CN109722743B - Carbon fiber for polyolefin resin matrix composite material and preparation method thereof - Google Patents
Carbon fiber for polyolefin resin matrix composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon fiber for polyolefin resin matrix composite material and a preparation method thereof, wherein the preparation process comprises the following steps: polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, drying before sizing, drying after sizing, winding and yarn winding. Wherein, the sizing agent of polyolefin resin-based suspension is adopted; the polyolefin resin-based suspension sizing agent consists of polyolefin resin powder, sodium polyacrylate, fatty alcohol-polyoxyethylene ether and deionized water; according to the total mass of the solid components being 100%, the polyolefin resin powder accounts for 65-75 wt%, the sodium polyacrylate accounts for 10-15 wt%, and the fatty alcohol-polyoxyethylene ether accounts for 15-20 wt%. The carbon fiber prepared by the method is suitable for preparing polyolefin resin matrix composite materials, and the prepared composite materials are excellent in technological performance and high in interface binding force.
Description
Technical Field
The invention belongs to the technical field of carbon fiber preparation, and particularly relates to a carbon fiber for a polyolefin resin matrix composite material and a preparation method thereof.
Background
Polyolefin resins are thermoplastic resins with low cost, easy processing and molding, and wide output and application, and are often used as matrix resins of composite materials. Carbon fiber is a light high-strength continuous reinforcing material, and is often used as a reinforcing phase of a composite material. The composite material prepared by combining the comprehensive advantages of the carbon fiber and the polyolefin resin, taking the carbon fiber as a reinforcing phase and taking the polyolefin resin as a matrix has good application prospect and industrial value.
The carbon fiber is subjected to a series of high-temperature treatment, the surface of the carbon fiber is relatively inert, the fiber is loose, and a layer of sizing agent is usually coated to perform surface treatment on the carbon fiber, so that the technological performance of the sized carbon fiber, particularly the large-tow carbon fiber, is improved on the one hand; on the other hand, the interface bonding force between the carbon fiber and the matrix resin is enhanced. At present, carbon fiber manufacturers generally adopt epoxy resin emulsion sizing agents which have a large number of active epoxy groups, and the epoxy resin emulsion sizing agents are easy to open and solidify after being processed at high temperature or stored for a long time, so that the fibers are locally or integrally aged and hardened, and the processing and product performances are deteriorated. Therefore, the preparation of the special carbon fiber which can be applied to the polyolefin resin matrix composite becomes an urgent need of carbon fiber manufacturers and users.
Chinese patent 201380046280.3 provides a modified chopped carbon fiber reinforced polyolefin composite material, which is prepared by mixing or extruding and granulating 20-75 wt% of polyolefin, 7-40 wt% of chopped carbon fibers, 2-20 wt% of compatibilizer, 5-20 wt% of epoxy resin and 0.2-5 wt% of curing agent. The method enables the epoxy resin to be cured on the surface of the chopped carbon fiber to form a coating layer, improves the roughness of the chopped carbon fiber, improves a two-phase interface to a certain extent, and still does not solve the problems that the epoxy resin is easy to open and cure, and the like.
Chinese patent 201210536799.7 discloses a carbon fiber sizing agent for reinforcing polypropylene, which is an emulsion sizing agent prepared from graphene oxide modified epoxy resin, and can solve the problem of poor interface bonding between carbon fiber and polypropylene. However, the main resin of the patent is still epoxy resin, and aging and curing are easy to occur; graphene oxide is expensive and difficult to apply industrially; the formula contains a large amount of organic solvent, and has poor safety and stability.
Disclosure of Invention
The invention provides a carbon fiber suitable for polyolefin resin matrix composite and a preparation method thereof, aiming at solving various problems in the industrial application of the existing carbon fiber reinforced polyolefin resin matrix composite. The novel suspension type carbon fiber sizing agent prepared by using polyolefin resin powder as a main body, sodium polyacrylate as a main dispersing agent and fatty alcohol-polyoxyethylene ether as a stabilizing auxiliary agent and adopting a physical stirring and mixing method is introduced into the sizing process, so that the problems of poor impregnation of polyolefin matrix resin, aging and hardening of carbon fibers and the like are solved. Meanwhile, an infrared radiation heating process before sizing and a drying process of drying by a horizontal hot air drying box after sizing are introduced, so that the problems of uniformity of spreading of a sizing agent of a polyolefin resin suspension on the surface of carbon fiber, fiber drying and the like are solved.
The surface of the carbon fiber prepared by the method is coated with the sizing agent prepared by taking polyolefin resin as a main body, does not contain epoxy resin or other resin components, and is suitable for preparing polyolefin resin matrix composite materials. The prepared carbon fiber can adjust the sizing amount and the width of the collected filament according to the subsequent processing requirements, the material consumption and the processing difficulty of the subsequent processing application are reduced, and the uniformity and the stability of products such as carbon fiber prepreg, fabric and the like are good. The prepared composite material has excellent process performance and high interface binding force.
The technical scheme of the invention is specifically introduced as follows.
The invention provides a preparation method of carbon fiber for polyolefin resin matrix composite, which comprises the production processes of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, washing, drying before sizing, drying after sizing and winding and filament winding in sequence; wherein: sizing is carried out in a dipping type sizing tank, and a sizing agent adopts a polyolefin resin-based suspension sizing agent; the polyolefin resin-based suspension sizing agent consists of polyolefin resin powder, sodium polyacrylate, fatty alcohol-polyoxyethylene ether and deionized water; according to the total mass of the solid components being 100%, the polyolefin resin powder accounts for 65-75 wt%, the sodium polyacrylate accounts for 10-15 wt%, and the fatty alcohol-polyoxyethylene ether accounts for 15-20 wt%.
In the invention, the mass content of the solid component in the polyolefin resin-based suspension sizing agent is 5-30%.
In the invention, the preparation method of the polyolefin resin-based suspension sizing agent comprises the following steps: firstly, putting polyolefin resin powder and sodium polyacrylate into a mixing container according to a proportion, adding deionized water, starting a machine to stir when the added water amount reaches 25-35 wt% of the total feeding amount of the polyolefin resin powder and the sodium polyacrylate, and continuously adding the rest water; controlling the stirring speed to be 50-250 rpm, and stirring for 30-60 min for homogenizing and dispersing to obtain uniform white emulsion; then, transferring the materials into a closed device provided with a high-speed emulsifier, and adding quantitative fatty alcohol-polyoxyethylene ether to ensure that the mass percentage of all the solid components in the suspension sizing agent is 5-30%; and finally, starting a high-speed emulsifying machine, and continuously stirring for 10-30 min at the rotating speed of 3000-10000 rpm to obtain the uniform and stable milky white suspension sizing agent.
In the present invention, the number average molecular weight of the polyolefin resin powder is 1.0 to 4.0 ten thousand, preferably 1.5 to 3.0 ten thousand. The particle size of the polyolefin resin powder is 10-60 microns, preferably 20-40 microns.
In the present invention, the polyolefin resin powder is any one or more of polyethylene, polypropylene, polybutylene, and polypentene.
In the invention, the number average molecular weight of the sodium polyacrylate is 1000-5000, preferably 2000-4000. The fatty alcohol-polyoxyethylene ether has a structure shown in formula (1):
wherein R is selected from C10～C20Any of alkyl groups; the polymerization degree n is an integer between 25 and 40.
In the invention, the pre-oxidation is carried out in an oxidation furnace, the oxidation furnace has 5 temperature zones, and the temperature is controlled to be 0-240 ℃, 0-250 ℃, 0-260 ℃, 0-270 ℃ and 0-280 ℃ respectively.
In the invention, low-temperature carbonization is carried out in a low-temperature carbonization furnace, the low-temperature carbonization furnace has 5 temperature zones, and the temperature is controlled to be 0-600 ℃, 0-650 ℃, 0-750 ℃, 0-850 ℃ and 0-950 ℃ respectively; the high-temperature carbonization is carried out in a high-temperature carbonization furnace, the high-temperature carbonization furnace is provided with 5 temperature zones, and the temperature is controlled to be 0-1300 ℃, 0-1400 ℃, 0-1500 ℃ and 0-1600 ℃ respectively.
In the invention, the infrared radiation heating process is adopted for drying before sizing, and the drying process of drying by a horizontal hot air drying box is adopted for drying after sizing.
The invention also provides the carbon fiber for the polyolefin resin matrix composite material prepared by the preparation method.
When the emulsion type epoxy resin-based sizing agent is used for sizing carbon fibers, the softening temperature of the epoxy resin is low, so that the excessively high drying temperature cannot be adopted. Under the condition that the drying temperature and the drying time are limited, the sizing amount of the carbon fiber prepared by adopting the emulsion type epoxy resin-based sizing agent cannot be too high, otherwise, the sizing fiber is difficult to dry, the surface contains a large amount of moisture, the subsequent processing and application are influenced, and the carbon fiber is limited to be prepared into cluster fiber.
Compared with the adoption of an emulsion type epoxy resin-based sizing agent, the carbon fiber prepared by the method adopts an infrared radiation heating process before sizing and a drying process of drying in a horizontal hot air drying box after sizing. By adopting the infrared radiation heating and drying process before sizing, the moisture of each carbon fiber in the carbon fiber tows can be removed quickly before the carbon fibers enter the sizing tank, and the consistency of the moisture content of the carbon fibers is kept. After the carbon fibers enter the sizing tank, the sizing agent can be quickly impregnated into the fiber bundle, so that the fiber sizing amount and the sizing speed are improved; meanwhile, the sizing agent and each carbon fiber can be ensured to have the same infiltration adsorption capacity, the sizing effect is ensured to be more uniform and stable, and the phenomenon of anti-wetting caused by inconsistent water content is avoided. By adopting the drying process of drying the sizing horizontal hot air drying box, the sizing carbon fiber can be dried more quickly under the tension control, the process difficulty and the energy consumption are reduced, and the fiber is spread into uniform ribbon fiber. The sizing carbon fiber prepared by the method has controllable sizing amount, can reduce the using amount of resin films during prepreg processing, and improves the overall economy of products. The width of the tows can be flexibly controlled by adjusting sizing amount and drying process parameters, and the like, and the method can be applied to different types of reprocessing equipment and processes, and can improve the process applicability of products.
Compared with the prior art, the invention has the beneficial effects that:
(1) the carbon fiber for the polyolefin resin matrix composite material is prepared by adopting the novel suspension type carbon fiber sizing agent which is prepared by adopting polyolefin resin powder as a main body, sodium polyacrylate as a main dispersing agent, fatty alcohol-polyoxyethylene ether as a stabilizing auxiliary agent and adopting a physical stirring and mixing method, and solves the problems of poor impregnation of polyolefin matrix resin, aging and hardening of the fiber and the like.
(2) In the preparation process of the carbon fiber for the polyolefin resin matrix composite material, the infrared radiation heating process before sizing and the drying process of drying in the horizontal hot air drying box after sizing are introduced, so that the problems of uniformity of the sizing agent of the polyolefin resin suspension spread on the surface of the carbon fiber, fiber drying and the like are solved.
(3) The carbon fiber prepared by the method does not contain epoxy resin or other resin components on the surface, and is suitable for preparing polyolefin resin matrix composite materials. The prepared carbon fiber can adjust the sizing amount and the tow width according to the subsequent processing requirements, reduces the material consumption and the processing difficulty of the subsequent processing application, and has wider product application range and higher economical efficiency. The prepared composite material has excellent process performance and high interface binding force.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Comparative example 1
Comparative example 1 is a method for manufacturing 45K carbon fiber, the specific process includes polymerization, spinning, pre-oxidation, low temperature carbonization, high temperature carbonization, surface treatment, water washing, drying before sizing, drying after sizing, winding and winding production processes. The specific process of comparative example 1 is the same as that of examples 1 to 4, wherein the parameters of polymerization, pre-oxidation, low-temperature carbonization, high-temperature carbonization and sizing are different.
Step 1: and (4) polymerizing. The polymerization production process is the same as the method described in the step 1 of the embodiment 1 to 4, and the solution polymerization is carried out by using a sodium thiocyanate aqueous solution as a solvent, wherein the parameters changed in the polymerization production process are that the mixture ratio of comonomers in the solution polymerization reaction is different, the weight ratio of acrylonitrile to methyl methacrylate to sodium itaconate is 91.0:8.0:0.5, the feed concentration of the total polymerization monomers is 28 wt%, the initiator is azobisisobutyronitrile, and the dosage of the azobisisobutyronitrile is 0.8 wt% of the total amount of all the polymerization monomers. The polymerization temperature was 85 ℃ and the reaction time was 110 minutes. Then the prepared polymeric slurry is demonomerized and defoamed to prepare polyacrylonitrile stock solution for spinning.
Step 2: and (4) spinning. The spinning production process and the method described in the step 2 of the embodiment 1-4.
And step 3: and (4) pre-oxidizing. The pre-oxidation production procedure is the same as the method described in step 3 of examples 1-4. Wherein the parameters changed in the pre-oxidation production process are that the furnace zone temperatures of No. 1 oxidation furnace, No. 2 oxidation furnace, No. 3 oxidation furnace, No. 4 oxidation furnace and No. 5 oxidation furnace are 238 ℃, 246 ℃, 254 ℃, 263 ℃ and 271 ℃. The draft multiple between each temperature zone of the oxidation furnace is respectively 6 percent, 0 percent, 1 percent and 1 percent.
And 4, step 4: and (4) carbonizing at low temperature. The low-temperature carbonization production procedure is the same as the method described in the step 4 of the embodiments 1 to 4. Wherein the parameters changed in the low-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the low-temperature carbonization furnace are respectively controlled to be 500 ℃, 600 ℃, 700 ℃, 800 ℃ and 850 ℃. The draft was controlled to 8.0%.
And 5: and (4) carbonizing at high temperature. The high-temperature carbonization production procedure is the same as the method described in the step 5 of the embodiment 1-4. Wherein the parameters changed in the high-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the high-temperature carbonization furnace are controlled to be 1200 ℃, 1300 ℃, 1350 ℃, 1410 ℃ and 1500 ℃ respectively. The draft was controlled to-7.0%.
Step 6: and (6) surface treatment. The surface treatment production procedure is the same as the method described in the step 6 of the embodiment 1-4.
And 7: and (5) washing with water, and drying before sizing. The production procedures of water washing and drying before sizing are the same as the method described in the step 7 of the embodiment 1-4.
And 8: sizing, drying and winding to obtain the silk. The production procedures of sizing, drying, winding and filament collecting are the same as the method described in the step 8 of the embodiment 1-4. The sizing agent is an SP-2 type emulsion carbon fiber sizing agent (produced by Shanghai organic of Chinese academy of sciences) prepared from bisphenol F epoxy resin/nonionic surfactant, the concentration of the sizing agent is 3.2%, and the 45K sized carbon fiber is prepared by winding and collecting filaments.
Comparative example 2
Comparative example 2 is a method for manufacturing 48K carbon fiber, which comprises the steps of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, drying before sizing, drying after sizing, and winding and reeling. The specific process of comparative example 2 is the same as that of examples 1 to 4, wherein the parameters of polymerization, pre-oxidation, low-temperature carbonization, high-temperature carbonization, and sizing are different.
Step 1: and (4) polymerizing. The polymerization production process is the same as the method described in the step 1 of the embodiment 1 to 4, and the solution polymerization is carried out by using a sodium thiocyanate aqueous solution as a solvent, wherein the parameters changed in the polymerization production process are that the mixture ratio of comonomers in the solution polymerization reaction is different, the weight ratio of acrylonitrile to methyl methacrylate to sodium itaconate is 91.2:8.17:0.63, the feed concentration of the total polymerization monomers is 27.5 wt%, the initiator is azobisisobutyronitrile, and the dosage of the azobisisobutyronitrile is 0.76 wt% of the total amount of all the polymerization monomers. The polymerization temperature was 84 ℃ and the reaction time was 108 minutes. Then the prepared polymeric slurry is demonomerized and defoamed to prepare polyacrylonitrile stock solution for spinning.
Step 2: and (4) spinning. The spinning production process and the method described in the step 2 of the embodiment 5-8.
And step 3: and (4) pre-oxidizing. The pre-oxidation production procedure is the same as the method described in step 3 of examples 1-4. Wherein the parameters changed in the pre-oxidation production process are that the furnace zone temperatures of the No. 1 oxidation furnace, the No. 2 oxidation furnace, the No. 3 oxidation furnace, the No. 4 oxidation furnace and the No. 5 oxidation furnace are 237 ℃, 245 ℃, 253 ℃, 262 ℃ and 270 ℃ respectively. The draft multiple between each temperature zone of the oxidation furnace is respectively 6 percent, 5.5 percent, 0 percent, -1 percent and-1 percent.
And 4, step 4: and (4) carbonizing at low temperature. The low-temperature carbonization production procedure is the same as the method described in the step 4 of the embodiments 1 to 4. Wherein the parameters changed in the low-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the low-temperature carbonization furnace are respectively controlled to be 495 ℃, 595 ℃, 700 ℃, 790 ℃ and 850 ℃. The draft was controlled to 8.0%.
And 5: and (4) carbonizing at high temperature. The high-temperature carbonization production procedure is the same as the method described in the step 5 of the embodiment 1-4. Wherein the parameters changed in the high-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the high-temperature carbonization furnace are respectively controlled to be 1150 ℃, 1250 ℃, 1330 ℃, 1400 ℃ and 1490 ℃. The draft was controlled to-7.0%.
Step 6: and (6) surface treatment. The surface treatment production procedure is the same as the method described in the step 6 of the examples 5 to 8.
And 7: and (5) washing with water, and drying before sizing. The production procedures of water washing and drying before sizing are the same as the method described in the step 7 of the embodiment 5-8.
And 8: sizing, drying and winding to obtain the silk. The production processes of sizing, drying, winding and filament collecting are the same as the method described in the step 8 of the embodiment 5-8. The sizing agent is an SP-2E type emulsion carbon fiber sizing agent (produced by Shanghai organic of Chinese academy of sciences) prepared from modified bisphenol F epoxy resin/cationic surfactant, the concentration of the sizing agent is 2.8%, and 48K sized carbon fibers are prepared by winding and collecting filaments.
Examples 1 to 4
Embodiments 1 to 4 are methods for manufacturing 45K carbon fibers suitable for polyolefin resin-based composite materials, which include the production processes of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, drying before sizing, drying after sizing, and winding and reeling. The specific process is as follows:
step 1: and (4) polymerizing.
The method comprises the steps of carrying out solution polymerization by using a sodium thiocyanate aqueous solution as a solvent, using acrylonitrile, methyl methacrylate and sodium itaconate as polymerization monomers, wherein the weight ratio of the acrylonitrile to the methyl methacrylate to the sodium itaconate is 91.9:7.1:1.0, the feeding concentration of the total polymerization monomers is 26.5 wt%, simultaneously adding an initiator azobisisobutyronitrile, wherein the initiator amount is 0.7 wt% of the total amount of all the polymerization monomers, the polymerization temperature is 83 ℃, and the reaction time is 102 minutes.
Taking 55.2 wt% sodium thiocyanate aqueous solution as a solvent, preparing polymerization slurry by adopting a continuous solution polymerization process, and preparing polyacrylonitrile stock solution after demonomerization and defoaming.
Step 2: and (4) spinning.
The method adopts a sodium thiocyanate (NaSCN) wet spinning production method to prepare raw silk by carrying out solidification forming, cold drawing, water washing, hot drawing, oiling, drying, steam drawing and sizing on polyacrylonitrile stock solution. The aperture of a spinneret plate is 0.058mm, the number of spinneret plate holes is 45000, the solidification forming temperature is-0.5 ℃, the flow rate of a solidification bath is 7500L/h, and the concentration of the solidification bath is 13.5%; the draft multiple of cold draft is 2.3 times; the water washing temperature is 50 ℃, and the water washing flow is 4000L/h; the hot drawing temperature is 90 ℃, and the drawing multiple of the hot drawing is 5.8 times; the concentration of the oiling oil agent is 2.3 percent; the drying temperature is 140 ℃; the steam drafting multiple is 2.2 times, and the steam pressure is 200 KPa; the setting temperature is 122 ℃.
And step 3: and (4) pre-oxidizing.
The protofilament sequentially passes through an oxidation furnace No. 1, an oxidation furnace No. 2, an oxidation furnace No. 3, an oxidation furnace No. 4 and an oxidation furnace No. 5 to be subjected to pre-oxidation treatment. The furnace zone temperatures of the No. 1 oxidation furnace, the No. 2 oxidation furnace, the No. 3 oxidation furnace, the No. 4 oxidation furnace and the No. 5 oxidation furnace are 236 ℃, 245 ℃, 251 ℃, 260 ℃ and 268 ℃ respectively. The draft multiple between each temperature zone of the oxidation furnace is 5 percent, 0 percent, 1 percent and 1 percent respectively. The residence time of each oxidation furnace is 15 minutes, and the total pre-oxidation time is 75 min.
And 4, step 4: and (4) carbonizing at low temperature.
And (3) the pre-oxidized fiber at the outlet of the No. 5 oxidation furnace enters a low-temperature carbonization furnace through a traction device, and is carbonized at low temperature by taking nitrogen as a medium to prepare the low-temperature carbonized fiber. The temperature of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the low-temperature carbonization furnace is controlled to be 485 ℃, 580 ℃, 680 ℃, 780 ℃ and 830 ℃ respectively. The draft multiple is controlled to be 7.5 percent, and the total residence time in the low-temperature carbonization furnace is 1.8 min.
And 5: and (4) carbonizing at high temperature.
And (3) the tows at the outlet of the low-temperature carbonization furnace enter the high-temperature carbonization furnace through a traction device, and are carbonized at high temperature by taking nitrogen as a medium to prepare the high-temperature carbonized filament. The temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the high-temperature carbonization furnace are respectively controlled to 1090 ℃, 1240 ℃, 1330 ℃, 1390 ℃ and 1470 ℃. The draft multiple is controlled to be-6.5 percent, and the total residence time in the high-temperature carbonization furnace is 1.8 min.
Step 6: and (6) surface treatment.
And the tows at the outlet of the high-temperature carbonization furnace enter 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 12.5%, and the retention time of the tows in the electrolyte is 4 min.
And 7: and (5) washing with water, and drying before sizing.
The tows after surface treatment sequentially pass through a rinsing bath and an infrared radiation heating dryer, and are subjected to rinsing and infrared radiation drying before sizing. The water washing flow rate is 2200L/h, the water washing temperature is 40 DEG C. The height distance between the carbon medium wave infrared radiator and the carbon fiber of the infrared radiation heating dryer is 70mm, and the power density is 42KW/m2And when the drying time is 15S, the water content of the carbon fiber tows is 60%.
And 8: sizing, drying and winding to obtain the silk.
Sequentially adding a certain amount of polypropylene resin powder and sodium polyacrylate into a mixing container A according to a certain proportion, gradually adding a certain amount of deionized water, starting a machine to stir when the added water amount reaches 30 wt% of the total feeding amount of the polyolefin resin powder and the sodium polyacrylate, and continuously adding the rest amount of water; controlling the stirring speed to be 50-250 rpm, and stirring for 30-60 min for homogeneous dispersion to obtain uniform white emulsion. And transferring the materials into a mixing container B provided with a high-speed emulsifier, adding a certain amount of fatty alcohol-polyoxyethylene ether, starting the high-speed emulsifier, and continuously stirring at the rotating speed of 3000-10000 rpm for 10-30 min to obtain the uniform and stable milky white suspension sizing agent. And transferring the sizing agent into the sizing tank through the feeding pump, and starting a circulating pump of the sizing tank to enable the sizing agent to slowly flow in the sizing tank.
The carbon fiber tows at the outlet of the infrared radiation heating dryer are directly introduced into a sizing tank for sizing, and the sized carbon fibers enter a horizontal hot air drying box for drying at the temperature of 150 ℃. And (3) feeding the sized and dried carbon fiber into a carbon fiber winding machine, and winding under the tension of 2300-2450 cN to obtain the 45K carbon fiber suitable for the polyolefin resin matrix composite.
Examples 5 to 8
In embodiments 5 to 8, a method for manufacturing 48K carbon fibers suitable for polyolefin resin-based composite materials includes polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, drying before sizing, drying after sizing, and winding and reeling production processes. The specific process of this example is the same as the specific process of examples 1 to 4, wherein the parameters of spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, and sizing are different.
Step 1: and (4) polymerizing. The polymerization production process is the same as the method described in the step 1 of the embodiment 1 to 4, and the solution polymerization is carried out by using a sodium thiocyanate aqueous solution as a solvent, wherein the parameters changed in the polymerization production process are that the mixture ratio of comonomers in the solution polymerization reaction is different, the weight ratio of acrylonitrile to methyl methacrylate to sodium itaconate is 91.0:5.0:4.0, the feed concentration of the total polymerization monomers is 22.5 wt%, the initiator is azobisisobutyronitrile, and the dosage of the azobisisobutyronitrile is 0.46 wt% of the total amount of all the polymerization monomers. The polymerization temperature was 80 ℃ and the reaction time was 90 minutes. Then the prepared polymeric slurry is demonomerized and defoamed to prepare polyacrylonitrile stock solution for spinning.
Step 2: and (4) spinning. The spinning production process is the same as the method described in the step 2 of the embodiment 1-4, and the parameters of the spinning process are different. The aperture of a spinneret plate is 0.058mm, the number of spinneret plate holes is 48000, the solidification forming temperature is-1 ℃, the flow rate of a solidification bath is 8000L/h, and the concentration of the solidification bath is 14 percent; the draft multiple of cold draft is 2.5 times; the washing temperature is 55 ℃, and the washing flow is 4500L/h; the hot drawing temperature is 92 ℃, and the drawing multiple of the hot drawing is 6.0 times; the concentration of the oiling oil agent is 2.5 percent; the drying temperature is 142 ℃; the steam drafting multiple is 2.4 times, and the steam pressure is 220 KPa; the setting temperature is 126 ℃.
And step 3: and (4) pre-oxidizing. The pre-oxidation production procedure is the same as the method described in step 3 of examples 1-4. Wherein the parameters changed in the pre-oxidation production process are that the furnace zone temperatures of the No. 1 oxidation furnace, the No. 2 oxidation furnace, the No. 3 oxidation furnace, the No. 4 oxidation furnace and the No. 5 oxidation furnace are 230 ℃, 238 ℃, 246 ℃, 253 ℃ and 260 ℃ respectively. The draft multiple between each temperature zone of the oxidation furnace is 3 percent, 0 percent, 1 percent and 1 percent respectively. The residence time of each oxidation furnace is 15 minutes, and the total pre-oxidation time is 75 min.
And 4, step 4: and (4) carbonizing at low temperature. The low-temperature carbonization production procedure is the same as the method described in the step 4 of the embodiments 1 to 4. Wherein the parameters changed in the low-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the low-temperature carbonization furnace are controlled to be 440 ℃, 530 ℃, 630 ℃, 720 ℃ and 780 ℃ respectively. The draft was controlled to 5.2%. The total residence time in the low temperature carbonization furnace was 1.8 min.
And 5: and (4) carbonizing at high temperature. The high-temperature carbonization production procedure is the same as the method described in the step 5 of the embodiment 1-4. Wherein the parameters changed in the high-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone and the 5 th zone of the high-temperature carbonization furnace are respectively controlled to be 1000 ℃, 1150 ℃, 1250 ℃, 1310 ℃ and 1390 ℃. The draft was controlled to-4.2%. The total residence time in the high temperature carbonization furnace was 1.8 min.
Step 6: and (6) surface treatment. The surface treatment production procedure is the same as the method described in the step 6 of the embodiment 1-4. And taking an ammonium bicarbonate aqueous solution as an electrolyte, controlling the voltage to be 25V, controlling the concentration of the electrolyte to be 13%, and controlling the retention time of the tows in the electrolyte to be 4 min.
And 7: and (5) washing with water, and drying before sizing. The production procedures of water washing and drying before sizing are the same as the method described in the step 7 of the embodiment 1-4, and the parameters are different. The water washing flow rate was 2500L/hr, and the water washing temperature was 42 ℃. Height distance between carbon medium wave infrared radiator and carbon fiber of infrared radiation heating dryer is 72mm, and power density is 45KW/m2And when the drying time is 15S, the water content of the carbon fiber tows is 60%.
And 8: sizing, drying and winding to obtain the silk.
The preparation method, the sizing method, the drying method and the winding and reeling method of the suspension sizing agent are the same as those described in the step 8 of the embodiment 1-4.
The carbon fiber tows at the outlet of the infrared radiation heating dryer are directly introduced into a sizing tank for sizing, and the sized carbon fibers enter a horizontal hot air drying box for drying at the temperature of 152 ℃. And (3) feeding the sized and dried carbon fibers into a carbon fiber winding machine, and winding and collecting the carbon fibers under the tension of 2500-2900 cN to obtain the 48K carbon fibers suitable for the polyolefin resin matrix composite.
The solid components of the suspension sizing agents prepared in the above examples 1 to 8 are shown in table 1, the composition amount and concentration of the sizing agent are shown in table 2, the preparation process parameters of the sizing agent are shown in table 3, and the performance evaluation results of the obtained carbon fibers are shown in table 4. The invention adopts a high-temperature sizing amount tester to test the sizing amount of the sized carbon fiber; testing the width of the sizing carbon fiber by using a ruler; testing the complete infiltration time from the beginning of the polyolefin resin liquid drop contacting the carbon fiber to the complete immersion of the polyolefin resin liquid drop into the carbon fiber by adopting an OCA20 contact angle measuring instrument; the interfacial shear strength between the polyolefin resin and the carbon fiber was measured by using a MODEL HM410 interfacial property evaluation apparatus, a Japan Dongrong industries Co., Ltd.
As can be seen from the test results of the 45K carbon fibers in examples 1 to 4, compared with comparative example 1 (45K carbon fibers sized by using an epoxy resin-based sizing agent), the sized carbon fibers prepared by using a suspension sizing agent have higher sizing amount, lower dispersion coefficient and smaller width dispersion, which indicates that the surfaces of the fibers are uniformly coated with more polyolefin sizing agents and the fibers have a sufficient spreading effect. The polyolefin resin has less soaking time on the sizing carbon fiber, better process performance, and better soaking effect and bonding capacity between the fiber and the polyolefin matrix resin. The same improvement effect was obtained with the 48K carbon fibers in examples 5 to 8.
TABLE 1 solid components of sizing agent
TABLE 2 sizing agent composition amounts and concentrations
TABLE 3 sizing agent preparation Process parameters
Table 4 evaluation results of carbon fiber properties
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A preparation method of carbon fiber for polyolefin resin matrix composite is characterized by comprising the production processes of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, washing, drying before sizing, drying after sizing and winding; wherein: sizing is carried out in a dipping type sizing tank, and a sizing agent adopts a polyolefin resin-based suspension sizing agent; the polyolefin resin-based suspension sizing agent consists of polyolefin resin powder, sodium polyacrylate, fatty alcohol-polyoxyethylene ether and deionized water; according to the total mass of the solid components being 100%, the polyolefin resin powder accounts for 65-75 wt%, the sodium polyacrylate accounts for 10-15 wt%, and the fatty alcohol-polyoxyethylene ether accounts for 15-20 wt%; the polyolefin resin powder is any one or more of polyethylene, polypropylene, polybutylene or polypentene; the drying before sizing adopts an infrared radiation heating process, and the drying after sizing adopts a drying process of drying by a horizontal hot air drying box;
the preparation method of the polyolefin resin-based suspension sizing agent comprises the following steps: firstly, putting polyolefin resin powder and sodium polyacrylate into a mixing container according to a proportion, adding deionized water, starting a machine to stir when the added water amount reaches 25-35 wt% of the total feeding amount of the polyolefin resin powder and the sodium polyacrylate, and continuously adding the rest water; controlling the stirring speed to be 50-250 rpm, and stirring for 30-60 min for homogenizing and dispersing to obtain uniform white emulsion; then, transferring the materials into a closed device provided with a high-speed emulsifier, and adding quantitative fatty alcohol-polyoxyethylene ether to ensure that the mass percentage of all the solid components in the suspension sizing agent is 5-30%; and finally, starting a high-speed emulsifying machine, and continuously stirring for 10-30 min at the rotating speed of 3000-10000 rpm to obtain the uniform and stable milky white suspension sizing agent.
2. The method according to claim 1, wherein the polyolefin resin powder has a number average molecular weight of 1.0 to 4.0 ten thousand and a particle diameter of 10 to 60 μm.
3. The preparation method of claim 1, wherein the number average molecular weight of the sodium polyacrylate is 1000-5000, and the fatty alcohol-polyoxyethylene ether has a structure shown in formula (1):
wherein R is selected from C10～C20Any one of alkyl groups; the polymerization degree n is an integer between 25 and 40.
4. The method according to claim 1, wherein the pre-oxidation is carried out in an oxidation furnace having 5 temperature zones controlled at 230 to 240 ℃, 238 to 250 ℃, 246 to 260 ℃, 253 to 270 ℃, and 260 to 280 ℃.
5. The method according to claim 1, wherein the low-temperature carbonization is performed in a low-temperature carbonization furnace having 5 temperature zones, and the temperature is controlled to be 440 to 600 ℃, 530 to 650 ℃, 630 to 750 ℃, 720 to 850 ℃, 780 to 950 ℃; the high-temperature carbonization is carried out in a high-temperature carbonization furnace, the high-temperature carbonization furnace is provided with 5 temperature zones, and the temperature is controlled to be 1000-1300 ℃, 1150-1400 ℃, 1250-1400 ℃, 1310-1500 ℃ and 1390-1600 ℃ respectively.
6. A carbon fiber for polyolefin resin-based composite material obtained by the production method according to any one of claims 1 to 5.
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| CN112760984B (en) * | 2019-10-21 | 2024-01-23 | 中国石油化工股份有限公司 | Method for preparing carbon fiber for composite material |
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