CN100392174C - Surface modification method for poly(p-phenylenebenzobisoxazole) fiber - Google Patents
Surface modification method for poly(p-phenylenebenzobisoxazole) fiber Download PDFInfo
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- CN100392174C CN100392174C CNB2005100619652A CN200510061965A CN100392174C CN 100392174 C CN100392174 C CN 100392174C CN B2005100619652 A CNB2005100619652 A CN B2005100619652A CN 200510061965 A CN200510061965 A CN 200510061965A CN 100392174 C CN100392174 C CN 100392174C
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Abstract
The present invention discloses a surface modification method for polyp-phenylene benzdioxazole (PBO) fibers. An organic modification solution of biological enzymes is poured in a container with favorable air tightness under the protection of inert gas. PBO fibers are completely immersed in the organic modification solution of biological enzymes for a reaction of 2 to 4 hours at the temperature of 30 to 40 DEG C., and a water solution of 3 wt% hydrogen peroxide is dropped into the organic modification solution for 10 to 30 min in the process of the reaction. After the reaction is completed, the modified PBO fibers are cleaned by acetone and water, dried by baking or dried in the air to complete the surface modification of the PBO fibers. In the present invention, biological enzymes are used for the surface modification of the PBO fibers. As reaction conditions are moderate, and the reaction time is short, the original thermology properties and the original mechanical properties of the fibers can not be damaged.
Description
Technical field
The present invention relates to the method for a kind of polyparaphenylene's benzo-dioxazole (hereinafter to be referred as PBO) fiber surface modification.
Background technology
In recent years, conflict and war all over the world is continuous, and war industry obtains fast development, and various countries more and more come into one's own to the research and development of high performance material.Composite is an important branch in material field, is bringing into play the effect that becomes more and more important in war industry, has occupied critical role.Along with the continuous development of high-tech level, also more and more higher to the requirement of composite property, not only require higher specific strength, specific modulus, but also to have more excellent weatherability, heat endurance, anti-ablation, anti-erosion, damping, suction ripple, saturating ripple, etc.Fiber is the basic composition of composite, and the quality of its performance has determined performance of composites to a great extent.Pbo fiber because of its outstanding physicochemical property by various countries researcher extensive concern, reach 5.8GPa as its intensity, modulus is up to 280GPa, limited oxygen index (LOI) is 68, maximum operation (service) temperature and decomposition temperature are respectively 350 ℃ and 650 ℃, these characteristics are much better than existing organic fiber, and are enough to make it and high-performance carbon fibre to compare favourably, so be described as the super fiber of 21 century.
Yet, because of pbo fiber surface-activity and self structure characteristics, the cementability of fiber and resin matrix is very poor, often have low layer with pbo fiber reinforced composite materials goods and cut intensity, compressive strength, and cut performance and compression performance by the layer that the method for introducing hydrogen bond can not improve the pbo fiber reinforced composite because of resin content is low.Therefore, by pbo fiber is carried out surface treatment,, may be layer effective way of cutting performance and compression performance that improves the pbo fiber reinforced composite to improve the cementability of pbo fiber and resin matrix.
The surface modifying method of fiber is more, flame method, chemical pretreatment solution oxidizing process, Low Temperature Plasma Treating,, surperficial high-energy radiation grafting method, surface heat gaseous cyaniding and top layer cladding process or the like, also have the compound use of several method.These methods are all at the surface property that has improved fiber in varying degrees, but are cost with the mechanical property or the hot property of loss fiber mostly.Therefore, the new surface modifying method of research and development has great importance.
Summary of the invention
In order to overcome the problem that background technology exists, the object of the present invention is to provide a kind of method of polyparaphenylene's benzo-dioxazole fiber surface modification.
The technical solution adopted for the present invention to solve the technical problems is that the step of this method is as follows:
1) under inert gas shielding, the organically-modified solution of biology enzyme is poured in the good container of air-tightness;
2) polyparaphenylene's benzo-dioxazole fiber is immersed in the organically-modified solution of biology enzyme fully, at 30～40 ℃ of reaction 2～4h, and in course of reaction, splash into the aqueous solution of 3wt% hydrogen peroxide with time of 10～30min, polyparaphenylene's benzo-dioxazole fibre Wesy's acetone and water with modification after reaction finishes clean, behind oven dry or the airing, promptly finish surface modification to polyparaphenylene's benzo-dioxazole fiber.
The organically-modified solution of described biology enzyme is the organic solution of peroxidase, and its composition comprises solvent, peroxidase, buffer solution, monomer and hydrogen peroxide.
Solvent in the organically-modified solution of described biology enzyme is dioxane or acetone.
Peroxidase in the organically-modified solution of described biology enzyme is peroxidating horseradish enzyme or peroxidating soybean enzyme.
The cushioning liquid that uses in the organically-modified solution of described biology enzyme is hydrophosphate solution, its pH=7.0 value.
The monomer that uses in the organically-modified solution of described biology enzyme is acrylic acid, methacrylic acid or acrylamide.
The proportioning of the composition of the organically-modified solution of described biology enzyme is: solvent quality is 3000～9000 times of peroxidase quality, the quality of cushioning liquid is 500～3000 times of peroxidase quality, monomer mass is 1000～5000 times of peroxidase quality, and the hydrogen peroxide quality is 100～200 times of peroxidase quality.
The present invention compares the beneficial effect that has with background technology: adopt biology enzyme that pbo fiber is carried out surface modification, owing to original calorifics of fiber and mechanical property are lacked, do not damaged to its reaction condition gentleness, reaction time.
Description of drawings
Accompanying drawing is an infrared spectrum (the modification pbo fiber that the modification pbo fiber that the original pbo fiber of A, B embodiment 1 obtain, C embodiment 3 obtain) before and after the pbo fiber surface treatment
The specific embodiment
Embodiment 1:
Under inert gas shielding; with dioxane 500g; hydrophosphate cushioning liquid 150g; acrylic acid 50g, peroxidating horseradish enzyme 0.1g add in the good flat there-necked flask of air-tightness, and pbo fiber is immersed wherein fully; intensification and control temperature are at 35 ± 0.5 ℃; add hydrogen peroxide (the 3wt% aqueous solution) 20g with 30min by dropping funel, reaction obtains the pbo fiber of surface modification behind the 3h, and its mechanical property and surface property see Table 1 and accompanying drawing.
Embodiment 2:
Under inert gas shielding; with dioxane 900g; hydrophosphate cushioning liquid 50g; methacrylic acid 100g, peroxidating horseradish enzyme 0.1g add in the good flat there-necked flask of air-tightness, and pbo fiber is immersed wherein fully; intensification and control temperature are at 30 ± 0.5 ℃; add hydrogen peroxide (the 3wt% aqueous solution) 10g with 10min by dropping funel, obtain the pbo fiber of surface modification behind the reaction 4h, its mechanical property and surface property see Table 1.
Embodiment 3:
Under inert gas shielding; with ether 500g; hydrophosphate cushioning liquid 200g; acrylic acid 50g, peroxidating soybean enzyme 0.1g add in the good flat there-necked flask of air-tightness, and pbo fiber is immersed wherein fully; intensification and control temperature are at 40 ± 0.5 ℃; add hydrogen peroxide 20g by dropping funel with the 10min time, obtain the pbo fiber of surface modification behind the reaction 3h, its mechanical property and surface property see Table 1 and accompanying drawing.
Embodiment 4:
Under inert gas shielding; with ether 300g; hydrophosphate cushioning liquid 300g; acrylamide 500g, peroxidating soybean enzyme 0.1g add in the good flat there-necked flask of air-tightness, and pbo fiber is immersed wherein fully; intensification and control temperature are at 40 ± 0.5 ℃; add hydrogen peroxide 15g by dropping funel with the 20min time, obtain the pbo fiber of surface modification behind the reaction 2h, its mechanical property and surface property see Table 1.
The performance of pbo fiber after table 1 surface treatment
| TENSILE STRENGTH (MPa) | With the contact angle of ethylene glycol (°) | |
| Pristine fibre | 4476.3 | 79.7 |
| The modification PBO that embodiment 1 obtains is fine accurate | 4526.5 | 61.8 |
| The modification PBO fiber that embodiment 2 obtains | 4529.0 | 62.0 |
| The modification PBO fiber that embodiment 3 obtains | 4484.4 | 60.8 |
| The modification PBO fiber that embodiment 4 obtains | 4481.8 | 61.1 |
Claims (5)
1. the method for polyparaphenylene's benzo-dioxazole fiber surface modification, the step of this method is as follows:
1) under inert gas shielding, the organically-modified solution of biology enzyme is poured in the good container of air-tightness;
2) polyparaphenylene's benzo-dioxazole fiber is immersed in the organically-modified solution of biology enzyme fully, at 30～40 ℃ of reaction 2～4h, and in course of reaction, splash into the aqueous solution of 3wt% hydrogen peroxide with time of 10～30min, polyparaphenylene's benzo-dioxazole fibre Wesy's acetone and water with modification after reaction finishes clean, behind oven dry or the airing, promptly finish surface modification to polyparaphenylene's benzo-dioxazole fiber; It is characterized in that:
The organically-modified solution of described biology enzyme is the organic solution of peroxidase, and its composition comprises solvent, peroxidase, buffer solution, monomer and hydrogen peroxide;
The proportioning of the composition of the organically-modified solution of described biology enzyme is: solvent quality is 3000～9000 times of peroxidase quality, the quality of cushioning liquid is 500～3000 times of peroxidase quality, monomer mass is 1000～5000 times of peroxidase quality, and the hydrogen peroxide quality is 100～200 times of peroxidase quality.
2. the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1 is characterized in that: the solvent in the organically-modified solution of described biology enzyme is dioxane or acetone.
3. the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1 is characterized in that: the peroxidase in the organically-modified solution of described biology enzyme is peroxidating horseradish enzyme or peroxidating soybean enzyme.
4. the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1 is characterized in that: the cushioning liquid that uses in the organically-modified solution of described biology enzyme is hydrophosphate solution, its pH=7.0 value.
5. the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1 is characterized in that: the monomer that uses in the organically-modified solution of described biology enzyme is acrylic acid, methacrylic acid or acrylamide.
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| CNB2005100619652A CN100392174C (en) | 2005-12-13 | 2005-12-13 | Surface modification method for poly(p-phenylenebenzobisoxazole) fiber |
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| CNB2005100619652A CN100392174C (en) | 2005-12-13 | 2005-12-13 | Surface modification method for poly(p-phenylenebenzobisoxazole) fiber |
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| CN100392174C true CN100392174C (en) | 2008-06-04 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445613B (en) * | 2008-12-16 | 2011-06-22 | 大连理工大学 | Interface modification method of poly(p-phenylene-benzobisoxazole) fiber-reinforced soluble polyaryl ether resin composite material |
| CN102094325A (en) * | 2010-11-23 | 2011-06-15 | 哈尔滨工业大学 | Preparation method of poly(p-phenylene benzabisoxazole) (PBO) fabric with hydrophobic property |
| CN102352556B (en) * | 2011-07-30 | 2013-12-04 | 苏州大学 | Polymer-coated aramid fiber and preparation method thereof |
| CN102808325B (en) * | 2012-07-10 | 2014-06-11 | 西北工业大学 | Surface modifying method of PBO (polybenzoxazole) fiber |
| CN102863634B (en) * | 2012-10-12 | 2014-08-20 | 西北工业大学 | Process for preparing poly-p-phenylenebenzobisthiazole (PBO) fiber/benzoxazine composite material |
| CN105755803A (en) * | 2016-04-19 | 2016-07-13 | 西安工程大学 | PBO (poly-p-phenylene benzobisoxazole) fiber molecular structure modification method |
| CN111205383B (en) * | 2020-02-28 | 2021-04-02 | 西北工业大学 | Random copolymer, preparation method and application thereof, modified PBO fiber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0290027A2 (en) * | 1987-05-05 | 1988-11-09 | Plauener Spitze Gesellschaft mit beschränkter Haftung | Process for the decoration of textile fabrics |
| JP2003027350A (en) * | 2001-07-19 | 2003-01-29 | Toyobo Co Ltd | High-strength woven fabric and method of producing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0290027A2 (en) * | 1987-05-05 | 1988-11-09 | Plauener Spitze Gesellschaft mit beschränkter Haftung | Process for the decoration of textile fabrics |
| JP2003027350A (en) * | 2001-07-19 | 2003-01-29 | Toyobo Co Ltd | High-strength woven fabric and method of producing the same |
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