CN116515105B - Poly (diphenyl ether) high molecular compound and preparation method and application thereof - Google Patents
Poly (diphenyl ether) high molecular compound and preparation method and application thereof Download PDFInfo
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- CN116515105B CN116515105B CN202310342689.5A CN202310342689A CN116515105B CN 116515105 B CN116515105 B CN 116515105B CN 202310342689 A CN202310342689 A CN 202310342689A CN 116515105 B CN116515105 B CN 116515105B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 239000000178 monomer Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 44
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 150000001345 alkine derivatives Chemical class 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 27
- 239000002904 solvent Substances 0.000 description 27
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 238000001914 filtration Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 5
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 5
- -1 ether triazole Chemical class 0.000 description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical class CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 235000010378 sodium ascorbate Nutrition 0.000 description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 4
- 229960005055 sodium ascorbate Drugs 0.000 description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HMUGRILXVBKBID-UHFFFAOYSA-N 1-(bromomethyl)-4-[4-(bromomethyl)phenyl]benzene Chemical group C1=CC(CBr)=CC=C1C1=CC=C(CBr)C=C1 HMUGRILXVBKBID-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- XXFUZSHTIOFGNV-UHFFFAOYSA-N 1-bromoprop-1-yne Chemical compound CC#CBr XXFUZSHTIOFGNV-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a poly diphenyl ether high molecular compound and a preparation method and application thereof. The polybiphenyl ether polymer compound has a structure shown as a formula (I): wherein R is Or (b)N is an integer of 32 to 48. The poly diphenyl ether polymer compound not only has photoluminescence performance, but also has better high temperature resistance, and can be dissolved in various organic solvents, so that the poly diphenyl ether polymer compound has excellent processability.
Description
Technical Field
The invention relates to the technical field of high molecular compounds, in particular to a poly biphenyl ether high molecular compound and a preparation method and application thereof.
Background
With the development of technology, organic luminescent materials are widely focused and applied in the fields of diodes, biology, sensing and the like, and the current research on the organic luminescent materials is based on two materials, namely fluorescent materials and aggregation-induced emission materials. Fluorescent materials are conventional luminescent materials, which have the disadvantage of being prone to quenching of the aggregated luminescence, resulting in a reduction or even quenching of the aggregated luminescence, whereas aggregation-induced luminescent materials generally do not emit or emit weakly in dilute solutions. In addition, the excitation and luminescence of the fluorescent material or the aggregation-induced emission material are easily disturbed by the environment, and the excitation luminescence itself is changed along with the environment, for example, the luminescence property is easily affected by temperature, which greatly limits the application of the existing luminescent material in high-temperature photoluminescence.
Although the prior art discloses a polyphenylsulfone ether triazole and a preparation method and application thereof, a rigid group is introduced into a polytriazole resin structure to increase the rigidity of polymer molecular chains and the stacking density among the molecular chains, so that the movement of a polymer chain segment is limited, the free volume is reduced, and the glass transition temperature and the thermal stability of the polymer are improved, but the polymer does not have photoluminescence performance.
Disclosure of Invention
The invention aims to overcome the defect or defect that the existing organic luminescent material cannot have stable photoluminescence performance in a high-temperature environment due to poor high-temperature resistance, and provides a poly-biphenyl ether high-molecular compound which not only has good photoluminescence performance in a high-temperature environment, but also can be dissolved in various organic solvents.
Another object of the present invention is to provide a method for producing the above-mentioned polybiphenyl ether polymer compound.
Another object of the present invention is to provide an application of the above-mentioned poly biphenyl ether polymer compound in preparing an organic light emitting material.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
A polybiphenyl ether polymer compound has a structure shown in a formula (I):
wherein R is Any one of them; n is an integer of 32 to 48.
The biphenyl ether high molecular compound contains alkynyl, azido groups and biphenyl structures, and the biphenyl double-benzene conjugated structure in the specific molecular structure can not only effectively increase the rigidity of polymer molecular chains and the stacking density among the molecular chains, thereby limiting the movement of a high molecular chain segment, reducing the free volume and further improving the glass transition temperature and the thermal stability of the polymer; the photoluminescent property of the poly (biphenyl ether) polymer compound can be endowed, so that the poly (biphenyl ether) polymer compound has excellent photoluminescent property in a high-temperature environment.
Specifically, the glass transition temperature (Tg) of the poly-biphenyl ether polymer is 132.8-152.4 ℃, tdmax (maximum thermal cracking temperature in nitrogen) reaches 360.5-368.9 ℃, and the poly-biphenyl ether polymer not only has good thermal performance, but also can be dissolved in various organic solvents, and has excellent processability.
Preferably, R in the polybiphenyl ether polymer compound of the present invention is
Preferably, n is an integer of 35 to 45.
Preferably, the average molecular weight of the poly (biphenyl ether) polymer compound of the invention is 15000-22000.
The invention also provides a preparation method of the poly diphenyl ether polymer compound, which comprises the following steps:
Carrying out click polymerization reaction on a two-end aromatic Die nitrogen monomer shown in a formula (II) and a two-end biphenyl ether alkyne monomer shown in a formula (III) under the action of a click polymerization catalyst to obtain the poly (biphenyl ether) polymer;
wherein R in formula (II) is Any one of them.
The preparation method provided by the invention is prepared by efficiently carrying out click reaction on the two-end aromatic Die nitrogen monomer and the two-end biphenyl ether alkyne monomer, and has the advantages of simple process, no intermediate product, mild reaction condition and high reaction efficiency.
Preferably, the two-terminal aromatic Die nitrogen monomer is obtained by the following process: 4,4' -dimethylbiphenyl, paraxylene or metaxylene are used as raw materials, and react with NBS (N-bromosuccinimide) under an initiator (such as dibenzoyl peroxide) to generate benzyl bromide, and nucleophilic substitution reaction of the benzyl bromide and sodium azide is carried out to obtain the two-end aromatic Die nitrogen monomer.
4,4' -Dimethylbiphenyl, paraxylene and metaxylene are cheap and easy to obtain, and the cost is low.
More preferably, the molar ratio of dibenzoyl peroxide, raw material and NBS is 1 (30-60) (80-120).
More preferably, the temperature of the reaction of the raw material with NBS is 70-80 ℃ and the time is 1-5 h.
More preferably, a solvent, such as CCl 4, is also present in the reaction system of the feedstock with NBS, where the concentration of the feedstock is 0.4 to 0.5g/L.
More preferably, the molar ratio of benzyl bromide to sodium azide is 1 (2-3).
More preferably, the reaction of the raw material and NBS further comprises the step of reduced pressure evaporation and silica gel column chromatography.
Specifically, the reaction process of the raw materials and NBS is as follows: mixing the raw materials, N-bromosuccinimide and dibenzoyl peroxide, adding CCl 4 solvent under the condition of nitrogen, stirring, condensing and refluxing at 70-80 ℃, and reacting overnight (reacting for 12 h); the solvent was removed by evaporation under reduced pressure after filtration, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (10:1/mL: mL) as eluent to give the benzyl bromide.
More preferably, the nucleophilic substitution reaction is carried out at a temperature of 55 to 65 ℃ for a time of 1 to 5 hours.
More preferably, a solvent such as DMF is also present in the reaction system of the nucleophilic substitution reaction, and the concentration of benzyl bromide in the reaction system is 0.4 to 0.5g/L.
More preferably, the nucleophilic substitution reaction further comprises the steps of extraction, washing, drying, reduced pressure evaporation and silica gel column chromatography.
Specifically, the nucleophilic substitution reaction process is as follows: adding benzyl bromide and sodium azide into a reactor, adding DMF solvent under nitrogen atmosphere, stirring at 55-65 ℃ for reaction overnight, pouring deionized water after the reaction liquid is cooled to room temperature, extracting with diethyl ether, collecting an organic layer, washing with saturated saline water, drying with anhydrous magnesium sulfate, filtering, removing diethyl ether solvent by evaporation under reduced pressure, and carrying out silica gel column chromatography on the product by using petroleum ether/dichloromethane (10:1/mL: mL) as eluent to obtain the two-terminal aromatic Die nitrogen monomer.
Preferably, the two-terminal biphenyl ether alkyne monomer is obtained by the following process: and reacting the 4,4' -dihydroxybiphenyl with bromopropyne in the presence of potassium carbonate and a solvent to obtain the di-end biphenyl ether alkyne monomer.
More preferably, the molar ratio of 4,4' dihydroxybiphenyl, 3-bromopropyne and potassium carbonate is =10 (10-40): 30-50.
More preferably, the reaction temperature is 30 to 80 ℃ and the reaction time is 1 to 5 hours.
More preferably, the solvent is DMF (N, N-dimethylformamide), and the concentration of 4,4' -dihydroxybiphenyl in the reaction system is 45-55 g/L.
More preferably, the reaction further comprises the steps of filtering, extracting, washing, drying and evaporating under reduced pressure.
Specifically, the two-terminal biphenyl ether alkyne monomer is obtained through the following processes: mixing 4,4' dihydroxybiphenyl, 3-bromopropyne, anhydrous potassium carbonate and DMF solvent, introducing nitrogen, stirring at 30-80 ℃ for overnight reaction, tracking the reaction by thin plate chromatography TLC, stopping the reaction after the reaction is completed, filtering to remove potassium carbonate, pouring the reaction solution into deionized water, extracting 3 times by methanol, collecting an organic layer, washing twice by saturated saline water, adding anhydrous magnesium sulfate for drying, and removing the solvent under reduced pressure to obtain a white solid product of the diphenyl ether alkyne monomer.
Preferably, the click polymerization catalyst is a monovalent copper salt catalyst.
Preferably, the molar ratio of the click polymerization catalyst to the two-terminal aromatic Die nitrogen monomer is (1-3): 50.
Preferably, the temperature of the click polymerization reaction is 30-80 ℃.
Preferably, the molar ratio of the two-terminal aryl Die nitrogen monomer to the two-terminal biphenyl ether alkyne monomer is 1:1.
Specifically, the click polymerization reaction process is as follows: sequentially adding a two-end biphenyl ether alkyne monomer and a two-end aryl Die nitrogen monomer into a reactor, adding a DMSO solvent to dissolve the two-end biphenyl ether alkyne monomer and the two-end aryl Die nitrogen monomer, and stirring for a period of time at 30-80 ℃ in a nitrogen atmosphere. Copper sulfate pentahydrate and sodium ascorbate were dissolved in deionized water, and added dropwise to the reaction solution with constant pressure drop leak, and reacted overnight (reaction 12 h). After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with deionized water for three times, filtering, dissolving a filter cake in DMSO solvent, pouring into mixed solution of methanol and water, precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain the poly (diphenyl ether) polymer.
The application of the poly diphenyl ether polymer compound in preparing the high temperature resistant photoluminescent device is also in the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
The poly (biphenyl ether) polymer compound provided by the invention not only has excellent photoluminescence performance in a high-temperature environment, but also can be dissolved in various organic solvents, and has better processability.
The preparation method provided by the invention is prepared by efficiently carrying out click reaction on the two-end aromatic Die nitrogen monomer and the two-end biphenyl ether alkyne monomer, and has the advantages of simple process, no intermediate product, mild reaction condition and high reaction efficiency.
Drawings
FIG. 1 is a 1 H NMR comparison of a di-terminal biphenyl ether alkyne monomer III, as well as its starting material, intermediate in DMSO.
Fig. 2 is a DSC curve of PT1, PT2, PT 3.
Fig. 3 is a TG diagram of PT1, PT2, PT 3.
Fig. 4 is a DTG diagram of PT1, PT2, PT 3.
FIG. 5 is a graph of the excitation emission spectrum of PT 2.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
(1) The two-end aromatic Die nitrogen monomer II-1 is prepared by the following preparation method:
9.1130g (50 mmol) of 4,4' -dimethylbiphenyl, 17.7984g (100 mmol) of N-bromosuccinimide and 0.2422g (1 mmol) of dibenzoyl peroxide are placed in a three-neck flask equipped with a reflux condenser, 200mL of CCl 4 solvent is added under nitrogen, and the mixture is stirred, condensed and refluxed at 78 ℃ for overnight reaction. After filtration, the solvent was removed by evaporation under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/dichloromethane (10:1/mL: mL) as eluent to give 12.6100g of 4,4' -dibromomethylbiphenyl as a white solid powder in 74.2% yield;
1.70g (5 mmol) of 4,4 '-dibromomethylbiphenyl, 0.780g (12 mmol) of sodium azide are added into a three-neck flask with a rotor, 20mL of DMF solvent is added under nitrogen atmosphere, the mixture is stirred and reacted overnight at 60 ℃, deionized water (30 mL) is poured after the reaction solution is cooled to room temperature, the mixture is extracted with diethyl ether (3X 20 mL), an organic layer is collected, the mixture is washed with saturated saline (3X 20 mL) and dried over anhydrous magnesium sulfate, the diethyl ether solvent is removed by reduced pressure evaporation after filtration, and the product is purified by silica gel column chromatography with petroleum ether/dichloromethane (20:1/mL: mL) as eluent to obtain 1.230g of white solid 4,4' -biphenyl dibenzyl azide which is the two-end aromatic Die nitrogen monomer II-1 with the yield of 93.1 percent.
(2) The two-end aromatic Die nitrogen monomer II-2 is prepared by the following preparation method:
17.80g N-bromosuccinimide (NBS, 100 mmol), 5.3082g paraxylene (50 mmol), 0.2422g dibenzoyl peroxide (BPO, 1 mmol) and 60mL carbon tetrachloride were added into a 250mL three-neck flask equipped with a rotor, the suspension was filtered after condensing and refluxing at 78 ℃ for 12 hours under nitrogen atmosphere, the filtrate was concentrated, and the filtrate was recrystallized with methanol to obtain 8.2312g of white crystals (1, 4-bis- (bromomethylbenzene) with a yield of 62.4%;
2.6395g (10 mmol) of 1, 4-bis- (bromomethylbenzene) and 1.430g (22 mmol) of sodium azide are added into a 100mL three-neck flask with a rotor, 20mL of DMF is added under nitrogen atmosphere, the reaction is carried out for 10h at 60 ℃, the reaction solution is poured into 100mL of deionized water, 30mL of anhydrous diethyl ether is used for extraction three times, an organic phase is collected, then 100mL of saturated saline solution is used for washing, anhydrous magnesium sulfate is used for drying, and after filtration, the solvent is evaporated to obtain 1.7216g of oily liquid p-diazidobenzyl, namely the two-terminal aromatic Die nitrogen monomer II-2, and the yield is 91.5%.
(3) The two-end aromatic Die nitrogen monomer II-3 is prepared by the following preparation method:
Into a 250mL three-necked flask equipped with a rotor was charged 17.80g N-bromosuccinimide (NBS, 100 mmol), 5.3083g meta-xylene (50 mmol), 0.2422g dibenzoyl peroxide (BPO, 1 mmol) and 60mL carbon tetrachloride, and the mixture was refluxed at 78℃for 12 hours under a nitrogen atmosphere. The suspension was filtered, the filtrate was concentrated, and recrystallized from methanol to give 6.8342g of white crystals (1, 3-bis- (bromomethylbenzene) in 51.8% yield;
2.6395g (10 mmol) of 1, 3-bis- (bromomethylbenzene) and 1.430g (22 mmol) of sodium azide are added into a 100mL three-neck flask with a rotor, 20mL of DMF is added under nitrogen atmosphere, the reaction is carried out for 10h at 60 ℃, the reaction solution is poured into 100mL of deionized water, 30mL of anhydrous diethyl ether is used for extraction three times, an organic phase is collected, then 100mL of saturated saline solution is used for washing, anhydrous magnesium sulfate is used for drying, and after filtration, the solvent is evaporated to obtain 1.7126g of oily liquid m-diazepin, namely the two-terminal aromatic Die nitrogen monomer II-3, and the yield is 91.0%.
(4) The two-end biphenyl ether alkyne monomer III is prepared by the following preparation method:
2.5027g (10 mmol) of 4,4' -dihydroxybiphenyl, 3.5688g (30 mmol) of 3-bromopropyne, 5.5284g (40 mmol) of anhydrous potassium carbonate and 50mL of anhydrous DMF solvent are added into a 100mL three-neck flask, nitrogen is introduced, the reaction is stirred at the temperature of 60 ℃ for overnight, thin plate chromatography TLC is used for tracking the reaction, the reaction is stopped after the reaction is completed, the potassium carbonate is removed by filtration, the reaction solution is poured into 100mL of deionized water, 50mL of ethyl acetate is used for extraction for 3 times, an organic layer is collected, the organic layer is washed twice by saturated saline, anhydrous magnesium sulfate is added for drying, and the solvent is removed under reduced pressure to obtain 2.7838g of white solid product, namely the biphenyl ether alkyne monomer III with the yield of 85.3 percent.
FIG. 1 is a 1 H NMR comparison of a di-terminal biphenyl ether alkyne monomer III and starting materials, intermediates, at CDCl 3. From the figure, the hydrogen of the raw material-OH disappears at 10.54ppm, characteristic absorption peaks of the hydrogen in-CH 2 and C≡CH respectively appear at 4.90ppm and 3.64ppm, and the area percentage of four peaks in the product 1,2,3 and 4 is 2:2:2:1, which is consistent with the theoretical value, so that the preparation of the two-terminal biphenyl ether alkyne monomer III is successfully carried out.
Example 1
A poly (biphenyl ether) polymer compound (marked as PT 1) is prepared by the following steps:
0.2623g (1 mmol) of the two-terminal biphenyl ether alkyne monomer III and 0.2643g (1 mmol) of 4,4' -biphenyl dibenzyl azide (two-terminal aryl Die nitrogen monomer II-1) are put into a three-neck flask with a rotor, 20mL of DMSO solvent is added to dissolve the two-neck flask, and the two-neck flask is stirred for 30min at 45 ℃ under nitrogen atmosphere. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10mL of deionized water and added dropwise to the reaction solution with constant pressure drop leak and reacted overnight. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20mL of deionized water for three times, filtering, dissolving a filter cake in DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/v: v), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.3995g of light yellow solid powder which is PT1, wherein the yield is 75.9 percent
Example 2
A poly (biphenyl ether) polymer compound (marked as PT 2) is prepared by the following steps:
0.2623g (1 mmol) of the two-terminal biphenyl ether alkyne monomer III and 0.1882g (1 mmol) of the p-diazepine benzyl (two-terminal aryl Die nitrogen monomer II-2) are placed in a three-neck flask with a rotor, 20mL of DMSO solvent is added to dissolve the monomers, and the mixture is stirred for 30min at 45 ℃ under nitrogen atmosphere. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10mL of deionized water and added dropwise to the reaction solution with constant pressure drop leak and reacted overnight. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20mL of deionized water for three times, filtering, dissolving a filter cake in DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/mL: mL), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.3312g of light yellow solid powder which is PT2, and the yield is 73.5%.
Example 3
A poly (biphenyl ether) polymer compound (marked as PT 3) is prepared by the following steps:
0.2623g (1 mmol) of the two-terminal biphenyl ether alkyne monomer III and 0.1882g (1 mmol) of the m-diazepin (two-terminal aryl Die nitrogen monomer II-3) are placed in a three-neck flask with a rotor, 20mL of DMSO solvent is added to dissolve the monomers, and the mixture is stirred for 30min at 45 ℃ under nitrogen atmosphere. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10mL of deionized water and added dropwise to the reaction solution with constant pressure drop leak and reacted overnight. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20mL of deionized water for three times, filtering, dissolving a filter cake in DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/mL: mL), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.3563g of light yellow solid powder which is PT3, wherein the yield is 79.1%.
Performance testing
(1) Determination of molecular weight and distribution coefficient
The molecular weights and distribution coefficients of PT1, PT2, PT3 provided in examples 1 to 3 were measured, and the results are shown in table 1.
TABLE 1 molecular weights and distribution coefficients of PT1, PT2 and PT3 provided in examples 1 to 3
| Category(s) | Mn | Mw | PDI |
| PT1 | 14328 | 18770 | 1.31 |
| PT2 | 15939 | 21518 | 1.35 |
| PT3 | 15229 | 21320 | 1.40 |
(2) Thermal performance testing
The thermal properties of PT1, PT2, PT3 provided in examples 1 to 3 were tested.
Tg test process and conditions are that the temperature is raised from 40 ℃ to 300 ℃ at a heating rate of 10 ℃/min, then the temperature is lowered to 40 ℃ at a cooling rate of 30 ℃/min, and finally the temperature is raised to 250 ℃ at a heating rate of 10 ℃/min.
And under the nitrogen atmosphere, the thermal weight loss test shows that the protective gas flow is 30mL/min, the purge gas flow is 30mL/min, and the temperature is increased from 40 ℃ to 600 ℃ at the heating rate of 10 ℃/min, so that the thermal weight loss spectrum of the sample is obtained.
Fig. 2 shows DSC curves of PT1, PT2, PT3, fig. 3 shows TG diagrams of PT1, PT2, PT3, fig. 4 shows DTG diagrams of PT1, PT2, PT3, and table 2 shows thermal performance test results of PT1, PT2, PT3, and it is clear from fig. 2, fig. 3, fig. 4, and table 2 that PT1, PT2, PT3 have better high temperature resistance.
TABLE 2 thermal performance test results for PT1, PT2, PT3
| Polymer | Tg(℃) | Td5％(℃) | Tdmax(℃) | 600 ℃ Residual ratio (%) |
| Example 1PT1 | 152.4 | 350.5 | 365.8 | 63.1 |
| EXAMPLE 2PT2 | 142.3 | 348.3 | 368.9 | 60.1 |
| EXAMPLE 3PT3 | 132.8 | 341.9 | 360.5 | 63.2 |
(3) Luminescence property test
FIG. 5 shows the excitation emission spectrum of the product PT2 of example 2, and it is clear from FIG. 5 that PT2 exhibits an emission peak of equal intensity at 430nm under excitation at 348nm, and that Stokes shift is 82nm, and blue fluorescence is emitted. The emission spectra of the product PT2 in example 1 and the product PT3 in example 3 under excitation of 348nm wavelength are basically the same as those of the product PT2 in example 2, and the poly diphenyl ether polymer compound has good thermal stability, and the molecular structure is not easy to be damaged under high temperature condition, namely, the poly diphenyl ether polymer compound has stable photoluminescence performance in high temperature environment.
(4) Dissolution test
Testing the solubility of the two-end biphenyl ether alkyne monomer III and PT1, PT2 and PT3 prepared in the embodiments 1-3, wherein the testing process comprises accurately weighing 0.05g of the to-be-tested object by an electronic balance, adding the to-be-tested object into 5mL of solvent, continuously stirring at normal temperature, standing for a certain time, taking an upper solution for analysis at a certain interval after solid phase is completely precipitated, ending the test after the concentration of the two is basically consistent, and comparing the solubility, and defining the to-be-tested object to be completely dissolved if no to-be-tested object remains; if the residual quantity of the object to be detected is 1% -90%, defining that the object to be detected is partially dissolved; if the residual amount of the object to be measured is more than 90%, it is defined as insoluble.
The test results are shown in Table 3, wherein "+" indicates dissolution, "-" indicates partial dissolution, and "-" indicates insolubility. From Table 3, it can be seen that the two-terminal biphenyl ether alkyne monomer III can be well dissolved in aprotic solvents with slightly stronger polarity, while PT1 to PT3 are relatively better in aprotic solvents with stronger polarity, and the main reason for the better solubility is probably because the monomer III has flexible methylene and alkoxy groups, and the flexibility of a molecular chain is improved after the monomer III is introduced into a main chain.
TABLE 3 dissolution test results of PT1, PT2 and PT3
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. A polybiphenyl ether polymer compound is characterized by having a structure represented by the formula (I):
wherein R is N is an integer of 32 to 48.
2. The poly (biphenyl ether) polymer compound according to claim 1, wherein n is an integer of 35 to 45.
3. The poly (biphenyl ether) polymer compound according to claim 1, wherein the average molecular weight of the poly (biphenyl ether) polymer compound is 15000 to 22000.
4. A method for producing the poly (biphenyl ether) polymer compound according to any one of claims 1 to 3, comprising the steps of:
Carrying out click polymerization reaction on a two-end aromatic Die nitrogen monomer shown in a formula (II) and a two-end biphenyl ether alkyne monomer shown in a formula (III) under the action of a click polymerization catalyst to obtain the poly (biphenyl ether) polymer;
wherein R in formula (II) is
5. The method for producing a polybiphenyl ether polymer as claimed in claim 4, wherein the click polymerization catalyst is a monovalent copper salt catalyst.
6. The method for producing a polybiphenyl ether polymer as claimed in claim 4, wherein the molar ratio of the catalyst for click polymerization to the nitrogen monomer of the aromatic Die with two end groups is = (1 to 3) 50.
7. The method for producing a polymer compound according to claim 4, wherein the reaction temperature of the click polymerization reaction is 30 to 80 ℃.
8. The method for producing a polybiphenyl ether polymer as claimed in claim 4, wherein the molar ratio of the two-terminal aromatic Die nitrogen monomer to the two-terminal biphenyl ether alkyne monomer=1:1.
9. Use of the poly (biphenyl ether) polymer compound prepared by any one of claims 1-3 or any one of claims 4-8 in the preparation of high temperature resistant photoluminescent devices.
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