CN103601883A - Modified polyaryletherketone (PAEK) polymer and preparation method thereof - Google Patents
Modified polyaryletherketone (PAEK) polymer and preparation method thereof Download PDFInfo
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 title abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 17
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 42
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000004305 biphenyl Substances 0.000 claims description 18
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- AUKRYONWZHRJRE-UHFFFAOYSA-N 9-anthrol Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=CC2=C1 AUKRYONWZHRJRE-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229930185605 Bisphenol Natural products 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 14
- 238000013019 agitation Methods 0.000 description 14
- 229920002530 polyetherether ketone Polymers 0.000 description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 description 13
- 235000011181 potassium carbonates Nutrition 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical group C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a modified polyaryletherketone (PAEK) polymer and preparation method thereof. The modified PAEK polymer is represented by the following structural formula (1), structural formula (2) or structural formula (3), wherein n is degree of polymerization, and the value range of n is from 50 to 150. The preparation method comprises the following steps: adding a solvent (sulfolane), bisphenol monomer and a catalyst in a reactor under the protection of nitrogen, stirring for 0.5h at 30-40 DEG.C, adding dihalide monomer in reaction solution, and then adding a proper amount of a water-carrying agent (toluene); heating to 130 DEG.C and keeping the reaction temperature for 3-4 hours; and then heating to 200-220 DEG.C and keeping the reaction temperature for 6-10 hours; adding biphenol and continuously reacting for 1-2 hours; after the reaction is finished, soaking, filtering and drying the product to obtain the modified PAEK product. The solubility of the PAEK polymer is improved, the original heat stability and mechanical property are maintained, and the application of the solvent in the processing field is enlarged.
Description
Technical field
The present invention relates to special engineering plastics, relate in particular to a kind of modified polyarylether ketone polymkeric substance and preparation method thereof.
Background technology
Polyaryletherketone (PEAK) is a kind of important engineering resin, and it has excellent performance.Polyether-ether-ketone (PEEK) is one of Typical Representative of polyaryletherketone base polymer, and as a kind of half hitch crystal formation thermoplastic resin, PEEK is conventionally by Resorcinol, 4, and 4 '-difluoro benzophenone forms through high-temperature polycondensation, and its structural formula is as follows:
Late 1970s, Britain Victrex company has successfully developed the synthetic method of PEEK first, and in successful industrialization in 1987.PEEK has good thermostability, mechanical-physical, radioresistance, electrical insulating property etc., in fields such as aerospace, automobile making, electric, medical, electricity power, coating and food-processings, has a wide range of applications, and prospect is very wide.
PEEK belongs to high heat thermoplastic resin, has higher second-order transition temperature T
g(143 ℃～170 ℃) and fusing point T
m(334 ℃), load thermal change type temperature is up to 316 ℃, can be at 250 ℃ life-time service.PEEK resin not only thermotolerance is more excellent than other high-temperature resistance plastice, and has high strength, high-modulus, high-fracture toughness and good dimensional stability.PEEK resin at high temperature can keep higher intensity, and its flexural strength in the time of 200 ℃ reaches 24MPa left and right, and at 250 ℃, flexural strength and compressive strength still have 12～13MPa; The rigidity of PEEK resin is larger, and dimensional stability is better, and coefficient of linear expansion is less, is in close proximity to metallic aluminum material; The Heat stability is good of PEEK resin, has excellent chemical proofing, in common pharmaceutical chemicals, only has the vitriol oil to dissolve or to destroy it; The good flame resistance of PEEK resin discharges cigarette under flame condition and toxic gas is few; PEEK resin capability of resistance to radiation is strong, good toughness, to the resistance to fatigue of repeated stress, be the most outstanding in all plastics, can match in excellence or beauty and there is outstanding tribological property with alloy material, resistance to skimming wear and Fretting are excellent, especially can at 250 ℃, keep high wear resistance and low frictional coefficient, be easy to extrude and injection molding, processing characteristics is excellent, and shaping efficiency is higher.
Although PEEK resin has the performance of many excellences, its solvability in common solvent is poor, conventionally only in the only a few solvents such as the vitriol oil, dissolves, and this has just limited its application in a lot of fields.Under current environment, along with the difference of application purpose and applied environment, need to there is the PEEK resin that can be dissolved in certain solvent.
Therefore, do not reducing under the stable on heating prerequisite of polyaryletherketone base polymer, synthesis of soluble, in the high-performance polyarylether ketone thermoplastic resin of common solvent, has important practical significance.
Summary of the invention
In view of the problem existing in background technology, the object of the present invention is to provide a kind of modified polyarylether ketone polymkeric substance and preparation method thereof, it has not only improved the solvability of polyaryletherketone base polymer, and keep the original thermostability of polyaryletherketone and mechanical property, expanded the application at solvent manufacture field.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of modified polyarylether ketone polymkeric substance, it is represented by following structural formula (1), structural formula (2) or structural formula (3):
Wherein, n is the polymerization degree, and the span of n is 50～150.
In a second aspect of the present invention, the invention provides a kind of preparation method of modified polyarylether ketone polymkeric substance, comprise the following steps:
Step 1: under nitrogen protection, add solvent sulfolane, biphenol monomer and catalyzer in reactor, stir 0.5h at 30～40 ℃;
Step 2: add dihalo-monomer in reaction solution, then add appropriate band aqua toluene, be heated to 130 ℃ and keep this temperature of reaction 3～4h;
Step 3: be then warmed up to 200～220 ℃, keep this temperature of reaction 6～10h;
Step 4: add '-biphenyl diphenol, continue reaction 1～2h;
Step 5: after final reaction finishes, product is obtained to modified polyarylether ketone product through soaking, filter, drying.
Beneficial effect of the present invention is:
1. modified polyarylether ketone polymkeric substance of the present invention dissolves in multiple common chemical solvents, as acetone, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO)), tetrahydrofuran (THF) (THF), chloroform etc., make it aspect solvent processing, have more advantage.
2. the modified polyarylether ketone polymkeric substance in the present invention has kept resistance toheat and the mechanical property that polyaryletherketone is good, T
gcan be up to 180 ℃, T
mcan be up to 370 ℃, tensile strength can be up to 100MPa.
3. the prepared modified polyarylether ketone polymkeric substance of the present invention can be widely used in the fields such as aerospace, automobile making, electric, medical, electricity power, coating, can be prepared in addition ion-exchange membrane and be applied to fuel cell field.
Embodiment
Describe in detail according to modified polyarylether ketone polymkeric substance of the present invention and preparation method thereof below.
First modified polyarylether ketone polymkeric substance according to first aspect present invention is described, it is represented by following structural formula (1), structural formula (2) or structural formula (3):
Wherein, n is the polymerization degree, and the span of n is 50～150.
Secondly explanation is according to the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention, comprise the following steps: step 1: under nitrogen protection, in reactor, add solvent sulfolane, biphenol monomer and catalyzer, at 30～40 ℃, stir 0.5h; Step 2: add dihalo-monomer in reaction solution, then add appropriate band aqua toluene, be heated to 130 ℃ and keep this temperature of reaction 3～4h; Step 3: be then warmed up to 200～220 ℃, keep this temperature of reaction 6～10h; Step 4: add '-biphenyl diphenol, continue reaction 1～2h; Step 5: after final reaction finishes, product is obtained to modified polyarylether ketone product through soaking, filter, drying.
According in the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention, described biphenol monomer can be Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-ethano-naphthalene-5,8-diphenol, 1,2,3,4-tetrahydrochysene-Isosorbide-5-Nitrae-ethano-naphthalene-5,8-diphenol, 1,4,5,8-tetrahydrochysene-Isosorbide-5-Nitrae: 5,8-bis-ethano--9,10-anthrol and 1,2,3,4,5,6,7,8-octahydro-Isosorbide-5-Nitrae: 5,8-bis-ethano--9, at least one in 10-anthrol.
According in the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention, described catalyzer can be at least one in salt of wormwood and sodium carbonate.
According in the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention, described catalyzer can be salt of wormwood and sodium carbonate, and its mol ratio is (5～10): 1.
According in the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention, the mol ratio of described biphenol monomer and catalyzer can be 1:(1.2～1.5).
According in the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention; described dihalo-monomer can be 4,4 '-difluoro benzophenone, 4,4 '-dichloro benzophenone, 1; at least one in 4-bis-(4-fluoro benzoyl) benzene and Isosorbide-5-Nitrae-bis-(4-fluoro benzoyl) biphenyl.
According in the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention, the mol ratio of described dihalo-monomer and biphenol monomer is 1:(0.91～1.05).
According in the preparation method of the modified polyarylether ketone polymkeric substance of second aspect present invention, the mol ratio of described dihalo-monomer and '-biphenyl diphenol monomer is 1:(0.01～0.11).
Next illustrate according to embodiment and the comparative example of modified polyarylether ketone polymkeric substance of the present invention and preparation method thereof.
Embodiment 1
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5,8-diphenol and 0.012mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 5:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone monomer, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h; Add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 110.
Embodiment 2
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5,8-diphenol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 5:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h; Add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 121.
Embodiment 3
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5, the mol ratio of 8-diphenol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate is 5:1, at 30～40 ℃, stir 0.5h, catalyzer and diphenol monomer are fully reacted; Add afterwards 0.0095mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h; Add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 89.
Embodiment 4
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5,8-diphenol and 0.013mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 10:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h, add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 2h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 150.
Embodiment 5
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5,8-diphenol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 5:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-dichloro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h, add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 50.
Embodiment 6
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,2,3,4-tetrahydrochysene-Isosorbide-5-Nitrae-ethano-naphthalene-5,8-diphenol and 0.013mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 8:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.01mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h; Add afterwards 0.0011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 100.
Embodiment 7
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4,5,8-tetrahydrochysene-1,4:5,8-bis-ethano--9,10-anthrol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 10:1, at 30～40 ℃, stir 0.5h, catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h, add afterwards 0.0011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 96.
Embodiment 8
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,2,3,4,5,6,7,8-octahydro-1,4:5,8-bis-ethano--9,10-anthrol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 10:1, at 30～40 ℃, stir 0.5h, catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 3h; Be warmed up to again 200～220 ℃, keep thermotonus 10h; Add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 2h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 115.
Embodiment 9
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5,8-diphenol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 9:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 8h; Add afterwards 0.0011mol '-biphenyl diphenol, continue reaction 2h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 120.
Embodiment 10
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5,8-diphenol and 0.015mol catalyzer Anhydrous potassium carbonate, at 30～40 ℃, stir 0.5h, catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 3h; Be warmed up to again 200～220 ℃, keep thermotonus 9h, add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 139.
Embodiment 11
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,4-dihydro-1,4-ethano-naphthalene-5,8-diphenol and 0.015mol catalyzer anhydrous sodium carbonate, at 30～40 ℃, stir 0.5h, catalyzer and diphenol monomer are fully reacted; Add afterwards 0.011mol4,4 '-difluoro benzophenone, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 3h; Be warmed up to again 200～220 ℃, keep thermotonus 9h, add afterwards 0.00011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (1), and polymerization degree n is 53.
Embodiment 12
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,2,3,4-tetrahydrochysene-Isosorbide-5-Nitrae-ethano-naphthalene-5,8-diphenol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 10:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.01mol1,4-bis-(4-fluoro benzoyl) benzene, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h; Add afterwards 0.0011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (2), and polymerization degree n is 140.
Embodiment 13
Under nitrogen protection, to being equipped with in the there-necked flask of magnetic agitation, water-and-oil separator and thermometer, add 48g(0.4mol) tetramethylene sulfone, 0.01mol1,2,3,4-tetrahydrochysene-Isosorbide-5-Nitrae-ethano-naphthalene-5,8-diphenol and 0.015mol catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate, its mol ratio is 10:1, at 30～40 ℃, stirs 0.5h, and catalyzer and diphenol monomer are fully reacted; Add afterwards 0.01mol1,4-bis-(4-fluoro benzoyl) biphenyl, then add 40mL band aqua toluene, and be heated to 130 ℃, keep temperature 4h; Be warmed up to again 200～220 ℃, keep thermotonus 6h; Add afterwards 0.0011mol '-biphenyl diphenol, continue reaction 1h; After reaction finishes, product is through soaking, filter, dry and to obtain polyaryletherketone product, and product structure is structural formula (3), and polymerization degree n is 144.
Comparative example
By 0.0115mol[3,6]-methylene radical-4 tetrahydrobenzene-4-Resorcinol and 0.0145mol Anhydrous potassium carbonate join in the there-necked flask that magnetic agitation, water-and-oil separator and thermometer are housed, and add 40mL N,N-dimethylacetamide.After stirring 0.5h under room temperature, add 0.0115mol4,4 '-difluoro benzophenone, adds 40mL N,N-dimethylacetamide, then adds 40mL band aqua toluene.Be heated to 130 ℃, keep temperature 4h.Be warmed up to again 166 ℃, keep temperature 22h, obtain unregulated polymer.More than reaction is all carried out in nitrogen protection.Through purification step, obtain refining polymkeric substance again.
Finally provide performance test and the test result of the modified polyarylether ketone polymkeric substance based on embodiment 1-13 and comparative example.
(1) test of second-order transition temperature: carry out on Shimadzu DSC-60 type automatic difference scanning calorimeter instrument, temperature rise rate is 10K/min, N
2atmosphere.
(2) test of fusing point: carry out on Shimadzu DSC-60 type automatic difference scanning calorimeter instrument, temperature rise rate is 10K/min, N
2atmosphere.
(3) test of tensile strength: carry out on domestic KT877S type electronic universal tester, rate of extension is 10mm/min.
(4) test of elongation at break: carry out on domestic KT877S type electronic universal tester, rate of extension is 10mm/min.
(5) solvability test: polymkeric substance is joined in solvent, observe dissolving situation, and the solubleness of test polymer in solvent.
Table 1 provides the performance test results of the modified polyarylether ketone polymkeric substance based on embodiment 1-13 and comparative example, wherein, "+" represents that the solubleness of polymkeric substance under room temperature is greater than 0.2g/ml, "+-" represent that the solubleness of polymkeric substance under room temperature is 0.05～0.2g/ml, the solubleness that is raised to more than 40 ℃ polymkeric substance when temperature is greater than 0.2g/ml.
From the contrast of embodiment 1-13 and comparative example, can find out, the resulting modified polyarylether ketone of the present invention polymkeric substance has not only kept excellent heat resistance energy and the mechanical property of polyaryletherketone itself.Meanwhile, improved the solvability of poly aryl ether ketone polymer, made it be dissolvable in water the conventional solvents such as acetone, DMSO, DMF, chloroform, THF, made it aspect processing, have more advantage.
Claims (10)
1. a modified polyarylether ketone polymkeric substance, is characterized in that, described modified polyarylether ketone polymkeric substance is represented by following structural formula (1), structural formula (2) or structural formula (3):
Wherein, n is the polymerization degree, and the span of n is 50～150.
2. a preparation method for modified polyarylether ketone polymkeric substance, for the preparation of modified polyarylether ketone polymkeric substance according to claim 1, is characterized in that, comprises the following steps:
Step 1: under nitrogen protection, add solvent sulfolane, biphenol monomer and catalyzer in reactor, stir 0.5h at 30～40 ℃;
Step 2: add dihalo-monomer in reaction solution, then add appropriate band aqua toluene, be heated to 130 ℃ and keep this temperature of reaction 3～4h;
Step 3: be then warmed up to 200～220 ℃, keep this temperature of reaction 6～10h;
Step 4: add '-biphenyl diphenol, continue reaction 1～2h;
Step 5: after final reaction finishes, product is obtained to modified polyarylether ketone product through soaking, filter, drying.
3. the preparation method of modified polyarylether ketone polymkeric substance according to claim 2, is characterized in that, described biphenol monomer is Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-ethano-naphthalene-5,8-diphenol, 1,2,3,4-tetrahydrochysene-Isosorbide-5-Nitrae-ethano-naphthalene-5,8-diphenol, Isosorbide-5-Nitrae, 5,8-tetrahydrochysene-Isosorbide-5-Nitrae: 5,8-bis-ethano--9,10-anthrol and 1,2,3,4,5,6,7,8-octahydro-Isosorbide-5-Nitrae: 5,8-bis-ethano--9, at least one in 10-anthrol.
4. the preparation method of modified polyarylether ketone polymkeric substance according to claim 2, is characterized in that, described catalyzer is at least one in salt of wormwood and sodium carbonate.
5. the preparation method of modified polyarylether ketone polymkeric substance according to claim 4, is characterized in that, described catalyzer is salt of wormwood and sodium carbonate.
6. the preparation method of modified polyarylether ketone polymkeric substance according to claim 5, is characterized in that, in described catalyzer, the mol ratio of salt of wormwood and sodium carbonate is (5～10): 1.
7. the preparation method of modified polyarylether ketone polymkeric substance according to claim 2, is characterized in that, the mol ratio of described biphenol monomer and catalyzer is 1:(1.2～1.5).
8. the preparation method of modified polyarylether ketone polymkeric substance according to claim 2; it is characterized in that; described dihalo-monomer is 4; 4 '-difluoro benzophenone, 4; 4 '-dichloro benzophenone, 1; at least one in 4-bis-(4-fluoro benzoyl) benzene and Isosorbide-5-Nitrae-bis-(4-fluoro benzoyl) biphenyl.
9. the preparation method of modified polyarylether ketone polymkeric substance according to claim 2, is characterized in that, the mol ratio of described dihalo-monomer and biphenol monomer is 1:(0.91～1.05).
10. the preparation method of modified polyarylether ketone polymkeric substance according to claim 2, is characterized in that, the mol ratio of described dihalo-monomer and '-biphenyl diphenol monomer is 1:(0.01～0.11).
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| CN114874432A (en) * | 2022-06-14 | 2022-08-09 | 中国科学院长春应用化学研究所 | High-temperature-resistant thermal shrinkage material and preparation method thereof |
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| CN113402706A (en) * | 2021-07-02 | 2021-09-17 | 天津师范大学 | Preparation method of polyaromatic ether |
| CN113402706B (en) * | 2021-07-02 | 2023-08-25 | 天津师范大学 | Preparation method of polyaromatic ether |
| CN114874432A (en) * | 2022-06-14 | 2022-08-09 | 中国科学院长春应用化学研究所 | High-temperature-resistant thermal shrinkage material and preparation method thereof |
| CN114874432B (en) * | 2022-06-14 | 2024-03-26 | 中国科学院长春应用化学研究所 | High-temperature-resistant heat-shrinkable material and preparation method thereof |
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