CN108948673A - A kind of dielectric composite material preparation method added with phenolic resin - Google Patents
A kind of dielectric composite material preparation method added with phenolic resin Download PDFInfo
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Abstract
The dielectric composite material preparation method added with phenolic resin that the invention discloses a kind of, this method is will to obtain ultrasonic oxidation modified powder through techniques such as oil bath heat preservations after the processing of the raw materials ultrasonic oxidation such as silicon tetrachloride, it is heat-treated jointly with raw materials such as benzocyclobutane olefine resins again, sulfonation modifying mixture then is made in heat treatment reaction mixture, then itself and 3- aminopropyl trimethoxysilane etc. are added in ethyl acetate solution jointly and are ultrasonically treated, phenolic resin is then added and carries out oil bath insulation reaction, it is mixed after centrifugal drying with raw materials such as dimethyl diphenyl methane diamines, temperature constant magnetic stirring is condensed back after heating, revolving is dried to obtain intermediary composite, blank is made again and is added to N, in dinethylformamide solution, the process such as heated stirring obtain finished product dielectric composite material.The dielectric composite material added with phenolic resin being prepared, heat distortion temperature with higher have a good application prospect in capacitor manufacture.
Description
Technical field
The present invention relates to electronics new material technology fields, and in particular to a kind of dielectric composite material added with phenolic resin
Preparation method.
Background technique
With the further development of electronic and electrical industry, the polymer matrix composite wood with high dielectric constant and low dielectric loss
Material has obtained extensive concern.In electrical engineering field, this kind of material can be used as the dielectric material of high density capacitors；
In microelectronic field, the polymer matrix composite with superior dielectric performance can be used as buried capacitors, and guarantee to collect
At the high speed and safe operation of circuit.Importantly, the composite material using polymer as matrix has gently in actual production
The advantages that matter, at low cost and easy processing, becomes the important development direction for preparing dielectric material.But it is existing with polymerization
Object is often poor as the composite material heat resistance of matrix, is easy to happen deformation when encountering high temperature, open fire, to life
It generates work and causes irremediable loss.
Phenolic resin is also bakelite, also known as phenolic moulding powder.It originally was colourless or yellowish-brown transparency, market sale often adds coloring
Agent and in the colors such as red, yellow, black, green, brown, blue, have particle, powdered.Weak acid resistant and weak base meet strong acid and decompose, and meet strong
Alkali corrodes.It is not soluble in water, it is dissolved in the organic solvents such as acetone, alcohol.Phenol aldehyde or derivatives thereof polycondensation and obtain.Phenolic aldehyde tree
The most important feature of rouge is exactly heat-resisting quantity, even if at very high temperatures, being also able to maintain the globality and size of its structure
Stability.Just because of this reason, phenolic resin is just applied to some high-temperature fields, such as refractory material, friction material,
Binder and casting industry.And the high temperature resistance that node composite how is improved using the above-mentioned performance of phenolic resin is
At present the problem of urgent need to resolve.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of dielectric composite material preparation side added with phenolic resin
Method, this method are will to obtain the modified powder of ultrasonic oxidation through techniques such as oil bath heat preservations after the processing of the raw materials ultrasonic oxidation such as silicon tetrachloride
End, then be heat-treated jointly with raw materials such as benzocyclobutane olefine resins, sulfonation modifying then is made in heat treatment reaction mixture
Itself and 3- aminopropyl trimethoxysilane etc. are then added in ethyl acetate solution jointly and are ultrasonically treated by mixture, then add
Enter phenolic resin and carry out oil bath insulation reaction, is mixed after centrifugal drying with raw materials such as dimethyl diphenyl methane diamines, it is permanent after heating
Warm magnetic agitation is condensed back, and revolving is dried to obtain intermediary composite, then blank is made and is added to N, N- dimethyl formyl
In amine aqueous solution, the process such as heated stirring obtain finished product dielectric composite material.Be prepared added with phenolic resin
Dielectric composite material, heat distortion temperature with higher have a good application prospect in capacitor manufacture.
Technical solution: to solve the above-mentioned problems, the invention discloses a kind of dielectric composite wood added with phenolic resin
Preparation method for material comprises the steps of:
(1) 8~10 parts of silicon tetrachloride, 7~9 parts of bismuth nitrate, 16~20 parts of alkenyl succinic anhydride are added to its weight 25
The H that mass concentration again is 30%2O2It in solution, is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 800
~1000W, processing time are 10~20 minutes, will then be ultrasonically treated mixed liquor and are sent into 130~140 DEG C of oil bath, heat preservation
Stirring 60~80 minutes, is then centrifuged, isolated precipitated product is dried in vacuo 6~8 hours at 80 DEG C,
Desciccate is placed in ball-milling treatment in planetary ball mill again, obtains ultrasonic oxidation modified powder；
(2) by 55~65 parts of benzocyclobutane olefine resin, 50~60 parts of oleic acid diethyl amide, oxidized polyethylene wax 45~55
The ultrasonic oxidation modified powder that part, 1~3 part of vulcanizing agent and step (1) obtain is added to jointly in heat treatment blender, 100
According to revolving speed heating stirring 120~150 minutes of 220~260 revs/min at~110 DEG C, heat treatment reaction mixture is obtained,
Heat treatment reaction mixture is added in the sulfuric acid solution that mass concentration is 80% and carries out ultrasonic mixing by 1:15 in mass ratio again,
The power of ultrasonic mixing is 750~850W, and incorporation time is 15~25 minutes, then filters ultrasonic mixing liquid, collects
Filter cake is washed with distilled water 2~3 times by filter cake, 12 hours dry at 80~90 DEG C, obtains sulfonation modifying mixture；
(3) 25~30 parts of 3- aminopropyl trimethoxysilane, 5~9 parts of N ' N- carbonyl dimidazoles are obtained with step (2)
Sulfonation modifying mixture is added in the ethyl acetate solution of 20 times of its weight, is ultrasonically treated 10~20 minutes, phenol is then added
30~40 parts of urea formaldehyde, then insulation reaction 80~100 minutes in 110 DEG C of oil bath, will be deposited in 70 DEG C after being centrifuged while hot
Lower vacuum drying 10~12 hours, then by desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) in mass ratio 1:
(2~3): (4~6) are added in reaction vessel, nitrogen are passed through into reaction vessel, the air in reaction vessel is discharged, be added
It 10~12 parts of barium stearate, continuess to mix and stirs evenly, be warming up to 75~85 DEG C, it is small that temperature constant magnetic stirring is condensed back 16~18
When, rotary evaporation concentration, 70~80 DEG C of vacuum drying obtain intermediary composite；
(4) intermediary composite that step (3) obtains is added to the steaming of 50 times of its weight with 6~8 parts of titanium acetylacetone
It in distilled water, stirs evenly, pH value of solution is adjusted to 8~9 by the sodium hydroxide that 1mol/L is added dropwise, and is stirred 10~20 minutes, by solution
Temperature is risen to 75~80 DEG C, insulated and stirred 25~35 minutes, precipitating washing 2~3 times is subsequently added to Sediment weight 8 by filtering
In~10 times of dimethylformamide, it is ultrasonically treated 10~20 minutes, is then dried in vacuo 4~6 hours at 60~70 DEG C,
Blank is pressed into the pressure of 16~18MPa at 150~160 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 15~20 times of its weight, it will
Mixed liquor is warming up to 60~70 DEG C of heating stirrings 40~50 minutes, puts into 1~3 part of coupling agent, 1~3 part of antioxidant, continues to stir
20~30 minutes, mixed liquor is then warming up to 150~160 DEG C of stirrings and obtains prepolymer within 2~3 hours, gained prepolymer is existed
Vacuum outgas 40~60 minutes at 120 DEG C, then heat to 190~200 DEG C of curing process 8~10 hours, and dielectric is obtained after demoulding
Composite material.
Further, the ratio of grinding media to material of ball-milling treatment is 20:1 in the step (1), and the revolving speed of ball mill is 500 revs/min
Clock, Ball-milling Time are 2~4 hours.
Further, the vulcanizing agent in the step (2) is selected from cumyl peroxide, tert-butyl hydroperoxide, 2,4-
Any one in dichlorobenzoperoxide.
Further, desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) are pressed in the step (3)
Mass ratio is 1:3:5.
Further, the coupling agent in the step (5) is selected from m-methyl benzoyl formyl chloride, three oleic acid acyloxy titanium of isopropyl
Any one in acid esters, 3- glycidyl ether oxypropyltrimethoxysilane.
Further, the antioxidant in the step (5) is selected from double stearyl alcohol pentaerythritol diphosphites, double
Any one in (2,4-dicumylphenyl) pentaerythritol diphosphites, three (2,4- di-tert-butyl-phenyl) phosphite esters.
Compared with prior art, the present invention has the advantages that:
(1) preparation method of the dielectric composite material added with phenolic resin of the invention is to surpass the raw materials such as silicon tetrachloride
Ultrasonic oxidation modified powder is obtained through techniques such as oil bath heat preservations after sound oxidation processes, then common with the raw materials such as benzocyclobutane olefine resin
It is heat-treated, sulfonation modifying mixture then is made in heat treatment reaction mixture, then by itself and 3- aminopropyl trimethoxy
Base silane etc. is added in ethyl acetate solution jointly and is ultrasonically treated, and phenolic resin is then added and carries out oil bath insulation reaction, centrifugation
It is mixed after drying with raw materials such as dimethyl diphenyl methane diamines, temperature constant magnetic stirring is condensed back after heating, and revolving is dried to obtain
Intermediary composite, then blank is made and is added in n,N-Dimethylformamide solution, the process such as heated stirring obtain
To finished product dielectric composite material.The dielectric composite material added with phenolic resin being prepared, thermal deformation with higher
Temperature has a good application prospect in capacitor manufacture.
(2) preparation dielectric is participated in present invention employs raw materials such as alkenyl succinic anhydride, oxidized polyethylene wax, phenolic resin to answer
Condensation material has carried out effective performance boost to dielectric composite material, although these materials are not compound applied to dielectric for the first time
In material, but after amount is with other material combinations according to a certain ratio, it is aided with corresponding modification mode, to being finally prepared
Dielectric composite material bring increasing substantially in service performance, this is never to report in previous research, right
Play the role of in realization technical effect of the invention conclusive.
Specific embodiment
Embodiment 1
(1) 8 parts of silicon tetrachloride, 7 parts of bismuth nitrate, 16 parts of alkenyl succinic anhydride are added to the mass concentration of 25 times of its weight
For 30% H2O2It in solution, is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 800W, and the processing time is
10 minutes, it will then be ultrasonically treated mixed liquor and be sent into 130 DEG C of oil bath, insulated and stirred 60 minutes, be then centrifuged,
Isolated precipitated product is dried in vacuo 6 hours at 80 DEG C, then desciccate is placed in ball milling in planetary ball mill
Processing, the ratio of grinding media to material of ball-milling treatment are 20:1, and the revolving speed of ball mill is 500 revs/min, and Ball-milling Time is 2 hours, obtain ultrasound
Oxidation modification powder；
(2) by 55 parts of benzocyclobutane olefine resin, 50 parts of oleic acid diethyl amide, 45 parts of oxidized polyethylene wax, peroxidating two
The ultrasonic oxidation modified powder that 1 part of isopropylbenzene and step (1) obtain is added to jointly in heat treatment blender, is pressed at 100 DEG C
According to revolving speed heating stirring 120 minutes of 220 revs/min, heat treatment reaction mixture is obtained, then 1:15 in mass ratio will be heat-treated
Reaction mixture, which is added in the sulfuric acid solution that mass concentration is 80%, carries out ultrasonic mixing, and the power of ultrasonic mixing is 750W,
Incorporation time is 15 minutes, then filters ultrasonic mixing liquid, collects filter cake, filter cake is washed with distilled water 2~3 times,
It is 12 hours dry at 80 DEG C, obtain sulfonation modifying mixture；
(3) 5 parts of 25 parts of 3- aminopropyl trimethoxysilane, N ' N- carbonyl dimidazoles sulfonation obtained with step (2) are changed
Property mixture be added in the ethyl acetate solution of 20 times of its weight, be ultrasonically treated 10 minutes, then be added 30 parts of phenolic resin,
Then insulation reaction 80 minutes in 110 DEG C of oil bath will be deposited at 70 DEG C after being centrifuged while hot and be dried in vacuo 10 hours, then will
Desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) 1:3:5 in mass ratio are added in reaction vessel, to anti-
It answers and is passed through nitrogen in container for the air discharge in reaction vessel, be added 10 parts of barium stearate, continues to mix and stir evenly, heat up
To 75 DEG C, temperature constant magnetic stirring is condensed back 16 hours, rotary evaporation concentration, and 70 DEG C of vacuum drying obtain intermediary composite；
(4) intermediary composite that step (3) obtains is added to the distilled water of 50 times of its weight with 6 parts of titanium acetylacetone
In, it stirs evenly, pH value of solution is adjusted to 8 by the sodium hydroxide that 1mol/L is added dropwise, and is stirred 10 minutes, and solution is risen temperature to 75
DEG C, insulated and stirred 25 minutes, precipitating washing 2~3 times was subsequently added to 8 times of Sediment weight of dimethylformamide by filtering
In, it is ultrasonically treated 10 minutes, is then dried in vacuo 4 hours at 60 DEG C, blank is pressed into the pressure of 16MPa at 150 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 15 times of its weight, will be mixed
Liquid is warming up to 60 DEG C of heating stirrings 40 minutes, puts into 1 part of m-methyl benzoyl formyl chloride, double stearyl alcohol pentaerythrite diphosphorous acids
1 part of ester, continue stirring 20 minutes, mixed liquor is then warming up to 150 DEG C of stirrings and obtains prepolymer within 2 hours, by gained prepolymer
Vacuum outgas 40 minutes at 120 DEG C, then heat to 190 DEG C of curing process 8 hours, and dielectric composite material is obtained after demoulding.
Embodiment 2
(1) 9 parts of silicon tetrachloride, 8 parts of bismuth nitrate, 18 parts of alkenyl succinic anhydride are added to the mass concentration of 25 times of its weight
For 30% H2O2It in solution, is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 900W, and the processing time is
15 minutes, it will then be ultrasonically treated mixed liquor and be sent into 135 DEG C of oil bath, insulated and stirred 70 minutes, be then centrifuged,
Isolated precipitated product is dried in vacuo 7 hours at 80 DEG C, then desciccate is placed in ball milling in planetary ball mill
Processing, the ratio of grinding media to material of ball-milling treatment are 20:1, and the revolving speed of ball mill is 500 revs/min, and Ball-milling Time is 3 hours, obtain ultrasound
Oxidation modification powder；
(2) by 60 parts of benzocyclobutane olefine resin, 55 parts of oleic acid diethyl amide, 50 parts of oxidized polyethylene wax, tert-butyl mistake
The ultrasonic oxidation modified powder that 2 parts of hydrogen oxide and step (1) obtain is added to jointly in heat treatment blender, is pressed at 105 DEG C
According to revolving speed heating stirring 135 minutes of 240 revs/min, heat treatment reaction mixture is obtained, then 1:15 in mass ratio will be heat-treated
Reaction mixture, which is added in the sulfuric acid solution that mass concentration is 80%, carries out ultrasonic mixing, and the power of ultrasonic mixing is 800W,
Incorporation time is 20 minutes, then filters ultrasonic mixing liquid, collects filter cake, filter cake is washed with distilled water 2~3 times,
It is 12 hours dry at 85 DEG C, obtain sulfonation modifying mixture；
(3) 7 parts of 28 parts of 3- aminopropyl trimethoxysilane, N ' N- carbonyl dimidazoles sulfonation obtained with step (2) are changed
Property mixture be added in the ethyl acetate solution of 20 times of its weight, be ultrasonically treated 15 minutes, then be added 35 parts of phenolic resin,
Then insulation reaction 90 minutes in 110 DEG C of oil bath will be deposited at 70 DEG C after being centrifuged while hot and be dried in vacuo 11 hours, then will
Desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) 1:3:5 in mass ratio are added in reaction vessel, to anti-
It answers and is passed through nitrogen in container for the air discharge in reaction vessel, be added 11 parts of barium stearate, continues to mix and stir evenly, heat up
To 80 DEG C, temperature constant magnetic stirring is condensed back 17 hours, rotary evaporation concentration, and 75 DEG C of vacuum drying obtain intermediary composite；
(4) intermediary composite that step (3) obtains is added to the distilled water of 50 times of its weight with 7 parts of titanium acetylacetone
In, it stirs evenly, pH value of solution is adjusted to 8.5 by the sodium hydroxide that 1mol/L is added dropwise, and is stirred 15 minutes, and solution is risen temperature to 77
DEG C, insulated and stirred 30 minutes, precipitating washing 2~3 times was subsequently added to 9 times of Sediment weight of dimethylformamide by filtering
In, it is ultrasonically treated 15 minutes, is then dried in vacuo 5 hours at 65 DEG C, blank is pressed into the pressure of 17MPa at 155 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 17.5 times of its weight, will be mixed
It closes liquid and is warming up to 65 DEG C of heating stirrings 45 minutes, put into three 2 parts of oleic acid acyloxy titanate esters of isopropyl, bis- (2,4- dicumyl benzene
Base) 2 parts of pentaerythritol diphosphites, continue stirring 25 minutes, is then warming up to mixed liquor 155 DEG C of stirrings 2.5 hours
To prepolymer, by gained prepolymer at 120 DEG C vacuum outgas 50 minutes, then heat to 195 DEG C of curing process 9 hours, take off
Dielectric composite material is obtained after mould.
Embodiment 3
(1) 10 parts of silicon tetrachloride, 9 parts of bismuth nitrate, 20 parts of the alkenyl succinic anhydride quality for being added to 25 times of its weight are dense
The H that degree is 30%2O2It in solution, is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 1000W, handles the time
It is 20 minutes, will be then ultrasonically treated mixed liquor and be sent into 140 DEG C of oil bath, insulated and stirred 80 minutes, then carries out centrifugation point
From isolated precipitated product being dried in vacuo 8 hours at 80 DEG C, then desciccate is placed in ball in planetary ball mill
Mill processing, the ratio of grinding media to material of ball-milling treatment are 20:1, and the revolving speed of ball mill is 500 revs/min, and Ball-milling Time is 4 hours, are surpassed
Sound oxidation modification powder；
(2) by 65 parts of benzocyclobutane olefine resin, 60 parts of oleic acid diethyl amide, 55 parts of oxidized polyethylene wax, 2,4- dichloro
The ultrasonic oxidation modified powder that 3 parts of benzoyl peroxide and step (1) obtain is added to jointly in heat treatment blender, 110
According to revolving speed heating stirring 150 minutes of 260 revs/min at DEG C, heat treatment reaction mixture is obtained, then 1:15 in mass ratio will
Heat treatment reaction mixture, which is added in the sulfuric acid solution that mass concentration is 80%, carries out ultrasonic mixing, and the power of ultrasonic mixing is
850W, incorporation time are 25 minutes, then filter ultrasonic mixing liquid, collect filter cake, filter cake is washed with distilled water 2~
It is 3 times, 12 hours dry at 90 DEG C, obtain sulfonation modifying mixture；
(3) 9 parts of 30 parts of 3- aminopropyl trimethoxysilane, N ' N- carbonyl dimidazoles sulfonation obtained with step (2) are changed
Property mixture be added in the ethyl acetate solution of 20 times of its weight, be ultrasonically treated 20 minutes, then be added 40 parts of phenolic resin,
Then insulation reaction 100 minutes in 110 DEG C of oil bath will be deposited at 70 DEG C after being centrifuged while hot and be dried in vacuo 12 hours, then
Desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) 1:3:5 in mass ratio are added in reaction vessel, to
It is passed through nitrogen in reaction vessel the air in reaction vessel is discharged, is added 12 parts of barium stearate, continuess to mix and stir evenly, rises
To 85 DEG C, temperature constant magnetic stirring is condensed back 18 hours temperature, rotary evaporation concentration, and 80 DEG C of vacuum drying obtain intermediate bluk recombination
Object；
(4) intermediary composite that step (3) obtains is added to the distilled water of 50 times of its weight with 8 parts of titanium acetylacetone
In, it stirs evenly, pH value of solution is adjusted to 9 by the sodium hydroxide that 1mol/L is added dropwise, and is stirred 20 minutes, and solution is risen temperature to 80
DEG C, insulated and stirred 35 minutes, precipitating washing 2~3 times was subsequently added to 10 times of Sediment weight of dimethylformamide by filtering
In, it is ultrasonically treated 20 minutes, is then dried in vacuo 6 hours at 70 DEG C, blank is pressed into the pressure of 18MPa at 160 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 20 times of its weight, will be mixed
Liquid is warming up to 70 DEG C of heating stirrings 50 minutes, puts into 3 parts of 3- glycidyl ether oxypropyltrimethoxysilane, three (2,4- bis-
Tert-butyl-phenyl) 3 parts of phosphite ester, continue stirring 30 minutes, then by mixed liquor be warming up to 160 DEG C of stirrings obtain within 3 hours it is pre-
Polymers, by gained prepolymer at 120 DEG C vacuum outgas 60 minutes, 200 DEG C of curing process are then heated to 10 hours, after demoulding
Obtain dielectric composite material.
Comparative example 1
(1) 10 parts of silicon tetrachloride, 9 parts of bismuth nitrate are added to the H that the mass concentration of 25 times of its weight is 30%2O2Solution
In, it is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 1000W, and the processing time is 20 minutes, will then be surpassed
Sonication mixed liquor is sent into 140 DEG C of oil bath, insulated and stirred 80 minutes, is then centrifuged, and isolated is sunk
Shallow lake product is dried in vacuo 8 hours at 80 DEG C, then desciccate is placed in ball-milling treatment in planetary ball mill, ball-milling treatment
Ratio of grinding media to material is 20:1, and the revolving speed of ball mill is 500 revs/min, and Ball-milling Time is 4 hours, obtains ultrasonic oxidation modified powder；
(2) by 65 parts of benzocyclobutane olefine resin, 60 parts of oleic acid diethyl amide, 55 parts of oxidized polyethylene wax, 2,4- dichloro
The ultrasonic oxidation modified powder that 3 parts of benzoyl peroxide and step (1) obtain is added to jointly in heat treatment blender, 110
According to revolving speed heating stirring 150 minutes of 260 revs/min at DEG C, heat treatment reaction mixture is obtained, then 1:15 in mass ratio will
Heat treatment reaction mixture, which is added in the sulfuric acid solution that mass concentration is 80%, carries out ultrasonic mixing, and the power of ultrasonic mixing is
850W, incorporation time are 25 minutes, then filter ultrasonic mixing liquid, collect filter cake, filter cake is washed with distilled water 2~
It is 3 times, 12 hours dry at 90 DEG C, obtain sulfonation modifying mixture；
(3) 9 parts of 30 parts of 3- aminopropyl trimethoxysilane, N ' N- carbonyl dimidazoles sulfonation obtained with step (2) are changed
Property mixture be added in the ethyl acetate solution of 20 times of its weight, be ultrasonically treated 20 minutes, then be added 40 parts of phenolic resin,
Then insulation reaction 100 minutes in 110 DEG C of oil bath will be deposited at 70 DEG C after being centrifuged while hot and be dried in vacuo 12 hours, then
Desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) 1:3:5 in mass ratio are added in reaction vessel, to
It is passed through nitrogen in reaction vessel the air in reaction vessel is discharged, is added 12 parts of barium stearate, continuess to mix and stir evenly, rises
To 85 DEG C, temperature constant magnetic stirring is condensed back 18 hours temperature, rotary evaporation concentration, and 80 DEG C of vacuum drying obtain intermediate bluk recombination
Object；
(4) intermediary composite that step (3) obtains is added to the distilled water of 50 times of its weight with 8 parts of titanium acetylacetone
In, it stirs evenly, pH value of solution is adjusted to 9 by the sodium hydroxide that 1mol/L is added dropwise, and is stirred 20 minutes, and solution is risen temperature to 80
DEG C, insulated and stirred 35 minutes, precipitating washing 2~3 times was subsequently added to 10 times of Sediment weight of dimethylformamide by filtering
In, it is ultrasonically treated 20 minutes, is then dried in vacuo 6 hours at 70 DEG C, blank is pressed into the pressure of 18MPa at 160 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 20 times of its weight, will be mixed
Liquid is warming up to 70 DEG C of heating stirrings 50 minutes, puts into 3 parts of 3- glycidyl ether oxypropyltrimethoxysilane, three (2,4- bis-
Tert-butyl-phenyl) 3 parts of phosphite ester, continue stirring 30 minutes, then by mixed liquor be warming up to 160 DEG C of stirrings obtain within 3 hours it is pre-
Polymers, by gained prepolymer at 120 DEG C vacuum outgas 60 minutes, 200 DEG C of curing process are then heated to 10 hours, after demoulding
Obtain dielectric composite material.
Comparative example 2
(1) 10 parts of silicon tetrachloride, 9 parts of bismuth nitrate, 20 parts of the alkenyl succinic anhydride quality for being added to 25 times of its weight are dense
The H that degree is 30%2O2It in solution, is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 1000W, handles the time
It is 20 minutes, will be then ultrasonically treated mixed liquor and be sent into 140 DEG C of oil bath, insulated and stirred 80 minutes, then carries out centrifugation point
From isolated precipitated product being dried in vacuo 8 hours at 80 DEG C, then desciccate is placed in ball in planetary ball mill
Mill processing, the ratio of grinding media to material of ball-milling treatment are 20:1, and the revolving speed of ball mill is 500 revs/min, and Ball-milling Time is 4 hours, are surpassed
Sound oxidation modification powder；
(2) by 65 parts of benzocyclobutane olefine resin, 60 parts of oleic acid diethyl amide, 3 parts of 2,4- dichlorobenzoperoxide and
The ultrasonic oxidation modified powder that step (1) obtains is added to jointly in heat treatment blender, according to 260 revs/min at 110 DEG C
Revolving speed heating stirring 150 minutes, obtain heat treatment reaction mixture, then 1:15 in mass ratio will heat treatment reaction mixture add
Enter and carry out ultrasonic mixing in the sulfuric acid solution for being 80% to mass concentration, the power of ultrasonic mixing is 850W, incorporation time 25
Minute, then ultrasonic mixing liquid is filtered, filter cake is collected, filter cake is washed with distilled water 2~3 times, is done at 90 DEG C
Dry 12 hours, obtain sulfonation modifying mixture；
(3) 9 parts of 30 parts of 3- aminopropyl trimethoxysilane, N ' N- carbonyl dimidazoles sulfonation obtained with step (2) are changed
Property mixture be added in the ethyl acetate solution of 20 times of its weight, be ultrasonically treated 20 minutes, then be added 40 parts of phenolic resin,
Then insulation reaction 100 minutes in 110 DEG C of oil bath will be deposited at 70 DEG C after being centrifuged while hot and be dried in vacuo 12 hours, then
Desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) 1:3:5 in mass ratio are added in reaction vessel, to
It is passed through nitrogen in reaction vessel the air in reaction vessel is discharged, is added 12 parts of barium stearate, continuess to mix and stir evenly, rises
To 85 DEG C, temperature constant magnetic stirring is condensed back 18 hours temperature, rotary evaporation concentration, and 80 DEG C of vacuum drying obtain intermediate bluk recombination
Object；
(4) intermediary composite that step (3) obtains is added to the distilled water of 50 times of its weight with 8 parts of titanium acetylacetone
In, it stirs evenly, pH value of solution is adjusted to 9 by the sodium hydroxide that 1mol/L is added dropwise, and is stirred 20 minutes, and solution is risen temperature to 80
DEG C, insulated and stirred 35 minutes, precipitating washing 2~3 times was subsequently added to 10 times of Sediment weight of dimethylformamide by filtering
In, it is ultrasonically treated 20 minutes, is then dried in vacuo 6 hours at 70 DEG C, blank is pressed into the pressure of 18MPa at 160 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 20 times of its weight, will be mixed
Liquid is warming up to 70 DEG C of heating stirrings 50 minutes, puts into 3 parts of 3- glycidyl ether oxypropyltrimethoxysilane, three (2,4- bis-
Tert-butyl-phenyl) 3 parts of phosphite ester, continue stirring 30 minutes, then by mixed liquor be warming up to 160 DEG C of stirrings obtain within 3 hours it is pre-
Polymers, by gained prepolymer at 120 DEG C vacuum outgas 60 minutes, 200 DEG C of curing process are then heated to 10 hours, after demoulding
Obtain dielectric composite material.
Comparative example 3
(1) 10 parts of silicon tetrachloride, 9 parts of bismuth nitrate, 20 parts of the alkenyl succinic anhydride quality for being added to 25 times of its weight are dense
The H that degree is 30%2O2It in solution, is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 1000W, handles the time
It is 20 minutes, will be then ultrasonically treated mixed liquor and be sent into 140 DEG C of oil bath, insulated and stirred 80 minutes, then carries out centrifugation point
From isolated precipitated product being dried in vacuo 8 hours at 80 DEG C, then desciccate is placed in ball in planetary ball mill
Mill processing, the ratio of grinding media to material of ball-milling treatment are 20:1, and the revolving speed of ball mill is 500 revs/min, and Ball-milling Time is 4 hours, are surpassed
Sound oxidation modification powder；
(2) by 65 parts of benzocyclobutane olefine resin, 60 parts of oleic acid diethyl amide, 55 parts of oxidized polyethylene wax, 2,4- dichloro
The ultrasonic oxidation modified powder that 3 parts of benzoyl peroxide and step (1) obtain is added to jointly in heat treatment blender, 110
According to revolving speed heating stirring 150 minutes of 260 revs/min at DEG C, heat treatment reaction mixture is obtained, then 1:15 in mass ratio will
Heat treatment reaction mixture, which is added in the sulfuric acid solution that mass concentration is 80%, carries out ultrasonic mixing, and the power of ultrasonic mixing is
850W, incorporation time are 25 minutes, then filter ultrasonic mixing liquid, collect filter cake, filter cake is washed with distilled water 2~
It is 3 times, 12 hours dry at 90 DEG C, obtain sulfonation modifying mixture；
(3) 9 parts of 30 parts of 3- aminopropyl trimethoxysilane, N ' N- carbonyl dimidazoles sulfonation obtained with step (2) are changed
Property mixture be added in the ethyl acetate solution of 20 times of its weight, be ultrasonically treated 20 minutes, then protected in 110 DEG C of oil bath
Temperature reaction 100 minutes, will be deposited at 70 DEG C and be dried in vacuo 12 hours after being centrifuged while hot, then by desciccate and dimethyl hexichol
Methane diamines and methyl iso-butyl ketone (MIBK) 1:3:5 in mass ratio are added in reaction vessel, and nitrogen is passed through into reaction vessel will be anti-
It answers the air in container to be discharged, is added 12 parts of barium stearate, continuess to mix and stir evenly, be warming up to 85 DEG C, temperature constant magnetic stirring
It is condensed back 18 hours, rotary evaporation concentration, 80 DEG C of vacuum drying obtain intermediary composite；
(4) intermediary composite that step (3) obtains is added to the distilled water of 50 times of its weight with 8 parts of titanium acetylacetone
In, it stirs evenly, pH value of solution is adjusted to 9 by the sodium hydroxide that 1mol/L is added dropwise, and is stirred 20 minutes, and solution is risen temperature to 80
DEG C, insulated and stirred 35 minutes, precipitating washing 2~3 times was subsequently added to 10 times of Sediment weight of dimethylformamide by filtering
In, it is ultrasonically treated 20 minutes, is then dried in vacuo 6 hours at 70 DEG C, blank is pressed into the pressure of 18MPa at 160 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 20 times of its weight, will be mixed
Liquid is warming up to 70 DEG C of heating stirrings 50 minutes, puts into 3 parts of 3- glycidyl ether oxypropyltrimethoxysilane, three (2,4- bis-
Tert-butyl-phenyl) 3 parts of phosphite ester, continue stirring 30 minutes, then by mixed liquor be warming up to 160 DEG C of stirrings obtain within 3 hours it is pre-
Polymers, by gained prepolymer at 120 DEG C vacuum outgas 60 minutes, 200 DEG C of curing process are then heated to 10 hours, after demoulding
Obtain dielectric composite material.
Specification, which is made, in the dielectric composite material that phenolic resin is added with made from embodiment 1-3 and comparative example 1-3 is
10cm × 4cm × 0.3cm thin slice, measures its heat distortion temperature under heating state respectively, and test result is as shown in table 1.
Table 1
The preparation method of dielectric composite material added with phenolic resin of the invention is by the raw materials such as silicon tetrachloride ultrasound
Obtain ultrasonic oxidation modified powder through techniques such as oil bath heat preservations after oxidation processes, then with the raw materials such as benzocyclobutane olefine resin jointly into
Then sulfonation modifying mixture is made, then by itself and 3- aminopropyl trimethoxy in heat treatment reaction mixture by row heat treatment
Silane etc. is added in ethyl acetate solution jointly and is ultrasonically treated, and phenolic resin is then added and carries out oil bath insulation reaction, centrifugation is dry
It is mixed after dry with raw materials such as dimethyl diphenyl methane diamines, temperature constant magnetic stirring is condensed back after heating, is rotated in being dried to obtain
Between nanocrystal composition, then blank is made and is added in n,N-Dimethylformamide solution, the process such as heated stirring obtain
Finished product dielectric composite material.The dielectric composite material added with phenolic resin being prepared, thermal deformation temperature with higher
Degree has a good application prospect in capacitor manufacture.Also, present invention employs alkenyl succinic anhydrides, oxidic polyethylene
The raw materials participation such as wax, phenolic resin prepares dielectric composite material, has carried out effective performance boost to dielectric composite material, although
These materials are not applied in dielectric composite material for the first time, but amount is aided with phase with after other material combinations according to a certain ratio
The modification mode answered brings increasing substantially in service performance to the dielectric composite material being finally prepared, this
It is never to report in previous research, for realizing that it is conclusive that technical effect of the invention plays the role of.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (6)
1. a kind of dielectric composite material preparation method added with phenolic resin, which is characterized in that comprise the steps of:
(1) 8~10 parts of silicon tetrachloride, 7~9 parts of bismuth nitrate, 16~20 parts of alkenyl succinic anhydride are added to 25 times of its weight
The H that mass concentration is 30%2O2In solution, it is ultrasonically treated in ultrasonic processor, the power of ultrasonic treatment is 800~
1000W, processing time are 10~20 minutes, will then be ultrasonically treated mixed liquor and are sent into 130~140 DEG C of oil bath, heat preservation is stirred
It mixes 60~80 minutes, is then centrifuged, isolated precipitated product is dried in vacuo 6~8 hours at 80 DEG C, then
Desciccate is placed in ball-milling treatment in planetary ball mill, obtains ultrasonic oxidation modified powder；
(2) by 55~65 parts of benzocyclobutane olefine resin, 50~60 parts of oleic acid diethyl amide, 45~55 parts of oxidized polyethylene wax,
The ultrasonic oxidation modified powder that 1~3 part of vulcanizing agent and step (1) obtain is added to jointly in heat treatment blender, 100~
According to revolving speed heating stirring 120~150 minutes of 220~260 revs/min at 110 DEG C, heat treatment reaction mixture is obtained, then
Heat treatment reaction mixture is added in the sulfuric acid solution that mass concentration is 80% and carries out ultrasonic mixing by 1:15 in mass ratio, surpasses
The power of sound mixing is 750~850W, and incorporation time is 15~25 minutes, then filters ultrasonic mixing liquid, collects filter
Filter cake is washed with distilled water 2~3 times by cake, 12 hours dry at 80~90 DEG C, obtains sulfonation modifying mixture；
(3) by 5~9 parts of 25~30 parts of 3- aminopropyl trimethoxysilane, N ' N- carbonyl dimidazoles sulfonation obtained with step (2)
Modified mixture is added in the ethyl acetate solution of 20 times of its weight, is ultrasonically treated 10~20 minutes, and phenolic aldehyde tree is then added
30~40 parts of rouge, then insulation reaction 80~100 minutes in 110 DEG C of oil bath, will be deposited at 70 DEG C true after being centrifuged while hot
Sky dry 10~12 hours, then by desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) 1:(2 in mass ratio~
3): (4~6) are added in reaction vessel, nitrogen are passed through into reaction vessel, the air in reaction vessel is discharged, and are added stearic
10~12 parts of sour barium, continuess to mix and stirs evenly, and is warming up to 75~85 DEG C, and temperature constant magnetic stirring is condensed back 16~18 hours,
Rotary evaporation concentration, 70~80 DEG C of vacuum drying, obtains intermediary composite；
(4) intermediary composite that step (3) obtains is added to the distilled water of 50 times of its weight with 6~8 parts of titanium acetylacetone
In, it stirs evenly, pH value of solution is adjusted to 8~9 by the sodium hydroxide that 1mol/L is added dropwise, and stirs 10~20 minutes, solution is heated up
Degree is to 75~80 DEG C, insulated and stirred 25~35 minutes, filtering, by precipitating washing 2~3 times, is subsequently added to Sediment weight 8~10
In dimethylformamide again, it is ultrasonically treated 10~20 minutes, is then dried in vacuo 4~6 hours at 60~70 DEG C, 150
Blank is pressed into the pressure of 16~18MPa at~160 DEG C；
(5) blank that step (4) obtains is added in the n,N-Dimethylformamide solution of 15~20 times of its weight, will be mixed
Liquid is warming up to 60~70 DEG C of heating stirrings 40~50 minutes, put into 1~3 part of coupling agent, 1~3 part of antioxidant, continue stirring 20~
30 minutes, mixed liquor is then warming up to 150~160 DEG C of stirrings and obtains prepolymer within 2~3 hours, by gained prepolymer at 120 DEG C
Lower vacuum outgas 40~60 minutes, then heats to 190~200 DEG C of curing process 8~10 hours, and dielectric composite wood is obtained after demoulding
Material.
2. the dielectric composite material preparation method according to claim 1 added with phenolic resin, which is characterized in that described
The ratio of grinding media to material of ball-milling treatment is 20:1 in step (1), and the revolving speed of ball mill is 500 revs/min, and Ball-milling Time is 2~4 hours.
3. the dielectric composite material preparation method according to claim 1 added with phenolic resin, which is characterized in that described
Vulcanizing agent appointing in cumyl peroxide, tert-butyl hydroperoxide, 2,4- dichlorobenzoperoxide in step (2)
It anticipates one kind.
4. the dielectric composite material preparation method according to claim 1 added with phenolic resin, which is characterized in that described
The mass ratio that desciccate and dimethyl diphenyl methane diamines and methyl iso-butyl ketone (MIBK) are pressed in step (3) is 1:3:5.
5. the dielectric composite material preparation method according to claim 1 added with phenolic resin, which is characterized in that described
Coupling agent in step (5) is selected from m-methyl benzoyl formyl chloride, three oleic acid acyloxy titanate esters of isopropyl, 3- glycidol ether oxygroup
Any one in propyl trimethoxy silicane.
6. the dielectric composite material preparation method according to claim 1 added with phenolic resin, which is characterized in that described
Antioxidant in step (5) is selected from double stearyl alcohol pentaerythritol diphosphites, bis- (2,4- dicumylphenyl) Ji Wusi
Any one in alcohol diphosphites, three (2,4- di-tert-butyl-phenyl) phosphite esters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973589A (en) * | 2021-02-05 | 2021-06-18 | 中国工程物理研究院激光聚变研究中心 | Preparation method of sulfonated RF aerogel microspheres |
| CN116900553A (en) * | 2023-07-13 | 2023-10-20 | 广东中实金属有限公司 | Preparation method of lead-free composite soldering paste with high spreading rate |
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| US20110224345A1 (en) * | 2010-03-15 | 2011-09-15 | Ming Jen Tzou | Novel low dielectric resin varnish composition for laminates and the preparation thereof |
| CN105838021A (en) * | 2016-04-12 | 2016-08-10 | 苏州科茂电子材料科技有限公司 | Electronic material with low dielectric loss and preparation method thereof |
| CN108047689A (en) * | 2018-01-25 | 2018-05-18 | 杨秀枝 | A kind of preparation method of fire-type low-k electronic material |
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2018
- 2018-07-13 CN CN201810771300.8A patent/CN108948673A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110224345A1 (en) * | 2010-03-15 | 2011-09-15 | Ming Jen Tzou | Novel low dielectric resin varnish composition for laminates and the preparation thereof |
| CN105838021A (en) * | 2016-04-12 | 2016-08-10 | 苏州科茂电子材料科技有限公司 | Electronic material with low dielectric loss and preparation method thereof |
| CN108047689A (en) * | 2018-01-25 | 2018-05-18 | 杨秀枝 | A kind of preparation method of fire-type low-k electronic material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112973589A (en) * | 2021-02-05 | 2021-06-18 | 中国工程物理研究院激光聚变研究中心 | Preparation method of sulfonated RF aerogel microspheres |
| CN112973589B (en) * | 2021-02-05 | 2022-04-29 | 中国工程物理研究院激光聚变研究中心 | Preparation method of sulfonated RF aerogel microspheres |
| CN116900553A (en) * | 2023-07-13 | 2023-10-20 | 广东中实金属有限公司 | Preparation method of lead-free composite soldering paste with high spreading rate |
| CN116900553B (en) * | 2023-07-13 | 2024-02-13 | 广东中实金属有限公司 | Preparation method of lead-free composite soldering paste with high spreading rate |
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