CN102924710A - Polyaryletherketone resin with carbazole ring in main chain and preparation method thereof - Google Patents
Polyaryletherketone resin with carbazole ring in main chain and preparation method thereof Download PDFInfo
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- CN102924710A CN102924710A CN2012104076871A CN201210407687A CN102924710A CN 102924710 A CN102924710 A CN 102924710A CN 2012104076871 A CN2012104076871 A CN 2012104076871A CN 201210407687 A CN201210407687 A CN 201210407687A CN 102924710 A CN102924710 A CN 102924710A
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Abstract
The technical issues of ketone-grouped resin and preparation method thereof of the main chain containing carbazole ring structure, it is limited to solve existing ketone-grouped resin heat resistance, limits its application. The constitutional repeating unit of ketone-grouped resin of the invention is
Weight average molecular weight is 20000-75000, in formula, R is methyl, ethyl, normal-butyl, isobutyl group, n-hexyl, trifluoromethyl, propylene oxide base, acrylic, propinyl, phenyl, 4- fluorophenyl, 4- trifluoromethyl, 4- ethenylphenyl, 4- alkynyl phenyl or 4- cyano-phenyl; The branched alkyl of R1, R2, R3, R4 H, Br, I, C1-C6 or the straight chained alkyl of C1-C6, Ar are that biphenol monomer removes the residue after double hydroxyls. Not only glass transition temperature is up to 293 DEG C to ketone-grouped resin of the main chain prepared by the present invention containing carbazole ring structure, and intrinsic viscosity is moderate, and dissolution processability is good, and toughness, excellent in mechanical performance are widely used.
Description
Technical field
The present invention relates to a kind of main chain and contain ketone-grouped resin of carbazole ring structure and preparation method thereof, belong to polymeric material field.
Background technology
Polyaryletherketone has excellent mechanical mechanics property, the resist chemical of anti-solvent performance, radioresistance and flame retardant resistance etc. as a kind of thermoplastic engineering plastic with special construction.Since last century, the seventies ICI company released commercial PEEK resin, in order further to enlarge the Application Areas of ketone-grouped resin, investigator's many-sided trial of comforming carried out study on the modification to it, wherein, the high thermal resistance of ketone-grouped resin and solvability are one of more fields of research.
Chinese patent CN85108751 discloses with phenolphthalein biphenol monomer and 4, the unformed polyaryletherketone (PEK-C) that the polycondensation of 4 '-Diflurodiphenyketone monomer makes, and its structural formula is as follows:
；
In this patent, although large Cardo side group is given the certain rigidity of polymer molecular chain and good dissolving processing characteristics in the phenolphthalein biphenol monomer, the second-order transition temperature of polymkeric substance is 228 ℃, but the development along with science and technology, people are in the urgent need to having the more polymkeric substance of high heat resistance, and the second-order transition temperature of this polyaryletherketone has limited its range of application to a certain extent.
Summary of the invention
In order further to improve the high thermal resistance of ketone-grouped resin, enlarge its Application Areas, the invention provides a kind of main chain and contain ketone-grouped resin of carbazole ring structure and preparation method thereof.
The invention provides the ketone-grouped resin that a kind of main chain contains carbazole ring structure, the weight-average molecular weight of this ketone-grouped resin is 20000-75000, and repeated structural unit is as follows:
In the formula, R is methyl, ethyl, normal-butyl, isobutyl-, n-hexyl, trifluoromethyl, propylene oxide base, propenyl, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-alkynyl phenyl or 4-cyano-phenyl;
R
1, R
2, R
3, R
4Identical or different, R
1, R
2, R
3, R
4Be H, Br, I, C
1-C
6Branched-chain alkyl or C
1-C
6Straight chained alkyl;
Ar is a kind of in the following structure:
,
,
,
,
,
,
,
,
Perhaps
The polymolecularity that the prepared main chain of the present invention contains the ketone-grouped resin of carbazole ring structure is preferably 1.0-2.5.
Described R is preferably methyl, ethyl, normal-butyl, propenyl, propylene oxide base, phenyl or 4-alkynyl phenyl.
Described Ar is preferably
Perhaps
The present invention also provides a kind of main chain to contain the preparation method of the ketone-grouped resin of carbazole ring structure, in inert atmosphere, with catalyzer, band aqua, solvent, mol ratio is active two halogen ketone carbazole monomers and the biphenol monomer of 1.0-1.1, join in the reaction unit, 100 ℃-150 ℃ band water that reflux steam the band aqua, be warming up to 151 ℃-320 ℃ and carry out polycondensation, namely obtain the ketone-grouped resin that main chain contains carbazole ring structure;
The structural formula of described biphenol monomer is
,
,
,
,
,
,
,
,
Perhaps
The structural formula of the two halogen ketone carbazole monomers of described activity is:
In the formula, R is methyl, ethyl, normal-butyl, isobutyl-, n-hexyl, trifluoromethyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl;
R
1, R
2, R
3, R
4Identical or different, R
1, R
2, R
3, R
4Be H, Br, I, C
1-C
6Branched-chain alkyl or C
1-C
6Straight chained alkyl;
X is F or Cl.
Described solvent is preferably tetramethylene sulfone, DMI, N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE or N, N '-dimethyl sulfoxide (DMSO).
Described catalyzer is preferably anhydrous alkali metal carbonate, more preferably Anhydrous potassium carbonate.
Described band aqua is preferably alkylbenzene or halogeno-benzene, more preferably dimethylbenzene or toluene.
Described backflow is preferably 2-20 hour with the time of water, more preferably 2-10 hour.
Described polycondensation temperature is preferably 151 ℃-220 ℃, and the time is preferably 3-30 hour.
Beneficial effect of the present invention:
(1) the present invention is take the resistance to elevated temperatures that strengthens the main chain rigidity and improve polymkeric substance as purpose, and active two halogen one monomers and the biphenol monomer that will contain carbazole ring structure carry out the high temperature nucleophilic condensation polymerization, prepare the ketone-grouped resin that main chain contains carbazole ring structure;
(2) the main chain of the present invention ketone-grouped resin that contains carbazole ring structure has resistance to elevated temperatures, second-order transition temperature is up to 293 ℃, 5% thermal weight loss temperature is 445 ℃, and has good dissolving processibility, under 25 ℃ of conditions, take NMP as solvent, change polymerization temperature and time, record the intrinsic viscosity of ketone-grouped resin at 0.30000-2.0000dl/g, the ketone-grouped resin that main chain of the present invention contains carbazole ring structure also has good mechanical property, and the polymolecularity of resin is 1.0-2.5;
(3) main chain of the present invention contains in the structure of ketone-grouped resin of carbazole ring structure, when R is propylene oxide base, allyl group, 4-ethynyl phenyl, can prepares by the mode that photo-crosslinking solidifies or heat cross-linking solidifies and have more photocuring or the thermofixation ketone-grouped resin of high heat resistance; When being allyl group such as R, the Tg of the ketone-grouped resin after the part heat cross-linking solidifies is 265 ℃;
(4) main chain of the present invention contains the preparation method of the ketone-grouped resin of carbazole ring structure, and technique is simple, and cost is low, is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is the infrared spectrogram that the main chain of the embodiment of the invention 1 preparation contains the ketone-grouped resin of carbazole ring structure;
Fig. 2 is the nmr spectrum that the main chain of the embodiment of the invention 1 preparation contains the ketone-grouped resin of carbazole ring structure;
Fig. 3 is the DSC curve that the main chain of the embodiment of the invention 1 preparation contains the ketone-grouped resin of carbazole ring structure.
Embodiment
The invention provides the ketone-grouped resin that a kind of main chain contains carbazole ring structure, the weight-average molecular weight of this ketone-grouped resin is 20000-75000, and polymolecularity is 1.0-2.5, and repeated structural unit is as follows:
In the formula, R is methyl, ethyl, normal-butyl, isobutyl-, n-hexyl, trifluoromethyl, propylene oxide base, propenyl, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl;
R
1, R
2, R
3, R
4Identical or different, R
1, R
2, R
3, R
4Be H, Br, I, C
1-C
6Branched-chain alkyl or C
1-C
6Straight chained alkyl;
Ar is a kind of in the following structure:
Described R is preferably methyl, ethyl, normal-butyl, propenyl, propylene oxide base, phenyl or 4-alkynyl phenyl.
Described Ar is preferably
Perhaps
The present invention also provides a kind of main chain to contain the preparation method of the ketone-grouped resin of carbazole ring structure, in the inert atmosphere, be active two halogen ketone carbazole monomers and the biphenol monomer of 1.0-1.1 with mol ratio, consumption is the 1.08-1.15 carbonate catalyzer doubly of biphenol monomer mole number, consumption is the 1.85-3.0 reaction solvent doubly of theoretical polymer quality, consumption is that the 0.50-1.50 band aqua doubly of reaction solvent volume joins in the reaction unit, 90 ℃-150 ℃ band water that reflux steamed the band aqua in 2-20 hour, being warming up to 151 ℃-320 ℃ carried out polycondensation 3-50 hour, in polycondensation reaction system, add thinner dilution dissolving, leave standstill, in alcohols, settle in water or the alcohol-water mixture, repeatedly boil eccysis salt through deionized water, be dried to constant weight in the vacuum drying oven, namely obtain the ketone-grouped resin that main chain contains carbazole ring structure;
The structural formula of described biphenol monomer is
,
,
,
,
,
,
,
,
Perhaps
The structural formula of the two halogen ketone carbazole monomers of described activity is:
In the formula, R is methyl, ethyl, normal-butyl, isobutyl-, n-hexyl, trifluoromethyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl;
R
1, R
2, R
3, R
4Identical or different, R
1, R
2, R
3, R
4Be H, Br, I, C
1-C
6Branched-chain alkyl or C
1-C
6Straight chained alkyl;
X is F or Cl.
Described solvent is so long as the high temperature aprotic solvent can both contain for the preparation of main chain of the present invention the ketone-grouped resin of carbazole ring structure, be preferably tetramethylene sulfone, 1,3-dimethyl-2-imidazolinone, N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE or N, N '-dimethyl sulfoxide (DMSO).
Described catalyzer is preferably anhydrous alkali metal carbonate, more preferably Anhydrous potassium carbonate.
Described band aqua is preferably alkylbenzene or halogeno-benzene, more preferably dimethylbenzene or toluene; When the laboratory prepares, can according to circumstances add to be with aqua fully a bit in order to be with water, if industrial production does not then need to add, in order to avoid cause the solvent waste.
Described thinner is preferably tetramethylene sulfone, DMI, dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc) or n-formyl sarcolysine base pyrrolidone (NMP).
The described backflow band water time is preferably 2-10 hour.
Described polycondensation temperature is preferably 151 ℃-220 ℃, and the time is preferably 3-30 hour.
Described time of repose was preferably more than 6 minutes.
The present invention prepares main chain, and to contain the chemical equation of ketone-grouped resin of carbazole ring structure as follows:
The present invention also provides the preparation method of the two halogen ketone carbazole monomers of a kind of activity,
(1) when R be methyl, ethyl, normal-butyl, isobutyl-, n-hexyl, trifluoromethyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, the 4-ethenylphenyl, when 4-ethynyl phenyl or 4-cyano-phenyl, the preparation method is:
The Fu Shi acylation reaction occurs in chemical compounds I and compound III, obtains compounds Ⅳ;
Compounds Ⅳ and methyl iodide, methyl-sulfate, monobromethane, bromination of n-butane, isobutane bromide, bromine hexyl, CF3I, bromopropylene oxide, bromo propylene, bromo propine, iodobenzene, to fluorine iodobenzene, 4-(trifluoromethyl) iodobenzene, to bromstyrol, to bromobenzene acetylene or to ioxynil substitution reaction on the N position occurs, obtain the compound V, i.e. active two halogen ketone carbazole monomers;
Chemical compounds I, compound III, compounds Ⅳ, compound V represent respectively the compound with following structural formula:
；
Preparation process is as follows:
(2) when R be methyl, ethyl, normal-butyl, isobutyl-, n-hexyl or trifluoromethyl, the preparation method can also for:
Substitution reaction on the N position occurs in chemical compounds I and methyl iodide, methyl-sulfate, monobromethane, bromination of n-butane, isobutane bromide, bromine hexyl or CF3I, obtains compound ii;
The Fu Shi acylation reaction occurs in compound ii and III, obtains the compound V, i.e. active two halogen ketone carbazole monomers;
Chemical compounds I, compound ii, compound III, compound V represent respectively the compound with following structural formula:
；
Preparation process is as follows:
Described N position substitution reaction and Fu Shi acylation reaction are technology well known in the art, and used catalyzer is AlCl in the Fu Shi acylation reaction
3, solvent for use can be non-polar solvent, neutral solvent or polar solvent, such as dithiocarbonic anhydride, methylene dichloride, trichloromethane, oil of mirbane.The purification of the two halogen ketone carbazole monomers of its lytic activity can be selected ethyl acetate, chloroform, acetone, tetrahydrofuran (THF) isopolarity solvent to carry out the recrystallization purification or be adopted column chromatography method to purify.
The structure that the main chain that the present invention obtains contains the ketone-grouped resin of carbazole ring structure is confirmed through nucleus magnetic resonance and Infrared spectroscopy.
The ketone-grouped resin that the prepared main chain of the present invention contains carbazole ring structure carries out the test of thermal property and mechanical property after via the solution-cast film forming, and the glass transition temperature Tg of polymkeric substance of the present invention is recorded by the dsc measurement instrument of METTLER company.
For making those skilled in the art better understand technical scheme of the present invention, further specify the present invention below in conjunction with specific embodiment and accompanying drawing.
Material all can be by commercially available among the embodiment.
Embodiment 1
In conjunction with Fig. 1-3 explanation embodiment 1
Main chain contains the preparation method of the ketone-grouped resin of N-ethyl carbazole ring structure:
(1) preparation of 3.6-two (4-fluoro benzoyl)-N-ethyl carbazole monomer
With N-ethyl carbazole 19.52g (0.10mol) and CHCl
3Solvent 150mL is added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 33.35g (0.25mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 26.00mL (0.22mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 12h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction, revolve inspissation and contract and use re-crystallizing in ethyl acetate, obtain 3.6-two (4-fluoro benzoyl)-N-ethyl carbazole monomer;
(2) in the nitrogen atmosphere; with phenolphthalein 3.1833 grams (0.01mol); 3.6-two (4-fluoro benzoyl)-N-ethyl carbazole monomers, 4.3945 grams (0.01mol); Anhydrous potassium carbonate 1.5899 grams (0.015mol); dimethylbenzene 15mL; tetramethylene sulfone 10.5mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature being raised to 150 ℃ reacts and the water that generates is taken out of by refluxing xylene and told by water trap; 2.5 after hour; and then be warming up to when between 210 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; keep this temperature after 4 hours; the cooling reaction solution also adds N,N-DIMETHYLACETAMIDE (DMAc) dilution; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain clean ketone-grouped resin; yield is 98%, and the structure of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Fig. 1 is the IR spectrogram that the main chain of the embodiment of the invention 1 preparation contains the ketone-grouped resin of N-ethyl carbazole ring structure, and as can be seen from the figure, there is the C=O absorption peak at 1650 places, and there is the C-O-C absorption peak at 1244 places;
Fig. 2 be the main chain of the embodiment of the invention 1 preparation NMR that contains the ketone-grouped resin of N-ethyl carbazole ring structure (
1H) figure, a among Fig. 2, b, c, d, e, f, g, h, i, j, k, l are respectively the polymer architecture formula
In the hydrogen atom of corresponding representative;
Can confirm the polymer architecture that the present invention prepares in conjunction with Fig. 1 and Fig. 2.
Fig. 3 is the DSC curve that the main chain of the embodiment of the invention 1 preparation contains the ketone-grouped resin polyaryletherketone of N-ethyl carbazole ring structure, as can be seen from the figure, locate to occur step at 273 ℃, the second-order transition temperature that ketone-grouped resin of the present invention is described is 273 ℃, and CN85108751 is disclosed with Chinese patent
Compare, thermotolerance obviously improves.
Embodiment 2
Main chain contains the preparation method of the ketone-grouped resin of N-methyl carbazole ring structure:
(1) preparation of 3.6-two (4-fluoro benzoyl)-N-methyl carbazole monomers
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 15.36mL (0.13mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising, then with aqueous hydrochloric acid with its cancellation, fully dissolving in the tetrahydrofuran solvent of solid product crude product under the reflux condition of gained after filtering, filtered while hot is fallen silica-gel powder after adding silica-gel powder backflow 4h in the above-mentioned tetrahydrofuran solution afterwards, gained solution obtains 3,6-two (to fluoro benzoyl)-N (H) carbazole after crystallisation by cooling is purified;
With above-mentioned 3,6-two (to fluoro benzoyl)-N (H) carbazole 6.2g (0.015mol) and 0.47g (0.0015mol) Tetrabutyl amonium bromide phase-transfer catalyst are added in the reaction flask that the 70mL toluene solvant is housed, add again stoichiometric ratio in the system and be 4 massfraction and be 50% potassium hydroxide solution, add and drip again 2.10g (0.0165mol) methyl-sulfate after complete, finish reaction behind the reaction 10h under 50 ℃ of conditions afterwards, gained crude product chloroform extraction, organic phase anhydrous sodium sulfate drying after the merging, also use Gossypol recrystallized from chloroform after revolving the inspissation contracting, obtain 3.6-two (4-fluoro benzoyl)-N-methyl carbazole monomers;
(2) in the nitrogen atmosphere; with bisphenol fluorene 3.5041 grams (0.01mol); 3.6-two (4-fluoro benzoyl)-N-methyl carbazole monomers, 4.2543 grams (0.01mol); Anhydrous potassium carbonate 1.5209 grams (0.011mol); toluene 12mL; tetramethylene sulfone 9.53mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature being raised to 115 ℃ reacted 3 hours; in the reaction process water that generates is taken out of by refluxing toluene and told by water trap; and then be warming up to when between 220 ℃ of assurance oligopolymer nucleophilic polycondensation occuring toluene is steamed; keep this temperature after 8 hours; the cooling reaction solution also adds the dimethylacetamide solvent dissolving; long period settles product in deionized water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; the ketone-grouped resin that obtains; yield 97%, the structural formula of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Embodiment 3
Main chain contains the preparation method of the ketone-grouped resin of N-hexyl carbazole ring structure:
(1) preparation of 3.6-two (4-fluoro benzoyl)-N-hexyl carbazole monomers
With N-hexyl carbazole 25.12g (0.10mol) and CHCl
3Solvent 150mL is added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 33.35g (0.25mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 26.00mL (0.22mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 12h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction, revolve inspissation and contract and use re-crystallizing in ethyl acetate, obtain 3.6-two (4-fluoro benzoyl)-N-hexyl carbazole monomers;
(2) in the nitrogen atmosphere; with phenolphthalein 100.0000 grams (0.31mol); 3.6-two (4-fluoro benzoyl)-N-hexyl carbazole monomers, 153.7476 grams (0.031mol); Anhydrous potassium carbonate 47.1262 grams (0.34mol); dimethylbenzene 200mL; tetramethylene sulfone 400mL join be equipped with mechanical stirring and water-taker reaction unit in; under the nitrogen protection temperature is raised to 150 ℃ and after 20 hours, will react the water that generates and be taken out of by refluxing xylene and told by water trap; and then be warming up to when between 210 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; kept this temperature 50 hours; the cooling reaction solution also adds N,N-DIMETHYLACETAMIDE (DMAc) dilution; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain clean ketone-grouped resin, the structure of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Main chain contains the preparation method of the ketone-grouped resin of N-propenyl carbazole ring structure:
(1) preparation of 3.6-two (4-chlorobenzene formacyl)-N-allyl group carbazole monomers
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 15.36mL (0.13mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising, then with aqueous hydrochloric acid with its cancellation.Fully dissolving in the tetrahydrofuran solvent of solid product crude product under the reflux condition of gained after filtering, add in the above-mentioned tetrahydrofuran solution afterwards silica-gel powder refluxed four hours after filtered while hot fall silica-gel powder, gained solution obtains 3,6-two (to fluoro benzoyl)-N (H) carbazole after crystallisation by cooling is purified;
With 3,6-two (to fluoro benzoyl)-N (H) carbazole 6g (0.015mol) and 0.47g (0.0015mol) Tetrabutyl amonium bromide phase-transfer catalyst are added in the reaction flask that the 70mL toluene solvant is housed, add again stoichiometric ratio in the system and be 4 massfraction and be 50% potassium hydroxide solution, add and drip again 2.00g (0.0165mol) bromopropylene after complete, finish afterwards reaction behind the reflux 10h, gained crude product chloroform extraction, organic phase anhydrous sodium sulfate drying after the merging, also use Gossypol recrystallized from chloroform after revolving the inspissation contracting, obtain 3.6-two (4-chlorobenzene formacyl)-N-allyl group carbazole monomers;
(2) in the nitrogen atmosphere; with Resorcinol 11.011 grams (0.1mol); 3.6-two (4-chlorobenzene formacyl)-N-allyl group carbazole monomers, 45.146 grams (0.1mol); Anhydrous potassium carbonate 15.894 grams (0.15mol); toluene 150mL; N; N '-N,N-DIMETHYLACETAMIDE 107.6 mL join be equipped with mechanical stirring and water-taker reaction unit in; under the nitrogen protection temperature is raised to 100 ℃ and reacts 10h; in the reaction process water that generates is taken out of by refluxing toluene and told by water trap; and then be warming up to when between 160 ℃ of assurance oligopolymer nucleophilic polycondensation occuring toluene is steamed; kept this temperature 25 hours; the cooling reaction solution also adds the solvent dimethylformamide dissolving; long period settles product in ethanolic soln after leaving standstill; boil with deionized water and to wash for several times; in 70 ℃ of lower vacuum-dryings to constant weight; obtain ketone-grouped resin; yield 95%, the structural formula of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Embodiment 5
Main chain contains the preparation method of the ketone-grouped resin of N-propylene oxide base carbazole ring structure:
(1) preparation of 3.6-two (4-fluoro benzoyl)-N-propylene oxide base carbazole monomers
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 14.22mL (0.12mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction, revolving inspissation contracts and uses re-crystallizing in ethyl acetate, get product 3,6-two (to fluoro benzoyl)-N (H) carbazole;
With 3,6-two (to fluoro benzoyl)-N (H) carbazole 6g (0.015mol) is dissolved in the 50mL acetone solvent, and then in mentioned solution, add 1.48 g (0.016mol) sodium cyanide catalyzer, slowly in above-mentioned system, add distilled water cancellation end reaction behind the heating reflux reaction 5h, gained crude product chloroform extraction, organic phase anhydrous sodium sulfate drying after the merging, also use Gossypol recrystallized from chloroform after revolving the inspissation contracting, obtain 3.6-two (4-fluoro benzoyl)-N-propylene oxide base carbazole monomers;
(2) in the nitrogen atmosphere; with dihydroxyphenyl propane 2.2829 grams (0.01mol); 3.6-two (4-fluoro benzoyl)-N-propylene oxide base carbazole monomers, 4.6746 grams (0.01mol); Anhydrous potassium carbonate 1.5894 grams (0.015mol); toluene 15mL; dimethyl sulfoxide (DMSO) 11.56 mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 110 ℃ and reacts 3h; in the reaction process water that generates is taken out of by refluxing toluene and told by water trap; and then be warming up to when between 160 ℃ of assurance oligopolymer nucleophilic polycondensation occuring toluene is steamed; keep this temperature 10 hours to required viscosity; the cooling reaction solution also adds the dimethyl sulfoxide solvent dissolving; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 70 ℃ of lower vacuum-dryings to constant weight; obtain ketone-grouped resin; yield 96%, the structural formula of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Embodiment 6
Main chain contains the preparation method of the ketone-grouped resin of N-phenyl carbazole ring structure:
(1) preparation of 3.6-two (4-fluoro benzoyl)-N-phenyl carbazole monomer
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 14.22mL (0.12mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction, revolving inspissation contracts and uses re-crystallizing in ethyl acetate, get product 3,6-two (to fluoro benzoyl)-N (H) carbazole;
Under the nitrogen atmosphere, with 7g (0.017mol) 3,6-two (to fluoro benzoyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 30mLDMF solvent is housed, and then in reaction flask, add iodobenzene 3.81g (0.018mol), cuprous iodide 0.32g (0.0017mol), anhydrous phenanthroline 0.31g (0.0017mol), fill and finish reaction after being warming up to 100 ℃ of reaction 48h after the ventilation, first crude product is filtered, to strip with a large amount of chloroforms again after the washing of gained filtrate, collect organic phase and use anhydrous sodium sulfate drying, carry out column chromatography purification (ethyl acetate/petroleum ether=1:6), obtain 3.6-two (4-fluoro benzoyl)-N-phenyl carbazole monomer after revolving the inspissation contracting;
(2) in the nitrogen atmosphere; with 4; 4 '-dihydroxybiphenyl, 1.8621 grams (0.01mol); 3.6-two (4-fluoro benzoyl)-N-phenyl carbazole monomers, 4.8714 grams (0.01mol); Anhydrous potassium carbonate 1.5894 grams (0.015mol); dimethylbenzene 15mL; N-Methyl pyrrolidone 11.40mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 150 ℃ and reacts 3h; in the reaction process water that generates is taken out of by refluxing xylene and told by water trap; and then be warming up to when between 195 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; kept this temperature 6 hours; the cooling reaction solution also adds the dimethylacetamide solvent dissolving; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain ketone-grouped resin; yield 96%, the structural formula of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Embodiment 7
Main chain contains the preparation method of the ketone-grouped resin of N-(4-fluorophenyl) carbazole ring structure:
(1) preparation of 3.6-two (4-fluoro benzoyl)-N-(4-fluorophenyl) carbazole monomers
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 15.85mL (0.13mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction, revolving inspissation contracts and uses re-crystallizing in ethyl acetate, get 3,6-two (to fluoro benzoyl)-N (H) carbazole;
Under the nitrogen atmosphere, with above-mentioned synthesize 3,6-two (to fluoro benzoyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 40mLNMP solvent is housed, and then in reaction flask, add fluorine iodobenzene 4.00g (0.018mol), cuprous iodide 0.32g (0.0017mol), anhydrous phenanthroline 0.31g (0.0017mol), fill and finish reaction after being warming up to 100 ℃ of reaction 48h after the ventilation, first crude product is filtered, to strip with a large amount of chloroforms again after the washing of gained filtrate, collect organic phase and use anhydrous sodium sulfate drying, carry out the recrystallization purification with methylene dichloride after revolving the inspissation contracting, obtain 3.6-two (4-fluoro benzoyl)-N-(4-fluorophenyl) carbazole monomers;
(2) in the nitrogen atmosphere; with bisphenol fluorene 3.5041 grams (0.01mol); 3.6-two (4-fluoro benzoyl)-N-(4-fluorophenyl) carbazole monomers, 5.0549 grams (0.01mol); Anhydrous potassium carbonate 1.5899 grams (0.015mol); dimethylbenzene 15mL; tetramethylene sulfone 12.05mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 150 ℃ and after 2.5 hours, will react the water that generates and be taken out of by refluxing xylene and told by water trap; and then be warming up to when between 220 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; kept this temperature 6 hours; cooling reaction solution and solubilizing agent N-Methyl pyrrolidone (NMP) dilution; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain clean ketone-grouped resin; yield is 98%, and the structure of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Embodiment 8
Main chain contains the preparation method of the ketone-grouped resin of N-ethynyl phenyl carbazole ring structure:
(1) preparation of 3.6-two (4-fluoro benzoyl)-N-(4-ethynyl phenyl) carbazole monomers
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 15.85mL (0.13mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction, revolving inspissation contracts and uses re-crystallizing in ethyl acetate, get 3,6-two (to fluoro benzoyl)-N (H) carbazole;
Under the nitrogen atmosphere, with above-mentioned synthesize 3,6-two (to fluoro benzoyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 40mLDMSO solvent is housed, and then in reaction flask, add bromobenzene acetylene 3.26g (0.018mol), cuprous iodide 0.32g (0.0017mol), anhydrous phenanthroline 0.31g (0.0017mol), fill and finish reaction after being warming up to 100 ℃ of reaction 48h after the ventilation, first crude product is filtered, to strip with a large amount of chloroforms again after the washing of gained filtrate, collect organic phase and use anhydrous sodium sulfate drying, carry out column chromatography purification (chloroform/sherwood oil=1:5), obtain 3.6-two (4-fluoro benzoyl)-N-(4-ethynyl phenyl) carbazole monomers after revolving the inspissation contracting;
(2) in the nitrogen atmosphere; with hexafluoro bisphenol-a 3.3623 grams (0.01mol); 3.6-two (4-fluoro benzoyl)-N-(4-alkynyl phenyl) carbazole monomers, 5.1152 grams (0.01mol); Anhydrous potassium carbonate 1.5894 grams (0.015mol); toluene 15mL; 1; 3-dimethyl-2-imidazolinone 14.20 mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 110 ℃ and reacts 2.5h; in the reaction process water that generates is taken out of by refluxing toluene and told by water trap; and then be warming up to when between 170 ℃ of assurance oligopolymer nucleophilic polycondensation occuring toluene is steamed; keep this temperature after 10 hours; the cooling reaction solution also adds the N-Methyl pyrrolidone dissolution with solvents; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 100 ℃ of lower vacuum-dryings to constant weight; obtain ketone-grouped resin; yield is greater than 92%, and the structural formula of resin is as follows:
The resin that obtains is carried out relevant characterization, and detected result sees Table 1.
Table 1 is the relevant characterization of the ketone-grouped resin of embodiment of the invention 1-8 gained:
Table 1
In the table, a) be the intrinsic viscosity of polymkeric substance when concentration is 0.5g/dL among the NMP under 25 ℃ of conditions; The second-order transition temperature of polymkeric substance when b) being 10 ℃/minute for the test rate of heating; C) for by DSC polymkeric substance being carried out the second-order transition temperature that the rear gained of three intensifications solidifies rear phase emergencing copolymer; D) be weight-average molecular weight; E) be number-average molecular weight; F) be polymolecularity; Dissolve under "+" expression normal temperature condition; "+-" expression normal temperature condition under swelling; TCE is sym.-tetrachloroethane.
Claims (10)
1. main chain contains the ketone-grouped resin of carbazole ring structure, it is characterized in that, the weight-average molecular weight of this ketone-grouped resin is 20000-75000, and repeated structural unit is as follows:
In the formula, R is methyl, ethyl, normal-butyl, isobutyl-, n-hexyl, trifluoromethyl, propylene oxide base, propenyl, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-alkynyl phenyl or 4-cyano-phenyl;
R
1, R
2, R
3, R
4Identical or different, R
1, R
2, R
3, R
4Be H, Br, I, C
1-C
6Straight chained alkyl or C
1-C
6Branched-chain alkyl;
Ar is a kind of in the following structure:
2. main chain according to claim 1 contains the ketone-grouped resin of carbazole ring structure, it is characterized in that, the polymolecularity of described ketone-grouped resin is 1.0-2.5.
3. main chain according to claim 1 contains the ketone-grouped resin of carbazole ring structure, it is characterized in that, described R is methyl, ethyl, normal-butyl, propenyl, propylene oxide base, phenyl or 4-alkynyl phenyl.
4. main chain according to claim 1 contains the ketone-grouped resin of carbazole ring structure, it is characterized in that, described Ar is
Perhaps
5. main chain contains the preparation method of the ketone-grouped resin of carbazole ring structure, it is characterized in that, in the inert atmosphere, with catalyzer, the band aqua, solvent, mol ratio is that active two halogen ketone carbazole monomers and the biphenol monomer of 1.0-1.1 joins in the reaction unit, and 90 ℃-150 ℃ band water that reflux steam the band aqua, be warming up to 151 ℃-320 ℃ and carry out polycondensation, obtain the ketone-grouped resin that main chain contains carbazole ring structure;
The structural formula of described biphenol monomer is
,
,
,
,
,
,
,
,
Perhaps
The structural formula of the two halogen ketone carbazole monomers of described activity is:
In the formula, R is methyl, ethyl, normal-butyl, isobutyl-, n-hexyl, trifluoromethyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl;
R
1, R
2, R
3, R
4Identical or different, R
1, R
2, R
3, R
4Be H, Br, I, C
1-C
6Straight chained alkyl or C
1-C
6Branched-chain alkyl;
X is F or Cl.
6. main chain according to claim 5 contains the preparation method of the ketone-grouped resin of carbazole ring structure, it is characterized in that, described solvent is tetramethylene sulfone, 1,3-dimethyl-2-imidazolinone, N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE or N, N '-dimethyl sulfoxide (DMSO).
7. main chain according to claim 5 contains the preparation method of the ketone-grouped resin of carbazole ring structure, it is characterized in that, described catalyzer is anhydrous alkali metal carbonate.
8. main chain according to claim 5 contains the preparation method of the ketone-grouped resin of carbazole ring structure, it is characterized in that, described band aqua is alkylbenzene or halogeno-benzene.
9. main chain according to claim 5 contains the preparation method of the ketone-grouped resin of carbazole ring structure, it is characterized in that, described backflow is 2-20 hour with the time of water.
10. main chain according to claim 5 contains the preparation method of the ketone-grouped resin of carbazole ring structure, it is characterized in that, the temperature of described polycondensation is 151 ℃-220 ℃, and the time is 3-30h.
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Cited By (5)
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| CN106674514A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Polyarylether with main chain containing carbazole, preparation method, nanocarbon modified material and composite |
| CN107814926A (en) * | 2017-10-31 | 2018-03-20 | 中国科学院长春应用化学研究所 | A kind of post-processing approach of soluble nitrogenous polyarylether resin |
| WO2020253283A1 (en) * | 2019-06-21 | 2020-12-24 | 江苏英力科技发展有限公司 | Novel diaroyl carbazole compound and use thereof as sensitising agent |
| CN113150265A (en) * | 2021-05-13 | 2021-07-23 | 吉林大学 | Special material for polyaryletherketone ultrathin film and preparation method of polyaryletherketone ultrathin film |
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| CN101274917A (en) * | 2008-05-21 | 2008-10-01 | 吉林大学 | Electroactive group-containing poly(aryl ether ketone)/polyether sulfone cyclic oligomer and preparation thereof |
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| CN106674514A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Polyarylether with main chain containing carbazole, preparation method, nanocarbon modified material and composite |
| CN107814926A (en) * | 2017-10-31 | 2018-03-20 | 中国科学院长春应用化学研究所 | A kind of post-processing approach of soluble nitrogenous polyarylether resin |
| CN107814926B (en) * | 2017-10-31 | 2020-04-21 | 芜湖万隆新材料有限公司 | Post-treatment method of soluble nitrogenous polyarylether resin |
| WO2020253283A1 (en) * | 2019-06-21 | 2020-12-24 | 江苏英力科技发展有限公司 | Novel diaroyl carbazole compound and use thereof as sensitising agent |
| CN113508106A (en) * | 2019-06-21 | 2021-10-15 | 艾坚蒙(安庆)科技发展有限公司 | Photoinitiator composition containing acylcarbazole derivative and carbazolyl oxime ester and application of photoinitiator composition in photocuring composition |
| CN113518774A (en) * | 2019-06-21 | 2021-10-19 | 艾坚蒙(安庆)科技发展有限公司 | Novel diarylacylcarbazole compound and application thereof as sensitizer |
| JP2022528738A (en) * | 2019-06-21 | 2022-06-15 | 艾▲堅▼蒙（安▲慶▼）科技▲発▼展有限公司 | New dialoylcarbazole compounds, and their use as sensitizers |
| CN113518774B (en) * | 2019-06-21 | 2024-10-18 | 艾坚蒙(安庆)科技发展有限公司 | Novel biaryl carbazole compounds and their use as sensitizers |
| CN113150265A (en) * | 2021-05-13 | 2021-07-23 | 吉林大学 | Special material for polyaryletherketone ultrathin film and preparation method of polyaryletherketone ultrathin film |
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