Polyetherimide polyethylene composite bonding resin with high heat resistance and high bonding performance and preparation method of polyetherimide polyethylene composite bonding resin

Abstract

The invention relates to the technical field of special high polymer materials, in particular to polyetherimide polyethylene composite bonding resin with high heat resistance and high bonding performance and a preparation method of the polyetherimide polyethylene composite bonding resin. 3 to 8 parts of polytetrafluoroethylene ultrafine powder plasticized by ionic liquid; 5-12 parts of a liquid metal core-shell structure filler; 15 to 30 parts of bio-based polyetherimide with a carbodicyclic structure; 35 to 55 parts of cyclodextrin coated metallocene polyethylene; 25 to 45 parts of radiation grafting functionalized polyethylene; 4-9 parts of a boron-silicon-containing double-bond functional monomer; 2 to 6 parts of hyperbranched polysiloxane; 1-4 parts of a rare earth complex antioxidant; and 20-35 parts of a polyurethane, epoxy resin and acrylate ternary complex. Wherein the porous ceramic microspheres enhance the mechanical strength and the thermal stability, so that the synergistic improvement of the bonding strength and the thermal stability of the polyetherimide polyethylene composite bonding resin in a high-temperature environment is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of special polymer materials, in particular to a polyetherimide polyethylene composite bonding resin with high heat resistance and high bonding performance and a preparation method thereof. BACKGROUND

[0002] The composite bonding resin with high heat resistance and high bonding performance has important value in aerospace, new energy battery packaging, high temperature cable insulation layer and other scenes due to its stable bonding ability in extreme environments. The core technical requirements put forward by these applications include: maintaining bonding strength in high temperature environment, having broad spectrum adhesion to various substrates, and not having interface peeling or performance decay in thermal cycle test. In addition, the material needs to pass the flame retardant certification, and the fluctuation of bonding performance in humid environment needs to be controlled within a reasonable range.

[0003] The existing solutions for this technical requirement at present mainly include the following:

[0004] Maleic anhydride grafting modification technology: grafting polar groups on polyethylene main chain through free radical initiator, introducing nanoclay lamellar structure to enhance interfacial force and heat resistance.

[0005] Silane and peroxide synergistic crosslinking system: using twin screw extrusion process to generate three-dimensional network structure, and cooperating with crosslinking reaction to improve thermal stability.

[0006] Graphene or carbon nanotube composite filling technology: preparing functionalized graphene sheet layer by in-situ intercalation method, forming heat conduction and barrier synergistic effect with polyethylene matrix, and using surface groups of nanocarbon materials to enhance interfacial bonding force.

[0007] Although the above methods have achieved certain results in specific scenarios, there are still the following problems:

[0008] Batch performance difference: the maleic anhydride grafting process has strong dependence on temperature and initiator concentration, resulting in significant fluctuation of grafting rate and affecting the consistency of the performance of the final product.

[0009] Equipment cost and process control defects: the silane and peroxide crosslinking system depends on high temperature and high pressure conditions, the equipment investment is high and the crosslinking degree is difficult to accurately control, which easily causes material embrittlement.

[0010] Functionalization limitation and dielectric performance contradiction: the agglomeration of graphene composite materials leads to interfacial stress concentration, and there is a contradiction between the addition of carbon materials and the demand for dielectric performance, which limits its applicability in specific fields. In addition, it needs to rely on complex post-processing process, and the comprehensive energy consumption is high, which does not meet the development trend of green manufacturing. SUMMARY

[0011] In view of the deficiencies of the prior art, the present application provides a polyetherimide polyethylene composite bonding resin with high heat resistance and high bonding performance and a preparation method thereof, which solves the problems in the above background art.

[0012] According to a first aspect of the present application, a polyetherimide polyethylene composite bonding resin with high heat resistance and high bonding performance is provided, which is composed of the following components in mass fraction:

[0013] Polycyclic aromatic heterocyclic ceramic microspheres (PAHCM): 8-15 parts;

[0014] Ion liquid plasticized polytetrafluoroethylene superfine powder: 3-8 parts;

[0015] Liquid metal core-shell structure filler: 5-12 parts;

[0016] Bio-based cardo ring structure polyetherimide: 15-30 parts;

[0017] Cyclodextrin-coated metallocene polyethylene: 35-55 parts;

[0018] Radiation grafted functionalized polyethylene: 25-45 parts;

[0019] Boron-silicon double bond containing functional monomer: 4-9 parts;

[0020] Hyperbranched polysiloxane: 2-6 parts;

[0021] Rare earth complex antioxidant: 1-4 parts;

[0022] Polyurethane, epoxy resin and acrylic ester ternary composite: 20-35 parts.

[0023] Polycyclic aromatic heterocyclic ceramic microspheres (PAHCM) are used to enhance the thermal stability and mechanical strength of the composite resin, and the multi-level pore structure can effectively disperse stress and inhibit the thermal motion of molecular chains at high temperature, while providing nanoscale anchoring points to enhance the interfacial bonding force.

[0024] Liquid metal core-shell structure filler (LMCSF) is used to improve the thermal conductivity and interfacial compatibility of the composite resin, and the liquid metal core undergoes phase change at the processing temperature to absorb heat, and the silica shell provides chemical bonding sites with the polymer matrix, forming an efficient heat conduction network.

[0025] Bio-based cardo polyetherimide (Bio-PEI) as a rigid backbone material of composite resin, its cardo ring structure and aromatic heterocyclic units limit molecular chain movement through steric hindrance effect, providing excellent thermal stability and mechanical strength, while the bio-based source improves the sustainability of the material.

[0026] Cyclodextrin encapsulated metallocene polyethylene (CD-mPE) is used to enhance the compatibility of polyethylene with other components, and the supramolecular inclusion effect of cyclodextrin effectively improves the polarity and dispersity of metallocene polyethylene, forming a stable interfacial transition layer through host-guest interaction.

[0027] Boron-silicon double bond functional monomer (BS-DFM) is used to build a heat-resistant crosslinking network, which contains boron and silicon double bonds that can react with various functional groups through click chemistry under thermal activation conditions, forming a three-dimensional network structure with self-repairing ability.

[0028] Hyperbranched polysiloxane (HPSi) is used to improve the flowability and interfacial performance of composite resin, its highly branched molecular structure and abundant terminal functional groups can effectively reduce the melt viscosity, and at the same time form a molecular level protective layer at the interface.

[0029] According to the embodiment of the application, the porous aromatic heterocyclic ceramic microspheres are multi-level porous structure ceramic microspheres sintered from an aromatic heterocyclic polymer precursor by a template method; the ion liquid plasticized polytetrafluoroethylene ultrafine powder is a plasticized composite powder obtained by reacting polytetrafluoroethylene with ethylimidazolium tetrafluoroborate; and the liquid metal core-shell structure filler is a core-shell structure particle formed by coating a silica shell on a gallium-indium-tin alloy through microfluidic electrospinning technology.

[0030] The aromatic heterocyclic polymer precursor is a polymer solution obtained by mixing polyimide and benzoxazine resin at a mass ratio of 1:0.8-1:1.2.

[0031] The mass ratio of polytetrafluoroethylene to ethylimidazolium tetrafluoroborate is 1:0.2-1:0.6.

[0032] The mass ratio of gallium, indium and tin in the gallium-indium-tin alloy is 6:3:1-7:2:1, and the mass ratio of the gallium-indium-tin alloy to the silica is 1:0.2-1:0.5.

[0033] Ionic liquid plasticized polytetrafluoroethylene ultrafine powder (IL-PTFE) is used to reduce the friction coefficient of the composite resin and improve the flowability, and the ionic liquid forms a molecular lubricating layer on the surface of the polytetrafluoroethylene particles, reduces the interface resistance through charge interaction, and maintains stable lubricating performance at high temperature.

[0034] According to the embodiment of the present application, the porous aromatic heterocyclic ceramic microspheres effectively disperse stress and anchor molecular chains through their multi-level pore structure, and cooperatively build a stable heat-resistant skeleton with the liquid metal core-shell structure filler, wherein the heat absorption characteristics of the liquid metal phase change and the heat barrier effect of the ceramic microspheres together guarantee high-temperature dimensional stability. The ionic liquid plasticized polytetrafluoroethylene ultrafine powder forms a molecular lubricating layer at the interface, and the charge interaction not only reduces the flow resistance, but also delays thermal oxidative degradation through the synergistic effect with the rare earth complex antioxidant.

[0035] According to the embodiment of the present application, the bio-based cardo ring structure polyetherimide is a polymer powder containing a cardo ring structure obtained by polycondensation of a bio-based aromatic diamine and an aromatic dianhydride; the cyclodextrin-coated metallocene polyethylene is a coated composite particle formed by β-cyclodextrin supermolecule inclusion metallocene polyethylene; the radiation grafted functionalized polyethylene is a grafted polyethylene containing epoxy groups or anhydride groups; and the hyperbranched polysiloxane is an amino-terminated hyperbranched polysiloxane.

[0036] And, during the preparation process, the amino-terminated hyperbranched polysiloxane reacts with the epoxy groups or anhydride groups of the radiation grafted functionalized polyethylene and the terminal active groups of the bio-based cardo ring structure polyetherimide to form an in-situ chemically bridged interface layer between the polyethylene phase and the polyetherimide phase.

[0037] The molar ratio of the bio-based aromatic diamine to the aromatic dianhydride is 1:0.95-1:1.05.

[0038] The mass ratio of the metallocene polyethylene to the β-cyclodextrin is 1:0.1-1:0.3.

[0039] The amino-terminated hyperbranched polysiloxane is a dendrimer powder obtained by ring-opening polymerization of an amino-terminated hyperbranched siloxane and octamethylcyclotetrasiloxane, and the mass ratio of the amino-terminated hyperbranched siloxane to the octamethylcyclotetrasiloxane is 1:0.8-1:1.2.

[0040] Radiation Grafted Functionalized Polyethylene (RG-PE) is used to provide active reaction sites and enhance interfacial adhesion by introducing polar functional groups on the polyethylene molecular chain through high-energy radiation. These active groups can form covalent bonds with other components during subsequent processing.

[0041] According to an embodiment of the present application, the bio-based cardo structure polyetherimide is obtained by condensation polymerization of aromatic diamine and dianhydride, and the terminal active groups react with the terminal amino hyperbranched polysiloxane; at the same time, the terminal amino groups of the terminal amino hyperbranched polysiloxane also form chemical bonds with the radiation grafted functionalized polyethylene. The compatibility is enhanced by supramolecular encapsulation of the cyclodextrin-coated metallocene polyethylene. By controlling the molar ratio and mass ratio of each component, an in-situ chemical bridging interface layer is constructed between the polyethylene phase and the polyetherimide phase, thereby achieving synergistic improvement of mechanical properties and functional characteristics.

[0042] According to an embodiment of the present application, the boron-containing silicon double bond functional monomer is a complex functional monomer generated by esterification reaction of vinyl boronic acid and methacryloyloxypropyl trimethoxysilane; the rare earth complex antioxidant is a rare earth particle formed by coordination of europium ions and acetylacetone; and the polyurethane-epoxy-acrylate ternary complex is a ternary hybrid powder obtained by in-situ polymerization of polyurethane, epoxy resin and acrylate;

[0043] The mass ratio of the vinyl boronic acid to the methacryloyloxypropyl trimethoxysilane is 1:1.5-1:2.5;

[0044] The molar ratio of the europium ions to the acetylacetone is 1:2-1:3;

[0045] The mass ratio of the polyurethane, the epoxy resin and the acrylate is 1:1:0.5-1:1:1.

[0046] The rare earth complex antioxidant (REC-AO) is used to improve the thermal oxidative stability of the composite resin. The empty orbit of the rare earth ion can effectively capture free radicals, and the organic ligand can decompose hydroperoxide, thereby delaying material aging through synergistic effect.

[0047] The polyurethane-epoxy-acrylate ternary complex (PEA-TC) is used as a toughness enhancing phase of the composite resin. The unique ternary synergistic structure realizes rigid-flexible balance through hydrogen bonding and phase separation mechanism, which not only maintains the heat resistance of the epoxy resin, but also has the toughness of the polyurethane and the processing performance of the acrylate.

[0048] According to the embodiment of the present application, the boron-silicon double bond functional monomer constructs an adaptive crosslinked network through dynamic covalent bonds, the borate ester bond and the siloxane group reversibly recombine under the action of heat to realize effective dissipation of interfacial stress. The hyperbranched polysiloxane is inserted into the crosslinked network, the interfacial bonding force is enhanced through molecular chain entanglement, and the terminal silicon hydroxyl group forms a coordination bond with the rare earth complex antioxidant to jointly build a thermal and oxidative stability barrier. The ternary composite forms a continuous interpenetrating structure through microphase separation, the epoxy resin segment provides rigid support, the polyurethane segment absorbs impact energy, and the acrylate segment promotes interfacial fusion, finally realizing the synergistic enhancement of heat resistance, toughness and bonding reliability.

[0049] According to the second aspect of the present application, a preparation method of the above-mentioned polyetherimide polyethylene composite bonding resin is provided, as shown in the formula, comprising the following steps: Figure 1 S1: The porous aromatic heterocyclic ceramic microspheres and the boron-silicon double bond functional monomer are compounded by vacuum pressure impregnation technology to prepare a functional ceramic composite;

[0050] S1: The porous aromatic heterocyclic ceramic microspheres and the boron-silicon double bond functional monomer are compounded by vacuum pressure impregnation technology to prepare a functional ceramic composite;

[0051] S2: The bio-based calixarene polyetherimide, cyclodextrin-coated metallocene polyethylene and the radiation grafted functional polyethylene are melt blended at 190-230°C under an inert atmosphere using ultrasonic-assisted solid-phase shear grinding technology to preliminarily entangle and activate the polymer chains, and a matrix blend is obtained;

[0052] S3: The functional ceramic composite, ion liquid plasticized polytetrafluoroethylene ultrafine powder, liquid metal core-shell structure filler, hyperbranched polysiloxane and the rare earth complex antioxidant are added to the matrix blend, and blended at 180-210°C for 10-20 minutes in an electromagnetic field oscillation blending device. During the blending process, the hyperbranched polysiloxane, bio-based calixarene polyetherimide and radiation grafted functional polyethylene undergo interfacial chemical reaction to obtain a catalytically activated mixture;

[0053] S4: The ternary composite of polyurethane, epoxy resin and acrylate is added to the catalytically activated mixture, and microwave crosslinking is carried out under the assistance of supercritical carbon dioxide to obtain a crosslinked composite;

[0054] S5: The crosslinked composite is cooled to room temperature in a microfluidic focusing rapid cooling device, and then subjected to melt electrospinning granulation by a co-rotating twin screw to obtain the polyetherimide polyethylene composite bonding resin.

[0055] According to an embodiment of the present application, the functionalized ceramic composite is prepared by compounding the porous aromatic heterocyclic ceramic microspheres and the functional monomer containing boron-silicon double bond through a vacuum pressure impregnation technique, comprising:

[0056] The porous aromatic heterocyclic ceramic microspheres are placed in a vacuum impregnation device and degassed under a vacuum degree of 0.1-0.5 kPa for 20-40 minutes to obtain degassed ceramic microspheres;

[0057] The functional monomer containing boron-silicon double bond is heated to 40-60℃ and then injected into the degassed ceramic microspheres at a pressure of 0.5-2 MPa for impregnation for 30-60 minutes to obtain the functionalized ceramic composite. The mass ratio of the degassed ceramic microspheres to the functional monomer containing boron-silicon double bond is 1:0.5-1:1.2.

[0058] According to an embodiment of the present application, the degassing treatment in the vacuum impregnation process effectively removes the gas barrier inside the porous aromatic heterocyclic ceramic microspheres, creating ideal conditions for the deep penetration of the functional monomer containing boron-silicon double bond. The functional monomer fills the pores under pressure driving, and the borate groups form coordinate bonding with the hydroxyl groups on the ceramic surface, while the siloxane end groups extend to the outside of the pores to construct an organic-inorganic interface bridging layer. This microstructure enables the functionalized ceramic composite to maintain the heat-resistant properties of the ceramic skeleton, and also provides active sites for subsequent crosslinking reactions through surface-grafted double bond groups, achieving dual optimization of stress transfer and interface compatibility.

[0059] According to an embodiment of the present application, the base blend comprises:

[0060] The bio-based cardo ring structure polyetherimide, cyclodextrin-coated metallocene polyethylene, and the radiation-grafted functionalized polyethylene are added into a solid-phase shear grinding device at a mass ratio of 1:2.5:1.5-1:3:2, nitrogen is introduced to maintain oxygen content ≤50 ppm, and the temperature is raised to 190-230℃ at a rate of 5-10℃ / min under ultrasonic frequency of 20-40 kHz and amplitude of 5-15 μm, and shear grinding is performed for 15-30 minutes to obtain the base blend.

[0061] According to an embodiment of the present application, in the solid-phase shear grinding process, the high-frequency mechanical vibration generated by the ultrasonic wave and the shear stress field synergistically act on the rigid segments of the bio-based cardo ring structure polyetherimide and the flexible molecular chains of the cyclodextrin-coated metallocene polyethylene to achieve nanoscale crosslinking. The polar functional groups introduced by the radiation-grafted functionalized polyethylene form supramolecular complexes with the cyclodextrin cavities under mechanical and chemical action, and the cardo ring structure of the polyetherimide strengthens the interface stability through π-π stacking. This thermal-mechanical synergistic activation process promotes the formation of a multi-level interpenetrating network of the three base materials, which builds a carrier platform with rigid skeleton and dynamic bonding ability for the introduction of subsequent functional components.

[0062] According to the embodiment of the present application, the functional ceramic composite, the ionic liquid plasticized polytetrafluoroethylene superfine powder, the liquid metal core-shell structure filler, the hyperbranched polysiloxane and the rare earth complex antioxidant are added into the base blend, and are blended in an electromagnetic field oscillation blending device at 180-210°C for 10-20 minutes. During the mixing process, the hyperbranched polysiloxane, the bio-based cardo structure polyetherimide and the radiation grafted functional polyethylene undergo interface chemical reactions to obtain a catalytically activated mixture, which includes:

[0063] The base blend is transferred into the electromagnetic field oscillation blending device, and the functional ceramic composite, the ionic liquid plasticized polytetrafluoroethylene superfine powder and the liquid metal core-shell structure filler are sequentially added into the initial mixed base in a mass ratio of 1:0.4:0.6-1:0.8:1.2 under the condition of an alternating electromagnetic field frequency of 1-5 kHz and a field strength of 0.5-2 T, and are mixed for 20-30 minutes to obtain an initial mixed base.

[0064] The hyperbranched polysiloxane and the rare earth complex antioxidant are added into the initial mixed base in a mass ratio of 1:0.2:0.1-1:0.4:0.3, and are blended at 180-210°C and 100-200 rpm for 10-20 minutes to obtain the catalytically activated mixture.

[0065] According to the embodiment of the present application, the alternating electromagnetic field induces the functional ceramic composite and the liquid metal core-shell structure filler to be arranged along the magnetic lines of force to form a multidimensional heat conduction network. The ionic liquid plasticized polytetrafluoroethylene superfine powder forms a molecular lubricating layer at the interface, and the charge interaction cooperates with the branched structure of the hyperbranched polysiloxane to improve the melt dispersibility. The rare earth complex antioxidant is combined with the hydroxyl groups on the surface of the ceramic through coordination bonds to construct a thermal stability barrier. The hyperbranched polysiloxane, the bio-based cardo structure polyetherimide and the radiation grafted functional polyethylene undergo interface chemical reactions under the action of the electromagnetic field to construct a molecular level synergistic network, so that the ceramic composite and the liquid metal filler are uniformly dispersed through ionic liquid modification, and finally a multifunctional composite system with catalytic activity is formed.

[0066] According to the embodiment of the present application, the crosslinked composite includes:

[0067] The catalytically activated mixture, the polyurethane, the epoxy resin and the acrylate ternary composite are placed in a supercritical reaction kettle in a mass ratio of 1:0.5-1:1, and are treated under the condition of a carbon dioxide supercritical pressure of 8-15 MPa and a temperature of 65-85°C, supplemented by microwave radiation power of 500-1000 W and a frequency of 2.45 GHz for 20-35 minutes to obtain the crosslinked composite.

[0068] According to the embodiment of the present application, in a supercritical carbon dioxide environment, its high permeability characteristics promote the ternary complex to fully swell, creating a uniform energy transmission channel for microwave radiation. The microwave field selectively activates the dynamic covalent bond of the boron-containing silicon double bond functional monomer through dipole polarization, and at the same time induces the metal coordination bond reorganization in the rare earth complex. The synergistic effect of supercritical fluid and microwave energy realizes the precise control of crosslinking reaction, so that the polyurethane segment, epoxy network and acrylate unit form a multi-level interpenetrating structure, and finally a three-dimensional network skeleton with high crosslinking density and interface compatibility is constructed.

[0069] According to the embodiment of the present application, the crosslinking compound is cooled to room temperature in a microfluidic focusing rapid cooling device, and then subjected to melt electrospinning granulation by a co-rotating twin screw extruder, to obtain the polyetherimide polyethylene composite bonding resin.

[0070] The crosslinking compound is rapidly cooled to 25-30 DEG C by the microfluidic focusing rapid cooling device under the condition that the cooling medium temperature is-10 to 5 DEG C and the flow rate is 2-5 m / s, to obtain a rapidly cooled solidified material;

[0071] The rapidly cooled solidified material is fed into a co-rotating twin screw extruder, and is melt-extruded under the condition that the screw temperature is 180-200 DEG C and the rotation speed is 200-400 rpm, while an electrostatic voltage of 10-20 kV is applied for spinning granulation, to obtain the polyetherimide polyethylene composite bonding resin.

[0072] The particle size of the rapidly cooled solidified material is controlled to be 1-3 mm, and the particle length of the polyetherimide polyethylene composite bonding resin is 2-4 mm.

[0073] According to the embodiment of the present application, the supercritical carbon dioxide fluid penetrates into the intermolecular chain gap of the ternary complex, effectively reducing the viscosity of the polymer system and promoting the interface fusion of each component. Microwave radiation excites the dynamic reorganization of the boron-containing silicon double bond functional monomer through molecular level energy transmission, and at the same time induces the coordination bond conversion of the rare earth complex. The double effect of fluid plasticization and electromagnetic excitation realizes the spatial precise control of crosslinking reaction, so that the polyurethane elastic segment, epoxy rigid chain and acrylate active group form a stable gradient interpenetrating structure, and finally a three-dimensional network skeleton with high crosslinking density and interface compatibility is constructed.

[0074] The present application has the following beneficial effects:

[0075] The present application significantly improves the heat resistance and interfacial bonding strength of the composite bonding resin through the synergistic effect of multiple components. The porous aromatic heterocyclic ceramic microspheres as the core reinforcing phase, its three-dimensional multi-level pore structure not only effectively disperses the thermal stress, but also strengthens the high temperature resistance of the matrix through chemical bonding. The composite application of liquid metal core-shell structure filler and bio-based cardo ring polyetherimide not only realizes the directional construction of heat conduction path, but also enhances the toughness of the material through the design of rigid-flexible embedded microstructure. This multi-scale synergistic reinforcement mechanism enables the resin to maintain excellent dimensional stability and bonding reliability in extreme temperature environment.

[0076] The present application greatly optimizes the interfacial compatibility and mechanical properties of the composite system through innovative functional modification technology. The dynamic chemical bond network formed by radiation grafting polyethylene and hyperbranched polysiloxane at the interface effectively eliminates the common interface defects in traditional composites. The self-lubricating microzone constructed by ion liquid plasticized polytetrafluoroethylene ultrafine powder in the matrix significantly improves the wear resistance and fatigue resistance of the material. This molecular level interface design strategy enables the resin to exhibit excellent long-term bonding capacity under mechanical load conditions, meeting the stringent use requirements of precision instruments and heavy equipment.

[0077] The present application adopts multiple flame retardant systems to build an efficient synergistic fire protection mechanism. The functional monomer containing boron-silicon double bond can generate a dense inorganic layer in situ when heated, combined with the free radical capture effect of rare earth complex antioxidant, forming a gas and solid dual flame retardant effect. The high thermal conductivity of liquid metal filler accelerates heat dissipation, further delaying the thermal decomposition process of the material. The composite system not only meets the high flame retardant standard, but also has low smoke and low toxicity characteristics, providing a safe and reliable bonding solution for electronic and electrical and rail transportation fields.

[0078] The present application realizes the breakthrough development of environmentally friendly materials through the innovative combination of bio-based components and green synthesis process. The synergistic application of bio-based cardo ring polyetherimide and cyclodextrin-coated polyethylene not only reduces the dependence on petroleum resources, but also endows the material with controllable degradation performance through molecular structure design. The whole process adopts solvent-free processing technology, combined with supercritical carbon dioxide assisted crosslinking and other clean manufacturing methods, significantly reducing waste emissions during production. This whole-chain green design from raw materials to process provides an innovative paradigm for sustainable material development.

[0079] The present application constructs a multifunctional composite bonding system through multi-dimensional performance optimization, which exhibits extensive engineering application adaptability. The synergistic effect of polyurethane, epoxy resin and acrylate in the ternary composite makes the material have high elastic modulus and excellent environmental resistance. The special designed microfluidic rapid cooling granulation process ensures the batch stability of the product, and the electrospinning technology realizes the precise shaping of complex shaped products. The resin performs well in the fields of building decoration, new energy equipment and medical devices, and its unique performance combination provides a new type of bonding material selection for high-end manufacturing.

[0080] Of course, implementing any product of the present application does not necessarily require achieving all the advantages described above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0081] Figure 1 The preparation method flow chart of the embodiment of the present application. DETAILED DESCRIPTION

[0082] The embodiment of the present application proposes a polyetherimide polyethylene composite bonding resin with high heat resistance and high bonding performance and a preparation method thereof.

[0083] Example 1: Standard Formulation Polyetherimide Polyethylene Composite Bonding Resin

[0084] Porous aromatic heterocyclic ceramic microspheres: 12 parts;

[0085] Ion liquid plasticized polytetrafluoroethylene superfine powder: 5 parts;

[0086] Liquid metal core-shell structure filler: 8 parts;

[0087] Bio-based cardo ring structure polyetherimide: 22 parts;

[0088] Cyclodextrin coated metallocene polyethylene: 45 parts;

[0089] Radiation grafted functionalized polyethylene: 35 parts;

[0090] Boron-silicon double bond containing functional monomer: 6 parts;

[0091] Hyperbranched polysiloxane: 4 parts;

[0092] Rare earth complex antioxidant: 2 parts;

[0093] Polyurethane, epoxy resin and acrylate ternary composite: 28 parts.

[0094] Example 2: Increase the content of bio-based cardo ring structure polyetherimide

[0095] Porous aromatic heterocyclic ceramic microspheres: 12 parts;

[0096] Ionic liquid plasticized polytetrafluoroethylene ultrafine powder: 5 parts;

[0097] Liquid metal core-shell structured filler: 8 parts;

[0098] Bio-based cardo structure polyetherimide: 30 parts;

[0099] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0100] Radiation-grafted functionalized polyethylene: 35 parts;

[0101] Boron-containing silicon double bond functional monomer: 6 parts;

[0102] Hyperbranched polysiloxane: 4 parts;

[0103] Rare earth complex antioxidant: 2 parts;

[0104] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0105] Example 3: Reduce the content of liquid metal core-shell structured filler

[0106] Porous aromatic heterocyclic ceramic microspheres: 12 parts;

[0107] Ionic liquid plasticized polytetrafluoroethylene ultrafine powder: 5 parts;

[0108] Liquid metal core-shell structured filler: 5 parts;

[0109] Bio-based cardo structure polyetherimide: 22 parts;

[0110] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0111] Radiation-grafted functionalized polyethylene: 35 parts;

[0112] Boron-containing silicon double bond functional monomer: 6 parts;

[0113] Hyperbranched polysiloxane: 4 parts;

[0114] Rare earth complex antioxidant: 2 parts;

[0115] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0116] Example 4: Enhance the bonding strength

[0117] Porous aromatic heterocyclic ceramic microspheres: 12 parts;

[0118] Ionic liquid plasticized polytetrafluoroethylene ultrafine powder: 5 parts;

[0119] Liquid metal core-shell structured filler: 8 parts;

[0120] Bio-based cardo-structured polyetherimide: 22 parts;

[0121] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0122] Radiation-grafted functionalized polyethylene: 45 parts;

[0123] Boron-containing silicon double bond functional monomer: 9 parts;

[0124] Hyperbranched polysiloxane: 4 parts;

[0125] Rare earth complex antioxidant: 2 parts;

[0126] Polyurethane, epoxy resin and acrylate ternary complex: 35 parts.

[0127] Example 5: Optimizing processing flowability

[0128] Porous aromatic heterocycle ceramic microspheres: 12 parts;

[0129] Ionic liquid plasticized polytetrafluoroethylene superfine powder: 8 parts;

[0130] Liquid metal core-shell structure filler: 8 parts;

[0131] Bio-based cardo-structured polyetherimide: 22 parts;

[0132] Cyclodextrin-coated metallocene polyethylene: 35 parts;

[0133] Radiation-grafted functionalized polyethylene: 35 parts;

[0134] Boron-containing silicon double bond functional monomer: 6 parts;

[0135] Hyperbranched polysiloxane: 6 parts;

[0136] Rare earth complex antioxidant: 2 parts;

[0137] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0138] Example 6: Improving thermal stability

[0139] Porous aromatic heterocycle ceramic microspheres: 15 parts;

[0140] Ionic liquid plasticized polytetrafluoroethylene superfine powder: 5 parts;

[0141] Liquid metal core-shell structure filler: 8 parts;

[0142] Bio-based cardo-structured polyetherimide: 28 parts;

[0143] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0144] Radiation grafted functionalized polyethylene: 35 parts;

[0145] Boron-containing silicon double bond functional monomer: 6 parts;

[0146] Hyperbranched polysiloxane: 4 parts;

[0147] Rare earth complex antioxidant: 4 parts;

[0148] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0149] Comparative Example 1: No bio-based polycyclo ring structure polyetherimide

[0150] Porous aromatic heterocycle ceramic microspheres: 12 parts;

[0151] Ionic liquid plasticized polytetrafluoroethylene superfine powder: 5 parts;

[0152] Liquid metal core-shell structure filler: 8 parts;

[0153] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0154] Radiation grafted functionalized polyethylene: 35 parts;

[0155] Boron-containing silicon double bond functional monomer: 6 parts;

[0156] Hyperbranched polysiloxane: 4 parts;

[0157] Rare earth complex antioxidant: 2 parts;

[0158] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0159] Comparative Example 2: No liquid metal core-shell structure filler

[0160] Porous aromatic heterocycle ceramic microspheres: 12 parts;

[0161] Ionic liquid plasticized polytetrafluoroethylene superfine powder: 5 parts;

[0162] Bio-based polycyclo ring structure polyetherimide: 22 parts;

[0163] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0164] Radiation grafted functionalized polyethylene: 35 parts;

[0165] Boron-containing silicon double bond functional monomer: 6 parts;

[0166] Hyperbranched polysiloxane: 4 parts;

[0167] Rare earth complex antioxidant: 2 parts;

[0168] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0169] Comparative Example 3: No boron-containing silicon double bond functional monomer

[0170] Porous aromatic heterocycle ceramic microspheres: 12 parts;

[0171] Ionic liquid plasticized polytetrafluoroethylene superfine powder: 5 parts;

[0172] Liquid metal core-shell structure filler: 8 parts;

[0173] Bio-based cardo ring structure polyetherimide: 22 parts;

[0174] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0175] Radiation grafted functionalized polyethylene: 35 parts;

[0176] Hyperbranched polysiloxane: 4 parts;

[0177] Rare earth complex antioxidant: 2 parts;

[0178] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0179] Comparative Example 4: No hyperbranched polysiloxane

[0180] Porous aromatic heterocycle ceramic microspheres: 12 parts;

[0181] Ionic liquid plasticized polytetrafluoroethylene superfine powder: 5 parts;

[0182] Liquid metal core-shell structure filler: 8 parts;

[0183] Bio-based cardo ring structure polyetherimide: 22 parts;

[0184] Cyclodextrin-coated metallocene polyethylene: 45 parts;

[0185] Radiation grafted functionalized polyethylene: 35 parts;

[0186] Boron-containing silicon double bond functional monomer: 6 parts;

[0187] Rare earth complex antioxidant: 2 parts;

[0188] Polyurethane, epoxy resin and acrylate ternary complex: 28 parts.

[0189] Experimental Example:

[0190] The properties of Examples 1-6 and Comparative Examples 1-4 above were determined, and the results are shown in Table 1. They include:

[0191] 1. Heat resistance test

[0192] The heat distortion temperature was measured by a heat distortion temperature tester at a heating rate of 2°C / min, and the 5% thermal weight loss temperature was recorded by a thermogravimetric analyzer.

[0193] 2. Adhesion strength test

[0194] The aluminum and aluminum lap shear strength was measured by a universal tensile testing machine according to ASTM D1002 standard, with a loading speed of 1.5 mm / min.

[0195] 3. Thermal conductivity test

[0196] The thermal diffusivity was measured by a laser thermal conductivity instrument at 25°C, and the thermal conductivity was calculated.

[0197] 4. Processing flowability test

[0198] The melt flow rate was measured by a melt indexer at 230°C under a load of 2.16 kg.

[0199] 5. Thermal stability test

[0200] The initial decomposition temperature and the residual carbon rate at 800°C were recorded by a thermogravimetric analyzer under nitrogen atmosphere at a heating rate of 10°C / min to 800°C.

[0201] Table 1. Experimental data of examples 1-6 and comparative examples 1-4 of the present application

[0202] Sample Heat distortion temperature (°C) Bonding strength (MPa) Thermal conductivity (W / m-K) Melt flow rate (g / 10 min) Initial decomposition temperature (°C) Char yield (%) Example 1 285 28.5 0.85 12.5 485 45.2 Example 2 315 26.8 0.82 9.8 510 48.6 Example 3 280 27.9 0.62 13.2 482 43.8 Example 4 288 35.2 0.87 10.5 490 46.5 Example 5 275 26.5 0.83 18.6 478 42.3 Example 6 305 27.8 0.88 11.2 525 51.8 Comparative Example 1 235 18.6 0.78 14.5 425 35.2 Comparative Example 2 270 25.3 0.35 13.8 465 38.6 Comparative Example 3 260 15.2 0.81 12.8 455 40.2 Comparative Example 4 278 24.8 0.79 8.5 475 41.5

[0203] From Table 1, the heat resistance performance is:

[0204] Increasing the content of bio-based cardo-structured polyetherimide (Example 2) and improving the thermal stability (Example 6) significantly improved the heat distortion temperature and the initial decomposition temperature of the material. The lack of bio-based cardo-structured polyetherimide (Comparative Example 1) led to a significant decrease in heat resistance performance.

[0205] Adhesion strength:

[0206] Example 4, which enhanced the adhesion strength, showed the highest adhesion strength, indicating that it effectively improved the interfacial bonding force by increasing the active crosslinking component. The lack of a boron-containing silicon double bond functional monomer (Comparative Example 3) led to a significant decrease in adhesion strength.

[0207] Thermal conductivity:

[0208] Standard formulation Example 1 showed balanced thermal conductivity, while reducing the content of liquid metal core-shell structure filler (Example 3) led to a significant decrease in thermal conductivity. The complete lack of liquid metal core-shell structure filler (Comparative Example 2) further deteriorated the thermal conductivity.

[0209] Processability:

[0210] Example 5, which was optimized for processability, exhibited the best melt flow properties, indicating that the synergistic effect of hyperbranched polysiloxane and ionic liquid plasticized PTFE ultrafine powder effectively improved the processability. The lack of hyperbranched polysiloxane (Comparative Example 4) resulted in a decrease in flowability.

[0211] Thermal stability:

[0212] Example 6, which was optimized for thermal stability, performed best in terms of carbon residue rate, demonstrating that the synergistic effect of porous heterocyclic ceramic microspheres and rare earth complex antioxidant effectively improved the thermal stability of the material.

[0213] Based on the above integrated experimental data, the high-heat-resistant and high-adhesion polyetherimide polyethylene composite bonding resin developed by the present application exhibits significant advantages in the fields of aerospace high-temperature structure bonding, electronic device heat-conducting packaging, new energy vehicle battery protection, and other high-end manufacturing fields through the synergistic effect of various components. Its unique bio-based rigid skeleton and dynamic crosslinking network design not only meet the use requirements in extreme environments, but also comply with the green and sustainable development concept. In the future, through further optimization of interface regulation processes and development of intelligent response characteristics, it will have a broader application prospect in the field of high-performance composites.

[0214] Although preferred embodiments of the application have been described, those skilled in the art will be able to make additional changes and modifications to these embodiments once they have the basic inventive concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of the present application.

[0215] Obviously, those skilled in the art can make various modifications and variations to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is also intended to include these modifications and variations.

Claims

1. A polyetherimide-polyethylene composite adhesive resin with high heat resistance and high bonding performance, characterized in that, According to the mass parts, it is composed of the following components: Porous aromatic heterocyclic ceramic microspheres: 8-15 parts; Ionic liquid plasticized polytetrafluoroethylene superfine powder: 3-8 parts; Liquid metal core-shell structure filler: 5-12 parts; Biobased cardo ring structure polyetherimide: 15-30 parts; Cyclodextrin coated metallocene polyethylene: 35-55 parts; Radiation grafting functionalized polyethylene: 25-45 parts; Boron-containing silicon double bond functional monomer: 4-9 parts; Hyperbranched polysiloxane: 2-6 parts; Rare earth complex antioxidant: 1-4 parts; Polyurethane, epoxy resin and acrylate ternary complex: 20-35 parts.

2. The polyetherimide polyethylene composite bonding resin of claim 1, wherein: The porous aromatic heterocyclic ceramic microspheres are multi-level porous structure ceramic microspheres sintered from aromatic heterocyclic polymer precursor by template method; The ionic liquid plasticized polytetrafluoroethylene superfine powder is a plasticized composite powder obtained by the reaction of polytetrafluoroethylene and ethylimidazolium tetrafluoroborate; The liquid metal core-shell structure filler is a core-shell structure particle formed by coating a silica shell on a gallium-indium-tin alloy by microfluidic electrospinning technology; The aromatic heterocyclic polymer precursor is a polymer solution obtained by mixing polyimide and benzoxazine resin at a mass ratio of 1:0.8-1:1.2; The mass ratio of polytetrafluoroethylene to ethylimidazolium tetrafluoroborate is 1:0.2-1:0.6; The mass ratio of gallium, indium and tin in the gallium-indium-tin alloy is 6:3:1-7:2:1, and the mass ratio of the gallium-indium-tin alloy to the silica is 1:0.2-1:0.

5.

3. The polyetherimide polyethylene composite bonding resin of claim 1, wherein: The biobased cardo ring structure polyetherimide is a polymer powder containing cardo ring structure obtained by polycondensation of biobased aromatic diamine and aromatic dianhydride; The cyclodextrin coated metallocene polyethylene is a coated composite particle formed by β-cyclodextrin supermolecule inclusion metallocene polyethylene; The radiation grafting functionalized polyethylene is a grafted polyethylene containing epoxy groups or anhydride groups; The hyperbranched polysiloxane is an amino-terminated hyperbranched polysiloxane; And, during the preparation process, the amino-terminated hyperbranched polysiloxane reacts with the epoxy groups or anhydride groups of the radiation grafting functionalized polyethylene and the terminal active groups of the biobased cardo ring structure polyetherimide, forming an in-situ chemical bridging interface layer between the polyethylene phase and the polyetherimide phase; The molar ratio of the biobased aromatic diamine to the aromatic dianhydride is 1:0.95-1:1.05; The mass ratio of the metallocene polyethylene to the β-cyclodextrin is 1:0.1-1:0.3; The amino-terminated hyperbranched polysiloxane is a dendritic polymer powder obtained by ring-opening polymerization of amino-terminated hyperbranched siloxane and octamethylcyclotetrasiloxane, and the mass ratio of the amino-terminated hyperbranched siloxane to the octamethylcyclotetrasiloxane is 1:0.8-1:1.

2.

4. The polyetherimide polyethylene composite bonding resin of claim 1, wherein: The boron-silicon double bond functional monomer is a complex functional monomer generated by esterification of vinyl boronic acid and methacryloyloxypropyl trimethoxysilane; the rare earth complex antioxidant is a rare earth particle formed by coordination of europium ions and acetylacetone; and the polyurethane, epoxy resin and acrylate ternary complex is a ternary hybrid powder generated by in-situ polymerization of polyurethane, epoxy resin and acrylate. The mass ratio of the vinyl boronic acid to the methacryloyloxypropyl trimethoxysilane is 1:1.5-1:2.

5. The molar ratio of the europium ions to the acetylacetone is 1:2-1:

3. The mass ratio of the polyurethane, the epoxy resin and the acrylate is 1:1:0.5-1:1:

1.

5. A process for the preparation of the polyetherimide polyethylene composite bonding resin according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: The porous aromatic heterocyclic ceramic microspheres and the boron-silicon double bond functional monomer are compounded by vacuum pressure impregnation technology to prepare a functionalized ceramic complex. The bio-based cardo structure polyetherimide, the cyclodextrin-coated metallocene polyethylene and the radiation grafted functionalized polyethylene are melt blended at 190-230 DEG C under an inert atmosphere by using ultrasonic-assisted solid-phase shearing grinding technology to preliminarily intertwine and activate the polymer chains, thereby obtaining a matrix blend. The functionalized ceramic complex, the ion liquid plasticized polytetrafluoroethylene superfine powder, the liquid metal core-shell structure filler, the hyperbranched polysiloxane and the rare earth complex antioxidant are added to the matrix blend, and the mixture is blended in an electromagnetic field oscillation blending device at 180-210 DEG C for 10-20 minutes. During the blending process, the hyperbranched polysiloxane, the bio-based cardo structure polyetherimide and the radiation grafted functionalized polyethylene undergo interface chemical reactions to obtain a catalytically activated mixture. The polyurethane, epoxy resin and acrylate ternary complex is added to the catalytically activated mixture, and microwave crosslinking is performed under the assistance of supercritical carbon dioxide to obtain a crosslinked complex. The crosslinked complex is cooled to room temperature in a microfluidic focusing rapid cooling device, and then homodirectional twin-screw melt electrospinning granulation is performed to obtain the polyetherimide polyethylene composite bonding resin.

6. The method of claim 5, wherein: The method for compounding the porous aromatic heterocyclic ceramic microspheres and the boron-silicon double bond functional monomer by vacuum pressure impregnation technology to prepare a functionalized ceramic complex comprises the following steps: The porous aromatic heterocyclic ceramic microspheres are placed in a vacuum impregnation device, and degassing treatment is performed on the ceramic microspheres under a vacuum degree of 0.1-0.5 kPa for 20-40 minutes to obtain degassed ceramic microspheres. The boron-silicon double bond functional monomer is heated to 40-60 DEG C, and then injected into the degassed ceramic microspheres at a pressure of 0.5-2 MPa for impregnation for 30-60 minutes to obtain the functionalized ceramic complex. The mass ratio of the degassed ceramic microspheres to the boron-silicon double bond functional monomer is 1:0.5-1:1.

2.

7. The method of claim 5, wherein: The matrix blend comprises: The bio-based cardo structure polyetherimide, cyclodextrin-coated metallocene polyethylene and the radiation grafted functionalized polyethylene are added into a solid-phase shearing grinding device in a mass ratio of 1:2.5:1.5-1:3:2, nitrogen is introduced to keep the oxygen content ≤50ppm, under the condition of ultrasonic frequency of 20-40kHz and amplitude of 5-15μm, the temperature is raised to 190-230℃ at a rate of 5-10℃ / min, and shearing grinding is performed for 15-30min to obtain the matrix blend.

8. The method of claim 5, wherein: The functionalized ceramic composite, ionic liquid plasticized polytetrafluoroethylene superfine powder, liquid metal core-shell structure filler, hyperbranched polysiloxane and the rare earth complex antioxidant are added into the matrix blend in an electromagnetic field oscillation blending device and blended at 180-210℃ for 10-20min. During the mixing process, the hyperbranched polysiloxane, bio-based cardo structure polyetherimide and radiation grafted functionalized polyethylene undergo interface chemical reaction to obtain a catalytically activated mixture, which includes: The matrix blend is transferred into the electromagnetic field oscillation blending device, and the functionalized ceramic composite, ionic liquid plasticized polytetrafluoroethylene superfine powder and liquid metal core-shell structure filler are sequentially added in a mass ratio of 1:0.4:0.6-1:0.8:1.2 under the condition of alternating electromagnetic field frequency of 1-5kHz and field strength of 0.5-2T, and mixed for 20-30min to obtain an initial mixed matrix. The hyperbranched polysiloxane and the rare earth complex antioxidant are added into the initial mixed matrix in a mass ratio of 1:0.2:0.1-1:0.4:0.3, and blended at 180-210℃ and 100-200rpm for 10-20min to obtain the catalytically activated mixture.

9. The method of claim 5, wherein: The crosslinked composite includes: The catalytically activated mixture, the polyurethane, epoxy resin and acrylate ternary composite are placed in a supercritical reaction kettle in a mass ratio of 1:0.5-1:1, treated under the condition of carbon dioxide supercritical pressure of 8-15MPa and temperature of 65-85℃, assisted by microwave radiation power of 500-1000W and frequency of 2.45GHz for 20-35min to obtain the crosslinked composite.

10. The method of claim 5, wherein: The crosslinked composite is cooled to room temperature by a microfluidic focusing rapid cooling device, and then subjected to melt electrospinning granulation by a co-rotating twin screw to obtain the polyetherimide polyethylene composite bonding resin, which includes: The crosslinked composite is rapidly cooled to 25-30℃ by the microfluidic focusing rapid cooling device under the condition of cooling medium temperature of-10 to 5℃ and flow rate of 2-5m / s to obtain a rapidly cooled solidified material; The rapidly cooled solidified material is fed into a co-rotating twin screw extruder, and subjected to melt extrusion under the condition of screw temperature of 180-200℃ and rotation speed of 200-400rpm, while an electrostatic voltage of 10-20kV is applied for spinning granulation to obtain the polyetherimide polyethylene composite bonding resin; wherein the particle size of the rapidly cooled solidified material is controlled to be 1-3mm, and the length of the particles of the polyetherimide polyethylene composite bonding resin is 2-4mm.

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