CN1048710A - The preparation method of high viscosity PPTA - Google Patents
The preparation method of high viscosity PPTA Download PDFInfo
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- CN1048710A CN1048710A CN90105870A CN90105870A CN1048710A CN 1048710 A CN1048710 A CN 1048710A CN 90105870 A CN90105870 A CN 90105870A CN 90105870 A CN90105870 A CN 90105870A CN 1048710 A CN1048710 A CN 1048710A
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- tpc
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- ppda
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/39—Plasticisers, homogenisers or feeders comprising two or more stages a first extruder feeding the melt into an intermediate location of a second extruder
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyamides (AREA)
Abstract
The present invention is the method for preparing high viscosity PPTA (aramid fiber II type resin) continuously.With Ursol D and part p-phthaloyl chloride (TPC) pre-polymerization, after mixing, the TPC of adding residue again enters polycondensation in the exhaust twin screw extruder in self-cleaning type twin shaft mixing tank earlier.Resin viscosity (the η that makes
Inh) be stabilized in 5.5-6.5.Add additive such as 1-30% (based on quantity of solvent) such as pyridine, organic amine or intensive polar solvent, can increase substantially resin viscosity (6.5-9, be up to 10), the resin good spinnability, institute's fiber colour that spins is good, the intensity height, stable performance is the raw material of preparation high strength, high-modulus, high-temperature resistant special fiber.
Description
The present invention relates to a kind of by Ursol D (PPDA) and the continuous condensed method of producing high viscosity PPTA (PPTA) of p-phthaloyl chloride (TPC).
PPTA claims the aramid fiber type again, is the raw material of preparation high strength, high-modulus, high-temperature resistant special fiber, and can be made into specific tenacity with it is that 5～6 times on steel wire, specific modulus are 2～3 times, 350 ℃ of pyritous aramid fibers of ability of steel wire; Also can be made into high-temperature insulation paper; Asbestos alternative and other formed article.Be widely used in departments such as space flight, aviation, traffic, communication, chemical industry.
The method for making patent report of PPTA is a lot of, USP3,850,888; 3,884,881 employing TPC and PPDA are raw material, (HMPA) is solvent with hexamethylphosphoramide, and be continuous condensed by cryogenic fluid, produces PPTA, adopt jet mixer batch mixing, double-screw reactor continuous condensed, the logarithmic specific concentration viscosity (η of polymkeric substance
Inh) be about 4.5.Because HMPA polarity is very strong, need not add solubility promoter and can make high viscosity resins, and the resin color and luster is good, ash is little.But HMPA has carcinogenesis, and jet mixer stops up easily, influences continuous condensedly to carry out smoothly.
The spy opens clear 53-133, and 296 employing N-Methyl pyrrolidone (NMP) are solvent, CaCl
2Be solubility promoter.In view of PPDA at high density CaCl
2Be difficult in the slurries disperse, simultaneously CaCl
2Can make the PPDA-NMP solution changes color, so this patent is with PPDA, CaCl
2With NMP respectively wiring solution-forming and slurries, with after fusion TPC mixes, enter polycondensation in the twin screw kneader, this law CaCl again in the S-1 mixing tank
2Consumption is up to 40%, and gained resin ash content is big, and the S-1 mixing tank stops up easily.
The spy opens clear 54-39494 and adopts NMP-CaCl
2Solvent system, PPDA generates following product with part TPC precondensation earlier:
Remaining TPC with molten state or with NMP wiring solution-forming and prepolycondensate without mixing, directly spray into and carry out polycondensation in the twin screw kneader.Though this method has been avoided the mixing tank blockage problem, mixed effect is poor, is difficult for obtaining high-viscosity products.When 1＜n≤10, prepolycondensate is unsettled, is difficult to realize long-term continuous production.TPC is dissolved among the NMP, though measure, carry conveniently, TPC and NMP have the reaction of paying, and gained resin acid resistance is poor, is unfavorable for fiber spinning from crystalline state.
The object of the present invention is to provide a kind of solubility promoter consumption little, simple to operate, stable; At batching, reactant easy oxidation discoloration not in the polycondensation process; Resin viscosity is easy to control, and can be with η
InhStably be controlled at about 5-6.5, also can make the manufacture method of high viscosity (8-10) PPTA simultaneously.
The objective of the invention is to reach: with PPDA elder generation and part TPC(PPDA/TPC 〉=2(mol ratio by following technical measures)) in solvent and solubility promoter, carry out precondensation, then pre-polymerization liquid and remaining molten state TPC are added through volume pump respectively and clamp-on self-cleaning type exhaust twin screw extruder (the system SLF-68 of morning twilight chemical research institute type double-screw reactor) after mixing in the self-cleaning type twin shaft mixing tank, and carry out polycondensation by volume pump adding additive simultaneously.Accompanying drawing-institute classifies aramid fiber type polycondensation part schema of the present invention as.
The solvent that the present invention adopts is N substituted amide class polar solvent such as N-Methyl pyrrolidone, the N-ethyl pyrrolidone, and dimethyl formamide, N,N-DIMETHYLACETAMIDE etc., the toxicity and the polarity of this kind solvent are littler than HMPA, need to add solubility promoter and are used.General solubility promoter commonly used is the muriate such as the CaCl of basic metal or alkaline-earth metal
2, LiCl or CaCl
2The mixture of-LiCl.The solution that PPDA and NMP solubility promoter are made into, because the katalysis of solubility promoter, PPDA is oxidation stain very easily, solution is not anti-to be deposited, and must bring very big inconvenience to production operation within an hour with finishing, and can only be used for batch production and semicontinuous production.The present invention adopts PPDA to carry out precondensation with part TPC earlier, and the amount of TPC is no more than 1/2 of PPDA mole number during pre-polymerization, i.e. PPDA/TPC 〉=2(mol ratio), generate two ends band-NH this moment
2Base than macromole diamines performed polymer:
This performed polymer is at NMP-CaCl
2Very stable in the solvent system, through depositing more than 72 hours, considerable change does not take place in the reactive behavior and the form and aspect of solution, so just can prepare burden on a large scale, is beneficial to successive reaction.
PPDA is at NMP-CaCl
2Concentration in the solvent system is advisable with 0.2～0.6 mol, and too low reaction speed is slow for concentration, and concentration is too high-leveled and difficult to obtain high viscosity resins.The solubility promoter consumption is generally 5～10%(based on quantity of solvent).The pre-polymerization temperature is-10～15 ℃, but pre-polymerization liquid is in long-term storage below 10 ℃.
Pre-polymerization liquid that makes and remaining TPC(fusion) by carrying out thorough mixing in the volume pump adding self-cleaning type twin shaft mixing tank.The feeding manner of TPC has three kinds, and with pressed powder charging influence factor minimum, but solid powder will continuous accurate measurement be inconvenient, so the powdery charging is used for batch production more; Solution feed has the reaction of paying because the TPC activity is bigger; The present invention adopts the fusion charging.
The polycondensation of PPDA and TPC, speed is exceedingly fast, and can generate gel in 1～2 minute, and the therefore thorough mixing of material during the reaction beginning all has great influence to the molecular weight and the molecular weight distribution of polycondensation resultant.The self-cleaning type twin shaft mixing tank (accompanying drawing two) that the present invention adopts is made up of two intermeshing screw rods, screw rod is made up of to the deep trouth threaded block multistage bull or single head just (or anti-) respectively, on the forward screw thread, also have the reverse shallow thread groove of bull, therefore mixing tank has intensive back mixing effect, from making good use of clearly.Screw rod shearing speed can reach 300～2000 seconds
-1, material (about 1 minute) at short notice reaches the microcosmic mixing, thereby can improve the homogeneity of the logarithmic specific concentration viscosity and the polycondensate of final product greatly.Screw slenderness ratio is 8～20, and screw rod can rotate in the same way, also can incorgruously rotate, and rotating speed can be regulated, and generally is controlled at 150～300r.p.m, and temperature generally is controlled at-5～2 ℃ during mixing, and material residence time in mixing tank is 1～5 minute.
Table one is the comparison of carrying out polycondensation behind the various mixing tank batch mixings of use.
The various mixing tanks of table 1 are to the influence of polycondensation
| The mixing tank kind | Resin η inh | Remarks |
| The spraying type mixing tank | 4.5 | Easily stop up |
| The cup type stirring mixer self-cleaning type of overflow twin shaft mixing tank | 5.2 6.5 | Easily whether obstruction or not |
As can be seen from Table I, with self-cleaning type twin shaft mixing tank batch mixing, can obtain the product of viscosity higher, and be difficult for stopping up.
Through the mixed material of self-cleaning type twin shaft mixing tank, directly clamp-on in the exhaust twin screw extruder, further carry out polycondensation.Polycondensation will be passed through " pole-climbing ", " gel ", " one-tenth powder " three phases, total residence time 8～15 minutes.Viscosity (the η of preceding two elementary reaction things
Inh) increase along with the growth in reaction times, having arrived " one-tenth powder " stage, the viscosity of reactant increasess slowly.The exhaust twin screw extruder is equipped with gas barrier in position, by vacuumizing low-molecular material such as water or the hydrogenchloride etc. that continuous discharge reaction produces.Because the installation of gas barrier can make the logarithmic specific concentration viscosity of product improve about 0.5 approximately.The rotating speed of exhaust twin screw extruder can be regulated on request, generally is controlled at shearing rate greater than 150 seconds
-1Condensation temperature is controlled at 60～80 ℃ and is advisable.
General polycondensation rule is followed in the polycondensation of PPDA and TPC, monomer with etc. the molecular weight of polycondensates that generates of mol ratio the highest, but because the error of material purity, operation, metering, deviation to some extent in real reaction.The monomer ratio that the present invention adopts is PPDA/TPC=1/(1～1.05) or (1～1.05)/1(mol ratio), deviation is too big, is difficult to obtain high molecular weight product.
Add some additive in the reaction, can increase substantially the molecular weight of resin, make resin logarithmic specific concentration viscosity (η
Inh) bring up to 7～9, can reach 10.By regulating the consumption of additive, can control the η of resin effectively
InhThe additive that the present invention suits has azines compound such as pyridine, α-Jia Jibiding, beta-picoline etc.; Organic amine such as triethylamine; And the solvent system of intensive polar solvent and solubility promoter composition, these strong solvents have N-Methyl pyrrolidone, the N-ethyl pyrrolidone, and dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl propylene acid amides and double solvents thereof etc., solubility promoter is CaCl
2, LiCl or CaCl
2-LiCl mixture.Pyridine can not directly be sneaked into charging in the pre-polymerization liquid, causes the layering of pre-polymerization liquid easily like this, therefore must add separately in reaction process.The joining day of pyridine can add self-cleaning type twin shaft mixing tank when batch mixing, also can add in the exhaust twin screw extruder.The intensive polar solvent system can only proceed to a certain degree back when forming " gel " (as " pole-climbing " or) in reaction and add, and enters " gel " with polycondensation and adds during the stage, and is the most effective to the molecular weight that improves product.
The consumption of additive: the azines compound with 1～4%(based on quantity of solvent, weight percentage) be advisable; Intensive polar solvent with 10～30%(based on quantity of solvent, weight percentage) be advisable, hydrotropy dosage be 5～10%(based on intensive polar solvent, weight percentage).
If additive adopts intensive polar solvent, and this intensive polar solvent is consistent with reaction solvent,, like this when aftertreatment, except that the yield that increases solvent slightly, the separated from solvent in the time of can not giving the resin aftertreatment, reclaim and bring new problem as N-Methyl pyrrolidone etc.Though the azines compound amount is little, later solvent recuperation, separation have been increased difficulty.
Logarithmic specific concentration viscosity (the η of resin
Inh) be solvent with 95～98% the vitriol oil, be made into the solution of 0.5g/100ml, adopt Ubbelohde viscometer, measure down in 30 ℃ of constant temperature, calculate by following formula:
η
inh＝ln（t/t
0）/c
T in the formula
0Be the solvent elution time, t is the solution elution time, and c is the amount of resin (gram) in the 100ml solution.
The preparation method of PPTA disclosed in this invention, adopt the method for pre-polymerization to solve the variable color of Ursol D solution oxide, the not anti-problem of depositing, activity and color and luster do not have considerable change through placing for a long time thereby make the solution that is made into, and greatly facilitate large scale continuous prod.Adopt self-cleaning type twin shaft mixing tank and exhaust twin screw extruder to carry out batch mixing and polycondensation, the resin that makes thus, logarithmic specific concentration viscosity can be stabilized in 5～6.5.The present invention can increase substantially the logarithmic specific concentration viscosity of resin by adding additives such as pyridine or intensive polar solvent, makes resin viscosity bring up to 7～9, can reach 10; Also can control the viscosity of resin,, find new way for the preparation high viscosity resins by regulating the consumption of additive.
The resin that makes by the present invention, solubility property in the vitriol oil is good, good spinnability, the formed lytropic liquid crystals of the resin of viscosity 5～6.5, after doing spray-wet spinning, the precursor brute force was 24～26 gram/dawn, and extension at break is 5～6%, and modulus was 350～400 gram/dawn, after thermal stretch, fiber strength was 23～25 gram/dawn, and extension at break is 2.8～3%, and modulus was 800 gram/dawn.Fiber colour is good, intensity height, stable performance.
Description of drawings:
Figure one is aramid fiber type polymerization (polycondensation) flow diagram.
Figure two is a self-cleaning type twin shaft mixer structure synoptic diagram.
Figure three is a self-cleaning type twin shaft mixing tank A-A sectional view.
1. transmission cases, 2. charging openings, 3. venting ports, 4. spy holes among the figure
5. hopper 6. cylindrical shells 7,8. screw rod
Embodiment 1.
In 93.6kgNMP solution, add the 6kg Calcium Chloride Powder Anhydrous and be made into NMP-CaCl
2Solution adds 4.32kg Ursol D (PPDA) about 20 ℃, allow it fully dissolve, and is cooled to 15 ℃, adds 4.06kg p-phthaloyl chloride (TPC), and reaction generates prepolycondensate, and 15 ℃ of following constant temperature are standby being lower than.With volume pump prepolycondensate and fused p-phthaloyl chloride being pumped into diameter with the speed of 108 Grams Per Minutes and 4.32 Grams Per Minutes respectively is φ 50m/m, length-to-diameter ratio is 15, rotating speed is in the self-cleaning type twin shaft mixing tank of 300r.p.m, forward conveying effect by mixing tank, mixed reactant is clamp-oned φ 55m/m, length-to-diameter ratio is 23, in the exhaust twin screw extruder of rotating speed 40～60r.p.m.The temperature of mixing tank is controlled at 0～2 ℃, and the temperature of twin screw extruder is controlled at 60～80 ℃, after about 15 minutes, promptly obtains faint yellow crumb shaped polymer serially.Polymer viscosity is 5～5.5, is 22～24 gram/dawn through doing the precursor brute force that obtains after the spray-wet spinning, and modulus was 350～400 gram/dawn, and elongation is 5～6%.
Embodiment 2
Equipment, operation, prescription are with embodiment 1.Add pyridine simultaneously, the faint yellow crumb shaped polymer of gained η at self-cleaning type twin shaft mixing tank opening for feed with the speed of 2 Grams Per Minutes
InhBe 6.5～7.0, after doing spray-wet spinning, the precursor brute force that obtains was 25～26 gram/dawn, and modulus was 350～400 gram/dawn, and elongation is 5～6%.
Embodiment 3
Equipment, operation, prescription are with embodiment 1.In polycondensation process, from the speed adding NMP-CaCl of double-screw reactor opening for feed with 20 Grams Per Minutes
2Solution is additive, the faint yellow crumb shaped polymer η that makes
InhBe 7.0, the mechanical property of gained precursor is with embodiment 2.
Comparative Examples 1
Prescription, equipment are with embodiment 1.Pre-polymerization liquid and fusion TPC directly squeeze into the exhaust twin screw extruder by volume pump without self-cleaning type twin shaft mixing tank batch mixing, and other are operated with embodiment 1, the faint yellow crumb shaped polymer η that makes
InhBe 4.5.
Comparative Examples 2
Equipment is with embodiment 1.In 97.66kgNMP, add 6kgCaCl
2, add 4.32 gram PPDA again, allow it fully dissolve, low-temp storage is standby.PPDA and TPC are without pre-polymerization, PPDA solution and fusion TPC are added batch mixing in the self-cleaning type twin shaft mixing tank with the speed of 108 Grams Per Minutes and 8.12 Grams Per Minutes respectively, borrow the forward conveying effect of mixing tank then, reactant is squeezed into carries out polycondensation in the exhaust twin screw extruder.Batch mixing, polycondensation condition be with embodiment 1, the η of resulting polymers
InhBe about 4.5, and along with the increase of continuous operation time, color of resin is more and more darker, until brown.
Claims (9)
1, a kind of by Ursol D (PPDA) earlier with part p-phthaloyl chloride (TPC) precondensation after the continuous condensed method of producing the high viscosity poly P phenylene diamine terephthalamide in double-screw reactor again, it is characterized in that:
(1) PPDA elder generation and part TPC[PPDA/TPC 〉=2 (mol ratio)] in solvent and solubility promoter ,-10～15 ℃ of following precondensation, monomer concentration is 0.2～0.6 mol (in the PPDA amount), hydrotropy dosage is 5～10% (based on quantity of solvent, weight percentage).
(2) prepolymer and remaining fusion TPC add self-cleaning type twin shaft mixing tank by volume pump respectively, mix 1～5 minute down at-5～2 ℃.
(3) mixture is clamp-oned the exhaust twin screw extruder continuously by mixing tank, and adds additive (as azines compound or intensive polar solvent) by volume pump simultaneously, carries out polycondensation under 60～80 ℃, 8～15 minutes residence time.
2,, it is characterized in that additive azines compound is pyridine, α-Jia Jibiding or beta-picoline according to the described method of claim 1.
3, according to claim 1 or 2 described methods, the add-on that it is characterized in that additive azines compound be 1～4%(based on quantity of solvent, weight percentage).
4,, it is characterized in that the additive pyridine adds self-cleaning type twin shaft mixing tank continuously according to claim 1 or 2 described methods.
5, according to the described method of claim 1, it is characterized in that additive is made up of intensive polar solvent and solubility promoter, intensive polar solvent can be a N-Methyl pyrrolidone, the N-ethyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, the double solvents that dimethyl propylene acid amides or they are formed, solubility promoter is a calcium chloride, lithium chloride or calcium chloride-lithium chloride mixture.
6, according to claim 1 or 5 described methods, it is characterized in that the intensive polar solvent add-on be 10～30%(based on quantity of solvent, weight percentage), the solubility promoter add-on is that 5～10%(is based on intensive polar solvent amount, weight percentage).
7,, it is characterized in that additive intensive polar solvent system added in " pole-climbing " or " gel " stage of polycondensation according to claim 1 or 5 described methods.
8, according to the equipment of the described method of claim 1, two intermeshing screw rods that it is characterized in that self-cleaning type twin shaft mixing tank, form to the deep trouth threaded block by multistage, single head or bull just (or anti-) respectively, also have the reverse shallow thread groove of bull on the forward screw thread, the length-to-diameter ratio of screw rod is 8～20, rotating speed 150～300r.p.m.
9,, it is characterized in that double-screw reactor is the self-cleaning type exhaust twin screw extruder that has gas barrier according to the equipment of the described method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105870A CN1028432C (en) | 1990-08-15 | 1990-08-15 | Process for preparing high-viscosity polypara-phenyl diformyl para-phenyl diamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105870A CN1028432C (en) | 1990-08-15 | 1990-08-15 | Process for preparing high-viscosity polypara-phenyl diformyl para-phenyl diamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048710A true CN1048710A (en) | 1991-01-23 |
| CN1028432C CN1028432C (en) | 1995-05-17 |
Family
ID=4879671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90105870A Expired - Lifetime CN1028432C (en) | 1990-08-15 | 1990-08-15 | Process for preparing high-viscosity polypara-phenyl diformyl para-phenyl diamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028432C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1480479B (en) * | 2002-09-05 | 2010-04-28 | 中蓝晨光化工研究院有限公司 | Technique method for preparing mother liquor of fullbodied aramid fiber III resin and preparation equipment |
| CN101798385A (en) * | 2010-03-15 | 2010-08-11 | 苏州兆达特纤科技有限公司 | Production technology of poly (p-phenytene terephthalamide) resin |
| CN101456950B (en) * | 2008-10-28 | 2010-12-01 | 烟台氨纶股份有限公司 | Method for preparing high molecular weight poly(p-phenyleneterephthalamide) and products |
| CN101218382B (en) * | 2005-07-06 | 2010-12-01 | 可隆株式会社 | Aromatic polyamide filament and method of manufacturing the same |
| CN101928395A (en) * | 2010-08-16 | 2010-12-29 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyphenylene terephthalamide resin |
| CN102040733A (en) * | 2010-11-12 | 2011-05-04 | 常州大学 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
| CN102199284A (en) * | 2011-03-31 | 2011-09-28 | 舒均锋 | Method for continuously preparing meta aromatic polysulfonamide with high viscosity and device thereof |
| CN102206882A (en) * | 2011-03-31 | 2011-10-05 | 舒均锋 | Method and equipment for continuously manufacturing poly (metaphenylene dimethyl formamide diamino diphenyl sulphone) fibers |
| US8309642B2 (en) | 2007-02-03 | 2012-11-13 | Teijin Aramid B.V. | Method for dissolving aramid polymer in sulfuric acid using a double shaft kneader |
| CN103059290A (en) * | 2012-11-26 | 2013-04-24 | 山东万圣博科技股份有限公司 | Continuous polymerization method of high-viscosity poly-p-phenylene terephthamide |
| CN104119526A (en) * | 2013-04-24 | 2014-10-29 | 中国石油化工股份有限公司 | Method for continuously preparing poly-p-phenylene terephthalamide resin |
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| CN113881037A (en) * | 2021-10-28 | 2022-01-04 | 株洲时代新材料科技股份有限公司 | Preparation method of colorless transparent aramid resin |
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1990
- 1990-08-15 CN CN90105870A patent/CN1028432C/en not_active Expired - Lifetime
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| CN1480479B (en) * | 2002-09-05 | 2010-04-28 | 中蓝晨光化工研究院有限公司 | Technique method for preparing mother liquor of fullbodied aramid fiber III resin and preparation equipment |
| CN101218382B (en) * | 2005-07-06 | 2010-12-01 | 可隆株式会社 | Aromatic polyamide filament and method of manufacturing the same |
| US8309642B2 (en) | 2007-02-03 | 2012-11-13 | Teijin Aramid B.V. | Method for dissolving aramid polymer in sulfuric acid using a double shaft kneader |
| CN101456950B (en) * | 2008-10-28 | 2010-12-01 | 烟台氨纶股份有限公司 | Method for preparing high molecular weight poly(p-phenyleneterephthalamide) and products |
| CN101798385A (en) * | 2010-03-15 | 2010-08-11 | 苏州兆达特纤科技有限公司 | Production technology of poly (p-phenytene terephthalamide) resin |
| CN101928395A (en) * | 2010-08-16 | 2010-12-29 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyphenylene terephthalamide resin |
| CN102040733B (en) * | 2010-11-12 | 2012-07-18 | 常州大学 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
| CN102040733A (en) * | 2010-11-12 | 2011-05-04 | 常州大学 | Method for preparing poly(terephthaloyl-p-phenylene diamine) resin |
| CN102206882A (en) * | 2011-03-31 | 2011-10-05 | 舒均锋 | Method and equipment for continuously manufacturing poly (metaphenylene dimethyl formamide diamino diphenyl sulphone) fibers |
| CN102199284A (en) * | 2011-03-31 | 2011-09-28 | 舒均锋 | Method for continuously preparing meta aromatic polysulfonamide with high viscosity and device thereof |
| CN102206882B (en) * | 2011-03-31 | 2012-12-19 | 舒均锋 | Method and equipment for continuously manufacturing poly (metaphenylene dimethyl formamide diamino diphenyl sulphone) fibers |
| CN102199284B (en) * | 2011-03-31 | 2012-12-19 | 舒均锋 | Method for continuously preparing meta aromatic polysulfonamide with high viscosity and device thereof |
| CN103059290A (en) * | 2012-11-26 | 2013-04-24 | 山东万圣博科技股份有限公司 | Continuous polymerization method of high-viscosity poly-p-phenylene terephthamide |
| CN104119526A (en) * | 2013-04-24 | 2014-10-29 | 中国石油化工股份有限公司 | Method for continuously preparing poly-p-phenylene terephthalamide resin |
| CN106496547A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of poly- paraphenylene terephthalamide to diphenylamines |
| CN113881037A (en) * | 2021-10-28 | 2022-01-04 | 株洲时代新材料科技股份有限公司 | Preparation method of colorless transparent aramid resin |
| CN113881037B (en) * | 2021-10-28 | 2023-10-20 | 株洲时代新材料科技股份有限公司 | Preparation method of colorless transparent aramid resin |
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| CN1028432C (en) | 1995-05-17 |
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