CN118932717A - Preparation method of sized large tow carbon fiber for reinforcing rubber composite materials and sized large tow carbon fiber - Google Patents
Preparation method of sized large tow carbon fiber for reinforcing rubber composite materials and sized large tow carbon fiber Download PDFInfo
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Abstract
The invention relates to the field of preparation of sizing large-tow carbon fibers, and discloses a preparation method of sizing large-tow carbon fibers for reinforced rubber materials and sizing large-tow carbon fibers. The method comprises the following steps: the method comprises the steps of pre-oxidizing polyacrylonitrile-based precursor, carbonizing at low temperature, carbonizing at high temperature, performing surface treatment, washing, sizing, drying, winding and filament collecting to obtain sized large-tow carbon fibers; sizing and drying comprises the following steps: pre-sizing and pre-drying the washed carbon fiber by adopting a pre-sizing agent containing polyvinyl alcohol and polyester polyurethane, and then performing secondary sizing and secondary drying by adopting resorcinol formaldehyde latex to obtain the sized large-tow carbon fiber; the contact angle of the pre-sizing agent is less than or equal to 35 degrees, and the surface tension is less than or equal to 35mN/m. The pre-drying is heat conduction oil hot roller drying, and the secondary drying is infrared radiation and vertical hot air drying sequentially. The sized large-tow carbon fiber obtained finally has excellent wear resistance and good binding force with a rubber matrix.
Description
Technical Field
The invention relates to the technical field of carbon fiber preparation, in particular to a preparation method of a sizing large-tow carbon fiber for a reinforced rubber composite material and the sizing large-tow carbon fiber.
Background
The carbon fiber reinforced rubber composite material has the advantages of high strength, high modulus, high elasticity, fatigue resistance, good dimensional stability and the like, has good mechanical properties, and has toughness and elasticity, thus being widely applied to the fields of industrial transportation, traffic, spare parts and the like. In carbon fiber reinforced resin matrix composites, surface coating sizing agents are generally used to improve interfacial bonding, but no special sizing agent suitable for carbon fiber reinforced rubber materials is currently known. Meanwhile, the carbon fiber reinforced rubber composite material has high wear resistance because of long-time high-strength friction conditions in many practical application occasions, and the carbon fiber and carbon fiber reinforced rubber composite material have high requirements, and the special sizing agent with low cost and high performance, which can meet industrial requirements, is not yet seen.
CN109762212a discloses a super wear-resistant conveyer belt and a preparation process thereof, wherein the wear-resistant fiber comprises polyamide fiber and modified carbon fiber in a weight ratio of 2:3; the modified carbon fiber is obtained after the carbon fiber is subjected to dispersion treatment, plasma treatment, washing and drying, and when the modified carbon fiber is compounded with polyamide fiber for use, the wear resistance of the conveyer belt can be remarkably improved. The carbon fiber modification method disclosed by the patent is complex, long in time and high in cost, and is not suitable for industrial continuous preparation.
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 application, it is found that the bonding capability between the RFL emulsion and the surface of the carbon fiber is not strong, and the bonding property between the carbon fiber and the rubber matrix after sizing cannot be effectively improved by only adopting the RFL emulsion. And can not realize the good sizing of the large tow carbon fiber of 150K and above, and then the carbon fiber after sizing has poor wear resistance, and the binding force with the rubber matrix is poor when the carbon fiber is applied to rubber materials.
Disclosure of Invention
The invention aims to solve the problems of poor binding force between a large-tow carbon fiber and a rubber matrix after sizing and limited application caused by poor wear resistance in the prior art, and provides a preparation method of the large-tow carbon fiber for reinforcing a rubber composite material and the large-tow carbon fiber for sizing. The contact angle of the pre-sizing agent is less than or equal to 35 degrees, the surface tension is less than or equal to 35mN/m, and the pre-sizing agent is combined with a specific sizing process, so that the wear resistance of the prepared sized large-tow carbon fiber can be remarkably improved on the premise of meeting the basic binding force requirement between the sized large-tow carbon fiber and a rubber matrix.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing sized large tow carbon fibers for reinforcing rubber composites, the method comprising: pre-oxidizing, carbonizing at low temperature, carbonizing at high temperature, performing surface treatment, washing, sizing, drying, winding and filament collecting the polyacrylonitrile-based precursor to obtain the sized large-tow carbon fiber;
The sizing and drying method comprises the following steps:
firstly, pre-sizing agent containing polyvinyl alcohol and polyester polyurethane is adopted to pre-sizing and pre-drying the carbon fiber after washing to obtain initial carbon fiber;
Secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by adopting resorcinol formaldehyde latex to obtain sized large-tow carbon fiber;
wherein the contact angle of the pre-sizing agent is less than or equal to 35 degrees, and the surface tension is less than or equal to 35mN/m;
the pre-drying mode is heat conduction oil hot roll drying;
the secondary drying step comprises the following steps: and sequentially carrying out infrared radiation drying and vertical hot air drying.
In a second aspect, the present invention provides a sized large tow carbon fiber prepared by the method of the first aspect of the present invention.
Through the technical scheme, the preparation method of the sized large-tow carbon fiber for reinforcing the rubber composite material provided by the invention has the following beneficial effects:
(1) According to the invention, the wear resistance of the sized large-tow carbon fibers can be obviously improved by introducing polyester polyurethane into the pre-sizing agent, meanwhile, the contact angle of the pre-sizing agent is controlled to be less than or equal to 35 degrees, the surface tension is controlled to be less than or equal to 35mN/m, the step sizing process of pre-sizing, pre-drying, secondary sizing and secondary drying is adopted, the pre-drying adopts heat conducting oil hot roller drying, and the secondary drying sequentially adopts infrared radiation and vertical hot air drying. When the sizing large-tow carbon fiber is applied to rubber materials, the basic binding force (125N) between the sizing large-tow carbon fiber and a rubber matrix is improved, the wear resistance of the sizing large-tow carbon fiber is further improved, and the sizing large-tow carbon fiber can be at least resistant to wear 34000 times.
(2) The method is suitable for the existing carbon fiber industrial production line, excessive transformation and upgrading are not needed, and the process adaptability is high; the sizing agent component and RFL emulsion adopted are low in cost and wide in industrial application prospect.
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 present invention provides a method for preparing sized large tow carbon fibers for reinforcing rubber composites, the method comprising: pre-oxidizing, carbonizing at low temperature, carbonizing at high temperature, performing surface treatment, washing, sizing, drying, winding and filament collecting the polyacrylonitrile-based precursor to obtain the sized large-tow carbon fiber;
The sizing and drying method comprises the following steps:
firstly, pre-sizing agent containing polyvinyl alcohol and polyester polyurethane is adopted to pre-sizing and pre-drying the carbon fiber after washing to obtain initial carbon fiber;
Secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by adopting resorcinol formaldehyde latex to obtain sized large-tow carbon fiber;
wherein the contact angle of the pre-sizing agent is less than or equal to 35 degrees, and the surface tension is less than or equal to 35mN/m;
the pre-drying mode is heat conduction oil hot roll drying;
the secondary drying step comprises the following steps: and sequentially carrying out infrared radiation drying and vertical hot air drying.
In the invention, the inventor researches and discovers that in the process of sizing the carbon fiber, a layer of hydrophilic pre-sizing agent is coated on the surface of the carbon fiber, and RFL emulsion is coated after drying, so that the bonding capability of the sized large-tow carbon fiber and a rubber matrix can be improved. Further researches of the inventors show that for the scheme of the invention, the random selection of the hydrophilic pre-sizing agent is not feasible, and the secondary uniform infiltration of the subsequent RFL emulsion on the surface of the carbon fiber can be realized only when the contact angle of the pre-sizing agent is less than or equal to 35 degrees and the surface tension is less than or equal to 35mN/m, so that the coupling effect is good, and meanwhile, the polyester polyurethane is introduced into the pre-sizing agent, so that the wear resistance of the sized large-tow carbon fiber can be remarkably improved and the bonding force between the sized large-tow carbon fiber and a rubber matrix can be improved.
In the present invention, the pre-oxidation process is performed in an oxidation furnace of a plurality of heating temperature zones, and illustratively, the present invention is preferably performed in an oxidation furnace of 4 heating temperature zones, the temperatures of the 4 heating temperature zones are respectively set to 0-250 ℃, 0-300 ℃ and 0-350 ℃, the total pre-oxidation time is 30-80min, the pre-oxidation time of each temperature zone is ensured to be the same, and the draft ratios in the oxidation furnaces of the 4 heating temperature zones are respectively 0-1.8, 0.8-1 and 0.8-1.
In the invention, the temperature of the 4 heating temperature areas, the total time of pre-oxidation and the draft ratio are controlled to meet the above ranges, so that the efficient and rapid pre-oxidation can be realized.
In the present invention, the low temperature carbonization process is performed in an oxidation furnace of a plurality of heating temperature zones, and illustratively, the present invention is preferably performed in a low temperature carbonization furnace of 5 heating temperature zones, the temperatures of which are set to 0-700 ℃, 0-800 ℃, 0-950 ℃ and 0-950 ℃, respectively. When the pre-oxidized carbon fiber runs 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 fiber is obtained.
In the present invention, the high temperature carbonization process is performed in an oxidation furnace of a plurality of heating temperature zones, and illustratively, the present invention is preferably performed in a high temperature carbonization furnace of 5 heating temperature zones having temperatures of 0 to 1300 ℃, 0 to 1400 ℃, 0 to 1700 ℃, 0 to 1900 ℃, and 0 to 2200 ℃, respectively. When the carbon fiber runs 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 yarn is 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.
In the present invention, the term "large tow" refers to carbon fibers of greater than 4.8 ten thousand carbon fibers per bundle (48K for short). According to a specific embodiment of the invention, the number of the large-tow carbon fibers is 150K, namely 15 ten thousand carbon fibers per bundle.
In the present invention, the preparation method of the pre-sizing agent can adopt the preparation method of general emulsion in the field, such as inversion emulsification method, ultrasonic emulsification method, colloid mill emulsification method, etc.
In the present invention, the surface tension refers to the surface tension when it is diluted with water to a concentration of 2 wt%.
In the invention, the RFL emulsion is a mixed emulsion formed by mixing resorcinol, formaldehyde and rubber emulsion through reaction. The preparation process comprises the following steps: adding sodium hydroxide and resorcinol into a first reaction kettle, then adding a proper amount of water, controlling the temperature to 20-40 ℃, then slowly adding formaldehyde, and carrying out ripening reaction for 2-4 hours to obtain a prepolymer; and adding the rubber emulsion into a second reaction kettle, controlling the temperature to 20-40 ℃, slowly dripping the synthesized prepolymer, and continuously reacting for 10-30h to finally prepare the RFL emulsion.
In the invention, the rubber emulsion in the RFL emulsion can be acrylic rubber emulsion, acrylonitrile-butadiene rubber emulsion, isoprene rubber emulsion, polyurethane rubber emulsion, ethylene-propylene rubber emulsion, chloroprene rubber emulsion, silicon rubber emulsion, hydrogenated nitrile rubber emulsion, styrene-butadiene rubber emulsion, polysulfide rubber emulsion, natural rubber emulsion, butadiene rubber emulsion, butyl rubber emulsion and the like.
According to the invention, the contact angle of the pre-sizing agent is less than or equal to 10 DEG and the surface tension is less than or equal to 25mN/m.
According to the invention, in the pre-sizing agent, the mass ratio of the polyvinyl alcohol to the polyester polyurethane is 1:0.6-1.
In the invention, when the mass ratio of the polyvinyl alcohol to the polyester polyurethane satisfies the above range, the wear resistance of the sized large-tow carbon fibers can be remarkably improved while the binding force between the sized large-tow carbon fibers and the rubber matrix is improved.
Further, in the pre-sizing agent, the mass ratio of the polyvinyl alcohol to the polyester polyurethane is 1:0.7-0.8.
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 78-99%, preferably 88-92%.
According to the invention, the polyvinyl alcohol has a number average molecular weight of 20000 to 200000g/mol, preferably 50000 to 150000g/mol.
According to the invention, the polyester polyurethane has a number average molecular weight of 3000 to 30000g/mol g/mol, preferably 7000 to 150000g/mol.
According to the invention, the polyester polyurethane comprises structural units A provided by polyisocyanates and structural units B provided by polyester polyols.
According to the invention, the molar ratio of structural unit A to structural unit B is 1-2:1.
According to the invention, the polyisocyanate is an aromatic polyisocyanate.
In the invention, the polyisocyanate is selected from aromatic polyisocyanates compared with aliphatic polyisocyanates, so that the adhesive force and the wear resistance of the sized large-tow carbon fibers and a rubber matrix can be further improved when the prepared polyester polyurethane is matched with RFL emulsion for use when the polyester polyurethane is applied to a pre-sizing agent.
In the present invention, the aromatic polyisocyanate is selected from Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), polymethylene polyphenyl isocyanate (PAPI), and the like, and preferably at least one of Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).
In the present invention, the polyester polyol is not particularly limited, and may be, for example, polycaprolactone polyol and polycarbonate polyol, preferably aromatic polyester polyol produced by polycondensation reaction of aromatic dibasic acid and diol.
In the present invention, the aromatic dibasic acid is commercially available, and may be, for example, phthalic acid, isophthalic acid, terephthalic acid.
In the present invention, the dihydric alcohol is commercially available, and may be, for example, ethylene glycol, propylene glycol, butylene glycol.
According to the invention, in step one, the pre-drying temperature is 60-100 ℃, preferably 70-90 ℃.
According to the invention, the temperature of the infrared radiation drying is 55-205 ℃, preferably 75-155 ℃;
According to the invention, the temperature of the vertical hot air drying is 90-240 ℃, preferably 110-190 ℃.
In the invention, the infrared radiation drying can be performed by adopting an infrared radiation dryer, the infrared radiation heating dryer comprises a carbon medium wave infrared radiator, and the vertical hot air drying can be performed by adopting a vertical hot air dryer.
In the invention, when the infrared radiation drying is carried out, the distance between the carbon medium wave infrared radiator and the carbon fiber of the infrared radiation heating dryer is 40-180mm, and the power density is 20-100kW/m 2.
According to the invention, in the resorcinol formaldehyde latex, the molar ratio of resorcinol to formaldehyde is 1:3-25, preferably 1:8-18.
According to the 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 after washing.
According to the present invention, the resorcinol-formaldehyde latex has a sizing amount of 5 to 35wt%, preferably 10 to 20wt%, based on the mass of the carbon fiber after washing with water.
In the invention, the prepared sizing large-tow carbon fiber can be used for reinforced rubber composite materials, wherein the content of the sizing large-tow carbon fiber in the reinforced rubber composite materials is 15-30wt%.
In the present invention, the reinforced rubber composite material may further contain zinc oxide, stearic acid, carbon black N330, an accelerator DM, an accelerator TMTD, sulfur, and the like.
In the present invention, the type of the rubber material is not particularly limited, and may be, 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, or the like, and is preferably the same type as the rubber emulsion in the RFL emulsion.
In a second aspect, the present invention provides a sized large tow carbon fiber prepared by the method of the first aspect of the present invention.
The present invention will be described in detail by examples. In the following examples, each parameter was obtained by the following method.
Infiltration time: 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 ℃. With an OCA20 high-speed contact angle meter, 3 microliters of deionized water was dropped onto the surface of the glass sheet, and the time taken to observe the time taken for the drop to start from dropping to the surface to complete wetting was recorded, and the complete wetting was counted with a contact angle of 0.
Surface tension: the pre-sizing agent was diluted to a concentration of 2wt% and tested for surface tension using a dynamic surface tensiometer at 25 ℃.
Adhesive force: the sized large-tow carbon fibers were embedded in unvulcanized natural rubber blocks (wherein the mass of the sized large-tow carbon fibers was 20% of the mass of the natural rubber blocks), 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 sized large tow carbon fibers are pulled out at a speed of 200 mm/min, and the tension required for pulling out the large tow carbon fibers for a length of 1cm is the bonding force between the fibers and rubber.
Sizing amount: and weighing the mass of the carbon fibers before and after sizing, and calculating the sizing amount according to the formula. The sizing amount% = (mass of carbon fiber after sizing-mass of carbon fiber before sizing)/mass of carbon fiber before sizing x 100%.
Number of wear-resistant times: the number of times required for the sized large tow carbon fibers to rub to break was tested using a TM200H yarn abrasion tester.
Polyester polyurethane, available from Shanghai organic, brand: texin340X, texin290, texin345, texin275N, texin180, texin220.
KTM-3F epoxy emulsion, purchased from national drug reagent;
polyvinyl alcohol PVA, purchased from chinese medicine agents.
Examples 1 to 6
Examples 1-6 are methods for producing a homogeneous 150K 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 239 ℃, 250 ℃, 260 ℃ and 271 ℃. 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 1.28, 0.97 and 0.96;
Low temperature carbonization: taking nitrogen as a medium, sequentially passing through 5 low-temperature carbonization furnaces with the temperature of 520 ℃, 620 ℃, 690 ℃, 800 ℃ and 850 ℃ in heating temperature areas, controlling the draft ratio of each area to be 1.08, and controlling the total residence time in the low-temperature carbonization furnaces to be 1.2 minutes to prepare the low-temperature carbonized silk;
High temperature carbonization: the method comprises the steps of taking nitrogen as a medium, sequentially passing through 5 high-temperature carbonization furnaces with the temperature of 950 ℃, 1250 ℃, 1270 ℃, 1335 ℃ and 1440 ℃ in a heating temperature zone, controlling the draft ratio of each zone to be 0.8, and controlling the total residence time in the high-temperature carbonization furnaces to be 1.2 minutes to prepare the high-temperature carbonization wires;
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 22V, the concentration of the electrolyte is 18wt%, and the treatment time is 60 seconds, so that the carbon fiber after surface treatment is obtained;
Washing: washing the surface-treated carbon fiber at a washing flow of 4500L/h and a washing temperature of 55 ℃ to obtain washed carbon fiber;
Sizing and drying: directly introducing the washed carbon fibers into a first sizing tank for pre-sizing, and then, through a heat-conducting oil hot roller, pre-drying under the condition of setting technological parameters; then the fiber enters a second sizing tank for secondary sizing, and then sequentially passes through an infrared radiation dryer and vertical hot air drying, and secondary drying is carried out under the condition of setting technological parameters, so that large-tow carbon fibers after sizing are obtained;
Winding and reeling: and winding and filament collecting the sized large-tow carbon fibers by using a carbon fiber winding machine under 2860-2950cN tension to obtain sized large-tow carbon fibers for reinforcing the rubber composite material.
Wherein, the types of the pre-sizing agent are shown in table 1, the properties of the pre-sizing agent, the mol ratio of resorcinol to formaldehyde in the secondary sizing agent RFL emulsion, the pre-sizing amount and the secondary sizing amount are shown in table 2, and the process parameters of the pre-sizing drying and the secondary sizing drying are shown in table 3.
Wherein, the brand of the polyester polyurethane is: texin340X, texin290, texin345, texin275N, texin180, texin220.
Comparative example 1
Comparative example 1 is a method for manufacturing 150K carbon fiber, according to the method of example 1, except that the sizing drying process is: and (3) sizing the unglued large tow carbon fibers by adopting a commercially available KTM-3F epoxy emulsion sizing agent, and drying by vertical hot air at a drying temperature of 150 ℃. Winding and filament collecting to prepare the sized large-tow carbon fiber.
Comparative example 2
Comparative example 2 is a method for producing 150K carbon fiber, according to the method of example 1, except that the non-sized large tow carbon fiber was sized with the RFL emulsion of example 2, dried with vertical hot air, and dried at 150 ℃. Winding and filament collecting to prepare the sized large-tow carbon fiber.
Comparative example 3
Comparative example 3 is a method for manufacturing 150K carbon fiber, according to the method of example 1, except that the ungumped large tow carbon fiber is pre-sized with a polyvinyl alcohol PVA aqueous sizing agent, dried with vertical hot air, and dried at 80 ℃; then, the RFL emulsion of example 2 was used for secondary sizing, and the drying temperature was 165 ℃. Winding and filament collecting to prepare the sized large-tow carbon fiber.
TABLE 1
TABLE 2
TABLE 3 Table 3
Ps, in the table, "distance" refers to the height between the carbon mid-wave infrared radiator and the carbon fiber of the infrared radiation heating dryer
Test case
The sized large tow carbon fibers prepared in examples and comparative examples were subjected to abrasion resistance and adhesion testing, and the results are shown in table 4.
TABLE 4 Table 4
| Wear resistance (secondary) | Cohesive force (N) | |
| Comparative example 1 | 21600 | 103 |
| Comparative example 2 | 23300 | 111 |
| Comparative example 3 | 25600 | 121 |
| Example 1 | 37850 | 126 |
| Example 2 | 36600 | 141 |
| Example 3 | 38780 | 136 |
| Example 4 | 34960 | 138 |
| Example 5 | 36430 | 134 |
| Example 6 | 37310 | 129 |
As can be seen from the results in the table, comparative example 1 only adopts the conventional epoxy emulsion, comparative example 2 only adopts the RFL emulsion, and the prepared carbon fiber has lower bonding force with the rubber matrix and poorer wear resistance. The comparative example 3 adopts the polyvinyl alcohol pre-sizing agent with overlarge contact angle and surface tension, and the improvement effect is not obvious.
Examples 1-6 use a polyvinyl alcohol-containing pre-sizing agent and RFL emulsion with a contact angle less than or equal to 35 degrees and a surface tension less than or equal to 35mN/m, and through a specific sizing and drying process, the adhesion force between the finally prepared carbon fiber and the rubber matrix is improved, and meanwhile, the wear resistance is greatly improved, and the overall improvement effect is obvious.
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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