CN101153074A - Aromatic polyamide containing fluorine and diamine monomer containing fluorine based on naphthyridine ketone structure and method of producing the same - Google Patents
Aromatic polyamide containing fluorine and diamine monomer containing fluorine based on naphthyridine ketone structure and method of producing the same Download PDFInfo
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- CN101153074A CN101153074A CNA2007100092412A CN200710009241A CN101153074A CN 101153074 A CN101153074 A CN 101153074A CN A2007100092412 A CNA2007100092412 A CN A2007100092412A CN 200710009241 A CN200710009241 A CN 200710009241A CN 101153074 A CN101153074 A CN 101153074A
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Abstract
The present invention discloses a poly aromatic amide compound containing fluorine and based on the structure of di-nitrone phthalazinone, a diamine monomer containing fluorine and a preparation method. The bisphenol type monomer with the structure of phthalazinone and the 2-chlorine-5-nitro toluene trifluoromethyl react to produce a dinitro compound through nucleophilic substitution; the dinitro compound is reduced to be diamine monomer containing fluorine. The poly aromatic amide uses diamine monomer containing fluorine and diacid for condensation and polymerization to get novel poly aromatic amide of good solubility; the specific viscosity is between 0.41dL/g to 0.87dL/g; the conversion rate of glass is above 302 DEG C; the decomposition temperature is above 437 DEG C. The high-molecule compound of the poly aromatic amide compound containing fluorine can be used for advanced technological fields such as aerospace, high-precision electronics and information industry and so on.
Description
Technical field
The invention belongs to the technical field of macromolecular material, relate to the fluorine-containing polyaramide compound and the synthetic method based on naphthyridine ketone structure of a kind of novel fire resistant, favorable solubility.
Background technology
Polyaramide is the high performance macromolecular material of a class, its constructional feature is that main chain is the full aromatic structure of rigidity, easily form hydrogen bond simultaneously between the main chain, this is just determining polyaramide that the incomparable thermotolerance of other materials is arranged, good flexibility, toughness, flowability and physical strength and excellent comprehensive performances are used for filamentary material in a large number.Aromatic polyamide fibre has that superelevation is strong, ultra high modulus, high temperature resistant and characteristics that proportion is little, is used widely in hard-core technology fields such as aerospace, precise electronic and information industries.
Based on space development and military necessity, the aromatic polyamide fibre that the position replaced between Dupont company had developed in 1967, and with " Nomex " realization industrialization, form through solution polycondensation by mphenylenediamine and m-phthalic acid acyl chlorides.The meaning of " Nomex " fiber has been to indicate that the cryogenic fluid polycondensation prepares the prospect of high molecular polyaramide.
U.S. Dupont company in 1970 has developed gathers benzamide, because the preparation molecular weight is lower, intensity is not high, does not form industrialization, and China claimed that PBA is aramid fiber I, began development in 1977, and nineteen ninety is finished 30 tons of pilot scales, and preparation process is as follows:
1972, Dupont company developed the PPDT of full contraposition and realizes that successfully commodity are called " Kevlar " fiber industryization.PPTA by Ursol D and p-phthaloyl chloride through solution polycondensation and in the vitriol oil fiber spinning from crystalline state and getting.That " Kevlar " fiber has is high-strength, Gao Mo, high heat-resisting and high-insulativity, obtains widespread use in hard-core technology fields such as aerospace, electronic apparatus and nuclear energy, and its structure is as follows:
" Kevlar " fiber specific tenacity height, relative intensity are 6-7 times of steel wire, and modulus is steel wire and glass fibre 2-3 a times, and proportion has only about 1/5 of steel wire, decomposes and not fusion down at 500 ℃.These remarkable performances once created much of a stir.It is 21000 tons/year that Dupont company in 1986 has the throughput of Kevlar.
Yet, when polyaramide has impayable advantageous property, the defective that is difficult to overcome is arranged also.Melt temperature is higher than decomposition temperature to make and can not carry out melt-processed, and relatively poor solvability makes it be unsuitable for solution processing again, and this has just limited the application of polyaramide greatly.Along with the increase of market, obtain the hot issue that solvability polyaramide good and the maintenance excellent heat resistance becomes academia and industry member to the aromatic polyamide fibre demand.
Summary of the invention
The objective of the invention is from Molecular Structure Design, a kind of novel fluorine-containing polyaramide compound and preparation method based on naphthyridine ketone structure are provided, make its vitrifying more than 302 ℃, heat decomposition temperature is more than 437 ℃, solvability is good simultaneously, overcome deliquescent increase to sacrifice the difficult problem of resistance toheat, enlarge the application of polyaramide.
Technical scheme of the present invention is:
Content of the present invention is to obtain being used for polymeric novel fluorine diamine monomer from class biphenol monomer that contains the naphthyridine structure and 2-chloro-5-nitro-trifluoromethyl toluene by nucleophilic substitution and catalytic reduction, and utilize the diamine monomer make and five kinds of diacid by the synthetic good heat-resisting fluorine-containing polyaramide of a series of solvabilities of polycondensation, it is characterized in that the structure of diamine monomer and the repeated structural unit of polyaramide distinguish as follows:
The synthetic method of diamine monomer was undertaken by two steps among the present invention: the first step is that nucleophilic substitution in aprotic polar solvent generates dinitro compound with class biphenol monomer that contains the naphthyridine structure and 2-chloro-5-nitro-trifluoromethyl toluene, with alkaline metal salt (Anhydrous potassium carbonate) is catalyzer, be reflected under 120 ± 10 ℃ of high temperature and carry out, reaction times is 12 ± 1h, the sedimentation in frozen water of product dinitro compound, filter and for several times with warm water washing, product places under 40 ℃ of vacuum dry, obtain dinitro compound 16g, productive rate is 87%.Second step was that the dinitro compound that previous step makes is dissolved in the ethylene glycol monomethyl ether, with Pd/C (5%) is catalyzer, dropwise add excess hydrazine hydrate in the stirring heating reflux course, back flow reaction 5h again after dropwising, after question response finished, heat filtering was removed Pd/C rapidly, again with solution concentration and drip a small amount of distilled water and leave standstill, treat to refilter out product after precipitation is separated out fully and repeatedly wash, place 60 ℃ in vacuum dry down, obtain diamine monomer with ether.
Class biphenol monomer of the present invention contains the naphthyridine structure, and its general formula is:
Among the present invention the concrete synthetic method content of polyaramide be with the diamine monomer that makes respectively with five kinds of diacid [terephthalic acid, m-phthalic acid, 2; 6-naphthalene diacid, phenyl ether diacid or 4; 4 '-(hexafluoro isopropylidene) dibenzoic acid]; polycondensation forms in polar aprotic solvent; with TPP (triphenyl phosphite) and pyridine is catalyzer; Calcium Chloride Powder Anhydrous is a solubilizing agent; use nitrogen atmosphere protection; the system solid content is about 20%; temperature of reaction is 110 ± 5 ℃, and the reaction times is about 4 ± 0.5 hours.After reaction finished, with the sedimentation in methyl alcohol of heavy-gravity polymers soln, filtration was also used the hot water injection, obtains the white fiber shaped polymer.
The equation of polyreaction can be expressed as among the present invention:
The diamine monomer of gained is confirmed through infrared spectra and nuclear magnetic resonance spectroscopy among the present invention, and the structure of synthetic polyaramide is confirmed by Infrared spectroscopy.Characterize the amorphousness that has confirmed polymkeric substance by XRD.
The present invention introduces the trifluoromethyl side group to improve the solvability of polyaramide with the distortion that reduces interchain and closely pile up and increase main chain on main polymer chain, improve the rigidity of main polymer chain simultaneously, and have the good temperature resistance energy.Its second-order transition temperature is more than 302 ℃, and heat decomposition temperature is more than 437 ℃.Simultaneously, obtain polymkeric substance by test in NMP, DMAc, DMF, pyridine, meta-cresol, chloroform and acetone and also have excellent solvability, room temperature is solvable in NMP, DMAC, DMF, pyridine, meta-cresol, in chloroform, be partly dissolved, the solvability that contrast does not contain the similar polyaramide of trifluoromethyl (heats solvable in the pyridine, heating is solvable or be partly dissolved in the meta-cresol), the solvability of the fluorine-containing polyaramide that this type of is novel has certain raising, has overcome deliquescent increase to sacrifice the difficult problem of resistance toheat.With the chloroform is that solvent passes through viscosity test, and the limiting viscosity of polymkeric substance is between 0.41～0.87dL/g.This polymkeric substance can be applied to hard-core technology fields such as aerospace, precise electronic and information industry.
Embodiment
(1) the synthetic most preferred embodiment of diamine monomer
In being furnished with the 250ml flask of mechanical stirrer, prolong, thermometer, water trap; add 4-(4-hydroxy phenyl) phthalazone 30mmol successively; 2-chloro-5-nitro-trifluoromethyl toluene 61.5mmol; Anhydrous potassium carbonate 63mmol; DMAC (N; N-two-methylacetamide) 40ml; under nitrogen protection, be warming up to 120 ℃ of stirring reaction 12h; pour the 600ml frozen water after the cooling into and stir sedimentation; there are a large amount of light yellow solids to separate out, filter and wash repeatedly for several times, again with 40 ℃ of vacuum-dryings of product with warm water; obtain dinitro compound 16g, thick productive rate is 87%.
In being housed, the 250ml flask of mechanical stirrer, prolong, thermometer and constant pressure funnel adds dinitro compound 2-(4-nitro-2-trifluoromethyl-phenyl)-4-[2,3-dimethyl-4-(4-nitro-2-trifluoromethyl-phenoxy group) phenyl] naphthyridine-1-ketone 25mmol, ethylene glycol monomethyl ether 100ml, catalyst P d/C (0.5%) 0.3g, after being heated to backflow, dropwise add hydrazine hydrate 25ml.Continue back flow reaction 5h, the stopped reaction filtered while hot is fallen Pd/C, mother liquor is concentrated into behind the 20ml Dropwise 5 drips distilled water and leave standstill, promptly have a large amount of faint yellow solids to separate out, filter and wash repeatedly with ether, again with product in 60 ℃ of vacuum-dryings, obtain the 11.2g diamines, thick productive rate is 81%.
(2) the synthetic most preferred embodiment of polyaramide
In being housed, the 100ml three-necked flask of magnetic agitation, thermometer, prolong and nitrogen protection adds diamine monomer 1.5mmol; terephthalic acid 1.5mmol; NMP (N-Methyl pyrrolidone) 3.5ml; TPP (triphenyl phosphite) 1.8ml; pyridine 1ml; Calcium Chloride Powder Anhydrous 0.3g, be warming up to 110 ℃ of reaction 1h under the nitrogen protection after system become sticky, continue reaction 3h.Pour polymers soln in methyl alcohol sedimentation, obtain the white fiber shaped polymer, filter and with the hot water injection repeatedly, obtain polyaramide 100 ℃ of vacuum-dryings.
Claims (7)
1. based on the fluorine-containing polyaramide of naphthyridine ketone structure, it is characterized in that: the repeated structural unit that constitutes this polyaramide is:
R：H，CH
3。
2. the preparation method of fluorine-containing polyaramide according to claim 1 is characterized in that: form with fluorinated diamine monomer and the reaction of diacid monomer direct condensation based on naphthyridine ketone structure.
3. as the preparation method of fluorine-containing polyaramide as described in the claim 2, it is characterized in that: diacid monomer is terephthalic acid, m-phthalic acid, 2,6-naphthalene diacid, phenyl ether diacid or 4,4 '-(hexafluoro isopropylidene) dibenzoic acid.
4. as the preparation method of fluorine-containing polyaramide as described in the claim 2; it is characterized in that: in the aprotic polar solvent N-Methyl pyrrolidone; under nitrogen atmosphere protection; with triphenyl phosphite and pyridine is catalyzer; Calcium Chloride Powder Anhydrous is a solubilizing agent, and at 110 ± 5 ℃ of following stirring reaction 4 ± 0.5h, reaction is precipitated out polymkeric substance after finishing in methyl alcohol etc. the fluorinated diamine monomer of mol ratio and diacid monomer; filtering separation is also dry, gets fluorine-containing polyaramide polymkeric substance.
5. as the preparation method of fluorine-containing polyaramide as described in the claim 4, it is characterized in that: after the filtering separation, in 100 ± 5 ℃ of dryings of vacuum, fluorine-containing polyaramide polymkeric substance.
6. based on the fluorinated diamine monomer of naphthyridine ketone structure, it is characterized in that constituting the monomeric repeated structural unit of this fluorinated diamine and be:
7. as the monomeric preparation method of fluorinated diamine as described in the claim 6, it is characterized in that: utilize the class biphenol monomer and the reaction of 2-chloro-5-nitro-trifluoromethyl toluene that contain naphthyridine ketone structure earlier, solvent is aprotic polar solvent N, the N-N,N-DIMETHYLACETAMIDE, alkaline metal salt is a catalyzer, temperature of reaction is 120 ± 10 ℃, reaction times is 12 ± 1h, nucleophilic substitution generates dinitro compound, be solvent again with the ethylene glycol monomethyl ether, hydrazine hydrate is a reductive agent, and Pd/C is a catalyzer, and reduction obtains the fluorinated diamine monomer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781400B (en) * | 2010-02-08 | 2011-12-07 | 四川辉腾科技有限公司 | Method for synthesizing nomex resin containing fluorine and synthesized resin thereby and application |
| CN104311819A (en) * | 2014-10-17 | 2015-01-28 | 常州大学 | Sulfonated aromatic polyamide containing fluorenyl and trifluoromethyl structures and preparation method thereof |
-
2007
- 2007-07-17 CN CNA2007100092412A patent/CN101153074A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781400B (en) * | 2010-02-08 | 2011-12-07 | 四川辉腾科技有限公司 | Method for synthesizing nomex resin containing fluorine and synthesized resin thereby and application |
| CN104311819A (en) * | 2014-10-17 | 2015-01-28 | 常州大学 | Sulfonated aromatic polyamide containing fluorenyl and trifluoromethyl structures and preparation method thereof |
| CN104311819B (en) * | 2014-10-17 | 2016-06-08 | 常州大学 | One class is containing fluorenyl and trifluoromethyl structure sulfonation Nomex and preparation method thereof |
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