CN105755803A - PBO (poly-p-phenylene benzobisoxazole) fiber molecular structure modification method - Google Patents
PBO (poly-p-phenylene benzobisoxazole) fiber molecular structure modification method Download PDFInfo
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- CN105755803A CN105755803A CN201610240862.0A CN201610240862A CN105755803A CN 105755803 A CN105755803 A CN 105755803A CN 201610240862 A CN201610240862 A CN 201610240862A CN 105755803 A CN105755803 A CN 105755803A
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- 239000000835 fiber Substances 0.000 title claims abstract description 150
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000002715 modification method Methods 0.000 title abstract 4
- 239000002253 acid Substances 0.000 claims abstract description 78
- 238000005215 recombination Methods 0.000 claims abstract description 59
- 230000006798 recombination Effects 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000012895 dilution Substances 0.000 claims description 19
- 238000010790 dilution Methods 0.000 claims description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 18
- 239000011707 mineral Substances 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000002736 nonionic surfactant Substances 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 17
- 239000000470 constituent Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 12
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- -1 op-10 Polymers 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 206010008190 Cerebrovascular accident Diseases 0.000 claims description 2
- 208000006011 Stroke Diseases 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 229920001410 Microfiber Polymers 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000003658 microfiber Substances 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000010306 acid treatment Methods 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical Kinetics & Catalysis (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a PBO (poly-p-phenylene benzobisoxazole) fiber molecular structure modification method.The PBO fiber molecular structure modification method particularly includes subjecting PBO fibers to modified treatment in a polyatomic recombination acid finishing agent, drying and curing so as to complete modification of PBO fibers.The PBO fiber molecular structure modification method has the advantages that PBO fiber modified treatment is conducted through compounding of polyatomic phosphoric acid and oxidation-free inorganic acid, and PBO fiber surface layers can be dissolved and etched and even can expose microfibers to increase roughness of the fiber surfaces, so that fiber and resin interface bonding is achieved with the PBO mechanical property being kept unchanged basically.
Description
Technical field
The invention belongs to composite modification field, relate to a kind of pbo fiber molecular structure method of modifying.
Background technology
Poly-p-phenylene-benzobisoxazole (is called for short PBO), and fiber has high-strength, heat resistance, is widely used, especially national defense applications.Fiber macromolecular structure marshalling, degree of crystallinity, the degree of orientation are high.Owing to the orientation texture that PBO molecule is regular makes fiber surface unusual light, and the polarity hetero atom overwhelming majority on strand is wrapped in fibrous inside, fiber surface polarity is also only small, and this makes fiber show extremely strong chemical inertness, and fiber is very weak with the connection of matrix.Accordingly, it would be desirable to change fiber surface roughness, increase the interfacial adhesion of fiber and group.The method improving fiber surface coarse adopted at present has the method such as chemical modification, Cement Composite Treated by Plasma, but fiber strength is decreased, and hinders pbo fiber application in high-performance composite materials field and development greatly.Therefore strengthen pbo fiber surface roughness, increase the caking property of fiber and matrix, reduce the emphasis that fibre damage is research at present.
Summary of the invention
It is an object of the invention to provide a kind of pbo fiber molecular structure method of modifying, solve existing pbo fiber molecular structure modified, the problem that fiber strength reduces.
The technical solution adopted in the present invention is, a kind of pbo fiber molecular structure method of modifying, by pbo fiber modification, then baking and curing in polyatomic recombination acid finishing agent, namely completes modifiying pbo fiber.
The feature of the present invention also resides in,
Concrete enforcement according to the following steps:
Step 1, prepares polyatomic recombination acid finishing agent:
Weigh polynary phosphoric acid, non-oxidation mineral acid, nonionic surfactant and stabilizer respectively, add in deionized water, mix homogeneously, namely obtain polyatomic recombination acid finishing agent;
Step 2, is modified pbo fiber processing:
The pbo fiber removing surface impurity is put into dipping absorption, then baking and curing in the polyatomic recombination acid finishing agent after dilution, namely completes modifiying pbo fiber.
In step 1, the ratio of each component of polyatomic recombination acid finishing agent is respectively as follows: polynary phosphoric acid 5~10%, non-oxidation mineral acid 3.5~7%, nonionic surfactant 0.5~1%, stabilizer 0.1~0.5% according to mass percent, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%.
Described polynary phosphoric acid is any one in polyphosphoric acid, polyphosphoric acids, pyrophosphoric acid, phosphorous acid.
Non-oxidation mineral acid is any one in the hydrochloric acid of boric acid, glacial acetic acid, mass fraction 36~38%.
Nonionic surfactant is any one in tween, op-10, polyester, fatty alcohol-polyoxyethylene ether, polyoxyethylene ester.
Stabilizer be phosphite ester, epoxy resin, ethanolamine, stearate apoplexy due to endogenous wind any one.
In step 2, the dilution ratio of polyatomic recombination acid finishing agent according to mass percent is: polyatomic recombination acid finishing agent 3%~5%, water 95%~97%, and above constituent mass percentage ratio sum is 100%.
Impregnating adsorption time in step 2 is 1~3h.
In step 2, baking and curing temperature is 100~130 DEG C.
The invention has the beneficial effects as follows, one pbo fiber molecular structure method of modifying of the present invention, trial polyatomic recombination acid finishing agent devises a kind of tencel macromolecular structure interface modification technology first, polyatomic recombination acid in this technology is a kind of inorganic solvent finishing agent, it can protonate with the hetero atom in PBO strand when processing pbo fiber, reduce intermolecular mutual attractive force, reduce intermolecular interaction energy, therefore etching pbo fiber surface layer can be dissolved, it even can be made to expose fento, thus increasing the degree of roughness of fiber surface, reach the purpose improving fiber with the interface cohesion of interlaminar resin, meanwhile, the mechanical property of pbo fiber does not reduce.
Accompanying drawing explanation
Fig. 1 is PBO fibril scanning electron microscope (SEM) photograph;
Fig. 2 is pbo fiber surface effect after employing multiple elements design acid treatment of the present invention;
Fig. 3 is the x-ray diffraction pattern adopting the pbo fiber before and after multiple elements design acid treatment of the present invention;
Fig. 4 is the infrared spectrogram adopting the pbo fiber before and after multiple elements design acid treatment of the present invention;
Fig. 5 is the mechanical property design sketch of pbo fiber after employing multiple elements design acid treatment of the present invention;
Fig. 6 adopts the wettability figure of pbo fiber before and after multiple elements design acid treatment of the present invention.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The invention provides a kind of pbo fiber molecular structure method of modifying, specifically implement according to the following steps:
Step 1, prepares polyatomic recombination acid finishing agent:
Following raw material is weighed respectively: polynary phosphoric acid 5~10%, non-oxidation mineral acid 3.5~7%, nonionic surfactant 0.5~1%, stabilizer 0.1~0.5% according to mass percent, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%;The raw material weighed is mixed 5~10min at normal temperatures, so as to uniformly close very much, namely obtains polyatomic recombination acid finishing agent.
Wherein, polynary phosphoric acid is any one in polyphosphoric acid, polyphosphoric acids, pyrophosphoric acid, phosphorous acid;Non-oxidation mineral acid is any one in the hydrochloric acid of boric acid, glacial acetic acid, mass fraction 36~38%;Nonionic surfactant is any one in tween, op-10, polyester, fatty alcohol-polyoxyethylene ether, polyoxyethylene ester;Stabilizer is any one in phosphite ester, epoxy resin, ethanolamine, stearates (such as aluminium stearate, magnesium stearate, calcium stearate etc.).
Step 2, adopts polyatomic recombination acid finishing agent that pbo fiber is carried out surface treatment:
Pbo fiber ethanol, deionized water are removed fiber surface impurity by 2.1, dry;
The polyatomic recombination acid finishing agent that 2.2 dilution step 1 prepare, dilution ratio is: polyatomic recombination acid finishing agent 3%~5%, water 95%~97%, above constituent mass percentage ratio sum is 100%, step 2.1 is obtained dipping absorption 1~3h in the polyatomic recombination acid finishing agent after pbo fiber dilution, then at 100~130 DEG C, baking and curing 3~5min, namely complete modifiying for pbo fiber.
Poly-p-phenylene-benzobisoxazole (PBO) fiber fibrous mechanical property after Strong oxdiative Bronsted acid effect certain time declines very big, and fiber surface has certain damage.
Pbo fiber is dissolved in 100% concentrated sulphuric acid, pyrovinic acid, chlorosulfonic acid, polyphosphoric acids, and strong acid treatment fiber can cause that fibrous mechanical property reduces.Therefore, the present invention mainly have studied the polyatomic recombination acid impact on pbo fiber surface texture, have studied polynary phosphoric acid finishing agent, and the mineral acid combined effect of non-oxidation performance is in pbo fiber, fortifying fibre interfacial adhesion performance, is tested the mechanical property of fiber after processing, chemical constitution, hot property etc. simultaneously.Result shows, adopts the modified pbo fiber mechanical property of polyatomic recombination acid to be held essentially constant, and fiber surface is coarse, and hot property increases, and the resistance to surface adhesive power of PBO material improves.
The pbo fiber scanning electron microscope (SEM) photograph that Fig. 1 and Fig. 2 respectively PBO fibril is modified with adopting polyatomic recombination acid finishing agent, contrast can be seen that, PBO fibril surface unusual light, modified pbo fiber, there is fine cracks in fiber surface, thus adding the degree of roughness of fiber surface, and then when pbo fiber mechanical property is held essentially constant, reach the purpose improving fiber with the interface cohesion of interlaminar resin.
Below by way of instantiation, change polyatomic recombination acid finishing agent consumption, change process time, study the change of modified pbo fiber brute force, coefficient of friction.
Embodiment 1
Step 1, prepares polyatomic recombination acid finishing agent:
Weighing following raw material respectively according to mass percent: polynary phosphoric acid 5%, non-oxidation mineral acid 3.5%, nonionic surfactant 0.5%, stabilizer 0.1%, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%;The raw material weighed is mixed 5~10min at normal temperatures, so as to uniformly close very much, namely obtains polyatomic recombination acid finishing agent.
Wherein, polynary phosphoric acid is polyphosphoric acid;Non-oxidation mineral acid is boric acid;Nonionic surfactant is tween;Stabilizer is phosphite ester.
Step 2, adopts polyatomic recombination acid finishing agent that pbo fiber is carried out surface treatment:
Pbo fiber ethanol, deionized water are removed fiber surface impurity by 2.1, dry;
The polyatomic recombination acid finishing agent that 2.2 dilution step 1 prepare, dilution ratio is: polyatomic recombination acid finishing agent 3%, water 95%, above constituent mass percentage ratio sum is 100%, step 2.1 is obtained dipping absorption 1h in the polyatomic recombination acid finishing agent after pbo fiber dilution, then at 100 DEG C, solidify 3~5min, namely complete modifiying for pbo fiber.
Detect modified pbo fiber strength retention be 96%, fiber confficient of static friction 0.207.
Embodiment 2
Step 1, prepares polyatomic recombination acid finishing agent:
Weighing following raw material respectively according to mass percent: polynary phosphoric acid 7%, non-oxidation mineral acid 5.5%, nonionic surfactant 0.75%, stabilizer 0.3%, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%;The raw material weighed is mixed 5~10min at normal temperatures, so as to uniformly close very much, namely obtains polyatomic recombination acid finishing agent.
Wherein, polynary phosphoric acid polyphosphoric acids;Non-oxidation mineral acid is glacial acetic acid;Nonionic surfactant is fatty alcohol-polyoxyethylene ether;Stabilizer is epoxy resin.
Step 2, adopts polyatomic recombination acid finishing agent that pbo fiber is carried out surface treatment:
Pbo fiber ethanol, deionized water are removed fiber surface impurity by 2.1, dry;
The polyatomic recombination acid finishing agent that 2.2 dilution step 1 prepare, dilution ratio is: polyatomic recombination acid finishing agent 4%, water 96%, above constituent mass percentage ratio sum is 100%, step 2.1 is obtained dipping absorption 1.5h in the polyatomic recombination acid finishing agent after pbo fiber dilution, then at 120 DEG C, solidify 3~5min, namely complete modifiying for pbo fiber.
Detect the strength retention of modified pbo fiber be 94.8%, fiber confficient of static friction 0.218.
Embodiment 3
Step 1, prepares polyatomic recombination acid finishing agent:
Weighing following raw material respectively according to mass percent: polynary phosphatase 11 0%, non-oxidation mineral acid 7%, nonionic surfactant 1%, stabilizer 0.5%, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%;The raw material weighed is mixed 5~10min at normal temperatures, so as to uniformly close very much, namely obtains polyatomic recombination acid finishing agent.
Wherein, polynary phosphoric acid is pyrophosphoric acid;Non-oxidation mineral acid is commercially available analytical pure hydrochloric acid (mass fraction is 36~38%);Nonionic surfactant is polyoxyethylene ester;Stabilizer is ethanolamine.
Step 2, adopts polyatomic recombination acid finishing agent that pbo fiber is carried out surface treatment:
Pbo fiber ethanol, deionized water are removed fiber surface impurity by 2.1, dry;
The polyatomic recombination acid finishing agent that 2.2 dilution step 1 prepare, dilution ratio is: polyatomic recombination acid finishing agent 5%, water 95%, above constituent mass percentage ratio sum is 100%, step 2.1 is obtained dipping absorption 2h in the polyatomic recombination acid finishing agent after pbo fiber dilution, then at 130 DEG C, solidify 3~5min, namely complete modifiying for pbo fiber.
Detect the strength retention of modified pbo fiber be 93%, fiber confficient of static friction 0.249.
Embodiment 4
Step 1, prepares polyatomic recombination acid finishing agent:
Weighing following raw material respectively according to mass percent: polynary phosphoric acid 8.5%, non-oxidation mineral acid 6%, nonionic surfactant 0.9%, stabilizer 0.4%, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%;The raw material weighed is mixed 5~10min at normal temperatures, so as to uniformly close very much, namely obtains polyatomic recombination acid finishing agent.
Wherein, polynary phosphoric acid is phosphorous acid;Non-oxidation mineral acid is boric acid;Nonionic surfactant is op-10;Stabilizer is aluminium stearate.
Step 2, adopts polyatomic recombination acid finishing agent that pbo fiber is carried out surface treatment:
Pbo fiber ethanol, deionized water are removed fiber surface impurity by 2.1, dry;
The polyatomic recombination acid finishing agent that 2.2 dilution step 1 prepare, dilution ratio is: polyatomic recombination acid finishing agent 4.5%, water 95.5%, above constituent mass percentage ratio sum is 100%, step 2.1 is obtained dipping absorption 3h in the polyatomic recombination acid finishing agent after pbo fiber dilution, then at 125 DEG C, solidify 3~5min, namely complete modifiying for pbo fiber.
Detect the strength retention of modified pbo fiber be 86%, fiber confficient of static friction 0.202.
Visible, adopt the modified pbo fiber of polyatomic recombination acid finishing agent, finishing agent consists of polynary phosphoric acid 5~10%, non-oxidation mineral acid 3.5~7%, nonionic surfactant 0.5~1%, stabilizer 0.1~0.5%, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%, and dipping adsorption time is 1~3h, the powerful maintenance of modified pbo fiber, is basically unchanged, confficient of static friction reduces relatively big, and fiber surface roughness increases, and is conducive to fiber to bond.
After before modified, pbo fiber macromolecular structure and configuration of surface are shown in shown in Fig. 3,4,5,6.
Fig. 3 is the X-ray diffractogram of pbo fiber before and after polyatomic recombination acid modification, can be seen that, PBO fibril is in 2 θ=15 °, 2 θ=27 °, 2 θ=38 °, 2 θ=58 ° present characteristic diffraction peak in various degree everywhere, and modified pbo fiber is in 2 θ=14 °, 2 θ=26 °, there is characteristic diffraction peak in various degree in 2 θ=51 ° three places.And characteristic diffraction peak all concentrates on 15 ° and about 27 °, illustrate that the lattice structure through the modified fiber of polyatomic recombination acid is substantially unchanged.From the area at peak, the area after multiple elements design acid treatment is slightly smaller than fibril, illustrates, the degree of crystallinity of pbo fiber has reduction by a small margin, but fiber is not damaged.
Fig. 4 is the pbo fiber infrared spectrogram before and after polyatomic recombination acid modification, it can be seen that modified pbo fiber is at 3675cm-1、2900cm-1、2352cm-1There is new characteristic absorption peak in place, illustrates that fiber surface has the introducing of OH, CH3 isoreactivity group, this considerably improves the surface property of fiber, add fiber surface activity.1400cm-1Place's C N key occurs small flexible, and phenyl ring is at 700cm-1Place's peak shape is complete, and after the polyatomic recombination acid modification such as intensity is relatively big, explanation, the framing structure of fiber keeps complete.
Fig. 5 is fiber strength and the coefficient of friction figure of the pbo fiber after polyatomic recombination acid modification, it can be seen that pbo fiber coefficient of friction overall variation has fluctuation, and when polynary phosphoric acid quality percentage ratio is 10%, confficient of static friction reaches maximum, and confficient of static friction is 0.249;Fiber strength decreases, and strength retention is 93%.Fiber strength, confficient of static friction tend towards stability gradually subsequently.
Fig. 6 is the capillary effect figure of pbo fiber before and after polyatomic recombination acid modification, it can be seen that untreated PBO fibril surface unusual light, capillary effect is non-normally low;Pbo fiber after process, there is groove in fiber surface, capillary effect increases, this shows that pbo fiber surface is had certain release effect by multiple elements design acid treatment, could alter that pbo fiber surface topography and increasing friction force, the capillary tube benefit of fiber increases, and finally makes the wettability of fiber increase, fiber surface roughness increases, the bond properties increase of fiber.
Conclusion: the pbo fiber after polyatomic recombination acid finishing agent processes, the brute force of fiber decreases, but the amplitude of reduction is in reasonable range of application, the coefficient of friction of fiber increases, illustrating that fiber surface roughness increases to some extent, the wettability of fiber increases to some extent, and the bond properties of fiber increases, be conducive to fiber and other Material cladding, improve the application performance of fiber.
Claims (10)
1. a pbo fiber molecular structure method of modifying, it is characterised in that by pbo fiber modification, then baking and curing in polyatomic recombination acid finishing agent, namely complete modifiying pbo fiber.
2. a kind of pbo fiber molecular structure method of modifying according to claim 1, it is characterised in that concrete enforcement according to the following steps:
Step 1, prepares polyatomic recombination acid finishing agent:
Weigh polynary phosphoric acid, non-oxidation mineral acid, nonionic surfactant and stabilizer respectively, add in deionized water, mix homogeneously, namely obtain polyatomic recombination acid finishing agent;
Step 2, is modified pbo fiber processing:
The pbo fiber removing surface impurity is put into dipping absorption, then baking and curing in the polyatomic recombination acid finishing agent after dilution, namely completes modifiying pbo fiber.
3. a kind of pbo fiber molecular structure method of modifying according to claim 2, it is characterized in that, in described step 1, the ratio of each component of polyatomic recombination acid finishing agent is respectively as follows: polynary phosphoric acid 5~10%, non-oxidation mineral acid 3.5~7%, nonionic surfactant 0.5~1%, stabilizer 0.1~0.5% according to mass percent, surplus is deionized water, and above-mentioned each constituent mass percentage ratio sum is 100%.
4. a kind of pbo fiber molecular structure method of modifying according to Claims 2 or 3, it is characterised in that described polynary phosphoric acid is any one in polyphosphoric acid, polyphosphoric acids, pyrophosphoric acid, phosphorous acid.
5. a kind of pbo fiber molecular structure method of modifying according to Claims 2 or 3, it is characterised in that described non-oxidation mineral acid is any one in the hydrochloric acid of boric acid, glacial acetic acid, mass fraction 36~38%.
6. a kind of pbo fiber molecular structure method of modifying according to Claims 2 or 3, it is characterised in that described nonionic surfactant is any one in tween, op-10, polyester, fatty alcohol-polyoxyethylene ether, polyoxyethylene ester.
7. a kind of pbo fiber molecular structure method of modifying according to Claims 2 or 3, it is characterised in that described stabilizer be phosphite ester, epoxy resin, ethanolamine, stearate apoplexy due to endogenous wind any one.
8. a kind of pbo fiber molecular structure method of modifying according to claim 2, it is characterized in that, in described step 2, the dilution ratio of polyatomic recombination acid finishing agent according to mass percent is: polyatomic recombination acid finishing agent 3%~5%, water 95%~97%, above constituent mass percentage ratio sum is 100%.
9. a kind of pbo fiber molecular structure method of modifying according to claim 2, it is characterised in that impregnating adsorption time in described step 2 is 1~3h.
10. a kind of pbo fiber molecular structure method of modifying according to claim 2, it is characterised in that in described step 2, baking and curing temperature is 100~130 DEG C.
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