melt flow under pressure to consolidate the prepreg into a composite board of acceptable quality. Therefore, the relatively low melt complex viscosity of reactive polyamide-imide oligomers provides advantages over both high molecular weight polyamide-imide and high molecular weight polyamide amic acid in the manufacture of fiber-reinforced composite materials.

[0197] The low melt complex viscosity of reactive polyamideimide oligomers compared to high molecular weight polyamideimide polymers also makes them ideally suited for 3D printing applications. Reactive polyamideimide oligomers can be used in filament, rod or powder form.

[0198] The present disclosure is further illustrated by the following aspects of the present disclosure, which are not intended to limit the claims.

[0199] Embodiments based on the current claims

[0200] Aspect 1. A reactive oligomer comprising a backbone derived from at least one of polyamideimide, polyimide, polyetherimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide, polyamide, polyester, polyarylate, polyesteramide, polycarbonate, polybenzoxazole or polybenzimidazole and functionalized with at least one unreacted functional group capable of thermal chain extension and crosslinking after formation of the reactive oligomer, wherein the number average molecular weight (M) of the reactive oligomer is n ) is calculated using the Carothers equation to be about 250 to about 10,000 g / mol.

[0201] Aspect 2. The reactive oligomer according to aspect 1, wherein the at least one unreacted functional group is maleimide, 5-norbornene-2,3-dicarboxylic acid imide, phthalonitrile, benzocyclobutene, biphenylene, cyanate, ketoacetylene, acetylene, methylacetylene, phenylacetylene, propargyl ether or benzoxazine.

[0202] Aspect 3. A reactive oligomer according to Aspect 1 or 2, which is functionalized with a first and a second unreacted functional group capable of thermal chain extension and cross-linking after the reactive oligomer is formed, wherein the first unreacted functional group self-reacts within a first temperature range, the second unreacted functional group self-reacts within a second temperature range, and the second temperature range is higher than the first temperature range.

[0203] Aspect 4. The reactive oligomer according to any one of aspects 1 to 3, wherein the backbone is linear or branched.

[0204] Aspect 5. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from polyamideimide.

[0205] Aspect 6. The reactive oligomer according to aspect 5, wherein the at least one unreacted functional group is derived from a monomer or a capping agent selected from the group consisting of:

[0206]

[0207]

[0208] and

[0209] Aspect 7. A reactive oligomer according to aspect 5, comprising units 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'-oxydiphenylamine and 4,4'-oxydiphenylamine, 4-methylethynylphthalic anhydride and optionally 4-phenylethynylphthalic anhydride.

[0210] Aspect 8. A reactive oligomer according to aspect 5, comprising units derived from: at least one dianhydride selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, at least one difunctional 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'-oxydiphenylamine and 4,4'-oxydiphenylamine, 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride.

[0211] Aspect 9. A reactive oligomer according to aspect 5, comprising units derived from: at least one dianhydride selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride, at least one difunctional 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'-oxydiphenylamine and 4,4'-oxydiphenylamine, 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride, and at least one anhydride selected from phthalic anhydride, 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride.

[0212] Aspect 10. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from a polyimide.

[0213] Aspect 11. The reactive oligomer according to aspect 10, which has formula (I):

[0214]

[0215] Among them, Ar 1 The tetravalent aromatic group represented by is at least one of the following:

[0216]

[0217] By Ar 2 The divalent aromatic group represented by is at least one of the following:

[0218]

[0219] Y 1 and Z 1 Each is independently derived from a capping agent selected from the group consisting of:

[0220]

[0221] and

[0222] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

[0223] Aspect 12. The reactive oligomer according to aspect 11, wherein Y and Z are different.

[0224] Aspect 13. The reactive oligomer according to any one of aspects 10 to 12, wherein the polyimide is a polyetherimide.

[0225] Aspect 14. The reactive oligomer according to aspect 13, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl or maleimide.

[0226] Aspect 15. The reactive oligomer according to aspect 13, wherein the unreacted functional group is derived from at least one of 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride or N-(4-aminophenyl)maleimide.

[0227] Aspect 16. The reactive oligomer according to aspect 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.

[0228] Aspect 17. The reactive oligomer according to aspect 13, comprising units derived from 2,3,3',4'-biphenyltetracarboxylic dianhydride, at least one aromatic diamine selected from the group consisting of 1,3-phenylenediamine, 3,4'-oxydiphenylamine and 4,4'-oxydiphenylamine, 4-methylethynylphthalic anhydride and optionally 4-phenylethynylphthalic anhydride.

[0229] Aspect 18. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from a polyaryletherketone.

[0230] Aspect 19. The reactive oligomer according to Aspect 18, which has formula (II):

[0231]

[0232] Among them, Ar 3 The divalent aromatic group represented by is at least one of the following:

[0233]

[0234] Where S 1 , S 2 , S 3 and S 4 Each independently selected from H, F, Cl, Br, C 1-6 The group consisting of a straight chain or branched alkyl group and a phenyl group; and W is:

[0235]

[0236] By Ar 4 The divalent aromatic group represented by is at least one of the following:

[0237]

[0238] Y 2 and Z2 Each is independently derived from a capping agent selected from the group consisting of:

[0239]

[0240] Where D is:

[0241] and

[0242] A is:

[0243] and

[0244] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

[0245] Aspect 20. The reactive oligomer according to aspect 19, wherein Y 3 and Z 3 different.

[0246] Aspect 21. The reactive oligomer according to aspect 19 or 20, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl or maleimide.

[0247] Aspect 22. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from polyethersulfone.

[0248] Aspect 23. The reactive oligomer according to aspect 22, wherein the backbone is derived from polysulfone (PSU), polyphenylsulfone (PPSU) or polyethersulfone (PES).

[0249] Aspect 24. The reactive oligomer according to Aspect 22, which has formula (III):

[0250]

[0251] Among them, Ar 5 The divalent aromatic group represented by is:

[0252]

[0253] By Ar 6 The divalent aromatic group represented by has the formula (IIIa):

[0254]

[0255] Y 3 and Z 3 Each is independently derived from a capping agent selected from the group consisting of:

[0256]

[0257] Where D is:

[0258] and

[0259] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

[0260] Aspect 25. The reactive oligomer according to Aspect 24, wherein Y 3 and Z 3 different.

[0261] Aspect 26. The reactive oligomer according to aspect 22 or 23, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl or maleimide.

[0262] Aspect 27. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from polyphenylene sulfide.

[0263] Aspect 28. The reactive oligomer according to Aspect 27, which has formula (IV):

[0264]

[0265] The divalent aromatic group represented by Ar is:

[0266]

[0267] Where W is:

[0268]

[0269] Y and Z are each independently derived from a capping agent selected from the group consisting of:

[0270]

[0271] Where D is:

[0272] and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

[0273] Aspect 29. The reactive oligomer according to Aspect 28, wherein Y and Z are different.

[0274] Aspect 30. The reactive oligomer according to aspect 27, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl or maleimide.

[0275] Aspect 31. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from a polyamide.

[0276] Aspect 32. The reactive oligomer according to aspect 31, which has formula (Va) or (Vb):

[0277]

[0278] Among them, A 1 and A 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene or 1,2-, 1,3- or 1,4-xylylene;

[0279] Y 4 and Z 4 Each is independently derived from a capping agent selected from the group consisting of:

[0280]

[0281] and

[0282] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

[0283] Aspect 33. The reactive oligomer according to aspect 32, wherein Y 4 and Z 4 different.

[0284] Aspect 34. The reactive oligomer according to aspect 31, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl or maleimide.

[0285] Aspect 35. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from a polyester.

[0286] Aspect 36. The reactive oligomer according to Aspect 35, which has formula (VIa) or (VIb):

[0287]

[0288] Among them, B 1 and B 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene,

[0289]

[0290] Y5 and Z 5 Each is independently derived from a capping agent selected from the group consisting of:

[0291]

[0292] Where D is:

[0293] and

[0294] X is -OH, -NH2, -COOH or -COCl; and

[0295] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

[0296] Aspect 37. The reactive oligomer according to Aspect 36, wherein Y 5 and Z 5 different.

[0297] Aspect 38. The reactive oligomer according to aspect 35, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl or maleimide.

[0298] Aspect 39. The reactive oligomer according to any one of aspects 1 to 4, wherein the backbone is derived from a polyester amide.

[0299] Aspect 40. The reactive oligomer according to Aspect 39, which has formula (VIIa) or (VIIb):

[0300]

[0301] Among them, D 1 and D 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene,

[0302]

[0303] Y 6 and Z 6 Each is independently derived from a capping agent selected from the group consisting of:

[0304]

[0305] Where D is:

[0306] and

[0307] X is -OH, -NH2, -COOH or -COCl; and

[0308] n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

[0309] Aspect 41. A reactive oligomer according to aspect 40, wherein Y 6 and Z 6 different.

[0310] Aspect 42. The reactive oligomer according to aspect 40, wherein the unreacted functional group is at least one of methylethynyl, phenylethynyl or maleimide.

[0311] Aspect 43. A composition comprising at least one reactive oligomer according to any one of aspects 1 to 42.

[0312] Aspect 44. A composition according to Aspect 43, comprising a first and a second reactive oligomer, wherein the first reactive oligomer is functionalized with a first unreacted functional group capable of thermal chain extension and crosslinking after the first reactive oligomer is formed, and the second reactive oligomer is functionalized with a second unreacted functional group capable of thermal chain extension and crosslinking after the second reactive oligomer is formed, the first unreacted functional group self-reacts within a first temperature range, the second unreacted functional group self-reacts within a second temperature range, and the second temperature range is higher than the first temperature range.

[0313] Aspect 45. A composition according to aspect 43, comprising a first and a second reactive oligomer, wherein the first reactive oligomer has a first number average molecular weight (M n ), and the second reactive oligomer has a second number average molecular weight (M n ).

[0314] Aspect 46. The composition according to any one of aspects 43 to 45, further comprising a thermoplastic polymer.

[0315] Aspect 47. The composition according to aspect 46, wherein the thermoplastic polymer comprises the same backbone repeating units as the at least one reactive oligomer.

[0316] Aspect 48. The composition according to any of aspects 43 or 47, further comprising an oligomer lacking unreacted functional groups capable of thermal chain extension and cross-linking.

[0317] Aspect 49. The composition according to any one of aspects 43 to 48, further comprising at least one of a filler or an additive.

[0318] Aspect 50. A composition comprising the reactive oligomer according to any one of aspects 1 to 42 coated on thermoplastic polymer particles or filaments.

[0319] Aspect 51. The composition according to aspect 50, wherein the thermoplastic polymer comprises the same backbone repeating unit as the reactive oligomer.

[0320] Aspect 52. A method of compounding a composition according to any one of aspects 43 to 51, comprising mixing the components of the composition at a sufficient temperature and time to form a homogeneous molten mixture, but without crosslinking the unreacted functional groups.

[0321] Aspect 53. A method of making an article, the method comprising heating the composition according to any one of aspects 43 to 51 at a sufficient temperature and for a sufficient time to shape and crosslink the reactive oligomers.

[0322] Aspect 54. The manufacturing method according to Aspect 53, wherein the method is additive manufacturing.

[0323] Aspect 55. An additive manufacturing method according to Aspect 54, wherein the method is fused filament fabrication (FFF), selective laser sintering (SLS), directed energy deposition (DED) laser engineered net shaping (LENS) or composite-based additive manufacturing (CBAM).

[0324] Aspect 56. An additive manufacturing method using the reactive oligomer according to Aspect 3, comprising the steps of: curing the first unreacted functional group within the first temperature range; and curing the second unreacted functional group within the second temperature range.

[0325] Aspect 57. An additive manufacturing method using the composition according to Aspect 44, comprising the steps of: curing the first reactive oligomer functionalized with the first unreacted functional group within the first temperature range; and curing the second reactive oligomer functionalized with the second unreacted functional group within the second temperature range.

[0326] Aspect 58. A manufacturing method according to Aspect 54, wherein the method is fused filament manufacturing, the method comprising extruding the composition in adjacent horizontal layers so that there is an interface between the layers, and exposing the layers to heat at a temperature and for a time sufficient to crosslink the reactive oligomers and form an article.

[0327] Aspect 59. The manufacturing method according to aspect 54, wherein the method is selective laser sintering, the method comprising selectively sintering and crosslinking particles of the composition with a laser to form an article.

[0328] Aspect 60. An article made by the method according to any one of aspects 53 to 58.

[0329] Aspect 101. A reactive polyamideimide oligomer comprising units derived from at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or a functional equivalent thereof, and at least one crosslinkable monomer or crosslinkable endcapping agent; wherein the crosslinkable monomer or crosslinkable endcapping agent is reactive with the at least one aromatic diamine or the at least one di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof and has at least one unreacted functional group capable of thermal chain extension and crosslinking after the reactive polyamideimide oligomer is formed; and wherein the number average molecular weight (M) of the reactive polyamideimide oligomer is n ) is calculated using the Carothers equation to be about 1000 to about 10000 g / mol.

[0330] Aspect 102. The reactive polyamideimide oligomer according to aspect 101, wherein the reactive polyamideimide oligomer is derived from a reactive polyamideamic acid oligomer intermediate by a dehydration cyclization reaction, and greater than 80% and less than or equal to 100% of the amic acid groups in the reactive polyamideamic acid intermediate are imidized.

[0331] Aspect 103. The reactive polyamideimide oligomer according to aspect 101, wherein the reactive polyamideimide oligomer is derived from a reactive polyamideamic acid oligomer intermediate by a dehydration cyclization reaction, and greater than or equal to 20% and less than or equal to 80% of the amic acid groups in the reactive polyamideamic acid intermediate are imidized.

[0332] Aspect 104. The reactive polyamideimide oligomer according to any one of aspects 101 to 103, wherein the crosslinkable monomer or crosslinkable endcapping agent has an unreacted functional group capable of thermal chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0333] Aspect 105. The reactive polyamideimide oligomer according to any one of aspects 101 to 104, wherein the at least one crosslinkable monomer or crosslinkable endcapping agent is at least one crosslinkable endcapping agent.

[0334] Aspect 106. The reactive polyamideimide oligomer according to any one of aspects 101 to 105, wherein the at least one aromatic diamine is two aromatic diamines.

[0335] Aspect 107. The reactive polyamideimide oligomer according to any one of aspects 101 to 106, wherein the at least one aromatic di-, tri- or tetra-functional carboxylic acid or a functional equivalent thereof is two aromatic di-, tri- or tetra-functional carboxylic acids or a functional equivalent thereof.

[0336] Aspect 108. A reactive polyamideimide oligomer according to any one of aspects 101 to 107, prepared by a process comprising simultaneously stepwise polymerization of at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or a functional equivalent thereof, and at least one crosslinkable monomer or crosslinkable endcapping agent.

[0337] Aspect 109. The reactive polyamideimide oligomer according to any one of aspects 101 to 108, wherein the aromatic diamine is at least one of:

[0338]

[0339] Aspect 110. The reactive polyamideimide oligomer according to any one of aspects 101 to 109, wherein the aromatic diamine is at least one of 1,3-phenylenediamine, 4,4'-oxydiphenylamine, and 3,4'-oxydiphenylamine.

[0340] Aspect 111. The reactive polyamideimide oligomer according to any one of aspects 101 to 110, wherein the di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof is at least one of:

[0341]

[0342] Aspect 112. The reactive polyamideimide oligomer according to any one of Aspects 101 to 111, wherein the di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof is at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthalic dichloride, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride.

[0343] Aspect 113. The reactive polyamideimide oligomer according to any one of aspects 101 to 112, wherein the unreacted functional group is at least one of acetylene, methylacetylene, phenylacetylene, ketoacetylene, propargyl ether, norbornene, maleimide, cyanate, phthalonitrile, benzocyclobutene, biphenylene, or benzoxazine.

[0344] Aspect 114. The reactive polyamideimide oligomer according to any one of aspects 101 to 113, wherein the crosslinkable monomer or crosslinkable endcapping agent is at least one of:

[0345]

[0346] Aspect 115. The reactive polyamideimide oligomer according to any one of aspects 101 to 114, wherein the crosslinkable monomer or crosslinkable endcapping agent is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA) or 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride.

[0347] Aspect 116. The reactive polyamideimide oligomer according to any one of aspects 101 to 115, comprising two crosslinkable monomers or crosslinkable endcapping agents reacting at different temperature ranges.

[0348] Aspect 117. The reactive polyamideimide oligomer according to any one of Aspects 101 to 116, further comprising units derived from at least one non-crosslinkable end-capping agent, wherein the non-crosslinkable end-capping agent is reactive with the at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof.

[0349] Aspect 118. The reactive polyamideimide oligomer according to aspect 117, wherein the non-crosslinkable end-capping agent is at least one of benzoic acid, benzoyl chloride, phthalic anhydride or aniline.

[0350] Aspect 119. The reactive polyamideimide oligomer according to any one of aspects 101 to 118, further comprising units derived from at least one of an aromatic triamine, an aromatic tricarboxylic acid, or an aromatic tricarboxylic acid chloride.

[0351] Aspect 120. A reactive polyamideimide oligomer according to any one of Aspects 101 to 119, wherein the reactive polyamideimide oligomer has a melt complex viscosity at 360°C of about 1000 to about 100,000 Pa·s, the melt complex viscosity being measured by oscillatory shear rheology between parallel plates under N2 at a heating rate of 10°C / min, a frequency of 2 rad / s, and a strain of 0.03% to 1.0%.

[0352] Aspect 121. A reactive polyamideimide oligomer comprising units derived from:

[0353] At least one aromatic diamine selected from the group consisting of:

[0354]

[0355] A di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof selected from at least one of the following: and at least one crosslinkable monomer or crosslinkable end-capping agent selected from the group consisting of:

[0356]

[0357]

[0358] Aspect 122. A reactive polyamideimide oligomer comprising units derived from: an aromatic diamine selected from at least one of 1,3-phenylenediamine, 4,4'-oxydiphenylamine, or 3,4'-oxydiphenylamine; a di-, tri-, or tetra-functional aromatic carboxylic acid or its functional equivalent selected from at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthalic dichloride, pyromellitic dianhydride, or biphenyltetracarboxylic dianhydride; and a crosslinkable monomer or crosslinkable end-capping agent selected from at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA), or 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride.

[0359] Aspect 123. A method for manufacturing a reactive polyamideimide oligomer according to any one of Aspects 101 to 122, the method comprising: copolymerizing at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent, and at least one cross-linkable monomer or cross-linkable end-capping agent in the presence of a polar solvent to form a reactive polyamide amic acid oligomer; and heating the reactive polyamide amic acid oligomer at a sufficient temperature and time to prepare the reactive polyamideimide oligomer; wherein the cross-linkable monomer or cross-linkable end-capping agent is reactive with the at least one aromatic diamine or the at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group capable of chain extension and cross-linking after the reactive polyamideimide oligomer is formed.

[0360] Aspect 124. The method of manufacturing according to aspect 123, wherein the sufficient temperature and time to prepare the reactive polyamideimide oligomer is from about 140° C. to about 220° C. for about 1 minute to about 120 minutes.

[0361] Aspect 125. The manufacturing method according to aspect 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.

[0362] Aspect 126. The manufacturing method according to any one of aspects 123 to 125, further comprising removing the polar solvent from the polyamideamic acid oligomer, and then heating the reactive polyamideamic acid oligomer at a sufficient temperature and time to prepare the reactive polyamideimide oligomer.

[0363] Aspect 127. The method of manufacturing according to aspect 126, wherein the sufficient temperature and time to prepare the reactive polyamideimide oligomer is from about 220° C. to about 300° C. for about 1 minute to about 120 minutes.

[0364] Aspect 128. The manufacturing method according to any one of aspects 123 to 127, wherein the method further comprises adding toluene to the reactive polyamide amic acid oligomer and azeotropically distilling toluene and water.

[0365] Aspect 129. The manufacturing method according to any one of aspects 123 to 127, wherein the method further comprises heating the reactive polyamide amic acid oligomer in the presence of acetic anhydride and a catalytic amount of a tertiary amine.

[0366] Aspect 130. The manufacturing method according to any one of aspects 123 to 127, wherein the method further comprises microwave irradiating the reactive polyamide amic acid oligomer.

[0367] Aspect 131. The manufacturing method according to any one of aspects 123 to 127, wherein the copolymerization is carried out in the presence of a phosphorylating agent and a catalytic amount of a salt.

[0368] Aspect 132. A method of making a reactive polyamideimide oligomer according to any one of aspects 1 to 16, the method comprising: reacting at least one of water or C at a sufficient temperature and time to 1-4 heating at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent, and at least one crosslinkable monomer or crosslinkable endcapping agent in the presence of an alcohol to form at least one reactive carboxylic acid ammonium salt; optionally removing excess water or C 1-4 alcohol; and heating the reactive carboxylic acid ammonium salt at a sufficient temperature and time to form the reactive polyamideimide oligomer; wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with the at least one aromatic diamine or the at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0369] Aspect 133. The method according to aspect 132, comprising reactively extruding the reactive carboxylic acid ammonium salt at a sufficient temperature and time to form the reactive polyamideimide oligomer.

[0370] Aspect 134. The method according to aspect 26, comprising dissolving the reactive carboxylic acid ammonium salt in a polar solvent and then heating at sufficient temperature, pressure and time to form the reactive polyamideimide oligomer.

[0371] Aspect 135. A method for making a reactive polyamideimide oligomer according to any one of Aspects 101 to 122, the method comprising reactively extruding at least one aromatic diamine or an activated derivative thereof, at least one aromatic di-, tri- or tetra-functional carboxylic acid or a functional equivalent thereof, and at least one crosslinkable monomer or crosslinkable endcapping agent at a sufficient temperature and time to prepare the reactive polyamideimide oligomer; wherein the crosslinkable monomer or crosslinkable endcapping agent is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof, and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0372] Aspect 136. The manufacturing method according to aspect 135, wherein the reactive extrusion is performed in the presence of a polar solvent, and the polar solvent is removed by distillation during the reactive extrusion.

[0373] Aspect 137. The manufacturing method according to aspect 135 or 136, wherein the reactive extrusion is carried out in the presence of an acidic catalyst.

[0374] Aspect 138. The manufacturing method according to aspect 137, wherein the acidic catalyst is acetic acid, and the acetic acid is removed by distillation during the reactive extrusion.

[0375] Aspect 139. The manufacturing method according to any one of aspects 135 to 138, wherein the reactive extrusion is performed in the presence of acetic anhydride, and the acetic anhydride is removed by distillation during the reactive extrusion.

[0376] Aspect 140. The manufacturing method according to any one of aspects 135 to 139, wherein the reactive extrusion is performed in a melt extruder having a plurality of preset heating zones equipped with vents.

[0377] Aspect 141. A blend composition comprising the reactive polyamideimide oligomer according to any one of aspects 101 to 122 and a thermoplastic polymer.

[0378] Aspect 142. A method of compounding a reactive polyamideimide oligomer according to any one of aspects 101 to 122, comprising mixing the reactive polyamideimide oligomer with at least one other material at a sufficient temperature and time to melt but not crosslink the reactive polyamideimide oligomer.

[0379] Aspect 143. A method of making an article, the method comprising heating the reactive polyamideimide oligomer according to any one of aspects 101 to 122 at a sufficient temperature and for a sufficient time to shape and crosslink the reactive polyamideimide oligomer.

[0380] Aspect 144. The method of manufacturing according to aspect 143, wherein the sufficient temperature and time is about 160 to about 450° C. for about 1 to about 60 minutes.

[0381] Aspect 145. An article manufactured by the method of aspect 143 or 144.

[0382] Aspect 146. An article comprising the reactive polyamideimide oligomer according to any one of aspects 101 to 122.

[0383] Aspect 147. The article according to aspect 146, wherein the reactive polyamideimide oligomer is cross-linked.

[0384] Aspect 148. A manufacturing method according to aspect 143 or 144, wherein the method is additive manufacturing.

[0385] Aspect 149. A manufacturing method according to Aspect 148, wherein the method is fused filament manufacturing, the method comprising extruding the reactive polyamideimide oligomer in adjacent horizontal layers so that there is an interface between each polyamideimide oligomer layer, and exposing the layers to heat at a temperature and for a time sufficient to crosslink the reactive polyamideimide oligomer and form an article.

[0386] Aspect 150. The manufacturing method according to aspect 148, wherein the method is selective laser sintering, the method comprising selectively sintering and crosslinking particles of the reactive polyamideimide oligomer with a laser to form an article.

[0387] Aspect 151. The manufacturing method according to aspect 148, wherein the method is directed energy deposition (DED) or laser engineered net shaping (LENS).

[0388] Aspect 152. An article made by the method according to any one of aspects 148 to 151.

[0389] Aspect 153. An additively manufactured article comprising the reactive polyamideimide oligomer according to any one of aspects 101 to 122.

[0390] Aspect 154. The additively manufactured article according to aspect 153, wherein the reactive polyamideimide oligomer is cross-linked.

[0391] Aspect 155. A reactive polyamide amic acid oligomer comprising units derived from at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or a functional equivalent thereof; and at least one crosslinkable monomer or crosslinkable end-capping agent, wherein the crosslinkable monomer or crosslinkable end-capping agent is reactive with the at least one aromatic diamine or the at least one di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamide amic acid oligomer is formed; and wherein the number average molecular weight (M) of the reactive polyamide amic acid oligomer is n ) is calculated using the Carothers equation to be about 1000 to about 10000 g / mol.

[0392] Aspect 156. The reactive polyamide amic acid oligomer according to aspect 155, wherein 0% to about 20% of the amic acid groups are imidized.

[0393] Aspect 157. The reactive polyamide amic acid oligomer according to aspect 155 or 156, wherein the crosslinkable monomer or crosslinkable endcapping agent has an unreacted functional group capable of thermal chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0394] Aspect 158. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 157, wherein the at least one crosslinkable monomer or crosslinkable endcapping agent is at least one crosslinkable endcapping agent.

[0395] Aspect 159. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 158, wherein the at least one aromatic diamine is two aromatic diamines.

[0396] Aspect 160. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 159, wherein the at least one aromatic di-, tri- or tetra-functional carboxylic acid or a functional equivalent thereof is two aromatic di-, tri- or tetra-functional carboxylic acids or a functional equivalent thereof.

[0397] Aspect 161. A reactive polyamide amic acid oligomer according to any one of aspects 155 to 160, prepared by a process comprising simultaneously stepwise polymerization of the at least one aromatic diamine, the at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent and the at least one crosslinkable monomer or crosslinkable endcapping agent.

[0398] Aspect 162. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 161, wherein the aromatic diamine is at least one of:

[0399]

[0400] Aspect 163. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 162, wherein the aromatic diamine is at least one of 1,3-phenylenediamine, 4,4'-oxydiphenylamine, or 3,4'-oxydiphenylamine.

[0401] Aspect 164. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 163, wherein the di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof is at least one of:

[0402]

[0403] Aspect 165. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 62a, wherein the di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof is at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthalic dichloride, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride.

[0404] Aspect 166. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 165, wherein the at least one unreacted functional group is at least one of acetylene, methylacetylene, phenylacetylene, ketoacetylene, propargyl ether, norbornene, maleimide, cyanate, phthalonitrile, benzocyclobutene, biphenylene, or benzoxazine.

[0405] Aspect 167. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 166, wherein the crosslinkable monomer or crosslinkable end-capping agent is at least one of:

[0406]

[0407] Aspect 168. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 167, wherein the crosslinkable monomer or crosslinkable endcapping agent is at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA) or 4,4′-(ethynyl-1,2-diyl)diphthalic anhydride.

[0408] Aspect 169. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 168, comprising two crosslinkable monomers or crosslinkable end-capping agents reacting at different temperature ranges.

[0409] Aspect 170. The reactive polyamide amic acid oligomer according to any one of aspects 155 to 169, further comprising units derived from at least one non-crosslinkable end-capping agent, wherein the non-crosslinkable end-capping agent is reactive with the at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof.

[0410] Aspect 171. The reactive polyamide amic acid oligomer according to aspect 170, wherein the non-crosslinkable end-capping agent is at least one of benzoic acid, benzoyl chloride, phthalic anhydride, or aniline.

[0411] Aspect 172. A reactive polyamide amic acid oligomer comprising units derived from:

[0412] At least one aromatic diamine selected from the group consisting of:

[0413]

[0414] A di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof selected from at least one of the following:

[0415] and at least one crosslinkable monomer or crosslinkable end-capping agent selected from the group consisting of:

[0416]

[0417]

[0418] Aspect 173. A reactive polyamide amic acid oligomer comprising units derived from: an aromatic diamine selected from at least one of 1,3-phenylenediamine, 4,4'-oxydiphenylamine or 3,4'-oxydiphenylamine; a di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent selected from at least one of trimellitic anhydride, 4-chloroformylphthalic anhydride, isophthalic anhydride, isophthalic dichloride, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride; and a crosslinkable monomer or crosslinkable end-capping agent selected from at least one of 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride (PEPA) or 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride.

[0419] Aspect 174. A method for manufacturing a reactive polyamide amic acid oligomer according to any one of Aspects 155 to 173, the method comprising: copolymerizing at least one aromatic diamine, at least one aromatic di-, tri- or tetra-functional carboxylic acid or its functional equivalent, and at least one cross-linkable monomer or cross-linkable end-capping agent in the presence of a polar solvent to form the reactive polyamide amic acid oligomer; wherein the cross-linkable monomer or cross-linkable end-capping agent is reactive with the at least one aromatic diamine or the at least one di-, tri- or tetra-functional aromatic carboxylic acid or its functional equivalent, and has at least one unreacted functional group capable of chain extension and cross-linking after the reactive polyamide amic acid oligomer is formed.

[0420] Aspect 175. The manufacturing method according to aspect 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.

[0421] Aspect 176. The manufacturing method according to aspect 174 or 175, further comprising isolating the reactive polyamide amic acid oligomer from the polar solvent.

[0422] Aspect 177. A blended composition comprising the reactive polyamide amic acid oligomer according to any one of aspects 155 to 173 and a thermoplastic polymer.

[0423] Aspect 178. A method of compounding a reactive polyamide amic acid oligomer according to any one of aspects 155 to 173, comprising reacting the reactive polyamide amic acid oligomer with at least one other material at a sufficient temperature and time to imidize the reactive polyamide amic acid oligomer without crosslinking.

[0424] Aspect 179. A method of making an article, the method comprising heating the reactive polyamide amic acid oligomer according to any one of aspects 155 to 173 at a sufficient temperature and for a sufficient time to imidize, shape, and crosslink the reactive polyamide amic acid oligomer.

[0425] Aspect 180. The manufacturing method according to aspect 179, wherein the sufficient temperature and time are about 160 to about 400° C. for about 10 to about 60 minutes.

[0426] Aspect 181. An article manufactured by the method according to aspect 179 or 180.

[0427] Aspect 182. An article comprising the reactive polyamide amic acid oligomer according to any one of aspects 155 to 173.

[0428] Aspect 183. A manufacturing method according to aspect 179 or 180, wherein the method is additive manufacturing.

[0429] Aspect 184. A manufacturing method according to Aspect 183, wherein the method is fused filament manufacturing, the method comprising extruding the reactive polyamide amic acid oligomer in adjacent horizontal layers so that there is an interface between each reactive polyamide amic acid oligomer layer, and exposing the layers to heat at a temperature and time sufficient to imidize and crosslink the reactive polyamide amic acid oligomer and form the article.

[0430] Aspect 185. The manufacturing method according to aspect 183, wherein the method is selective laser sintering, the method comprising selectively sintering, imidizing and crosslinking particles of the reactive polyamide amic acid oligomer with a laser to form an article.

[0431] Aspect 186. The manufacturing method according to aspect 183, wherein the method is directed energy deposition (DED) or laser engineered net shaping (LENS).

[0432] Aspect 187. An article manufactured by the method according to any one of aspects 183 to 186.

[0433] Aspect 188. An additively manufactured article comprising the reactive polyamide amic acid oligomer according to any one of aspects 155 to 173.

[0434] Example

[0435] Materials and methods

[0436] Abbreviations for materials used or referred to herein are defined in Table 2. For those materials used in the Examples, sources are provided. Keywords for other abbreviations used herein are provided in Table 3.

[0437] Table 2. Materials

[0438]

[0439]

[0440] Table 3. Other abbreviations

[0441]

[0442]

[0443] Rheology.Melt complex viscosity was measured by oscillatory shear rheology at a heating rate of 10°C / min, a frequency of 2 rad / sec, and a strain of 0.03% to 1.0% under N2. A 13-mm diameter sample was centered between 25-mm diameter parallel plates for the measurement.

[0444] Thermogravimetric analysis (TGA). To determine T d，5％重量损失 : TA Instruments TGA 5500, Pt pan, 10 °C / min, N2, 10 mg sample.

[0445] Differential scanning calorimetry (DSC). For determination of T g : TA Instruments DSC2500, Tzero pan with sealed lid, 10℃ / min, N2, about 7mg sample. In this method, T g Determined by the inflection point.

[0446] Dynamic Mechanical Thermal Analysis (DMTA). TA Instruments RSAG2 in tension mode, 2°C / min from 25°C to 400°C, N2 atmosphere, sample size = 0.030 mm x 2 mm x 10 mm. In this method, T g Determined by the maximum value of the loss modulus peak.

[0447] Stress and strain measurements. TA Instruments RSA G2 (32N load cell), strain rate 1 mm / min, sample dimensions = about 0.030 mm x about 2 mm x 10 mm. Young's modulus was determined by linear fit of the stress-strain curve between the elastic region; 0.1 and 0.3% strain.

[0448] Gel permeation chromatography (GPC). The Shimadzu Prominence ultrafast liquid chromatography (UFLC) system was equipped with an LC20AD pump, a SIL-20A HT autosampler, a CTO-20A column oven at 60 °C, and a RID-20A refractive index detector. For the measurements, the chromatographic column used was SHODEX TM LF-804. The eluent used for the measurement was NMP containing 0.05M LiBr and 0.05M H3PO4, running at a constant flow rate of 0.5mL / min. TM The relative molecular weight was obtained by comparison with polystyrene standards.

[0449] Example 1

[0450] The preparation of reactive polyamideimide oligomers is illustrated in Scheme 5 below. The molecular weight of the oligomer affects the thermal, (thermo)mechanical and melt properties of the reactive polyamideimide oligomers. In this example, a phenylethynyl end-capping agent (PEPA) was used to prepare Mn The reactive polyamideimide oligomers with M values ​​of 5000 g / mol (Examples 1B-1E), 3000 g / mol (Examples 1F-1G) and 8000 g / mol (Examples 1H-1I) were prepared. The Carothers equation (Eq. 2) was used to calculate the reaction conditions for preparing the oligomers with the desired M values. n The amount of monomer required to prepare the reactive polyamide-imide oligomer. n When more than one diamine monomer is used, the relative molar amounts of the diamine monomers will affect the rigidity of the oligomeric backbone. Therefore, the thermal, (thermo)mechanical and melt properties of the reactive polyamideimide oligomer can be changed by changing the ratio of the diamine monomers. n The molar ratio of the two diamines is 0.72:0.28, and the backbone is composed of 4,4'-ODA and 1,3-PD. Changing the molar ratio of the two diamines will result in changes in the properties of the oligomers. The molar ratio of 4,4'-ODA to 1,3-PD in Examples 1A-1I is 0.72:0.28, in Examples 1J-1K it is 0.62:0.32, and in Examples 1L-1M it is 0.813:0.197.

[0451]

[0452] Scheme 5. Synthesis of reactive polyamideimide oligomers with phenylethynyl reactive end groups.

[0453] Example 1A - Reactive polyamide amic acid oligomer solution, M n =5000g / mol

[0454] In a 150mL 2-necked round bottom flask equipped with a stirring rod and a nitrogen inlet tube, 1,3-phenylenediamine (6.38mmol, 0.69g), 4,4'-oxydiphenylamine (16.33mmol, 3.27g) and 37g NMP were charged. The mixture was stirred until a uniform solution was obtained. The solution was cooled to 0°C. Trimellitic anhydride chloride (21.28mmol, 4.48g) and 4-(phenylethynyl)phthalic anhydride (2.9mmol, 0.72g) were added all at once. The reaction mixture was stirred at 0°C for 1 to 2 hours under a nitrogen atmosphere, and then the ice bath was removed, and the reaction mixture was stirred and warmed to 25°C overnight (about 16h) to provide a solution of reactive polyamide amic acid oligomer in NMP.

[0455] Example 1B - Reactive polyamideimide oligomer film, M n =5000g / mol

[0456] This is an example of preparing a free-standing reactive polyamideimide oligomer film without curing the phenylethynyl end groups. 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 for 1 h, 200°C for 1 h and 300°C for 1 h to obtain a reactive polyamideimide oligomer with unreacted phenylethynyl end groups. The film was brittle and difficult to handle, which is a direct consequence of the low molecular weight. g is 248°C, measured by differential scanning calorimetry (N2, 10°C / min).

[0457] Example 1C - Cured polyamideimide oligomer film, M n =5000g / mol

[0458] This is an example of preparing a flexible, free-standing film with cured phenylethynyl end groups. A reactive polyamide amic acid oligomer solution (10 mL) as prepared in Example 1A was poured onto a glass plate and dried in vacuo at 60°C. The temperature was gradually raised to 100°C for 1 h, 200°C for 1 h and 300°C for 1 h to dehydrate the reactive polyamide amic acid oligomer to obtain a reactive polyamideimide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After the film was cooled to 25°C, a flexible and tough film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 483°C. Differential scanning calorimetry (N2, 10°C / min) showed T g Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') was 3.2 GPa at 33°C and 0.81 GPa at 300°C. g The stress-strain experiment (25°C) showed that the film had a Young's modulus of 3.4 GPa, a fracture strength of 134 MPa, and a fracture strain of 17%. The film properties exceeded expectations for high molecular weight polymer films.

[0459] Example 1D - Isolated reactive polyamideimide oligomer powder, M n =5000g / mol

[0460] The reactive polyamide-imide oligomer powder of imidization is obtained by precipitating the solution of the reactive polyamide-amic acid of Example 1A in NMP in MeOH. By pouring 50mL of the polyamide-amic acid solution of Example 1A into 200mL MeOH in a Warring blender and mixing for 1-3min, the polyamide-amic acid is precipitated. The precipitate is collected by filtering on a Buchner funnel and washed with another 200mL MeOH. The washed polyamide-amic acid powder is dried in an oven at 60°C for 2 hours under vacuum. Gradually warming up to 100°C for 1h, 200°C for 1h and 260°C for 1h, the reactive polyamide-amic acid oligomer is dehydrated, and the reactive polyamide-imide oligomer powder with unreacted phenylethynyl end groups is obtained. Parallel plate rheology (N2, 10°C / min) of the fully imidized reactive polyamideimide oligomer showed a melt complex viscosity of 19000 Pa·s at 361°C.

[0461] Example 1E - Cured polyamideimide oligomer film, M n =5000g / mol

[0462] This is another example of preparing a flexible, free-standing film with cured phenylethynyl end groups. The reactive polyamide amic acid oligomer solution of Example 1A was imidized as follows. Anhydrous toluene was added to the reaction flask. The water formed during the cyclodehydration (amic acid to imide) was removed by azeotropic distillation. After 2 hours, the reactive polyamide amic acid oligomer was 98% imidized and the remaining toluene was removed by distillation. A solution (10 mL) of the resulting reactive polyamide imide oligomer in NMP (30 wt.% solid) was poured onto a glass plate and dried under vacuum at 60°C. After cooling to room temperature, the temperature was gradually increased to 40°C for 2h, 60°C for 2h, 100°C, 200°C, 300°C for 30min and 370°C for 1h. After the film was cooled to 25°C, a flexible and tough film was obtained. Differential scanning calorimetry (N2, 10°C / min) showed T g It is 326°C, which is about 46°C higher than the Tg (280°C) of the currently available PAI film.

[0463] Example 1F, Cured Polyamide-Imide Oligomer Film, M n =3000g / mol

[0464] Preparation of M using 4-phenylethynylphthalic anhydride as a capping agent n=3000g / mol reactive polyamideimide oligomer. A 150mL 2-neck round-bottom flask equipped with a stirring rod and a nitrogen inlet tube was charged with 1,3-phenylenediamine (22.84mmol, 2.47g), 4,4'-oxydiphenylamine (62.07mmol, 12.43g) and 82g NMP. The mixture was stirred until a uniform solution was obtained. The solution was cooled to 0°C. Trimellitic anhydride chloride (76.08mmol, 16.02g) and 4-(phenylethynyl)phthalic anhydride (17.64mmol, 4.38g) were added all at once. The reaction mixture was stirred at 0°C for 1 to 2 hours under a nitrogen atmosphere, and then the ice bath was removed, and the reaction mixture was stirred and warmed to 25°C overnight (about 16h), providing a solution of reactive polyamide amic acid oligomer in NMP. The reactive polyamide amic acid oligomer solution (10 mL) was poured onto a glass plate and dried under vacuum at 60°C. The temperature was gradually raised to 100°C for 1 h, 200°C for 1 h and 300°C for 1 h to dehydrate the reactive polyamide amic acid oligomer to obtain a reactive polyamide imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After the film was cooled to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 500°C. Differential scanning calorimetry (N2, 10°C / min) showed a Tg of 291°C. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') was 1.71 GPa at 35°C, 0.25 GPa at 300°C, and T g The stress-strain test (25°C) shows that the film has a Young's modulus of 3.0 GPa, a fracture strength of 110 MPa, and a fracture strain of 16.4%.

[0465] Example 1G - Isolated reactive polyamideimide oligomer powder, M n =3000g / mol

[0466] The imidized reactive polyamide-imide oligomer powder was obtained by precipitating a solution of the reactive polyamide-amic acid of Example 1D in NMP 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 in a Warring blender and mixing for 1-3 min. The precipitate was collected by filtration on a Buchner funnel and washed with an additional 200 mL of MeOH. The washed polyamide-amic acid powder was dried in an oven at 60 ° C for 2 hours under vacuum. The temperature was gradually raised to 100 ° C for 1 h, 200 ° C for 1 h, and 260 ° C for 1 h to dehydrate the reactive polyamide-amic acid oligomer to obtain a reactive polyamide-imide oligomer powder with unreacted phenylethynyl end 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.

[0467] Example 1H - Cured polyamideimide oligomer film, M n =8000g / mol

[0468] Preparation of reactive polyamideimide oligomers having 4-phenylethynylphthalic anhydride reactive end groups, M n =8000g / mol. A 150mL 2-neck round-bottom flask equipped with a stirring rod and a nitrogen inlet tube was charged with 1,3-phenylenediamine (22.84mmol, 2.47g), 4,4'-oxydiphenylamine (56.43mmol, 11.30g) and 73g NMP. The mixture was stirred until a uniform solution was obtained. The solution was cooled to 0°C. Trimellitic anhydride chloride (76.08mmol, 16.02g) and 4-(phenylethynyl)phthalic anhydride (6.04mmol, 1.5g) were added all at once. The reaction mixture was stirred at 0°C for 1 to 2 hours under a nitrogen atmosphere, and then the ice bath was removed, and the reaction mixture was stirred and warmed to 25°C overnight (about 16h) to provide a solution of reactive polyamide amic acid oligomers in NMP. The reactive polyamide amic acid oligomer solution (10 mL) was poured onto a glass plate and dried under vacuum at 40°C for 2 hours and at 60°C for 2 hours. The temperature was gradually raised to 100°C for 1 hour, 200°C for 1 hour and 300°C for 1 hour to dehydrate the reactive polyamide amic acid oligomer to obtain a reactive polyamide imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After cooling to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 490°C. Differential scanning calorimetry (N2, 10°C / min) showed T gDynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') was 3.0 GPa at 35°C and 0.75 GPa at 300°C, T g The stress-strain test (25°C) showed that the Young's modulus of the film was 3.1 GPa, the fracture strength was 139 MPa, and the fracture strain was 57.4%.

[0469] Example II - Isolated reactive polyamideimide oligomer powder, M n =8000g / mol

[0470] The imidized reactive polyamide-imide oligomer powder was obtained by precipitating the reactive polyamide-amic acid solution of Example 1F in NMP in MeOH. The polyamide-amic acid was precipitated by pouring 50 mL of the polyamide-amic acid solution into 200 mL of MeOH in a Warring blender and mixing for 1-3 min. The precipitate was collected by filtration on a Buchner funnel and washed with an additional 200 mL of MeOH. The washed polyamide-amic acid powder was vacuum dried in a tam oven at 60°C for 2 hours. The temperature was gradually increased to 100°C for 1h, 200°C for 1h and 260°C for 1h to dehydrate the reactive polyamide-amic acid oligomer to obtain a reactive polyamide-imide oligomer powder with unreacted phenylethynyl end groups. The parallel plate rheology (N2, 10°C / min) of the fully imidized reactive polyamide-imide oligomer showed a melt complex viscosity of 49902Pa·s at 333°C.

[0471] Example 1J - Cured oligomeric polyamideimide oligomer film, 4,4'-ODA:1,3-PD ratio = 0.62: 0.32,M n =5000g / mol

[0472] In this example, the molar ratio of two diamines; 4,4'-ODA and 1,3-PD is 0.62:0.32. A 150mL 2-neck round-bottom flask equipped with a stirring bar and a nitrogen inlet tube is charged with 1,3-phenylenediamine (37.54mmol, 4.06g), 4,4'-oxydiphenylamine (62.52mmol, 12.52g) and 92g NMP. The mixture is stirred until a uniform solution is obtained. The solution is cooled to 0°C. Trimellitic anhydride chloride (93.89mmol, 19.77g) and 4-(phenylethynyl)phthalic anhydride (12.41mmol, 3.08g) are added all at once. This reaction mixture is stirred at 0°C for 1 to 2 hours under a nitrogen atmosphere, and then the ice bath is removed and the reaction mixture is stirred and warmed to 25°C overnight (about 16 hours) to provide a solution of reactive polyamide amic acid oligomers in NMP. The reactive polyamide amic acid oligomer solution (10 mL) was poured onto a glass plate and dried at 40°C for 2 hours and at 60°C for 2 hours under vacuum. The temperature was gradually raised to 100°C for 1 hour, 200°C for 1 hour and 300°C for 1 hour to dehydrate the reactive polyamide amic acid oligomer to obtain a reactive polyamide imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After cooling to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 478°C. Differential scanning calorimetry (N2, 10°C / min) showed T g Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') was 2.0 GPa at 35°C and 0.24 GPa at 300°C, T g The stress-strain test (25°C) showed that the Young's modulus of the film was 2.5 GPa, the breaking strength was 82.5 MPa, and the breaking strain was 10.1%.

[0473] Example 1K - Isolated reactive polyamideimide oligomer powder, 4,4'-ODA:1,3-PD ratio = 0.62:0.32,M n =5000g / mol

[0474] The reactive polyamide-amic acid oligomer powder of imidization is obtained by precipitating the solution of the reactive polyamide-amic acid oligomer of Example 1I in NMP in MeOH. By pouring 50mL reactive polyamide-amic acid oligomer solution into 200mL MeOH in a Waring blender and mixing for 1-3 minutes, the reactive polyamide-amic acid oligomer is precipitated. The precipitate is collected by filtering on a Buchner funnel and washed with another 200mL MeOH. The washed reactive polyamide-amic acid oligomer powder is dried in an oven at 60°C under vacuum for 2 hours. Gradually warming up to 100°C for 1h, 200°C for 1h and 260°C for 1h, the reactive polyamide-amic acid oligomer is dehydrated, and a reactive polyamide-imide oligomer powder with unreacted phenylethynyl end groups is obtained. Parallel plate rheology (N2, 10°C / min) of the fully imidized reactive polyamideimide oligomer showed a melt complex viscosity of 40339 Pa·s at 370°C.

[0475] Example 1L - Cured oligomeric polyamideimide oligomer film, 4,4'-ODA:1,3-PD ratio = 0.813: 0.197,M n =5000g / mol

[0476] In this example, the molar ratio of two diamines; 4,4'-ODA and 1,3-PD is 0.813:0.187. A 150mL 2-necked round-bottom flask equipped with a stirring rod and a nitrogen inlet tube was charged with 1,3-phenylenediamine (18.77mmol, 2.03g), 4,4'-oxydiphenylamine (81.70mmol, 16.36g) and 96g NMP. The mixture was stirred until a uniform solution was obtained. The solution was cooled to 0°C. Trimellitic anhydride chloride (93.89mmol, 19.77g) and 4-(phenylethynyl)phthalic anhydride (12.41mmol, 3.08g) were added all at once. The reaction mixture was stirred at 0°C for 1 to 2 hours under a nitrogen atmosphere, and then the ice bath was removed, and the reaction mixture was stirred and warmed to 25°C overnight (about 16h) to provide a solution of reactive polyamide amic acid oligomers in NMP. The reactive polyamide amic acid oligomer solution (10 mL) was poured onto a glass plate and dried at 40°C for 2 hours and at 60°C for 2 hours under vacuum. The temperature was gradually raised to 100°C for 1 hour, 200°C for 1 hour and 300°C for 1 hour to dehydrate the reactive polyamide amic acid oligomer to obtain a reactive polyamide imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After cooling to 25°C, a flexible film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 496°C. Differential scanning calorimetry (N2, 10°C / min) showed T gDynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') was 2.5 GPa at 35°C and 1.0 GPa at 300°C, T g The stress-strain experiment (25°C) showed that the Young's modulus of the film was 3.7 GPa, the fracture strength was 132 MPa, and the fracture strain was 12.6%.

[0477] Example 1M - Isolated reactive polyamideimide oligomer powder, 4,4'-ODA:1,3-PD ratio = 0.813:0.197,M n =5000g / mol

[0478] The reactive polyamide-imide oligomer powder of imidization is obtained by precipitating the solution of reactive polyamide-amic acid oligomer in NMP in MeOH. By pouring 50mL reactive polyamide-amic acid oligomer solution into 200mL MeOH in Warring blender and mixing for 1-3min, reactive polyamide-amic acid oligomer is precipitated. The mixture is washed in Warring blender for 1-3 minutes. The precipitate is collected by filtering on Buchner funnel and washed with another 200mL MeOH. The washed reactive polyamide-amic acid oligomer powder is dried in an oven at 60°C under vacuum for 2 hours. The temperature is gradually increased to 100°C for 1h, 200°C for 1h and 260°C for 1h, and the reactive polyamide-amic acid oligomer is dehydrated to obtain reactive polyamide-imide oligomer powder with unreacted phenylethynyl end groups. Parallel plate rheology (N2, 10°C / min) of the fully imidized reactive polyamideimide showed a melt complex viscosity of 49502 Pa·s at 359°C.

[0479] Example 2

[0480] Two different capping agents were used to make M n A reactive polyamideimide (PAI) oligomer of 5000 g / mol is shown below in Scheme 6. The two different end-capping agents are 4-(phenylethynyl)phthalic anhydride and 4-(methylethynyl)phthalic anhydride.

[0481]

[0482] Scheme 6. Synthesis of M with two different reactive end groups n =5000 g / mol fully aromatic reactive polyamideimide oligomer. 50 / 50 4-(phenylethynyl)phthalic anhydride / 4-(methylethynyl)phthalic anhydride.

[0483] 1,3-phenylenediamine (6.38mmol, 0.69g), 4,4'-oxydiphenylamine (16.33mmol, 3.27g) and 36g NMP were placed in a 150mL 2-neck round-bottom flask equipped with a stirring rod and a nitrogen inlet tube. The mixture was stirred until a uniform solution was obtained. The solution was cooled to 0°C. Trimellitic anhydride chloride (21.28mmol, 4.48g), 4-(phenylethynyl)phthalic anhydride (1.45mmol, 0.36g) and 4-(methylethynyl)phthalic anhydride (1.45mmol, 0.27g) were added all at once. The reaction mixture was stirred at 0°C for 1 to 2 hours under a nitrogen atmosphere, and then the ice bath was removed, and the reaction mixture was stirred and warmed to 25°C overnight (about 16 hours). The prepared reactive polyamide amic acid oligomer solution (10mL) was poured onto a glass plate and dried at 60°C under vacuum. The temperature was gradually raised to 100°C for 1 hour, 200°C for 1 hour and 300°C for 1 hour to dehydrate the reactive polyamide amic acid oligomer and obtain a reactive polyamide imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After the film was cooled to 25°C, a flexible and tough film was obtained.

[0484] Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 466°C. Differential scanning calorimetry (N2, 10°C / min) showed T g Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') was 2.6 GPa at 33°C and 0.64 GPa at 300°C, T g The viscosity of the film at 301°C was 98560 Pa·s at 301°C by parallel plate rheology (N2, 10°C / min). Stress-strain experiments at 25°C showed that the film had a Young's modulus of 3.6 GPa, a breaking strength of 155 MPa, an elongation at break of 75%, and a toughness of 94.3 MJ / m 3 In contrast, a review of the existing literature shows that currently available PAIs have only about 10 MJ / m 3 The PAI films made from reactive polyamideimide oligomers can have toughness of 100 MPa, strength at break of 140 MPa, and elongation at break of 10 to 15%. Thus, the toughness of PAI films made from reactive polyamideimide oligomers can be almost 10 times higher than the toughness of currently available PAI, the elongation at break can be about 5 times higher, and the strength at break can be about 10% higher. Typically, crosslinking of polymers results in a decrease in elongation at break. Surprisingly, when the reactive polyamideimide oligomers are crosslinked, both the strength at break and the elongation at break increase, resulting in a substantial increase in toughness.

[0485] In additive manufacturing methods such as fused filament fabrication and selective laser sintering, the low molecular weight of the reactive polyamideimide oligomer promotes rapid diffusion across the interface between two filaments or particles. In addition, the reactive functional groups can be selected to polymerize (chain extension / crosslinking) over a wide temperature range. In this embodiment, the reactive polyamideimide oligomer is capable of two-step curing at different temperatures. The methyl ethynyl group is cured in the temperature range of 280 to 330°C, and the phenyl ethynyl group is cured in the temperature range of 330 to 400°C. In the additive manufacturing method, the low-temperature cured methyl ethynyl group ensures rapid fixation of the structure, and the high-temperature cured phenyl ethynyl group allows additional chain diffusion and chain extension / crosslinking after the low-temperature group is cured without losing structural integrity.

[0486] Example 3

[0487] Another reactive polyamideimide oligomer is made as shown in Scheme 7 below. TMACl is expensive, so it is desirable to minimize its use in the reactive polyamideimide oligomer manufacture. TMACl has an acyl chloride group and a carboxylic anhydride group. Instead of using one equivalent of TMACl, 1 / 2 equivalent of pyromellitic dianhydride (PMDA) and 1 / 2 equivalent of isophthalic acid chloride (IPC) were used. Preparation of M with 4-(phenylethynyl)phthalic anhydride reactive end groups n It is a reactive oligomer of 5000 g / mol.

[0488]

[0489] Scheme 7. M with 4-(phenylethynyl)phthalic anhydride reactive end group n = Synthesis of 5000 g / mol fully aromatic reactive polyamideimide oligomer. The trimellitic anhydride chloride of Example 2 was replaced by pyromellitic dianhydride and isophthaloyl chloride.

[0490] In a 150mL 2-neck round bottom flask equipped with a stirring rod and a nitrogen inlet tube, pyromellitic anhydride (10.64mmol, 2.32g), isophthaloyl chloride (10.64mmol, 2.16g), 4-(phenylethynyl)phthalic anhydride (2.9mmol, 0.72g) and 37g NMP were loaded. The suspension was stirred for 15min and cooled to 0°C. Diamine, 1,3-phenylenediamine (6.38mmol, 0.69g) and 4,4'-oxydiphenylamine (16.33mmol, 3.27g) were all added at once. The reaction mixture was stirred at 0°C for 1 hour under a nitrogen atmosphere, and then the ice bath was removed, and the reaction mixture was stirred and warmed to 25°C overnight (about 16 hours). The prepared reactive polyamide amic acid oligomer solution (10mL) was poured onto a glass plate and dried at 60°C under vacuum. The temperature was gradually raised to 100°C for 1 hour, 200°C for 1 hour and 300°C for 1 hour to dehydrate the reactive polyamide amic acid oligomer to obtain a reactive polyamide imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After the film was cooled to 25°C, a flexible and tough film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 476°C. Differential scanning calorimetry (N2, 10°C / min) showed T g Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') was 2.8 GPa at 33°C and 0.93 GPa at 300°C, T g The stress-strain experiment at 25°C showed that the Young's modulus of the film was 3.2 GPa, the breaking strength was 121 MPa, and the breaking elongation was 25%.

[0491] Example 4

[0492] Another reactive polyamideimide oligomer was prepared as shown below in Scheme 8. A cross-linkable dianhydride monomer (4,4'-(ethynyl-1,2-diyl) diphthalic dianhydride or EBPA) was incorporated into the reactive oligomer backbone. n ) is limited to 5000 g / mol, using phthalic anhydride (non-reactive) as the end-capping agent.

[0493]

[0494] Scheme 8. Synthesis of M n=5000 g / mol fully aromatic reactive polyamideimide oligomer with crosslinkable acetylene-based dianhydride monomer (4,4'-(acetylene-1,2-diyl) diphthalic dianhydride or EBPA) in the backbone. The molecular weight (M) was increased by using a non-reactive phthalic anhydride end-capping agent. n ) is limited to 5000 g / mol.

[0495] 4,4'-oxydiphthalic anhydride (ODPA) (7.98mmol, 2.48g), isophthaloyl chloride (10.64mmol, 2.16g), EBPA (2.66mmol, 0.85g), phthalic anhydride (2.9mmol, 0.43g) and 42g NMP were loaded into a 150mL 2-neck round-bottom flask equipped with a stirring rod and a nitrogen inlet tube. The suspension was stirred for 15min and cooled to 0°C. Diamine 4,4'-oxydiphenylamine (22.71mmol, 4.55g) was added all at once. The reaction mixture was stirred at 0°C for 1 hour under a nitrogen atmosphere, and then the ice bath was removed, and the reaction mixture was stirred and warmed to 25°C overnight (about 16 hours). The prepared reactive polyamide amic acid oligomer solution (10mL) was cast onto a glass plate and dried at 60°C under vacuum to form a film. The temperature was gradually raised to 100°C for 1 hour, 200°C for 1 hour and 300°C for 1 hour to dehydrate the reactive polyamide amic acid oligomer to obtain a reactive polyamide imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. After the film was cooled to 25°C, a flexible and tough film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 463°C. Differential scanning calorimetry (N2, 10°C / min) showed T g It is 268℃.

[0496] Another film was formed in the same manner, except that the reactive polyamideimide oligomer film was cured at 400°C instead of 370°C for 1 hour. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 459°C. Dynamic mechanical thermal analysis (N2, 10°C / min, 1 Hz) showed a storage modulus (E') of 2.0 GPa at 33°C and 0.16 GPa at 300°C, T g The stress-strain experiment at 25°C showed that the Young's modulus of the film was 2.1 GPa, the breaking strength was 56 MPa, and the breaking elongation was 3%.

[0497] Example 5

[0498] Another reactive polyamideimide oligomer was prepared as shown below in Scheme 9. A cross-linkable dianhydride monomer (4,4'-(ethynyl-1,2-diyl) diphthalic dianhydride or EBPA) was incorporated into the reactive oligomer backbone. n ) was limited to 5000 g / mol, and 4-(phenylethynyl)phthalic anhydride reactive end-capping agent was used.

[0499]

[0500] Scheme 9. Synthesis of M n =5000 g / mol fully aromatic reactive polyamideimide oligomer with crosslinkable acetylene-based dianhydride monomer (4,4'-(ethynyl-1,2-diyl) diphthalic dianhydride or EBPA) in the backbone. The molecular weight (M) was increased to 100 g / mol using a reactive 4-(phenylethynyl)phthalic anhydride end-capping agent. n ) is limited to 5000 g / mol.

[0501] A 150 mL 2-necked round bottom flask equipped with a stirring bar and a nitrogen inlet was charged with 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 NMP. The suspension was stirred for 15 minutes and cooled to 0°C. The diamine 4,4'-oxydiphenylamine (22.71 mmol, 4.55 g) was added all at once. The reaction mixture was stirred at 0°C for 1 hour under a nitrogen atmosphere, after which the ice bath was removed and the reaction mixture was stirred and warmed to 25°C overnight (about 16 hours).

[0502] Example 5A

[0503] This is an example of preparing a free-standing polyamide-imide film obtained by selectively curing phenylethynyl end groups instead of backbone ethynyl groups. The reactive polyamide-amic acid oligomer solution (10 mL) prepared in Example 5 was poured onto a glass plate and dried in vacuo at 60°C. The temperature was gradually raised to 100°C for 1 h, 200°C for 1 h, and 300°C for 1 h to dehydrate the reactive polyamide-amic acid oligomer to obtain a reactive polyamide-imide oligomer having unreacted phenylethynyl end groups and 1,2-diphenylethynyl backbone groups. The temperature was raised to 370°C and the film was kept at this temperature for 1 hour. At this temperature, the phenylethynyl end groups were cured, but the 1,2-diphenylethynyl backbone groups were not cured. After the film was cooled to 25°C, a flexible and tough film was obtained. Differential scanning calorimetry (N2, 10°C / min) showed that Tg Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed that the storage modulus (E') at 33°C was 2.3 GPa, T g It is 302℃.

[0504] Example 5B

[0505] This is an example of preparing an independent polyamide-imide film with cured phenylethynyl end groups and 1,2-diphenylethynyl backbone groups. The reactive polyamide-amic acid oligomer solution (10 mL) prepared in Example 5 was poured onto a glass plate and dried in vacuo at 60°C. The temperature was gradually raised to 100°C for 1 h, 200°C for 1 h, and 300°C for 1 h to dehydrate the reactive polyamide-amic acid oligomer to obtain a reactive polyamide-imide oligomer with unreacted phenylethynyl end groups. The temperature was raised to 400°C and the film was kept at this temperature for 1 hour. At this temperature, both the phenylethynyl end groups and the 1,2-diphenylethynyl backbone groups were cured. After the film was cooled to 25°C, a flexible and tough film was obtained. Thermogravimetric analysis (N2, 10°C / min) showed a weight loss of 5% at 453°C. Dynamic mechanical thermal analysis (N2, 10°C / min, 1Hz) showed a storage modulus (E') of 2.7 GPa at 33°C, T g The stress-strain test at 25°C showed that the Young's modulus of the film was 2.6 GPa, the breaking strength was 78 MPa, and the breaking elongation was 4%.

[0506] Example 6

[0507] Using the ammonium carboxylate pathway to make another M n = 5000 g / mol of a reactive polyamideimide oligomer as shown in Scheme 10 below.

[0508]

[0509] Scheme 10. Synthesis of M via the ammonium carboxylate route n =5000 g / mol fully aromatic reactive polyamideimide oligomer.

[0510] A flame-dried 3-neck 500 mL round-bottom flask equipped with a reflux condenser and a nitrogen inlet connector was charged with 0.2556 mol (49.11 g) of trimellitic anhydride, 0.036 mol (8.94 g) of 4-(phenylethynyl)phthalic anhydride and 85 g of MeOH. The mixture was refluxed at 70° C. for 2 hours under nitrogen. To this mixture was added 0.2730 mol (54.67 g) of 4,4'-oxydiphenylamine in batches. The mixture was refluxed for 24 hours and methanol was removed by evaporation. The resulting carboxylic acid ammonium salt was dried in vacuo at 70° C. The salt was heated to 300° C. at 10° C. / min under nitrogen and kept isothermally at 300° C. for 1 hour at a pressure of 3 atm to obtain a reactive polyamideimide oligomer.

[0511] Thermogravimetric analysis (N2, 10°C / min) showed a 5% weight loss at 510°C. Differential scanning calorimetry (N2, 10°C / min) showed that the oligomers had a T of 2.34 Å before cross-linking. g After thermal crosslinking of the reactive oligomer (1 hour at 370°C), T g Increased from 226°C to 287°C. Fourier transform infrared spectroscopy (FTIR) using PerkinElmer Spectroscopy, ATR mode: 1718 cm -1 (Imide C=O), 1660cm -1 (amide C=O) and 1374 cm -1 (Imide CN).

[0512] Example 7

[0513] The preparation of reactive polyamideimide (PAI) oligomers by reactive extrusion is illustrated in Scheme 11 below. Phenylethynyl end-capping agent (PEPA) was used to prepare M n It is a reactive oligomer of 5000 g / mol.

[0514]

[0515] Scheme 11. Synthesis of M with phenylethynyl reactive end groups by melt polymerization n =5000 g / mol fully aromatic reactive polyamideimide oligomer.

[0516] A 500 mL 2-neck round bottom flask equipped with an overhead stirrer and a nitrogen inlet tube was charged with 1,3-phenylenediamine (63.8 mmol, 6.9 g), 4,4'-oxydiphenylamine (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 glacial acetic acid. The resulting reaction mixture was heated at reflux for 2 hours, then 20 mL of acetic anhydride was added and the reaction was refluxed for another hour. The acetic acid formed during the reaction, residual acetic anhydride and water were removed by vacuum distillation. The resulting yellow monomer mixture was fed into an Xplore twin-screw extruder with venting capability at 290°C. The melt was circulated in the extruder at 290°C and 50 rpm for 55 minutes for polymerization. The polymerization was monitored by measuring the relationship between the axial force (N) and time (min), as Figure 2 When the axial force of 5000N was reached (55min), the polymerization was judged to be complete. At this point, the reactive PAI oligomer was extruded as a continuous amber filament and analyzed.

[0517] To confirm that reactive oligomers rather than cross-linked material were obtained, a small sample was dissolved in NMP. GPC analysis against polystyrene standards showed M n The viscosity of the resulting filaments was 4500 and the polydispersity index (PDI) was 2.22. TGA was run on the resulting filaments at 10°C / min under nitrogen and showed a 1% mass loss at 395°C and a 5% mass loss at 448°C. The powder samples were compressed in a 13 mm tablet press die and subjected to oscillatory shear ramping from 30°C to 350°C at 0.03% strain and 2 rad / s at a ramp rate of 10°C / min. The lowest viscosity recorded was 33000 Pa·s.

[0518] The filament sample was ground into powder and dissolved in NMP at 20wt% overnight, and then cast into a film with a thickness of about 40μm. 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 showed an optimal fracture stress of 115MPa at 17% strain and 3GPa modulus. The sample was subjected to uniaxial oscillation heating from 30°C to 400°C at a heating rate of 2°C / min with 0.03% strain and 2rad / s. The sample showed a modulus of 3GPa and a T of 290°C. g .

[0519] Example 8

[0520] The following illustrates a solution with an M of 5000 g / mol. n , T of about 200°Cg and a reactive polyetherimide (PEI) oligomer with two different end capping agents. The two different end capping agents are 4-(methylethynyl)phthalic anhydride and N-arylmaleimide. In this embodiment, the reactive polyetherimide oligomer is capable of two-step curing at different temperatures. The N-arylmaleimide group is cured in the temperature range of 200 to 250°C, and the methylethynyl group is cured in the temperature range of 280 to 330°C. In the additive manufacturing method, the low-temperature cured N-arylmaleimide group ensures rapid fixation of the structure, and the high-temperature cured methylethynyl group allows additional chain diffusion and chain extension / cross-linking after the low-temperature group cures without losing structural integrity.

[0521]

[0522] Example 9

[0523] Two different capping agents were used to make M n A reactive polyetherimide (PEI) oligomer with a molecular weight of 5000 g / mol is shown in Scheme 12 below. The two different end-capping agents are 4-(phenylethynyl)phthalic anhydride and 4-(methylethynyl)phthalic anhydride. Also in this example, the reactive polyetherimide oligomer is capable of two-step curing at different temperatures. The methylethynyl group is cured in the temperature range of 280 to 330°C, and the phenylethynyl group is cured in the temperature range of 330 to 400°C. In the additive manufacturing process, the lower temperature cured methylethynyl group ensures rapid fixation of the structure, while the higher temperature cured phenylethynyl group allows additional chain diffusion and chain extension / crosslinking after the lower temperature group is cured without losing structural integrity.

[0524]

[0525] Scheme 12. Synthesis of M with two different reactive end groups n =5000 g / mol fully aromatic reactive polyetherimide oligomer. 50 / 50 4-(phenylethynyl)phthalic anhydride / 4-(methylethynyl)phthalic anhydride.

[0526] The reactive oligomers described herein, such as reactive polyamideimide oligomers and reactive polyamideamic acid oligomers, may also be referred to as "macromers."

[0527] 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 tetra-functional aromatic carboxylic acid or its functional equivalent and has unreacted functional groups that are capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0528] As used herein, "crosslinkable endcapping agent" refers to an endcapping agent that is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof and has at least one unreacted functional group capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0529] As used herein, "non-crosslinkable end-capping agent" refers to an end-capping agent that is reactive with at least one aromatic diamine or at least one di-, tri- or tetra-functional aromatic carboxylic acid or a functional equivalent thereof, but has no unreacted functional groups that are capable of chain extension and crosslinking after the reactive polyamideimide oligomer is formed.

[0530] "Functional equivalents" of carboxylic acids include compounds in which the carbon atom of the carboxylic acid group is in the same oxidation state, and include esters, chlorides, and anhydrides thereof.

[0531] As used herein, curing refers collectively to any combination of chain extension, branching, and crosslinking that results in enhanced thermomechanical properties. Curing can be initiated by heat, actinic (electromagnetic) radiation, or electron beam radiation. The terms "thermal curing," "thermal post-treatment," and "thermal post-curing" are used interchangeably for curing initiated by heat.

[0532] The terms "acetylene" and "alkyne" are used interchangeably herein.

[0533] The terms “additive manufacturing” and “3D printing” are used interchangeably in this article.

[0534] The terms "fused filament fabrication" and "fused deposition modeling" are used interchangeably herein.

[0535] As used herein, "at least one of" in conjunction with a list means that the list includes each element individually, as well as combinations of two or more elements of the list and combinations of at least one element of the list with unnamed similar elements.

[0536] The compositions, methods and articles may alternatively comprise, consist of or consist essentially of any suitable material, step or component disclosed herein. The compositions and methods may additionally or alternatively be formulated to be free of or substantially free of any material (or type), step or component that is not necessary to achieve the function or purpose of the compositions and methods.

[0537] All ranges disclosed herein include endpoints, and the endpoints can be independently combined with each other (e.g., "less than or equal to 25 wt.%, or more specifically, 5 wt.% to 20 wt.%" includes all intermediate values ​​of the endpoints and ranges, including, for example, "5 wt.% to 25 wt.%"). References herein to "about" a certain value or parameter include (and describe) embodiments for the value or parameter itself. In certain embodiments, the term "about" includes an indication of ±50%. In certain other embodiments, the term "about" includes an indication of ±20%. In certain other embodiments, the term "about" includes an indication of ±10%. In other embodiments, the term "about" includes an indication of ±5%. In certain other embodiments, the term "about" includes an indication of ±1%. In certain other embodiments, the term "about" includes an indication of ±0.5%, and in certain other embodiments, 0.1%. Such changes are suitable for performing the disclosed method or employing the disclosed composition. In addition, the term "about x" includes a description of "x".

[0538] "Combination" includes blends, mixtures, alloys, reaction products, and the like. Unless otherwise indicated herein or clearly contradicted by context, the terms "a", "an", and "the" do not denote a limitation of quantity, and should be construed to cover both the singular and the plural. Unless expressly stated otherwise, "or" means "and / or".

[0539] References throughout this specification to "some embodiments," "one embodiment," etc. mean that a particular element described in conjunction with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. Furthermore, it should be understood that the described elements may be combined in any suitable manner in the various embodiments.

[0540] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which this application belongs. All cited patents, patent applications and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term incorporated in a reference, the term in this application takes precedence over the conflicting term incorporated in the reference.

[0541] Although specific embodiments have been described, the applicant or other persons skilled in the art may think of alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseeable or may not be foreseeable. Therefore, the appended aspects submitted, and since they can be modified, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A reactive oligomer comprising a backbone derived from at least one of polyphenylene sulfide, polybenzoxazole or polybenzimidazole and functionalized with at least one unreacted functional group capable of thermal chain extension and crosslinking after the reactive oligomer is formed, wherein the number average molecular weight (M) of the reactive oligomer is calculated using the Carothers equation n ) is from about 250 g / mol to about 10000 g / mol.

2. The reactive oligomer of claim 1, wherein the at least one unreacted functional group is maleimide, 5-norbornene-2,3-dicarboxylic acid imide, phthalonitrile, benzocyclobutene, biphenylene, cyanate, ketoacetylene, acetylene, methylacetylene, phenylacetylene, propargyl ether or benzoxazine. The reactive oligomer according to claim 1 , wherein the backbone is linear or branched.

4. A reactive oligomer comprising a backbone derived from polyamideimide functionalized with at least one unreacted functional group capable of thermal chain extension and crosslinking after formation of the reactive oligomer, wherein the at least one unreacted functional group is derived from a monomer or end-capping agent selected from the group consisting of: and The number average molecular weight (M) of the reactive oligomer is calculated using the Carothers equation. n ) is from about 250 g / mol to about 10000 g / mol.

5. The reactive oligomer according to claim 4, comprising units 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'-oxydiphenylamine and 4,4'-oxydiphenylamine, and a capping agent selected from the group consisting of 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride.

6. The reactive oligomer according to claim 4, comprising units derived from: at least one dianhydride selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride; at least one difunctional 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'-oxydiphenylamine and 4,4'-oxydiphenylamine; and a capping agent selected from the group consisting of 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride.

7. The reactive oligomer according to claim 4, comprising units derived from: at least one dianhydride selected from the group consisting of pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride and 4,4'-(ethynyl-1,2-diyl)diphthalic anhydride; at least one difunctional 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'-oxydiphenylamine and 4,4'-oxydiphenylamine; and anhydrides selected from the group consisting of phthalic anhydride, 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride.

8. A reactive oligomer comprising a backbone derived from a polyimide and having formula (I): Among them, Ar 1 The tetravalent aromatic group represented by is at least one of the following: By Ar 2 The divalent aromatic group represented by is at least one of the following: Y 1 and Z 1 Derived from a capping agent selected from the group consisting of: and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

9. The reactive oligomer according to claim 8, wherein the polyimide is a polyetherimide.

10. The reactive oligomer according to claim 9, comprising unreacted methylethynyl, phenylethynyl or maleimide functional groups. 11 . The reactive oligomer according to claim 9 , comprising an unreacted functional group derived from 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4,4′-(ethynyl-1,2-diyl)diphthalic anhydride or N-(4-aminophenyl)maleimide.

12. The reactive oligomer according to claim 9, comprising units derived from 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (CAS 38103-06-9), 1,3-phenylenediamine, and a capping agent selected from 4-methylethynylphthalic anhydride and N-(4-aminophenyl)maleimide.

13. The reactive oligomer according to claim 9, comprising units derived from: 2,3,3',4'-biphenyltetracarboxylic dianhydride; at least one aromatic diamine selected from the group consisting of 1,3-phenylenediamine, 3,4'-oxydiphenylamine and 4,4'-oxydiphenylamine; and a capping agent selected from 4-methylethynylphthalic anhydride and 4-phenylethynylphthalic anhydride.

14. A reactive oligomer comprising a backbone derived from a polyaryletherketone and having formula (II): Among them, Ar 3 The divalent aromatic group represented by is at least one of the following: Where S 1 , S 2 , S 3 and S 4 Each independently selected from H, F, Cl, Br, C 1-6 The group consisting of a straight or branched alkyl group and a phenyl group; and W is: By Ar 4 The divalent aromatic group represented by is at least one of the following: Y 2 and Z 2 Derived from a capping agent selected from the group consisting of: Where D is: And A is: and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

15. The reactive oligomer according to claim 14, comprising unreacted methylethynyl, phenylethynyl or maleimide functional groups.

16. A reactive oligomer comprising a backbone derived from polyethersulfone and having formula (III): Among them, Ar 5 The divalent aromatic group represented by is: By Ar 6 The divalent aromatic group represented by has the formula (IIIa): Y 3 and Z 3 Derived from a capping agent selected from the group consisting of: Where D is: and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

17. The reactive oligomer according to claim 16, which has formula (IIIc), (IIId) or (IIIe):

18. The reactive oligomer according to claim 17, comprising unreacted methylethynyl, phenylethynyl or maleimide functional groups.

19. A reactive oligomer comprising a backbone derived from polyphenylene sulfide and having formula (IV): The divalent aromatic group represented by Ar is: Where W is: Y and Z are derived from a capping agent selected from the group consisting of: Where D is: and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

20. The reactive oligomer of claim 19, comprising unreacted methylethynyl, phenylethynyl or maleimide functional groups.

21. A reactive oligomer comprising a backbone derived from a polyamide and having formula (Va) or (Vb): Among them, A 1 and A 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene or 1,2-, 1,3- or 1,4-xylylene; Y 4 and Z 4 Derived from a capping agent selected from the group consisting of: and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

22. The reactive oligomer of claim 21, comprising unreacted methylethynyl, phenylethynyl or maleimide functional groups.

23. A reactive oligomer comprising a backbone derived from a polyester and having formula (VIa) or (VIb): Among them, B 1 and B 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, Y 5 and Z 5 Derived from a capping agent selected from the group consisting of: Where D is: X is -OH, -NH2, -COOH or -COCl; and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

24. The reactive oligomer of claim 23, comprising unreacted methylethynyl, phenylethynyl or maleimide functional groups.

25. A reactive oligomer comprising a backbone derived from a polyester amide and having formula (VIIa) or (VIIb): Among them, D 1 and D 2 The divalent groups represented are each independently C4-C 12 Alkylene, cycloalkylene, alkylcycloalkylene, cycloalkylalkylene, Y 6 and Z 6 Derived from a capping agent selected from the group consisting of: Where D is: and X is -OH, -NH2, -COOH or -COCl; and n is selected to provide a calculated M in the range of about 250 to about 10,000 g / mol. n .

26. The reactive oligomer of claim 25, comprising unreacted methylethynyl, phenylethynyl or maleimide functional groups.

27. A composition comprising at least one reactive oligomer according to any one of claims 1 to 26.

28. The composition of claim 27, comprising a first reactive oligomer and a second reactive oligomer, wherein the first reactive oligomer has a first number average molecular weight (M n ), and the second reactive oligomer has a second number average molecular weight (M n ).

29. The composition of claim 27, further comprising a thermoplastic polymer.

30. The composition of claim 29, wherein the thermoplastic polymer comprises the same backbone repeating units as the at least one reactive oligomer.

31. The composition of claim 27, further comprising an oligomer lacking unreacted functional groups capable of thermal chain extension and cross-linking.

32. The composition of claim 27, further comprising at least one of a filler or an additive.

33. The composition of claim 27, wherein the composition is coated on thermoplastic polymer particles or filaments.

34. The composition of claim 33, wherein the thermoplastic polymer comprises the same backbone repeating units as the reactive oligomer.

35. A method of compounding the composition according to claim 27 comprising mixing the components of the composition at a temperature and for a time sufficient to form a homogeneous molten mixture but not to crosslink the unreacted functional groups.

36. A method of making an article comprising heating the composition according to claim 27 at a temperature and for a time sufficient to form and crosslink the reactive oligomers.

37. The manufacturing method of claim 36, wherein the method is additive manufacturing.

38. The additive manufacturing method of claim 37, wherein the method is fused filament fabrication (FFF), selective laser sintering (SLS), directed energy deposition (DED) laser engineered net shaping (LENS), or composite-based additive manufacturing (CBAM).

39. A method of manufacturing according to claim 37, wherein the method is fused filament manufacturing, the method comprising extruding the composition in adjacent horizontal layers so that there are interfaces between the layers, and exposing the layers to heat at a temperature and for a time sufficient to crosslink the reactive oligomers and form an article.

40. The method of manufacturing according to claim 37, wherein the method is selective laser sintering, the method comprising selectively sintering and cross-linking particles of the composition with a laser to form an article.

41. An article made by the method of claim 37.

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