CN105624826B - A kind of polyoxymethylene conductive fiber and preparation method thereof - Google Patents
A kind of polyoxymethylene conductive fiber and preparation method thereof Download PDFInfo
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- CN105624826B CN105624826B CN201610051464.4A CN201610051464A CN105624826B CN 105624826 B CN105624826 B CN 105624826B CN 201610051464 A CN201610051464 A CN 201610051464A CN 105624826 B CN105624826 B CN 105624826B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
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Abstract
The invention provides a kind of polyoxymethylene conductive fiber and preparation method thereof.Described polyoxymethylene conductive fiber, it is characterised in that including：The mass parts of polyoxymethylene 100, the mass parts of conductive black 11~29 of surface grafting formal, 0.1~10 part of mass parts of antioxidant and the mass parts of bulking agent 0.1~10.The polyoxymethylene conductive fiber of the present invention can still have good durable conductive effect under the low humidity, expand the purposes and application field of polyoxymethylene fiber.And compared to directly by the method for conductive black and polyoxymethylene blend melt spinning, in the polyoxymethylene conductive fiber that preparation method in accordance with the present invention is obtained, because conductive black has been grafted formal short chain, compatibility with polyoxymethylene matrix is more preferable, disperse evenly, electric conductivity is more excellent.
Description
Technical field
The invention belongs to chemical products preparation field, and in particular to a kind of polyoxymethylene conductive fiber and its preparation side
Method.
Background technology
Polyoxymethylene is a kind of engineering plastics of excellent performance, with very high intensity and hardness, and wider uses temperature
Excellent performance, including corrosion-resistant, high intensity and preferable size conservation rate etc. can be kept in degree and humidity range, so poly-
Oxymethylene is also referred to as " plastic-steel ", is widely used in many-sided field such as machinework, auto parts and components.With polyoxymethylene
For raw material, the polyoxymethylene fiber of preparation has high-strength and high-modulus, excellent chemical resistance and creep-resistant property, can be extensive
For the reinforcing fiber of the matrixes such as cement base, plastics, rubber, and hawser, fishing net, screen pack etc..But polyoxymethylene is fine
The characteristics of dimension is due to itself chemical constitution, resistivity is very high, belongs to electrically insulating material.
Conductive fiber typically refer in normal conditions (20 degrees Celsius, 65% relative humidity), ratio resistance 107Ω·m
Following fiber, this fiber has good electric conductivity and durability, particularly can keep excellent conduction under the low humidity
The fiber of property, has very big application prospect in the field such as industrial, civilian.Improving the common methods of conducting polymer rate at present is
Add conductive black, direct fabrics in polymeric matrix, or be prepared into the conductive agglomerate of phase emergencing copolymer and then spin and lead
Electric fiber.For example：Patent《A kind of Polyester-fiber conductive masterbatch pre-dispersion and preparation method thereof》(application number
201310139104.6) a kind of conductive agglomerate of suitable polyester matrix is disclosed, using powder silane coupler KH-302, metal
Soap and paraffin hydro carbons composite diffusion lubricant are combined with conductive black, improve conductive black scattered equal in polyester matrix
Even property；Patent《Application process and clothes master batch of conductive fiber of the carbon black in master batch of conductive fiber》(application number
200910015717.2) a kind of application method of carbon black in master batch of conductive fiber is disclosed, using by monoalkoxy class metatitanic acid
Ester and the burnt compound obtained titante coupling agent of phosphide type titanate esters, using atoleine as diluent, to conductive black
It is modified, to increase conductive black in vector resin (polypropylene, polyethylene terephthalate, polyamide and polypropylene
Nitrile) in dispersiveness, so as to improve the electric conductivity of final fiber.Mention entering conductive black using coupling agent in above-mentioned patent
Row modification, it is therefore an objective to connect organic matter short chain on conductive black surface in the way of covalently or non-covalently, such as alkyl chain and
Polyester chain etc., so that the compatibility of conductive black and polymeric matrix is improved, point of the increase conductive black in polymeric matrix
Dissipate uniformity, it is to avoid reunite, so that conductive black can farthest play electric conductivity.But it is due to polyoxymethylene
The compatibility of the polymer segment such as the reason for itself chemical constitution, polyoxymethylene and polyester, polyolefin, polyamide is all very poor,
Can occur significantly split-phase, conductive black is after coupling agent treatment, and its dispersiveness in polyoxymethylene matrix can not be obtained
To effectively improving, so the method for coupling agent treatment conductive black is come for polyoxymethylene resin and polyoxymethylene fiber
Say that effect is limited.
The relevant report of polyoxymethylene resin conductive performance is improved using carbon black at present.Patent《Conductive polyformaldehyde
Material》(application number 02137916.5) by polyformaldehyde, carbon black and dibutyl ester plasticizer mix and then granulation obtains conductive poly-
Formaldehyde materials.Patent《Electroconductive resin compound based on polyformaldehyde and highly structured carbon black》(application number 200780017825.2)
It is middle by by polyformaldehyde, PAG, metal oxide, high structured particulate carbon black and comb-shaped polymer constitute it is compound
Thing, carries out melt-kneaded, obtains electroconductive resin compound.Patent《Static dissipative polyacetal compositions》(application number
200780043435.2) a kind of poly- first being made up of polyformaldehyde, conductive carbon black, substituted urea and hindered amine as light stabilizer is described
Aldehyde compositions, with good static dissipative energy.Patent《Conductive polyformaldehyde material and preparation method thereof》(application number
201210297007.5) a kind of conductive polyformaldehyde material is described, by polyformaldehyde, polytetrafluoroethylene (PTFE), dibutyl ester, carbon black, benzene second
Alkylene phenol, antioxidant 1010 and calcium silicates are melted after drying, super mixer mixing by double-screw extruding pelletizing machine
It is made.Patent《Novel conductive polyformaldehyde material and preparation method》Conductive polyformaldehyde disclosed in (application number 201310138131.1)
Material, is made up of acetal resin, antistatic additive and conductive agent, and wherein antistatic additive is multiple by polyvinyl alcohol, Sulfonates, amine salt
Formed with one or both of class and stearic acid and above combinations of substances, conductive agent is fine by CNT, carbon fiber, metal
One or both of dimension, metal whisker and conductive black and above combinations of substances are formed.Above-mentioned report is all by polyoxy
Conductive black is added in methylene resin and the conductance of matrix is improved, and utilizes some existing polymer and small organic molecule
Conductive black in the base scattered is assisted, not according to the chemical constitution feature of polyoxymethylene matrix, to conductive black
Targetedly it is modified, so conductive black and polyoxymethylene matrix poor compatibility are not solved, in blending processing
Easily reunite and can not be dispersed, it is difficult to form effective this fundamental issue of conductive network passage.In addition, with the addition of gold
The polymer of the conducting mediums such as category fiber, carbon fiber is not suitable for spinning fibre.Therefore existing technical deficiency how is overcome
Be current technical field of macromolecules particularly polyoxymethylene conductive fiber field urgent need to resolve the problem of.
The content of the invention
It is an object of the invention to overcome the shortcomings of prior art exist there is provided a kind of polyoxymethylene conductive fiber and
Its preparation method, the polyoxymethylene fiber can still have good durable conductive effect under the low humidity, expand poly-
The purposes and application field of Oxymethylene fiber.
In order to solve the above-mentioned technical problem, the technical scheme is that：
A kind of polyoxymethylene conductive fiber, it is characterised in that including：The mass parts of polyoxymethylene 100, surface grafting contracting
The mass parts of conductive black 11~29 of formaldehyde, 0.1~10 part of mass parts of antioxidant and the mass parts of bulking agent 0.1~10.
Preferably, described antioxidant is at least one of antioxidant 1010 and antioxidant 1076.
Preferably, described bulking agent is one kind in calcium stearate, magnesium stearate and vinyl bis-stearamides (EBS)
Or two kinds of mixtures arbitrarily matched.
Preferably, the volume resistivity of described polyoxymethylene conductive fiber is 102~106Ω·m。
Present invention also offers the preparation method of above-mentioned polyoxymethylene conductive fiber, it is characterised in that including：
Step a：Oxidizing agent solution and conductive black (CB) are added in reaction vessel, when reacting one section at a certain temperature
Between, after reaction terminates, room temperature is cooled to, filters, uses deionized water cyclic washing, until filtrate is in neutrality, filter residue is filtrated to get,
By filter residue and drying, the conductive black (CB-OH) of Surface Oxidation Modification is obtained；
Step b：By the conductive black (CB-OH) of Surface Oxidation Modification and formal oligomer of the structure as shown in formula (I)
Add in reaction vessel, stir under nitrogen protection, react at a certain temperature after a period of time, filtering obtains filter residue, is used in combination
Deionized water cyclic washing, dries after a period of time, obtains the conductive black (CB- of surface grafting formal at a certain temperature
(CH2O)n)；
Step c. by the conductive black of the surface grafting formal of gained and polyoxymethylene, antioxidant and bulking agent press than
Example mixing, by single screw rod or double screw extruder melt spinning, is cooled and shaped, and through drafting forming, it is sub- that winding obtains polyoxy
Methyl conductive fiber.
Preferably, the oxidizing agent solution in described step a is the mixed solution of salpeter solution and aqueous hydrogen peroxide solution.
It is highly preferred that the concentration of described salpeter solution is 30%~50%, the concentration of hydrogenperoxide steam generator for 10%~
30%, the volume ratio of salpeter solution and hydrogenperoxide steam generator is 1: 1~1: 3.
Preferably, the rate of charge of described oxidizing agent solution and conductive black is：Every 100 milliliters of oxidizing agent solutions add 5
~10 grams of conductive blacks.
Preferably, the reaction in described step a is carried out under conditions of mechanical agitation and oil bath heating.
It is highly preferred that described step a oil bath temperature is 40~90 degrees Celsius, the reaction time is 30~90 minutes.
Preferably, the drying temperature in described step a is 80~110 degrees Celsius, and drying time is 2~24 hours.
Preferably, in described formula (I), n is integer, and the scope of n values is 1≤n≤15.
Preferably, in described step b, the conductive black (CB-OH) of Surface Oxidation Modification and the matter of formal oligomer
The scope for measuring ratio is 1: 10~1: 20.
Preferably, described step b reaction temperature is 30~120 degrees Celsius, and the reaction time is 30~120 minutes.
Preferably, 5~10 washings are carried out in described step b to filter residue with deionized water.Described drying temperature is
In 60~120 degree Celsius ranges, drying time is 5~48 hours.
Preferably, in described step c, the single screw rod or double screw extruder processing temperature used is 120~250 Celsius
Degree, drawing temperature is 60~210 degrees Celsius, and drafting multiple is 5~10 times, and winding speed is 200~2000 ms/min.
The principle of the present invention is that conductive black (CB) obtains the carbon black (CB- that surface carries hydroxyl after oxidizing
OH), then reacted again with formal oligomer, polyoxymethylene short chain in grafting obtains the conductive charcoal of surface grafting formal
Black (CB- (CH2O)n), it is mixed in proportion with polyoxymethylene, antioxidant and bulking agent, squeezed by single screw rod or twin-screw
Go out machine and carry out spinning, polyoxymethylene conductive fiber is made.
Compared with prior art, the present invention has the advantages that：
1st, preparation technology route of the present invention is shorter, all raw material commercializations, it is possible to achieve prepared by large-scale production；
2nd, with by adding hydrophilic compounds, improving fiber hygroscopicity so as to which anlistatig method is compared, this method makes
Conductive black is as conductive agent, and conductive effect is not influenceed by ambient humidity, can still have under the low humidity well
Durable conductive effect, expands its application field significantly.
3rd, compared to directly by conductive black and polyoxymethylene through single screw rod or twin-screw co-blended spinning, according to the present invention
In the polyoxymethylene conductive fiber that described preparation method is obtained, because conductive black has been grafted formal short chain, with polyoxy
The compatibility of methylene matrix more preferably, is disperseed evenly, electric conductivity is more excellent.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
A kind of polyoxymethylene conductive fiber, by the mass parts of polyoxymethylene 100, the conductive black of surface grafting formal
(CB-(CH2O)1) 13 mass parts, the mass parts of antioxidant 1010 1, the mass parts of calcium stearate 2.5 composition.Its preparation method is：
Step a：According to the ratio of volume 1: 1, the salpeter solution that concentration is 30% and the peroxide that concentration is 10% are taken respectively
Change hydrogen solution, progress is mixed to get oxidizing agent solution and adds reaction vessel, and 5 grams are added according to every 100 milliliters of oxidizing agent solutions
The rate of charge of conductive black, addition conductive black (CB), reaction is carried out under conditions of mechanical agitation and oil bath heating, oil bath temperature
Spend for 40 degrees Celsius, after reacting 45 minutes, be cooled to room temperature, filter and simultaneously use deionized water cyclic washing, until filtrate is in neutrality
Afterwards, filter residue is filtrated to get, filter residue is dried at 80 degrees celsius 5 hours, the conductive black (CB- of surface oxidation is obtained
OH)。
Step b：From the formal oligomer of (n=1) structure such as formula (I) Suo Shi, according to the conductive black of surface oxidation
(CB-OH) with the rate of charge of formal oligomer mass ratio 1: 10, both is added into reaction vessel, stirred under nitrogen protection
Mix, after reacting 60 minutes at 60 c, be filtrated to get filter residue, and filter residue is washed with deionized 5 times, it is dry at 80 degrees Celsius
After dry 10 hours, the conductive black (CB- (CH of surface grafting formal are obtained2O)1)。
Step c：Take polyoxymethylene (the equal relative molecular weight 80,000 of number) 100 mass parts, the conductive charcoal of surface grafting formal
Black (CB- (CH2O)1) 13 mass parts, the mass parts of antioxidant 1010 1, the mass parts of calcium stearate 2.5, be well mixed, pass through single spiral shell
Bar extruder melt spinning, the processing temperature of single screw extrusion machine is controlled between 120~220 degrees Celsius, at room temperature cross air blasting
It is cooled and shaped, and through drafting forming, drawing temperature is 80 degrees Celsius degrees Celsius, drafting multiple is 5 times, and winding obtains polyoxy methylene
Base conductive fiber, winding speed is 600 ms/min.
Embodiment 2
A kind of polyoxymethylene conductive fiber, by the mass parts of polyoxymethylene 100, the conductive black of surface grafting formal
13 mass parts, the mass parts of antioxidant 1010 2, the mass parts of calcium stearate 3 composition.Its preparation method is：
Step a：According to the ratio of volume 1: 1.5, the salpeter solution that concentration is 35% and the mistake that concentration is 15% are taken respectively
Hydrogen peroxide solution, progress is mixed to get oxidizing agent solution and adds reaction vessel, and 6 are added according to every 100 milliliters of oxidizing agent solutions
The rate of charge of gram conductive black, addition conductive black (CB), reaction is carried out under conditions of mechanical agitation and oil bath heating, oil bath
Temperature is 50 degrees Celsius, after reacting 60 minutes, is cooled to room temperature, filters and simultaneously uses deionized water cyclic washing, until during filtrate is in
After property, filter residue is filtrated to get, filter residue is dried 10 hours under 85 degrees Celsius, the conductive black (CB- of surface oxidation is obtained
OH)。
Step b：From the formal oligomer of (n=2) structure such as formula (I) Suo Shi, according to the conductive black of surface oxidation
(CB-OH) with the rate of charge of formal oligomer mass ratio 1: 15, both is added into reaction vessel, stirred under nitrogen protection
Mix, after reacting 90 minutes at 80 degrees celsius, be filtrated to get filter residue, and filter residue is washed with deionized 8 times, it is dry at 80 degrees Celsius
After dry 15 hours, the conductive black (CB- (CH of surface grafting formal are obtained2O)2)。
Step c：Take polyoxymethylene (the equal relative molecular weight 100,000 of number) 100 mass parts, the conduction of surface grafting formal
The mass parts of carbon black 13, the mass parts of antioxidant 1010 2, the mass parts of calcium stearate 3 are well mixed, melted by single screw extrusion machine
Spinning, the processing temperature of single screw extrusion machine is controlled between 150~210 degrees Celsius, and cross air blasting is cooled and shaped at room temperature, and is passed through
Drafting forming, drawing temperature is 90 degrees Celsius, and drafting multiple is 6.2 times, and winding obtains polyoxymethylene conductive fiber, winding speed
Spend for 550 ms/min.
Embodiment 3
A kind of polyoxymethylene conductive fiber, by the mass parts of polyoxymethylene 100, the conductive black of surface grafting formal
15 mass parts, antioxidant 1010,2.5 mass parts, the mass parts of calcium stearate 3.5 composition.Its preparation method is：
Step a：According to the ratio of volume 1: 2, the salpeter solution that concentration is 40% and the peroxide that concentration is 20% are taken respectively
Change hydrogen solution, progress is mixed to get oxidizing agent solution and adds reaction vessel, and 7 grams are added according to every 100 milliliters of oxidizing agent solutions
The rate of charge of conductive black, addition conductive black (CB), reaction is carried out under conditions of mechanical agitation and oil bath heating, oil bath temperature
Spend for 60 degrees Celsius, after reacting 90 minutes, be cooled to room temperature, filter and simultaneously use deionized water cyclic washing, until filtrate is in neutrality
Afterwards, filter residue is filtrated to get, filter residue is dried 15 hours under 90 degrees Celsius, the conductive black (CB- of surface oxidation is obtained
OH)。
Step b：From the formal oligomer of (n=3) structure such as formula (I) Suo Shi, according to the conductive black of surface oxidation
(CB-OH) with the rate of charge of formal oligomer mass ratio 1: 10, both is added into reaction vessel, stirred under nitrogen protection
Mix, after being reacted 100 minutes under 90 degrees Celsius, be filtrated to get filter residue, and filter residue is washed with deionized 7 times, at 90 degrees Celsius
After drying 24 hours, the conductive black (CB- (CH of surface grafting formal are obtained2O)3)。
Step c：Take polyoxymethylene (the equal relative molecular weight 150,000 of number) 100 mass parts, the conduction of surface grafting formal
The mass parts of carbon black 15, antioxidant 1010,2.5 mass parts, the mass parts of calcium stearate 3.5 are well mixed, pass through double screw extruder
Melt spinning, the processing temperature of single screw extrusion machine is controlled between 120~250 degrees Celsius, and cross air blasting is cooled and shaped at room temperature,
And through drafting forming, drawing temperature is 110 degrees Celsius, and drafting multiple is 7.3, and winding obtains polyoxymethylene conductive fiber, is rolled up
It it is 530 ms/min around speed.
Embodiment 4
A kind of polyoxymethylene conductive fiber, by the mass parts of polyoxymethylene 100, the conductive black of surface grafting formal
20 mass parts, the mass parts of antioxidant 1076 3, the mass parts of magnesium stearate 4 composition.Its preparation method is：
Step a：According to the ratio of volume 1: 2.5, the salpeter solution that concentration is 45% and the mistake that concentration is 25% are taken respectively
Hydrogen peroxide solution, progress is mixed to get oxidizing agent solution and adds reaction vessel, is added according to every 100 milliliters of oxidizing agent solutions
The rate of charge of 7.5 grams of conductive blacks, addition conductive black (CB), reaction is carried out under conditions of mechanical agitation and oil bath heating,
Oil bath temperature is 70 degrees Celsius, after reacting 75 minutes, is cooled to room temperature, filters and simultaneously uses deionized water cyclic washing, until filtrate
After neutrality, filter residue is filtrated to get, filter residue is dried 20 hours under 95 degrees Celsius, the conductive black of surface oxidation is obtained
(CB-OH)。
Step b：From the formal oligomer of (n=4) structure such as formula (I) Suo Shi, according to the conductive black of surface oxidation
(CB-OH) with the rate of charge of formal oligomer mass ratio 1: 15, both is added into reaction vessel, stirred under nitrogen protection
Mix, after being reacted 90 minutes under 100 degrees Celsius, be filtrated to get filter residue, and filter residue is washed with deionized 9 times, at 100 degrees Celsius
After drying 36 hours, the conductive black (CB- (CH of surface grafting formal are obtained2O)4)。
Step c：Take polyoxymethylene (the equal relative molecular weight 9.5 ten thousand of number) 100 mass parts, the conduction of surface grafting formal
The mass parts of carbon black 20, the mass parts of antioxidant 1076 3, the mass parts of magnesium stearate 4 are well mixed, melted by single screw extrusion machine
Spinning, the processing temperature of single screw extrusion machine is controlled between 140~200 degrees Celsius, and cross air blasting is cooled and shaped at room temperature, and is passed through
Drafting forming, drawing temperature is 110 degrees Celsius, and drafting multiple is 9 times, and winding obtains polyoxymethylene conductive fiber, winding speed
Spend for 600 ms/min.
Embodiment 5
A kind of polyoxymethylene conductive fiber, by the mass parts of polyoxymethylene 100, the conductive black of surface grafting formal
(CB-(CH2O)6) 25 mass parts, the mass parts of antioxidant 1010 2, the mass parts of magnesium stearate 5 composition.Its preparation method is：
Step a：According to the ratio of volume 1: 3, the salpeter solution that concentration is 50% and the peroxide that concentration is 30% are taken respectively
Change hydrogen solution, progress is mixed to get oxidizing agent solution and adds reaction vessel, and 9 grams are added according to every 100 milliliters of oxidizing agent solutions
The rate of charge of conductive black, addition conductive black (CB), reaction is carried out under conditions of mechanical agitation and oil bath heating, oil bath temperature
Spend for 75 degrees Celsius, after reacting 90 minutes, be cooled to room temperature, filter and simultaneously use deionized water cyclic washing, until filtrate is in neutrality
Afterwards, filter residue is filtrated to get, filter residue is dried 24 hours under 110 degrees Celsius, the conductive black (CB- of surface oxidation is obtained
OH)。
Step b：From the formal oligomer of (n=6) structure such as formula (I) Suo Shi, according to the conductive black of surface oxidation
(CB-OH) with the rate of charge of formal oligomer mass ratio 1: 20, both is added into reaction vessel, stirred under nitrogen protection
Mix, after being reacted 120 minutes under 110 degrees Celsius, be filtrated to get filter residue, and filter residue is washed with deionized 10 times, it is Celsius 110
After degree is dried 48 hours, the conductive black (CB- (CH of surface grafting formal are obtained2O)6)。
Step c：Take polyoxymethylene (the equal relative molecular weight 60,000 of number) 100 mass parts, the conductive charcoal of surface grafting formal
Black (CB- (CH2O)6) 25 mass parts, the mass parts of antioxidant 1076 1, the mass parts of magnesium stearate 5, be well mixed, pass through single screw rod
Extruder melt spinning, the processing temperature of single screw extrusion machine is controlled between 180~215 degrees Celsius, side-blown air-cooled at room temperature
But it is molded, and through drafting forming, drawing temperature is 95 degrees Celsius, drafting multiple is 4.9 times, and it is conductive that winding obtains polyoxymethylene
Fiber, winding speed is 650 ms/min.
Comparative example 1
Take the mass parts of polyoxymethylene 100, the mass parts of conductive black 15, antioxidant 1010,3 mass parts, the matter of calcium stearate 5
Part is measured, uniform mixing by single screw extrusion machine melt spinning, at room temperature cross air blasting cooling and shaping, and through drafting forming, is wound
Obtain fiber；The processing temperature of single screw extrusion machine is controlled between 120~230 degrees Celsius, and drawing temperature is 90 degrees Celsius, is led
It is 5.5 times to stretch multiple, and winding speed is 500 ms/min.
Comparative example 2
Take the mass parts of polyoxymethylene 100, the mass parts of conductive black 13, antioxidant 1010,2 mass parts, calcium stearate 5.5
Mass parts, uniform mixing, by single screw extrusion machine melt spinning, cross air blasting is cooled and shaped, and through drafting forming, winding is obtained
Fiber；The processing temperature of single screw extrusion machine is controlled between 120~230 degrees Celsius, and drawing temperature is 100 degrees Celsius, drawing-off
Multiple is 6 times, and winding speed is 350 ms/min.
Comparative example 3
Take the mass parts of polyoxymethylene 100, the mass parts of conductive black 17, antioxidant 1010,3 mass parts, calcium stearate 2.5
Mass parts, uniform mixing, by single screw extrusion machine melt spinning, cross air blasting is cooled and shaped at room temperature, and through drafting forming, is rolled up
Around obtaining fiber；The processing temperature of single screw extrusion machine is controlled between 120~230 degrees Celsius, and drawing temperature is 110 Celsius
Degree, drafting multiple is 6 times, and winding speed is 550 ms/min.
The electric conductivity of each embodiment and comparative example is the results detailed in Table 1.
The polyoxymethylene filamentary conductive of table 1 can compare
By the comparison of embodiment 1~5 and comparative example 1~3, the ratio resistance of the fiber in embodiment is than the fibre in comparative example
The electronics of dimension is lower, because common conductive carbon black and polyoxymethylene matrix poor compatibility, work in-process are easily reunited, it is difficult
With dispersed, it is impossible to form effective conductive network passage；By modified to conductive black, conductive charcoal is greatly improved
The black compatibility with polyoxymethylene matrix, adds the dispersiveness of conductive black, so as to form effective conductive channel
Network, improves the conductive capability of polyoxymethylene conductive fiber.
Claims (8)
1. a kind of preparation method of polyoxymethylene conductive fiber, described polyoxymethylene conductive fiber, including：Polyoxy methylene
The mass parts of base 100, the mass parts of conductive black 11 ~ 29 of surface grafting formal, 0.1 ~ 10 part of mass parts of antioxidant and bulking agent
0.1 ~ 10 mass parts, it is characterised in that including：
Step a：Oxidizing agent solution and conductive black are added in reaction vessel, at a certain temperature reaction a period of time, reaction
After end, room temperature is cooled to, filters, uses deionized water cyclic washing, until filtrate is in neutrality, filter residue is filtrated to get, by filter residue
Dry, obtain the conductive black of Surface Oxidation Modification；
Step b：By the conductive black of Surface Oxidation Modification and structure such as formula（I）Shown formal oligomer adds reaction vessel
In, stir, react at a certain temperature after a period of time under nitrogen protection, filtering obtains filter residue, and with deionized water repeatedly
Washing, dries after a period of time, obtains the conductive black of surface grafting formal at a certain temperature；
（I）
Described formula（I）In, n is integer, and the scope of n values is 1≤n≤15；
Step c. by the conductive black of the surface grafting formal of gained and polyoxymethylene, antioxidant and bulking agent in proportion
Mixing, by single screw rod or double screw extruder melt spinning, is cooled and shaped, and through drafting forming, winding obtains polyoxy methylene
Base conductive fiber.
2. the preparation method of polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that described antioxidant is
At least one of antioxidant 1010 and antioxidant 1076；Described bulking agent is that calcium stearate, magnesium stearate and vinyl are double
The mixture that one or both of stearmide is arbitrarily matched.
3. the preparation method of polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that described polyoxy methylene
The volume resistivity of base conductive fiber is 102~106Ω·m。
4. the preparation method of polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that in described step a
Oxidizing agent solution for salpeter solution and aqueous hydrogen peroxide solution mixed solution.
5. the preparation method of polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that described oxidant is molten
The rate of charge of liquid and conductive black is：Every 100 milliliters of oxidizing agent solutions add 5 ~ 10 grams of conductive blacks.
6. the preparation method of polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that in described step a
Reaction carried out under conditions of mechanical agitation and oil bath heating.
7. the preparation method of polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that in described step b,
The scope of the conductive black of Surface Oxidation Modification and the mass ratio of formal oligomer is 1:10~1:20.
8. the preparation method of polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that in described step c,
The single screw rod or double screw extruder processing temperature used is 120 ~ 250 degrees Celsius, and drawing temperature is 60 ~ 210 degrees Celsius, drawing-off
Multiple is 5 ~ 10 times, and winding speed is 200 ~ 2000 ms/min.
Priority Applications (1)
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| JPS53111348A (en) * | 1977-03-10 | 1978-09-28 | Asahi Chem Ind Co Ltd | Polyoxymethylene composition |
| JP3029204B2 (en) * | 1990-04-16 | 2000-04-04 | 旭化成工業株式会社 | Highly conductive polyoxymethylene resin molded body |
| US5902517A (en) * | 1996-10-28 | 1999-05-11 | Cabot Corporation | Conductive polyacetal composition |
| US6852790B2 (en) * | 2001-04-06 | 2005-02-08 | Cabot Corporation | Conductive polymer compositions and articles containing same |
| CN1234766C (en) * | 2002-07-04 | 2006-01-04 | 吴建业 | Conductive polyformaldehyde material |
| US7396492B2 (en) * | 2006-03-30 | 2008-07-08 | Kenneth Leon Price | Electrically conductive resin compounds based on polyoxymethylene and highly structured carbon black |
| US8128845B2 (en) * | 2006-11-22 | 2012-03-06 | E.I. Du Pont De Nemours And Company | Static dissipative polyacetal compositions |
| CN103627134A (en) * | 2012-08-20 | 2014-03-12 | 上海盈致橡塑制品有限公司 | Conductive polyformaldehyde material and preparation method thereof |
| JP6334842B2 (en) * | 2012-12-20 | 2018-05-30 | 旭化成株式会社 | Conductive polyacetal resin composition pellets and method for producing the same |
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