CN1171930C - Preparation method of dichlorophthalein imide and dichlorodiphenylketone or dichlorodiphenylsulfone copolymer - Google Patents
Preparation method of dichlorophthalein imide and dichlorodiphenylketone or dichlorodiphenylsulfone copolymer Download PDFInfo
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- CN1171930C CN1171930C CNB021042691A CN02104269A CN1171930C CN 1171930 C CN1171930 C CN 1171930C CN B021042691 A CNB021042691 A CN B021042691A CN 02104269 A CN02104269 A CN 02104269A CN 1171930 C CN1171930 C CN 1171930C
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Abstract
The present invention belongs to a preparation method of a copolymer of dichlorophthalimide and dichlorobenzophenone or dichloro diphenylsulfone, which comprises the following specific synthesis steps: firstly, dichlorophthalimide and anhydrous sodium sulfide are added into an aprotic solvent according to the molar ratio of 1:2 to react at the temperature of 60DEG C to 80DEG C for 1 to 2 hours; secondly, dichlorobenzophenone or dichloro diphenylsulfone of the molar weight equal to that of the dichlorophthalimide is added to polymerize the dichlorophthalimide and the dichlorobenzophenone or the dichloro diphenylsulfone at the temperature of 140 to 200DEG C for 2 to 12 hours, and methanol is poured in to precipitate out a product. The characteristic viscosity of the obtained polymer is from 0.12 to 0.2 dl/g.
Description
Background technology: the preparation method who the invention belongs to dichlorophthalein imide and two chloro benzophenones or dichloro diphenyl sulfone multipolymer.
Polyimide is as macromolecular material, because its special performance and application prospects thereof and extremely pay attention to, but because synthesis of polyimides is synthetic by dianhydride and diamines usually at present, cost is too high, thereby its application in wider scope is restricted.With the chloro-benzoic anhydride is that raw material need not pass through dianhydride, directly prepares polyimide and can reduce its cost by a relatively large margin.Though polyaryletherketone and polyether sulphone resinoid have been realized commercialization, its thermotolerance is lower.With dichlorophthalein imide and two chloro benzophenones or dichloro diphenyl sulfone copolymerization, both can reduce the cost of polyimide with sulfide effectively, can improve the thermostability of polyethersulfone and polyetherketone again, the novel thermally stable polymer of a class thereby may develop.
Summary of the invention: the preparation method who the purpose of this invention is to provide a kind of dichlorophthalein imide and two chloro benzophenones or dichloro diphenyl sulfone multipolymer.This method is reacted dichlorophthalein imide and sodium sulphite in aprotic solvent under the low temperature, generate the disodium salt of two sulfydryl phthalimides, carries out polymerization with two chloro benzophenones or the dichloro diphenyl sulfone that add then.
The present invention adopts the multipolymer of the synthetic dichlorophthalein imide of following component and two chloro benzophenones or dichloro diphenyl sulfone.
(1) 3 or the 4-chloro-benzoic anhydride:
Two kinds of compounds can be used alone, but also also mix together.
(2) diamine
This diamines is selected from:
(3) 4,4`-two chloro benzophenones or 4, two kinds of compounds of 4`-dichloro diphenyl sulfone can use or mix use separately;
(4) Sodium sulphate anhydrous, 99min
(5) aprotic solvent that uses among the present invention is:
N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc),
Dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP), hexamethyl phosphinylidyne
Amine or tetramethylene sulfone;
Concrete synthesis step is as follows:
Two chloro phthalimides and the Sodium sulphate anhydrous, 99min mol ratio by 1: 2 is joined in the aprotic solvent, 60 ℃～80 ℃ were reacted 1-2 hour, add then and two equimolar two chloro benzophenones of chloro phthalimide or dichloro diphenyl sulfone, at 140～200 ℃ of following polymerization 2-12 hours, pour methyl alcohol into, be settled out product, the resulting polymers limiting viscosity is 0.12～0.2dl/g.
Embodiment is as follows:
Embodiment 1:
With 5.2934g (0.01mol) 4, two (4-chloro phthalimide) phenyl ether of 4`-and 1.5600g sodium sulphite and 45ml tetramethylene sulfone join in the 250ml three-necked bottle, stir down at 80 ℃, system becomes redness, reacts to add 2.5110g two chloro benzophenones after 2 hours, rises to 200 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 70%), limiting viscosity be 0.16dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 2:
With 5.2934g (0.01mol) 4, two (the 3-chloro phthalimide) phenyl ether of 4`-and 1.5600g sodium sulphite and 45ml N, dinethylformamide (DMF) joins in the 250ml three-necked bottle, become redness 60 ℃ of following stirring systems, react adding 2.5110g two chloro benzophenones after 2 hours, rise to 150 ℃ of reactions 12 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 72%), limiting viscosity be 0.17dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 3:
With 5.2734g (0.01mol) 4, two (4-chloro phthalimide) ditanes of 4`-and 1.5600g sodium sulphite and 45ml tetramethylene sulfone are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, reacted 2 hours, and added 2.5110g two chloro benzophenones then, rise to 200 ℃ of reactions 2 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 78%), limiting viscosity be 0.20dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 4:
With 5.2734g (0.01mol) 4, two (the 3-chloro phthalimide) ditanes of 4`-and 1.5600g sodium sulphite and 45ml N, N-N,N-DIMETHYLACETAMIDE (DMAc) becomes redness 80 ℃ of following stirring systems in the 250ml three-necked bottle, reacted 2 hours, add 2.5110g two chloro benzophenones then, rise to 200 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 65%), limiting viscosity is (30 ℃ of 0.15dl/g, 0.125g/dl, DMAc).
Embodiment 5:
With 5.1334g (0.01mol) 4, two (4-chloro phthalimide) biphenyls of 4`-and 1.5600g sodium sulphite and 45ml tetramethylene sulfone are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, reacted 2 hours, and added the 2.8900g dichloro diphenyl sulfone then, rise to 200 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 60%), limiting viscosity be 0.12dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 6:
With 5.5734g (0.01mol) 2,2`-(4, two (the 3-chloro phthalimide) phenylbenzene of 4`-) different propane and 1.5600g sodium sulphite and 45ml tetramethylene sulfone are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add the 2.8900g dichloro diphenyl sulfone then, rise to 200 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 70%), limiting viscosity is (30 ℃ of 0.18dl/g, 0.125g/dl, DMAc).
Embodiment 7:
With 5.7734g (0.01mol) 4, two (4-chloro phthalimide) sulfobenzides of 4`-and 1.5600g sodium sulphite and 45ml N-Methyl pyrrolidone (NMP) are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, reacted 2 hours, and added the 2.8900g dichloro diphenyl sulfone then, rise to 170 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 65%), limiting viscosity be 0.16dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 8:
With 5.2734g (0.01mol) 4, two (3-chloro phthalimide) ditanes of 4`-and 1.5600g sodium sulphite and 45ml hexamethylphosphoramide are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, reacted 2 hours, and added the 2.8900g dichloro diphenyl sulfone then, rise to 180 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 67%), limiting viscosity be 0.16dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 9:
With 5.4534g (0.01mol) 4, two (3-chloro phthalimide) diphenyl sulfides of 4`-and 1.5600g sodium sulphite and 45ml dimethyl sulfoxide (DMSO) (DMSO) are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, reacted 2 hours, and added the 2.8900g dichloro diphenyl sulfone then, rise to 160 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 66%), limiting viscosity be 0.16dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 10:
With 6.2134g (0.01mol) 4, two (the 4-chloro phthalimide) phenylbenzene-4`` of 4`-, 4```-benzene diether and 1.5600g sodium sulphite and 45ml N-Methyl pyrrolidone (NMP) are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add the 2.8900g dichloro diphenyl sulfone then, rise to 170 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 68%), limiting viscosity is (30 ℃ of 0.16dl/g, 0.125g/dl, DMAc).
Embodiment 11:
With 2.1856g (0.005mol) N, phenyl between N--two (4-chloro phthalimide), 2.1856g (0.005mol) N, phenyl between N--two (3-chloro phthalimide) is added in the 250ml three-necked bottle with 1.5600g sodium sulphite and 45ml N-Methyl pyrrolidone (NMP), become redness 80 ℃ of following stirring systems, reacted 2 hours, and added the 2.8900g dichloro diphenyl sulfone then, rise to 170 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 65%), limiting viscosity be 0.20dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 12:
With 6.9712g (0.01mol) 4, two (4-chloro phthalimide) two phenoxy groups-4`` of 4`-, 4```-biphenyl and 1.5600g sodium sulphite and 45ml N-Methyl pyrrolidone (NMP) are added in the 250ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add the 2.8900g dichloro diphenyl sulfone then, rise to 170 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 69%), limiting viscosity is (30 ℃ of 0.18dl/g, 0.125g/dl, DMAc).
Embodiment 13:
With 7.1312g (0.01mol) 4, two (4-chloro phthalimide) two phenoxy groups-4`` of 4`-, 4```-phenyl ether and 1.5600g sodium sulphite and 45ml hexamethylphosphoramide are added in the 1 50ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add 2.5110g two chloro benzophenones then, rise to 170 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 71%), limiting viscosity is (30 ℃ of 0.18dl/g, 0.125g/dl, DMAc).
Embodiment 14:
With 7.6112g (0.01mol) 4, two (4-chloro phthalimide) two phenoxy groups-4`` of 4`-, 4```-sulfobenzide and 1.5600g sodium sulphite and 45ml hexamethylphosphoramide are added in the 150ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add 2.5110g two chloro benzophenones then, rise to 170 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 65%), limiting viscosity is (30 ℃ of 0.16dl/g, 0.125g/dl, DMAc).
Embodiment 15:
With 5.9612g (0.01mol) 2, two (the 4-chloro phthalimides)-4 of 2`-two chloro-, 4`-ditane and 1.5600g sodium sulphite and 45ml hexamethylphosphoramide are added in the 150ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add 2.5110g two chloro benzophenones then, rise to 170 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 70%), limiting viscosity is (30 ℃ of 0.16dl/g, 0.125g/dl, DMAc).
Embodiment 16:
With 5.9612g (0.01mol) 3, two (the 4-chloro phthalimides)-4 of 3`-two chloro-, 4`-ditane and 1.5600g sodium sulphite and 45ml hexamethylphosphoramide are added in the 150ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add 2.5110g two chloro benzophenones then, rise to 200 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 69%), limiting viscosity is (30 ℃ of 0.15dl/g, 0.125g/dl, DMAc).
Embodiment 17:
With 5.5512g (0.01mol) 3,3`-dimethyl-two (4-chloro phthalimide)-4,4`-ditane and 1.5600g sodium sulphite and 45ml dimethyl formamide are added in the 150ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add 2.5110g two chloro benzophenones then, rise to 150 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 69%), limiting viscosity is (30 ℃ of 0.14dl/g, 0.125g/dl, DMAc).
Embodiment 18:
With two (the 4-chloro phthalimides)-1 of 4.4512g (0.01mol), 6-hexane and 1.5600g sodium sulphite and 45ml hexamethylphosphoramide are added in the 150ml three-necked bottle, become redness 80 ℃ of following stirring systems, reacted 2 hours, and added 2.5110g two chloro benzophenones then, rise to 170 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 69%), limiting viscosity be 0.15dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 19:
With 4.3712g (0.01mol) N, N-is added in the 150ml three-necked bottle phenyl-two (4-chloro phthalimides) and 1.5600g sodium sulphite and 45ml tetramethylene sulfone, become redness 80 ℃ of following stirring systems, reacted 2 hours, and added 1.4450g dichloro diphenyl sulfone and 1.3381g two chloro benzophenones then, rise to 170 ℃ of reactions 6 hours gradually, cooling slightly, reaction mixture is thread to going in the 450ml methyl alcohol, gets throw out, the decompress filter collecting precipitation, through alcohol reflux, filter, wash three times, drain, get product (productive rate is 69%), limiting viscosity be 0.15dl/g (30 ℃, 0.125g/dl, DMAc).
Embodiment 20:
With 7.3912g (0.01mol) 4, two (4-chloro the phthalimide)-two phenoxy groups-4`` of 4`-, different propane of 4```-phenylbenzene and 1.5600g sodium sulphite and 45ml dimethyl sulfoxide (DMSO) are added in the 150ml three-necked bottle, become redness 80 ℃ of following stirring systems, react 2 hours, add 2.5110g two chloro benzophenones then, rise to 140 ℃ of reactions 6 hours gradually, cooling is thread to going in the 450ml methyl alcohol with reaction mixture slightly, get throw out, the decompress filter collecting precipitation through alcohol reflux, filters, wash three times, drain, get product (productive rate is 70%), limiting viscosity is (30 ℃ of 0.16dl/g, 0.125g/dl, DMAc).
Claims (1)
1. the preparation method of a dichlorophthalein imide and two chloro benzophenones or dichloro diphenyl sulfone multipolymer is that diamines is dissolved in dichlorobenzene or the dimethylbenzene, adds chloro-benzoic anhydride in batches, and the band water that refluxes is to theoretical aquifer yield, and cooling is filtered, the two chloro phthalimides of product; It is characterized in that adopting
Following component:
(1) 3 or the 4-chloro-benzoic anhydride:
Two kinds of compounds can be used alone, but also also mix together;
(2) diamine
This diamines is selected from
(3) 4,4`-two chloro benzophenones or 4, the 4`-dichloro diphenyl sulfone
Two kinds of compounds can be used alone, but also also mix together;
(4) Sodium sulphate anhydrous, 99min
(5) aprotic solvent is:
N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP), hexamethylphosphoramide or tetramethylene sulfone;
Concrete synthesis step is as follows:
Two chloro phthalimides and the Sodium sulphate anhydrous, 99min mol ratio by 1: 2 is joined in the aprotic solvent, in 60 ℃～80 ℃ reactions 2 hours, add then and two equimolar two chloro benzophenones of chloro phthalimide or dichloro diphenyl sulfone, 160～200 ℃ of following polymerizations 6 hours, go out product with methanol extraction, the resulting polymers limiting viscosity is 0.12～0.2dl/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021042691A CN1171930C (en) | 2002-03-04 | 2002-03-04 | Preparation method of dichlorophthalein imide and dichlorodiphenylketone or dichlorodiphenylsulfone copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021042691A CN1171930C (en) | 2002-03-04 | 2002-03-04 | Preparation method of dichlorophthalein imide and dichlorodiphenylketone or dichlorodiphenylsulfone copolymer |
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| CN1171930C true CN1171930C (en) | 2004-10-20 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110065891A1 (en) * | 2007-12-19 | 2011-03-17 | Changchun Hipolyking Co.,Ltd. | Polythioetherimides and method for producing thereof |
| CN102030903B (en) * | 2009-09-25 | 2013-03-06 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polythioether ketone imide terpolymer |
| CN102250469B (en) * | 2010-05-20 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | Polythioether imide and polyarylene sulfide alloy material and preparation method thereof |
| CN106164029B (en) | 2014-04-15 | 2018-06-29 | 沙特基础工业全球技术有限公司 | The method for manufacturing the salt and polyetherimide of the aromatic compound of hydroxyl substitution |
| EP3131949B1 (en) | 2014-04-15 | 2019-01-30 | SABIC Global Technologies B.V. | Methods of manufacture of polyetherimides |
| CN110121496B (en) | 2016-12-31 | 2022-07-12 | 高新特殊工程塑料全球技术有限公司 | Synthesis of reactive intermediates for polyetherimides and uses thereof |
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