CN101270073A - Biphenyl compound with dissymmetrical structure, preparation method and application thereof - Google Patents
Biphenyl compound with dissymmetrical structure, preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a biphenyl compound that has an asymmetric structure as shown in the formula in the right. The biphenyl imide monomer with an asymmetric structure and the biphenyl dianhydride monomer with an asymmetric structure can be used in the structure of polyimide so as to improve the solubility and the fusibility of the polyimide. The present invention also provides a synthetic method of the asymmetric biphenyl imide monomer, the biphenyl dianhydride and the asymmetric biphenyl dianhydride monomer from the monomers of the category of halogenated phthalimide. The reaction conditions of the method can be easily operated; the products can be easily purified and the economic cost is lower.
Description
Technical field
The biphenyl dianhydride monomer that the present invention relates in asymmetric biphenol compound of a class and preparation method thereof and this compounds is introduced in the polyimide molecule structure to improve the purposes technical field of its solvable meltability.
Background technology
Polyimide (PI) is the high-performance polymer that the 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, tackiness agent and polymer matrix composites.
All aromatic polyimide structures general formula
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 (as shown in Figure 2) 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 polyamic acid polyimide
Polyamic acid processing synoptic diagram
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 that asymmetric structure is incorporated in the molecular chain of polyimide, with reduction molecule interchain reactive force, thus the solvable meltability of increase polyimide.
For separate benzene nuclei compound, its traditional synthetic method is with halogenated polyimide compound (United States Patent 5081281) in the anhydrous and oxygen-free environment of strictness, catalyzed reaction by nickel forms, its severe reaction conditions can increase the Financial cost of separate benzene nuclei compound simultaneously.Separate benzene nuclei compound can also generate by single sodium salt or the disodium salt reaction with palladium carbon catalysis phthalic acid compounds, such reaction need not strict anhydrous and oxygen-free environment, but its reaction is comparatively complicated, and the by product that obtains is more, can increase Financial cost equally in the purification of products stage.
In addition, the employed raw material of method of making the Preparation of Catalyst biphenol compound with palladium/carbon is halogenated phthalic acid list sodium salt or disodium salt (chemical industry journal, 2005,56 (9), 1805), and this will increase the content influence degree of purity of production of inorganic sodium ion undoubtedly.
Summary of the invention
An object of the present invention is to synthesize novel dibenzoyl imide monomers, be used for the biphenyl dianhydride monomer that contains unsymmetrical structure of synthesizing new with unsymmetrical structure.
The object of the present invention is achieved like this: a kind of dibenzoyl imide monomers with unsymmetrical structure has following structure:
Another object of the present invention is to synthesize novel asymmetric biphenyl dianhydride monomer, and it be directed in the polyimide structures, to improve the organic soluble of polyimide.
Another object of the present invention is achieved in that a kind of biphenyl dianhydride monomer with unsymmetrical structure, has following structure:
A further object of the present invention provides a kind of from synthetic asymmetric dibenzoyl imide monomers of halophthalimide class monomer and the monomeric route of asymmetric biphenyl dianhydride.
A further object of the present invention is achieved in that a kind of from synthetic asymmetric dibenzoyl imines of halophthalimide class monomer and the monomeric route of biphenyl dianhydride, this reaction conditions easy handling, and purification of products is more or less freely.
Embodiment
Asymmetric separate benzene nuclei compound of the present invention, this monomer structure general formula is as follows:
In the formula,
R
2＝-NO
2、OH、
R
3=H, CH
3Or CH
2CH
3
Asymmetric separate benzene nuclei compound shown in the general formula is particularly including the monomer of following structure:
I class monomer
In the general formula,
The time,
II class monomer
In the general formula,
The time,
Asymmetric separate benzene nuclei compound of the present invention is a synthetic as follows:
(1), the synthetic route of I class monomer (R1 is an imide group) is as follows:
R
3＝H CH
3 CH
2CH
3
The monomeric synthesis technologic parameter of I-1:
In component A, B component: component A is 1.5-3.5 in molar ratio: 1 is dissolved in the solvent orange 2 A fully, adds catalyst A again, heats up 80-120 ℃ then, adds catalyst B, stirs 4-24 hour.Reacted the back heat filtering, obtained filtrate, regulating the pH value with acid solution is 1, separates out precipitation, and filtration drying promptly gets intermediate 1.With nitrosonitric acid: intermediate 1 is 1.5-3.5 in molar ratio: 1 adds in the vitriol oil, stirs 4-24 hour at 10-80 ℃ then, after having reacted reaction solution is poured in the water and precipitates, and filtration drying promptly gets required product.
The component A that aforesaid method relates to is following structure:
The B component that aforesaid method relates to is chosen as: among LiOH, NaOH, the KOH one or more.
The related I-1 monomer of aforesaid method specifically comprises following structure:
The monomeric synthesis technologic parameter of I-2:
In the I-1 monomer, with catalyzer C: catalyzer D: the I-1 monomer is 0.8-1.5: 0.7-1.5 in molar ratio: 1 is dissolved among the solvent B, nitrogen protection, and 70-160 ℃ was stirred 8-24 hour.After having reacted reaction solution poured into the pH value and be in 2～3 the acid solution and precipitate, filtration drying promptly obtains required product.
The related I-2 monomer of aforesaid method specifically comprises following structure:
The I-3 monomer is to the monomeric synthesis technologic parameter of I-7:
In the I-1 monomer, with component C: catalyzer E: the I-1 monomer is 0.8-1.5 in molar ratio: 0.8-1.5: 1 is dissolved in the solvent C, and nitrogen protection was stirred 8-24 hour in 10-90 ℃.After having reacted reaction solution poured into and precipitate in the water, filtration drying promptly obtains the I-3 monomer.The I-4 monomer is synthetic by the method identical with synthesizing the I-3 monomer to the I-7 monomer.
The component C that aforesaid method relates to is following structure:
Related I-3 monomer to the I-7 monomer of aforesaid method specifically comprises following structure:
The used solvent orange 2 A of aforesaid method is selected: water, methyl alcohol, ethanol and methylene dichloride; The used solvent B of aforesaid method selects: N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N,N-dimethylacetamide DMAC or N-Methyl pyrrolidone (NMP); The used solvent C of aforesaid method is selected: N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N,N-dimethylacetamide DMAC or N-Methyl pyrrolidone (NMP).
The used catalyst A of aforesaid method is selected: 10% Pd/C, 5%Pd/C; The used catalyst B of aforesaid method is selected: 5% oxammonium sulfate solution, 10% oxammonium sulfate solution, 20% oxammonium sulfate solution or oxammonium hydrochloride solution; The used catalyzer C of aforesaid method selects: Anhydrous potassium carbonate, anhydrous sodium carbonate; The used catalyzer D of aforesaid method selects: Sodium Nitrite, potassium nitrite; The used catalyzer E of aforesaid method selects: Anhydrous potassium carbonate, anhydrous sodium carbonate.
The synthetic route of (2) II class monomers (R1 is an anhydride group) is as shown below:
R
3＝H?CH
3?CH
2CH
3
The monomeric synthesis technologic parameter of II-1:
In the I-1 monomer, will urge agent F: the I-1 monomer is 4-13 in molar ratio: 1 is dissolved among the solvent D reflux 8-30 hour, this reactant is precipitated in pH is the acid solution of 1-3, filtration drying is deposited in this among solvent E backflow 4-10 hour then again, filtration drying promptly obtains required product.
The related I-1 monomer of aforesaid method specifically comprises following structure:
The monomeric synthesis technologic parameter of II-2:
In the I-2 monomer, will urge agent F: the I-2 monomer is 4-13 in molar ratio: 1 is dissolved among the solvent D reflux 8-30 hour, this reactant is precipitated in pH is the acid solution of 1-3, filtration drying is deposited in this among solvent E backflow 4-10 hour then again, filtration drying promptly obtains required product.
The related I-2 monomer of aforesaid method specifically comprises following structure:
The II-3 monomer is identical to the monomeric synthesis technologic parameter of II-7 and II-1 and II-2:
Related II-3 monomer to the II-7 monomer of aforesaid method specifically comprises following structure:
The used solvent D of aforesaid method is water and ethanol, the mixed solvent of propyl alcohol or Virahol (volume ratio 0.5-2: 1); Solvent E selects: diacetyl oxide.
The used catalyzer F of aforesaid method selects: potassium hydroxide, sodium hydroxide.
Reaction 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 contains monomeric the synthesizing of I-1 of N-methyl structural
Add sodium hydroxide 1.52g (0.038mol) in the 100mL three-necked bottle, N-methyl-4-bromine phthalic imidine 4.5g (0.019mol) adds in the 15mL distilled water again, add palladium carbon 0.225g, heat up 90 ℃ then, be added dropwise to oxammonium sulfate solution (1.53g, 15ml water), stirred 10 hours.Reacted the back heat filtering, obtained filtrate, regulating the pH value with acid solution is 1.5, separates out precipitation, and filtration drying promptly gets and contains N-methyl structural intermediate 1.In the 100mL three-necked bottle, add 2.0g intermediate 1, add vitriol oil 15g, be warming up to 40 ℃ and be stirred to homogeneous phase, be added dropwise to nitrosonitric acid 0.64ml, stirred 6 hours.After having reacted reaction solution is poured in the beaker that contains 100ml distilled water, precipitation, suction filtration is used the 50ml methanol wash, promptly obtains containing the I-1 monomer of N-methyl structural after air-dry.
Contain the I-1 monomer (nitro is at 3) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.15(s，6H，CH
3)，7.89-7.92(dd，1H，Ar-H)，8.18-8.20(d，1H，Ar-H)，8.34-8.36(d，1H，Ar-H)，8.73-8.75(d，1H，Ar-H)，8.83-8.85(d，1H，Ar-H).
Ultimate analysis calculated value: C:59.18, H:3.04, N:11.50, O:26.28.2, N:11.46, O:26.30.
Ultimate analysis measured value: C:59.21, H:3.0
Contain the I-1 monomer (nitro is at 4) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.17(s，6H，CH
3)，7.88-7.92(dd，1H，Ar-H)，8.17-8.20(d，1H，Ar-H)，8.33-8.35(d，1H，Ar-H)，8.60-8.62(s，1H，Ar-H)，9.11-9.13(s，1H，Ar-H).
Ultimate analysis calculated value: C:59.18, H:3.04, N:11.50, O:26.28.
Ultimate analysis measured value: C:59.22, H:3.01, N:11.47, O:26.32.
Embodiment 2 contains monomeric the synthesizing of I-2 of N-methyl structural
In the 500mL three-necked bottle, add the I-1 monomer 23.38g (0.064mol) that contains the N-methyl structural successively, N, dinethylformamide (DMF) 250mL, Anhydrous potassium carbonate 10.61g (0.0768mol), Sodium Nitrite 5.74g (0.0832mol) stops after 18 hours in 130 ℃ of reactions in nitrogen atmosphere.Reaction solution is slowly poured into precipitation (pH=2-3) in the aqueous hydrochloric acid of 1000mL, fully stirred, have a large amount of yellow mercury oxides to occur, the suction filtration precipitation, and wash air-dry.Use the distilled water recrystallization, promptly obtain containing the I-2 monomer of N-methyl structural.
Contain the I-2 monomer (hydroxyl is at 3) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.14(s，6H，CH
3)，7.37-7.39(d，1H，Ar-H)，7.89-7.92(m，2H，Ar-H)，8.18-8.20(d，1H，Ar-H)，8.34-8.36(d，1H，Ar-H)，9.31(s，1H，OH).
Ultimate analysis calculated value: C:64.29, H:3.60, N:8.33, O:23.29.
Ultimate analysis measured value: C:64.34, H:3.57, N:8.30, O:23.32.
Contain the I-2 monomer (hydroxyl is at 4) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.17(s，6H，CH
3)，7.65-7.67(d，1H，Ar-H)，7.89-7.93(dd，1H，Ar-H)，8.16-8.20(m，2H，Ar-H)，8.34-8.36(d，1H，Ar-H)，9.23(s，1H，OH).
Ultimate analysis calculated value: C:64.29, H:3.60, N:8.33, O:23.29.
Ultimate analysis measured value: C:64.31, H:3.59, N:8.31, O:23.33.
Embodiment 3 contains monomeric the synthesizing of I-3 of N-methyl structural
In the 250mL three-necked bottle, add phenol 3.612g (0.0384mol), the I-1 monomer 11.69g (0.032mol) and the DMF60mL of Anhydrous potassium carbonate 5.746g (0.0416mol), N-methyl structural, nitrogen protection was stirred 24 hours down at 10 ℃.After having reacted reaction solution poured into and precipitate in the water, filtration drying promptly obtains containing the I-3 monomer of N-methyl structural.
Contain the I-3 monomer (phenoxy group is at 3) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.16(s，6H，CH
3)，6.92-7.22(m，5H，Ar-H)，7.56-7.58(d，1H，Ar-H)，7.90-7.92(dd，1H，Ar-H)，8.06-8.08(d，1H，Ar-H)，8.18-8.20(d，1H，Ar-H)，8.34-8.36(d，1H，Ar-H).
Ultimate analysis calculated value: C:69.90, H:3.91, N:6.79, O:19.40.
Ultimate analysis measured value: C:69.94, H:3.90, N:6.77, O:19.43.
Contain the I-3 monomer (phenoxy group is at 4) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.16(s，6H，CH
3)，6.91-7.23(m，5H，Ar-H)，7.84-7.86(d，1H，Ar-H)，7.91-7.93(dd，1H，Ar-H)，8.19-8.21(d，1H，Ar-H)，8.30-8.32(d，1H，Ar-H)，8.33-8.35(d，1H，Ar-H).
Ultimate analysis calculated value: C:69.90, H:3.91, N:6.79, O:19.40.
Ultimate analysis measured value: C:69.92, H:3.89, N:6.76, O:19.44.
Embodiment 4 contains monomeric the synthesizing of I-6 of N-methyl structural
In the 250mL three-necked bottle, add 4-cyanophenol 5.72g (0.048mol), the I-1 monomer 11.69g (0.032mol) and the DMF60mL of Anhydrous potassium carbonate 6.63g (0.048mol), N-methyl structural, nitrogen protection was stirred 14 hours down at 30 ℃.After having reacted reaction solution poured into and precipitate in the water, filtration drying promptly obtains containing the I-6 monomer of N-methyl structural.
Contain the I-6 monomer (the 4-cyano-benzene oxygen is at 3) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.15(s，6H，CH
3)，7.10-7.47(dd，4H，Ar-H)，7.56-7.58(d，1H，Ar-H)，7.90-7.92(dd，1H，Ar-H)，8.06-8.08(d，1H，Ar-H)，8.18-8.20(d，1H，Ar-H)，8.34-8.36(d，1H，Ar-H).
Ultimate analysis calculated value: C:68.65, H:3.46, N:9.61, O:18.29.
Ultimate analysis measured value: C:68.68, H:3.45, N:9.60, O:18.32.
Contain the I-6 monomer (the 4-cyano-benzene oxygen is at 4) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.16(s，6H，CH
3)，6.92-7.22(dd，4H，Ar-H)，7.85-7.87(d，1H，Ar-H)，7.90-7.92(dd，1H，Ar-H)，8.18-8.21(d，1H，Ar-H)，8.30-8.32(d，1H，Ar-H)，8.33-8.35(d，1H，Ar-H).
Ultimate analysis calculated value: C:68.65, H:3.46, N:9.61, O:18.29.
Ultimate analysis measured value: C:68.69, H:3.44, N:9.58, O:18.30.
Embodiment 5 contains monomeric the synthesizing of I-7 of N-methyl structural
In the 250mL three-necked bottle, add 4-hydroxyl-4 '-cyanobiphenyl 6.87g (0.032mol), the I-1 monomer 11.69g (0.032mol) and the DMF60mL of Anhydrous potassium carbonate 4.42g (0.032mol), N-methyl structural, nitrogen protection was stirred 8 hours down at 40 ℃.After having reacted reaction solution poured into and precipitate in the water, filtration drying promptly obtains containing the I-6 monomer of N-methyl structural.
Contain the I-7 monomer (substituting group is at 3) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.16(s，6H，CH
3)，6.98-7.44(dd，4H，Ar-H)，7.57-7.66(dd，4H，Ar-H)，7.56-7.58(d，1H，Ar-H)，7.89-7.92(dd，1H，Ar-H)，8.06-8.08(d，1H，Ar-H)，8.17-8.20(d，1H，Ar-H)，8.34-8.36(d，1H，Ar-H).
Ultimate analysis calculated value: C:72.51, H:3.73, N:8.18, O:15.58.
Ultimate analysis measured value: C:72.53, H:3.70, N:8.15, O:15.62.
Contain the I-7 monomer (substituting group is at 4) of N-methyl structural
1H-NMR (DMSO-d
6, ppm):
3.16(s，6H，CH
3)，6.97-7.43(dd，4H，Ar-H)，7.56-7.65(dd，4H，Ar-H)，7.84-7.86(d，1H，Ar-H)，7.90-7.92(dd，1H，Ar-H)，8.18-8.20(d，1H，Ar-H)，8.30-8.32(d，1H，Ar-H)，8.35-8.37(d，1H，Ar-H).
Ultimate analysis calculated value: C:72.51, H:3.73, N:8.18, O:15.5 8.
Ultimate analysis measured value: C:72.55, H:3.71, N:8.14, O:15.61.
Embodiment 6II-1 is monomeric synthetic
Add potassium hydroxide 6.73g (0.12mol) in the 250mL three-necked bottle, I-1 monomer 10.96g (0.03mol) makes it to be dissolved in the distilled water, reflux 12 hours.This reactant is precipitated in the hydrochloric acid solution of 1-3 in the pH value, filtration drying is deposited in this then in the diacetyl oxide and refluxed 8 hours again, and filtration drying promptly obtains the II-1 monomer.
Nitro is monomeric at 3 II-1
1H-NMR (DMSO-d
6, ppm):
8.01-8.05(dd，1H，Ar-H)，8.39-8.41(d，1H，Ar-H)，8.55-8.57(d，1H，Ar-H)，8.94-8.95(d，1H，Ar-H)，8.97-8.98(d，1H，Ar-H).
Ultimate analysis calculated value: C:56.65, H:1.49, N:4.13, O:37.73.
Ultimate analysis measured value: C:56.67, H:1.47, N:4.12, O:37.76.
Nitro is monomeric at 4 II-1
1H-NMR (DMSO-d
6, ppm):
8.02-8.06(dd，1H，Ar-H)，8.40-8.41(d，1H，Ar-H)，8.56-8.58(d，1H，Ar-H)，8.81-8.83(d，1H，Ar-H)，8.88-8.89(d，1H，Ar-H).
Ultimate analysis calculated value: C:56.65, H:1.49, N:4.13, O:37.73.
Ultimate analysis measured value: C:56.68, H:1.46, N:4.11, O:37.77.
Embodiment 7II-2 is monomeric synthetic
Add potassium hydroxide 8.42g (0.15mol) in the 250mL three-necked bottle, I-2 monomer 10.09g (0.03mol) makes it to be dissolved in distilled water/dehydrated alcohol (volume ratio 1: 1) reflux 8 hours.This reactant is precipitated in the hydrochloric acid solution of 1-3 in the pH value, filtration drying is deposited in this then in the diacetyl oxide and refluxed 4 hours again, and filtration drying promptly obtains the II-2 monomer.
Hydroxyl is monomeric at 3 II-2
1H-NMR (DMSO-d
6, ppm):
7.49-7.51(d，1H，Ar-H)，8.02-8.06(dd，1H，Ar-H)，8.11-8.13(d，1H，Ar-H)，8.39-8.41(d，1H，Ar-H)，8.55-8.57(d，1H，Ar-H)，9.46(s，1H，OH).
Ultimate analysis calculated value: C:61.95, H:1.95, O:36.10.
Ultimate analysis measured value: C:61.99, H:1.90, O:36.11.
Hydroxyl is monomeric at 4 II-2
1H-NMR (DMSO-d
6, ppm):
7.86-7.88(d，1H，Ar-H)，8.01-8.05(dd，1H，Ar-H)，8.38-8.40(d，1H，Ar-H)，8.38-8.40(d，1H，Ar-H)，8.56-8.58(d，1H，Ar-H)，9.38(s，1H，OH).
Ultimate analysis calculated value: C:61.95, H:1.95, O:36.10.
Ultimate analysis measured value: C:61.98, H:1.91, O:36.11.
Embodiment 8 II-3 are monomeric synthetic
Add sodium hydroxide 7.2g (0.18mol) in the 250mL three-necked bottle, I-3 monomer 12.37g (0.03mol) makes it to be dissolved in distilled water/Virahol (volume ratio 2: 1) reflux 30 hours.This reactant is precipitated in the hydrochloric acid solution of 1-3 in the pH value, filtration drying is deposited in this then in the diacetyl oxide and refluxed 8 hours again, and filtration drying promptly obtains the II-3 monomer.
Phenoxy group is monomeric at 3 II-3
1H-NMR (DMSO-d
6, ppm):
6.92-7.22(m，5H，Ar-H)，7.68-7.70(d，1H，Ar-H)，8.02-8.04(dd，1H，Ar-H)，8.27-8.29(d，1H，Ar-H)，8.39-8.41(d，1H，Ar-H)，8.55-8.57(d，1H，Ar-H).
Ultimate analysis calculated value: C:68.40, H:2.61, O:28.99.
Ultimate analysis measured value: C:68.42, H:2.57, O:29.02.
Phenoxy group is monomeric at 4 II-3
1H-NMR (DMSO-d
6, ppm):
6.91-7.23(m，5H，Ar-H)，8.02-8.04(dd，1H，Ar-H)，8.04-8.06(d，1H，Ar-H)，8.51-8.53(d，1H，Ar-H)，8.40-8.42(d，1H，Ar-H)，8.54-8.56(d，1H，Ar-H).
Ultimate analysis calculated value: C:68.40, H:2.61, O:28.99.
Ultimate analysis measured value: C:68.43, H:2.57, O:29.03.
Embodiment 9 II-6 are monomeric synthetic
Add sodium hydroxide 9.6g (0.24mol) in the 250mL three-necked bottle, I-6 monomer 13.12g (0.03mol) makes it to be dissolved in (volume ratio 0.5: 1) in distilled water/propyl alcohol reflux 26 hours.This reactant is precipitated in the hydrochloric acid solution of 1-3 in the pH value, filtration drying is deposited in this then in the diacetyl oxide and refluxed 6 hours again, and filtration drying promptly obtains the II-6 monomer.
The 4-cyano-benzene oxygen is monomeric at 3 II-6
1H-NMR (DMSO-d
6, ppm):
7.10-7.47(dd，4H，Ar-H)，7.68-7.70(d，1H，Ar-H)，8.02-8.04(dd，1H，Ar-H)，8.27-8.29(d，1H，Ar-H)，8.39-8.41(d，1H，Ar-H)，8.55-8.57(d，1H，Ar-H).
Ultimate analysis calculated value: C:67.16, H:2.21, N:3.41, O:27.23.
Ultimate analysis measured value: C:67.18, H:2.19, N:3.40, O:27.25.
The 4-cyano-benzene oxygen is monomeric at 4 II-6
1H-NMR (DMSO-d
6, ppm):
7.11-7.46(dd，4H，Ar-H)，8.01-8.05(dd，1H，Ar-H)，8.05-8.07(d，1H，Ar-H)，8.39-8.41(d，1H，Ar-H)，8.51-8.53(d，1H，Ar-H)，8.54-8.56(d，1H，Ar-H).
Ultimate analysis calculated value: C:67.16, H:2.21, N:3.41, O:27.23.
Ultimate analysis measured value: C:67.19, H:2.20, N:3.38, O:27.24.
Embodiment 10 II-7 are monomeric synthetic
Add sodium hydroxide 12g (0.39mol) in the 250mL three-necked bottle, I-7 monomer 15.41g (0.03mol) makes it to be dissolved in the distilled water, reflux 16 hours.This reactant is precipitated in the hydrochloric acid solution of 1-3 in the pH value, filtration drying is deposited in this then in the diacetyl oxide and refluxed 5 hours again, and filtration drying promptly obtains the II-7 monomer.
Nitro is monomeric at 3 II-7
1H-NMR (DMSO-d
6, ppm):
6.98-7.44(dd，4H，Ar-H)，7.57-7.66(dd，4H，Ar-H)，7.68-7.70(d，1H，Ar-H)，8.02-8.04(dd，1H，Ar-H)，8.27-8.29(d，1H，Ar-H)，8.39-8.41(d，1H，Ar-H)，8.55-8.57(d，1H，Ar-H).
Ultimate analysis calculated value: C:71.46, H:2.69, N:2.87, O:22.98.
Ultimate analysis measured value: C:71.47, H:2.65, N:2.84, O:23.02.
Nitro is monomeric at 4 II-7
1H-NMR (DMSO-d
6, ppm):
6.97-7.43(dd，4H，Ar-H)，7.56-7.65(dd，4H，Ar-H)，8.01-8.03(dd，1H，Ar-H)，8.05-8.07(d，1H，Ar-H)，8.40-8.42(d，1H，Ar-H)，8.51-8.53(d，1H，Ar-H)，8.56-8.58(d，1H，Ar-H).
Ultimate analysis calculated value: C:71.46, H:2.69, N:2.87, O:22.98.
Ultimate analysis measured value: C:71.50, H:2.66, N:2.84, O:23.01.
Claims (9)
1, a kind of biphenol compound with unsymmetrical structure, it is characterized in that: it has the structure of following general formula:
In the formula,
R
2＝-NO
2、OH、
R
3=H, CH
3Or CH
2CH
3
2, according to the described a kind of biphenol compound of claim 1, it is characterized in that with unsymmetrical structure: in the described general formula,
3, according to the described a kind of biphenol compound of claim 1, it is characterized in that with unsymmetrical structure: in the described general formula,
The time, the monomer with following structure:
4, a kind of synthetic method as dibenzoyl imide monomers I-1 as described in the claim 2, it is characterized in that: fully be dissolved in solvent orange 2 A at 1.5～3.5: 1 B component and component A in molar ratio, add catalyst A again, be warming up to 80-120 ℃ then, add catalyst B, 4～24 hours intact after-filtration of stirring reaction, obtain filtrate, regulating the pH value with acid solution is 1, separates out precipitation, and filtration drying gets intermediate 1; With nitrosonitric acid: intermediate 1 is 1.5-3.5 in molar ratio: 1 adds in the vitriol oil, stirs 4-24 hour at 10-80 ℃ then, after having reacted reaction solution is poured in the water and precipitates, and filtration drying promptly gets required product;
The component A that aforesaid method relates to is following structure:
The B component that aforesaid method relates to is chosen as: one or more of LiOH, NaOH, KOH;
The used solvent orange 2 A of aforesaid method is selected from water, methyl alcohol, ethanol or methylene dichloride;
Above-mentioned reaction catalyst system therefor A is 5%～10%Pd/C;
Above-mentioned reaction catalyst system therefor B is 5%～20% oxammonium sulfate solution or oxammonium hydrochloride solution.
5, a kind of synthetic method as dibenzoyl imide monomers I-2 as described in the claim 2 is characterized in that:
In the I-1 monomer, with catalyzer C: catalyzer D: the I-1 monomer is to be dissolved in solvent B at 0.8～1.5: 0.7～1.5: 1 in molar ratio, nitrogen protection, and 70-160 ℃ was stirred 8～24 hours; After having reacted reaction solution poured into the pH value and be in 2～3 the acid solution and precipitate, filtration drying promptly obtains required product;
Aforesaid method solvent for use B is selected from: N, dinethylformamide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide or N-Methyl pyrrolidone;
Catalyzer C is selected from anhydrous sodium carbonate or Anhydrous potassium carbonate;
Catalyzer D is selected from Sodium Nitrite or potassium nitrite.
6, a kind of synthetic method as dibenzoyl imide monomers I-3 to I-7 as described in the claim 2 is characterized in that:
In the I-1 monomer, with component C: catalyzer E: the I-1 monomer is 0.8-1.5 in molar ratio: 0.8-1.5: 1 is dissolved in the solvent C, and nitrogen protection was stirred 8-24 hour in 10-90 ℃.After having reacted reaction solution poured into and precipitate in the water, filtration drying promptly obtains required product;
The component C that aforesaid method relates to is following structure:
Solvent C is selected from N, dinethylformamide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide or N-Methyl pyrrolidone;
Catalyzer E is Anhydrous potassium carbonate or anhydrous sodium carbonate.
7, a kind of as the synthetic method of biphenyl dianhydride monomer II-1 as described in the claim 3 to II-7, it is characterized in that:
Respectively in the I-a monomer, a=1,2,3,4,5,6 or 7, with catalyzer F: the I-a monomer is 4-13 in molar ratio: 1 is dissolved among the solvent D, reflux 8-30 hour, this reactant is precipitated in pH is the acid solution of 1-3, filtration drying is deposited in this among solvent E backflow 4-10 hour then again, filtration drying promptly obtains required product II-a;
The solvent D that aforesaid method relates to is water and ethanol, the mixed solvent of propyl alcohol or Virahol, and its volume ratio is 0.5-2: 1;
Solvent E is a diacetyl oxide; Catalyzer F is potassium hydroxide or sodium hydroxide.
8. one kind from the synthetic monomeric route of biphenyl dianhydride of halophthalimide class monomer, it is characterized in that:
B component and component A fully are dissolved in solvent orange 2 A in molar ratio at 1.5～3.5: 1, add catalyst A again, be warming up to 80-120 ℃ then, add catalyst B, 4～24 hours intact after-filtration of stirring reaction obtain filtrate, regulating the pH value with acid solution is 1, separates out precipitation, and filtration drying gets intermediate 1; With catalyzer F: intermediate 1 is 4-13 in molar ratio: 1 is dissolved among the solvent D, reflux 8-30 hour, this reactant is precipitated in pH is the acid solution of 1-3 again, filtration drying, then this is deposited among the solvent E backflow 4-10 hour, filtration drying promptly obtains required product;
The component A that aforesaid method relates to is following structure:
The B component that aforesaid method relates to is chosen as: one or more of LiOH, NaOH, KOH;
The used solvent orange 2 A of aforesaid method is selected from water, methyl alcohol, ethanol or methylene dichloride;
Above-mentioned reaction catalyst system therefor A is 5%～10%Pd/C;
Above-mentioned reaction catalyst system therefor B is 5%～20% oxammonium sulfate solution or oxammonium hydrochloride solution;
The solvent D that aforesaid method relates to is water and ethanol, the mixed solvent of propyl alcohol or Virahol, and its volume ratio is 0.5-2: 1;
Solvent E is a diacetyl oxide; Catalyzer F is potassium hydroxide or sodium hydroxide.
9, a kind ofly be introduced in the polyimide molecule structure to improve the purposes of its solvable meltability as biphenyl dianhydride monomer as described in the claim 3.
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Cited By (2)
| 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 |
| CN108530660A (en) * | 2018-04-17 | 2018-09-14 | 福州大学 | A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof |
-
2008
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Cited By (3)
| 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 |
| CN108530660A (en) * | 2018-04-17 | 2018-09-14 | 福州大学 | A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof |
| CN108530660B (en) * | 2018-04-17 | 2019-10-15 | 福州大学 | A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof |
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