CN109735294A - A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof - Google Patents
A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109735294A CN109735294A CN201811569836.8A CN201811569836A CN109735294A CN 109735294 A CN109735294 A CN 109735294A CN 201811569836 A CN201811569836 A CN 201811569836A CN 109735294 A CN109735294 A CN 109735294A
- Authority
- CN
- China
- Prior art keywords
- bis
- amino
- benzene
- benzene oxygen
- bdadtbhq
- 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
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of BDADTBHQ type silicon-containing adhesives and preparation method thereof, by 2,5- di-tert-butyl -1,4- bis- (2,4- diamino phenoxy) benzene BDADTBHQ, maleic anhydride, aromatic diamine, aromatic dicarboxylic acid anhydride and 3- aminopropyltrialkoxysilane 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 BDADTBHQ 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 BDADTBHQ type silicon-containing adhesives and preparation method thereof, should
Silicon-containing adhesive comprehensive performance is good, can be applied to glass, ceramics, composite material, extraordinary polarity weaving prepreg and its compound
The bonding of material substrate has good market application prospect.
The present invention provides a kind of BDADTBHQ type silicon-containing adhesive, the adhesive is 1:2:5-10 by molar ratio:
Bis- (2,4- diamino phenoxy) the benzene BDADTBHQ of the 2,5- di-tert-butyl -1,4- of 6.5-12:1-2, maleic anhydride, aromatic series two
First amine, the reaction product of aromatic dicarboxylic acid anhydride and 3- aminopropyltrialkoxysilane and organic solvent 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-, 4,4 '-diamino -4 "-hydroxyl triphen first
Alkane, 2- (4- aminophenyl) -5- aminobenzimidazole, 3,3 '-diamino -4,4 '-dihydroxybiphenyl, the bis- (3- amino -4- of 2,2-
Hydroxy phenyl) propane, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, bis- (3- amino-benzene oxygen) benzene of 1,3-, 1,3- be bis-
Bis- (4- amino-benzene oxygen) benzene of (4- amino-benzene oxygen) benzene, 1,4-, 1,3- bis- (2- trifluoromethyl-4-aminophenoxyl) benzene, 1,
Bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 4-, bis- (4- amino-benzene oxygen) toluene of 2,6-, 2,5- bis- (4- amino-benzene oxygens)
Bis- (2- trifluoromethyl-4-aminophenoxyl) benzoic acid of toluene, 3,5-, bis- (2- trifluoromethyl-4-aminophenoxyl) first of 2,6-
Bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of benzene, 2,5-, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,2-
Bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane, 2,2- bis- [4- (3- amino-benzene oxygen) phenyl] propane, 4,
4 '-bis- (4- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyls-
4- amino-benzene oxygen) diphenyl-methane, bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-, bis- [4- (the 2- fluoroforms of 2,2-
Base -4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2- bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane, 4,4 '-bis- (4-
Amino-benzene oxygen) diphenyl sulphone (DPS), 4,4 '-bis- (3- amino-benzene oxygen) diphenyl sulphone (DPS)s, 4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen
Base) it is diphenyl sulphone (DPS), 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfides, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl sulfides, 4,4 '-bis-
(2- trifluoromethyl-4-aminophenoxyl) diphenyl sulfide, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (3- amino
Phenoxy group) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl ether, 4,4 '-bis- (4- amino-benzene oxygens) two
Benzophenone, 4,4 '-bis- (3- amino-benzene oxygen) benzophenone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) hexichol first
Ketone, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, 4,4 '-bis- (2- trifluoromethyl -4-
One or more of amino-benzene oxygen) biphenyl.
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 2,5- di-tert-butyl-
Bis- (2,4- diamino phenoxy) the benzene BDADTBHQ of 1,4-, maleic anhydride, aromatic diamine, aromatic dicarboxylic acid anhydride and 3- ammonia third
Base trialkoxy silane.
The present invention also provides a kind of preparation methods of BDADTBHQ type silicon-containing adhesive, include the following steps:
According to the ratio, bis- (2,4- diamino phenoxy) the benzene BDADTBHQ of 2,5- di-tert-butyl-Isosorbide-5-Nitrae-and organic solvent are put
Enter in reaction kettle, at room temperature after stirring and dissolving, maleic anhydride is added, after being stirred to react 15min-30min at room temperature, fragrance is added
After stirring and dissolving, aromatic dicarboxylic acid anhydride is added in race's diamine, and after being stirred to react -4.0 hours 1.0 hours at room temperature, 3- ammonia is added
Propyl trialkoxy silane is stirred to react -2 hours 0.5 hour at room temperature to get BDADTBHQ 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 is introduced in adhesive molecular structure of the invention, provides not only adhesive
The cured crosslinking reactivity group of system, and good anchor cooperation can be generated with substrate and used, to the interface characteristics of improvement bonding plane
It can be of great benefit to adhesive strength.
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- (2,4- diamino phenoxy) benzene (BDADTBHQ) of 43.4 grams (0.1 mole) of 2,5- di-tert-butyl -1,4-
With 1780 grams of N, N dimethyl acetamide is put into reaction kettle, and at room temperature after stirring and dissolving, 19.6 grams of (0.2 mole) Malaysias are added
Acid anhydrides, after stirring and dissolving, after being stirred to react 15min at room temperature, be added 40.0 grams of (0.2 mole) 3,4 '-diaminodiphenyl ethers,
Bis- (4- amino-benzene oxygen) benzene of 29.2 grams of (0.1 mole) 1,3- and the bis- [4- (4- amino-benzene oxygen) of 82.0 grams of (0.2 mole) 2,2-
Phenyl] propane, after stirring and dissolving, 209.3 grams of (0.65 mole) 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydrides are added, at room temperature
Stirring and dissolving after being stirred to react 1.0 hours, is added 22.1 grams of (0.1 mole) 3- aminopropyl triethoxysilanes, stirs at room temperature
SA-1 is denoted as to get the BDADTBHQ type silicon-containing adhesive homogeneous to 2225.6 grams of clear viscous within reaction 2 hours.
Embodiment 2
By bis- (2,4- diamino phenoxy) benzene (BDADTBHQ) of 43.4 grams (0.1 mole) of 2,5- di-tert-butyl -1,4-,
2100 grams of N, N dimethyl acetamide and 1100 grams of N- ethyl-2-pyrrolidones are put into reaction kettle, at room temperature after stirring and dissolving,
19.6 grams of (0.2 mole) maleic anhydrides are added, after stirring and dissolving, after being stirred to react 30min at room temperature, are added 43.5 gram (0.15
Mole) 4,4 '-diamino -4 "-hydroxyl triphenylmenthane, 110.0 grams of (0.55 mole) 3,4 '-diaminodiphenyl ethers, 29.2 grams
Bis- (3- amino-benzene oxygen) benzene of (0.1 mole) 1,3- and 103.6 grams of (0.2 mole) 2,2- bis- [4- (4- amino-benzene oxygen) phenyl]
After stirring and dissolving, 93.0 grams of (0.3 mole) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydrides, 104.0 gram (0.2 are added in hexafluoropropane
Mole) bis- [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 2,2- and 225.4 grams of (0.7 mole) 3,3 ', 4,4 '-tetracarboxylic acids
Base benzophenone dianhydride, stirring and dissolving, after being stirred to react 4.0 hours, is added 44.2 grams of (0.2 mole) 3- aminopropyls three at room temperature
Ethoxysilane is stirred to react 0.5 hour at room temperature and contains silica gel to get to the homogeneous BDADTBHQ type of 4015.9 grams of clear viscous
Stick is denoted as SA-2.
Embodiment 3
By bis- (2,4- diamino phenoxy) benzene (BDADTBHQ) of 43.4 grams (0.1 mole) of 2,5- di-tert-butyl -1,4-,
4550 grams of n,N dimethylformamide and 2000 grams of N- ethyl-2-pyrrolidones are put into reaction kettle, at room temperature after stirring and dissolving,
19.6 grams of (0.2 mole) maleic anhydrides are added, after stirring and dissolving, after being stirred to react 25min at room temperature, being added 60.0 grams, (0.3 rubs
You) 3,4 '-diaminodiphenyl ethers and bis- [4- (4- amino-benzene oxygen) phenyl] propane of 164.0 grams of (0.4 mole) 2,2-, stirring is molten
62.0 grams of (0.2 mole) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydrides, 338.0 grams of bis- [4- of (0.65 mole) 2,2- are added in Xie Hou
(3,4- di carboxyl phenyloxy) phenyl] propane dianhydride, stirring and dissolving, after being stirred to react 2.0 hours, is added 22.1 grams at room temperature
(0.1 mole) 3- aminopropyl triethoxysilane and 17.9 grams of (0.1 mole) 3- aminopropyl trimethoxysilanes, are stirred at room temperature
SA-3 is denoted as to get the BDADTBHQ type silicon-containing adhesive homogeneous to 7277 grams of clear viscous within reaction 1.5 hours.
Embodiment 4
The BDADTBHQ type silicon-containing adhesive of suitable 1~embodiment of embodiment 3, i.e. SA-1~SA-3 are taken respectively, and are divided
It is not uniformly applied in standard stainless steel test piece, overlaps, clamp, be put into convection oven and solidified: being risen since room temperature
Temperature is to 80 DEG C, 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, is kept for 0.5 hour
Afterwards, 260 DEG C are continuously heating to, after being kept for 0.5 hour, cooled to room temperature.Using electronic tensile machine, room is carried out to it respectively
Tensile shear strength test under the conditions of warm (25 DEG C) and high temperature (250 DEG C), the results are shown in Table 1.
The BDADTBHQ type silicon-containing adhesive of suitable 1~embodiment of embodiment 3, i.e. SA-1~SA-3 are taken respectively, and are divided
It is not impregnated with equably on glass cloth, is overlapped and clamped with standard stainless steel test piece, be put into convection oven and solidified: from room temperature
It starts to warm up to 80 DEG C, after being kept for 1 hour, is continuously heating to 150 DEG C, after being kept for 2 hours, be continuously heating to 200 DEG C, keep
After 0.5 hour, 260 DEG C are continuously heating to, after being kept for 0.5 hour, cooled to room temperature.It is right respectively using electronic tensile machine
It carries out the tensile shear strength test under the conditions of room temperature (25 DEG C) and high temperature (250 DEG C), and 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 BDADTBHQ type silicon-containing adhesive of table
Claims (7)
1. a kind of BDADTBHQ type silicon-containing adhesive, it is characterised in that: the adhesive is 1:2:5-10:6.5- by molar ratio
Bis- (2,4- diamino phenoxy) the benzene BDADTBHQ of the 2,5- di-tert-butyl -1,4- of 12:1-2, maleic anhydride, aromatic dicarboxylic
Amine, the reaction product of aromatic dicarboxylic acid anhydride and 3- aminopropyltrialkoxysilane and organic solvent composition.
2. a kind of BDADTBHQ type silicon-containing adhesive according to claim 1, it is characterised in that: the aromatic diamine
Selected 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 '-two
Methyl -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 base -4,4 '-diaminodiphenylmethane, 2,6-, bis- (3- amino-benzene oxygen) benzonitriles of 2,6-,
Bis- (4- amino-benzene oxygen) benzoic acid of 3,5-, 4,4 '-diamino -4 "-hydroxyl triphenylmenthane, 2- (4- aminophenyl) -5- amino
Bis- (3- amino-4-hydroxylphenyl) propane of benzimidazole, 3,3 '-diamino -4,4 '-dihydroxybiphenyl, 2,2-, the bis- (3- of 2,2-
Amino-4-hydroxylphenyl) hexafluoropropane, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,3-, 1,4- be bis-
Bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of (4- amino-benzene oxygen) benzene, 1,3-, the bis- (2- trifluoromethyl -4- aminobenzenes of 1,4-
Oxygroup) benzene, bis- (4- amino-benzene oxygen) toluene of 2,6-, bis- (4- amino-benzene oxygen) toluene of 2,5-, bis- (the 2- trifluoromethyls-of 3,5-
4- amino-benzene oxygen) benzoic acid, bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of 2,6-, the bis- (2- trifluoromethyl -4- of 2,5-
Amino-benzene oxygen) toluene, bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-, the bis- [4- (2- trifluoromethyl -4- amino of 2,2-
Phenoxy group) phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] propane of 2,2-, 4,4 '-bis- (4- amino-benzene oxygen) hexichol first
Alkane, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl-methanes, 2,
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2-, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] six of 2,2-
Bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of fluoro-propane, 2,2-, 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)s, 4,4 '-bis- (4- amino
Phenoxy group) diphenyl sulfide, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl sulfides, 4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen
Base) it is diphenyl sulfide, 4,4 '-bis- (4- amino-benzene oxygen) 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
Phenoxy group) benzophenone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis- (4- aminobenzene oxygen
Base) biphenyl, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, one in 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) biphenyl
Kind is several.
3. a kind of BDADTBHQ type silicon-containing adhesive according to claim 1, it is characterised in that: the aromatic dicarboxylic acid anhydride
Selected 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 '-tetracarboxylic acids
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of base biphenyl dianhydride, 2,2-, bis- [4- (the 3,4- dicarboxyls of 2,2-
Phenoxy group) phenyl] propane dianhydride, bis- (3,4- di carboxyl phenyloxy) benzene dianhydrides of 1,4-, 1,3- be bis--(3,4- di carboxyl phenyloxy)
Benzene dianhydride, 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,
One or more of 4 '-bis- (3,4- di carboxyl phenyloxy) benzophenone dianhydrides.
4. a kind of BDADTBHQ type silicon-containing adhesive according to claim 1, it is characterised in that: three alkane of 3- aminopropyl
Oxysilane is selected from one or both of 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane.
5. a kind of BDADTBHQ 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- second
One or more of base -2-Pyrrolidone, dimethyl sulfoxide.
6. a kind of BDADTBHQ type silicon-containing adhesive according to claim 1, it is characterised in that: the organic solvent and anti-
The mass ratio for answering object is 2.5-9.5:1；Wherein, reactant refers to that 2,5- di-tert-butyl-Isosorbide-5-Nitrae-is bis- (2,4- diamino phenoxy)
Benzene BDADTBHQ, maleic anhydride, aromatic diamine, aromatic dicarboxylic acid anhydride and 3- aminopropyltrialkoxysilane.
7. a kind of preparation method of BDADTBHQ type silicon-containing adhesive as described in claim 1, includes the following steps:
According to the ratio, bis- (2,4- diamino phenoxy) the benzene BDADTBHQ of 2,5- di-tert-butyl-Isosorbide-5-Nitrae-and organic solvent are put into instead
It answers in kettle, at room temperature after stirring and dissolving, maleic anhydride is added, after being stirred to react 15min-30min at room temperature, aromatic series two is added
After stirring and dissolving, aromatic dicarboxylic acid anhydride is added in first amine, and after being stirred to react -4.0 hours 1.0 hours at room temperature, 3- aminopropyl is added
Trialkoxy silane is stirred to react -2 hours 0.5 hour at room temperature to get BDADTBHQ type silicon-containing adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811569836.8A CN109735294A (en) | 2018-12-21 | 2018-12-21 | A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811569836.8A CN109735294A (en) | 2018-12-21 | 2018-12-21 | A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109735294A true CN109735294A (en) | 2019-05-10 |
Family
ID=66360936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811569836.8A Pending CN109735294A (en) | 2018-12-21 | 2018-12-21 | A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109735294A (en) |
Citations (5)
| 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 |
| CN101245026A (en) * | 2008-03-21 | 2008-08-20 | 东华大学 | Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene |
| CN101289537A (en) * | 2008-05-19 | 2008-10-22 | 东华大学 | Method for preparing 1,4-di(2,4-diaminophenoxy)benzenoid form self-plasticizing unsaturated polyimides powder |
| 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 |
| CN106633866A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA type BDADTBHQ branched polyimide resin thin film and preparation method thereof |
-
2018
- 2018-12-21 CN CN201811569836.8A patent/CN109735294A/en active Pending
Patent Citations (5)
| 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 |
| CN101245026A (en) * | 2008-03-21 | 2008-08-20 | 东华大学 | Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene |
| CN101289537A (en) * | 2008-05-19 | 2008-10-22 | 东华大学 | Method for preparing 1,4-di(2,4-diaminophenoxy)benzenoid form self-plasticizing unsaturated polyimides powder |
| 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 |
| CN106633866A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA type BDADTBHQ branched polyimide resin thin film and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 叶青萱等: "《胶粘剂》", 31 October 1999 * |
| 孙忠贤: "《电子化学品》", 31 March 2001 * |
| 林鸣玉等: "《电泳涂装工艺与管理》", 30 September 2015 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103013414B (en) | Alpha-cyanogroup-beta-ethyl ethoxyacrylate modified epoxy resin 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 | |
| CN109705799A (en) | A kind of YASI epoxy organic imides silica gel and preparation method thereof | |
| CN109722212A (en) | A kind of acid imide epoxy organic silica gel and preparation method thereof | |
| CN103131369B (en) | 4,4'-bis(2,4-diamidophenoxy)diphenylsulphone high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN103146330B (en) | 2,2-bis[4-(2,4-diamidophenoxy)phenyl]hexafluoropropane high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN109722214A (en) | A kind of DAHTM type silicon-containing adhesive and preparation method thereof | |
| CN103131368B (en) | 4,4'-bis(2,4-diamidophenoxy)diphenyl ether high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN109735294A (en) | A kind of BDADTBHQ type silicon-containing adhesive and preparation method thereof | |
| CN109679570A (en) | A kind of BDAPOFP type silicon-containing adhesive and preparation method thereof | |
| CN109705800A (en) | A kind of 14BDAPB type silicon-containing adhesive and preparation method thereof | |
| CN109679569A (en) | A kind of BDAPOPP type silicon-containing adhesive and preparation method thereof | |
| CN109628056A (en) | A kind of 13BDAPB 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 | |
| CN109735292A (en) | A kind of BDADDS type silicon-containing adhesive and preparation method thereof | |
| CN109735293A (en) | A kind of DAB biphenyl tetramine type silicon-containing adhesive and preparation method thereof | |
| CN109722211A (en) | A kind of BDADDM type silicon-containing adhesive and preparation method thereof | |
| CN109628055A (en) | A kind of BDADDE type silicon-containing adhesive and preparation method thereof | |
| CN109722210A (en) | A kind of TADE type silicon-containing adhesive and preparation method thereof | |
| CN109628057A (en) | A kind of BDABP type silicon-containing adhesive and preparation method thereof | |
| CN109852330A (en) | A kind of 3,5- diaminobenzoic acid type silicon-containing adhesive and preparation method thereof | |
| CN109679571A (en) | A kind of DADHBP type silicon-containing adhesive and preparation method thereof | |
| CN109735295A (en) | A kind of acid imide organic silica gel 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 |
Application publication date: 20190510 |
|
| RJ01 | Rejection of invention patent application after publication |