CN105924644A - Polyarylsulfone and preparation method thereof - Google Patents
Polyarylsulfone and preparation method thereof Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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Abstract
The invention provides polyarylsulfone and a preparation method thereof. Polyarylsulfone has a structure shown in the formula (I) or a structure shown in the formula (II). By making the structure shown in the formula (I) or the structure shown in the formula (II) have the structure shown as Ar, prepared polyarylsulfone is high in glass-transition temperature (Tg can reach 365 DEG C), capable of being dissolved in halogenated alkane such as chloroform and dichloromethane and aprotic solvents such as NMP at the room temperature, and capable of being dissolved in aprotic polar solvents such as DMF and DMAc after being heated. Thus, the processability of polyarylsulfone obtained through the method becomes better. In addition, the preparation method is simple, the raw material source is wide, and industrial production can be achieved.
Description
Technical field
The present invention relates to polymer arts, particularly relate to a kind of polyarylsulfone (PAS) and preparation method thereof.
Background technology
Polyarylsulfone (PAS) is a novel amorphous aromatic series fire resistant resin of class, it is excellent that it has temperature classification height, mechanical property, electrical property and radiation resistance, the advantages such as endurance, fire-retardant, impact resistance, creep resistant, it is especially suitable for use as high-performance compound resin matrix and superengineering plastics, there is purposes widely at many high-technology fields such as aerospace, electronic information, the energy, become a big focus of macromolecular material research field.
In recent years, along with new and high technology develops further, the requirement to polyarylsulfone (PAS) material is more and more higher, higher with physical modification research and development temperature classification by chemistry, processes the most novel polyarylsulfone (PAS) and polyaryl ether sulphone resin is a most active problem.The more polyarylsulfone (PAS) of existing application mainly has Udel, Radel etc., Tg(glass transition temperature) is respectively 185 DEG C and 220 DEG C, and life-time service temperature is up to 150 DEG C and 190 DEG C, when temperature is more than TgAfter, the hydraulic performance decline of material is quickly.
McGill University reports a kind of polyarylsulfone (PAS) polymer containing benzimidazolone on ACS Macro Lett, and its glass transition temperature, up to 348 DEG C, dissolves in NMP, is partly dissolved in chloroform,
Polymer architecture is as follows:
The introducing of imidazoles can improve polymer Tg greatly and improve the thermostability of polymer.What this monomer was used in PAEK prepares in formula, and e.g., Chinese patent ZL 201310440208.0 discloses a kind of aromatic polyketones containing glyoxaline structure, Tg up to 326 DEG C, but, polymer solubility is the best.Polymer formulae is
Wherein X is oxygen or sulphur atom.
Chinese patent ZL 201310440106.0 also discloses a kind of poly (aryl ether ketone) copolymer containing glyoxaline structure, and the glass transition temperature of modified polyarylether ketone may be up to 270 DEG C, and 5% thermal weight loss temperature may be up to 541 DEG C, and 600 DEG C of carbon yields can reach 70.7%.By introducing new structure, the dissolubility of party thing can be improved so that it is 1, the halogenated hydrocarbons such as 1-dichloroethanes, vinyl trichloride and DMF, DMAc, NMP have preferable dissolubility.Copolymer structure formula is:
At present, reduce its difficulty of processing in a solvent often through being dissolved by macromolecular material, but, the dissolubility of polyarylsulfone (PAS) is the most bad.So, obtain that a kind of not only dissolubility is good but also heat-resist polyarylsulfone (PAS) is to be presently required to solve the technical problem that.
Summary of the invention
In view of this, the technical problem to be solved is to provide a kind of polyarylsulfone (PAS) and preparation method thereof, and the polyarylsulfone (PAS) that the present invention provides dissolubility in a solvent is good, and glass transition temperature is high.
The invention provides a kind of polyarylsulfone (PAS), there is formula (I) structure or formula (II) structure,
Described Ar is formula (Ar-1) or formula (Ar-2)；
Wherein, A1And A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2It is asynchronously H；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Described Ar' is selected from from Third monomer H-Ar'-H, described H-Ar'-H to be had the aromatic of two active function groups or has the heteroaromatic compound of two active function groups；
Described n is the integer of >=2；
Described m is the integer of >=2.
Preferably, described R3Selected from H, phenyl and 4-fluorophenyl, 4-chlorphenyl, 4-aminophenyl or 4-nitrobenzophenone.
Preferably, described R4Selected from H, phenyl and 4-fluorophenyl, 4-chlorphenyl, 4-aminophenyl or 4-nitrobenzophenone.
Preferably, having the active function groups in the aromatic of two active function groups described in is phenolic hydroxyl group or amido；
Active function groups in the described heteroaromatic compound with two active function groups is phenolic hydroxyl group or amido.
nullPreferably，Described H-Ar'-H is selected from H-Ar-H、Hydroquinone、4,4'-dihydroxybiphenyl、4,4'-dihydroxy benzophenone、4,4'-dihydroxydiphenylsulisomer、4,4'-dihydroxy diphenyl ether、4,4'-dihydroxy diphenyl sulfide、 2,Double (4-hydroxy phenyl) propane of 2-、4,4'-(hexafluoroisopropyli,ene) bis-phenol、4,4'-(1,4-phenylene diisopropyl) biphenol、3,Double (4-hydroxy phenyl)-1 (the 3H)-isobenzofuranone of 3-、3,Double (4-hydroxy phenyl) phthalimidine of 3'-、6-(2-hydroxyphenyl)-piperazine-3-(6H)-one、6-(4-hydroxyphenyl)-piperazine-3-(6H)-one、4-(4-hydroxy phenyl)-2,3-phthalazone、2-hydroxycarbazole、3-hydroxycarbazole、9,9-bis-(4-hydroxy phenyl) fluorenes、6,The double triptycene diphenol of 13-、2,5-triptycene diphenol、5,5'-is double (2-4-(hydroxy phenyl)-benzimidazole) or 2,Double (4-the hydroxyphenoxy)-4'-(2 of 6-,3,4,5,6-pentapheneyl phenyl) benzophenone.
Present invention also offers the preparation method of polyarylsulfone (PAS) shown in a kind of formula (I), including:
By H-Ar-H, formula (III) compound, catalyst, water entrainer and solvent hybrid reaction, obtain polyarylsulfone (PAS) shown in formula (I),
Ar in described H-Ar-H is formula (Ar-1) or formula (Ar-2)；
Wherein, A1With A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2It is asynchronously H；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Wherein, X is halogen or NO2。
Preferably, one or more during described solvent is N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, DMF, N,N-dimethylacetamide, sulfolane, methylimidazole ketone and diphenyl sulphone (DPS).
Preferably, described catalyst is carbonate, preferably the one in potassium carbonate, sodium carbonate, sodium bicarbonate and calcium carbonate and several.
Present invention also offers the preparation method of polyarylsulfone (PAS) shown in a kind of formula (II), including:
By H-Ar-H, formula (III) compound, H-Ar'-H, catalyst, water entrainer and solvent hybrid reaction, obtain polyarylsulfone (PAS) shown in formula (I),
Ar in described H-Ar-H is formula (Ar-1) or formula (Ar-2)；
Wherein, A1With A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2It is asynchronously H；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Wherein, X is halogen or NO2；
Described H-Ar'-H is selected from having the aromatic of two active function groups or having the heteroaromatic compound of two active function groups.
Preferably, described first aprotic solvent addition is 8wt%～40wt% for making solid content.
Compared with prior art, the polyarylsulfone (PAS) that the present invention provides, there is formula (I) structure or formula (II) structure, wherein, by making formula (I) structure or formula (II) structure have the structure shown in Ar, make the polyarylsulfone (PAS) not only glass transition temperature prepared high, and its in a solvent dissolubility might as well, and then the polyarylsulfone (PAS) processing characteristics making the present invention obtain improves, test result indicate that, the glass transition temperature of the polyarylsulfone (PAS) that the present invention provides may be up to 365 DEG C, it is at room temperature dissolvable in water chloroform, in the aprotic solvent such as halogenated alkane and NMP such as dichloromethane, DMF it is dissolvable in water after heating, the aprotic polar solvents such as DMAc.Additionally, the preparation method that the present invention provides is simple, raw material sources are extensive, can realize industrialized production.
Accompanying drawing explanation
Fig. 1 is the DSC secondary temperature elevation curve chart of the polyarylsulfone (PAS) shown in formula (I-a) that the embodiment of the present invention 1 prepares；
Fig. 2 is the thermogravimetric analysis figure of the polyarylsulfone (PAS) shown in formula (I-a) that the embodiment of the present invention 1 prepares.
Detailed description of the invention
The invention provides a kind of polyarylsulfone (PAS), there is formula (I) structure or formula (II) structure,
Described Ar is formula (Ar-1) or formula (Ar-2)；
Wherein, A1With A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2It is asynchronously H；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Described Ar' is selected from from Third monomer H-Ar'-H, described H-Ar'-H to be had the aromatic of two active function groups or has the heteroaromatic compound of two active function groups；
Described n is the integer of >=2；
Described m is the integer of >=2.
According to the present invention, described A1It is preferably O, described A2It is preferably O.
According to the present invention, described R1It is preferably H, NH2、NO2, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl or neopentyl, more preferably NH2、NO2, methyl, ethyl or propyl group.
According to the present invention, described R1It is preferably H, NH2、NO2, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl or neopentyl, more preferably NH2、NO2, methyl, ethyl or propyl group.
According to the present invention, described R2It is preferably H, NH2、NO2, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl or neopentyl, more preferably NH2、NO2, methyl, ethyl or propyl group.Wherein, described R1And R2It is asynchronously H.
According to the present invention, described R3It is preferably the aryl of H, C10～C30 or the aryl of the substituted aryl of C10～C30, more preferably H, C15～C20 or the substituted aryl of C15～C20；More specifically, described R3Selected from H, phenyl and 4-fluorophenyl, 4-chlorphenyl, 4-aminophenyl or 4-nitrobenzophenone.
According to the present invention, described R4It is preferably the aryl of H, C10～C30 or the aryl of the substituted aryl of C10～C30, more preferably H, C15～C20 or the substituted aryl of C15～C20；More specifically, described R4Selected from H, phenyl and 4-fluorophenyl, 4-chlorphenyl, 4-aminophenyl or 4-nitrobenzophenone.Wherein, described R3And R4It is H time preferably different.
According to the present invention, described Ar' is selected from from Third monomer H-Ar'-H, described H-Ar'-H to be had the aromatic of two active function groups or has the heteroaromatic compound of two active function groups；Wherein, the carbon number of described aromatic is preferably 6～80, more preferably 10～60, most preferably 15～50, most preferably 30～40；The carbon number of described heteroaromatic compound is preferably 5～80, more preferably 10～60, most preferably 15～50, most preferably 30～40；Described active function groups be two active function groups in phenolic hydroxyl group or amido, and compound can be same functional group or different functional groups；nullMore specifically，Described H-Ar'-H is selected from H-Ar-H、Hydroquinone、4,4'-dihydroxybiphenyl、4,4'-dihydroxy benzophenone、4,4'-dihydroxydiphenylsulisomer、4,4'-dihydroxy diphenyl ether、4,4'-dihydroxy diphenyl sulfide、2,Double (4-hydroxy phenyl) propane of 2-、4,4'-(hexafluoroisopropyli,ene) bis-phenol、4,4'-(1,4-phenylene diisopropyl) biphenol、3,Double (4-hydroxy phenyl)-1 (the 3H)-isobenzofuranone of 3-、3,Double (4-hydroxy phenyl) phthalimidine of 3'-、6-(2-hydroxyphenyl)-piperazine-3-(6H)-one、6-(4-hydroxyphenyl)-piperazine-3-(6H)-one、4-(4-hydroxy phenyl)-2,3-phthalazone、2-hydroxycarbazole、3-hydroxycarbazole、9,9-bis-(4-hydroxy phenyl) fluorenes、6,The double triptycene diphenol of 13-、2,5-triptycene diphenol、5,5'-is double (2-4-(hydroxy phenyl)-benzimidazole) or 2,Double (4-the hydroxyphenoxy)-4'-(2 of 6-,3,4,5,6-pentapheneyl phenyl) benzophenone.
According to the present invention, described n is preferably the integer of >=2, more preferably 3≤n≤200, most preferably 5≤n≤100, most preferably 10≤n≤50；M is preferably the integer of >=2, more preferably 3≤m≤200, most preferably 5≤m≤100, most preferably 10≤m≤50.
More specifically, described polyarylsulfone (PAS) is formula (I-a), formula (I-b), formula (I-c), formula (I-d), formula (II-a), formula (II-b) or formula (II-c).
Wherein, n is the integer of >=2, and m is the integer of >=2.
The polyarylsulfone (PAS) that the present invention provides, there is formula (I) structure or formula (II) structure, wherein, by making formula (I) structure or formula (II) structure have the structure shown in Ar, make the polyarylsulfone (PAS) not only glass transition temperature prepared high, and its in a solvent dissolubility might as well, and then the polyarylsulfone (PAS) processing characteristics that the present invention is obtained improves.
Present invention also offers the preparation method of polyarylsulfone (PAS) shown in a kind of formula (I), including:
By H-Ar-H, formula (III) compound, water entrainer, catalysts and solvents hybrid reaction, obtain polyarylsulfone (PAS) shown in formula (I),
Ar in described H-Ar-H is formula (Ar-1) or formula (Ar-2)；
Wherein, A1And A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2It is asynchronously H；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Wherein, X is halogen or NO2。
According to the present invention, in described H-Ar-H, A1、A2、R1、R2、R3And R4The middle range of choice is identical with the range of choice of the substituent group in polyarylsulfone (PAS) shown in above formula (I)；In described formula (III), its X is preferably F, Cl, Br or NO2；Described solvent is preferably non-protonic solvent, concrete, described solvent is preferably one or more in N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, DMF, N,N-dimethylacetamide, sulfolane, methylimidazole ketone and diphenyl sulphone (DPS)；Described catalyst is preferably carbonate, more preferably one or both in calcium carbonate and potassium carbonate；The present invention does not has particular/special requirement to the source of each raw material yet, and those skilled in the art can directly buy or make by oneself.The mol ratio of described H-Ar-H and formula (III) compound is preferably 1:(1～1.01)；Described H-Ar-H is preferably 1:(1～5 with the mol ratio of carbonate), more preferably 1:(1～3), most preferably 1:(1～2)；The addition of described solvent preferably makes the solid content of reaction system be 8wt%～40wt%, more preferably 15wt%～35wt%, most preferably 18wt%～30wt%.
And preferably carry out to react, the present invention the most first by H-Ar-H, formula (III) compound, water entrainer, catalysts and solvents mixing azeotropic water removing, the mixed liquor after obtaining except water；Then by except the mixed liquor reacting by heating after water, polyarylsulfone (PAS) is obtained；Wherein, described water entrainer is preferably toluene, described is preferably 110～130 DEG C except the temperature of water, described is preferably 2～4 hours except the time of water；The temperature of described reacting by heating is preferably 130～300 DEG C, more preferably 150～250 DEG C, most preferably 190～220 DEG C.
So that the polyarylsulfone (PAS) arrived is purer, the polyarylsulfone (PAS) solvent obtained after reacting by heating is preferably diluted by the present invention, is subsequently adding precipitant precipitation, obtains sulfone compound after purification.Wherein, this solvent is preferably one or more in N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, DMF, N,N-dimethylacetamide, sulfolane, methylimidazole ketone and diphenyl sulphone (DPS), it can be the same or different with anti-solvent-applied, there is no special restriction；And the addition of solvent preferably makes the solid content of reaction system be 5～10%, more preferably 8%～10%；The precipitant that described precipitant is well known to those skilled in the art, there is no special restriction, the present invention is preferably one or more in water, ethanol, acetic acid, hydrochloric acid, the mixed solution of more preferably three kinds, the present invention is the most unrestricted to the ratio of three, can be arbitrary proportion mixing.
Present invention also offers the preparation method of polyarylsulfone (PAS) shown in a kind of formula (II), including:
By H-Ar-H, formula (III) compound, H-Ar'-H, water entrainer, catalysts and solvents hybrid reaction, obtain polyarylsulfone (PAS) shown in formula (I),
Ar in described H-Ar-H is formula (Ar-1) or formula (Ar-2)；
Wherein, A1With A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2It is asynchronously H；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Wherein, X is halogen or NO2；
Described H-Ar'-H is selected from having the aromatic of two active function groups or having the heteroaromatic compound of two active function groups.
According to the present invention, in described H-Ar-H, A1、A2、R1、R2、R3And R4The middle range of choice is identical with the range of choice of the substituent group in polyarylsulfone (PAS) shown in above formula (I)；In described formula (III), its X is preferably F, Cl, Br or NO2；In described H-Ar'-H, Ar' selects identical with the Ar' selection described in polyarylsulfone (PAS) shown in formula (II)；Described solvent is preferably non-protonic solvent, concrete, described solvent is preferably one or more in N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, DMF, N,N-dimethylacetamide, sulfolane, methylimidazole ketone and diphenyl sulphone (DPS)；Described catalyst is preferably carbonate, more preferably the one in potassium carbonate, sodium carbonate, sodium bicarbonate and calcium carbonate and several, most preferably one or both in calcium carbonate and potassium carbonate；The present invention does not has particular/special requirement to the source of each raw material yet, and those skilled in the art can directly buy or make by oneself.The mol ratio of described H-Ar-H and formula (III) compound is preferably 1:(1～1.01)；The mol ratio of described H-Ar-H and formula (III) compound is preferably 1:(1～1.01)；Described H-Ar'-H is preferably 1:(1～5 with the mol ratio of carbonate), more preferably 1:(1～3), most preferably 1:(1～2)；The addition of described solvent preferably makes the solid content of reaction system be 8wt%～40wt%, more preferably 15wt%～35wt%, most preferably 18wt%～30wt%.
And preferably carry out to react, the present invention is the most first by H-Ar-H, formula (III) compound, H-Ar'-H, water entrainer, catalysts and solvents mixing azeotropic water removing, the mixed liquor after obtaining except water；Then by except the mixed liquor reacting by heating after water, polyarylsulfone (PAS) is obtained；Wherein, described water entrainer is preferably toluene, described is preferably 110～130 DEG C except the temperature of water, described is preferably 2～4 hours except the time of water；The temperature of described reacting by heating is preferably 130～300 DEG C, more preferably 150～250 DEG C, most preferably 190～220 DEG C.
So that the polyarylsulfone (PAS) arrived is purer, the polyarylsulfone (PAS) solvent obtained after reacting by heating is preferably diluted by the present invention, is subsequently adding precipitant precipitation, obtains sulfone compound after purification.Wherein, this solvent is preferably one or more in N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, DMF, N,N-dimethylacetamide, sulfolane, methylimidazole ketone and diphenyl sulphone (DPS), it can be the same or different with anti-solvent-applied, there is no special restriction；And the addition of solvent preferably makes the solid content of reaction system be 5～10wt%, more preferably 8～10wt%；The precipitant that described precipitant is well known to those skilled in the art, there is no special restriction, the present invention is preferably one or more in water, ethanol, acetic acid, hydrochloric acid, the mixed solution of more preferably three kinds, the present invention is the most unrestricted to the ratio of three, can be arbitrary proportion mixing.
The preparation method of the polyarylsulfone (PAS) that the present invention provides, obtained by just H-Ar-H, formula (III) compound, catalysts and solvents hybrid reaction, or H-Ar-H, formula (III) compound, H-Ar'-H, catalysts and solvents hybrid reaction are obtained, this preparation method is simple, raw material sources are extensive, low cost, the not only glass transition temperature of the polymer obtained is high, and its dissolubility might as well in a solvent；There is prospects for commercial application widely.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment 1
1.622g (0.01mol) dimethylbenzimidazole ketone (DmHBI) it is sequentially added in 100ml three neck round bottom flask, 2.543g (0.01mol) difluorodiphenyl sulfone (DFS), 2.763g potassium carbonate, 20g sulfolane and 20ml toluene, it is heated to 130 DEG C of azeotropic water removings, insulation 2h, heat up and remove toluene, continue to be heated to 210 DEG C, reaction 5h, cooling, add the dilution of 20ml dimethyl acetylamide, at ethanol, water and the mixed solution of acetic acid precipitate, after precipitate filters, deionized water extraction 12h is used in apparatus,Soxhlet's, remove inorganic salt and reaction dissolvent, it is dried, obtain the polyarylsulfone (PAS) shown in formula (I-a),
Its reaction equation is as follows:
The polyarylsulfone (PAS) shown in the differential scanning calorimetry formula (I-a) to obtaining in embodiment 1 is utilized to test, obtain its DSC secondary temperature elevation curve chart, as shown in Figure 1, Fig. 1 is the DSC secondary temperature elevation curve chart of the polyarylsulfone (PAS) shown in formula (I-a) that the embodiment of the present invention 1 prepares, as shown in Figure 1, its Tg is 365 DEG C, illustrates that this polyarylsulfone (PAS) has higher heat resisting temperature.
The polyarylsulfone (PAS) shown in the thermogravimetric analyzer formula (I-a) to obtaining in embodiment 1 is utilized to test, obtain its thermogravimetric analysis figure, as in figure 2 it is shown, the thermogravimetric analysis figure of the polyarylsulfone (PAS) shown in formula (I-a) that Fig. 2 is the embodiment of the present invention 1 to be prepared；As shown in Figure 2, its 5% thermal weight loss temperature is up to 470 DEG C, and 800 DEG C of carbon yields are 42.0%, illustrates that the thermal decomposition performance of this polyarylsulfone (PAS) is good, has higher ablation resistance.
Polyarylsulfone (PAS) shown in the formula (I-a) obtained is carried out solubility property test, and its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
Table 1
Embodiment 2
null1.482g (0.01mol) 5-methyl benzimidazolone (mHBI) it is sequentially added in 100ml three neck round bottom flask、2.543g (0.01mol) difluorodiphenyl sulfone (DFS)、1.590g potassium carbonate、12.5g N-cyclohexyl pyrrolidone (CHP) and 15ml toluene，It is heated to 150 DEG C，Insulation 2h，Azeotropic water removing，Heat up and remove toluene，Continue to be heated to 190 DEG C，Reaction 4.5h，It is again heated to 205 DEG C，Reaction 2h，Cooling，Add the dilution of 10ml dimethyl acetylamide，At ethanol、Water and the mixed solution of hydrochloric acid precipitate，After precipitate filters，Deionized water extraction 15h is used in apparatus,Soxhlet's，Remove inorganic salt and reaction dissolvent，It is dried，Obtain the polyarylsulfone (PAS) shown in formula (I-b)，
Its reaction equation is as follows:
Polyarylsulfone (PAS) shown in the formula (I-b) obtained in embodiment 2 is carried out glass transition temperature test, and obtaining its Tg is 325 DEG C.
Polyarylsulfone (PAS) shown in the formula (I-b) obtained is carried out solubility property test, and its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
Embodiment 3
0.811g 5 it is sequentially added in 100ml three neck round bottom flask, 6-dimethylbenzimidazole ketone (DmHBI), 0.672g benzimidazolone (HBI), 2.543g difluorodiphenyl sulfone (DFS), 2.763g potassium carbonate, 0.500g calcium carbonate, 22g sulfolane and 18ml toluene, it is heated to 130 DEG C, insulation 2h, azeotropic water removing, heat up and remove toluene, continue to be heated to 200 DEG C, reaction 3.5h, cooling, add the dilution of 20ml dimethyl acetylamide, at ethanol, water and the mixed solution of acetic acid precipitate, after precipitate filters, deionized water extraction 12h is used in apparatus,Soxhlet's, remove inorganic salt and reaction dissolvent, it is dried, obtain the polyarylsulfone (PAS) copolymer shown in formula (II-a), its reaction equation is as follows:
Polyarylsulfone (PAS) shown in the formula (II-a) obtained in embodiment 3 is carried out glass transition temperature test, and obtaining its Tg is 360 DEG C.
Polyarylsulfone (PAS) shown in the formula (II-a) obtained is carried out solubility property test, and its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
Embodiment 4
1.184g 4 it is sequentially added in 100ml three neck round bottom flask, 5-imidazole diphenyl ketone, 0.550g hydroquinone, 2.543g difluorodiphenyl sulfone (DFS), 2.763g potassium carbonate, 1.500g calcium carbonate, 25g sulfolane and 18ml toluene, it is heated to 130 DEG C, insulation 2h, azeotropic water removing, heat up and remove toluene, continue to be heated to 185 DEG C, reaction 7h, cooling, add the dilution of 20g sulfolane, at ethanol, water and the mixed solution of hydrochloric acid precipitate, after precipitate filters, deionized water extraction 24h is used in apparatus,Soxhlet's, remove inorganic salt and reaction dissolvent, it is dried, obtain the polyarylether sulfone copolymer shown in formula (II-b),
Its reaction equation is as follows:
Polyarylsulfone (PAS) shown in the formula (II-b) obtained in embodiment 4 is carried out glass transition temperature test, and obtaining its Tg is 235 DEG C.
Polyarylsulfone (PAS) shown in the formula (II-b) obtained is carried out solubility property test, and result shows, its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
Embodiment 5
1.502g 2-mercaptobenzimidazole (MBI) it is sequentially added in 100ml three neck round bottom flask, 2.543g difluorodiphenyl sulfone (DFS), 2.763g potassium carbonate, 1.500g calcium carbonate, 25g sulfolane and 12ml toluene, it is heated to 130 DEG C, insulation 2h, azeotropic water removing, heat up and remove toluene, continue to be heated to 175 DEG C, reaction 3h, cooling, add the dilution of 20ml dimethyl acetylamide, at ethanol, water and the mixed solution of acetic acid precipitate, after precipitate filters, deionized water extraction 12h is used in apparatus,Soxhlet's, remove inorganic salt and reaction dissolvent, it is dried, obtain the polyarylsulfone (PAS) shown in formula (I-c), its reaction equation is as follows:
Polyarylsulfone (PAS) shown in the formula (I-c) obtained in embodiment 5 is carried out glass transition temperature test, and obtaining its Tg is 205 DEG C.
Polyarylsulfone (PAS) shown in the formula (I-c) obtained is carried out solubility property test, and its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
Embodiment 6
0.896g 5-Nitro-2-benzimidazolinone (nHBI) it is sequentially added in 100ml three neck round bottom flask, 1.256g dichloro diphenyl sulfone (DCS), 1.000g potassium carbonate, 0.550g calcium carbonate, 10ml sulfolane and 12ml toluene, it is heated to 130 DEG C, insulation 2h, azeotropic water removing, heat up and remove toluene, continue to be heated to 185 DEG C, reaction 7h, cooling, add the dilution of 12ml dimethyl acetylamide, at ethanol, water and the mixed solution of acetic acid precipitate, after precipitate filters, deionized water extraction 12h is used in apparatus,Soxhlet's, remove inorganic salt and reaction dissolvent, it is dried, obtain the polyarylsulfone (PAS) shown in formula (I-d), its reaction equation is as follows:
Polyarylsulfone (PAS) shown in the formula (I-d) obtained in embodiment 6 is carried out glass transition temperature test, and obtaining its Tg is 322 DEG C.
Polyarylsulfone (PAS) shown in the formula (I-d) obtained is carried out solubility property test, and its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
Embodiment 7
null0.746g 5-Amino-2-benzimidazolinone (aHBI) it is sequentially added in 100ml three neck round bottom flask、2.543g difluorodiphenyl sulfone (DFS)、1.592g phenolphthalein，1.590g potassium carbonate、12.5g N-cyclohexyl pyrrolidone and 12ml toluene，It is heated to 150 DEG C，Insulation 2h，Azeotropic water removing，Heat up and remove toluene，Continue to be heated to 190 DEG C，Reaction 4.5h，It is again heated to 205 DEG C，Reaction 2h，Cooling，Add the dilution of 10ml N-cyclohexyl pyrrolidone，At ethanol、Water and the mixed solution of acetic acid precipitate，After precipitate filters，Deionized water extraction 12h is used in apparatus,Soxhlet's，Remove inorganic salt and reaction dissolvent，It is dried，Obtain the polyarylether sulfone copolymer shown in formula (II-c)，Its reaction equation is as follows:
Polyarylsulfone (PAS) shown in the formula (II-c) obtained in embodiment 7 is carried out glass transition temperature test, and obtaining its Tg is 320 DEG C.
Polyarylsulfone (PAS) shown in the formula (II-c) obtained is carried out solubility property test, and its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
Comparative example 1
0.276g benzimidazolone (HBI) it is sequentially added in 25ml three neck round bottom flask, 0.51g difluorodiphenyl sulfone (DFS), 0.28g potassium carbonate, 0.20g calcium carbonate, 1.6g sulfolane and 3ml water entrainer 1-chlorobenzene, it is heated to 130 DEG C, insulation 2h, azeotropic water removing, heat up and remove 1-chlorobenzene, continue to be heated to 200 DEG C, reaction 2h, add 2g sulfolane, 200 DEG C of insulation reaction 2.5h, dilute in dichloromethane after cooling, pour 100ml methanol and precipitation in the mixed solution (v/v:100:1) of acetic acid into, after precipitate filters, deionized water extraction 12h is used in apparatus,Soxhlet's, remove inorganic salt and reaction dissolvent, it is dried, obtain polymer formulae as shown in I-c:
The polyarylsulfone (PAS) obtained in embodiment 8 is carried out glass transition temperature test, and obtaining its Tg is 348 DEG C.
Polyarylsulfone (PAS) shown in the formula (I-c) obtained is carried out solubility property test, and its method of testing, for accurately to weigh testing sample 5mg, is dissolved in 1mL solvent.++ represent and be completely dissolved；+ represent heating solvable ,+-represent swellable ,-represent almost totally insoluble.Solvent abbreviations: DMF is N,N-dimethylformamide；DMAc is DMAC N,N' dimethyl acetamide；NMP is N-Methyl pyrrolidone；THF is oxolane, and test result is shown in Table 1, the solubility property test result of the polyarylsulfone (PAS) that table 1 is embodiment and prepared by comparative example.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a polyarylsulfone (PAS), has formula (I) structure or formula (II) structure,
Described Ar is formula (Ar-1) or formula (Ar-2)；
Wherein, A1And A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2No
It is H simultaneously；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Described Ar' is selected from from Third monomer H-Ar'-H, described H-Ar'-H has two active function groups
Aromatic or there is the heteroaromatic compound of two active function groups；
Described n is the integer of >=2；
Described m is the integer of >=2.
Polymer the most according to claim 1, it is characterised in that described R3Selected from H, phenyl with
4-fluorophenyl, 4-chlorphenyl, 4-aminophenyl or 4-nitrobenzophenone.
Polymer the most according to claim 1, it is characterised in that described R4Selected from H, phenyl with
4-fluorophenyl, 4-chlorphenyl, 4-aminophenyl or 4-nitrobenzophenone.
Polymer the most according to claim 1, it is characterised in that described in there are two active official's energy
Active function groups in the aromatic of group is phenolic hydroxyl group or amido；
Active function groups in the described heteroaromatic compound with two active function groups be phenolic hydroxyl group or
Amido.
Polymer the most according to claim 1, it is characterised in that described H-Ar'-H selected from H-Ar-H,
Hydroquinone, 4,4' dihydroxy diphenyl, 4,4'-dihydroxy benzophenone, 4,4' dihydroxydiphenyl sulfone, 4,4'-bis-
Dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl sulfide, 2,2-double (4-hydroxy phenyl) propane, 4,4'-(hexafluoro isopropyl
Fork) bis-phenol, 4,4'-(1,4-phenylene diisopropyl) biphenol, double (4-hydroxy phenyl)-1 (the 3H)-different benzo of 3,3-
Furanone, 3,3'-double (4-hydroxy phenyl) phthalimidine, 6-(2-hydroxyphenyl)-piperazine-3-(6H)-one, 6-(4-
Hydroxyphenyl)-piperazine-3-(6H)-one, 4-(4-hydroxy phenyl)-phthalazone, 2-hydroxycarbazole, 3-hydroxyl
Base carbazole, 9,9-bis-(4-hydroxy phenyl) fluorenes, 6,13-double triptycene diphenol, 2,5-triptycene diphenol, 5,5'-
Double (4-the hydroxyphenoxy)-4'-(2,3,4,5,6-pentapheneyl phenyl) of double (2-4-(hydroxy phenyl)-benzimidazoles) or 2,6-
Benzophenone.
6. a preparation method for polyarylsulfone (PAS) shown in formula (I), including:
By H-Ar-H, formula (III) compound, catalyst, water entrainer and solvent hybrid reaction, obtain formula
(I) polyarylsulfone (PAS) shown in,
Ar in described H-Ar-H is formula (Ar-1) or formula (Ar-2)；
Wherein, A1With A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2No
It is H simultaneously；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Wherein, X is halogen or NO2。
Preparation method the most according to claim 6, it is characterised in that described solvent is N-methyl pyrrole
Pyrrolidone, N-cyclohexyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, ring fourth
One or more in sulfone, methylimidazole ketone and diphenyl sulphone (DPS).
Preparation method the most according to claim 6, it is characterised in that described catalyst is carbonate,
It is preferably the one in potassium carbonate, sodium carbonate, sodium bicarbonate and calcium carbonate and several.
9. a preparation method for polyarylsulfone (PAS) shown in formula (II), including:
By H-Ar-H, formula (III) compound, H-Ar'-H, catalyst, water entrainer and solvent hybrid reaction,
Obtain polyarylsulfone (PAS) shown in formula (I),
Ar in described H-Ar-H is formula (Ar-1) or formula (Ar-2)；
Wherein, A1With A2Independently selected from S or O；
Described R1And R2Independently selected from H, NH2、NO2Or the alkyl of C1～C5, and R1And R2No
It is H simultaneously；
Described R3And R4Aryl or the substituted aryl of C6～C50 independently selected from H, C6～C50；
Wherein, X is halogen or NO2；
Described H-Ar'-H is selected from having the aromatic of two active function groups or having two active officials
The heteroaromatic compound that can roll into a ball.
Preparation method the most according to claim 9, it is characterised in that described first non-proton molten
Agent addition is 8wt%～40wt% for making solid content.
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| CN113667124A (en) * | 2021-08-02 | 2021-11-19 | 江苏傲伦达科技实业股份有限公司 | Tert-butyl-containing polyarylsulfone resin and preparation method thereof |
| CN115417990A (en) * | 2022-08-18 | 2022-12-02 | 宁夏清研高分子新材料有限公司 | High-fluidity polysulfone polymer and preparation method thereof |
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| US4279637A (en) * | 1979-06-02 | 1981-07-21 | Velsicol Chemical Corporation | Herbicidal N-substituted 4-imidazolin-2-ones |
| US20130085251A1 (en) * | 2011-09-29 | 2013-04-04 | The Royal Institution For The Advancement Of Learning / Mcgill University | Polymers and copolymers containing 2h-benzimidazol-2-one moieties |
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| US4279637A (en) * | 1979-06-02 | 1981-07-21 | Velsicol Chemical Corporation | Herbicidal N-substituted 4-imidazolin-2-ones |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113667124A (en) * | 2021-08-02 | 2021-11-19 | 江苏傲伦达科技实业股份有限公司 | Tert-butyl-containing polyarylsulfone resin and preparation method thereof |
| CN115417990A (en) * | 2022-08-18 | 2022-12-02 | 宁夏清研高分子新材料有限公司 | High-fluidity polysulfone polymer and preparation method thereof |
| CN115417990B (en) * | 2022-08-18 | 2023-08-29 | 宁夏清研高分子新材料有限公司 | High-fluidity polysulfone polymer and preparation method thereof |
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