CN106084550A - A kind of fiber reinforced fire-retardant cable material and preparation method thereof - Google Patents
A kind of fiber reinforced fire-retardant cable material and preparation method thereof Download PDFInfo
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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
- C08L27/00—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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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
- C08L2201/02—Flame or fire retardant/resistant
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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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- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of fiber reinforced fire-retardant cable material, it is made up of the raw material of following weight parts: aphthenic acids lithium 0.1 0.2, Guanidine Sulfamate 99 67, CNT 20 23, N, N' Dicyclohexylcarbodiimide 0.3 0.4, hexachlorocyclotriph,sphazene 45, sodium hydroxide 0.2 0.4, thiourea 12, bis-phenol a diglycidyl ether 0.1 0.3, hydroxypropyl methyl cellulose 23, cellulose propionate 12, ammonium octamolybdate 0.7 1, ethoxylated alkyl ammonium sulfate 0.7 1, decanoyl/octanoyl glycerides 34, APP 12, nylon 17 20, polrvinyl chloride 120 130.Present invention adds cellulose propionate, hydroxypropyl methyl cellulose, effectively raise the pliability of finished-product material.
Description
Technical field
The present invention relates to mass technical field, particularly relate to a kind of fiber reinforced fire-retardant cable material and preparation method thereof.
Background technology
Nanotechnology is in the eighties rise in last century, and is widely used in multiple fields.Research finds,
Polymer adds after nanoparticle, can the performance of significantly lift-off material.Such as when add in polymer a small amount of graphite skilful,
During the nanoparticle such as CNT, molybdenum bisuphide, the mechanical strength of material will be obviously improved IWI.Research finds, only adds pole
A small amount of nano material just can be greatly reduced the HRR of material combustion, the most also can the mechanics of lift-off composite strong
Degree.The nano flame retardant system that research is relatively more at present mainly has several: (1) inorganic nano-particle, such as nanometer ammoxidation town, nanometer
Ammoxidation lead and nano silicon etc..This based flame retardant is relatively low due to himself flame retarding efficiency, fire retardant mechanism also with other
Nanoparticle is different, needs bigger addition when reality is applied, therefore can not be classified as flame retardant nano-materials completely.And fill out
The filling of material also can produce impact to the mechanical property of material self.(2) laminated inorganic matter, as nanoclay, brucite, can
Expanded graphite etc..(3) pipe carbon and acicular nanoparticles, such as CNT, halloysite nanotubes and meerschaum etc..In 21 century
In the tenth day of lunar month year, a large amount of report galapectite in recent years and meerschaum about polymer/carbon nano-tube flame-retardant system is had to be increasingly becoming
The focus nano flame retardant technology of research occurs two during the last ten years, although gradually grows up and achieves a series of achievement in research,
But the polymeric material of nanorize combustion to extensively application, still has very long road to walk from research;
About the application in the polymer of nano flame retardant technology, some problem following is currently mainly had to need to solve: 1. nanometer resistance
Combustion additive significant advantage is that in trying for taper calorimetric, HRR reduces for a lot nanoparticles, only
Need to add few amount and just the HRR of material combustion can be greatly reduced by W.But for traditional fire-retardant trial work section,
As oxygen index (OI) and vertical combustion test effect significantly, negative effect the most also can be played.Therefore, need to consider nanoparticle
Son is modified or reaches the effect of cooperative flame retardant by compounding use with conventional flame retardant.The most in recent years, to nanoparticle
Modified research gets more and more, the particularly intercalation modifying to nanoclay.But the intercalation of existing frequently-used nanoclay changes
Property agent be the burning base amine salt of long-chain mostly, lack and be specifically designed to flame-retardant modified intercalator or surface modifier.And it is most of
Modifying agent itself not there is anti-flammability, some self the most flammable;Heat stability is the most poor, and initial decomposition degree is low, difficult suitable
Iron for engineering plastics etc. and melt the polymer that temperature is higher.Therefore, change for having the nanoparticle of anti-flammability and heat stability concurrently
Property agent is a direction of future studies.3. with the fire retardant such as halogen flame, phosphor nitrogen combustion inhibitor, there is clear and definite fire retardant mechanism
Difference, the present stage explanation to the mechanism shortage system of nano flame retardant.Current approved mechanism mainly has oneself of nanoclay
The obstruct mechanism of mechanism, solid phase is caught by base;Synergistic catalytic mechanism with expanding fire retardant;The network structure of CNT intercepts
Impact etc. on system rheological characteristic in mechanism and combustion process.Therefore, for nanoparticle resistance during polymer combustion
The elaboration of combustion engine reason will be the direction of future studies, and CNT lacks polar functional group, with polymer base due to surface simultaneously
The compatibility of body is poor;The structure of high length-diameter ratio can cause the winding in the course of processing, gathering, thus is difficult to well divide
Dissipate.Additionally, CNT only to reduce HRR have obvious effect, but can not effectively carry material oxygen index (OI) and
Vertical combustion grade.In order to improve the CNT compatibility in the polymer and dispersibility, coupling agent, surface activity can be used
Agent or polymer etc. carry out surface to CNT and change, but class method of modifying often difficulty puies forward its fire resistance, and some is very
To destroying original anti-flammability;.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of fiber reinforced fire-retardant cable material and system thereof
Preparation Method.
The present invention is achieved by the following technical solutions:
A kind of fiber reinforced fire-retardant cable material, it is made up of the raw material of following weight parts:
Aphthenic acids lithium 0.1-0.2, Guanidine Sulfamate 99 6-7, CNT 20-23, N, N'-Dicyclohexylcarbodiimide 0.3-0.4,
Hexachlorocyclotriph,sphazene 4-5, sodium hydroxide 0.2-0.4, thiourea 1-2, bis-phenol a diglycidyl ether 0.1-0.3, hydroxypropyl methyl are fine
Dimension element 2-3, cellulose propionate 1-2, ammonium octamolybdate 0.7-1, ethoxylated alkyl ammonium sulfate 0.7-1, decanoyl/octanoyl glycerides 3-4,
APP 1-2, nylon 17-20, polrvinyl chloride 120-130.
A kind of preparation method of described fiber reinforced fire-retardant cable material, it is made up of the raw material of following weight parts:
(1) being joined by above-mentioned CNT in the mixed acid solution of its weight 80-100 times, described nitration mixture is to be by mass ratio
The hydrochloric acid solution composition of the sulphuric acid of the 96-98% of 3-4:1 and 87-90%, at 50-60 DEG C ultrasonic 17-20 minute, filters, will be heavy
Form sediment and wash 2-3 time, be vacuum dried 30-40 minute at 70-76 DEG C, obtain acidifying CNT;
(2) above-mentioned ethoxylated alkyl ammonium sulfate is joined in its weight 40-50 times, 17-20% acetum, stirring
Uniformly, rise high-temperature and be 57-60 DEG C, add hydroxypropyl methyl cellulose, cellulose propionate mixing, insulated and stirred 5-7 minute, add
Entering above-mentioned acidifying CNT, rise high-temperature and be 80-90 DEG C, insulated and stirred to water is done, and obtains fiber composite CNT;
(3) 47-50% of above-mentioned fiber composite carbon nanotubes is taken, with Guanidine Sulfamate 99, N, N'-Dicyclohexylcarbodiimide
Mixing, joins in the DMF of compound weight 70-80 times, ultrasonic 100-120 minute, sends into reactor
In, it is passed through nitrogen, rises high-temperature and be 120-127 DEG C, insulation reaction 35-40 hour, discharging, by product sucking filtration, use washing with acetone
3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain sulfonic acid guanidine grafting carbon nanotube;
(4) by remaining fiber composite CNT, APP mixing, the dehydrated alcohol of compound weight 3-5 times is joined
In, add aphthenic acids lithium under stirring condition, send in the water-bath of 70-80 DEG C, insulated and stirred 10-17 minute, discharging, filter, will
Precipitation washing 2-3 time, mixes with above-mentioned ammonium octamolybdate, is vacuum dried 1-2 hour, obtains modified carbon nano-tube at 50-60 DEG C;
(5) by above-mentioned modified carbon nano-tube, hexachlorocyclotriph,sphazene, sodium hydroxide mixing, compound weight 60-70 times is joined
In oxolane, ultrasonic 100-110 minute, send in reactor, be passed through nitrogen, rise high-temperature and be 68-70 DEG C, insulation reaction
35-40 hour, discharging, by product sucking filtration, with washing with acetone 3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain ring
Three phosphonitrile grafting carbon nanotubes;
(6) take the 10-16% of above-mentioned nylon weight, add in its weight 20-27 times, 17-20% formalin, stirring mixing
20-30 minute, dropping concentration was the hydrochloric acid of 3-6mol/l, and regulation pH is 2-3, is passed through nitrogen, is heated to boiling, keeps boiling
57-60 minute, discharging, it is cooled to room temperature, obtains hydroxylating nylon liquid;
(7) by above-mentioned sulfonic acid guanidine grafting carbon nanotube, ring three phosphonitrile grafting carbon nanotube, the mixing of hydroxylating nylon liquid, at 87-90
Preheat 4-6 minute at DEG C, rise high-temperature and be 155-160 DEG C, insulated and stirred 3-4 minute, filters, is washed by precipitation oxolane
2-3 time, it is vacuum dried 30-40 minute at being placed in 70-80 DEG C, obtains modified nylon CNT;
(8) above-mentioned modified nylon CNT is mixed with remaining each raw material, stir, dry, put into screw extruder and melt
Melt extrusion, cool down, sieve, obtain described mass.
The invention have the advantage that the mass of the present invention has good fire-retardant fireproof performance, the present invention first uses amino sulphur
The pre-nylon blending of CNT that acid guanidine, chlorine ring three phosphonitrile are grafted respectively, the nylon after hydroxylating discharging can be with grafting
After CNT have the good compatibility, improve this composite dispersibility in finished cable material the most further, this is multiple
The fire retardant mechanism of condensation material is: when nylon in combustion, CNT is at polymer melt surface aggregation, and is formed netted
The layer of charcoal of structure, these netted carbon-coatings are fine and close and almost without hole, are effectively prevented outside heat and oxygen when burning
Entering, such that it is able to effectively reduce HRR and mass loss rate, and the Guanidine Sulfamate 99 being grafted can be coated on
Carbon nano tube surface, its catabolite contributes to CNT and forms the finest and close network structure layer of charcoal, and Guanidine Sulfamate 99 is certainly
Status solution can produce ammonia, and ammonia can react again the degraded promoting nylon with nylon, and both jointly produce substantial amounts of ammonia gas and water and steam
The non-flammable compressive gas such as gas and carbon dioxide, the oxygen in dilute combustion district and fuel gas, play the effect that gas phase is fire-retardant;Grafting
Chlorine ring three phosphonitrile plays the effect of similar patch, and the mesh of the netted layer of charcoal that filling carbon nano-pipe is formed, chlorine the most therein is former
Sub-combustion process can be formed Cl-, and catch the free radical that burning produces, thus terminate the chain reaction of combustion process, carry
The fire resistance of high finished-product material.Present invention adds cellulose propionate, hydroxypropyl methyl cellulose, effectively raise finished product
The pliability of material.
Detailed description of the invention
A kind of fiber reinforced fire-retardant cable material, it is made up of the raw material of following weight parts:
Aphthenic acids lithium 0.1, Guanidine Sulfamate 99 6, CNT 20, N, N' Dicyclohexylcarbodiimide 0.3, hexachlorocyclotriph,sphazene 4,
Sodium hydroxide 0.2, thiourea 1, bis-phenol a diglycidyl ether 0.1, hydroxypropyl methyl cellulose 2, cellulose propionate 1, ammonium octamolybdate
0.7, ethoxylated alkyl ammonium sulfate 0.7, decanoyl/octanoyl glycerides 3, APP 1, nylon 17, polrvinyl chloride 120.
A kind of preparation method of described fiber reinforced fire-retardant cable material, it is made up of the raw material of following weight parts:
(1) being joined by above-mentioned CNT in the mixed acid solution of its weight 80 times, described nitration mixture is 3:1 by mass ratio
The sulphuric acid of 96% and the hydrochloric acid solution composition of 87%, at 50 DEG C ultrasonic 17 minutes, filter, by precipitation washing 2 times, vacuum at 70 DEG C
It is dried 30 minutes, obtains acidifying CNT;
(2) above-mentioned ethoxylated alkyl ammonium sulfate is joined in its weight 40 times, the acetum of 17%, stir, rise
High-temperature is 57 DEG C, adds hydroxypropyl methyl cellulose, cellulose propionate mixing, insulated and stirred 5 minutes, adds above-mentioned acidifying carbon
Nanotube, rising high-temperature is 80 DEG C, and insulated and stirred to water is done, and obtains fiber composite CNT;
(3) taking the 47% of above-mentioned fiber composite carbon nanotubes, with Guanidine Sulfamate 99, N, N' Dicyclohexylcarbodiimide mixes,
Join in the DMF of compound weight 70 times, ultrasonic 100 minutes, send in reactor, be passed through nitrogen, rise
High-temperature is 120 DEG C, insulation reaction 35 hours, discharging, by product sucking filtration, with washing with acetone 3 times, is placed in the baking oven of 70 DEG C dry
Dry to constant weight, obtain sulfonic acid guanidine grafting carbon nanotube;
(4) by remaining fiber composite CNT, APP mixing, join in the dehydrated alcohol of compound weight 3 times,
Add aphthenic acids lithium under stirring condition, send in the water-bath of 70 DEG C, insulated and stirred 10 minutes, discharging, filter, by precipitation washing 2
Secondary, mix with above-mentioned ammonium octamolybdate, be vacuum dried 1 hour at 50 DEG C, obtain modified carbon nano-tube;
(5) by above-mentioned modified carbon nano-tube, hexachlorocyclotriph,sphazene, sodium hydroxide mixing, the four of compound weight 60 times are joined
In hydrogen furan, ultrasonic 100 minutes, sending in reactor, be passed through nitrogen, rising high-temperature is 68 DEG C, and insulation reaction 35 hours goes out
Material, by product sucking filtration, with washing with acetone 3 times, is placed in the baking oven of 70 DEG C and is dried to constant weight, obtain ring three phosphonitrile grafting carbon nanometer
Pipe;
(6) take the 10% of above-mentioned nylon weight, add in its weight 20 times, the formalin of 17%, stirring mixing 20 minutes, drip
Adding the hydrochloric acid that concentration is 3mol/l, regulation pH is 2, is passed through nitrogen, is heated to boiling, keeps boiling 57 minutes, discharging, is cooled to
Room temperature, obtains hydroxylating nylon liquid;
(7) by above-mentioned sulfonic acid guanidine grafting carbon nanotube, ring three phosphonitrile grafting carbon nanotube, the mixing of hydroxylating nylon liquid, at 87 DEG C
Lower preheating 4 minutes, rising high-temperature is 155 DEG C, and insulated and stirred 3 minutes filters, and is washed 2 times by precipitation oxolane, is placed in 70
It is vacuum dried 30 minutes at DEG C, obtains modified nylon CNT;
(8) above-mentioned modified nylon CNT is mixed with remaining each raw material, stir, dry, put into screw extruder and melt
Melt extrusion, cool down, sieve, obtain described mass.
Performance test:
Hot strength: 19.9 MPa;
Low temperature brittleness impact temperature (DEG C) :-30 DEG C are passed through;
Fire-retardant rank: V-0;
After 100 DEG C × 240h hot air aging: hot strength rate of change (%)-7.4;
Extension at break rate of change (%)-8.0.
Claims (2)
1. a fiber reinforced fire-retardant cable material, it is characterised in that it is made up of the raw material of following weight parts:
Aphthenic acids lithium 0.1-0.2, Guanidine Sulfamate 99 6-7, CNT 20-23, N, N'-Dicyclohexylcarbodiimide 0.3-0.4,
Hexachlorocyclotriph,sphazene 4-5, sodium hydroxide 0.2-0.4, thiourea 1-2, bis-phenol a diglycidyl ether 0.1-0.3, hydroxypropyl methyl are fine
Dimension element 2-3, cellulose propionate 1-2, ammonium octamolybdate 0.7-1, ethoxylated alkyl ammonium sulfate 0.7-1, decanoyl/octanoyl glycerides 3-4,
APP 1-2, nylon 17-20, polrvinyl chloride 120-130.
2. the preparation method of a fiber reinforced fire-retardant cable material as claimed in claim 1, it is characterised in that it is by following
The raw material composition of weight portion:
(1) being joined by above-mentioned CNT in the mixed acid solution of its weight 80-100 times, described nitration mixture is to be by mass ratio
The hydrochloric acid solution composition of the sulphuric acid of the 96-98% of 3-4:1 and 87-90%, at 50-60 DEG C ultrasonic 17-20 minute, filters, will be heavy
Form sediment and wash 2-3 time, be vacuum dried 30-40 minute at 70-76 DEG C, obtain acidifying CNT;
(2) above-mentioned ethoxylated alkyl ammonium sulfate is joined in its weight 40-50 times, 17-20% acetum, stirring
Uniformly, rise high-temperature and be 57-60 DEG C, add hydroxypropyl methyl cellulose, cellulose propionate mixing, insulated and stirred 5-7 minute, add
Entering above-mentioned acidifying CNT, rise high-temperature and be 80-90 DEG C, insulated and stirred to water is done, and obtains fiber composite CNT;
(3) 47-50% of above-mentioned fiber composite carbon nanotubes is taken, with Guanidine Sulfamate 99, N, N'-Dicyclohexylcarbodiimide
Mixing, joins in the DMF of compound weight 70-80 times, ultrasonic 100-120 minute, sends into reactor
In, it is passed through nitrogen, rises high-temperature and be 120-127 DEG C, insulation reaction 35-40 hour, discharging, by product sucking filtration, use washing with acetone
3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain sulfonic acid guanidine grafting carbon nanotube;
(4) by remaining fiber composite CNT, APP mixing, the dehydrated alcohol of compound weight 3-5 times is joined
In, add aphthenic acids lithium under stirring condition, send in the water-bath of 70-80 DEG C, insulated and stirred 10-17 minute, discharging, filter, will
Precipitation washing 2-3 time, mixes with above-mentioned ammonium octamolybdate, is vacuum dried 1-2 hour, obtains modified carbon nano-tube at 50-60 DEG C;
(5) by above-mentioned modified carbon nano-tube, hexachlorocyclotriph,sphazene, sodium hydroxide mixing, compound weight 60-70 times is joined
In oxolane, ultrasonic 100-110 minute, send in reactor, be passed through nitrogen, rise high-temperature and be 68-70 DEG C, insulation reaction
35-40 hour, discharging, by product sucking filtration, with washing with acetone 3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain ring
Three phosphonitrile grafting carbon nanotubes;
(6) take the 10-16% of above-mentioned nylon weight, add in its weight 20-27 times, 17-20% formalin, stirring mixing
20-30 minute, dropping concentration was the hydrochloric acid of 3-6mol/l, and regulation pH is 2-3, is passed through nitrogen, is heated to boiling, keeps boiling
57-60 minute, discharging, it is cooled to room temperature, obtains hydroxylating nylon liquid;
(7) by above-mentioned sulfonic acid guanidine grafting carbon nanotube, ring three phosphonitrile grafting carbon nanotube, the mixing of hydroxylating nylon liquid, at 87-90
Preheat 4-6 minute at DEG C, rise high-temperature and be 155-160 DEG C, insulated and stirred 3-4 minute, filters, is washed by precipitation oxolane
2-3 time, it is vacuum dried 30-40 minute at being placed in 70-80 DEG C, obtains modified nylon CNT;
(8) above-mentioned modified nylon CNT is mixed with remaining each raw material, stir, dry, put into screw extruder and melt
Melt extrusion, cool down, sieve, obtain described mass.
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CN109777007A (en) * | 2019-02-22 | 2019-05-21 | 华研(佛山)纳米材料有限公司 | A kind of carbon nanotube polyvinyl chloride composite materials and preparation method thereof |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107141633A (en) * | 2017-04-27 | 2017-09-08 | 安徽玉发塑业有限公司 | A kind of composite fibre toughening polyvinyl chloride plastic tube and preparation method thereof |
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