CN113185806B - Polyimide microsphere modified thermosetting resin-based composite material and preparation method and application thereof - Google Patents
Polyimide microsphere modified thermosetting resin-based composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyimide microsphere modified thermosetting resin-based composite material and a preparation method and application thereof. The preparation method comprises the following steps: firstly, adding the prepared polyimide microspheres into thermosetting resin for dispersion to obtain a uniform blend, then adding a certain amount of an auxiliary agent into the blend for continuous dispersion, then transferring the blend and pouring the blend into a mold, and degassing and curing to obtain the polyimide microsphere modified thermosetting resin-based composite material. The thermosetting resin composite material disclosed by the invention has the advantages of high mechanical property, excellent thermal stability, high heat resistance and the like, and has wide application prospects in the fields of printed circuit boards, electric appliance pouring and encapsulating materials, laminated materials, molds and the like.
Description
Technical Field
The invention belongs to the field of thermosetting resin materials, and particularly relates to a polyimide microsphere modified thermosetting resin-based composite material, and a preparation method and application thereof.
Background
Thermosetting resins are widely used in the fields of printed circuit boards, semiconductor packaging materials, engineering mechanical structural members, and the like because of their excellent electrical insulation, dimensional stability, and chemical resistance. However, the use of conventional thermosetting resins is limited due to their inherent high brittleness, poor crack resistance and weak impact resistance. Furthermore, with the continuous development of advanced microelectronic technology, the development of contamination-free lead-free solders is imperative, and higher reflow temperatures place higher demands on the thermal properties of a large number of thermosetting resins for semiconductor components and substrates. Therefore, researchers have tried to add various modifying materials (e.g., elastomers, inorganic nanoparticles) to improve the properties of thermosetting resins. Although the rubber elastomer can improve the toughness of the thermosetting resin, the strength, the elastic modulus and the thermal performance of the composite material are greatly reduced; the inorganic materials have poor compatibility with the thermosetting resin matrix, agglomeration is easy to occur, the relative density of some inorganic materials is high, and the modified composite material is difficult to achieve light weight. In addition, the thermoplastic resin modified thermosetting resin is expected to improve the mechanical property and the thermal property of the thermosetting resin in a coordinated manner, but the poor solubility of the thermoplastic resin can improve the viscosity of the blend, and a large amount of solvent is required to be used in the processing process, so that the process is complex, and the actual application requirement is difficult to meet.
In recent years, the use of preformed polymers in composite materials has received a great deal of scientific attention. Researchers adopt methods such as emulsion polymerization or suspension polymerization to prepare thermoplastic polymers into micro-nano particles, and then compound the micro-nano particles with other polymer matrixes, so that the respective advantages of two materials can be combined, the processing technology is simplified, and the comprehensive performance of the materials can be enhanced. For example, prasun Kumar Roy et al prepared epoxy-coated Polydimethylsiloxane (PDMS) microspheres with a particle size of 177-250 μm and then added the PDMS microspheres to room temperature cured unsaturated polyester significantly improved the impact strength and fracture energy of the thermoset, while the tensile strength and glass transition temperature were slightly reduced (P.K. Roy, N.Iqbal, D.Kumar, et al. Rubber penetration of unsamrated polyester with core-shell polymers [ J ]. Polymer Bulletin,2014, 71 (10): 2733-2748). Chaudhary et al added Amine-Functionalized polystyrene Microspheres (52-183 μm) prepared by a suspension polymerization process to an Epoxy resin, and when 3wt% Microspheres were added, the tensile strength, impact strength and fracture toughness of the prepared Epoxy resin composite were all significantly improved (Chaudhary, S. et al, amine-Functionalized Poly (styrene) Microspheres as Thermoplastic binder for Epoxy resin Composites 2015.36 (1): p.174-183). Chinese patent CN109456584A discloses a core-shell structure microsphere toughening unsaturated polyester resin material and a preparation method thereof. The method takes styrene and ethyl orthosilicate as main raw materials, polystyrene/silicon dioxide core-shell microspheres with the particle size of 50 nm-10 mu m are prepared through emulsion polymerization, and are subjected to ball milling, dilution and stirring together with unsaturated polyester to prepare resin mixed liquor, and then the resin mixed liquor is solidified to obtain the unsaturated resin composite material. The addition of the polystyrene/silicon dioxide core-shell microspheres can improve the toughness and the impact strength of the unsaturated resin. Chinese patent CN108752866A discloses a modified nano-polystyrene reinforced and toughened epoxy resin nano-composite material and a preparation method thereof, the method mechanically blends epoxy chloropropane modified polystyrene microspheres and epoxy resin at room temperature, and the tensile strength of the prepared epoxy resin nano-microsphere composite material is improved. Yang et al synthesized highly crosslinked poly (cyclotriphosphazene-resveratrol) (PRV) microspheres (about 1 μm) and used the resulting PRV microspheres to improve the flame retardancy and mechanical properties of epoxy resins. The prepared epoxy resin/PRV microsphere composite material has excellent thermal stability, and in addition, the PRV microspheres can play a role in mechanical reinforcement under the condition of uniform dispersion, so that the tensile property of the thermosetting resin is improved. (Yang, D.E., et al, synthesis of bio-based poly (cyclotriphosphazene-resveratrol) microspheres acting as bed flame retardant and regeneration agent to epoxide resins, polymers for Advanced Technologies,2020.31 (1): p.135-145)
Compared with the polymer microspheres, the polyimide microspheres have the advantages of high heat resistance, high strength, high solvent resistance and the like. At present, although there is a document or a patent that polyimide microspheres with controllable particle size and large specific surface area are prepared by an emulsion method, the microspheres are only applied to a small amount in the fields of electrode materials, isolation materials, low dielectric films and the like at present, and the polyimide microspheres are applied to thermosetting resin-based composite materials as a functional filler, so far, no document report is found. More importantly, the thermosetting resin-based composite material modified by the polyimide microspheres is expected to overcome the bottlenecks of difficult processing, high cost, limited application and the like of the existing polyimide, and can fully utilize the unique advantages of the polyimide microspheres to realize the synergistic improvement of the toughness, tensile strength, impact strength and thermal property of the thermosetting resin-based composite material.
Therefore, the polyimide microsphere modified high-performance thermosetting resin composite material is prepared by simply and physically blending the polyimide microsphere and the thermosetting resin. The polyimide microsphere modified thermosetting resin-based composite material is not reported in domestic and foreign documents.
Disclosure of Invention
The invention aims to overcome the defects of high brittleness, low thermal stability, low heat resistance and the like of some thermosetting resins at present, and provides a light polyimide microsphere modified thermosetting resin-based composite material with the functions of strengthening and toughening, high temperature resistance and the like, and a preparation method and application thereof.
The polyimide microsphere modified thermosetting resin-based composite material is prepared by utilizing polyimide microspheres, thermosetting resin and corresponding auxiliaries. Wherein the polyimide microspheres are prepared by a chemical imidization and thermal imidization two-step imidization method. The microsphere has adjustable particle size distribution, high thermal stability, high modulus and good solvent resistance.
The purpose of the invention is realized by the following technical scheme.
A thermosetting resin-based composite material modified by polyimide microspheres comprises thermosetting resin, polyimide microspheres and an auxiliary agent; the content of the polyimide microspheres in the composite material is 3wt% -8 wt%.
Preferably, the polyimide microspheres are fully imidized microspheres after two-step treatment of chemical imidization and thermal imidization.
Preferably, the average particle diameter of the polyimide microspheres is 1 to 50 μm.
Preferably, the auxiliary agent is one or more of a curing agent and an accelerator.
Preferably, the addition amount of the auxiliary agent in the composite material is 3-20 wt%.
Preferably, the auxiliary agent is one or more of diaminodiphenylmethane, m-phenylenediamine, cobalt naphthenate, methyl ethyl ketone peroxide and hexamethylene tetramine.
Preferably, the thermosetting resin is any one of epoxy resin, unsaturated polyester and phenolic resin.
The preparation method of the polyimide microsphere modified thermosetting resin-based composite material comprises the following steps:
s1: preparing polyimide microspheres with uniform particle size;
s2: adding the polyimide microspheres into thermosetting resin to obtain a uniformly dispersed blend;
s3: and adding the auxiliary agent into the blend for continuous dispersion, then transferring the blend, pouring the blend into a mold, and degassing and curing to obtain the polyimide microsphere modified thermosetting resin-based composite material.
Preferably, the curing temperature in the step S3 is 25-160 ℃; the continuous dispersion is stirring and ultrasound.
The polyimide microsphere modified thermosetting resin-based composite material is applied to the fields of preparation of printed circuit boards, pouring and encapsulating materials of electric appliances, laminating materials, molds and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention has excellent mechanical property that the polyimide microspheres are used as fillers, can be uniformly dispersed in a thermosetting resin matrix to form good interface bonding, and can restrain crack propagation by pinning cracks, deflecting or bridging the cracks. The polyimide microspheres can also be subjected to plastic deformation and tearing under dynamic damage, and the expansion energy of the damage energy is absorbed. In addition, cavitation caused by debonding of the polyimide microspheres from the thermoset resin matrix changes the state of matrix stress around the particles from planar strain to planar stress and causes shear deformation of the matrix, thereby dissipating large amounts of energy and significantly improving the strength and toughness of the thermoset resin.
(2) Good thermal properties: in the thermosetting resin-based composite material modified by the polyimide microspheres, the polyimide microspheres with high thermal stability can simultaneously and obviously improve the thermal stability and the heat resistance of the thermosetting resin, and realize the synergistic improvement of the mechanical property and the thermal property of the thermosetting resin.
(3) And (3) lightening: the polyimide microsphere modified thermosetting resin-based composite material prepared by the invention has lower density and can meet the requirement of lightweight manufacturing.
(4) Low dielectric properties: the intrinsic low dielectric constant of the polyimide is benefited, compared with the traditional thermosetting resin modified by inorganic filler, the dielectric constant of the thermosetting resin-based composite material modified by the polyimide microspheres prepared by the invention is obviously reduced, and the polyimide microsphere modified thermosetting resin-based composite material can be widely applied to the fields of microelectronic industrial components and parts, high-performance laminated plates and the like which have requirements on reducing circuit signal delay.
(5) The process is simple and easy to implement: the polyimide microsphere modified thermosetting resin-based composite material prepared by the invention has simple and easy molding process and does not need complex solvent treatment; the polyimide microspheres have a good gain effect under a low addition amount, and have potential industrial value. This also provides a new direction for the application of polyimides in modified polymers.
Detailed Description
The present invention is further described in detail with reference to specific examples, which are implemented on the premise of the technical solution of the present invention, but the implementation manner of the present invention is not limited thereto, and for the process parameters not specifically noted, reference may be made to the conventional techniques.
Example 1
Under nitrogen atmosphere, 2.002g (10 mmol) of 4,4' -diaminodiphenyl ether is dissolved in 17.6ml of N, N-dimethylformamide, added into a mixed solution containing 70.7ml of liquid paraffin and 8.55g of Span85/Tween80 compound surfactant (the mass ratio of Span85 to Tween80 is 4: 1), and subjected to ultrasonic treatment and stirring at 40 ℃ to emulsify for 2 hours to form stable emulsion. 2.224g (10.2 mmol) of pyromellitic anhydride were added portionwise to the above emulsion at 0 ℃ and the polycondensation was carried out with stirring for 6h until no solid was present in the solution. And slowly dropwise adding a pyridine/acetic anhydride mixed solution with the molar ratio of 1: 1 (the molar ratio of acetic anhydride to pyromellitic anhydride is 1: 0.2) into the polymer solution system under the condition of normal temperature and stirring, carrying out chemical imidization for 2 hours, taking out, centrifuging to obtain a solid, and respectively cleaning the solid for 3 times by using petroleum ether and acetone. And transferring the solid into a vacuum tube furnace, heating and preserving heat according to a set program, preserving heat for 1h at 100 ℃,150 ℃, 200 ℃, 250 ℃ and 300 ℃, and cooling to room temperature to obtain the polyimide microspheres with the average particle size of 30 mu m.
Adding 0.779g of fully imidized polyimide microspheres with the average particle size of 30 mu m (the content of the polyimide microspheres in the blend is 3 wt%) into 20g of epoxy resin E-51 at a hot water bath of 80 ℃, carrying out ultrasonic treatment and stirring for 1h, then adding 5.190g of curing agent diaminodiphenylmethane (the content of the diaminodiphenylmethane in the blend is 20 wt%), continuing carrying out ultrasonic treatment and stirring for dispersion for 30min, then carrying out vacuum degassing for 30min, transferring the blend and pouring into a preheated polytetrafluoroethylene standard mold, curing at 110 ℃ for 1h, curing at 130 ℃ for 2h, then raising the temperature to 160 ℃ for 1h, and cooling to obtain the polyimide microsphere modified thermosetting resin-based composite material.
Example 2
Under nitrogen atmosphere, 2.002g (10 mmol) of 4,4' -diaminodiphenyl ether is dissolved in 17.6ml of N, N-dimethylformamide, added into a mixed solution containing 70.7ml of liquid paraffin and 13.58g of Span85/Tween80 compound surfactant (the mass ratio of Span85 to Tween80 is 4: 1), and subjected to ultrasonic treatment and stirring at 40 ℃ to emulsify for 2 hours to form stable emulsion. 2.224g (10.2 mmol) of pyromellitic anhydride were added portionwise to the above emulsion at 0 ℃ and the polycondensation was carried out with stirring for 6h until no solid was present in the solution. And slowly dropwise adding a pyridine/acetic anhydride mixed solution with the molar ratio of 1: 1 (the molar ratio of acetic anhydride to pyromellitic anhydride is 1: 0.2) into the polymer solution system under the condition of normal temperature and stirring, carrying out chemical imidization for 2 hours, taking out, centrifuging to obtain a solid, and respectively cleaning the solid for 3 times by using petroleum ether and acetone. And transferring the solid into a vacuum tube furnace, heating and preserving heat according to a set program, preserving heat for 1h at 100 ℃,150 ℃, 200 ℃, 250 ℃ and 300 ℃, and cooling to room temperature to obtain the polyimide microspheres with the average particle size of 10 mu m.
Adding 2.13g of fully imidized polyimide microspheres with the average particle size of 10 mu m into 20g of epoxy resin E-44 (the content of the polyimide microspheres in the blend is 8 wt%) in a hot water bath at 70 ℃, carrying out ultrasonic treatment and stirring for 100min, then adding 4.530g of curing agent m-phenylenediamine (the content of the m-phenylenediamine in the blend is 17 wt%), continuing carrying out ultrasonic treatment and stirring for dispersion for 30min, then carrying out vacuum degassing for 20min, transferring the blend, pouring the blend into a preheated polytetrafluoroethylene standard die, curing for 1h at 120 ℃, curing for 2h at 150 ℃, and cooling to obtain the polyimide microsphere modified thermosetting resin-based composite material. The composite material has excellent thermal stability, and the maximum thermal weight loss rate temperature and the thermal residual rate of the composite material are both obviously improved.
Example 3
Under nitrogen atmosphere, 2.002g (10 mmol) of 4,4' -diaminodiphenyl ether is dissolved in 17.6ml of N, N-dimethylformamide, added into a mixed solution containing 70.7ml of liquid paraffin and 19.24g of Span85/Tween80 compound surfactant (the mass ratio of Span85 to Tween80 is 4: 1), and subjected to ultrasonic treatment and stirring at 40 ℃ to emulsify for 2h to form stable emulsion. To the above emulsion was added 2.224g (10.2 mmol) of pyromellitic anhydride in portions at 0 ℃ and polycondensation was carried out for 6h with stirring until no solid was present in the solution. And slowly dropwise adding a pyridine/acetic anhydride mixed solution with the molar ratio of 1: 1 (the molar ratio of acetic anhydride to pyromellitic anhydride is 1: 0.2) into the polymer solution system under the condition of normal temperature and stirring, carrying out chemical imidization for 2 hours, taking out, centrifuging to obtain a solid, and respectively cleaning the solid for 3 times by using petroleum ether and acetone. And transferring the solid into a vacuum tube furnace, heating and preserving heat according to a set program, preserving heat for 1h at 100 ℃,150 ℃, 200 ℃, 250 ℃ and 300 ℃, and cooling to room temperature to obtain the polyimide microspheres with the average particle size of 1 mu m.
Taking 1.08g of fully imidized polyimide microspheres with the average particle size of 1 mu m, adding the fully imidized polyimide microspheres into 20g of unsaturated polyester 191 (the content of the polyimide microspheres in the blend is 5 wt%) in a hot water bath at 60 ℃, carrying out ultrasonic treatment and stirring for 2h, then sequentially adding 0.217g of promoter cobalt naphthenate and 0.435g of curing agent methyl ethyl ketone peroxide (the content of the cobalt naphthenate and the methyl ethyl ketone peroxide in the blend is 3 wt%), continuing carrying out ultrasonic treatment and stirring for dispersion for 10min, then carrying out vacuum degassing for 10min, transferring the blend, pouring the blend into a polytetrafluoroethylene standard mold, and curing for 20h at normal temperature (25 ℃) to obtain the thermosetting resin-based composite material modified by the polyimide microspheres. Compared with pure unsaturated polyester, the glass transition temperature of the composite material is obviously improved, and the composite material has better heat resistance.
Example 4
Under nitrogen atmosphere, 2.002g (10 mmol) of 4,4' -diaminodiphenyl ether is dissolved in 17.6ml of N, N-dimethylformamide, added into a mixed solution containing 70.7ml of liquid paraffin and 6.70g of Span85/Tween80 compound surfactant (the mass ratio of Span85 to Tween80 is 4: 1), and subjected to ultrasonic treatment and stirring at 40 ℃ to emulsify for 2 hours to form stable emulsion. To the above emulsion was added 2.224g (10.2 mmol) of pyromellitic anhydride in portions at 0 ℃ and polycondensation was carried out for 6h with stirring until no solid was present in the solution. And slowly dropwise adding a pyridine/acetic anhydride mixed solution with the molar ratio of 1: 1 (the molar ratio of acetic anhydride to pyromellitic anhydride is 1: 0.2) into the polymer solution system under the condition of normal temperature and stirring, carrying out chemical imidization for 2 hours, taking out, centrifuging to obtain a solid, and respectively cleaning the solid for 3 times by using petroleum ether and acetone. And transferring the solid into a vacuum tube furnace, heating and preserving heat according to a set program, preserving heat for 1h at 100 ℃,150 ℃, 200 ℃, 250 ℃ and 300 ℃, and cooling to room temperature to obtain the polyimide microspheres with the average particle size of 50 microns.
Taking 2.13g of fully imidized polyimide microspheres with the average particle size of 50 mu m, adding the fully imidized polyimide microspheres into 40g of phenolic resin 2130 at 70 ℃ in a hot water bath (the content of the polyimide microspheres in the blend is 4 wt%), carrying out ultrasonic treatment and stirring for 1.5h, then adding 4.651g of curing agent hexamethylene tetramine (the content of the hexamethylene tetramine in the blend is 10 wt%), continuing carrying out ultrasonic treatment and stirring for dispersion for 40min, then carrying out vacuum degassing for 40min, transferring the blend and pouring the blend into a preheated polytetrafluoroethylene standard mold, curing for 2h at 100 ℃, curing for 2h at 130 ℃ and cooling to obtain the polyimide microsphere modified thermosetting resin-based composite material.
To more clearly illustrate the performance advantages of the thermosetting resin-based composite material prepared by the invention, the thermal weight loss behavior of the material at 25-700 ℃ is measured by a HAAKE400P thermogravimetric analyzer (TGA, netsch, germany) under an air atmosphere. The dynamic thermo-mechanical properties of the materials were measured in the range of 25 to 280 c (5 c/min, 1 Hz) using a dynamic mechanical analyzer Q800 (DMA, usa, TA). The quasi-static tensile properties (according to ISO standard 527) of the polyimide microsphere modified thermosetting resin composite standard specimens (type IV dumbbell specimens, 75 mm. Times.5 mm. Times.2 mm) prepared in examples 1 to 4 and comparative examples 1 to 4 were measured by an AGS-10KNI electronic Universal Material Servo (Shimadzu, japan). To evaluate the fracture toughness of the material; the single-edge notched three-point bending test (according to standard ISO-13586) was carried out using the same instrument on standard bars (notched bar, 80 mm. Times.10 mm. Times.4 mm, residual thickness 7.5 mm). The impact strength of the polyimide microsphere-modified thermosetting resin composite standard specimens (80 mm. Times.10 mm. Times.4 mm) prepared in examples 1 to 4 and comparative examples 1 to 4 was measured using a simple beam impact tester (SUNS, inc., china) (according to the standard ISO-180). The mechanical and thermal property test results of the polyimide microsphere modified thermosetting resin-based composite materials prepared in examples 1 to 4 and the corresponding unmodified thermosetting resins are summarized in tables 1 and 2, respectively.
TABLE 1
TABLE 2
As can be seen from table 1, the polyimide microsphere modified thermosetting resin-based composite materials prepared in examples 1 to 4 have significantly enhanced tensile strength, fracture toughness, and impact strength, as compared to the corresponding unmodified thermosetting resins. The polyimide microsphere modified thermosetting resin-based composite material prepared by the method has good reinforcing and toughening effects.
As can be seen from table 2, compared with the corresponding unmodified thermosetting resin, the polyimide microsphere modified thermosetting resin-based composite materials prepared in examples 1 to 4 have significantly improved maximum thermal weight loss rate temperature, residual amount, and glass transition temperature, significantly enhanced thermal stability and heat resistance, and more excellent thermal properties.
To better illustrate the necessity of adding polyimide microspheres having an average particle size of 1 to 50 μm and an addition amount of 3 to 8% to a thermosetting resin in the present invention, on the basis of examples 2 and 3, comparative examples 1 to 4 examined the influence of the average particle size of the added polyimide microspheres of 60 μm and 100 μm or the addition amount of polyimide microspheres of 1wt% and 9wt% on a thermosetting resin-based composite material.
Comparative example 1
In this comparative example, the blending process of the epoxy resin E-44 and the polyimide microspheres, the addition amount of the curing agent, and the curing temperature conditions were the same as those of example 2 except that the average particle diameter of the polyimide microspheres used was changed to 60 μm. The tensile strength of the obtained thermosetting resin-based composite material is 58Mpa, and the fracture toughness K IC Is 1.35Mpa m 1/2 Specific energy to break G IC Is 1.27KJ/m 2 Impact strength of 7.5KJ/m 2 。
Comparative example 2
In this comparative example, the blending process of the epoxy resin E-44 and the polyimide microspheres, the addition amount of the curing agent, and the curing temperature conditions were the same as those of example 2 except that the average particle diameter of the polyimide microspheres used was changed to 100. Mu.m. The obtained thermosetting resin-based composite material has tensile strength of 48Mpa and fracture toughness K IC Is 0.92 mpa.m 1/2 Specific energy to break G IC Is 0.86KJ/m 2 Impact strength of 3.5KJ/m 2 。
Comparative example 3
In the comparative example, the blending process, the addition amount of the curing agent and the curing temperature conditions of the unsaturated polyester 191 and the polyimide microspheres are the same as those of example 3, and only the addition amount of the polyimide microspheres is changed to 1wt%. The tensile strength of the obtained thermosetting resin-based composite material is 36Mpa, and the fracture toughness K IC Is 0.96Mpa m 1/2 Specific energy to break G IC Is 0.95KJ/m 2 Impact strength of 2.9KJ/m 2 。
Comparative example 4
In the comparative example, the blending process, the addition amount of the curing agent and the curing temperature conditions of the unsaturated polyester 191 and the polyimide microspheres are the same as those in example 3, and only the addition amount of the polyimide microspheres is changed to 9wt%. The obtained thermosetting resin-based composite material has tensile strength of 30Mpa and fracture toughness K IC Is 0.77 Mpa.m 1/2 Proportional to absolute deviationEnergy of rupture G IC Is 0.75KJ/m 2 Impact strength of 2.2KJ/m 2 。
In order to more clearly illustrate the advantages of controlling the average particle size of the added polyimide microspheres to be 1 to 50 μm and controlling the addition amount thereof to be 3 to 8wt%, the mechanical property test results of examples 2 and 4 and comparative examples 1 to 4 are summarized in table 3.
TABLE 3
As can be seen from Table 3, when the average particle size of the added polyimide microspheres is larger than 50 μm, the mechanical properties of the obtained thermosetting resin-based composite material are low, the improvement is small, and when the average particle size reaches 100 μm, the mechanical properties of the composite material are lower than those of the modified resin. In example 2, the tensile strength was 78 MPa and the impact strength was 12.5KJ/m after adding the polyimide microspheres having an average particle size of 10 μm 2 And the fracture toughness is also greatly improved. On the other hand, when the addition amount of the polyimide microspheres is 1wt%, the mechanical properties of the composite material are almost unchanged, and when the addition amount is 9wt%, the mechanical properties are obviously reduced compared with unmodified resin.
The above examples and comparative examples of the present invention are only specific examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. It will be apparent to those skilled in the art that other variations on the foregoing description may be made. Any simple modifications, equivalent variations and improvements made to the above embodiments according to the technical and methodological principles of the invention are intended to be included within the scope of the claims.
Claims (5)
1. A polyimide microsphere modified thermosetting resin-based composite material is characterized by comprising thermosetting resin, polyimide microspheres and an auxiliary agent; the content of the polyimide microspheres in the composite material is 3-8 wt%;
the polyimide microspheres are completely imidized microspheres after two-step treatment of chemical imidization and thermal imidization;
when the thermosetting resin is epoxy resin, the auxiliary agent is one or two of diaminodiphenylmethane and m-phenylenediamine;
when the thermosetting resin is unsaturated polyester, the auxiliary agent is one or more of cobalt naphthenate, methyl ethyl ketone peroxide and hexamethylene tetramine;
the average grain size of the polyimide microspheres is 1-50 mu m.
2. The polyimide microsphere modified thermosetting resin-based composite material as claimed in claim 1, wherein the additive is added in an amount of 3-20 wt% in the composite material.
3. The preparation method of the polyimide microsphere modified thermosetting resin-based composite material as claimed in any one of claims 1 to 2, characterized by comprising the following steps:
s1: preparing polyimide microspheres with uniform particle size;
s2: adding the polyimide microspheres into thermosetting resin to obtain a uniformly dispersed blend;
s3: and adding the auxiliary agent into the blend for continuous dispersion, then transferring the blend, pouring the blend into a mold, and degassing and curing to obtain the polyimide microsphere modified thermosetting resin-based composite material.
4. The method for preparing the resin composition according to claim 3, wherein the curing temperature in the step S3 is 25 ℃ to 160 ℃; the continuous dispersion is stirring and ultrasonic.
5. The use of a polyimide microsphere modified thermosetting resin-based composite material as claimed in any one of claims 1 to 2 in the preparation of printed circuit boards, electrical appliance casting and potting materials, laminates and molds.
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| JP2011082480A (en) * | 2009-03-13 | 2011-04-21 | Sekisui Chem Co Ltd | Die attach film and dicing die attach film |
| JP2016150483A (en) * | 2015-02-17 | 2016-08-22 | 住友ベークライト株式会社 | Release film and production method of molding |
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