CN105801844A - Poly(m-phenylene) terephthamide and solution polycondensation preparing method thereof - Google Patents
Poly(m-phenylene) terephthamide and solution polycondensation preparing method thereof Download PDFInfo
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- CN105801844A CN105801844A CN201610229733.1A CN201610229733A CN105801844A CN 105801844 A CN105801844 A CN 105801844A CN 201610229733 A CN201610229733 A CN 201610229733A CN 105801844 A CN105801844 A CN 105801844A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
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Abstract
The invention discloses poly(m-phenylene) terephthamide and a solution polycondensation preparing method thereof.Solution polycondensation is conducted with LiCl/NMP serving as a mixed solvent, PPD and IPC serving as a monomer and 2-picoline serving as an acid-binding agent.The route condition is mild and easy to control, and an effective method for preparing poly(m-phenylene) terephthamide is provided.The molecular chain structure of poly(m-phenylene) terephthamide is neat and rigid and has intermolecular hydrogen bonding acting force, and poly(m-phenylene) terephthamide can serve as a high-temperature-resisting material and a high-performance high polymer material.
Description
Technical field
The present invention relates to the technical field of macromolecular material, especially relate to a kind of poly-mphenylen terephthalamide and
Solution polycondensation preparation method and application.
Background technology
Aramid fiber refers to the synthetic fibers prepared through polycondensation spinning with aromatic compound for raw material.U.S. trade community will
Aramid fiber named " aramid fibers ", its definition be at least 85% amide chain be directly connected with two phenyl ring.Aramid fiber
Including aromatic polyamide fibre and aromatic polyimide fibre.
Traditional aromatic polyamide fibrid can be divided into para-position and the big class of meta two by its attachment structure.P-aramid fiber master
PPTA to be included, poly(p-benzamide) and copolymer fibre thereof etc., meta-aramid mainly includes poly-isophthalic
Two formyl m-diaminobenzene. and copolymer fibres thereof.
First industrialized p-aramid fiber product is the Kevlar fiber that du pont company releases for 1972, for many years with
Occupy most of market of p-aramid fiber, the Twaron fiber of Dutch Aksu company, Japan's Supreme Being people's public affairs by 1986 always
Technora fiber and the Muscovite Amos fiber of department occur the most in succession.The research of meta-aramid and production start from last century six
In the ten's, now oneself is the most ripe for the meta-aramid production technology of beautiful, Deng state, and it is excellent successfully to develop multiple varieties and characteristics
Fiber product more, the most famous product has the Nomex series fiber that du pont company produces, and day, book Supreme Being people was public
The Conex series fiber that department produces, the Apyeil of You Ni contract card company, Muscovite Fenilon fiber etc..
New varieties-poly-mphenylen terephthalamide in the Ze Shi aromatic polyamide family that the present invention is directed to.
Poly-mphenylen terephthalamide is a kind of brand-new aromatic polyamide, and from structure, poly-isophthaloyl is to benzene two
The structure of amine has the feature of PPTA and poly(isophthaloyl metaphenylene diamine) concurrently, has multiple phenyl ring and acyl
Amine groups interval be connected feature, therefore this polymer be likely to become in aromatic compound potential realize commercialization should
Kind.The present invention mainly discloses poly-mphenylen terephthalamide and solution polycondensation preparation method and application thereof.
Summary of the invention
The technical problem to be solved is for the deficiencies in the prior art, it is provided that a kind of poly-isophthaloyl is to benzene
Diamidogen and solution polycondensation preparation method thereof, using lithium chloride (LiCl)/N-methyl ketopyrrolidine (NMP) as mixed solvent, with right
Phenylenediamine (PPD) and m-phthaloyl chloride (IPC) are as monomer, and 2-picoline, as acid binding agent, carries out solution polycondensation, this road
Line mild condition is easily-controllable.
For reaching above-mentioned purpose, the present invention is achieved by the following technical solutions:
A kind of poly-mphenylen terephthalamide, has a following molecular formula:
。
The solution polycondensation preparation method of a kind of poly-mphenylen terephthalamide, comprises the following steps:
(1) in reaction vessel, add N-methyl ketopyrrolidine and lithium chloride, stirring, prepare mixed solvent；
(2) under nitrogen protection, p-phenylenediamine is joined in the reaction vessel of step (1), stirring, make p-phenylenediamine dissolve；
(3) 2-picoline is joined in the reaction vessel of step (1)；
(4) add N-methyl ketopyrrolidine and lithium chloride, stirring in a reservoir, prepare mixed solvent, m-phthaloyl chloride is added
Enter in mixed solvent, dissolve and make solution, standby；
(5) solution prepared in step (4) is divided into two parts of equivalent, is added sequentially in the reaction vessel of step (1), period
Separated in time, is kept stirring for；
(6) continue stirring reaction 0.5-5 hour, add distilled water, stopped reaction, generate white depositions；
(7) pour the mixed liquor that step (6) obtains into buchner funnel, wash through sucking filtration, washing, ethanol, and at a certain temperature
It is dried.
The amount of the N-methyl ketopyrrolidine in described step (1) is 5-100ml, the amount of the lithium chloride in described step (1)
For 0.2-6g；The amount of the p-phenylenediamine in described step (2) is 0.5-10g；The amount of the 2-picoline in described step (3) is
0.5-20ml；The amount of the N-methyl ketopyrrolidine in described step (4) is 5-100ml, the amount of the lithium chloride in described step (4)
For 0.2-6g, the amount of the m-phthaloyl chloride in described step (4) is 0.5-20g；The amount of the ethanol in described step (7) is 5-
500ml。
Described reaction vessel is the there-necked flask being furnished with thermometer, agitating device and condensing tube.
The productivity of described poly-mphenylen terephthalamide is 36.6-92.9%.
Period in described step (5) is spaced 20 minutes, is dried 24h in described step (7) at 80 DEG C.
Synthetic route is:
。
A kind of poly-mphenylen terephthalamide application in exotic material or high performance polymer material field.
Beneficial effects of the present invention is as follows:
The poly-mphenylen terephthalamide of the present invention is a kind of brand-new aromatic polyamide, from structure, poly-isophthalic
The structure of two formyl p-phenylenediamine has the feature of PPTA and poly(isophthaloyl metaphenylene diamine) concurrently, has
Multiple phenyl ring and amide group are spaced the structure being connected, and therefore this polymer is likely to become in aromatic polymer potential
Realize the new varieties of commercial applications.
The poly-mphenylen terephthalamide of the present invention and solution polycondensation preparation method thereof, the route using solution reduction of area poly-comes
Preparing poly-mphenylen terephthalamide, this route reaction operating condition gentleness is controlled, is to prepare poly-isophthaloyl to benzene two
The effective ways of amine.The poly-regular rigidity of mphenylen terephthalamide's molecular chain structure and there is intermolecular hydrogen bonding active force,
Can be used as exotic material and high performance polymer material.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of poly-mphenylen terephthalamide prepared by the present invention.
Fig. 2 is the thermogravimetric curve of poly-mphenylen terephthalamide prepared by the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
The preparation method of the poly-mphenylen terephthalamide of the present invention, comprises the following steps:
(1) in reaction vessel, add N-methyl ketopyrrolidine 5-100ml and lithium chloride 0.2-6g, stirring, prepare mixing molten
Agent；
(2) under nitrogen protection, p-phenylenediamine 0.5-10g is joined in the reaction vessel of step (1), stirring, make benzene two
Amine solvent；
(3) 0.5-20ml 2-picoline is joined in the reaction vessel of step (1)；
(4) add N-methyl ketopyrrolidine 5-100ml and lithium chloride 0.2-6g, stirring in a reservoir, prepare mixed solvent, between inciting somebody to action
Phthalyl chloride 0.5-20g joins in mixed solvent, dissolves and makes solution, standby；
(5) solution prepared in step (4) is divided into two parts of equivalent, is added sequentially in the reaction vessel of step (1), period
It is spaced 20 minutes, is kept stirring for；
(6) continue stirring reaction 0.5-5 hour, add distilled water, stopped reaction, generate white depositions；
(7) pouring the mixed liquor that step (6) obtains into buchner funnel, wash through sucking filtration, washing, 5-500ml ethanol, 80 DEG C are dried
24h。
Reaction vessel used in the present invention is the there-necked flask being furnished with thermometer, agitating device and condensing tube.
The synthetic route of the present invention is:
。
The productivity of poly-mphenylen terephthalamide is 36.6-92.9%.
Embodiment 1
In the there-necked flask being furnished with thermometer, agitating device and condensing tube, add 25ml NMP, weigh 0.4722g LiCl, add
Enter in there-necked flask, stirring, prepare NMP/LiCl mixed solvent.Under nitrogen protection, weigh 1.2264g PPD and join three
In mouth flask, stirring, make PPD dissolve.2.223ml 2-picoline is joined in there-necked flask.25ml is added in beaker
NMP, weighs 0.4722g LiCl, joins in beaker, stirring, prepares NMP/LiCl mixed solvent, by 2.2780g isophthalic diformazan
Acyl chlorides (IPC) joins in mixed solvent, dissolves and makes solution.The solution of m-phthaloyl chloride is divided into two parts of equivalent, depends on
In secondary addition there-necked flask, period is spaced 20 minutes, is kept stirring for.Continue stirring reaction 2 hours, add distilled water, stop anti-
Should, generate white depositions.Pouring obtained mixed liquor into buchner funnel, wash through sucking filtration, washing, ethanol, 80 DEG C are dried
24h, obtains hard resin.Productivity 79.6%.
Embodiment 2
In the there-necked flask being furnished with thermometer, agitating device and condensing tube, add 100ml NMP, weigh 2g LiCl, join
In there-necked flask, stirring, prepare NMP/LiCl mixed solvent.Under nitrogen protection, weigh 8g PPD and join in there-necked flask,
Stirring, makes PPD dissolve.8ml 2-picoline is joined in there-necked flask.In beaker, add 100ml NMP, weigh 2g
LiCl, joins in beaker, stirring, prepares NMP/LiCl mixed solvent, 8g m-phthaloyl chloride (IPC) joins mixing molten
In agent, dissolve and make solution.The solution of m-phthaloyl chloride is divided into two parts of equivalent, is sequentially added in there-necked flask, period
It is spaced 20 minutes, is kept stirring for.Continue stirring reaction 2 hours, add distilled water, stopped reaction, generate white depositions.By institute
Buchner funnel poured into by the mixed liquor obtained, and through sucking filtration, washing, washes with 500mL ethanol, 80 DEG C of dry 24h, obtains hard resin.
Productivity 40%.
Embodiment 3
In the there-necked flask being furnished with thermometer, agitating device and condensing tube, add 5ml NMP, weigh 0.2g LiCl, join
In there-necked flask, stirring, prepare NMP/LiCl mixed solvent.Under nitrogen protection, weigh 0.5g PPD and join there-necked flask
In, stirring, make PPD dissolve.1ml 2-picoline is joined in there-necked flask.In beaker, add 5ml NMP, weigh
0.2g LiCl, joins in beaker, stirring, prepares NMP/LiCl mixed solvent, is joined by 1g m-phthaloyl chloride (IPC)
In mixed solvent, dissolve and make solution.The solution of m-phthaloyl chloride is divided into two parts of equivalent, is sequentially added into there-necked flask
In, period is spaced 20 minutes, is kept stirring for.Continue stirring reaction 2 hours, add distilled water, stopped reaction, generate white precipitate
Thing.Pour obtained mixed liquor into buchner funnel, through sucking filtration, washing, wash with 5mL ethanol, 80 DEG C of dry 24h, obtain solid
Resin.Productivity 92%.
Embodiment 4
In the there-necked flask being furnished with thermometer, agitating device and condensing tube, add 52.5ml NMP, weigh 2.1g LiCl, add
Enter in there-necked flask, stirring, prepare NMP/LiCl mixed solvent.Under nitrogen protection, weigh 4.3g PPD and join three mouthfuls
In flask, stirring, make PPD dissolve.10.3ml 2-picoline is joined in there-necked flask.52.5ml is added in beaker
NMP, weighs 2.1g LiCl, joins in beaker, stirring, prepares NMP/LiCl mixed solvent, by 8.6g m-phthaloyl chloride
(IPC) join in mixed solvent, dissolve and make solution.The solution of m-phthaloyl chloride is divided into two parts of equivalent, adds successively
Entering in there-necked flask, period is spaced 20 minutes, is kept stirring for.Continue stirring reaction 2 hours, add distilled water, stopped reaction, life
Become white depositions.Pour obtained mixed liquor into buchner funnel, through sucking filtration, washing, wash with 252.5mL ethanol, 80 DEG C
It is dried 24h, obtains hard resin.Productivity 64.75%.
Fig. 1 is the infared spectrum of the poly-mphenylen terephthalamide of preparation.Wherein, 3282.84cm-1For stretching of N-H key
Contracting vibration, 1643.35cm-1For the stretching vibration of C=O bond, 1548.84cm-1、1514.12cm-1、1402.25cm-1For benzene
The stretching vibration of ring skeleton, 1311.59cm-1For the deformation vibration of N-H key, 1246.02 is the stretching vibration of C N key,
817.82cm-1For the deformation vibration of phenyl ring meta two replacement C H key, 680.87cm-1For phenyl ring meta two replacement C H key
Deformation vibration.
Embodiment 5: the application of poly-mphenylen terephthalamide
By Theoretical Calculation, poly-mphenylen terephthalamide is respectively along a, tri-axial Young's moduluss of b, c
442.6192 Gpa, 94.1808 Gpa, 416.5910 Gpa, illustrate that poly-mphenylen terephthalamide has good mechanics
Performance, therefore can serve as high performance polymer material.
Embodiment 6: the application of poly-mphenylen terephthalamide
Fig. 2 is the thermogravimetric curve of poly-mphenylen terephthalamide.From thermogravimetric curve it will be seen that main decomposition temperature about
Being 450 DEG C, temperature corresponding to decomposition mechanism, at about 540 DEG C, meets the requirement of applied at elevated temperature, therefore can serve as resistance to height
Adiabator.
The poly-mphenylen terephthalamide that the present invention prepares, is a kind of novel fragrant amide polymer, for high property
New varieties in energy aramid fiber family.
The poly-mphenylen terephthalamide of the present invention has both length of aramid fiber 1313 and Fanglun l414 concurrently, because link
The regular rigidity of structure and have intermolecular hydrogen bonding active force, heat decomposition temperature is high, and therefore excellent in mechanical performance can be used as high temperature resistant
Material and high performance polymer material.As Thermal Protective material with for the parts etc. of industrial high temperature resistant products；As with
Make in the parts of aircraft or high speed means of transport, in Aero-Space, each side such as automobile high-strength parts of loss of weight have important should
With.
Above-described embodiment is only used for illustrating the inventive concept of the present invention, rather than the restriction to rights protection of the present invention,
All changes utilizing this design that the present invention carries out unsubstantiality, all should fall into protection scope of the present invention.
Claims (8)
1. a poly-mphenylen terephthalamide, it is characterised in that there is following molecular formula:
。
2. the solution polycondensation preparation method of a poly-mphenylen terephthalamide, it is characterised in that comprise the following steps:
(1) in reaction vessel, add N-methyl ketopyrrolidine and lithium chloride, stirring, prepare mixed solvent；
(2) under nitrogen protection, p-phenylenediamine is joined in the reaction vessel of step (1), stirring, make p-phenylenediamine dissolve；
(3) 2-picoline is joined in the reaction vessel of step (1)；
(4) add N-methyl ketopyrrolidine and lithium chloride, stirring in a reservoir, prepare mixed solvent, m-phthaloyl chloride is added
Enter in mixed solvent, dissolve and make solution, standby；
(5) solution prepared in step (4) is divided into two parts of equivalent, is added sequentially in the reaction vessel of step (1), period
Separated in time, is kept stirring for；
(6) continue stirring reaction 0.5-5 hour, add distilled water, stopped reaction, generate white depositions；
(7) pour the mixed liquor that step (6) obtains into buchner funnel, wash through sucking filtration, washing, ethanol, and at a certain temperature
It is dried.
The preparation method of poly-mphenylen terephthalamide the most as claimed in claim 2, it is characterised in that: in described step (1)
The amount of N-methyl ketopyrrolidine be 5-100ml, the amount of the lithium chloride in described step (1) is 0.2-6g；In described step (2)
The amount of p-phenylenediamine be 0.5-10g；The amount of the 2-picoline in described step (3) is 0.5-20ml；In described step (4)
The amount of N-methyl ketopyrrolidine be 5-100ml, the amount of the lithium chloride in described step (4) is 0.2-6g, in described step (4)
The amount of m-phthaloyl chloride be 0.5-20g；The amount of the ethanol in described step (7) is 5-500ml.
The preparation method of poly-mphenylen terephthalamide the most as claimed in claim 2, it is characterised in that: described reaction vessel
For being furnished with the there-necked flask of thermometer, agitating device and condensing tube.
The preparation method of poly-mphenylen terephthalamide the most as claimed in claim 2, it is characterised in that: described poly-isophthalic diformazan
The productivity of acyl p-phenylenediamine is 36.6-92.9%.
The preparation method of poly-mphenylen terephthalamide the most as claimed in claim 2, it is characterised in that: in described step (5)
Period be spaced 20 minutes, in described step (7) at 80 DEG C be dried 24h.
The preparation method of poly-mphenylen terephthalamide the most as claimed in claim 2, it is characterised in that: synthetic route is:
。
8. the poly-mphenylen terephthalamide application in exotic material or high performance polymer material field.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109180932A (en) * | 2018-09-25 | 2019-01-11 | 江苏扬农化工集团有限公司 | It is a kind of it is poly- between phenyl-diformyl m-xylene diamine polycondensation synthetic method |
| CN109369908A (en) * | 2018-08-27 | 2019-02-22 | 江苏扬农化工集团有限公司 | A kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine |
| CN113851782A (en) * | 2021-08-10 | 2021-12-28 | 河北金力新能源科技股份有限公司 | High-temperature-resistant diaphragm slurry with lithium pre-supplement function, diaphragm and lithium battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369908A (en) * | 2018-08-27 | 2019-02-22 | 江苏扬农化工集团有限公司 | A kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine |
| CN109180932A (en) * | 2018-09-25 | 2019-01-11 | 江苏扬农化工集团有限公司 | It is a kind of it is poly- between phenyl-diformyl m-xylene diamine polycondensation synthetic method |
| CN113851782A (en) * | 2021-08-10 | 2021-12-28 | 河北金力新能源科技股份有限公司 | High-temperature-resistant diaphragm slurry with lithium pre-supplement function, diaphragm and lithium battery |
| CN113851782B (en) * | 2021-08-10 | 2023-04-28 | 河北金力新能源科技股份有限公司 | High-temperature-resistant diaphragm slurry with pre-lithium supplementing function, diaphragm and lithium battery |
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Application publication date: 20160727 |