CN101045786A - Polyether ketonic and ketonic high performance material containing thio-ether structure and preparation method thereof - Google Patents
Polyether ketonic and ketonic high performance material containing thio-ether structure and preparation method thereof Download PDFInfo
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- 239000012761 high-performance material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000000101 thioether group Chemical group 0.000 title abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 title 1
- 229920000570 polyether Polymers 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 229920001643 poly(ether ketone) Polymers 0.000 claims abstract description 65
- 150000003568 thioethers Chemical group 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
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- 239000000843 powder Substances 0.000 claims description 16
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 14
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- -1 2-trifluoromethylphenyl Chemical group 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 31
- 238000004132 cross linking Methods 0.000 abstract description 10
- 229920001652 poly(etherketoneketone) Polymers 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 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
- 229920001400 block copolymer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
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- HHCIXYJPQDEUPS-UHFFFAOYSA-N 6-(4-hydroxyphenyl)-7-thiabicyclo[4.1.0]hepta-2,4-dien-3-ol Chemical compound C1=CC(O)=CC2SC21C1=CC=C(O)C=C1 HHCIXYJPQDEUPS-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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Abstract
This invention belong to high molecular material region, relates to a new style high performance materials of polyetherketone and polyetherketone with thio ether structure, and the preparation method. By regularly introducing thio-ether structure to polyetherketone backbone structure, this invention prepares new style polyetherketone high performance materials with thio-ether structure, and by further introducing large lateral group to backbone structure to gain better solubility and crosslink performance. Because at hot conditions thio-ether structure could occur cross linking reaction and obtain crosslink type polyetherketone stuff, through regulation of crosslink density realizing regulation and control of material property, advance service temperature and using range of stuff, thereby achieve aim of satisfy different operating requirement.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a novel polyether ketone and polyether ketone high-performance material with a thioether structure and a preparation method of the series of materials.
Background
Semi-crystalline unreinforced polymer Polyetherketone (PEK) with high temperature resistance, mechanical strength and chemical resistance was sold in the world market by Victrex corporation, uk, beginning in 1999. The PEK can maintain high tensile strength and flexural modulus in a wide temperature range, is widely applied to the fields of machinery, petrochemical industry, nuclear power, rail transit and the like, and can be used for manufacturing compressor valve plates, high-pressure steam ball valve seats and bearing maintenanceMachine parts such as frame, chemical pump gear, slide bearing, sealing member, piston ring, crawler shoe, etc. the product quality is light, long service life can also reduce machine running noise. In addition, since PEK has excellent electrical properties, a sensor can be made. Such materials are expected to be useful in a variety of different applications in the automotive and aerospace fields where continuous operation at high temperatures is required. With the further development of scientific technology, the requirements on the material performance are higher and higher, and many researchers modify polyether ketone materials to improve the performance of the materials. Firstly, the properties of each polymer component can be balanced by blending modification of special engineering plastics such as PEK and the like, thereby making up for deficiencies and overcoming the defects of the properties of a single polymer component, and further obtaining the polymer blending material with ideal comprehensive properties. The PEK can be blended with other polymers such as Polytetrafluoroethylene (PTFE), Polyethersulfone (PESU), Polyetheretherketone (PEEK), Polyimide (PI), etc., and carbon fiber, glass fiber, whisker, ZrO, etc2CuO, etc. are compounded and enhanced to form the composite material with more excellent performance. In addition, PEK can meet some special requirements by blending with other polymers, a series of novel polymer materials with novel properties are prepared, and certain polymer systems can generate special properties such as antistatic property, conductivity, flame retardance, lubricity and the like by blending, so that the polymer materials become 'functionalized' plastic alloys. For example: the research result of the polyphenylene sulfide/polyether ketone blended alloy shows that the crystallization performance of the polyphenylene sulfide can be enhanced by adding a proper amount of PEK, and the requirements of various industries can be met conveniently. The PEK can also be used for toughening and modifying thermoplastic resin of epoxy resin, and can be used as engineering plastic with excellent toughness, high modulus and good heat resistance, and can be used as a toughening agent to be blended into the epoxy resin in a hot melting mode to form second-phase particles. The addition of PEK obviously improves the toughness of the epoxy resin, and the modulus and the heat resistance of a cured product are not influenced or even higher. Secondly, a rigid structure is introduced into the main chain of the polyaryletherketone, and the use temperature of the polyaryletherketone is increased by increasing Tg and Tm. New varieties of Polyetheretherketone (PEEKK), Polyetheretherketone (PEDEK), and Polyetheretherketone (PEDEKK) are developed in succession, and meet the urgent needs of some advanced technologies. But instead of the other end of the tubeWith the increasing Tg and Tm, the processing becomes more and more difficult, and it is difficult to make the material usable. The main reason is that the material is difficult to be formed into practical products. In addition, attempts have been made to introduce crosslinking points into polyaryletherketone materials to obtain high-performance materials by forming a crosslinked structure, but the selected crosslinking points are accompanied by degradation reactions during the crosslinking reaction, so that the performance of the materials is reduced, and the expected purpose is not achieved.
High molecular materials can be classified into two broad categories, thermoplastic materials and thermosetting materials, according to the processing method, and the two materials have their own advantages and disadvantages. The thermoplastic material has excellent processing performance, but the use temperature is lower; thermoset materials have a relatively high use temperature, but present certain difficulties in machining fixed size shape castings. Based on the design idea of organically combining the excellent processing performance of the thermoplastic material and the excellent thermal performance of the thermosetting material into one material, the invention introduces a thioether structure which can generate a crosslinking reaction under a certain condition into a polyether ketone main chain structure, successfully prepares a series of novel polyether ketone high-performance materials containing thioether structures, can perform thermoplastic processing, and then obtains the thermosetting material with more excellent performance through crosslinking. The crosslinkable polyether ketone high-performance material with the thioether structure is obtained by introducing large side groups into the polyether ketone main chain structure with the thioether structure, so that the processing and using windows of the material are widened. The material performance can be regulated and controlled by regulating and controlling the distribution mode and content of a thioether structure in a polyether ketone chain segment, and the method has great practical value and development value for high performance of the polyether ketone material.
Disclosure of Invention
One of the purposes of the invention is to provide a polyether ketone material with a brand-new structure and a preparation method of the polyether ketone material;
the second purpose of the invention is to provide a high-performance material of polyether ketone containing thioether structure and a preparation method of the high-performance material of polyether ketone containing thioether structure.
According to the preparation method, a thioether structure is regularly introduced into a polyether ketone main chain structure, so that a novel polyether ketone high-performance material containing the thioether structure is prepared, and then a large side group is introduced into the polyether ketone main chain structure containing the thioether structure to obtain the polyether ketone high-performance material containing the thioether structure, which has good dissolubility and can be crosslinked. Because the thioether structure can generate a crosslinking reaction under a high-temperature condition to obtain the crosslinking type polyether ketone material, the regulation and control of the material performance can be realized through the regulation and control of the crosslinking density, and the use temperature and the use range of the material are improved, so that the purpose that the performance of the polyether ketone material containing the thioether structure and the crosslinked polyether ketone material can meet different use requirements is achieved.
The reaction process of polyether ketone (PEK) is as follows: adding 4, 4 ' -difluorobenzophenone and 4, 4 ' -dihydroxybenzophenone with the molar ratio of 1-1.02: 1 into diphenyl sulfone which is an organic solvent at room temperature, wherein the solid content in a reaction system is 20% -35%, heating and melting, adding a mixed salt catalyst of potassium carbonate and sodium carbonate with the molar ratio of 3-5% excessive relative to 4, 4 ' -difluorobenzophenone, wherein the content of potassium carbonate in the mixed salt catalyst is 3-10%; stirring, heating, carrying out temperature control reaction for multiple times to obtain a polymer product, discharging the polymer product in cold water, crushing a crude product by a crusher, washing the obtained powder sample for multiple times by using acetone to remove an organic solvent, then boiling and washing the powder sample for multiple times by using distilled water to remove inorganic salt, and finally drying the product at 110-120 ℃ for 10-15 hours to obtain a white polyether ketone polymer powder sample, wherein the yield is 96-98%;
the multiple temperature control reactions in the method are that in the process of stirring and heating, the temperature of a reaction system is controlled to be unchanged or changed within a small range at a certain temperature, then a reaction is carried out for a certain time, and after the reaction is finished, the temperature of the reaction system is rapidly increased to the next reaction temperature (5-10 minutes);
further, the multiple temperature control reactions in the method are carried out for 2-5 times at a temperature range of 180-320 ℃, the temperature interval of every two temperature control reactions is 10-50 ℃, the time of every temperature control reaction is 1-5 hours, and the temperature control range of every temperature control reaction is 5-20 ℃;
furthermore, the temperature control reaction for multiple times in the method is carried out for 1-3 hours at the temperature of 210-220 ℃, 240-260 ℃ and 280-290 ℃ respectively, and for 3-5 hours at the temperature of 310-320 ℃.
Synthesis of polyether ketone Polymer containing thioether Structure: the polyether ketone material is synthesized through a nucleophilic substitution route, and then a thioether structure is introduced into a polyether ketone main chain structure in a block mode.
Specifically, 4 ' -difluorobenzophenone and 4, 4 ' -dihydroxybenzophenone are added into an organic solvent at room temperature, after heating and melting, a mixed salt catalyst of potassium carbonate and sodium carbonate is added, wherein the molar weight of the mixed salt catalyst is 3-5% of that of the 4, 4 ' -difluorobenzophenone, and the content of the potassium carbonate in the mixed salt catalyst is 3-10%; stirring and heating, carrying out temperature control reaction for 2-4 times, adding 4, 4' -dihydroxy diphenyl sulfide, carrying out temperature control reaction for 1-3 times, discharging the obtained polymer in cold water, crushing the crude product by a crusher, washing the obtained powder sample by acetone to remove an organic solvent, boiling and washing the powder sample by distilled water to remove inorganic salts, and drying the product at 110-120 ℃ for 10-15 h to obtain a white polymer powder sample, wherein the yield is 96-98%.
In the above method, the molar ratio of 4, 4 '-difluorobenzophenone to the sum of 4, 4' -dihydroxybiphenyl sulfide and 4, 4 '-dihydroxybenzophenone is 1-1.02: 1, and the molar content of the sulfide structure is 5% -30%, i.e., the molar ratio of 4, 4' -dihydroxybiphenyl sulfide/(4, 4 '-dihydroxybiphenyl sulfide +4, 4' -dihydroxybenzophenone) is 5% -30%.
In the above method, the organic solvent is diphenyl sulfone or sulfolane, and the solid content in the reaction system is 20% to 35%.
Further, when the diphenyl sulfone organic solvent is used in the method, the temperature control reaction is carried out for 2-4 times at the temperature of 180-280 ℃, the temperature control reaction interval of every two times is 10-50 ℃, and the temperature control reaction is carried out for 1-3 hours every time; then adding 4, 4' -dihydroxy diphenyl sulfide, and carrying out temperature control reaction for 1-3 times within the temperature range of 300-320 ℃, wherein the temperature control reaction interval of every two times is 10-30 ℃, the temperature control reaction time is 1-5 hours, and the temperature control reaction time is 5-20 ℃;
when the sulfolane organic solvent is used, the temperature control reaction is carried out for 2-4 times at the temperature range of 150-200 ℃, the temperature control reaction interval of every two times is 10-30 ℃, and the temperature control reaction is carried out for 1-3 hours every time; then adding 4, 4' -dihydroxy diphenyl sulfide, and carrying out temperature control reaction for 1-3 times within a temperature range of 210-240 ℃, wherein the temperature control reaction interval of every two times is 10-20 ℃, the temperature control reaction time is 1-5 hours, and the temperature control reaction time is 5-20 ℃;
furthermore, when the diphenyl sulfone organic solvent is used in the method, the temperature control reaction is carried out for 1-2 h at the temperature ranges of 210-220 ℃, 250-260 ℃ and 280-290 ℃, then 4, 4' -dihydroxy diphenyl sulfide is added, the temperature is raised to 310-320 ℃, and then the temperature control reaction is carried out for 2-5 h;
when a sulfolane organic solvent is used, the temperature control reaction is carried out for 1-2 h at the temperature of 160-170 ℃ and 180-190 ℃, then 4, 4' -dihydroxy diphenyl sulfide is added, the temperature is raised to 210-230 ℃, and then the temperature control reaction is carried out for 2-5 h;
in the above method, the 4, 4 '-dihydroxybiphenyl sulfide compound may also be 2-phenyl pendant-4, 4' -dihydroxybiphenyl sulfide, 2-trifluoromethylphenyl pendant-4, 4 '-dihydroxybiphenyl sulfide, 2-methylphenyl pendant-4, 4' -dihydroxybiphenyl sulfide, 2-methoxybenzene pendant-4, 4 '-dihydroxybiphenyl sulfide, or 2-sulfophenyl pendant-4, 4' -dihydroxybiphenyl sulfide.
The polymer obtained in examples 1 and 2 has the following structural formula:
(I) n represents polymerization degree and is a positive integer
The polymers obtained in examples 3 and 4 have the following structural formula:
(II) m and n are positive integers
The polymers obtained in examples 5 and 6 have the following structural formula:
(III) m and n are positive integers
The polymers obtained in examples 7 and 8 have the following structural formula:
wherein,
(IV) m and n are positive integers
The synthesis reaction formula of the polymer is as follows: (examples 1 and 2)
Synthesis of the Polymer reaction formula two: (examples 3 and 4)
The synthesis reaction formula of the polymer is III: (examples 5 and 6)
The synthesis reaction of the polymer is shown as the fourth formula: (examples 7 and 8)
Wherein,
the polyether ketone high-performance material containing the thioether structure and the soluble and crosslinkable polyether ketone high-performance material prepared by the method have three remarkable advantages.
The method comprises the following steps of firstly, utilizing the characteristic that a thioether structure can generate a crosslinking reaction under a certain condition, successfully introducing a thioether-containing structural unit into a polyether ketone main chain structure to obtain a series of crosslinkable polyether ketone high-performance polymers containing thioether structures;
secondly, the structure and the performance of the crosslinkable polyether ketone high-performance polymer containing the thioether structure are regulated and controlled through two ways: firstly, the distribution mode of a thioether structure is controlled: introducing a thioether-containing structural unit into a polyether ketone main chain structure in a block mode, so that the thioether-containing structural unit is singly and uniformly distributed in a polyether ketone high polymer; secondly, regulating the content of a thioether structure within a certain proper range;
and thirdly, introducing a thioether-containing structural unit with a large side group into a high-performance polyether ketone main chain structure in a block mode to obtain a crosslinkable polyether ketone high-performance material with good solubility, thereby widening the application range and the processing window of the material.
Drawings
FIG. 1: DSC curve of polyetherketone Polymer (PEK) prepared in example 1;
FIG. 2: thermogravimetry of polyetherketone Polymer (PEK) prepared in example 1.
Detailed Description
Example 1:
43.64g (0.20mol) of 4, 4 '-difluorobenzophenone, 42.84g (0.20mol) of 4, 4' -dihydroxybenzophenone and 195.00g (0.90mol) of diphenylsulfone are added into a 1000ml three-necked flask with a mechanical stirrer, a thermometer and nitrogen gas, 2.21g (0.016mol) of anhydrous potassium carbonate and 20.14g (0.19mol) of anhydrous sodium carbonate are added after heating and melting, the mixture is stirred and heated to 210 ℃ for reaction for 1h, heated to 240 ℃ for reaction for 1h, heated to 280 ℃ for reaction for 1h, finally heated to 310 ℃ for continuous reaction for 3h, the reaction product is discharged in cold water, the crude product is crushed by a crusher, boiled and washed by acetone and distilled water for 6-8 times respectively to remove organic solvents and inorganic salts, and finally dried at 120 ℃ for 12h to obtain a white polyether ketone powder sample with the yield of 97%. The molecular weight of the polyether ketone measured by a viscosity method is about 5 ten thousand, DSC research results show that the glass transition temperature and the melting point of the polyether ketone prepared in the embodiment are 156 ℃ and 372 ℃ respectively, and the thermal weight loss result shows that the thermal weight loss 5% temperature is 590 ℃.
Example 2:
the method is as in example 1, the molar contents of 4, 4' -difluorobenzophenone are changed to 0.201mol, 0.202mol, 0.203mol and 0.204mol in sequence, and after the same treatment as in example 1, white polyether ketone powder samples with the molecular weight of between 3 and 5 ten thousand are respectively obtained, and the yield of the obtained samples is between 96 and 98 percent.
Example 3:
43.640g (0.200mol) of 4, 4 ' -difluorobenzophenone, 41.773g (0.190mol) of 4, 4 ' -dihydroxybenzophenone and 220.000g (1.008mol) of diphenyl sulfone are added into a 1000ml three-necked bottle provided with a mechanical stirrer, a thermometer and nitrogen gas, 2.21g (0.016mol) of anhydrous potassium carbonate and 20.140g (0.190mol) of anhydrous sodium carbonate are added after heating and melting, the mixture is stirred and heated to 210 ℃ for reaction for 1h, the reaction temperature is increased and controlled at 250 ℃ and 280 ℃ respectively for 1h (for other thioether compounds, the mixture is added into a reaction system when the organic solvent of the reaction system is the same and the temperature is the same), then 2.183g (0.010mol) of 4, 4 ' -dihydroxydiphenyl sulfide is added, the reaction temperature is increased to 310 ℃ for 3h, the reaction product is discharged in cold water, the crude product is crushed by a crusher, and is boiled and washed by acetone and distilled water for 6-8 times respectively to remove the organic solvent and the inorganic salt, the final product was dried at 120 ℃ for 12 hours to give a white powder sample of a block copolymer having a thioether structure molar content of 5% [4, 4 ' -dihydroxybiphenyl sulfide/(4, 4 ' -dihydroxybiphenyl sulfide +4, 4 ' -dihydroxybenzophenone) molar ratio of 5% ], with a yield of 98%. The molecular weight of the polymer is 3.5 ten thousand, the glass transition temperature is 148 ℃, and the polymer has good solubility in organic solvents such as tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
Example 4:
the procedure was as in example 3 except that the molar contents of 4, 4 '-dihydroxydiphenyl sulfide were changed in the order of 10%, 15%, 20%, 25% and 30%, and the same treatments as in example 3 were carried out to obtain white powder samples of block copolymers having sulfide structures (4, 4' -dihydroxydiphenyl sulfide) of 10%, 15%, 20%, 25% and 30%, respectively, in a yield of 98% and a molecular weight of 3 to 5 ten thousand. The product also has good solubility in organic solvents such as tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and the like.
Example 5:
43.640g (0.200mol) of 4, 4 ' -difluorobenzophenone, 41.773g (0.190mol) of 4, 4 ' -dihydroxybenzophenone and 170.233g (1.417mol) of sulfolane are added into a 1000ml three-necked bottle provided with a mechanical stirrer, a thermometer and nitrogen, 2.21g (0.016mol) of anhydrous potassium carbonate and 20.140g (0.190mol) of anhydrous sodium carbonate are added after heating and melting, the temperature is increased to 160 ℃ by stirring for reaction for 1h, the reaction temperature is increased and controlled at 180 ℃ for reaction for 1h, then 2.944g (0.010mol) of 2-phenyl side group-4, 4 ' -dihydroxybenzophenone is added, the temperature is increased to 220 ℃ and the reaction is continued for 3 h. Discharging a reaction product in cold water, crushing the crude product by a crusher, washing the crude product for 8-10 times by using distilled water to remove an organic solvent and inorganic salts, and drying the final product at 120 ℃ for 12 hours to obtain a block copolymer white powder sample with a thioether structure (2-phenyl side group-4, 4' -dihydroxy diphenyl sulfide) of which the molar content is 5%, wherein the yield is 97%, and the molecular weight is about 4 ten thousand. The glass transition temperature is about 146 ℃, and the polymer has good solubility in organic solvents such as tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
Example 6:
the procedure was carried out as in example 5 while changing the molar contents of 2-phenyl pendant-4, 4 '-dihydroxydiphenyl sulfide to 10%, 15%, 20%, 25%, and 30% in this order, and the same treatments as in example 5 were carried out to obtain white powdery samples of block copolymers having sulfide structures (2-phenyl pendant-4, 4' -dihydroxydiphenyl sulfide) in molar contents of 10%, 15%, 20%, 25%, and 30%, respectively, at a yield of 97%.
Example 7:
43.640g (0.200mol) of 4, 4 ' -difluorobenzophenone, 41.773g (0.190mol) of 4, 4 ' -dihydroxybenzophenone and 170.233g (1.417mol) of sulfolane are added into a 1000ml three-necked bottle provided with a mechanical stirrer, a thermometer and nitrogen, 2.21g (0.016mol) of anhydrous potassium carbonate and 20.140g (0.190mol) of anhydrous sodium carbonate are added after heating and melting, the mixture is stirred and heated to 160 ℃ for reaction for 1h, the reaction temperature is increased, the reaction system is controlled to react for 1h at 180 ℃, then 3.624g (0.010mol) of 2-trifluoromethylbenzene side group-4, 4 ' -dihydroxybenzophenone is added, the temperature is increased to 220 ℃ for further reaction for 3h, the reaction product is discharged in cold water, the crude product is crushed by a crusher, is washed by distilled water for 8-10 times to remove an organic solvent and an inorganic salt, and finally the product is dried for 12h at 120 ℃ to obtain a thioether structure (2-trifluoromethylbenzene-4, 4 '-dihydroxydiphenyl sulfide) was 5% [ i.e., 2-trifluoromethylphenyl pendant-4, 4' -dihydroxydiphenyl sulfide/(2-trifluoromethylphenyl pendant-4, 4 '-dihydroxydiphenyl sulfide +4, 4' -dihydroxydiphenyl ketone) ] as a 5% sample of a white powder of the block copolymer, with a yield of 97%. The structural formula of the polymer is compared with that of example 5, and the difference is that 2-phenyl pendant-4, 4 '-dihydroxydiphenyl sulfide unit in the structural formula of example 5 is replaced by 2-trifluoromethylphenyl pendant-4, 4' -dihydroxydiphenyl sulfide unit. The molecular weight is about 4 ten thousand, the glass transition temperature is about 146 ℃, and the polymer has good solubility in organic solvents such as tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
The molar contents of 2-trifluoromethylphenyl pendant-4, 4 '-dihydroxydiphenyl sulfide were changed to 10%, 15%, 20%, 25% and 30%, respectively, and white powder samples of block copolymers having sulfide structures (2-trifluoromethylphenyl pendant-4, 4' -dihydroxydiphenyl sulfide) in molar contents of 10%, 15%, 20%, 25% and 30% were obtained by the same treatments as in examples 5 to 6, with a yield of 96% to 98%.
Example 8:
the method is as in example 7, sequentially replacing 2-trifluoromethylbenzene side group-4, 4 '-dihydroxydiphenyl sulfide with thioether structure monomers such as 2-methylbenzene side group-4, 4' -dihydroxydiphenyl sulfide, 2-methoxybenzene side group-4, 4 '-dihydroxydiphenyl sulfide or 2-sulfobenzene side group-4, 4' -dihydroxydiphenyl sulfide, and adjusting the molar contents to 5%, 10%, 15%, 20%, 25%, 30%, and obtaining white block copolymer powder samples with the thioether structure monomer molar contents of 5%, 10%, 15%, 20%, 25%, 30% respectively after the same treatments as in examples 5 to 7, with the yield of 96% -98%.
Claims (10)
1. The structural formula of the polyether ketone high-performance material is shown as follows:
wherein N represents the degree of polymerization and is a positive integer.
2. The method for preparing the polyether ketone high-performance material as claimed in claim 1 comprises the following steps: adding 4, 4 ' -difluorobenzophenone and 4, 4 ' -dihydroxybenzophenone in a molar ratio of 1-1.02: 1 into diphenyl sulfone which is an organic solvent at room temperature, wherein the solid content in a reaction system is 20% -35%, heating and melting, adding a mixed salt catalyst of potassium carbonate and sodium carbonate, wherein the molar amount of the mixed salt catalyst is 3-5% of that of the 4, 4 ' -difluorobenzophenone, and the content of the potassium carbonate in the mixed salt catalyst is 3-10%; stirring and heating, carrying out temperature control reaction for multiple times to obtain a polymer product, discharging the polymer product in cold water, crushing a crude product by a crusher, washing to remove an organic solvent and inorganic salt, and finally drying the product at 110-120 ℃ for 10-15 h to obtain a white polyether ketone polymer powder sample, wherein the yield is 96-98%.
3. The method for preparing the polyether ketone high-performance material as claimed in claim 2, wherein the method comprises the following steps: the multiple temperature control reactions are temperature control reactions carried out for 2-5 times within a temperature range of 180-320 ℃, the temperature interval of every two temperature control reactions is 10-50 ℃, the time of every temperature control reaction is 1-5 hours, the temperature control range of every temperature control reaction is 5-20 ℃, and the temperature of a reaction system is rapidly increased to the temperature of the next reaction after the reaction is finished.
4. A process for preparing a polyetherketone high performance material as claimed in claim 3, wherein: the multiple temperature control reactions are carried out for 1-3 hours at the temperature of 210-220 ℃, 240-260 ℃ and 280-290 ℃ respectively, and for 3-5 hours at the temperature of 310-320 ℃.
5. The polyether ketone high-performance material containing the thioether structure has the structural formula shown as follows:
wherein,
m and n are integers.
6. The preparation method of the thioether structure containing polyether ketone high-performance material as claimed in claim 5, comprises the following steps: adding 4, 4 ' -difluorobenzophenone and 4, 4 ' -dihydroxybenzophenone into an organic solvent at room temperature, heating and melting, and adding a mixed salt catalyst of potassium carbonate and sodium carbonate with the molar weight being 3-5% of that of the 4, 4 ' -difluorobenzophenone, wherein the content of the potassium carbonate in the mixed salt catalyst is 3-10%; stirring and heating, carrying out temperature control reaction for 2-4 times, adding thioether, carrying out temperature control reaction for 1-3 times, discharging the obtained polymer in cold water, crushing the crude product by a crusher, washing to remove an organic solvent and inorganic salt, and drying the product at 110-120 ℃ for 10-15 hours to obtain a white polymer powder sample, wherein the yield is 96-98%; the molar ratio of 4, 4 ' -difluorobenzophenone to the sum of thioether and 4, 4 ' -dihydroxybenzophenone is 1-1.02: 1, and the molar content of the thioether structure in the total consumption of thioether and 4, 4 ' -dihydroxybenzophenone is 5-30%.
7. The method for preparing the thioether structure-containing polyether ketone high-performance material as claimed in claim 6, wherein the method comprises the following steps: the organic solvent is diphenyl sulfone or sulfolane, and the solid content in the reaction system is 20-35%.
8. The method for preparing the thioether structure-containing polyether ketone high-performance material as claimed in claim 7, wherein the method comprises the following steps: the organic solvent is diphenyl sulfone, the temperature control reaction is carried out for 2-4 times at the temperature of 180-280 ℃, the temperature control reaction interval is 10-50 ℃ every time, and the temperature control reaction is carried out for 1-3 hours every time; adding thioether, and performing temperature control reaction for 1-3 times within a temperature range of 300-320 ℃, wherein the temperature control reaction interval for every two times is 10-30 ℃, the temperature control reaction for every time is 1-5 hours, and the temperature range of the temperature control reaction for every time is 5-20 ℃.
9. The method for preparing the thioether structure-containing polyether ketone high-performance material as claimed in claim 7, wherein the method comprises the following steps: the organic solvent is sulfolane, the temperature control reaction is carried out for 2-4 times at the temperature range of 150-200 ℃, the temperature control reaction interval of every two times is 10-30 ℃, and the temperature control reaction time is 1-3 hours; adding thioether, and performing temperature control reaction for 1-3 times within a temperature range of 210-240 ℃, wherein the temperature control reaction interval of every two times is 10-20 ℃, the temperature control reaction time is 1-5 hours, and the temperature range of every temperature control reaction time is 5-20 ℃.
10. The method for preparing the thioether structure-containing polyether ketone high-performance material as claimed in any one of claims 6 to 9, wherein the method comprises the following steps: the thioether is 4, 4 '-dihydroxydiphenyl sulfide, 2-phenyl side group-4, 4' -dihydroxydiphenyl sulfide, 2-trifluoromethylphenyl side group-4, 4 '-dihydroxydiphenyl sulfide, 2-methylphenyl side group-4, 4' -dihydroxydiphenyl sulfide, 2-methoxybenzene side group-4, 4 '-dihydroxydiphenyl sulfide or 2-sulfophenyl side group-4, 4' -dihydroxydiphenyl sulfide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992472A (en) * | 2014-05-22 | 2014-08-20 | 吉林大学 | Polyether ketone resin and method for preparing same by polymerization termination |
| CN115109253A (en) * | 2022-05-07 | 2022-09-27 | 北京理工大学 | High-temperature self-crosslinking fluorine-containing polyaryletherketone, preparation method thereof, coating and preparation method thereof |
-
2007
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992472A (en) * | 2014-05-22 | 2014-08-20 | 吉林大学 | Polyether ketone resin and method for preparing same by polymerization termination |
| CN103992472B (en) * | 2014-05-22 | 2016-03-02 | 吉林大学 | The preparation method that a kind of polyether ketone resin and polymerization thereof stop |
| CN115109253A (en) * | 2022-05-07 | 2022-09-27 | 北京理工大学 | High-temperature self-crosslinking fluorine-containing polyaryletherketone, preparation method thereof, coating and preparation method thereof |
| CN115109253B (en) * | 2022-05-07 | 2023-08-11 | 铜陵精达特种电磁线股份有限公司 | High-temperature self-crosslinking fluorine-containing polyaryletherketone, preparation method thereof, coating and preparation method thereof |
| WO2023216537A1 (en) * | 2022-05-07 | 2023-11-16 | 铜陵精达特种电磁线股份有限公司 | High-temperature self-crosslinking fluorine-containing polyaryletherketone and preparation method therefor, and coating and preparation method therefor |
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