CN109337338A - A kind of titanium dioxide poly (arylene ether nitrile) hybrid material and preparation method thereof - Google Patents
A kind of titanium dioxide poly (arylene ether nitrile) hybrid material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of titanium dioxide poly (arylene ether nitrile) hybrid materials and preparation method thereof.The composite material that titanium dioxide poly (arylene ether nitrile) hybrid material is made of titanium dioxide and poly (arylene ether nitrile) forms chemical bond as linking group using phthalocyanine ring between the two and links together.The preparation method of titanium dioxide poly (arylene ether nitrile) hybrid material is by nano-titanium dioxide dioxygen water process, its surface is set to form great amount of hydroxy group, then it reacts to obtain the titanium dioxide of phthalonitrile grafting with 4- nitrophthalonitrile again, the titanium dioxide of phthalonitrile grafting and phthalonitrile-terminated poly (arylene ether nitrile) are subjected to compound and machine-shaping later, curing cross-linking reaction after the phthalonitrile for the titanium dioxide surface for being finally grafted at high temperature phthalonitrile and the phthalonitrile groups of sealing end poly (arylene ether nitrile) end carry out, phthalocyanine ring is formed to obtain titanium dioxide poly (arylene ether nitrile) hybrid material.Titanium dioxide in titanium dioxide poly (arylene ether nitrile) hybrid material of the invention can be uniformly dispersed in poly (arylene ether nitrile) matrix.For the glass transition temperature of titanium dioxide poly (arylene ether nitrile) hydridization material at 200 DEG C or more, tensile strength is greater than 80MPa, and dielectric constant is greater than 10.0 at 1 khz.
Description
Technical field
The present invention relates to a kind of titanium dioxide poly (arylene ether nitrile) hybrid materials and preparation method thereof, belong to fire resistant polymer material
Expect manufacturing field.The titanium dioxide poly (arylene ether nitrile) hybrid material can be used as high temperature resistant dielectric applied to high temperature energy-storage field.
Background technique
Poly (arylene ether nitrile) (polyarylene ether nitriles, PEN) is a kind of main chain key containing aryl oxide, and side chain contains nitrile
Base, the linear half crystal form macromolecule of compound with regular structure.By 2,6- dichlorobenzonitrile or 2,6- difluorobenzonitrile and dihydric phenol non-
In proton polar solvent with potassium carbonate etc. be catalyst action under, by the available polyarylether of nucleophilic displacement of fluorine step-reaction polymerization
Nitrile.By changing the structure of dihydric phenol, a series of poly (arylene ether nitrile) of available different structures and performance.Poly (arylene ether nitrile) is due to master
There is a large amount of C ≡ N side group, and C ≡ N is in the side of phenyl ring on chain, there is strong dipole moment, thus also there is high Jie
Electric constant.The dielectric constant of usual poly (arylene ether nitrile) homopolymer is polyacrylic twice between 4.0~4.8.The height of poly (arylene ether nitrile)
Dielectric constant properties make it be highly suitable for dielectric energy storage thin-film material.
Although the dielectric constant major part commercial polymerization object of poly (arylene ether nitrile) wants high, for preparing high energy storage density
Capacitor for be still inadequate.Titanium dioxide is a kind of white solid or powdered amphoteric oxide.It is a kind of
White inorganic pigment has nontoxic, optimal opacity, best whiteness and brightness, it is considered to be performance in the world now
A kind of best white pigment.It is widely used in the works such as coating, plastics, papermaking, printing ink, chemical fibre, rubber, cosmetics
Industry.In addition to this, the dielectric constant of titanium dioxide is higher, therefore has excellent electric property.It will be by poly (arylene ether nitrile) and dioxy
Change titanium and carries out the compound dielectric constant that can be further improved polymer.However, compatible between titanium dioxide and poly (arylene ether nitrile)
Performance is poor, after direct combination obtained composite material will appear it is incompatible significantly increase dielectric loss also, this lack
Point, which determines, to be directly difficult to reach capacitor light weight, requirement small in size, energy storage density is high using this kind of material.
Researches show that titanium dioxide and composite material dielectric loss obtained after poly (arylene ether nitrile) direct combination obviously to increase
It is due to the two is greatly respectively inorganic matter and organic matter, it is difficult to compatible, big interface easy to form between the two, so as to cause boundary
Surface polarization.Titanium dioxide is directly linked together with poly (arylene ether nitrile) if can use covalent bond, can effectively be reduced
Between the two incompatible, to reduce dielectric loss.The phthalonitrile of early-stage study display sealing end poly (arylene ether nitrile) end exists
Self-crosslinking reaction can occur under high temperature.It, can be poly- with sealing end if connecting phthalonitrile groups in titanium dioxide surface
The phthalonitrile one of aryl oxide nitrile end reacts that the two is made to form hybrid material, and then avoids the presence at interface.Therefore
Present invention proposition prepares novel titanium dioxide poly (arylene ether nitrile) hybrid material and is directly mixed with solving titanium dioxide with poly (arylene ether nitrile)
The excessively high problem of dielectric loss afterwards.
Summary of the invention
The purpose of the present invention is overcome existing poly (arylene ether nitrile) dielectric constant not high and poly (arylene ether nitrile) directly and high dielectric constant
The deficiency that filler compound tense is easy to cause dielectric loss excessively high, high dielectric constant can be prepared and keep lower dielectric by providing one kind
The high performance heat resistant titanium dioxide poly (arylene ether nitrile) hybrid material and its manufacturing method of loss solve poly (arylene ether nitrile) in heatproof, Gao Xing
The problem of energy, high dielectric field can not be used for a long time, widens the application range of poly (arylene ether nitrile).Specifically, titanium dioxide is carried out
Then surface hydroxylation is grafted upper phthalonitrile groups, finally make the phthalonitrile groups and sealing end polyarylether on its surface
Curing reaction obtains corresponding titanium dioxide poly (arylene ether nitrile) hybrid material after the phthalonitrile groups of nitrile end carry out together.
Described titanium dioxide poly (arylene ether nitrile) hybrid material and preparation method thereof, it is characterised in that: titanium dioxide polyarylether
The composite material that nitrile hybrid material is made of titanium dioxide and poly (arylene ether nitrile) is formed using phthalocyanine ring as linking group between the two
Chemical bond links together.
Described titanium dioxide poly (arylene ether nitrile) hybrid material and preparation method thereof, it is characterised in that: preparation methods steps
Below:
(1) preparation of hydroxyl oxide/titanium dioxide: nano-titanium dioxide is added in hydrogen peroxide, 4~10h of return stirring,
After filter, clean 2~5 times with deionized water later, then by product dry 6 in 60~100 DEG C of vacuum ovens~
10h；
Wherein, the deionization when amount ratio of titanium dioxide and hydrogen peroxide is 1g:20~50mL, hydrogen peroxide and each washing
The volume ratio of water is 1:2~5；
(2) preparation of the titanium dioxide of phthalonitrile grafting: the hydroxyl oxide/titanium dioxide that step (1) is prepared,
4- nitrophthalonitrile, potassium carbonate are added in reaction flask, and n,N-Dimethylformamide is added as solvent, 80~110
5~10h is stirred to react at DEG C, after filter, cleaned 2~5 times with deionized water later, then by product at 60~100 DEG C
Dry 6~10h in vacuum oven；
Wherein, the mass ratio of hydroxyl oxide/titanium dioxide, 4- nitrophthalonitrile and potassium carbonate is 1:0.2~0.5:0.5
~1, potassium carbonate, the amount ratio of n,N-Dimethylformamide and each deionized water is 1g:80~120mL:150~400mL；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide and phthalonitrile-terminated poly (arylene ether nitrile) are added in N-Methyl pyrrolidone, are stirred to phthalonitrile-terminated
Poly (arylene ether nitrile) be completely dissolved, the then dry out solvent at 200~220 DEG C, and composite processing is formed finally will processing
Molding composite material 2~6h of curing reaction at 310~360 DEG C obtains titanium dioxide poly (arylene ether nitrile) hybrid material；
Wherein, the titanium dioxide of phthalonitrile grafting and the mass ratio of phthalonitrile-terminated poly (arylene ether nitrile) are 1:
0.1~4, the amount ratio of phthalonitrile-terminated poly (arylene ether nitrile) and N-Methyl pyrrolidone is 1g:10~25mL, composite material
The shape being processed into has the shapes such as film, piece, stick, block.
Described titanium dioxide poly (arylene ether nitrile) hybrid material and preparation method thereof, it is characterised in that: the poly- virtue of the titanium dioxide
For the glass transition temperature of ether nitrile hybrid material at 200 DEG C or more, tensile strength is greater than 80MPa, and dielectric constant is big at 1 khz
In 10.0.
Beneficial effects of the present invention: titanium dioxide is uniform in titanium dioxide poly (arylene ether nitrile) hybrid material produced by the present invention
It is dispersed in poly (arylene ether nitrile) matrix, and due to forming hybrid material, there is good compatibility between the two.The method of the present invention
The introduction volume of titanium dioxide can effectively be regulated and controled.The shapes such as film forming, piece, stick, block can be processed in hybrid material.The titanium dioxide is poly-
The glass transition temperature of aryl oxide nitrile hybrid material is at 200 DEG C or more, and tensile strength is greater than 80MPa, and dielectric constant is at 1 khz
Greater than 10.0.The manufacturing method of titanium dioxide poly (arylene ether nitrile) hybrid material of the invention is simple and easy to operate, easily realizes industry
Change.
Detailed description of the invention
Fig. 1 is that the titanium dioxide of phthalonitrile grafting prepares schematic diagram
Fig. 2 is the schematic diagram of titanium dioxide poly (arylene ether nitrile) hybrid material
Fig. 3 is the stereoscan photograph of titanium dioxide poly (arylene ether nitrile) hybrid material
Specific embodiment
The embodiment of preparation method of the present invention introduced below, but following embodiment be for illustrating example of the invention, and
Any restriction to the claims in the present invention is not constituted.
Embodiment 1
The schematic diagram for preparing the titanium dioxide of phthalonitrile grafting is as shown in Fig. 1.
(1) preparation of hydroxyl oxide/titanium dioxide: 2.06g nano-titanium dioxide is added in 100mL hydrogen peroxide, reflux is stirred
Mix 6h, after filter, clean 3 times with 200mL deionized water later, it is then that product is dry in 100 DEG C of vacuum ovens
6h；
(2) preparation of the titanium dioxide of phthalonitrile grafting: the hydroxyl oxide/titanium dioxide that step (1) is prepared
0.41g, 4- nitrophthalonitrile 0.16g, potassium carbonate 0.24g are added in reaction flask, and 25mL N, N- dimethyl formyl is added
Amine is stirred to react 10h at 80 DEG C as solvent, after filter, clean 3 times with 60mL deionized water later, then will produce
Object dry 6h in 100 DEG C of vacuum ovens；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.5g and phthalonitrile-terminated poly (arylene ether nitrile) 0.5g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 320 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The schematic diagram of the titanium dioxide poly (arylene ether nitrile) hybrid material is as shown in Fig. 2, stereoscan photograph such as 3 institute of attached drawing
Show, glass transition temperature is 236 DEG C, and tensile strength 85MPa, dielectric constant is 10.5 at 1 khz.
Embodiment 2
(1) preparation of hydroxyl oxide/titanium dioxide: consistent with the process in embodiment 1；
(2) preparation of the titanium dioxide of phthalonitrile grafting: consistent with the process in embodiment 1；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.5g and phthalonitrile-terminated poly (arylene ether nitrile) 0.5g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and by composite processing at stick
Shape, finally by the composite material of machine-shaping at 320 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 235 DEG C, and dielectric constant is at 1 khz
10.5。
Embodiment 3
(1) preparation of hydroxyl oxide/titanium dioxide: consistent with the process in embodiment 1；
(2) preparation of the titanium dioxide of phthalonitrile grafting: consistent with the process in embodiment 1；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.5g and phthalonitrile-terminated poly (arylene ether nitrile) 0.5g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 320 DEG C curing reaction 2h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 230 DEG C, tensile strength 92MPa, is situated between
Electric constant is 10.2 at 1 khz.
Embodiment 4
(1) preparation of hydroxyl oxide/titanium dioxide: consistent with the process in embodiment 1；
(2) preparation of the titanium dioxide of phthalonitrile grafting: consistent with the process in embodiment 1；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.5g and phthalonitrile-terminated poly (arylene ether nitrile) 0.5g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 360 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 239 DEG C, tensile strength 83MPa, is situated between
Electric constant is 12.0 at 1 khz.
Embodiment 5
(1) preparation of hydroxyl oxide/titanium dioxide: consistent with the process in embodiment 1；
(2) preparation of the titanium dioxide of phthalonitrile grafting: consistent with the process in embodiment 1；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.8g and phthalonitrile-terminated poly (arylene ether nitrile) 0.2g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 360 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 250 DEG C, tensile strength 81MPa, is situated between
Electric constant is 15.0 at 1 khz.
Embodiment 6
(1) preparation of hydroxyl oxide/titanium dioxide: consistent with the process in embodiment 1；
(2) preparation of the titanium dioxide of phthalonitrile grafting: consistent with the process in embodiment 1；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.6g and phthalonitrile-terminated poly (arylene ether nitrile) 0.4g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 360 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 243 DEG C, tensile strength 82MPa, is situated between
Electric constant is 13.3 at 1 khz.
Embodiment 7
(1) preparation of hydroxyl oxide/titanium dioxide: consistent with the process in embodiment 1；
(2) preparation of the titanium dioxide of phthalonitrile grafting: consistent with the process in embodiment 1；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.2g and phthalonitrile-terminated poly (arylene ether nitrile) 0.8g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 360 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 234 DEG C, tensile strength 99MPa, is situated between
Electric constant is 10.3 at 1 khz.
Embodiment 9
(1) preparation of hydroxyl oxide/titanium dioxide: 2.06g nano-titanium dioxide is added in 50mL hydrogen peroxide, reflux is stirred
Mix 6h, after filter, clean 3 times with 200mL deionized water later, it is then that product is dry in 100 DEG C of vacuum ovens
6h；
(2) preparation of the titanium dioxide of phthalonitrile grafting: the hydroxyl oxide/titanium dioxide that step (1) is prepared
0.41g, 4- nitrophthalonitrile 0.08g, potassium carbonate 0.2g are added in reaction flask, and 25mL N, N- dimethyl formyl is added
Amine is stirred to react 10h at 80 DEG C as solvent, after filter, clean 3 times with 60mL deionized water later, then will produce
Object dry 6h in 100 DEG C of vacuum ovens；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.5g and phthalonitrile-terminated poly (arylene ether nitrile) 0.5g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 320 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 234 DEG C, tensile strength 98MPa, is situated between
Electric constant is 10.1 at 1 khz.
Embodiment 10
(1) preparation of hydroxyl oxide/titanium dioxide: consistent with the process in embodiment 1；
(2) preparation of the titanium dioxide of phthalonitrile grafting: the hydroxyl oxide/titanium dioxide that step (1) is prepared
0.41g, 4- nitrophthalonitrile 0.16g, potassium carbonate 0.30g are added in reaction flask, and 25mL N, N- dimethyl formyl is added
Amine is stirred to react 10h at 80 DEG C as solvent, after filter, clean 3 times with 60mL deionized water later, then will produce
Object dry 6h in 100 DEG C of vacuum ovens；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the phthalonitrile grafting that step (2) is prepared
Titanium dioxide 0.7g and phthalonitrile-terminated poly (arylene ether nitrile) 0.3g are added in 15mL N-Methyl pyrrolidone, and stirring is extremely
Phthalonitrile-terminated poly (arylene ether nitrile) is completely dissolved, then the dry out solvent at 200 DEG C, and composite processing is formed a film,
Finally by the composite material of machine-shaping at 320 DEG C curing reaction 6h, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
The glass transition temperature of the titanium dioxide poly (arylene ether nitrile) hybrid material is 252 DEG C, tensile strength 80MPa, is situated between
Electric constant is 15.3 at 1 khz.
Claims (3)
1. a kind of titanium dioxide poly (arylene ether nitrile) hybrid material and preparation method thereof, it is characterised in that: titanium dioxide poly (arylene ether nitrile) is miscellaneous
Change the composite material that material is made of titanium dioxide and poly (arylene ether nitrile), forms chemistry using phthalocyanine ring as linking group between the two
Key connection is together.
2. titanium dioxide poly (arylene ether nitrile) hybrid material according to claim 1, it is characterised in that: preparation methods steps with
Under:
(1) preparation of hydroxyl oxide/titanium dioxide: nano-titanium dioxide is added in hydrogen peroxide, 4~10h of return stirring, is terminated
After filter, clean 2~5 times with deionized water later, then by product in 60~100 DEG C of vacuum ovens dry 6~10h；
Wherein, the amount ratio of titanium dioxide and hydrogen peroxide is 1g:20~50mL, hydrogen peroxide and deionized water when washing every time
Volume ratio is 1:2~5；
(2) preparation of the titanium dioxide of phthalonitrile grafting: the hydroxyl oxide/titanium dioxide that step (1) is prepared, 4- nitre
Base phthalonitrile, potassium carbonate are added in reaction flask, and n,N-Dimethylformamide is added as solvent, at 80~110 DEG C
Be stirred to react 5~10h, after filter, cleaned 2~5 times with deionized water later, then by product in 60~100 DEG C of vacuum
Dry 6~10h in drying box；
Wherein, the mass ratio of hydroxyl oxide/titanium dioxide, 4- nitrophthalonitrile and potassium carbonate is 1:0.2~0.5:0.5~1,
The amount ratio of potassium carbonate, n,N-Dimethylformamide and each deionized water is 1g:80~120mL:150~400mL；
(3) preparation of titanium dioxide poly (arylene ether nitrile) hybrid material: the dioxy for the phthalonitrile grafting that step (2) is prepared
Change titanium and phthalonitrile-terminated poly (arylene ether nitrile) is added in N-Methyl pyrrolidone, stirs to phthalonitrile-terminated and gather
Aryl oxide nitrile is completely dissolved, then the dry out solvent at 200~220 DEG C, and composite processing is formed, finally by machine-shaping
Composite material at 310~360 DEG C 2~6h of curing reaction, obtain titanium dioxide poly (arylene ether nitrile) hybrid material；
Wherein, the titanium dioxide of phthalonitrile grafting and the mass ratio of phthalonitrile-terminated poly (arylene ether nitrile) be 1:0.1~
4, the amount ratio of phthalonitrile-terminated poly (arylene ether nitrile) and N-Methyl pyrrolidone is 1g:10~25mL, composite processing
At shape have the shapes such as film, piece, stick, block.
3. titanium dioxide poly (arylene ether nitrile) hybrid material according to claim 1, it is characterised in that: the titanium dioxide polyarylether
For the glass transition temperature of nitrile hybrid material at 200 DEG C or more, tensile strength is greater than 80MPa, and dielectric constant is greater than at 1 khz
10.0。
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| CN111153433A (en) * | 2020-01-16 | 2020-05-15 | 南通大学 | Preparation method of composite light-colored conductive titanium dioxide powder |
| CN113649068A (en) * | 2021-07-26 | 2021-11-16 | 电子科技大学 | Magnetic polyaryl ether nitrile composite photocatalyst and preparation method thereof |
| CN113603887A (en) * | 2021-09-02 | 2021-11-05 | 大同共聚(西安)科技有限公司 | Preparation method of barium titanate and polyimide hybrid material |
| CN113603887B (en) * | 2021-09-02 | 2023-01-17 | 大同共聚(西安)科技有限公司 | Preparation method of barium titanate and polyimide hybrid material |
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