CN106117550A - A kind of Application way of PPTA resin oligomers - Google Patents
A kind of Application way of PPTA resin oligomers Download PDFInfo
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- CN106117550A CN106117550A CN201610587407.8A CN201610587407A CN106117550A CN 106117550 A CN106117550 A CN 106117550A CN 201610587407 A CN201610587407 A CN 201610587407A CN 106117550 A CN106117550 A CN 106117550A
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- ppta
- oligomer
- resin
- solution
- suspension
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- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 title claims abstract description 143
- 239000011347 resin Substances 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000725 suspension Substances 0.000 claims description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 13
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- 239000006184 cosolvent Substances 0.000 claims description 11
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 10
- 238000006073 displacement reaction Methods 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000002166 wet spinning Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 6
- 150000001263 acyl chlorides Chemical group 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of method that PPTA resin oligomers recycles, method more particularly to a kind of PPTA resin oligomers synthesis PPTA resin, including: PPTA oligomer phosgene is carried out pretreatment, after process, PPTA oligomer reacts with p-phenylenediamine and paraphthaloyl chloride and prepares PPTA resin, the molar ratio of p-phenylenediamine and paraphthaloyl chloride is 1:0.9～1.1, preferably 1:1.01.
Description
Technical field
The present invention relates to a kind of method that PPTA resin oligomers recycles, more particularly
The method relating to a kind of PPTA resin oligomers synthesis PPTA resin.
Background technology
PPTA (PPTA) resin, is to prepare high intensity, high-modulus, high temperature resistant, resistance to chemical attack
With the para-aramid fiber of light specific gravity and the raw material of the Fanglun slurry cake with high-wearing feature, polymolecularity.By molten for PPTA resin
The liquid crystal state spinning liquid that solution is formed in concentrated sulfuric acid, through the spinning process of overdrying spray-wet spinning make specific strength be 5-6 times of steel wire,
Specific modulus is 2-3 times of steel wire, the para-aramid fiber of resistance to 350 DEG C of high temperature.Staple has the Kevlar of Du Pont, Supreme Being people
Twaron etc., are widely used in the industries such as space flight and aviation, traffic communication, chemical industry.The performance of PPTA resin directly determines the property of fiber
Can, high intensity to be spinned, the PPTA fiber of high-modulus, the reduced viscosity of the polymer of PPTA must be at more than 5.0dl/g, molecule
The performance measuring the most spun the highest PPTA fiber is the best.
The method preparing PPTA resin conventional is low-temperature solution polycondensation, will monomer paraphthaloyl chloride (TPC) and right
Phenylenediamine (PPDA) is dissolved in aprotic polar solvent such as dimethyl acetylamide (DMAc), N-Methyl pyrrolidone (NMP), pregnancy
In the amide type solvents such as base phosphamide (HMPA), carry out polycondensation reaction under mild conditions.But, it is found that HMPA later
There is a carcinogenesis, and reclaim upper the most difficult, industrial use the safe amide of comparison-salt solvent system instead.Due to NMP solubility property
More less better than HMPA, therefore can increase its dissolubility, present NMP/CaCl by addition cosolvent calcium chloride, lithium chloride2
Dicyandiamide solution is industrially widely used.
Producing 1 ton of PPTA resin according to existing technique and produce 0.05 ton of PPTA oligomer, the processing mode of current PPTA oligomer is main
For landfill and burning.PPTA processes very difficult degraded as the fibrous raw material of stable performance by land-fill method；Additionally, PPTA molecule
In containing nitrogen element, burning process can produce nitrogen oxides.Therefore, there is environment dirt in the existing processing mode of PPTA oligomer
Dye, high in cost of production are not enough.
The deficiency existed based on existing PPTA oligomer processing mode, by research, inventor finds that PPTA oligomer generates
Reason, mainly in course of reaction, the existence of minor amount of water makes paraphthaloyl chloride partial hydrolysis, generates p-phthalic acid list
Acyl chlorides forms END CAPPED GROUP, thus reduces PPTA molecular weight and generate oligomer.Therefore, the present invention is using PPTA oligomer as raw material
One of carry out polymerization preparation PPTA resin.
Summary of the invention
The technical problem to be solved is to provide a kind of method that PPTA oligomer prepares PPTA resin, the method
Have simple to operate, relatively low to the requirement ratio of consersion unit, stable reaction, the advantages such as molecular weight is big and is evenly distributed.
A kind of method that it is an object of the invention to be to provide PPTA oligomer to prepare PPTA resin.Including: by PPTA
Oligomer phosgene carries out pretreatment (see reaction equation 1), and after process, PPTA oligomer is anti-with p-phenylenediamine and paraphthaloyl chloride
Should prepare PPTA resin (see reaction equation 2), the molar ratio of p-phenylenediamine and paraphthaloyl chloride is 1:0.9～1.1,
Preferably 1:1.01.Described preparation technology comprises the following steps:
Reaction equation 1
Reaction equation 2
(1) phosgene is dissolved in a solvent, be configured to phosgene solution；
(2) add solvent and PPTA oligomer in the reactor, be configured to certain density suspension, logical nitrogen replacement
Air in system, heats up suspension, drips a certain amount of phosgene solution insulation reaction, and residue in logical nitrogen purging system is finished in reaction
Phosgene, PPTA oligomer pretreatment suspension is down to room temperature；
(3) pretreated PPTA oligomer suspension, p-phenylenediamine and paraphthaloyl chloride are put into respectively containing helping
In the dicyandiamide solution of solvent, carry out prepolymerization reaction and prepare performed polymer；
(4) performed polymer prepared by remaining for theoretical amount paraphthaloyl chloride and solvent solution-forming and step (3) is pumped into
Screw extruder carries out polycondensation reaction and obtains PPTA resin；
(5) step (4) gained PPTA resin washed through water, filter, dry and obtain PPTA resin.
Phosgene described in step of the present invention (1) can be one or more in monochromatic light gas, surpalite, triphosgene, preferably
Triphosgene；Described solvent can be one or more in benzene, chlorination benzene,toluene,xylene, preferably dimethylbenzene；Described phosgene
Solution concentration is 5～60%, preferably 20～30%；Phosgene solution preparation temperature is 0～50 DEG C, preferably 10～20 DEG C.
Solvent described in step of the present invention (2), PPTA oligomer aqueous less than 200ppm, preferably smaller than 100ppm；Molten
Agent can be one or more in N-Methyl pyrrolidone, N-ethyl pyrrolidone, HMPA, preferably N-methyl
Ketopyrrolidine；PPTA oligomer suspension concentration is 10～80%, preferably 40～50%；PPTA oligomer suspension is molten with phosgene
Liquid reaction temperature is 30～90 DEG C, preferably 50～60 DEG C；Phosgene solution dripping quantity be PPTA oligomer suspension weight 3～
10%, preferably 4～6%；The insulation reaction time is 1～3 hour, preferably 2 hours.
After process described in step of the present invention (3) PPTA oligomer quantities of suspension be p-phenylenediamine weight 5～
20%, preferably 10～15%；Paraphthaloyl chloride consumption is the 25～99% of its gross weight, preferably 50～60%；Solvent is permissible
For one or more in N-Methyl pyrrolidone, N-ethyl pyrrolidone, HMPA, preferably N-crassitude
Ketone；Cosolvent can be the one or many in chloride such as calcium chloride, magnesium chloride, the lithium chloride of alkali metal or alkaline-earth metal
Kind, preferably calcium chloride；In dicyandiamide solution, the content of cosolvent is 3～12%, preferably 6～8%；Solvent load containing cosolvent is
20～40 times of p-phenylenediamine weight, preferably 25～35 times；Prepolymerization reaction temperature is-20～20 DEG C, preferably 0～10 DEG C；In advance
Polycondensation reaction time is 10～60 minutes, preferably 20～30 minutes.
It is 10～60% that paraphthaloyl chloride described in step of the present invention (4) and N-Methyl pyrrolidone are configured to concentration
Solution, preferably 40～50%；Described screw machine be in the same direction engagement or non-engaging twin-screw extruder, its draw ratio be 1:25～
60, preferably 1:45～55；The reaction mass time of staying in screw extruder is 5～30 minutes, preferably 15～20 minutes；Instead
Answering temperature is 50～80 DEG C, preferably 60～70 DEG C.
The washing of PPTA described in step of the present invention (5) uses the mode of making beating washing to carry out by several times and washs, and washing times is
10～20 times, preferably 13～15 times；The single water yield is 3～15 times of PPTA weight, preferably 8～10 times；PPTA dries temperature
110～150 DEG C, preferably 120～130 DEG C；PPTA drying time is 12～48 hours, preferably 20～24 hours.
Detailed description of the invention
The PPTA resin prepared according to present invention process is faint yellow, and logarithmic viscosity number is 5～10dl/g.PPTA resin
Logarithmic viscosity number be with 95～98% concentrated sulphuric acid as solvent, be made into the solution of 0.5g/100ml, use Ubbelohde viscometer,
Measure under 30 DEG C of constant temperature, calculate as the following formula:
ηinh=ln (t/t0)/C
T in formula0For the solvent delivery time；T is the solution delivery time；C is polymer solution concentration, and unit is g/100ml.
Logarithmic viscosity number be 5～10dl/g PPTA resin form lysotropic liquid crystal in concentrated sulfuric acid, through dry spray-wet spinning
After, the fiber obtained, measure according to GB9997-88 (chemical fibre single fiber fracture strength and extension at break).Its precursor intensity is
20～24cn/dtex, extension at break is 1～6%, and modulus is 300～500cn/dtex.
With concrete example, technical scheme is described below, but protection scope of the present invention is not limited to this.
Embodiment 1
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.5 kilogram of PPTA oligomer, 0.5 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 60 DEG C, dropping concentration is the triphosgene two of 30%
Toluene solution 50 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 8% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 200 kilograms, adds the p-phenylenediamine (PPDA) of 6.0 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, be cooled to-5 DEG C, be slowly added to 0.8 kilogram process after PPTA oligomer suspension, 9.02 kilograms to benzene two
Formyl chloride (TPC), reacts 20 minutes and forms performed polymer；3. by the NMP-TPC solution of the performed polymer of 0 DEG C and content 50% respectively with
The double spiral shell of engagement in the same direction that 1000g/min and 20.4g/min pumps into a diameter of Φ 65 simultaneously, draw ratio is 50, rotating speed is 100rpm
Carrying out polycondensation reaction in bar extruder, the temperature controlling extruder is 60～70 DEG C, extruding machine with two screw rods engaging in the same direction extrude
Faint yellow powder be PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15
Secondary；5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 6.35dl/g, through dry spray-wet spinning
After precursor intensity be 23.5cn/dtex, modulus is 451.4cn/dtex, and elongation at break is 2.34%.
Embodiment 2
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.4 kilogram of PPTA oligomer, 0.6 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 50 DEG C, dropping concentration is the triphosgene two of 30%
Toluene solution 50 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 7% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 200 kilograms, adds the p-phenylenediamine (PPDA) of 7.0 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, it is cooled to-5 DEG C, is slowly added to PPTA oligomer suspension after 1 kilogram of process, the terephthaldehyde of 10.53 kilograms
Acyl chlorides (TPC), reacts 20 minutes and forms performed polymer；3. by the NMP-TPC solution of the performed polymer of 10 DEG C and content 50% respectively with
The double spiral shell of engagement in the same direction that 1000g/min and 23.8g/min pumps into a diameter of Φ 65 simultaneously, draw ratio is 50, rotating speed is 100rpm
Carrying out polycondensation reaction in bar extruder, the temperature controlling extruder is 60～70 DEG C, extruding machine with two screw rods engaging in the same direction extrude
Faint yellow powder be PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15
Secondary；5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 6.78dl/g, through dry spray-wet spinning
After precursor intensity be 23.7cn/dtex, modulus is 431.5cn/dtex, and elongation at break is 2.31%.
Embodiment 3
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.5 kilogram of PPTA oligomer, 0.5 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 60 DEG C, dropping concentration is the triphosgene two of 30%
Toluene solution 40 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 7% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 200 kilograms, adds the p-phenylenediamine (PPDA) of 6.5 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, be cooled to-5 DEG C, be slowly added to 0.9 kilogram process after PPTA oligomer suspension, 9.77 kilograms to benzene two
Formyl chloride (TPC), reacts 20 minutes and forms performed polymer；3. by the NMP-TPC solution of the performed polymer of 0 DEG C and content 50% respectively with
The double spiral shell of engagement in the same direction that 1000g/min and 22.2g/min pumps into a diameter of Φ 65 simultaneously, draw ratio is 50, rotating speed is 100rpm
Carrying out polycondensation reaction in bar extruder, the temperature controlling extruder is 60～70 DEG C, extruding machine with two screw rods engaging in the same direction extrude
Faint yellow powder be PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15
Secondary；5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 6.15dl/g, through dry spray-wet spinning
After precursor intensity be 21.3cn/dtex, modulus is 441.5cn/dtex, and elongation at break is 2.35%.
Embodiment 4
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.5 kilogram of PPTA oligomer, 0.5 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 60 DEG C, dropping concentration is the triphosgene two of 20%
Toluene solution 60 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 8% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 250 kilograms, adds the p-phenylenediamine (PPDA) of 8.0 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, it is cooled to-5 DEG C, is slowly added to PPTA oligomer suspension after 1 kilogram of process, the terephthaldehyde of 12.57 kilograms
Acyl chlorides (TPC), reacts 20 minutes and forms performed polymer；3. by the NMP-TPC solution of the performed polymer of 0 DEG C and content 50% respectively with
The double spiral shell of engagement in the same direction that 1000g/min and 22.2g/min pumps into a diameter of Φ 65 simultaneously, draw ratio is 50, rotating speed is 100rpm
Carrying out polycondensation reaction in bar extruder, the temperature controlling extruder is 60～70 DEG C, extruding machine with two screw rods engaging in the same direction extrude
Faint yellow powder be PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15
Secondary；5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 6.68dl/g, through dry spray-wet spinning
After precursor intensity be 23.9cn/dtex, modulus is 436.5cn/dtex, and elongation at break is 2.36%.
Embodiment 5
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.4 kilogram of PPTA oligomer, 0.6 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 50 DEG C, dropping concentration is the triphosgene two of 30%
Toluene solution 50 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 6% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 200 kilograms, adds the p-phenylenediamine (PPDA) of 6.0 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, be cooled to-5 DEG C, be slowly added to 0.7 kilogram process after PPTA oligomer suspension, 9.02 kilograms to benzene two
Formyl chloride (TPC), reacts 20 minutes and forms performed polymer；3. by the NMP-TPC solution of the performed polymer of 0 DEG C and content 40% respectively with
The double spiral shell of engagement in the same direction that 1000g/min and 25.5g/min pumps into a diameter of Φ 65 simultaneously, draw ratio is 50, rotating speed is 100rpm
Carrying out polycondensation reaction in bar extruder, the temperature controlling extruder is 60～70 DEG C, extruding machine with two screw rods engaging in the same direction extrude
Faint yellow powder be PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15
Secondary；5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 6.83dl/g, through dry spray-wet spinning
After precursor intensity be 23.5cn/dtex, modulus is 433.6cn/dtex, and elongation at break is 2.29%.
Embodiment 6
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.5 kilogram of PPTA oligomer, 0.5 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 60 DEG C, dropping concentration is the triphosgene two of 30%
Toluene solution 40 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 8% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 220 kilograms, adds the p-phenylenediamine (PPDA) of 7.0 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, be cooled to-5 DEG C, be slowly added to 0.9 kilogram process after PPTA oligomer suspension, 10.53 kilograms to benzene two
Formyl chloride (TPC), reacts 30 minutes and forms performed polymer；3. by the NMP-TPC solution of the performed polymer of 0 DEG C and content 50% respectively with
The meshed double screw in the same direction that 1000g/min and 21.8g/min pumps into a diameter of Φ 65 simultaneously, major diameter is 50, rotating speed is 100rpm
Carrying out polycondensation reaction in extruder, the temperature controlling extruder is 60～70 DEG C, by the extrusion of extruding machine with two screw rods engaging in the same direction
Faint yellow powder is PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15 times；
5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 7.21dl/g, after dry spray-wet spinning
Precursor intensity be 23.9cn/dtex, modulus is 423.3cn/dtex, and elongation at break is 2.20%.
Embodiment 7
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.5 kilogram of PPTA oligomer, 0.5 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 60 DEG C, dropping concentration is the triphosgene two of 30%
Toluene solution 50 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 7% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 200 kilograms, adds the p-phenylenediamine (PPDA) of 7.0 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, be cooled to-5 DEG C, be slowly added to 0.8 kilogram process after PPTA oligomer suspension, 10.53 kilograms to benzene two
Formyl chloride (TPC), reacts 20 minutes and forms performed polymer；3. by performed polymer and the NMP-TPC solution difference of content 50% of 10 DEG C
Pump into a diameter of Φ 65 with 1000g/min and 29.7g/min simultaneously, major diameter be 50, the double spiral shell of the rotating speed engagement in the same direction as 100rpm
Carrying out polycondensation reaction in bar extruder, the temperature controlling extruder is 60～70 DEG C, extruding machine with two screw rods engaging in the same direction extrude
Faint yellow powder be PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15
Secondary；5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 6.93dl/g, through dry spray-wet spinning
After precursor intensity be 23.2cn/dtex, modulus is 445.4cn/dtex, and elongation at break is 2.28%.
Embodiment 8
1. in tetra-mouthfuls of reaction bulbs of 1L of band stirring and thermometer, 0.4 kilogram of PPTA oligomer, 0.6 kilogram of N-methyl are added
Ketopyrrolidine (NMP), the air in logical nitrogen displacement system, it is to slowly warm up to 50 DEG C, dropping concentration is the triphosgene two of 30%
Toluene solution 60 grams, insulation reaction 2 hours, purge remaining phosgene with nitrogen, PPTA oligomer pretreatment suspension is down to room
Temperature is standby；2., in the 250L stainless steel cauldron with chuck, inject dissolved with 8% calcium chloride (CaCl2) N-methylpyrrole
Alkanone (NMP) solution 230 kilograms, adds the p-phenylenediamine (PPDA) of 8.0 kilograms so that it is fully dissolve, be made into CaCl2-NMP-
After PPDA solution, be cooled to-5 DEG C, be slowly added to 1.2 kilograms process after PPTA oligomer suspension, 12.57 kilograms to benzene two
Formyl chloride (TPC), reacts 30 minutes and forms performed polymer；3. by the NMP-TPC solution of the performed polymer of 0 DEG C and content 50% respectively with
The meshed double screw in the same direction that 1000g/min and 25.0g/min pumps into a diameter of Φ 65 simultaneously, major diameter is 50, rotating speed is 100rpm
Carrying out polycondensation reaction in extruder, the temperature controlling extruder is 60～70 DEG C, by the extrusion of extruding machine with two screw rods engaging in the same direction
Faint yellow powder is PPTA resin；4. the PPTA resin deionized water of its weight 10 times is pulled an oar, filters, is washed 15 times；
5. after washing, PPTA resin is dried 24 hours at 120 DEG C, and recording logarithmic viscosity number is 7.68dl/g, after dry spray-wet spinning
Precursor intensity be 24.1cn/dtex, modulus is 436.8cn/dtex, and elongation at break is 2.26%.
Claims (10)
1. the method that a PPTA oligomer prepares PPTA resin, it is characterised in that comprise the following steps:
(1) phosgene is dissolved in a solvent, be configured to phosgene solution；
(2) add solvent and PPTA oligomer in the reactor, be configured to certain density suspension, in logical nitrogen displacement system
Air, suspension is heated up, drips a certain amount of phosgene solution insulation reaction, remaining light in logical nitrogen purging system is finished in reaction
Gas, is down to room temperature by PPTA oligomer pretreatment suspension；
(3) pretreated PPTA oligomer suspension, p-phenylenediamine and paraphthaloyl chloride are put into respectively containing cosolvent
Dicyandiamide solution in, carry out prepolymerization reaction and prepare performed polymer；
(4) performed polymer prepared by remaining paraphthaloyl chloride and solvent solution-forming and step (3) is pumped into screw extruder
In carry out polycondensation reaction and obtain PPTA resin；
(5) step (4) gained PPTA resin washed through water, filter, dry and obtain PPTA resin.
The method that PPTA oligomer the most according to claim 1 prepares PPTA resin, it is characterised in that institute in step (1)
Stating phosgene is one or more in monochromatic light gas, surpalite, triphosgene, and described solvent is in benzene, chlorination benzene,toluene,xylene
One or more, described phosgene solution concentration is 5～60%；Phosgene solution preparation temperature is 0～50 DEG C.
The method that PPTA oligomer the most according to claim 2 prepares PPTA resin, it is characterised in that described phosgene solution
Concentration is 20～30%；Phosgene solution preparation temperature is 10～20 DEG C.
The method that PPTA oligomer the most according to claim 1 prepares PPTA resin, it is characterised in that institute in step (2)
State solvent, PPTA oligomer aqueous less than 200ppm；Solvent is N-Methyl pyrrolidone, N-ethyl pyrrolidone, hexamethyl
One or more in phosphoric triamide；PPTA oligomer suspension concentration is 10～80%；PPTA oligomer suspension and phosgene
Solution reaction temperature is 30～90 DEG C；Phosgene solution dripping quantity is the 3～10% of PPTA oligomer suspension weight；Insulation reaction
Time is 1～3 hour.
The method that PPTA oligomer the most according to claim 4 prepares PPTA resin, it is characterised in that institute in step (2)
State solvent, PPTA oligomer aqueous less than 100ppm；PPTA oligomer suspension concentration is 40～50%；PPTA oligomer hangs
Supernatant liquid and phosgene solution reaction temperature are 50～60 DEG C；Phosgene solution dripping quantity be PPTA oligomer suspension weight 4～
6%；The insulation reaction time is 2 hours.
The method that PPTA oligomer the most according to claim 1 prepares PPTA resin, it is characterised in that institute in step (3)
After the process stated, PPTA oligomer quantities of suspension is the 5～20% of p-phenylenediamine weight；Paraphthaloyl chloride consumption is that it is total
The 25～99% of weight；Solvent is the one or many in N-Methyl pyrrolidone, N-ethyl pyrrolidone, HMPA
Kind；Cosolvent is the chloride of alkali metal or alkaline-earth metal；In dicyandiamide solution, the content of cosolvent is 3～12%；Containing cosolvent
Solvent load is p-phenylenediamine weight 20～40 times；Prepolymerization reaction temperature is-20～20 DEG C；The prepolymerization reaction time is
10～60 minutes.
The method that PPTA oligomer the most according to claim 6 prepares PPTA resin, it is characterised in that institute in step (3)
After the process stated, PPTA oligomer quantities of suspension is the 10～15% of p-phenylenediamine weight；Paraphthaloyl chloride consumption is that it is total
The 50～60% of weight；Cosolvent is one or more in calcium chloride, magnesium chloride, lithium chloride；Cosolvent in dicyandiamide solution
Content is 6～8%；Solvent load containing cosolvent is 25～35 times of p-phenylenediamine weight；Prepolymerization reaction temperature is 0～10
℃；The prepolymerization reaction time is 20～30 minutes.
The method that PPTA oligomer the most according to claim 1 prepares PPTA resin, it is characterised in that institute in step (4)
The paraphthaloyl chloride stated and N-Methyl pyrrolidone are configured to the solution that concentration is 10～60%；Described screw machine is for nibble in the same direction
Closing or non-engaging twin-screw extruder, its draw ratio is 1:25～60；The reaction mass time of staying in screw extruder is 5
～30 minutes；Reaction temperature is 50～80 DEG C.
The method that the most according to Claim 8, the PPTA oligomer stated prepare PPTA resin, it is characterised in that described in step (4)
Paraphthaloyl chloride and N-Methyl pyrrolidone be configured to the solution that concentration is 40～50%；Described screw machine is for engage in the same direction
Or non-engaging twin-screw extruder, its draw ratio is 1:45～55；The reaction mass time of staying in screw extruder is 15
～20 minutes；Reaction temperature is 60～70 DEG C.
The method that PPTA oligomer the most according to claim 1 prepares PPTA resin, it is characterised in that institute in step (5)
The mode stating PPTA washing employing making beating washing carries out washing by several times, and washing times is 10～20 times, preferably 13～15 times；Single
The water yield is 3～15 times of PPTA weight, preferably 8～10 times；It is 110～150 DEG C that PPTA dries temperature, preferably 120～130 DEG C；
PPTA drying time is 12～48 hours, preferably 20～24 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115873237A (en) * | 2021-09-27 | 2023-03-31 | 中蓝晨光化工有限公司 | Continuous polymerization method and system of aramid fiber III |
| CN116253875A (en) * | 2023-05-15 | 2023-06-13 | 上海科进生物技术有限公司 | Modified polyaniline conductive polymer, conductive plastic and preparation method thereof |
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| CN101476173A (en) * | 2009-01-20 | 2009-07-08 | 赵海鹏 | Direct spinning process for preparing PPTA fibre by end capping resin method |
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| CN101476173A (en) * | 2009-01-20 | 2009-07-08 | 赵海鹏 | Direct spinning process for preparing PPTA fibre by end capping resin method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115873237A (en) * | 2021-09-27 | 2023-03-31 | 中蓝晨光化工有限公司 | Continuous polymerization method and system of aramid fiber III |
| CN116253875A (en) * | 2023-05-15 | 2023-06-13 | 上海科进生物技术有限公司 | Modified polyaniline conductive polymer, conductive plastic and preparation method thereof |
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