High-temperature-resistant dimensionally stable nylon material and preparation method thereof

Abstract

This invention belongs to the field of polymer composite materials and provides a high-temperature resistant, dimensionally stable nylon material and its preparation method. The invention employs a multi-stage premixing technology route, preparing a coordination composite masterbatch intermediate through melt blending of a coordinated polyamide intermediate with a phytic acid-silane bifunctionalized coordination interface glass fiber intermediate, followed by melt blending with polyamide 66. Utilizing the zinc coordination crosslinking network of the matrix and the covalent-coordination coupling mechanism of the phosphate ester-amino interface on the fiber surface, the dimensional stability and comprehensive mechanical properties of the material under high-temperature conditions are significantly improved. While improving interfacial bonding strength and creep resistance, it effectively maintains hydrolysis resistance and electrical insulation stability, resolving the contradiction between high-temperature low creep and easy processing, interfacial toughness and high impact resistance, and dimensional stability and resistance to damp heat. This invention has broad application value in high-temperature and precision applications such as automotive structural components and electronic and electrical precision connectors.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials, specifically to a high-temperature resistant, dimensionally stable nylon material and its preparation method. Background Technology

[0002] Polyamide 66 (PA66), with its high melting point, excellent mechanical strength, and good dimensional stability, occupies a core position in high-temperature service fields such as automotive engine compartment components, precision structural components for new energy electronic control systems, fasteners for industrial automation, and high-density electronic connectors. With the continuous upgrading of electric vehicles and advanced manufacturing equipment, engineering plastic components are subjected to sustained loads at temperatures of 130°C and even higher, placing extremely stringent requirements on maintaining dimensional accuracy and assembly reliability. Against this backdrop, glass fiber reinforced PA66 composites have become the mainstream solution in the industry. High-quality matrix-fiber interface bonding not only determines load transfer efficiency but also affects overall mechanical properties through interface crack propagation and energy dissipation mechanisms. Simultaneously, in actual service environments where humidity and high temperatures coexist, the material's hydrolytic stability and electrical insulation retention are also key indicators. Therefore, synergistic modification of the matrix and interface to simultaneously improve high-temperature dimensional stability, overall interfacial mechanical properties, and humid heat durability while maintaining good processing rheology is a core technological challenge in the field of high-performance engineering plastics, possessing significant scientific research value and broad industrial application prospects.

[0003] To address the practical application needs of glass fiber reinforced PA66 composite materials, existing technologies still have significant limitations in simultaneously optimizing high-temperature dimensional stability, interfacial strength and toughness, and humid heat durability. Firstly, the traditional PA66 matrix lacks effective coordination crosslinking constraints to inhibit high-temperature creep, making it prone to viscoelastic relaxation under continuous heat loads, thus limiting dimensional stability. Secondly, existing interfacial treatments often employ single silane coupling agents, making interfacial bonding temperature-sensitive and prone to interfacial debonding and strength reduction at high temperatures. Thirdly, the synergistic effect of phosphorus-based coordination modification and interfacial functionalization has not been systematically developed in the PA66 / GF system, leaving considerable room for multifunctional integration. For example, Chinese patent CN110643167B discloses a linear polyphosphazene halogenated flame-retardant and toughened modified glass fiber reinforced polyamide 6 / polyamide 66 composite material, but it suffers from limitations such as a single interfacial bonding method, insufficient interfacial hydrolysis resistance under both high temperature and humid conditions, and a lack of effective mechanisms to inhibit high-temperature creep behavior of the PA66 matrix. Summary of the Invention

[0004] The purpose of this invention is to provide a high-temperature resistant, dimensionally stable nylon material and its preparation method, thereby solving the current pain points of PA66 / glass fiber reinforced composite materials, which are difficult to balance between high temperature and low creep and low viscosity and easy processing, strong interface, high strength and high modulus and high toughness and impact resistance, and the difficulty in simultaneously improving interface strength and maintaining hydrolytic stability and electrical insulation stability after introducing ionomer and phosphate ester interface structures.

[0005] This invention introduces zinc acetate dihydrate into a polyamide 66 matrix for melt coordination ionization, constructing an ionopolyamide intermediate network containing zinc coordination sites. Simultaneously, it applies a tandem bifunctional interface treatment of 3-aminopropyltrialkoxysilane and phytic acid to the glass fiber, giving the fiber surface both covalent amino anchoring and phosphate ester coordination active sites. During melt blending, the zinc coordination centers in the ionopolyamide matrix and the phosphate ester coordination groups on the glass fiber surface form dynamic cross-interfacial coordination bonds, achieving a synergistic effect of matrix coordination modification and interface functionalization within the same system. This results in a significant overall improvement in three key properties—high-temperature creep resistance, interface toughening, and resistance to damp heat—in a single formulation system, demonstrating a significantly amplified performance enhancement compared to modifying the matrix or treating the interface alone.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A high-temperature resistant dimensionally stable nylon material, comprising, by total mass of the high-temperature resistant dimensionally stable nylon material: A. Polyamide 66 is 30–80 wt%; B. The intermediate of the coordination complex masterbatch is 20–70 wt%; And the sum of the mass percentages of A and B is 100 wt%; Among them, the coordination composite masterbatch intermediate is prepared by melt blending of ionopolyamide intermediate and coordination interface glass fiber intermediate; the ionopolyamide intermediate is prepared by reacting polyamide 66 with zinc acetate dihydrate in the molten state; and the coordination interface glass fiber intermediate is prepared by treating glass fiber with 3-aminopropyltrialkoxysilane and then with phytic acid solution.

[0007] Furthermore, the polyamide intermediate is prepared through the following steps: A1. Raw materials: 100 parts by weight of polyamide 66; 0.05–3.00 parts by weight of zinc acetate dihydrate; A2. Pre-drying: Dry polyamide 66 to a moisture content of 0.02–0.15 wt%; A3. Melt reaction: Under a nitrogen atmosphere, the polyamide 66 obtained in step A2 is melt-blended with zinc acetate dihydrate at a blending temperature of 270–310℃ and a blending time of 30–180s. A4. Granulation and post-treatment: After extrusion granulation, the product is dried to a moisture content of 0.02–0.15 wt% to obtain an ion-polyamide intermediate; A5. Quality control: The zinc content in the ionopolyamide intermediate is 0.01–0.87 wt% (calculated as zinc element).

[0008] Furthermore, the coordination interface glass fiber intermediate is prepared through the following steps: B1. Raw materials: 100 parts by weight of glass fiber; 0.10–2.00 parts by weight of 3-aminopropyltrialkoxysilane; 0.10–5.00 parts by weight of phytic acid solution (based on phytic acid purity); deionized water; B2. Silane treatment: 3-aminopropyltrialkoxysilane is added to deionized water to prepare a silane treatment solution. The mass fraction of 3-aminopropyltrialkoxysilane in the silane treatment solution is 0.10–2.00 wt%, and the pH of the silane treatment solution is 9.0–11.0. Glass fibers are immersed in the silane treatment solution at a treatment temperature of 25–60℃ for a treatment time of 0.5–2.0 h. B3. Drying and curing: Dry the glass fiber obtained in step B2 at 110–130℃ for 0.5–2.0 h; B4. Phytic acid treatment: Dilute the phytic acid solution with deionized water to prepare a phytic acid treatment solution. The phytic acid treatment solution has a mass fraction of 1.0–30.0 wt% based on phytic acid and a pH of 1.0–3.0. Immerse the glass fiber obtained in step B3 in the phytic acid treatment solution at a temperature of 25–60℃ for 0.5–2.0 h. B5. Washing and post-treatment: Wash with deionized water until the pH of the washing solution is 4.0–6.5, and dry at 110–130℃ to constant weight to obtain the coordination interface glass fiber intermediate; B6. Quality control: The moisture content of the coordination interface glass fiber intermediate is 0.02–0.20 wt%.

[0009] Furthermore, the coordination complex masterbatch intermediate is prepared through the following steps: C1. Raw materials: Isopolyamide intermediate and coordination interface glass fiber intermediate; C2. Proportioning: The coordination interface glass fiber intermediate accounts for 40–70 wt% of the coordination composite masterbatch intermediate, and the ionopolyamide intermediate accounts for 30–60 wt% of the coordination composite masterbatch intermediate, with the total of the two being 100 wt%. C3. Melt blending: Melt blending is carried out under a nitrogen atmosphere at a temperature of 260–310℃ for a blending time of 30–180s; C4. Granulation and post-processing: After extrusion granulation, dry to a moisture content of 0.02–0.15 wt% to obtain coordination composite masterbatch intermediate.

[0010] Furthermore, the zinc content in the high-temperature resistant dimensionally stable nylon material is 0.01–0.30 wt% (calculated as zinc element).

[0011] Furthermore, the 3-aminopropyltrialkoxysilane is 3-aminopropyltrimethoxysilane.

[0012] As a concept of this invention, the present invention employs a synergistic design of a coordination-ionized polyamide 66 matrix and a phytic acid-silane bifunctionalized glass fiber interface, primarily used to enhance the high-temperature creep resistance and overall interfacial performance of high-temperature dimensionally stable nylon materials. At the matrix level, zinc acetate dihydrate and polyamide 66 undergo a coordination-ionization reaction in the molten state, with zinc ions forming metal-ligand coordination bonds with amide groups. This constructs a non-covalent coordination crosslinking network between polymer segments, effectively constraining the creep displacement of molecular segments under sustained high-temperature loads, significantly improving high-temperature dimensional stability. Simultaneously, the dynamic reversibility of the molten coordination network ensures good melt flowability and processing rheology. At the interface level, 3-aminopropyltrialkoxysilane imparts nucleophilic amino groups to the glass fiber surface, providing active sites for subsequent multi-point anchoring of phytic acid polyphosphate. The six phosphate groups of phytic acid construct a multifunctional chemical bond layer on the aminosilane-modified fiber surface, strengthening the interfacial bonding while inhibiting the adsorption of water molecules by interfacial hydroxyl groups through phosphate chelation and electron donor effects, significantly improving hydrolysis resistance and electrical insulation stability. In the melt blending of the two intermediates, the zinc coordination centers of the matrix and the phosphate groups on the fiber surface form cross-interfacial coordination bonds, enabling matrix modification and interface activation to produce synergistic effects within the same system. High-temperature dimensional stability, interfacial bonding strength, hydrolysis resistance, and electrical insulation stability are all improved overall, with performance improvement significantly better than modifying the matrix or treating the interface alone.

[0013] This invention also discloses a method for preparing the high-temperature resistant, dimensionally stable nylon material as described above, comprising the following steps: S1. Provide polyamide 66 and dry the polyamide 66 to a moisture content of 0.02–0.15 wt%; S2. Provides coordination complex masterbatch intermediates; S3. Under a nitrogen atmosphere, the polyamide 66 obtained in step S1 and the coordination composite masterbatch intermediate provided in step S2 are added to a co-rotating twin-screw extruder for melt blending. The total mass of polyamide 66 and coordination composite masterbatch intermediate is 30–80 wt% and 20–70 wt%, respectively, with a total mass of 100 wt%. The melt blending temperature is 260–320 °C and the blending time is 30–180 s. S4. The melt blend obtained in step S3 is extruded, granulated, and dried to a moisture content of 0.02–0.15 wt% to obtain a high-temperature resistant dimensionally stable nylon material.

[0014] Furthermore, the coordination composite masterbatch intermediate provided in step S2 is a coordination composite masterbatch intermediate obtained by melt blending an ionopolyamide intermediate and a coordination interface glass fiber intermediate, wherein the coordination interface glass fiber intermediate accounts for 40–70 wt% of the coordination composite masterbatch intermediate, the ionopolyamide intermediate accounts for 30–60 wt% of the coordination composite masterbatch intermediate, and the two together account for 100 wt%; the melt blending is carried out under a nitrogen atmosphere at a temperature of 260–310 °C for a time of 30–180 s; the melt blend is extruded, granulated, and dried to a moisture content of 0.02–0.15 wt%.

[0015] Furthermore, in step S4, the high-temperature dimensionally stable nylon material after extrusion granulation is dried at 80–110 °C for 4–16 h until the moisture content is 0.02–0.15 wt%.

[0016] Furthermore, the zinc content in the obtained high-temperature resistant dimensionally stable nylon material, calculated as zinc element, is 0.01–0.30 wt%.

[0017] Furthermore, in step B2, the pH of the silane treatment solution is adjusted to 9.0–11.0 by adding 0.1–1.0 mol / L sodium hydroxide aqueous solution or 0.1–1.0 mol / L ammonia solution. The adjustment process is completed at room temperature and then verified with a precision pH meter.

[0018] Further, in step B4, the pH of the phytic acid treatment solution is adjusted to 1.0–3.0: when the measured pH is higher than 3.0, 0.1–1.0 mol / L hydrochloric acid aqueous solution is added dropwise; when the measured pH is lower than 1.0, 0.1–1.0 mol / L sodium hydroxide aqueous solution or 0.1–1.0 mol / L ammonia solution is added dropwise; the adjustment process is completed at room temperature, and the pH is checked with a precision pH meter after adjustment.

[0019] Furthermore, the interval between two weighings shall not exceed 60 minutes. The criterion for drying to constant weight in step B5 is that the mass difference between two consecutive weighings shall not exceed 0.1% of the mass of the previous weighing. The drying equipment is a forced-air circulating oven.

[0020] Furthermore, the melt blending in step A3, the melt blending in step C3, and the melt blending in step S3 are all completed using a co-rotating twin-screw extruder with a screw speed of 150–350 rpm; the temperature is the set temperature of each section of the barrel, and the time is the residence time of the material in the screw.

[0021] Furthermore, in step C3, during the preparation of the coordination composite masterbatch intermediate, the coordination interface glass fiber intermediate is added through the side feed port of the twin-screw extruder.

[0022] Furthermore, when the polyamide intermediate was characterized by ATR-FTIR, compared with the control polyamide 66 without the addition of zinc acetate dihydrate, the N–H stretching vibration peaks were in the range of 3270–3310 cm⁻¹. -1 The region showed repeatable peak position changes, and the amide I band showed detectable peak position shifts. These changes can serve as spectroscopic evidence that the microenvironment of the amide group has changed after the introduction of zinc salt. The zinc content in the ionopolyamide intermediate was quantitatively determined by ICP-OES to verify that it meets the quality control specifications of step A5.

[0023] Furthermore, the coordination interface glass fiber intermediate exhibited a thermal weight loss of no more than 5 wt% in the N2 atmosphere TGA test within the temperature range of 260–310 °C; the coordination composite masterbatch intermediate obtained after melt blending in step C3, when characterized by ATR-FTIR, showed a 1150–1250 cm⁻¹ -1 The region showed characteristic absorption peaks associated with phytic acid phosphate groups, which were confirmed by difference spectrum analysis with a blank sample of the same composition that had not been treated with phytic acid.

[0024] Furthermore, the pre-drying conditions for polyamide 66 in steps A2 and S1 are as follows: drying in a blast-drying oven at 80–100 °C for 12–24 h, with the moisture content determined by Karl Fischer titration.

[0025] Furthermore, the post-drying conditions for the extruded granules in steps A4 and C4 are as follows: drying in a blast-blown oven at 80–100 °C for 8–16 h until the moisture content is 0.02–0.15 wt%.

[0026] Furthermore, in step B2, when the glass fiber is immersed in the silane treatment solution, the volume / mass ratio of the silane treatment solution to the glass fiber is 5–20 mL / g, and the immersion process is accompanied by stirring at 50–200 rpm.

[0027] Furthermore, in step B4, when the glass fiber is impregnated with the phytic acid treatment solution, the volume / mass ratio of the phytic acid treatment solution to the glass fiber is 5–20 mL / g, and the impregnation process is supplemented with stirring at 50–200 rpm.

[0028] Furthermore, in step B5, the liquid-to-material volume ratio of the deionized water washing process is 10–30 mL / g, the stirring and soaking time is not less than 5 min each time, and the number of washing cycles is not less than 3.

[0029] As another aspect of this invention, a multi-stage premixing process is employed to ensure uniform dispersion between the coordination composite masterbatch intermediate and the polyamide 66 main resin, and to achieve the complete construction of the cross-interfacial coordination bond network. This method first prepares an ionomer polyamide intermediate and a coordination interface glass fiber intermediate separately, then melt-blends the two at a high filling ratio to obtain the coordination composite masterbatch intermediate. Finally, a third-stage melt blending process is used to mix the coordination composite masterbatch with the main polyamide 66 resin to form the final product. The core advantages of the multi-stage premixing strategy are as follows: The first stage ensures a uniform distribution of the coordination crosslinking network within the ionopolyamide matrix through a thorough coordination reaction between polyamide 66 and zinc acetate dihydrate at a defined temperature and residence time. The second stage uses a high glass fiber content to melt-blend the coordination interface glass fiber intermediate with the ionopolyamide into a masterbatch. The side-feeding method effectively reduces glass fiber breakage during subsequent dispersion, maintaining an effective aspect ratio. The third stage completes the final blending through melt blending under nitrogen protection, preventing PA66 oxidative degradation and maintaining the activity and integrity of the ionopoly groups and phosphate ester coordination groups. Compared to the traditional one-step blending process, this method significantly improves the uniformity of the coordination network and interfacial coordination layer through staged premixing, resulting in simultaneous improvements in the high-temperature mechanical properties, dimensional stability, and batch reproducibility of the final product.

[0030] The polyamide intermediate, through the introduction of zinc acetate dihydrate into the polyamide 66 segments to form a coordination crosslinking structure, primarily enhances the high-temperature creep resistance of the matrix: the metal coordination bonds formed by zinc ions and amide groups have a higher constraint strength than physical entanglement, effectively limiting segment creep displacement at high temperatures and directly contributing to high-temperature dimensional stability. The coordination interface glass fiber intermediate, through bi-level surface modification with 3-aminopropyltrialkoxysilane and phytic acid, constructs a covalent amino layer and a polyphosphate active layer on the fiber surface. Its main function is to improve the fiber-matrix interfacial bonding strength and hygrothermal stability: the aminosilane enhances the physicochemical compatibility of the interface, while the phytic acid phosphate groups form multi-point coordination anchors and inhibit the adsorption of water molecules by interfacial hydroxyl groups through the phosphate electron donor effect, significantly improving the interface's hydrolysis resistance and electrical insulation retention. In melt blending, the zinc coordination centers of the matrix and the phosphate groups on the fiber surface can form trans-interfacial coordination bonds, organically linking and mutually reinforcing the matrix coordination crosslinking network and the fiber interfacial bonding force. Compared with the individual modification of any component, the high-temperature creep resistance and interfacial damp heat resistance of the synergistic modification system significantly outperform the effects of individual modification, fully demonstrating the unique advantages and overall synergistic effect mechanism of matrix-interface multi-scale synergistic modification.

[0031] Beneficial technical effects 1. Through the melt coordination ionization of zinc acetate dihydrate and polyamide 66, zinc ions and amide groups form metal coordination bonds, constructing a non-covalent coordination crosslinking network between chain segments, effectively constraining the creep displacement of molecular chain segments under continuous high-temperature load; the coordination crosslinking network maintains effective constraint at high temperature, significantly reducing creep deformation variables, meeting the geometric accuracy requirements of precision parts under high-temperature service conditions, while the dynamic reversibility of the molten coordination network ensures good injection molding rheological properties, achieving a balance between high-temperature dimensional stability and easy processing.

[0032] 2. The coordination interface glass fiber intermediate is subjected to a tandem dual-stage functionalization treatment of 3-aminopropyltrialkoxysilane and phytic acid, which sequentially forms a covalent amino layer and a multi-point phosphate anchoring layer on the fiber surface. The dual interface effect synergistically constructs a covalent-coordination composite interface bonding mechanism. Compared with the single silane coupling treatment, the interface bonding strength is significantly higher under high temperature conditions. The interfacial energy dissipation capability conferred by the multi-point bonding of phytic acid phosphate effectively improves the impact toughness, and achieves a synergistic improvement in high strength and high toughness of the interface.

[0033] 3. The phosphate ester active layer formed by phytic acid molecules on the fiber surface significantly shields the adsorption of water molecules by hydrophilic silanol groups on the fiber surface through chelation and electron donor effects; the interfacial zinc-phosphate ester coordination bond effectively blocks the water molecule penetration path in the interfacial region, slowing down the hydrolysis rate of the polyamide 66 main chain and the attenuation of interfacial bonding strength in high temperature and humid environment, so that the mechanical properties and dimensional stability retention rate of the high temperature resistant nylon material under humid aging conditions are significantly better than those of the reference material treated with only single-stage silane.

[0034] 4. Phytic acid phosphate groups form a dense functionalized layer on the glass fiber surface through multi-point chemical bonding. This layer works synergistically with the weak polarity of the polyamide 66 matrix to effectively suppress the formation of conductive pathways in the interfacial region. The coordination ionization modification does not introduce conductive functional groups, ensuring that the high-temperature dimensionally stable nylon material retains better electrical insulation performance than the reference system without coordination modification after high-temperature and humid heat composite service, thus meeting the stringent requirements of long-term insulation stability for precision electronic and electrical connectors.

[0035] 5. The multi-stage premixing process effectively retains the effective aspect ratio of glass fiber through the side feeding method of high-filled masterbatch, ensuring that mechanical properties such as flexural modulus, tensile strength and notched impact strength are at a high level; nitrogen protection throughout the process and controllable blending time maintain the integrity of polyamide 66 molecular weight and ionomer network, ensuring stable reproducibility of product performance between batches, which is conducive to industrial-scale scaling and quality control. Attached Figure Description

[0036] Figure 1 The ATR-FTIR of the ionopolyamide intermediates of Examples 1, 1, and 8 was 4000–400 cm⁻¹.-1 Overlay curve graph.

[0037] Figure 2 The ATR-FTIR magnification of the N–H stretching region (3400–3100 cm²) of the ionopolyamide intermediates of Examples 1, 1, and 8 is shown in Figure 8. -1 Overlay curve graph.

[0038] Figure 3 The ATR-FTIR amplification of the amide I region (1750–1550 cm⁻¹) of the ionopolyamide intermediates of Examples 1, 1 Comparative Examples 1, and 8 is shown in Figure 8. -1 Overlay curve graph.

[0039] Figure 4 The above are narrow scan comparison spectra of XPS Zn 2p intermediates of ionopolyamide in Example 1 and Comparative Example 1.

[0040] Figure 5 The glass fiber intermediate powders of Examples 1, 3, and 4 were subjected to ATR-FTIR 4000–400 cm⁻¹. -1 Overlay curve graph.

[0041] Figure 6 The glass fiber intermediates of Examples 1, 3, and 4 were amplified using ATR-FTIR to create the phosphate ester region (1300–900 cm⁻¹). -1 Overlay curve graph.

[0042] Figure 7 The above are XPS P 2p narrow scan comparison spectra of GF surfaces in Examples 1, 3, and 5.

[0043] Figure 8 The above are XPS N 1s narrow scan comparison spectra of the GF surface in Examples 1, 3, and 5.

[0044] Figure 9 The images show narrow scan comparisons of XPS Si 2p spectra on the GF surface of Examples 1, 3, and 5.

[0045] Figure 10 Macroscopic optical photograph of the high-temperature resistant, dimensionally stable nylon material prepared in Example 1.

[0046] Figure 11 This is a high-magnification SEM micrograph of the sample from Example 1. Detailed Implementation

[0047] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0048] Example 1

[0049] (a) Preparation of polyamide intermediates Step A1, the raw materials for the polyamide intermediate in this embodiment are: polyamide 66, 100 parts by weight; zinc acetate dihydrate, 1.50 parts by weight.

[0050] Step A2: The polyamide 66 of this embodiment is placed in a 90°C circulating oven and dried for 18 h. The moisture content is determined by Karl Fischer titration. The pre-dried polyamide 66 is obtained by drying until the moisture content is 0.09 wt%.

[0051] In step A3, under a nitrogen atmosphere, the polyamide 66 obtained in step A2 and zinc acetate dihydrate are added to a co-rotating twin-screw extruder for melt blending. The screw speed is 250 rpm, the temperature of each section of the barrel is set at 290℃, and the residence time of the material in the screw is 100 s.

[0052] Step A4: The extrudate obtained in step A3 is granulated and dried in a 90°C circulating oven for 12 h. The water content is determined by Karl Fischer titration to be 0.09 wt%, thus obtaining the ionopolyamide intermediate of this embodiment.

[0053] Step A5: The zinc content (calculated as zinc element) in the ionopolyamide intermediate of this embodiment was quantitatively determined by ICP-OES to be 0.44 wt%, which meets the quality control specification of 0.01–0.87 wt%. When characterized by ATR-FTIR, compared with the control polyamide 66 without the addition of zinc acetate dihydrate, the N–H stretching vibration peak was at 3270–3310 cm⁻¹. -1 The region shows repeatable peak position changes, and the amide I band shows detectable peak position shifts. These changes can serve as spectroscopic evidence that the microenvironment of the amide group has changed after the introduction of zinc salt.

[0054] (II) Preparation of coordination interface glass fiber intermediates Step B1, the raw materials for the coordination interface glass fiber intermediate in this embodiment are: glass fiber, 100 parts by weight; 3-aminopropyltrimethoxysilane, 1.00 parts by weight; phytic acid solution, the amount of which is 2.50 parts by weight based on the purity of phytic acid; and deionized water, appropriate amount.

[0055] Step B2: 1.00 parts by weight of 3-aminopropyltrimethoxysilane were added to deionized water to prepare a silane treatment solution with a 3-aminopropyltrimethoxysilane mass fraction of 1.00 wt%. 0.5 mol / L sodium hydroxide aqueous solution was added dropwise to the silane treatment solution of this embodiment to adjust the pH to 10.0. The adjustment process was completed at room temperature, and the pH was verified using a precision pH meter after adjustment. The glass fiber of this embodiment was immersed in the silane treatment solution, with a liquid-to-solid volume / mass ratio of silane treatment solution to glass fiber of 12 mL / g. The immersion process was accompanied by stirring at 120 rpm, the treatment temperature was 42℃, and the treatment time was 1.0 h.

[0056] Step B3: Place the glass fiber obtained in step B2 in a 120℃ forced-air circulating oven and dry for 1.0 h to complete the drying and curing.

[0057] Step B4: Dilute the phytic acid solution with deionized water to prepare a phytic acid treatment solution. In this embodiment, the phytic acid treatment solution contains 15.0 wt% phytic acid. When the measured pH is higher than 3.0, add 0.5 mol / L hydrochloric acid aqueous solution to adjust the pH to 2.0. When the measured pH is lower than 1.0, add 0.5 mol / L sodium hydroxide aqueous solution to adjust to the target value. The adjustment process is completed at room temperature. After adjustment, verify with a precision pH meter to confirm that the pH of the phytic acid treatment solution is 2.0. Immerse the glass fiber obtained in step B3 in the phytic acid treatment solution of this embodiment. The liquid-to-material volume / mass ratio of the phytic acid treatment solution to the glass fiber is 12 mL / g. The immersion process is supplemented with stirring at 120 rpm, the treatment temperature is 42℃, and the treatment time is 1.0 h.

[0058] Step B5: Wash the glass fiber obtained in step B4 with deionized water. The liquid-to-material volume ratio during washing is 20 mL / g. Each stirring and soaking time is not less than 5 min, and the washing is repeated at least 3 times until the pH of the washing solution is 5.0. Then, place it in a 120℃ forced-air circulating oven to dry to constant weight. The interval between two weighings shall not exceed 60 min, and the mass difference between two consecutive weighings shall not exceed 0.1% of the mass of the previous weighing. The drying equipment is a forced-air circulating oven, thus obtaining the coordination interface glass fiber intermediate of this embodiment.

[0059] In step B6, the water content of the coordination interface glass fiber intermediate in this embodiment was determined by Karl Fischer titration to be 0.12 wt%, which meets the quality control specification of 0.02–0.20 wt%. In the N2 atmosphere TGA test, the thermal weight loss rate in the range of 260–310℃ does not exceed 5 wt%, which meets the thermal stability requirements for subsequent melt blending processing.

[0060] (III) Preparation of coordination complex masterbatch intermediates Step C1: Take the ionized polyamide intermediate obtained in step A4 and the coordination interface glass fiber intermediate obtained in step B5 as raw materials.

[0061] Step C2: Based on the total mass of the coordination composite masterbatch intermediates in this embodiment, the coordination interface glass fiber intermediate accounts for 55 wt%, the ionopolyamide intermediate accounts for 45 wt%, and the two together amount to 100 wt%.

[0062] In step C3, under a nitrogen atmosphere, the ionomer polyamide intermediate and the coordination interface glass fiber intermediate prepared in step C2 are added to a co-rotating twin-screw extruder for melt blending. In this embodiment, the coordination interface glass fiber intermediate is added through the side feed port of the twin-screw extruder, the screw speed is 250 rpm, the temperature of each section of the barrel is set at 285°C, and the residence time of the material in the screw is 100 s.

[0063] Step C4: The melt blend obtained in step C3 is extruded and granulated, then dried in a 90°C circulating oven for 12 h. The moisture content is determined by Karl Fischer titration to be 0.09 wt%, yielding the coordination composite masterbatch intermediate of this embodiment. When characterized by ATR-FTIR, the 1150–1250 cm⁻¹ -1 The region showed characteristic absorption peaks associated with phytic acid phosphate groups, which were confirmed by difference spectrum analysis with a blank sample of the same composition that had not been treated with phytic acid.

[0064] (iv) Preparation of high-temperature dimensionally stable nylon material Step S1: Provide polyamide 66. Place the polyamide 66 of this embodiment in a 90°C circulating oven and dry it for 18 hours. Determine the moisture content to 0.09 wt% by Karl Fischer titration. Set aside for later use.

[0065] Step S2: Provide the coordination composite masterbatch intermediate obtained in step C4 for later use.

[0066] In step S3, under a nitrogen atmosphere, the polyamide 66 obtained in step S1 and the coordination composite masterbatch intermediate obtained in step S2 are added to a co-rotating twin-screw extruder for melt blending; based on the total feed mass of polyamide 66 and coordination composite masterbatch intermediate, polyamide 66 is 55 wt% and coordination composite masterbatch intermediate is 45 wt%, totaling 100 wt%; the screw speed is 250 rpm, the temperature of each section of the barrel is set at 290℃, and the residence time of the material in the screw is 100 s.

[0067] In step S4, the melt blend obtained in step S3 is extruded and granulated, and then dried in a 95°C circulating oven for 10 h. The moisture content is determined by Karl Fischer titration to be 0.09 wt%, thus obtaining the high-temperature resistant dimensionally stable nylon material of this embodiment. The zinc content in the high-temperature resistant dimensionally stable nylon material of this embodiment, calculated as zinc element, is 0.089 wt% by ICP-OES method, which meets the quality control specification of 0.01–0.30 wt%.

[0068] This embodiment of the high-temperature dimensionally stable nylon material uses 66-55 wt% polyamide and 45 wt% coordination composite masterbatch intermediate to form a balanced reinforcing system. All parameters in each step are at typical moderate levels, resulting in a good overall balance of mechanical properties, high-temperature dimensional stability, and processing fluidity. It also exhibits a wide process window and strong batch-to-batch reproducibility. This embodiment is suitable for engineering applications requiring balanced comprehensive performance and high stability in mass production, such as automotive interior structural components, consumer electronics housings, industrial electrical connectors, and precision instrument load-bearing structural components.

[0069] Example 2

[0070] (a) Preparation of polyamide intermediates Step A1, the raw materials for the polyamide intermediate in this embodiment are: polyamide 66, 100 parts by weight; zinc acetate dihydrate, 2.00 parts by weight.

[0071] Step A2: The polyamide 66 of this embodiment is placed in a 95°C circulating oven and dried for 20 h. The moisture content is determined by Karl Fischer titration. The pre-dried polyamide 66 is obtained by drying until the moisture content is 0.08 wt%.

[0072] In step A3, under a nitrogen atmosphere, the polyamide 66 obtained in step A2 and zinc acetate dihydrate are added to a co-rotating twin-screw extruder for melt blending. The screw speed is 280 rpm, the temperature of each section of the barrel is set at 295℃, and the residence time of the material in the screw is 120 s.

[0073] Step A4: The extrudate obtained in step A3 is granulated and dried in a 95°C circulating oven for 14 h. The water content is determined by Karl Fischer titration to be 0.08 wt%, thus obtaining the ionopolyamide intermediate of this embodiment.

[0074] Step A5: The zinc content (calculated as zinc element) in the ionopolyamide intermediate of this embodiment was quantitatively determined by ICP-OES to be 0.58 wt%, which meets the quality control specification of 0.01–0.87 wt%. When characterized by ATR-FTIR, compared with the control polyamide 66 without the addition of zinc acetate dihydrate, the N–H stretching vibration peak was at 3270–3310 cm⁻¹. -1The region shows repeatable peak position changes, and the amide I band shows detectable peak position shifts. These changes can serve as spectroscopic evidence that the microenvironment of the amide group has changed after the introduction of zinc salt.

[0075] (II) Preparation of coordination interface glass fiber intermediates Step B1, the raw materials for the coordination interface glass fiber intermediate in this embodiment are: glass fiber, 100 parts by mass; 3-aminopropyltrimethoxysilane, 1.40 parts by mass; phytic acid solution, the amount of which is 3.50 parts by mass based on the purity of phytic acid; and deionized water, appropriate amount.

[0076] Step B2: 1.40 parts by weight of 3-aminopropyltrimethoxysilane were added to deionized water to prepare a silane treatment solution with a 3-aminopropyltrimethoxysilane mass fraction of 1.40 wt%. 0.7 mol / L sodium hydroxide aqueous solution was added dropwise to the silane treatment solution of this embodiment to adjust the pH to 10.5. The adjustment process was completed at room temperature, and the pH was verified using a precision pH meter after adjustment. The glass fiber of this embodiment was immersed in the silane treatment solution, with a liquid-to-solid volume / mass ratio of silane treatment solution to glass fiber of 15 mL / g. The immersion process was accompanied by stirring at 150 rpm, the treatment temperature was 50°C, and the treatment time was 1.5 h.

[0077] Step B3: Place the glass fiber obtained in step B2 in a 125℃ forced-air circulating oven and dry for 1.5 h to complete the drying and curing.

[0078] Step B4: Dilute the phytic acid solution with deionized water to prepare a phytic acid treatment solution. In this embodiment, the phytic acid treatment solution contains 20.0 wt% phytic acid. When the measured pH is higher than 3.0, add 0.7 mol / L hydrochloric acid aqueous solution to adjust the pH to 1.5. When the measured pH is lower than 1.0, add 0.7 mol / L sodium hydroxide aqueous solution to adjust to the target value. The adjustment process is completed at room temperature. After adjustment, verify with a precision pH meter to confirm that the pH of the phytic acid treatment solution is 1.5. Immerse the glass fiber obtained in step B3 in the phytic acid treatment solution of this embodiment. The liquid-to-material volume / mass ratio of the phytic acid treatment solution to the glass fiber is 15 mL / g. The immersion process is supplemented with stirring at 150 rpm, the treatment temperature is 50°C, and the treatment time is 1.5 h.

[0079] Step B5: Wash the glass fiber obtained in step B4 with deionized water. The liquid-to-material volume / mass ratio during washing is 25 mL / g. Each stirring and soaking time is not less than 5 min, and the washing is repeated at least 3 times until the pH of the washing solution is 4.5. Then, place it in a 125℃ forced-air circulating oven to dry to constant weight. The interval between two weighings shall not exceed 60 min, and the mass difference between two consecutive weighings shall not exceed 0.1% of the mass of the previous weighing. The drying equipment is a forced-air circulating oven, thus obtaining the coordination interface glass fiber intermediate of this embodiment.

[0080] In step B6, the water content of the coordination interface glass fiber intermediate in this embodiment was determined by Karl Fischer titration to be 0.10 wt%, which meets the quality control specification of 0.02–0.20 wt%. In the N2 atmosphere TGA test, the thermal weight loss rate in the range of 260–310℃ does not exceed 5 wt%, which meets the thermal stability requirements for subsequent melt blending processing.

[0081] (III) Preparation of coordination complex masterbatch intermediates Step C1: Take the ionized polyamide intermediate obtained in step A4 and the coordination interface glass fiber intermediate obtained in step B5 as raw materials.

[0082] Step C2: Based on the total mass of the coordination composite masterbatch intermediates in this embodiment, the coordination interface glass fiber intermediate accounts for 62 wt%, the ionopolyamide intermediate accounts for 38 wt%, and the two together account for 100 wt%.

[0083] In step C3, under a nitrogen atmosphere, the ionomer polyamide intermediate and the coordination interface glass fiber intermediate prepared in step C2 are added to a co-rotating twin-screw extruder for melt blending. In this embodiment, the coordination interface glass fiber intermediate is added through the side feed port of the twin-screw extruder, the screw speed is 280 rpm, the temperature of each section of the barrel is set at 295°C, and the residence time of the material in the screw is 120 s.

[0084] Step C4: The melt blend obtained in step C3 is extruded and granulated, then dried in a 95°C circulating oven for 14 h. The moisture content is determined by Karl Fischer titration to be 0.08 wt%, yielding the coordination composite masterbatch intermediate of this embodiment. When characterized by ATR-FTIR, the 1150–1250 cm⁻¹ -1 The region showed characteristic absorption peaks associated with phytic acid phosphate groups, which were confirmed by difference spectrum analysis with a blank sample of the same composition that had not been treated with phytic acid.

[0085] (iv) Preparation of high-temperature dimensionally stable nylon material Step S1: Provide polyamide 66. Place the polyamide 66 of this embodiment in a 95°C circulating oven and dry for 20 hours. Determine the moisture content to 0.08 wt% by Karl Fischer titration. Set aside for later use.

[0086] Step S2: Provide the coordination composite masterbatch intermediate obtained in step C4 for later use.

[0087] In step S3, under a nitrogen atmosphere, the polyamide 66 obtained in step S1 and the coordination composite masterbatch intermediate obtained in step S2 are added to a co-rotating twin-screw extruder for melt blending. Based on the total feed mass of polyamide 66 and coordination composite masterbatch intermediate, polyamide 66 is 43 wt% and coordination composite masterbatch intermediate is 57 wt%, totaling 100 wt%. The screw speed is 280 rpm, the temperature of each section of the barrel is set at 300℃, and the residence time of the material in the screw is 120 s.

[0088] In step S4, the melt blend obtained in step S3 is extruded and granulated, and then dried in a 100°C circulating oven for 12 hours. The moisture content is determined by Karl Fischer titration to be 0.08 wt%, thus obtaining the high-temperature resistant dimensionally stable nylon material of this embodiment. The zinc content in the high-temperature resistant dimensionally stable nylon material of this embodiment, calculated as zinc element, is 0.126 wt% by ICP-OES method, which meets the quality control specification of 0.01–0.30 wt%.

[0089] This embodiment uses a high-temperature dimensionally stable nylon material with 66.43 wt% polyamide and 57 wt% coordination composite masterbatch intermediate, resulting in a final product with a zinc content of approximately 0.126 wt%. The higher glass fiber content and more complete interfacial coordination layer synergistically enhance the material's rigidity and high-temperature dimensional stability. This embodiment is suitable for engineering applications requiring high rigidity and operating at high temperatures, such as heat-resistant structural load-bearing components around automotive engine compartments and transmissions, brackets for high-precision industrial measuring instruments, housing skeletons for communication equipment, and structural components for new energy battery management systems.

[0090] Example 3

[0091] (a) Preparation of polyamide intermediates Step A1, the raw materials for the polyamide intermediate in this embodiment are: polyamide 66, 100 parts by weight; zinc acetate dihydrate, 1.00 parts by weight.

[0092] Step A2: The polyamide 66 of this embodiment is placed in an 85°C circulating oven and dried for 15 h. The moisture content is determined by Karl Fischer titration. The pre-dried polyamide 66 is obtained by drying until the moisture content is 0.10 wt%.

[0093] In step A3, under a nitrogen atmosphere, the polyamide 66 obtained in step A2 and zinc acetate dihydrate are added to a co-rotating twin-screw extruder for melt blending. The screw speed is 210 rpm, the temperature of each section of the barrel is set at 282℃, and the residence time of the material in the screw is 80 s.

[0094] Step A4: The extrudate obtained in step A3 is granulated and dried in an 85°C circulating oven for 10 h. The water content is determined by Karl Fischer titration to be 0.10 wt%, thus obtaining the ionopolyamide intermediate of this embodiment.

[0095] Step A5: The zinc content (calculated as zinc element) in the ionopolyamide intermediate of this embodiment was quantitatively determined by ICP-OES to be 0.30 wt%, which meets the quality control specification of 0.01–0.87 wt%. When characterized by ATR-FTIR, compared with the control polyamide 66 without the addition of zinc acetate dihydrate, the N–H stretching vibration peak was at 3270–3310 cm⁻¹. -1 The region shows repeatable peak position changes, and the amide I band shows detectable peak position shifts. These changes can serve as spectroscopic evidence that the microenvironment of the amide group has changed after the introduction of zinc salt.

[0096] (II) Preparation of coordination interface glass fiber intermediates Step B1, the raw materials for the coordination interface glass fiber intermediate in this embodiment are: glass fiber, 100 parts by mass; 3-aminopropyltrimethoxysilane, 0.80 parts by mass; phytic acid solution, the amount of which is 1.60 parts by mass based on the purity of phytic acid; and deionized water, appropriate amount.

[0097] Step B2: Add 0.80 parts by weight of 3-aminopropyltrimethoxysilane to deionized water to prepare a silane treatment solution with a 3-aminopropyltrimethoxysilane mass fraction of 0.80 wt%. Add 0.3 mol / L sodium hydroxide aqueous solution to the silane treatment solution of this embodiment to adjust the pH to 9.5. The adjustment process is completed at room temperature, and the pH is checked with a precision pH meter after adjustment. Immerse the glass fiber of this embodiment in the silane treatment solution. The volume / mass ratio of silane treatment solution to glass fiber is 8 mL / g. The immersion process is accompanied by stirring at 80 rpm. The treatment temperature is 35°C and the treatment time is 0.8 h.

[0098] Step B3: Place the glass fiber obtained in step B2 in a 115℃ circulating oven and dry for 0.8 h to complete the drying and curing process.

[0099] Step B4: Dilute the phytic acid solution with deionized water to prepare a phytic acid treatment solution. In this embodiment, the phytic acid treatment solution contains 10.0 wt% phytic acid. When the measured pH is higher than 3.0, add 0.3 mol / L hydrochloric acid aqueous solution to adjust the pH to 2.5. When the measured pH is lower than 1.0, add 0.3 mol / L sodium hydroxide aqueous solution to adjust to the target value. The adjustment process is completed at room temperature. After adjustment, verify with a precision pH meter to confirm that the pH of the phytic acid treatment solution is 2.5. Immerse the glass fiber obtained in step B3 in the phytic acid treatment solution of this embodiment. The volume / mass ratio of phytic acid treatment solution to glass fiber is 8 mL / g. The immersion process is accompanied by stirring at 80 rpm, the treatment temperature is 35°C, and the treatment time is 0.8 h.

[0100] Step B5: Wash the glass fiber obtained in step B4 with deionized water. The liquid-to-material volume / mass ratio during washing is 15 mL / g. Each stirring and soaking time is not less than 5 min, and the washing is repeated at least 3 times until the pH of the washing solution is 6.0. Then, place it in a 115℃ forced-air circulating oven to dry to constant weight. The interval between two weighings shall not exceed 60 min, and the mass difference between two consecutive weighings shall not exceed 0.1% of the mass of the previous weighing. The drying equipment is a forced-air circulating oven, thus obtaining the coordination interface glass fiber intermediate of this embodiment.

[0101] In step B6, the water content of the coordination interface glass fiber intermediate in this embodiment was determined by Karl Fischer titration to be 0.15 wt%, which meets the quality control specification of 0.02–0.20 wt%. In the N2 atmosphere TGA test, the thermal weight loss rate in the range of 260–310℃ does not exceed 5 wt%, which meets the thermal stability requirements for subsequent melt blending processing.

[0102] (III) Preparation of coordination complex masterbatch intermediates Step C1: Take the ionized polyamide intermediate obtained in step A4 and the coordination interface glass fiber intermediate obtained in step B5 as raw materials.

[0103] Step C2: Based on the total mass of the coordination composite masterbatch intermediates in this embodiment, the coordination interface glass fiber intermediate accounts for 47 wt%, the ionopolyamide intermediate accounts for 53 wt%, and the two together amount to 100 wt%.

[0104] In step C3, under a nitrogen atmosphere, the ionomer polyamide intermediate and the coordination interface glass fiber intermediate prepared in step C2 are added to a co-rotating twin-screw extruder for melt blending. In this embodiment, the coordination interface glass fiber intermediate is added through the side feed port of the twin-screw extruder, the screw speed is 210 rpm, the temperature of each section of the barrel is set at 278°C, and the residence time of the material in the screw is 80 s.

[0105] Step C4: The melt blend obtained in step C3 is extruded and granulated, then dried in an 85°C circulating oven for 10 h. The moisture content is determined by Karl Fischer titration to be 0.10 wt%, yielding the coordination composite masterbatch intermediate of this embodiment. When characterized by ATR-FTIR, the 1150–1250 cm⁻¹ -1 The region showed characteristic absorption peaks associated with phytic acid phosphate groups, which were confirmed by difference spectrum analysis with a blank sample of the same composition that had not been treated with phytic acid.

[0106] (iv) Preparation of high-temperature dimensionally stable nylon material Step S1: Provide polyamide 66. Place the polyamide 66 of this embodiment in an 85°C circulating oven and dry it for 15 hours. Determine the moisture content to 0.10 wt% by Karl Fischer titration. Set aside for later use.

[0107] Step S2: Provide the coordination composite masterbatch intermediate obtained in step C4 for later use.

[0108] In step S3, under a nitrogen atmosphere, the polyamide 66 obtained in step S1 and the coordination composite masterbatch intermediate obtained in step S2 are added to a co-rotating twin-screw extruder for melt blending. Based on the total feed mass of polyamide 66 and coordination composite masterbatch intermediate, polyamide 66 is 63 wt% and coordination composite masterbatch intermediate is 37 wt%, totaling 100 wt%. The screw speed is 210 rpm, the temperature of each section of the barrel is set at 278℃, and the residence time of the material in the screw is 80 s.

[0109] In step S4, the melt blend obtained in step S3 is extruded and granulated, and dried in an 88°C circulating oven for 8 hours. The moisture content is determined by Karl Fischer titration to be 0.10 wt%, thus obtaining the high-temperature resistant dimensionally stable nylon material of this embodiment. The zinc content in the high-temperature resistant dimensionally stable nylon material of this embodiment, calculated as zinc element, is 0.058 wt% by ICP-OES method, which meets the quality control specification of 0.01–0.30 wt%.

[0110] This embodiment uses a high-temperature resistant, dimensionally stable nylon material with 63 wt% polyamide 66 and 37 wt% coordination composite masterbatch intermediate, increasing the proportion of the matrix polymer. The higher proportion of polyamide 66 matrix imparts good toughness and impact strength to the material, while the moderate glass fiber content ensures basic rigidity and dimensional stability. It also exhibits good melt flow and high process tolerance. This embodiment is suitable for complex thin-walled precision injection molded parts, precision functional components for consumer electronics (such as hinge load-bearing components and snap-fit ​​structural components), internal support structures for household appliances, and medium-to-low load engineering components that require a balance between toughness and dimensional stability and have high process tolerance requirements.

[0111] Example 4

[0112] (a) Preparation of polyamide intermediates Step A1, the raw materials for the polyamide intermediate in this embodiment are: polyamide 66, 100 parts by weight; zinc acetate dihydrate, 1.20 parts by weight.

[0113] Step A2: The polyamide 66 of this embodiment is placed in a 97°C circulating oven and dried for 22 h. The moisture content is determined by Karl Fischer titration. The pre-dried polyamide 66 is obtained by drying until the moisture content is 0.08 wt%.

[0114] In step A3, under a nitrogen atmosphere, the polyamide 66 obtained in step A2 and zinc acetate dihydrate are added to a co-rotating twin-screw extruder for melt blending. The screw speed is 320 rpm, the temperature of each section of the barrel is set at 288℃, and the residence time of the material in the screw is 100 s.

[0115] Step A4: The extrudate obtained in step A3 is granulated and dried in a 97°C circulating oven for 15 h. The water content is determined by Karl Fischer titration to be 0.08 wt%, thus obtaining the ionopolyamide intermediate of this embodiment.

[0116] Step A5: The zinc content (calculated as zinc element) in the ionopolyamide intermediate of this embodiment was quantitatively determined by ICP-OES to be 0.35 wt%, which meets the quality control specification of 0.01–0.87 wt%. When characterized by ATR-FTIR, compared with the control polyamide 66 without the addition of zinc acetate dihydrate, the N–H stretching vibration peak was at 3270–3310 cm⁻¹. -1 The region shows repeatable peak position changes, and the amide I band shows detectable peak position shifts. These changes can serve as spectroscopic evidence that the microenvironment of the amide group has changed after the introduction of zinc salt.

[0117] (II) Preparation of coordination interface glass fiber intermediates Step B1, the raw materials for the coordination interface glass fiber intermediate in this embodiment are: glass fiber, 100 parts by mass; 3-aminopropyltrimethoxysilane, 0.25 parts by mass; phytic acid solution, the amount of which is 2.00 parts by mass based on the purity of phytic acid; and deionized water, appropriate amount.

[0118] Step B2: Add 0.25 parts by weight of 3-aminopropyltrimethoxysilane to deionized water to prepare a silane treatment solution with a 3-aminopropyltrimethoxysilane mass fraction of 0.25 wt%. Add 0.8 mol / L sodium hydroxide aqueous solution to the silane treatment solution of this embodiment to adjust the pH to 10.0. The adjustment process is completed at room temperature, and the pH is checked with a precision pH meter after adjustment. Immerse the glass fiber of this embodiment in the silane treatment solution. The volume / mass ratio of silane treatment solution to glass fiber is 15 mL / g. The immersion process is accompanied by stirring at 150 rpm. The treatment temperature is 42℃ and the treatment time is 1.0 h.

[0119] Step B3: Place the glass fiber obtained in step B2 in a 120℃ forced-air circulating oven and dry for 1.0 h to complete the drying and curing.

[0120] Step B4: Dilute the phytic acid solution with deionized water to prepare a phytic acid treatment solution. In this embodiment, the phytic acid treatment solution contains 15.0 wt% phytic acid. When the measured pH is higher than 3.0, add 0.8 mol / L hydrochloric acid aqueous solution to adjust the pH to 2.0. When the measured pH is lower than 1.0, add 0.8 mol / L sodium hydroxide aqueous solution to adjust to the target value. The adjustment process is completed at room temperature. After adjustment, verify with a precision pH meter to confirm that the pH of the phytic acid treatment solution is 2.0. Immerse the glass fiber obtained in step B3 in the phytic acid treatment solution of this embodiment. The volume / mass ratio of phytic acid treatment solution to glass fiber is 15 mL / g. The immersion process is supplemented with stirring at 150 rpm, the treatment temperature is 42℃, and the treatment time is 1.0 h.

[0121] Step B5: Wash the glass fiber obtained in step B4 with deionized water. The liquid-to-material volume / mass ratio during washing is 25 mL / g. Each stirring and soaking time is not less than 5 min, and the washing is repeated at least 3 times until the pH of the washing solution is 5.0. Then, place it in a 120℃ forced-air circulating oven to dry to constant weight. The interval between two weighings shall not exceed 60 min, and the mass difference between two consecutive weighings shall not exceed 0.1% of the mass of the previous weighing. The drying equipment is a forced-air circulating oven, thus obtaining the coordination interface glass fiber intermediate of this embodiment.

[0122] In step B6, the water content of the coordination interface glass fiber intermediate in this embodiment was determined by Karl Fischer titration to be 0.10 wt%, which meets the quality control specification of 0.02–0.20 wt%. In the N2 atmosphere TGA test, the thermal weight loss rate in the range of 260–310℃ does not exceed 5 wt%, which meets the thermal stability requirements for subsequent melt blending processing.

[0123] (III) Preparation of coordination complex masterbatch intermediates Step C1: Take the ionized polyamide intermediate obtained in step A4 and the coordination interface glass fiber intermediate obtained in step B5 as raw materials.

[0124] Step C2: Based on the total mass of the coordination composite masterbatch intermediates in this embodiment, the coordination interface glass fiber intermediate accounts for 65 wt%, the ionopolyamide intermediate accounts for 35 wt%, and the two together amount to 100 wt%.

[0125] In step C3, under a nitrogen atmosphere, the ionomer polyamide intermediate and the coordination interface glass fiber intermediate prepared in step C2 are added to a co-rotating twin-screw extruder for melt blending. In this embodiment, the coordination interface glass fiber intermediate is added through the side feed port of the twin-screw extruder, the screw speed is 320 rpm, the temperature of each section of the barrel is set at 288°C, and the residence time of the material in the screw is 100 s.

[0126] Step C4: The melt blend obtained in step C3 is extruded and granulated, then dried in a 97°C circulating oven for 15 h. The moisture content is determined by Karl Fischer titration to be 0.08 wt%, yielding the coordination composite masterbatch intermediate of this embodiment. When characterized by ATR-FTIR, the 1150–1250 cm⁻¹ -1 The region showed characteristic absorption peaks associated with phytic acid phosphate groups, which were confirmed by difference spectrum analysis with a blank sample of the same composition that had not been treated with phytic acid.

[0127] (iv) Preparation of high-temperature dimensionally stable nylon material Step S1: Provide polyamide 66. Place the polyamide 66 of this embodiment in a 97°C circulating oven and dry for 22 hours. Determine the moisture content to 0.08 wt% by Karl Fischer titration. Set aside for later use.

[0128] Step S2: Provide the coordination composite masterbatch intermediate obtained in step C4 for later use.

[0129] In step S3, under a nitrogen atmosphere, the polyamide 66 obtained in step S1 and the coordination composite masterbatch intermediate obtained in step S2 are added to a co-rotating twin-screw extruder for melt blending. Based on the total feed mass of polyamide 66 and coordination composite masterbatch intermediate, polyamide 66 is 74 wt% and coordination composite masterbatch intermediate is 26 wt%, totaling 100 wt%. The screw speed is 320 rpm, the temperature of each section of the barrel is set at 295℃, and the residence time of the material in the screw is 100 s.

[0130] In step S4, the melt blend obtained in step S3 is extruded and granulated, and then dried in a 105°C circulating oven for 12 hours. The moisture content is determined by Karl Fischer titration to be 0.08 wt%, thus obtaining the high-temperature resistant dimensionally stable nylon material of this embodiment. The zinc content in the high-temperature resistant dimensionally stable nylon material of this embodiment, calculated as zinc element, is 0.032 wt% by ICP-OES method, which meets the quality control specification of 0.01–0.30 wt%.

[0131] This embodiment uses a high-temperature resistant, dimensionally stable nylon material formulated with 74 wt% polyamide 66 and 26 wt% coordination composite masterbatch intermediate, resulting in a final product with a zinc content of approximately 0.032 wt%. The high proportion of polyamide 66 matrix imparts low warpage and good toughness to the material. Even at low addition levels, the highly concentrated masterbatch provides effective reinforcement and dimensional stabilization through a coordination interface mechanism, resulting in good overall melt flowability and strong mold filling capacity. This embodiment is suitable for precision thin-walled structural parts, lightweight industrial components, and precision injection molded products with high flowability requirements and complex cavities, especially for mass production of slender, multi-gating, thin-walled parts.

[0132] Comparative Example 1: Basically the same as Example 1, except that the amount of zinc acetate dihydrate in step A1 is changed to 0.02 parts by mass, while the amounts of other components and preparation conditions remain unchanged.

[0133] Comparative Example 2: It is basically the same as Example 1, except that the amount of zinc acetate dihydrate in step A1 is changed to 5.00 parts by mass, while the amounts of other components and preparation conditions remain unchanged.

[0134] Comparative Example 3: It is basically the same as Example 1, except that steps B2 (silane treatment) and B3 (drying and curing) are omitted when preparing the coordination interface glass fiber intermediate. The original glass fiber without silane treatment is directly treated with phytic acid according to the conditions of step B4, and then washed and post-treated according to step B5. Other conditions remain unchanged.

[0135] Comparative Example 4: It is basically the same as Example 1, except that step B4 (phytic acid treatment) is omitted when preparing the coordination interface glass fiber intermediate. The glass fiber obtained by silane curing in step B3 is directly washed and post-treated according to step B5, and other conditions remain unchanged.

[0136] Comparative Example 5: Basically the same as Example 1, except that in step B2, 3-aminopropyltrimethoxysilane is replaced with γ-methacryloxypropyltrimethoxysilane, and the mass fraction of γ-methacryloxypropyltrimethoxysilane in the silane treatment solution is the same as in Example 1 (1.00 wt%), while the amounts of other components and preparation conditions remain unchanged.

[0137] Comparative Example 6: It is basically the same as Example 1, except that the proportion of the coordination interface glass fiber intermediate in step C2 is changed to 30 wt%, and the proportion of the polyamide intermediate is changed to 70 wt% accordingly, while other conditions remain unchanged.

[0138] Comparative Example 7: Basically the same as Example 1, except that in step C2, the proportion of the coordination interface glass fiber intermediate is changed to 80 wt%, and the proportion of the polyamide intermediate is changed to 20 wt%, while other conditions remain unchanged.

[0139] Comparative Example 8: Basically the same as Example 1, except that the melt blending temperature of the polyamide intermediate in step A3 was changed from 290°C to 240°C, while the amounts of other components and preparation conditions remained unchanged.

[0140] Experiment 1: The structure of the ionomer polyamide intermediate and the glass fiber intermediate at the coordination interface was characterized by ATR-FTIR in tablets / powders to verify the changes in the coordination microenvironment between zinc ions and amide groups, and to determine the grafting state of phytate phosphate groups on the glass fiber surface; by comparing the changes in the position and intensity of the functional group characteristic peaks, the focus was on N–H stretching (3270–3310 cm⁻¹). -1 ), Amide I band (1630–1680 cm) -1 ) and P=O (1200–1270 cm) -1 ) and P–O–C (1020–1120 cm) -1 Absorption differences. The test was conducted in ATR mode, with the sample directly pressed onto the ATR crystal, at a resolution of 4 cm⁻¹. -1 Scanning range 4000–400 cm -1 The data were accumulated 32 times; three parallel samples were prepared for each group, and Ge or diamond crystals were used for ATR. The data were exported as CSV files in wavenumber and absorbance, and Origin overlay plots were used for comparison and annotation of key peak shifts.

[0141] Experiment 2: Bending performance tests were conducted on standard injection-molded bending specimens (80 mm × 10 mm × 4 mm) for each sample. After injection molding, the specimens were dried in an 80°C oven for 4 hours and then cooled to room temperature. Bending strength and flexural modulus were measured to evaluate the high-strength and high-modulus level of the material. Three-point bending loading was used, and bending stress / strain was calculated based on the force-displacement curve to obtain bending strength and initial elastic modulus. The tests were conducted using a universal testing machine with a span of 64 mm, a loading speed of 2 mm / min, and an ambient temperature of 23±2°C and 50±10% RH. Five specimens were used in each group. Results are expressed as mean ± standard deviation (n=5), with strength in MPa and modulus in GPa. Outliers were removed according to the Grubbs criterion before recalculation.

[0142] Experiment 3: Notched Charpy impact strength tests were performed on standard injection-molded notched impact specimens (80 mm × 10 mm × 4 mm, Type A notch, notch depth 2 mm, notch tip radius 0.25 mm; pre-drying as in Experiment 2) to characterize the notched toughness of the material and evaluate the overall balance between strength / modulus and impact resistance. Under Charpy pendulum horizontal support impact conditions, the specimens experienced stress concentration and fractured at the notch. The notched impact strength was calculated using the fracture energy. A Charpy impact apparatus was used, with the pendulum energy selected to match the sample strength. The temperature was 23 ± 2°C. At least 10 specimens were tested per group, and valid values ​​were recorded. Results are expressed as the mean ± standard deviation of the 10 valid values, in kJ / m³. 2 The data is exported to CSV for comparison with Origin bar charts.

[0143] Experiment 4: Heat distortion temperature (HDT) tests were performed on each injection-molded beam-shaped specimen (80 mm × 10 mm × 4 mm; pre-dried as in Experiment 2) to evaluate the thermal softening behavior of the material under a specified bending stress and characterize its high-temperature dimensional stability and creep resistance. The specimens were immersed in liquid silicone oil heat transfer medium and heated at a constant rate under a specified bending load (0.45 MPa, Method B). The temperature corresponding to the standard deflection of 0.34 mm was recorded. The test used a Vicat thermometer with silicone oil medium, a heating rate of 120°C / h, a span of 64 mm, and at least three specimens per group. Results are expressed as mean ± standard deviation (n≥3), in °C, and exported as CSV.

[0144] Experiment 5: Melt flow rate (MFR) tests were conducted on the granular samples. Before testing, the samples were dried in an 80°C oven for 4 hours to reduce the moisture content to below 0.15 wt%, which characterizes the material's flowability at processing temperatures and evaluates its overall performance in terms of low viscosity, ease of processing, and melt stability. The mass of molten material passing through a standard die per unit time under specified temperature and load reflects shear viscosity behavior. The test was conducted using a melt flow rate meter. The barrel was preheated to 280°C and held at that temperature for 10 min. The load was 2.16 kg, and the die inner diameter was 2.095 mm. Approximately 3 g was taken each time, and three consecutive segments were collected to calculate the equivalent mass over 10 min. This was repeated three times. Results are expressed as the mean ± standard deviation of the three replicates, in g / 10 min. Data were exported to CSV for comparison with Origin.

[0145] Experiment 6: Water Absorption Test. Injection-molded round samples (60 mm diameter, 3 mm thickness) were pre-dried to constant weight in an 80°C oven (the difference between two consecutive weighings should not exceed 0.1% of the previous weighing), and the initial dry weight m0 was recorded. The experiment aimed to evaluate the material's hygroscopic behavior and verify its low water absorption and its ability to maintain hydrolysis resistance and electrical insulation stability. The ratio of the mass increase after immersion to the initial dry weight is the water absorption rate, reflecting the barrier effect of the matrix and interface on moisture. During the test, the sample was completely immersed in deionized water at 23±1°C for 24 h. After removal, the surface moisture was quickly wiped dry, and the wet weight m1 was measured using an electronic balance with an accuracy of 0.1 mg. The result was calculated using the formula: Water Absorption Rate = (m1-m0) / m0 × 100%. Each group had at least three samples. The final value was the mean ± standard deviation of the three samples, expressed as a percentage, and exported in CSV format.

[0146] Figure 1 ATR-FTIR ionomer polyamide intermediate 4000–400 cm -1 The superimposed curves were used to characterize the ionopolyamide intermediates of Example 1, Comparative Example 1 with insufficient zinc content, and Comparative Example 8 with insufficient reaction temperature, using ATR mode. The basic parameters were a scan range of 4000–400 cm⁻¹. -1 Resolution 4 cm -1 The experiment was repeated 32 times, with 3 parallel samples in each group. The variable parameters were the amount of zinc acetate dihydrate and the melting reaction temperature. The results showed that Example 1 showed repeatable differences in the N-H stretching region and amide-related absorption band compared with Comparative Example 1 and Comparative Example 8. This indicates that sufficient zinc salt and sufficient reaction temperature can effectively change the microenvironment of amide groups, thereby supporting the rationality of the formation of ionomerization coordination network.

[0147] Figure 2 For ATR-FTIR magnification, the N–H scaling range is 3400–3100 cm. -1 The superimposed curves, using ATR mode, magnified and compared the N–H stretching vibration characteristic region of the ionopolyamide intermediates of Example 1, Comparative Example 1 with insufficient zinc content, and Comparative Example 8 with insufficient reaction temperature. The basic parameters were a scan range of 3400–3100 cm⁻¹. -1 Resolution 4 cm -1 Accumulated 32 times, with 3 parallel samples per group, the variable parameters being the amount of zinc salt introduced and the reaction temperature. The results showed that Example 1 was performed at 3270–3310 cm⁻¹. -1 The peak positions within the range showed repeatable shifts compared to the two controls, indicating that zinc ions coordinate with amide groups and lead to changes in the N–H microenvironment. This difference is consistent with the increased degree of ionization.

[0148] Figure 3ATR-FTIR amplification of the amide I region 1750–1550 cm⁻¹ -1 The superimposed curves, using ATR mode, compared the ionopolyamide intermediates of Example 1 (insufficient zinc content), Comparative Example 1 (insufficient reaction temperature), and Comparative Example 8 (insufficient reaction temperature) in the characteristic region of the amide I band. The basic parameters were a scan range of 1750–1550 cm⁻¹. -1 Resolution 4 cm -1 Accumulated 32 times, with 3 parallel samples per group, the variable parameters being the zinc salt feeding temperature and the melting reaction temperature. The results showed that Example 1 was within the range of 1630–1680 cm⁻¹. -1 The presence of a detectable peak shift trend in the vicinity, while the shift in the control sample is weak or insignificant, indicates that the coordination microenvironment of the amide group in Example 1 is more stable and consistent, thereby enhancing the integrity of the evidence chain for the construction path of the ionomerization network.

[0149] Figure 4 For comparison of the Zn 2p 3 / 2-containing Zn 2p narrow scan spectrum obtained by XPS, the chemical state analysis of the Zn 2p energy region of the insufficient zinc sample in Example 1 and Comparative Example 1 was performed using XPS narrow scan. The basic parameters were to collect narrow scan spectra in the Zn 2p energy region and compare the binding energy position of Zn 2p 3 / 2. The variable parameter was the difference in coordination degree caused by the amount of zinc salt added. The results showed that the binding energy of Zn 2p 3 / 2 in Example 1 was located at about 1023–1024 eV and formed a distinguishable binding energy difference with Comparative Example 1. This proved that the zinc in Example 1 was more likely to be in a chemical state coordinated with amide groups, which supports the correctness of the formation of the ionomer network and the rationality of the causal attribution from the perspective of elemental chemical state.

[0150] Figure 5 ATR-FTIR GF coordination interface intermediate powder 4000–400 cm -1 The superimposed curves were used to characterize the glass fiber intermediate powders of Example 1, Comparative Example 3 (without silane treatment), and Comparative Example 4 (without phytic acid treatment) using ATR-FTIR to verify the construction of the interface functional layer. The basic parameters were a scan range of 4000–400 cm⁻¹. -1 Resolution 4 cm -1 The samples were accumulated 32 times, with 3 parallel samples in each group. The variable parameters were whether the silane treatment step and the phytic acid treatment step were performed. The results showed that Example 1 exhibited obvious absorption characteristics in the phosphate ester-related band, while the corresponding characteristics of Comparative Example 3 and Comparative Example 4 were weakened or missing. This proves that the tandem two-step treatment can effectively construct the interfacial chemical structure containing phosphate ester and amino groups, thereby improving the rationality of interfacial coordination anchoring.

[0151] Figure 6 Amplification of the phosphate ester region (1300–900 cm⁻¹) using ATR-FTIR -1The superimposed curves were compared using ATR-FTIR to magnify and contrast the glass fiber intermediates of Example 1, Comparative Example 3 (without silane treatment), and Comparative Example 4 (without phytic acid treatment) in the key functional group regions. The basic parameters were a scanning range of 1300–900 cm⁻¹. -1 Resolution 4 cm -1 The samples were accumulated 32 times, with 3 parallel samples per group. The variable parameters were the presence or absence of the silane precursor layer and the phytic acid layer. The results showed that Example 1 was effective at 1200–1270 cm⁻¹. -1 With 1020–1120cm -1 The absorption enhancement observed was consistent with P=O stretching and P–O–C stretching, while the corresponding features of the two control samples were significantly weakened. This demonstrates that the sequential treatment of silane and phytic acid plays a key role in the stable existence of the phosphate ester layer, thus making the conclusions on the construction of the interfacial coordination layer more reproducible and credible.

[0152] Figure 7 The comparison spectrum of the GF surface obtained by XPS P 2p narrow scan is shown. The P 2p energy region of the samples of Example 1, Comparative Example 3 without silane, and Comparative Example 5 with non-aminosilane replacement were analyzed by XPS narrow scan. The basic parameters were to collect narrow scan spectra in the P 2p energy region and compare peak intensity and peak position characteristics. The variable parameters were the absence of silane steps or changes in silane functional group type in the interface processing route. The results showed that there was a stable phosphorus-related signal in Example 1, while it was significantly weakened in Comparative Example 3. This indicates that the silane precursor layer plays a fundamental role in the effective anchoring of the phosphorus-containing functional layer and supports the rationality of the interface bilayer construction mechanism.

[0153] Figure 8 The comparison spectrum of the GF surface obtained by XPS N 1s narrow scan is shown. The N 1s energy region of the samples of Example 1, Comparative Example 3 without silane, and Comparative Example 5 without amino silane replacement were analyzed by XPS narrow scan. The basic parameters were to collect the N 1s energy region narrow scan spectrum and compare the presence and intensity of amino-related signals. The variable parameters were the presence of amino silane layer and its functional group type. The results showed that Example 1 had a detectable amino-related N 1s signal, while Comparative Example 3 and Comparative Example 5 were significantly weakened or absent. This proves that amino functional groups have an irreplaceable contribution to interfacial coordination anchoring, thus making the structural basis of the interfacial co-coordination pathway clearer.

[0154] Figure 9The comparison spectra of the Si 2p surface obtained by XPS narrow scanning were obtained. The Si 2p energy region of the samples in Example 1, Comparative Example 3 (without silane), and Comparative Example 5 (without amino silane replacement) were analyzed using XPS narrow scanning. The basic parameters were to acquire narrow scanning spectra in the Si 2p energy region and compare the silicon-oxygen bond related signals. The variable parameters were whether silane treatment was performed and whether the type of silane was changed. The results showed that Example 1 had a stable Si 2p signal, while Comparative Example 3 showed a significant decrease. Meanwhile, Comparative Example 5 retained the characteristic combination of Si 2p but with the absence of N 1s. This proves that the presence of the silane layer and the absence of amino functionality can be distinguished by spectroscopic analysis, thus verifying the correctness of the interface layer composition and the causal rationality of the control design at the elemental level.

[0155] Figure 10 This is a macroscopic optical photograph of the high-temperature resistant, dimensionally stable nylon material prepared in Example 1. By controlling the intrinsic color of the raw material matrix, adjusting the strong scattering whitening effect caused by the glass fiber content (approximately 25 wt%), and combining it with a low-moisture extrusion granulation process, the sample exhibits a uniform opaque milky white to ivory white color, with a surface gloss tending towards semi-gloss to matte, and no obvious bubbles or fiber agglomeration defects. This demonstrates the synergistic effect of scientific component design and fine processing technology, achieving excellent controllability of the macroscopic phase of the granules, laying a macroscopic structural foundation for its excellent mechanical and thermal properties.

[0156] Figure 11 This is a high-magnification SEM micrograph of the sample from Example 1. The image focuses on the fiber-matrix interface contact state and fracture morphology. A clearly visible increase in fiber breakage is observed, and the surface of the fibers pulled from the matrix is ​​not smooth, but rather covered with a large amount of matrix resin residue / tear fragments. The edges of the pull-out holes also exhibit the ductile shear yielding and plastic tensile fibrosis characteristics of the PA66 matrix. These microscopic morphological fingerprints strongly demonstrate that the coordination between phosphate groups introduced through APTMS / phytic acid surface treatment and Zn ions in the matrix creates extremely strong intermolecular interfacial adhesion, altering the material's fracture mechanism.

[0157] Table 1 Summary of performance comparisons between each embodiment and the comparative example ;

[0158] As can be seen from the performance of the embodiments and comparative examples in Table 1, the flexural strength, flexural modulus, notched impact strength, and heat distortion temperature of the four embodiments are significantly better than those of the comparative examples, fully verifying the comprehensive performance advantages of the coordination composite masterbatch intermediate system. Comparative Example 1 showed a significant decline in flexural strength and HDT due to insufficient ionization, indicating that the effective construction of the zinc ion coordination network depends on the introduction of sufficient zinc salt. Although Comparative Example 2 showed a slight improvement in HDT, its notched impact strength plummeted to 10.1 kJ / m². 2Furthermore, the MFR was only 31 g / 10 min, indicating that excessive ionic crosslinking led to severe material embrittlement and significantly impaired processing fluidity, resulting in an extremely narrow processing window. Comparative Example 3 showed the largest decrease in all mechanical and thermal properties among all comparative examples, followed by Comparative Example 4. This combined indicates that silane treatment and phytic acid treatment are indispensable in sequential interface engineering, and that aminosilane plays a fundamental role as an anchoring precursor for phosphate ester grafting. Comparative Example 5's properties were close to those of Comparative Example 3, further confirming that the amino functional group is the structural key to the formation of the coordination interface and cannot be easily replaced by other types of coupling agents. Comparative Example 6 had low flexural strength and HDT due to insufficient reinforcement content, but high fluidity, indicating that high-temperature dimensional stability cannot be achieved with low GF content. Although Comparative Example 7's flexural modulus and HDT were close to those of some examples, its notched impact strength was only 7.5 kJ / m². 2 Furthermore, the MFR was as low as 29 g / 10 min, resulting in severe material embrittlement and near-impossible processing. Its water absorption rate was lower than that of the other examples, a direct consequence of the high inorganic filler ratio, and an isolated exception that could not compensate for its overall defects in toughness and processability. Comparative Example 8 exhibited the worst overall performance, indicating that a sufficient melt reaction temperature is a necessary prerequisite for ensuring the degree of ionization. In summary, all examples demonstrate a comprehensive superiority over the comparative examples in achieving a synergistic balance of multiple objectives, including flexural mechanical properties, toughness, high-temperature dimensional stability, and processing fluidity.

[0159] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that any equivalent structural transformations made under the concept of the present invention and using the contents of the specification and drawings of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A high-temperature resistant, dimensionally stable nylon material, characterized in that, The total mass of the high-temperature resistant dimensionally stable nylon material includes: A. Polyamide 66 is 30–80 wt%; B. The intermediate of the coordination complex masterbatch is 20–70 wt%; And the sum of the mass percentages of A and B is 100 wt%; Among them, the coordination composite masterbatch intermediate is prepared by melt blending of ionopolyamide intermediate and coordination interface glass fiber intermediate; the ionopolyamide intermediate is prepared by reacting polyamide 66 with zinc acetate dihydrate in the molten state; and the coordination interface glass fiber intermediate is prepared by treating glass fiber with 3-aminopropyltrialkoxysilane and then with phytic acid solution.

2. The high-temperature resistant, dimensionally stable nylon material according to claim 1, characterized in that, The ionomer polyamide intermediate is prepared by the following steps: A1. Raw materials: 100 parts by weight of polyamide 66; 0.05–3.00 parts by weight of zinc acetate dihydrate; A2. Pre-drying: Dry polyamide 66 to a moisture content of 0.02–0.15 wt%; A3. Melt reaction: Under a nitrogen atmosphere, the polyamide 66 obtained in step A2 is melt-blended with zinc acetate dihydrate at a blending temperature of 270–310℃ and a blending time of 30–180s. A4. Granulation and post-treatment: After extrusion granulation, the product is dried to a moisture content of 0.02–0.15 wt% to obtain an ion-polyamide intermediate; A5. Quality control: The zinc content in the ionopolyamide intermediate is 0.01–0.87 wt% (calculated as zinc element).

3. The high-temperature resistant, dimensionally stable nylon material according to claim 1, characterized in that, The coordination interface glass fiber intermediate is prepared by the following steps: B1. Raw materials: 100 parts by weight of glass fiber; 0.10–2.00 parts by weight of 3-aminopropyltrialkoxysilane; 0.10–5.00 parts by weight of phytic acid solution (based on phytic acid purity); deionized water; B2. Silane treatment: 3-aminopropyltrialkoxysilane is added to deionized water to prepare a silane treatment solution. The mass fraction of 3-aminopropyltrialkoxysilane in the silane treatment solution is 0.10–2.00 wt%, and the pH of the silane treatment solution is 9.0–11.

0. Glass fibers are immersed in the silane treatment solution at a treatment temperature of 25–60℃ for a treatment time of 0.5–2.0 h. B3. Drying and curing: Dry the glass fiber obtained in step B2 at 110–130℃ for 0.5–2.0 h; B4. Phytic acid treatment: Dilute the phytic acid solution with deionized water to prepare a phytic acid treatment solution. The phytic acid treatment solution has a mass fraction of 1.0–30.0 wt% based on phytic acid and a pH of 1.0–3.

0. Immerse the glass fiber obtained in step B3 in the phytic acid treatment solution at a temperature of 25–60℃ for 0.5–2.0 h. B5. Washing and post-treatment: Wash with deionized water until the pH of the washing solution is 4.0–6.5, and dry at 110–130℃ to constant weight to obtain the coordination interface glass fiber intermediate; B6. Quality control: The moisture content of the coordination interface glass fiber intermediate is 0.02–0.20 wt%.

4. The high-temperature resistant, dimensionally stable nylon material according to claim 1, characterized in that, The coordination complex masterbatch intermediate is prepared by the following steps: C1. Raw materials: Isopolyamide intermediate and coordination interface glass fiber intermediate; C2. Proportioning: The coordination interface glass fiber intermediate accounts for 40–70 wt% of the coordination composite masterbatch intermediate, and the ionopolyamide intermediate accounts for 30–60 wt% of the coordination composite masterbatch intermediate, with the total of the two being 100 wt%. C3. Melt blending: Melt blending is carried out under a nitrogen atmosphere at a temperature of 260–310℃ for a blending time of 30–180s; C4. Granulation and post-processing: After extrusion granulation, dry to a moisture content of 0.02–0.15 wt% to obtain coordination composite masterbatch intermediate.

5. The high-temperature resistant, dimensionally stable nylon material according to claim 1, characterized in that, The zinc content in the high-temperature resistant dimensionally stable nylon material is 0.01–0.30 wt% (calculated as zinc element).

6. The high-temperature resistant, dimensionally stable nylon material according to claim 3, characterized in that, The 3-aminopropyltrialkoxysilane is 3-aminopropyltrimethoxysilane.

7. A method for preparing a high-temperature resistant, dimensionally stable nylon material as described in any one of claims 1-6, characterized in that, Includes the following steps: S1. Provide polyamide 66 and dry the polyamide 66 to a moisture content of 0.02–0.15 wt%; S2. Provides coordination complex masterbatch intermediates; S3. Under a nitrogen atmosphere, the polyamide 66 obtained in step S1 and the coordination composite masterbatch intermediate provided in step S2 are added to a co-rotating twin-screw extruder for melt blending. The total mass of polyamide 66 and coordination composite masterbatch intermediate is 30–80 wt% and 20–70 wt%, respectively, with a total mass of 100 wt%. The melt blending temperature is 260–320 °C and the blending time is 30–180 s. S4. The melt blend obtained in step S3 is extruded, granulated, and dried to a moisture content of 0.02–0.15 wt% to obtain a high-temperature resistant dimensionally stable nylon material.

8. The method according to claim 7, characterized in that, The coordination composite masterbatch intermediate provided in step S2 is a coordination composite masterbatch intermediate obtained by melt blending an ionomer polyamide intermediate and a coordination interface glass fiber intermediate. The coordination interface glass fiber intermediate accounts for 40–70 wt% of the coordination composite masterbatch intermediate, and the ionomer polyamide intermediate accounts for 30–60 wt% of the coordination composite masterbatch intermediate, with the total of the two being 100 wt%. The melt blending is carried out under a nitrogen atmosphere at a temperature of 260–310 °C for a time of 30–180 s. The melt blend is then extruded, granulated, and dried to a moisture content of 0.02–0.15 wt%.

9. The method according to claim 7, characterized in that, In step S4, the high-temperature dimensionally stable nylon material after extrusion granulation is dried at 80–110 °C for 4–16 h until the moisture content is 0.02–0.15 wt%.

10. The method according to claim 7, characterized in that, The zinc content in the obtained high-temperature resistant dimensionally stable nylon material, calculated as zinc element, is 0.01–0.30 wt%.

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