CN105838315A - High-temperature-resistant benzoxazine resin adhesive and preparation method thereof - Google Patents
High-temperature-resistant benzoxazine resin adhesive and preparation method thereof Download PDFInfo
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- CN105838315A CN105838315A CN201610362741.3A CN201610362741A CN105838315A CN 105838315 A CN105838315 A CN 105838315A CN 201610362741 A CN201610362741 A CN 201610362741A CN 105838315 A CN105838315 A CN 105838315A
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- benzoxazine resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a high-temperature-resistant benzoxazine resin adhesive and a preparation method thereof, relates to a benzoxazine resin adhesive and a preparation method thereof, and aims to solve the problems of poor resistance of an existing benzoxazine resin adhesive to high temperature and weak tensile shear strength at high temperature. The adhesive comprises acetylene-terminated benzoxazine resin, a toughening agent, an organic solvent, a coupling agent and an inorganic filler. The method comprises the following steps: 1, placing dihydric phenol, aminophenylacetylene and paraformaldehyde in a four-neck flask, performing heating reaction and cooling, adding trichloromethane for dissolution, performing extraction, performing washing to neutral with de-ionized water, and performing drying to obtain the acetylene-terminated benzoxazine resin; 2, uniformly mixing the acetylene-terminated benzoxazine resin, the toughening agent and the organic solvent to obtain a base adhesive; 3, sequentially adding the coupling agent and the inorganic filler into the base adhesive, and performing uniform mixing to obtain the high-temperature-resistant benzoxazine resin adhesive. The adhesive is resistant to high temperature, has strong tensile shear strength at high temperature, and is used in the field of adhesives.
Description
Technical field
The present invention relates to a kind of benzoxazine resin adhesive and preparation method thereof.
Background technology
Along with the development of science and technology, the application of high-temperature resistance adhesive is further extensive, the most in recent years Aeronautics and Astronautics,
The technical fields such as electronics, automobile and machine building industry propose requirements at the higher level to the resistance to elevated temperatures of synthetic adhesive.Benzene
And oxazines is as the novel thermosetting resin of a class, it has the advantage of phenolic resin thermostability, anti-flammability, has again simultaneously
Having the performance that some are special, such as MOLECULE DESIGN flexibly, solidification process discharges without little molecule, and volume shrinks close to zero,
Goods porosity is low, and it also has relatively low dielectric constant simultaneously, and water absorption rate is much smaller than phenolic resin etc..Therefore, benzo
Oxazines can be as the matrix material of high-temperature resistance adhesive.Due to the construction features of himself, cause crosslinked after polymerization density
Low, temperature resistant grade is the highest.Benzoxazine resin matter after solidification is crisp, and internal stress is big, impact resistance is poor.Therefore, as
Thermostability and the toughness of what raising benzoxazine resin are to prepare the subject matter that high-temperature resistance adhesive faces.
Summary of the invention
The present invention is to solve that existing benzoxazine resin adhesive resistance to elevated temperatures is poor, at high temperature tensile shear strength is low
Problem, it is provided that a kind of high temperature resistant benzoxazine resin adhesive and preparation method thereof.
Benzoxazine resin adhesive includes by weight 100 parts of end alkynyl radical benzoxazine resin that the present invention is high temperature resistant, 5～50
Part toughener, 30～150 parts of organic solvents, 0.1～5 part of coupling agent and 10～150 parts of inorganic fillers.
Further, described end alkynyl radical benzoxazine resin structural formula is:
Wherein X is:
Further, described toughener is polyphenylene sulfide, polysulfones, polyarylsulfone (PAS), polyether sulfone, Merlon, polybenzoate, gathers
Ether ether ketone, aromatic polysulfonamide, poly-to benzamide, PPTA, PMMI, polyamide
One or more in-acid imide, PABM, Polyetherimide, liquid crystal polymer are by arbitrarily than composition
Mixture.
Further, described organic solvent is methanol, ethanol, normal propyl alcohol, isopropanol, ethyl acetate, Ethyl formate, second
Acid isobutyl ester, methyl acetate, propyl acetate, acetone, dichloromethane, chloroform, carbon tetrachloride, normal hexane, hexamethylene
Alkane, hexahydrotoluene, petroleum ether, benzene,toluene,xylene, chlorobenzene, N,N-dimethylformamide, N, N-dimethyl
Acetamide, acetonitrile, dimethyl sulfoxide, 1,4-dioxane, tetrahydronaphthalene, pyridine, oxolane, N-crassitude
One or more in ketone are by arbitrarily than the mixture of composition.
Further, described coupling agent is γ-chloropropyl triethoxysilane, vinyl trichlorosilane, vinyl three ethoxy
Base silane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4-epoxy hexamethylene
Base) ethyl trimethoxy silane, γ-ureidopropyltriethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-shrink be sweet
Oil ether epoxide propyl trimethoxy silicane, γ-(methacryloxy) propyl trimethoxy silicane, γ-mercapto propyl group front three
TMOS, gamma-mercaptopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-
β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, double (γ-
Triethoxysilylpropyl)-tetrasulfide, anilinomethyl triethoxysilane, γ-chloropropyl triethoxysilane, isopropyl
Three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters,
One or more in tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters are by arbitrarily than the mixture of composition.
Further, described inorganic filler be asbestos, glass fibre, aluminium powder, copper powder, iron powder, argentum powder, porcelain powder, quartz,
Chromium oxide, ferrum oxide, zinc oxide, graphite, Muscovitum, silicon powder, kieselguhr, titanium dioxide, calcium carbonate, Pulvis Talci, carbon
One or more in SiClx, boron nitride, boron carbide, Kaolin are by arbitrarily than the mixture of composition.
The preparation method of above-mentioned high temperature resistant benzoxazine resin adhesive, sequentially includes the following steps:
One, dihydric phenol, 3-aminophenylacetylene and paraformaldehyde are positioned in four-hole bottle, are heated to 100～150 DEG C, reaction
0.1～2h, it is then cooled to room temperature, adds chloroform and dissolve, then extract with the sodium hydrate aqueous solution of 1～3mol/L
3 times, then be washed with deionized water to neutrality, 40～80 DEG C of vacuum drying ovens are dried 6～72h, obtain end alkynyl radical benzoxazine
Resin；Wherein the mol ratio of dihydric phenol, 3-aminophenylacetylene and paraformaldehyde is 1:2:(4～4.4), dihydric phenol and three chloromethanes
The mol ratio of alkane is 1:(2～8)；
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 5～50 parts of toughener and 30～150 parts of organic solvents
Mix homogeneously, obtains base glue；
Three, 0.1～5 part of coupling agent and 10～150 parts of inorganic fillers are added sequentially in base glue and mix homogeneously, i.e. obtain
High temperature resistant benzoxazine resin adhesive.
Further, the dihydric phenol structural formula described in step one is:
Wherein R is:
Beneficial effects of the present invention:
High temperature resistant benzoxazine resin adhesive prepared by the present invention is with end alkynyl radical benzoxazine resin monomer as material of main part,
Alkynyl in monomer can increase the crosslink density of solidfied material by polyreactions such as Diels-Alder, Strauss, Glaser,
Form more stable network structure, thus improve the temperature resistant grade of adhesive.At high temperature (200 DEG C, 400 DEG C) still have
Higher tensile shear strength.
High temperature resistant benzoxazine resin adhesive prepared by the present invention uses polyphenylene sulfide, polysulfones, polyarylsulfone (PAS) etc. as toughness reinforcing body
System, while improving matrix resin toughness, little on the impact of its glass transition temperature, modulus and heat resistance.
High temperature resistant benzoxazine resin adhesive prepared by the present invention glues for the structure between metal and metal inclusive NAND metal
Connect, there is heat resistance and the adhesive property of excellence, can be applicable to the necks such as Aeronautics and Astronautics, electronics, automobile and machine-building
In territory.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes appointing between each detailed description of the invention
Meaning combination.
Detailed description of the invention one: present embodiment is high temperature resistant, and benzoxazine resin adhesive includes 100 parts of Terminal Acetylenes by weight
Base benzoxazine resin, 5～50 parts of toughener, 30～150 parts of organic solvents, 0.1～5 part of coupling agent and 10～150 parts are inorganic
Filler.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: described end alkynyl radical benzoxazine tree
Fat structural formula is:
Wherein X is:
.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: described toughener is polyphenyl
Thioether, polysulfones, polyarylsulfone (PAS), polyether sulfone, Merlon, polybenzoate, polyether-ether-ketone, aromatic polysulfonamide, poly-to benzamide,
PPTA, PMMI, polyamide-imides, PABM, poly-
One or more in etherimide, liquid crystal polymer are by arbitrarily than the mixture of composition.Other with detailed description of the invention one or
Two is identical.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: described organic solvent
For methanol, ethanol, normal propyl alcohol, isopropanol, ethyl acetate, Ethyl formate, isobutyl acetate, methyl acetate, acetic acid third
Ester, acetone, dichloromethane, chloroform, carbon tetrachloride, normal hexane, hexamethylene, hexahydrotoluene, petroleum ether, benzene,
Toluene, dimethylbenzene, chlorobenzene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetonitrile, dimethyl sulfoxide, 1,4-
One or more in dioxane, tetrahydronaphthalene, pyridine, oxolane, N-Methyl pyrrolidone are by arbitrarily than composition
Mixture.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: described coupling agent is
γ-chloropropyl triethoxysilane, vinyl trichlorosilane, VTES, vinyltrimethoxy silane,
Vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-urea groups
Propyl-triethoxysilicane, gamma-aminopropyl-triethoxy-silane, γ-glycydoxy trimethoxy silane, γ
-(methacryloxy) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, γ-mercapto propyl-triethoxysilicane
Alkane, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl trimethoxy silicon
Alkane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, double (γ-triethoxysilylpropyl)-tetrasulfide, aniline
MTES, γ-chloropropyl triethoxysilane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters,
Isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, tetra isopropyl two (dioctyl phosphito acyloxy) titanium
One or more in acid esters are by arbitrarily than the mixture of composition.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: described inorganic filler
For asbestos, glass fibre, aluminium powder, copper powder, iron powder, argentum powder, porcelain powder, quartz, chromium oxide, ferrum oxide, zinc oxide,
Graphite, Muscovitum, silicon powder, kieselguhr, titanium dioxide, calcium carbonate, Pulvis Talci, carborundum, boron nitride, boron carbide, height
One or more in the soil of ridge are by arbitrarily than the mixture of composition.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo is disliked
Piperazine resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 10～45 parts of toughener, 50～120 parts
Organic solvent, 0.5～4.5 part of coupling agent and 30～130 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo is disliked
Piperazine resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 15～40 parts of toughener, 60～110 parts
Organic solvent, 1～4 part of coupling agent and 50～110 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo is disliked
Piperazine resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 20～35 parts of toughener, 70～90 parts have
Machine solvent, 2～3 parts of coupling agents and 70～90 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo is disliked
Piperazine resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 20～35 parts of toughener, 70～90 parts have
Machine solvent, 2～3 parts of coupling agents and 70～90 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention 11: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo
Oxazines resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 15 parts of toughener, 60 parts organic molten
Agent, 0.4 part of coupling agent and 50 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention 12: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo
Oxazines resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 20 parts of toughener, 60 parts organic molten
Agent, 0.4 part of coupling agent and 50 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention 13: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo
Oxazines resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 15 parts of toughener, 90 parts organic molten
Agent, 0.5 part of coupling agent and 55 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention 14: present embodiment is unlike one of detailed description of the invention one to six: high temperature resistant benzo
Oxazines resin adhesive include by weight 100 parts of end alkynyl radical benzoxazine resin, 12 parts of toughener, 75 parts organic molten
Agent, 0.2 part of coupling agent and 42 parts of inorganic fillers.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention 15: the preparation method of present embodiment is high temperature resistant benzoxazine resin adhesive, according to the following steps
Carry out:
One, dihydric phenol, 3-aminophenylacetylene and paraformaldehyde are positioned in four-hole bottle, are heated to 100～150 DEG C, reaction
0.1～2h, it is then cooled to room temperature, adds chloroform and dissolve, then extract with the sodium hydrate aqueous solution of 1～3mol/L
3 times, then be washed with deionized water to neutrality, 40～80 DEG C of vacuum drying ovens are dried 6～72h, obtain end alkynyl radical benzoxazine
Resin；
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 5～50 parts of toughener and 30～150 parts of organic solvents
Mix homogeneously, obtains base glue；
Three, 0.1～5 part of coupling agent and 10～150 parts of inorganic fillers are added sequentially in base glue and mix homogeneously, i.e. obtain
High temperature resistant benzoxazine resin adhesive.
Detailed description of the invention 16: present embodiment is unlike detailed description of the invention 15: the binary described in step one
Phenol structural formula is:
Wherein R is:
.Other is identical with detailed description of the invention 15.
Detailed description of the invention 17: present embodiment is unlike detailed description of the invention 15 or 16: in step one two
The mol ratio of unit's phenol, 3-aminophenylacetylene and paraformaldehyde is 1:2:(4～4.4).Other is with detailed description of the invention 15 or ten
Six is identical.
Detailed description of the invention 18: present embodiment is unlike one of detailed description of the invention ten five to ten seven: step one
The mol ratio of middle dihydric phenol and chloroform is 1:(2～8).Other is identical with one of detailed description of the invention ten five to ten seven.
Detailed description of the invention 19: present embodiment is unlike one of detailed description of the invention ten five to ten seven: step one
The mol ratio of middle dihydric phenol and chloroform is 1:5.Other is identical with detailed description of the invention 15.
By tests below checking beneficial effects of the present invention:
Embodiment one: the present embodiment is high temperature resistant benzoxazine resin adhesive preparation method, comprises the steps:
One, 1mol bisphenol-A, 2mol 3-aminophenylacetylene and 4mol paraformaldehyde are positioned in four-hole bottle, are heated to
120 DEG C, react 0.5h.Being cooled to room temperature, add 5mol chloroform and dissolve, the sodium hydroxide with 1L 3mol/L is water-soluble
Liquid extracts 3 times, then is washed with deionized water to neutrality, is dried 24h, obtains end alkynyl radical benzoxazine in 60 DEG C of vacuum drying ovens
Resin.
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 5 parts of polyether-ether-ketones and 60 parts of N, N-dimethyl methyls
Amide mix homogeneously, obtains base glue.
Three, 0.4 part of gamma-aminopropyl-triethoxy-silane and 50 parts of aluminium powders are added sequentially in base glue and mix homogeneously,
To 1#High temperature resistant benzoxazine resin adhesive.
Wherein, in step one, the end alkynyl radical benzoxazine resin structural formula of preparation is:
Dihydric phenol used by the present embodiment is bisphenol-A, and structural formula is:
Embodiment two: the present embodiment is step 2 unlike embodiment one: by weight 100 parts of end alkynyl radical benzos are disliked
Piperazine resin, 10 parts of polyether-ether-ketones and 60 parts of DMF mix homogeneously, obtain base glue.Other step parameter
Identical with embodiment one.Finally give 2#High temperature resistant benzoxazine resin adhesive.
Embodiment three: the present embodiment is step 2 unlike embodiment one: by weight 100 parts of end alkynyl radical benzos are disliked
Piperazine resin, 15 parts of polyether-ether-ketones and 60 parts of DMF mix homogeneously, obtain base glue.Other step parameter
Identical with embodiment one.Finally give 3#High temperature resistant benzoxazine resin adhesive.
Embodiment four: the present embodiment is step 2 unlike embodiment one: by weight 100 parts of end alkynyl radical benzos are disliked
Piperazine resin, 20 parts of polyether-ether-ketones and 60 parts of DMF mix homogeneously, obtain base glue.Other step parameter
Identical with embodiment one.Finally give 4#High temperature resistant benzoxazine resin adhesive.
By above 1#～4#High temperature resistant benzoxazine resin adhesive, scratches No. 45 steel disc surface (sand in three times with Glass rod
Acetone wiped clean is used after paper polishing), it is positioned over after smearing in 100 DEG C of baking ovens every time and is dried 30min, then steel disc is taken
Connect by 160 DEG C, 4h+180 DEG C, 4h+220 DEG C, 2h program Solidification.Tensile shear strength is carried out by GB/T 7124-2008
Test, test speed is 15mm/min, and test result is as shown in table 1:
Table 1
Embodiment five: the present embodiment is high temperature resistant benzoxazine resin adhesive preparation method, comprises the steps:
One, 1mol 4,4 '-dihydroxy diphenyl ether, 2mol 3-aminophenylacetylene and 4mol paraformaldehyde are positioned over four-hole bottle
In, it is heated to 100 DEG C, reacts 1h.It is cooled to room temperature, adds 5mol chloroform and dissolve, with the hydrogen of 1L 3mol/L
Aqueous solution of sodium oxide extracts 3 times, then is washed with deionized water to neutrality, is dried 24h, obtains Terminal Acetylenes in 65 DEG C of vacuum drying ovens
Base benzoxazine resin.
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 12 parts of polyarylsulfone (PAS) and 75 parts of N, N-dimethyl second
Amide mix homogeneously, obtains base glue.
Three, 0.2 part of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters and 42 parts of quartz are added sequentially to successively
In base glue and mix homogeneously, obtain 5#High temperature resistant benzoxazine resin adhesive.
Wherein, in step one, the end alkynyl radical benzoxazine resin structural formula of preparation is:
Dihydric phenol used by the present embodiment is 4,4 '-dihydroxy diphenyl ether, and structural formula is:
Embodiment six: the present embodiment is step 3 unlike embodiment five: by 0.2 part of isopropyl three (dioctylphyrophosphoric acid
Acyloxy) titanate esters and 42 parts of Kaolin are added sequentially in base glue and mix homogeneously, other step parameter and embodiment one
Identical, obtain 6#High temperature resistant benzoxazine resin adhesive.
Embodiment seven: the present embodiment is step 3 unlike embodiment five: by 0.2 part of isopropyl three (dioctylphyrophosphoric acid
Acyloxy) titanate esters and 42 parts of asbestos are added sequentially in base glue and mix homogeneously, other step parameter and embodiment one phase
With, obtain 7#High temperature resistant benzoxazine resin adhesive.
Embodiment eight: the present embodiment is step 3 unlike embodiment five: by 0.2 part of isopropyl three (dioctylphyrophosphoric acid
Acyloxy) titanate esters and 42 parts of boron nitride are added sequentially in base glue and mix homogeneously, other step parameter and embodiment one
Identical, obtain 8#High temperature resistant benzoxazine resin adhesive.
By above 5#～8#High temperature resistant benzoxazine resin adhesive, scratches No. 45 steel disc surface (sand in three times with Glass rod
Acetone wiped clean is used after paper polishing), it is positioned over after smearing in 100 DEG C of baking ovens every time and is dried 30min, then steel disc is taken
Connect by 160 DEG C, 4h+180 DEG C, 4h+220 DEG C, 2h program Solidification.Tensile shear strength is carried out by GB/T 7124-2008
Test, test speed is 15mm/min, and test result is as shown in table 2:
Table 2
Embodiment nine: the present embodiment is high temperature resistant benzoxazine resin adhesive preparation method, comprises the steps:
One, by 1mol 4,4 '-'-biphenyl diphenol, 2mol 3-aminophenylacetylene and 4mol paraformaldehyde are positioned in four-hole bottle,
It is heated to 130 DEG C, reacts 2h.It is cooled to room temperature, adds 5mol chloroform and dissolve, by the hydroxide of 1L 3mol/L
Sodium water solution extracts 3 times, then is washed with deionized water to neutrality, is dried 48h, obtains end alkynyl radical benzene in 45 DEG C of vacuum drying ovens
And oxazines resin.
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 15 parts of polyamide-imides and 90 parts of N, N-bis-
Methylacetamide mix homogeneously, obtains base glue.
Three, 0.5 part of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and 55 parts of graphite are added sequentially in base glue
And mix homogeneously, obtain 9#High temperature resistant benzoxazine resin adhesive.
Wherein, in step one, the end alkynyl radical benzoxazine resin structural formula of preparation is:
Embodiment ten: the present embodiment is high temperature resistant benzoxazine resin adhesive preparation method, comprises the steps:
One, 1mol 4,4 '-dihydroxydiphenylsulisomer, 2mol 3-aminophenylacetylene and 4mol paraformaldehyde are positioned over four-hole bottle
In, it is heated to 130 DEG C, reacts 1.5h.It is cooled to room temperature, adds 5mol chloroform and dissolve, with 1L 3mol/L's
Sodium hydrate aqueous solution extracts 3 times, then is washed with deionized water to neutrality, is dried 36h, is held in 60 DEG C of vacuum drying ovens
Alkynyl benzoxazine resin.
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 12.5 parts of Polyetherimide and 75 parts of N, N-diformazans
Yl acetamide mix homogeneously, obtains base glue.
Three, 0.5 part of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and 60 parts of aluminium powders are added sequentially in base glue
And mix homogeneously, obtain 10#High temperature resistant benzoxazine resin adhesive.
Wherein, in step one, the end alkynyl radical benzoxazine resin structural formula of preparation is:
Embodiment 11: the present embodiment is high temperature resistant benzoxazine resin adhesive preparation method, comprises the steps:
One, 1mol bis-phenol M, 2mol 3-aminophenylacetylene and 4mol paraformaldehyde are positioned in four-hole bottle, are heated to
115 DEG C, react 1h.Being cooled to room temperature, add 5mol chloroform and dissolve, the sodium hydroxide with 1L 3mol/L is water-soluble
Liquid extracts 3 times, then is washed with deionized water to neutrality, is dried 60h, obtains end alkynyl radical benzoxazine in 45 DEG C of vacuum drying ovens
Resin.
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 12.5 parts of Polyetherimide and 75 parts of N, N-diformazans
Yl acetamide mix homogeneously, obtains base glue.
Three, 0.5 part of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and 60 parts of aluminium powders are added sequentially in base glue
And mix homogeneously, obtain 11#High temperature resistant benzoxazine resin adhesive.
Wherein, in step one, the end alkynyl radical benzoxazine resin structural formula of preparation is:
By above 9#～11#High temperature resistant benzoxazine resin adhesive, scratches No. 45 steel disc surfaces in three times with Glass rod
(using acetone wiped clean after sand papering), is positioned over after smearing in 100 DEG C of baking ovens every time and is dried 30min, then by steel
Oblique cut grafting presses 160 DEG C, 4h+180 DEG C, 4h+220 DEG C, 2h program Solidification.Tensile shear strength is entered by GB/T 7124-2008
Row test, test speed is 15mm/min, and test result is as shown in table 3:
Table 3
Claims (10)
1. a high temperature resistant benzoxazine resin adhesive, it is characterised in that this adhesive includes 100 parts of Terminal Acetylenes by weight
Base benzoxazine resin, 5～50 parts of toughener, 30～150 parts of organic solvents, 0.1～5 part of coupling agent and 10～150 parts are inorganic to be filled out
Material.
One the most according to claim 1 is high temperature resistant benzoxazine resin adhesive, it is characterised in that
Described end alkynyl radical benzoxazine resin structural formula is:
Wherein X is:
-、-CH2-、-O-、
One the most according to claim 1 is high temperature resistant benzoxazine resin adhesive, it is characterised in that described toughener is
Polyphenylene sulfide, polysulfones, polyarylsulfone (PAS), polyether sulfone, Merlon, polybenzoate, polyether-ether-ketone, aromatic polysulfonamide, poly-to benzene
Amide, PPTA, PMMI, polyamide-imides, PABM,
One or more in Polyetherimide, liquid crystal polymer are by arbitrarily than the mixture of composition.
One the most according to claim 1 is high temperature resistant benzoxazine resin adhesive, it is characterised in that described organic solvent
For methanol, ethanol, normal propyl alcohol, isopropanol, ethyl acetate, Ethyl formate, isobutyl acetate, methyl acetate, acetic acid third
Ester, acetone, dichloromethane, chloroform, carbon tetrachloride, normal hexane, hexamethylene, hexahydrotoluene, petroleum ether, benzene,
Toluene, dimethylbenzene, chlorobenzene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetonitrile, dimethyl sulfoxide, 1,4-
One or more in dioxane, tetrahydronaphthalene, pyridine, oxolane, N-Methyl pyrrolidone are by arbitrarily than composition
Mixture.
One the most according to claim 1 is high temperature resistant benzoxazine resin adhesive, it is characterised in that described coupling agent is
γ-chloropropyl triethoxysilane, vinyl trichlorosilane, VTES, vinyltrimethoxy silane,
Vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-urea groups third
Ethyl triethoxy silicane alkane, gamma-aminopropyl-triethoxy-silane, γ-glycydoxy trimethoxy silane, γ-(first
Base acryloxy) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane,
N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,
N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, double (γ-triethoxysilylpropyl)-tetrasulfide, anilinomethyl three
Ethoxysilane, γ-chloropropyl triethoxysilane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl
In two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters
One or more are by arbitrarily than the mixture of composition.
One the most according to claim 1 is high temperature resistant benzoxazine resin adhesive, it is characterised in that described inorganic filler
For asbestos, glass fibre, aluminium powder, copper powder, iron powder, argentum powder, porcelain powder, quartz, chromium oxide, ferrum oxide, zinc oxide,
Graphite, Muscovitum, silicon powder, kieselguhr, titanium dioxide, calcium carbonate, Pulvis Talci, carborundum, boron nitride, boron carbide, height
One or more in the soil of ridge are by arbitrarily than the mixture of composition.
The preparation method of high temperature resistant benzoxazine resin adhesive the most as claimed in claim 1, it is characterised in that the method is pressed
Following steps are carried out:
One, dihydric phenol, 3-aminophenylacetylene and paraformaldehyde are positioned in four-hole bottle, are heated to 100～150 DEG C, reaction
0.1～2h, it is then cooled to room temperature, adds chloroform and dissolve, then extract 3 with the sodium hydrate aqueous solution of 1～3mol/L
Secondary, then be washed with deionized water to neutrality, 40～80 DEG C of vacuum drying ovens are dried 6～72h, obtain end alkynyl radical benzoxazine resin；
Two, by weight by 100 parts of end alkynyl radical benzoxazine resin, 5～50 parts of toughener and 30～150 parts of organic solvents
Mix homogeneously, obtains base glue；
Three, 0.1～5 part of coupling agent and 10～150 parts of inorganic fillers are added sequentially in base glue and mix homogeneously, i.e. obtain resistance to
High temperature benzoxazine resin adhesive.
The preparation method of high temperature resistant benzoxazine resin adhesive the most according to claim 7, it is characterised in that
Dihydric phenol structural formula described in step one is:
Wherein R is:
-、-CH2-、-O-、
The preparation method of high temperature resistant benzoxazine resin adhesive the most according to claim 7, it is characterised in that step one
The mol ratio of middle dihydric phenol, 3-aminophenylacetylene and paraformaldehyde is 1:2:(4～4.4).
The preparation method of high temperature resistant benzoxazine resin adhesive the most according to claim 7, it is characterised in that step
In one, the mol ratio of dihydric phenol and chloroform is 1:(2～8).
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| CN106832922A (en) * | 2017-01-19 | 2017-06-13 | 浙江理工大学 | A kind of Xin types benzoxazine colophony method for toughening |
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| CN116478523A (en) * | 2023-04-27 | 2023-07-25 | 东莞市百富塑料科技有限公司 | Preparation process of nano hybrid particle reinforced polycarbonate |
| CN117964870A (en) * | 2024-03-29 | 2024-05-03 | 成都飞机工业（集团）有限责任公司 | Benzoxazine resin-based fiber sizing agent and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633055A (en) * | 2016-10-10 | 2017-05-10 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant benzoxazine resin and method for preparing same |
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| CN106832922A (en) * | 2017-01-19 | 2017-06-13 | 浙江理工大学 | A kind of Xin types benzoxazine colophony method for toughening |
| CN110698682A (en) * | 2019-09-27 | 2020-01-17 | 武汉华星光电半导体显示技术有限公司 | Polyimide composite material, preparation method and application thereof |
| CN113174650A (en) * | 2021-06-10 | 2021-07-27 | 杭州红港化纤有限公司 | Wear-resistant DTY and production process thereof |
| CN116478523A (en) * | 2023-04-27 | 2023-07-25 | 东莞市百富塑料科技有限公司 | Preparation process of nano hybrid particle reinforced polycarbonate |
| CN116478523B (en) * | 2023-04-27 | 2024-02-06 | 东莞市百富塑料科技有限公司 | Preparation process of nano hybrid particle reinforced polycarbonate |
| CN117964870A (en) * | 2024-03-29 | 2024-05-03 | 成都飞机工业（集团）有限责任公司 | Benzoxazine resin-based fiber sizing agent and preparation method and application thereof |
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Application publication date: 20160810 |