CN106117517B - A kind of siliceous epoxy acid imide matrix resin of BDADDM types and preparation method thereof - Google Patents
A kind of siliceous epoxy acid imide matrix resin of BDADDM types and preparation method thereof Download PDFInfo
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- CN106117517B CN106117517B CN201610613454.5A CN201610613454A CN106117517B CN 106117517 B CN106117517 B CN 106117517B CN 201610613454 A CN201610613454 A CN 201610613454A CN 106117517 B CN106117517 B CN 106117517B
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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Abstract
The present invention relates to siliceous epoxy acid imide matrix resin of a kind of BDADDM types and preparation method thereof, the matrix resin is by 4,4 ' double (2,4 diamino phenoxy) diphenyl-methane BDADDM, epoxy resin, 3 aminopropyltrialkoxysilanes, imide oligomer thing and curing agent composition.Preparation method includes the following steps：(1) imide oligomer thing is prepared；(2) by 4,4 ' double (2,4 diamino phenoxies) methane, epoxy resin is put into reaction kettle, after being stirred reaction, add imide oligomer thing and continue stirring reaction, the stirring reaction of 3 aminopropyltrialkoxysilanes is then added, curing agent is added and is uniformly mixed, you can.The bonding between the base material such as the metals such as steel, copper, aluminium and ceramics, glass, polymer matrix composites, and the preparation of glass fibre, aramid fiber, carbon fibre reinforced composite are the composite can be widely applied to, there is good industrialization prospect.
Description
Technical field
The invention belongs to macromolecule matrix resin and its preparation field, more particularly to a kind of siliceous epoxy acyl of BDADDM types is sub-
Amine matrix resin and preparation method thereof.
Background technology
It is well known that epoxy resin has many excellent performances：(1) good adhesive property：Adhesive strength is high, bonding
It is wide, it with many metals (such as iron, steel, copper, aluminium, metal alloy) or nonmetallic materials (such as glass, ceramics, resin base are answered
Condensation material, timber, plastics etc.) adhesive strength it is very high, some is even more than intensity by viscous material in itself, therefore can be used for
It is one of main component of structural adhesive in many stress members；(2) good processing performance：Formulaion of epoxy resin
Flexibility, the diversity of processing technology and product properties be the most prominent in high molecular material；(3) good stability
Energy：The curing of epoxy resin mainly relies on the ring opening polyaddition of epoxy group, therefore low-molecular material is not produced in solidification process,
Its cure shrinkage is one of kind minimum in thermosetting resin, generally 1%-2%, if selecting appropriate filler to make
Shrinking percentage is down to 0.2% or so；Epoxy main chains after curing are ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore with excellent
Resistance to acid and alkali.
Therefore, epoxy resin is widely used in the every field of national economy：Either high-technology field is still
Its trace can be seen in field of general technology, either defence and military or civilian industry, or even daily life.
At present, epoxy-resin systems are there is also some problems, as heat resistance is relatively low, much not as good as heteroaromatic Type of Collective object
It is (such as polyimides, polybenzimidazoles, polybenzoxazole, polyphenyl based quinoxaline, polybenzothiozole).
Polyimides is developed in the sixties, and most common one kind is by pyromellitic acid anhydride and aromatic diamine system
.Contain multiple aromatic heterocycle construction unit in polyimide molecule, therefore polyimide resin is that have extremely superior heat resistance
A kind of high molecular material of property.Conventional polyimide structures, its heat decomposition temperature is generally more than 500 DEG C, while also have
There is obdurability.Therefore, thermosetting resin is also frequently utilized for, the heat-resisting toughness reinforcing of such as epoxy resin, bimaleimide resin changes
Property agent.
Chinese invention patent CN103146330A discloses a kind of double [4- (2,4- diamino phenoxies) phenyl] six of 2,2-
Fluoro-propane type high temperature resistant epoxy adhesive and preparation method thereof, is 1 by mass ratio:Component A and the B component composition of 1-2, wherein, A
Component is the copolymer formed by double [4- (2,4- diamino phenoxies) phenyl] hexafluoropropane of 2,2- with epoxy resin reaction；B
Component is in highly polar non-matter by double [4- (2,4- diamino phenoxies) phenyl] hexafluoropropane of 2,2- with aromatic dicarboxylic anhydride
The solid content reacted in sub- organic solvent and toluene is the homogeneous phase transparent solution of 15%-30%.Preparation method includes：Room temperature
Under, by A, B component in mass ratio 1:1-2 is uniformly mixed.
It is resistance to that Chinese invention patent CN103131369A discloses a kind of double (2,4- diamino phenoxies) the diphenyl sulphone (DPS) types of 4,4'-
High-temp epoxy adhesive and preparation method thereof, is 1 by mass ratio:Component A and the B component composition of 1-2, wherein component A be by 4,
The copolymer that 4 '-bis- (2,4- diamino phenoxies) diphenyl sulphone (DPS)s are formed with epoxy resin reaction；B component be by 4,4 '-bis- (2,4-
Diamino phenoxy) diphenyl sulphone (DPS) reacts consolidating of forming with aromatic dicarboxylic anhydride in highly polar aprotic organic solvent and toluene
Content is the homogeneous phase transparent solution of 15%-30%.Preparation method includes：At room temperature, by A, B component in mass ratio 1:1-2 is stirred
It is uniformly mixed.
Chinese invention patent CN103146331A discloses a kind of resistance to height of double (2,4- diamino phenoxies) biphenyl types of 4,4'-
Temperature epoxy adhesive and preparation method thereof, is 1 by mass ratio:Component A and the B component composition of 1-2, wherein component A be by 4,4 '-
The copolymer that double (2,4- diamino phenoxies) biphenyl are formed with epoxy resin reaction；B component be by 4,4 '-bis- (2,4- diaminos
Phenoxyl) solid content that is reacted with aromatic dicarboxylic anhydride in highly polar aprotic organic solvent and toluene of biphenyl is
The homogeneous phase transparent solution of 15%-30%.Preparation method includes：At room temperature, by A, B component in mass ratio 1:1-2 is stirred
It is even.
Yan Rui, Yu Xinhai et al.【The preparation of novel epoxy adhesive and performance study, insulating materials, 2012,45 (2)：
12-14,18】A kind of neo-epoxy resin adhesive and preparation method thereof is disclosed, and systematic research has been carried out to its performance.
Yu Xin seas et al.【The preparation of organosilicon epoxy system adhesive and performance study, insulating materials, 2012,45 (2)：
1-3,11】A kind of adhesive composition of organic siliconresin modified epoxy is disclosed, and its performance is studied, at the same time
The superior adhesive of comprehensive performance is obtained.
Chinese invention patent CN102220102A has been applied in Yu Xin seas et al., discloses a kind of high-temperature-resistant adhesive and its system
Preparation Method.
Chinese invention patent CN102260480A discloses a kind of high-temperature-resistant modified epoxy resin adhesive and its preparation side
Method.
Chinese invention patent CN102181251A discloses the epoxyn that a kind of unsaturated polyimides are modified
And preparation method thereof.
Chinese invention patent CN102031082A discloses a kind of benzimidazole diamine curing type epoxy adhesive and its system
Preparation Method.
Chinese invention patent CN101649174A discloses a kind of high temperature resistant one-component solvent-free epoxy adhesive and its system
Preparation Method.
Chinese invention patent CN101544879A discloses a kind of preparation method of high strength solventless epoxy adhesive.
Wu Min et al.【The development of novel high-strength one-component epoxy resin adhesive, bonding, 2009,30 (9)：54-57】
A kind of epoxy binder in monocomponent in is disclosed, excellent combination property, particularly has very high tensile shear strength.
Chen Hongjiang et al.【The cure kinetics research of neo-epoxy resin adhesive system, bonding, 2009,30 (8)：43-
45】A kind of epoxyn system is disclosed, and its cure kinetics is studied.
Perhaps plum virtue et al.【The cure kinetics research of polyimide-epoxy resin adhesive, chemistry and bonding, 2011,33
(2)：17-20】A kind of polyimide-epoxy resin adhesive is disclosed, and cure kinetics research has been carried out to it.
Chinese invention patent CN101148656A, discloses a kind of preparation method of heat-resistant solvent-free epoxy adhesive, its
It is characterized mainly in that：TGDDM epoxy resin, toughener, hydrogenated bisphenol A, curing agent, accelerating agent are uniformly mixed, and resistance to height has been made
Warm non-solvent epoxy adhesive.But its resistance to elevated temperatures still has larger limitation, fail to meet under many hot environments
Practical application.
Chinese invention patent CN101397486A, discloses a kind of preparation side of bi-component solvent-free epoxy resin adhesive
Method, is primarily characterized in that：It includes component A and B component, and wherein component A contains novolac epoxy resin, alicyclic type epoxy resin
And nbr carboxyl terminal；B component is double (2,4- diamino phenoxies) the benzene aromatic polyvalent amine hardeners of 1,3-.Alicyclic ring type ring
The additive amount of oxygen tree fat and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.
The additive amount of double (2,4- diamino phenoxies) the benzene aromatic polyvalent amine hardeners of 1,3- is the 15-20% of novolac epoxy resin
(mass percent), gained adhesive system good manufacturability.But its heat resistance is preferable not enough.
Chinese invention patent CN1927908A, discloses a kind of preparation method of phenolic hydroxyl group containing polyimide powder, due to
The presence of phenolic hydroxyl group, its polyimide powder can form covalent bond with epoxy reaction, so as to improve thermoplasticity polyamides Asia
The compatibility of polyimide resin and epoxy resin, and epoxy-resin systems is reached good toughening effect.Yu Xinhai etc.
People【Development [J] bondings of high-temperature resistant single-component epoxy adhesive, 2008,29 (12)：16-19】Disclose a kind of high temperature resistant list
The preparation method of component epoxy adhesive, is primarily characterized in that：With maleic anhydride (MA) for end-capping reagent, with double (the 3- ammonia of 2,2-
Base -4- hydroxy phenyls) hexafluoropropane (BAHPFP), 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane (BAPOPP), 2,2-
Double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides (BPADA) have obtained phenolic hydroxy group polyetherimide for main Material synthesis
Polyimide resin (HPEI)；Using synthesized obtained HPEI as resistant, toughened dose, with N, N, N', N'- four glycidyl groups -4,4'-
Diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent etc., preparation have obtained synthesis
The high-temperature resistant single-component epoxy adhesive of excellent performance.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of siliceous epoxy acid imide matrix resin of BDADDM types and its
Preparation method, preparation process of the present invention is simple, environmental-friendly, excellent combination property, can be widely applied to the metals such as steel, copper, aluminium
And the bonding between the base material such as ceramics, glass, polymer matrix composites, and glass fibre, aramid fiber, fibre reinforced
The preparation of composite material, has good industrialization prospect.
A kind of siliceous epoxy acid imide matrix resin of BDADDM types of the present invention, is 1-5 by mass ratio:100:2-8:1-5:
The 4,4 ' of 30-50-bis- (2,4- diamino phenoxies) diphenyl-methane BDADDM, epoxy resin, 3- aminopropyltrialkoxysilanes,
Imide oligomer thing and curing agent composition；Wherein, imide oligomer thing be by molar ratio be 2:1:Double (3- amino-the 4- of 2 2,2-
Hydroxy phenyl) hexafluoropropane, double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides of 2,2- and maleic anhydride reaction and obtain.
The 3- aminopropyltrialkoxysilanes are selected from 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes
One or both of mixture.
The epoxy resin is selected from E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 asphalt mixtures modified by epoxy resin
Fat, CE793 epoxy resin, glycidyl amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol
One or more in aldehyde type epoxy resin, glycidyl ester type epoxy resin.
The glycidyl amine type epoxy resin is selected from N, N, N ', N '-four glycidyl group -4,4 '-diaminourea hexichol first
Alkane epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-diaminodiphenylmethane epoxy resin, N,
N, N ', N '-four glycidyl group -3,3 '-diethyl -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four shrinks
The chloro- 4,4 '-diaminodiphenylmethane epoxy resin of glyceryl -3,3 '-two, N, N, N ', N '-four glycidyl group -4,4 '-diamino
Yl diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylsulfone epoxy resin, N, N, N ', N ' -
Four glycidyl group -3,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-diaminourea hexichol
Sulfone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-benzidine epoxy resin, N, N, N ', N '-four shrinks sweet
Oil base p-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, N ', N '-four shrinks
Glyceryl -1,4- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', double (the 3- aminobenzenes of N '-four glycidyl group -1,4-
Epoxide) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,3- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ',
N '-four glycidyl group -1,3- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,4- is double
(2- trifluoromethyl-4-aminophenoxyls) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,3- pairs (2- trifluoromethyls -
4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N ', O- five glycidyls -4,4 '-diaminourea -4 "-hydroxyl triphenylmenthane
Epoxy resin, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N,
N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane epoxy resin, N, N, N ', N '-four
Glycidyl -2,2- double [4- (3- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,
2- double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2-
Double [4- (3- amino-benzene oxygens) phenyl] hexafluoropropane epoxy resin, N, N, N ', the double [4- (2- of N '-four glycidyl group -2,2-
Trifluoromethyl-4-aminophenoxyl) phenyl] hexafluoropropane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4-
Amino-benzene oxygen) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl -4- aminobenzenes
Epoxide) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) asphalt mixtures modified by epoxy resin
Fat, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N,
N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', the glycidols of N '-four
Base -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,
4 '-bis- (4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- fluoroforms
Base -4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens)
Benzophenone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) hexichol
Ketone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ',
N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resin, N, N, N ', N ', O, O ' -
Six glycidyl -2,2- double (3- amino-4-hydroxylphenyls) hexafluoropropane epoxy resin, N, N, O-triglycidyl group is to ammonia
Base phenol epoxy resin, N, the one or more in N, O-triglycidyl meta-aminophenol epoxy resin.
The diglycidyl ether type epoxy resin is selected from 1,3- diglycidyls resorcinol, 1,4- diglycidyls
Double (4- glycidyl phenyls) hexafluoropropane of hydroquinone, 4,4 '-diglycidyl bisphenol S, 2,2-, 2,2- are double, and (4- contracts
Water glycerine butylcyclohexyl) propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol-A 2-glycidyl
One or more in ether, fatty alcohol polyglycidyl ether.
The alicyclic type epoxy resin is selected from 3,4- epoxycyclohexyethylSiOis acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxies
Base -6- methyl cyclohexanes acid -3 ', the one or more in 4 '-epoxy group -6 '-methyl cyclohexane methyl esters, Dipentenedioxide.
The phenol aldehyde type epoxy resin is selected from phenol-formaldehyde phenolic resin type epoxy resin, o-cresol-formaldehyde novolac tree
Epoxy-type epoxy resin, resorcinol-formaldehyde phenolic resin type epoxy resin, m-cresol-formaldehyde phenolic resin type epoxy resin,
Catechol-formaldehyde phenolic resin type epoxy resin, bisphenol A-formaldehyde phenolic resin type epoxy resin, bisphenol S-formaldehyde novolac tree
Epoxy-type epoxy resin, bisphenol AF-formaldehyde phenolic resin type epoxy resin, '-biphenyl diphenol-formaldehyde phenolic resin type epoxy resin, neighbour
One or more in phenylphenol-formaldehyde phenolic resin type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
The glycidyl ester type epoxy resin is selected from terephthalic acid diglycidyl ester epoxy resin, M-phthalic acid
2-glycidyl ester epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid two
Ethylene oxidic ester epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters epoxy resin, two octanoic acid two of adjacent benzene
One or more in polyglycidyl epoxy resin.
The curing agent is selected from hexahydrophthalic anhydride, K-12 curing agent, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, dodecenyl succinate
Acid anhydrides, methyl hexahydrophthalic anhydride, tung oil acid anhydride, 80 acid anhydrides formed with dicyclopentadiene and maleic acid anhydride reactant, with terpene two
Acid anhydrides that alkene and maleic acid anhydride reactant form, liquid acid anhydrides, the N formed with turpentine oil and maleic acid anhydride reactant, N-
Dimethylaniline, N, N- dimethyl open-chain crown ether, N, N- dimethyl benzylamines, 2-ethyl-4-methylimidazole, imidazoles, 2,4,6-
One or more in three (dimethylamino methyl) phenol, 1,8- diazas-bicyclic [5.4.0] hendecene -7.
A kind of preparation method of the siliceous epoxy acid imide matrix resin of BDADDM types of the present invention, includes the following steps：
(1) by double (3- amino-4-hydroxylphenyls) hexafluoropropane of 2,2-, o-cresol, double [4- (the 3,4- dicarboxyl benzene of 2,2-
Epoxide) phenyl] propane dianhydride and maleic anhydride be put into reaction kettle, be passed through nitrogen, stir, be heated to 80 DEG C, be added dropwise different
Quinoline, is heated to 100 DEG C -110 DEG C, when stirring reaction 5-12 is small after, be cooled to 60 DEG C, reactant poured into and fills precipitating agent
In precipitating kettle, high-speed stirred, separates out solids, filtering, when 80 DEG C of vacuum drying 10 are small, obtains imide oligomer thing；
(2) by 4,4 '-bis- (2,4- diamino phenoxy) diphenyl-methanes (BDADDM), epoxy resin is put into reaction kettle,
In 80 DEG C -100 DEG C be stirred reaction 0.5-1 it is small when after, add imide oligomer thing continue stirring reaction 1-2 it is small when, then
3- aminopropyltrialkoxysilanes stirring reaction 5-15 minutes is added, is cooled to room temperature, adds curing agent, be uniformly mixed
.
Isoquinolin and the mass ratio of double (3- amino-4-hydroxylphenyls) hexafluoropropane of 2,2- described in step (1) are 1-
4:20。
Precipitating agent described in step (1) is selected from methanol, ethanol, propyl alcohol, isopropanol, ethylene glycol, glycol monoethyl ether, second
One or more in glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, acetone, butanone；Wherein, precipitating agent and 2,
The mass ratio of double (3- amino-4-hydroxylphenyls) hexafluoropropane of 2- is 20-40:1.
O-cresol and the mass ratio of double (3- amino-4-hydroxylphenyls) hexafluoropropane of 2,2- described in step (1) are 10-
20:1。
Beneficial effect
(1) viscosity controllability of the present invention is good, can be adjusted in broader scope, preparation process is simple, environmental-friendly, comprehensive
Excellent performance is closed, can be widely applied between the base material such as the metals such as steel, copper, aluminium and ceramics, glass, polymer matrix composites
Bonding, and the preparation of glass fibre, aramid fiber, carbon fibre reinforced composite, have good industrialization prospect；
(2) present invention can complete preparation process in common apparatus, be advantageously implemented industrialized production.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Scope.
Embodiment 1
By double (3- amino-4-hydroxylphenyls) hexafluoropropane (BAHPFP, 366g/mol) of 73.2 grams of (0.2 mole) 2,2-,
Double [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 735.0 grams of o-cresols, 52.0 grams of (0.1 mole) 2,2- (BPADA,
520g/mol) it is put into 19.6 grams of (0.2 mole) maleic anhydrides (MA, 98g/mol) in reaction kettle, is passed through nitrogen, is stirred, heating
Be warming up to 80 DEG C, 3.8 grams of isoquinolin be added dropwise, be heated to 100 DEG C, when stirring reaction 5 is small after, be cooled to 60 DEG C, reactant fallen
In the precipitating kettle for entering to fill 1500 grams of methanol, high-speed stirred, separates out solids, filtering, when 80 DEG C of vacuum drying 10 are small, obtains
308.3 grams of imide oligomer thing (theoretical yields：314.0 grams), yield 98.2%, is denoted as BBMO-1.
Embodiment 2
By double (3- amino-4-hydroxylphenyls) hexafluoropropane (BAHPFP, 366g/mol) of 73.2 grams of (0.2 mole) 2,2-,
Double [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 1460 grams of o-cresols, 52.0 grams of (0.1 mole) 2,2- (BPADA,
520g/mol) it is put into 19.6 grams of (0.2 mole) maleic anhydrides (MA, 98g/mol) in reaction kettle, is passed through nitrogen, is stirred, heating
Be warming up to 80 DEG C, 14.0 grams of isoquinolin be added dropwise, be heated to 110 DEG C, when stirring reaction 12 is small after, 60 DEG C are cooled to, by reactant
Pour into the precipitating kettle for filling 2000 grams of ethanol and 920 grams of glycol monoethyl ethers, high-speed stirred, separate out solids, filter, 80 DEG C
Be dried in vacuo 10 it is small when, obtain 313.4 grams of imide oligomer thing (theoretical yields：314.0 grams), yield 99.8%, is denoted as BBMO-
2。
Embodiment 3
By 1.0 gram 4,4 '-bis- (2,4- diamino phenoxies) diphenyl-methanes (BDADDM), 10.0 grams of N, N, N ', N ', O,
The glycidyls of O '-six -2,2- double (3- amino-4-hydroxylphenyls) hexafluoropropane epoxy resin, 10.0 grams of N, N, N ', N '-four
Double (4- amino-benzene oxygens) the benzene epoxy resin of glycidyl-1,4-, 10.0 grams of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two contract
Water glycerine ester epoxy resin, 25.0 grams of CE793 epoxy resin and 45.0 grams of N, N, N ', the double [4- of N '-four glycidyl group -2,2-
(4- amino-benzene oxygens) phenyl] propane epoxy resin is put into reaction kettle, in 100 DEG C be stirred reaction 0.5 it is small when after, add
2.0 grams of BBMO-1 imide oligomer things continue stirring reaction 1 it is small when, then add 3.0 grams of 3- aminopropyl trimethoxysilanes stir
Reaction 5 minutes is mixed, is cooled to room temperature, adds 18.0 grams of 1,8- diazas-bicyclic [5.4.0] hendecene -7 and 32.0 grams of methyl
Tetrahydrophthalic anhydride, is uniformly mixed, and obtains the siliceous epoxy acid imide matrix resin of 156.0 grams of BDADDM types, is denoted as M-1.
Embodiment 4
By 3.0 gram 4,4 '-bis- (2,4- diamino phenoxies) diphenyl-methanes (BDADDM), 10.0 grams of N, N, N ', N ', O,
The glycidyls of O '-six -2,2- double (3- amino-4-hydroxylphenyls) hexafluoropropane epoxy resin, 25.0 grams of M-phthalic acids two
Ethylene oxidic ester epoxy resin, 15.0 grams of ES216 epoxy resin and 50.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-two
Diaminodiphenylmethane epoxy resin is put into reaction kettle, in 80 DEG C be stirred reaction 1 it is small when after, add 1.8 grams of BBMO-1 and
The imide oligomer thing of 3.2 grams of BBMO-2 continue stirring reaction 2 it is small when, then add 2.0 grams of 3- aminopropyl trimethoxysilanes
Reacted 5 minutes with 6.0 grams of 3- aminopropyl triethoxysilanes stirrings, be cooled to room temperature, add 30.0 grams of 2- ethyl -4- methyl
Imidazoles, is uniformly mixed, and obtains the siliceous epoxy acid imide matrix resin of 146.0 grams of BDADDM types, is denoted as M-2.
Embodiment 5
By 5.0 gram 4,4 '-bis- (2,4- diamino phenoxies) diphenyl-methanes (BDADDM), 10.0 grams of N, N, N ', N ', O,
The glycidyls of O '-six -2,2- double (3- amino-4-hydroxylphenyls) hexafluoropropane epoxy resin, 10.0 grams of 4,5- epoxy hexamethylenes
Alkane -1,2- dicarboxylic acid diglycidyl esters epoxy resin, 20.0 grams of o-cresols-formaldehyde phenolic resin type epoxy resin, 30.0
Gram hydrogenated bisphenol A diglycidyl ether and 30.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether asphalt mixtures modified by epoxy resin
Fat is put into reaction kettle, in 80 DEG C be stirred reaction 1 it is small when after, add 3.0 grams of BBMO-2 imide oligomer thing continue to stir
Mix reaction 2 it is small when, then add 2.0 grams of 3- aminopropyl triethoxysilanes stirring reaction 15 minutes, be cooled to room temperature, add
20.0 grams of 2-ethyl-4-methylimidazoles and 25.0 grams of methyl tetrahydro phthalic anhydrides, are uniformly mixed, and obtain 155.0 grams of BDADDM types
Siliceous epoxy acid imide matrix resin, is denoted as M-3.
Embodiment 6
Take the siliceous epoxy acid imide matrix resin of BDADDM types of suitable 3~embodiment of embodiment 5 respectively, i.e. M-1~
M-3, and be uniformly applied to respectively in standard stainless steel test piece, overlap, clamp, be put into convection oven and cured：From room
Temperature is started to warm up to 80 DEG C, keep 2 it is small when after, be continuously heating to 120 DEG C, keep 1 it is small when after, be continuously heating to 150 DEG C, keep
0.5 it is small when after, cooled to room temperature.Using electronic tensile machine, room temperature (25 DEG C) and high temperature (180 DEG C) bar are carried out to it respectively
Tensile shear strength test under part, the results are shown in Table 1.
Take the siliceous epoxy acid imide matrix resin of BDADDM types of suitable 3~embodiment of embodiment 5 respectively, i.e. M-1~
M-3, and be uniformly applied to respectively in plate glass test piece, overlap, clamp, be put into convection oven and cured：From room temperature
Start to warm up to 80 DEG C, keep 2 it is small when after, be continuously heating to 120 DEG C, keep 1 it is small when after, be continuously heating to 150 DEG C, keep
0.5 it is small when after, cooled to room temperature.Using electronic tensile machine, room temperature (25 DEG C) and high temperature (180 DEG C) bar are carried out to it respectively
Tensile shear strength test under part, the results are shown in Table 1.
Take the siliceous epoxy acid imide matrix resin of BDADDM types of suitable 3~embodiment of embodiment 5 respectively, i.e. M-1~
M-3, and be equably impregnated with respectively on glass cloth, overlapped and clamped with the test piece of standard stainless steel, be put into convection oven and consolidated
Change：Started to warm up from room temperature to 80 DEG C, keep 2 it is small when after, be continuously heating to 120 DEG C, keep 1 it is small when after, be continuously heating to 150
DEG C, keep 0.5 it is small when after, cooled to room temperature.Using electronic tensile machine, room temperature (25 DEG C) and high temperature are carried out to it respectively
Tensile shear strength test under the conditions of (180 DEG C), the results are shown in Table 1.
1 tensile shear strength of table, unit：MPa
Claims (10)
- A kind of 1. siliceous epoxy acid imide matrix resin of BDADDM types, it is characterised in that：It is 1-5 by mass ratio:100:2-8:1- 5:The 4,4 ' of 30-50-bis- (2,4- diamino phenoxies) diphenyl-methane BDADDM, epoxy resin, 3- aminopropyl tri-alkoxy silicon Alkane, imide oligomer thing and curing agent composition；Wherein, imide oligomer thing be by molar ratio be 2:1:Double (the 3- ammonia of 2 2,2- Base -4- hydroxy phenyls) hexafluoropropane, double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides of 2,2- and maleic anhydride reaction And obtain.
- A kind of 2. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 1, it is characterised in that：The 3- Aminopropyltrialkoxysilane is selected from one or both of 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes Mixture.
- A kind of 3. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 1, it is characterised in that：The ring Oxygen tree fat is selected from E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, CE793 asphalt mixtures modified by epoxy resin Fat, glycidyl amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol aldehyde type epoxy resin, contracting One or more in water glycerine ester type epoxy resin.
- A kind of 4. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 3, it is characterised in that：The contracting Water glyceramine type epoxy resin is selected from N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four shrink sweet Oil base -3,3 '-diethyl -4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-two Chloro- 4,4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether asphalt mixtures modified by epoxy resin Fat, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylsulfone epoxy resin, N, N, N ', N '-four glycidyl group -3, 4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-diaminodiphenylsulfone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group p-phenylenediamine epoxy Resin, N, N, N ', N '-four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, N ', the double (4- of N '-four glycidyl group -1,4- Amino-benzene oxygen) benzene epoxy resin, N, N, N ', double (3- amino-benzene oxygens) the benzene epoxy resin of N '-four glycidyl group -1,4-, N, N, N ', N '-four glycidyl group -1,3- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four glycidyl group - 1,3- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the double (2- trifluoromethyl -4- ammonia of N '-four glycidyl group -1,4- Phenoxyl) benzene epoxy resin, N, N, N ', double (2- trifluoromethyl-4-aminophenoxyls) benzene of N '-four glycidyl group -1,3- Epoxy resin, N, N, N ', N ', O- five glycidyls -4,4 '-diaminourea -4 "-hydroxyl triphenylmenthane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', the glycidols of N '-four Base -2,2- double [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double [4- (3- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', double [4- (the 2- fluoroforms of N '-four glycidyl group -2,2- Base -4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', double [4- (the 3- aminobenzene oxygen of N '-four glycidyl group -2,2- Base) phenyl] hexafluoropropane epoxy resin, N, N, N ', the double [4- (2- trifluoromethyl -4- aminobenzenes of N '-four glycidyl group -2,2- Epoxide) phenyl] hexafluoropropane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl ether Epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether asphalt mixtures modified by epoxy resin Fat, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four contracts Water glyceryl -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', the glycidols of N '-four Base -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- tri- Methyl fluoride -4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- aminobenzenes Epoxide) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) Diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) benzophenone asphalt mixtures modified by epoxy resin Fat, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ', the glycidols of N '-four Base -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resin, N, N, N ', N ', O, O '-six glycidyl - 2,2- couples of (3- amino-4-hydroxylphenyls) hexafluoropropane epoxy resin, N, N, O-triglycidyl group para-aminophenol asphalt mixtures modified by epoxy resin Fat, N, the one or more in N, O-triglycidyl meta-aminophenol epoxy resin.
- A kind of 5. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 3, it is characterised in that：The contracting Water ethoxylated glycerol type epoxy resin is selected from 1,3- resorcinol diglycidyl ethers, 1,4- resorcinol diglycidyl ethers, 4,4 '-bis-phenol Double (the 4- glycidyl ethers phenyl) hexafluoropropane of S diglycidyl ethers, 2,2-, 2,2- are double (4- glycidol ethers butylcyclohexyl) Propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, fatty alcohol shrink sweet more One or more in oily ether.
- A kind of 6. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 3, it is characterised in that：The fat Ring-like epoxy resin is selected from 3,4- epoxycyclohexyethylSiOis acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxy group -6- methyl cyclohexanes Acid -3 ', the one or more in 4 '-epoxy group -6 '-methyl cyclohexane methyl esters, Dipentenedioxide.
- A kind of 7. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 3, it is characterised in that：The phenol Aldehyde type epoxy resin be selected from phenol-formaldehyde phenolic resin type epoxy resin, o-cresol-formaldehyde phenolic resin type epoxy resin, Resorcinol-formaldehyde phenolic resin type epoxy resin, m-cresol-formaldehyde phenolic resin type epoxy resin, catechol-formaldehyde Phenolic resin type epoxy resin, bisphenol A-formaldehyde phenolic resin type epoxy resin, bisphenol S-formaldehyde phenolic resin type epoxy resin, Bisphenol AF-formaldehyde phenolic resin type epoxy resin, '-biphenyl diphenol-formaldehyde phenolic resin type epoxy resin, o-phenyl phenol-formaldehyde One or more in phenolic resin type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
- A kind of 8. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 3, it is characterised in that：The contracting Water glycerine ester type epoxy resin is selected from terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate ring Oxygen tree fat, o-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid 2-glycidyl ester epoxy Resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters epoxy resin, the sad diglycidyl ether asphalt mixtures modified by epoxy resin of adjacent benzene two One or more in fat.
- A kind of 9. siliceous epoxy acid imide matrix resin of BDADDM types according to claim 1, it is characterised in that：It is described solid Agent is selected from hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride, methyl hexahydrophthalic anhydride, eleostearic acid Acid anhydride, 80 acid anhydrides formed with dicyclopentadiene with maleic acid anhydride reactant, formed with limonene and maleic acid anhydride reactant Acid anhydrides, the liquid acid anhydrides, the N that are formed with turpentine oil and maleic acid anhydride reactant, accelerine, N, N- dimethyl is to first Base aniline, N, N- dimethyl benzylamines, 2-ethyl-4-methylimidazole, imidazoles, 2,4,6- tri- (dimethylamino methyl) phenol, 1,8- One or more in diaza-bicyclic [5.4.0] hendecene -7.
- 10. a kind of preparation method of the siliceous epoxy acid imide matrix resin of BDADDM types as claimed in claim 1, including it is as follows Step：(1) by double (3- amino-4-hydroxylphenyls) hexafluoropropane of 2,2-, o-cresol, the double [4- (3,4- di carboxyl phenyloxies) of 2,2- Phenyl] propane dianhydride and maleic anhydride be put into reaction kettle, be passed through nitrogen, stir, be heated to 80 DEG C, isoquinolin is added dropwise, Be heated to 100 DEG C -110 DEG C, when stirring reaction 5-12 is small after, be cooled to 60 DEG C, reactant poured into the precipitating for filling precipitating agent In kettle, stirring, separates out solids, filters, and vacuum drying, obtains imide oligomer thing；(2) by 4,4 '-bis- (2,4- diamino phenoxy) diphenyl-methane BDADDM, epoxy resin is put into reaction kettle, in 80 DEG C- 100 DEG C be stirred reaction 0.5-1 it is small when after, add imide oligomer thing continue stirring reaction 1-2 it is small when, then add 3- ammonia Propyl trialkoxy silane stirring reaction 5-15 minutes, is cooled to room temperature, adds curing agent, be uniformly mixed.
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| CN102618200B (en) * | 2012-03-21 | 2013-11-13 | 东华大学 | Organosilicone-epoxy-polyimide adhesive and preparation method thereof |
| CN103146330B (en) * | 2013-03-11 | 2014-08-13 | 东华大学 | 2,2-bis[4-(2,4-diamidophenoxy)phenyl]hexafluoropropane high-temperature-resistant epoxy adhesive and preparation method thereof |
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