CN1804201A - Surface modification method for poly(p-phenylenebenzobisoxazole) fiber - Google Patents
Surface modification method for poly(p-phenylenebenzobisoxazole) fiber Download PDFInfo
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- CN1804201A CN1804201A CN 200510061965 CN200510061965A CN1804201A CN 1804201 A CN1804201 A CN 1804201A CN 200510061965 CN200510061965 CN 200510061965 CN 200510061965 A CN200510061965 A CN 200510061965A CN 1804201 A CN1804201 A CN 1804201A
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- Prior art keywords
- polyparaphenylene
- benzo
- organically
- surface modification
- peroxidase
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- 239000000835 fiber Substances 0.000 title claims abstract description 51
- -1 poly(p-phenylenebenzobisoxazole) Polymers 0.000 title claims abstract description 19
- 238000002715 modification method Methods 0.000 title abstract 2
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 title 1
- 239000000243 solution Substances 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 102000004190 Enzymes Human genes 0.000 claims description 25
- 108090000790 Enzymes Proteins 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 25
- 230000004048 modification Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- PEPBFCOIJRULGJ-UHFFFAOYSA-N 3h-1,2,3-benzodioxazole Chemical compound C1=CC=C2NOOC2=C1 PEPBFCOIJRULGJ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 16
- 102000003992 Peroxidases Human genes 0.000 claims description 14
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 240000003291 Armoracia rusticana Species 0.000 claims description 4
- 235000011330 Armoracia rusticana Nutrition 0.000 claims description 4
- 244000068988 Glycine max Species 0.000 claims description 4
- 235000010469 Glycine max Nutrition 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003733 fiber-reinforced composite Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The disclosed surface modification method for a polyp-phenylene benzdioxazole (PBO) fiber comprises: with the protection by inert gas, pouring the bio-enzyme organic modifying solution into a seal-well container; dipping the PBO filter into the solution completely to react for 2-4h at 30-40Deg while dripping aqueous solution with 3wt% H2O2 within 10-30min during the reaction; finally, drying or airing the fiber cleaned by acetone and water. This invention has no damage to original thermal and mechanic properties with mild reaction condition and short time.
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 fiber that embodiment 1 obtains | 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 (7)
1, a kind of method of polyparaphenylene's benzo-dioxazole fiber surface modification is characterized in 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.
2, the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1, 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.
3, the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1, it is characterized in that: the solvent in the organically-modified solution of described biology enzyme is dioxane or acetone.
4, 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.
5, the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1, it 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.
6, the method for a kind of polyparaphenylene's benzo-dioxazole fiber surface modification according to claim 1, it is characterized in that: the monomer that uses in the organically-modified solution of described biology enzyme is acrylic acid, methacrylic acid or acrylamide.
7, according to the method for claim 1 and 2 described a kind of polyparaphenylene's benzo-dioxazole fiber surface modifications, it is characterized in that: 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.
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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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Cited By (7)
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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 |
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 |
CN102352556A (en) * | 2011-07-30 | 2012-02-15 | 苏州大学 | Polymer-coated aramid fiber and preparation method thereof |
CN102808325A (en) * | 2012-07-10 | 2012-12-05 | 西北工业大学 | Surface modifying method of PBO (polybenzoxazole) fiber |
CN102863634A (en) * | 2012-10-12 | 2013-01-09 | 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 |
CN111205383A (en) * | 2020-02-28 | 2020-05-29 | 西北工业大学 | Random copolymer, preparation method and application thereof, modified PBO fiber and preparation method thereof |
Family Cites Families (2)
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DD295686B5 (en) * | 1987-05-05 | 1995-03-09 | Plauener Spitze Gmbh | Method for decorating textiles |
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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Cited By (11)
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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 |
CN102352556A (en) * | 2011-07-30 | 2012-02-15 | 苏州大学 | Polymer-coated aramid fiber and preparation method thereof |
CN102352556B (en) * | 2011-07-30 | 2013-12-04 | 苏州大学 | Polymer-coated aramid fiber and preparation method thereof |
CN102808325A (en) * | 2012-07-10 | 2012-12-05 | 西北工业大学 | Surface modifying method of PBO (polybenzoxazole) fiber |
CN102808325B (en) * | 2012-07-10 | 2014-06-11 | 西北工业大学 | Surface modifying method of PBO (polybenzoxazole) fiber |
CN102863634A (en) * | 2012-10-12 | 2013-01-09 | 西北工业大学 | Process for preparing poly-p-phenylenebenzobisthiazole (PBO) fiber/benzoxazine composite material |
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 |
CN111205383A (en) * | 2020-02-28 | 2020-05-29 | 西北工业大学 | Random copolymer, preparation method and application thereof, modified PBO fiber and preparation method thereof |
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 |
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