CN117626658A - Preparation method of sizing carbon fiber for rubber-based composite materials and sizing carbon fiber - Google Patents
Preparation method of sizing carbon fiber for rubber-based composite materials and sizing carbon fiber Download PDFInfo
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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Abstract
The invention relates to the technical field of carbon fiber preparation, and discloses a preparation method of sizing carbon fiber for a rubber-based composite material and the sizing carbon fiber. Pre-oxidizing polyacrylonitrile-based precursor, carbonizing at low temperature, carbonizing at high temperature, performing surface treatment, washing, sizing, drying, winding and collecting the precursor to obtain sized carbon fibers; sizing and drying comprises the following steps: firstly, pre-sizing and pre-drying are carried out by adopting a pre-sizing agent containing polyacrylamide and polyvinyl alcohol, so as to obtain initial carbon fibers; secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by adopting resorcinol formaldehyde latex to obtain the sized carbon fiber; the contact angle of the pre-sizing agent is less than or equal to 30 DEG and the surface tension is less than or equal to 50mN/m. The contact angle of the pre-sizing agent in the method is smaller than or equal to 30 degrees, the surface tension is smaller than or equal to 50mN/m, and the sizing agent is combined with a step sizing method, so that the bundling property of sizing carbon fibers can be greatly improved, and meanwhile, the binding force of the sizing carbon fibers and a rubber matrix is improved.
Description
Technical Field
The invention relates to the technical field of carbon fiber preparation, in particular to a preparation method of sizing carbon fiber for a rubber-based composite material and the sizing carbon fiber.
Background
The carbon fiber reinforced rubber-based composite material has the comprehensive characteristics of excellent strength modulus, temperature resistance, fatigue resistance and the like, and is widely applied to the fields of manufacturing tire cord, tread rubber, conveyor belts, friction materials, electromagnetic materials and the like. In carbon fiber reinforced rubber composites, the actual interface between the carbon fiber and the rubber is a sizing-based transition layer. The existing multi-purpose epoxy sizing agent in the carbon fiber industry cannot generate good bonding capability on a rubber matrix, so that the advantages of the carbon fiber cannot be fully exerted. Because the carbon fiber is a brittle material, various functions such as stretching, friction, extrusion, hooking and the like can be received in the process of subsequent rubber-based composite material layering, braiding, winding and the like, higher requirements are put on the bundling performance of the carbon fiber, the carbon fiber after sizing has good bundling performance, and meanwhile, the carbon fiber needs to have good two-phase interface bonding performance, and higher requirements are put on sizing agents.
CN106349526a discloses a brake band based on modified carbon fiber and a preparation method thereof, wherein the carbon fiber is modified by adopting a base film solution and a polymer solution, the base film solution is ethanol solution of vinyl triethoxysilane, triethanolamine and polyethylene glycol, the polymer solution is tetrahydrofuran solution of dodecyl methacrylate and styrene monomer copolymer, the method takes several hours, and a plurality of organic solvent systems are adopted, so that the practical production and application difficulties are high.
CN106433148A applied for a carbon fiber cloth reinforced/heat vulcanized rubber ablation-resistant composite material and a preparation method thereof, in order to improve a two-phase interface, a method of cleaning/high-temperature removing a sizing agent on the surface of carbon fiber is adopted, the process is complex, the damage to the carbon fiber is large, the surface inertia of the carbon fiber after sizing is removed is large, and the adhesiveness with a rubber matrix is not high.
In the current industrial carbon fiber production process, a surface interface treatment method is generally adopted to solve the two-phase combination problem of the carbon fiber and the rubber matrix, including electrochemical treatment, acid-base treatment, surface sizing and the like, wherein the most common method is to adopt resorcinol formaldehyde latex (RFL emulsion for short) for sizing treatment. However, in practical applications, it was found that the use of only RFL emulsion did not effectively improve the adhesion between the carbon fiber and the rubber matrix after sizing. This is because the RFL emulsion itself is an aqueous emulsion, and the wet spreading on the surface of the inert carbon fiber is poor, resulting in discontinuous and weak bonding points. Therefore, it is necessary to provide a sizing method capable of improving the interfacial effect of the two phases of the carbon fiber and the RFL emulsion and enhancing the binding force of the sized carbon fiber and the rubber matrix.
Disclosure of Invention
The invention aims to solve the problems that the existing method for preparing sizing carbon fibers cannot meet the requirement of the adhesive force between the sizing carbon fibers and a rubber matrix and the sizing carbon fibers are poor in technical property, and provides a preparation method of sizing carbon fibers for rubber-based composite materials and sizing carbon fibers. By adopting the specific pre-sizing agent and the specific sizing method, the bundling property of the sized carbon fiber can be obviously improved, and meanwhile, the binding force between the prepared sized carbon fiber and the rubber matrix is further improved.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing sized carbon fibers for rubber-based composites, comprising: the sizing carbon fiber is obtained after pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, sizing drying and winding wire collection of polyacrylonitrile-based precursor;
the sizing and drying method comprises the following steps:
firstly, pre-sizing agent containing polyacrylamide and polyvinyl alcohol is adopted to perform pre-sizing and pre-drying on carbon fiber tows after water washing, so as to obtain initial carbon fibers;
secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by adopting resorcinol formaldehyde latex to obtain the sized carbon fiber;
wherein the contact angle of the pre-sizing agent is less than or equal to 30 degrees and the surface tension is less than or equal to 50mN/m.
In a second aspect, the present invention provides a sized carbon fiber prepared by the preparation method of the first aspect.
Through the technical scheme, the preparation method of the sizing carbon fiber for the rubber-based composite material provided by the invention has the following beneficial effects:
(1) The sizing and drying modes of pre-sizing, pre-drying, secondary sizing and secondary drying are adopted, and a specific pre-sizing agent containing polyacrylamide and polyvinyl alcohol components and having a contact angle of less than or equal to 30 degrees and a surface tension of less than or equal to 50mN/m is matched for pre-sizing, and resorcinol formaldehyde latex is matched for secondary sizing, so that the interpenetration of the pre-sizing agent, the secondary sizing agent and multiphase interfaces on the surfaces of the carbon fibers can be promoted, and the bundling property of the sized carbon fibers can be remarkably improved.
(2) The step sizing method can exert the function of RFL emulsion to the maximum extent, and improves the bonding force between sizing carbon fiber and the rubber matrix to a certain extent.
(3) The pre-sizing agent and the secondary sizing agent have low cost and wide industrial application prospect, and the method for sizing in steps is simple, convenient and feasible and is suitable for the existing carbon fiber industrial production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a method for preparing sizing carbon fibers for rubber-based composite materials, which is characterized by comprising the following steps: the sizing carbon fiber is obtained after pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, sizing drying and winding wire collection of polyacrylonitrile-based precursor;
the sizing and drying method comprises the following steps:
firstly, pre-sizing agent containing polyacrylamide and polyvinyl alcohol is adopted to perform pre-sizing and pre-drying on carbon fiber tows after water washing, so as to obtain initial carbon fibers;
secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by adopting resorcinol formaldehyde latex to obtain the sized carbon fiber;
wherein the contact angle of the pre-sizing agent is less than or equal to 30 degrees and the surface tension is less than or equal to 50mN/m.
In the invention, the method is utilized, and the specific pre-sizing agent containing polyacrylamide and polyvinyl alcohol components and having a contact angle of less than or equal to 30 ℃ and a surface tension of less than or equal to 50mN/m is matched for pre-sizing, and resorcinol formaldehyde latex is matched for secondary sizing, so that the pre-sizing agent, the secondary sizing agent and the interpenetration of multiphase interfaces on the surfaces of the carbon fibers can be promoted, the bundling property of the sized carbon fibers is obviously improved, and the carbon fibers and a rubber matrix are enhanced after sizing.
In the invention, the production process of pre-oxidation is respectively carried out in an oxidation furnace with 4 heating temperature areas, and the temperatures of the 4 heating temperature areas are respectively 0-250 ℃, 0-300 ℃ and 0-350 ℃. The pre-oxidation time of each temperature zone is the same, and the total pre-oxidation time is 30-80min. The draft ratio in the oxidation furnace of each temperature zone is controlled to be 0-1.8, 0.8-1 and 0.8-1 respectively.
In the invention, the low-temperature carbonization production process is respectively carried out in a low-temperature carbonization furnace with 5 heating temperature areas, and the temperatures of the 5 heating temperature areas are respectively 0-700 ℃, 0-800 ℃, 0-950 ℃ and 0-950 ℃. When the pre-oxidized filament bundles run in a low-temperature carbonization furnace, the draft ratio is controlled to be 1-1.2, and the total residence time in the low-temperature carbonization furnace is 1-10min, so that the low-temperature carbonized filament is obtained.
In the invention, the high-temperature carbonization production process is respectively carried out in high-temperature carbonization furnaces with 5 heating temperature areas, and the temperatures of the 5 heating temperature areas are respectively 0-1300 ℃, 0-1400 ℃, 0-1700 ℃, 0-1900 ℃ and 0-2200 ℃. When the tows run in the high-temperature carbonization furnace, the draft ratio is controlled to be 0.6-0.95, and the total residence time in the high-temperature carbonization furnace is 1-10min, so that the high-temperature carbonized yarns are obtained.
In the present invention, the surface treatment conditions include: the ammonium bicarbonate aqueous solution is used as electrolyte, the voltage is 15-25V, the concentration of the electrolyte is 10-30wt%, and the treatment time is 50-80 seconds.
In the present invention, the conditions for washing with water include: washing with water at 40-60deg.C and water flow of 2500-6500L/h.
In the present invention, the winding and filament receiving may be performed under a tension of 2000 to 4000 cN.
According to the invention, the polyvinyl alcohol is an aqueous solution of polyvinyl alcohol.
In the invention, the polyvinyl alcohol can be selected from polyvinyl alcohols with different alcoholysis degrees, and preferably partially-alcoholyzed polyvinyl alcohol.
According to the invention, the alcoholysis of the polyvinyl alcohol is 78-99mol%.
In the invention, when the alcoholysis degree of the polyvinyl alcohol meets the range, the presoaking agent containing the alcoholysis degree can obviously improve the bundling property of the sized carbon fibers when the presoaking agent is applied.
According to the invention, the alcoholysis of the polyvinyl alcohol is 88-92mol%.
According to the invention, the polyvinyl alcohol has a number average molecular weight of 20000 to 200000, preferably 50000 to 150000.
According to the invention, the number average molecular weight of the polyacrylamide is 8000-18000, preferably 10000-14000.
According to the invention, the mass ratio of the polyvinyl alcohol to the polyacrylamide is 1:0.4-1:0.9.
In the invention, when the mass ratio of the polyvinyl alcohol to the polyacrylamide satisfies the above range, the bundling property of the sizing carbon fiber can be further improved when the pre-sizing agent is applied.
According to the invention, the mass ratio of the polyvinyl alcohol to the polyacrylamide is 1:0.5-1:0.7.
According to the present invention, the presize agent has a contact angle of 10 ° or less and a surface tension of 45mN/m or less.
According to the present invention, in the first step, the pre-drying mode is a first infrared radiation drying mode.
According to the invention, the temperature of the pre-drying is 60-100 ℃, preferably 70-90 ℃.
According to the present invention, in the second step, the secondary drying mode is as follows: and sequentially performing second infrared radiation drying and electric heating roller drying.
According to the invention, the second infrared radiation drying temperature is 70-220 ℃, preferably 90-170 ℃.
According to the invention, the electrically heated roller drying temperature is 90-240 ℃, preferably 110-190 ℃.
According to the invention, the pre-drying adopts an infrared radiation drying mode, the secondary drying adopts an infrared radiation and electric heating hot roller drying mode sequentially, and the pre-drying is synergistic with the step sizing process, so that the surface structure and composition of the carbon fiber can be accurately regulated and controlled, and the effects of enhancing the interface between the carbon fiber and the rubber matrix and improving the bundling performance of the fiber are realized.
In the invention, the first infrared radiation and the second infrared radiation are each independently performed using an infrared radiation heating dryer containing a carbon medium wave infrared radiator.
In the present invention, when the first infrared radiation is performed,the distance between the carbon medium wave infrared radiator and the carbon fiber of the infrared radiation heating dryer is 44-74mm, and the power density is 26-44KW/m 2 。
In the invention, when the second infrared radiation is carried out, the distance between the carbon medium wave infrared radiator and the carbon fiber of the infrared radiation heating dryer is 52-163mm, and the power density is 31-97KW/m 2 。
In the invention, the resorcinol formaldehyde latex contains a rubber emulsion.
In the present invention, the resorcinol formaldehyde latex (RFL emulsion) may be an acrylic rubber emulsion, an acrylonitrile-butadiene rubber emulsion, an isoprene rubber emulsion, a polyurethane rubber emulsion, an ethylene-propylene rubber emulsion, a chloroprene rubber emulsion, a silicone rubber emulsion, a hydrogenated nitrile rubber emulsion, a styrene-butadiene rubber emulsion, a polysulfide rubber emulsion, a natural rubber emulsion, a butadiene rubber emulsion, a butyl rubber emulsion, etc., and the present invention is preferably a butyl rubber emulsion.
According to the invention, the resorcinol-formaldehyde latex has a molar ratio of resorcinol to formaldehyde of 1:3 to 1:25, preferably 1:8 to 1:18.
In the present invention, the resorcinol formaldehyde latex may be prepared by conventional emulsion polymerization methods.
In the present invention, the pre-sizing amount of the pre-sizing agent is 0.1 to 30wt%, preferably 0.5 to 20wt%, based on the mass of the carbon fiber tow after washing.
In the invention, the secondary sizing amount of the secondary sizing agent is 5-35wt%, preferably 10-20wt%, based on the mass of the carbon fiber tows after water washing.
In a second aspect, the present invention provides a sized carbon fiber prepared by the preparation method of the first aspect.
According to the invention, when the sizing carbon fiber is applied to rubber materials, the binding force between the sizing carbon fiber and the rubber materials can be improved.
In the present invention, the rubber material may be a rubber material commonly used in the art, for example, acrylic rubber, acrylonitrile-butadiene rubber, isoprene rubber, urethane rubber, ethylene-propylene rubber, chloroprene rubber, silicone rubber, hydrogenated nitrile rubber, styrene-butadiene rubber, polysulfide rubber, natural rubber, butadiene rubber, butyl rubber, etc., and is preferably the same kind as the rubber emulsion in the RFL emulsion.
The present invention will be described in detail by examples.
In the following preparation examples and examples, each parameter was obtained by the following method.
Contact angle: the pre-sizing agent is uniformly coated on a glass slide, and after being placed for 12 hours at room temperature, the film sample is obtained by drying at 50 ℃. At room temperature, deionized water is dripped onto the surface of the glass sheet by using an OCA20 high-speed contact angle measuring instrument, and the static contact angle formed by the water drop on the surface of the pre-sizing agent is tested.
Surface tension: the pre-sizing agent was diluted with water to a concentration of 2wt%, and the surface tension was measured using a dynamic surface tensiometer at 25 ℃.
Sizing amount: and weighing the mass of the fiber before and after sizing, and calculating the sizing amount according to the formula. Sizing amount= (mass of carbon fiber after sizing-mass of carbon fiber before sizing)/mass of carbon fiber before sizing x 100%.
Bundling properties: the bundling properties were evaluated by testing the tow width of the sized fibers. The smaller the tow width, the better the bundling.
Adhesive force: the sized carbon fiber was embedded in an unvulcanized natural rubber block (wherein the mass of the sized carbon fiber was 20wt% of the mass of the natural rubber block), and vulcanized at 140℃for 40 minutes under a pressing pressure of 3 MPa. The vulcanization formula system comprises 100 parts of natural rubber, 4 parts of zinc oxide, 1.5 parts of stearic acid, 330 parts of carbon black N, 1.2 parts of accelerator DM, 0.2 part of accelerator TMTD and 3 parts of sulfur. On a universal strength tester, the sizing carbon fiber is pulled out at the speed of 200 mm/min, and the tension required for pulling out the sizing carbon fiber to 1 cm length is the binding force between the sizing carbon fiber and rubber.
KTM-1M epoxy emulsion and polyvinyl alcohol PVA1788 are all purchased from national medicine reagent;
wherein PVA1788 has a number average molecular weight of 80000 and an alcoholysis degree of 88mol%.
The following preparation examples are presented to illustrate the preparation of the pre-sizing agent
Preparation examples 1 to 6
Adding a proper amount of deionized water into a reaction kettle, heating to 90 ℃, adding polyvinyl alcohol and polyacrylamide, and stirring at a high speed to obtain a stable dispersion liquid with uniform distribution, wherein the stable dispersion liquid is the pre-sizing agents A1-A6.
The components and the amounts of the components in the pre-sizing agent are shown in Table 1, and the mass ratio of the polyvinyl alcohol to the polyacrylamide in the pre-sizing agent and the properties of the pre-sizing agent are shown in Table 2.
TABLE 1
TABLE 2
The following preparation examples are presented to illustrate the preparation of the secondary sizing agent
Preparation example 7
10g of sodium hydroxide and resorcinol were put into a reaction vessel, then a proper amount of water was added, stirred and warmed to 35 ℃, and a quantitative amount of formaldehyde was slowly added, wherein the total amount of resorcinol and formaldehyde was 30g. After 3 hours of reaction, slowly cooling to obtain a resin prepolymer; adding 97g of natural rubber emulsion into another reaction kettle, stirring and heating to 35 ℃, slowly dripping the synthesized resin prepolymer, continuously reacting for 20 hours, and slowly cooling to obtain RFL emulsion, wherein the mol ratio of resorcinol to formaldehyde in the RFL emulsion is 1:25.
Preparation examples 8 to 12
The total amount of resorcinol and formaldehyde was controlled to 30g in accordance with preparation 7, except that the molar ratio of resorcinol to formaldehyde in the RFL emulsion was controlled to be 1:12, 1:3, 1:8, 1:9 and 1:18, respectively.
The following examples are presented to illustrate the preparation of sized carbon fibers
Examples 1 to 6
Examples 1-6 are methods for producing a homogeneous 50K carbon fiber, comprising:
pre-oxidation: the polyacrylonitrile-based precursor sequentially passes through a No. 1 oxidation furnace, a No. 2 oxidation furnace, a No. 3 oxidation furnace and a No. 4 oxidation furnace for pre-oxidation treatment. The four heating temperature zones are respectively 236 ℃, 245 ℃, 256 ℃ and 268 ℃. The pre-oxidation time is the same in each temperature zone, and the total pre-oxidation time is 60 minutes. The draft ratios between the oxidation furnaces of the four heating temperature zones are respectively 1.27, 0.98 and 0.96;
low temperature carbonization: taking nitrogen as a medium, sequentially passing the pre-oxidized filament bundles through 5 low-temperature carbonization furnaces with the temperature of 490 ℃ and 580 ℃ and 650 ℃ and 760 ℃ and 820 ℃ respectively, controlling the draft ratio of each region to be 1.06, and controlling the total residence time in the low-temperature carbonization furnaces to be 1.2 minutes to prepare the low-temperature carbonized filament;
high temperature carbonization: taking nitrogen as a medium, sequentially passing the filament bundle through 5 high-temperature carbonization furnaces with the temperature of 920 ℃, 1180 ℃, 1230 ℃, 1300 ℃ and 1410 ℃ respectively, controlling the draft ratio of each region to be 0.78, and controlling the total residence time in the high-temperature carbonization furnaces to be 1.2 minutes to prepare high-temperature carbonized filaments;
surface treatment: the high-temperature carbonized wire enters a surface treatment tank through a traction device, an ammonium bicarbonate aqueous solution is used as electrolyte, the voltage is 18V, the concentration of the electrolyte is 12wt%, and the treatment time is 60 seconds, so that the carbon fiber after surface treatment is obtained;
washing: washing the surface-treated carbon fiber with water at a water washing flow of 2900L/h and a water washing temperature of 50 ℃ to obtain a washed carbon fiber tow;
sizing and drying: directly introducing the carbon fiber tows subjected to water washing into a first sizing tank for pre-sizing, and then, through an infrared radiation dryer, pre-drying under the condition of set technological parameters; then the carbon fiber enters a second sizing tank for secondary sizing, and then sequentially passes through an infrared radiation dryer and an electric heating hot roller for secondary drying under the condition of setting technological parameters to obtain the sized carbon fiber;
winding and reeling: and winding and filament collecting the sized carbon fiber by using a carbon fiber winding machine under the tension of 2380-2510cN to obtain the sized carbon fiber for reinforcing the rubber material.
Wherein the types of the sizing agent, the pre-sizing amount, the secondary sizing amount and the types of the secondary sizing agent (the molar ratio of resorcinol to formaldehyde) are shown in table 3, and the pre-sizing drying and the secondary sizing drying process parameters are shown in table 4.
Comparative example 1
Comparative example 1 is a method for manufacturing 50K carbon fiber, which is identical to the method of example 1, except that the sizing drying process is: and (3) carrying out dipping sizing on the unglued carbon fiber by adopting a commercially available KTM-1M epoxy emulsion sizing agent, and carrying out horizontal hot air drying at a drying temperature of 100 ℃.
Comparative example 2
Comparative example 2 is a method for manufacturing 50K carbon fiber, which is identical to the method of example 1, except that the sizing and drying process is: the unglued carbon fiber is dipped and sized by adopting the RFL emulsion prepared in the preparation example 7, and is dried by horizontal hot air at the drying temperature of 150 ℃.
Comparative example 3
Comparative example 3 is a method for manufacturing 50K carbon fiber, consistent with the method of example 1, except that the ungumped carbon fiber is pre-sized with a polyvinyl alcohol PVA1788 aqueous sizing agent, pre-dried is horizontal hot air dried, and the pre-drying temperature is 80 ℃; and (3) carrying out secondary sizing on the carbon fiber by adopting the RFL emulsion prepared in the preparation example 7, wherein the secondary drying is horizontal hot air drying, and the secondary drying temperature is 165 ℃.
TABLE 3 Table 3
TABLE 4 Table 4
Test case
The sizing carbon fibers prepared in examples and comparative examples were subjected to bundling and adhesion tests, and the results are shown in table 5.
TABLE 5
| Numbering device | Tow width (mm) | Cohesive force (N/cm) |
| Comparative example 1 | 36.4 | 102 |
| Comparative example 2 | 42.9 | 115 |
| Comparative example 3 | 31.6 | 129 |
| Example 1 | 18.6 | 158 |
| Example 2 | 19.5 | 153 |
| Example 3 | 19 | 146 |
| Example 4 | 19.8 | 150 |
| Example 5 | 20 | 156 |
| Example 6 | 21 | 154 |
As can be seen from the data in tables 1 to 4 and the results in Table 5, examples 1 to 6 adopting the technical scheme of the invention have better effects, the pre-sizing agent contains polyacrylamide and polyvinyl alcohol, the contact angle is less than or equal to 30 degrees, the surface tension is less than or equal to 50mN/m, the sizing and drying process is cooperated with RFL emulsion to perform stepwise sizing, the bundling property of the finally prepared sizing carbon fiber is obviously improved, the tow width is not more than 21mm, the binding force of the sizing carbon fiber and a rubber matrix is not less than 146N/cm, and the overall improvement effect is obvious.
The comparative example 1 only adopts the traditional epoxy emulsion KTM-1M, the comparative example 2 only adopts the RFL emulsion, and the prepared carbon fiber has lower binding force with the rubber matrix and poorer bundling property. The comparative example 3 adopts the pre-sizing polyvinyl alcohol solution with overlarge contact angle and surface tension, and the improvement effect is not obvious.
Compared with comparative examples 1-3, the sizing carbon fiber of the invention has greatly improved bundling property and enhanced adhesion force with rubber matrix.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1175651A (en) * | 1968-01-02 | 1969-12-23 | Burlington Industries Inc | Process for Treating Glass Textiles |
| JP2005023481A (en) * | 2003-07-03 | 2005-01-27 | Toho Tenax Co Ltd | Carbon fiber cord for rubber reinforcement and fiber reinforced rubber material |
| KR20120085417A (en) * | 2011-01-24 | 2012-08-01 | 인하대학교 산학협력단 | Sizing method of carbon fibers having high electrical conductivity and high unrolling ability |
| CN108004621A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of polyamide resin resin-based composite carbon fiber and preparation method thereof |
| CN112760984A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing carbon fiber for composite material |
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- 2022-08-17 CN CN202210985091.3A patent/CN117626658A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1175651A (en) * | 1968-01-02 | 1969-12-23 | Burlington Industries Inc | Process for Treating Glass Textiles |
| JP2005023481A (en) * | 2003-07-03 | 2005-01-27 | Toho Tenax Co Ltd | Carbon fiber cord for rubber reinforcement and fiber reinforced rubber material |
| KR20120085417A (en) * | 2011-01-24 | 2012-08-01 | 인하대학교 산학협력단 | Sizing method of carbon fibers having high electrical conductivity and high unrolling ability |
| CN108004621A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of polyamide resin resin-based composite carbon fiber and preparation method thereof |
| CN112760984A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing carbon fiber for composite material |
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