CN1820033A - Polymer for carbon fiber precursor - Google Patents
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- CN1820033A CN1820033A CN 200480002657 CN200480002657A CN1820033A CN 1820033 A CN1820033 A CN 1820033A CN 200480002657 CN200480002657 CN 200480002657 CN 200480002657 A CN200480002657 A CN 200480002657A CN 1820033 A CN1820033 A CN 1820033A
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Abstract
A polymer for carbon fiber precursors which comprises a polymer comprising 50 wt% or more polyacrylonitrile ingredient, wherein the proportion of isotactic triads contained in structural acrylonitrile chains made up of acrylonitrile units is 35 mol% or higher based on the proportion of all triads contained in the structural acrylonitrile chains made up of acrylonitrile units. The polymer for carbon fiber precursors can hence be flameproofed gradually by heating from a temperature in a low-temperature region and has satisfactory flameproof characteristics, such as reduced heat generation.
Description
Technical field
The present invention relates to make the carbon fiber precursor polymkeric substance to produce carbon fiber, carbon fiber precursor that obtains by this polymkeric substance of spinning and the fire-retardant carbon fiber precursor that obtains by its thermal treatment.More specifically, the present invention relates to obtain the carbon fiber precursor polymkeric substance and the carbon fiber precursor of high quality, high-performance carbon fibre, wherein in order to reduce desired energy of fire-retardant finish and time, can be by the taxis of vinyl cyanide repeating unit in the control polyacrylonitrile, thereby reduce the temperature of fire-retardant finish, wherein even when carrying out carbonization, fusion or thermolysis do not take place between fiber.
Background technology
Carbon fiber has good mechanical property and particularly high specific tenacity and specific modulus usually, therefore is widely used as the intensity modifier of various strongtheners in aerospace applications, amusement article, Industrial materials etc.Because its excellent mechanical property, so they have potential aspect the motor vehicle weight and are using reducing, and receive more and more many concerns as the important advance that solves the pressing issues that reduce carbonic acid gas.
By making the precursor organic polymer fiber carry out fire-retardant finish, roasting in the presence of oxygen (firing) and carbonization, thus produce this carbon fiber.Can mention various precursors, comprising Mierocrystalline cellulose, resol, polyvinyl alcohol, vinylidene chloride, pitch, polyacrylonitrile (hereinafter referred is " PAN ") etc.The carbon fiber that is derived from the PAN fibrid is especially excellent aspect dynamic property such as specific tenacity and the specific modulus and because they can be produced under the situation in all even stabilised quality and performance, so they can be produced in batches on technical scale.
Handle when the PAN fibrid being carried out fire retardant, when then carbon fiber is produced in carbonization,, need usually in 200-400 ℃ high temperature oxidation atmosphere, to heat-treat for a long time as the condition that fire retardant is handled.This is to produce the exothermal decomposition reactions of moment because attempt the fire-retardant finish of precursor PAN fibrid at short notice immediately under 500 ℃ or higher temperature, and this decomposition reaction causes the decomposition of spontaneous combustion and polymkeric substance, forms required carbon skeleton thereby hinder.In addition, the high-temperature heat treatment that prolongs not only since high energy consumption and low-yield cause being a problem at economic aspect, and with regard to quality, owing to fuse between the single fiber, be considered to problem from the angle of strength degradation, with since at high temperature long filament easily fracture cause the technical process aspect also to be a problem because these former carrying on as before need be carried out industry improvement.
For fear of these problems, various suggestions have been proposed in the prior art.For example, propose to use PAN class precursor that the polymerisable unsaturated carboxylic acid ammonium salt by the copolymerization specified quantitative obtains (for example, referring to patent documentation 1 and 2) and use following precursor, described precursor is the PAN (for example, referring to patent documentation 3) that the long-chain alkyl groups by the polymerisable unsaturated carboxylic acid of copolymerization obtains.
These precursors demonstrate the certain effect that promotes flame retarding reaction, but the low end-blocking that usually causes multipolymer of the copolymerization of unsaturated carboxylic acid.In addition, the carboxyl acid component that thermotolerance is low be disadvantageous at high proportion because the pyrolysated result is that it can cause lower output during the fire-retardant step after polymerization procedure.
On the other hand, prove that the copolymerization of α-Lv Daibingxijing and vinyl cyanide can significantly be shortened duration of fire resistance and solve the problem (for example, referring to patent documentation 4 and 5) of productive rate difference.Have again,, must use a large amount of expensive α-Lv Daibingxijing components to be used for copolymerization, so exist and the afoul economical disadvantages of yield improvement in order fully to shorten duration of fire resistance.
Also disclose to use and mixed methylene-succinic acid and acrylamide monomers and terpolymer of acrylonitrile and (for example can improve flame retardant properties, referring to patent documentation 6), but except being difficult to obtain to have the homogeneous copolymers of three kinds of different monomers, any excessive methylene-succinic acid also can cause violent thermopositive reaction, destroy thereby in fibrous texture, produce, simultaneously excessive acrylamide monomer can produce fibre fusion, and then the control that multipolymer is formed is complicated and influence productive rate.Other suggestion comprises (for example uses the hydroxyl methylene radical, referring to patent documentation 7), the halogenated alkyl ester of unsaturated carboxylic acid (for example, referring to patent documentation 8), with the unsaturated monomer (for example) of siliceous or fluorine, as the copolymerization component referring to patent documentation 9, but consider from cost and performance perspective, these none demonstrate satisfied effect.
On the other hand, also in the flame retarding reaction field of PAN fibrid, study.For example, existing known by the oxidation nitrile skeleton adjacent with cyclisation, the flame retarding reaction (for example, referring to non-patent literature 1) of initiation PAN fibrid.
In addition, by the research in past, reported for thermoinducible reaction, the taxis of polymer micro-structural and the main polymer chain described by its tacticity particularly can influence temperature of reaction and speed of response.For example, prove that by heating, form the imines skeleton by itrile group and preferentially carry out at low temperatures, it has isotactic chain rather than atactic or syndiotaxy chain (for example, referring to non-patent literature 2 and 3).
Radical polymerization by routine obtains does not have the three-dimensional arrangement regularity, and promptly atactic PAN multipolymer is as conventional carbon fiber precursor polymkeric substance and carbon fiber precursor.Moreover, following document or report were not disclosed up to now, the single PAN with three-dimensional arrangement regularity is used in these documents or report research, i.e. and isotaxy PAN is as carbon fiber precursor polymkeric substance and carbon fiber precursor with good flame retarding reaction.
[patent documentation 1]
The open SHO No.48-63029 of Japanese unexamined patent publication No.
[patent documentation 2]
Japan has examined patent disclosure SHO No.58-48643
[patent documentation 3]
The open SHO No.61-152812 of Japanese unexamined patent publication No.
[patent documentation 4]
Japan has examined patent disclosure SHO No.49-14404
[patent documentation 5]
Japan has examined patent disclosure HEI No.6-27368
[patent documentation 6]
The open HEI No.11-117123 of Japanese unexamined patent publication No.
[patent documentation 7]
The open SHO No.52-53995 of Japanese unexamined patent publication No.
[patent documentation 8]
The open SHO No.52-55725 of Japanese unexamined patent publication No.
[patent documentation 9]
The open HEI No.2-14013 of Japanese unexamined patent publication No.
[non-patent literature 1]
W.Watt etc., " Proceedings of the International Carbon FiberConference London ", Paper No.4,1971
[non-patent literature 2]
N.A.Kobasova etc., " VYSOKOMOLEKULYAR NYE SOEDINENIYA SERIYAA ", Russia, 13 (1), 1971, P.162-167
[non-patent literature 3]
M.A.Geiderikh，“VYSOKOMOLEKULYAR?NYE?SOEDINENIYA?SERIYAA”，Russia，15(6)，1973，P.1239-1247
Disclosure of the Invention
The objective of the invention is in order to be suppressed at fusion or the thermolysis between the fiber, do not using under the monomeric situation of a large amount of costlinesses or specific purposes, by remarkable carbon fiber precursor polymkeric substance and the precursor that descends of temperature that fire-retardant step is provided, thereby solve foregoing problems of the prior art.
Implement optimal mode of the present invention
Carbon fiber precursor polymkeric substance of the present invention must be made up of the polymkeric substance that contains 50wt% or bigger vinyl cyanide component, with the ratio based on whole triad (triad) of the vinyl cyanide structural chain of being made up of the vinyl cyanide component, the ratio of the isotactic triad of the vinyl cyanide structural chain of being made up of the vinyl cyanide component is necessary for 35mol% or bigger.
Producing carbon fiber with the atactic PAN-base polymer that uses routine compares, by using this based carbon fiber precursor polymer, can realize at low temperatures fire-retardant finish and short time, therefore not only significantly reduced capacity usage ratio, and overcome strength degradation and technical process problem such as the filament breakage of quality problems as causing because of the fusion between the single fiber.
After polymerization contains the polymkeric substance of 50wt% or bigger vinyl cyanide component, but before being molded as desired shape, carbon fiber precursor polymkeric substance of the present invention is the polymkeric substance that is the pre-molding of piece material or pellet form, be meant after polymerization contains the polymkeric substance of 50wt% or bigger vinyl cyanide component with carbon fiber precursor of the present invention, and, be molded as filament form state afterwards by spinning technique such as wet-spinning, dry-jet wet-spinning silk or dry-spinning.In other words, the latter is meant the state before fire-retardant finish and hot carbonizing treatment.
Carbon fiber precursor polymkeric substance of the present invention must be made up of the polymkeric substance that contains 50wt% or bigger vinyl cyanide component, but if existence is less than the vinyl cyanide component of 50wt%, then compare with using atactic PAN analog copolymer, can not show the improved abundant effect of flame retardant properties, therefore be difficult to realize purpose of the present invention.
The carbon fiber precursor polymkeric substance can be the simple aggregation thing of the isotaxy PAN of stereoregular, wherein the ratio of isotactic triad is 35mol% or bigger, perhaps it can be two or more different mixture of polymers of copolymerization 50wt% or bigger isotaxy PAN, perhaps by the multipolymer of following copolymerization acquisition, described copolymerization will produce 50wt% or bigger isotactic PAN.
Carbon fiber precursor polymkeric substance of the present invention preferably includes the polymkeric substance of being made up of as main copolymerization component vinyl cyanide component, acrylic compounds component and acrylic ester compound component, preferred wherein vinyl cyanide component constitutes the total weight percentage of the 80wt% at least of multipolymer and acrylic compounds component and acrylic ester compound component greater than 0% and less than 20%.
" mainly " be meant that aforementioned three kinds of components (vinyl cyanide component, acrylic compounds component and acrylic ester compound component) sum accounts for the 80wt% at least of whole copolymer components and more preferably 90wt% at least herein.
The vinyl cyanide component preferably constitutes the 80wt% at least of multipolymer, and this six sides (hexagonal) plane layer that allows fully to form carbon fiber precursor to be being fed to fire-retardant step, and also causes the adequate performance of carbon fiber product.The preferred 90wt% of vinyl cyanide components contents or bigger.
Acrylic compounds component and the total weight percentage of acrylic ester compound component are preferably greater than 0% and less than 20% in the multipolymer, six side's plane layers that this scope is same to allow fully to form carbon fiber precursor to be being fed to fire-retardant step, and also cause the adequate performance of carbon fiber product.
In polymkeric substance of the present invention, based on the ratio of triad total in the vinyl cyanide structural chain of forming by the vinyl cyanide component, the content ratio (mm triad %) of the isotactic triad of the vinyl cyanide structural chain of forming by the vinyl cyanide component (its relate to by
13The vinyl cyanide deutero-peak value that C-NMR estimates), be necessary for 35mol% at least.If it is in this scope, then when being fed to fire-retardant step, the distance that in structural chain, increases between the adjacent cyano group will hinder six side's plane layers of forming carbon fiber precursor and as the dynamic strength of the carbon fiber of final product acquisition with deficiency.Based on the ratio of triad total in the vinyl cyanide structural chain of being made up of the vinyl cyanide component, the content of isotactic triad (mm triad %) is 65mol% at least preferably.
The content of isotactic triad (mm triad %) is the ratio of three adjacent repeating units (ternary structural chain) in the addition polymerization type polymer, and wherein all adjacent monomeric unit side chains are meso (m) configuration.
Other type triad comprises heterotactic triad (mr) and syndiotaxy triad (rr)." r " is meant the racemize configuration herein.
In other words, the content of isotactic triad is the ratio of mm in mm, mr and rr triad.
If triad content (mm%) is less than 35mol%, then the sterie configuration of PAN will can not show the abundant influence to flame retardant properties, thereby cause with atactic PAN as broad as long basically.
According to the present invention, also but copolymerization is preferably less than other component of 50wt%, as long as demonstrate effect of the present invention, but although with the unsaturated compound that can use the known copolymerization of any routine, but there are preferred unsaturated carboxylic acid and/or esters of unsaturated carboxylic acids and particularly vinylformic acid, methacrylic acid, methylene-succinic acid and/or its alkyl ester.
As alkyl ester, especially preferably has the C1-6 alkyl, for example one or more esters that are selected from the group in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl and the cyclohexyl.
As other copolymerization component, the preferred vinyl cyanide component of using, polar vinyl compounds, as acrylic compounds, acrylic ester compound, methacrylonitrile, vinyl-acetic ester, acrylamide, maleic anhydride and N-vinyl pyrrolidone, and aromatic vinyl compound, as vinylbenzene, vinyl pyridine and vinyl imidazole.These copolymerization components can separately or be used in combination, be selected from polar vinyl compounds with preferred one or more compounds, comprising vinylformic acid, methacrylic acid, methylene-succinic acid and alkyl ester thereof, methacrylonitrile, vinyl-acetic ester, acrylamide, maleic anhydride and N-vinyl pyrrolidone, and aromatic vinyl compound, as vinylbenzene, vinyl pyridine and vinyl imidazole, wherein especially preferably use vinyl cyanide component, acrylic compounds and acrylic ester compound.
The copolymerization of these components obtains the random copolymers of vinyl cyanide random arrangement, perhaps forms the segmented copolymer of the block of vinyl cyanide chain and other copolymerization component chain.
Another effect of other copolymerization component is the self-heating that takes place when suppressing intramolecular cyclization in the fire-retardant finish process, in order that alleviate cause thermal damage to carbon fiber precursor, but another copolymerization component of excessive for this reason copolymerization can cause the carbon fiber performance that reduces sometimes, and therefore when using another copolymerization component, preferably its amount is less than 20mol% carbon fiber precursor polymkeric substance.
Be not particularly limited the method for production carbon fiber precursor polymkeric substance of the present invention, as long as it is the method that allows production isotaxy PAN, comprise with the example of effective means, use urea/monomeric clathrate complex, (78 ℃) solid phase photopolymerization at low temperatures, as D.M.White etc. at J.Am.Chem.Soc., reported in 1960,82,5671, use organic-magnesium or analogue anionic polymerisation process (Y.Nakano etc. as reaction initiator, Polym.Int., 1994,35 (3), 249-55), perhaps use magnesium chloride or analogue free radical polymerisation process (H.Kuwaha ra etc., Polymer Preprints, 2002 as molecular template/carrier, 43 (2), 978); Yet most preferably the unsaturated copolymerization component of mainly being made up of the vinyl cyanide component is absorbed on the crystalline metal compound as template compound, and the formation complex compound carries out the solid-phase polymerization of high molecular to described complex compound.
The crystalline metal compound of employed in the case template compound preferred cycle table the IIA-IIB family, in the middle of these, can mention halogenide, oxide compound, oxyhydroxide, sulfide, nitrate, nitrite, vitriol, carbonate, thiosulphate, phosphoric acid salt, aliphatic carboxylate and aromatic carboxylic acid salt, wherein preferred especially halogenide.
When the above precipitates in solid-phase polymerization by the complex compound that obtains in absorption on the template compound, the crystalline metal compound have metallic cation and paired counter ion thereof in order and structure arranged and vinyl cyanide component and unsaturated copolymerization component can pass through unpaired electron and metallic cation coordination in carboxyl, amide group or carboxylic acid ester groups Sauerstoffatom or the nitrogen-atoms.
Order, size and interionic distance by metallic cation and counter ion thereof are from the arrangement of determining vinyl cyanide component and unsaturated copolymerization component.The type that depends on selected crystalline metal compound is arranged difference, but the IIa-IIb family metal halide of preferred cycle table is as the template compound of isotaxy stereo pair thing.
As this examples for compounds, can mention iron(ic) chloride, cobalt chloride, nickelous chloride, magnesium chloride, chromium chloride, Magnesium Chloride Anhydrous, Calcium Chloride Powder Anhydrous, anhydrous lanthanum chloride, anhydrous chlorides of rase yttrium, iron bromide, cobaltous bromide, nickelous bromide, Manganese dibromide, chromic bromide, anhydrous magnesium bromide, anhydrous calcium bromide, anhydrous lanthanum bromide, anhydrous yttrium bromide, ferric iodide, cobaltous iodide, nickelous iodide, magnesium iodide, iodate chromium, anhydrous magnesium iodide, anhydrous calcium iodide, anhydrous lanthanum iodide, anhydrous yttrium iodide or the like.Also can be used in combination in these two or more, perhaps can use at complex salts such as the alum or the hydrotalcite of monocrystalline system internal memory at two or more metallic cations.
The crystal system of metallic compound is hexahedron system and/or tripartite (trigonal) system most preferably.Most of metallic compounds of hexahedron system and tripartite system adopt the laminate structure on macroscopic scale, and vinyl cyanide component or the usefulness polar group encirclement (enclose) of orientation in the same direction between the crystalline metal compound layer of unsaturated copolymerization component, the layout that generation rule is orderly.This six sides and/or tripartite metallic compound comprise six hydration Calcium Bromides, calcium iodide, six hydration calcium iodides, cobalt chloride (II), cobaltous bromide (II), cobaltous iodide (II), six hydration cobaltous iodides (II), cesium nitrate, Cadmium chloride fine powder, cadmium bromide, cadmium iodide, iron(ic) chloride (II), iron(ic) chloride (III), iron bromide (II), iron bromide (III), ferric iodide (II), curing potassium, two hydration potassium nitrites, three hydration lithium iodides, magnesium chloride, six hydration magnesium bromides, magnesium hydroxide, magnesium chloride (II), magnesium bromide (II), Sodium Nitrite, nickelous chloride (II), two hydration tin sulphates, titanium chloride (II), titanium chloride (III), vanadium chloride (II), bromination vanadium (II), bromination vanadium (III) and zinc chloride, in the middle of these, preferred iron(ic) chloride (III), cobalt chloride (II) and magnesium chloride, and especially preferred magnesium chloride.
The vinyl cyanide component contacts with template compound with unsaturated copolymerization component (the two is referred to as " monomer component " hereinafter), form complex compound, preferably in the atmosphere of inert gases of nitrogen or argon gas, carry out with this step, because if use the words of oxygen containing mixed gas such as air, free radical growing end possibility inactivation, this makes and is difficult to the carbon fiber precursor polymkeric substance that final acquisition has the sufficient polymerization degree.
In order to obtain macromolecular compound, the mol ratio (A/M) of the crystalline metal compound of the IIA-IIB family of monomer component and periodictable preferably at least 0.1, and less than 5.0, because this scope obtains the monomer component with template compound coordinate optimum content, and make the three-dimensional regularity of gained carbon fiber precursor multipolymer further increase, because there is not the side effect that causes because of the excess monomer component.
The granularity of crystalline metal compound also is important, with be 50000 or bigger carbon fiber precursor polymkeric substance for the viscosity-average molecular weight that obtains to have sufficient spinning properties (hereinafter referred is " Mv "), preferably at least 1 micron and of the granularity of metallic compound less than 100 millimeters and more preferably at least 5 millimeters and less than 50 millimeters.
If using the metallic compound granularity is 1 micron or littler particulate, then the Mv of gained carbon fiber precursor polymkeric substance will be lower than 50000 and therefore spinning be subjected to great obstruction.On the other hand, granularity preferably is not 100 millimeters or bigger, because monomer component may penetrate into the time that metallic compound is inner and the formation complex compound is finished in prolongation, the formation itself of complex compound simultaneously can take place in mode heterogeneous.
Especially should avoid back one situation, because in solid-phase polymerization process subsequently, it can cause the variation of Mv.
Before solid-phase polymerization, will under atmosphere of inert gases, transfer in the suitable containers with the complex compound that above-described mode forms.
Solid-phase polymerization technology mainly is two classes, and a class is to use the thermosetting phase-polymerization and the another kind of electromagnetic free radical radiating electromagnetism solid state polymerization of generation that is to use that can generate the reaction initiator of free radical by thermolysis.
The thermosetting phase-polymerization comprises wherein before adding, reaction initiator is dissolved in the method in a small amount of organic solvent, wherein the solution of prepared reaction initiator in monomer component is joined the method in the crystalline metal compound, consider that from the equally distributed angle of reaction initiator back one method is considered to preferred pattern.Can or realize adding with the method for the spontaneous absorption complex compound of static state or the method that is stirred on the complex compound that applies appropriate level, condition be stir so inviolent to destroying complex compound.
Reaction initiator of the present invention can be usually any as the reaction initiator of radical polymerization, can discharge the transistion metal compound that promotes radical polymerization by single electron with using suitably, comprising being the azo-compound of representative with following: Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-two (the 4-methoxyl groups-2 of azo, the 4-methyl pentane nitrile), dimethyl-2,2-azo two (2 Methylpropionic acid ester), 1,1-(hexanaphthene-1-nitrile), 2,2-azo two (2-methylbutyronitrile) and 2,2-azo two [N-(2-propenyl)-2-methyl propanamide]; With the benzoyl peroxide is the organo-peroxide of representative; With Potassium Persulphate/Sodium Nitrite or N, N '-xylidine/benzoyl peroxide binding substances is the redox reaction initiator of representative; And manganese acetylacetonate (III), acetylacetone cobalt (II), pentacyano benzyl cobalt acid esters and ferric sulfate (II)/hydrogen peroxide (Fenton reagent).
On the other hand, the advantage of electromagnetism solid state polymerization is not require the interpolation reaction initiator, because generated free radical by electromagenetic wave radiation.Employed hertzian wave can be to generate any enough energy of free radical in monomer molecule, and can mention ultraviolet ray, X-ray, gamma-radiation, monochromatic visible light ray, available light, electron beam and analogue.
The suitable temp condition of solid-phase polymerization is-80 ℃ to 150 ℃.The temperature that is lower than-80 ℃ can not only significantly reduce polymerization rate, and increases the desired energy consumption of cooling.Be higher than 150 ℃ temperature and can cause that monomeric gaseous state dissociates from the crystalline metal compound, thereby make the carbon fiber precursor polymkeric substance that can not obtain to have satisfied Mv.
Form by crystalline metal compound and carbon fiber precursor monomer by the complex compound that solid-phase polymerization is produced.Therefore can obtain final carbon fiber precursor polymkeric substance with the residue form of water, methyl alcohol, ethanol or analogue wash-out metallic compound.
Can pass through
1H-NMR and
13The composition of the quantitative resulting polymers of C-NMR and the tacticity of polyacrylonitrile backbone.
Can be by the carbon fiber precursor polymkeric substance of conventional technique known spinning by above-described production method acquisition.Be not particularly limited concrete spinning processes and can be common wet-spinning, dry-spinning or dry-jet wet-spinning silk.According to the present invention, the carbon fiber precursor polymer filaments that obtains when this point is called as carbon fiber precursor.By the way, owing in the spinning step process, be used for tensile thermal treatment etc. and cause sometimes part to carry out unitary fire-retardant and these modified structures of rich isotactic PAN being also included within the scope of carbon fiber precursor of the present invention.
By under 150-300 ℃ temperature, heating fire-retardant finish, under atmosphere of inert gases 300-2000 ℃ of heating carbonizing treatment and at 2000-2500 ℃ of following growth of graphite down, thereby carbon fiber precursor of the present invention is changed into carbon fiber.The atmosphere of fire-retardant finish can be an atmosphere of inert gases,, but considers preferred reactive gas atmosphere such as air as nitrogen from the angle that shortens the fire-retardant finish time.Be lower than the problem that 300 ℃ low carbonization temperature can cause gained carbon fiber flexibility decrease.Optionally, can randomly further carry out surface treatment or oil coating or starching to carbon fiber handles.
The reason of the fire-retardant finish of the quicker and lesser temps of carbon fiber precursor polymkeric substance of the present invention and carbon fiber precursor thinks as described below.
Particularly, as mentioned above, under the situation of adjacent itrile group flame retarding reaction taking place, therefore considers from the position angle of the adjacent itrile group of cyclisation in this structural chain of intramolecular cyclization, wherein to be in the isotactic structure of meso configuration be favourable to itrile group, so that adopt lower activation energy to react.Therefore, can carry out fire-retardant finish to isotactic structure at a lower temperature.
In addition, because carbon fiber precursor has because of its isotaxy inductive 3/1 spirane structure, therefore, it forms straight chain condensed pyridine ring in fire-retardant step process, perhaps poly-naphthylidene (polynaphthylidine) skeleton.
Therefore, the size of six side's plane layers of growing in the stage in carbonization or greying has size that the conventional carbon fiber precursor of atactic structure realizes greater than use and therefore the intensity of gained carbon fiber increase.
Embodiment
Now explain the present invention in more detail, and should be appreciated that, never therefore limit the present invention by reference example and embodiment.
By
1H-NMR is determined at the composition of conversion of monomer speed in the polymerization process and resulting polymers and passes through
13C-NMR (270MHz, the DMSO-d6 solvent, by Nihon Denshi DatumCo., Ltd. quantitative three-dimensional regularity (tacticity) JNR-EX-270 of Zhi Zaoing) is to determine content (mm%), the content (rr%) of syndiotaxy triad and the content (mr%) of heterotactic triad of isotactic triad.
Embodiment 1
Flowing down at drying nitrogen, is that the six side's Magnesium Chloride Anhydrouss part of 10-30 millimeter is loaded in the three-necked flask as template compound with the 50g granularity, and keeps in being lower than 10 ℃ ice bath.
With the three-necked flask that nitrogen replacement prepares independently, merge 34.6ml vinyl cyanide, 2.0ml methyl acrylate, 1.2ml dibutyl itaconate then within it as monomer solution.
Then this mixture is joined in the three-necked flask that contains Magnesium Chloride Anhydrous, and make it thorough absorption, with the complex compound of preparation A/M=1/1.
Next, this three-necked flask is laid in the hot air circulate moisture eliminator that is 70 ℃ of following solid state polymerizations 12 hours.After solid state polymerization, this complex compound is poured in the methyl alcohol and by solvent extraction removes Magnesium Chloride Anhydrous, obtain insoluble carbon fiber precursor multipolymer in methyl alcohol, filter then and collect it, wash in proper order with this, spend the night at 40 ℃ of following drying under reduced pressure then with ion exchanged water and acetone.
The output of gained carbon fiber precursor multipolymer is 18.2g (65.4%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 94.5%, 2.4% and 3.1%.
Carry out
13C-NMR measures, and determines tacticity, thus the isotaxy of proof height, wherein mm/mr/rr=68.3/21.3/10.4.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 2.04.
Embodiment 2
Flowing down at drying nitrogen, is that the six side's Magnesium Chloride Anhydrouss part of 10-30 millimeter is loaded in the three-necked flask as template compound with the 50g granularity, and keeps in being lower than 10 ℃ ice bath.
With the three-necked flask that nitrogen replacement prepares independently, merge 34.6ml vinyl cyanide, 2.0ml methyl acrylate, 1.2ml dibutyl itaconate then within it as monomer solution.Then this mixture is joined in the three-necked flask that contains Magnesium Chloride Anhydrous, and make it thorough absorption, with the complex compound of preparation A/M=1/1.
Next, this three-necked flask and 300ml screw neck vial are placed in the glove box of nitrogen replacement, and this complex compound is transferred to the screw neck vial from three-necked flask.The screw neck vial that will contain this complex compound is placed in to have
60In the radiogenic gamma-radiation radiation devices of Co, for electromagnetism solid state polymerization under the dosage of 10KGy.The output of gained carbon fiber precursor multipolymer is 16.6g (59.5%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 94.5%, 2.6% and 2.9%.Carry out
13C-NMR measures, and determines tacticity, thus the isotaxy of proof height, wherein mm/mr/rr=68.1/21.5/10.4.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 2.96.
Embodiment 3
To carry out identical operation with embodiment 1 the samely, different is to use six side's waterless cobaltous chlorides to substitute Magnesium Chloride Anhydrous.
After finishing solid state polymerization, this complex compound is poured in the 5wt% dilute hydrochloric acid, and removes waterless cobaltous chloride by extraction, obtain insoluble carbon fiber precursor multipolymer in dilute hydrochloric acid, then with its filtration and collection.Wash it with ion exchanged water and acetone in proper order with this subsequently, spend the night at 40 ℃ of following drying under reduced pressure then.
The output of gained carbon fiber precursor multipolymer is 11.9g (42.7%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 93.3%, 2.8% and 3.9%.Carry out
13C-NMR measures, and determines tacticity, thus the isotaxy of proof height, wherein mm/mr/rr=85.1/13.1/1.8.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 1.67.
Embodiment 4
To carry out identical operation with embodiment 3 the samely, different is to use six side's Anhydrous Ferric Chlorides to substitute waterless cobaltous chloride.
The output of gained carbon fiber precursor multipolymer is 14.4g (51.6%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 95.7%, 2.6% and 1.7%.Carry out
13C-NMR measures, and determines tacticity, thus the isotaxy of proof height, wherein mm/mr/rr=81.3/13.9/4.8.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 1.46.
Embodiment 5
To carry out identical operation with embodiment 1 the samely, different is to use 42g quadrature six side's beryllium chlorides to substitute Magnesium Chloride Anhydrous.
The output of gained carbon fiber precursor multipolymer is 17.1g (61.3%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 95.4%, 2.9% and 1.7%.Carry out
13C-NMR measures, and determines tacticity, wherein mm/mr/rr=38.0/38.2/23.8.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 1.98.
Embodiment 6
To carry out identical operation with embodiment 1 the samely, different is for A/M=3/1, in conjunction with 50g Magnesium Chloride Anhydrous, 103.8ml vinyl cyanide, 6.0ml methyl acrylate, 3.6ml dibutyl itaconate and 0.75g Diisopropyl azodicarboxylate.
The output of gained carbon fiber precursor multipolymer is 82.2g (91.8%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 95.9%, 2.5% and 1.6%.Carry out
13C-NMR measures, and determines tacticity, wherein mm/mr/rr=38.2/38.0/23.8.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 2.62.
Embodiment 7
To carry out identical operation with embodiment 1 the samely, different is to use granularity is 1 micron or littler finely powdered magnesium chloride.
The output of gained carbon fiber precursor multipolymer is 25.6g (91.8%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 95.9%, 2.7% and 1.8%.Carry out
13C-NMR measures, and determines tacticity, wherein mm/mr/rr=67.9/21.6/10.5.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 1.95.
Embodiment 8
To carry out identical operation with embodiment 1 the samely, different is that vinyl cyanide is used alone as parent material, and does not have methyl acrylate or dibutyl itaconate.
The output of gained carbon fiber precursor multipolymer is 18.8g (67.7%).
Carry out
13C-NMR measures, and determines tacticity, wherein mm/mr/rr=68.4/24.4/7.2.
Under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 1.81.
Comparative Examples 1
Carry out polymerization under the condition identical with embodiment 1, different is not add Magnesium Chloride Anhydrous as template compound.
The output of gained carbon fiber precursor multipolymer is 21.9g (78.5%).
By
1H-NMR measures the composition of estimating multipolymer, shows that vinyl cyanide component, methyl acrylate component and dibutyl itaconate components contents are respectively 95.3%, 2.9% and 1.8%.
Carry out
13C-NMR measures, and determines the tacticity of triad, mm/mr/rr=27.0/50.4/22.6 wherein, thus proof has obtained the carbon fiber precursor multipolymer of random upright structure basically.Use Ubbelohde viscometer, under 35 ℃, at N, the intrinsic viscosity of measuring in N '-dimethyl formamide [η] is 1.83.
Compare with more atactic Comparative Examples, the rich isotactic carbon fiber precursor multipolymer of these embodiment has the top temperature to the exothermic peak of the cyclization of lesser temps skew in the fire-retardant finish process, and has the peak value central authorities height of increase and the heat production that reduces.
These results show that the isotactic carbon fiber precursor polymkeric substance of richness of the present invention allows to carry out fire-retardant finish in lower temperature range, the progress that simultaneously big central authorities' height and low heat production show the flame retarding reaction milder.
Therefore demonstrate the main effect that between carbon fiber, does not have fusion or thermolysis and good fire-retardant finish feature by carbon fiber precursor polymkeric substance and carbon fiber precursor.
Claims (17)
1. carbon fiber precursor polymkeric substance, it is made up of the polymkeric substance that contains 50wt% or bigger vinyl cyanide component, wherein based on the ratio of triad total in the vinyl cyanide structural chain of being made up of the vinyl cyanide component, the ratio of the isotactic triad of the vinyl cyanide structural chain of being made up of the vinyl cyanide component is 35mol% or bigger.
2. the carbon fiber precursor polymkeric substance of claim 1, it is except the vinyl cyanide component, also further comprise the multipolymer of forming as main copolymerization component by acrylic compounds component and acrylic ester compound component, at least the total weight percentage of the 80wt% of wherein said vinyl cyanide ingredients constitute multipolymer and acrylic compounds component and acrylic ester compound component is greater than 0% and less than 20%.
3. the carbon fiber precursor polymkeric substance of claim 1, wherein the ratio of the isotactic triad of the vinyl cyanide structural chain of being made up of the vinyl cyanide component is 65mol% at least.
4. the carbon fiber precursor polymkeric substance of claim 1, wherein the intrinsic viscosity of polymkeric substance is 0.1-10.0.
5. the carbon fiber precursor that obtains of the polymkeric substance by spinning claim 1.
6. fire-retardant carbon fiber precursor, it is by in the presence of oxygen, obtains at the carbon fiber precursor of 200-300 ℃ of following thermal treatment claim 5.
7. one kind is passed through to use the main unsaturated copolymerization component of being made up of the vinyl cyanide component as template compound, it is absorbed in the crystalline metal compound form complex compound, with make this complex compound carry out the solid-phase polymerization of high molecular, produce the method for carbon fiber precursor polymkeric substance, this method obtains the carbon fiber precursor polymkeric substance be made up of the polymkeric substance that contains 50wt% or bigger vinyl cyanide component, wherein based on the ratio of triad total in the vinyl cyanide structural chain of being made up of the vinyl cyanide component, the ratio of isotactic triad is 35mol% or bigger in the vinyl cyanide structural chain of being made up of the vinyl cyanide component.
8. the method for the production carbon fiber precursor polymkeric substance of claim 7, wherein the crystalline metal compound is the compound of periodictable IIA-IIB family metal.
9. the method for the production carbon fiber precursor polymkeric substance of claim 7, wherein said metallic compound is a halogenide.
10. the method for the production carbon fiber precursor polymkeric substance of claim 7, wherein said metallic compound is six sides and/or tripartite metallic compound.
11. the method for the production carbon fiber precursor polymkeric substance of claim 10, wherein said metallic compound has the laminate structure that is selected from least a compound in cadmium iodide, Cadmium chloride fine powder and the Cadmium Sulfide compounds.
12. the method for the production carbon fiber precursor polymkeric substance of claim 7 is wherein passed through to add radical polymerization initiator in described complex compound, and is heated this mixture, thereby carries out solid-phase polymerization.
13. the method for the production carbon fiber precursor polymkeric substance of claim 7 wherein by with the described complex compound of electromagnetic wave radiation, is carried out solid-phase polymerization.
14. the method for the production carbon fiber precursor polymkeric substance of claim 8, wherein the unsaturated copolymerization component of mainly being made up of vinyl cyanide and the mol ratio (A/M) of crystalline metal compound are 0.1-5.0.
15. the method for the production carbon fiber precursor polymkeric substance of claim 7, wherein the granularity of crystalline metal compound is 1 micron to 100 millimeters.
16. the method for the production carbon fiber precursor polymkeric substance of claim 7, wherein the granularity of crystalline metal compound is 5 millimeters to 50 millimeters.
17. the method for the production carbon fiber precursor polymkeric substance of claim 7, wherein the solid-phase polymerization temperature is-80 ℃ to 150 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102382623A (en) * | 2011-08-02 | 2012-03-21 | 山东大学 | Preparation method of carbon-based composite wave-absorbing material |
| CN102485980A (en) * | 2010-12-06 | 2012-06-06 | 财团法人工业技术研究院 | Polyacrylonitrile fiber precursor plasticizer, composition and preparation method of carbon fiber thereof |
| CN103409854A (en) * | 2013-08-28 | 2013-11-27 | 西安元创化工科技股份有限公司 | Production method of carbon fiber |
| CN109810222A (en) * | 2017-11-22 | 2019-05-28 | 财团法人工业技术研究院 | The preparation method of carbon fiber precursor composition and carbon fiber predecessor |
| CN110062773A (en) * | 2017-09-29 | 2019-07-26 | 株式会社Lg化学 | It is used to prepare the preparation method of (methyl) acrylonitrile polymers of carbon fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62282016A (en) * | 1986-05-27 | 1987-12-07 | Asahi Chem Ind Co Ltd | Highly stereoregular acrylic fiber |
| JPH0376823A (en) * | 1989-05-24 | 1991-04-02 | Asahi Chem Ind Co Ltd | Production of acrylonitrile polymer-based carbon fiber |
| JPH07109358A (en) * | 1993-10-12 | 1995-04-25 | Asahi Chem Ind Co Ltd | Highly crystalline polyacrylonitrile structure and production thereof |
| JPH0921019A (en) * | 1995-06-30 | 1997-01-21 | Mitsubishi Rayon Co Ltd | Acrylic copolymer for carbon fiber precursor |
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2004
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102485980A (en) * | 2010-12-06 | 2012-06-06 | 财团法人工业技术研究院 | Polyacrylonitrile fiber precursor plasticizer, composition and preparation method of carbon fiber thereof |
| CN102382623A (en) * | 2011-08-02 | 2012-03-21 | 山东大学 | Preparation method of carbon-based composite wave-absorbing material |
| CN103409854A (en) * | 2013-08-28 | 2013-11-27 | 西安元创化工科技股份有限公司 | Production method of carbon fiber |
| CN103409854B (en) * | 2013-08-28 | 2015-11-04 | 西安元创化工科技股份有限公司 | A kind of production method of carbon fiber |
| CN110062773A (en) * | 2017-09-29 | 2019-07-26 | 株式会社Lg化学 | It is used to prepare the preparation method of (methyl) acrylonitrile polymers of carbon fiber |
| CN110062773B (en) * | 2017-09-29 | 2021-05-25 | 株式会社Lg化学 | Method for producing (meth) acrylonitrile polymer for producing carbon fiber |
| US11046792B2 (en) | 2017-09-29 | 2021-06-29 | Lg Chem, Ltd. | Method of preparing (meth)acrylonitrile-based polymer for preparing carbon fiber |
| CN109810222A (en) * | 2017-11-22 | 2019-05-28 | 财团法人工业技术研究院 | The preparation method of carbon fiber precursor composition and carbon fiber predecessor |
| CN109810222B (en) * | 2017-11-22 | 2021-03-30 | 财团法人工业技术研究院 | Carbon fiber precursor composition and preparation method of carbon fiber precursor |
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