CN1039337C - Purification method of polyacrylonitrile - Google Patents
Purification method of polyacrylonitrile Download PDFInfo
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- CN1039337C CN1039337C CN92113445A CN92113445A CN1039337C CN 1039337 C CN1039337 C CN 1039337C CN 92113445 A CN92113445 A CN 92113445A CN 92113445 A CN92113445 A CN 92113445A CN 1039337 C CN1039337 C CN 1039337C
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Abstract
To provide a process for efficiently removing impurity electrolyte from an acrylonitrile polymer produced by an aqueous suspension polymerization method. Monomers containing acrylonitrile as a main component are subjected to aqueous suspension polymerization in an aluminum polymerizer in the presence of an iron-containing inorganic redox initiator. The obtained acrylonitrile polymer is dissolved in a solvent and the solution is purified by contacting with an ion-exchange material to remove the iron compound or its ion and aluminum compound or its ion. An acrylonitrile having decreased content of iron compound or its ion and aluminum compound or its ion can be produced by using the above purification process.
Description
The present invention relates to the method for purifying polyacrylonitrile, this polyacrylonitrile is obtained by the aqueous dispersion polymerization reaction of using inorganic oxide-reduction initiator; Relate to the described polyacrylonitrile solution of using purifying and have the method for the acrylic fiber of high spinning stability as starting raw material production; With the method for preparing carbon fiber by this acrylic fiber of carbonization.
Some performances that acrylic fiber has, for example good bulk ability, with similar feel of wool and color and luster, therefore be used to various uses.As the acrylic fiber of product, promptly staple fibre or macrofiber are by the polyacrylonitrile as starting raw material being dissolved in a kind of organic or inorganic solvent, then gained solution being carried out spinning with wet method, dry method or semi-dry desulfurization and make.Usually, initial polyacrylonitrile is by with acrylonitrile monemer and a kind ofly can carry out Raolical polymerizable with the monomer of its copolymerization and make.The acrylic fiber that is obtained by aforesaid method can be a carbon fiber with its carbonization by carburising step, and this carbon fiber has high performance nature, as high intensity, modulus of elasticity and thermotolerance, and is used to various uses, as is used to make the material of aircraft.
Heterogeneous body suspension polymerization in moisture content system has historical records and is to produce a kind of method that polyacrylonitrile extensively adopts, and it has many advantages, as: be easy to the controlled polymerization amount, be easy to reclaim unreacted monomer, and be easy to control whole process.In order to prepare polyacrylonitrile, adopting with water is the continuous suspension polymerization of reaction medium.No organic initiators is used as polymerization starter usually in this method.
When using no organic initiators (as the oxidation-reduction system of ammonium persulphate-ammonium bisulfite-ferrous sulfate) and being reaction medium with the water of sulfuric acid acidation, with wherein most of when being the monomer polymerization of acrylonitrile monemer, resulting polyacrylonitrile is a particulate state, and promptly polyacrylonitrile is obtained with the dispersion at aqueous phase.Polyacrylonitrile as the acrylic fiber raw material can obtain by polymer aqueous dispersion filtration, washing and the dry gained throw out that polymerization is finished.If use the iron content initiator in this method, the polyacrylonitrile of gained contains iron cpd or iron ion.
In order to be equipped with polyacrylonitrile by continuous aqueous dispersion polymerization legal system, the reactive aluminum device is necessary.This is because when using stainless steel reactor or glass-lined reactor and being equipped with polyacrylonitrile with continuous aqueous dispersion polymerization legal system, because the deposition of polyacrylonitrile, it is quite difficult that successive polymerization becomes.It is said that when using the reactive aluminum device, because reaction system is an acidic aqueous solution, the aluminium surface of reactor is corroded and dissolves,, so prevented the deposition of polyacrylonitrile.
Should adopt a kind of shortstopper for finishing polyreaction, when the use suspension polymerization prepared polyacrylonitrile, the shortstopper of employing can neutralize as the acidic aqueous solution of reaction system.Can be with electrolytical aqueous solution such as sodium oxalate, disodium EDTA, sodium bicarbonates as shortstopper.
Thereby polyacrylonitrile is to reach in the presence of the ionogen that adds as shortstopper at the ionogen that the ionogen that has at least polymerization starter to bring, polyreaction corrosion produce to prepare.And along with the carrying out of polyreaction, polyacrylonitrile forms tens of microns polymer beads, and is present in the aqueous phase system with the form of discrete particles.Therefore, polymer beads is above-mentioned various ionogen, such as iron cpd, aluminum compound etc. pollution.
When the polyacrylonitrile that is made by the aqueous dispersion polymerization method with this routine prepares acrylic fiber, the polymkeric substance that obtains through polymerization will pass through washing step and drying step subsequently, and be dissolved in a kind of solvent of solubilized polyacrylonitrile to make the spinning solution of polyacrylonitrile, it can be obtained acrylic fiber with wet method or dry-spinning.But conventional polyacryl-nitrile spinning fluid brings variety of issue in the current high quality acrylic fiber process of preparation.For example when the spinning solution that is used to make acrylic fiber under heating (about 100 ℃) when being placed for a long time, its yellowing becomes obviously, the pectisation of spinning solution self generation simultaneously causes the flow of solution reduction.The yellowing of spinning solution has caused the yellowing of acrylic fiber self, and the pectisation of spinning solution has caused the mobile low of solution, so can not guarantee stable spinning property.The result causes the termination fracture and produces high-quality acrylic fiber and becomes difficult.In addition, above-mentioned various ionogen remain in the carbon fiber that makes by the burning acrylic fiber, have reduced its intensity and quality.Therefore, above-mentioned various ionogen, particularly iron cpd or its ion and aluminum compound or its ion have detrimentally affect to the thermostability of polyacryl-nitrile spinning fluid, spinning property during the spinning system fiber and the aspects such as physical properties of fiber.
The invention solves using the polyacrylonitrile that makes by the aqueous dispersion polymerization method to make in the acrylic fiber process and preparing the problem that the aqueous dispersion polymerization method that adopts in the carbon fiber process is run into by the carbonization acrylic fiber as starting raw material, ionogen problem just, (promptly preparing the impurity of sneaking into inevitably in the polymer process at the use suspension polymerization) resides in the problem in the polymkeric substance, and this problem makes the high-quality acrylic fiber of production become difficult.The present invention attempts by removing the ionogen in the acrylic fiber that is made by the aqueous dispersion polymerization method fully, or it is reduced to minute quantity acrylic fiber with gratifying spinning property and its high-quality carbon fiber that is formed by the acrylic fiber carbonization are provided.
The inventor finds following situation: the solvent solution of the polyacrylonitrile that is made by continuous aqueous dispersion polymerization method, yellowing and gelling (it causes low flow) owing to long-time heating, be by above-mentioned various ionogen, reside in promptly that impurity in the polyacrylonitrile causes.Can not remove ionogen fully with conventional washing after the polymerization.As mentioned above, the continuous aqueous dispersion polymerization method of preparation polyacrylonitrile is to reach in the presence of add as shortstopper electrolytical at the ionogen that the ionogen that polymerization starter brings, polymerization reactor corrosion produce to implement, polyacrylonitrile particulate inside for this reason, be the discrete particles of aqueous phase, polluted by various ionogen.
The water washing of the routine after the polymerization can be removed the ionogen of polymer surfaces, but is difficult to remove the ionogen that polymkeric substance inside is adhered to by washing.Particularly when the aqueous dispersion polymerization method of using inorganic polymerization starter was used, the polyacrylonitrile end that polymerization obtains existed with ionic species, and various ionogen impurity form with these ionic counter ion and are present in the polymkeric substance.Therefore washing is difficult to remove these ionogen.The inventor finds, by polyacrylonitrile is made solution in organic solvent, spent ion exchange resin is purified to remove (it can be removed or is reduced to a minimum quantity fully) satisfactorily and, takes this to finish the present invention as the ionogen of impurity.
The invention provides the method for purifying polyacrylonitrile, comprising from the solution of the organic solvent that contains polyacrylonitrile and this polymkeric substance of solubilized, remove iron cpd or its ion and aluminum compound or its ion that the impurity form in the polyacrylonitrile that is made by aqueous dispersion polymerization method (it uses inorganic oxide-reduction initiator) exists by the material that use has ion-exchange capacity and is insoluble to described organic solvent; Provide by to carrying out spinning has the acrylic fiber of gratifying spinning property with production method by the resulting solution of above-mentioned purification process; And provide by the described acrylic fiber of carbonization to produce the method for high-quality carbon fiber.
When using the extremely low polyacrylonitrile of impurity (being iron cpd or its ion and aluminum compound or its ion) content, even place down in heating (about 100 ℃), the spinning solution that is used to produce acrylic fiber is yellowing or the gelling phenomenon takes place hardly also.And when adopting wet-spinning to prepare the acrylic macrofiber, on the yarn carrier of spinning bath, the above-mentioned electrolytical cohesion that is dissolved in the polyacryl-nitrile spinning fluid as impurity does not cause the termination fracture yet.So productive rate has improved.In addition, in the carbon fiber that the acrylic fiber that carbonization is produced as stated above makes, fibre breakage, strength property reduce and the similar influence that causes owing to above-mentioned ionogen has also reduced.
The polyacrylonitrile of being produced by the aqueous dispersion polymerization method of using inorganic oxide reduction initiator can become via following high quality washing and not contain or contain the electrolytical purified product of minute quantity.The polyacrylonitrile that polymerization is obtained is dissolved in and a kind ofly can will makes spinning solution in its dissolved organic solvent, the material of ion-exchange capacity is not dissolved and has in use in described organic solvent, as ion exchange resin or ion-exchange fiber, to remove the impurity that resides in the described polyacrylonitrile, as iron cpd or its ion and aluminum compound or its ion.
According to polyacrylonitrile solution of the present invention,, the acrylic fiber of transparent light color and the precursor fiber of carbon fiber have been obtained being very outstanding aspect thermostability and the removal impurity efficient.Furthermore, guaranteed its further expansion by having carbon fiber high-quality and that precursor fiber high performance nature makes in the application of field of compound material according to of the present invention, and resultant important industrial significance.
The present invention relates to polyacrylonitrile by the aqueous dispersion polymerization method production of using inorganic oxide reduction initiator.
Inorganic oxide reduction initiator can be selected from conventional Oxidizing and Reducing Agents.When redox initiator was made up of a kind of oxygenant and a kind of reductive agent, the exemplary of oxygenant was conventional ammonium persulphate, Potassium Persulphate, Sodium Persulfate etc.; The exemplary of reductive agent is conventional S-WAT, ammonium sulphite, sodium bisulfite, ammonium bisulfite, Sulfothiorine, ammonium thiosulfate, sodium bisulfite, formaldehyde sodium sulfoxylate, L-xitix, glucose etc.Compound such as ferrous sulfate or copper sulfate also can be used in combination with Oxidizing and Reducing Agents.In these combinations, the combination of ammonium persulfate-sodium bisulfite (ammonium)-ferrous sulfate is preferred.Although reductive agent can be any ratio to oxygenant, more effectively carry out for making polymerization, reductive agent is 1 to 4 to the mol ratio of oxygenant preferably.
Polyacrylonitrile of the present invention can be contain acrylonitrile monemer and can with the polymkeric substance of the monomeric repeating unit of monoene of its copolymerization.Therefore the unitary content of acrylonitrile monemer should account for 60% (weight) or more in polyacrylonitrile.This is that the acrylic fiber that is made by polyacrylonitrile does not have the due performance of synthesis of acrylonitrile series fiber because when acrylonitrile monemer unit content is lower than 60% (weight).But copolymerization monoene monomer comprises, as vinylformic acid, methacrylic acid, their ester, acrylic acid amides, ethyl vinyl acetate, vinylbenzene, vinylchlorid, vinylidene chloride, maleic anhydride, N-substituted maleimide amine, divinyl and isoprene.P-sulphonyl methallyl ethers, methallyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinylformic acid 2-sulfoethyl methyl esters and salt thereof also can be used as copolymerisable monomer.
The polymerization of acrylonitrile monemer is carried out as follows.Preferred polymerization temperature is 30～80 ℃.When polymerization temperature is higher than 80 ℃,, vinyl cyanide cause polymerisation conversion to reduce because of evaporating to overflow from reaction system.When polymerization temperature was lower than 30 ℃, percent polymerization reduced, thereby not only causes low-yield but also cause low polymerization stability.When making water be the medium of polyreaction, preferably use ion exchanged water.Although ion exchanged water and monomeric ratio (after this being expressed as water/monomer ratio) can be arbitrarily, preferred water/the monomer ratio is 1.0 to 5.0.The mean residence time of monomer in polymerization reactor can be that the use suspension polymerization prepares the used conventional time of polyacrylonitrile.As long as catalyzer can produce redox reaction fast, hydrogen ion concentration can be arbitrarily in the polymerizer.Preferred acidity scope is PH2.0～3.5.
In the aqueous polymer solution that from the polymerizer reaction, takes out, add shortstopper and get final product stopped reaction.Can adopt with normally used shortstopper in the aqueous dispersion polymerization method production polyacrylonitrile is shortstopper.After adding shortstopper, from aqueous polymer solution, reclaim unreacted monomer.As a kind of method that reclaims unreacted monomer, but the straight run distillation aqueous polymer solution, or from polymkeric substance, separates unreacted monomer with evaporation, distill then.Can adopt in two kinds of methods any.Usually adopt rotary vacuum filter (it is a kind of filtration and water extracter of knowing for the public), centrifuge or its analogue as the dehydration and the washer that in back a kind of method, adopt.Using this kind equipment from aqueous polymer solution during isolating polymer, carrying out to such an extent that more fully adopt following method for making to separate: add flocculation agent, as ammonium sulfate, Tai-Ace S 150, sodium sulfate or its analogue; The heating aqueous polymer solution is to quicken the gathering of polymkeric substance.Can use the conventional drying method to remove the water that resides in the polymkeric substance.
To be dissolved in a kind of organic solvent by the polyacrylonitrile that aforesaid method makes.The organic solvent that adopts among the present invention should be able to dissolve polyacrylonitrile.In these solvents, dimethyl formamide, N,N-DIMETHYLACETAMIDE and methyl-sulphoxide are preferred.Preferably be made into the solution that contains the described polyacrylonitrile that 5～35% (weight) obtain by the aqueous dispersion polymerization method and contain the above-mentioned organic solvent of 95～65% the described polyacrylonitrile of solubilized.The reason that the polyacrylonitrile ratio is adjusted between 5～35% is because consider that described solution will be used to spinning.When ratio was lower than 5%, the too low acrylic fiber that can not guarantee of polymer concentration had gratifying spinning property.When ratio surpassed 35%, polymer viscosity was too high, can not guarantee gratifying spinning property equally.
Have ion-exchange capacity and be insoluble to the material of organic solvent as what use among the present invention, can cross-linked ion exchange resin and the cross-linking ion exchange fiber be example.Wherein, the cross-linked ion exchange resin that is made by Vinylstyrene and vinylbenzene is preferentially adopted.For polyacrylonitrile being formed in the spinning solution in the organic solvent and adopting cross-linked ion exchange resin to remove impurity in the polymkeric substance, ion exchange resin should have avidity with organic solvent and should be that cross-linked resin is insoluble to organic solvent to guarantee it, and this is necessary.
As a kind of like this ion exchange resin, can have sulfonic group is functional group, and the strong cation-exchanging resin with ion-exchange capacity is an example.When a kind of cationic sample and a kind of anionic sample all during with the purifying polyacrylonitrile, adopt the reinforcing yin essence ion exchange resin that has sulfonic strong cation-exchanging resin and have season amino by ion-exchange.For capturing heavy metal, can adopt iminodiacetic acid (salt) acid type sequestrant and polyamine type resin.The weak anion exchange resin that also can use as the weak cation exchange resin that makes by methacrylic acid and vinylformic acid and by primary, the second month in a season or tertiary amine makes.The two can be united use weak cation exchange resin and weak anion exchange resin.Preferred especially use is to have sulfonic strong cation-exchanging resin in above-mentioned ion exchange resin, or has sulfonic strong cationic resin and the reinforcing yin essence ion exchange resin with season amino.
Preferred ion exchange resin usage quantity is 0.01～100% of a polyacrylonitrile solution weight.When usage quantity was lower than 0.01% (weight), ion-exchange capacity reduced greatly, so usage quantity is unpractical.On the other hand, it is also impracticable that usage quantity surpasses 100% (weight), because uneconomical and reclaim ion exchange resin and need spend additional effort.
When using the ion-exchange resin purification polyacrylonitrile solution, tubular reactor and tank reactor all may be utilized.Filling ion-exchange resin in tubular reactor is with the continuous injecting reactor of polyacryl-nitrile spinning fluid and to make it flow through reactor be practical to carry out purifying.Use the ion-exchange resin purification polyacrylonitrile in 15～150 ℃ of scopes, to carry out.The increase of polyacrylonitrile solution viscosity causes low flowability when being lower than 15 ℃, thereby makes the ion exchange reaction process become very difficult.When being higher than 150 ℃, the thermostability deficiency of the ion exchange resin of employing self, and can not be used for a long time.
The method according to this invention use ion-exchange resin purification polyacrylonitrile solution can be with impurity concentration, and promptly iron cpd or its ionic concentration and aluminum compound or its ionic concentration are reduced to 0～3ppm and 0～10ppm respectively.Preferably can be correspondingly iron cpd or its ionic concn and aluminum compound or its ionic concn be reduced to 0～1ppm and 0～5ppm respectively.
When iron cpd or its ion and aluminum compound or its ionic concentration surpass 3 or 10ppm respectively, the thermostability of polyacryl-nitrile spinning fluid will be lowered.The reduction of polyacryl-nitrile spinning fluid thermostability has various aforesaid detrimentally affects to the manufacturing processed of acrylic fiber, and the quality that acrylic fiber is reached the carbon fiber that is prepared by acrylic fiber has very big detrimentally affect.
The polyacrylonitrile solution of purifying is configured as acrylic fiber by following spinning processes.
Although spinning processes is not harsh, uses conventional wet method or conventional semi semi-wet method that purification solution is carried out spinning and can make parent (fiber).Particularly adopt wet method or semi-dry desulfurization that purification solution is injected the solidifying product that curing medium obtains, washing and stretching in hot water bath according to a conventional method added process oil, then by dry multiviscosisty.If desired, can use as xeothermic stretching or steam stretching.
Acrylic fiber is made into carbon fiber by following carburising step.
Carburising step is not harsh, adopts ordinary method to get final product.Particularly, can be at 200～400 ℃, the at first preoxidation of parent that will obtain by aforesaid method in the oxygen-containing atmosphere, then at least 1000 ℃, in the inert gas with its carbonization.If desired, can under 3000 ℃ or lower temperature, carry out greying.
The present invention specifically illustrates with following embodiment, and wherein umber and per-cent are all by weight.
Embodiment 1
To volume is 11.6m
3, be equipped with in the polymeric kettle of agitator and add 8m
3Ion exchanged water (transferring to PH3), (reactor: aluminium vessel, agitator blades, the vortex patern of aluminizing).With vinyl cyanide, ethyl vinyl acetate, ammonium persulphate, sodium bisulfite, ferrous sulfate (FeSO
47H
2O) and sulfuric acid be dissolved in the ion exchanged water with the ratio of 91.4 parts, 8.6 parts, 0.4 part, 1.3 parts, 0.00005 part and 0.085 part respectively, begin feed after the dissolving immediately.
In addition, other adds ion exchanged water to make the total amount of ion exchanged water is 200 parts.Polyreaction remains on 55 ℃ at polymerization temperature, fully stirs, adjusts the starting raw material mean residence time and be 90 minutes and added continuously under the condition of starting raw material and carry out.Draw the aqueous polymer dispersion that makes continuously from the overflow port of reactor.0.5 part of sodium oxalate of dissolving, 1.5 parts of bicarbonate of ammonia and 0.5 part of disodium EDTA make the aqueous solution that is used as shortstopper in 100 parts of ion exchanged waters, and add in dispersion liquid with the ratio of 0.2 part of per 100 parts of dispersion liquids adding.In addition, behind the residue of removing unreacted monomer and excessive reagent and additive in polymerization with rotary vacuum filter by washing, add ion exchanged water.The wet extruded polymer that will make with screw extrusion press is in flakes and with tubular moisture eliminator drying then, and the polyacrylonitrile that obtains is listed in table 1.
24.3 parts of above-mentioned dry polymers of dissolving obtain polymers soln in 75.7 parts of N,N-DIMETHYLACETAMIDEs, amount adding by 5 parts of per 100 parts of polymkeric substance addings contains sulfonic strong ion exchange resin (DIAION PK228LH, mfd byMitsubishi Kasei Corp).Adjusting mean residence time is 30 minutes, with gained mixture continuously stirring in agitator, passes through 100 order silk screen filter then with the deionizing exchange resin, obtains polyacrylonitrile solution by this.
By 0.06mm_, the spinning top in 35,000 holes injects the 55% dimethyl formamide aqueous solution can finish wet-spinning with this polyacrylonitrile solution (40 ℃).With after scouring spinning product, again to its stretching.Ratio in 0.5% (being as the criterion with acrylic fiber weight) in the acrylic fiber that obtains thereafter adds a kind of positively charged ion-non-ionic lubricant.The acrylic fiber product that obtained for 3 dawn is cut off in fiber drying after will handling then, curling, slow cooling.The acrylic fiber performance that makes is listed in table 1.
Embodiment 2
To agitator is housed, volume is 8.5m
3Polymerization reactor (reactor: aluminium vessel, agitator blades, the Scroll-type of aluminizing) in add 5m
3Ion exchanged water (being adjusted to PH3) is with vinyl cyanide, ethyl vinyl acetate, sodium methallyl sulfonate, ammonium persulphate, sodium bisulfite, ferrous sulfate (FeSO
47H
2O) and sulfuric acid be dissolved in the ion exchanged water in the ratio of 90.9 parts, 8.9 parts, 0.2 part, 0.5 part, 2.0 parts, 0.00005 part and 0.085 part respectively, begin feed after the dissolving immediately.Adding ion exchanged water in addition in addition, to make its total amount be 250 parts.Polyreaction is 90 minutes and supplies with continuously under the condition of starting raw material and carry out keeping 55 ℃ of polymerization temperatures, fully stir, regulate mean residence time.Take out prepared waterborne polymeric dispersion liquid continuously from the overflow outlet of reactor, 0.5 part of sodium oxalate, 1.5 parts of sodium bicarbonates, 0.5 part of disodium EDTA are dissolved in 100 parts of ion exchanged waters and make the aqueous solution that is used as shortstopper, and its ratio in 0.2 part is added in the dispersion liquid.In addition, after removing the residue of unreacted monomer and excessive reagent and additive in polymerization by washing, add ion exchanged water with the rotation vacuum.The wet polymkeric substance that obtains is suppressed in flakes with screw extruder, and be dried with tubular moisture eliminator, the polyacrylonitrile of gained is listed in table 1.
26 parts of above-mentioned dry polymers of dissolving are to make polymers soln in 74 parts of N,N-DIMETHYLACETAMIDEs, ratio adding in 5 parts of per 100 parts of polymkeric substance addings has sulfonic strong ion exchange resin (DIAION PK228LH, mfd.byMitsubishi Kasei Corp.).The gained mixture is carried out continuously stirring at 80 ℃ in agitator, regulate mean residence time to 30 minute simultaneously,, take this to obtain polyacrylonitrile solution by 100 order silk screen filter deionizing exchange resins.
Via 0.15mm_, the spinning top in 60 holes injects 73% the N,N-DIMETHYLACETAMIDE aqueous solution (40 ℃), carries out the semi-dry desulfurization spinning with this polyacrylonitrile solution.Subsequently with washing of spinning product and stretching.Ratio in 0.5% (with fibre weight) adds a kind of negatively charged ion-non-ionic lubricant in the acrylic fiber of gained, the fiber drying after will handling then, slow cooling, twine to obtain the acrylic macrofiber at 3 dawn then.The long stapled performance of gained acrylic is listed in table 1.
Terminal fracture appears in acrylic macrofiber hardly that make with semi-dry desulfurization in spinning.
Embodiment 3
To agitator is housed, volume is 8.5m
3Polymerization reactor (reactor: aluminium vessel, agitator blades: add ion exchanged water (being adjusted to PH3) the turbine type of aluminizing).With vinyl cyanide, methyl acrylate, sodium methallyl sulfonate, ammonium persulphate, sodium bisulfite, ferrous sulfate (FeSO
47H
2O) and sulfuric acid be dissolved in the ion exchanged water in the ratio of 94 parts, 5.5 parts, 0.5 part, 2.0 parts, 0.00005 part and 0.07 part respectively, begin feed after the dissolving immediately.In addition, other adds ion exchanged water to adjust ion-exchange water inventory to 250 part.Polyreaction is 90 minutes and adds continuously under the condition of starting raw material and carry out in that to keep polymeric reaction temperature be 55 ℃, fully stir, adjust the starting raw material mean residence time.Take out the waterborne polymeric dispersion liquid that makes continuously from the reactor overflow outlet, 0.5 part of sodium oxalate, 1.5 parts of sodium bicarbonates, 0.5 part of disodium EDTA are dissolved in 100 parts of ion exchanged waters and make the aqueous solution that is used as shortstopper, and its ratio in 0.2 part is added in the dispersion liquid.In addition, behind the residue of removing unreacted monomer and excessive reagent and additive in polymerization with rotary vacuum filter by washing, add ion exchanged water.
The wet polyacrylonitrile that makes is in blocks with the screw extruder compacting, be dried to obtain listing in the polyacrylonitrile of table 1 with tubular moisture eliminator then.
In 70 parts of dimethyl formamides, dissolve in 30 parts of above-mentioned dry polymers to make polymers soln, to have sulfonic strong ion exchange resin (DIAION PK228LH, mfd.by Mitgubishi Kasei Corp.) adds 5 parts ratio with per 100 parts of polymkeric substance and adds to wherein.With gained mixture continuously stirring in agitator, adjusting mean residence time simultaneously is 30 minutes, removes ion exchange resin with 100 order silk screen filter, takes this to make polyacrylonitrile solution.
This polyacrylonitrile solution is introduced spinning stack (wherein being 230 ℃ nitrogen atmosphere), and by 0.2mm_, the spinning top in 800 holes carries out dry-spinning.Subsequently with washing of spinning product and stretching.Negatively charged ion-the non-ionic lubricant that in the acrylic fiber that makes, adds 1.5% amount (by fibre weight), with the fiber drying after handling, lax, curl and cut off to make the acrylic fiber at 3 dawn.The performance of the acrylic fiber that makes is listed in table 1.
Embodiment 4
To agitator, volume are housed is 80 liters polymerizer (reactor: aluminium vessel, agitator blades: add 35 turbine type of aluminizing) and lift away from sub-exchanged water (being adjusted to PH3).With vinyl cyanide, methacrylic acid, ammonium persulphate, ammonium bisulfite, ferrous sulfate (FeSO
47H
2O) and sulfuric acid be dissolved in ion exchanged water in the ratio of 98.0 parts, 2.0 parts, 1.5 parts, 4.5 parts, 0.00005 part and 0.085 part respectively, begin feed after the dissolving immediately.
In addition, add other ion exchanged water to regulate ion-exchange water inventory to 400 part.Polyreaction is to be 60 ℃ keeping polymerization temperature, fully stirs, and regulates starting raw material mean residence time to 80 minute, supplies with and carry out under the condition of starting raw material continuously.
Draw the waterborne polymeric dispersion liquid that makes continuously from the overflow outlet of reactor, 0.5 part of ammonium oxalate and 1.5 parts of bicarbonate of ammonia are dissolved in the aqueous solution of making in 100 parts of ion exchanged waters as shortstopper, and its amount by 0.2 part is added in the dispersion liquid.In addition, behind the residue of removing unreacted monomer and excessive reagent and additive in polymerization with rotary vacuum filter by washing, add ion exchanged water.With the wet polymkeric substance that makes in flakes, and with tubular drying machine drying with the screw extruder compacting to make the polyacrylonitrile of listing in table 1.
22 parts of above-mentioned dry polymers of dissolving in 78 parts of dimethyl formamides add in the polymers soln of gained and contain sulfonic strong ion exchange resin (DIAIONHPK55H, mfd by Mitsubishi Kasei Corp.).The gained mixture is mixed in agitator under 80 ℃, stirred 30 minutes, filter with the deionizing exchange resin by 100 eye mesh screens then, take this to obtain to list in the polyacrylonitrile solution of table 1.Measuring result to this polyacrylonitrile solution thermostability is listed in table 1.
Make this polyacrylonitrile solution by 0.15mm_, the imitative silk head in 1500 holes injects the 78% dimethyl formamide aqueous solution (15 ℃) to carry out the semi-dry desulfurization spinning.Subsequently with washing of spinning product and stretching.The amount of aminosiloxane type lubricant by 1.0% (in fibre weight) added in the precursor fiber that makes.With the fiber dewatering thickening after handling, take this to obtain the parent (fiber) at 1.0 dawn.
According to ordinary method, have in this parent added under continuous rolling drives warm air atmosphere and thermograde be in 225～260 ℃ the process furnace obtaining flame retardant resistance, when adjust the residence time when being 34 minutes parent become flame retardant resistance.Then with carbonization and the burning in nitrogen atmosphere, temperature gradient are the heat treatment furnace of 320-700 ℃ carbonization process furnace and 1350 ℃ of the flame retardant fiber that obtains, regulate its residence time in the former and in the latter simultaneously to be respectively 7 minutes and 45 minutes.Promptly make carbon fiber thus.
The properties of carbon that makes is listed in table 1.
Comparative Examples 1
With making polyacrylonitrile with embodiment 1 identical method.In 70 parts of dimethyl formamides, dissolve 30 parts of above-mentioned polymkeric substance to make polymers soln, i.e. polyacrylonitrile solution.Use this polymers soln, use with embodiment 1 in identical method carry out spinning and make acrylic fiber, but without the ion exchange treatment described in the embodiment 1.The performance of the acrylic fiber of gained is listed in table 1.
Termination fracture and yellowing appear in the acrylic fiber that this kind makes with wet-spinning in spinning.
Comparative Examples 2
With making polyacrylonitrile with embodiment 1 identical method.In 74 parts of N,N-DIMETHYLACETAMIDEs, dissolve 26 parts of above-mentioned polymkeric substance to make polymers soln, i.e. polyacrylonitrile solution.Use this polymers soln, that uses that the method identical with embodiment 2 carry out spinning does not carry out the ion exchange treatment described in the embodiment 2.The performance of the acrylic fiber that makes is listed in table 1.
Termination fracture and yellowing appear in the acrylic fiber that makes with this kind semi-dry desulfurization in spinning.
Comparative Examples 3
With making polyacrylonitrile with embodiment 3 identical methods.30 parts of above-mentioned polymkeric substance of dissolving are with the preparation polymers soln in 70 parts of dimethyl formamides, it is polyacrylonitrile solution, use this polymers soln, use with embodiment 3 in identical method carry out spinning with the preparation acrylic fiber, but do not carry out the ion exchange treatment described in the embodiment 3.The performance of the acrylic fiber that makes is listed in table 1.
Termination fracture and yellowing appear in the acrylic fiber that makes with this kind dry-spinning in spinning.
Comparative Examples 4
With making polyacrylonitrile with embodiment 4 identical methods.In 78 parts of dimethyl formamides, dissolve 22 parts of above-mentioned polymkeric substance to make polymers soln, i.e. polyacrylonitrile solution.Use this polymers soln, use the method identical to carry out spinning, but do not carry out the ion exchange treatment described in the embodiment 4 with the preparation parent with embodiment 4.The performance of gained parent is listed in table 1.Termination fracture and fiber yellowing appear in the parent that makes as stated above in spinning.
The parent that obtains is pressed the carbonizing treatment identical with embodiment with the preparation carbon fiber.The results are shown in table 1.Compare with embodiment 4, the thermostability of its spinning solution is low, and the properties of carbon characteristic that makes is relatively poor and inhomogeneous.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | ||
| Polymkeric substance | Polymerisation conversion (%) specific viscosity polymer forms (%) AN component comonomer component AV component MA component MS component MAA impurity content aluminium (ppm) iron ammonium ion (ppm) sodium ion (ppm) | 85.2 0.198 91.4 8.6 50 5 58 450 | 83.5 0.205 90.9 8.9 0.2 45 6.5 39 520 | 84.5 0.190 94.0 5.5 0.5 48 4.4 28 550 | 83.3 0.250 98.0 2.0 50 4.5 75 0 | 85.2 0.198 91.4 8.5 50 5 58 450 | 83.5 0.205 90.9 8.9 0.2 45 6.5 39 520 | 84.5 0.190 94.0 5.5 0.5 48 4.4 28 550 | 83.3 0.250 98.0 50 4.5 75 0 |
Table 1 (continuing)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | ||
| Polymer solution purifying polyacrylonitrile | 6 days exposure pools of tone impurity content aluminium (ppm) iron ammonium ion (ppm) sodium ion (ppm) heat endurance (viscosity) of the polymer of the tone purifying that the viscosity (pool) that the polymer dope behind the colourity spent ion exchange resin purifying that the viscosity that polymer dope is measured immediately (pool) is measured is immediately measured is immediately measured immediately (85 ℃ expose experiment)) exposed pool in 10 days) | 220 bands yellow 150 yellow whites 3.5 0.2 89 150 170 | -150 yellow whites 3.0 0.3 9 11 150 170 | -150 yellow whites 2.6 0.6 15 22 150 170 | -150 yellow whites 3.5 0.3 80 150 170 | ----be solidified into gel rufous | ----be solidified into gel rufous | ----be solidified into gel rufous | ----be solidified into gel rufous |
Table 1 (continuing)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | ||
| The acrylic fibers carbon fiber | Color and luster impurity content aluminium (ppm) iron ammonium ion (ppm) sodium ion (ppm) termination fracture grade impurity content aluminium (ppm) iron (ppm) ammonium ion (ppm) sodium ion (ppm) of fiber | White 3.5 0.2 89 0.01 product per ton termination breaks- | White 3.0 0.3 9 11 0.5 product per ton termination breaks- | White 2.6 0.6 15 22 0.03 product per ton termination breaks- | White 3.5 0.3 80 0.1 product per ton termination breaks 3.5 0.3 80 | Light yellow 50 5 58 450 0.2 product per ton termination breaks- | Light yellow 45 6.5 39 520 7.3 product per ton termination breaks- | Light yellow 48 4.4 28 550 0.4 product per ton termination breaks- | Light yellow 50 4.5 75 0 3.5 product per ton termination breaks 50 4.5 75 0 |
Table 1 (continuing)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | ||
| Carbon fiber | Single end strength (kg/mm 2) CV value (%) single thread modulus of elasticity (t/mm 2) CV value (%) | - - | - - | - - | 580 (7.2) 27 (1.9) | - - | - - | - - | 460 (12.6) 26 (3.2) |
The AN vinyl cyanide
The AV ethyl vinyl acetate
The MA methyl acrylate
The MS sodium methallyl sulfonate
The MAA methacrylic acid
The measuring method of every numerical value is as follows in the table 1.Polymerisation conversion
The aqueous liquid dispersion that collection is made by polyreaction with its filtered and recycled polymeric components, is looked polymer yield and is done polymerisation conversion.Specific viscosity
Dissolving 0.5g polymkeric substance in the 100ml dimethyl formamide is in the viscosity of this solution of 25 ℃ of measurements (Ubbelohde viscometer).The sodium ion amount
With polymkeric substance or fiber burning, measure the sodium ion amount by the color of observation flame and with the ash that obtains.The ammonium ion amount
Polymkeric substance or fiber are added the extraction heat ammonium ion in water, measure the amount of ammonium ion with this color method.Iron and aluminum ion amount
With polymkeric substance or fiber burning, with gained ash its iron of atomic absorption spectrophotometry and aluminum ions amount.Polymer solution viscosity
Measure fall required time in the spinning solution with described polymer concentration in 85 ℃ of oil baths, take this to measure the viscosity of solution, the also the same method of change of viscosity is measured in for some time.The tone of polymers soln
The spinning solution that will have described polymer concentration is estimated the colored state of spinning solution after being heated to 85 ℃ in 85 ℃ of oil baths immediately.The composition of polymkeric substance
The composition of polymkeric substance is by proton N MR mass spectrometric determination.AN represents vinyl cyanide.The grade of termination fracture
With a spinning-drawing machine continuous spinning 30 days, write down the termination fracture number of product per ton.In each embodiment and Comparative Examples, all adopt same spinning-drawing machine, under identical spinning condition, measure the grade of its termination fracture.Single end strength
According to measuring about the regulation of solvent impregnated resin single end strength measuring method in JIS-R7601, measurement number of times (n) is that the average result of 10,10 measurements is listed in table 1.Various single end strength moduluses and single thread modulus of elasticity
Use following Equation for Calculating:
X: mean value wherein:
S: standard deviation CV: Z-factor Xi: each observed value
N: measure number of times
Claims (3)
1. make the method for acrylic fiber, it comprises from the solution of being made up of the organic solvent of described polyacrylonitrile and this polyacrylonitrile of solubilized, by using heavy the having ion-exchange capacity and be insoluble to the material of described organic solvent of described relatively solution weight 0.01-100%, iron cpd or its ion and aluminum compound or its ion as impurity that in the 15-150 ℃ of polyacrylonitrile of removing with the preparation of the aqueous dispersion polymerization method of inorganic oxide-reduction initiator, may contain, and the solution that will handle carries out spinning with wet method, semi-dry desulfurization or dry method; Described solvent accounts for the 95-65% of described solution weight.
According to the process of claim 1 wherein with the polyacrylonitrile purifying with reduce wherein aluminum compound and ionic concentration to 0-10ppm.
According to the process of claim 1 wherein with the polyacrylonitrile purifying with reduce wherein aluminum compound and ionic concentration and iron cpd wherein and ionic concentration thereof respectively to 0-10ppm and 0-3ppm.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP307904/91 | 1991-11-22 | ||
| JP307911/91 | 1991-11-22 | ||
| JP3307911A JP3041655B2 (en) | 1991-11-22 | 1991-11-22 | Acrylonitrile fiber and method for producing the same |
| JP30790491 | 1991-11-22 | ||
| JP03350330A JP3073580B2 (en) | 1991-12-09 | 1991-12-09 | Acrylonitrile-based carbon fiber and method for producing the same |
| JP350330/91 | 1991-12-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1079751A CN1079751A (en) | 1993-12-22 |
| CN1039337C true CN1039337C (en) | 1998-07-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92113445A Expired - Lifetime CN1039337C (en) | 1991-11-22 | 1992-11-21 | Purification method of polyacrylonitrile |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1039337C (en) |
| TW (1) | TW231297B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165072B (en) * | 2006-10-18 | 2010-09-15 | 中国石化上海石油化工股份有限公司 | Method for removing alkali metal impurity in polyacrylonitrile resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3395133A (en) * | 1966-08-08 | 1968-07-30 | Monacelli Walter J | Acrylonitrile polymerization in the presence of ion-exchange resin having-so3h groups |
| JPS6172010A (en) * | 1984-09-17 | 1986-04-14 | Mitsubishi Rayon Co Ltd | Production of acrylonitrile copolymer |
| US4636540A (en) * | 1985-07-08 | 1987-01-13 | Atlantic Richfield Company | Purification of polymer solutions |
-
1992
- 1992-11-20 TW TW81109292A patent/TW231297B/zh not_active IP Right Cessation
- 1992-11-21 CN CN92113445A patent/CN1039337C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3395133A (en) * | 1966-08-08 | 1968-07-30 | Monacelli Walter J | Acrylonitrile polymerization in the presence of ion-exchange resin having-so3h groups |
| JPS6172010A (en) * | 1984-09-17 | 1986-04-14 | Mitsubishi Rayon Co Ltd | Production of acrylonitrile copolymer |
| US4636540A (en) * | 1985-07-08 | 1987-01-13 | Atlantic Richfield Company | Purification of polymer solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| TW231297B (en) | 1994-10-01 |
| CN1079751A (en) | 1993-12-22 |
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