CN108070142A - A kind of polypropylene resin-based cable shield composite material and preparation method thereof - Google Patents
A kind of polypropylene resin-based cable shield composite material and preparation method thereof Download PDFInfo
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- CN108070142A CN108070142A CN201611000500.0A CN201611000500A CN108070142A CN 108070142 A CN108070142 A CN 108070142A CN 201611000500 A CN201611000500 A CN 201611000500A CN 108070142 A CN108070142 A CN 108070142A
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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
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
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- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The invention discloses a kind of polypropylene resin-based cable shield composite materials and preparation method thereof, are prepared including following parts by weight raw material：30 60 parts of acrylic resin, 5 15 parts of isoamyl alcohol, 5 15 parts of poly quinoline, 25 parts of tartaric acid, 0.1 0.5 parts of carbon nano-fiber, 0.5 2 parts of nano-carbon powder, 0.5 1 parts of nano bismuth oxide, 13 parts of coupling agent, 15 parts of crosslinking agent；The present invention makes composite material have the advantages of electric field shielding effect is good, high mechanical properties using polymer crosslinking and organic inorganic hybridization principle.
Description
Technical field
The present invention relates to cable material fields, and in particular to a kind of polypropylene resin-based cable shield composite material and
Its preparation method.
Background technology
It is disturbed to reduce cable pair by external electromagnetic field, the outer layer of cable conductor（The inner layer of sheath）Coat metal
Cable core is isolated from the outside by shielded layer.According to use occasion and the difference of requirement, common shielding belt type has following several
Kind, bare aluminium strip, double plastic-coated aluminium strip, copper strips, copper-clad stainless steel band, high intensity Modified Cu band, naked aluminium, naked steel bimetallic strip,
Double plastic-coated aluminium and steel bimetallic strip etc..
Cable and wire structure production stage is wire drawing, synnema, extruded insulation layer, stranding, armouring, shielding and sheath.Tradition
Electric wire manufacture craft：Using aluminum foil shielded outside shielded layer, then with woven wire, surface layer uses PVC（Acrylic resin）Shield
Set, since woven wire works out complexity, efficiency is low, thus the making of electric wire must carry out step by step, use and its inconvenience.
In early days, there have been many to assign the trial of resin combination electric conductivity, thereby using said composition with
Vehicle and various electronic devices, electronic device or cable is allowed to show EMI shielding properties etc..Existing conductive resin composition
Generally by by the conductive additive such as coated inorganic powder of carbon black, carbon fiber, metal powder, metal or metallic fiber with polymerizeing
Object is mixed to prepare.However, as long as no the conductive additive for adding in sufficient amount, being difficult to obtain has electric conductivity preferable enough
Conductive resin composition.Also, in the case of the carbon material such as polymer complex of carbon black, carbon fiber is used, input
A large amount of inorganic material, cause that resin hardness is higher, surface roughness is higher and physical property deterioration, and therefore, it is difficult to realize it is expected
High conductivity.
Later, people had attempted to assign conducting polymer as conductive additive with good by using carbon nanotubes again
Electric conductivity.However, by by carbon nanotubes and mixed with polymers and carrying out squeezing out-spraying the situation for obtaining electrically conductive composite
In, due to the shear stress generated in extrusion-course of injection, carbon nanotubes is caused to be reunited or alignment, and carbon nanotubes have it is scarce
It is scattered in sunkenly in conducting polymer, therefore is difficult to obtain electric conductivity preferable enough.
The content of the invention
It is an object of the invention to overcome shield effectiveness existing for existing polymeric barrier layer materials poor, poor mechanical property
Defect provides a kind of polypropylene resin-based cable shield composite material and preparation method thereof；The present invention utilizes high molecular
Crosslinking and hybrid inorganic-organic principle make composite material have the advantages of shield effectiveness is good, and mechanical property is good, promote cable
Use in more multi-environment.
In order to realize foregoing invention purpose, the present invention provides a kind of polypropylene resin-based cable shield composite woods
Material, is prepared including following parts by weight raw material：30-60 parts of acrylic resin, 5-15 parts of isoamyl alcohol, 5-15 parts poly-
Quinoline, 2-5 parts of acetic anhydride, 0.1-0.5 parts of carbon nano-fiber, 0.5-2 parts of nano-carbon powder, 0.5-1 parts nano oxidized
Bismuth, 1-3 parts of coupling agent, 1-5 parts of crosslinking agent.
A kind of polypropylene resin-based cable shield composite material utilizes the polymerization that is cross-linked with each other of gas chromatography, shape
Into stable structure, high temperature-resistant polymer three-dimensional net structure, while the hydridization difference electric field induction material in three-dimensional net structure
Material forms carbon fiber-carbon dust-bismuth oxide three and forms a bulk shield, and the shielding action of electric field is enhanced；Meanwhile three
Dimension network structure increases mechanical properties of polymer, and environmental suitability is stronger；The composite material use scope bigger, is conducive to electricity
The development of cable industry.
Preferably, wherein the acrylic resin degree of polymerization is 100-500, the degree of polymerization is too big, and strand is too long, is formed
Three-dimensional net structure stablize it is poor, composite materials property reduction；The degree of polymerization is too small, and strand is too short, is unfavorable for electric field sense
Hydridization and the insertion of material are answered, inductive material disperses irregularly, it is possible to create agglomeration, product shielding properties reduce.
Preferably, wherein the poly quinoline degree of polymerization is 40-80, the degree of polymerization is too big, and strand is too long, the three-dimensional of formation
It is poor that network structure is stablized, and composite materials property reduces；The degree of polymerization is too small, and strand is too short, is unfavorable for electric-field inducing material
Hydridization and insertion, inductive material disperse irregularly, it is possible to create agglomeration, product shielding properties reduce.
Preferably, wherein a diameter of 2-10nm of the carbon nano-fiber, length 20-100nm, diameter and length are too
Greatly, the hydridization in three-dimensional net structure and insertion, electric-field inducing material for being unfavorable for electric-field inducing material are disperseed irregularly, can
Agglomeration can be generated, product shielding properties reduces, and diameter and length are too small, difficulties in dispersion, easily reunites, and is also unfavorable for carbon fibre
The foundation of dimension-carbon dust-bismuth oxide bulk shield.
Preferably, wherein the grain size of the nano-carbon powder is 20-60 nanometers, grain size is too big, is unfavorable for electric field induction material
The hydridization in three-dimensional net structure and insertion, electric-field inducing material of material are disperseed irregularly, it is possible to create agglomeration, product
Shielding properties reduces, and grain size is too small, difficulties in dispersion, easily reunites.
Preferably, wherein the grain size of the nano bismuth oxide is 20-50 nanometers, grain size is too big, is unfavorable for electric field induction
The hydridization in three-dimensional net structure and insertion, electric-field inducing material of material are disperseed irregularly, it is possible to create agglomeration, production
Product shielding properties reduces, and grain size is too small, difficulties in dispersion, easily reunites.
Preferably, wherein the coupling agent is silane coupling agent, silane coupling agent imitates the coupling of electric-field inducing material
Fruit is best.
Preferably, a kind of polypropylene resin-based cable shield composite material, including following parts by weight raw material
It is prepared：40-50 parts of acrylic resin, 5-10 parts of isoamyl alcohol, 10-15 parts of poly quinoline, 2-3 parts of acetic anhydride,
0.1-0.3 parts of carbon nano-fiber, 0.5-1 parts of nano-carbon powder, 0.8-1 parts of nano bismuth oxide, 1-2 parts of coupling agent, 2-3
The crosslinking agent of part.
In order to realize foregoing invention purpose, further, the present invention provides a kind of polypropylene resin-based cable shields
With the preparation method of composite material, comprise the following steps：
（1）Carbon nano-fiber, nano-carbon powder, nano bismuth oxide are dispersed in isoamyl alcohol and form suspension；
（2）The suspension that step 1 is obtained is esterified with acetic anhydride, coupling agent, coupling reaction, obtains acetic acid isoamyl alcohol ester hydridization
Mixture；
（3）The acetic acid isoamyl alcohol ester hybridized mixed object and acrylic resin that step 2 is obtained, poly quinoline, crosslinking agent mixing are laggard
Row cross-linking reaction obtains polypropylene resin-based cable shield composite material.
A kind of preparation method of polypropylene resin-based cable shield composite material, first passes through electric-field inducing material different
Amylalcohol uniformly disperses out, and esterification and coupling agent is recycled to be coupled the ester of synthesis and electric-field inducing material, and it is different to form acetic acid
Amylalcohol ester hybridized mixed object, so that the arrangement of the uniform rule of electric-field inducing material is dispersed in three-dimensional net structure, Bu Huituan
It is poly-, and carbon fiber-carbon dust-bismuth oxide bulk shield is formed, the shielding action of electric field is enhanced；Finally by with other high scores
The crosslinking of sub- material forms the polypropylene resin-based cable shield composite material with three-dimensional net structure, makes polymerization
Object mechanical property increases；The preparation method of the polypropylene resin-based cable shield composite material is simple, stablizes, is reliable, fits
Close extensive, the industrialized production of polypropylene resin-based cable shield composite material.
Preferably, the esterification reaction temperature is 80-90 DEG C, and reaction temperature is excessively high, and reaction is violent, and control is difficult, reaction
Temperature is too low, and reaction speed is slow, and the production cycle is long.
Preferably, the reaction time of esterification is 2-5h, and the reaction time is long, and the production cycle is long, and efficiency is low, the reaction time
Too short, reaction is incomplete, and properties of product reduce.
Preferably, the cross-linking reaction temperature is 180-250 DEG C, and crosslinking temperature is excessively high, is crosslinked transition, the three dimensional network of formation
Network irregular structure, properties of product reduce, and crosslinking temperature is too low, and the reaction time is too long, and the production cycle is long.
Preferably, the time of the cross-linking reaction is 1-3h, and the reaction time is long, and the production cycle is long, and efficiency is low, during reaction
Between it is too short, reaction is incomplete, and properties of product reduce.
Compared with prior art, beneficial effects of the present invention：
1st, the polypropylene resin-based cable shield composite material of the present invention contains three-dimensional net structure and carbon fiber-carbon dust-oxygen
Change bismuth bulk shield, there is higher electric field shielding effect and higher mechanical property.
2nd, the polypropylene resin-based cable shield of the present invention first passes through esterification and hydridization with the preparation method of composite material, then
Using crosslinking, by electric-field inducing material Monodispersed in three-dimensional net structure system, stood parallel into carbon fiber-carbon dust-bismuth oxide
Body shielding layer structure, so as to add the shield effectiveness of composite material and mechanical property.
3rd, the preparation method of the polypropylene resin-based cable shield composite material of the present invention is simple, stablizes, is reliable, is suitble to
Extensive, the industrialized production of polypropylene resin-based cable shield composite material.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）The nano bismuth oxide of the carbon nano-fiber of 0.3 parts by weight, the nano-carbon powder of 1 parts by weight, 0.8 parts by weight is dispersed in
Solution is formed in the isoamyl alcohol of 10 parts by weight；
（2）Solution and the acetic anhydride of 3 parts by weight that step 1 is obtained, the silane coupling agent of 2 parts by weight are under conditions of 150 DEG C
It is esterified, coupling reaction 5h, obtains acetic acid isoamyl alcohol ester hybridized mixed object；
（3）The acetic acid isoamyl alcohol ester hybridized mixed object and the degree of polymerization of 40 parts by weight that step 2 is obtained are 200 polypropylene tree
Fat, the degree of polymerization of 10 parts by weight are 40 poly quinoline, are crosslinked after the crosslinking agent mixing of 2 parts by weight at a temperature of 180 DEG C
3h is reacted, obtains polypropylene resin-based cable shield composite material.
Embodiment 2
（1）The nano bismuth oxide of the carbon nano-fiber of 0.1 parts by weight, the nano-carbon powder of 0.5 parts by weight, 1 parts by weight is dispersed in 5
Solution is formed in the isoamyl alcohol of parts by weight；
（2）The solution that step 1 obtains and the acetic anhydride of 2 parts by weight, the coupling agent of 1 parts by weight are carried out at a temperature of 190 DEG C
Esterification, coupling reaction 2h, obtain acetic acid isoamyl alcohol ester hybridized mixed object；
（3）The acetic acid isoamyl alcohol ester hybridized mixed object and the degree of polymerization of 50 parts by weight that step 2 is obtained are 500 polypropylene tree
Fat, the degree of polymerization of 10 parts by weight are 80 poly quinoline, are crosslinked after the crosslinking agent mixing of 3 parts by weight at a temperature of 250 DEG C
1h is reacted, obtains polypropylene resin-based cable shield composite material.
Embodiment 3
（1）The nano bismuth oxide of the carbon nano-fiber of 0.1 parts by weight, the nano-carbon powder of 2 parts by weight, 0.5 parts by weight is dispersed in 5
Solution is formed in the isoamyl alcohol of parts by weight；
（2）Solution and the acetic anhydride of 5 parts by weight, the coupling agent of 1 parts by weight that step 1 is obtained are esterified, coupling reaction, are obtained
Acetic acid isoamyl alcohol ester hybridized mixed object；
（3）The acetic acid isoamyl alcohol ester hybridized mixed object and the acrylic resin of 30 parts by weight that step 2 is obtained, 15 parts by weight are gathered
Quinoline carries out cross-linking reaction after the crosslinking agent mixing of 1 parts by weight, obtains polypropylene resin-based cable shield composite material.
Embodiment 4
（1）The nano bismuth oxide of the carbon nano-fiber of 0.1 parts by weight, 0.5 parts by weight is dispersed in the isoamyl alcohol of 15 parts by weight
Form solution；
（2）Solution and the acetic anhydride of 2 parts by weight, the coupling agent of 3 parts by weight that step 1 is obtained are esterified, coupling reaction, are obtained
Acetic acid isoamyl alcohol ester hybridized mixed object；
（3）The acetic acid isoamyl alcohol ester hybridized mixed object and the acrylic resin of 60 parts by weight that step 2 is obtained, 15 parts by weight are gathered
Quinoline carries out cross-linking reaction after the crosslinking agent mixing of 1 parts by weight, obtains polypropylene resin-based cable shield composite material.
Claims (10)
1. a kind of shielded layer composite material, which is characterized in that be prepared including following parts by weight raw material：30-60 parts
Acrylic resin, 5-15 parts of isoamyl alcohol, 5-15 parts of poly quinoline, 2-5 parts of acetic anhydride, 0.1-0.5 parts of carbon nano-fiber,
0.5-2 parts of nano-carbon powder, 0.5-1 parts of nano bismuth oxide, 1-3 parts of coupling agent, 1-5 parts of crosslinking agent.
2. shielded layer composite material according to claim 1, which is characterized in that the acrylic resin degree of polymerization is
100-500。
3. shielded layer composite material according to claim 1, which is characterized in that the poly quinoline degree of polymerization is 40-80.
4. shielded layer composite material according to claim 1, which is characterized in that a diameter of 2- of the carbon nano-fiber
10nm, length 20-100nm.
5. shielded layer composite material according to claim 1, which is characterized in that the grain size of the nano-carbon powder is 20-
60nm。
6. shielded layer composite material according to claim 1, which is characterized in that the grain size of the bismuth oxide is 20-
50nm。
7. shielded layer composite material according to claim 1, which is characterized in that prepared including following parts by weight raw material
It forms：40-50 parts of acrylic resin, 5-10 parts of isoamyl alcohol, 10-15 parts of poly quinoline, 2-3 parts of acetic anhydride, 0.1-0.3
Part carbon nano-fiber, 0.5-1 parts of nano-carbon powder, 0.8-1 parts of nano bismuth oxide, 1-2 parts of coupling agent, 2-3 parts of friendship
Join agent.
8. the preparation method of shielded layer composite material described in a kind of claim 1, which is characterized in that comprise the following steps：
（1）Carbon nano-fiber, nano-carbon powder, nano bismuth oxide are dispersed in isoamyl alcohol and form suspension；
（2）The suspension that step 1 is obtained is esterified with acetic anhydride, coupling agent, coupling reaction, obtains acetic acid isoamyl alcohol ester hydridization
Mixture；
（3）The acetic acid isoamyl alcohol ester hybridized mixed object and acrylic resin that step 2 is obtained, poly quinoline, crosslinking agent mixing are laggard
Row cross-linking reaction obtains polypropylene resin-based cable shield composite material.
9. preparation method according to claim 8, which is characterized in that esterification reaction temperature is 150-190 DEG C in step 2,
Time is 2-5h.
10. preparation method according to claim 8, which is characterized in that cross-linking reaction temperature is 180-250 DEG C in step 3,
Time is 1-3h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611000500.0A CN108070142A (en) | 2016-11-17 | 2016-11-17 | A kind of polypropylene resin-based cable shield composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611000500.0A CN108070142A (en) | 2016-11-17 | 2016-11-17 | A kind of polypropylene resin-based cable shield composite material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN108070142A true CN108070142A (en) | 2018-05-25 |
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| CN201611000500.0A Withdrawn CN108070142A (en) | 2016-11-17 | 2016-11-17 | A kind of polypropylene resin-based cable shield composite material and preparation method thereof |
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2016
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