CN1190452C - High-performance material of soluble controlled crosslinkable polyarylether ketone and preparation thereof - Google Patents
High-performance material of soluble controlled crosslinkable polyarylether ketone and preparation thereof Download PDFInfo
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Abstract
The present invention relates to a high performance material in a dissoluble controllable crosslinked polyaryletherketone class, and a preparation method thereof. M-trifluoromethylphenyl hydroquinone, 4, 4'-difluoro benzophenone, etc. react with a small molecule oligomer FKOSOKF in a solvent of N-methyl pyrrolidone or in sulfolane. The reaction product is discharged in distilled water and is simultaneously and endlessly stirred, and white polymer filaments are obtained. After the filaments are pulverized by a pulverizer, the powder polymer material is washed with acetone for 6 to 8 times to remove organic solvent, and is washed with distilled water through boiling for 6 to 8 times to remove inorganic salt. The product is dried at 110 to 120 DEG C for 10 to 12 hours, of which the rate of production is 96 to 98%, and the molecular weight is between 40 thousand and 60 thousand. The material of the class has excellent processing performance, can be shaped through conventional processing methods or solution processing, and can realize normal temperature crosslinked solidifying through electron beam irradiation when the material is shaped. The material can be used for coating materials, encapsulating materials and film materials, particularly can be used as favorable resin matrix of composite materials.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the technology of preparing of the novel solvable controlled crosslinked high-performance materials of polyarylether ketones of a class and this material.
Background technology
Material is the milestone of human social development, and the scientific-technical progress of each period of history is all closely related with material, and along with science and technology development, people are more and more higher to the requirement of material, and many difficult problems of high-tech sector have the problem that much is actually material.The Application and Development that does not have novel material, new technical products and industrial progress just are far from being.Flourish along with world's new science and technology revolution, the high performance structures material has been proposed increasingly extensive and urgent demand, those have the base mateiral that high strength, high tenacity, high temperature resistant, wear-resistant, erosion-resisting structured material have become hi-tech industries such as development new forms of energy, nuclear technique, space development, oceanographic engineering, also are the critical materials of rebuilding traditional industry.The poly aryl ether ketone material has excellent physical chemistry as a kind of complete fragrant semicrystalline polymeric, thereby is widely used in fields such as electronic apparatus, machinery instrument, communications and transportation, aerospace.But the polyaryletherketone material also has the weak point of himself.As polyether-ether-ketone, though its heat decomposition temperature more than 500 ℃, its second-order transition temperature is lower, has only 142 ℃, descends very soon along with the modulus of the rising material of temperature more than second-order transition temperature, causes its use temperature lower.Therefore people adopt means such as blend, copolymerization that material is carried out modification, in the hope of further improving the performance, particularly resistance toheat of material.The second-order transition temperature of the novel polyaryletherketone material of our seminar development and fusing point are respectively up to 212 ℃ with 468 ℃ (molecular designing of Zhou Hongwei Jilin University doctorate paper 1999 polyaryletherketones and research of chain structure and condensed state structure), have the so high second-order transition temperature and the material of fusing point and can satisfy life-time service under 350 ℃ high temperature fully, but dystectic material like this is difficult to machine-shaping, therefore, the use temperature that improve material just must be sought other feasible way.
Being used as the matrix material of structured material at present, is enhancing ingredients with macroscopic fiber such as glass fibre, carbon fibers normally, is that matrix is composited with thermoset or thermoplastic resin.Although the research of macroscopic fiber reinforced composite materials has obtained immense success, it is to be solved that but some problems still have, the bounding force of the most outstanding is fiber and reisn base material is not ideal enough, and both thermal expansivity differ the internal stress problem that causes more greatly.In addition, particularly in the occasion of using glass fibre as toughener, the high viscosity of batching and the not only exigent energy expenditure of high friction, and cause the damage of equipment easily.Seeking new composite system at these problems has great importance undoubtedly.
Summary of the invention
Purpose of the present invention is exactly by in the big replacement of the introducing side group in the molecular chain of polyaryletherketone, sulfide based structural is incorporated in the polyaryletherketone backbone structure as the mode of cross-linking set with block copolymerization, thereby the technology of preparing of a kind of novel solvable controlled crosslinked high-performance materials of polyarylether ketones and this material is provided.
Major technique characteristics of the present invention are:
One: by in the molecular chain of polyaryletherketone, introducing the big side group that replaces, destroy the tacticity that macromolecular chain is piled up, prepare the solubility amorphous polymer, make it in conventional organic solvent, have good solubility, as tetrahydrofuran (THF), chloroform, ethanol, acetone, butanone, methylene dichloride, DMF, NMP, DMSO, DMAc, 1,2-ethylene dichloride etc.Utilize its good solubility can adopt the solution method for processing to process.
Two: introduce when replacing side group greatly, utilize sulfide based structural that the characteristics of crosslinking reaction can take place under high temperature and electron beam irradiation condition, sulfide based structural is incorporated in the polyaryletherketone backbone structure as the mode of cross-linking set with block copolymerization, makes that it is single, be evenly distributed in the polyaryletherketone segmented structure.Adopt after the conventional working method machine-shaping crosslinkedly under high temperature, electron beam irradiation condition, solvable crosslinkable type polyaryletherketone is converted into does not dissolve not fused thermoset engineering plastics, the use temperature of material is greatly improved.In preparation process, change the content regulation and control cross-linking density of cross-linking set, the content range of cross-linking set by to controllable to crosslinked front and back material structure and performance of the controllable realization of the distribution mode of cross-linking set and cross-linking density, satisfies different service requirementss between 1%-50%.
Three: solvable controlled crosslinked polyaryletherketone can be used for coating material, Embedding Material and thin-film material, especially uses as good composite resin matrix.As preparing matrix material with carbon fiber or glass fibre.Its advantage is and can solidifies at ambient temperature that solidification value is low more, and internal stress is just more little in the fibre resin matrix material that fiber and resin difference of thermal expansion coefficients cause; After cross-link bond forms, is connected by the chemical bond of pretending firmly between layer and the layer, the interlaminar shear strength increase, the flexural strength increase can solve fiber and the not strong problem of resin bond power.Based on this imagination, solvable controlled crosslinked polyaryletherketone base polymer has been synthesized in design, the self-vulcanizing moulding, and crosslinked and fiber formation inierpeneirating network structure on the basis that keeps the original performance of polyaryletherketone, further improves the temperature classification of material after the moulding.This class novel material is in the same place the advantages of thermoplastic material and thermosetting material, has both had the good processing properties of thermoplastic material, has the high characteristics of thermosetting material use temperature simultaneously again.
The optimum molar content of oligopolymer FKOSOKF is 2%-30%; be FKOSOKF/ (FKOSOKF+4; 4 '-difluoro benzophenone) mol ratio or FKOSOKF/ (FKOSOKF+4; 4 '-(4-fluorine) dibenzoyl benzene) mol ratio or the mol ratio of FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) are 2%-30%.M-trifluoromethyl phenyl Resorcinol is with FKOSOKF and 4,4 '-difluoro benzophenone sum, FKOSOKF and 4, and 4 '-(4-fluorine) dibenzoyl benzene sum, FKOSOKF and 4, the mol ratio of 4 '-dichloro diphenyl sulfone sum is 1: 1; N-Methyl pyrrolidone (NMP) or tetramethylene sulfone are solvent, and the add-on of solvent is that 15-20% is the best to contain thing admittedly, and salt of wormwood is as catalyzer, and its consumption is on the basis of identical mole number with biphenol monomer, excessive 1-3%.
The synthetic reaction process of polymkeric substance is: with monomer m-trifluoromethyl phenyl Resorcinol and 4; 4 '-difluoro benzophenone (or 4; 4 '-(4-fluorine) dibenzoyl benzene or 4; 4 '-dichloro diphenyl sulfone) dropping into 1000ml has in the there-necked flask of agitator, thermometer, nitrogen protection device and water-and-oil separator; add catalysts salt of wormwood; solvent N-Methyl pyrrolidone (NMP) or tetramethylene sulfone add band aqua toluene 150-200ml at last.Reaction system is warming up to 145-160 ℃, and toluene band water refluxes, and constantly emits the water generation reaction branch, band water reaction 2-3h; Reaction system is warming up to 210-220 ℃ then, reaction 2-3h, reaction system is cooled to 100-120 ℃ then, (its synthetic method is seen Chinese patent: ZL00105146.6 to add small molecules oligopolymer FKOSOKF, the applying date: on April 1st, 2000, denomination of invention: the preparation of high-performance materials of polyarylether ketones), toluene unnecessary in the reaction system is removed in evaporation, reaction system is warming up to 220 ℃, reaction 2-3h, reaction product is discharging in distilled water, constantly stirs simultaneously, obtain the white polymer filament, after pulverizer is pulverized, polymer powders with washing with acetone six to eight times to remove organic solvent, distilled water boiling washing six to eight times is to remove inorganic salt, at 110-120 ℃ of dry 10-12h, productive rate 96-98%, molecular weight is between 40,000 to 60,000.End product carries out electron beam to irradiate crosslinked at 100-1000Kgy dosage under the 8-80min condition, obtain having a series of solvable controlled crosslinked polyaryletherketone based block copolymer of different degree of crosslinking.
The preparation of monomeric compound m-trifluoromethyl phenyl Resorcinol:
The first step: diazonium salt synthetic
Get liquid m-trifluoromethyl aniline and place the 5000ml beaker for 1 mole, under constantly stirring, add 2 moles of concentrated hydrochloric acids, form milky emulsion, temperature is controlled at 0 ℃-5 ℃, in above-mentioned system, slowly drip 1 mole of Sodium Nitrite dilute solution, after reaction finished, whole reaction system was a clear liquid, remains on 0 ℃-5 ℃.
Reaction equation is:
Second step: linked reaction
Add 1 mole of benzoquinones and 2 moles of sodium bicarbonates in having churned mechanically 10000ml reaction vessel, add 1000ml distilled water, be configured to the tawny suspension liquid, temperature of reaction system remains on 12 ℃-15 ℃.Add the colourless liquid that the first step forms in this system, in the dropping process, the dropping liquid temperature is controlled at 0 ℃-5 ℃.Dropwise the back and continue stirring reaction 1h, filter, obtain the yellow powder solid matter, repeatedly wash, become colorless until considering liquid with distilled water.
Reaction equation is:
The 3rd step: reduction reaction
The yellow solid matter that obtains is put into the there-necked flask of the 3000ml that has stirring, reflux and Dropping feeder in second step, add distilled water 600ml, add 2.5 moles of reductive agent zinc powders, constantly stir to be heated to down and begin to have the water backflow to drip constant temperature, begin to drip concentrated hydrochloric acid solution, add-on is 3.5 moles, and the dropping process must be slow, allows the hydrogen that generates have time enough to emit, after reacting completely, keep refluxing 1 hour.Heat filtering obtains red oily liquids, adds distilled water, stirs fast, and in temperature-fall period, oily matter solidifies and obtains white solid, promptly is our designed synthetic monomeric compound.
Reaction equation is:
The 4th step: recrystallization
The white mass that obtains after 60 ℃ of dryings of vacuum drying oven, is put into the three mouthfuls of reaction flasks of 1000ml that have stirring, nitrogen protection and reflux for block, adds toluene 500ml; reflux, after the dissolving, heat filtering obtains light grey solution fully; cooling is filtered, and obtains white needle-like crystals.Be placed in the vacuum drying oven, maintain the temperature at 60 ℃ and carry out drying and promptly obtained us in 72 hours and design synthetic monomeric substance m-trifluoromethyl phenyl Resorcinol, purity is more than 99.
The structural formula of three kinds of polymkeric substance that the present invention obtains is as follows:
The building-up reactions formula one of polymkeric substance (I): (embodiment 1 and 2)
The building-up reactions formula two of polymkeric substance (II): (embodiment 3 and 4)
The building-up reactions formula three of polymkeric substance (III): (embodiment 5 and 6)
In reaction process, by changing the molar content of sulfide based structural FKOSOKF, promptly by adjusting n value size, can prepare sulfide based structural FKOSOKF molar content is a series of solvable controlled crosslinked polyaryletherketone segmented copolymer of 2%-30%.
Two fluorine monomers and biphenol monomer mol ratio are on 1: 1 the basis in keeping reaction system, can regulate and control the molecular weight of polymkeric substance by the concentration that increases the fluorine end group, molecular weight is with the variation tendency of fluorine end group concentration as shown in Figure 1: along with the increase of fluorine end group concentration, polymer viscosity (molecular weight) is on a declining curve, especially surpass after 1.5% at the excessive number of fluorine end group concentration, even the fluorine end group concentration differs very little, polymeric viscosity also can differ greatly, therefore can come the molecular weight of controlling polymers by fluorine end group concentration in the telomerized polymer, thereby obtain the polymkeric substance of different molecular weight, to obtain functional and to be beneficial to the polymkeric substance of the optimum weight of processing.
The cross-linking set of polymkeric substance belongs to (10
-10) order of magnitude, can't use the electron microscope direct viewing, still prove crosslinked existing with the variation of transitivity so far with the increase of insoluble part in change of molecular weight and the solvent.With sulfide based structural content in weight-average molecular weight 60,000 systems is 10% to be example explanation electron beam irradiation to effect of material performance:
Polymkeric substance (Polymers) Mn Mw Mz Mw/Mn
Without radiation polymerization thing 0KGy 34,340 61,859 98,115 1.80
(unirradiated)
Mw-6×10
4 50KGy 42,073 174,218 2,947,661 4.14
Thio-10％ 100KGy 38,847 331,451 13,398,805 8.53
Just can know from top GPC data: the viscosity cause of increased is that polymericular weight is increasing.Measure the later gel percentage composition of 10% thioether bond molar content polymer-electronics bundle irradiation in weight-average molecular weight 60,000 systems:
Irradiation dose (Dose) 100KGy 150KGy 200KGy 250KGy 300KGy 350KGy
Mw
6×10
4 Sol Sol Sol Gel Gel Gel
Content (Content) (%) 8.08 8.92 10.83
Polymkeric substance should have sufficiently high mechanical strength as Material Used and be absolutely necessary.We wish to obtain outside the needed performance after introducing functional group, also keep the favorable mechanical performance as far as possible.From experimental data as can be known: along with the increase of electron beam irradiation dosage, tensile modulus and tensile strength increase, and elongation reduces.
Irradiation dose (dose) 0KGy 100 150 200 250 300 350
Mw KGy KGy KGy KGy KGy KGy
Tensile modulus (Modulus) (GPa) 1.34 1.35 1.36 1.36 1.40 1.41 1.43
Tensile strength (Strength) (Mpa) 76.44 77.50 77.54 78.26 77.27 79.19 86.67
6 * 10
4(Elongation at 36.10 24.07 26.43 15.51 16.07 10.87 9.95 for elongation at break
break)(％)
Description of drawings
Fig. 1: excessive percentage ratio of fluorine end group and molecular weight concern synoptic diagram;
Fig. 2: the tensile modulus of 10% sulfide based structural content segmented copolymer and electron beam irradiation dose relationship figure;
Fig. 3: the tensile strength of 10% sulfide based structural content segmented copolymer and electron beam irradiation dose relationship figure;
Fig. 4: the elongation of 10% sulfide based structural content segmented copolymer and the graph of a relation of electron beam irradiation dosage.
Embodiment
Embodiment one
Mechanical stirring is being housed; add 17.46g (0.08mol) 4 in the 1000ml three-necked bottle of thermometer and nitrogen protection; 4 '-difluoro benzophenone; 22.88g (0.09mol) m-trifluoromethylphenyl Resorcinol; add 12.24g (0.09mol) Anhydrous potassium carbonate; add solvent sulfolane 200ml; band aqua toluene 100ml stirs and heats up, and reaction system is warming up to 160 ℃; toluene band water refluxes; band water reaction 2h, reaction system is warming up to 220 ℃ then, reaction 2h; reaction system is cooled to 100 ℃ then; add small molecules oligopolymer (FKOSOKF) 6.15g (0.01mol), be warming up to 160 ℃ of evaporations and remove toluene in the reaction system, reaction system is warming up to 220 ℃; continue reaction 3h; reactant is annotated discharging in 5000ml distilled water, and constantly stirs, and obtains white strip solid.Thick product is after organizing the pulverizer pulverizing, with washing with acetone eight times to remove the organic solvent in the polymkeric substance, distilled water boiling washing eight times is to remove inorganic salt, final product is at 120 ℃ of dry 10h, obtain the FKOSOKF molar content and be 10% white polymer powdered sample, the mol ratio that is FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) is 10%.Productive rate 97%.
Embodiment two
Method such as embodiment one, changing the molar content of FKOSOKF in reaction system is 2%, 5%, 15%, 20%, 25%, 30%, be FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) mol ratio is 2%, 5%, 15%, 20%, 25%, 30%, the polyreaction formula is referring to reaction formula one, polymer architecture formula and embodiment one are similar, and difference is FKOSOKF molar content difference, the chain length difference of polyaryletherketone between the cross-linking set.Prepare the solvable controlled crosslinked polyaryletherketone segmented copolymer of the different molar content of a series of FKOSOKF, productive rate 96-98%.
Embodiment three
Method such as embodiment one; with 4; 4 '-difluoro benzophenone replaces with 4,4 '-(4-fluorine) dibenzoyl benzene, and the polyreaction formula is referring to polyreaction formula two; with 4; 4 '-(4-fluorine) dibenzoyl benzene monomer replaces 4, and 4 '-difluoro benzophenone is in the polymer architecture formula 4; 4 '-(4-fluorine) dibenzoyl benzene unit replaces 4,4 '-difluoro benzophenone unit.Obtain the FKOSOKF molar content and be 10% white polymer powdered sample, promptly the mol ratio of FKOSOKF/ (FKOSOKF+4,4 '-(4-fluorine) dibenzoyl benzene) is 10%, productive rate 97%.
Embodiment four
Method such as embodiment three, changing the molar content of FKOSOKF in reaction system is 2%, 5%, 15%, 20%, 25%, 30%, be FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) mol ratio is 2%, 5%, 15%, 20%, 25%, 30%, polymer architecture formula and embodiment three are similar, difference is FKOSOKF molar content difference, the chain length difference of polyaryletherketone between the cross-linking set.Prepare the solvable controlled crosslinked polyaryletherketone segmented copolymer of a series of FKOSOKF different contents, productive rate 96-98%.
Embodiment five
Method such as embodiment one, with 4,4 '-difluoro benzophenone replaces with 4,4 '-dichloro diphenyl sulfone, and the polyreaction formula is referring to polyreaction formula three, with 4,4 '-dichloro diphenyl sulfone monomer replaces 4, and 4 '-difluoro benzophenone is in the polymer architecture formula 4,4 '-dichloro diphenyl sulfone unit replaces 4,4 '-difluoro benzophenone unit.Obtain the FKOSOKF molar content and be 10% white polymer powdered sample, promptly the mol ratio of FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) is 10%, productive rate 97%.
Embodiment six
Method such as embodiment five, changing the molar content of FKOSOKF in reaction system is 2%, 5%, 15%, 20%, 25%, 30%, be FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) mol ratio is 2%, 5%, 15%, 20%, 25%, 30%, polymer architecture formula and embodiment five are similar, difference is FKOSOKF molar content difference, the chain length difference of polyaryletherketone between the cross-linking set.Prepare the solvable controlled crosslinked polyaryletherketone segmented copolymer of a series of FKOSOKF different contents, productive rate 96-98%.
Embodiment seven
The segmented copolymer of the different cross-linking set content (2%, 5%, 15%, 20%, 25%, 30%) of embodiment one to embodiment six preparation, irradiation dose at 100KGy, irradiation time is to carry out electron beam to irradiate crosslinked under the 8min condition, obtains having a series of crosslinked polyaryletherketone segmented copolymer of different degree of crosslinking.
Embodiment eight
Method such as embodiment seven, the segmented copolymer of the different cross-linking set content (2%, 5%, 15%, 20%, 25%, 30%) of embodiment one to embodiment six preparation, change the irradiation dose of electron beam irradiation, irradiation dose at 150-1000KGy, irradiation time is to carry out electron beam to irradiate crosslinked under the 12-80min condition, obtains having a series of crosslinked polyaryletherketone segmented copolymer of different degree of crosslinking.
Claims (3)
1, solvable controlled crosslinked poly aryl ether ketone material, its structural formula is as follows:
Or
2, the described solvable controlled crosslinked poly aryl ether ketone preparation methods of claim 1 the steps include:
(1) with mol ratio is 1: 1 monomer m-trifluoromethyl phenyl Resorcinol and 4,4 '-difluoro benzophenone or 4,4 '-(4-fluorine) dibenzoyl benzene or 4,4 '-dichloro diphenyl sulfone, dropping into 1000ml has in the there-necked flask of agitator, thermometer, nitrogen protection device and water-and-oil separator, add catalysts salt of wormwood with the excessive 1-3% of monomer mole ratio, solvent N-Methyl pyrrolidone or tetramethylene sulfone, the add-on of solvent is 15-20% to contain thing admittedly, adds band aqua toluene 150-200ml;
(2) reaction system is warming up to 145-160 ℃, and toluene band water refluxes, and constantly emits the water generation reaction branch, band water reaction 2-3h; Reaction system is warming up to 210-220 ℃, reaction 2-3h, reaction system is cooled to 100-120 ℃ then, add small molecules oligopolymer FKOSOKF, the molar content of oligopolymer FKOSOKF is 2%-30%, be FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) or FKOSOKF/ (FKOSOKF+4,4 '-(4-fluorine) dibenzoyl benzene) or FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) mol ratio is 2%-30%, toluene unnecessary in the reaction system is removed in evaporation, and reaction system is warming up to 220 ℃, reaction 2-3h;
(3) reaction product discharging in distilled water, constantly stir simultaneously, obtain the white polymer filament, after pulverizer is pulverized, polymer powders with washing with acetone six to eight times to remove organic solvent, distilled water boiling washing six to eight times to remove inorganic salt, at 110-120 ℃ of dry 10-12h, get productive rate 96-98%, molecular weight is the white polymer powder between 40,000 to 60,000;
(4) product carries out electron beam to irradiate crosslinked at 100-1000Kgy dosage under the 8-80min condition, obtains having a series of solvable controlled crosslinked poly aryl ether ketone block copolymer material of different degree of crosslinking.
3, solvable controlled crosslinked poly aryl ether ketone preparation methods as claimed in claim 2 is characterized in that:
Can come the molecular weight of controlling polymers by fluorine end group concentration in the telomerized polymer, thereby obtain the polymkeric substance of different molecular weight, to obtain functional and to be beneficial to the polymkeric substance of the optimum weight of processing.
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| CN105482097A (en) * | 2015-12-25 | 2016-04-13 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet crosslinking polyetherketoneketone and preparation method thereof |
| CN109749562A (en) * | 2019-01-08 | 2019-05-14 | 杨记周 | A kind of new-energy automobile fire retardant insulating coating and preparation method thereof |
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