CN101215404B - Special-purpose material for spinning-stage polyetheretherketone resin and preparation method thereof - Google Patents
Special-purpose material for spinning-stage polyetheretherketone resin and preparation method thereof Download PDFInfo
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- CN101215404B CN101215404B CN200810050213XA CN200810050213A CN101215404B CN 101215404 B CN101215404 B CN 101215404B CN 200810050213X A CN200810050213X A CN 200810050213XA CN 200810050213 A CN200810050213 A CN 200810050213A CN 101215404 B CN101215404 B CN 101215404B
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Abstract
The invention relates to a special material of fiber-grade polyetheretherketone resin and a process for preparation, which comprises 90.0-100.0wt% polyetheretherketone resin powder, 0-3.0wt% high-temperature lubricant and 0-10.0wt% polyaromatic ether ketone liquid crystal polymer which are used as basal body of fiber-grade resin, lubricating agent and regulator of melt viscosity in turn, and granulations are squeezed out by melting in 340-400 DEG C in a double screw extruder after premixing in a high-speed stirring mixer. Logarithmic specific concentration viscosity of polyetheretherketone resin is 0.76-0.80, and melting index is 12-30g/10min. High-temperature lubricant is granular or powdery GENIOPLAST Pellet S which is produced by German Wacker company, the polyaromatic ether ketone liquid crystal polymer is polyaromatic ether ketone liquid crystal polymer which contains fluorin. Polyetheretherketone fiber single filament or multifilament is prepared through melting, spinning, extending and winding through the special material of fiber spinning-grade polyetheretherketone resin which is prepared The prepared special material of fiber-grade polyetheretherketone resin can be made into polyetheretherketone fiber single-filament or multifilament through melting, spinning, extending and winding.
Description
Technical field
The invention belongs to macromolecular material and textile technology field, be specifically related to a kind of special-purpose material for spinning-stage polyetheretherketoneresin resin and preparation method thereof.
Background technology
Polyether-ether-ketone resin has characteristics such as temperature classification height, radiation hardness, shock strength height, wear resistance and resistance to fatigue are good, fire-retardant, electrical property excellence.Since commercialization, obtained to use more widely in fields such as aerospace, automobile, electric, chemical industry, machinery and medical treatment.The polyether-ether-ketone goods that are applied to above-mentioned field generally are the structure-type goods of making by injection molding method, but some Application Areas needs polyetheretherketonefiber fiber or monofilament goods, fuel filter filter screen, matrix material, high-performance rope and string, mesh grid and the medicine equipment etc. of travelling belt, space shuttle and the automobile that uses as paper industry.Purpose of the present invention is exactly the special-purpose material for spinning-stage polyetheretherketoneresin resin for preparing in order to prepare the polyether-ether-ketone special fibre that satisfies the different user needs.
Background technology related to the present invention is the synthetic method technology (Chinese patent: " preparation method of polyether ethersulfone and polyetheretherketoneterpolymer terpolymer " of polyether-ether-ketone resin, application number: 200610016723.6, not only can prepare polyether ethersulfone but also can prepare polyether-ether-ketone resin and their multipolymer).Further, utilize above-mentioned patent synthetic polyether-ether-ketone resin to add processing aid or properties-correcting agent, make special-purpose material for spinning-stage polyetheretherketoneresin resin by melt extruding process for granulating.
Summary of the invention
The objective of the invention is to prepare a kind of special-purpose material for spinning-stage polyetheretherketoneresin resin, promptly utilize additives such as polyether-ether-ketone resin and high temperature lubricant, melt viscosity modifiers to make special-purpose material for spinning-stage polyetheretherketoneresin resin by melt extruding process for granulating.Spinning grade resin general requirement molecular weight is higher, and molecular weight distribution is narrower, but the melt viscosity of resin is higher like this, and processing fluidity is bad.
It (is poly aromatic ether ketone liquid crystal copolymer that the present invention adopts high temperature lubricant, melt viscosity modifiers, concrete preparation method has applied for patent of invention, the preparation of poly aromatic ether ketone liquid crystal copolymer, ZL 01103522.6) etc. additive improve the processing characteristics of spinning-stage polyetheretherketoneresin resin, make resin can satisfy the molecular weight requirement of spinning grade resin, enough processing fluidities are arranged again, thereby can prepare the polyether-ether-ketone special fibre to satisfy the user demand of different field by melt spinning method.
Special-purpose material for spinning-stage polyetheretherketoneresin resin of the present invention, it is characterized in that: press each component and 100wt% and calculate, contain 90.0～100.0wt% polyether-ether-ketone resin, the high temperature lubricant of 0～3.0wt% and the poly aromatic ether ketone liquid crystal copolymer of 0～10.0wt% structural formula shown in (II).
Further preferred implementation comprises following four kinds of prescriptions,
Prescription a:
PEEK resin 100.0wt%
Prescription b:
PEEK resin 97.0～99.5wt%
High temperature lubricant 0.5～3.0wt%
Prescription c:
PEEK resin 90.0～98.0wt%
Poly aromatic ether ketone liquid crystal copolymer 2.0～10.0wt%
Prescription d:
PEEK resin 90.0～97.5wt%
High temperature lubricant 0.5～3.0wt%
Poly aromatic ether ketone liquid crystal copolymer 2.0～9.5wt%
The logarithmic specific concentration viscosity of polyether-ether-ketone (PEEK) is 0.76～0.80, melting index is 12～30g/10min, and its structural formula is shown in (I), and n is 〉=1 integer, the expression polymerization degree.
High temperature lubricant is that particulate state or the pulverulent GENIOPLASTPellet S that German Wacker company produces (is abbreviated as GPPS, the processing temperature of polyether-ether-ketone resin is very high, general lubricant can't satisfy service requirements at all, has just decomposed before 360 ℃.This lubricant is that our seminar filters out for many years, and unique processing temperature that satisfies us is very effective again, has only this English name, does not have Chinese).
The structural formula of poly aromatic ether ketone liquid crystal copolymer is shown in (II):
R＝Cl，Ph，CH
3O，t-C
4H
9，
(II)
Y=0.2～0.8, n is a positive integer, the expression polymerization degree
The preparation process of above-mentioned special-purpose material for spinning-stage polyetheretherketoneresin resin is as follows:
(1) with 4,4 '-difluoro benzophenone, sulfobenzide join in the polymeric kettle that mechanical stirring, thermometer, nitrogen feeding mouth, thermoelectric Europe are housed, nitrogen protection, heated and stirred, in 140～170 ℃ of temperature ranges, add mixed salt catalyzer, '-biphenyl diphenol, Resorcinol more successively, obtain logarithmic specific concentration viscosity 0.76～0.80, the polyether-ether-ketone of melting index 12-30g/10min (PEEK) polymkeric substance after the temperature control reaction; With obtaining pressed powder after polymkeric substance cooling, pulverizing, the filtration, again pressed powder is boiled, filters with ethanol or acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in rotatory drier, dry at last, obtain purified polyether-ether ketone copolymer powder; Wherein '-biphenyl diphenol accounts for and mixes 0.1～3% of biphenol monomer total mole number; 4,4 '-difluoro benzophenone monomer and two kinds of biphenol monomers and mol ratio be 1.000: 0.98～0.99; The mol ratio of biphenol monomer and mixed salt catalyzer is 1: 1.05～1.20; The polymeric reaction solution solid content is 15～35%;
(2) pressing each component sum 100wt% calculates; take by weighing polyether-ether-ketone (PEEK) the copolymer resin powder that obtains in 90～100%wt above-mentioned steps; 0～3%wt high temperature lubricant and 0～10%wt poly aromatic ether ketone liquid crystal copolymer; use the high-speed stirring mixer premix; put into the feeding hopper of twin screw extruder then; in extruder barrel under 340～400 ℃ of temperature fusion plastification; form melt; head through filtering net is installed and four aperture template extruded stock bars; the material bar is carried through travelling belt; air cooling; lead into the hobboing cutter dicing machine; obtaining diameter is 2～4mm, and length is the cylindrical pellet of 4～6mm, promptly gets special-purpose material for spinning-stage polyetheretherketoneresin resin.
Temperature control reaction described in the aforesaid method is under agitation, be heated to 180～220 ℃ of temperature control reactions 0.5～2 hour, progressively stir again and be warmed up to 250～260 ℃ of isothermal reactions 0.5～1 hour, be warmed up to 280-300 ℃ of temperature control reaction 0.5～2 hour, be heated to 300～320 ℃ of reactions 3～6 hours at last, described mixed salt catalyzer is the mixing of salt of wormwood and yellow soda ash, and wherein the salt of wormwood mole number accounts for 10～90% of mixed salt catalyzer.
Above-mentioned special-purpose material for spinning-stage polyetheretherketoneresin resin is through fusion, spray silk, stretch, reel, can make polyetheretherketonefiber fiber monofilament or multifilament.
Description of drawings
Fig. 1: the adding of high temperature lubricant is to the curve of twin screw extruder screw torque influence;
Fig. 2: the adding of high temperature lubricant is to the thermally-stabilised sex curve of resin PP Pipe Compound;
Fig. 3: the adding of fluorinated poly arylene ether ketone liquid crystalline polymers is to the curve of resin PP Pipe Compound melting index (MI) influence;
The infrared spectra of Fig. 4: embodiment 1 synthetic polyetheretherketonepolymer polymer.
As shown in Figure 1, after curve represents that polyether-ether-ketone resin does not add high-temperature lubricant and adds high-temperature lubricant, the situation of change of double-screw extruder screw moment of torsion when producing special-purpose material for spinning-stage polyetheretherketoneresin resin, as seen from the figure, the interpolation percetage by weight is 1% high-temperature lubricant GPPS, the moment of torsion of extruder screw drops to 62Nm by original 88Nm, the interpolation percetage by weight is 3% high-temperature lubricant GPPS, the moment of torsion of extruder screw drops to 57Nm by original 88Nm, this shows, can significantly reduce the melt viscosity of polyether-ether-ketone resin behind the adding high-temperature lubricant.
Whether can the hot property of polyether-ether-ketone resin be impacted after studying the adding high-temperature lubricant, we have tested pure polyether-ether-ketone resin and have added the thermal weight loss of the polyether-ether-ketone resin of high-temperature lubricant. As shown in Figure 2, two curves are arranged wherein, one is pure polyether-ether-ketone resin PP Pipe Compound heat endurance curve, and one is that as seen polyether-ether-ketone resin PP Pipe Compound heat endurance curve does not almost have difference between the two after adding high-temperature lubricant.
After Fig. 3 shows that polyether-ether-ketone resin adds fluorinated poly arylene ether ketone liquid crystal polymer, the situation of change of resin melting index, curve following among the figure is that shear stress is 5kg/mm2, the polyether-ether-ketone resin that records under 360 ℃ and change with the melt index of fluorinated poly arylene ether ketone LCP blends; Top curve is that shear stress is 7kg/mm2, the polyether-ether-ketone resin that records under 360 ℃ and change with the melt index of fluorinated poly arylene ether ketone LCP blends. Clearly, can significantly increase the melt index of polyether-ether-ketone resin after liquid crystal polymer adds.
Among Fig. 4,1650cm-1The place is the stretching vibration absworption peak of carbonyl; 1492cm-1And 1600cm-1The place is the phenyl ring vibration absorption peak; 1415cm-1The place is ehter bond stretching vibration absworption peak; 1222cm-1The place is the vibration absorption peak of phenylate group, shows that the polymer that is synthesized is polyether-ether-ketone resin.
Embodiment
Embodiment 1:
With 4 of purifying, 4 '-difluoro benzophenone, sulfobenzide join in the polymeric kettle that mechanical stirring, thermometer, nitrogen feeding mouth, thermopair are housed, nitrogen protection, heated and stirred, in 150 ℃ of temperature ranges, add mixed salt catalyzer, '-biphenyl diphenol, Resorcinol more successively, continue to be stirred and heated to 180 ℃ of temperature control reactions 1 hour, progressively stir again and be warmed up to 250 ℃ of isothermal reactions 0.5 hour, be warmed up to 290 ℃ of temperature control reactions 1 hour, be heated to 320 ℃ of reactions 4 hours at last, obtain polyether-ether-ketone (PEEK) polymkeric substance; With obtaining pressed powder after polymkeric substance cooling, pulverizing, the filtration, again pressed powder is boiled, filters with ethanol or acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in rotatory drier, dry at last, obtain purified polyether-ether ketone copolymer product; Wherein '-biphenyl diphenol accounts for and mixes 0.1% of biphenol monomer total mole number; 4,4 '-difluoro benzophenone monomer and two kinds of biphenol monomers and mol ratio be 1.000: 0.985; The mol ratio of biphenol monomer and mixed salt catalyzer is 1: 1.10; The polymeric reaction solution solid content is 30%; The mixed salt catalyzer is the mixing of salt of wormwood and yellow soda ash, and wherein the salt of wormwood mole number accounts for 10% of mixed salt catalyzer, makes logarithmic specific concentration viscosity and be 0.78 spinning-stage polyetheretherketoneresin resin, and melting index is 22g/10min.
The reduced viscosity of taking the logarithm is 0.78 polyether-ether-ketone resin (PEEK) 1000 grams, melt extrudes granulation at 340～360 ℃, and screw torque is 78～80Nm, makes non-additive special-purpose material for spinning-stage polyetheretherketoneresin resin.
Embodiment 2:
As described in embodiment 1, the reduced viscosity of just taking the logarithm is 0.78 polyether-ether-ketone resin (PEEK) 990 grams, granular high temperature lubricant GENIOPLAST Pellet S 10 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 340～360 ℃, screw torque is 52～54Nm, and making particulate state high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 1%wt, and the thermostability of PP Pipe Compound is same as pure polyether-ether-ketone resin PP Pipe Compound (as shown in Figure 2).
Embodiment 3:
As described in embodiment 2, the reduced viscosity of just taking the logarithm is 0.78 polyether-ether-ketone resin (PEEK) 970 grams, granular high temperature lubricant GENIOPLAST Pellet S 30 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 340～360 ℃, screw torque is 50～52Nm, and making particulate state high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 3%wt.
Embodiment 4:
As described in embodiment 2, just change granular high temperature lubricant into pulverulent high temperature lubricant, behind the high-speed stirring mixer premix, melt extrude granulation at 340～360 ℃, screw torque is 52～54Nm, and making powder shape high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 1%wt.
Embodiment 5:
As described in embodiment 3, just change granular high temperature lubricant into pulverulent high temperature lubricant, behind the high-speed stirring mixer premix, melt extrude granulation at 340～360 ℃, screw torque is 49～51Nm, and making powder shape high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 3%wt.
Embodiment 6:
With 4 of purifying, 4 '-difluoro benzophenone, sulfobenzide join in the polymeric kettle that mechanical stirring, thermometer, nitrogen feeding mouth, thermopair are housed, nitrogen protection, heated and stirred, in 150 ℃ of temperature ranges, add mixed salt catalyzer, '-biphenyl diphenol, Resorcinol more successively, continue to be stirred and heated to 180 ℃ of temperature control reactions 1 hour, progressively stir again and be warmed up to 250 ℃ of isothermal reactions 1 hour, be warmed up to 290 ℃ of temperature control reactions 1 hour, be heated to 320 ℃ of reactions 4 hours at last, obtain polyether-ether-ketone (PEEK) polymkeric substance; With obtaining pressed powder after polymkeric substance cooling, pulverizing, the filtration, again pressed powder is boiled, filters with ethanol or acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in rotatory drier, dry at last, obtain purified polyether-ether ketone copolymer product; Wherein '-biphenyl diphenol accounts for and mixes 0.1% of biphenol monomer total mole number; 4,4 '-difluoro benzophenone monomer and two kinds of biphenol monomers and mol ratio be 1.000: 0.99; The mol ratio of biphenol monomer and mixed salt catalyzer is 1: 1.10; The polymeric reaction solution solid content is 30%; The mixed salt catalyzer is the mixing of salt of wormwood and yellow soda ash, and wherein the salt of wormwood mole number accounts for 15% of mixed salt catalyzer, makes logarithmic specific concentration viscosity and be 0.80 spinning-stage polyetheretherketoneresin resin, and melting index is 13g/10min.
The reduced viscosity of taking the logarithm is 0.80 polyether-ether-ketone resin (PEEK) 1000 grams, melt extrudes granulation at 360～380 ℃, and screw torque is 88～90Nm, makes non-additive special-purpose material for spinning-stage polyetheretherketoneresin resin.
Embodiment 7:
As described in embodiment 6, the reduced viscosity of just taking the logarithm is 0.80 polyether-ether-ketone resin (PEEK) 990 grams, granular high temperature lubricant GENIOPLAST Pellet S 10 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 60～62Nm (as shown in Figure 1), and making particulate state high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 1%wt.
Embodiment 8:
As described in embodiment 7, the reduced viscosity of just taking the logarithm is 0.80 polyether-ether-ketone resin (PEEK) 970 grams, granular high temperature lubricant GENIOPLAST Pellet S 30 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 56～59Nm (as shown in Figure 1), and making particulate state high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 3%wt.
Embodiment 9:
As described in embodiment 6, just change granular high temperature lubricant into pulverulent high temperature lubricant, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 60～62Nm, and making particulate state high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 1%wt.
Embodiment 10:
As described in embodiment 7, just change granular high temperature lubricant into pulverulent high temperature lubricant, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 55～57Nm, and making powder shape high temperature lubricant addition is the special-purpose material for spinning-stage polyetheretherketoneresin resin of 3%wt.
Embodiment 11:
Getting the melting index that embodiment 6 makes is polyether-ether-ketone resin (PEEK) 980 grams of 13g/10min, fluorinated poly arylene ether ketone liquid crystalline polymers 20 grams, its structural formula is shown in (III), the numerical value of y is 0.3, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, make the special-purpose material for spinning-stage polyetheretherketoneresin resin that the liquid crystalline polymers addition is 2%wt, the PP Pipe Compound melting index is 17g/10min (as shown in Figure 3).
Embodiment 12:
As described in embodiment 11, just get the polyether-ether-ketone resin that melting index is 13g/10min (PEEK) 960 grams, fluorinated poly arylene ether ketone liquid crystalline polymers 40 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, make the special-purpose material for spinning-stage polyetheretherketoneresin resin that the liquid crystalline polymers addition is 4%wt, the PP Pipe Compound melting index is 19g/10min (accompanying drawing 3).
Embodiment 13:
As described in embodiment 11, just get the polyether-ether-ketone resin that melting index is 13g/10min (PEEK) 940 grams, fluorinated poly arylene ether ketone liquid crystalline polymers 60 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, make the special-purpose material for spinning-stage polyetheretherketoneresin resin that the liquid crystalline polymers addition is 6%wt, the PP Pipe Compound melting index is 27g/10min (accompanying drawing 3).
Embodiment 14:
As described in embodiment 11, just get the polyether-ether-ketone resin that melting index is 13g/10min (PEEK) 920 grams, fluorinated poly arylene ether ketone liquid crystalline polymers 80 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, make the special-purpose material for spinning-stage polyetheretherketoneresin resin that the liquid crystalline polymers addition is 8%wt, the PP Pipe Compound melting index is 26g/10min (accompanying drawing 3).
Embodiment 15:
As described in embodiment 11, just get the polyether-ether-ketone resin that melting index is 13g/10min (PEEK) 900 grams, fluorinated poly arylene ether ketone liquid crystalline polymers 100 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, make the special-purpose material for spinning-stage polyetheretherketoneresin resin that the liquid crystalline polymers addition is 10%wt, the PP Pipe Compound melting index is 28g/10min (accompanying drawing 3).
Embodiment 16:
As described in embodiment 6, make logarithmic specific concentration viscosity and be 0.80 spinning-stage polyetheretherketoneresin resin, get polyether-ether-ketone resin 935 grams, granular high temperature lubricant GENIOPLAST Pellet S 5 grams, fluorinated liquid crystal polymkeric substance 60 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 62～64Nm, making particulate state high temperature lubricant addition is 0.5%wt, fluorinated liquid crystal polymkeric substance addition is 6% special-purpose material for spinning-stage polyetheretherketoneresin resin, the thermostability of PP Pipe Compound is same as pure polyether-ether-ketone resin PP Pipe Compound, and the moment of torsion of extruder screw is lower.
Embodiment 17:
As described in embodiment 16, get polyether-ether-ketone resin 930 grams, granular high temperature lubricant GENIOPLAST Pellet S 10 grams, fluorinated liquid crystal polymkeric substance 60 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 54～57Nm, making particulate state high temperature lubricant addition is that 1%wt, fluorinated liquid crystal polymkeric substance addition are 6% special-purpose material for spinning-stage polyetheretherketoneresin resin, the thermostability of PP Pipe Compound is same as pure polyether-ether-ketone resin PP Pipe Compound, and the moment of torsion of extruder screw is lower.
Embodiment 18:
As described in embodiment 16, get polyether-ether-ketone resin 910 grams, granular high temperature lubricant GENIOPLAST Pellet S 30 grams, fluorinated liquid crystal polymkeric substance 60 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 50～53Nm, making particulate state high temperature lubricant addition is that 3%wt, fluorinated liquid crystal polymkeric substance addition are 6% special-purpose material for spinning-stage polyetheretherketoneresin resin, the thermostability of PP Pipe Compound is same as pure polyether-ether-ketone resin PP Pipe Compound, and the moment of torsion of extruder screw is lower.
Embodiment 19:
As described in embodiment 16, get polyether-ether-ketone resin 950 grams, granular high temperature lubricant GENIOPLAST Pellet S 10 grams, fluorinated liquid crystal polymkeric substance 40 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 58～60Nm, making particulate state high temperature lubricant addition is that 1%wt, fluorinated liquid crystal polymkeric substance addition are 4% special-purpose material for spinning-stage polyetheretherketoneresin resin, the thermostability of PP Pipe Compound is same as pure polyether-ether-ketone resin PP Pipe Compound, and the moment of torsion of extruder screw is lower.
Embodiment 20:
As described in embodiment 16, get polyether-ether-ketone resin 930 grams, granular high temperature lubricant GENIOPLAST Pellet S 30 grams, fluorinated liquid crystal polymkeric substance 40 grams, behind the high-speed stirring mixer premix, melt extrude granulation at 360～380 ℃, screw torque is 54～56Nm, making particulate state high temperature lubricant addition is that 3%wt, fluorinated liquid crystal polymkeric substance addition are 4% special-purpose material for spinning-stage polyetheretherketoneresin resin, the thermostability of PP Pipe Compound is same as pure polyether-ether-ketone resin PP Pipe Compound, and the moment of torsion of extruder screw is lower.
Claims (3)
1. special-purpose material for spinning-stage polyetheretherketoneresin resin is characterized in that:
Press each component and 100wt% and calculate, form by 90.0～97.5wt% polyether-ether-ketone resin, 0.5～3.0wt% high temperature lubricant and 2.0～9.5wt% poly aromatic ether ketone liquid crystal copolymer;
Wherein, the logarithmic specific concentration viscosity of polyether-ether-ketone resin is 0.76～0.80, melting index is 12～30g/10min, and by the preparation of following method: with 4,4 '-difluoro benzophenone, sulfobenzide join and are equipped with that mechanical stirring, thermometer, nitrogen feed mouthful, in the polymeric kettle of thermopair, nitrogen protection, heated and stirred, in 140～170 ℃ of temperature ranges, add mixed salt catalyzer, '-biphenyl diphenol, Resorcinol more successively, obtain polyetheretherketonepolymer polymer after the temperature control reaction; With obtaining pressed powder after polymkeric substance cooling, pulverizing, the filtration, again pressed powder is boiled, filters with ethanol or acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in rotatory drier, dry at last, obtain purified polyether-ether ketone copolymer powder; Wherein '-biphenyl diphenol accounts for and mixes 0.1～3% of biphenol monomer total mole number, 4,4 '-difluoro benzophenone monomer and two kinds of biphenol monomers and mol ratio be 1.000: 0.98～0.99, the mol ratio of biphenol monomer and mixed salt catalyzer is 1: 1.05～1.20, and the polymeric reaction solution solid content is 15～35%;
Wherein, the structural formula of poly aromatic ether ketone liquid crystal copolymer is as follows,
R=Cl, Ph, CH
3O, t-C
4H
9Or
Y=0.2～0.8, n is a positive integer, the expression polymerization degree;
Wherein, high temperature lubricant is particulate state or the powder shape GENIOPLAST Pellet S lubricant that German Wacker company produces;
The mixed salt catalyzer is the mixing of salt of wormwood and yellow soda ash, and wherein the salt of wormwood mole number accounts for 10～90% of mixed salt catalyzer;
The temperature control reaction is 180～220 ℃ of temperature control reactions 0.5～2 hour, progressively stirs and is warmed up to 250～260 ℃ of isothermal reactions 0.5～1 hour, is warmed up to 280～300 ℃ of temperature control reactions 0.5～2 hour, is heated to 300～320 ℃ of reactions 3～6 hours at last.
2. the preparation method of special-purpose material for spinning-stage polyetheretherketoneresin resin, its step is as follows:
(1) with 4,4 '-difluoro benzophenone, sulfobenzide join in the polymeric kettle that mechanical stirring, thermometer, nitrogen feeding mouth, thermopair are housed, nitrogen protection, heated and stirred, in 140～170 ℃ of temperature ranges, add mixed salt catalyzer, '-biphenyl diphenol, Resorcinol more successively, obtain polyetheretherketonepolymer polymer after the temperature control reaction; With obtaining pressed powder after polymkeric substance cooling, pulverizing, the filtration, again pressed powder is boiled, filters with ethanol or acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in rotatory drier, dry at last, obtain purified polyether-ether ketone copolymer powder; Wherein '-biphenyl diphenol accounts for and mixes 0.1～3% of biphenol monomer total mole number, 4,4 '-difluoro benzophenone monomer and two kinds of biphenol monomers and mol ratio be 1.000: 0.98～0.99, the mol ratio of biphenol monomer and mixed salt catalyzer is 1: 1.05～1.20, and the polymeric reaction solution solid content is 15～35%;
(2) pressing each component sum 100wt% calculates, take by weighing 90.0～97.5wt% polyether-ether ketone copolymer powder, 0.5～3.0wt% high temperature lubricant and 2.0～9.5wt% poly aromatic ether ketone liquid crystal copolymer, use the high-speed stirring mixer premix, put into the feeding hopper of twin screw extruder then, in extruder barrel under 340～400 ℃ of temperature fusion plastification, form melt, head through filtering net is installed and four aperture template extruded stock bars, the material bar is carried through travelling belt, air cooling, lead into the hobboing cutter dicing machine, obtaining diameter is 2～4mm, and length is the cylindrical pellet of 4～6mm, promptly gets special-purpose material for spinning-stage polyetheretherketoneresin resin;
Wherein, the structural formula of poly aromatic ether ketone liquid crystal copolymer is as follows,
R=Cl, Ph, CH
3O, t-C
4H
9Or
Y=0.2～0.8, n is a positive integer, the expression polymerization degree;
Wherein, high temperature lubricant is particulate state or the powder shape GENIOPLAST Pellet S lubricant that German Wacker company produces;
The mixed salt catalyzer is the mixing of salt of wormwood and yellow soda ash, and wherein the salt of wormwood mole number accounts for 10～90% of mixed salt catalyzer;
The temperature control reaction is 180～220 ℃ of temperature control reactions 0.5～2 hour, progressively stirs and is warmed up to 250～260 ℃ of isothermal reactions 0.5～1 hour, is warmed up to 280～300 ℃ of temperature control reactions 0.5～2 hour, is heated to 300～320 ℃ of reactions 3～6 hours at last.
3. claim 1 or 2 described special-purpose material for spinning-stage polyetheretherketoneresin resin are through fusion, spray silk, stretching or coiling, the polyetheretherketonefiber fiber monofilament or the multifilament that make.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974204A (en) * | 2010-11-18 | 2011-02-16 | 吉林大学 | Basalt fibre reinforced polyetheretherketone (PEEK) composite and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974204A (en) * | 2010-11-18 | 2011-02-16 | 吉林大学 | Basalt fibre reinforced polyetheretherketone (PEEK) composite and preparation method thereof |
| CN101974204B (en) * | 2010-11-18 | 2013-01-30 | 吉林大学 | Basalt fibre reinforced polyetheretherketone (PEEK) composite and preparation method thereof |
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| CN101215404A (en) | 2008-07-09 |
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