CN103601886B - A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance - Google Patents
A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance Download PDFInfo
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- CN103601886B CN103601886B CN201310617589.5A CN201310617589A CN103601886B CN 103601886 B CN103601886 B CN 103601886B CN 201310617589 A CN201310617589 A CN 201310617589A CN 103601886 B CN103601886 B CN 103601886B
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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
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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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
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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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
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
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- Physics & Mathematics (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance.The present invention includes prepolymerization and aftercondensated two-step reaction, the reaction times of prepolymer in twin screw extruder is 10 ~ 60min, twin screw extruder, according to being sequentially set with three warm areas from opening for feed to discharge port, is respectively 160 ~ 180 DEG C, 180 ~ 190 DEG C and 190 ~ 200 DEG C.The present invention adopts twin screw extruder to carry out finishing reaction, and adopt specific temperature and time controling parameters, make the intrinsic viscosity=28-30dL/g of the PIPD polymkeric substance of last output, substantially increase its molecular weight, and reach simultaneously be beneficial to stir and be more prone to PIPD polymer transport to be transferred to spinning workshop section, improve into product efficiency, reduce production cost.
Description
Technical field
The present invention relates to a kind of method of the polymkeric substance for the preparation of fiber, more particularly the present invention relates to a kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance, belong to PIPD technical field of polymer preparation.
Background technology
Poly-[2,5-dihydroxyl-1,4-pyridobismidazole] be liquid crystal virtue heterocycle Rigid-rod polymer, the PIPD fiber (being also referred to as M5 fiber) prepared by this polymkeric substance, tensile strength and Young's modulus are respectively 5.3GPa and 330GPa, compare favourably with the pbo fiber have " king of organic fibre " good reputation.Special hydrogen bond network structure particularly in PIPD polymkeric substance, makes the axial compression strength of the fiber prepared up to 1.7GPa, is 5.7 times of pbo fiber, suitable with carbon fiber.In addition, PIPD fiber also has excellent thermotolerance, flame retardant resistance, electrical insulating property, interfacial adhesion and damage-resistant.Thus, PIPD fiber has broad application prospects at numerous areas such as aerospace, weaponry, fire engineering, outdoor activity goods.1998, PIPD was succeeded in developing by people such as Dutch AkzoNobel research centre Sikkema.2003, this transfer of technology was given one and the related company of the US military-Mai Zhelun world (MagellanSystemInternational) by AkzoNobel.At present, the said firm and Na Mu Lovell E.I.Du Pont Company of the U.S. (DuPontdeNemours) cooperate, by the spining technology advantage of its advanced person, and the PIPD fiber of exploitation excellent combination property.U.S.'s Na Dike infantry soldiers center (U.S.ArmySoldierandBiologicalChemicalCommand) is just in active research PIPD fiber purposes militarily.As can be seen here, develop PIPD fiber and there is important strategic importance.
But, synthesize the key that the polymkeric substance with higher molecular weight is the PIPD fiber of processability excellence.First public in the United States Patent (USP) authorizing the people such as Sikkema: US5 about the method preparing PIPD polymkeric substance, 674,969.This patent gives preparation PIPD two kinds of basic skills of polymkeric substance: one is employing 2, the tri hydrochloride monohydrate (TAP) of 5-dihydric para-phthalic acid (DHTA) and 4-aminopyridine is polymerized in polyphosphoric acid (PPA) medium as basic raw material, and reaction equation is as follows:
Another kind uses dihydric para-phthalic acid's 4-aminopyridine drone (TD salt) to replace the tri hydrochloride monohydrate of 4-aminopyridine as initiator, and reaction equation is as follows:
Although adopt second method can improve the stability of raw material, shorten polymerization time, prepare high-purity TD salt difficulty comparatively large, be unfavorable for suitability for industrialized production.In TD salt, the existence of impurity can destroy the equimolar ratio of monomer, causes polymer chain to stop, and is unfavorable for the PIPD polymkeric substance preparing high molecular.When adopting first method to prepare the polymkeric substance of high molecular, this patent has two key issues never to relate to: one is in polymerization process, the viscosity of system raises gradually, reach 2000Pas, thus cause polymkeric substance to be attached on agitator, make it lose the function of stirring and dispersed material, adopt special agitator (patent: ZL02294359.5) though can partly deal with problems, only the molecular weight of PIPD is still difficult to improve like this; Two is that polymerization system viscosity is very high, and mobility is very poor, and polyphosphoric acid system contacts easy moisture absorption with air, causes material to be difficult to transfer and is transported to spinning workshop section and prepares fiber.
It is CN101418073 that State Intellectual Property Office discloses a publication number in 2009.4.29, the patent of invention that name is called " preparation methods of poly-(2; 5-dihydroxyl-1; 4-pyridobismidazole) ", this patent relates to a kind of poly-(2,5-dihydroxy-1,4-pyridobismidazole) preparation method, it relates to a kind of preparation method of polymkeric substance.The invention solves existing preparation PIPD technology and there is long reaction time and TAP was easily oxidized at the polymerization initial stage, cannot the problem of equimolar ratio polymerization.The present invention with 2,5-Dihydroxyterephthalic acid and 2,3,5,6-4-aminopyridine hydrochloride is that raw material gathers (2,5-dihydroxy-1,4-pyridobismidazole) respectively by direct dehydrochlorination method and the preparation of TD salt polymerization in polyphosphoric acid solvent.The molecular weight that method of the present invention has that reaction time is short, raw material is not oxidizable, monomer obtains polymkeric substance by equimolar ratio polymerization is high, good product performance, technological operation is simple and be easy to industrialized advantage.
It is CN103224625A that State Intellectual Property Office discloses a publication number in 2013.7.31, name is called " gathers (2, 5-dihydroxyl-1, 4-pyridobismidazole) preparation method " patent of invention, this patent relates to poly-(2, 5-dihydroxyl-1, 4-pyridobismidazole) preparation method, realize according to following synthetic method: with 2, 3, 5, 6-4-aminopyridine (TAP) hydrochloride and 2, 5-dihydric para-phthalic acid (DHTA) is raw material, reacted by acid-base neutralisation and carry out salify, obtain 2, 3, 5, 6-4-aminopyridine-2, 5-dihydric para-phthalic acid salt composite salt (TD salt), again by the solution polymerization process of temperature programming, in polyphosphoric acid (PPA) system, condensation polymerization prepares the PIPD fiber of high molecular.The method is easily oxidized in the course of the polymerization process for amino, the difficult point that whole process equimolar ratio cannot be kept to react, and solves the problem that molecular weight is on the low side, polymerizing condition is harsh that existing method obtains.The method is via the process of synthesis 2,5-hydroxyterephthalic acid-2,3,5,6-4-aminopyridine (TD) composite salt, and the TD salt stable in properties obtained is easy to store; Polyreaction operates the advantage in conjunction with direct method and TD salt method, under the prerequisite not changing polyreaction environment and polymerization unit, obtains the PIPD polymkeric substance that molecular weight is higher.
In above-mentioned two patent documents, the preparation method of PIPD all deposits in the course of the polymerization process, and the viscosity of polymerization system is high, is difficult to dispersed with stirring, causes PIPD molecular weight not high, and the problem that conveying transfer is more difficult.
It is CN102936342A that State Intellectual Property Office discloses a publication number in 2013.2.20, name is called the patent of invention of " a kind of process for semicontinuous preparation of polyparaphenylene's benzo dioxazole polymkeric substance ", this patent relates to a kind of process for semicontinuous preparation of polyparaphenylene's benzo dioxazole polymkeric substance, belongs to high-performance fiber production field.Raw material adds in kneading still by the present invention, mediating the dehydrochlorination carrying out monomer in still, increasing the Surface Renewal ability of high viscosity systems, adding the speed of dehydrochlorination; Then enter in mixing kettle, remove the bubble of polymkeric substance, and mix, pump in strainer with volume pump again, strainer is directly connected with more than 2 screw extrusion presss of connecting, after the material filtering after dehydrochlorination and bubble, be polymerized, continuity of operation improves.
It is CN102943316A that State Intellectual Property Office discloses a publication number in 2013.2.27, name is called the patent of invention of " a kind of technique of producing polyparaphenylene's benzo dioxazole pbo fiber ", this patent relates to a kind of technique of producing polyparaphenylene's benzo dioxazole pbo fiber, belongs to high-performance fiber production field.The present invention is by A, degassed, prepolymerization and deaeration; B, post polymerization, deaeration; C, spinning, to solidify; D, aftertreatment; The step such as E, thermal treatment, by optimizing equipment and controling parameters, solves problems of the prior art.Technological process in basic technical scheme of the present invention, equipment coordinate and controling parameters is a rounded system, work in coordination, indispensable, can effectively shift material, realize the scale polymerization of PBO polymkeric substance and follow-up scale spinning, obtain high-quality pbo fiber product.
In above-mentioned two patents, the defect brought greatly to overcome system viscosity employs screw extrusion press, although there is certain effect, but the setting of controling parameters can not solve the high problem of system viscosity well when it reacts in screw extrusion press, more be not suitable for application prepared by PIPD polymkeric substance, polymerization system viscosity in preparation PIPD polymer process cannot be solved high, be difficult to dispersed with stirring, cause PIPD molecular weight not high, and the problem that conveying transfer is more difficult.
Summary of the invention
The present invention is intended in solution prior art because the viscosity of PIPD polymerization system high causing stirs and difficulty of transportation, and the problem that polymericular weight is not high, there is provided a kind of poly-[2,5-dihydroxyl-1,4-pyridobismidazole] preparation method of polymkeric substance, reach reduction polymerization system viscosity, be beneficial to and stir and transport, improve the object of PIPD polymericular weight.
In order to realize foregoing invention object, concrete technical scheme is as follows:
A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance, is characterized in that: comprise following processing step:
A, prepolymerization
The tri hydrochloride monohydrate (TAP) of 2,5-Dihydroxyterephthalic acid (DHTA), 4-aminopyridine, polyphosphoric acid (PPA) are dropped in polymeric kettle together, fully removes hydrogen chloride gas after mixing, then carry out prepolymerization, obtain prepolymer;
B, aftercondensated
The discharge port of the polymeric kettle in steps A is connected with the opening for feed of twin screw extruder, use dry nitrogen by the twin screw extruder described in prepolymer press-in, prepolymer completes finishing reaction in twin screw extruder, gathered [2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance; The reaction times of described prepolymer in twin screw extruder is 10 ~ 60min, and described twin screw extruder, according to being sequentially set with three warm areas from opening for feed to discharge port, is respectively 160 ~ 180 DEG C, 180 ~ 190 DEG C and 190 ~ 200 DEG C.
In step, the mass concentration containing Vanadium Pentoxide in FLAKES in described polyphosphoric acid is 80 ~ 86% in the present invention.
In step, described abundant mixing refers to and fully to mix at 80 DEG C in the present invention.
In step, the described prepolymerization that carries out refers to reaction 6 ~ 10h at 100 ~ 120 DEG C, then is warming up to 140 ~ 180 DEG C of reaction 4 ~ 6h in the present invention.
In stepb, the screw diameter of described twin screw extruder is 20 ~ 180mm, and screw slenderness ratio is 20 ~ 50:1 in the present invention.
In stepb, the screw speed of described twin screw extruder is 5 ~ 100r/min, and extrusion pressure is 1 ~ 20MPa, and in twin screw extruder, vacuum tightness is-0.01 ~-0.095MPa in the present invention.
The present invention is according to the preparation technology of routine, the feeding quantity of 4-aminopyridine tri hydrochloride monohydrate (TAP) is 2,1.345 times of 5-dihydric para-phthalic acid (DHTA), TAP and DHTA must ensure equimolar ratio, the preparation method of two kinds of monomers is as United States Patent (USP): US5,674, the method disclosed in 969.Reaction raw materials polyphosphoric acid (PPA) used in the present invention can commercially obtain, such as commercially available P
2o
5the mass concentration of content is the PPA of 80%, by adding P during use
2o
5, make P
2o
5the mass concentration of content reaches about 84%.The add-on of polyphosphoric acid (PPA) is 12 ~ 18% to be advisable to make the mass concentration of PIPD polymkeric substance.
The molecular weight of Inventive polymers characterizes with the intrinsic viscosity of its dilute solution, intrinsic viscosity is measured by following methods, with methylsulfonic acid by prepolymer or PIPD polymer dilution to 0.25g/dL polymer concentration, adopt conventional Ubbelohde viscometer at 25 ± 0.1 DEG C, measure the intrinsic viscosity of this dilute solution:
1, at the Zero shear viscosity of the prepolymer PIPD/PPA solution that the present invention is obtained in step is about 350Pas(180 DEG C), and the intrinsic viscosity=5 ~ 8dL/g of now PIPD.
2, the present invention in stepb, the intrinsic viscosity=25 ~ 35dL/g of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance that finishing reaction obtains.
The Advantageous Effects that the present invention brings:
1, the invention solves in prior art and cause because the viscosity of PIPD polymerization system is high stirring and difficulty of transportation, and the problem that polymericular weight is not high, there is provided a kind of poly-[2, 5-dihydroxyl-1, 4-pyridobismidazole] preparation method of polymkeric substance, the process of preparation PIPD polymkeric substance is divided into prepolymerization and aftercondensated two steps, in the finishing reaction that polymerization system viscosity is larger, twin screw extruder is adopted to carry out finishing reaction, and adopt specific temperature and time controling parameters, polymerization system viscosity can be solved well and cause greatly the problem that PIPD molecular weight is not high, make the intrinsic viscosity=25 ~ 35dL/g of the PIPD polymkeric substance of last output, substantially increase its molecular weight, and reach simultaneously be beneficial to stir and be more prone to PIPD polymer transport to be transferred to spinning workshop section, improve into product efficiency, reduce production cost.
2, the employing twin screw temperature zonal control that the present invention is concrete, wherein said twin screw extruder is according to being sequentially set with three warm areas from opening for feed to discharge port, be respectively 160 ~ 180 DEG C, 180 ~ 190 DEG C and 190 ~ 200 DEG C, above-mentioned progressively raising warm area is that the method for specified temp is conducive to PIPD in post polymerization process, the lifting of molecular weight, under the setting of this warm area temperature, PIPD is under twin screw shearing action, can be good at forming mesomorphic phase, and form liquid crystal and to be on good terms the significant viscosity reducing polymkeric substance, realize extruding smoothly of high-molecular weight polymer.In addition, the reaction times of prepolymer in twin screw extruder is 10 ~ 60min, by controlling the residence time of prepolymer in screw rod, conveniently can regulate the intrinsic viscosity of the PIPD polymkeric substance finally obtained.
3, the present invention in step, and the described prepolymerization that carries out refers to reaction 6 ~ 10h at 100 ~ 120 DEG C, then is warming up to 140 ~ 180 DEG C of reaction 4 ~ 6h.Polymerization single polymerization monomer 4-aminopyridine hydrochloride is easily oxidized, and controls said temperature and both can reduce its oxidation, be conducive to again deviating from of HCl; The solvability of another monomer 2,5-Dihydroxyterephthalic acid (DHTA) in PPA is not enough, and along with the rising of temperature, DHTA easily distils.The viscosity of reaction polymerization system in early stage is lower, in the tri hydrochloride monohydrate (TAP) of 4-aminopyridine HCl remove than being easier to, at 100 ~ 120 DEG C, the solvability of DHTA is relatively better, not easily distils, the speed that speed of reaction and TAP remove HCl matches, and polyreaction is more steady.In the later stage of pre-polymerization, system viscosity raises, and needs HCl at a higher temperature just can remove completely; Now DHTA concentration reduces, and a small amount of DHTA, by full-bodied polymer wrapped, not easily distils, and can realize better dissolution and transport in higher temperature, at 140 ~ 180 DEG C, reaction can be made more abundant.
4, the present invention in stepb, and the screw diameter of described twin screw extruder is 20 ~ 180mm, and screw slenderness ratio is 20 ~ 50:1.Adopt above-mentioned diameter parameters and length-to-diameter ratio can improve mixing and the plasticizing of PIPD polymkeric substance, reduce leakage current and adverse current, and the shearing action time of twin screw extruder to PIPD can extend, make the better orientation of PIPD polymkeric substance of viscosity higher, form liquid crystal, and form the further raising that mesomorphic phase is conducive to PIPD polymericular weight.And reduce leakage current and the adverse current of PIPD polymkeric substance, polymkeric substance actual residence time in screw rod can be made to reach unanimity, the molecular weight homogeneity of the polymkeric substance obtained is better, is of value to the better fiber of processability.
5, the present invention in stepb, and the screw speed of described twin screw extruder is 5 ~ 100r/min, and extrusion pressure is 1 ~ 20MPa, and in twin screw extruder, vacuum tightness provides value range-0.01 ~-0.095MPa for-0.09MPa.The selection of above-mentioned twin screw extruder parameter can solve the full-bodied problem of system better, be conducive to polyreaction, the speed of rotating speed determines PIPD polymkeric substance residence time in screw rod, the i.e. level of response of PIPD post polymerization, thus determine the height of molecular weight, under the rotating speed that the present invention limits, be conducive to PIPD post polymerization more abundant.Setting up the vacuum tightness that the present invention limits in twin screw extruder inside, is to further remove remaining HCl gas, making reaction more abundant.Maintenance extrusion pressure is 1-20MPa, is conducive to the raising of polymericular weight.
Embodiment
embodiment 1
A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance, comprises following processing step:
A, prepolymerization
The tri hydrochloride monohydrate (TAP) of 2,5-Dihydroxyterephthalic acid (DHTA), 4-aminopyridine, polyphosphoric acid (PPA) are dropped in polymeric kettle together, fully removes hydrogen chloride gas after mixing, then carry out prepolymerization, obtain prepolymer;
B, aftercondensated
The discharge port of the polymeric kettle in steps A is connected with the opening for feed of twin screw extruder, use dry nitrogen by the twin screw extruder described in prepolymer press-in, prepolymer completes finishing reaction in twin screw extruder, gathered [2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance; The reaction times of described prepolymer in twin screw extruder is 10min, and described twin screw extruder, according to being sequentially set with three warm areas from opening for feed to discharge port, is respectively 160 DEG C, 180 DEG C and 190 DEG C.
embodiment 2
A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance, comprises following processing step:
A, prepolymerization
The tri hydrochloride monohydrate (TAP) of 2,5-Dihydroxyterephthalic acid (DHTA), 4-aminopyridine, polyphosphoric acid (PPA) are dropped in polymeric kettle together, fully removes hydrogen chloride gas after mixing, then carry out prepolymerization, obtain prepolymer;
B, aftercondensated
The discharge port of the polymeric kettle in steps A is connected with the opening for feed of twin screw extruder, use dry nitrogen by the twin screw extruder described in prepolymer press-in, prepolymer completes finishing reaction in twin screw extruder, gathered [2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance; The reaction times of described prepolymer in twin screw extruder is 60min, and described twin screw extruder, according to being sequentially set with three warm areas from opening for feed to discharge port, is respectively 180 DEG C, 190 DEG C and 200 DEG C.
embodiment 3
A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance, comprises following processing step:
A, prepolymerization
The tri hydrochloride monohydrate (TAP) of 2,5-Dihydroxyterephthalic acid (DHTA), 4-aminopyridine, polyphosphoric acid (PPA) are dropped in polymeric kettle together, fully removes hydrogen chloride gas after mixing, then carry out prepolymerization, obtain prepolymer;
B, aftercondensated
The discharge port of the polymeric kettle in steps A is connected with the opening for feed of twin screw extruder, use dry nitrogen by the twin screw extruder described in prepolymer press-in, prepolymer completes finishing reaction in twin screw extruder, gathered [2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance; The reaction times of described prepolymer in twin screw extruder is 35min, and described twin screw extruder, according to being sequentially set with three warm areas from opening for feed to discharge port, is respectively 170 DEG C, 185 DEG C and 195 DEG C.
embodiment 4
A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance, comprises following processing step:
A, prepolymerization
The tri hydrochloride monohydrate (TAP) of 2,5-Dihydroxyterephthalic acid (DHTA), 4-aminopyridine, polyphosphoric acid (PPA) are dropped in polymeric kettle together, fully removes hydrogen chloride gas after mixing, then carry out prepolymerization, obtain prepolymer;
B, aftercondensated
The discharge port of the polymeric kettle in steps A is connected with the opening for feed of twin screw extruder, use dry nitrogen by the twin screw extruder described in prepolymer press-in, prepolymer completes finishing reaction in twin screw extruder, gathered [2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance; The reaction times of described prepolymer in twin screw extruder is 55min, and described twin screw extruder, according to being sequentially set with three warm areas from opening for feed to discharge port, is respectively 178 DEG C, 183 DEG C and 192 DEG C.
embodiment 5
On the basis of embodiment 1-4:
Preferably, in step, the mass concentration containing Vanadium Pentoxide in FLAKES in described polyphosphoric acid is 80%.
Preferably, in step, described abundant mixing refers to and fully to mix at 80 DEG C.
Preferably or further, in step, the described prepolymerization that carries out refers to react 6h at 100 DEG C, then is warming up to 140 DEG C of reaction 4h.
Preferably, in stepb, the screw diameter of described twin screw extruder is 20mm, and screw slenderness ratio is 20:1.
Preferably or further, in stepb, the screw speed of described twin screw extruder is 5r/min, and extrusion pressure is 1MPa, and in twin screw extruder, vacuum tightness is-0.095MPa.
embodiment 6
On the basis of embodiment 1-4:
Preferably, in step, the mass concentration containing Vanadium Pentoxide in FLAKES in described polyphosphoric acid is 86%.
Preferably, in step, described abundant mixing refers to and fully to mix at 80 DEG C.
Preferably or further, in step, the described prepolymerization that carries out refers to react 10h at 120 DEG C, then is warming up to 180 DEG C of reaction 6h.
Preferably, in stepb, the screw diameter of described twin screw extruder is 180mm, and screw slenderness ratio is 50:1.
Preferably or further, in stepb, the screw speed of described twin screw extruder is 100r/min, and extrusion pressure is 20MPa, and in twin screw extruder, vacuum tightness is-0.01MPa.
embodiment 7
On the basis of embodiment 1-4:
Preferably, in step, the mass concentration containing Vanadium Pentoxide in FLAKES in described polyphosphoric acid is 83%.
Preferably, in step, described abundant mixing refers to and fully to mix at 80 DEG C.
Preferably or further, in step, the described prepolymerization that carries out refers to react 8h at 110 DEG C, then is warming up to 160 DEG C of reaction 5h.
Preferably, in stepb, the screw diameter of described twin screw extruder is 100mm, and screw slenderness ratio is 35:1.
Preferably or further, in stepb, the screw speed of described twin screw extruder is 55r/min, and extrusion pressure is 10.5MPa, and in twin screw extruder, vacuum tightness is-0.0525MPa.
embodiment 8
On the basis of embodiment 1-4:
Preferably, in step, the mass concentration of described polyphosphoric acid is 84%.
Preferably, in step, the mass concentration containing Vanadium Pentoxide in FLAKES in described polyphosphoric acid is 81%.
Preferably or further, in step, the described prepolymerization that carries out refers to react 9h at 105 DEG C, then is warming up to 150 DEG C of reaction 4.5h.
Preferably, in stepb, the screw diameter of described twin screw extruder is 50mm, and screw slenderness ratio is 45:1.
Preferably or further, in stepb, the screw speed of described twin screw extruder is 80r/min, and extrusion pressure is 17MPa, and in twin screw extruder, vacuum tightness is-0.08MPa.
embodiment 9
Being equipped with patent: the P once adding 6637.21g in the 20L prepolymerization kettle of agitator described in ZL02294359.5
2o
5mass concentration is the P of the polyphosphoric acid (PPA) of 80%, the tri hydrochloride monohydrate (TAP) of the 4-aminopyridine of 1000g (3.753mol), the 2,5-Dihydroxyterephthalic acid (DHTA) of 743.35g (3.753mol) and 331.86g
2o
5, sealed reactor.
Material in reactor is warming up to 80 DEG C, stir 5h(and remove partial oxidation hydrogen), slowly the pressure in reactor is evacuated to 150Pa, and maintain this pressure, reaction system is warming up to 120 DEG C of reaction 6h, be warming up to 140 DEG C of reaction 6h again, obtain the performed polymer of intrinsic viscosity=5dL/g;
Use dry nitrogen that performed polymer is pressed into twin screw extruder, complete finishing reaction, the residence time of performed polymer in twin screw is 20min, three warm areas of screw rod are set as 175 DEG C, 180 DEG C and 190 DEG C, screw diameter D=60-150mm, screw slenderness ratio L/D=20-40 respectively, screw speed is 5-100r/min, the extrusion pressure of twin screw extruder is 15-20MPa, and in screw rod, vacuum tightness is-0.09MPa, obtains the PIPD polymkeric substance of intrinsic viscosity=28dL/g.
embodiment 10
Being equipped with patent: the P once adding 6637.21g in the 20L prepolymerization kettle of agitator described in ZL02294359.5
2o
5mass concentration is the P of the polyphosphoric acid (PPA) of 80%, the tri hydrochloride monohydrate (TAP) of the 4-aminopyridine of 1000g (3.753mol), the 2,5-Dihydroxyterephthalic acid (DHTA) of 743.35g (3.753mol) g and 165.93g
2o
5, sealed reactor.
Material in reactor is warming up to 80 DEG C, stir 5h(and remove partial oxidation hydrogen), slowly the pressure in reactor is evacuated to 150Pa, and maintain this pressure, reaction system is warming up to 120 DEG C of reaction 8h, be warming up to 140 DEG C of reaction 6h again, obtain the performed polymer of intrinsic viscosity=6.8dL/g;
Use dry nitrogen that performed polymer is pressed into twin screw extruder, complete finishing reaction, the residence time of performed polymer in twin screw is 20min, three warm areas of screw rod are set as 180 DEG C, 185 DEG C and 195 DEG C, screw diameter D=100-150mm, screw slenderness ratio L/D=30-40 respectively, screw speed is 5-100r/min, the extrusion pressure of twin screw extruder is 15-20MPa, and in screw rod, vacuum tightness is-0.09MPa, obtains the PIPD polymkeric substance of intrinsic viscosity=29.3dL/g.
embodiment 11
Being equipped with patent: the P once adding 6637.21g in the 20L prepolymerization kettle of agitator described in ZL02294359.5
2o
5mass concentration is the P of the polyphosphoric acid (PPA) of 80%, the tri hydrochloride monohydrate (TAP) of the 4-aminopyridine of 1000g (3.753mol) g, the 2,5-Dihydroxyterephthalic acid (DHTA) of 743.35g (3.753mol) gg and 414.82g
2o
5, sealed reactor.
Material in reactor is warming up to 80 DEG C, stir 5h(and remove partial oxidation hydrogen), slowly the pressure in reactor is evacuated to 150Pa, and maintain this pressure, reaction system is warming up to 120 DEG C of reaction 10h, be warming up to 140 DEG C of reaction 5h again, obtain the performed polymer of intrinsic viscosity=8dL/g;
Use dry nitrogen that performed polymer is pressed into twin screw extruder, complete finishing reaction, the residence time of performed polymer in twin screw is 20min, three warm areas of screw rod are set as 175 DEG C, 185 DEG C and 190 DEG C, screw diameter D=100-120mm, screw slenderness ratio L/D=30-35 respectively, screw speed is 5-50r/min, the extrusion pressure of twin screw extruder is 15-18MPa, and in screw rod, vacuum tightness is-0.09MPa, obtains the PIPD polymkeric substance of intrinsic viscosity=30dL/g.
Claims (5)
1. the preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance, is characterized in that: comprise following processing step:
A, prepolymerization
The tri hydrochloride monohydrate of 2,5-Dihydroxyterephthalic acid, 4-aminopyridine, polyphosphoric acid are dropped in polymeric kettle together, fully removes hydrogen chloride gas after mixing, then carry out prepolymerization, obtain prepolymer; The described prepolymerization that carries out refers to reaction 6 ~ 10h at 100 ~ 120 DEG C, then is warming up to 140 ~ 180 DEG C of reaction 4 ~ 6h;
B, aftercondensated
The discharge port of the polymeric kettle in steps A is connected with the opening for feed of twin screw extruder, use dry nitrogen by the twin screw extruder described in prepolymer press-in, prepolymer completes finishing reaction in twin screw extruder, gathered [2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance; The reaction times of described prepolymer in twin screw extruder is 10 ~ 60min, and described twin screw extruder, according to being sequentially set with three warm areas from opening for feed to discharge port, is respectively 160 ~ 180 DEG C, 180 ~ 190 DEG C and 190 ~ 200 DEG C.
2. the preparation method of poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] polymkeric substance of one according to claim 1, it is characterized in that: in step, the mass concentration containing Vanadium Pentoxide in FLAKES in described polyphosphoric acid is 80 ~ 86%.
3. the preparation method of poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] polymkeric substance of one according to claim 1, is characterized in that: in step, and described abundant mixing refers to and fully to mix at 80 DEG C.
4. one according to claim 1 poly-[2,5-dihydroxy-1,4-pyridobismidazole] preparation method of polymkeric substance, it is characterized in that: in stepb, the screw diameter of described twin screw extruder is 20 ~ 180mm, and screw slenderness ratio is 20 ~ 50:1.
5. the one according to claim 1 or 4 poly-[2,5-dihydroxyl-1,4-pyridobismidazole] preparation method of polymkeric substance, it is characterized in that: in stepb, the screw speed of described twin screw extruder is 5 ~ 100r/min, extrusion pressure is 1 ~ 20MPa, and in twin screw extruder, vacuum tightness is-0.01 ~-0.095MPa.
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| CN117364273B (en) * | 2023-10-10 | 2024-04-26 | 江苏亨博复合材料有限公司 | Preparation method of transverse reinforced PBO (Poly-p-phenylene oxide) fiber |
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| CN101418073A (en) * | 2008-10-17 | 2009-04-29 | 哈尔滨工业大学 | Method for preparing poly(2,5-dihydroxy-1,4-pyridobismidazole) |
| CN102943316A (en) * | 2012-11-30 | 2013-02-27 | 中蓝晨光化工研究设计院有限公司 | Technology for producing poly(p-phenylene benzobisoxazole) (PBO) fibers |
| CN103224625A (en) * | 2013-04-23 | 2013-07-31 | 南京理工大学 | Preparation method for poly(2,5-dihydroxyl-1,4-phenylene pyridobisimidazole) |
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| CN101418073A (en) * | 2008-10-17 | 2009-04-29 | 哈尔滨工业大学 | Method for preparing poly(2,5-dihydroxy-1,4-pyridobismidazole) |
| CN102943316A (en) * | 2012-11-30 | 2013-02-27 | 中蓝晨光化工研究设计院有限公司 | Technology for producing poly(p-phenylene benzobisoxazole) (PBO) fibers |
| CN103224625A (en) * | 2013-04-23 | 2013-07-31 | 南京理工大学 | Preparation method for poly(2,5-dihydroxyl-1,4-phenylene pyridobisimidazole) |
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