CN101735455B - Method for preparing special aromatic polyoxadiazole and flame-retardant high-temperature resistant polyoxadiazole fiber thereof - Google Patents
Method for preparing special aromatic polyoxadiazole and flame-retardant high-temperature resistant polyoxadiazole fiber thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing special aromatic polyoxadiazole and flame-retardant high-temperature resistant polyoxadiazole fiber thereof. The special aromatic polyoxadiazole is prepared by the following method that the special aromatic polyoxadiazole is prepared from terephthalic acid, compound of which the structural general formula is expressed as formula I and hydrazine salt serving as monomers through condensation polymerization reaction. The polyoxadiazole fiber with high flame retardancy and high temperature resistance is prepared by using the special aromatic polyoxadiazole as a raw material. The fiber number of the prepared polyoxadiazole fiber is 1 to 20 dtex, the breaking strength is 2.5 to 5 cN.dtex-1, the elongation at break is 10 to 40 percent, the initial modulus is 50 to 250 cN.dtex-1, the moisture regain is 5.0 to 12.0 percent, the limited oxygen index is 30 to 38 percent, and the initial decomposition temperature is above 480 DEG C. The fiber can be widely used in the fields of protective products, filter materials, electric insulating materials, frictional sealed materials, various industrial textiles, high-temperature resistant paper, aviation and aerospace materials and the like.
Description
Technical field
The present invention relates to a kind of fragrant Zu polyoxadiazole of Fang and flame-resistant high-temperature-resistant polyoxadiazole fibers preparation method thereof of special use.
Background technology
The fragrant Zu polyoxadiazole of Fang (being called for short POD) is a kind of aromatic heterocycle polymer material that possesses performances such as good heat-resisting, antioxidant, resistance to chemical attack and electrical isolation; Be insoluble to common organic solvents and most inorganic solvent; Only decompose not fusion under the high temperature, thereby wide application prospect is arranged in fields such as high temperature resistant, electrical isolations.But because of its synthetic difficulty, poor mobile performance, be difficult to machine-shaping, so the research and development achievement of the aspects such as forming process of the synthesizing of POD superpolymer, fiber is less relatively.
The preparation and the research of the fragrant Zu polyoxadiazole of Fang start from the sixties in 20th century, are initiated at first by the U.S..Two-step approach is adopted in the preparation of initial stage POD; Promptly adopt N-Methyl pyrrolidone (NMP) or hexamethylphosphoramide (HMPA) etc. as solvent; Aromatic series two hydrazides and diacid chloride are monomer, synthetic polyhydrazide under low temperature (0-10 ℃), and the high temperature dehydration cyclisation becomes the POD material after the machine-shaping.This method exists technological line complicacy, deficiencies such as raw materials cost is high, the material structure defective is many, poor mechanical property.Though two step method also has more research now, mainly is limited to the laboratory study stage, be desirably in special dimensions such as photovaltaic material and be applied.After the single stage method invention, obtained very fast development, and be applied to the preparation of fiber.This method adopts oleum (oleum) or polyphosphoric acid strong acid such as (PPA) as solvent and dewatering agent; Diacid and hydrazonium salt (hydrazonium sulfate, hydrazine hydrogen chloride etc.) are as monomer; Building-up process adopts the two-part mode of prepolymerization and polymerization and cyclisation; Directly obtain POD solution, then directly machine-shaping.
The forming method of polyoxadiazole fibers mainly adopts solution spinning, and wet method and dried wet method all have employing.Wherein, the sixties in 20th century, U.S. Dupont company adopted two-step approach, earlier synthetic polyhydrazide, and long-time high temperature dehydration cyclisation forms polyoxadiazole fibers behind the spinning moulding.The seventies in 20th century, the Japanese Teijin company and the India Institute of Technology adopt single stage method directly to carry out the wet-spinning trial, and phase early 1980s U.S. Celanese company adopts single stage method to carry out the dry-wet spinning trial.Adopt patent, the achievement of single stage method and two-step approach processing POD fiber though some have occurred, implement the high-strength high-modulus fibre X-720 that commercial fiber only has Muscovite Oxalon fiber and Monsanto Gong Si De oxadiazole and hydrazides alternating structure.
The Russia investigator is through further improving the single stage method polymerization process; Do solvent, terephthalic acid and hydrazonium sulfate with oleum and do monomer; Employing wet-spinning technology; Developed the production technology of polyoxadiazole fibers, and small serial production polyoxadiazole fibers, commodity are called Oxalon.This product has become one of important kind of Russia's sieve high-performance fiber, and is applied in various fields.Advantages such as raw material sources are extensive and cheap, heat decomposition temperature is high although the Oxalon fiber has, the chemical solvent resistance ability is good, electrical insulation capability is good; But its flame retardant properties bad (the limiting oxygen index(LOI) LOI value of report is 22～23%) also makes the use of this product receive certain limitation.And the flame retardant resistance of X-720 and Oxalon are approaching, also belong to non-fire-retardant fibre.Shortcoming to the Oxalon poor fire; The patent of states such as Russia (NL7502905; DE2408426 RU2211263) adopts the method for halo terephthalic acid as fire-retardant monomer copolymerization of introducing, and adopts the method for bromoterephthalic acid as fire-retardant monomer copolymerization of introducing; Or Oxalon and aramid fiber and polybenzimidazole fibre blending prepared the method for textiles, with the flame retardant resistance that improves the Oxalon fiber or the flame retardant resistance of its textiles.The former adopts flame-retardant modified terephthalic acid as fire-retardant monomer; Building-up process is complicated; One replaces or the very difficult control of two replacements; Cause numerous and diverse, the unstable properties of polymer architecture, and need the bromine content above 10% just can reach flame retardant effect (LOI >=30%), fiber produces a large amount of hydrogen bromide toxic gas in combustion processes.The latter only through carrying out the fire-retardant requirement that fabric is satisfied in blend with other fire-retardant fibres, has increased cost, brings into play the not advantage of polyoxadiazole fibers itself.
Summary of the invention
The preparation method who the purpose of this invention is to provide fragrant Zu polyoxadiazole of a kind of special-purpose Fang and flame-resistant high-temperature-resistant polyoxadiazole fibers thereof.
The fragrant Zu polyoxadiazole of the special-purpose Fang of flame-resistant high-temperature-resistant polyoxadiazole fibers provided by the present invention prepares according to following method: with terephthalic acid, flame-retardant modified m-phthalic acid (general structure compound shown by formula I) and hydrazonium salt is monomer, carries out that polycondensation obtains.
Monomeric polycondensation described in the said polycondensation is with the oxadiazole cyclization process is carried out just so-called single stage method simultaneously.
(formula I)
Wherein, R is Cl, Br,
or
Said polycondensation is carried out in oleum or number-average degree of polymerization are the polyphosphoric acid of 4-8.
Oleum or number-average degree of polymerization be the polyphosphoric acid of 4-8 in reaction as solvent and dewatering agent.
When being reaction solvent and dewatering agent with the oleum; In the reaction system of said polycondensation; The molar ratio of oleum, terephthalic acid, general structure compound shown by formula I and hydrazonium salt is (3.5～8): (0.90～0.95): (0.10～0.05): (1.02～1.2); Wherein, the mole number of oleum is with SO contained in the oleum
3The mole number meter; Said oleum is preferably SO
3The quality percentage composition is 10～50% oleum.
The concrete adding mode of above-mentioned each reactant can be: hydrazonium salt is dissolved in the oleum at 60～100 ℃, then successively or mix to add the flame-retardant modified m-phthalic acid shown in terephthalic acid, the formula I.
When the polyphosphoric acid that with the number-average degree of polymerization is 4-8 is reaction solvent and dewatering agent; In the reaction system of said polycondensation, said number-average degree of polymerization is that the molar ratio of polyphosphoric acid, terephthalic acid, general structure compound shown by formula I and the hydrazonium salt of 4-8 is (5～15): (0.90～0.95): (0.10～0.05): (1.02～1.2); Wherein, the mole number of polyphosphoric acid is with wherein contained P
2O
5The mole number meter.
The concrete adding mode of above-mentioned each reactant can be: hydrazonium salt is dissolved in P at 80～100 ℃
2O
5Mass content is in 60～90% the polyphosphoric acid, successively or mix and add the flame-retardant modified m-phthalic acid shown in terephthalic acid, the formula I.
Hydrazonium salt described in the present invention specifically can be hydrazonium sulfate or hydrazine hydrogen chloride.
After each reactant fed intake according to ratio of the present invention, carry out polycondensation in three stages:
1) temperature of reaction of fs is 80～120 ℃, and the reaction times is 3～5h;
2) temperature of reaction of subordinate phase is 110～160 ℃, and the reaction times is 2～6h, when subordinate phase is accomplished, adds chain terminator;
3) temperature of reaction of phase III is 140～200 ℃, and the reaction times is 2～6h.
The add-on of said chain terminator be terephthalic acid in the said polycondensation reaction system mole number 0.5～2%.Said chain terminator can be monocarboxylic acid, as: phenylformic acid, naphthoic acid etc.
Wherein, the fs is a prepolymerisation stage, and monomer condenses becomes performed polymer; Subordinate phase is a polymerization stage, and the performed polymer polymerization increases molecular weight, part hydrazides structure cyclisation shape is taken place simultaneously become the oxadiazole ring, during finishing polymerization, adds chain terminator such as phenylformic acid etc. and carries out end-blocking; Phase III is the oxadiazole cyclisation stage, and this stage MWD improves, and limiting viscosity reaches 1～4dLg
-1， oxadiazole cyclisation rate is increased to more than 90%, and the AV of solution drops to below the 200Pa.s (to be measured down for 90 ℃).The polymer dope that so makes has better spinnability.
General structure can prepare by existing compound method suc as formula the flame-retardant modified monomer that contains the R group shown in the I among the present invention.
For example:
(formula I)
R is that the compound of Cl or Br can prepare as follows among the formula I:
Concrete reaction equation (1) is:
X shown in the equation (1) is fire-retardant group halogen, can be the chlorine or bromine element, in the preparation process, m-phthalic acid is dissolved in the vitriol oil, bromine or chlorine is fed in the solution again, adopts sulphur trioxide (SO
3) or metal halide such as iron halide (FeBr
3Or FeCl
3) make catalyzer; In 70～130 ℃ of following stirring reaction 5～12h; After finishing, reaction removes unnecessary gas; Obtain the replacement rate at the fire-retardant monomer solution more than 80%, obtain the fire-retardant monomer of modification m-phthalic acid through purifying, fire-retardant monomer solution can directly be used for the polymerization of the fragrant Zu polyoxadiazole of Fang provided by the present invention; Wherein the mol ratio of each reactant is: m-phthalic acid: SO
3: X
2(X is a halogen): FeX
3=1: (10～20): (1.2～3.0): (0.05～0.2).
R can prepare for the compound of
or
as follows among the formula I:
Concrete reaction equation is:
R shown in the equation (2) is that fire-retardant group diphenyloxide (sulphur) is changed the phosphine substituting group, in the preparation process with diphenyloxide (sulphur) change phosphine in THF, dioxane, pyridine equal solvent with m-phthalic acid or m-xylene Lewis acid (leweis acid) like the katalysis of aluminum chloride, zinc chloride under the fire-retardant monomer of prepared in reaction.Wherein the mol ratio of each reactant is: solvent: Lewis acid: substituent R: m-phthalic acid (m-xylene)=(10～20): (1.1～1.5): (1.5～2.5): 1.
If adopt the m-xylene oxidation style, also need carry out oxidation with potassium permanganate, the consumption of twice potassium permanganate and the molar ratio of m-xylene are respectively (5～8): 1 and (1.5～2): 1.Productive rate is 70～85% (molar yield).
The preparation method of flame-resistant high-temperature-resistant polyoxadiazole fibers provided by the present invention is that feedstock production obtains with the fragrant Zu polyoxadiazole of special-purpose Fang provided by the present invention.
Said method comprising the steps of:
1) prepares spinning solution with the fragrant Zu polyoxadiazole of Fang provided by the present invention;
2) with the spinning solution of step 1) through wet-spinning, coagulation forming, obtain nascent strand;
3) with step 2) nascent strand carry out heating bath and plasticization drawing, after boundling, alkali cleaning, washing, squeezing, obtain nascent fibre again;
4) nascent fibre with step 3) carry out drying, the 300-400 ℃ of processing of finalizing the design, obtain described polyoxadiazole fibers.
Said method also can comprise obtaining the step that the De polyoxadiazole fibers oils and dries.
Concrete preparation method is following:
1, the preparation of spinning solution
The solution of the fragrant Zu polyoxadiazole of Fang provided by the invention is carried out press filtration, elimination impurity, insoluble resin piece etc. in special filtering equipment.Solution after the filtration is transferred in the special-purpose deaeration container, under uniform temp, carries out vacuum defoamation, removes the micro-bubble in the solution and residues in the SO in the solution
3Gas leaves standstill for some time again, obtains pure still spinning solution.The stoste AV is 20～200Pa.s at 70～95 ℃.
2, stoste spinning and coagulation forming
To deliver to spinning manifold by air pressure or hydro-pump through the spinning solution of filtration, deaeration, get into filament spinning component, from the orifice of yellow platinum or nitriding spinning jet, extrude, get into coagulation forming in the precipitation bath by volume pump metering back.Peptizer is selected from water and sulfuric acid or soluble sulphate solution.The draw ratio of ejection strand can be that just to stretch also can be that negative stretch or zero stretches in precipitation bath.Spinning and coagulation forming device are acid corrosion-resistant material such as polyvinyl chloride, polytetrafluoroethylplastic plastic or 316, Mo-contained alloy steel.
3, the stretching and the washing of nascent strand
The nascent strand of coagulation forming is carried out the heating bath stretching by drawing mechanism, and after one hot wash, strand further solidifies, and gets into then to carry out plasticization drawing in the hot steam, obtains the nascent strand of hygrometric state.The nascent strand of hygrometric state is via boundling, and (or before washing, cutting off) alkali cleaning is washed, and after the squeezing, obtains nascent (weak point) fiber of hygrometric state.
4, the heat setting type processing and the aftertreatment of nascent fibre
Nascent (weak point) fiber of hygrometric state is admitted to and carries out drying in the hot air drier; After the exsiccant fiber sent into short time high temperature in the high-temperature processing case (300-400 ℃) and handle, make fibrous texture further fine and close, stable, send into oiling device then; Add finish; Handle through hot-air seasoning (staple fibre increases the shredding process) again, can detect and pack, obtain the high temperature resistant POD fiber of high flame retardant type.
After aftertreatment, obtain finished fiber compact structure, thermostability and chemical resistance and strengthen, fiber number is 1～20dtex, and breaking tenacity is 2.0～5.0cNdtex
-1, elongation at break is 10～40%, initial modulus is 50～250cN/dtex; Moisture regain is 5.0～12.0%, can for a long time anti-250 ℃ of following temperature, and anti-350～450 ℃ of high temperature of short period of time; Initial decomposition temperature is greater than 480 ℃, and flame retardant properties is stable, and (limiting oxygen index(LOI) is meant the per-cent that in the mixture of oxygen and nitrogen, burns material requisite oxygen gas amasss to limiting oxygen index(LOI) LOI; Limiting oxygen index(LOI) is big more, and its flame retardant properties is just good more) be 30～38%.
The invention provides the preparation method of fragrant Zu polyoxadiazole (POD) of a kind of special-purpose Fang and flame-resistant high-temperature-resistant polyoxadiazole fibers thereof.To bad this deficiency of POD fiber flame retardant resistance, go up introducing through position (5-replacement) between m-phthalic acid and contain halogenic substituent or diphenyloxide (sulphur) change phosphine substituting group, make it to become the monomer that possesses anti-flaming function; Take improved single stage method three stage control novel methods; With oleum or polyphosphoric acid is solvent and dewatering agent; Terephthalic acid, flame-retardant modified m-phthalic acid, hydrazonium salt (hydrazonium sulfate or hydrazine hydrogen chloride etc.) are for monomer carries out condensation polymerization, and De is Dao the fragrant Zu polyoxadiazole of the Fang of oxadiazole cyclisation degree height, molecular weight big (intrinsic viscosity is big), flowing property better (AV is low); The traditional wet spinning processes is improved,, prepare the high temperature resistant POD fiber that possesses the excellent flame retardancy ability through implementing measures such as solution preparation, extruding spinning coagulation forming, heating bath and plasticization drawing, washing and drying, short time high temperature typings.This fibrid can use 350～400 ℃ of short-terms at 180～300 ℃ of life-time service, and 450～500 ℃ of short period of time use; Do not shrink not fusion under the high temperature, do not have contraction, " cracking ", molten drop phenomenon during burning, the carbon residue rate is high, and the conformality of material residue is fine, and the smog that combustion processes produces is few, and the toxicity of combustion gases is little.This fibrid will be ideal fire-retardant, high temperature resistant protective material, can be widely used in fields such as protective article, filtering material, electrically insulating material, friction sealed material, various technical fabric, high temperature resistant paper and aerospace material.
The present invention compared with prior art has following advantage:
(1) on m-phthalic acid, introduce fire-retardant group, structure is single, adopts single bath process, and is easily synthetic;
(2) main raw material such as solvent, monomeric wide material sources, low price;
(3) polymerization method is simple, and the one-tenth ring effect and the flame retardant properties of polymkeric substance are controlled;
(4) the synthetic polymer dope has low, the good fluidity of AV, and spinning property is excellent;
(5) the fiber mechanics intensity of spinning, resistance to elevated temperatures, dyeing behavior etc. are good;
(6) the fire-retardant POD fiber of structure-type has nonvolatil flame retardant effect, and flame retarding efficiency height and handle of fibre, outward appearance are good.
Description of drawings
Fig. 1 is the process flow sheet of preparation flame-resistant high-temperature-resistant polyoxadiazole fibers provided by the present invention.
Embodiment
Through instance the present invention is specifically described below.Following instance only is used for the present invention is further specified, and can not be interpreted as the restriction to protection domain of the present invention, and the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the foregoing invention content.
Embodiment 1, be that solvent prepares halogen-containing flame-resistant high-temperature-resistant polyoxadiazole fibers and special-purpose POD polymkeric substance thereof with the oleum
Polyoxadiazole fibers can prepare by process flow sheet shown in Figure 1.
1, the preparation of POD polymkeric substance
Flame-retardant modified monomeric preparation
The bromine feeding is contained in the closed reactor of m-phthalic acid and oleum, with FeCl
3Or FeBr
3As catalyzer, in 120 ℃ of following stirring reaction 5h, after finishing, reaction removes unnecessary gas, obtain containing the flame-retardant modified m-phthalic acid of Br.The equivalent ratio (mol ratio) of each reactant is: m-phthalic acid: SO
3: Br
2: FeCl
3(FeBr
3)=1:20:1.2:0.05.With the ultraviolet spectrophotometer test, halogen replacement rate is 85～95%.
The polymerization of POD solution
With hydrazonium sulfate (NH
2NH
2.H
2SO
4) be dissolved in SO at 85 ℃
3The quality percentage composition is in 20% the oleum, adds terephthalic acid successively, contains the flame-retardant modified m-phthalic acid (R is the compound of Br among the formula I) of Br, and various reactant molar ratio examples are SO
3: terephthalic acid: flame-retardant modified m-phthalic acid: hydrazonium sulfate=5:0.90:0.10:1.02.The prepolymerisation stage temperature of reaction is 85 ℃, and the reaction times is 3h; The temperature of reaction of polymerization stage is 120 ℃, and the reaction times is 4h, when reaction finishes, adds 1.0mol% phenylformic acid (to the molecular fraction of dioctyl phthalate monomer) and makes chain regulator; Oxadiazole cyclodehydration elementary reaction temperature is 160 ℃, and the reaction times is 2h, obtains POD solution.Adopting the polymer intrinsic viscosity of Ubbelohde viscometer test (30 ℃) is 2.0dLg
-1
2, the preparation of flame-resistant high-temperature-resistant polyoxadiazole fibers
The preparation of spinning solution
The POD solution of step 1) preparation is filtered, and filtration temperature is 70 ℃, and pressure is 0.2MPa, and strainer is the core filter assemblies; The vacuum defoamation temperature is 70 ℃, and vacuum tightness is-0.05Mpa, and time of repose is 24h, obtains pure still spinning solution, and the stoste AV is 150PaS at 70 ℃.
Stoste extruding spinning and coagulation forming
To deliver to spinning manifold by air pressure or hydro-pump (transfer pressure is 0.6Mpa) through the spinning solution of filtration, deaeration; Get into filament spinning component by volume pump metering (the volume pump operational throughput is 0.6mL.rpm) back; From the orifice of yellow platinum or nitriding spinning jet, extrude, get into coagulation forming in the precipitation bath.Wherein spinning with solidify parameter and be controlled at: spinning temperature is 70 ℃, and the volume pump rotating speed is 15rpm, and orifice diameter is 0.06mm, and hole count is 2000 holes, and the spinning nozzle extruded velocity is 20m.min
-1Peptizer is selected from the mixture of water and sulfuric acid or soluble sulphate (like sodium sulfate), and the percentage ratio that sulfuric acid or vitriol account for the peptizer gross weight is 20%, and the temperature of precipitation bath is 40 ℃, and the draw ratio of ejection strand is-20% in precipitation bath.
The stretching and the washing of nascent strand
The nascent strand of coagulation forming is carried out the heating bath stretching by drawing mechanism, after one hot wash, get in the hot steam and carry out plasticization drawing, obtain the nascent strand of hygrometric state.The nascent strand of hygrometric state is via boundling, and (or before washing, cutting off) alkali cleaning is washed, and after the squeezing, obtains nascent (weak point) fiber of hygrometric state.Heating bath tensile draft temperature is 80 ℃, and draw ratio is 5 times; The steam bath temperature of plasticization drawing is 90 ℃, and stretch ratio is 1.5 times; The concentration of lye of alkaline cleaning procedure is controlled at 3% (quality percentage composition), and wash temperature is controlled at 40 ℃.
The heat setting type processing and the aftertreatment of nascent fibre
Nascent (weak point) fiber of hygrometric state is admitted to and carries out drying in the hot air drier; The exsiccant fiber is sent in the high-temperature processing case after the short period of time pyroprocessing, made fibrous texture further fine and close, stable, send into oiling device then; Add finish; Handle through hot-air seasoning (staple fibre increases the shredding process) again, can detect and pack, obtain the high temperature resistant POD fiber of high flame retardant type.The warm air drying temperature divides two to three grades to be controlled at 110～250 ℃, and the pyroprocessing temperature is 350 ℃, and the treatment time is 10 seconds, and fiber receives 1.1 times stretching during processing.
After aftertreatment, obtain finished fiber, fiber number is 1.8dtex, and breaking tenacity is 3.6cNdtex
-1, elongation at break is 15%, initial modulus is 150cNdtex
-1, moisture regain is 7%, and limiting oxygen index(LOI) LOI is 33%, and initial decomposition temperature is greater than 480 ℃.
Embodiment 2, oleum are that solvent prepares phosphorated flame-resistant high-temperature-resistant polyoxadiazole fibers and special-purpose POD polymkeric substance thereof
1, the preparation of POD polymkeric substance
Flame-retardant modified monomeric preparation
Diphenyloxide (sulphur) is changed phosphine be dissolved in the dioxane (Dioxane), in solvent, add catalyst A lCl again
3, drip down slowly m-xylene in 85 ℃ of backflows, after dropwising, back flow reaction 6h, reaction finish after wash, the recrystallization processing obtains purified m-xylene substituent.The m-xylene substituent is carried out the oxide treatment secondary with potassium permanganate, obtain diphenyloxide (sulphur) and change the substituted fire-retardant m-phthalic acid monomer of phosphine, the mol ratio of each reactant is: solvent: AlCl
3: substituting group: m-xylene=15:1.15:1.5:1, the amount of twice potassium permanganate and monomer (m-xylene substituent) mol ratio is respectively 5:1 and 2:1, and productive rate is 81% (molar yield).
Method for subsequent processing is with embodiment 1.
The fiber number of phosphorous flame-retardant finished fiber is 2.2dtex, and breaking tenacity is 2.3cNdtex
-1, elongation at break is 10.2%, and initial modulus is 100cN/dtex, and moisture regain is 5.0%, and limiting oxygen index(LOI) LOI is 34%, initial decomposition temperature is greater than 480 ℃.
Instance 3, polyphosphoric acid are that solvent prepares halogen-containing flame-resistant high-temperature-resistant polyoxadiazole fibers and special-purpose POD polymkeric substance thereof
1, the preparation of POD polymkeric substance
Flame-retardant modified monomeric preparation and embodiment 1 are together.
The polymerization of POD solution
With hydrazonium sulfate (NH
2NH
2.H
2SO
4) be dissolved in P at 110 ℃
2O
5The quality percentage composition is 80%, the polymerization degree is in 4 the polyphosphoric acid, adds terephthalic acid successively, contains the flame-retardant modified m-phthalic acid (R is the compound of Br among the formula I) of Br, and various reactant molar ratio examples are P
2O
5: terephthalic acid: flame-retardant modified m-phthalic acid: hydrazonium sulfate=10:0.90:0.10:1.02.The prepolymerisation stage temperature of reaction is 110 ℃, and the reaction times is 4h; The temperature of reaction of polymerization stage is 160 ℃, and the reaction times is 5h, when reaction finishes, adds 1.0mol% phenylformic acid (to the molecular fraction of dioctyl phthalate monomer) and makes chain regulator; Oxadiazole cyclodehydration elementary reaction temperature is 180 ℃, and the reaction times is 3h, obtains POD solution.Adopting the polymer intrinsic viscosity of Ubbelohde viscometer test (30 ℃) is 1.0dLg
-1
2, the preparation of flame-resistant high-temperature-resistant polyoxadiazole fibers
The preparation of spinning solution
The POD solution of step 1) preparation is filtered, and filtration temperature is 90 ℃, and pressure is 0.2MPa, and strainer is the core filter assemblies; The vacuum defoamation temperature is 90 ℃, and vacuum tightness is-0.05Mpa, and time of repose is 24h, obtains pure still spinning solution, and the stoste AV is 200PaS at 90 ℃.
Stoste extruding spinning and coagulation forming
To deliver to spinning manifold by air pressure or hydro-pump (transfer pressure is 0.6Mpa) through the spinning solution of filtration, deaeration; Get into filament spinning component by volume pump metering (the volume pump operational throughput is 0.6mL.rpm) back; From the orifice of yellow platinum or nitriding spinning jet, extrude, get into coagulation forming in the precipitation bath.Wherein spinning with solidify parameter and be controlled at: spinning temperature is 90 ℃, and the volume pump rotating speed is 15rpm, and orifice diameter is 0.06mm, and hole count is 2000 holes, and the spinning nozzle extruded velocity is 20m.min
-1Peptizer is selected from the mixture of water and phosphoric acid, and the mass percent that phosphoric acid accounts for the peptizer gross weight is 30%, and the temperature of precipitation bath is 50 ℃, and the draw ratio of ejection strand is-30% in precipitation bath.
The subsequent disposal of fiber is identical with instance 1.
After aftertreatment, obtain finished fiber, fiber number is 2.5dtex, and breaking tenacity is 2.2cNdtex
-1, elongation at break is 25%, initial modulus is 80cNdtex
-1, moisture regain is 8%, and limiting oxygen index(LOI) LOI is 34%, and initial decomposition temperature is greater than 480 ℃.
Claims (7)
1. the preparation method of the fragrant Zu polyoxadiazole of Fang is to be monomer with terephthalic acid, general structure compound shown by formula I and hydrazonium salt, carries out that polycondensation obtains;
(formula I)
Wherein, R is Cl, Br,
Said polycondensation is carried out in oleum or number-average degree of polymerization are the polyphosphoric acid of 4-8;
Said polycondensation is carried out in three stages:
1) temperature of reaction of fs is 80～120 ℃, and the reaction times is 3～5h;
2) temperature of reaction of subordinate phase is 110～160 ℃, and the reaction times is 2～6h, and when subordinate phase is accomplished, adds chain terminator;
3) temperature of reaction of phase III is 140～200 ℃, and the reaction times is 2～6h.
2. method according to claim 1 is characterized in that: said polycondensation is carried out in oleum; In the reaction system of said polycondensation; The molar ratio of said oleum, terephthalic acid, general structure compound shown by formula I and hydrazonium salt is (3.5～8): (0.90～0.95): (0.10～0.05): (1.02～1.2); Wherein, the mole number of oleum is with SO contained in the oleum
3The mole number meter.
3. method according to claim 1 is characterized in that: said polycondensation is carried out in number-average degree of polymerization is the polyphosphoric acid of 4-8; In the reaction system of said polycondensation, said number-average degree of polymerization is that the molar ratio of polyphosphoric acid, terephthalic acid, general structure compound shown by formula I and the hydrazonium salt of 4-8 is (5～15): (0.90～0.95): (0.10～0.05): (1.02～1.2); Wherein, the mole number of polyphosphoric acid is with contained P in the polyphosphoric acid
2O
5The mole number meter.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: said hydrazonium salt is hydrazonium sulfate or hydrazine hydrogen chloride.
5. method according to claim 1 is characterized in that: the add-on of said chain terminator be in the reaction system of said polycondensation the terephthalic acid mole number 0.5～2%.
6. a method for preparing polyoxadiazole fibers is that the fragrant fragrant family polyoxadiazole for preparing with the arbitrary said method of claim 1-5 is that raw material prepares;
Said method comprising the steps of:
1) the fragrant Zu polyoxadiazole of Fang with the arbitrary said method preparation of claim 1-5 prepares spinning solution;
2) with the spinning solution of step 1) through wet-spinning, coagulation forming, obtain nascent strand;
3) with step 2) nascent strand carry out heating bath and plasticization drawing, after boundling, alkali cleaning, washing, squeezing, obtain nascent fibre again;
4) nascent fibre with step 3) carry out drying, the 300-400 ℃ of processing of finalizing the design, obtain described polyoxadiazole fibers.
7. method according to claim 6 is characterized in that: said method also comprises obtaining the step that the De polyoxadiazole fibers oils and dries.
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Cited By (1)
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|---|---|---|---|---|
| US9150693B2 (en) | 2012-06-15 | 2015-10-06 | E I Du Pont De Nemours And Company | Preparation of sulfonated naphthalene polyoxadiazoles polymers |
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