CN108070207A - A kind of melmac based high molecular shielding composite and preparation method thereof - Google Patents
A kind of melmac based high molecular shielding composite and preparation method thereof Download PDFInfo
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- CN108070207A CN108070207A CN201611010973.9A CN201611010973A CN108070207A CN 108070207 A CN108070207 A CN 108070207A CN 201611010973 A CN201611010973 A CN 201611010973A CN 108070207 A CN108070207 A CN 108070207A
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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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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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
- H01B3/38—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 condensation products of aldehydes with amines or amides
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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
- C08K2201/00—Specific properties of additives
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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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Abstract
The invention discloses a kind of melmac based high molecular shielding composites and preparation method thereof, are prepared including following parts by weight raw material:30 60 parts of melmac, 10 20 parts of polytetrafluoroethylene (PTFE), 20 35 parts of phosphoric acid methylene base ester, 5 15 parts of nitrocellulose, 5 10 parts of polypyrrole, 5 10 parts of poly- dibromoethylene, 0.5 1.5 parts of nano-graphene, 15 parts of crosslinking agent;Principle is precipitated using high molecular polymerization, crosslinking and crystal in the present invention, make it have it is more preferable to the shield effectiveness of electric field, the advantages of mechanical property higher.
Description
Technical field
The present invention relates to shielding material fields, and in particular to a kind of melmac based high molecular shielding composite 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(Polyvinyl chloride)Sheath,
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 polyvinyl chloride-based cable shield composite material and preparation method thereof;The present invention is gathered using high molecular
Principle is precipitated in conjunction, crosslinking and crystal, and composite material is made to have the advantages of shield effectiveness is good, and mechanical property is good, cable is promoted and exists
Use in more multi-environment.
In order to realize foregoing invention purpose, the present invention provides a kind of melmac based high moleculars to shield composite wood
Material, is prepared including following parts by weight raw material:30-60 parts of melmac, 10-20 parts of polytetrafluoroethylene (PTFE), 20-
35 parts of phosphoric acid methylene base ester, 5-15 parts of nitrocellulose, 5-10 parts of polypyrrole, 5-10 parts of poly- dibromoethylene, 0.5-
1.5 parts of nano-graphene, 1-5 parts of crosslinking agent.
A kind of melmac based high molecular shielding composite utilizes mutual polymerization, the friendship between gas chromatography
Connection forms stable structure, high temperature-resistant polymer three-dimensional net structure, while contains in three-dimensional net structure and utilize nucleating agent
The polymer crystallization of formation forms a bulk shield between the polymer crystallization, and the shielding action of electric field is enhanced;Together
When, three-dimensional net structure increases mechanical properties of polymer, and environmental suitability is stronger;The composite material use scope bigger, has
Beneficial to the development of cable industry.
Preferably, wherein the melmac molecular weight is 1000-20000, molecular weight is too big, and strand is too
Long, the three-dimensional net structure of formation stablizes poor, composite materials property reduction;Molecular weight is too small, and strand is too short, is unfavorable for
To the cladding of polymer crystallization, product shielding properties reduces.
Preferably, wherein the polyphosphoric acid methylene polyisocyanate polyaddition degree is 100-200, molecular weight is bigger, to the work of electric field
With weaker, electric field shielding variation.
Preferably, wherein the polytetrafluoroethylene (PTFE) degree of polymerization is 200-500, 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 polymerization
The cladding of object crystallization.
Preferably, wherein the nitrocellulose degree of polymerization is 100-200, 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 polymerization
The cladding of object crystallization.
Preferably, wherein the polypyrrole degree of polymerization is 100-200, the degree of polymerization is too big, and electric conductivity is deteriorated;The degree of polymerization
It is too small, poor mechanical property.
Preferably, wherein the grain size of the nano-graphene is 5-20 nanometers, grain size is too big, is unfavorable for high molecular material
Crystallization nucleation;Grain size is too small, difficulties in dispersion, easily reunites.
Preferably, a kind of melmac based high molecular shielding composite, including following parts by weight raw material
It is prepared:40-50 parts of melmac, 10-15 parts of polytetrafluoroethylene (PTFE), 25-30 parts of phosphoric acid methylene base ester, 10-
15 parts of nitrocellulose, 5-8 parts of polypyrrole, 8-10 parts of poly- dibromoethylene, 0.5-1.0 parts of nano-graphene, 2-3 parts
Crosslinking agent.
In order to realize foregoing invention purpose, further, the present invention provides a kind of melmac based high molecular screens
The preparation method of composite material is covered, is comprised the following steps:
(1)Phosphoric acid methylene base ester is dissolved to form solution with glycerine, nano barium titanate calcium is added in the solution, is carried out after being uniformly dispersed
Crystallization is precipitated, and obtains phosphoric acid methylene base ester crystalline material;
(2)Phosphoric acid methylene base ester crystalline material that step 1 is obtained and melmac, polytetrafluoroethylene (PTFE), poly- dibromoethylene,
Cross-linking reaction is carried out after polypyrrole, nitrocellulose, crosslinking agent mixing, obtains melmac based high molecular shielding composite wood
Material.
Phosphoric acid methylene base ester is first dissolved shape by a kind of preparation method of melmac based high molecular shielding composite
Into solution, nano barium titanate calcium is recycled to cook nucleating agent, the crystallization precipitation of phosphoric acid methylene base ester is become can be with the interaction of electric field
And the crystalline material of shield effectiveness is generated, so that the shield effectiveness increase of polymer material;Finally with other high molecular materials
Crosslinking, form the melmac based high molecular shielding composite with three-dimensional net structure, make polymer mechanics
Performance increases, operating temperature higher;The preparation method of the melmac based high molecular shielding composite is simple, steady
It is fixed, reliable, it is suitble to extensive, the industrialized production of melmac based high molecular shielding composite.
Preferably, the cross-linking reaction temperature is 240-280 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, melmac based high molecular shielding composite of the present invention contains the phosphoric acid methylene being precipitated using nucleating agent crystallization
Base ester crystalline material has to the stronger characteristic of the shielding action of electric field.
2nd, the preparation method of melmac based high molecular shielding composite of the present invention first passes through recrystallization, recycles
Crosslinking, crystalline material is dispersed in three-dimensional net structure system, so as to add the mechanical property of composite material and screen
Cover effect.
3rd, the preparation method of melmac based high molecular shielding composite of the present invention is simple, stablizes, is reliable, is suitble to
Extensive, the industrialized production of melmac based high molecular shielding composite.
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 polyphosphoric acid methylene base ester that 30 weight parts of polymer degree are 150 is dissolved to form solution with glycerine, is added in the solution
0.8 parts by weight nano barium titanate calcium, crystallization precipitation is carried out after being uniformly dispersed, and obtains polyphosphoric acid methylene base ester crystalline material;
(2)The polyphosphoric acid methylene base ester crystalline material and the molecular weight of 40 parts by weight that step 1 is obtained are 5000 melamine
Polytetrafluoroethylene (PTFE) that resin, the degree of polymerization of 10 parts by weight are 300, the poly- dibromoethylene of 8 parts by weight, 5 weight parts of polymer degree are 150
Polypyrrole, 10 parts by weight the degree of polymerization be 150 nitrocellulose, 3 parts by weight crosslinking agent mixing after, in 260 DEG C of temperature
Degree is lower to carry out cross-linking reaction 3h, obtains melmac based high molecular shielding composite.
Embodiment 2
(1)The polyphosphoric acid methylene base ester that 25 weight parts of polymer degree are 100 is dissolved to form solution with glycerine, is added in the solution
1.0 parts by weight nano barium titanate calcium, crystallization precipitation is carried out after being uniformly dispersed, and obtains polyphosphoric acid methylene base ester crystalline material;
(2)The polyphosphoric acid methylene base ester crystalline material and the molecular weight of 50 parts by weight that step 1 is obtained are 1000 melamine
Polytetrafluoroethylene (PTFE) that resin, the degree of polymerization of 15 parts by weight are 500, the poly- dibromoethylene of 10 parts by weight, 8 weight parts of polymer degree are
After 200 polypyrrole, the nitrocellulose that the degree of polymerization of 15 parts by weight is 100, the crosslinking agent of 5 parts by weight mix, at 280 DEG C
At a temperature of carry out cross-linking reaction 1h, obtain melmac based high molecular shielding composite.
Embodiment 3
(1)The polyphosphoric acid methylene base ester that 20 weight parts of polymer degree are 200 is dissolved to form solution with glycerine, is added in the solution
0.5 parts by weight nano barium titanate calcium, crystallization precipitation is carried out after being uniformly dispersed, and obtains polyphosphoric acid methylene base ester crystalline material;
(2)The polyphosphoric acid methylene base ester crystalline material and the molecular weight of 20 parts by weight that step 1 is obtained are 20000 melamine
Polytetrafluoroethylene (PTFE) that resin, the degree of polymerization of 10 parts by weight are 200, the poly- dibromoethylene of 5 parts by weight, 10 weight parts of polymer degree are
After 100 polypyrrole, the nitrocellulose that the degree of polymerization of 5 parts by weight is 200, the crosslinking agent of 5 parts by weight mix, at 240 DEG C
At a temperature of carry out cross-linking reaction 3h, obtain melmac based high molecular shielding composite.
Embodiment 4
(1)The polyphosphoric acid methylene base ester that 35 weight parts of polymer degree are 200 is dissolved to form solution with glycerine, is added in the solution
1.5 parts by weight nano barium titanate calcium, crystallization precipitation is carried out after being uniformly dispersed, and obtains polyphosphoric acid methylene base ester crystalline material;
(2)The polyphosphoric acid methylene base ester crystalline material and the molecular weight of 60 parts by weight that step 1 is obtained are 20000 melamine
Polytetrafluoroethylene (PTFE) that resin, the degree of polymerization of 20 parts by weight are 200, the poly- dibromoethylene of 10 parts by weight, 5 weight parts of polymer degree are
After 100 polypyrrole, the nitrocellulose that the degree of polymerization of 15 parts by weight is 200, the crosslinking agent of 1 parts by weight mix, at 270 DEG C
At a temperature of carry out cross-linking reaction 1.5h, obtain melmac based high molecular shielding composite.
Claims (10)
1. a kind of shielding composite, which is characterized in that be prepared including following parts by weight raw material:30-60 parts of trimerization
Melamine resin, 10-20 parts of polytetrafluoroethylene (PTFE), 20-35 parts of phosphoric acid methylene base ester, 5-15 parts of nitrocellulose, 5-10 parts
Polypyrrole, 5-10 parts of poly- dibromoethylene, 0.5-1.5 parts of nano-graphene, 1-5 parts of crosslinking agent.
2. shielding composite according to claim 1, which is characterized in that the melmac molecular weight is
1000-20000。
3. shielding composite according to claim 1, which is characterized in that the polytetrafluoroethylene (PTFE) degree of polymerization is 200-
500。
4. shielding composite according to claim 1, which is characterized in that the nitrocellulose degree of polymerization is 100-
200。
5. shielding composite according to claim 1, which is characterized in that the polypyrrole degree of polymerization is 100-200.
6. shielding composite according to claim 1, which is characterized in that the grain size of the nano-graphene is 1-
20nm。
7. shielding composite according to claim 1, which is characterized in that including the preparation of following parts by weight raw material
Into:40-50 parts of melmac, 10-15 parts of polytetrafluoroethylene (PTFE), 25-30 parts of phosphoric acid methylene base ester, 10-15 parts
Nitrocellulose, 5-8 parts of polypyrrole, 8-10 parts of poly- dibromoethylene, 0.5-1.0 parts of nano-graphene, 2-3 parts of crosslinking
Agent.
8. the preparation method of shielding composite described in a kind of claim 1, which is characterized in that comprise the following steps:
(1)Phosphoric acid methylene base ester is dissolved to form solution with glycerine, nano barium titanate calcium is added in the solution, is carried out after being uniformly dispersed
Crystallization is precipitated, and obtains phosphoric acid methylene base ester crystalline material;
(2)Phosphoric acid methylene base ester crystalline material that step 1 is obtained and melmac, polytetrafluoroethylene (PTFE), poly- dibromoethylene,
Cross-linking reaction is carried out after polypyrrole, nitrocellulose, crosslinking agent mixing, obtains melmac based high molecular shielding composite wood
Material.
9. preparation method according to claim 8, which is characterized in that cross-linking reaction temperature is 240-280 DEG C in step 3.
10. preparation method according to claim 8, which is characterized in that cross-linking reaction time is 1-3h in step 3.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113527836A (en) * | 2021-07-28 | 2021-10-22 | 国网河南省电力公司西峡县供电公司 | Electromagnetic shielding composite material and preparation method thereof |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113527836A (en) * | 2021-07-28 | 2021-10-22 | 国网河南省电力公司西峡县供电公司 | Electromagnetic shielding composite material and preparation method thereof |
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Application publication date: 20180525 |