CN109722743A - A kind of polyolefin resin based composites carbon fiber and preparation method thereof - Google Patents
A kind of polyolefin resin based composites carbon fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polyolefin resin based composites carbon fiber and preparation method thereof, preparation process include: before polymerization, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, washing, starching dry after drying, starching, starching, winding receive silk production process.Polyolefin resin base suspension sizing agent is wherein used when starching；The polyolefin resin base suspension sizing agent is made of polyolefin resin powder, Sodium Polyacrylate, fatty alcohol polyoxyethylene ether and deionized water；Gross mass according to solid component is 100%, and polyolefin resin powder accounts for 65~75wt%, and Sodium Polyacrylate accounts for 10~15wt%, and fatty alcohol polyoxyethylene ether accounts for 15~20wt%.Carbon fiber prepared by the present invention is suitable for preparing polyolefin resin based composites, and prepared composite technology is had excellent performance, and interface binding power is high.
Description
Technical field
The invention belongs to technical field of carbon fiber preparation, in particular to a kind of polyolefin resin based composites carbon fiber
And preparation method thereof.
Background technique
Polyolefin resin is that one kind is low in cost, easy processing molding, yield and very widely used thermoplastic resin, often
Matrix resin application as composite material.Carbon fiber is a kind of continuous reinforcing material of high-strength light, frequently as composite material
Reinforced phase application.In conjunction with the comprehensive advantage of carbon fiber and polyolefin resin, reinforced phase is done with carbon fiber, is done with polyolefin resin
Multiple material prepared by matrix has a good application prospect and industrial value.
Carbon fiber is handled by series of high temperature, and surface is in relative inertness, and fiber is loose, it usually needs one layer of sizing agent of coating
Carbon fiber is surface-treated, the processing performance of starching carbon fiber, especially large-tow carbon fiber is on the one hand improved；Another party
The interface binding power of face enhancing carbon fiber and matrix resin.Carbon fiber manufacturer generallys use in epoxy resin latex type at present
Slurry agent is easy to happen curing reaction after high temperature process or long-time storage, causes fiber with a large amount of active epoxy groups
Partly or wholly age hardening, processing and properties of product deteriorate.Therefore, preparing one kind, to can be applied to polyolefin resin base compound
The dedicated carbon fiber of material, becomes carbon fiber producer and the urgent need of user.
Chinese patent 201380046280.3 provides a kind of modified chopped carbon fiber enhancing composite polyolefine material, adopts
With the polyolefin of 20wt%~75wt%, the chopped carbon fiber of 7wt%~40wt%, 2wt%~20wt% expanding material,
The epoxy resin of 5wt%~20wt% and the curing agent of 0.2wt%~5wt% carry out mixing or extruding pelletization, obtain being modified short
Cut fibre reinforced composite polyolefine material.This method makes epoxy resin cure on chopped carbon fiber surface, forms clad, mentions
The high roughness of chopped carbon fiber, improves two-phase interface, but still without solving the easy open loop of epoxy resin to a certain extent
The problems such as solidification.
Chinese patent 201210536799.7 discloses a kind of carbon fiber sizing agent of reinforced polypropylene, uses oxidation stone
Black alkene modified epoxy is prepared into emulsion pasting agent, can improve the problem of carbon fiber Yu polypropylene interface cohesion difference.But it should
Patent matrix resin is still epoxy resin, Yi Fasheng aging solidification；Graphene oxide is with high costs, it is difficult to industrial application；Formula
Containing a large amount of organic solvents, safety and stability is poor.
Summary of the invention
To solve the problems, such as various, this hair occur in current fibre reinforced polyolefin resin based composites industrial application
It is bright to propose a kind of carbon fiber and preparation method thereof suitable for polyolefin resin based composites, this method include polymerization, spinning,
Dry after drying, starching, starching and winding receives silk before pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, washing, starching
Production process.The present invention introduces in sizing technique to be dispersed based on polyolefin resin powder, based on Sodium Polyacrylate
Agent, using fatty alcohol polyoxyethylene ether as stabilization aid, using physical agitation mixed method prepare novel suspended supernatant liquid based carbon fiber
Sizing agent solves the problems such as bad polyolefin base resin dipping and carbon fiber ageing hardening.Meanwhile it is infrared before introducing starching
The drying process that horizontal hot air drying box is dried after radiant heat process, starching, solves polyolefin resin suspension sizing agent
The problems such as the uniformity and fiber that carbon fiber surface is sprawled are dried.
The carbon fiber prepared using the method for the invention, surface coating is by the starching for preparing based on polyolefin resin
Agent is free of epoxy resin or other resin Compositions, suitable for preparing polyolefin resin based composites.Prepared carbon fiber can
According to following process needs, adjusts starching amount and receive silk breadth, the material utilization amount and difficulty of processing of road processed and applied, carbon after reduction
The uniformity and stability of the products such as fiber prepreg material, fabric are good.Prepared composite technology is had excellent performance, interface cohesion
Power is high.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of preparation method of polyolefin resin based composites carbon fiber comprising successively polymerize,
Dry after drying, starching, starching and winding before spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, washing, starching
Receive the production process of silk；Wherein: starching carries out in impregnated sizing groove, and sizing agent uses the suspension starching of polyolefin resin base
Agent；The polyolefin resin base suspension sizing agent by polyolefin resin powder, Sodium Polyacrylate, fatty alcohol polyoxyethylene ether and
Deionized water composition；Gross mass according to solid component is 100%, and polyolefin resin powder accounts for 65~75wt%, polyacrylic acid
Sodium accounts for 10~15wt%, and fatty alcohol polyoxyethylene ether accounts for 15~20wt%.
In the present invention, the mass content of the solid component in polyolefin resin base suspension sizing agent is between 5~30%.
In the present invention, polyolefin resin base suspension sizing agent the preparation method is as follows: firstly, by polyolefin resin powder
It is put in proportion into mixing vessel with Sodium Polyacrylate, deionized water is added, reach polyolefin resin powder to amount of water and gathered
When sodium acrylate 25~35wt% of total amount of feeding, mechanical stirring is opened, and continuously add the water of surplus；Control speed of agitator 50
~250rpm, 30~60min of stirring carry out homogenous disperse, obtain flat-white emulsion；Then, above-mentioned material is transferred to dress
Have in the silent device of high speed emulsifier, quantitative fatty alcohol polyoxyethylene ether is added, above-mentioned all solids component is made to suspend
Mass percent in liquid sizing agent is 5%~30%；Finally, open high-speed emulsifying machine, with 3000~10000rpm revolving speed after
10~30min of continuous stirring, obtains uniform and stable milk-white coloured suspension sizing agent.
In the present invention, the number-average molecular weight of polyolefin resin powder is between 1.0 ten thousand~4.0 ten thousand, it is preferred that the equal molecule of number
Amount is between 1.5 ten thousand~3.0 ten thousand.The partial size of polyolefin resin powder is between 10~60 microns, it is preferred that 20~40 microns.
In the present invention, polyolefin resin powder is any one or several in polyethylene, polypropylene, polybutene or polypenthylene.
In the present invention, Sodium Polyacrylate number-average molecular weight is between 1000~5000, it is preferred that number-average molecular weight 2000
~4000.Shown in the structure of the fatty alcohol polyoxyethylene ether such as formula (1):
Wherein, R is selected from C10~C20It is any in alkyl；Polymerization degree n is the integer between 25~40.
In the present invention, pre-oxidation carries out in oxidation furnace, and oxidation furnace has 5 warm areas, temperature control is respectively 0~240 DEG C,
0~250 DEG C, 0~260 DEG C, 0~270 DEG C, 0~280 DEG C.
In the present invention, low-temperature carbonization carries out in low temperature carbonization furnace, and low temperature carbonization furnace has 5 warm areas, temperature control difference
It is 0~600 DEG C, 0~650 DEG C, 0~750 DEG C, 0~850 DEG C, 0~950 DEG C；High temperature cabonization carries out in high temperature carbonization furnace, high
Warm carbide furnace has 5 warm areas, temperature control is respectively 0~1300 DEG C, 0~1400 DEG C, 0~1400 DEG C, 0~1500 DEG C, 0~
1600℃。
It is dry before starching to use infrared radiation heating technique in the present invention, it is dry after starching to use horizontal hot air drying box
The drying process of drying.
The present invention also provides a kind of polyolefin resin based composites carbon fibers that above-mentioned preparation method obtains.
Using emulsion-type epoxy resin-matrix sizing agent carry out carbon fiber starching when, due to epoxy resin softening temperature compared with
It is low, therefore excessively high drying temperature cannot be used.Under the conditions of drying temperature and restricted drying time, using lotion type ring
The starching amount that epoxy resin-based sizing agent prepares carbon fiber cannot be too high, otherwise will cause sized fiber and is difficult to dry, surface is contained
Large quantity of moisture influences rear road processed and applied, while also limiting carbon fiber and must be prepared into collection bundle fiber.
Compared with using emulsion-type epoxy resin-matrix sizing agent, carbon fiber prepared by this patent is using infrared before starching
The drying process that horizontal hot air drying box is dried after radiant heat process, starching.Using infrared radiation heating back tender before starching
Skill can quickly remove the moisture of every carbon fiber in carbon fibre tow before carbon fiber enters sizing groove, carbon fiber is kept to contain
The consistency of water rate.After so that carbon fiber is entered sizing groove, sizing agent can be quickly impregnated into inside fibre bundle, be improved on fiber
Slurry amount and starching speed；It can guarantee sizing agent and every carbon fiber infiltration adsorption capacity having the same simultaneously, guarantee starching
Effect is more uniformly stablized, avoid because moisture content it is inconsistent caused by dewetting phenomenon.Using horizontal hot air drying box after starching
The drying process of drying, it can be ensured that starching carbon fiber can complete drying faster under tension force, reduce technology difficulty
And energy consumption, so that fiber lay down is transformed into uniform ribbon fiber.The starching carbon fiber prepared using the above method, starching amount height is controllable,
The dosage of resin film, improves product overall economy quality when can reduce prepreg processing.Tow width can pass through starching amount, baking
The flexibly controls such as dry technological parameter adjusting, can be applied to various types of reprocessing equipment and technique, increase Product Process
Applicability.
Compared to the prior art, the beneficial effects of the present invention are:
(1) a kind of polyolefin resin based composites carbon fiber of the present invention, uses with polyolefin resin powder
Based on, using Sodium Polyacrylate as main dispersant, using fatty alcohol polyoxyethylene ether as stabilization aid, using physical agitation mixing side
The novel suspended supernatant liquid based carbon fiber sizing agent of method preparation solves polyolefin base resin and impregnates bad and fiber ageing hardening etc.
Problem.
(2) in a kind of preparation process of polyolefin resin based composites carbon fiber of the present invention, starching is introduced
The drying process that horizontal hot air drying box is dried after preceding infrared radiation heating technique, starching, solves polyolefin resin suspension
Sizing agent, the problems such as the uniformity and fiber that carbon fiber surface is sprawled are dried.
(3) epoxy resin or other resin Compositions are free of using the carbon fiber surface of the method for the invention preparation, are applicable in
In preparing polyolefin resin based composites.Prepared carbon fiber can need to adjust starching amount and tow width according to following process
Width, the material utilization amount and difficulty of processing of road processed and applied after reduction, application range of products is wider, and economy is higher.Prepared
Composite technology is had excellent performance, and interface binding power is high.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Comparative example 1
Comparative example 1 is a kind of manufacturing method of 45K carbon fiber, and detailed process includes polymerization, spinning, pre-oxidation, cryogenic carbon
Dry after drying, starching, starching before change, high temperature cabonization, surface treatment, washing, starching, winding receives silk production process.Comparative example 1
Detailed process it is identical as the detailed process of Examples 1 to 4, wherein polymerization, pre-oxidation, low-temperature carbonization, high temperature cabonization, starching
Parameter is different.
Step 1: polymerization.The polymerization process is identical as method described in Examples 1 to 4 step 1, using sulphur cyanogen
Acid sodium aqueous solution is that solvent carries out polymerisation in solution, and the parameter that wherein polymerization process changes is the copolymerization list of solution polymerization
Body proportion is different, acrylonitrile, methyl methacrylate, sodium itaconate weight ratio be 91.0:8.0:0.5, total polymerization monomer
Input concentration is 28wt%, and initiator uses azodiisobutyronitrile, and dosage of azodiisobutyronitrile is in terms of all polymerized monomer total amounts
For 0.8wt%.85 DEG C of polymeric reaction temperature, the reaction time is 110 minutes.Then polymerization slurry obtained, through de- single, deaeration
Afterwards, the polyacrylonitrile matrix of spinning is made.
Step 2: spinning.Method described in the spinning production process and Examples 1 to 4 step 2.
Step 3: pre-oxidation.The pre-oxidation production process is identical as method described in Examples 1 to 4 step 3.Wherein
Pre-oxidizing the parameter that production process changes is No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnace furnaces
Area's temperature is respectively 238 DEG C, 246 DEG C, 254 DEG C, 263 DEG C, 271 DEG C.Drafting multiple between each warm area of oxidation furnace is respectively
6%, 6%, 0%, -1%, -1%.
Step 4: low-temperature carbonization.The low-temperature carbonization production process is identical as method described in Examples 1 to 4 step 4.
The parameter that wherein low-temperature carbonization production process changes is the 1st area of low temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the temperature control of the 5th area
System is respectively 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 850 DEG C.Controlling drafting multiple is 8.0%.
Step 5: high temperature cabonization.The high temperature cabonization production process is identical as method described in Examples 1 to 4 step 5.
The parameter that wherein high temperature cabonization production process changes is the 1st area of high temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the temperature control of the 5th area
System is respectively 1200 DEG C, 1300 DEG C, 1350 DEG C, 1410 DEG C, 1500 DEG C.Controlling drafting multiple is -7.0%.
Step 6: surface treatment.The surface treatment production process is identical as method described in Examples 1 to 4 step 6.
Step 7: dry before washing, starching.Dry production process and Examples 1 to 4 step 7 institute before the washing, starching
The method of description is identical.
Step 8: dry after starching and starching, winding receives silk.Dry after the starching, winding is received silk production process and is implemented
Method described in 1~4 step 8 of example is identical.Sizing agent is using bisphenol F epoxy resin/nonionic surfactant preparation SP-
2 type lotion carbon fiber sizing agents (production of Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry), sizing agent concentration 3.2%, winding are received silk and are prepared on 45K
Starch carbon fiber.
Comparative example 2
Comparative example 2 is a kind of manufacturing method of 48K carbon fiber, and detailed process includes polymerization, spinning, pre-oxidation, cryogenic carbon
Dry after drying, starching, starching before change, high temperature cabonization, surface treatment, washing, starching, winding receives silk production process.Comparative example 2
Detailed process it is identical as the detailed process of Examples 1 to 4, wherein polymerization, pre-oxidation, low-temperature carbonization, high temperature cabonization, starching
Parameter is different.
Step 1: polymerization.The polymerization process is identical as method described in Examples 1 to 4 step 1, using sulphur cyanogen
Acid sodium aqueous solution is that solvent carries out polymerisation in solution, and the parameter that wherein polymerization process changes is the copolymerization list of solution polymerization
Body proportion is different, acrylonitrile, methyl methacrylate, sodium itaconate weight ratio be 91.2:8.17:0.63, total polymerization monomer
Input concentration be 27.5wt%, initiator uses azodiisobutyronitrile, and dosage of azodiisobutyronitrile is total with all polymerized monomers
Amount is calculated as 0.76wt%.84 DEG C of polymeric reaction temperature, the reaction time is 108 minutes.Then polymerization slurry obtained, through de-
After single, deaeration, the polyacrylonitrile matrix of spinning is made.
Step 2: spinning.Method described in the spinning production process and 5~8 step 2 of embodiment.
Step 3: pre-oxidation.The pre-oxidation production process is identical as method described in Examples 1 to 4 step 3.Wherein
Pre-oxidizing the parameter that production process changes is No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnace furnaces
Area's temperature is respectively 237 DEG C, 245 DEG C, 253 DEG C, 262 DEG C, 270 DEG C.Drafting multiple between each warm area of oxidation furnace is respectively
6%, 5.5%, 0%, -1%, -1%.
Step 4: low-temperature carbonization.The low-temperature carbonization production process is identical as method described in Examples 1 to 4 step 4.
The parameter that wherein low-temperature carbonization production process changes is the 1st area of low temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the temperature control of the 5th area
System is respectively 495 DEG C, 595 DEG C, 700 DEG C, 790 DEG C, 850 DEG C.Controlling drafting multiple is 8.0%.
Step 5: high temperature cabonization.The high temperature cabonization production process is identical as method described in Examples 1 to 4 step 5.
The parameter that wherein high temperature cabonization production process changes is the 1st area of high temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the temperature control of the 5th area
System is respectively 1150 DEG C, 1250 DEG C, 1330 DEG C, 1400 DEG C, 1490 DEG C.Controlling drafting multiple is -7.0%.
Step 6: surface treatment.The surface treatment production process is identical as method described in 5~8 step 6 of embodiment.
Step 7: dry before washing, starching.Dry production process and 5~8 step 7 institute of embodiment before the washing, starching
The method of description is identical.
Step 8: dry after starching and starching, winding receives silk.Dry after the starching, winding is received silk production process and is implemented
Method described in 5~8 step 8 of example is identical.Sizing agent is using modified bisphenol F epoxy resin/cationic surfactant preparation
SP-2E type lotion carbon fiber sizing agent (production of Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry), sizing agent concentration 2.8%, winding receive silk be prepared into
To 48K starching carbon fiber.
Examples 1 to 4
The present embodiment 1~4 is a kind of manufacturing method of 45K carbon fiber suitable for polyolefin resin based composites, packet
It includes and is done after drying, starching, starching before polymerization, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, washing, starching
Dry, winding receives silk production process.Detailed process is as follows:
Step 1: polymerization.
Sodium thiocyanate water solution is used to carry out polymerisation in solution for solvent, with acrylonitrile, methyl methacrylate, sodium itaconate
For polymerized monomer, acrylonitrile, methyl methacrylate, sodium itaconate weight ratio be 91.9:7.1:1.0, total polymerization monomer
Input concentration is 26.5wt%, while initiator azodiisobutyronitrile is added, and initiator amount is in terms of all polymerized monomer total amounts
For 0.7wt%, 83 DEG C of polymeric reaction temperature, the reaction time is 102 minutes.
Using concentration for 55.2wt% sodium thiocyanate water solution as solvent, using continuous solution polymerization process prepare polymerization slurry
Polyacrylonitrile matrix is made after de- single, deaeration in liquid.
Step 2: spinning.
Using sodium sulfocyanate (NaSCN) wet spinning production method, by polyacrylonitrile matrix by solidification forming, cold lead
It stretches, wash, hot gas spring, oil, dry, steam drafting, sizing, precursor is made.The hole diameter of spinneret 0.058mm, spinneret hole number
45000, -0.5 DEG C of solidification forming temperature, coagulating bath flow 7500L/ hours, solidification bath concentration 13.5%；The drawing-off of cold drawing-off
2.3 times of multiple；It 50 DEG C of washing temperature, washes flow 4000L/ hours；90 DEG C of hot gas spring temperature, the drafting multiple 5.8 of hot gas spring
Times；Oil oil concentration 2.3%；140 DEG C of drying temperature；2.2 times of steam drafting multiple, steam pressure 200KPa；Setting temperature
122℃。
Step 3: pre-oxidation.
Precursor sequentially passes through No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnaces and carries out pre- oxygen
Change processing.No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnace furnace area temperature are respectively 236 DEG C,
245℃,251℃,260℃,268℃.Drafting multiple between each warm area of oxidation furnace is respectively 5%, 5%, 0%, -1%, -
1%.15 minutes each oxidation furnace residence times, pre-oxidation total time are 75min.
Step 4: low-temperature carbonization.
The oxidization fiber of No. 5 oxidation outlet of stills enters low temperature carbonization furnace by traction device, using nitrogen as medium, carries out low temperature
Low-temperature carbonization silk is made in carbonization.The 1st area of low temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the control of the 5th area's temperature are respectively 485
℃,580℃,680℃,780℃,830℃.Controlling drafting multiple is 7.5%, and total residence time is in low temperature carbonization furnace
1.8min。
Step 5: high temperature cabonization.
The tow of low-temperature carbonization outlet of still enters high temperature carbonization furnace by traction device, using nitrogen as medium, carries out high temperature
High temperature cabonization silk is made in carbonization.The 1st area of high temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the control of the 5th area's temperature are respectively 1090
℃,1240℃,1330℃,1390℃,1470℃.Controlling drafting multiple is -6.5%, the total residence time in high temperature carbonization furnace
For 1.8min.
Step 6: surface treatment.
The tow of high temperature cabonization outlet of still enters surface processing trough by traction device, is electrolysis with ammonium bicarbonate aqueous solution
Liquid, voltage 22V, concentration of electrolyte 12.5%, the residence time is 4min to tow in the electrolytic solution.
Step 7: dry before washing, starching.
Tow sequentially passes through rinsing bowl, infrared radiation heating drying machine after surface treatment, carries out washing and starching to tow
Preceding infrared radiation drying.Washing flow 2200L/ hours, 40 DEG C of washing temperature.The carbon medium-wave infrared of infrared radiation heating drying machine
Height distance 70mm, power density 42KW/m between radiator and carbon fiber2, drying time 15S when, carbon fibre tow is aqueous
Rate is 60%.
Step 8: dry after starching and starching, winding receives silk.
It will quantitatively polypropylene powder resin and Sodium Polyacrylate successively put into mixing vessel A according to a certain percentage, gradually
Quantitative deionized water is added, when amount of water reaches polyolefin resin powder and Sodium Polyacrylate total amount of feeding 30wt%, opens
Mechanical stirring is opened, and continuously adds the water of surplus；50~250rpm of speed of agitator is controlled, 30~60min of stirring carries out homogeneous
Dispersion, obtains flat-white emulsion.Above-mentioned material is transferred in the mixing vessel B equipped with high speed emulsifier, is added quantitative
Fatty alcohol polyoxyethylene ether, be then turned on high-speed emulsifying machine, 10~30min of stirring continued with 3000~10000rpm revolving speed,
Obtain uniform and stable milk-white coloured suspension sizing agent.Sizing agent is transferred in sizing groove by charging pump, opens sizing groove
Circulating pump flows sizing agent slowly in sizing groove.
The carbon fibre tow of infrared radiation heating drying machine outlet, is introduced directly into sizing groove and carries out starching, after starching
Carbon fiber enters horizontal hot air drying box and is dried, and 150 DEG C of temperature.Carbon fiber after starching is dry enters carbon fiber wound
Machine, winding receives silk and the 45K carbon fiber for being suitable for polyolefin resin based composites is made under 2300~2450cN tension.
Embodiment 5~8
The present embodiment 5~8 is a kind of manufacturing method of 48K carbon fiber suitable for polyolefin resin based composites, tool
Body process include polymerization, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, washing, drying before starching, starching, on
Dry after slurry, winding receives silk production process.The detailed process of the present embodiment and the detailed process of Examples 1 to 4 are identical, wherein spinning
Silk, pre-oxidation, low-temperature carbonization, high temperature cabonization, the parameter of starching are different.
Step 1: polymerization.The polymerization process is identical as method described in Examples 1 to 4 step 1, using sulphur cyanogen
Acid sodium aqueous solution is that solvent carries out polymerisation in solution, and the parameter that wherein polymerization process changes is the copolymerization list of solution polymerization
Body proportion is different, acrylonitrile, methyl methacrylate, sodium itaconate weight ratio be 91.0:5.0:4.0, total polymerization monomer
Input concentration is 22.5wt%, and initiator uses azodiisobutyronitrile, and dosage of azodiisobutyronitrile is with all polymerized monomer total amounts
It is calculated as 0.46wt%.80 DEG C of polymeric reaction temperature, the reaction time is 90 minutes.Then it polymerization slurry obtained, is taken off single, de-
After bubble, the polyacrylonitrile matrix of spinning is made.
Step 2: spinning.The spinning production process is identical as method described in Examples 1 to 4 step 2, spinning process
Parameter is different.The hole diameter of spinneret 0.058mm, spinneret hole number 48000, -1 DEG C of solidification forming temperature, coagulating bath flow
8000L/ hours, solidification bath concentration 14%；2.5 times of the drafting multiple of cold drawing-off；55 DEG C of washing temperature, washing flow 4500L/ is small
When；92 DEG C of hot gas spring temperature, 6.0 times of the drafting multiple of hot gas spring；Oil oil concentration 2.5%；142 DEG C of drying temperature；Steam
2.4 times of drafting multiple, steam pressure 220KPa；126 DEG C of setting temperature.
Step 3: pre-oxidation.The pre-oxidation production process is identical as method described in Examples 1 to 4 step 3.Wherein
Pre-oxidizing the parameter that production process changes is No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnace furnaces
Area's temperature is respectively 230 DEG C, 238 DEG C, 246 DEG C, 253 DEG C, 260 DEG C.Drafting multiple between each warm area of oxidation furnace is respectively
3%, 3%, 0%, -1%, -1%.15 minutes each oxidation furnace residence times, pre-oxidation total time are 75min.
Step 4: low-temperature carbonization.The low-temperature carbonization production process is identical as method described in Examples 1 to 4 step 4.
The parameter that wherein low-temperature carbonization production process changes is the 1st area of low temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the temperature control of the 5th area
System is respectively 440 DEG C, 530 DEG C, 630 DEG C, 720 DEG C, 780 DEG C.Controlling drafting multiple is 5.2%.Always stop in low temperature carbonization furnace
Staying the time is 1.8min.
Step 5: high temperature cabonization.The high temperature cabonization production process is identical as method described in Examples 1 to 4 step 5.
The parameter that wherein high temperature cabonization production process changes is the 1st area of high temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the temperature control of the 5th area
System is respectively 1000 DEG C, 1150 DEG C, 1250 DEG C, 1310 DEG C, 1390 DEG C.Controlling drafting multiple is -4.2%.In high temperature carbonization furnace
Middle total residence time is 1.8min.
Step 6: surface treatment.The surface treatment production process is identical as method described in Examples 1 to 4 step 6.
Using ammonium bicarbonate aqueous solution as electrolyte, voltage 25V, concentration of electrolyte 13%, the residence time is tow in the electrolytic solution
4min。
Step 7: dry before washing, starching.Dry production process and Examples 1 to 4 step 7 institute before the washing, starching
The method of description is identical, and parameter is different.Washing flow 2500L/ hours, 42 DEG C of washing temperature.Infrared radiation heating is dry
Height distance 72mm, power density 45KW/m between the carbon medium-wave infrared radiator and carbon fiber of machine2, drying time 15S when,
Carbon fibre tow moisture content is 60%.
Step 8: dry after starching and starching, winding receives silk.
Suspension sizing agent preparation method, method for sizing, drying means, winding receipts silk method and the Examples 1 to 4
Method described in step 8 is identical.
The carbon fibre tow of infrared radiation heating drying machine outlet, is introduced directly into sizing groove and carries out starching, after starching
Carbon fiber enters horizontal hot air drying box and is dried, and 152 DEG C of temperature.Carbon fiber after starching is dry enters carbon fiber wound
Machine, winding receives silk and the 48K carbon fiber for being suitable for polyolefin resin based composites is made under 2500~2900cN tension.
Suspension sizing agent solid component prepared by above-described embodiment 1~8 is shown in Table 1, and sizing agent forms dosage and concentration
2 are shown in Table, sizing agent preparation technology parameter is shown in Table 3, and gained carbon fiber Evaluation results are shown in Table 4.The present invention uses High Temperature Sizing
Tester tests the starching amount of starching carbon fiber；It is tested using breadth of the ruler to starching carbon fiber；Using
It is complete inside carbon fiber to being totally submerged Zi contact carbon fiber is started that OCA20 contact angle measurement tests polyolefin resin drop
Full infiltrating time；Polyolefin resin and carbon are tested using Japanese Dong Rong industry companies MODEL HM410 interface performance evaluating apparatus
The interface shear strength of fiber.
By the test result of 45K carbon fiber in Examples 1 to 4 as it can be seen that (using epoxy resin-matrix sizing agent with comparative example 1
The 45K carbon fiber of starching) it compares, the starching carbon fiber starching amount being prepared using suspension sizing agent is higher, coefficient of dispersion
Lower, breadth is discrete smaller, shows that fiber surface is uniformly coated with more polyolefin sizing agent and has obtained fiber sufficiently
Expanding effect.Polyolefin resin is less to starching carbon fiber infiltrating time, better technological properties, fiber and polyolefin substrate tree
There is better effect of impregnation and binding ability between rouge.48K carbon fiber obtains same improvement in embodiment 5~8.
1 sizing agent solid component of table
2 sizing agent of table forms dosage and concentration
3 sizing agent preparation technology parameter of table
4 carbon fiber Evaluation results of table
Although the present invention discloses preferred embodiment as above, the content that however, it is not to limit the invention is any ripe
Know this those skilled in the art, do not departing from main spirits and context of the invention, when can make it is various change and retouch, because of the invention
Protection scope should be subject to the actual claim range applied for a patent.
Claims (10)
1. a kind of preparation method of polyolefin resin based composites carbon fiber, which is characterized in that it includes successively polymerizeing, spinning
Dry after drying, starching, starching and winding is received before silk, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, washing, starching
The production process of silk；Wherein: starching carries out in impregnated sizing groove, and sizing agent uses the suspension starching of polyolefin resin base
Agent；The polyolefin resin base suspension sizing agent by polyolefin resin powder, Sodium Polyacrylate, fatty alcohol polyoxyethylene ether and
Deionized water composition；Gross mass according to solid component is 100%, and polyolefin resin powder accounts for 65~75wt%, polyacrylic acid
Sodium accounts for 10~15wt%, and fatty alcohol polyoxyethylene ether accounts for 15~20wt%.
2. preparation method according to claim 1, which is characterized in that the solid in polyolefin resin base suspension sizing agent
The mass content of component is between 5~30%.
3. preparation method according to claim 1, which is characterized in that the preparation side of polyolefin resin base suspension sizing agent
Method is as follows: firstly, polyolefin resin powder and Sodium Polyacrylate are put in proportion into mixing vessel, deionized water is added, to
When amount of water reaches polyolefin resin powder and Sodium Polyacrylate 25~35wt% of total amount of feeding, mechanical stirring is opened, and continue
The water of surplus is added；50~250rpm of speed of agitator is controlled, 30~60min of stirring carries out homogenous disperse, obtains flat-white
Emulsion；Then, above-mentioned material is transferred in the silent device equipped with high speed emulsifier, quantitative fatty alcohol polyoxy second is added
Alkene ether makes mass percent 5%~30% of the above-mentioned all solids component in suspension sizing agent；Finally, opening high speed
Mulser continues 10~30min of stirring with 3000~10000rpm revolving speed, obtains uniform and stable milk-white coloured suspension starching
Agent.
4. preparation method according to claim 1, which is characterized in that the number-average molecular weight of polyolefin resin powder is 1.0
Between ten thousand~4.0 ten thousand, the partial size of polyolefin resin powder is between 10~60 microns.
5. preparation method according to claim 1, which is characterized in that polyolefin resin powder is polyethylene, polypropylene, gathers
It is any one or several in butylene or polypenthylene.
6. preparation method according to claim 1, which is characterized in that the number-average molecular weight of Sodium Polyacrylate 1000~
Between 5000, shown in the structure of the fatty alcohol polyoxyethylene ether such as formula (1):
Wherein, R is selected from C10~C20Any one in alkyl；Polymerization degree n is the integer between 25~40.
7. preparation method according to claim 1, which is characterized in that pre-oxidation carries out in oxidation furnace, and oxidation furnace has 5
Warm area, temperature control are respectively 0~240 DEG C, 0~250 DEG C, 0~260 DEG C, 0~270 DEG C, 0~280 DEG C.
8. preparation method according to claim 1, which is characterized in that low-temperature carbonization carries out in low temperature carbonization furnace, low temperature
Carbide furnace has 5 warm areas, and temperature control is respectively 0~600 DEG C, 0~650 DEG C, 0~750 DEG C, 0~850 DEG C, 0~950 DEG C；It is high
Temperature carbonization carries out in high temperature carbonization furnace, and high temperature carbonization furnace has 5 warm areas, and temperature control is respectively 0~1300 DEG C, 0~1400
DEG C, 0~1400 DEG C, 0~1500 DEG C, 0~1600 DEG C.
9. preparation method according to claim 1, which is characterized in that it is dry before starching to use infrared radiation heating technique,
The dry drying process using the drying of horizontal hot air drying box after starching.
10. a kind of polyolefin resin based composites carbon fiber that preparation method described in one of -9 obtains according to claim 1
Dimension.
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