CN108004621A - A kind of polyamide resin resin-based composite carbon fiber and preparation method thereof - Google Patents
A kind of polyamide resin resin-based composite carbon fiber and preparation method thereof Download PDFInfo
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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Abstract
The invention discloses a kind of polyamide resin resin-based composite carbon fiber and preparation method thereof, preparation method of the present invention includes the step of polymerization, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, starching, drying and winding receive silk.The present invention selects polyamide resin aliphatic radical suspension sizing agent, and starching is realized by infusion process.Heated during carbon fiber starching at the same time using steam hot-rolling；Dry after starching and be dried by the way of the drying of vertical hot air drier.The beneficial effects of the present invention are：Preparation method of the present invention is simple, and prepared carbon fiber is suitable for preparing polyamide resin resin-based composite, and prepared composite technology excellent performance, interface mechanical characteristic is high, and wear resistance is good.
Description
Technical field
The invention belongs to carbon fiber preparation field, more particularly to a kind of polyamide resin resin-based composite carbon fiber and its
Preparation method.
Background technology
Become increasingly conspicuous recently as the problems such as energy shortage, environmental pollution, carbon fibre composite Lightweight Technology, follow
Ring is accelerated using technology, rapid shaping technique development, is especially increasingly closed in industrial circles such as automotive field, pressurized tanks
Note.As breach, fibre reinforced thermoplasticity composite material is able to fast development.Carbon fiber reinforced polyamide resin with
Its excellent wear-resistant and mechanical property etc. receives significant attention, but there are resin dipping is tired using multiple material prepared by current technology
Difficult, many technological difficulties such as serious, the multiple material performance of hole defect is unstable, to find out its cause, being due on the one hand to be processed at present
Type technology still has some deficits, and in addition answers material system primarily directed to thermosetting epoxy resin mainly due to current carbon fiber and grinds
System, the coating of its surface is mostly epoxy resin or modified epoxy class sizing agent.Such sizing agent standing time it is long or
Part or all of curing can be produced under higher drying, processing temperature, causes fibre bundle to be hardened, ossify, reunite, further
Cause matrix resin impregnation difficulties, easily produce fault gap, multiple material is produced local mechanical defect.Particular for polyamide resin
Carbon fiber prepared by resin-based composite is more rare.Chinese patent (Application No. 201310052755.1) provide it is a kind of by
The modified polyamide class sizing agent and its carbon fiber of preparation that polyamide, organic solvent, surface modifier, water etc. are prepared,
But due to containing solvent, its security stability is poor, has been eliminated substantially in sizing agent industrial application.
The content of the invention
In order to overcome the prior art, it is an object of the invention to provide a kind of polyamide resin resin-based composite carbon fiber
And preparation method thereof.It is controllable using carbon fiber starching amount height made of the method for the present invention, it can sprawl to form wide ribbon-like fibre,
Increase tow width, reduce the difficulty of product processing among follow-up, the product among follow-up that reduce process required resin demand, improve
Prepreg processing uniformity and stability.Prepared carbon fiber surface coats one layer of starching prepared completely by polyamide
Agent, without epoxy resin group, suitable for preparing polyamide resin resin-based composite, prepared composite technology performance is excellent
Different, interface mechanical characteristic is high, and wear resistance is good.
The present invention is using polymerization, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, starching, drying and winding
Receive silk production process.The problems such as to solve bad polyamide substrate resin dipping and fiber ageing hardening, the present invention is used with poly-
Amide resin powder is main body, introduces polyacrylamide amine dispersant, while introduce the fatty alcohol polyoxy with long chain oleophillic group
Vinethene stabilizer, can produce with polyacrylamide with polyamide and effectively combine, have well amphipathic, can prepare
Obtain suspension sizing agent stable and reliable for performance；To solve the problems, such as that fiber is dried under the conditions of high starching amount, improves polyamide resin
The uniformity that cosmetics end is sprawled in carbon fiber surface, present invention back tender after sizing process introduces the heating of steam hot-rolling, starching
Sequence introduces the drying process of vertical hot air drier drying.
The present invention provides a kind of preparation method of polyamide resin resin-based composite carbon fiber, which includes poly-
The step of conjunction, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, starching, drying and winding receive silk；Wherein：Starching
When by infusion process using polyamide resin aliphatic radical suspension sizing agent carry out；The polyamide resin aliphatic radical suspension sizing agent is by gathering
Amide resin, dispersant, stabilizer and deionized water composition；Counted according to the gross mass of solid constituent for 100%, polyamide
60~80% are accounted for, dispersant accounts for 5~15%, and stabilizer accounts for 15~25%.
In the present invention, low-temperature carbonization carries out in low temperature carbonization furnace, and low temperature carbonization furnace has 6 warm areas, temperature control difference
For 0~650 DEG C, 0~650 DEG C, 0~750 DEG C, 0~900 DEG C, 0~900 DEG C, 0~900 DEG C.
In the present invention, high temperature cabonization carries out in high temperature carbonization furnace, and high temperature carbonization furnace has 6 warm areas, temperature control difference
For 0~1250 DEG C, 0~1350 DEG C, 0~1600 DEG C, 0~1800 DEG C, 0~2000 DEG C and 0~2000 DEG C.
In the present invention, the preparation method of the polyamide resin aliphatic radical suspension sizing agent is as follows：First by polyamide, point
Powder is uniformly mixed in deionized water, adds stabilizer, is emulsified in high-speed emulsifying machine with 2000~10000rpm rotating speeds
Suspension sizing agent is obtained after 10~25min.
In the present invention, the polyamide has the general structure such as following formula I：
Wherein p is the degree of polymerization of polyamide, m and n numerical value can be identical or different.The equal molecule of polyamide number
Amount is 1.0 ten thousand~3.0 ten thousand, preferably 1.5 ten thousand~2.5 ten thousand.The polyamide powder average diameter is excellent between 20~50 microns
Select 30~40 microns.
In the present invention, the polyamide is selected from polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide
610th, any one or a few in polyamide 612, polyamide 1010 or polyamide 1012.
In the present invention, the dispersant is polyacrylamide, and number-average molecular weight is between 1.0 ten thousand~3.0 ten thousand, preferably
1.5 ten thousand~2.0 ten thousand.The stabilizer is fatty alcohol polyoxyethylene ether, it has such as the general structure of formula II：
Wherein, R is selected from the saturated aliphatic groups for including 15~20 carbon atoms；Polyoxyethylene polymerization degree n scope is 20
~40.
In the present invention, in polyamide resin aliphatic radical suspension sizing agent, the content of solid constituent is 5%~30%；During starching
Starching amount control 1%~20%.
In the present invention, during starching, the carbon fiber after starching passes through steam hot-rolling again.Temperature control model on steam hot-rolling roll surface
Enclose 0~360 DEG C.When fiber after starching is by steam hot-rolling, partial moisture is on the one hand removed, prevents fiber from entering rear road high temperature
Violent vaporization causes dangerous during drying box；On the other hand, the polyamide powder that surface is stained with melts at high temperature to be sprawled, just
Step forms more homogeneous continuous one layer of polyamide resin.
It is dry to be carried out using vertical hot air drier in the present invention；The warm area of the vertical drying case is 4, each area's temperature
Degree control is respectively 0~350 DEG C, 0~300 DEG C, 0~200 DEG C and 0~150 DEG C.The method that vertical drying is used in the present invention,
Make the further melt-flow of carbon fiber surface polyamide, the slow levelling under Gravitative Loads, makes carbon fiber surface polyamide
Resin film is more uniformly distributed completely；It can ensure all to remove fiber surface moisture under the conditions of high starching amount at the same time.
The present invention also provides the polyamide resin resin-based composite carbon fiber that a kind of above-mentioned preparation method obtains.
In the prior art, when carrying out carbon fiber starching using emulsion-type epoxy resin-matrix sizing agent, due to epoxy resin
Softening temperature is relatively low, therefore cannot use excessive drying temperature.Under the conditions of drying temperature and drying time are restricted, adopt
The starching amount that carbon fiber is prepared with emulsion-type epoxy resin-matrix sizing agent cannot be too high, no to be difficult to dry it will cause sized fiber
Dry, large quantity of moisture is contained on surface, influences rear road processed and applied, while also limit carbon fiber and must be prepared into collection bundle fiber.
Compared with using emulsion-type epoxy resin-matrix sizing agent starching production Carbon Fiber Technology, polyamides of the present invention
Polyimide resin base suspension starching carbon fiber can use the starching agent concentration of higher, have the starching amount of higher, prepared carbon
It can sprawl to form broadband after the drying process that fiber is dried using the heating of steam hot-rolling, vertical hot air drier described in this patent
Shape fiber, increases tow width, and breadth improves 50%~130%, effectively reduces fiber thickness.Carbon fiber can be sprawled preferably
Difficulty even, that polyamide is infiltrated to fibrous inside infiltration when advantageously reducing product processing among follow-up composite material, at the same time
The dosage of resin film, improves prepreg processing uniformity and stability when can reduce prepreg processing, reduces production cost.
Compared to the prior art, the beneficial effects of the present invention are：
(1) a kind of polyamide resin resin-based composite carbon fiber surface of the present invention, polyamide coating resin base
Carbon fiber sizing agent, without epoxy resin group, long-time storage will not produce ageing hardening phenomenon, can and polyamide substrate
Resin has good infiltration and binding ability, and processing performance and abrasion resistance properties are excellent.
(2) suspension carbon fiber sizing agent of the present invention introduces polyacrylamide amine dispersant, while introduces to have and grow
The fatty alcohol polyoxyethylene ether stabilizer of chain lipophilic group, can produce with polyamide and polyacrylamide and effectively combine,
With good amphipathic, prepared sizing agent is of low cost, simple process, safety and stability meet engineering process need
Will.
(3) drying process of the heating of steam hot-rolling and the drying of starching rear vertical type hot air drier when the present invention uses starching,
Both the polyamide powder that can be stained with carbon fiber surface melts at high temperature to be sprawled, and forms homogeneous continuous polyamide
Film, while the slow levelling under Gravitative Loads, polyamide resin powders can quickly and evenly sprawl infiltration carbon fiber, carbon fiber
Starching is more uniform.
(4) polyamide resin resin-based composite of the present invention controllable, the Ke Yipu of carbon fiber surface starching amount height
Spread increases tow width, improves tow breadth, reduce fiber thickness, reduce among follow-up composite material into wide ribbon-like fibre
The difficulty of product processing, reduces the resin demand of the follow-up centre of material again product processing, improves processing uniformity and stability.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people 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
Scope.
Comparative example 1
Comparative example 1 is a kind of manufacture method of 3K carbon fibers, and detailed process includes polymerization, spinning, pre-oxidation, cryogenic carbon
Change, high temperature cabonization, surface treatment, starching, drying, winding receive silk production process.The detailed process of comparative example 1 and embodiment 1~4
Detailed process it is identical, wherein polymerization, pre-oxidation, low-temperature carbonization, high temperature cabonization, the parameter of starching are different.
Step 1, it polymerize.The polymerization process is identical with the described method of 1~4 step 1 of embodiment, wherein polymerizeing
The parameter that production process changes is that the comonomer type of ternary aqueous polymerization reaction is different with proportioning, acrylonitrile, metering system
Sour methyl esters, the weight ratio of itaconic acid are 95.2:3.0:1.8, the input concentration of total polymerization monomer is 22wt%, and initiator uses chlorine
Sour sodium and sodium pyrosulfite, sodium chlorate dosage are calculated as 0.05wt%, sodium pyrosulfite and sodium chlorate with all polymerized monomer total amounts
The ratio between molal quantity is 1.4：1.60 DEG C of polymeric reaction temperature, reaction time are 102 minutes.
Step 2, spinning.The spinning production process and the described method of 1~4 step 2 of embodiment.
Step 3, pre-oxidize.The pre-oxidation production process is identical with the described method of 1~4 step 3 of embodiment.Wherein
It is No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnaces, 6 to pre-oxidize the parameter that production process changes
Number oxidation furnace stove area temperature is respectively 223 DEG C, 232 DEG C, 245 DEG C, 250 DEG C, 256 DEG C, 264 DEG C.Between each warm area of oxidation furnace
Drafting multiple is respectively -0.2%, -1.3%, -4.2%, -4.2%, -0.5%, -0.5%.
Step 4, low-temperature carbonization.The low-temperature carbonization production process is identical with the described method of 1~4 step 4 of embodiment.
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 5th area, the 6th area
Temperature control is respectively 450 DEG C, 520 DEG C, 580 DEG C, 650 DEG C, 720 DEG C, 760 DEG C.It is 3.0% to control drafting multiple.
Step 5, high temperature cabonization.The high temperature cabonization production process is identical with the described method of 1~4 step 5 of embodiment.
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 5th area, the 6th area
Temperature control is respectively 820 DEG C, 920 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C, 1350 DEG C.It is -4.0% to control drafting multiple.
Step 6, it is surface-treated.The surface treatment production process is identical with the described method of 1~4 step 6 of embodiment.
Step 7, starching and drying, winding receive silk.Sizing agent uses bisphenol A epoxide resin base emulsion type carbon fiber sizing agent
(Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry production, KTM-1 types), starching agent concentration 3.0%, directly uses horizontal circulation heated-air drying after starching,
120 DEG C of drying temperature, winding receives silk and 3K starching carbon fibers is prepared under 1000~1350cN tension force.
Comparative example 2
Comparative example 2 is a kind of manufacture method of 6K carbon fibers, and detailed process includes polymerization, spinning, pre-oxidation, cryogenic carbon
Change, high temperature cabonization, surface treatment, starching, drying, winding receive silk production process.The polymerization of comparative example 2, Pre oxidation and each
Area's drafting multiple, low-temperature carbonization temperature and drafting multiple, high temperature cabonization temperature and drafting multiple, surface treatment detailed process and
Parameter is identical with comparative example 1.Pre-oxidize total residence time, low-temperature carbonization total residence time, high temperature cabonization total residence time and reality
It is identical to apply 5~8 step 3~5 of example.The spinning parameter of comparative example 2 is identical with 5~8 step 2 of embodiment.The sizing process of comparative example 2
Identical with comparative example 1, the parameter of wherein starching is different.Sizing agent uses bisphenol F epoxy resin base emulsion type carbon fiber sizing agent
(Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry production, KTM-2 types), starching agent concentration 2.5%, directly uses horizontal circulation heated-air drying after starching,
130 DEG C of drying temperature, winding receives silk and 6K starching carbon fibers is prepared under 1400~1650cN tension force.
Embodiment 1~4
The present embodiment is a kind of manufacture method of the 3K carbon fibers suitable for polyamide resin resin-based composite, including poly-
Conjunction, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, starching, drying, winding receive silk production process.Detailed process
It is as follows：
Step 1：Polymerization.
Polymerisation is carried out using acrylonitrile aqueous suspension polymerization technique, with acrylonitrile, methyl methacrylate, itaconic acid
Ammonium is polymerized monomer, and acrylonitrile, methyl methacrylate, the weight ratio of itaconic acid ammonium are 95.3:2.8:1.9, total polymerization monomer
Input concentration be 23wt%, while add initiator ammonium persulfate, initiator amount is calculated as with all polymerized monomer total amounts
0.53wt%, 63 DEG C of polymeric reaction temperature, reaction time are 110 minutes.Then obtained condensate is dissolved in concentration is
In the dense sodium thiocyanate solution of 52wt%, dissolving is stirred, spinning is made after deaeration is filtered in dissolved thick stoste
Polyacrylonitrile matrix.
Step 2：Spinning.
Using sodium sulfocyanate (NaSCN) wet spinning production method, by polyacrylonitrile matrix by solidification forming, cold lead
Stretch, wash, hot gas spring, oil, dry, steam drafting, sizing, be made precursor.The hole diameter of spinneret 0.062mm, solidification forming temperature
When 0 DEG C of degree, coagulating bath flow 1500L/ are small, solidify bath concentration 14.2%；1.93 times of the drafting multiple of cold drawing-off；Washing temperature 50
DEG C, when washing flow 1400L/ is small；92 DEG C of hot gas spring temperature, 5.2 times of the drafting multiple of hot gas spring；Oil oil concentration 2%；It is dry
Dry 125 DEG C of temperature；2.0 times of steam drafting multiple, steam pressure 100KPa；110 DEG C of setting temperature.
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, No. 6 oxidations
Stove carries out pre-oxidation treatment.No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnaces, No. 6 oxidation furnaces
Stove area temperature is respectively 215 DEG C, 226 DEG C, 232 DEG C, 240 DEG C, 250 DEG C, 260 DEG C.Drafting multiple between each warm area of oxidation furnace
Respectively -0.1%, -1.2%, -4%, -4%, -0.5%, -0.5%.Each 14 minutes oxidation furnace residence times, pre-oxidation are total
Time is 84min.
Step 4：Low-temperature carbonization
The oxidization fiber of No. 6 oxidation outlet of stills enters low temperature carbonization furnace by draw-gear, using nitrogen as medium, carries out low temperature
Carbonization, is made low-temperature carbonization silk.The 1st area of low temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the 5th area, the 6th area's temperature control difference
For 440 DEG C, 510 DEG C, 560 DEG C, 630 DEG C, 700 DEG C, 750 DEG C.It is 3.5% to control drafting multiple, is always stopped in low temperature carbonization furnace
It is 1.6min to stay the time.
Step 5：:High temperature cabonization
The tow of low-temperature carbonization outlet of still enters high temperature carbonization furnace by draw-gear, using nitrogen as medium, carries out high temperature
Carbonization, is made high temperature cabonization silk.The 1st area of high temperature carbonization furnace, the 2nd area, the 3rd area, the 4th area, the 5th area, the 6th area's temperature control difference
For 810 DEG C, 900 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1320 DEG C.It is -3.0% to control drafting multiple, in high temperature carbonization furnace
Total residence time is 1.6min.
Step 6：Surface treatment
The tow of high temperature cabonization outlet of still enters surface processing trough by draw-gear, using ammonium bicarbonate aqueous solution as electrolysis
Liquid, voltage 20V, concentration of electrolyte 12%, the residence time is 3min to tow in the electrolytic solution.
Step 7：Starching and drying, winding receive silk
Quantitative polyamide resin powders, polyacrylamide are uniformly mixed spare；Quantitative water is added in reaction kettle A
And mechanical agitation is opened, keep under certain rotating speed, be gradually added into said mixture, continue the timing of stirring one after being added completely into
Between；Above-mentioned aqueous mixture is transferred in reaction kettle B by dosing pump, adds quantitative fatty alcohol polyoxyethylene ether, is opened
High-speed emulsifying machine, suspension sizing agent is prepared with the emulsification of certain rotating speed after a certain period of time.Then by charging pump by starching
Agent is transferred in sizing groove, is opened sizing groove circulating pump, sizing agent is slowly flowed in sizing groove.
The tow for being surface-treated outlet is impregnated by sizing agent first in the first live-roller in sizing groove, sizing groove successively
Roller, the second live-roller, the second dip roll, steam hot-rolling, the 3rd live-roller, pressure roller.Wherein lead at the steam inlet of steam hot-rolling
It is 40kgf/cm to enter absolute pressure2Saturated vapor, 250 DEG C of temperature controlling range on steam hot-rolling roll surface.Carbon after starching
Fiber is dried into vertical hot air drier, and 4 warm area temperature controls are respectively 330 DEG C, 280 DEG C, 180 DEG C, 120 DEG C.
The dried carbon fiber of starching enters carbon fiber wound machine, and winding is received silk and is made suitable for polyamides under 1000~1350cN tension force
The 3K carbon fibers of polyimide resin based composites.
Embodiment 5~8
The present embodiment is a kind of manufacture method of the 6K carbon fibers suitable for polyamide resin resin-based composite, detailed process
Silk production process is received including polymerization, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, starching, drying, winding.This
The detailed process of embodiment is identical with the detailed process of embodiment 1~4, wherein polymerization, spinning, pre-oxidation, low-temperature carbonization, high temperature
Carbonization, the parameter of starching are different.
Step 1, it polymerize.The polymerization process is identical with the described method of 1~4 step 1 of embodiment, wherein polymerizeing
The parameter that production process changes is that the comonomer proportioning of ternary aqueous polymerization reaction is different, acrylonitrile, methyl methacrylate,
The weight ratio of itaconic acid ammonium is 95.0:3.3:1.7, the input concentration of total polymerization monomer is 21wt%, and initiator ammonium persulfate is used
Amount is calculated as 0.51wt%, 61 DEG C of polymeric reaction temperature with all polymerized monomer total amounts, and the reaction time is 100 minutes.
Step 2, spinning.The spinning production process is identical with the described method of 1~4 step 2 of embodiment, solidification forming
When 0.5 DEG C of temperature, coagulating bath flow 2000L/ are small, solidify bath concentration 14%；1.9 times of the drafting multiple of cold drawing-off；Washing temperature
52 DEG C, when washing flow 1800L/ is small；95 DEG C of hot gas spring temperature, 5.0 times of the drafting multiple of hot gas spring；Oil oil concentration
2.2%；130 DEG C of drying temperature；1.88 times of steam drafting multiple, steam pressure 105KPa；115 DEG C of setting temperature.
Step 3, pre-oxidize.The pre-oxidation production process is identical with the described method of 1~4 step 3 of embodiment.Wherein
It is No. 1 oxidation furnace, No. 2 oxidation furnaces, No. 3 oxidation furnaces, No. 4 oxidation furnaces, No. 5 oxidation furnaces, 6 to pre-oxidize the parameter that production process changes
Number oxidation furnace stove area temperature is respectively 220 DEG C, 230 DEG C, 240 DEG C, 248 DEG C, 254 DEG C, 262 DEG C.Between each warm area of oxidation furnace
Drafting multiple is respectively -0.1%, -1.2%, -4%, -4%, -0.5%, -0.5%.Each 15 minutes oxidation furnace residence times,
Pre-oxidation total time is 90min.
Step 4, low-temperature carbonization.The low-temperature carbonization production process is identical with the described method of 1~4 step 4 of embodiment.
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 5th area, the 6th area
Temperature control is respectively 455 DEG C, 530 DEG C, 590 DEG C, 670 DEG C, 710 DEG C, 760 DEG C.It is 3.2% to control drafting multiple.In low temperature
Total residence time is 1.7min in carbide furnace.
Step 5, high temperature cabonization.The high temperature cabonization production process is identical with the described method of 1~4 step 5 of embodiment.
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 5th area, the 6th area
Temperature control is respectively 826 DEG C, 930 DEG C, 1250 DEG C, 1280 DEG C, 1320 DEG C, 1360 DEG C.It is -3.5% to control drafting multiple.
Total residence time is 1.7min in high temperature carbonization furnace.
Step 6, it is surface-treated.The surface treatment production process is identical with the described method of 1~4 step 6 of embodiment.
Step 7, starching and drying, winding receive silk.
Suspension sizing agent preparation method, method for sizing, drying means, winding receipts silk method and the embodiment 1~4
The described method of step 7 is identical.It is 48kgf/cm that absolute pressure is wherein passed through at the steam inlet of steam hot-rolling2Saturated water
Steam, 260 DEG C of temperature on steam hot-rolling roll surface.Vertical 4 warm area temperature controls of hot air drier are respectively 320 DEG C, 275 DEG C,
175℃、120℃.It is 1400~1650cN to control winding tension, the final 6K being made suitable for polyamide resin resin-based composite
Carbon fiber.
Suspension sizing agent solid constituent 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 SP10 high temperature
Starching amount of the starching tester to starching carbon fiber is tested；The breadth of starching carbon fiber is tested using ruler；
Using OCA20 contact angle measurements test polyamide drop from contact carbon fiber is started to being totally submerged inside carbon fiber
The complete wetting time；Polyamide is tested using Japanese Dong Rong industry companies MODEL HM410 interface performances evaluating apparatus
With the interface shear strength of carbon fiber.
By the test result of 3K carbon fibers in embodiment 1~4 as it can be seen that with comparative example 1 (using on epoxy resin-matrix sizing agent
The carbon fiber of slurry) to compare, the starching carbon fiber starching amount higher being prepared using suspension sizing agent, breadth is substantially increased,
Starching amount coefficient of dispersion is low, shows that fiber surface is uniformly coated with more polyamide sizing agent and fiber has been obtained sufficiently
Expanding effect.Polyamide is less to starching carbon fiber infiltrating time, better technological properties, interface shear strength higher, fine
Dimension has more preferable effect of impregnation and binding ability with polyamide substrate interlaminar resin.6K carbon fibers obtain together in embodiment 5~8
The improvement of sample.
1 sizing agent solid constituent 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, so it is not limited to present disclosure, any ripe
Know this those skilled in the art, do not departing from the present invention main spirits and context in, when can make it is various change and retouch, because of the invention
Protection domain should be subject to the actual claim scope applied for a patent.
Claims (10)
1. a kind of preparation method of polyamide resin resin-based composite carbon fiber, it is characterised in that the preparation process includes poly-
The step of conjunction, spinning, pre-oxidation, low-temperature carbonization, high temperature cabonization, surface treatment, starching, drying and winding receive silk；Wherein：Starching
When by infusion process using polyamide resin aliphatic radical suspension sizing agent carry out；The polyamide resin aliphatic radical suspension sizing agent is by gathering
Amide resin, dispersant, stabilizer and deionized water composition；Counted according to the gross mass of solid constituent for 100%, polyamide
60~80% are accounted for, dispersant accounts for 5~15%, and stabilizer accounts for 15~25%.
2. preparation method according to claim 1, it is characterised in that low-temperature carbonization carries out in low temperature carbonization furnace, low temperature
Carbide furnace has 6 warm areas, and temperature control is respectively 0~650 DEG C, 0~650 DEG C, 0~750 DEG C, 0~900 DEG C, 0~900 DEG C and 0
~900 DEG C.
3. preparation method according to claim 1, it is characterised in that high temperature cabonization carries out in high temperature carbonization furnace, high temperature
Carbide furnace has 6 warm areas, temperature control is respectively 0~1250 DEG C, 0~1350 DEG C, 0~1600 DEG C, 0~1800 DEG C, 0~2000
DEG C and 0~2000 DEG C.
4. preparation method according to claim 1, it is characterised in that the system of the polyamide resin aliphatic radical suspension sizing agent
Preparation Method is as follows：First polyamide, dispersant are uniformly mixed in deionized water, add stabilizer, is emulsified in high speed
Suspension sizing agent is obtained after emulsifying 10~25min in machine with 2000~10000rpm rotating speeds.
5. preparation method according to claim 1, it is characterised in that the polyamide is selected from polyamide 6, polyamide
11st, any one in polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010 or polyamide 1012 or
It is several.
6. preparation method according to claim 1, it is characterised in that the dispersant is polyacrylamide, and number is divided equally
Son amount is between 1.0 ten thousand~3.0 ten thousand；The stabilizer is fatty alcohol polyoxyethylene ether.
7. preparation method according to claim 1, it is characterised in that in polyamide resin aliphatic radical suspension sizing agent, solid
The content of component is 5%~30%；Starching amount during starching is controlled 1%~20%.
8. preparation method according to claim 1, it is characterised in that when carbon fiber carries out sizing process, introduce steam heat
Roller heats.
9. preparation method according to claim 1, it is characterised in that dry to be carried out using vertical hot air drier；It is described
The warm area of vertical drying case is 4, and each area's temperature control is respectively 0~350 DEG C, 0~300 DEG C, 0~200 DEG C and 0~150 DEG C.
10. the polyamide resin resin-based composite carbon that a kind of preparation method according to one of claim 1-9 obtains is fine
Dimension.
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