CN109722212A - A kind of acid imide epoxy organic silica gel and preparation method thereof - Google Patents
A kind of acid imide epoxy organic silica gel and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of acid imide epoxy organic silica gels and preparation method thereof, by 4,4 '-diamino -4 "-hydroxyl triphenylmenthane DAHTM, both-end aminopropyl polydimethylsiloxone YASI, N; N; N '; four glycidyl group -4 N ' -, 4 '-diaminodiphenylmethane TGDDM, 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 acid imide epoxy organic silica gel 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 is characterized mainly in that:
(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 stirring, is filtered, and vacuum drying obtains imide oligomer object；
(2) will be bis- (γ-aminopropyl) polydimethylsiloxone YASI, epoxy resin be 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.
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.
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.
Chinese invention patent CN106220047A discloses a kind of YASI type granolith plate and preparation method thereof, main
It is characterized in that:
(1) epoxy resin and bis- (γ-aminopropyl) polydimethylsiloxone YASI are put into reaction kettle, stirring is mixed
It closes, in 115 DEG C after -125 DEG C of reactions 0.5-1 hours, is cooled to 60 DEG C hereinafter, addition latent curing agent LRC30 and liquid acid
Acid anhydride is uniformly mixed, and obtains YASI type resin；
(2) after mixing by YASI type resin and granite powder, it being put into stainless steel flat plate frame, pressing is preforming,
Heat-pressure curing molding；Wherein, the temperature range of heating is room temperature to 180 DEG C；The pressure limit of pressurization be 0.5MPa extremely
5MPa；Curing time is 2-5 hours.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of acid imide epoxy organic silica gels and preparation method thereof, this has
Machine silica gel comprehensive performance is good, can be applied to glass, ceramics, composite material, extraordinary polarity weaving prepreg and its composite material
The bonding of substrate has good market application prospect.
The present invention provides a kind of acid imide epoxy organic silica gel, the organic silica gel is 1:0.1-0.5 by molar ratio:
The 4,4 ' of 0.2-0.8:5-10:6.5-12:1-2-diamino-4 "-hydroxyl triphenylmenthane DAHTM, both-end aminopropyl poly diformazan
Radical siloxane YASI, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylmethane TGDDM, aromatic diamine, virtue
The reaction product and organic solvent of fragrant race's dibasic anhydride and 3- aminopropyltrialkoxysilane 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 '-diaminodiphenylsulfones, 3,3 '-diamino two
Benzene sulfone, 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane, 3,3 '-two chloro- 4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 ' -
Bis- (4- amino-benzene oxygen) benzonitriles of tetramethyl -4,4 '-diaminodiphenylmethane, 2,6-, bis- (3- amino-benzene oxygen) benzene of 2,6-
Formonitrile HCN, 2- (4- aminophenyl) -5- aminobenzimidazole, 3,3 '-diamino -4,4 '-dihydroxybiphenyl, bis- (the 3- amino-of 2,2-
4- hydroxy phenyl) propane, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, 1,3- bis- (3- amino-benzene oxygen) benzene, 1,3-
Bis- (4- amino-benzene oxygen) benzene of bis- (4- amino-benzene oxygen) benzene, 1,4-, bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,3-,
Bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, bis- (4- amino-benzene oxygen) toluene of 2,6-, bis- (the 4- aminobenzene oxygen of 2,5-
Base) toluene, bis- (2- trifluoromethyl-4-aminophenoxyl) benzoic acid of 3,5-, 2,6- bis- (2- trifluoromethyl-4-aminophenoxyls)
Bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of toluene, 2,5-, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,
Bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2-, 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 4,4 '-diamino-
4 "-hydroxyl triphenylmenthane DAHTM, both-end aminopropyl polydimethylsiloxone YASI, N, N, N ', four glycidyl group -4 N ' -,
4 '-diaminodiphenylmethane TGDDM, aromatic diamine, aromatic dicarboxylic acid anhydride and 3- aminopropyltrialkoxysilane.
The molecular structural formula of the both-end aminopropyl polydimethylsiloxone YASI are as follows:
Wherein, m is and the natural number less than 15 greater than 1.
The present invention also provides a kind of preparation methods of acid imide epoxy organic silica gel, 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, both-end aminopropyl polydimethylsiloxone YASI, aromatic diamine is added, after stirring and dissolving, is added
After being stirred to react -4.0 hours 1.0 hours at room temperature, 3- aminopropyltrialkoxysilane is added, at room temperature in aromatic dicarboxylic acid anhydride
It is stirred to react -2 hours 0.5 hour, N, N, N is added ', four glycidyl group -4 N ' -, 4 '-diaminodiphenylmethane TGDDM, room
Up to acid imide epoxy organic silica gel after the lower stirring and dissolving of temperature.
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, both-end aminopropyl poly two are introduced in adhesive molecular structure of the invention
Methylsiloxane YASI provides not only the cured crosslinking reactivity group of adhesive system or silicon oxygen silicon base group is made to enter high score
Sub- skeleton structure, and good anchor cooperation use or affinity interaction can be generated with substrate, to improve the interface performance of bonding plane with
Adhesive strength is of great benefit to.
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), 850 grams of methyl tetrahydro furans
It mutters and is put into reaction kettle with 600 grams of n,N dimethylformamide, at room temperature after stirring and dissolving, 9.9 grams of (0.01 mole) both-ends are added
Aminopropyl polydimethylsiloxone (YASI, m average value are 11), after stirring and dissolving is complete, 20.0 grams of (0.1 moles) 3 to be added,
4 '-diaminodiphenyl ethers, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 73.2 grams of (0.2 mole) 2,2- and 80.0 gram (0.2
Mole) 4,4 '-bis- (4- amino-benzene oxygen) diphenyl sulfides, after stirring and dissolving, 209.3 grams of (0.65 moles) 3,3 ', 4,4 '-are added
Tetracarboxylic benzophenone dianhydride, stirring and dissolving, after being stirred to react 1.0 hours, is added 22.1 grams of (0.1 mole) 3- ammonia third at room temperature
Ethyl triethoxy silicane alkane is stirred to react 2 hours at room temperature, and 40.0 grams of (0.08 mole) N, N, N ' ,-four glycidol of N ' is added
4,4 '-diaminodiphenylmethane TGDDM of base-(is calculated) by epoxide number 0.8, at room temperature to get viscous to 1933 grams after stirring and dissolving
Thick acid imide epoxy organic silica gel, is denoted as DTSA-1.
Embodiment 2
By the 4,4 '-diamino -4 of 29.0 grams (0.1 mole) "-hydroxyl triphenylmenthane (DAHTM), 1500 grams of tetrahydrofurans,
500 grams of N, N dimethyl acetamide and 1000 grams of N- ethyl-2-pyrrolidones are put into reaction kettle, at room temperature after stirring and dissolving, are added
Enter 20.8 grams of (0.03 mole) both-end aminopropyl polydimethylsiloxones (YASI, m average value be 7), after stirring and dissolving is complete,
22.4 grams of (0.1 mole) 2- (4- aminophenyl) -5- aminobenzimidazoles, 31.7 grams of bis- (4- amino of (0.1 mole) 2,6- are added
Phenoxy group) benzonitrile, 100.0 grams of (0.5 mole) 3,4 '-diaminodiphenyl ethers and 120.0 grams (0.3 mole) 4,4 '-bis- (4- ammonia
Phenoxyl) diphenyl sulfide, after stirring and dissolving, be added 186.0 grams of (0.6 mole) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydrides and
193.2 grams (0.6 mole) 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydrides, stirring and dissolving, is stirred to react 4.0 hours at room temperature
Afterwards, 44.2 grams of (0.2 mole) 3- aminopropyl triethoxysilanes are added, are stirred to react at room temperature 0.5 hour, are added 10.0 grams
(0.02 mole) N, N, N ', four glycidyl group -4 N ' -, 4 '-diaminodiphenylmethane TGDDM (are calculated) by epoxide number 0.8, room
To get to 3757 grams of sticky acid imide epoxy organic silica gels after the lower stirring and dissolving of temperature, it is denoted as DTSA-2.
Embodiment 3
By the 4,4 '-diamino -4 of 29.0 grams (0.1 mole) "-hydroxyl triphenylmenthane (DAHTM), 2000 grams of tetrahydrofurans,
The organic solvent of 2000 grams of n,N dimethylformamide and 1800 grams of N- ethyl-2-pyrrolidones is put into reaction kettle, is stirred at room temperature
After mixing dissolution, 23.5 grams of (0.05 mole) both-end aminopropyl polydimethylsiloxones are added, and (YASI, m average value are 4) stirring
After dissolution completely, 20.0 grams of (0.1 mole) 3,4 '-diaminodiphenyl ethers, 160.0 grams of (0.4 moles) 4,4 '-bis- (4- ammonia are added
Phenoxyl) diphenyl sulfide and 43.2 grams of (0.2 mole) 3,3 '-diamino -4,4 '-dihydroxybiphenyls after stirring and dissolving, are added
225.4 grams (0.7 mole) 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydrides, 78.0 grams of bis- [4- (3,4- bis- of (0.15 mole) 2,2-
Carboxyphenoxy) phenyl] propane dianhydride, stirring and dissolving, after being stirred to react 2.0 hours, is added 22.1 grams (0.1 mole) at room temperature
3- aminopropyl triethoxysilane and 17.9 grams of (0.1 mole) 3- aminopropyl trimethoxysilanes, it is small to be stirred to react 1.5 at room temperature
When, 25.0 grams of (0.05 mole) N, N, N ', four glycidyl group -4 N '-are added, 4 '-diaminodiphenylmethane TGDDM (press epoxy
Value 0.8 calculates), DTSA-3 is denoted as to get to 6444 grams of sticky acid imide epoxy organic silica gels after stirring and dissolving at room temperature.
Embodiment 4
Take the acid imide epoxy organic silica gel of suitable 1~embodiment of embodiment 3 respectively, i.e. DTSA-1~DTSA-3, and
It is uniformly applied in standard stainless steel test piece, overlaps respectively, clamp, 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.
Take the acid imide epoxy organic silica gel of suitable 1~embodiment of embodiment 3 respectively, i.e. DTSA-1~DTSA-3, and
It is equably impregnated with respectively on glass cloth, is overlapped and clamped with standard stainless steel test piece, be put into convection oven and solidified: from room
Temperature is started 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, is continuously heating to 200 DEG C, is kept
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 acid imide epoxy organic silica gel of table
Claims (8)
1. a kind of acid imide epoxy organic silica gel, it is characterised in that: the organic silica gel is 1:0.1-0.5:0.2- by molar ratio
The 4,4 ' of 0.8:5-10:6.5-12:1-2-diamino-4 "-hydroxyl triphenylmenthane DAHTM, both-end aminopropyl poly dimethyl-silicon
Oxygen alkane YASI, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylmethane TGDDM, aromatic diamine, aromatic series
The reaction product and organic solvent of dibasic anhydride and 3- aminopropyltrialkoxysilane composition.
2. a kind of acid imide epoxy organic silica gel 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, 4,4 '-benzidines, 3,3 '-dimethyl -4,4 '-diamino connection
Benzene, 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 -4,4 '-diamino hexichol
Bis- (4- amino-benzene oxygen) benzonitriles of methane, 2,6-, bis- (3- amino-benzene oxygen) benzonitriles of 2,6-, 2- (4- aminophenyl) -5-
Bis- (3- amino-4-hydroxylphenyl) propane of aminobenzimidazole, 3,3 '-diamino -4,4 '-dihydroxybiphenyl, 2,2-, 2,2- are bis-
Bis- (3- amino-benzene oxygen) benzene of (3- amino-4-hydroxylphenyl) hexafluoropropane, 1,3-, 1,3- bis- (4- amino-benzene oxygen) benzene, 1,
Bis- (4- amino-benzene oxygen) benzene of 4-, bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, the bis- (2- trifluoromethyl -4- ammonia of 1,4-
Phenoxyl) benzene, bis- (4- amino-benzene oxygen) toluene of 2,6-, bis- (4- amino-benzene oxygen) toluene of 2,5-, bis- (the 2- fluoroforms of 3,5-
Base -4- amino-benzene oxygen) benzoic acid, bis- (2- trifluoromethyl-4-aminophenoxyl) toluene of 2,6-, bis- (the 2- trifluoromethyls-of 2,5-
4- amino-benzene oxygen) toluene, bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-, the bis- [4- (2- trifluoromethyl -4- ammonia of 2,2-
Phenoxyl) phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] propane of 2,2-, 4,4 '-bis- (4- amino-benzene oxygen) hexichol
Methane, 4,4 '-bis- (3- amino-benzene oxygen) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyl) diphenyl-methanes,
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-, 2,2- bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl]
Bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of hexafluoropropane, 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- ammonia
Phenoxyl) 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 acid imide epoxy organic silica gel 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 acid imide epoxy organic silica gel 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 acid imide epoxy organic silica gel 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 acid imide epoxy organic silica gel 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, both-end ammonia
Propyl polydimethylsiloxone YASI, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylmethane TGDDM, fragrance
Race's diamine, aromatic dicarboxylic acid anhydride and 3- aminopropyltrialkoxysilane.
7. a kind of acid imide epoxy organic silica gel according to claim 1, it is characterised in that: the both-end aminopropyl poly
The molecular structural formula of dimethyl siloxane YASI are as follows:
Wherein, m is and the natural number less than 15 greater than 1.
8. a kind of preparation method of acid imide epoxy organic silica gel 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, both-end aminopropyl polydimethylsiloxone YASI, aromatic diamine is added, after stirring and dissolving, fragrance is added
Race's dibasic anhydride after being stirred to react -4.0 hours 1.0 hours at room temperature, is added 3- aminopropyltrialkoxysilane, stirs at room temperature
N, N, N is added in reaction -2 hours 0.5 hour ', four glycidyl group -4 N ' -, 4 '-diaminodiphenylmethane TGDDM, at room temperature
Up to acid imide epoxy organic silica gel after stirring and dissolving.
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| CN111073282A (en) * | 2019-11-28 | 2020-04-28 | 李南文 | Solvent-resistant colorless transparent cross-linked polyimide film and preparation method thereof |
| CN111073283A (en) * | 2019-11-28 | 2020-04-28 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
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| CN111073283A (en) * | 2019-11-28 | 2020-04-28 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
| CN111073283B (en) * | 2019-11-28 | 2022-05-31 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
| CN111073282B (en) * | 2019-11-28 | 2022-05-31 | 李南文 | Solvent-resistant colorless transparent cross-linked polyimide film and preparation method thereof |
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