CN107057116A - A kind of preparation method of porous dielectric composite - Google Patents
A kind of preparation method of porous dielectric composite Download PDFInfo
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- CN107057116A CN107057116A CN201710382286.8A CN201710382286A CN107057116A CN 107057116 A CN107057116 A CN 107057116A CN 201710382286 A CN201710382286 A CN 201710382286A CN 107057116 A CN107057116 A CN 107057116A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/10—Epoxy resins modified by unsaturated compounds
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Abstract
The invention provides a kind of preparation method of porous dielectric composite.The hud typed material (DVB GMA@MWNTs) of epoxide group is carried on the surface that multi-walled carbon nanotube (MWNTs) surface and copolymerized reaction is obtained using divinylbenzene (DVB) and GMA (GMA), this hud typed material is cross-linked to each other with epoxy hardener and solidify to form cellular dielectric composite.Core-shell material DVB GMA@MWNTs and ethanol are mixed first, is added after ultrasonic disperse and solvent is removed under curing agent, low temperature, solidification obtains composite.By adjusting the addition between two kinds of monomers, a series of different-thickness and the core-shell material of epoxide group quantity are obtained, and then adjust the performance of composite.This method is simple, different from the preparation method of traditional composite.The performance of gained composite Ultra light-weight and composite is controllable.Composite industryization application prospect is extensive.
Description
Technical field
The present invention is the core-shell material that epoxide group is carried using surface, adds the direct hot setting of curing agent and obtains poroid
Composite.Belong to the technical field of composite preparation.
Background technology
By CNT and polymer matrix bluk recombination, its unique aspect ratio structures can be utilized, excellent electrical conduction, heat are passed
The ability of leading prepares the composite of excellent properties.Composite material and preparation method thereof widely used at present is still by CNT
With polymeric matrix mixing, following several method is broadly divided into：First, solution mixing method：By CNT with being dissolved in solvent
Polymer is sufficiently mixed, and is then removed solvent, is finally obtained composite.This method is not only applicable to thermosetting polymer
Enhancing, is also applied for the enhancing of thermoplastic polymer.But solution mixing method needs to vapor away a large amount of solvents and is not easily recycled, and has
Machine solvent has grievous injury to environment, is not suitable for large-scale industrial production.2nd, melt mixing methods：By CNT and melting
Mixed with polymers, by extrusion or injection molding obtain composite method.Melt mixing methods are simple to operate, it is adaptable to work
Industry metaplasia is produced.But strict to the requirement of the conditions such as temperature and power in process, CNT in the polymer scattered
Effect also is difficult to control.3rd, situ aggregation method：Monomer is carried out what polymerisation generation high polymer was obtained in carbon nano tube surface
A kind of nano composite material.Monomer polymer in carbon nano tube surface grafting is mainly triggered by free radical, can be improved
The dispersiveness of CNT in the solution.But surface polymer skewness, material property is poor, and practical application is poor.
This method provides a kind of new thinking for the preparation of composite, is received using simple controllable coating technology in carbon
Nanotube surface introduces reactive functionality, using the chemical reaction between functional group, can directly obtain composite.Material not only has
There is excellent homogeneity, and substantial amounts of solvent need not be wasted, better than the preparation method of traditional composite.
The content of the invention
It is novel porous that acquisition is directly reacted the invention reside in a kind of core-shell material of the utilization surface of offer with epoxide group
The method of dielectric composite material.
A kind of preparation method of porous dielectric composite, it is characterised in that comprise the concrete steps that：
(a) 0.5g core-shell type nano filler DVB-GMA@MWNTs and 20ml solvent are mixed, ultrasonic 1h is well mixed；
DVB-GMA@MWNTs are that kernel is multi-walled carbon nanotube, and shell is divinylbenzene DVB and GMA GMA
Cross-linked copolymer；
(b) 0.3-0.7g curing agent polyetheramines D-230 is added and stirred in mixture；
(c) mixture is put into mould, solvent is eliminated at room temperature, placed placed at 2h, 100 DEG C at 80 DEG C successively
2h, 2h temperature programming solidification is placed at 120 DEG C, composite is finally given；
DVB is more than or equal to 240mg in DVB-GMA@MWNTs, and GMA is more than or equal to 160mg, keeps mass ratio DVB:GMA=
3:2。
Further, solvent uses ethanol in step (a).
Coating thickness is obtained more than 5nm by changing the addition of two kinds of monomers, and surface epoxide group quantity is more than
0.002mol/g core-shell material.
The new method that the present invention is provided prepares comprising the concrete steps that for composite：
(a) 50mg original carbon nanotubes, 70ml acetonitrile solvents are mixed, ultrasonic 1h.Two kinds of monomers of different quality (are protected
Hold mass ratio DVB:GMA=3:2) add in above-mentioned suspension.Initiator A IBN is added into above-mentioned system, nitrogen is passed through and rises
Temperature is to 75 DEG C, and with this conditioned response 12h.After reaction stops, being washed with DMF, suction filtration, be dried to obtain core-shell material DVB-GMA@
MWNTs。
(b) 0.5g DVB-GMA@MWNTs and 20ml solvent are mixed, ultrasonic 1h is well mixed.
(c) curing agent polyetheramine D-230 is added and stirred in mixture.
(d) mixture is put into mould, solvent is eliminated at room temperature, placed placed at 2h, 100 DEG C at 80 DEG C successively
2h, 2h temperature programming solidification is placed at 120 DEG C, composite is finally given.
What the present invention was provided carries the CNT core-shell material of reactive functionality by surface and then prepares NEW TYPE OF COMPOSITE
The method characteristic of material is：
1st, core-shell material coating thickness can be controlled by adjusting the addition of two kinds of monomers, and then adjusts composite
Performance.The coating thickness of core-shell material is most important.
2nd, traditional method for preparing composite is changed, a kind of new thinking is provided to prepare composite.No
The usage amount of solvent is only reduced, the overall dispersion effect of material is also advantageous for.So as to be conducive to the raising of material property.
Brief description of the drawings
Fig. 1：Different coating thickness core-shell material DVB-GMA@MWNTs TEM figures.
(a) pure multi-walled carbon nanotube (MWNTs)
(b) divinylbenzene (DVB) and GMA (GMA) addition be respectively 240mg and
160mg, prepares core-shell material coating thickness about 5nm
(c) divinylbenzene (DVB) and GMA (GMA) addition be respectively 300mg and
200mg, prepares core-shell material coating thickness about 25nm
(d) divinylbenzene (DVB) and GMA (GMA) addition be respectively 360mg and
240mg, prepares core-shell material coating thickness about 35nm
Fig. 2：Infrared change curve before and after core-shell material DVB-GMA@MWNTs solidifications.
(a) coating thickness is about 5nm core-shell material DVB-GMA@MWNTs
(b) coating thickness is about 35nm core-shell material DVB-GMA@MWNTs
Fig. 3：The SEM shape appearance figures of composite
(a) coating thickness is about 5nm core-shell material DVB-GMA@MWNTs
(b) coating thickness is about 25nm core-shell material DVB-GMA@MWNTs
Fig. 4：The dielectric properties of composite
(a), (a ') coating thickness is about 5nm core-shell material DVB-GMA@MWNTs
(b), (b ') coating thickness is about 25nm core-shell material DVB-GMA@MWNTs
(c), (c ') coating thickness is about 35nm core-shell material DVB-GMA@MWNTs
Embodiment：
Embodiment 1
50mg original carbon nanotubes, 70ml acetonitrile solvents are mixed, ultrasonic 1h.By two kinds of monomer divinylbenzenes (DVB)
240mg and GMA (GMA) 160mg is added in above-mentioned suspension.20mg is added into above-mentioned system to draw
Agent AIBN is sent out, nitrogen is passed through and is warming up to 75 DEG C, and with this conditioned response 12h.After reaction stops, being washed with DMF, it is suction filtration, dry
The core-shell material DVB-GMA@MWNTs that the dry cladding thickness prepared is 5nm.Fig. 1 (b) is that the present embodiment cladding thickness is
The TEM pictures of 5nm core-shell material, and Fig. 1 (a) contrasts are it can be seen that MWNTs outer walls have uniform clad.Then will
Core-shell material of the 0.5g surfaces with epoxide group is added in 20ml ethanol, ultrasonic 1h.0.3g polyetheramines D-230 is added and mixed
Stirred in thing, eliminate and place 2h after solvent at 80 DEG C, the temperature programming that placement 2h at 2h, 120 DEG C is placed at 100 DEG C is consolidated
Change, finally give composite.It is can be seen that by infrared curve comparison before and after the solidification of Fig. 2 (a) core-shell materials after solidification (1)
Epoxide group at curve a is disappeared, and ehter bond is generated at (2) curve b.This phenomenon fully demonstrates the ring on core-shell material surface
Oxygen groups are reacted, and as a result fully prove successfully to prepare composite by this method.Pass through SEM pictures in Fig. 3 (a)
It was found that composite is a kind of porous structure.The dielectric constant of composite is 7597 in 1kHZ in Fig. 4 (a), (a '), is situated between
Electrical loss is 23.Core-shell material coating thickness is larger in the dielectric loss of composite obtained by 5nm or so.
Embodiment 2
50mg original carbon nanotubes, 70ml acetonitrile solvents are mixed, ultrasonic 1h.By two kinds of monomer divinylbenzenes (DVB)
300mg and GMA (GMA) 200mg is added in above-mentioned suspension.25mg is added into above-mentioned system to draw
Agent AIBN is sent out, nitrogen is passed through and is warming up to 75 DEG C, and with this conditioned response 12h.After reaction stops, being washed with DMF, it is suction filtration, dry
It is dry to prepare the core-shell material DVB-GMA@MWNTs that cladding thickness is 25nm.Fig. 1 (c) is that the present embodiment cladding thickness is
The TEM pictures of 25nm core-shell material, and Fig. 1 (a) contrasts are it can be seen that MWNTs outer walls have uniform clad.Then will
Core-shell material of the 0.5g surfaces with epoxide group is added in 20ml ethanol, ultrasonic 1h.0.5g polyetheramines D-230 is added and mixed
Stirred in thing, eliminate and place 2h after solvent at 80 DEG C, the temperature programming that placement 2h at 2h, 120 DEG C is placed at 100 DEG C is consolidated
Change, finally give composite.Find that composite is a kind of porous structure by SEM pictures in Fig. 3 (b).Fig. 4 (b),
The dielectric constant of composite is 172 in 1kHZ in (b '), and dielectric loss is 0.09.Core-shell material coating thickness is in 25nm
Composite obtained by left and right has excellent dielectric properties, can be used as dielectric material.
Embodiment 3
50mg original carbon nanotubes, 70ml acetonitrile solvents are mixed, ultrasonic 1h.By two kinds of monomer divinylbenzenes (DVB)
360mg and GMA (GMA) 240mg is added in above-mentioned suspension.30mg is added into above-mentioned system to draw
Agent AIBN is sent out, nitrogen is passed through and is warming up to 75 DEG C, and with this conditioned response 12h.After reaction stops, being washed with DMF, it is suction filtration, dry
It is dry to prepare the core-shell material DVB-GMA@MWNTs that cladding thickness is 35nm.Fig. 1 (d) is that the present embodiment cladding thickness is
The TEM pictures of 35nm core-shell material, and Fig. 1 (a) contrasts are it can be seen that MWNTs outer walls have uniform clad.Then will
Core-shell material of the 0.5g surfaces with epoxide group is added in 20ml ethanol, ultrasonic 1h.0.7g polyetheramines D-230 is added and mixed
Stirred in thing, eliminate and place 2h after solvent at 80 DEG C, the temperature programming that placement 2h at 2h, 120 DEG C is placed at 100 DEG C is consolidated
Change, finally give composite.It is can be seen that by infrared curve comparison before and after the solidification of Fig. 2 (b) core-shell materials after solidification (1)
Epoxide group at curve a is disappeared, and ehter bond is generated at (2) curve b.This phenomenon fully demonstrates the ring on core-shell material surface
Oxygen groups are reacted, and as a result fully prove successfully to prepare composite by this method.Composite wood in Fig. 4 (c), (c ')
The dielectric constant of material is 28 in 1kHZ, and dielectric loss is 0.02.Core-shell material coating thickness is more than composite wood obtained by 35nm
Expect dielectric constant reduction, can be used as dielectric material.Prepared by three kinds of different core-shell materials for coating thickness
Composite dielectric properties contrast as can be seen that composite performance it is relevant with coating thickness, the performance of composite
It can be regulated and controled according to actual needs.
Claims (3)
1. a kind of preparation method of porous dielectric composite, it is characterised in that comprise the concrete steps that：
(a) 0.5g core-shell type nano filler DVB-GMA@MWNTs and 20ml solvent are mixed, ultrasonic 1h is well mixed；DVB-
GMA@MWNTs are that kernel is multi-walled carbon nanotube, and shell is divinylbenzene DVB and GMA GMA friendship
Ally the communists polymers；
(b) 0.3-0.7g curing agent polyetheramines D-230 is added and stirred in mixture；
(c) mixture is put into mould, solvent is eliminated at room temperature, placed at 80 DEG C place 2h, 120 at 2h, 100 DEG C successively
2h temperature programming solidification is placed at DEG C, composite is finally given；
DVB is more than or equal to 240mg in DVB-GMA@MWNTs, and GMA is more than or equal to 160mg, keeps mass ratio DVB:GMA=3:2.
2. a kind of preparation method of porous dielectric composite according to claim 1, it is characterised in that：In step (a)
Solvent uses ethanol.
3. a kind of preparation method of porous dielectric composite according to claim 1, it is characterised in that：By changing two
The addition for planting monomer obtains coating thickness more than 5nm, and surface epoxide group quantity is more than 0.002mol/g core-shell material.
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| CN201710382286.8A CN107057116A (en) | 2017-05-26 | 2017-05-26 | A kind of preparation method of porous dielectric composite |
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Citations (6)
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| CN101735416A (en) * | 2009-12-29 | 2010-06-16 | 浙江大学 | Method for preparing water-soluble cross-linked polymer grafted carbon nano tube |
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| CN103146231A (en) * | 2013-03-15 | 2013-06-12 | 北京化工大学 | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid |
| CN104927404A (en) * | 2015-06-15 | 2015-09-23 | 北京化工大学 | Method for preparing core-shell type carbon nano tube dielectric packing through in-situ copolymerization technology |
| CN105385196A (en) * | 2015-11-15 | 2016-03-09 | 北京化工大学 | Preparation method of core-shell carbon nano-tube hybridization packing with epoxy group |
| CN105565295A (en) * | 2015-12-31 | 2016-05-11 | 北京化工大学 | Preparation method of oriented carbon nanotube film |
-
2017
- 2017-05-26 CN CN201710382286.8A patent/CN107057116A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735416A (en) * | 2009-12-29 | 2010-06-16 | 浙江大学 | Method for preparing water-soluble cross-linked polymer grafted carbon nano tube |
| KR20120023447A (en) * | 2010-09-03 | 2012-03-13 | 인하대학교 산학협력단 | Producing method of carbon nanotube grafted by vinyl polymer |
| CN103146231A (en) * | 2013-03-15 | 2013-06-12 | 北京化工大学 | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid |
| CN104927404A (en) * | 2015-06-15 | 2015-09-23 | 北京化工大学 | Method for preparing core-shell type carbon nano tube dielectric packing through in-situ copolymerization technology |
| CN105385196A (en) * | 2015-11-15 | 2016-03-09 | 北京化工大学 | Preparation method of core-shell carbon nano-tube hybridization packing with epoxy group |
| CN105565295A (en) * | 2015-12-31 | 2016-05-11 | 北京化工大学 | Preparation method of oriented carbon nanotube film |
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| HONGFENG TANG,ET AL.: "Epoxy-based high-k composites with low dielectric loss caused by reactive core-shell-structured carbon nanotube hybrids", 《MATERIALS LETTERS》 * |
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Application publication date: 20170818 |