CN113201109B - Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material - Google Patents

Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material Download PDF

Info

Publication number
CN113201109B
CN113201109B CN202110499410.5A CN202110499410A CN113201109B CN 113201109 B CN113201109 B CN 113201109B CN 202110499410 A CN202110499410 A CN 202110499410A CN 113201109 B CN113201109 B CN 113201109B
Authority
CN
China
Prior art keywords
carbon material
based composite
composite material
resin based
benzoxazine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110499410.5A
Other languages
Chinese (zh)
Other versions
CN113201109A (en
Inventor
王智
杜杰
李水泉
刘浩浪
刘占鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North University of China
Original Assignee
North University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North University of China filed Critical North University of China
Priority to CN202110499410.5A priority Critical patent/CN113201109B/en
Publication of CN113201109A publication Critical patent/CN113201109A/en
Application granted granted Critical
Publication of CN113201109B publication Critical patent/CN113201109B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The invention relates to the field of resin synthesis and modification, in particular to a method for preparing a benzoxazine resin based composite material by in-situ dispersion of a carbon material; the preparation method comprises the steps of dispersing a carbon material in m-cresol by ultrasonic and stirring for 1 hour, then reacting the m-cresol with a well-dispersed carbon material as a phenol source and primary amine as an amine source with paraformaldehyde to synthesize a benzoxazine monomer with the carbon material dispersed in situ, and performing thermocuring to obtain the carbon material/benzoxazine resin matrix composite material. The resin has the advantages of easily obtained raw materials, simple steps, environmental friendliness, no need of any solvent, optimized preparation process and easy realization of industrial production.

Description

Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material
Technical Field
The invention relates to the field of resin synthesis and modification, in particular to a method for preparing a benzoxazine resin based composite material by using an in-situ dispersed carbon material.
Background
Benzoxazines are a new class of thermosetting phenolic resins with many attractive properties, such as no by-products during curing, very low melt viscosity, good adhesion properties, high glass transition temperature of the polymer, high thermal stability, good mechanical strength and modulus, low dielectric constant and high resistance to combustion and chemicals. The extremely low melt viscosity and good adhesion of benzoxazine resins allow them to be easily wetted and mixed with fillers during the molding compound preparation process, with excellent matrix material properties, especially for the manufacture of highly filled composites. The carbon material mainly comprises activated carbon, carbon fiber, graphene, graphite, a carbon nanotube, diamond, fullerene and the like. The carbon material has a series of excellent characteristics of small density, high strength, good rigidity, high temperature resistance, chemical corrosion resistance, radiation resistance, fatigue resistance, high electric conductivity, high heat conductivity, ablation resistance, small thermal expansion, good physiological compatibility and the like, is a new material for military and civil use, and is called as a fourth type industrial material. The material is widely applied to the fields of metallurgy, chemical industry, machinery, automobiles, medical treatment, environmental protection, daily life of buildings and the like, and is an indispensable engineering structure material for doors of the aerospace and nuclear industries.
However, difficult dispersion and high cost are key factors affecting the use performance and application of carbon materials. It is difficult to obtain a uniformly dispersed carbon material even in an organic solvent having good dispersibility. Meanwhile, the carbon material is incompatible with most organic polymers, and is easy to agglomerate in the organic polymers with high viscosity, and the thermal and electrical properties of the carbon material/resin composite material are greatly reduced due to the serious agglomeration problem.
The existing method for improving the dispersibility of the carbon material is mainly to modify the carbon material by surface functionalization. Acid-base treatment, covalent or non-covalent modification are reported to be important methods for surface modification. However, it is a great problem to sufficiently remove the solvent used for modification in the case of ensuring that the carbon material is well dispersed without affecting the polymerization of the resin. The other method is to prepare a high-porosity graphene three-dimensional network in advance to improve the dispersibility of the graphene and form a heat-conducting through network. For example, graphene sponge, foam, aerogel, etc. are first prepared, followed by impregnation of the polymer. However, the preparation processes of the methods are complex and long in period, and the method is not beneficial to large-scale preparation of the carbon material resin matrix composite material.
Disclosure of Invention
The invention aims to provide a method for preparing a benzoxazine resin based composite material by using an in-situ dispersed carbon material. The carbon material/benzoxazine resin based composite material with good dispersion is obtained by a low-cost and simple method, so that the problems in the prior art are solved, and the carbon material forms a perfect and uniform inorganic network in the composite material. The results of electric conduction and heat conduction tests show that compared with the method for preparing the benzoxazine resin based composite material by using other dispersed carbon materials, the electric conduction and heat conduction properties of the benzoxazine resin based composite material prepared by using the in-situ dispersed carbon material are obviously improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing a benzoxazine resin based composite material by in-situ dispersing a carbon material comprises the steps of dispersing the carbon material in m-cresol by ultrasound and stirring for 1 hour, then taking the m-cresol of the well-dispersed carbon material as a phenol source, taking primary amine as an amine source, reacting with paraformaldehyde to synthesize a benzoxazine monomer of the in-situ dispersed carbon material, and thermally curing to obtain the carbon material/benzoxazine resin based composite material.
Further, the carbon material is graphene or carbon nanotubes.
Further, the amine source is one of aniline, methylamine, n-propylamine, cyclohexylamine, benzylamine, diaminophenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone or hexamethylenediamine.
Further, the mass ratio of the carbon material to m-cresol is 1: 100 to 1: 10, respectively.
Further, the mol ratio of the m-cresol to the primary amine to the paraformaldehyde is 1: 2: 1.
further, m-cresol, primary amine and paraformaldehyde react to synthesize the benzoxazine monomer of the in-situ dispersed carbon material by a solvent-free method of heating and stirring at 95 ℃ for 1 hour.
Further, the synthesized benzoxazine monomer was subjected to vacuum drying at 100 ℃ for 2 hours before thermal curing.
Further, the thermal curing condition is that the benzoxazine monomer is thermally cured for two hours at 160 ℃ and 170 ℃.
The invention also provides the carbon material/benzoxazine resin based composite material prepared by the preparation method.
In addition, the invention also provides application of the carbon material/benzoxazine resin based composite material in preparation of electric and heat conducting materials.
Compared with the prior art, the invention has the following beneficial effects:
the benzoxazine resin prepared by the invention is uniformly and stably dispersed with carbon materials, and the carbon materials form a perfect and uniform inorganic network in the composite material, so that the electric conduction and heat conduction properties of the benzoxazine resin based composite material are obviously improved.
The resin has the advantages of easily obtained raw materials, simple steps, environmental friendliness, no need of any solvent, optimized preparation process and easy realization of industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum diagram of a carbon material/benzoxazine resin based composite material prepared by in-situ dispersion of graphene (in FIG. 1, hydrogen atoms in methyl groups on 2.18ppm of m-cresol, 4.58ppm is-CH)2H atom in-N-, 5.32ppm of-O-CH2H atom in N-, 6.7 to 7.3ppm is proton absorption peak on benzene ring).
Fig. 2 is a real object diagram of the benzoxazine monomer prepared by in-situ dispersion of graphene (after 6 months of the benzoxazine monomer prepared by in-situ dispersion of a carbon material, the graphene still maintains good dispersibility in the benzoxazine monomer).
FIG. 3 is a diagram of a sample prepared by in-situ dispersing graphene and carbon nanotubes to obtain a benzoxazine resin based composite material (wherein the left and right diagrams are respectively a wafer with a diameter of 2cm and a thickness of 1mm, which is prepared by in-situ dispersing graphene and carbon nanotubes to prepare the benzoxazine resin based composite material).
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Firstly, mixing graphene and m-cresol in a mass ratio of 1: dispersing the mixture in m-cresol by 20 ultrasonic waves and stirring for 1 hour, and then reacting the m-cresol with a well-dispersed carbon material as a phenol source and aniline as an amine source with paraformaldehyde, wherein the molar ratio of the m-cresol to the aniline to the paraformaldehyde is 1: 2: 1, synthesizing a benzoxazine monomer (shown in figure 2) of an in-situ dispersed carbon material by a solvent-free method under the condition of heating at 95 ℃ for 1 hour, drying the benzoxazine monomer in vacuum at 100 ℃ for 1 hour, and then thermally curing the benzoxazine monomer at 160 ℃ and 170 ℃ for two hours respectively to obtain the carbon material/benzoxazine resin matrix composite material (a real object is shown in figure 3, and a nuclear magnetic hydrogen spectrum of the composite material is shown in figure 1). The measured thermal conductivity coefficient is as high as 2.06W/mK, and the maximum in-plane electrical conductivity is 3.53S/cm. The thermal conductivity of pure polybenzoxazine is only 0.17W/mK. The benzoxazine resin based composite material prepared by physically blending and dispersing the same content of graphene has the measured thermal conductivity coefficient of 0.42W/mK and the highest in-plane conductivity of 1.52S/cm.
Example 2
Firstly, mixing carbon nano tubes and m-cresol according to a mass ratio of 1: 10, dispersing in m-cresol by ultrasonic and stirring for 1 hour, and then reacting with paraformaldehyde by taking the m-cresol with well dispersed carbon nano tubes as a phenol source and aniline as an amine source, wherein the molar ratio of the m-cresol to the aniline to the paraformaldehyde is 1: 2: 1, synthesizing a benzoxazine monomer of an in-situ dispersed carbon material by a solvent-free method under the condition of heating at 95 ℃ for 1 hour, and then thermally curing the benzoxazine monomer at 160 ℃ and 170 ℃ for two hours respectively to obtain the carbon material/benzoxazine resin-based composite material (a substance is shown in figure 3). The measured thermal conductivity coefficient is as high as 2.52W/mK, and the highest in-plane electrical conductivity is 3.91S/cm. The thermal conductivity of pure polybenzoxazine is only 0.17W/mK. The benzoxazine resin based composite material prepared by physically blending and dispersing the carbon nano tubes with the same content has the measured thermal conductivity coefficient of 0.58W/mK and the highest in-plane conductivity of 2.03S/cm.

Claims (9)

1. A method for preparing a benzoxazine resin based composite material by in-situ dispersing a carbon material is characterized in that the carbon material is dispersed in m-cresol by ultrasonic and stirring for 1 hour, then the m-cresol of the well-dispersed carbon material is taken as a phenol source, primary amine is taken as an amine source, and reacts with paraformaldehyde to synthesize a benzoxazine monomer of the in-situ dispersed carbon material, and the benzoxazine monomer is thermally cured to obtain the carbon material/benzoxazine resin based composite material; the carbon material is graphene or carbon nanotubes.
2. The method for preparing the benzoxazine resin based composite material according to claim 1, wherein the amine source is one of aniline, methylamine, n-propylamine, cyclohexylamine, benzylamine, diaminodiphenyl ether, diaminodiphenyl sulfone or hexamethylenediamine.
3. The method for preparing the benzoxazine resin based composite material according to claim 1, wherein the mass ratio of the carbon material to m-cresol is 1: 100 to 1: 10, respectively.
4. The method for preparing the benzoxazine resin based composite material according to claim 1, wherein the molar ratio of m-cresol, primary amine and paraformaldehyde is 1: 2: 1.
5. the method for preparing the benzoxazine resin based composite material according to claim 1, wherein the reaction of m-cresol, primary amine and paraformaldehyde is performed by heating and stirring at 95 ℃ for 1 hour by a solvent-free method to synthesize the benzoxazine monomer of the in-situ dispersed carbon material.
6. The method for preparing the benzoxazine resin based composite material according to claim 1, wherein the synthesized benzoxazine monomer is subjected to vacuum drying at 100 ℃ for 2 hours before thermal curing.
7. The method for preparing the benzoxazine resin based composite material according to claim 1, wherein the thermal curing condition is that benzoxazine monomers are thermally cured at 160 ℃ and 170 ℃ for two hours respectively.
8. A carbon material/benzoxazine resin based composite material produced by the production method according to any one of claims 1 to 7.
9. Use of the carbon material/benzoxazine resin based composite material according to claim 8 in the preparation of an electrically and thermally conductive material.
CN202110499410.5A 2021-05-08 2021-05-08 Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material Active CN113201109B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110499410.5A CN113201109B (en) 2021-05-08 2021-05-08 Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110499410.5A CN113201109B (en) 2021-05-08 2021-05-08 Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material

Publications (2)

Publication Number Publication Date
CN113201109A CN113201109A (en) 2021-08-03
CN113201109B true CN113201109B (en) 2022-05-24

Family

ID=77030452

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110499410.5A Active CN113201109B (en) 2021-05-08 2021-05-08 Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material

Country Status (1)

Country Link
CN (1) CN113201109B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004103495A (en) * 2002-09-12 2004-04-02 Sansho Kako:Kk Fuel cell separator, its manufacturing method, and fuel cell using the fuel cell separator
CN105111437A (en) * 2015-09-28 2015-12-02 中国地质大学（武汉） Functionalized graphene oxide enhanced benzoxazine-based composite resin and preparation method thereof
CN107973888A (en) * 2017-12-05 2018-05-01 武汉理工大学 A kind of functional graphene oxide/full bio-based benzoxazine colophony composite material and preparation method thereof
CN109180889A (en) * 2018-08-31 2019-01-11 淮北绿洲新材料有限责任公司 A kind of preparation method and applications of full biological source benzoxazine resin
KR20200124356A (en) * 2019-04-23 2020-11-03 단국대학교 산학협력단 Method for preparation of carbon-benzoxazine complex and its carbon-polymer composite material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004103495A (en) * 2002-09-12 2004-04-02 Sansho Kako:Kk Fuel cell separator, its manufacturing method, and fuel cell using the fuel cell separator
CN105111437A (en) * 2015-09-28 2015-12-02 中国地质大学（武汉） Functionalized graphene oxide enhanced benzoxazine-based composite resin and preparation method thereof
CN107973888A (en) * 2017-12-05 2018-05-01 武汉理工大学 A kind of functional graphene oxide/full bio-based benzoxazine colophony composite material and preparation method thereof
CN109180889A (en) * 2018-08-31 2019-01-11 淮北绿洲新材料有限责任公司 A kind of preparation method and applications of full biological source benzoxazine resin
KR20200124356A (en) * 2019-04-23 2020-11-03 단국대학교 산학협력단 Method for preparation of carbon-benzoxazine complex and its carbon-polymer composite material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Highly Filled Graphene-Benzoxazine Composites as Bipolar Plates in Fuel Cell Applications;Plengudomkit, R 等;《POLYMER COMPOSITES》;20160630;第37卷(第6期);第1715-1727页 *
苯并噁嗪/氧化石墨烯导热复合材料的制备与性能研究;孟献瑞 等;《中国塑料》;20180930;第32卷(第9期);第78-84页 *

Also Published As

Publication number Publication date
CN113201109A (en) 2021-08-03

Similar Documents

Publication Publication Date Title
Prolongo et al. Influence of graphene nanoplatelets on curing and mechanical properties of graphene/epoxy nanocomposites
Hu et al. Preparation and properties of dopamine reduced graphene oxide and its composites of epoxy
Huang et al. Spherical and flake-like BN filled epoxy composites: Morphological effect on the thermal conductivity, thermo-mechanical and dielectric properties
CN112778703B (en) High-toughness and heat-conducting epoxy resin composite material and preparation method thereof
CN104592950A (en) High-thermal conductivity graphite alkenyl polymer heat conducting film and preparation method thereof
CN102850717A (en) High thermal conductivity phenolic resin and preparation method
Nayak et al. Mechanical properties and thermal conductivity of epoxy composites enhanced by h-BN/RGO and mh-BN/GO hybrid filler for microelectronics packaging application
CN106987123B (en) Graphene/boron nitride loaded nano-silver heat-conducting special high polymer material and preparation method thereof
Choi et al. Effect of crosslink density on thermal conductivity of epoxy/carbon nanotube nanocomposites
Wang et al. Preparation and properties of MWCNTs-BNNSs/epoxy composites with high thermal conductivity and low dielectric loss
WO2008054034A1 (en) Method for manufacturing epoxy nanocomposite material containing vapor-grown carbon nanofibers and its products thereby
KR100665130B1 (en) Method for manufacturing epoxy nanocomposite material containing vapor-grown carbon nanofibers and its products thereby
Zhang et al. Tuning the polymerization sequence of alkynyl-functionalized benzoxazine: application as precursor for efficient magnetic EMI shielding materials
CN105368046A (en) Composition of cyanate ester resin and thermal conducting filler, and prepreg and application thereof
CN111621253A (en) Graphite-based high-strength heat-conducting epoxy resin adhesive and preparation method thereof
Sul et al. Effect of the addition of multi‐walled carbon nanotubes on the thermomechanical properties of epoxy resin
KR102198383B1 (en) Method for preparation of carbon-benzoxazine complex and its carbon-polymer composite material
CN113201109B (en) Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material
CN105255154A (en) Method for preparing thermosetting-resin-based heat conduction composite
CN108929521B (en) High-thermal-conductivity and high-electric-conductivity graphene-based composite material and preparation method thereof
Cui et al. Preparation of highly thermally conductive epoxy composites featuring self‐healing and reprocessability
Zhou et al. A bio‐based compatibilizer for improved interfacial compatibility in thermally conductive and electrically insulating graphite/high density poly (ethylene) composites
Chen et al. Preparation and characterization of graphite/thermosetting composites
CN112745544B (en) Crosslinked polymer composite material with isolated filler network structure and preparation method thereof
Zheng et al. Improved thermal conductivity and excellent electrical insulation properties of polysiloxane nanocomposite-incorporated functional boron nitride sheets via in situ polymerization

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant