CN1245434C - Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same - Google Patents
Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same Download PDFInfo
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- CN1245434C CN1245434C CN 200410025469 CN200410025469A CN1245434C CN 1245434 C CN1245434 C CN 1245434C CN 200410025469 CN200410025469 CN 200410025469 CN 200410025469 A CN200410025469 A CN 200410025469A CN 1245434 C CN1245434 C CN 1245434C
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Abstract
The present invention discloses a poly-benzobisoxazole polymer containing the base group of a hydroxyl group and a preparation method thereof. A polymer solution obtained by the present invention can be used for preparing high-performance fibers by using dried spray and wet spinning through a screw extruder. The molecular structural fragment of the polybenzoxazole polymer of the present invention discloses in the specification.
Description
Technical field
The present invention relates to a kind of Ju Ben Bing Er oxazole polymkeric substance and preparation method thereof.
Background technology
The sixties in last century, the successful exploitation of poly terephthalic acid Ursol D (PPTA) fiber has started the research boom of high-performance fiber.By molecular designing and fiber spinning from crystalline state technology, the high-performance fiber of various excellent performances is constantly developed, and is that the prepared high-performance fiber of heteroaromatic polymkeric substance of representative is exactly outstanding figure wherein with polyparaphenylene Ben Bing Er oxazole (PBO).On the research basis of United States Air Force material laboratory and Dow chemical company, Japanese Japan spins company and has successfully realized the suitability for industrialized production of pbo fiber the nineties in last century, and its commodity are called " Zylon ".The tensile strength of Zylon is 5.8Gpa, and tensile modulus is 300GPa, is respectively the twice of PPTA fiber.In addition, Zylon also has excellent thermostability (heat decomposition temperature is up to 650 ℃) and flame retardant resistance (LOI=68).Therefore, Zylon has important use to be worth in fields such as aerospace, military project national defence, communications and transportation, sports equipment, building, high temperature protections, the irreplaceable effect of other material is arranged.Particularly the mankind entered since the information age, and the competition of various countries aspect overall national strength is growing more intense, and the exploitation of future war weaponry and space resources were explored deepen continuously, and these need be support with lighter, stronger, more energy-conservation advanced material all.Be the development of high-strength, the Gao Mo of representative, high temperature resistant, flame-retarding high performance filamentary material and advanced composite material thereof with Zylon and be applied in the developmental level that has reflected a national hard-core technology to a certain extent, and become the material resources that a class has strategic importance.
Yet Zylon is not perfection, and its compressive strength, torsion modulus etc. still are apparent not enough.The axial compression strength of Zylon is 200～400MPa, far below its tensile strength; The problem that also has the poor adhesion between fiber and matrix when preparing matrix material with Zylon, this is that the macromolecular structure characteristic of raw material PBO by preparation Zylon is determined.PBO is terephthalic acid (TA) and 4, and polymerization obtains 6-diamino resorcin hydrochlorate (DAR) in polyphosphoric acid (PPA) medium, and its synthetic route is as follows:
From molecular structure, PBO is bar-shaped stiff chain macromole, only exists Van der Waals to interact between the molecule, lacks entanglement; And lack polar group in the molecular structure.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of polybenzoxazole base polymer and preparation method thereof, to obtain the more good high-performance fiber of over-all properties.
The chemical name of polybenzoxazole base polymer of the present invention is for gathering 2, and 5-dihydroxyl penylene benzene and two oxazoles are called for short DHPBO, and it has following molecular structure fragment:
Wherein: n=89～100, number-average molecular weight are 23000～27000;
Above-mentioned gathers 2, and the preparation method of 5-dihydroxyl penylene benzene and two oxazoles comprises the steps:
With 4, the 6-diamino resorcin hydrochlorate (is called for short DAR, down with) in inert atmosphere with 2, the 5-dihydric para-phthalic acid (is called for short DHTA, carry out polycondensation down together) in polyphosphoric acid (being called for short PPA, down together), temperature of reaction is 50～100 ℃, react to the HCl of DAR and remove fully, available pH detection paper reaction institute escaping gas is neutral;
Reacted 3-6 hour down at 130 ℃～150 ℃ then, reacted 10-14 hour down at 170-175 ℃ again, reacted 16～24 hours down at 185 ℃～200 ℃ at last, finish polyreaction, adopt conventional method from reaction product, to collect said polymkeric substance then, general available big water gaging cleans thoroughly to remove the polyphosphoric acid in the system, vacuum-drying then.
In polyreaction, DAR is 1: 0.8～1.2 with the ratio of the mole number of DHTA.
Said 4, the chemical structure of 6-diamino resorcin hydrochlorate is as follows:
Said 2,5-dihydric para-phthalic acid's chemical structure is as follows:
4,6-diamino resorcin hydrochlorate and 2, the 5-dihydric para-phthalic acid can adopt document Wolfe J.F., Arnorld F.E., and Macromolecules 1981,14,909 and document Klop E A, Lammers M.Polymer 1998,39,5981 disclosed methods are prepared, or adopt commercially available finished product.
Said polyphosphoric acid is H
6P
4O
13
Polyphosphoric acid with the ratio of the mole number of DAR is: 1: 0.3～0.6
This polymkeric substance that the present invention obtained can form hydrogen bond action (Klop E A between macromole or in the macromole, Lammers M.Polymer 1998,39,5987, Hageman J C L, vander Horst J W, de Groot R A.Polymer 1999,40,1313-1323), thereby can improve the compression performance of high-performance fiber by its preparation.The polymers soln that the present invention obtains can adopt dry-jet wet-spinning to prepare high-performance fiber through screw extrusion press, and can adopt the three point bending test method to measure its modulus of compression.
Embodiment
Embodiment 1
Be equipped with powerful whipping appts, N
2Import and export, in the 0.5L reactor of charging opening, at first feed high-purity N
2Air is fallen in displacement, at N
2Protection adds 5.4455g 4,6-diamino resorcin hydrochlorate (DAR), 5.0620g2,5-dihydric para-phthalic acid (DHTA), 25.67g H down successively
6P
4O
13(P
2O
5Concentration is 80wt%) and 10.3649g P
2O
5, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 3 hours, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 5 hours, material is further dissolved.Temperature of reaction kettle is risen to 100 ℃ of reactions 24 hours, be muted color, represent that promptly system removes HCl fully until detecting at gas evolution mouth place with the pH test paper.Be warming up to 130 ℃ of reactions 3 hours, 150 ℃ were reacted 5 hours, were warming up to 175 ℃ of reactions 14 hours again, 185 ℃ of reactions 24 hours, finished polyreaction at last.[the η]=20.7dL/g of polymerisate.。Solid
13C-NMR analytical results (ppm): δ=162.1,149.3,137.7,113.4,93.3.FTIR analytical results (KBr pressed disc method, cm
-1): 3417,1627,1573,1488,1428,1366,1228,1190,1105,1057,937,868,803,776.Results of elemental analyses: each constituent content theoretical value is: C:63.16%, H:2.26%, N:10.53%; Experimental value is C:59.44%, H:1.98%, N:10.46%
Polymers soln adopts dry-jet wet spinning process to be prepared into the fiber that fiber number is 2dtex through screw extrusion press, and the modulus of compression of fiber is 512MPa; Heat decomposition temperature is 504 ℃ in air, and the heat decomposition temperature in the nitrogen is 522 ℃.
Embodiment 2
Be equipped with powerful whipping appts, N
2Import and export, in the 0.5L reactor of charging opening, at first feed high-purity N
2Air is fallen in displacement, at N
2Protection adds 5.4455g 4,6-diamino resorcin hydrochlorate (DAR), 5.0620g2,5-dihydric para-phthalic acid (DHTA), 25.67g H down successively
6P
4O
13(P
2O
5Concentration is 80wt%) and 10.3649g P
2O
5, sealed reactor.
Reactor internal reaction material is warming up to 65 ℃, kept 3 hours, material is tentatively mixed, slowly be warming up to 80 ℃ again, kept 5 hours, material is further dissolved.Temperature of reaction kettle is risen to 150 ℃ of reactions 24 hours, be muted color, represent that promptly system removes HCl fully until detecting at gas evolution mouth place with the pH test paper.Be warming up to 175 ℃ of reactions 22 hours again, 200 ℃ of reactions 24 hours, finish polyreaction at last.[the η]=25.9dL/g of polymerisate.Solid
13C-NMR analytical results (ppm): δ=162.3,149.3,137.6,113.2,93.3.FTIR analytical results (KBr pressed disc method, cm
-1): 3405,1720,1633,1551,1449,1417,1369,1196,1119,1044,993,956,881,718,677,629.Results of elemental analyses: each constituent content theoretical value C:63.16%, H:2.26%, N:10.53%; Experimental value C:62.32%, H:2.07%, N:10.48%.
Polymers soln adopts dry-jet wet spinning process to be prepared into the fiber that fiber number is 1.8dtex through screw extrusion press, and the modulus of compression of fiber is 557MPa; Heat decomposition temperature is 524 ℃ in air, and the heat decomposition temperature in the nitrogen is 543 ℃.
Claims (3)
1. poly-benzene that contains oh group and two oxazole polymkeric substance is characterized in that having following molecular structure fragment:
Wherein: n=89～100.
2. the preparation method of Ju Ben Bing Er oxazole polymkeric substance according to claim 1 is characterized in that comprising the steps:
With 4,6-diamino resorcin hydrochlorate and 2, the 5-dihydric para-phthalic acid carries out polycondensation in polyphosphoric acid, and temperature of reaction is 50～100 ℃, and reaction is to 4, and the HCl of 6-diamino resorcin hydrochlorate removes fully;
Under 130 ℃～150 ℃, reacted 3-6 hour then, reacted 10-14 hour down at 170-175 ℃ again, reacted 16～24 hours down at 185 ℃～200 ℃ at last, finish polyreaction, react back water cleaning, vacuum-drying then.
3. method according to claim 2 is characterized in that, in polyreaction, and 4,6-diamino resorcin hydrochlorate and 2, the ratio of 5-dihydric para-phthalic acid's mole number is: 1: 0.8～1.2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410025469 CN1245434C (en) | 2004-06-25 | 2004-06-25 | Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same |
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|---|---|---|---|
| CN 200410025469 CN1245434C (en) | 2004-06-25 | 2004-06-25 | Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same |
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| CN1594398A CN1594398A (en) | 2005-03-16 |
| CN1245434C true CN1245434C (en) | 2006-03-15 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430430C (en) * | 2006-09-15 | 2008-11-05 | 华东理工大学 | Benzooxazole kind block copolymer |
| CN103304817B (en) * | 2013-05-14 | 2015-12-02 | 徐州斯尔克纤维科技股份有限公司 | A kind of preparation method of modified polyphenyl Bing bis-oxazole resinous polymer |
| CN105297165B (en) * | 2015-11-17 | 2017-12-19 | 中国科学院长春应用化学研究所 | A kind of polyimide fiber and preparation method thereof |
| CN105503847A (en) * | 2016-01-15 | 2016-04-20 | 中国科学院兰州化学物理研究所 | Method for synthesizing benzodioxazole type compound |
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