CN109722214A - A kind of DAHTM type silicon-containing adhesive and preparation method thereof - Google Patents
A kind of DAHTM type silicon-containing adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109722214A CN109722214A CN201811569937.5A CN201811569937A CN109722214A CN 109722214 A CN109722214 A CN 109722214A CN 201811569937 A CN201811569937 A CN 201811569937A CN 109722214 A CN109722214 A CN 109722214A
- Authority
- CN
- China
- Prior art keywords
- bis
- amino
- benzene
- benzene oxygen
- oxygen
- 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.)
- Pending
Links
Abstract
The present invention relates to a kind of DAHTM type silicon-containing adhesives and preparation method thereof, by 4,4 '-diamino -4 "-hydroxyl triphenylmenthane DAHTM, aromatic diamine, aromatic dicarboxylic acid anhydride, 3- aminopropyltrialkoxysilane and γ-(2; the third oxygen of 3- epoxy) propyl trimethoxy silicane reaction product and organic solvent composition.Raw material sources of the invention are convenient, and simple process is easy to operate, and product comprehensive performance is good, can be applied to the bonding of glass, ceramics, composite material, extraordinary polarity weaving prepreg and its composite material base, have good market application prospect.
Description
Technical field
The invention belongs to adhesive area, in particular to a kind of DAHTM type silicon-containing adhesive and preparation method thereof.
Background technique
Adhesive system is widely used in the every field of national economy: either high-technology field or general
Its trace can be seen in technical field, either defence and military or civilian industry or even daily life.
Related adhesive system or containing silicone resin system have had many research reports, also there is many patents of invention:
Chinese invention patent CN102786902A discloses a kind of organosilicon Organic fluoride epoxy adhesive and preparation method thereof.
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.
Chinese invention patent CN106220851A discloses a kind of siliceous epoxy acid imide matrix resin of YASI type and its system
Preparation Method.
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.
Chinese invention patent CN102220102A discloses a kind of high-temperature-resistant adhesive and preparation method thereof.
Chinese invention patent CN106146841A discloses a kind of preparation of siliceous epoxy acid imide matrix resin of DAHTM type
Method 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) by 4,4 '-diamino -4 "-hydroxyl triphenylmenthane (DAHTM), epoxy resin is 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.
Chinese invention patent CN102181251A discloses a kind of epoxyn that unsaturated polyimides are modified
And preparation method thereof.
Chinese invention patent CN101649174A discloses a kind of high temperature resistant one-component solvent-free epoxy adhesive and its system
Preparation Method.
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.
Fei Fei et al. [preparation of high temperature resistant epoxy binder in monocomponent in, bonding, 2009,30 (12): 34-37] discloses one
Kind one-component thermostable epoxy adhesive.
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 CN104844801A discloses a kind of Silicone Containing Polyimides copper coated foil plate, it is characterised in that: by
Copper foil, alkali-free glass cloth and Silicone Containing Polyimides resin composition；Wherein, it is 1:1-5 that Silicone Containing Polyimides resin, which is by mass ratio,
A, B component polymerization reaction and obtain；And component A is reacted with aromatic dianhydride by the organosilicon diamines that molar ratio is 1:2 and is obtained；B
Component is by molar ratio are as follows: the aromatic diamine of 2:1.8-1.9:0.1-0.3 is reacted with aromatic dianhydride, maleic anhydride and obtained.
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 4,4 '-bis- (2,4- diamino phenoxy) diphenyl ether aromatic polyvalent amine hardeners.Rouge
The additive amount of ring-like epoxy resin and nbr carboxyl terminal is respectively the 20-35% and 12% (quality hundred of novolac epoxy resin
Score).The additive amount of 4,4 '-bis- (2,4- diamino phenoxy) diphenyl ether aromatic polyvalent amine hardeners is epoxy novolac
Chinese patent CN101397486A discloses a kind of preparation method of bi-component solvent-free epoxy resin adhesive,
Be characterized mainly in that: it includes component A and B component, and wherein component A contains novolac epoxy resin, alicyclic type epoxy resin and end
Carboxy nitrile rubber；B component is bis- (2,4- diamino phenoxy) the benzene aromatic polyvalent amine hardeners of 1,4-.Alicyclic ring type asphalt mixtures modified by epoxy resin
The additive amount of rouge and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.1,4-
The additive amount of bis- (2,4- diamino phenoxy) benzene aromatic polyvalent amine hardeners is the 15-20% (quality of novolac epoxy resin
Percentage), gained adhesive system good manufacturability.But its heat resistance is ideal not enough.
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.
This method, although containing the polyetherimide resin of active reactive group (hydroxyl, unsaturated double-bond) by synthesis
(HPEI), toughening modifying has been carried out to epoxy resin, and has achieved preferable technical effect.But there is also some disadvantages:
(1) reactable group is limited, and the content of especially unsaturated double-bond is relatively low.Because maleic anhydride is as sealing end
Agent come using, the dosage of maleic anhydride is seldom.
The monomers such as bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (BAHPFP) of (2) 2,2- are expensive, lead to polyethers acyl
The cost of imide resin (HPEI) and adhesive is very high, is unfavorable for large-scale promotion application, can only be confined to certain special dimensions.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of DAHTM type silicon-containing adhesives and preparation method thereof, this contains
Silicon adhesive comprehensive performance is good, can be applied to glass, ceramics, composite material, extraordinary polarity weaving prepreg and its composite wood
Expect the bonding of substrate, there is good market application prospect.
The present invention provides a kind of DAHTM type silicon-containing adhesive, the adhesive is 1:5-10:6.5-12 by molar ratio:
The 4,4 ' of 1-2:1-diamino-4 "-hydroxyl triphenylmenthane DAHTM, aromatic diamine, aromatic dicarboxylic acid anhydride, 3- aminopropyl three
The reaction product and organic solvent of alkoxy silane and γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane composition.
The aromatic diamine is selected from m-phenylene diamine (MPD), p-phenylenediamine, 2- methylresorcinol diamines, 2,4,6- trimethyl isophthalic
Diamines, 3,4 '-diaminodiphenyl ethers, 4,4 '-diaminodiphenyl ethers, 3,3 '-diaminodiphenyl ethers, 3,5- diaminobenzoic acid,
4,4 '-benzidines, 3,3 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino two
Benzene sulfone, 3,3 '-diaminodiphenylsulfones, 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane, 3,3 '-two chloro- 4,4 '-diamino
Diphenyl-methane, 3,3 ', 5,5 '-tetramethyls -4,4 '-diaminodiphenylmethane, 2,6- bis- (4- amino-benzene oxygen) benzonitriles, 2,6-
Bis- (4- amino-benzene oxygen) benzoic acid of bis- (3- amino-benzene oxygen) benzonitriles, 3,5-, 2- (4- aminophenyl) -5- amino benzo miaow
Bis- (3- amino-4-hydroxylphenyl) propane of azoles, 3,3 '-diamino -4,4 '-dihydroxybiphenyl, 2,2-, the bis- (3- amino -4- of 2,2-
Hydroxy phenyl) hexafluoropropane, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (the 4- amino of 1,4-
Phenoxy group) benzene, bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, 1,4- bis- (2- trifluoromethyl-4-aminophenoxyls)
Bis- (4- amino-benzene oxygen) toluene of benzene, 2,6-, bis- (4- amino-benzene oxygen) toluene of 2,5-, the bis- (2- trifluoromethyl -4- amino of 3,5-
Phenoxy group) benzoic acid, bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of 2,6-, the bis- (2- trifluoromethyl -4- aminobenzenes of 2,5-
Oxygroup) toluene, bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-, the bis- [4- (2- trifluoromethyl-4-aminophenoxyl) of 2,2-
Phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] propane of 2,2-, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl-methanes, 4,
4 '-bis- (3- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl-methanes, 2,2- are bis-
Bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] hexafluoros third of [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2-
It is bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of alkane, 2,2-, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS)s, 4,4 '-bis-
(3- amino-benzene oxygen) diphenyl sulphone (DPS), 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS)s, 4,4 '-bis- (4- aminobenzenes
Oxygroup) diphenyl sulfide, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl sulfides, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls)
Diphenyl sulfide, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (2- tri-
Methyl fluoride -4- amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (4- amino-benzene oxygen) benzophenone, 4,4 '-bis- (3- aminobenzene oxygen
Base) benzophenone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis- (4- amino-benzene oxygens) connection
One of benzene, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) biphenyl are several
Kind.
The aromatic dicarboxylic acid anhydride be selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydrides, 3,3 ', 4,
Bis- (3,4- dicarboxyphenyi) hexafluoros third of 4 '-tetracarboxylic diphenyl sulfone dianhydrides, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydrides, 2,2-
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of alkane dianhydride, 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydrides, 2,2-,
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 2,2-, 1,4- bis- (3,4- di carboxyl phenyloxy) benzene dianhydrides, 1,3-
Double-(3,4- di carboxyl phenyloxy) benzene dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxy) biphenyl dianhydrides, 4,4 '-bis- (3,4- bis-
Carboxyphenoxy) diphenyl sulfone dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxy) diphenyl ether dianhydrides, 4,4 '-bis- (3,4- dicarboxyls
Phenoxy group) diphenyl ether dianhydride, one or more of 4,4 '-bis- (3,4- di carboxyl phenyloxy) benzophenone dianhydrides.
The 3- aminopropyltrialkoxysilane is selected from 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane
One or both of.
The organic solvent is selected from N, N-dimethylformamide, N, N dimethyl acetamide, tetrahydrofuran, methyl tetrahydro furan
It mutters, one or more of n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, dimethyl sulfoxide.
The mass ratio of the organic solvent and reactant is 2.5-9.5:1；Wherein, reactant refers to 4,4 '-diamino-
4 "-hydroxyl triphenylmenthane DAHTM, aromatic diamine, aromatic dicarboxylic acid anhydride, 3- aminopropyltrialkoxysilane and γ-(2,3-
The third oxygen of epoxy) propyl trimethoxy silicane.
The present invention also provides a kind of preparation methods of DAHTM type silicon-containing adhesive, include the following steps:
According to the ratio, by 4,4 '-diamino -4 "-hydroxyl triphenylmenthane DAHTM and organic solvent be put into reaction kettle, room temperature
After lower stirring and dissolving, aromatic diamine is added, after stirring and dissolving, aromatic dicarboxylic acid anhydride is added, it is small to be stirred to react 1.0 at room temperature
When -4.0 hours after, 3- aminopropyltrialkoxysilane is added, is stirred to react -2 hours 0.5 hour at room temperature, γ-is then added
(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, is stirred to react 15min in 80 DEG C -90 DEG C up to DAHTM type silicon-containing adhesive.
Beneficial effect
(1) present invention has a good hot mechanical performance, and excellent combination property, can be applied to glass, ceramics, compound
The bonding of material, extraordinary polarity weaving prepreg and its composite material base, has good market application prospect；
(2) preparation process of the invention is simple, at low cost, easy to operate, reaction raw materials convenient sources, can set general
Standby middle completion preparation process, is advantageously implemented industrialized production；
(3) 3- aminopropyltrialkoxysilane, γ-(the third oxygen of 2,3- epoxy) are introduced in adhesive molecular structure of the invention
Propyl trimethoxy silicane provides not only the cured crosslinking reactivity group of adhesive system, and can generate very with substrate
Good anchor cooperation is used, and is of great benefit to the interface performance and adhesive strength that improve bonding plane.
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 the 4,4 '-diamino -4 of 29.0 grams (0.1 mole) "-hydroxyl triphenylmenthane (DAHTM) and 1450 grams of N, N diformazan
Base formamide is put into reaction kettle, and at room temperature after stirring and dissolving, 120.0 grams of (0.3 moles) 4,4 '-bis- (4- aminobenzene oxygen are added
Base) diphenyl sulfide, bis- (3- amino-benzene oxygen) benzene of 29.2 grams of (0.1 mole) 1,3- and 51.8 grams of bis- [4- of (0.1 mole) 2,2-
(3- amino-benzene oxygen) phenyl] hexafluoropropane, after stirring and dissolving, 209.3 grams of (0.65 mole) 3,3 ', 4,4 '-tetracarboxylics are added
Benzophenone dianhydride, stirring and dissolving, after being stirred to react 1.0 hours, is added 22.1 grams of three second of (0.1 mole) 3- aminopropyl at room temperature
Oxysilane is stirred to react 2 hours at room temperature, and 23.6 grams of (0.1 mole) γ-(2,3- the third oxygen of epoxy) propyl front threes are then added
Oxysilane is stirred to react 15min in 80 DEG C and obtains the homogeneous DAHTM type silicon-containing adhesive of 1935 grams of clear viscous, is denoted as
SA-1。
Embodiment 2
By the 4,4 '-diamino -4 of 29.0 grams (0.1 mole) "-hydroxyl triphenylmenthane (DAHTM), 2130 grams of N, N dimethyl
Acetamide and 800 grams of N- ethyl-2-pyrrolidones are put into reaction kettle, and at room temperature after stirring and dissolving, being added 44.8 grams, (0.2 rubs
You) 2- (4- aminophenyl) -5- aminobenzimidazole, 120.0 grams of (0.6 mole) 3,4 '-diaminodiphenyl ethers, 51.8 gram (0.1
Mole) bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2- and bis- (the 4- aminobenzene oxygen of 40.0 grams of (0.1 moles) 4,4 '-
Base) diphenyl sulfide, after stirring and dissolving, 186.0 grams of (0.6 mole) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydrides and 193.2 are added
Gram (0.6 mole) 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, stirring and dissolving, after being stirred to react 4.0 hours, is added at room temperature
44.2 grams of (0.2 mole) 3- aminopropyl triethoxysilanes, are stirred to react 0.5 hour at room temperature, are then added 23.6 gram (0.1
Mole) γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, be stirred to react in 90 DEG C 15min obtain 3662.6 grams it is sticky
The DAHTM type silicon-containing adhesive of clear homogeneous, is denoted as SA-2.
Embodiment 3
By the 4,4 '-diamino -4 of 29.0 grams (0.1 mole) "-hydroxyl triphenylmenthane (DAHTM), 4400 grams of N, N dimethyl
The organic solvent of formamide and 1500 grams of N- ethyl-2-pyrrolidones is put into reaction kettle, at room temperature after stirring and dissolving, is added
Bis- (4- amino-benzene oxygen) diphenyl sulfides of 240.0 grams of (0.6 moles) 4,4 '-and 22.4 grams of (0.1 mole) 2- (4- aminophenyl)-
5- aminobenzimidazole, after stirring and dissolving, be added 225.4 grams of (0.7 mole) 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydrides,
Bis- [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 78.0 grams of (0.15 mole) 2,2-, stirring and dissolving, is stirred at room temperature
After reaction 2.0 hours, 22.1 grams of (0.1 mole) 3- aminopropyl triethoxysilanes and 17.9 grams of (0.1 mole) 3- ammonia third are added
Base trimethoxy silane is stirred to react 1.5 hours at room temperature, and 23.6 grams of (0.1 mole) γ-(2,3- the third oxygen of epoxy) are then added
Propyl trimethoxy silicane is stirred to react 15min in 85 DEG C and obtains the homogeneous DAHTM type of 6558.4 grams of clear viscous containing silica gel
Stick is denoted as SA-3.
Embodiment 4
The DAHTM type silicon-containing adhesive of suitable 1~embodiment of embodiment 3, i.e. SA-1~SA-3 are taken respectively, and difference is equal
Evenly coated in standard stainless steel test piece, overlap, clamp, be put into convection oven and solidified: from room temperature start to warm up to
80 DEG C, after being kept for 1 hour, 150 DEG C are continuously heating to, after being kept for 2 hours, is continuously heating to 200 DEG C, after being kept for 0.5 hour, after
It is continuous to be warming up to 260 DEG C, after being kept for 0.5 hour, cooled to room temperature.Using electronic tensile machine, room temperature (25 is carried out to it respectively
DEG C) and high temperature (250 DEG C) under the conditions of tensile shear strength test, the results are shown in Table 1.
The DAHTM type silicon-containing adhesive of suitable 1~embodiment of embodiment 3, i.e. SA-1~SA-3 are taken respectively, and difference is equal
It is impregnated with evenly on glass cloth, is overlapped and clamped with standard stainless steel test piece, be put into convection oven and solidified: since room temperature
80 DEG C are warming up to, after being kept for 1 hour, is continuously heating to 150 DEG C, after being kept for 2 hours, is continuously heating to 200 DEG C, holding 0.5 is small
Shi Hou is continuously heating to 260 DEG C, after being kept for 0.5 hour, cooled to room temperature.Using electronic tensile machine, it is carried out respectively
Tensile shear strength test under the conditions of room temperature (25 DEG C) and high temperature (250 DEG C), the results are shown in Table 1.
Using Guilin Electro Scientific research institute produce megger test its solidfied material volume resistivity ρ v (1MHz, 25
DEG C), the results are shown in Table 1.
The dielectric loss (D) of its solidfied material is tested using the TH2828S tester of Changzhou Tong Hui Electron equipment Co., Ltd
(1MHz, 25 DEG C), the results are shown in Table 1.
Deionized water (25 DEG C) are soaked in after the square coupons weighing (W1) of above-mentioned drying using precision electronic balance
In, it after 72 hours, takes out, dries surface with filter paper, weigh (W2), water absorption rate is calculatedData it is as shown in table 1.
Climatic chamber (85 is placed in after the square coupons weighing (G1) of above-mentioned drying using precision electronic balance
DEG C, RH85%) in, it after 72 hours, takes out, dries surface with filter paper, weigh (G2), the data of hydroscopicity (ψ) are calculated such as
Shown in table 1.
The performance data of 1 DAHTM type silicon-containing adhesive of table
Claims (7)
1. a kind of DAHTM type silicon-containing adhesive, it is characterised in that: the adhesive is 1:5-10:6.5-12:1-2 by molar ratio:
The 4,4 ' of 1-diamino-4 "-hydroxyl triphenylmenthane DAHTM, aromatic diamine, aromatic dicarboxylic acid anhydride, three alcoxyl of 3- aminopropyl
The reaction product and organic solvent of base silane and γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane composition.
2. a kind of DAHTM type silicon-containing adhesive according to claim 1, it is characterised in that: the aromatic diamine choosing
From m-phenylene diamine (MPD), p-phenylenediamine, 2- methylresorcinol diamines, 2,4,6- trimethyl m-phenylene diamine (MPD), 3,4 '-diaminodiphenyl ethers, 4,
4 '-diaminodiphenyl ethers, 3,3 '-diaminodiphenyl ethers, 3,5- diaminobenzoic acid, 4,4 '-benzidines, 3,3 '-diformazans
Base -4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylsulfones, 3,3 '-diaminodiphenylsulfones, 3,
3 '-dimethyl -4,4 '-diaminodiphenylmethane, 3,3 '-two chloro- 4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetramethyls -
Bis- (4- amino-benzene oxygen) benzonitriles of 4,4 '-diaminodiphenylmethane, 2,6-, 2,6- bis- (3- amino-benzene oxygen) benzonitriles, 3,
Bis- (4- amino-benzene oxygen) benzoic acid of 5-, 2- (4- aminophenyl) -5- aminobenzimidazole, 3,3 '-diamino -4,4 '-dihydroxy
Bis- (3- amino-4-hydroxylphenyl) propane of base biphenyl, 2,2-, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, 1,3- are bis-
Bis- (4- amino-benzene oxygen) benzene of (3- amino-benzene oxygen) benzene, 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (the 2- trifluoros of 1,3-
Methyl -4- amino-benzene oxygen) benzene, bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, bis- (4- amino-benzene oxygen) first of 2,6-
Bis- (4- amino-benzene oxygen) toluene of benzene, 2,5-, bis- (2- trifluoromethyl-4-aminophenoxyl) benzoic acid of 3,5-, the bis- (2- tri- of 2,6-
Methyl fluoride -4- amino-benzene oxygen) toluene, bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of 2,5-, bis- [4- (the 4- amino of 2,2-
Phenoxy group) phenyl] propane, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, bis- [4- (the 3- amino of 2,2-
Phenoxy group) phenyl] propane, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl-methanes,
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoros third of 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl-methanes, 2,2-
Bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] hexafluoropropane of alkane, 2,2-, bis- [4- (3- amino-benzene oxygen) benzene of 2,2-
Base] it is hexafluoropropane, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl sulphone (DPS)s, 4,4 '-bis-
(2- trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS), 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfides, 4,4 '-bis- (3- amino
Phenoxy group) diphenyl sulfide, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl sulfides, 4,4 '-bis- (4- aminobenzene oxygen
Base) diphenyl ether, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl ether,
4,4 '-bis- (4- amino-benzene oxygen) benzophenone, 4,4 '-bis- (3- amino-benzene oxygen) benzophenone, 4,4 '-bis- (2- fluoroforms
Base -4- amino-benzene oxygen) benzophenone, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl,
One or more of 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) biphenyl.
3. a kind of DAHTM type silicon-containing adhesive according to claim 1, it is characterised in that: the aromatic dicarboxylic acid anhydride choosing
From pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydrides, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydrides, 3,3 ',
4,4 '-tetracarboxylic benzophenone dianhydrides, 2,2- bis- (3,4- dicarboxyphenyi) hexafluoropropane dianhydrides, 3,3 ', 4,4 '-tetracarboxylics connection
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of benzene dianhydride, 2,2-, bis- [4- (the 3,4- dicarboxyl benzene oxygen of 2,2-
Base) phenyl] propane dianhydride, bis- (3,4- di carboxyl phenyloxy) benzene dianhydrides of 1,4-, 1,3- be bis--(3,4- di carboxyl phenyloxy) benzene two
Acid anhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxy) biphenyl dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxy) diphenyl sulfone dianhydrides, 4,
4 '-bis- (3,4- di carboxyl phenyloxy) diphenyl ether dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxy) diphenyl ether dianhydrides, 4,4 '-
One or more of bis- (3,4- di carboxyl phenyloxy) benzophenone dianhydrides.
4. a kind of DAHTM type silicon-containing adhesive according to claim 1, it is characterised in that: three alcoxyl of 3- aminopropyl
Base silane is selected from one or both of 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane.
5. a kind of DAHTM type silicon-containing adhesive according to claim 1, it is characterised in that: the organic solvent is selected from N, N
Dimethylformamide, N, N dimethyl acetamide, tetrahydrofuran, methyltetrahydrofuran, n-methyl-2-pyrrolidone, N- ethyl-
One or more of 2-Pyrrolidone, dimethyl sulfoxide.
6. a kind of DAHTM type silicon-containing adhesive according to claim 1, it is characterised in that: the organic solvent with react
The mass ratio of object is 2.5-9.5:1；Wherein, reactant refers to 4,4 '-diamino -4 "-hydroxyl triphenylmenthane DAHTM, aromatic series
Diamine, aromatic dicarboxylic acid anhydride, 3- aminopropyltrialkoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane.
7. a kind of preparation method of DAHTM type silicon-containing adhesive as described in claim 1, includes the following steps:
According to the ratio, by 4,4 '-diamino -4 "-hydroxyl triphenylmenthane DAHTM and organic solvent be put into reaction kettle, stir at room temperature
After mixing dissolution, aromatic diamine is added, after stirring and dissolving, aromatic dicarboxylic acid anhydride is added, be stirred to react at room temperature 1.0 hours-
After 4.0 hour, 3- aminopropyltrialkoxysilane is added, is stirred to react -2 hours 0.5 hour at room temperature, be then added γ-(2,
The third oxygen of 3- epoxy) propyl trimethoxy silicane, 15min is stirred to react in 80 DEG C -90 DEG C up to DAHTM type silicon-containing adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811569937.5A CN109722214A (en) | 2018-12-21 | 2018-12-21 | A kind of DAHTM type silicon-containing adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811569937.5A CN109722214A (en) | 2018-12-21 | 2018-12-21 | A kind of DAHTM type silicon-containing adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109722214A true CN109722214A (en) | 2019-05-07 |
Family
ID=66297011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811569937.5A Pending CN109722214A (en) | 2018-12-21 | 2018-12-21 | A kind of DAHTM type silicon-containing adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109722214A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429927A (en) * | 2021-05-12 | 2021-09-24 | 浙江中科玖源新材料有限公司 | Polyimide binder, preparation method thereof and silicon-carbon negative plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742732A (en) * | 1980-08-27 | 1982-03-10 | Hitachi Chem Co Ltd | Production of polyamido acid silicone type intermediate and polyimidoisoindoloquinazolinedione/silicone copolymer resin |
| CN101003716A (en) * | 2007-01-19 | 2007-07-25 | 东华大学 | Method for preparing binder of polyimide of containing phenolic hydroxyl group |
| CN101629062A (en) * | 2009-08-20 | 2010-01-20 | 东华大学 | Polyimide-epoxy resin adhesive and preparation method and application thereof |
| CN105295792A (en) * | 2015-08-26 | 2016-02-03 | 北京化工大学 | High-performance polyimide crosslinked and modified epoxy resin and preparation method thereof |
-
2018
- 2018-12-21 CN CN201811569937.5A patent/CN109722214A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742732A (en) * | 1980-08-27 | 1982-03-10 | Hitachi Chem Co Ltd | Production of polyamido acid silicone type intermediate and polyimidoisoindoloquinazolinedione/silicone copolymer resin |
| CN101003716A (en) * | 2007-01-19 | 2007-07-25 | 东华大学 | Method for preparing binder of polyimide of containing phenolic hydroxyl group |
| CN101629062A (en) * | 2009-08-20 | 2010-01-20 | 东华大学 | Polyimide-epoxy resin adhesive and preparation method and application thereof |
| CN105295792A (en) * | 2015-08-26 | 2016-02-03 | 北京化工大学 | High-performance polyimide crosslinked and modified epoxy resin and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 叶青萱等: "《胶粘剂》", 31 October 1999 * |
| 孔萍等: "《塑料材料》", 31 July 2017 * |
| 孙忠贤: "《电子化学品》", 31 March 2001 * |
| 席慧智等: "《材料化学导论 第3版》", 31 August 2017 * |
| 林鸣玉等: "《电泳涂装工艺与管理》", 30 September 2015 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429927A (en) * | 2021-05-12 | 2021-09-24 | 浙江中科玖源新材料有限公司 | Polyimide binder, preparation method thereof and silicon-carbon negative plate |
| CN113429927B (en) * | 2021-05-12 | 2022-05-31 | 浙江中科玖源新材料有限公司 | Polyimide binder, preparation method thereof and silicon-carbon negative plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103119085B (en) | Resin combination and manufacture method thereof | |
| CN103261278B (en) | Polyamic acid resin composition and method of producing the same | |
| CN105111927A (en) | High temperature resistant BAHPFP (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) wire enamel and preparation method thereof | |
| CN103131370B (en) | 1,3-bis(2,4-diamidophenoxy)benzene high-temperature-resistant epoxy adhesive and preparation method thereof | |
| JPH06136122A (en) | Diaminobenzene derivative, polyimide, and liquid crystal orientation film | |
| CN109722212A (en) | A kind of acid imide epoxy organic silica gel and preparation method thereof | |
| CN109705799A (en) | A kind of YASI epoxy organic imides silica gel and preparation method thereof | |
| CN109722214A (en) | A kind of DAHTM type silicon-containing adhesive and preparation method thereof | |
| WO2002051908A1 (en) | Diaminobenzene derivatives, polyimide precursors and polyimides prepared by using tha same, and liquid crystal aligning agents | |
| CN109722213A (en) | A kind of BAHPP type silicon-containing adhesive and preparation method thereof | |
| CN109679571A (en) | A kind of DADHBP type silicon-containing adhesive and preparation method thereof | |
| CN109628057A (en) | A kind of BDABP type silicon-containing adhesive and preparation method thereof | |
| CN109722210A (en) | A kind of TADE type silicon-containing adhesive and preparation method thereof | |
| CN109722208A (en) | A kind of 12BDAPB type silicon-containing adhesive and preparation method thereof | |
| CN109705798A (en) | A kind of BDATHQ type silicon-containing adhesive and preparation method thereof | |
| CN109628055A (en) | A kind of BDADDE type silicon-containing adhesive and preparation method thereof | |
| CN109705800A (en) | A kind of 14BDAPB type silicon-containing adhesive and preparation method thereof | |
| CN109628056A (en) | A kind of 13BDAPB type silicon-containing adhesive and preparation method thereof | |
| CN109735292A (en) | A kind of BDADDS type silicon-containing adhesive and preparation method thereof | |
| CN109722211A (en) | A kind of BDADDM type silicon-containing adhesive and preparation method thereof | |
| CN109628054A (en) | A kind of BAHPFP type silicon-containing adhesive and preparation method thereof | |
| CN109735294A (en) | A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof | |
| CN109735293A (en) | A kind of DAB biphenyl tetramine type silicon-containing adhesive and preparation method thereof | |
| CN109852331A (en) | A kind of bis- (4- amino-benzene oxygen) benzoic acid type organic silica gels of 3,5- and preparation method thereof | |
| CN109679570A (en) | A kind of BDAPOFP type silicon-containing adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190507 |