CN106117554B - A kind of siliceous epoxy acid imide matrix resin of BDADDS type and preparation method thereof - Google Patents
A kind of siliceous epoxy acid imide matrix resin of BDADDS type and preparation method thereof Download PDFInfo
- Publication number
- CN106117554B CN106117554B CN201610614045.7A CN201610614045A CN106117554B CN 106117554 B CN106117554 B CN 106117554B CN 201610614045 A CN201610614045 A CN 201610614045A CN 106117554 B CN106117554 B CN 106117554B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- bis
- resin
- glycidyl group
- amino
- 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.)
- Expired - Fee Related
Links
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
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
Abstract
The present invention relates to siliceous epoxy acid imide matrix resins of a kind of BDADDS type and preparation method thereof, the matrix resin is by 4,4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS) BDADDS, epoxy resin, 3- aminopropyltrialkoxysilane, imide oligomer object and curing agent composition.Preparation method includes the following steps: that (1) prepares imide oligomer object；(2) by 4,4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS), epoxy resin is put into reaction kettle, after being stirred reaction, imide oligomer object is added to continue to be stirred to react, 3- aminopropyltrialkoxysilane is then added to be stirred to react, adds curing agent and is uniformly mixed.It the composite can be widely applied to the bonding between the substrates 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, there is good industrialization prospect.
Description
Technical field
The invention belongs to macromolecule matrix resin and its preparation field, in particular to a kind of siliceous epoxy acyl of BDADDS type is sub-
Amine matrix resin and preparation method thereof.
Background technique
It is well known that epoxy resin has many excellent performances: (1) good adhesive property: adhesive strength is high, bonding
Wide, (such as glass, ceramics, resin base are multiple for it and many metals (such as iron, steel, copper, aluminium, metal alloy) or nonmetallic materials
Condensation material, timber, plastics etc.) adhesive strength it is very high, some, which is even more than, is glued the intensity of material 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, processing technology and product properties diversity be the most outstanding in high molecular material；(3) good stability
Can: the ring opening polyaddition of epoxy resin solidified mainly by epoxy group, therefore low-molecular material is not generated in solidification process,
Its cure shrinkage is one of kind minimum in thermosetting resin, generally 1%-2%, if selecting filler appropriate that can make
Shrinking percentage is down to 0.2% or so；Epoxy main chains after solidification are ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore are had 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.
Currently, there is also some problems for epoxy-resin systems, if heat resistance is lower, much not as good as heteroaromatic Type of Collective object
It is (such as polyimides, polybenzimidazoles, polybenzoxazoles, polyphenylene quinoxaline, polybenzothiozole).
Polyimides is developed in the sixties, and most common one is by pyromellitic acid anhydride and aromatic diamine system
?.Contain multiple aromatic heterocycle structural 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, thermal decomposition temperature generally have at 500 DEG C or more, while also
There is obdurability.Therefore, it is also frequently utilized for thermosetting resin, such as the heat-resisting toughening of epoxy resin, bimaleimide resin changes
Property agent.
Chinese invention patent CN103146330A discloses a kind of bis- [4- (2,4- diamino phenoxy) phenyl] six of 2,2-
Fluoro-propane type high temperature resistant epoxy adhesive and preparation method thereof is made of, wherein A component A and B component that mass ratio is 1:1-2
Component is copolymer made of being reacted as bis- [4- (2,4- diamino phenoxy) phenyl] hexafluoropropane of 2,2- with epoxy resin；B
Component is by bis- [4- (2,4- diamino phenoxy) phenyl] hexafluoropropane of 2,2- and aromatic dicarboxylic anhydride in highly polar non-matter
Solid content made of reacting in sub- organic solvent and toluene is the homogeneous phase transparent solution of 15%-30%.Preparation method includes: room temperature
Under, A, B component 1:1-2 in mass ratio are uniformly mixed.
It is resistance to that Chinese invention patent CN103131369A discloses a kind of bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS) types of 4,4'-
High-temp epoxy adhesive and preparation method thereof is made of component A and B component that mass ratio is 1:1-2, wherein component A be by 4,
Copolymer made of 4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS)s are reacted with epoxy resin；B component is by 4,4 '-bis- (2,4-
Diamino phenoxy) diphenyl sulphone (DPS) is solid made of reacting in highly polar aprotic organic solvent and toluene with aromatic dicarboxylic anhydride
Content is the homogeneous phase transparent solution of 15%-30%.Preparation method includes: that at room temperature, A, B component 1:1-2 in mass ratio are stirred
It is uniformly mixed.
Chinese invention patent CN103146331A discloses a kind of resistance to height of bis- (2,4- diamino phenoxy) biphenyl types of 4,4'-
Temperature epoxy adhesive and preparation method thereof is made of component A and B component that mass ratio is 1:1-2, and wherein component A is by 4,4 '-
Copolymer made of bis- (2,4- diamino phenoxy) biphenyl are reacted with epoxy resin；B component is by 4,4 '-bis- (2,4- diaminos
Phenoxyl) solid content made of biphenyl reacts in highly polar aprotic organic solvent and toluene with aromatic dicarboxylic anhydride is
The homogeneous phase transparent solution of 15%-30%.Preparation method includes: that at room temperature, A, B component 1:1-2 in mass ratio are stirred
It is even.
Yan Rui, Yu Xinhai et al. [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 Xinhai et al. [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, simultaneously
The superior adhesive of comprehensive performance is obtained.
Yu Xinhai et al. has applied for Chinese invention patent CN102220102A, 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 a kind of epoxyn that 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. [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 especially 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.
Xu Meifang 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,
Be characterized mainly in that: TGDDM epoxy resin, toughener, hydrogenated bisphenol A, curing agent, promotor are uniformly mixed, and resistance to height has been made
Warm non-solvent epoxy adhesive.But its high temperature resistance still has biggish limitation, is not able to satisfy 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 bis- (2,4- diamino phenoxy) the benzene aromatic polyvalent amine hardeners of 1,3-.Alicyclic ring type ring
The additive amount of oxygen resin and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.
The additive amount of bis- (2,4- diamino phenoxy) 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 ideal 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, polyimide powder can form covalent bond with epoxy reaction, sub- so as to improve thermoplasticity polyamides
The compatibility of polyimide resin and epoxy resin, and so that epoxy-resin systems is reached good toughening effect.
Yu Xinhai et al. [development [J] of high-temperature resistant single-component epoxy adhesive is bonded, 2008,29 (12): 16-19] is public
The preparation method for having opened a kind of high-temperature resistant single-component epoxy adhesive, is primarily characterized in that: being sealing end with maleic anhydride (MA)
Agent, with bis- [4- (4- amino-benzene oxygen) phenyl] third of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (BAHPFP) of 2,2-, 2,2-
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydrides (BPADA) of alkane (BAPOPP), 2,2- are that main Material synthesis obtains
Phenolic hydroxy group polyetherimide resin (HPEI)；With synthesized obtained HPEI for resistant, toughened dose, with N, N, N', N'- tetra-
Glycidyl -4,4'- diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent
Deng, preparation obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of siliceous epoxy acid imide matrix resin of BDADDS type 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 bonding and glass fibre, aramid fiber, fibre reinforced between the substrates such as ceramics, glass, polymer matrix composites
The preparation of composite material has good industrialization prospect.
The siliceous epoxy acid imide matrix resin of a kind of BDADDS type of the invention is 1-5:100:2-8:1-5 by mass ratio:
Bis- (2,4- diamino phenoxy) the diphenyl sulphone (DPS) BDADDS in the 4,4 ' of 30-50-, epoxy resin, 3- aminopropyltrialkoxysilane, acyl
Imide oligomer and curing agent composition；Wherein, imide oligomer object is the bis- (3- amino -4- hydroxyls of 2,2- for being 2:1:2 by molar ratio
Base phenyl) hexafluoropropane, bis- [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 2,2- and maleic anhydride reaction and obtain.
The 3- aminopropyltrialkoxysilane is selected from 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane
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
Rouge, CE793 epoxy resin, glycidyl amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenol
One or more of 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 '-diamino 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 '-diamino 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- bis- (4- amino-benzene oxygen) benzene epoxy resin, N, N, N ', bis- (the 3- aminobenzenes of N '-four glycidyl group -1,4-
Oxygroup) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,3- bis- (4- amino-benzene oxygen) benzene epoxy resin, N, N, N ',
N '-four glycidyl group -1,3- bis- (3- amino-benzene oxygen) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,4- is double
(2- trifluoromethyl-4-aminophenoxyl) benzene epoxy resin, N, N, N ', bis- (the 2- trifluoromethyls-of N '-four glycidyl group -1,3-
4- amino-benzene oxygen) benzene epoxy resin, N, N, N ', N ', O- five glycidyls -4,4 '-diamino -4 " and-hydroxyl triphenylmenthane
Epoxy resin, N, N, N ', N '-four glycidyl group -2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane epoxy resin, N, N,
N ', N '-four glycidyl group -2,2- bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane epoxy resin, N, N, N ', N '-four
Glycidyl -2,2- bis- [4- (3- amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', four glycidyl group -2 N ' -,
2- bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2-
Bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane epoxy resin, N, N, N ', the bis- [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- aminobenzene
Oxygroup) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS) asphalt mixtures modified by epoxy resin
Rouge, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS) epoxy resin, N, N,
N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ',-four glycidol of N '
Base -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl sulfide epoxy resin, N, N, N ', four glycidyl group -4 N ' -,
4 '-bis- (4- amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- fluoroform
Base -4- amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygen)
Benzophenone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) hexichol
Ketone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygen) biphenyl epoxy resin, N, N, N ',
N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, N, N ', N ', O, O ' -
Six glycidyl -2,2- bis- (3- amino-4-hydroxylphenyl) hexafluoropropane epoxy resin, N, N, O-triglycidyl group is to ammonia
Base phenol epoxy resin, N, one or more of N, O-triglycidyl meta-aminophenol epoxy resin.
The diglycidyl ether type epoxy resin is selected from 1,3- diglycidyl resorcinol, 1,4- diglycidyl
Bis- (the 4- contractings of bis- (4- glycidyl phenyl) hexafluoropropane of hydroquinone, 4,4 '-diglycidyl bisphenol Ss, 2,2-, 2,2-
Water glycerol butylcyclohexyl) propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol-A 2-glycidyl
One or more of ether, fatty alcohol polyglycidyl ether.
The alicyclic type epoxy resin is selected from 3,4- epoxycyclohexyethylSiOi sour -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxy
One or more of sour -3 ', 4 '-epoxy groups-the 6 '-methyl cyclohexane methyl esters of base -6- methyl cyclohexane, 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 of 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 ester epoxy resin, two octanoic acid two of adjacent benzene
One or more of 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, with 80 acid anhydrides made of dicyclopentadiene and maleic acid anhydride reactant, with terpene two
Acid anhydrides made of alkene and maleic acid anhydride reactant, with liquid acid anhydrides, N made of turpentine oil and maleic acid anhydride reactant, N-
Dimethylaniline, N, N- dimethyl open-chain crown ether, N, N- dimethyl benzylamine, 2-ethyl-4-methylimidazole, imidazoles, 2,4,6-
One or more of three (dimethylamino methyl) phenol, 1,8- diaza-bicyclic [5.4.0] hendecene -7.
A kind of preparation method of the siliceous epoxy acid imide matrix resin of BDADDS type of the invention, includes the following steps:
(1) by bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, o-cresol, bis- [4- (the 3,4- dicarboxyl benzene of 2,2-
Oxygroup) 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, after being stirred to react 5-12 hours, is cooled to 60 DEG C, reactant is poured into and fills precipitating agent
In precipitating kettle, solids is precipitated in high-speed stirred, and filtering, 80 DEG C are dried in vacuo 10 hours, obtain imide oligomer object；
(2) 4,4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS)s (BDADDS), epoxy resin are put into reaction kettle, in
After 80 DEG C -100 DEG C are stirred reaction 0.5-1 hours, imide oligomer object is added and continues to be stirred to react 1-2 hours, then adds
Enter 3- aminopropyltrialkoxysilane to be stirred to react 5-15 minutes, is cooled to room temperature, adds curing agent, be uniformly mixed i.e.
It can.
Isoquinolin described in step (1) and the mass ratio of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2- are 1-
4:20。
Precipitating agent described in step (1) is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, ethylene glycol, glycol monoethyl ether, second
One or more of glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, acetone, butanone；Wherein, precipitating agent and 2,
The mass ratio of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2- is 20-40:1.
O-cresol described in step (1) and the mass ratio of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2- are 10-
20:1。
Beneficial effect
(1) viscosity controllability of the present invention is good, can adjust in broader range, and preparation process is simple, environmental-friendly, comprehensive
Conjunction is had excellent performance, and can be widely applied between the substrates 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.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled 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
Range.
Embodiment 1
By bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (BAHPFP, 366g/mol) of 73.2 grams of (0.2 mole) 2,2-,
Bis- [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,
It 520g/mol) is put into reaction kettle with 19.6 grams of (0.2 mole) maleic anhydrides (MA, 98g/mol), is passed through nitrogen, stirred, heating
80 DEG C are warming up to, 3.8 grams of isoquinolin are added dropwise, are heated to 100 DEG C, after being stirred to react 5 hours, 60 DEG C is cooled to, reactant is fallen
In the precipitating kettle for entering to fill 1500 grams of methanol, solids is precipitated in high-speed stirred, and filtering, 80 DEG C are dried in vacuo 10 hours, obtain
308.3 grams of imide oligomer objects (theoretical yield: 314.0 grams), yield 98.2% is denoted as BBMO-1.
Embodiment 2
By bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (BAHPFP, 366g/mol) of 73.2 grams of (0.2 mole) 2,2-,
Bis- [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,
It 520g/mol) is put into reaction kettle with 19.6 grams of (0.2 mole) maleic anhydrides (MA, 98g/mol), is passed through nitrogen, stirred, heating
80 DEG C are warming up to, 14.0 grams of isoquinolin are added dropwise, are heated to 110 DEG C, after being stirred to react 12 hours, 60 DEG C are cooled to, by reactant
It pours into the precipitating kettle for filling 2000 grams of ethyl alcohol and 920 grams of glycol monoethyl ethers, high-speed stirred, solids is precipitated, filter, 80 DEG C
Vacuum drying 10 hours, obtains 313.4 grams of imide oligomer objects (theoretical yield: 314.0 grams), yield 99.8% is denoted as BBMO-
2。
Embodiment 3
By 1.0 gram of 4,4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS)s (BDADDS), 20.0 grams of N, N, N ', N '-four shrinks
Bis- (4- amino-benzene oxygen) the benzene epoxy resin of glyceryl-1,4-, 20.0 grams of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two shrink sweet
Grease epoxy resin, 15.0 grams of CE793 epoxy resin and 45.0 grams of N, N, N ', bis- [4- (the 4- ammonia of N '-four glycidyl group -2,2-
Phenoxyl) phenyl] propane epoxy resin is put into reaction kettle, after 100 DEG C are stirred reaction 0.5 hour, it is added 2.0 grams
BBMO-1 imide oligomer object continues to be stirred to react 1 hour, and 3.0 grams of 3- aminopropyl trimethoxysilanes are then added and are stirred to react
It 5 minutes, is cooled to room temperature, adds 15.0 grams of 1,8- diazas-bicyclic [5.4.0] hendecene -7 and 35.0 grams of methyl tetrahydro benzene
Acid anhydride is uniformly mixed, and is obtained the siliceous epoxy acid imide matrix resin of 156.0 grams of BDADDS types, is denoted as M-1.
Embodiment 4
By 3.0 gram of 4,4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS)s (BDADDS), 20.0 grams of N, N, N ', N '-four shrinks
Bis- (4- amino-benzene oxygen) the benzene epoxy resin of glyceryl -1,4-, 15.0 grams of Diglycidyl M-phthalate epoxy resin,
10.0 grams of ES216 epoxy resin, 15.0 grams of N, N, N ', N '-four glycidyl group -2,2- bis- [4- (4- amino-benzene oxygen) phenyl]
Propane epoxy resin and 40.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylmethane epoxy resin is put into instead
Answer in kettle, after 80 DEG C are stirred reaction 1 hour, be added the imide oligomer object of 1.5 grams of BBMO-1 and 3.5 gram of BBMO-2 after
It is continuous to be stirred to react 2 hours, 3.0 grams of 3- aminopropyl trimethoxysilanes and 5.0 grams of 3- aminopropyl triethoxysilanes are then added
It is stirred to react 5 minutes, is cooled to room temperature, add 20.0 grams of 2-ethyl-4-methylimidazoles, 5.0 hexahydrophthalic anhydride and 5.0 gram 2,4,
6- tri- (dimethylamino methyl) phenol, is uniformly mixed, and obtains the siliceous epoxy acid imide matrix tree of 146.0 grams of BDADDS types
Rouge is denoted as M-2.
Embodiment 5
By 5.0 gram of 4,4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS)s (BDADDS), 10.0 grams of N, N, N ', N '-four shrinks
Bis- (4- amino-benzene oxygen) the benzene epoxy resin of glyceryl-1,4-, 20.0 grams of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two shrink sweet
Grease epoxy resin, 10.0 grams of o-cresols-formaldehyde phenolic resin type epoxy resin, 20.0 grams of hydrogenated bisphenol A 2-glycidyls
Ether and 40.0 grams of N, N, N ', four glycidyl group -4 N ' -, 4 '-diaminodiphenylmethane epoxy resin are put into reaction kettle, in 80
After DEG C being stirred reaction 1 hour, the imide oligomer object that 3.0 grams of BBMO-2 are added continues to be stirred to react 2 hours, is then added
2.0 grams of 3- aminopropyl triethoxysilanes are stirred to react 15 minutes, are cooled to room temperature, and 30.0 grams of 2- ethyl -4- methyl are added
Imidazoles and 15.0 grams of tung oil acid anhydrides, are uniformly mixed, and obtain the siliceous epoxy acid imide matrix resin of 155.0 grams of BDADDS types,
It is denoted as M-3.
Embodiment 6
Take the siliceous epoxy acid imide matrix resin of the BDADDS type of suitable 3~embodiment of embodiment 5 respectively, i.e. M-1~
M-3, and be uniformly applied in standard stainless steel test piece respectively, it overlaps, clamps, be put into convection oven and solidified: from room
Temperature is started to warm up to 80 DEG C, after being kept for 2 hours, is continuously heating to 120 DEG C, after being kept for 1 hour, is continuously heating to 150 DEG C, is kept
After 0.5 hour, cooled to room temperature.Using electronic tensile machine, room temperature (25 DEG C) and high temperature (180 DEG C) item 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 the BDADDS type of suitable 3~embodiment of embodiment 5 respectively, i.e. M-1~
M-3, and be uniformly applied in plate glass test piece respectively, it overlaps, clamps, be put into convection oven and solidified: from room temperature
It starts to warm up to 80 DEG C, after being kept for 2 hours, is continuously heating to 120 DEG C, after being kept for 1 hour, be continuously heating to 150 DEG C, keep
After 0.5 hour, cooled to room temperature.Using electronic tensile machine, room temperature (25 DEG C) and high temperature (180 DEG C) item 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 the BDADDS type of suitable 3~embodiment of embodiment 5 respectively, i.e. M-1~
M-3, and be equably impregnated with respectively on glass cloth, it is overlapped and is clamped with standard stainless steel test piece, be put into convection oven and consolidated
Change: starting to warm up from room temperature to 80 DEG C, after being kept for 2 hours, is continuously heating to 120 DEG C, after being kept for 1 hour, is continuously heating to 150
DEG C, after being kept for 0.5 hour, 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 (9)
1. a kind of siliceous epoxy acid imide matrix resin of BDADDS type, it is characterised in that: by mass ratio be 1-5:100:2-8:1-
Bis- (2,4- diamino phenoxy) the diphenyl sulphone (DPS) BDADDS in the 4,4 ' of 5:30-50-, epoxy resin, 3- aminopropyltrialkoxysilane,
Imide oligomer object and curing agent composition；Wherein, imide oligomer object is the bis- (3- amino -4- of 2,2- for being 2:1:2 by molar ratio
Hydroxy phenyl) hexafluoropropane, bis- [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 2,2- and maleic anhydride reaction and obtain；
Preparation method includes the following steps:
(1) by bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, o-cresol, the bis- [4- (3,4- di carboxyl phenyloxy) 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,
100 DEG C -110 DEG C are heated to, after being stirred to react 5-12 hours, 60 DEG C is cooled to, reactant is poured into the precipitating for filling precipitating agent
In kettle, solids is precipitated in stirring, is filtered, and vacuum drying obtains imide oligomer object；
(2) 4,4 '-bis- (2,4- diamino phenoxy) diphenyl sulphone (DPS) BDADDS, epoxy resin are put into reaction kettle, in 80 DEG C-
After 100 DEG C are stirred reaction 0.5-1 hours, imide oligomer object is added and continues to be stirred to react 1-2 hours, 3- ammonia is then added
Propyl trialkoxy silane is stirred to react 5-15 minutes, is cooled to room temperature, is added curing agent, is uniformly mixed.
2. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type according to claim 1, it is characterised in that: the 3-
Aminopropyltrialkoxysilane is selected from one or both of 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane
Mixture.
3. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type according to claim 1, it is characterised in that: the ring
Oxygen resin is selected from glycidyl amine type epoxy resin, diglycidyl ether type epoxy resin, alicyclic type epoxy resin, phenolic epoxy
One or more of resin, glycidyl ester type epoxy resin.
4. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type 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 shrinks 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
Rouge, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylsulfone epoxy resin, N, N, N ', four glycidyl group -3 N ' -,
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 bis- (4- of N '-four glycidyl group -1,4-
Amino-benzene oxygen) benzene epoxy resin, N, N, N ', bis- (3- amino-benzene oxygen) the benzene epoxy resin of N '-four glycidyl group -1,4-,
N, N, N ', N '-four glycidyl group -1,3- bis- (4- amino-benzene oxygen) benzene epoxy resin, N, N, N ', N '-four glycidyl group -
1,3- bis- (3- amino-benzene oxygen) benzene epoxy resin, N, N, N ', the bis- (2- trifluoromethyl -4- ammonia of N '-four glycidyl group -1,4-
Phenoxyl) benzene epoxy resin, N, N, N ', bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of N '-four glycidyl group -1,3-
Epoxy resin, N, N, N ', N ', O- five glycidyls -4,4 '-diamino -4 "-hydroxyl triphenylmenthane epoxy resin, N, N, N ',
N '-four glycidyl group -2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ',-four glycidol of N '
Base -2,2- bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double
[4- (3- amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', bis- [4- (the 2- fluoroforms of N '-four glycidyl group -2,2-
Base -4- amino-benzene oxygen) phenyl] propane epoxy resin, N, N, N ', bis- [4- (the 3- aminobenzene oxygen of N '-four glycidyl group -2,2-
Base) phenyl] hexafluoropropane epoxy resin, N, N, N ', the bis- [4- (2- trifluoromethyl -4- aminobenzenes of N '-four glycidyl group -2,2-
Oxygroup) 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-aminophenoxyl) diphenyl ether asphalt mixtures modified by epoxy resin
Rouge, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four contracts
Water glyceryl -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS) epoxy resin, N, N, N ',-four glycidol of N '
Base -4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- tri-
Methyl fluoride -4- amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- aminobenzene
Oxygroup) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl)
Diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygen) benzophenone asphalt mixtures modified by epoxy resin
Rouge, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) benzophenone epoxy resin, N,
N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygen) biphenyl epoxy resin, N, N, N ',-four glycidol of N '
Base -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resins, N, N, N ', N ', O, O '-six glycidyl -
2,2- bis- (3- amino-4-hydroxylphenyl) hexafluoropropane epoxy resin, N, N, O-triglycidyl group para-aminophenol asphalt mixtures modified by epoxy resin
Rouge, N, one or more of N, O-triglycidyl meta-aminophenol epoxy resin.
5. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type according to claim 3, it is characterised in that: the contracting
Water ethoxylated glycerol type epoxy resin is selected from 1,3- diglycidyl resorcinol, 1,4- diglycidyl hydroquinone, 4,4 '-
Bis- (4- glycidyl phenyl) hexafluoropropane of diglycidyl bisphenol S, 2,2-, 2,2- bis- (4- glycidyl cyclohexyls)
Propane, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, fatty alcohol shrink sweet more
One or more of oily ether.
6. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type according to claim 3, it is characterised in that: the rouge
Ring-like epoxy resin is selected from 3,4- epoxycyclohexyethylSiOi sour -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxy group -6- methyl cyclohexane
One or more of sour -3 ', 4 '-epoxy groups -6 '-methyl cyclohexane methyl esters, Dipentenedioxide.
7. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type 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 of phenolic resin type epoxy resin, naphthols-formaldehyde phenolic resin type epoxy resin.
8. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type according to claim 3, it is characterised in that: the contracting
Water glycerol ester type epoxy resin is selected from terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate ring
Oxygen resin, 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 ester epoxy resin, the sad diglycidyl ether asphalt mixtures modified by epoxy resin of adjacent benzene two
One or more of rouge.
9. the siliceous epoxy acid imide matrix resin of a kind of BDADDS type according to claim 1, it is characterised in that: described solid
Agent is selected from hexahydrophthalic anhydride, K-12 curing agent, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride, methyl hexahydrobenzene
Acid anhydride, tung oil acid anhydride, with 80 acid anhydrides made of dicyclopentadiene and maleic acid anhydride reactant, with limonene and maleic anhydride
Acid anhydrides made of reaction, with liquid acid anhydrides, N made of turpentine oil and maleic acid anhydride reactant, accelerine, N, N- bis-
Methyl open-chain crown ether, N, N- dimethyl benzylamine, 2-ethyl-4-methylimidazole, imidazoles, 2,4,6- tri- (dimethylamino methyl) benzene
One or more of phenol, 1,8- diaza-bicyclic [5.4.0] hendecene -7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610614045.7A CN106117554B (en) | 2016-07-29 | 2016-07-29 | A kind of siliceous epoxy acid imide matrix resin of BDADDS type and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610614045.7A CN106117554B (en) | 2016-07-29 | 2016-07-29 | A kind of siliceous epoxy acid imide matrix resin of BDADDS type and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106117554A CN106117554A (en) | 2016-11-16 |
| CN106117554B true CN106117554B (en) | 2019-02-26 |
Family
ID=57255363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610614045.7A Expired - Fee Related CN106117554B (en) | 2016-07-29 | 2016-07-29 | A kind of siliceous epoxy acid imide matrix resin of BDADDS type and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106117554B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101487190A (en) * | 2009-02-17 | 2009-07-22 | 东华大学 | Polyimide carbon fiber sizing agent and method for producing the same |
| CN104559059A (en) * | 2014-12-26 | 2015-04-29 | 东华大学 | High-temperature-resistant matrix resin for high-Tg copper-clad plate and preparation method of high-temperature-resistant matrix resin |
-
2016
- 2016-07-29 CN CN201610614045.7A patent/CN106117554B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101487190A (en) * | 2009-02-17 | 2009-07-22 | 东华大学 | Polyimide carbon fiber sizing agent and method for producing the same |
| CN104559059A (en) * | 2014-12-26 | 2015-04-29 | 东华大学 | High-temperature-resistant matrix resin for high-Tg copper-clad plate and preparation method of high-temperature-resistant matrix resin |
Non-Patent Citations (1)
| Title |
|---|
| 有机硅环氧体系粘合剂的研制与性能研究;虞鑫海等;《绝缘材料》;20121231;第45卷(第2期);参见第1-2页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106117554A (en) | 2016-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103122231B (en) | 1,4-di(2,4-diamino phenoxy) benzenoid form high-temperature epoxy adhesive and preparation method thereof | |
| CN103146331B (en) | 4,4'-bis(2,4-diamidophenoxy)biphenyl high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN103131370B (en) | 1,3-bis(2,4-diamidophenoxy)benzene high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN102181251A (en) | Epoxy resin adhesive modified by unsaturated polyimide and preparation method thereof | |
| CN103214793A (en) | Advanced composite material matrix resin and preparation method thereof | |
| CN103146330B (en) | 2,2-bis[4-(2,4-diamidophenoxy)phenyl]hexafluoropropane high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN103131369B (en) | 4,4'-bis(2,4-diamidophenoxy)diphenylsulphone high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN103122232B (en) | 2,2-di[4-(2,4-diamino phenoxy) phenyl] propane form high-temperature epoxy adhesive and preparation method thereof | |
| CN106220851B (en) | A kind of siliceous epoxy acid imide matrix resin of YASI types and preparation method thereof | |
| CN103131368B (en) | 4,4'-bis(2,4-diamidophenoxy)diphenyl ether high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN103396529B (en) | A kind of high temperature resistant electric insulation veneer sheet matrix resin and preparation method thereof | |
| CN106146842B (en) | A kind of siliceous epoxy acid imide matrix resin of 13BDAPB types and preparation method thereof | |
| CN106146843B (en) | A kind of siliceous epoxy acid imide matrix resin of BDAPP types and preparation method thereof | |
| CN106117554B (en) | A kind of siliceous epoxy acid imide matrix resin of BDADDS type and preparation method thereof | |
| CN106243353B (en) | A kind of siliceous epoxy acid imide matrix resin of BDATHQ types and preparation method thereof | |
| CN106146841B (en) | A kind of siliceous epoxy acid imide matrix resin of DAHTM types and preparation method thereof | |
| CN106146845B (en) | A kind of siliceous epoxy acid imide matrix resin of BDADDE types and preparation method thereof | |
| CN106220850B (en) | A kind of siliceous epoxy acid imide matrix resin of DADHBP types and preparation method thereof | |
| CN106146844B (en) | A kind of siliceous epoxy acid imide matrix resin of BDAPFP types and preparation method thereof | |
| CN106146847B (en) | A kind of siliceous epoxy acid imide matrix resin of BAHPFP types and preparation method thereof | |
| CN106146846B (en) | A kind of siliceous epoxy acid imide matrix resin of BAHPP types and preparation method thereof | |
| CN106146848B (en) | A kind of siliceous epoxy acid imide matrix resin of 14BDAPB types and preparation method thereof | |
| CN106220852B (en) | A kind of siliceous epoxy acid imide matrix resin of BDABP types and preparation method thereof | |
| CN109722212A (en) | A kind of acid imide epoxy organic silica gel and preparation method thereof | |
| CN106117517B (en) | A kind of siliceous epoxy acid imide matrix resin of BDADDM types and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190226 Termination date: 20210729 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |