CN105624826A - Polyoxymethylene conductive fibers and preparation method thereof - Google Patents
Polyoxymethylene conductive fibers and preparation method thereof Download PDFInfo
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- CN105624826A CN105624826A CN201610051464.4A CN201610051464A CN105624826A CN 105624826 A CN105624826 A CN 105624826A CN 201610051464 A CN201610051464 A CN 201610051464A CN 105624826 A CN105624826 A CN 105624826A
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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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- 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
- 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
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The invention provides polyoxymethylene conductive fibers and a preparation method thereof. The polyoxymethylene conductive fibers are characterized by being prepared from the following components in parts by mass: 100 parts of polyoxymethylene, 11-29 parts of conductive carbon black grafted with formal on the surface, 0.1-10 parts of an antioxidant and 0.1-10 parts of a bulking agent. The polyoxymethylene conductive fibers prepared by the invention still have a good durable conductive effect under low humidity, and usage and application fields of the polyoxymethylene fibers are expanded. Compared with a method for directly commixing, fusing and spinning the conductive carbon black and the polyoxymethylene, the conductive carbon black in the polyoxymethylene conductive fibers prepared by the preparation method provided by the invention is grafted with formal short chains, so that the conductive carbon black has relatively good compatibility with a polyoxymethylene base body; and the dispersion is relatively uniform and the conductivity is relatively excellent.
Description
Technical field
The invention belongs to chemical products preparation field, be specifically related to a kind of polyoxymethylene conductive fiber and preparation method thereof.
Background technology
Polyoxymethylene is the engineering plastics of a kind of excellent performance, there is significantly high intensity and hardness, excellent performance can be kept within the scope of wider use temperature and humidity, including corrosion-resistant, high intensity and good size conservation rate etc., so polyoxymethylene is also referred to as " plastic-steel ", it 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 widely used for the fortifying fibre of the matrixes such as cement based, plastics, rubber and hawser, fishing net, drainage screen etc. But polyoxymethylene fiber is due to self chemical constitution, and resistivity is significantly high, belongs to electrically insulating material.
Conductive fiber typically refers in normal conditions (20 degrees Celsius, 65% relative humidity), than resistance 107The fiber of below �� m, this fibrid has good electric conductivity and durability, particularly can keep the fiber of superior electrical conductivity under the low humidity, has very big application prospect in the field such as industrial, civilian. The common methods improving conducting polymer rate at present is that then interpolation conductive black, direct fabrics, or the conductive agglomerate preparing into phase emergencing copolymer spin conductive fiber in polymeric matrix. Such as: patent " a kind of Polyester-fiber conductive masterbatch pre-dispersion and preparation method thereof " (application number 201310139104.6) discloses the conductive agglomerate of a kind of applicable polyester matrix, adopt powder body silane coupler KH-302, metallic soap and paraffin hydro carbons composite diffusion lubricant and conductive black to carry out compound, improve conductive black dispersing uniformity in polyester matrix; Patent " white carbon black application process in master batch of conductive fiber and clothing master batch of conductive fiber " (application number 200910015717.2) discloses a kind of white carbon black using method in master batch of conductive fiber, use the titante coupling agent obtained by monoalkoxy class titanate esters with burnt phosphide type titanate esters compound, use liquid paraffin as diluent, conductive black is modified, to increase conductive black dispersibility in vector resin (polypropylene, polyethylene terephthalate, polyamide and polyacrylonitrile), thus improving the electric conductivity of final fiber. Above-mentioned patent is all mentioned use coupling agent be modified conductive black processing, purpose is to connect Organic substance short chain on conductive black surface in the way of covalently or non-covalently, such as alkyl chain and polyester chain etc., thus improving the compatibility of conductive black and polymeric matrix, increase conductive black dispersing uniformity in polymeric matrix, avoid reuniting, so that conductive black can farthest play electric conductivity. But the reason due to polyoxymethylene self chemical constitution, the compatibility of the polymer segments such as polyoxymethylene and polyester, polyolefin, polyamide is all very poor, point phase significantly can be there is, conductive black is after coupling agent treatment, its dispersibility in polyoxymethylene matrix cannot be effectively improved, so the method for coupling agent treatment conductive black is for limited efficiency polyoxymethylene resin and polyoxymethylene fiber.
The existing relevant report utilizing white carbon black to improve polyoxymethylene resin conductive performance at present. Polyformaldehyde, white carbon black and dibutyl ester plasticizer are carried out mixing then pelletize and obtain conductive polyformaldehyde material by patent " conductive polyformaldehyde material " (application number 02137916.5). The complex being made up of polyformaldehyde, poly alkylene glycol, metal-oxide, high structured particulate white carbon black and comb-shaped polymer in patent " the electroconductive resin complex based on polyformaldehyde and highly structured white carbon black " (application number 200780017825.2), carry out melt-kneaded, obtain electroconductive resin complex. Patent " static dissipative polyacetal compositions " (application number 200780043435.2) describes a kind of polyformaldehyde composition being made up of polyformaldehyde, conductive carbon black, substituted urea and hindered amine as light stabilizer, has good static dissipative energy. Patent " conductive polyformaldehyde material and preparation method thereof " (application number 201210297007.5) describes a kind of conductive polyformaldehyde material; by polyformaldehyde, politef, dibutyl ester, white carbon black, styrenated phenol, antioxidant 1010 and calcium silicates after super-dry, super mixer mixing, melted prepared through double-screw extruding pelletizing machine. Conductive polyformaldehyde material disclosed in patent " Novel conductive polyformaldehyde material and preparation method " (application number 201310138131.1), it is made up of acetal resin, antistatic additive and conductive agent, wherein antistatic additive is formed by one or both in polyvinyl alcohol, Sulfonates, the composite class of amine salt and stearic acid and above combinations of substances, and conductive agent is formed by one or both in CNT, carbon fiber, metallic fiber, metal whisker and conductive black and above combinations of substances. Above-mentioned report is all the conductivity improving matrix by adding conductive black in polyoxymethylene resin, some existing polymer and small organic molecule is utilized to assist conductive black dispersion in the base, the not chemical constitution feature according to polyoxymethylene matrix, conductive black is modifiied targetedly, so being not solved by conductive black and polyoxymethylene matrix poor compatibility, blended processing is easily reunited and cannot be dispersed, it is difficult to form effective this fundamental issue of conductive network passage. Additionally, with the addition of the polymer of the conducting medium such as metallic fiber, carbon fiber not to be suitable for spinning fibre. Therefore how overcoming existing technical deficiency is the current technical field of macromolecules problem that particularly solution is needed in polyoxymethylene conductive fiber field badly.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, provide a kind of polyoxymethylene conductive fiber and preparation method thereof, this polyoxymethylene fiber can still have good durable conductive effect under the low humidity, has expanded purposes and the application of polyoxymethylene fiber.
In order to solve above-mentioned technical problem, the technical scheme is that
A kind of polyoxymethylene conductive fiber, it is characterised in that including: polyoxymethylene 100 mass parts, surface grafting formal conductive black 11��29 mass parts, 0.1��10 part of mass parts of antioxidant and bulking agent 0.1��10 mass parts.
Preferably, described antioxidant is at least one in antioxidant 1010 and antioxidant 1076.
Preferably, described bulking agent is the mixture of one or both any proportionings in calcium stearate, magnesium stearate and vinyl bis-stearamides (EBS).
Preferably, the volume resistivity of described polyoxymethylene conductive fiber is 102��106����m��
The preparation method that present invention also offers 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, react a period of time at a certain temperature, after reaction terminates, it is cooled to room temperature, filters, use deionized water cyclic washing, until filtrate is in neutrality, it is filtrated to get filtering residue, by filter residue and drying, obtains the conductive black (CB-OH) of Surface Oxidation Modification;
Step b: the conductive black (CB-OH) of Surface Oxidation Modification and the formal oligomer shown in structure such as formula (I) are added in reaction vessel; stir under nitrogen protection; after reaction a period of time at a certain temperature; filter; obtain filtering residue; and use deionized water cyclic washing, after dry a period of time at a certain temperature, obtain the conductive black (CB-(CH of surface grafting formal2O)n);
The conductive black of the surface grafting formal of gained is mixed in proportion by step c. with polyoxymethylene, antioxidant and bulking agent, by single screw rod or double screw extruder melt spinning, cooling molding, and through drafting forming, winding obtains polyoxymethylene conductive fiber.
Preferably, the described mixed solution that the oxidizing agent solution in step a is 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 is 10%��30%, and the volume ratio of salpeter solution and hydrogenperoxide steam generator is 1: 1��1: 3.
Preferably, described oxidizing agent solution with the rate of charge of conductive black is: every 100 milliliters of oxidizing agent solutions add 5��10 grams of conductive blacks.
Preferably, the reaction in described step a carries out when heating in mechanical agitation and oil bath.
It is highly preferred that the oil bath temperature of described step a is 40��90 degrees Celsius, the response time is 30��90 minutes.
Preferably, the described baking temperature in step a is 80��110 degrees Celsius, and drying time is 2��24 hours.
Preferably, in described formula (I), n is integer, n value range for 1��n��15.
Preferably, in described step b, the conductive black (CB-OH) of Surface Oxidation Modification ranges for 1: 10��1: 20 with the mass ratio of formal oligomer.
Preferably, the reaction temperature of described step b is 30��120 degrees Celsius, and the response time is 30��120 minutes.
Preferably, filtering residue is carried out 5��10 times with deionized water by described step b wash. Described baking temperature is in 60��120 degree Celsius range, and drying time is 5��48 hours.
Preferably, in described step c, single screw rod of use or double screw extruder processing temperature are 120��250 degrees Celsius, and drawing temperature is 60��210 degrees Celsius, and drafting multiple is 5��10 times, and winding speed is 200��2000 ms/min.
Principles of the invention is, conductive black (CB) obtains the surface white carbon black (CB-OH) with hydroxyl after oxidizing, then react with formal oligomer again, polyoxymethylene short chain in grafting, obtains the conductive black (CB-(CH of surface grafting formal2O)n), it is mixed in proportion with polyoxymethylene, antioxidant and bulking agent, carries out spinning by single screw rod or double screw extruder, prepare polyoxymethylene conductive fiber.
Compared with prior art, there is advantages that
1, preparation technology route of the present invention is shorter, all raw material commercializations, it is possible to achieve prepared by large-scale production;
2 and by add hydrophilic compounds, improve fiber hygroscopicity thus anlistatig method is compared, the conductive black that this method uses is as conductive agent, conductive effect is not by the impact of ambient humidity, can still have good durable conductive effect under the low humidity, significantly expand its application.
3, compared to directly by conductive black with polyoxymethylene through single screw rod or twin screw co-blended spinning, according in the polyoxymethylene conductive fiber that preparation method of the present invention obtains, the formal short chain due to conductive black grafting, the compatibility with polyoxymethylene matrix is better, evenly, electric conductivity is more excellent in dispersion.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further. Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention. In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
A kind of polyoxymethylene conductive fiber, by polyoxymethylene 100 mass parts, the conductive black (CB-(CH of surface grafting formal2O)1) 13 mass parts, antioxidant 1010 1 mass parts, calcium stearate 2.5 mass parts forms. Its preparation method is:
Step a: according to the ratio of volume 1: 1, take salpeter solution that concentration is 30% respectively and concentration is the hydrogenperoxide steam generator of 10%, carry out being mixed to get oxidizing agent solution and adding reaction vessel, the rate of charge of 5 grams of conductive blacks is added according to every 100 milliliters of oxidizing agent solutions, add conductive black (CB), react and carry out when heating in mechanical agitation and oil bath, oil bath temperature is 40 degrees Celsius, after reacting 45 minutes, it is cooled to room temperature, filter and use deionized water cyclic washing, until filtrate is after neutrality, it is filtrated to get filtering residue, filtering residue is dried at 80 degrees celsius 5 hours, obtain the conductive black (CB-OH) of surface oxidation.
Step b: select the formal oligomer of (n=1) shown in structure such as formula (I); rate of charge according to conductive black (CB-OH) and the formal oligomer mass ratio 1: 10 of surface oxidation; both are added reaction vessel; it is stirred under nitrogen protection; after reacting 60 minutes at 60 c; it is filtrated to get filtering residue; and with deionized water wash filtering residue 5 times; after drying 10 hours at 80 degrees Celsius, obtain the conductive black (CB-(CH of surface grafting formal2O)1)��
Step c: take polyoxymethylene (the equal relative molecular weight 80,000 of number) 100 mass parts, the conductive black (CB-(CH of surface grafting formal2O)1) 13 mass parts, antioxidant 1010 1 mass parts, calcium stearate 2.5 mass parts, mix homogeneously, by single screw extrusion machine melt spinning, the processing temperature of single screw extrusion machine controls between 120��220 degrees Celsius, quenching molding on the downside of room temperature, and through drafting forming, drawing temperature is 80 degrees Celsius degrees Celsius, drafting multiple is 5 times, and winding obtains polyoxymethylene conductive fiber, and winding speed is 600 ms/min.
Embodiment 2
A kind of polyoxymethylene conductive fiber, by polyoxymethylene 100 mass parts, conductive black 13 mass parts of surface grafting formal, antioxidant 1010 2 mass parts, calcium stearate 3 mass parts forms. Its preparation method is:
Step a: according to the ratio of volume 1: 1.5, take salpeter solution that concentration is 35% respectively and concentration is the hydrogenperoxide steam generator of 15%, carry out being mixed to get oxidizing agent solution and adding reaction vessel, the rate of charge of 6 grams of conductive blacks is added according to every 100 milliliters of oxidizing agent solutions, add conductive black (CB), react and carry out when heating in mechanical agitation and oil bath, oil bath temperature is 50 degrees Celsius, after reacting 60 minutes, it is cooled to room temperature, filter and use deionized water cyclic washing, until filtrate is after neutrality, it is filtrated to get filtering residue, filtering residue is dried 10 hours under 85 degrees Celsius, obtain the conductive black (CB-OH) of surface oxidation.
Step b: select the formal oligomer of (n=2) shown in structure such as formula (I); rate of charge according to conductive black (CB-OH) and the formal oligomer mass ratio 1: 15 of surface oxidation; both are added reaction vessel; it is stirred under nitrogen protection; after reacting 90 minutes at 80 degrees celsius; it is filtrated to get filtering residue; and with deionized water wash filtering residue 8 times; after drying 15 hours at 80 degrees Celsius, obtain the conductive black (CB-(CH of surface grafting formal2O)2)��
Step c: take polyoxymethylene (the equal relative molecular weight 100,000 of number) 100 mass parts, conductive black 13 mass parts of surface grafting formal, antioxidant 1010 2 mass parts, calcium stearate 3 mass parts, mix homogeneously, by single screw extrusion machine melt spinning, the processing temperature of single screw extrusion machine controls between 150��210 degrees Celsius, quenching molding on the downside of room temperature, and through drafting forming, drawing temperature is 90 degrees Celsius, drafting multiple is 6.2 times, winding obtains polyoxymethylene conductive fiber, and winding speed is 550 ms/min.
Embodiment 3
A kind of polyoxymethylene conductive fiber, by polyoxymethylene 100 mass parts, conductive black 15 mass parts of surface grafting formal, antioxidant 1010,2.5 mass parts, calcium stearate 3.5 mass parts forms. Its preparation method is:
Step a: according to the ratio of volume 1: 2, take salpeter solution that concentration is 40% respectively and concentration is the hydrogenperoxide steam generator of 20%, carry out being mixed to get oxidizing agent solution and adding reaction vessel, the rate of charge of 7 grams of conductive blacks is added according to every 100 milliliters of oxidizing agent solutions, add conductive black (CB), react and carry out when heating in mechanical agitation and oil bath, oil bath temperature is 60 degrees Celsius, after reacting 90 minutes, it is cooled to room temperature, filter and use deionized water cyclic washing, until filtrate is after neutrality, it is filtrated to get filtering residue, filtering residue is dried 15 hours under 90 degrees Celsius, obtain the conductive black (CB-OH) of surface oxidation.
Step b: select the formal oligomer of (n=3) shown in structure such as formula (I); rate of charge according to conductive black (CB-OH) and the formal oligomer mass ratio 1: 10 of surface oxidation; both are added reaction vessel; it is stirred under nitrogen protection; after reacting 100 minutes under 90 degrees Celsius; it is filtrated to get filtering residue; and with deionized water wash filtering residue 7 times; after drying 24 hours at 90 degrees Celsius, obtain the conductive black (CB-(CH of surface grafting formal2O)3)��
Step c: take polyoxymethylene (the equal relative molecular weight 150,000 of number) 100 mass parts, conductive black 15 mass parts of surface grafting formal, antioxidant 1010,2.5 mass parts, calcium stearate 3.5 mass parts, mix homogeneously, by double screw extruder melt spinning, the processing temperature of single screw extrusion machine controls between 120��250 degrees Celsius, quenching molding on the downside of room temperature, and through drafting forming, drawing temperature is 110 degrees Celsius, drafting multiple is 7.3, winding obtains polyoxymethylene conductive fiber, and winding speed is 530 ms/min.
Embodiment 4
A kind of polyoxymethylene conductive fiber, by polyoxymethylene 100 mass parts, conductive black 20 mass parts of surface grafting formal, antioxidant 1076 3 mass parts, magnesium stearate 4 mass parts forms. Its preparation method is:
Step a: according to the ratio of volume 1: 2.5, take salpeter solution that concentration is 45% respectively and concentration is the hydrogenperoxide steam generator of 25%, carry out being mixed to get oxidizing agent solution and adding reaction vessel, the rate of charge of 7.5 grams of conductive blacks is added according to every 100 milliliters of oxidizing agent solutions, add conductive black (CB), react and carry out when heating in mechanical agitation and oil bath, oil bath temperature is 70 degrees Celsius, after reacting 75 minutes, it is cooled to room temperature, filter and use deionized water cyclic washing, until filtrate is after neutrality, it is filtrated to get filtering residue, filtering residue is dried 20 hours under 95 degrees Celsius, obtain the conductive black (CB-OH) of surface oxidation.
Step b: select the formal oligomer of (n=4) shown in structure such as formula (I); rate of charge according to conductive black (CB-OH) and the formal oligomer mass ratio 1: 15 of surface oxidation; both are added reaction vessel; it is stirred under nitrogen protection; after reacting 90 minutes under 100 degrees Celsius; it is filtrated to get filtering residue; and with deionized water wash filtering residue 9 times; after drying 36 hours at 100 degrees Celsius, obtain the conductive black (CB-(CH of surface grafting formal2O)4)��
Step c: take polyoxymethylene (the equal relative molecular weight 9.5 ten thousand of number) 100 mass parts, conductive black 20 mass parts of surface grafting formal, antioxidant 1076 3 mass parts, magnesium stearate 4 mass parts, mix homogeneously, by single screw extrusion machine melt spinning, the processing temperature of single screw extrusion machine controls between 140��200 degrees Celsius, quenching molding on the downside of room temperature, and through drafting forming, drawing temperature is 110 degrees Celsius, drafting multiple is 9 times, winding obtains polyoxymethylene conductive fiber, and winding speed is 600 ms/min.
Embodiment 5
A kind of polyoxymethylene conductive fiber, by polyoxymethylene 100 mass parts, the conductive black (CB-(CH2O) of surface grafting formal6) 25 mass parts, antioxidant 1010 2 mass parts, magnesium stearate 5 mass parts forms. Its preparation method is:
Step a: according to the ratio of volume 1: 3, take salpeter solution that concentration is 50% respectively and concentration is the hydrogenperoxide steam generator of 30%, carry out being mixed to get oxidizing agent solution and adding reaction vessel, the rate of charge of 9 grams of conductive blacks is added according to every 100 milliliters of oxidizing agent solutions, add conductive black (CB), react and carry out when heating in mechanical agitation and oil bath, oil bath temperature is 75 degrees Celsius, after reacting 90 minutes, it is cooled to room temperature, filter and use deionized water cyclic washing, until filtrate is after neutrality, it is filtrated to get filtering residue, filtering residue is dried 24 hours under 110 degrees Celsius, obtain the conductive black (CB-OH) of surface oxidation.
Step b: select the formal oligomer of (n=6) shown in structure such as formula (I); rate of charge according to conductive black (CB-OH) and the formal oligomer mass ratio 1: 20 of surface oxidation; both are added reaction vessel; it is stirred under nitrogen protection; after reacting 120 minutes under 110 degrees Celsius; it is filtrated to get filtering residue; and with deionized water wash filtering residue 10 times; after drying 48 hours at 110 degrees Celsius, obtain the conductive black (CB-(CH of surface grafting formal2O)6)��
Step c: take polyoxymethylene (the equal relative molecular weight 60,000 of number) 100 mass parts, the conductive black (CB-(CH2O) of surface grafting formal6) 25 mass parts, antioxidant 1076 1 mass parts, magnesium stearate 5 mass parts, mix homogeneously, by single screw extrusion machine melt spinning, the processing temperature of single screw extrusion machine controls between 180��215 degrees Celsius, quenching molding on the downside of room temperature, and through drafting forming, drawing temperature is 95 degrees Celsius, drafting multiple is 4.9 times, and winding obtains polyoxymethylene conductive fiber, and winding speed is 650 ms/min.
Comparative example 1
Take polyoxymethylene 100 mass parts, conductive black 15 mass parts, antioxidant 1010,3 mass parts, calcium stearate 5 mass parts, Homogeneous phase mixing, by single screw extrusion machine melt spinning, quenching molding on the downside of room temperature, and through drafting forming, winding obtains fiber; The processing temperature of single screw extrusion machine controls between 120��230 degrees Celsius, and drawing temperature is 90 degrees Celsius, and drafting multiple is 5.5 times, and winding speed is 500 ms/min.
Comparative example 2
Taking polyoxymethylene 100 mass parts, conductive black 13 mass parts, antioxidant 1010,2 mass parts, calcium stearate 5.5 mass parts, Homogeneous phase mixing, by single screw extrusion machine melt spinning, cross air blasting cooling molding, and through drafting forming, winding obtains fiber; The processing temperature of single screw extrusion machine controls between 120��230 degrees Celsius, and drawing temperature is 100 degrees Celsius, and drafting multiple is 6 times, and winding speed is 350 ms/min.
Comparative example 3
Take polyoxymethylene 100 mass parts, conductive black 17 mass parts, antioxidant 1010,3 mass parts, calcium stearate 2.5 mass parts, Homogeneous phase mixing, by single screw extrusion machine melt spinning, quenching molding on the downside of room temperature, and through drafting forming, winding obtains fiber; The processing temperature of single screw extrusion machine controls between 120��230 degrees Celsius, and drawing temperature is 110 degrees Celsius, and 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.
Table 1 polyoxymethylene filamentary conductive can compare
Comparison by embodiment 1��5 with comparative example 1��3, the electronics than the fiber in resistance ratio comparative example of the fiber in embodiment is lower, this is because common conductive white carbon black and polyoxymethylene matrix poor compatibility, work in-process is easily reunited, it is difficult to dispersed, it is impossible to form effective conductive network passage; By conductive black is modified, the compatibility of conductive black and polyoxymethylene matrix is greatly improved, adds the dispersibility of conductive black such that it is able to form effective conductive channel network, improve the conductive capability of polyoxymethylene conductive fiber.
Claims (10)
1. a polyoxymethylene conductive fiber, it is characterised in that including: polyoxymethylene 100 mass parts, surface grafting formal conductive black 11��29 mass parts, 0.1��10 part of mass parts of antioxidant and bulking agent 0.1��10 mass parts.
2. polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that described antioxidant is at least one in antioxidant 1010 and antioxidant 1076; Described bulking agent is the mixture of one or both any proportionings in calcium stearate, magnesium stearate and vinyl bis-stearamides.
3. polyoxymethylene conductive fiber as claimed in claim 1, it is characterised in that the volume resistivity of described polyoxymethylene conductive fiber is 102��106����m��
4. the preparation method of the polyoxymethylene conductive fiber according to any one of claim 1-3, it is characterised in that including:
Step a: oxidizing agent solution and conductive black are added in reaction vessel, react a period of time at a certain temperature, after reaction terminates, it is cooled to room temperature, filters, use deionized water cyclic washing, until filtrate is in neutrality, it is filtrated to get filtering residue, by filter residue and drying, obtains the conductive black of Surface Oxidation Modification;
Step b: the conductive black of Surface Oxidation Modification and the formal oligomer shown in structure such as formula (I) are added in reaction vessel; stir under nitrogen protection; after reaction a period of time at a certain temperature; filter; obtain filtering residue; and use deionized water cyclic washing, after dry a period of time at a certain temperature, obtain the conductive black (CB-(CH of surface grafting formal2O)n);
The conductive black of the surface grafting formal of gained is mixed in proportion by step c. with polyoxymethylene, antioxidant and bulking agent, by single screw rod or double screw extruder melt spinning, cooling molding, and through drafting forming, winding obtains polyoxymethylene conductive fiber.
5. the preparation method of polyoxymethylene conductive fiber as claimed in claim 4, it is characterised in that the described mixed solution that the oxidizing agent solution in step a is salpeter solution and aqueous hydrogen peroxide solution.
6. the preparation method of polyoxymethylene conductive fiber as claimed in claim 4, it is characterised in that described oxidizing agent solution with the rate of charge of conductive black is: every 100 milliliters of oxidizing agent solutions add 5��10 grams of conductive blacks.
7. the preparation method of polyoxymethylene conductive fiber as claimed in claim 4, it is characterised in that the reaction in described step a carries out when heating in mechanical agitation and oil bath.
8. the preparation method of polyoxymethylene conductive fiber as claimed in claim 4, it is characterised in that in described formula (I), n is integer, n value range for 1��n��15.
9. the preparation method of polyoxymethylene conductive fiber as claimed in claim 4, it is characterised in that in described step b, the mass ratio of the conductive black of Surface Oxidation Modification and formal oligomer range for 1: 10��1: 20.
10. the preparation method of polyoxymethylene conductive fiber as claimed in claim 4, it is characterized in that, in described step c, the single screw rod or the double screw extruder processing temperature that use are 120��250 degrees Celsius, drawing temperature is 60��210 degrees Celsius, drafting multiple is 5��10 times, and winding speed is 200��2000 ms/min.
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