Nylon elastomer material suitable for 3D printing and method for its preparation

Abstract

The application discloses a kind of nylon elastomer material suitable for 3D printing and preparation method thereof, the nylon elastomer molecular chain has soft / hard segment block structure, wherein hard segment structure is made of long carbon chain polyamide copolymerized by binary carboxylic acid and binary amine, and the proportion in molecular chain is 30-60wt%, soft segment structure is made of polyether diamine and polyether triamine, polyether triamine introduces branching point in soft segment, and the proportion of soft segment structure in molecular chain is 40-70wt%, and soft segment is connected with hard segment by amide bond.The application introduces trifunctional polyether amine component in soft segment composition by molecular structure design, introduces branching structure in soft segment of molecular chain and realizes accurate control, improves the difference between soft segment and hard segment in flexibility and chain segment movement ability from molecular level, so as to effectively control the melt performance of material, improves the forming stability in wire extrusion process, printing speed in melt deposition process and interlayer bonding strength.

Description

Technical Field

[0001] This invention relates to a nylon elastomer material and its preparation method, particularly a nylon elastomer material suitable for 3D printing and its preparation method. Background Technology

[0002] Fused Deposition Modeling (FDM) is currently the most widely used and lowest-cost 3D printing technology. Its basic process involves first shaping a thermoplastic material into filaments. During printing, the filaments are heated and melted through a nozzle, then deposited layer by layer along a slicing path. After cooling and solidification, the finished product is obtained. Commonly used 3D printing filaments include thermoplastics such as PLA (polylactic acid), ABS (acrylonitrile-butadiene-styrene), PC (polycarbonate), PA-CF (carbon fiber), PETG (polyethylene terephthalate), and PEEK (polyetheretherketone), as well as thermoplastic elastomers such as TPU (thermoplastic polyurethane), TPAE (thermoplastic polyamide), and TPEE (thermoplastic polyether ester). Among thermoplastic elastomers, TPU is the most widely used, but it has significant limitations: it requires high-performance printing equipment, is prone to nozzle clogging, and has a relatively high failure rate; its printing speed is slow, significantly reducing production cost-effectiveness; and it struggles to meet the demands of high-end applications in terms of lightweighting, resilience, and environmental adaptability.

[0003] TPAE, a thermoplastic elastomer formed by block copolymerization of rigid polyamide hard segments and flexible polyether soft segments, combines the high strength and abrasion resistance of nylon with the flexibility and resilience of polyether. It is one of the lightest engineering-grade TPE materials currently available, possessing excellent comprehensive performance and providing new ideas for 3D printing elastic filaments. For example, Chinese patent CN109280361A describes a mixture obtained by blending thermoplastic elastomer, viscosity thixotropic agent, and additives at room temperature. The functional group R of the polyhedral oligomeric silsesquioxane forms hydrogen bonds with the thermoplastic elastomer polymer molecular chain, which can improve the interlayer adhesion of 3D printed products and simultaneously solve the problems of filament pulling and warping deformation of thermoplastic elastomer materials in 3D printing. For example, Chinese patent CN113637176A obtains thermoplastic polyamide elastomer filaments through twin-screw melt extrusion of thermoplastic polyamide elastomer, antioxidant, resin, and inorganic filler. The obtained filaments are not prone to breakage or fraying during printing and exhibit strong interlayer adhesion. The printed products are less prone to warping, have high precision, and possess certain strength and excellent flexibility. Furthermore, Chinese patent CN121271262A discloses a high-resilience, low-warpage nylon elastomer for FDM 3D printing and its preparation method. This high-resilience, low-warpage nylon elastomer is prepared from nylon hard segments, polyether polyol, catalyst, nano-inorganic filler, and crosslinking agent. Utilizing the synergistic effect of inorganic filler and crosslinking agent on the nylon elastomer (PEBA), the warpage of the material during FDM 3D printing is significantly reduced, and resilience is improved to a certain extent. The above patents are all based on existing commercially available nylon elastomers. They address issues such as poor processing stability of existing nylon elastomer grades in filament fabrication, difficulty in matching melt flow rate with printing speed during fused deposition modeling (FDM), and insufficient interlayer bond strength even at high speeds. These patents propose using blending modification and fabrication to adapt to 3D printing production. However, this blending modification method faces challenges such as increased usage costs, poor performance stability, and conflicting performance improvements. For example, the introduction of chain extenders / crosslinking agents presents dispersion uniformity issues, and while the introduction of inorganic fillers can control melt flow, it affects interlayer bond strength and the specific gravity and elasticity of the final product. Therefore, developing a nylon elastomer with stable processing performance, controllable melt flow rate, and good interlayer bond strength to meet the process requirements of fused deposition modeling (FDM) 3D printing has significant practical value. Summary of the Invention

[0004] The purpose of this invention is to provide a nylon elastomer material suitable for 3D printing and its preparation method. Through molecular structure design, a trifunctional polyetheramine component is introduced into the soft segment composition, and branching structures are precisely introduced and controlled at specific points within the soft segments of the molecular chain. This improves the differences in flexibility and chain segment mobility between the soft and hard segments at the molecular level, thereby effectively controlling the melt properties of the material and improving the molding stability during filament extrusion, the printing speed during fused deposition modeling, and the interlayer adhesion strength.

[0005] The technical solution of this invention: A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dicarboxylic acid and diamine, accounting for 30-60 wt% of the molecular chain, and the soft segment structure is composed of polyether diamine and polyether triamine, wherein the polyether triamine introduces branching points in the soft segment, and the soft segment structure accounts for 40-70 wt% of the molecular chain, and the soft and hard segments are connected by amide bonds, the sum of the soft and hard segments being 100 wt%;

[0006] The general formula for the hard segment structure is as follows:

[0007]

[0008] Where a = 2 - 11, b = 4 - 15, and at least one of a and b satisfies: a ≥ 8 or b ≥ 10;

[0009] The soft segment structure includes the following structure:

[0010]

[0011] and

[0012]

[0013] Where: x = 0 or 1, y = 1 or 2.

[0014] A method for preparing nylon elastomer material suitable for 3D printing includes the following steps: adding diacid, diamine, polyether diamine, polyether triamine, antioxidant, catalyst, end-capping agent, and deionized water into a reaction vessel; heating to 200–220°C under stirring; then maintaining pressure at 0.8–1.5 MPa for 1–3 hours; after depressurization, conducting a heat preservation reaction at 230–270°C for 2–5 hours; followed by a vacuum reaction at a relative pressure below -0.095 MPa for 1–3 hours; and finally granulating and drying to obtain the nylon elastomer material.

[0015] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the dicarboxylic acid is an aliphatic diacid with 4-13 carbon atoms, preferably one or more of glutaric acid, adipic acid, sebacic acid, dodecanoic acid, and tridecanoic acid.

[0016] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the diamine is an aliphatic diamine with 4-15 carbon atoms, preferably one or more of acetyldiamine, octyldiamine, decanediamine, and dodecanediamine.

[0017] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the polyether diamine is one or more of polyethylene oxide ether diamine, polypropylene oxide ether diamine, and polytetrahydrofuran ether diamine, and the molecular weight of the polyether diamine is 500-5000 g / mol.

[0018] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the polyether triamine is one or more of polyethylene oxide ether triamine and polypropylene oxide ether triamine, the molecular weight of the polyether triamine is 450-5000 g / mol, and the amount of the polyether triamine is 0.2wt%-10wt% of the total amount of the material.

[0019] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the antioxidant is one or more of antioxidant 616, antioxidant 168, antioxidant 1010, antioxidant 1098, and antioxidant 1076, and the amount added accounts for 0.1wt% to 0.5wt% of the total feed amount.

[0020] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the catalyst is one or more of phosphoric acid, phosphorous acid, hypophosphorous acid and their salt derivatives, and the catalyst accounts for 0.1wt% to 0.5wt% of the total feed amount.

[0021] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the end-capping agent comprises one or more of a dicarboxylic acid having 6 to 12 carbon atoms.

[0022] In the aforementioned method for preparing a nylon elastomer material suitable for 3D printing, the end-capping agent is one or more of adipic acid, sebacic acid, and dodecanoic acid, and the amount added accounts for 0.1wt% to 0.5wt% of the total feed amount.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] 1. This invention introduces a trifunctional polyetheramine component into the soft segment composition. Through formulation design, a branched structure is introduced at specific points in the soft segment of the molecular chain and can be precisely controlled. This improves the differences in flexibility and chain segment mobility between the soft segment and the hard segment of the molecular chain at the molecular level, thereby effectively controlling the melt properties of the material.

[0025] 2. This invention uses a one-step polymerization method to directly prepare nylon elastomer materials suitable for 3D printing, without the need for subsequent blending modification. This avoids problems such as uneven dispersion, unstable performance, and increased costs caused by blending modification. The process is simple and easy to industrialize.

[0026] 3. The nylon elastomer material prepared in this application has the advantages of controllable melt index, good stability of wire extrusion, fast printing speed, strong interlayer adhesion, and lightweight, high elasticity and high strength of finished product. It can improve the uniformity of wire diameter and molding stability during the 3D printing wire extrusion process, and improve the speed of melt flow and solidification during the melt deposition process, thereby increasing the 3D printing speed. Detailed Implementation

[0027] The present invention will be further described below with reference to embodiments, but these embodiments are not intended to limit the scope of the invention.

[0028] Example 1. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and decanediamine, and the soft segment structure is composed of polyethylene oxide ether diamine (molecular weight 1000) and polypropylene oxide ether triamine (molecular weight 450), wherein the polypropylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0029] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2500g of polyethylene oxide ether diamine (molecular weight 1000), 20g of polyethylene oxide ether triamine (molecular weight 450), 1848g of dodecanoic acid, 941g of decanediamine, 1000g of deionized water, 10g of phosphoric acid, and 5g of adipic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at a pressure of 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 230℃ and held for 3 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 1012 as the hard segment is obtained. The elastomer has a soft segment content of 50%, a melting point of 168℃, a hardness of 43D, a tensile strength of 25MPa, and a melt index of 15g / 10min (190℃, 2.16kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0030] Example 2. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from sebacic acid and hexamethylenediamine, and the soft segment structure is composed of polypropylene oxide ether diamine (molecular weight 2000) and polypropylene oxide ether triamine (molecular weight 1000), wherein the polypropylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0031] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2500g of polypropylene oxide ether diamine (molecular weight 2000), 30g of polypropylene oxide ether triamine (molecular weight 1000), 1898g of sebacic acid, 940g of hexamethylenediamine, 1000g of deionized water, 10g of phosphorous acid, and 10g of sebacic acid to a polymerization reactor. The reactor is heated to 220℃ under nitrogen protection and held at 1.5MPa for 1 hour. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 250℃ and held for 2 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 2 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 610 as the hard segment is obtained. The elastomer has a soft segment content of 50%, a melting point of 173℃, a hardness of 45D, a tensile strength of 28MPa, and a melt index of 18g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0032] Example 3. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and hexamethylenediamine, and the soft segment structure is composed of polytetrahydrofuran ether diamine (molecular weight 1000) and polyethylene oxide ether triamine (molecular weight 450). The polyethylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0033] A method for preparing nylon elastomer material suitable for 3D printing involves adding 2500g of polytetrahydrofuran ether diamine (molecular weight 1000), 20g of polyethylene oxide ether triamine (molecular weight 450), 2075g of dodecanedioic acid, 749g of hexamethylenediamine, 1000g of deionized water, 5g of hypophosphorous acid, and 15g of sebacic acid to a polymerization reactor. The reactor is heated to 200℃ under nitrogen protection and held at 0.8MPa for 3 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 260℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 2 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 612 as the hard segment is obtained. The elastomer has a soft segment content of 50%, a melting point of 175℃, a hardness of 45D, a tensile strength of 28MPa, and a melt index of 12g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0034] Example 4. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from sebacic acid and sebacic diamine, and the soft segment structure is composed of polyethylene oxide ether diamine (molecular weight 2000) and polyethylene oxide ether triamine (molecular weight 450), wherein the polyethylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0035] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2500g of polyethylene oxide ether diamine (molecular weight 2000), 35g of polyethylene oxide ether triamine (molecular weight 450), 1634g of sebacic acid, 1157g of decanediamine, 1000g of deionized water, 15g of phosphorous acid, and 25g of dodecanedioic acid to a polymerization reactor. The reactor is heated to 220℃ under nitrogen protection and held at 1.5MPa for 1 hour. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 260℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 1 hour. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 1010 as the hard segment. The elastomer has a soft segment content of 50%, a melting point of 170℃, a hardness of 43D, a tensile strength of 25MPa, and a melt index of 22g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0036] Example 5. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from sebacic acid and hexamethylenediamine, and the soft segment structure is composed of polytetrahydrofuran ether diamine (molecular weight 2000) and polypropylene oxide ether triamine (molecular weight 1000), wherein the polypropylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0037] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2000g of polytetrahydrofuran ether diamine (molecular weight 2000), 35g of polypropylene oxide ether triamine (molecular weight 1000), 2236g of sebacic acid, 1162g of hexamethylenediamine, 1000g of deionized water, 25g of sodium hypophosphite, and 20g of sebacic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 270℃ and held for 2 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 610 as the hard segment. The elastomer has a soft segment content of 40%, a melting point of 180℃, a hardness of 50D, a tensile strength of 35MPa, and a melt index of 10g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0038] Example 6. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and hexamethylenediamine, and the soft segment structure is composed of poly(propylene oxide ether diamine) (molecular weight 2000) and poly(ethylene oxide ether triamine) (molecular weight 1000), wherein the poly(ethylene oxide ether triamine) introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0039] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2000g of poly(propylene oxide ether diamine) (molecular weight 2000), 25g of poly(ethylene oxide ether triamine) (molecular weight 1000), 2315g of dodecanedioic acid, 1047g of hexamethylenediamine, 1000g of deionized water, 5g of phosphoric acid, and 5g of sebacic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 260℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 612 as the hard segment is obtained. The elastomer has a soft segment content of 40%, a melting point of 177℃, a hardness of 48D, a tensile strength of 32MPa, and a melt index of 12g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0040] Example 7. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and decanediamine, and the soft segment structure is composed of polyethylene oxide ether diamine (molecular weight 2000) and polypropylene oxide ether triamine (molecular weight 1000), wherein the polypropylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0041] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2000g of polyethylene oxide ether diamine (molecular weight 2000), 15g of polypropylene oxide ether triamine (molecular weight 1000), 1998g of dodecanoic acid, 1315g of decanediamine, 1000g of deionized water, 10g of phosphorous acid, and 10g of sebacic acid to a polymerization reactor. The reactor is heated to 220℃ under nitrogen protection and held at 1.5MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 250℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 1012 as the hard segment. The elastomer has a soft segment content of 40%, a melting point of 173℃, a hardness of 48D, a tensile strength of 34MPa, and a melt index of 12g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0042] Example 8. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from sebacic acid and hexamethylenediamine, and the soft segment structure is composed of poly(ethylene oxide ether diamine) (molecular weight 3000) and poly(propylene oxide ether triamine) (molecular weight 5000), wherein the poly(propylene oxide ether triamine) (molecular weight 5000) introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0043] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2500g of polyethylene oxide ether diamine (molecular weight 3000), 500g of trifunctional propylene oxide ether (5000), 1522g of sebacic acid, 754g of hexamethylenediamine, 1000g of deionized water, 10g of phosphorous acid, and 10g of sebacic acid to a polymerization reactor. The reactor is heated to 260℃ under nitrogen protection and held at 1.7MPa for 1 hour. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 260℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 610 as the hard segment. The elastomer has a soft segment content of 60%, a melting point of 160℃, a hardness of 35D, a tensile strength of 22MPa, and a melt index of 18g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0044] Example 9. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from sebacic acid and sebacic diamine, and the soft segment structure is composed of polytetrahydrofuran ether diamine (molecular weight 5000) and polyethylene oxide ether triamine (molecular weight 5000), wherein the polyethylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0045] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2800g of polytetrahydrofuran ether diamine (molecular weight 5000), 200g of polyethylene oxide ether triamine (molecular weight 5000), 1258g of sebacic acid, 966g of decanediamine, 1000g of deionized water, 10g of phosphorous acid, and 10g of sebacic acid to a polymerization reactor. The reactor is heated to 200℃ under nitrogen protection and held at 0.8MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 260℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 2 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 1010 as the hard segment is obtained. The elastomer has a soft segment content of 60%, a melting point of 157℃, a hardness of 33D, a tensile strength of 22MPa, and a melt index of 24g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0046] Example 10. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and decanediamine, and the soft segment structure is composed of polypropylene oxide ether diamine (molecular weight 4000) and polypropylene oxide ether triamine (molecular weight 450), wherein the polypropylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0047] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 3000g of polypropylene oxide ether diamine (molecular weight 4000), 30g of polypropylene oxide ether triamine (molecular weight 450), 1339g of dodecanedioic acid, 870g of decanediamine, 1000g of deionized water, 15g of phosphorous acid, and 15g of sebacic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 230℃ and held for 5 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 2 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 1012 as the hard segment. The elastomer has a soft segment content of 60%, a melting point of 152℃, a hardness of 33D, a tensile strength of 23MPa, and a melt index of 25g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0048] Example 11. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from sebacic acid and dodecanediamine, and the soft segment structure is composed of polyethylene oxide ether diamine (molecular weight 4000) and polyethylene oxide ether triamine (molecular weight 1000), wherein the polyethylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0049] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 3500g of polyethylene oxide ether diamine (molecular weight 4000), 40g of polyethylene oxide ether triamine (molecular weight 1000), 926g of sebacic acid, 738g of dodecanoic acid diamine, 1000g of deionized water, 10g of phosphorous acid, and 10g of dodecanoic acid into a polymerization reactor. The reactor is heated to 220℃ under nitrogen protection and held at 1.5MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 230℃ and held for 5 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 2 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 1210 as the hard segment. The elastomer has a soft segment content of 70%, a melting point of 140℃, a hardness of 25D, a tensile strength of 18MPa, and a melt index of 28g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0050] Example 12. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and dodecanoic diamine, and the soft segment structure is composed of polypropylene oxide ether diamine (molecular weight 4000) and polypropylene oxide ether triamine (molecular weight 2000), wherein the polypropylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0051] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 3500g of polypropylene oxide ether diamine (molecular weight 4000), 35g of polypropylene oxide ether triamine (molecular weight 2000), 981g of dodecanoic acid, 673g of dodecanoic acid diamine, 1000g of deionized water, 20g of phosphorous acid, and 20g of adipic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 240℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 1212 as the hard segment is obtained. The elastomer has a soft segment content of 70%, a melting point of 142℃, a hardness of 25D, a tensile strength of 20MPa, and a melt index of 30g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0052] Example 13. A nylon elastomer material suitable for 3D printing, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and decanediamine, and the soft segment structure is composed of polyethylene oxide ether diamine (molecular weight 1000) and polyethylene oxide ether triamine (molecular weight 1000), wherein the polyethylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds.

[0053] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2500g of polyethylene oxide ether diamine (molecular weight 1000), 10g of polyethylene oxide ether triamine (molecular weight 1000), 15g of polyethylene oxide ether triamine (molecular weight 2000), 1827g of dodecanedioic acid, 935g of decanediamine, 1000g of deionized water, 5g of phosphoric acid, and 5g of sebacic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 260℃ and held for 4 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 1012 as the hard segment. The elastomer has a soft segment content of 50%, a melting point of 157℃, a hardness of 34D, a tensile strength of 22MPa, and a melt index of 15g / 10min (190℃, 2.16Kg). Taking a wire diameter of 1.75mm as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is <±0.02mm.

[0054] Comparative Example 1. A nylon elastomer material, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and decanediamine, and the soft segment structure is polyethylene oxide ether diamine (molecular weight 1000), and the soft segment does not contain branching points.

[0055] A method for preparing a nylon elastomer material suitable for 3D printing involves adding 2500g of polyethylene oxide ether diamine (molecular weight 1000), 1848g of dodecanoic acid, 941g of decanediamine, 1000g of deionized water, 10g of phosphoric acid, and 5g of adipic acid to a polymerization reactor. Under nitrogen protection, the mixture is heated to 210℃ and held at a pressure of 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure, and the temperature is raised to 230℃ and held for 3 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 1012 as the hard segment is obtained. This elastomer has a soft segment content of 50%, a melting point of 168℃, a hardness of 42D, a tensile strength of 18MPa, and a melt index of 35g / 10min (190℃, 2.16Kg). Taking a 1.75mm wire diameter as an example, under the process conditions of extrusion temperature of 185-200℃ and extrusion speed of 0.5-1m / s, the wire diameter fluctuation is > ±0.10mm. Moreover, during the use of the wire, due to its strong melt fluidity, the product is prone to deformation when the melt is not cooled enough after the printing speed is increased.

[0056] Comparative Example 2. A nylon elastomer material, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid and decanediamine, and the soft segment structure is composed of polyethylene oxide ether diamine (molecular weight 1000) and 750g of polypropylene oxide ether triamine (molecular weight 5000). The polyethylene oxide ether triamine introduces branching points in the soft segment, and the soft segment and hard segment are connected by amide bonds, but the amount of polyethylene oxide ether triamine added exceeds 10wt% of the total feed amount.

[0057] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 1750g of polyethylene oxide ether diamine (molecular weight 1000), 750g of polyethylene oxide ether triamine (molecular weight 5000), 1690g of dodecanoic acid, 1075g of decanediamine, 1000g of deionized water, 10g of phosphoric acid, and 5g of adipic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 230℃ and held for 3 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. The material is then cooled, pelletized, and dried to obtain a nylon elastomer with nylon 1012 as the hard segment. The elastomer has a soft segment content of 50%, a melting point of 162℃, a hardness of 35D, a tensile strength of 27MPa, and a melt flow index of 5g / 10min (190℃, 2.16Kg). Taking a 1.75mm wire diameter as an example, under extrusion conditions of 210-230℃ and 0.5-1m / s extrusion speed, the wire diameter fluctuates by more than ±0.20mm. Furthermore, the melt flow is poor during wire use, resulting in slow printing speed and poor product dimensions.

[0058] Comparative Example 3. A nylon elastomer material, wherein the nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of a long carbon chain polyamide copolymerized from dodecanoic acid, decanediamine and citric acid, and the hard segment contains branching points introduced by citric acid; the soft segment structure is polyethylene oxide ether diamine (molecular weight 1000), and the soft segment does not contain branching points; the soft segment and the hard segment are connected by amide bonds.

[0059] A method for preparing nylon elastomer materials suitable for 3D printing involves adding 2500g of polyethylene oxide ether diamine (molecular weight 1000), 1824g of dodecanoic acid, 20g of citric acid, 941g of decanediamine, 1000g of deionized water, 10g of phosphoric acid, and 5g of adipic acid to a polymerization reactor. The reactor is heated to 210℃ under nitrogen protection and held at a pressure of 1.2MPa for 2 hours. The pressure is then released to atmospheric pressure. After depressurization, the temperature is raised to 230℃ and held for 3 hours. A vacuum is then applied to -0.1MPa, and the reaction continues for 3 hours. After the vacuum reaction is completed, nitrogen is introduced to restore the system to atmospheric pressure, and the material is released. After cooling, pelletizing, and drying, a nylon elastomer with nylon 1012 as the hard segment is obtained. This elastomer contains 50% soft segments and branching points in its hard segments. It has a melting point of 148℃, a hardness of 34D, a tensile strength of 24MPa, and a melt flow index of 12g / 10min (190℃, 2.16Kg). Taking a 1.75mm wire diameter as an example, at an extrusion temperature of 180-200℃, the optimal extrusion speed is 0.3-0.5m / s, with wire diameter fluctuations close to ±0.20mm. Increasing the extrusion speed significantly increases wire diameter fluctuations. During fused deposition modeling (FDM) printing, the slow crystallization rate and decreased crystallinity of the formed wire limit the printing speed, and the resulting product is prone to deformation.

[0060] In summary, this application modulates the rheological behavior of the melt at the molecular level by introducing a controllable branched structure into the soft segment. This allows the material to maintain dimensional stability (small diameter fluctuation) when extruded into filaments, while also exhibiting suitable melt flowability and rapid solidification during high-speed printing. Furthermore, a one-step polymerization method is used to directly prepare nylon elastomer materials suitable for 3D printing, eliminating the need for subsequent blending modifications. This avoids problems such as uneven dispersion, unstable performance, and increased costs associated with blending modifications. The process is simple and easy for industrial production.

Claims

1. A nylon elastomer material suitable for 3D printing, characterized in that, The nylon elastomer molecular chain has a soft / hard segment block structure, wherein the hard segment structure is composed of long-chain polyamide copolymerized from dicarboxylic acid and diamine, accounting for 30-60 wt% of the molecular chain; the soft segment structure is composed of polyether diamine and polyether triamine, with polyether triamine introducing branching points in the soft segment, and the soft segment structure accounting for 40-70 wt% of the molecular chain; the soft and hard segments are connected by amide bonds, and the sum of the soft and hard segments is 100 wt%. The general formula for the hard segment structure is as follows: Where a = 2 - 11, b = 4 - 15, and at least one of a and b satisfies: a ≥ 8 or b ≥ 10; The soft segment structure includes the following structure: and Where: x = 0 or 1, y = 1 or 2.

2. The method for preparing a nylon elastomer material suitable for 3D printing according to claim 1, characterized in that, The process includes the following steps: adding diacid, diamine, polyether diamine, polyether triamine, antioxidant, catalyst, end-capping agent, and deionized water into a reactor; heating to 200–220°C under stirring; maintaining pressure at 0.8–1.5 MPa for 1–3 hours; releasing pressure and then holding the reaction at 230–270°C for 2–5 hours; followed by a vacuum reaction at a relative pressure below -0.095 MPa for 1–3 hours; and finally granulation and drying to obtain nylon elastomer material.

3. The method for preparing a nylon elastomer material suitable for 3D printing according to claim 2, characterized in that, The dicarboxylic acid is one or more aliphatic diacids with 4-13 carbon atoms.

4. The method for preparing a nylon elastomer material suitable for 3D printing according to claim 2, characterized in that, The diamine is one or more aliphatic diamines with 4-15 carbon atoms.

5. The method for preparing a nylon elastomer material suitable for 3D printing according to claim 2, characterized in that, The polyether diamine is one or more of polyethylene oxide ether diamine, polypropylene oxide ether diamine, and polytetrahydrofuran ether diamine, and the molecular weight of the polyether diamine is 500 to 5000 g / mol.

6. The method for preparing a nylon elastomer material suitable for 3D printing according to claim 2, characterized in that, The polyether triamine is one or more of polyethylene oxide ether triamine and polypropylene oxide ether triamine, the molecular weight of the polyether triamine is 450-5000 g / mol, and the amount of the polyether triamine is 0.2wt%-10wt% of the total amount of the material.

7. The method for preparing a nylon elastomer material suitable for 3D printing according to claim 2, characterized in that, The antioxidant is one or more of antioxidant 616, antioxidant 168, antioxidant 1010, antioxidant 1098, and antioxidant 1076, and the amount added accounts for 0.1wt% to 0.5wt% of the total feed amount.

8. A method for preparing a nylon elastomer material suitable for 3D printing according to claim 2, characterized in that, The catalyst is one or more of phosphoric acid, phosphorous acid, hypophosphorous acid and their salt derivatives, and the catalyst accounts for 0.1wt% to 0.5wt% of the total feed.

9. A method for preparing a nylon elastomer material suitable for 3D printing according to claim 2, characterized in that, The capping agent comprises one or more of a dicarboxylic acid having 6 to 12 carbon atoms.

10. A method for preparing a nylon elastomer material suitable for 3D printing according to claim 9, characterized in that, The capping agent is one or more of adipic acid, sebacic acid, and dodecanoic acid, and the amount added accounts for 0.1wt% to 0.5wt% of the total feed.

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