CN109852331A - A kind of bis- (4- amino-benzene oxygen) benzoic acid type organic silica gels of 3,5- and preparation method thereof - Google Patents
A kind of bis- (4- amino-benzene oxygen) benzoic acid type organic silica gels of 3,5- and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to one kind 3, bis- (4- amino-benzene oxygen) benzoic acid type organic silica gels of 5- and preparation method thereof, by 3, bis- (4- amino-benzene oxygen) benzoic acid of 5-, 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 bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- of one kind
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 siliceous ring of bis- (4- amino-benzene oxygen) benzoic acid types of 3,5-
The preparation method of oxygen acid imide matrix resin, 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 bis- (4- amino-benzene oxygen) the benzoic acid type organosilicons of 3,5-
Glue and preparation method thereof, the organic silica gel comprehensive performance is good, can be applied to glass, ceramics, composite material, extraordinary polarity weaving
The bonding of prepreg and its composite material base has good market application prospect.
The present invention provides bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- of one kind, the adhesive by mole
(4- amino-benzene oxygen) benzoic acid more bis- than 3,5- for 1:5-10:6.5-12:1-2:1, aromatic diamine, aromatic dicarboxylic
Acid anhydride, the reaction product of 3- aminopropyltrialkoxysilane and γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane 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, 4,4 '-benzidines, 3,
3 '-dimethyl -4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino -4 "-hydroxyl triphenylmenthane, 4,
It is 4 '-diaminodiphenylsulfones, 3,3 '-diaminodiphenylsulfones, 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane, 3,3 '-two chloro-
4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetramethyls -4,4 '-diaminodiphenylmethane, 2,6- bis- (4- amino-benzene oxygens)
Bis- (3- amino-benzene oxygen) benzonitriles of benzonitrile, 2,6-, 2- (4- aminophenyl) -5- aminobenzimidazole, 3,3 '-diamino -
Bis- (3- amino-4-hydroxylphenyl) propane of 4,4 '-dihydroxybiphenyls, 2,2-, bis- (3- amino-4-hydroxylphenyl) hexafluoros third of 2,2-
Bis- (3- amino-benzene oxygen) benzene of alkane, 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,3-, 1,4- bis- (4- amino-benzene oxygen) benzene, 1,3-
Bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of bis- (2- trifluoromethyl-4-aminophenoxyl) benzene, 1,4-, bis- (the 4- amino of 2,6-
Phenoxy group) toluene, bis- (4- amino-benzene oxygen) toluene of 2,5-, 3,5- bis- (2- trifluoromethyl-4-aminophenoxyl) benzoic acid, 2,
Bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of 6-, bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of 2,5-, 2,2- are bis-
Bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of [4- (4- amino-benzene oxygen) phenyl] propane, 2,2-, 2,2- are bis-
[4- (3- amino-benzene oxygen) phenyl] propane, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (3- aminobenzene oxygen
Base) diphenyl-methane, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl-methanes, the bis- [4- (4- amino-benzene oxygen) of 2,2-
Phenyl] hexafluoropropane, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] hexafluoropropane of 2,2-, bis- [4- (the 3- ammonia of 2,2-
Phenoxyl) phenyl] hexafluoropropane, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- amino-benzene oxygen) hexichol
Sulfone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS)s, 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 sulfides, 4,4 '-bis- (4-
Amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen
Base) it is diphenyl ether, 4,4 '-bis- (4- amino-benzene oxygen) benzophenone, 4,4 '-bis- (3- amino-benzene oxygen) benzophenone, 4,4 '-bis-
(2- trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- aminobenzenes
Oxygroup) biphenyl, one or more of 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) 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 bis- (the 4- amino of 3,5-
Phenoxy group) benzoic acid, aromatic diamine, aromatic dicarboxylic acid anhydride, 3- aminopropyltrialkoxysilane and γ-(2,3- epoxy third
Oxygen) propyl trimethoxy silicane.
The present invention also provides the preparation methods of bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- of one kind, including
Following steps:
According to the ratio, bis- (4- amino-benzene oxygen) benzoic acid of 3,5- and organic solvent are put into reaction kettle, are stirred at room temperature
After dissolution, aromatic diamine is added, after stirring and dissolving, aromatic dicarboxylic acid anhydride is added, is stirred to react at room temperature 1.0 hours -4.0
After hour, 3- aminopropyltrialkoxysilane is added, is stirred to react at room temperature -2 hours 0.5 hour, γ-(2,3- is then added
The third oxygen of epoxy) propyl trimethoxy silicane, 15min is stirred to react in 80 DEG C -90 DEG C up to bis- (4- amino-benzene oxygen) benzene of 3,5-
Formic acid type organic silica gel.
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 bis- (4- amino-benzene oxygen) benzoic acid of the 3,5- of 33.6 grams (0.1 moles) and 1340 grams of N, N-dimethylformamide
It is put into reaction kettle, at room temperature after stirring and dissolving, 40.0 grams of (0.2 mole) 3,4 '-diaminodiphenyl ethers and 120.0 grams is added
After stirring and dissolving, 209.3 grams of (0.65 moles) 3,3 ' are added in (0.3 mole) 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfides,
4,4 '-tetracarboxylic benzophenone dianhydrides, stirring and dissolving, after being stirred to react 1.0 hours, is added 22.1 grams (0.1 mole) at room temperature
3- aminopropyl triethoxysilane is stirred to react 2 hours at room temperature, and 23.6 grams of (0.1 mole) γ-(2,3- epoxies are then added
Third oxygen) propyl trimethoxy silicane, 15min is stirred to react in 80 DEG C, and to obtain 3 homogeneous, 5- of 1788.6 grams of clear viscous bis-
(4- amino-benzene oxygen) benzoic acid type organic silica gel, is denoted as SA-1.
Embodiment 2
By bis- (4- amino-benzene oxygen) benzoic acid of the 3,5- of 33.6 grams (0.1 moles), 2000 grams of N, N dimethyl acetamide and
1000 grams of N- ethyl-2-pyrrolidones are put into reaction kettle, and at room temperature after stirring and dissolving, 22.4 grams of (0.1 mole) 2- (4- are added
Aminophenyl) -5- aminobenzimidazole, 100.0 grams of (0.5 mole) 3,4 '-diaminodiphenyl ethers and 160.0 grams (0.4 mole)
After stirring and dissolving, 186.0 grams of (0.6 mole) 3,3 ', 4,4 '-tetracarboxylics are added in 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfides
Diphenyl ether dianhydride and 193.2 grams (0.6 mole) 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydrides, stirring and dissolving, is stirred at room temperature
After reactions 4.0 hours, 44.2 grams of (0.2 mole) 3- aminopropyl triethoxysilanes are added, are stirred to react at room temperature 0.5 hour,
23.6 grams of (0.1 mole) γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicanes are then added, are stirred to react 15min in 90 DEG C
Homogeneous bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- of 3763 grams of clear viscous are obtained, SA-2 is denoted as.
Embodiment 3
By bis- (4- amino-benzene oxygen) benzoic acid of the 3,5- of 33.6 grams (0.1 moles), 4150 grams of N, N-dimethylformamide and
The organic solvent of 1500 grams of N- ethyl-2-pyrrolidones is put into reaction kettle, at room temperature after stirring and dissolving, is added 40.0 gram (0.2
Mole) 3,4 '-diaminodiphenyl ethers, bis- (4- amino-benzene oxygen) diphenyl sulfides of 160.0 grams of (0.4 moles) 4,4 '-and 29.2 grams
After stirring and dissolving, 225.4 grams of (0.7 mole) 3,3 ', 4,4 '-tetracarboxylic acids are added in (0.1 mole) 1,3- bis- (3- amino-benzene oxygen) benzene
Bis- [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydrides of base benzophenone dianhydride, 78.0 grams of (0.15 mole) 2,2-, room temperature
After being stirred to react 2.0 hours, 22.1 grams of (0.1 mole) 3- aminopropyl triethoxysilanes and 17.9 grams are added in lower stirring and dissolving
(0.1 mole) 3- aminopropyl trimethoxysilane, is stirred to react 1.5 hours at room temperature, and 23.6 grams (0.1 mole) is then added
γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, 15min is stirred to react in 85 DEG C, and to obtain 6279.8 grams of clear viscous equal
Bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- of phase, are denoted as SA-3.
Embodiment 4
Bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- of suitable 1~embodiment of embodiment 3 are taken respectively, i.e.,
SA-1~SA-3, and be uniformly applied in standard stainless steel test piece respectively, it overlaps, clamps, be put into convection oven and consolidated
Change: starting to warm up from room temperature 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, after being kept for 0.5 hour, 260 DEG C are continuously heating to, after being kept for 0.5 hour, cooled to room temperature.Using electronic tensile machine,
The tensile shear strength test under the conditions of room temperature (25 DEG C) and high temperature (250 DEG C) is carried out to it respectively, the results are shown in Table 1.
Bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- of suitable 1~embodiment of embodiment 3 are taken respectively, i.e.,
SA-1~SA-3, and be equably impregnated with respectively on glass cloth, it is overlapped and is clamped with standard stainless steel test piece, is put into convection oven
Solidified: being started to warm up from room temperature to 80 DEG C, after being kept for 1 hour, 150 DEG C is continuously heating to, after being kept for 2 hours, after of continuing rising
Temperature is to 200 DEG C, after being kept for 0.5 hour, is continuously heating to 260 DEG C, after being kept for 0.5 hour, cooled to room temperature.Utilize electronics
Puller system carries out the tensile shear strength test under the conditions of room temperature (25 DEG C) and high temperature (250 DEG C), as a result such as table 1 to it respectively
It is shown.
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 bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 1 3,5- of table
Claims (7)
1. one kind 3, bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 5-, it is characterised in that: the organic silica gel by mole
(4- amino-benzene oxygen) benzoic acid more bis- than 3,5- for 1:5-10:6.5-12:1-2:1, aromatic diamine, aromatic dicarboxylic
Acid anhydride, the reaction product of 3- aminopropyltrialkoxysilane and γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane and organic
Solvent composition.
2. bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of a kind of 3,5- according to claim 1, it is characterised in that:
The aromatic diamine is 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, 4,4 '-benzidines, 3,3 '-diformazans
Base -4,4 '-benzidine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino -4 "-hydroxyl triphenylmenthane, 4,4 '-diaminos
Base diphenyl sulphone (DPS), 3,3 '-diaminodiphenylsulfones, 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane, 3,3 '-two chloro- 4,4 '-two
Diaminodiphenylmethane, 3,3 ', bis- (4- amino-benzene oxygen) benzonitriles of 5,5 '-tetramethyls -4,4 '-diaminodiphenylmethane, 2,6-,
Bis- (3- amino-benzene oxygen) benzonitriles of 2,6-, 2- (4- aminophenyl) -5- aminobenzimidazole, 3,3 '-diamino -4,4 '-two
Bis- (3- amino-4-hydroxylphenyl) propane of xenol, 2,2-, 2,2- bis- (3- amino-4-hydroxylphenyl) hexafluoropropane, 1,3-
Bis- (4- amino-benzene oxygen) benzene of bis- (3- amino-benzene oxygen) benzene, 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,4-, the bis- (2- tri- of 1,3-
Methyl fluoride -4- amino-benzene oxygen) benzene, bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, 2,6- bis- (4- amino-benzene oxygens)
Bis- (4- amino-benzene oxygen) toluene of toluene, 2,5-, bis- (2- trifluoromethyl-4-aminophenoxyl) benzoic acid of 3,5-, the bis- (2- of 2,6-
Trifluoromethyl-4-aminophenoxyl) toluene, bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of 2,5-, bis- [4- (the 4- ammonia of 2,2-
Phenoxyl) phenyl] propane, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, bis- [4- (the 3- ammonia of 2,2-
Phenoxyl) phenyl] propane, 4,4 '-bis- (4- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (3- amino-benzene oxygen) hexichol first
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoros of alkane, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl-methanes, 2,2-
Bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] hexafluoropropane of propane, 2,2-, the bis- [4- (3- amino-benzene oxygen) of 2,2-
Phenyl] 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. bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of a kind of 3,5- according to claim 1, it is characterised in that:
The aromatic dicarboxylic acid anhydride is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydrides, 3,3 ', 4,4 '-tetracarboxylic acids
Bis- (3,4- dicarboxyphenyi) hexafluoropropane dianhydrides of base diphenyl sulfone dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydrides, 2,2-,
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydrides, 2,2-, 2,2- are bis-
[4- (3,4- di carboxyl phenyloxy) 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- dicarboxyl benzene
Oxygroup) diphenyl sulfone dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxy) diphenyl ether dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxies)
One or more of diphenyl ether dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxy) benzophenone dianhydrides.
4. bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of a kind of 3,5- according to claim 1, it is characterised in that:
The 3- aminopropyltrialkoxysilane is selected from one of 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane
Or two kinds.
5. bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of a kind of 3,5- 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-
One or more of 2-Pyrrolidone, N- ethyl-2-pyrrolidone, dimethyl sulfoxide.
6. bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of a kind of 3,5- according to claim 1, it is characterised in that:
The mass ratio of the organic solvent and reactant is 2.5-9.5:1；Wherein, reactant refers to bis- (4- amino-benzene oxygen) benzene of 3,5-
Formic acid, aromatic diamine, aromatic dicarboxylic acid anhydride, 3- aminopropyltrialkoxysilane and γ-(the third oxygen of 2,3- epoxy) propyl three
Methoxy silane.
7. a kind of preparation method of bis- (4- amino-benzene oxygen) the benzoic acid type organic silica gels of 3,5- as described in claim 1, packet
Include following steps:
According to the ratio, bis- (4- amino-benzene oxygen) benzoic acid of 3,5- and organic solvent are put into reaction kettle, at room temperature stirring and dissolving
Afterwards, aromatic diamine is added, after stirring and dissolving, aromatic dicarboxylic acid anhydride is added, is stirred to react at room temperature -4.0 hours 1.0 hours
Afterwards, 3- aminopropyltrialkoxysilane is added, is stirred to react at room temperature -2 hours 0.5 hour, γ-(2,3- epoxies is then added
Third oxygen) propyl trimethoxy silicane, 15min is stirred to react in 80 DEG C -90 DEG C up to bis- (4- amino-benzene oxygen) benzoic acid of 3,5-
Type organic silica gel.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW200743658A (en) * | 2006-05-25 | 2007-12-01 | Ind Tech Res Inst | Thermoplastic polyimide composition and method of making double-sided flexible copper clad laminate using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200743658A (en) * | 2006-05-25 | 2007-12-01 | Ind Tech Res Inst | Thermoplastic polyimide composition and method of making double-sided flexible copper clad laminate using the same |
Non-Patent Citations (2)
| Title |
|---|
| 李恩等: "《3,5-双（4-氨基苯氧基）苯甲酸的合成及其聚酰亚胺薄膜的性能研究》，，", 《化学与粘合》 * |
| 杨俊华: "《有机硅改性聚酰亚胺》，", 《塑料科技》 * |
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