CN101613473B - High-glass transition temperature polyazomethines containing ether ketone structure and preparation method thereof - Google Patents
High-glass transition temperature polyazomethines containing ether ketone structure and preparation method thereof Download PDFInfo
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- CN101613473B CN101613473B CN2009100672794A CN200910067279A CN101613473B CN 101613473 B CN101613473 B CN 101613473B CN 2009100672794 A CN2009100672794 A CN 2009100672794A CN 200910067279 A CN200910067279 A CN 200910067279A CN 101613473 B CN101613473 B CN 101613473B
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- poly methylene
- transition temperature
- methylene imine
- ether ketone
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- GNYLAADDIDGYJN-UHFFFAOYSA-N COc(cc1)c(C(c(cc2)ccc2Oc(cc2)ccc2N)=O)c(cc2)c1c(C(c(cc1)ccc1Oc(cc1)ccc1N)=O)c2OC Chemical compound COc(cc1)c(C(c(cc2)ccc2Oc(cc2)ccc2N)=O)c(cc2)c1c(C(c(cc1)ccc1Oc(cc1)ccc1N)=O)c2OC GNYLAADDIDGYJN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of polymer materials, particularly relating to a high-solubility and high-glass transition temperature (about 230 DEG C) polyazomethines and a preparation method thereof. In the method, a novel diamine monomer containing naphthalene ring is polymerized with terephthalaldehyde at room temperature under the conditions of different time, different solvents and different catalysts (dehydrating agent), the polymer is discharged in distilled water to obtain the polyazomethines. For the high-glass transition temperature polyazomethines containing an ether ketone structure, the molecular weight is large, the solubility and the filming property are good, thereby providing possibility for being a coating material.
Description
Technical field
The invention belongs to macromolecular material and preparing technical field thereof, particularly a kind of high resolution, poly methylene imine material high glass-transition temperature, that contain ether ketone structure and preparation method thereof.
Background technology
Poly methylene imine is the emerging polymkeric substance of a class, because its distinctive carbon-to-nitrogen double bon, flexible and changeable backbone structure, make it at heat-stable material, liquid crystal material, nonlinear optical material, have broad prospects, become a focus of polymer research field in recent years as the Application and Development of aspects such as metal ion trapping agent.
Because the structure rigidity of poly methylene imine is more intense, its solvability is not fine.This just makes it have a lot of problems aspect preparation and the processing.Usually polymerization all needs high temperature in solution, and because the molecular weight that solubility problem obtains poly methylene imine is not very big.In order to address this problem, scientific workers have done a lot of work, as introducing the aliphatics flexible chain on the monomer, introduce ehter bond, class ether sulfone structure etc. in backbone structure.
Summary of the invention
The technical problem to be solved in the present invention is, prepared a kind of new diamine monomer, makes reaction to carry out at low temperatures; Can obtain the bigger soluble poly azomethine material of molecular weight by this diamine monomer, it has high glass transition, and its film-forming properties is good, and making it become coated material becomes possibility.
The diamines that contains ether ketone structure and naphthalene nucleus of the present invention's preparation, owing to introduced naphthalene nucleus, thus improved the second-order transition temperature of polymkeric substance, and, improved the solvability of polymkeric substance because of introducing bulky group; The introducing of ether ketone structure has kept high-heat performance especially as much as possible under the deliquescent condition of increase.Owing to improved the solvability of polymkeric substance, can carry out polyreaction at ambient temperature, saved the energy greatly.
Its structural formula of new diamine monomer of the present invention's design is:
Structural formula by its novel poly methylene imine that makes is:
Wherein, n is a positive integer, the expression polymerization degree;
The preparation process of diamine monomer of the present invention is:
2,6-dimethoxy-naphthalene and fluorobenzoyl chloride joined fill 500mL CHCl
2CHCl
2There-necked flask in, add anhydrous ZnCl again
2Stirred under the room temperature 1～3 hour, and be warmed up to 80～90 ℃, continue again to stir 12～14 hours; Then reaction mixture is poured in the dilute hydrochloric acid, heating boils off ethylene dichloride, obtains solid, filters the back and collects solid, uses the acetone thorough washing again, obtains 1 after the drying, 5-two (4-fluorine) phenylcarbamoyl-2,6-dimethoxy-naphthalene.
At N
2Under the protection, 1,5-two (4-fluorine) phenylcarbamoyl-2,6-dimethoxy-naphthalene, para hydroxybenzene amine, Anhydrous potassium carbonate adding fill in the there-necked flask that has water-taker of 30～40mL DMF and 20～30ml toluene; 120～130 ℃ were refluxed 1～3 hour, emitted behind the toluene again in 140～150 ℃ of reactions 4～5 hours, then reaction mixture were poured in the frozen water, separated out solid; Suction strainer after the oven dry, is used the column chromatography method separation and purification, and eluent is that volume ratio is 5: 1 methylene dichloride and a tetrahydrofuran (THF), obtains yellow solid, is 1,5-two [4-(4-amino-benzene oxygen)] phenylcarbamoyl-2,6-dimethoxy-naphthalene diamine monomer.
In the above-mentioned steps, 2,6-dimethoxy-naphthalene and be 1: 2～4,2 to the fluorobenzoyl cl molar ratio, the mol ratio of 6-dimethoxy-naphthalene and Zinc Chloride Anhydrous is 1: 2～4; In 500mL CHCl2CHCl2,2, the solid content of 6-dimethoxy-naphthalene is 8%～10%, 1,5-two (4-fluorine) phenylcarbamoyl-2, the mol ratio of 6-dimethoxy-naphthalene and para hydroxybenzene amine is 1: 2～2.5,1,5-two (4-fluorine) phenylcarbamoyl-2, the mol ratio of 6-dimethoxy-naphthalene and Anhydrous potassium carbonate is 1: 1～1.5; In the solvent that fills 30～40mL DMF and 20～30ml toluene, 1,5-two (4-fluorine) phenylcarbamoyl-2, the solid content of 6-dimethoxy-naphthalene is 8wt%～10wt%.
Poly methylene imine polymer manufacture step of the present invention is:
In the 50ml three-necked bottle in 20～30 ℃ of oil baths that stirrer, nitrogen protection are housed, add above-mentioned diamine monomer, terephthalaldehyde, Lithium chloride (anhydrous) or calcium chloride, adding volume ratio again is 1: 1 NMP and the mixed solvent of HMPA, reacts 24～72 hours; Discharging is in distilled water then, and the solid that obtains washes 3～5 times repeatedly with distilled water, the methyl alcohol extracting of spending the night, and 50～80 ℃ of dryings of vacuum 8～10 hours obtain yellow solid, i.e. the poly methylene imine polymkeric substance.
In the above-mentioned steps, 1,5-two [4-(4-amino-benzene oxygen)] phenylcarbamoyl-2, the mol ratio of 6-dimethoxy-naphthalene and terephthalaldehyde is 1～0.8: 0.8～1.In 1%～3%NMP of the consumption mixed solvent of Lithium chloride (anhydrous) or calcium chloride and the mixed solvent of HMPA, the solid content of diamine monomer is 8wt%～12wt%.
The casting film step of poly methylene imine polymkeric substance of the present invention is:
The poly methylene imine polymkeric substance is dissolved in the organic solvent, and the indication organic solvent is NMP or meta-cresol, casts on the clean sheet glass, and 80～90 ℃ kept 8～10 hours, and 120～130 ℃ kept 3～5 hours, thereby obtain the poly methylene imine film on sheet glass; Poly methylene imine polymkeric substance concentration in organic solvent is 0.8～1g/10ml.
Description of drawings:
The second-order transition temperature of Fig. 1: embodiment 3 described polymkeric substance;
As seen from the figure its second-order transition temperature be 234 (℃).
Fig. 2: embodiment 2 described monomeric proton magnetic spectrum figure;
It is fine that each peak position all belongs to.
The proton magnetic spectrum figure of Fig. 3: embodiment 3 described polymkeric substance.
It is fine that each peak position all belongs to, and especially the peak of 7 positions has illustrated the polymeric success.
Embodiment
Embodiment 1:
2, (47.00g, 0.25mol) and to fluorobenzoyl chloride (88.70g, 0.75mol) adding fills 500mL CHCl to the 6-dimethoxy-naphthalene
2CHCl
2There-necked flask in, add anhydrous ZnCl again
2(5.10g, 0.75mol).Stirred 1 hour under the room temperature, be warmed up to 80 ℃, continue again to stir 12 hours.Reaction mixture is poured in the dilute hydrochloric acid, and heating boils off ethylene dichloride, obtains solid.With filtering the solid acetone thorough washing that collect the back, obtain 1 after the drying, 5-two (4-fluorine) phenylcarbamoyl-2,6-dimethoxy-naphthalene.Through its molecular weight of mass spectrometric measurement is 432.4.
Embodiment 2:
At N
2Under the protection, 1,5-two (4-fluorine) phenylcarbamoyl-2; the 6-dimethoxy-naphthalene (4.32g, 0.01mol), para hydroxybenzene amine (2.40g; 0.022mol), (1.60g, 0.012mol) adding fills in the there-necked flask that has the Dean-Stark device of 30mLDMF and 20ml toluene salt of wormwood.130 ℃ were refluxed 2.5 hours, emitted behind the toluene 150 ℃ of reactions 4.5 hours.Reaction mixture is poured in the frozen water, separated out solid.Suction strainer after the oven dry, is used the column chromatography method separation and purification, and eluent is methylene dichloride and tetrahydrofuran (THF) (volume ratio is 5: 1), obtains yellow solid: 1, and 5-two [4-(4-amino-benzene oxygen)] phenylcarbamoyl-2,6-dimethoxy-naphthalene.Through its molecular weight of mass spectrometric measurement is 610.6.
Embodiment 3:
Stirrer is being housed, add in the 50ml three-necked bottle in 25 ℃ the oil bath of nitrogen protection above-mentioned diamines (0.88g, 1.44mmol), terephthalaldehyde (0.19g, 1.44mmol) and the 0.65g Lithium chloride (anhydrous).Add the mixing solutions (volume ratio 1: 1) of 6ml NMP and HMPA then, reacted 48 hours.Discharging is in distilled water, and the solid that obtains washes several times repeatedly with distilled water, the methyl alcohol extracting of spending the night, and 50 ℃ of dryings of vacuum 8 hours obtain the yellow solid sample.
Embodiment 4:
The 0.35g polymkeric substance is dissolved among the 3mlNMP, is poured on the sheet glass of 80 ℃ of preheatings, be warming up to 120 ℃ behind the 10h, keep taking off behind the 4h, obtain toughness mould material preferably.
Claims (4)
1. the poly methylene imine that contains ether ketone structure of high glass-transition temperature, its structural formula is as follows:
Wherein, n is a positive integer, the expression polymerization degree.
2. the preparation method of the poly methylene imine that contains ether ketone structure of the described high glass-transition temperature of claim 1, its step is as follows: in the 50ml three-necked bottle that stirrer, nitrogen protection, 20～30 ℃ of oil baths are housed, add diamine monomer, terephthalaldehyde, Lithium chloride (anhydrous) or calcium chloride, adding volume ratio again is 1: 1 NMP and the mixed solvent of HMPA, reacts 24～72 hours; Discharging is in distilled water then, and the solid that obtains washes 3～5 times repeatedly with distilled water, the methyl alcohol extracting of spending the night, and 50～80 ℃ of dryings of vacuum 8～10 hours obtain yellow solid, i.e. the poly methylene imine polymkeric substance;
In the above-mentioned steps, the mol ratio of diamine monomer and terephthalaldehyde is 1～0.8: 0.8～1, and the consumption of Lithium chloride (anhydrous) or calcium chloride is 1%～3% of a mixed solvent, and in the mixed solvent, the solid content of diamine monomer is 8wt%～12wt%;
Diamine monomer is 1,5-two [4-(4-amino-benzene oxygen)] phenylcarbamoyl-2, and the 6-dimethoxy-naphthalene, its structural formula is as follows,
3. the poly methylene imine that contains ether ketone structure of the described high glass-transition temperature of claim 1 is used for casting film.
4. the poly methylene imine that contains ether ketone structure of high glass-transition temperature as claimed in claim 3 is used for casting film, the steps include: the poly methylene imine polymkeric substance is dissolved in NMP or meta-cresol, cast on the clean sheet glass, 80～90 ℃ kept 8～10 hours, 120～130 ℃ kept 3～5 hours, thereby obtain the poly methylene imine film on sheet glass; Poly methylene imine polymkeric substance concentration in NMP or meta-cresol is 0.8～1g/10ml.
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Citations (5)
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|---|---|---|---|---|
| US4048148A (en) * | 1975-05-09 | 1977-09-13 | E. I. Du Pont De Nemours And Company | Polyazomethine fibers and films |
| EP0750016A1 (en) * | 1995-06-20 | 1996-12-27 | Honda Giken Kogyo Kabushiki Kaisha | Molecular composite material composed of polyazomethine and thermoplastic polymer and method for producing same |
| CN1786049A (en) * | 2005-12-06 | 2006-06-14 | 河北工业大学 | Nylon 6/ poly methylene imine molecular composite material and its preparation method |
| KR20070055307A (en) * | 2005-11-24 | 2007-05-30 | 삼성에스디아이 주식회사 | Proton conductive solid polymer electrolyte and fuel cell comprising the same |
| JP2008266539A (en) * | 2007-04-25 | 2008-11-06 | Toyobo Co Ltd | Polyazomethine and manufacturing method for its film |
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- 2009-07-10 CN CN2009100672794A patent/CN101613473B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048148A (en) * | 1975-05-09 | 1977-09-13 | E. I. Du Pont De Nemours And Company | Polyazomethine fibers and films |
| EP0750016A1 (en) * | 1995-06-20 | 1996-12-27 | Honda Giken Kogyo Kabushiki Kaisha | Molecular composite material composed of polyazomethine and thermoplastic polymer and method for producing same |
| KR20070055307A (en) * | 2005-11-24 | 2007-05-30 | 삼성에스디아이 주식회사 | Proton conductive solid polymer electrolyte and fuel cell comprising the same |
| CN1786049A (en) * | 2005-12-06 | 2006-06-14 | 河北工业大学 | Nylon 6/ poly methylene imine molecular composite material and its preparation method |
| JP2008266539A (en) * | 2007-04-25 | 2008-11-06 | Toyobo Co Ltd | Polyazomethine and manufacturing method for its film |
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| 万俊杰，钟宏.聚甲亚胺类导电高分子的研究核进展.《材料导报》.2009,第17卷180-183. * |
| 娄山宁,张玉姿,吕兆萍,张润生,刘冰,刘道辉,焦战士.共轭性芳杂环聚甲亚胺的合成及性能研究.《材料导报:研究篇》.2010,第24卷(第4期),25-28. * |
| 张其震，李小放，杨兆荷.含甲氧基悬挂基聚甲亚胺醚的合成及其液晶行为.《高等学校化学学报》.1994,第15卷(第2期),299-302. * |
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