CN103147153B - High-intensity aramid fiber and preparation method thereof - Google Patents
High-intensity aramid fiber and preparation method thereof Download PDFInfo
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- CN103147153B CN103147153B CN201310098558.3A CN201310098558A CN103147153B CN 103147153 B CN103147153 B CN 103147153B CN 201310098558 A CN201310098558 A CN 201310098558A CN 103147153 B CN103147153 B CN 103147153B
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Abstract
The invention discloses a high-intensity aramid fiber---poly-1,4-terephthaloyl-2,5-p-phenylenediamine fiber, and the fiber is obtained by steps of: using 2,5-diamine p-xylene as raw material to obtain a 2,5-diamine terephthalic acid monomer by three steps of amidation, oxidization and hydrolyzation, then adopting a general concentrated sulfuric acid catalytic method for polymerization, and thus obtaining the fiber by liquid crystal spinning. Poly-1,4-terephthaloyl-2,5-p-phenylenediamine has quite good planarity, so the prepared fiber has quite high degree of crystallinity and degree of orientation; and benzene rings are connected with two short chains to enhance the strength of a weak part, therefore the aramid fiber has quite high intensity which is as high as 5 GPa.
Description
Technical field
The present invention relates to field of material engineering technology, particularly relate to a kind of high-intensity aramid fiber and preparation method thereof.
Background technology
Aromatic polyamide fibre, is commonly called as aramid fiber, has the premium properties such as superhigh intensity, high-modulus, acid and alkali-resistance, quality be light, is important defence and military material, is with a wide range of applications.
Aramid fiber I i.e. poly fiber is meta-aramid, and because molecule lacks flatness, degree of crystallinity is not high, and the degree of orientation is relatively low, so intensity is lower, but good heat resistance.Aramid II and Fanglun 1414, it is p-aramid fiber, because amido link and benzene radicals form conjugated structure, inward turning potential energy is quite high, become rigid chain macromolecular structure, molecules align is regular, therefore molecular crystallinity and the degree of orientation high, so the strength and modulus of fiber is also high, militarily have been widely used.
At present, both at home and abroad all at research and development third generation aramid fiber, super aramid fiber III is called.Third generation aramid fiber mainly heterocycle aramid fiber.When designing the structure of third generation aramid fiber, heterocyclic moiety containing phenyl structure can be larger, thus degree of crystallinity and the degree of orientation higher, the modulus of material and intensity obtain and increase substantially (intensity of super aramid fiber III reaches 4.5GPa, and aramid II is generally 2.5 ~ 2.8GPa).
In aramid II, III generation, common problem was that the main chain between phenyl ring is all coupled together by a covalent bond, and this is the fragile part of molecule, it is the position first starting to rupture, this have impact on the intensity of aramid fiber, and connect if design two chains between Benzene Molecule, its intensity can increase considerably.Up to the present, there is no correlative study report.
Summary of the invention
The object of the present invention is to provide a kind of high-intensity aramid fiber and preparation method thereof.The present invention has synthesized a kind of novel high molecular polymer---poly-Isosorbide-5-Nitrae paraphenylene terephthalamide 2,5 p-phenylenediamine (PPD), and obtain high-intensity aramid fiber by fiber spinning from crystalline state, intensity can reach 5.0 GPa.This polymer has higher flatness, produces more crystal region, has two covalent bonds to be connected simultaneously, therefore have higher modulus and brute force between Benzene Molecule.
Principle of the present invention is: the degree of crystallinity of raising fiber and the degree of orientation can improve brute force and the modulus of fiber.The main chain that instant invention overcomes between aramid II, III generation phenyl ring is all the defect coupled together by a covalent bond, between Benzene Molecule, devise two chains connect, in the molecular structure of design, be actually an octatomic ring between two phenyl ring, chemical constitution is very stable.Owing to there being two chains to connect between two benzene radicals, can not rotate completely between group, so the flatness of molecule is higher than aramid II, the fibre crystallinity made is higher, and the degree of orientation is higher.From molecular structure, when fracture occurs strand under strong External Force Acting, what first start fracture is connect the strand between Benzene Molecule, and between Benzene Molecule, therefore design two chains connect, its intensity can increase considerably.
A kind of high-intensity aramid fiber of the present invention---poly-Isosorbide-5-Nitrae paraphenylene terephthalamide 2,5 p-phenylenediamine (PPD) fiber, its structural formula is:
?n＝350～400
A kind of high-intensity aramid fiber of the present invention---poly-1,4 paraphenylene terephthalamides 2, the preparation method of 5 p-phenylenediamine (PPD) fibers, with 2,5 diamines paraxylene are raw material, obtain 2 by amidatioon, oxidation, hydrolysis three step, 5 diamines terephthalic acid monomers, adopt conventional sulphuric acid catalysis method to be polymerized again, and obtained by fiber spinning from crystalline state, realize especially by following steps:
(1) by 2,5 diamines paraxylene are dissolved in glacial acetic acid, 2, the mass volume ratio of 5 diamines paraxylene and glacial acetic acid is 1g:20mL, then add acetic anhydride, 2, the mass volume ratio of 5 diamines paraxylene and acetic anhydride is 1g:3.4mL, filter after reaction 30min, obtain benzene diacetayl amide paraxylene;
(2) will be added to the water benzene diacetayl amide paraxylene, be 1g:40 ~ 50mL to the mass volume ratio of benzene diacetayl amide paraxylene and water, and add potassium permanganate in the ratio being 1:4.2 ~ 4.6 to the mass ratio of benzene diacetayl amide paraxylene and potassium permanganate, after 90 DEG C of reaction 4h ~ 12h, adding watery hydrochloric acid regulates pH to 5 ~ 6 to be separated out by product, filtration obtains 2,5 pairs of benzene diacetayl amide terephthalic acid (TPA)s;
(3) by 2, it is in the sodium hydroxide solution of 10% than concentration that 5 pairs of benzene diacetayl amide terephthalic acid (TPA)s are dissolved in quality, uses nitrogen for protection gas, back flow reaction 12h, then add watery hydrochloric acid and regulate pH to 5 ~ 6, after filtration, distilled water flushing, oven dry obtain monomer 2,5 diamines terephthalic acid (TPA)s; Then according to a conventional method by monomer 2,5 diamines terephthalic acid (TPA)s are dissolved in the concentrated sulfuric acid and react, and adopt fiber spinning from crystalline state to obtain aramid fiber after polymerization.Course of reaction is shown below:
n＝350～400
advantage of the present invention is
Poly-Isosorbide-5-Nitrae paraphenylene terephthalamide 2,5 p-phenylenediamine (PPD) has good flatness, and the fiber therefore made has very high degree of crystallinity and the degree of orientation; Have two short chains to be connected between phenyl ring, add the brute force of fragile part, therefore this aramid fiber has very high intensity, can reach 5GPa.
Detailed description of the invention
Example 1
By 10g 2,5 diamines paraxylene are dissolved in 200mL glacial acetic acid, add after 34mL acetic anhydride reacts 30min at normal temperatures and filter, obtain 10.02g 2,5 pairs of benzene diacetayl amide paraxylene; Joined in 500mL water, and added 43g potassium permanganate after 90 DEG C of reaction 4h, drip quality and regulate pH to 5 ~ 6 to be separated out by product than the watery hydrochloric acid that concentration is 15%, filter and obtain 5.6g 2,5 pairs of benzene diacetayl amide terephthalic acid (TPA)s; Being dissolved in quality is in the sodium hydroxide solution of 10% than concentration, use nitrogen for protection gas, back flow reaction 12h, then drip quality and regulate pH to 5 ~ 6 than the dilute hydrochloric acid solution that concentration is 15%, filtration, distilled water flushing, oven dry obtain monomer 2,5 diamines terephthalic acid (TPA)s; Again by monomer 2, it is react in the concentrated sulfuric acid of 98% than concentration that 5 diamines terephthalic acid (TPA)s are dissolved in quality, adopts fiber spinning from crystalline state to obtain aramid fiber after polymerization.Recording intensity is 4.8Gpa.
Example 2
By 200g 2,5 diamines paraxylene are dissolved in 4L glacial acetic acid, add after 680mL acetic anhydride reacts 30min at normal temperatures and filter, obtain 200g 2,5 pairs of benzene diacetayl amide paraxylene; Joined in 8L water, and added 840g potassium permanganate after 90 DEG C of reaction 8h, add quality and regulate pH to 5 ~ 6 to be separated out by product than the watery hydrochloric acid that concentration is 15%, filter and obtain 103g 2,5 pairs of benzene diacetayl amide terephthalic acid (TPA)s; Being dissolved in quality is in the sodium hydroxide solution of 10% than concentration, use nitrogen for protection gas, back flow reaction 12h, then add quality and regulate pH to 5 ~ 6 than the dilute hydrochloric acid solution that concentration is 15%, filtration, distilled water flushing, oven dry obtain monomer 2,5 diamines terephthalic acid (TPA)s; Again by monomer 2, it is react in the concentrated sulfuric acid of 98% than concentration that 5 diamines terephthalic acid (TPA)s are dissolved in quality, adopts fiber spinning from crystalline state to obtain aramid fiber after polymerization.Recording intensity is 5.0Gpa.
Example 3
By 1.5Kg 2,5 diamines paraxylene are dissolved in 30L glacial acetic acid, add after 5.1L acetic anhydride reacts 30min at normal temperatures and filter, obtain 1.51Kg 2,5 pairs of benzene diacetayl amide paraxylene; Added in 70L water, and added 6.8Kg potassium permanganate after 90 DEG C of reaction 12h, add quality and regulate pH to 5 ~ 6 to be separated out by product than the watery hydrochloric acid that concentration is 15%, filter and obtain 8.5Kg 2,5 pairs of benzene diacetayl amide terephthalic acid (TPA)s; Being dissolved in quality is in the sodium hydroxide solution of 10% than concentration, use nitrogen for protection gas, back flow reaction 12h, then add quality and regulate pH to 5 ~ 6 than the dilute hydrochloric acid solution that concentration is 15%, filtration, distilled water flushing, oven dry obtain monomer 2,5 diamines terephthalic acid (TPA)s; Again by monomer 2, it is react in the concentrated sulfuric acid of 98% than concentration that 5 diamines terephthalic acid (TPA)s are dissolved in quality, adopts fiber spinning from crystalline state to obtain aramid fiber after polymerization.Recording intensity is 4.9Gpa.
Claims (1)
1. a high-intensity aramid fiber, its chemistry poly-Isosorbide-5-Nitrae-paraphenylene terephthalamide-2,5-p-phenylenediamine (PPD) by name, its structural formula is:
n=350 ~ 400, is characterized in that being prepared by following steps:
(1) by 2,5-diamines paraxylene is dissolved in glacial acetic acid, 2, the mass volume ratio of 5-diamines paraxylene and glacial acetic acid is 1g: 20mL, then add acetic anhydride, the mass volume ratio of 2,5-diamines paraxylene and acetic anhydride is 1g: 3.4mL, filter after reaction 30min, obtain benzene diacetayl amide paraxylene;
(2) will be added to the water benzene diacetayl amide paraxylene, be 1g: 40 ~ 50mL to the mass volume ratio of benzene diacetayl amide paraxylene and water, and add potassium permanganate in the ratio being 1: 4.2 ~ 4.6 to the mass ratio of benzene diacetayl amide paraxylene and potassium permanganate, after 90 DEG C of reaction 4h ~ 12h, adding watery hydrochloric acid regulates pH to 5 ~ 6 to be separated out by product, filtration obtains 2,5-to benzene diacetayl amide terephthalic acid (TPA);
(3) by 2, it is in the sodium hydroxide solution of 10% than concentration that 5-is dissolved in quality to benzene diacetayl amide terephthalic acid (TPA), use nitrogen for protection gas, back flow reaction 12h, then add watery hydrochloric acid and regulate pH to 5 ~ 6, after filtration, distilled water flushing, oven dry obtain monomer 2,5-diamines terephthalic acid (TPA); Then according to a conventional method monomer 2,5-diamines terephthalic acid (TPA) is dissolved in the concentrated sulfuric acid and reacts, after polymerization, adopt fiber spinning from crystalline state to obtain aramid fiber.
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