CN102796015A - Double trifluoromethyl substituent-containing asymmetric aromatic diamine monomer and preparation method thereof - Google Patents
Double trifluoromethyl substituent-containing asymmetric aromatic diamine monomer and preparation method thereof Download PDFInfo
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- CN102796015A CN102796015A CN2012103031394A CN201210303139A CN102796015A CN 102796015 A CN102796015 A CN 102796015A CN 2012103031394 A CN2012103031394 A CN 2012103031394A CN 201210303139 A CN201210303139 A CN 201210303139A CN 102796015 A CN102796015 A CN 102796015A
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Abstract
A double trifluoromethyl substituent-containing asymmetric aromatic diamine monomer is 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,3,5-trimethylbenzene. The synthetic route of the monomer is simple, the yield is high, the purification is easy, and the monomer is stable at room temperature and can be used for the preparation of soluble fluorine-containing polyimide polymers. The preparation method of the double trifluoromethyl substituent-containing asymmetric aromatic diamine monomer includes the following steps: reacting 2,3,5-trimethylhydroquinone with 2-chloro-5-nitrobenzotrifluoride under alkaline conditions with the protection of nitrogen, sufficiently stirring, precipitating and leaching, washing the product with hot water, further recrystallizing to get a fluorine-containing dinitrocompound which is 1,4-bis(4-nitro-2-trifluoromethylphenoxy)-2,3,5-trimethylbenzene, and reacting the fluorine-containing dinitrocompound with a catalyst and a reducing agent in the presence of an organic solvent to get 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,3,5-trimethylbenzene by reduction.
Description
Technical field
The invention belongs to fluorine-containing aromatic diamine compound and preparation field thereof, particularly contain bis trifluoromethyl and replace asymmetric aromatic diamine monomers and preparation method thereof.
Background technology
Polyimide is one type of important function property high-temperature polymer, can be used as matrices of composite material, electronic package material, gas separation membrane etc. and is applied in the modern high-tech field.Although this type high temperature material has excellent thermal property and mechanical property; But because the strong interaction of stiff backbone structure that they had and intermolecular existence and molecular chain is tightly packed; Cause most of commercialization polyimide all to have very high melt temperature; Be insoluble to organic solvent (only being dissolved in the vitriol oil mostly) again, bring difficulty for its forming process.In addition, traditional polyimide is owing to the aromatic conjugated property and the interior electric charge complexing transferance of molecular chain of molecular backbone chain height, and its film has very dark color and relatively poor optical transparence mostly.For overcoming these deficiencies, further develop new type polyimide with well applied film-forming properties and light high optical transparency property, the various countries researchist has dropped into very big effort.
Polyimide is mainly made by aromatic diamine monomers and the polycondensation of aromatic dianhydride monomer, and monomeric structure directly determines polymer properties.Conventional aromatic diamine monomers generally has symplex structure, does not have the side group of replacement, causes its corresponding polyimide to show relatively poor film-forming properties and optical transparence; In addition, conventional diamine monomer is easy to oxidation, and stability is also relatively poor under the room temperature.Therefore to have the novel aromatic diamine monomer of special construction and substituted radical be to prepare the imido key of functional polyalkylene to designing and preparing.
Summary of the invention
The technical problem that the present invention will solve is: overcome that polyimide is insoluble to organic solvent in the prior art, color is dark and the relatively poor deficiency of optical transparence; Provide a kind of bis trifluoromethyl that contains to replace asymmetric aromatic diamine monomers and preparation method thereof; This aromatic diamines purity is high, good stability under the normal temperature.Contain bis trifluoromethyl replace asymmetric aromatic diamine monomers the preparation polyimide application in; In macromolecular main chain, introduce big trifluoromethyl and unsymmetrical structure; Not only dissolving film-forming properties, optical property and the dielectric properties of resulting polymers can be improved greatly, and excellent thermal property of said material and mechanical property etc. can also be kept.
For the technical scheme that solves the problems of the technologies described above the present invention's employing is: a kind of bis trifluoromethyl that contains replaces asymmetric aromatic diamine monomers, and monomer whose is 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-, and the 5-Three methyl Benzene, its structural formula is:
Be the white powder solid, fusing point is 233～234 ℃.
The described bis trifluoromethyl that contains replaces the preparation that asymmetric aromatic diamine monomers is used for the soluble fluorine-containing polyimide polymer.
A kind of preparation contains the method that bis trifluoromethyl replaces asymmetric aromatic diamine monomers, and step is following:
(1) under nitrogen protection, be 2,3 of 1:2.0 ~ 2.3 with mol ratio; 5-Trimethyl Hydroquinone and 2-chloro-5-nitro-trifluoromethyl toluene be 100～150 ℃ of reaction 8～24h under alkaline condition, fully stir deposition and filter, and wash product repeatedly with hot water; Further recrystallization obtains dinitro compound 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-; 3, the 5-Three methyl Benzene;
(2) with dinitro compound with catalyzer and reductive agent 60-100 ℃ of reaction 4～10h in the presence of organic solvent, reduction promptly obtains 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-, 5-Three methyl Benzene.Concrete synthetic route is following:
The described recrystallization of step (1) carries out in the mixed solvent of dinethylformamide and methyl alcohol at N, and the mol ratio of NN-N and methyl alcohol is 3:2 in the mixing solutions.
The described alkaline condition of step (1) is the N of salt of wormwood or yellow soda ash, the DMAC N,N solution of dinethylformamide solution, salt of wormwood or yellow soda ash or the N-Methyl pyrrolidone solution of salt of wormwood or yellow soda ash; In the system 2; 3, the massfraction of 5-Trimethyl Hydroquinone and 2-chloro-5-nitro-trifluoromethyl toluene is 20～50%, and the mole number of salt of wormwood or yellow soda ash is 2; 3,1.5～3.0 times of 5-Trimethyl Hydroquinone mole number.
The described catalyzer of step (2) is 5% or 10% palladium carbon, and catalyst levels is 1～4% of a dinitro compound quality; Described reductive agent is that massfraction is the aqueous solution of the Hydrazine Hydrate 80 of 70-85%, and the reductive agent consumption is 4～12 times of dinitro compound mole number.
Fluorine-containing dinitro compound is at catalyzer and organic solvent in the step (2), fully is stirred and heated to reflux down, splashes into behind the reductive agent at 60-100 ℃ of reaction 4 ~ 10h; Heat filtering is removed catalyzer; Further use ethyl alcohol recrystallization, make aromatic diamines 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2 of 4-; 3, the 5-Three methyl Benzene.
The described organic solvent of step (2) is methyl alcohol, ethanol and 1, one or more in the 4-dioxane, and the organic solvent quality is 10～30 times of dinitro compound quality.
The invention has the beneficial effects as follows: to replace asymmetric aromatic diamine monomers synthetic route simple for the bis trifluoromethyl that contains of (1) the present invention preparation, and productive rate is high, is easy to purify separate, and normal temperature is stable down;
(2) have following excellent comprehensive performance to contain the fluorinated polyimide that bis trifluoromethyl replaces the preparation of asymmetric aromatic diamine monomers: good solubility can; Not only dissolve in N-Methyl pyrrolidone, N; N-N,N-DIMETHYLACETAMIDE, N; High boiling solvents such as dinethylformamide can also be dissolved in the low boiling point solvents such as chloroform, THF; Excellent heat resisting, second-order transition temperature and initial decomposition temperature are respectively more than 280 and 480 ℃; Excellent mechanical property and good film-forming properties, the tensile strength of film is between 60～90MPa, and elongation at break is between 5～15%, and initial modulus is more than 1.8GPa; Excellent optical property, cut-off wavelength has high transmittance in the visible-range between 350～380nm; Low specific inductivity, the specific inductivity of wherein made polyimide is between 2.5 ~ 3.0.
Description of drawings
Fig. 1 is 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-, the infared spectrum of 5-Three methyl Benzene.
Fig. 2 is 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-, the 5-Three methyl Benzene
1The HNMR collection of illustrative plates.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-, the preparation of 5-Three methyl Benzene:
1. under nitrogen protection, with 15.22g (0.1mol) 2,3; 5-Trimethyl Hydroquinone and 45.11g (0.2mol) 2-chloro-5-nitro-trifluoromethyl toluene joins in the there-necked flask of 500ml, adds 28.98g (0.21mol) salt of wormwood and 130mlN more respectively, dinethylformamide; At 120 ℃ of reaction 12h, product poured in the 1000ml methanol (1:1) fully stir deposition and filter, and wash product repeatedly with hot water; Further use NN-N/methyl alcohol (3:2) mixed solvent recrystallization to obtain faint yellow fluorine-containing dinitro compound: 1; Two (the 4-nitros-2-4-trifluoromethylphenopendant)-2,3 of 4-, the 5-Three methyl Benzene; Productive rate 85%, 256～257 ℃ of fusing points.
1H?NMR(DMSO-d
6,400MHz)δ:8.64(d,J＝2.8Hz,1H),8.62(d,J＝2.8Hz,1H),8.32(dd,J
1=2.8Hz,J
2=9.2Hz,1H),8.30(dd,J
1=2.8Hz,J
2=9.2Hz,1H),6.91(s,1H),6.80(d,J＝9.2Hz,1H),6.62(d,J＝9.2Hz,1H),2.13(s,3H),2.11(s,3H),2.10(s,3H);IR(KBr)v:2928,1611,1532,1347,1269,1144cm
-1.Anal.calcd?for?C
23H
16F
6N
2O
6:C52.09,H3.04,N5.28;found?C51.97,H3.08,N5.31。
2. with the fluorine-containing dinitro compound 1 of 26.52g (0.05mol), two (the 4-nitros-2-4-trifluoromethylphenopendant)-2,3 of 4-; The 5-Three methyl Benzene joins in the 500ml there-necked flask, adds palladium-carbon catalyst and the 300ml ethanol of 0.3g10% more respectively, and fully stirring heating refluxes down for about 80 ℃; Splash into the about 6h of 20ml80% Hydrazine Hydrate 80 continued back flow reaction in half hour with constant pressure funnel, heat filtering is removed palladium carbon, concentrates to obtain shallow white solid crude product; Further obtain white crystal and be aromatic diamines 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-with ethyl alcohol recrystallization; The 5-Three methyl Benzene, productive rate 85%, 233～234 ℃ of fusing points.
1H-NMR(DMSO-d
6,400MHz)δ：6.94(m,2H),6.78(dd,J
1=2.8Hz,J
2=8.8Hz,1H),6.68(d,J＝8.8Hz,1H),6.66(dd,J
1=2.8Hz,J
2=8.8Hz,1H),6.57（s,1H),6.18(d,J＝8.8Hz,1H),5.33(s,2H),5.12(s,2H),2.12(s,3H),2.01(s,3H),1.94(s,3H);IR(KBr)v:3429,3331,3226,2928,1624,1236,1149cm
-1.Anal.calcd?for?C
23H
20F
6N
2O
2:C58.72,H4.29,N5.96;found?C58.60,H4.33,N6.01.?。
Claims (7)
1. one kind contains bis trifluoromethyl and replaces asymmetric aromatic diamine monomers, and it is characterized in that: monomer is 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-, and the 5-Three methyl Benzene, its structural formula is:
2. the bis trifluoromethyl that contains according to claim 1 replaces asymmetric aromatic diamine monomers, is used for the preparation of soluble fluorine-containing polyimide polymer.
3. one kind prepares that claim 1 is described to contain the method that bis trifluoromethyl replaces asymmetric aromatic diamine monomers, and it is characterized in that: step is following:
(1) under nitrogen protection, be 2,3 of 1:2.0 ~ 2.3 with mol ratio; 5-Trimethyl Hydroquinone and 2-chloro-5-nitro-trifluoromethyl toluene be 100～150 ℃ of reaction 8～24h under alkaline condition, fully stir deposition and filter, and wash product repeatedly with hot water; Further recrystallization obtains dinitro compound 1, two (the 4-nitros-2-4-trifluoromethylphenopendant)-2 of 4-; 3, the 5-Three methyl Benzene;
(2) with dinitro compound with catalyzer and reductive agent 60-100 ℃ of reaction 4～10h in the presence of organic solvent, product promptly obtains 1, two (the 4-amidos-2-4-trifluoromethylphenopendant)-2,3 of 4-, 5-Three methyl Benzene through further recrystallization.
4. preparation according to claim 3 contains the method that bis trifluoromethyl replaces asymmetric aromatic diamine monomers; It is characterized in that: the described recrystallization of step (1) is at N; Carry out in the mixed solvent of dinethylformamide and methyl alcohol; N in the mixing solutions, the mol ratio of dinethylformamide and methyl alcohol is 3:2; The described recrystallization of step (2) carries out in ethanol.
5. preparation according to claim 3 contains the method that bis trifluoromethyl replaces asymmetric aromatic diamine monomers; It is characterized in that: the described alkaline condition of step (1) is the N of salt of wormwood or yellow soda ash, the DMAC N,N solution of dinethylformamide solution, salt of wormwood or yellow soda ash or the N-Methyl pyrrolidone solution of salt of wormwood or yellow soda ash; In the system 2; 3, the massfraction of 5-Trimethyl Hydroquinone and 2-chloro-5-nitro-trifluoromethyl toluene is 20～50%, and the mole number of salt of wormwood or yellow soda ash is 2; 3,1.5～3.0 times of 5-Trimethyl Hydroquinone mole number.
6. preparation according to claim 3 contains the method that bis trifluoromethyl replaces asymmetric aromatic diamine monomers, it is characterized in that: the described catalyzer of step (2) is 5% or 10% palladium carbon, and catalyst levels is 1～4% of a dinitro compound quality; Described reductive agent is that massfraction is the aqueous solution of the Hydrazine Hydrate 80 of 70-85%, and the reductive agent consumption is 4～12 times of dinitro compound mole number.
7. preparation according to claim 3 contains the method that bis trifluoromethyl replaces asymmetric aromatic diamine monomers; It is characterized in that: the described organic solvent of step (2) is methyl alcohol, ethanol and 1; In the 4-dioxane one or more, organic solvent quality are 10～30 times of dinitro compound quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162922A (en) * | 2017-05-24 | 2017-09-15 | 吉林大学 | A kind of diamine monomer of polyimides containing pi-allyl and its polyimide polymer and preparation method |
| JP2020070255A (en) * | 2018-10-31 | 2020-05-07 | セイカ株式会社 | Bis(amino or nitrophenoxy) benzene compound, method for producing the same, and polyimide |
| CN112679734A (en) * | 2020-12-28 | 2021-04-20 | 常州大学 | Soluble polyimide containing bis (trifluoromethyl) benzene substituted asymmetric meta-position structure and preparation method thereof |
| CN115894258A (en) * | 2022-11-07 | 2023-04-04 | 万华化学集团股份有限公司 | Aromatic diamine monomer and preparation and application thereof |
-
2012
- 2012-08-24 CN CN2012103031394A patent/CN102796015A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 汪称意等: "Synthesis and Properties of New Fluorinated Polyimides Derived from an Unsymmetrical and Noncoplanar Diamine", 《CHIN. J. CHEM.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162922A (en) * | 2017-05-24 | 2017-09-15 | 吉林大学 | A kind of diamine monomer of polyimides containing pi-allyl and its polyimide polymer and preparation method |
| CN107162922B (en) * | 2017-05-24 | 2020-04-21 | 吉林大学 | Allyl-containing polyimide diamine monomer, polyimide polymer thereof and preparation method |
| JP2020070255A (en) * | 2018-10-31 | 2020-05-07 | セイカ株式会社 | Bis(amino or nitrophenoxy) benzene compound, method for producing the same, and polyimide |
| JP2023015209A (en) * | 2018-10-31 | 2023-01-31 | セイカ株式会社 | Bis(amino- or nitrophenoxy-)benzene compound and production method thereof, and polyimide |
| JP7315135B2 (en) | 2018-10-31 | 2023-07-26 | セイカ株式会社 | Bis(amino or nitrophenoxy) benzene compound, method for producing the same, and polyimide |
| JP7390754B2 (en) | 2018-10-31 | 2023-12-04 | セイカ株式会社 | Bis(amino or nitrophenoxy)benzene compound, method for producing the same, and polyimide |
| CN112679734A (en) * | 2020-12-28 | 2021-04-20 | 常州大学 | Soluble polyimide containing bis (trifluoromethyl) benzene substituted asymmetric meta-position structure and preparation method thereof |
| CN115894258A (en) * | 2022-11-07 | 2023-04-04 | 万华化学集团股份有限公司 | Aromatic diamine monomer and preparation and application thereof |
| CN115894258B (en) * | 2022-11-07 | 2024-06-25 | 万华化学集团股份有限公司 | Aromatic diamine monomer, and preparation and application thereof |
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Application publication date: 20121128 |