CN104611787A - Oil agent for polyacrylonitrile-based carbon fiber precursor manufacturing, manufacturing and use method thereof - Google Patents
Oil agent for polyacrylonitrile-based carbon fiber precursor manufacturing, manufacturing and use method thereof Download PDFInfo
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- CN104611787A CN104611787A CN201410619020.7A CN201410619020A CN104611787A CN 104611787 A CN104611787 A CN 104611787A CN 201410619020 A CN201410619020 A CN 201410619020A CN 104611787 A CN104611787 A CN 104611787A
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Abstract
The invention provides an oil agent for polyacrylonitrile(PAN)-based carbon fiber precursor manufacturing, a manufacturing and use method thereof. The oil agent has excellent stability, the production process is simplified, and at the same time the use effect is not affected. By adjusting the proportion of hydrophilic groups in the whole polysiloxane molecule and the variety, the hydrophilicity can be greatly enhanced and the hydrophilic groups even can be dissolved in water, so that a true solution or microemulsion form oil agent can be obtained. While the stability of the oil agent is greatly improved, the oil agent also facilitates observation of the operation condition of cellosilk bundles in oiling troughs, and the use effect cannot be affected. And high performance PAN precursor and carbon fiber can also be obtained.
Description
Technical field
The present invention relates to fabric manufacturing area, particularly relate to a kind of polyacrylonitrile base carbon fiber precursors oil for manufacturing and manufacture thereof and using method.
Background technology
Carbon fiber is owing to having excellent specific strength and than mechanical characteristics such as elastic modelling quantity, therefore as reinforcing material, being widely used in high-performance composite materials.At aerospace fields such as aircraft, spaceship, satellites, the high-end sports goods fields such as golf clubs, fishing rod, racket, bicycle, and have in the general industrial circle such as automobile making, air vane, civil construction, pressure vessel and apply quite widely.
In carbon fiber, what be most widely used is PAN base carbon fibre, by predecessor PAN copolymer after wet spinning or dry-and wet-type spinning obtain precursor fibre, pre-oxidized fibers is converted in 200 ~ 400 DEG C of oxidizing atmospheres, heat treated carbonization in nitrogen atmosphere at the temperature of at least 1000 DEG C again, namely this is the industrially preparing process of common carbon fiber.
In the manufacture process of carbon fiber, include several process of at high temperature fiber being carried out to drawing-off.Under the effect of high temperature, fiber occurs softening, easily doubling occurs between monofilament.In addition in the production process of whole fiber, the various deflector roll carry fiber and fiber surface, to effect, become one of producing cause of fiber surface defect.In order to reduce above-mentioned two kinds of phenomenons as far as possible, the way usually taked carries out finish process to PAN precursor.Finish forms diaphragm on the surface of fiber, both can avoid fiber and the direct contact friction of roll surface, can prevent again the doubling of fiber when being subject to thermal softening between monofilament.
The finish used in PAN base carbon fiber protofilament production process, its principle active component is the silicones of modification.Because the viscosity of silicones is very large, being formed film to be evenly distributed in PAN fiber surface, needing to be prepared into the form with good dispersion, such as emulsion or solution.Due to the hydrophobic lipophile of silicones, if will be prepared into solution form, required solvent is generally organic solvent, such as acetone etc.Due to combustibility and the volatility of organic solvent, consider from safety, this is very disadvantageous, and the finish of therefore industrial use all adopts the form of water serial emulsion.
But emulsion is a kind of thermodynamic unstable system, easy breakdown of emulsion under the disturbance in the external world, such as low temperature, high temperature, impurity, pH change etc.Once breakdown of emulsion, namely finish becomes waste product, cannot use again.This storage for finish, transport and use are proposed comparatively harsh requirement.In addition, in order to obtain the less stable emulsion of particle diameter, in emulsion process, need long high speed shear, emulsifying device is complicated, improves manufacturing cost.
In addition, industrial when carrying out oiling treatment to fiber, normally adopt infusion process, namely the finish prepared is placed in finishing bathtray, fiber is with certain speed through finishing bathtray, and namely finish is adsorbed on fiber surface.But use finishing bathtray to oil, the existence of deflector roll must be had below the liquid level of finish bath.Because emulsion is opaque, if thus subsurface deflector roll twines silk, can not be found timely and process, result very easily causes and seriously twines silk and even fracture of wire.
Contrary with emulsion, microemulsion and true solution are at dispersion all stable on thermodynamics and kinetics.Emulsion, microemulsion, true solution are generally distinguished by the particle diameter of dispersate, and the particle diameter of emulsion is generally between 100nm ~ 10 μm, and the particle diameter of microemulsion is generally between 1 ~ 100nm, and the particle diameter of true solution is generally at below 1nm.Emulsion is opaque, can occur Tyndall effect, and microemulsion and true solution are visually transparent, do not have Tyndall effect.
Therefore, solve the problem and just seem particularly important.
Summary of the invention
The object of this invention is to provide a kind of polyacrylonitrile base carbon fiber precursors oil for manufacturing and manufacture thereof and using method, there is excellent stability, simplify its production process, ensure that its result of use is unaffected simultaneously, solve the problems referred to above.
The invention provides a kind of polyacrylonitrile base carbon fiber precursors oil for manufacturing, the constituent mass of described finish is than as follows: modified polyorganosiloxane: 15% ~ 25%, second third block polyether: 0 ~ 5%, water: 70% ~ 85%.
A manufacture method for polyacrylonitrile base carbon fiber precursors oil for manufacturing, described manufacturing step is as follows:
Step one: second third block polyether is dissolved in deionized water according to quality proportioning and obtains solution, and Keep agitation;
Step 2: slowly add modified polyorganosiloxane, Keep agitation obtained finished product after 1 hour.
Further improvement is: the rotating speed stirred in described step one, two is 200 ~ 300rpm.
A using method for polyacrylonitrile base carbon fiber precursors oil for manufacturing, described using method is as follows:
Step one: PAN polymer fluid is sprayed in coagulating bath by spinning head and is frozen into solid fabric;
Step 2: fiber is cleaned through hot water and after drawing-off, oiled through the oil groove containing finish;
Step 3: through super-dry and steam drawing-off, again through oiling containing the oil groove containing finish;
Step 4: drying is carried out to fiber and receives silk.
Further improvement is: the oil content after described step 4 is disposed in fiber is 0.8% ~ 1.2%.
The maximum feature of finish of the present invention for its form be microemulsion or true solution, clear appearance is transparent.The average grain diameter that above-mentioned finish uses laser particle analyzer to measure is at below 50nm.The decentralized medium of above-mentioned finish system is deionized water.Above-mentioned finish has following quality proportioning: modified polyorganosiloxane: 15 ~ 25, second third block polyether: 0 ~, water: 70 ~ 85.
Present invention also offers a kind of method preparing above-mentioned finish.First second third block polyether is dissolved in deionized water according to quality proportioning and obtains solution, keep the stirring of 200 ~ 300rpm, slowly add modified polyorganosiloxane, Keep agitation 1 hour.
Present invention also offers the method using above-mentioned finish to carry out the production of PAN precursor.PAN polymer fluid is sprayed in coagulating bath by spinning head and is frozen into solid fabric, fiber through hot water clean and drawing-off after, through oiling containing the finish groove in claim 1, afterwards through super-dry and steam drawing-off, again through oiling containing the finish groove in claim 1, then carrying out drying and receiving silk.In fiber, oil content is 0.8 ~ 1.2%.
In the present invention, the principle active component of finish is through the silicones of modification.The basic feature of silicones be its using-Si-O-as the elementary cell being formed molecular backbone, no matter how the X of its end group and the R of side base changes, as long as main chain is-Si-O-, in this, material is exactly silicones.Wherein X1, X2 can be methyl, hydrogen atom and hydrophilic radical, are methyl under general case, when it is hydrogen atom, become containing hydrogen silicone oil or unsaturated silicone oil, when it is hydrophilic radical, are called the silicone oil of terminal groups modification.X1, X2 can be identical, also can be different, not strict restriction; R1, R2 are hydrophilic radical, and R1, R2 can be identical, also can be different, do not have strict restriction equally.M, n are natural number, but can not be 0. simultaneously
Usually, type siloxane material exhibits goes out hydrophobicity, thus, can only deposit be dispersed in water formation emulsion in case at emulsifying agent.If but the R of careful control and the kind of X group and quantity, just can obtain and there is good water miscible modified polyorganosiloxane.Kind about hydrophilic radical during acquisition water soluble silicones can be amino, carboxyl, hydroxyl, polyether segment, amide groups etc., according to our test and the result of documentation integrators, when comprising amino in hydrophilic radical, finish is best at the film forming of fiber surface, when hydrophilic radical is polyether segment, polysiloxanes water-soluble best, therefore in the present invention in silicones, preferably comprises polysiloxanes that is amino and polyether segment modification.As for position and the quantity of modified group, the namely kind of X, R and the numerical value of m and n.
The hydrophily of above-mentioned silicones, characterizes by its solubility in water and the average grain diameter that is dispersed in water.Average grain diameter after requiring it to disperse in water in the present invention is not more than 50nm, the smaller the better.If be greater than 50nm, the light transmittance of finish dispersion reduces gradually, is more or less the same with common finish, when modified polyorganosiloxane hydrophily is enough good time, it can be dissolved in water completely and form true solution, and now the average grain diameter of finish dispersion is at below 1nm or can not survey.Because particle diameter is enough little, the finish system therefore in the present invention can not show Tyndall effect.
The quality accounting of modified polyorganosiloxane class material in finish system in the present invention, should between 15 ~ 20%.Because finish is not prepare use online, but the rear storage of preparation separately, use after dilution during application.If very little as the concentration of the silicones of active ingredient in finish, storage area required for the finish so made is larger, and time of consuming of production process and energy cost also higher, but owing to being confined to the solubility of silicones, its concentration also can not reach very high, therefore considers its quality accounting and controls between 15 ~ 25%.
In the present invention, the principle active component of finish is except modified polyorganosiloxane, also comprises block polyether class material.Block polyether refers to the polyethers be made up of with the form of block ethoxy segment and the third oxygen segment.Add block polyether and have two objects, first block polyether can as the softener of fiber, and it two is that block polyether can as the emulsifying agent of polysiloxanes.Block polyether in the present invention, the mol ratio of ethyoxyl and propoxyl group is between 3:2 ~ 2:3, and molecular weight is more than 3000.The quality accounting of block polyether in finish system, between 0 ~ 5%.When modified polyorganosiloxane water-soluble enough good, block polyether can not be added, because the flexibility of the fiber after water-soluble good polysiloxane molecule process is also fine.The content of block polyether more than 5%, otherwise should can not cause the decline of the overall resistance to elevated temperatures of finish, affects the effect preventing monofilament adhesion doubling of finish in preoxidation process.
The water used in the present invention is deionized water.General industrial pure water prepares the pure water that facility manufactures.The various disinfectants, impurity etc. that contain in running water running water cannot be used, because can have a huge impact to the performance of finish.
Owing to employing the modified polyorganosiloxane class material with good aqueous solubility, the process for preparation of the finish thus in the present invention is quite simple, does not need high speed machine shear and mix dispersion process for a long time, does not also have strict charging sequence.As long as stir carrying out the short time again after active ingredient and deionized water mixing under the stirring state of gentleness.Stir speed (S.S.) during preparation remains on 300rpm, continues about mixing time 10min again after reinforced.
Below the method using the finish in the present invention to carry out the production of PAN precursor is described in detail.
PAN precursor of the present invention, that PAN copolymer is by after wet method or dry-wet spinning, washing, process with the fiber of finish to water swelling state, then 130 ~ 200 DEG C of heat treatments, fiber after heat treatment through steam drawing machine drawing-off 2-5 doubly, and then processes with finish, obtains after finally carrying out dry receipts silk.
In the composition of PAN copolymer, the molar content of acrylonitrile monemer at least should more than 95%, preferably more than 98%.All the other copolymerization component are can have a material of facilitation to preoxidation process with acrylonitrile compolymer through what select.Concrete as acrylic acid, methacrylic acid, itaconic acid etc.
Spinning solution is obtained by solution polymerization process, and the solvent used in polymerization process is dimethyl sulfoxide (DMSO).Spinning process adopts wet spinning, and spinning solution directly enters coagulating bath from spinnerets and is frozen into silk.Coagulating bath is grouped into solidifying to promote into by solvent identical in spinning solution.Solidify and promote that composition is generally water.In coagulating bath, solvent promotes that the temperature of the ratio of composition and coagulating bath can carry out suitable adjustment according to the compactness surface smoothness of the coagulated yarn obtained and spinnability with solidifying.
The strand that solidifies obtained is washed one or many, drawing-off in 50 ~ 98 DEG C of controlled tepidariums.Draft ratio suitably can be selected in the scope that fracture of wire or fiber doubling do not occur.After washing, drawing-off, should to finish of the present invention on the fiber of the swelling state obtained.The method of oiling is placed in finishing bathtray by previously prepared good finish dispersion through certain dilution, and fiber is with certain speed through finishing bathtray, and finish is just adsorbed on fiber surface.
The upper strand crossing finish should carry out rapidly drying process, adopts the method with multiple hot-rolling contact drying.The high cross-linking reaction that can promote finish of baking temperature, and be also conducive to improving production performance, what be therefore set under the prerequisite that monofilament doubling does not occur is higher as far as possible.Should more than 130 DEG C, the upper limit of baking temperature is 200 DEG C.Drying time is as the criterion with the abundant drying of fiber.In addition, in order to homogeneous heats strand, tow should be carried out contact drying with hot-rolling under as far as possible wide condition.
Dried strand, considers from the compactness and productivity improving precursor, should further drawing-off in steam under pressure.Steam pressure during drawing-off, temperature and draft ratio can be selected flexibly in the scope that fracture of wire and burr do not occur.Fiber after drawing-off is used for above-mentioned identical method to carry out oiling and dry process again.The adhesion amount of finish on fibre bundle after oiling for twice, the finish composition beyond removing dispersant should account for dry precursor weight 0.5 ~ 2%.Preferably control between 0.8 ~ 1.2%.If less than 0.5%, can not prevent from interfibrously melting doubling, the carbon fiber tensile strength obtained is low, if more than 2%, is difficult to embody effect of the present invention.
Dried fiber carries out receipts silk and namely obtains PAN precursor.
The precursor tow of above-mentioned acquisition, again through pre-oxidation treatment, just can obtain pre-oxidized fibers.Pre oxidation generally should between 200 ~ 300 DEG C.Carbonization is carried out to pre-oxidized fibers, can carbon fiber be obtained.Carbonisation is divided into low-temperature carbonization and two stages of high temperature cabonization, and low-temperature carbonization should be carried out, between the draw ratio to 1.05 in process ~ 1.10 at 300 ~ 800 DEG C.High temperature cabonization process should be carried out between 800 ~ 2000 DEG C, and maximum temperature can carry out suitable flexible selection according to the performance of the desired carbon fiber obtained.If less than 800 DEG C, the intensity of the carbon fiber obtained and elastic modelling quantity are too low.Draw ratio in carbonisation, controls between 0.98 ~ 1.00.Fiber after high temperature cabonization just can carry out dry rolling after surperficial electrolytic treatments and sizing agent process.
The invention has the beneficial effects as follows: by the proportion of adjustment hydrophilic radical in whole polysiloxane molecule and its kind, its hydrophily can be made greatly to strengthen, and even can be water-soluble, thus obtain the finish of true solution or microemulsion form, this finish is while stability significantly improves, facilitate the observation of the operation conditions to fibre bundle in finishing bathtray, and its result of use can not be affected, namely can obtain high performance PAN precursor and carbon fiber equally.
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
Embodiment 1
First use the L720 Siloxane-Oxyalkylene Copolymers of Dow Corning Corporation, this product has good water-soluble.By its in deionized water 80rpm stir be configured to 20% solution.Measure its stability and particle diameter, carried out being diluted to 4% loading finishing bathtray stand-by.
By concentration 21%, the PAN spinning solution of limiting viscosity 1.7 remains on 55 DEG C, and spraying into temperature by spinnerets is 60 DEG C, and concentration is solidificating fiber in the dimethyl sulphoxide aqueous solution of 60%.The fiber obtained is drawing-off 4.5 times in the hot water, carries out washing removing DMSO simultaneously.Oiling treatment is carried out to the above-mentioned diluted finish of the fiber after hot water drawing-off, dry.Dried fiber carries out drawing-off in the steam under pressure of 0.4MPa, makes the draft ratio of overall process reach 14 times.Again oil, dry.The precursor monofilament number obtained is 6000, and filament number is 0.9dtex, and the adhesion amount of finish is 1.0%.
Precursor after drawing-off 1.00 pre-oxidation treatment 100min, is detained 2min the temperature ranges of 200 ~ 400 DEG C in the air of 250 DEG C, and then heat up 400 ~ 500 DEG C of speed according to 150 DEG C/min, draw ratio 1.05 carries out low-temperature carbonization process.Carbonization treatment again through maximum temperature 1500 DEG C obtains carbon fiber, obtains carbon fiber after anodic oxidation and starching process.
Embodiment 2
Finish main component changed into outside Dow Corning Corporation L2120, all the other conditions are identical with embodiment 1.
Embodiment 3
Use amino modified polysiloxane, Siloxane-Oxyalkylene Copolymers, block polyether as the main component of finish, its mass ratio is 1:18:1, is configured to the finish microemulsion of 20%.All the other conditions are identical with embodiment 1.
Embodiment 4
Use amino modified polysiloxane, nonionic emulsifier, polytrimethylene ether to add deionized water according to after the mass ratio mixing of 8:1:1, use the emulsification of high speed shear emulsifier, shear rate 3000rpm, emulsification 30min.Obtain the finish emulsion that concentration is 20%.All the other conditions are identical with embodiment 1.
Comparative examples 1-4, the particle diameter in embodiment 1 is 54nm, appearance transparent, good stability, and lousiness is few, carbon fiber strength 5.54Gpa;
Particle diameter in embodiment 2 is 66nm, appearance transparent, good stability, and lousiness is few, carbon fiber strength 5.61Gpa;
Particle diameter in embodiment 3 is 98nm, appearance transparent, good stability, and lousiness is few, carbon fiber strength 5.58Gpa;
Particle diameter in embodiment 4 is 189nm, and outward appearance is white emulsion, good stability, and lousiness is few, carbon fiber strength 5.67Gpa;
Finish, stability-enhanced while, facilitates the observation of the operation conditions to fibre bundle in finishing bathtray, and substantially can not affect its result of use, can obtain high performance PAN precursor and carbon fiber.
Claims (5)
1. a polyacrylonitrile base carbon fiber precursors oil for manufacturing, is characterized in that: the constituent mass of described finish is than as follows: modified polyorganosiloxane: 15% ~ 25%, second third block polyether: 0 ~ 5%, water: 70% ~ 85%.
2. a manufacture method for polyacrylonitrile base carbon fiber precursors oil for manufacturing as claimed in claim 1, is characterized in that: described manufacturing step is as follows:
Step one: second third block polyether is dissolved in deionized water according to quality proportioning and obtains solution, and Keep agitation;
Step 2: slowly add modified polyorganosiloxane, Keep agitation obtained finished product after 1 hour.
3. the manufacture method of polyacrylonitrile base carbon fiber precursors oil for manufacturing as claimed in claim 2, is characterized in that: the rotating speed stirred in described step one, two is 200 ~ 300rpm.
4. a using method for polyacrylonitrile base carbon fiber precursors oil for manufacturing as claimed in claim 1, is characterized in that: described using method is as follows:
Step one: PAN polymer fluid is sprayed in coagulating bath by spinning head and is frozen into solid fabric;
Step 2: fiber is cleaned through hot water and after drawing-off, oiled through the oil groove containing finish;
Step 3: through super-dry and steam drawing-off, again through oiling containing the oil groove containing finish;
Step 4: drying is carried out to fiber and receives silk.
5. the using method of a kind of polyacrylonitrile base carbon fiber precursors oil for manufacturing as claimed in claim 4, is characterized in that: the oil content after described step 4 is disposed in fiber is 0.8% ~ 1.2%.
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| CN106868616A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The method that fiber oils |
| CN114787434A (en) * | 2019-08-30 | 2022-07-22 | 帝人株式会社 | Method for producing carbon fiber bundle |
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Application publication date: 20150513 |