CN101434698A - Method for preparing aromatic polyamides by using structure containing bisphthalazinone and trifluoromethyl substituted aroma diamine monomer - Google Patents
Method for preparing aromatic polyamides by using structure containing bisphthalazinone and trifluoromethyl substituted aroma diamine monomer Download PDFInfo
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- CN101434698A CN101434698A CNA2008102076103A CN200810207610A CN101434698A CN 101434698 A CN101434698 A CN 101434698A CN A2008102076103 A CNA2008102076103 A CN A2008102076103A CN 200810207610 A CN200810207610 A CN 200810207610A CN 101434698 A CN101434698 A CN 101434698A
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- trifluoromethyl substituted
- polyaramide
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- substituted aroma
- diamine monomer
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Abstract
The invention relates to a method for preparing aromatic polyamide containing phthyridine structure and trifluoromethyl substituted aromatic diamine monomer. The method is as follows: under the protection of nitrogen, the phthyridine structure and trifluoromethyl substituted aromatic diamine and diacid monomer are dissolved in an N-methyl pyrrolidone organic solvent according to mole ratio and a solution with the mass percent of total solid between 10 percent to 40 percent is obtained; triphenyl phosphite and pyridine are taken as catalysts, anhydrous calcium chloride is added to solubilize, condensation reaction lasts 3h to 5h at the temperature of 100 DEG C to 140 DEG C, products are poured into methanol or ethanol, then precipitates are collected and dried and a fibrous white aromatic polyamide polymer is obtained. The aromatic polyamide obtained by the method has excellent solubility property, heating resistance, mechanical property, film forming capability and optical performance and low dielectric constant between 1.75 and 3.0 and can dissolve in normal organic solvents; the glass state temperature and initial decomposition temperature are respectively over 270 DEG C and 450 DEG C.
Description
Technical field
The invention belongs to the preparation field of polyaramide, particularly relate to and contain the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide.
Background technology
Polyaramide is the heat-proof macromolecule material of excellent combination property.Since six the seventies began industrialization, they were applied in every field.Especially have a wide range of applications in industries such as aerospace, machinery, microelectronics, petrochemical compleies as high-performance fiber, high heat-resisting composite matrix and electronic package material.Although this class high temperature material has the excellent comprehensive performance, but because tightly packed than strong interaction and molecular chain of stiff backbone structure that they had and intermolecular existence, cause most of polyaramide that very high melt temperature is arranged, be insoluble to organic solvent (only being dissolved in the vitriol oil mostly) again, bring difficulty for its forming process.This has limited their further application in association area, especially is difficult to be applied in high-temperature resistant coating, the film.In order to overcome these shortcomings and to prepare that processing characteristics is good, the polyimide of excellent combination property, people have dropped into very big effort.
The solubility polyaramide is the focus of Recent study, reports that in recent years more is ether-containing key and trifluoromethyl (CF
3) replacement polyethers virtue acid amides.Because contain flexible ehter bond and big replacement side group in the molecular backbone chain, this base polymer shows good solubility usually, dissolves in N,N-dimethylacetamide (DMAc), N under the room temperature, dinethylformamide conventional solvents such as (DMF).Simultaneously because the physicochemical property of fluorine atom uniqueness as bigger electronegativity, less atomic radius, lower mole polarizability etc., make this class material have optical property and dielectric properties preferably, lower rate of moisture absorption etc.
Summary of the invention
Technical problem to be solved by this invention provides and contains the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide, gained polyaramide of the present invention has the good solubility energy, dissolve in conventional organic solvent, excellent heat resisting, second-order transition temperature and initial decomposition temperature are respectively more than 270 and 450 ℃; Excellent mechanical property, good film-forming properties and optical property, low specific inductivity, specific inductivity is between 1.75～3.0.
Of the present inventionly contain the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide, comprising:
Under nitrogen protection; to contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine and diacid monomer with etc. mol ratio be dissolved in the N-Methyl pyrrolidone organic solvent; getting the total solids mass percent is 10～40% solution; make catalyzer with triphenyl phosphite and pyridine; add the Calcium Chloride Powder Anhydrous solubilising simultaneously, behind 100～140 ℃ of condensation reaction 3～5h, reaction product is poured in methyl alcohol or the ethanol; collecting precipitation thing drying gets fibrous white polyaramide polymkeric substance.
Describedly contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer is introduced in another piece application " contains two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer and preparation thereof ".
Described diacid monomer is terephthalic acid, m-phthalic acid, 4,4 '-dicarboxylic acid phenyl ether or 2, the different propane of 2 '-two (4-carboxylic acid phenyl) hexafluoros.
Described triphenyl phosphite and pyridine consumption are respectively to contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine (or diacid) mole number 3～8 times.
Described Calcium Chloride Powder Anhydrous consumption is 10～40% of diamines and a diacid total mass.
Gained polyaramide structural formula following showing:
Wherein, Ar ' is
Or
N is 40～70.
The preparation of polyaramide is to be principal monomer to contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer, respectively with commercially available aromatic diacid monomer, with the synthetic polyaramide of known response procedures.
Beneficial effect
(1) gained polyaramide of the present invention has the good solubility energy, dissolve in conventional organic solvent such as N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamides etc., partial polymer can be dissolved in the low boiling point solvents such as chloroform, tetrahydrofuran (THF);
(2) excellent heat resisting, second-order transition temperature and initial decomposition temperature are respectively more than 270 and 450 ℃;
(3) You Yi mechanical property and good film-forming properties, the tensile strength of film is between 70～150MPa, and elongation at break is between 5～20%, and initial modulus is more than 1.8GPa;
(4) You Yi optical property, cut-off wavelength have high transmittance in the visible-range between 350～380nm; Low specific inductivity, specific inductivity is between 1.75～3.0.
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 and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications 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
Dry and be connected with and add 1.5mmol respectively in three mouthfuls of round-bottomed flasks of 50ml of nitrogen and contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine and 1.5mmol 4,4 '-dicarboxylic acid phenyl ether, add the 5ml N-Methyl pyrrolidone and make solvent (the system solid content is 10～40%), add the 2.5ml triphenyl phosphite respectively again and the 1.0ml pyridine is made catalyzer, add 0.3g Calcium Chloride Powder Anhydrous solubilising simultaneously, with reaction system be warming up to 100～140 ℃ the reaction 3～5h after, polymers soln is poured in 300ml methyl alcohol or the ethanol, by filtering the collecting precipitation thing, ethanol bubble with boiling water and heat is washed multipass, and vacuum-drying obtains white fiber shape polyaramide.
Embodiment 2
Dry and be connected with and add 1.5mmol respectively in three mouthfuls of round-bottomed flasks of 50ml of nitrogen and contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine and 1.5mmol terephthalic acid, add the 7ml N-Methyl pyrrolidone and make solvent (the system solid content is 10～40%), add the 3ml triphenyl phosphite respectively again and the 0.6ml pyridine is made catalyzer, add 0.24g Calcium Chloride Powder Anhydrous solubilising simultaneously, with reaction system be warming up to 110 ℃ the reaction 3～5h after, polymers soln is poured in 300ml methyl alcohol or the ethanol, by filtering the collecting precipitation thing, ethanol bubble with boiling water and heat is washed multipass, and vacuum-drying obtains white fiber shape polyaramide.
Claims (5)
1. contain the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide, comprising:
Under nitrogen protection; to contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine and diacid monomer with etc. mol ratio be dissolved in the N-Methyl pyrrolidone organic solvent; getting the total solids mass percent is 10～40% solution; make catalyzer with triphenyl phosphite and pyridine; add the Calcium Chloride Powder Anhydrous solubilising simultaneously, behind 100～140 ℃ of condensation reaction 3～5h, reaction product is poured in methyl alcohol or the ethanol; collecting precipitation thing drying gets fibrous white polyaramide polymkeric substance.
2. according to claim 1ly contain the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide, it is characterized in that: described diacid monomer is terephthalic acid, m-phthalic acid, 4,4 '-dicarboxylic acid phenyl ether or 2, the different propane of 2 '-two (4-carboxylic acid phenyl) hexafluoros.
3. according to claim 1ly contain the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide, it is characterized in that: described triphenyl phosphite and pyridine consumption are respectively to contain two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine or diacid mole number 3～8 times.
4. according to claim 1ly contain the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide, it is characterized in that: described Calcium Chloride Powder Anhydrous consumption is 10～40% of diamines and a diacid total mass.
5. according to claim 1ly contain the method that two assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer prepare polyaramide, it is characterized in that: gained polyaramide structural formula is:
Wherein, Ar ' is
Or
N is 40～70.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102076103A CN101434698A (en) | 2008-12-23 | 2008-12-23 | Method for preparing aromatic polyamides by using structure containing bisphthalazinone and trifluoromethyl substituted aroma diamine monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102076103A CN101434698A (en) | 2008-12-23 | 2008-12-23 | Method for preparing aromatic polyamides by using structure containing bisphthalazinone and trifluoromethyl substituted aroma diamine monomer |
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| CN101434698A true CN101434698A (en) | 2009-05-20 |
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| CNA2008102076103A Pending CN101434698A (en) | 2008-12-23 | 2008-12-23 | Method for preparing aromatic polyamides by using structure containing bisphthalazinone and trifluoromethyl substituted aroma diamine monomer |
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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 |
| CN103497110A (en) * | 2013-11-06 | 2014-01-08 | 常州大学 | Rigid aromatic diamine monomer as well as preparation method and application thereof |
| CN104311819A (en) * | 2014-10-17 | 2015-01-28 | 常州大学 | Sulfonated aromatic polyamide containing fluorenyl and trifluoromethyl structures and preparation method thereof |
-
2008
- 2008-12-23 CN CNA2008102076103A patent/CN101434698A/en active Pending
Cited By (5)
| 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 |
| CN103497110A (en) * | 2013-11-06 | 2014-01-08 | 常州大学 | Rigid aromatic diamine monomer as well as preparation method and application thereof |
| CN103497110B (en) * | 2013-11-06 | 2015-09-30 | 常州大学 | A kind of Rigid aromatic diamine monomer and its preparation method 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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Open date: 20090520 |