CN101503398A - Novel sulfide or sulfone containing dianhydride, and preparation and use thereof - Google Patents
Novel sulfide or sulfone containing dianhydride, and preparation and use thereof Download PDFInfo
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Abstract
The invention discloses a novel thioether- or sulphone-containing dianhydride, as well as a preparation method and a usage thereof. The dianhydride has a general formula as below. The invention also discloses a method for taking the dianhydride as the raw material and using a diamine compound to prepare polyimide containing the thioether- or sulphone-containing dianhydride. By utilizing a sunoke nucleophilic substitution reaction, the invention obtains a novel dianhydride monomer with a pendant group by means of compounding, thereby avoiding the use of the expensive metal palladium composite catalyst which has complex compounding process. The dianhydride monomer containing a thioether and sulphone structure can be used for compounding the polyimide with better dissolution property and processing property.
Description
Technical field
The present invention relates to the novel sulfurized ether of a class or sulfone dianhydride and preparation method thereof and and in the application in polyimide material field.
Background technology
Polyimide (PI) is the high-performance polymer that a class main chain contains imide ring, and is wherein the most noticeable with all aromatic polyimide.Because it has excellent thermostability, mechanical property, unreactiveness, dielectric properties and radiation resistance, polyimide has obtained widespread use at hi-tech neighborhoods such as aerospace, electronic industries with commercial form such as film, coating, fiber, plastics, adheseve and polymer matrix composites.
Because the common infusibility indissoluble of all aromatic polyimide, thereby a lot of difficulties of such material in the machine-shaping process have been caused.At present, the complete full aromatic polyimide material of aromatics is converted into polyimide by thermal treatment with amido acid more normally the machine-shaping of fusible soluble polyamic acid intermediate.But this method can cause some negative effects.For example: be in the imido process in the amido acid closed loop, can discharge some small-molecule substances (as: water), they can stay hole in material, thereby cause the defective of material on mechanical property; Moreover the thermostability of amido acid is relatively poor, and amido acid can all not be converted into imide in closed loop procedure, and therefore, residual amido acid can reduce the thermal stability of material.
The reason of all aromatic polyimide infusibility indissoluble is that its molecular chain contains a large amount of aromatic ring structures, and intermolecular interaction simultaneously is very strong.Characteristic on these molecular structures has also caused the shortcoming of its infusibility indissoluble when having given all aromatic polyimide material excellent properties.Therefore, synthetic have solvable meltability and keep high performance new type polyimide to be subjected to people again more and more pay close attention to.Wherein a valid approach is exactly to introduce side group in the molecular chain of polyimide, with reduction molecule interchain reactive force, thus the solvable meltability of increase polyimide.United States Patent (USP) U.S.Patent 5,395,918 discloses the polyimide that a kind of novel biphenyl dianhydride is used for synthesizing soluble, but the synthetic expensive palladium metal composite catalyst of use that needs of this dianhydride, so the synthesis technique complexity, the cost height has limited the use of polyimide.
Summary of the invention
The purpose of this invention is to provide a kind of novel dianhydride monomer that contains sulfide based structural or contain the sulfone structure that synthesizes, to be used for the polyimide of synthesizing new structure.
The object of the present invention is achieved like this: a kind of novel sulfurized ether or sulfone dianhydride, and thioether type dianhydride is for having the compound of following general formula (I):
X1=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene,
X2=H, halogen, SH
X3=H, halogen, SH, CN
X4=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene
R＝—，S
R wherein
2Can select and R
1Identical group also can be selected different groups; But do not select the H substituting group simultaneously;
Described sulfone type dianhydride is for having the compound of following general formula (II):
X1=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene,
X2=H, halogen, SO
3H
X3=H, halogen, SO
3H, CN
X4=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene
R=-, sulfone,
R wherein
2Can select and R
1Identical group also can be selected different groups; But do not select the H substituting group simultaneously.
Another object of the present invention provides the above-mentioned synthetic method that contains sulfide based structural or contain the dianhydride monomer of sulfone structure.
Another object of the present invention is achieved in that the synthetic method of a kind of novel sulfurized ether or sulfone dianhydride, and dianhydride I (II)-2 is as follows to 11 synthetic route:
The synthesis technologic parameter of intermediate 1:
In BPDA or SDPA, be that 2-6:1 and BPDA or SDPA drop among the entrainer A in molar ratio with the organic amine reagent A, 0-60 ℃ is stirred 20min-10h; Then, temperature rising reflux separates being drying to obtain intermediate 1 till do not have obvious water and steam;
The organic amine reagent A comprises: aqueous methylamine solution, ethylamine solution;
Entrainer A comprises: toluene, chlorobenzene, dimethylbenzene, dichlorobenzene, ethylbenzene, diethylbenzene, bromobenzene;
Intermediate 2 and 2 ' synthesis technologic parameter:
In intermediate 1, be 1.0-2.5:1 (intermediate 2) in molar ratio with nitrosonitric acid; 2.5-6.0:1 (intermediate 2 ') adds in the vitriol oil, stirs 2-24 hour at 10-50 ℃ then, after react reaction solution poured in the water and precipitates, separation being drying to obtain intermediate 2 or 2 ';
Intermediate 3 and 3 ' synthesis technologic parameter:
Operational path 1: in intermediate 2, with nucleophilic reagent A: catalyst A: intermediate 2 1.0-3.0:1.0-4.0:1 in molar ratio drops in the solvent orange 2 A, and 20-160 ℃ is stirred 3-24h; After having reacted reaction solution is poured in the water, separated drying and both got intermediate 3; Operational path 2: nucleophilic reagent A and catalyst A are dropped in the solvent, add entrainer B again, be back to after no obvious water steams, add intermediate 2 again, at 20-160 ℃ of stirring 3-24h; After having reacted reaction solution is poured in the water, separated drying and both got intermediate 3;
The synthesis technique of intermediate 3 ' and intermediate 3 are equal to, and just the mole proportioning changes nucleophilic reagent A into: catalyst A: intermediate 2 '=2.0-4.0:2.0-6.0:1
Only need mix the nuclear reagent A of going and live with relatives and get final product when R1 is not equal to R2, nucleophilic reagent A comprises:
Simple substance S, Sodium sulphate anhydrous, 99min, and the sulfhydryl compound of following structure
X1＝CH
3，CH
2CH
3，
X2=H, halogen, SH
X3=H, halogen, SH, CN
Catalyst A comprises:
Alkali-metal carbonate and oxyhydroxide are as yellow soda ash and sodium hydroxide;
Solvent B comprises:
Dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP), acetone and tetrahydrofuran (THF);
Entrainer B comprises:
Toluene, chlorobenzene, dimethylbenzene, dichlorobenzene, ethylbenzene, diethylbenzene, bromobenzene;
Dianhydride I (II)-2 is to the synthesis technologic parameter of I (II)-11:
In intermediate 3 (3 '), with catalyst B in molar ratio 4-20:1 drop in the mixing solutions of water and solvent B, reflux 6-30 hour, the pH of reaction solution is transferred to 1-3 with concentrated hydrochloric acid, concentrate back adding dewatering agent A and be back to till anhydrous the steaming thermal separation, behind the crystallisation by cooling, separate to be drying to obtain I-2 to I-11, or after the acid adjustment product separated, directly vacuum heat dewater I-2 to I-11;
The acid adjustment product is dropped into the 20min-3h that refluxes among the oxygenant A, steam unnecessary water, residue promptly gets II-2 to II-11 by the dehydration of vacuum heat again;
Catalyst B is alkali-metal oxyhydroxide such as potassium hydroxide, sodium hydroxide;
Solvent B comprises: water, ethanol, methyl alcohol, alcohols such as Virahol;
Dewatering agent A comprises: toluene, chlorobenzene, dimethylbenzene, dichlorobenzene, ethylbenzene, diethylbenzene, benzene class entrainers such as bromobenzene; Or diacetyl oxide;
Oxygenant A comprises: 15 or 30% aqueous hydrogen peroxide solution;
The synthesis technique of dianhydride monomer I (II)-1 is as shown below:
The synthesis technique of intermediate 4:
In BPDA or SDPA, with catalyzer C in molar ratio 2-6:1 and BPDA drop in the solvent C, adding halide reagent A mole proportioning is 1-4:1, at 60-100 ℃ of reaction 2-24h, transfers pH=1-3 with concentrated hydrochloric acid, separate dry, the dehydration of vacuum heat both intermediate 4;
Catalyzer C: alkali-metal oxyhydroxide;
Halide reagent A: bromine, chlorine, iodine, alkali-metal hypohalite;
Solvent C: water, ethanol, Virahol, methyl alcohol or its mixing solutions;
Intermediate 5 is identical with intermediate 1 to I-2 to the synthesis technique of dianhydride I-1.
A further object of the present invention is to utilize above-mentioned two kinds of dianhydride monomers to prepare the polyimide of novel sulfurized ether or sulfone structure.
A further object of the present invention is achieved in that a kind of novel sulfurized ether or the preparation of sulfone dianhydride monomer contain the method for the polyimide of thioether or sulfone structure, and its synthetic route is as follows:
Synthesis technologic parameter is:
In I or II compound, in polar solvent D, add above-mentioned diamine compound A, after being stirred to two amine solvents, add I or II with diamines 1:1 mol ratio, adding is 4-20:1 dewatering agent B with the diamines mol ratio behind the stirring at room 4-24h, behind room temperature-200 ℃ reaction 2-24h, reaction solution is poured among the precipitation agent A, got the type polyimide after the separation drying;
The described solvent D:DMF of aforesaid method (N, dinethylformamide), DMSO (dimethyl sulfoxide (DMSO)), DMAC (N,N-dimethylacetamide), NMP (N-Methyl pyrrolidone); The described precipitation agent A of aforesaid method: water, methyl alcohol, ethanol or mixing solutions;
The dewatering agent B that aforesaid method uses comprises two kinds: physics dewatering agent and chemical dehydrator; The physics dewatering agent comprises toluene, dimethylbenzene, chlorobenzene, N, benzene kind solvents such as N-di-n-butyl aniline, dichlorobenzene, ethylbenzene; Chemical dehydrator comprises: diacetyl oxide/pyridine; Diacetyl oxide/triethylamine; Acetic anhydride/acetic acid sodium; Phthalic anhydride/pyridine; Trifluoroacetic anhydride/triethylamine; Trifluoroacetic anhydride/pyridine; DCC; Sulfur oxychloride; Phosphorus oxychloride;
The diamine compound A that aforesaid method relates to comprises following structure and can two classes or use with more than two classes:
X
1=H, halogen, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy
X
2=H, halogen, trifluoromethyl, trifluoromethoxy, the tertiary butyl, methyl
R
1=O, S, trifluoro sec.-propyl, sulfuryl, arone
R
2＝O，S，
R
3=O, S, the trifluoro sec.-propyl, sulfuryl, arone ,-
n＝0-1
And Chinese invention patent (application number: 200810044713.2; 200510124054; 02108422; 02102546; 02102544; The diamines of all structures that relate to 02102543).
The invention has the beneficial effects as follows:
Advantage of the present invention is the novel dianhydride monomer that has synthesized the band side group by simple nucleophilic substitution reaction, has avoided using costing an arm and a leg the palladium metal composite catalyst of synthesis technique complexity.
By containing the dianhydride monomer of thioether and sulfone structure, can synthesize polyimide with better dissolution characteristics and processibility.
Embodiment
Provide example below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as the restriction to the invention protection domain; the person skilled in the art in this field to some nonessential improvement and adjustment that the present invention makes, must belong to protection scope of the present invention according to the invention described above content.
Embodiment 1:
I (II)-1 is monomeric synthetic:
(1) in reaction flask, (48.00g, 1.2mol), water 400ml is stirred to dissolving fully to add NaOH.Under agitation add BPDA (87.40g, 0.29706mol), under nitrogen protection, slowly drip bromine (50g, 0.31287mol), hierarchy of control temperature≤50 ℃.Drip to finish and begin to be warming up to 90 ℃, insulation reaction 6h.Stopped reaction, static spending the night.Transfer pH=1-2 with concentrated hydrochloric acid, stirring at room is after for some time, the separated and collected filter cake, 250 ℃ of vacuum heat dewater 4-bromine-biphenyl dianhydride (intermediate 4).
(2) (6.64g, 53.6mmol) (10g 26.8mmol) drops in the 50ml toluene, and 0 ℃ is stirred 2h with 4-bromine-biphenyl dianhydride with 25% aqueous methylamine solution.Then, temperature rising reflux promptly gets N-methyl-4-bromo-dibenzoyl imine intermediate 5 after separating drying till do not have obvious water and steam.
(3) with N-methyl-4-bromo-dibenzoyl imines (10g 25mmol) drops into the vitriol oil, treat dissolving fully after, the adding nitrosonitric acid (3.32g, 50mmol), stirring at room 12h, pour in the water, get N-methyl-4-bromo-4 '-nitro-dibenzoyl imine intermediate 6 after the separation drying.
(4) with thiophenol (2.72g, 24.75mmol), NaOH (1.09g, 27.225mmol), drop among the DMAC of 30ml, add 15ml toluene, be back to till no obvious water steams adding N-methyl-4-bromo-4 '-nitro-dibenzoyl imines (10g, 22.5mmol), behind 60 ℃ of reaction 2h, pour in the water, get N-methyl-4-bromo-4 '-benzene mercapto ether-dibenzoyl imine intermediate 7 after the separation drying.
(5) with N-methyl-4-bromo-4 '-benzene mercapto ether-dibenzoyl imines (10g, 19.7mmol), KOH (13.2g, 236.5mmol), drop in 25ml water and the 25ml ethanolic soln, behind the backflow 24h, transfer pH=1-2 with concentrated hydrochloric acid, after the separation acid adjustment product is got final product I-1 260 ℃ of vacuum hydro-extractions.
Behind backflow 2h in the aqueous hydrogen peroxide solution of 10g acid adjustment product input 100ml30%, with the water evaporate to dryness, 300 ℃ of vacuum hydro-extractions get final product II-1;
The 1H-NMR of product I-1 (DMSO-d6, ppm):
8.57(s，1H，Ar-H)，8.45(s，1H，Ar-H)，8.36(s，1H，Ar-H)，8.34(s，1H，Ar-H)，7.20(d，2H，Ar-H)，7.06(dd，2H，Ar-H)，7.01(d，1H，Ar-H).
Ultimate analysis calculated value: C:54.9, H:1.88,0:19.95, S:6.66.
Ultimate analysis measured value: C:53.8, H:1.76,0:19.30, S:6.54.
The 1H-NMR of II-1 (DMSO-d6, ppm):
8.56(s，1H，Ar-H)，8.45(s，1H，Ar-H)，8.73(s，1H，Ar-H)，9.04(s，1H，Ar-H)，7.9(d，2H，Ar-H)，7.70(dd，2H，Ar-H)，7.3(d，1H，Ar-H).
Ultimate analysis calculated value: C:51.48, H:1.77,0:24.94, S:6.25
Ultimate analysis measured value: C:51.53, H:1.76,0:24.86, S:6.32.
Synthesizing of polyimide:
At polar solvent DMF ((N, dinethylformamide)) after adding phenyl ether diamines is stirred to two amine solvents in, the I (II)-1 of mol ratios such as adding and diamines, behind the stirring at room 12h, the toluene that adds the 5:1 mol ratio is poured reaction solution in the precipitation agent methanol into behind 120 ℃ of reaction 12h, must contain the polyimide of thioether or sulfone after the separation drying.This polyimide is dissolved in DMAC (N,N-dimethylacetamide), DMF ((N, dinethylformamide), NMP (N-Methyl pyrrolidone) isopolarity solvent.
Embodiment 2:
I (II)-8 is monomeric synthetic:
(1) (24.48g, 136mmol) (10g 34mmol) drops in the 50ml toluene, and 20 ℃ are stirred 1h with biphenyl dianhydride with 25% ethylamine solution.Then, temperature rising reflux separates being drying to obtain N-methyl diphenyl imide intermediate 1 till do not have obvious water and steam.
(2) with N-ethyl-dibenzoyl imines (10g 28.7mmol) drops into the vitriol oil, treat dissolving fully after, the adding nitrosonitric acid (9.52g, 143.55mmol), 30 ℃ are stirred 7h, pour in the water, get N-ethyl-4,4 '-dinitrobenzene-dibenzoyl imine intermediate 2 after the separation drying.
(3) will to the phenyl thiophenol (12.7g, 68.4mmol), NaOH (3.65g, 91.2mmol), drop among the DMAC of 40ml, add 20ml toluene, be back to till no obvious water steams, add N-ethyl-4, and 4 '-dinitrobenzene-dibenzoyl imines (10g, 22.8mmol), behind 80 ℃ of reaction 2h, pour in the water, get N-methyl-4,4 '-two pairs of phenyl benzene mercapto ether-dibenzoyl imine intermediate 3 after the separation drying.
(4) with N-ethyl-4, and 4 '-two pairs of phenyl benzene mercapto ether dibenzoyl imines (10g, 13.9mmol), (4.68g 83.7mmol), drops in the 50ml water KOH, behind the backflow 12h, transfer pH=1-2, after the separation acid adjustment product is got final product I-8 300 ℃ of vacuum hydro-extractions with concentrated hydrochloric acid.
Behind backflow 2h in the aqueous hydrogen peroxide solution of 10g acid adjustment product input 80ml30%, with the water evaporate to dryness, 320 ℃ of vacuum hydro-extractions get final product II-8.
The 1H-NMR of dianhydride I-8 (DMSO-d6, ppm):
8.34(s，2H，Ar-H)，8.38(s，2H，Ar-H)，7.48(d，2H，Ar-H)，7.32(d，2H，Ar-H)，7.28(d，2H，Ar-H)，7.26(d，2H，Ar-H)，7.22(s，1H，Ar-H)
Ultimate analysis calculated value: C:72.49, H:3.35,0:14.49, S:9.68
Ultimate analysis measured value: C:72.53.H:3.25,0:13.64, S:9.54.
The 1H-NMR of dianhydride II-8 (DMSO-d6, ppm):
9.04(s，2H，Ar-H)，8.73(s，2H，Ar-H)，7.96(d，2H，Ar-H)，7.65(d，2H，Ar-H)，7.48(d，2H，Ar-H)，7.32(dd，2H，Ar-H)，7.22(s，1H，Ar-H)
Ultimate analysis calculated value: C:66.11, H:3.05,0:22.02, S:8.82.
Ultimate analysis measured value: C:65.19, H:3.09,0:21.87, S:8.91.
Synthesizing of polyimide:
After the adding mphenylenediamine is stirred to two amine solvents in polar solvent NMP (N-Methyl pyrrolidone), the I (II)-8 of mol ratios such as adding and diamines, behind the stirring at room 8h, diacetyl oxide/the pyridine that adds the 4:1 mol ratio is poured reaction solution in the precipitation agent water into behind room temperature reaction 24h, must contain the polyimide of thioether or sulfone after the separation drying.This polyimide is dissolved in DMAC (N,N-dimethylacetamide), DMF (N, dinethylformamide), NMP (N-Methyl pyrrolidone) isopolarity solvent.
Embodiment 3:
I (II)-9/11 is monomeric synthetic:
(1) (11.4g, 91.9mmol) (10g 30.6mmol) drops in the 60ml toluene, and 30 ℃ are stirred 2h with the diphenyl sulfide dianhydride with 25% aqueous methylamine solution.Then, temperature rising reflux separates being drying to obtain N-methyldiphenyl thioether imide intermediate 1 till do not have obvious water and steam.
(2) with N-methyl-diphenyl sulfide imide (10g 28.38mmol) drops into the vitriol oil, treat dissolving fully after, the adding nitrosonitric acid (7.53g, 113.5mmol), 60 ℃ are stirred 7h, pour in the water and get N-methyl-3,3 '-dinitrobenzene-diphenyl sulfide imide intermediate 2 after the separation drying.
(3) with 2-naphthalene coloured glaze phenol (3.62g, 22.6mmol), to benzene two coloured glaze phenol (3.21g, 22.6mmol), anhydrous K
2CO
3(12.5g, 90.4mmol), drop among the NMP of 52ml, add N-methyl-4 then, 4 '-dinitrobenzene diphenyl sulfide imide (10g, 22.6mmol), behind 80 ℃ of reaction 2h, pour in the water, get N-methyl-3-naphthalene mercapto ether-3 '-(4 '-sulfydryl benzene mercapto ether) diphenyl sulfide imide intermediate 3 after the separation drying.
(4) with N-methyl-4-naphthalene mercapto ether-4 '-(4 '-sulfydryl benzene mercapto ether) diphenyl sulfide imide (10g, 15.36mmol), NaOH (12.3g, 307.3mmol), drop in the 60ml water, behind the backflow 8h, transfer pH=1-2, after the separation acid adjustment product is got final product I-9/11 250 ℃ of vacuum hydro-extractions with concentrated hydrochloric acid.
Behind backflow 2h in the aqueous hydrogen peroxide solution of 10g acid adjustment product input 200ml30%, with the water evaporate to dryness, 290 ℃ of vacuum hydro-extractions get final product II-9/11.
The 1H-NMR of dianhydride I-9/11 (DMSO-d6, ppm):
8.08(s，1H，Ar-H)，8.10(s，1H，Ar-H)，8.15(s，1H，Ar-H)，7.94(s，1H，Ar-H)，7.67(d，2H，Ar-H)，7.32(dd，2H，Ar-H)，7.22(s，1H，Ar-H)，7.41(d，1H，Ar-H)，7.12(dd，1H，Ar-H)，7.26(d，1H，Ar-H)，7.04(d，2H，Ar-H)，6.98(d，2H，Ar-H)，4.2(s，1H，S-H)
Ultimate analysis calculated value: C:61.52, H:2.58,0:15.37, S:20.53
Ultimate analysis measured value: C:61.46.H:2.48,0:15.45, S:20.85.
The 1H-NMR of dianhydride II-9/11 (DMSO-d6, ppm):
9.20(s，2H，Ar-H)，9.15(s，2H，Ar-H)，8.18(d，2H，Ar-H)，8.10(d，2H，Ar-H)，7.67(d，2H，Ar-H)，7.32(dd，2H，Ar-H)，7.7(d，1H，Ar-H)，7.49(dd，1H，Ar-H)，8.05(d，1H，Ar-H).
Ultimate analysis calculated value: C:50,00H:2.10,0:31.22, S:16.68.
Ultimate analysis measured value: C:50.19, H:2.09,0:30.87, S:17.00.
Synthesizing of polyimide:
In polar solvent NMP (N-Methyl pyrrolidone), add 2-trifluoromethyl-phenyl ether diamines, after being stirred to two amine solvents, the I (II)-9/11 of mol ratios such as adding and diamines, behind the stirring at room 8h, behind the chlorobenzene backflow 12h of adding 10:1 mol ratio reaction solution is poured in the precipitation agent methanol, must be contained the polyimide of thioether or sulfone after the separation drying.This polyimide is dissolved in DMAC (N,N-dimethylacetamide), DMF (N, dinethylformamide), NMP (N-Methyl pyrrolidone) isopolarity solvent.
Embodiment 4:
I's (II)-6 is synthetic:
(1) (11.4g, 91.9mmol) (10g 30.6mmol) drops in the 60ml toluene, and 30 ℃ are stirred 2h with the diphenyl sulfide dianhydride with 25% aqueous methylamine solution.Then, temperature rising reflux separates being drying to obtain N-methyldiphenyl thioether imide intermediate 1 till do not have obvious water and steam.
(2) with N-methyl-diphenyl sulfide imide (10g 28.38mmol) drops into the vitriol oil, treat dissolving fully after, the adding nitrosonitric acid (2.82g, 42.57mmol), 15 ℃ are stirred 7h, pour in the water and precipitate, get N-methyl-4-nitro-diphenyl sulfide imide intermediate 2 after the separation drying.
(3) with 2,5-dimercapto-1,3, the 4-thiadiazoles (4.15g, 27.68mmol), KOH, drop among the 40ml NMP, add the 20ml chlorobenzene, be back to till no obvious water steams, adding N-methyl-4-nitro-diphenyl sulfide imide (10g, 25.17mmol), behind 120 ℃ of reaction 1h, pour in the water, get N-methyl-4-(2-sulfydryl-1,3,4-thiadiazoles mercapto ether)-diphenyl sulfide imide intermediate 3 after separating drying.
(4) with N-methyl-4-(2-sulfydryl-1,3,4-thiadiazoles mercapto ether)-diphenyl sulfide imide (10g, 18.26mmol), NaOH (13.14g, 328.7mmol), drop in 30ml propyl alcohol and the 40ml water, behind the backflow 15h, transfer pH=1-2, after the separation acid adjustment product is got final product I-6 230 ℃ of vacuum hydro-extractions with concentrated hydrochloric acid.
Behind backflow 30min in the aqueous hydrogen peroxide solution of 10g acid adjustment product input 150ml30%, with the water evaporate to dryness, 290 ℃ of vacuum hydro-extractions get final product II-6.
The 1H-NMR of dianhydride I-6 (DMSO-d6, ppm):
8.14(s，1H，Ar-H)，8.12(s，1H，Ar-H)，8.30(d，1H，Ar-H)，7.84(dd，1H，Ar-H)，8.20(d，1H，Ar-H)，4.0(s，1H，S-H)
Ultimate analysis calculated value: C:45.56, H:1.27,0:20.23, S:27.03
Ultimate analysis measured value: C:45.66.H:1.28,0:21.23, S:26.09
The 1H-NMR of dianhydride II-6 (DMSO-d6, ppm):
9.25(s，1H，Ar-H)，9.30(s，1H，Ar-H)，9.01(d，1H，Ar-H)，8.6(dd，1H，Ar-H)，8.77(d，1H，Ar-H)，
Ultimate analysis calculated value: C:34,95H:0.98,0:38.80, S:20.74.
Ultimate analysis measured value: C:34.10H:1.09,0:37.27, S:19.01.
Synthesizing of polyimide:
In polar solvent NMP (N-Methyl pyrrolidone), add 2-trifluoromethyl-phenyl ether diamines, after being stirred to two amine solvents, the I (II)-6 of mol ratios such as adding and diamines, behind the stirring at room 8h, behind the chlorobenzene backflow 12h of adding 10:1 mol ratio reaction solution is poured in the precipitation agent methanol, must be contained the polyimide of thioether or sulfone after the separation drying.This polyimide is dissolved in DMAC (N,N-dimethylacetamide), DMF (N, dinethylformamide), NMP (N-Methyl pyrrolidone) isopolarity solvent.
Embodiment 5:
The synthesis technique of dianhydride I (II)-10
(1) (16.85g, 135.96mmol) (10g 33.99mmol) drops in the 60ml dichlorobenzene, and 40 ℃ are stirred 1h with biphenyl dianhydride with 25% aqueous methylamine solution.Then, temperature rising reflux separates being drying to obtain N-methyl diphenyl imide intermediate 1 till do not have obvious water and steam.
(2) with N-methyl-dibenzoyl imines (10g 31.22mmol) drops into the vitriol oil, treat dissolving fully after, the adding nitrosonitric acid (10.35g, 156.1mmol), 50 ℃ are stirred 7h, pour in the water and precipitate, get N-methyl-3,3 '-dinitrobenzene-dibenzoyl imine intermediate 2 after the separation drying.
(3) will to the cyano group thiophenol (8.54g, 63.36mmol), Na
2CO
3(7.72g 72.9mmol), drops among the 40ml DMAC, adds N-methyl-3 then, 3 '-dinitrobenzene-dibenzoyl imines (10g, 24.3mmol), behind 90 ℃ of reaction 3h, pour in the water, get N-methyl-3,3 '-two (to cyano group benzene mercapto ether)-dibenzoyl imine intermediate 3 after the separation drying.
(4) with N-methyl-3, and 3 '-two (to cyano group benzene mercapto ether)-dibenzoyl imines (10g, 17.04mmol), (6.81g 170.4mmol), drops in the 80ml water NaOH, behind the backflow 24h, transfer pH=1-2, after the separation acid adjustment product is got final product I-10. 220 ℃ of vacuum hydro-extractions with concentrated hydrochloric acid
Behind backflow 40min in the aqueous hydrogen peroxide solution of 10g acid adjustment product input 160ml30%, with the water evaporate to dryness, 270 ℃ of vacuum hydro-extractions get final product II-10.
The 1H-NMR of dianhydride I-10 (DMSO-d6, ppm):
8.134(s，2H，Ar-H)，8.40(s，2H，Ar-H)，7.38(d，2H，Ar-H)，7.31(d，2H，Ar-H)，
Ultimate analysis calculated value: C:64.28, H:2.16,0:17.23, S:11.44
Ultimate analysis measured value: C:65.36.H:2.09,0:16.98, S:11.69.
The 1H-NMR of dianhydride II-10 (DMSO-d6, ppm):
9.10(s，2H，Ar-H)，8.98(s，2H，Ar-H)，8.20(d，2H，Ar-H)，7.67(d，2H，Ar-H)
Ultimate analysis calculated value: C:57.69H:1.94,0:25.62, S:10.27.
Ultimate analysis measured value: C:56.15H:2.01,0:25.78, S:10.32.
Synthesizing of polyimide:
In polar solvent NMP (N-Methyl pyrrolidone), add 2,2 '-two trifluoromethyls-phenyl ether diamines, after being stirred to two amine solvents, the I (II)-10 of mol ratios such as adding and diamines, behind the stirring at room 6h, behind the ethylbenzene backflow 12h of adding 10:1 mol ratio reaction solution is poured in the precipitation agent methanol, must be contained the polyimide of thioether or sulfone after the separation drying.This polyimide is dissolved in DMAC (N,N-dimethylacetamide), DMF (N, dinethylformamide), NMP (N-Methyl pyrrolidone) isopolarity solvent.
Claims (3)
1, a kind of novel sulfurized ether or sulfone dianhydride is characterized in that: described thioether type dianhydride is for having the compound of following general formula (I):
R
1=-H or halogen
1
X1=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene,
X2=H, halogen, SH
X3=H, halogen, SH, CN
X4=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene
R＝—，S
R wherein
2Can select and R
1Identical group also can be selected different groups; But do not select the H substituting group simultaneously;
Described sulfone type dianhydride is for having the compound of following general formula (II):
R
1=-H or halogen
1
X1=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene,
X2=H, halogen, SO
3H
X3=H, halogen, SO
3H, CN
X4=H, CH
3, CH
2CH
3, CF
3, OCF
3, OCH
3, halogen, phenylacetylene
R=-, sulfone,
R wherein
2Can select and R
1Identical group also can be selected different groups; But do not select the H substituting group simultaneously.
2, the synthetic method of a kind of novel sulfurized according to claim 1 ether or sulfone dianhydride, it is characterized in that: described dianhydride I (II)-2 is as follows to 11 synthetic route:
The synthesis technologic parameter of intermediate 1:
In BPDA or SDPA, be that 2-6:1 and BPDA or SDPA drop among the entrainer A in molar ratio with the organic amine reagent A, 0-60 ℃ is stirred 20min-10h; Then, temperature rising reflux separates being drying to obtain intermediate 1 till do not have obvious water and steam;
The organic amine reagent A comprises: aqueous methylamine solution, ethylamine solution;
Entrainer A comprises: toluene, chlorobenzene, dimethylbenzene, dichlorobenzene, ethylbenzene, diethylbenzene, bromobenzene;
Intermediate 2 and 2 ' synthesis technologic parameter:
In intermediate 1, be 1.0-2.5:1 (intermediate 2) in molar ratio with nitrosonitric acid; 2.5-6.0:1 (intermediate 2 ') adds in the vitriol oil, stirs 2-24 hour at 10-50 ℃ then, after react reaction solution poured in the water and precipitates, separation being drying to obtain intermediate 2 or 2 ';
Intermediate 3 and 3 ' synthesis technologic parameter:
Operational path 1: in intermediate 2, with nucleophilic reagent A: catalyst A: intermediate 2 1.0-3.0:1.0-4.0:1 in molar ratio drops in the solvent orange 2 A, and 20-160 ℃ is stirred 3-24h; After having reacted reaction solution is poured in the water, separated drying and both got intermediate 3; Operational path 2: nucleophilic reagent A and catalyst A are dropped in the solvent, add entrainer B again, be back to after no obvious water steams, add intermediate 2 again, at 20-160 ℃ of stirring 3-24h; After having reacted reaction solution is poured in the water, separated drying and both got intermediate 3;
The synthesis technique of intermediate 3 ' and intermediate 3 are equal to, and just the mole proportioning changes nucleophilic reagent A into: catalyst A: intermediate 2 '=2.0-4.0:2.0-6.0:1
Only need mix the nuclear reagent A of going and live with relatives and get final product when R1 is not equal to R2, nucleophilic reagent A comprises:
Simple substance S, Sodium sulphate anhydrous, 99min, and the sulfhydryl compound of following structure
X1＝CH
3，CH
2CH
3 
X2=H, halogen, SH
X3=H, halogen, SH, CN
Catalyst A comprises:
Alkali-metal carbonate and oxyhydroxide are as yellow soda ash and sodium hydroxide;
Solvent B comprises:
Dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP), acetone and tetrahydrofuran (THF);
Entrainer B comprises:
Toluene, chlorobenzene, dimethylbenzene, dichlorobenzene, ethylbenzene, diethylbenzene, bromobenzene;
The synthesis technologic parameter of dianhydride I (II) 2 to I (II)-11:
In intermediate 3 (3 '), with catalyst B in molar ratio 4-20:1 drop in the mixing solutions of water and solvent B, reflux 6-30 hour, the pH of reaction solution is transferred to 1-3 with concentrated hydrochloric acid, concentrate back adding dewatering agent A and be back to till anhydrous the steaming thermal separation, behind the crystallisation by cooling, separate to be drying to obtain I-2 to I-11, or after the acid adjustment product separated, directly vacuum heat dewater I-2 to I-11;
The acid adjustment product is dropped into the 20min-3h that refluxes among the oxygenant A, steam unnecessary water, residue promptly gets II-2 to II-11 by the dehydration of vacuum heat again;
Catalyst B is alkali-metal oxyhydroxide such as potassium hydroxide, sodium hydroxide;
Solvent B comprises: water, ethanol, methyl alcohol, alcohols such as Virahol;
Dewatering agent A comprises: toluene, chlorobenzene, dimethylbenzene, dichlorobenzene, ethylbenzene, diethylbenzene, benzene class entrainers such as bromobenzene; Or diacetyl oxide;
Oxygenant A comprises: 15 or 30% aqueous hydrogen peroxide solution;
The synthesis technique of dianhydride monomer I (II)-1 is as shown below:
The synthesis technique of intermediate 4:
In BPDA or SDPA, with catalyzer C in molar ratio 2-6:1 and BPDA drop in the solvent C, adding halide reagent A mole proportioning is 1-4:1, at 60-100 ℃ of reaction 2-24h, transfers pH=1-3 with concentrated hydrochloric acid, separate dry, the dehydration of vacuum heat both intermediate 4;
Catalyzer C: alkali-metal oxyhydroxide;
Halide reagent A: bromine, chlorine, iodine, alkali-metal hypohalite;
Solvent C: water, ethanol, Virahol, methyl alcohol or its mixing solutions;
Intermediate 5 is identical with intermediate 1 to I-2 to the synthesis technique of dianhydride I-1.
3, a kind of method that contains the polyimide of thioether or sulfone structure as novel sulfurized ether as described in the claim 2 or the preparation of sulfone dianhydride monomer of utilizing, it is characterized in that: its synthetic route is as follows:
Synthesis technologic parameter is:
In I or II compound, in polar solvent D, add above-mentioned diamine compound A, after being stirred to two amine solvents, add I or II with diamines 1:1 mol ratio, adding is 4-20:1 dewatering agent B with the diamines mol ratio behind the stirring at room 4-24h, behind room temperature-200 ℃ reaction 2-24h, reaction solution is poured among the precipitation agent A, got the type polyimide after the separation drying;
The described solvent D:DMF of aforesaid method (dimethyl formamide), DMSO (dimethyl sulfoxide (DMSO)), DMAC (N,N-DIMETHYLACETAMIDE), NMP (methyl-2-pyrrolidone); The described precipitation agent A of aforesaid method: water, methyl alcohol, ethanol or mixing solutions;
The dewatering agent B that aforesaid method uses comprises two kinds: physics dewatering agent and chemical dehydrator; The physics dewatering agent comprises toluene, dimethylbenzene, chlorobenzene, N, benzene kind solvents such as N-di-n-butyl aniline, dichlorobenzene, ethylbenzene; Chemical dehydrator comprises: diacetyl oxide/pyridine; Diacetyl oxide/triethylamine; Acetic anhydride/acetic acid sodium; Phthalic anhydride/pyridine; Trifluoroacetic anhydride/triethylamine; Trifluoroacetic anhydride/pyridine; DCC; Sulfur oxychloride; Phosphorus oxychloride;
The diamine compound A that aforesaid method relates to comprises following structure and can two classes or use with more than two classes:
X
1=H, halogen, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy
X
2=H, halogen, trifluoromethyl, trifluoromethoxy, the tertiary butyl, methyl
R
1=0, S, trifluoro sec.-propyl, sulfuryl, arone
R
2＝0，S，
R
3=0, S, the trifluoro sec.-propyl, sulfuryl, arone ,-
n＝0-1
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704806B (en) * | 2009-10-30 | 2011-10-19 | 四川大学 | Side-chain modified dianhydride intermediate containing biphenyl structure and preparation method and application thereof |
| CN105001419A (en) * | 2015-06-11 | 2015-10-28 | 华南理工大学 | Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide |
| CN109627238A (en) * | 2018-12-24 | 2019-04-16 | 山东盛华新材料科技股份有限公司 | One kind is containing two compound anhydride of thiophene derivant and its synthetic method and application |
| CN111909375A (en) * | 2019-05-07 | 2020-11-10 | 斯凯孚公司 | Imide compositions and preservative compositions comprising the same |
| CN112778339A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | Polythiophene dianhydride compound and synthesis method thereof |
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2009
- 2009-03-17 CN CN2009100586182A patent/CN101503398B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704806B (en) * | 2009-10-30 | 2011-10-19 | 四川大学 | Side-chain modified dianhydride intermediate containing biphenyl structure and preparation method and application thereof |
| CN105001419A (en) * | 2015-06-11 | 2015-10-28 | 华南理工大学 | Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide |
| CN109627238A (en) * | 2018-12-24 | 2019-04-16 | 山东盛华新材料科技股份有限公司 | One kind is containing two compound anhydride of thiophene derivant and its synthetic method and application |
| CN111909375A (en) * | 2019-05-07 | 2020-11-10 | 斯凯孚公司 | Imide compositions and preservative compositions comprising the same |
| CN112778339A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | Polythiophene dianhydride compound and synthesis method thereof |
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|---|---|
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