Preparation method of supramolecular polyamide-imide optical chip packaging material

Abstract

The application discloses a kind of supramolecular polyamide-imide optical chip packaging material preparation methods, belong to semiconductor packaging material technical field;The application is with trimellitic anhydride, biobased decanediamine and isophorone diisocyanate as comonomer, load type palladium catalyst is added, and high-temperature reaction extrusion polymerization is carried out by same direction double-screw extruder, and supramolecular polyamide-imide master batch is prepared, and then optical chip packaging support is obtained by injection molding;The application constructs polyamide-imide-polyurea dynamic supramolecular network structure by introducing rigid imide ring and dynamic urea bond in main chain;Infrared spectroscopy, X-ray diffraction and differential scanning calorimetry analysis confirm the formation of target chemical structure and aggregate structure;The application can obtain high molecular weight product under the synergistic effect of transition metal catalyst and reaction extrusion, has good thermal stability, mechanical property, insulating property and recyclable characteristics, and is suitable for optical chip packaging field.

Description

Technical Field

[0001] This invention relates to the field of semiconductor packaging materials technology, and specifically to a method for preparing supramolecular polyamide-imide optical chip packaging materials. Background Technology

[0002] As optical chips (such as light-emitting diodes, lasers, and photodetectors) develop towards higher power and higher integration, packaging materials must simultaneously meet requirements such as high thermal stability, high light transmittance, excellent mechanical properties, and long-term aging resistance. Polyimide (PI) materials, with their superior heat resistance, excellent mechanical properties, and outstanding dielectric characteristics, play an irreplaceable role in strategic emerging fields such as integrated circuits, new energy, and aerospace. However, traditional aromatic polyimides exhibit a dark brown color due to intramolecular charge transfer complexation effects, resulting in insufficient light transmittance in the visible light region, making it difficult to meet the high light transmittance requirements of optical devices.

[0003] Polyamide-imide (PAI) is a class of high-performance polymers whose main chain contains both amide bonds and imide rings, combining the heat resistance of polyimide with the processability of polyamide. Current research reports on polyamide-imide films with high transparency, high heat resistance, and high strength, which can be used in device substrates, display cover plates, optical films, and integrated circuit packaging. However, existing PAI materials are mostly prepared using solution polycondensation, which involves long processing cycles, large solvent consumption, and the products are mostly in thin film form, making them difficult to directly use for optical chip support packaging.

[0004] In the field of optical chip packaging brackets, the materials widely used in the industry currently include thermosetting epoxy resin (EMC) and thermoplastic polyamide (such as PA10T, PA9T, etc.). EMC materials have the advantages of high heat resistance and low coefficient of expansion, but they have problems such as long processing cycle (requiring long-term thermosetting), brittle texture (easily cracked by impact), and non-recyclability. Thermoplastic polyamide is easy to process, but its heat resistance and dimensional stability are insufficient, making it difficult to meet the packaging requirements of high-power optical chips.

[0005] To address the aforementioned problems, this invention provides a method for preparing supramolecular polyamide-imide optical chip packaging materials. This invention uses trimellitic anhydride, bio-based decanediamine, and isophorone diisocyanate as comonomers to prepare high-molecular-weight PAI materials in a one-step reactive extrusion process. Dynamic urea bonds are introduced to construct a supramolecular network structure, giving the material high thermal stability, good light transmittance, excellent toughness, and recyclability, making it suitable for the field of optical chip packaging supports. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing supramolecular polyamide-imide optical chip packaging materials.

[0007] To achieve the above objectives, the present invention provides the following technical solution: In a first aspect, the present invention provides a method for preparing a supramolecular polyamide-imide optical chip packaging material, comprising the following steps: S1. Trimeric triglyceride, bio-based diamine and isocyanate are mixed in a certain ratio, a supported palladium catalyst is added, and the mixture is fed into a co-rotating twin-screw extruder for reactive extrusion polymerization to obtain supramolecular polyamide-imide masterbatch; S2. The masterbatch is used to obtain an optical chip packaging bracket through injection molding.

[0008] In a preferred embodiment of the preparation method of the present invention, the bio-based diamine is decanediamine, and the isocyanate is isophorone diisocyanate.

[0009] As a preferred embodiment of the preparation method of the present invention, the molar ratio of the decanediamine to trimellitic anhydride is 1:1 to 1.05:1; the molar number of the isophorone diisocyanate accounts for 5% to 30% of the total molar number of diamine.

[0010] As a preferred embodiment of the preparation method of the present invention, the supported palladium catalyst is a palladium / carbon catalyst with a palladium loading of 1-10 wt% and an amount of 0.05-0.5% of the total mass of the monomer.

[0011] As a preferred embodiment of the preparation method of the present invention, the process conditions of the reactive extrusion polymerization are as follows: the length-to-diameter ratio of the twin-screw extruder is 68:1, the temperature of each zone is 340-380℃, the screw speed is 50-120rpm, and the pressure of the vacuum degassing port is ≤30000Pa.

[0012] As a preferred embodiment of the preparation method of the present invention, the injection molding process parameters are: injection temperature 350-380℃, mold temperature 140-160℃, and holding time 30-60s.

[0013] As a preferred embodiment of the preparation method of the present invention, a functional comonomer is added during the reactive extrusion process. The functional comonomer is 2-mercaptoethylamine, and its addition amount accounts for 0-5% of the total molar number of diamines.

[0014] Secondly, the present invention provides a supramolecular polyamide-imide composite material prepared by the above method, wherein the material has a polyamide-imide backbone and dynamic urea bond crosslinking nodes, and contains copolymer segments of trimellitic anhydride units, decanediamine units and isophorone diisocyanate units, with a number average molecular weight of 15000-35000 g / mol.

[0015] As a preferred embodiment of the composite material of the present invention, its infrared spectrum is at 1780 cm⁻¹. - ¹、1720cm- ¹、1370cm - ¹ It has a characteristic peak of the imide ring; its X-ray diffraction pattern is shifted to a lower angle compared to PA10T, with characteristic peaks at 2θ=15° and 16°; its differential scanning calorimetry curve shows a glass transition step in the range of 125-135℃, and there is no crystallization melting peak.

[0016] Thirdly, the present invention provides an optical chip packaging bracket, which is prepared by the above method or made of the above supramolecular polyamide-imide composite material.

[0017] Compared with the prior art, the present invention has the following beneficial effects: Synergistic Effect of Catalyst and Reactive Extrusion: This invention is the first to combine a supported palladium catalyst with a high-temperature reactive extrusion process for the melt polycondensation of polyamide-imide. As a heterogeneous catalytic system, the supported palladium catalyst effectively promotes the amidation and imidization reactions, while reactive extrusion provides a high-temperature, high-shear, and continuous devolatilization polymerization environment. The synergistic effect of both allows for the production of high-molecular-weight PAI with a number-average molecular weight of 15,000-35,000 g / mol through a single-step melt polycondensation process. Compared with conventional catalysts (such as sodium hypophosphite), the supported palladium catalyst exhibits higher catalytic activity and recyclability advantages; it can be separated and recovered from the product through simple filtration after the reaction.

[0018] The overall performance meets the requirements of optical chip packaging: the rigid imide ring gives the material good thermal and dimensional stability; the six-membered ring introduced by IPDI and the strong hydrogen bonding of the dynamic urea bond improve the molecular chain spacing and form a locally ordered structure, giving the material excellent mechanical and insulation properties; at the same time, it has good high and low temperature stability, overcoming the defects of traditional PA10T such as high brittleness, non-recyclable EMC, and difficulty in melt processing of solution-processed PAI.

[0019] The process is green and environmentally friendly: This invention uses bio-based decanediamine as raw material. The reaction extrusion process does not require organic solvents, the catalyst is non-toxic, and the entire preparation process is green and environmentally friendly, meeting the requirements of sustainable development. Attached Figure Description

[0020] Figure 1 Comparison of X-ray diffraction (XRD) patterns of supramolecular polyamide-imide (PAI) and pure PA10T in this invention.

[0021] Figure 2 Differential scanning calorimetry (DSC) thermograms of supramolecular polyamide-imide (PAI) and pure PA10T in this invention.

[0022] Figure 3: A magnified view of the infrared spectrum (FTIR) of the supramolecular polyamide-imide (PAI) material of this invention. Detailed Implementation

[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Furthermore, in this invention, an element referred to as fixed to or disposed on another element may be directly disposed on the other element, or there may be an intermediate element. When an element is considered to be connected to another element, it may be directly connected to the other element, or there may be an intermediate element present simultaneously. The terms vertical, horizontal, left, right, and similar expressions used herein are for illustrative purposes only and do not represent the only possible implementation.

[0025] The trimellitic anhydride (TMA, purity ≥99%), decanediamine (bio-based, purity ≥99%), isophorone diisocyanate (IPDI, industrial grade), and 2-mercaptoethylamine (industrial grade) used in the embodiments of this invention are all commercially available products. The supported palladium catalyst is a palladium / carbon catalyst (Pd / C), with a palladium loading of 1-10 wt%, which can be commercially available or self-made. A co-rotating twin-screw extruder is used, with a length-to-diameter ratio (L / D) of 68:1, equipped with a loss-in-weight feeder, a vacuum degassing device, and a cooling water tank. Number-average molecular weight is determined using gel permeation chromatography (GPC) with hexafluoroisopropanol as solvent and polystyrene as a standard.

[0026] General instructions for preparation methods The present invention provides a method for preparing supramolecular polyamide-imide optical chip packaging material. Using trimellitic anhydride as an anhydride monomer, bio-based decanediamine as a diamine monomer, and isophorone diisocyanate as a dynamic urea bond introduction unit, the process is carried out by high-temperature reactive extrusion polymerization through a co-rotating twin-screw extruder under the promotion of a supported palladium catalyst. The amidation, imidization, and ureation reactions are completed in one step to obtain a supramolecular polymer masterbatch with a polyamide-imide main chain backbone and dynamic urea bond crosslinking nodes. The masterbatch is then injection molded to obtain an optical chip packaging bracket.

[0027] Monomer ratio: The preferred molar ratio of decanediamine to trimellitic anhydride is 1:1 to 1.05:1. The molar amount of IPDI accounts for 5% to 30% of the total diamine molar amount. By adjusting the IPDI content, a balance can be achieved between thermal stability, mechanical properties, and recyclability. When the IPDI content is low (5-10%), the material has high light transmittance, low crosslinking density, and good melt flowability; when the IPDI content is high (20-30%), the dynamic urea bond density increases, the elongation at break and impact strength of the material improve, and the toughness is enhanced, making it suitable for applications requiring high impact resistance.

[0028] Catalyst: A supported palladium catalyst is used, preferably a palladium / carbon catalyst (Pd / C), with a palladium loading of 1-10 wt% and an amount of 0.05-0.5% of the total mass of the monomer.

[0029] Reactive extrusion process: Extruder length-to-diameter ratio 68:1, temperature in each zone 340-380℃, screw speed 50-120rpm, vacuum degassing port pressure ≤30000Pa.

[0030] Functional comonomers: 2-mercaptoethylamine can be added, with the amount added accounting for 0-5% of the total molar amount of diamine, to improve the interfacial bonding between the material and the metal substrate.

[0031] Structural characteristics and performance characterization of the product Molecular weight: The number average molecular weight of the supramolecular polyamide-imide composite material obtained in this invention is 15,000-35,000 g / mol (GPC determination, hexafluoroisopropanol as solvent, polystyrene standard).

[0032] X-ray diffraction (XRD): XRD patterns are as follows Figure 1 As shown in the XRD pattern, compared to ordinary PA10T, the main diffraction peaks of the material obtained in this invention shift towards lower angles, indicating that the introduction of IPDI increases the interchain spacing. Simultaneously, clearer diffraction peaks appear near 2θ=15° and 16°, corresponding to the short-range locally ordered structure generated by the dynamic urea bonds and imide ring stacking. Overall, the crystallinity of the material is lower than that of PA10T, exhibiting amorphous or microcrystalline characteristics.

[0033] Differential Scanning Calorimetry (DSC): DSC thermograms are as follows Figure 2 As shown, the material exhibits a single glass transition step in the 125-135℃ range, and no crystallization melting peak was observed. This result is consistent with the XRD analysis results, further confirming that the material is in an amorphous or microcrystalline aggregated state.

[0034] Infrared spectroscopy (FTIR): Infrared spectroscopy such as Figure 3 As shown, at 1780cm - ¹ and 1720cm- ¹A double peak characteristic of asymmetric and symmetric stretching vibrations of the imide ring carbonyl group appears near 1370 cm⁻¹. - The presence of a characteristic peak of the CNC stretching vibration of the imide ring near ¹ indicates the successful occurrence of the imidization reaction.

[0035] Mechanical properties: The material of this invention has good tensile strength and flexural strength, which meets the load-bearing requirements of optical chip packaging brackets.

[0036] Thermal and dimensional stability: The material has a low coefficient of linear expansion and good high and low temperature stability, which can adapt to temperature fluctuations during the operation of optical chips.

[0037] Insulation performance: The material has high volume resistivity and breakdown voltage, as well as suitable dielectric constant and dielectric loss, which meet the electrical insulation requirements of optical chip packaging.

[0038] As an alternative implementation, if the raw material system is replaced with a polyamide backbone (PA10T type) composed of bio-based diamine and terephthalic acid, the present invention can also be achieved using a prepolymerization and solid-state thickening process, specifically including: S1. Prepolymerization reaction: Bio-based diamine (decanediamine), diacid (terephthalic acid), and isocyanate (IPDI) are added to a high-pressure polymerization reactor in the specified proportions. Under a nitrogen atmosphere, a salt formation reaction is carried out by stirring at 80-120℃ for 1-2 hours to obtain nylon salt; then the temperature and pressure are increased to 240-260℃, and a melt polycondensation reaction is carried out at a pressure of 1.8-2.0MPa for 2-4 hours to obtain the prepolymer.

[0039] S2. Solid-phase thickening: The obtained prepolymer is transferred into a vacuum drum dryer, the rotation speed is set to 5-15 r / min, and the temperature is heated to 200-260℃ at a heating rate of 10-20℃ / min. Solid-phase thickening is carried out under nitrogen protection (12-24 hours). After the intrinsic viscosity reaches the target, the material is discharged to obtain supramolecular polyamide masterbatch.

[0040] S3. Injection molding: The dried masterbatch is put into the injection molding machine for injection molding. The injection temperature is 310-350℃, the mold temperature is 120-150℃, the holding time is 45-60s, and after cooling and demolding, it is annealed to obtain the optical chip packaging bracket.

[0041] This optional process can also introduce dynamic urea bonds into polymer segments, giving the material excellent impact toughness and recyclability while maintaining high molecular weight and high heat resistance.

[0042] Example 1 This embodiment provides a supramolecular polyamide-imide optical chip packaging material with low dynamic bond content and its preparation method.

[0043] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 0.5 mol of isophorone diisocyanate (IPDI, approximately 4.9% of the molar amount of decanediamine) were mixed in a molar ratio, and a palladium / carbon catalyst (5 wt% palladium loading) was added at 0.2% of the total monomer mass. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures of each zone were set to 340℃, 350℃, 360℃, 360℃, and 355℃. The screw speed was 100 rpm, and the vacuum degassing port pressure was set to 20000 Pa. Three vacuum exhaust ports were provided along the screw axis. After reactive extrusion, the material was stretched, water-cooled, and pelletized to obtain a supramolecular polyamide-imide masterbatch.

[0044] After the obtained masterbatch is fully dried in a vacuum oven, it is put into an injection molding machine for injection molding. The injection temperature is 360℃, the mold temperature is 150℃, the holding pressure time is 45s, and after cooling and demolding, the optical chip packaging bracket is obtained.

[0045] The performance of the product obtained in this embodiment was tested, and the results are listed in Table 1.

[0046] Example 2 This embodiment provides a supramolecular polyamide-imide optical chip packaging material with a medium dynamic bond content and its preparation method.

[0047] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 1.5 mol of isophorone diisocyanate (IPDI, approximately 14.7% of the molar weight of decanediamine) were mixed and added to a palladium / carbon catalyst (5 wt% palladium loading) at 0.3% of the total monomer mass. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures in each zone were set to 350℃, 360℃, 370℃, 370℃, and 365℃. The screw speed was 90 rpm, and the vacuum degassing port pressure was set to 25000 Pa. Three vacuum exhaust ports were installed along the screw axis. After reactive extrusion, the material was stretched, water-cooled, and pelletized to obtain a supramolecular polyamide-imide masterbatch.

[0048] After the obtained masterbatch is fully dried in a vacuum oven, it is put into an injection molding machine for injection molding. The injection temperature is 365℃, the mold temperature is 150℃, the holding pressure time is 45s, and after cooling and demolding, the optical chip packaging bracket is obtained.

[0049] The performance of the product obtained in this embodiment was tested, and the results are listed in Table 1.

[0050] Example 3 This embodiment provides a supramolecular polyamide-imide optical chip packaging material with high dynamic bond content and its preparation method.

[0051] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 2.5 mol of isophorone diisocyanate (IPDI, approximately 24.5% of the molar amount of decanediamine) were mixed and added to a palladium / carbon catalyst (5 wt% palladium loading) at 0.4% of the total monomer mass. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures in each zone were set to 360℃, 370℃, 380℃, 380℃, and 375℃. The screw speed was 70 rpm, and the vacuum degassing port pressure was set to 25000 Pa. Three vacuum exhaust ports were installed along the screw axis. After reactive extrusion, the material was stretched, water-cooled, and pelletized to obtain a supramolecular polyamide-imide masterbatch.

[0052] After the obtained masterbatch is fully dried in a vacuum oven, it is put into an injection molding machine for injection molding. The injection temperature is 375℃, the mold temperature is 155℃, the holding pressure time is 50s, and after cooling and demolding, the optical chip packaging bracket is obtained.

[0053] The performance of the product obtained in this embodiment was tested, and the results are listed in Table 1.

[0054] Example 4 This embodiment provides a high number-average molecular weight supramolecular polyamide-imide optical chip packaging material and its preparation method.

[0055] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 1.5 mol of isophorone diisocyanate (IPDI, approximately 14.7% of the molar weight of decanediamine) were mixed and added to a palladium / carbon catalyst (5 wt% palladium loading) at 0.5% of the total monomer mass. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures in each zone were set to 350℃, 360℃, 370℃, 370℃, and 365℃. The screw speed was 50 rpm, and the vacuum degassing port pressure was set to 30000 Pa. Three vacuum exhaust ports were installed along the screw axis. After reactive extrusion, the material was stretched, water-cooled, and pelletized to obtain a supramolecular polyamide-imide masterbatch.

[0056] After the obtained masterbatch is fully dried in a vacuum oven, it is put into an injection molding machine for injection molding. The injection temperature is 365℃, the mold temperature is 150℃, the holding pressure time is 50s, and after cooling and demolding, the optical chip packaging bracket is obtained.

[0057] The performance of the product obtained in this embodiment was tested, and the results are listed in Table 1.

[0058] Example 5 This embodiment provides a supramolecular polyamide-imide optical chip packaging material with different process conditions and its preparation method.

[0059] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 1.5 mol of isophorone diisocyanate (IPDI, approximately 14.7% of the molar weight of decanediamine) were mixed and added to a palladium / carbon catalyst (10 wt% palladium loading) at 0.15% of the total monomer mass. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures in each zone were set to 355℃, 365℃, 375℃, 375℃, and 370℃. The screw speed was 120 rpm, and the vacuum degassing port pressure was set to 15000 Pa. Three vacuum exhaust ports were installed along the screw axis. After reactive extrusion, the material was stretched, water-cooled, and pelletized to obtain a supramolecular polyamide-imide masterbatch.

[0060] After the obtained masterbatch is thoroughly dried in a vacuum oven, it is put into an injection molding machine for injection molding. The injection temperature is 360℃, the mold temperature is 145℃, the holding pressure time is 40s, and after cooling and demolding, the optical chip packaging bracket is obtained.

[0061] The performance of the product obtained in this embodiment was tested, and the results are listed in Table 1.

[0062] Example 6 This embodiment provides a functionalized supramolecular polyamide-imide optical chip packaging material and its preparation method.

[0063] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, 1.5 mol of isophorone diisocyanate (IPDI, approximately 14.7% of the molar weight of decanediamine), and 0.3 mol of 2-mercaptoethylamine (approximately 2.8% of the total molar weight of diamine) were mixed in a molar ratio, and a palladium / carbon catalyst (5 wt% palladium loading) was added at 0.25% of the total monomer mass. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures of each zone were set to 345℃, 355℃, 365℃, 365℃, and 360℃. The screw speed was 80 rpm, and the vacuum degassing port pressure was set to 28000 Pa. Three vacuum exhaust ports were provided along the screw axis. After reactive extrusion, the material was stretched, water-cooled, and pelletized to obtain a functionalized supramolecular polyamide-imide masterbatch.

[0064] After the obtained masterbatch is fully dried in a vacuum oven, it is put into an injection molding machine for injection molding. The injection temperature is 360℃, the mold temperature is 145℃, the holding pressure time is 45s, and after cooling and demolding, the optical chip packaging bracket is obtained.

[0065] The performance of the product obtained in this embodiment was tested, and the results are listed in Table 1.

[0066] Comparative Example 1 This comparative example provides a method for preparing supramolecular polyamide-imide materials using a solid-phase thickening process, for comparison with the embodiments of the present invention.

[0067] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 1.5 mol of isophorone diisocyanate (IPDI, approximately 14.7% of the molar amount of decanediamine) were mixed and added to a palladium / carbon catalyst (5 wt% palladium loading) at 0.3% of the total monomer mass. The mixture was placed in a high-pressure reactor and stirred at 80 °C for 1.5 h under a nitrogen atmosphere to carry out a salt formation reaction. Then, the temperature was raised to 260 °C and melt polycondensed at 2.0 MPa for 3 h to obtain a prepolymer. The obtained prepolymer was transferred to a vacuum drum dryer and subjected to solid-phase thickening at 220 °C under nitrogen protection for 24 h to obtain the product.

[0068] The performance of the product obtained in this comparative example was tested, and the results are listed in Table 2.

[0069] Comparative Example 2 This comparative example provides a method for preparing supramolecular polyamide-imide materials using reactive extrusion under catalyst-free conditions, for comparison with the embodiments of the present invention.

[0070] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 1.5 mol of isophorone diisocyanate (IPDI, approximately 14.7% of the molar amount of decanediamine) were mixed without any catalyst. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures in each zone were set to 350℃, 360℃, 370℃, 370℃, and 365℃. The screw speed was 90 rpm, and the vacuum degassing port pressure was set to 25000 Pa. Three vacuum exhaust ports were installed along the screw axis. After reactive extrusion, the material was stretched into strands, water-cooled, and pelletized to obtain the final product.

[0071] The performance of the product obtained in this comparative example was tested, and the results are listed in Table 2.

[0072] Comparative Example 3 This comparative example provides a method for reactive extrusion polymerization using a different type of catalyst (stannous chloride) instead of a supported palladium catalyst, for comparison with the embodiments of the present invention.

[0073] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 1.5 mol of isophorone diisocyanate (IPDI, approximately 14.7% of the molar amount of decanediamine) were mixed and added to 0.3% of the total monomer mass of stannous chloride (SnCl2) as a catalyst. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures of each zone were set to 350℃, 360℃, 370℃, 370℃, and 365℃. The screw speed was 90 rpm, and the vacuum degassing port pressure was set to 25000 Pa. Three vacuum exhaust ports were provided along the screw axis. After reactive extrusion, the material was stretched into strands, water-cooled, and pelletized to obtain the product.

[0074] The performance of the product obtained in this comparative example was tested, and the results are listed in Table 2.

[0075] Comparative Example 4 This comparative example provides a method for preparing supramolecular polyamide-imide materials by using other diisocyanates instead of isophorone diisocyanate (IPDI), for comparison with the embodiments of the present invention.

[0076] 10.2 mol of decanediamine, 10.0 mol of trimellitic anhydride, and 1.5 mol of diphenylmethane diisocyanate (MDI, approximately 14.7% of the molar amount of decanediamine) were mixed in a molar ratio, and a palladium / carbon catalyst (5 wt% palladium loading) was added at 0.3% of the total monomer mass. The mixture was fed into a co-rotating twin-screw extruder via a loss-in-weight feeder. The extruder had a length-to-diameter ratio of 68:1, and the temperatures of each zone were set to 350℃, 360℃, 370℃, 370℃, and 365℃. The screw speed was 90 rpm, and the vacuum degassing port pressure was set to 25000 Pa. Three vacuum exhaust ports were provided along the screw axis. After reactive extrusion, the material was stretched into strands, water-cooled, and pelletized to obtain the product.

[0077] The performance of the product obtained in this comparative example was tested, and the results are listed in Table 2.

[0078] Performance test results The performance of the LED packaging brackets prepared in Examples 1-6 and Comparative Examples 1-2 was tested, and the test results are summarized below: Table 1. Performance Test Results of Examples 1-6 Table 2. Performance Test Results of Comparative Examples 1-2 The test results show that, compared with the pure PA10T material of Comparative Example 1, the supramolecular polyamide-imide optical chip packaging materials prepared in Examples 1-6 of this invention have significantly improved elongation at break and notched impact strength while maintaining high tensile strength and glass transition temperature, indicating that the toughness of the material has been significantly improved. In particular, the samples with moderate IPDI content in Examples 2, 3, and 6 have the best comprehensive mechanical properties, achieving a good balance between heat resistance, strength, and toughness. Compared with the high-filled composite material of Comparative Example 2, the material of this invention maintains good light transmittance and processing performance, and does not require extreme injection molding processes.

[0079] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0080] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing a supramolecular polyamide-imide optical chip packaging material, characterized in that, Includes the following steps: S1. Trimeric triglyceride, bio-based diamine and isocyanate are mixed in a certain ratio, a supported palladium catalyst is added, and the mixture is fed into a co-rotating twin-screw extruder for reactive extrusion polymerization to obtain supramolecular polyamide-imide masterbatch; S2. The masterbatch is used to obtain an optical chip packaging bracket through injection molding.

2. The preparation method according to claim 1, characterized in that, The bio-based diamine is decanediamine, and the isocyanate is isophorone diisocyanate.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the decanediamine to trimellitic anhydride is 1:1 to 1.05:1; the molar amount of the isophorone diisocyanate accounts for 5% to 30% of the total molar amount of diamine.

4. The preparation method according to claim 1, characterized in that, The supported palladium catalyst is a palladium / carbon catalyst with a palladium loading of 1-10 wt% and an amount of 0.05-0.5% of the total mass of the monomers.

5. The preparation method according to claim 1, characterized in that, The process conditions for reactive extrusion polymerization are as follows: the length-to-diameter ratio of the twin-screw extruder is 68:1, the temperature of each zone is 340-380℃, the screw speed is 50-120rpm, the residence time is determined according to the screw speed and the feeding rate, and the vacuum degassing port pressure is ≤30000Pa.

6. The preparation method according to claim 1, characterized in that, The injection molding process parameters are: injection temperature 350-380℃, mold temperature 140-160℃, and holding time 30-60s.

7. The preparation method according to claim 1, characterized in that, A functional comonomer, 2-mercaptoethylamine, is added during the reactive extrusion process, and its addition amount accounts for 0-5% of the total molar number of diamines.

8. A supramolecular polyamide-imide composite material prepared by the method according to any one of claims 1-7, characterized in that, The material has a polyamide-imide backbone and dynamic urea bond crosslinking nodes, and contains copolymer segments of trimellitic anhydride units, decanediamine units and isophorone diisocyanate units, with a number average molecular weight of 15,000-35,000 g / mol.

9. The composite material according to claim 8, characterized in that, Its infrared spectrum is at 1780 cm⁻¹ - ¹、1720cm - ¹、1370cm - ¹ It has a characteristic peak of the imide ring; its X-ray diffraction pattern is shifted to a lower angle compared to PA10T, with characteristic peaks at 2θ=15° and 16°; its differential scanning calorimetry curve shows a glass transition step in the range of 125-135℃, and there is no crystallization melting peak.

10. An optical chip packaging bracket, characterized in that, It is prepared by the method described in any one of claims 1-7, or made from the supramolecular polyamide-imide composite material described in claim 8 or 9.

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