CN105421042B - A kind of single green composite fibre of high-strength light high-ductility and preparation method thereof - Google Patents
A kind of single green composite fibre of high-strength light high-ductility and preparation method thereof Download PDFInfo
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- CN105421042B CN105421042B CN201610025147.5A CN201610025147A CN105421042B CN 105421042 B CN105421042 B CN 105421042B CN 201610025147 A CN201610025147 A CN 201610025147A CN 105421042 B CN105421042 B CN 105421042B
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- 239000000835 fiber Substances 0.000 title claims abstract description 101
- 239000011174 green composite Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 240000002853 Nelumbo nucifera Species 0.000 claims description 6
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 6
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 239000004626 polylactic acid Substances 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- IBFYXTRXDNAPMM-BVTMAQQCSA-N Geniposide Chemical compound O([C@@H]1OC=C([C@@H]2[C@H]1C(=CC2)CO)C(=O)OC)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O IBFYXTRXDNAPMM-BVTMAQQCSA-N 0.000 claims description 3
- IBFYXTRXDNAPMM-FZEIBHLUSA-N Geniposide Natural products COC(=O)C1=CO[C@@H](O[C@H]2O[C@@H](CO)[C@H](O)[C@@H](O)[C@@H]2O)[C@H]2[C@@H]1CC=C2CO IBFYXTRXDNAPMM-FZEIBHLUSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000003956 Luffa Nutrition 0.000 claims description 3
- VGLLGNISLBPZNL-RBUKDIBWSA-N arborescoside Natural products O=C(OC)C=1[C@@H]2C([C@H](O[C@H]3[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O3)OC=1)=C(CO)CC2 VGLLGNISLBPZNL-RBUKDIBWSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 244000050983 Luffa operculata Species 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 241000219138 Luffa Species 0.000 description 2
- 244000280244 Luffa acutangula Species 0.000 description 2
- 235000009814 Luffa aegyptiaca Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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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
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
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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
- D06M11/30—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 oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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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
- D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
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Abstract
The invention discloses single green composite fibre of a kind of high-strength light high-ductility and preparation method thereof, belong to chemical-biological engineering field.The preparation method is chosen natural fiber and carried out after cleaning shearing, in NaOH, NaClO or H2O2Immersion treatment in solution, then impregnate in a polymer solution and crosslinking Treatment, finally obtain the single green composite fibre of high-strength light high-ductility of the present invention, the fiber has environment friendly, recyclability and excellent mechanical performance, its intensity is 60MPa~750MPa, modulus is 2GPa~10GPa, and toughness is 10MJm‑3~100MJm‑3.The single composite fibre excellent performance of high-strength light high-ductility green, raw material obtained by the present invention are easy to get, can prepared on a large scale and environment-friendly, are expected to be used in actual production and living.
Description
Technical field
The invention belongs to prepare the method for the single green composite fibre of high-strength light in chemical-biological engineering field, specifically relate to
And a kind of single green composite fibre of high-strength light high-ductility and preparation method thereof.
Background technology
Exacerbation and the scarcity of resource with environmental problem, green renewable composite are increasingly closed by people
Note.Wherein, green single fiber, as the important component for preparing high strength composite, its mechanical property is for material
Production application be particularly important.At present, it is wet spinning twisting method, this method mistake to prepare the conventional method of high strength fibre
Journey is complicated and its raw material is largely the material that cost is high and can not degrade, and such as graphite is dilute, CNT (bibliography 1：
Shin M K,Lee B,Kim S H,et al.Synergistic toughening of composite fibres by
self-alignment of reduced graphene oxide and carbon nanotubes.Nature
communications,2012,3:650.).The existing Green Composites using natural green fiber as raw material, substantially
Natural fiber is compounded in formation fiber/polymer thing block materials (bibliography 2 in polymer substrate：La Mantia F P,
Morreale M.Green composites:A brief review.Composites Part A:Applied Science
and Manufacturing,2011,42(6):579-588. bibliography 3：Wu M,Shuai H,Cheng Q,et
al.Bioinspired Green Composite Lotus Fibers.Angewandte Chemie International
Edition,2014,53(13):3358-3361.), the report for preparing single green composite fibre is seldom.
The content of the invention
The invention provides a kind of method that two steps method of chemical treatment prepares the single green composite fibre of high-strength light high-ductility,
Pre-processed by fiber and polymer it is compound, utilize the interaction fiber specific structure of chemical reaction and molecular link, this hair
It is bright to be successfully prepared the single green composite fibre of high-strength light high-ductility, it is expected to obtain in terms of weaving, automobile and Aero-Space
Using.
The present invention provides a kind of single green composite fibre of high-strength light high-ductility, and the composite fibre is main by natural fiber
And polymer is constituted, the mechanical property of the composite fibre can by adjust the concentration of preprocessing solution, the concentration of polymer and
The parameters such as processing time are controlled.
The present invention also provides a kind of preparation method of the single green composite fibre of the high-strength light high-ductility, at two steps
Prepared by logos, specifically include following steps：
The first step, the selection of raw material：
Natural fiber is cleaned, sheared, a diameter of 0.01mm~1mm is obtained, length is 1cm~3cm natural fiber A.
Second step, fiber pretreatment：
The natural fiber A obtained in the first step is placed in the solution B that mass concentration is 0.5wt%~20wt%, processing
1h~80h, takes out, is cleaned, dried at room temperature with ethanol and deionized water, you can obtain the fiber with diverse microcosmic structure
A1。
3rd step, it is polymer impregnated with being crosslinked：
Fiber A1 is put into the polymer solution C that mass concentration is 1wt%~20wt%, impregnates 10h~100h, take
Go out, dry, you can obtain the composite fibre after two-step pretreatment, then carry out crosslinking Treatment, that is, obtain the high-strength light of the present invention
The single green composite fibre A2 of high-ductility.
Described natural fiber A is one in the natural fibers of containing cellulose such as luffa, coir fibre or lotus leaf stem silk
Kind.
Described solution B is NaOH, NaClO or H2O2In one kind.The mass concentration of described solution B is preferably 1wt%
~10wt%, processing time is preferably 2h~10h.
Described polymer solution C is one in PVAC polyvinylalcohol, polyurethane PU, polylactic acid PLA or chitosan CS etc.
Kind.Described polymer solution C mass concentration is preferably 1wt%~15wt%, and dip time is preferably 10h~50h.
Described diverse microcosmic structure includes exposed nanofibrillar structure, nanometer flowers, the porous surface of fibril composition
Structure and pore space structure etc..
The method of the crosslinking Treatment is heating, adds glutaraldehyde or Geniposide crosslinking agent.
The single green a diameter of 0.01mm~1mm of composite fibre A2 of described high-strength light high-ductility.It is preferred that the nanometer
Fibre diameter is 0.05mm~0.5mm.
The single green composite fibre A2 of described high-strength light high-ductility has environment friendly, recyclability and excellent mechanical
Performance, its tensile strength is 60MPa~750MPa, and modulus is 2GPa~10GPa, and toughness is 10MJm-3~100MJm-3。
Described lightweight refers to that fiber is microcosmic in loose structure, and density range is 0.5g/cm3~2.15g/cm3。
The present invention is entered by solution infusion method to natural fiber first using natural reproducible fiber and polymer as raw material
Pretreatment is gone, then on this basis, the single compound fibre of high-intensity high-tenacity green has been prepared with polymer casting cladding process
Dimension, main enhancing mechanism is related to chemical reaction, molecular link interaction and its produced fiber specific structure.Gained of the invention
Single composite fibre (such as Coir/NaOH/PVA) excellent performance of high-strength light high-ductility green, raw material is easy to get, can prepare on a large scale
And it is environment-friendly, it is expected to be used in actual production and living.
The method that the present invention is provided compared with preparing the method for the green composite fibre of high intensity in the prior art, excellent results
It is as follows：
(1) compared with the existing methods, preparation method of the invention is simple, easy to operate, can realize large-scale system
It is standby.
(2) composite fibre for preparing of the present invention belongs to single green fiber, raw material be easy to get it is renewable, it is environment-friendly degradable
And performance is controllable, there is very big application prospect in weaving, Aero-Space and automotive field.
(3) present invention uses two step methods of chemical treatment, you can realize the lifting of the big degree of mechanical property, and compound rear intensity
Strengthened simultaneously with toughness.
Brief description of the drawings
The preparation process schematic diagram of the single green composite fibre of high-strength light high-ductility in Fig. 1 present invention；
The single green composite fibre schematic diagram that Fig. 2 present invention is prepared；
The single green composite fibre load-deformation curve of high-strength light high-ductility that Fig. 3 present invention is prepared.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1.
Coir fibre is cleaned, sheared, one group of average diameter is obtained for 0.23mm, length is 3cm coir fibre.With reference to
Fig. 1, is placed in coir fibre in the NaOH that mass concentration is 5wt%, soaks 20h, take out, cleaned with ethanol and deionized water,
Dry at room temperature, obtain the fiber A1 with pore space structure.Then fiber is put into the PVA that mass concentration is 1wt%, dipping
10h, takes out, dries at room temperature.Finally crosslinking Treatment is carried out with glutaraldehyde, you can obtain one group of single green of high-strength light high-ductility
Composite fibre, such as Fig. 2, the composite fibre pattern prepared are uniform.Its force diagram is as shown in figure 3, tensile strength of fiber
478MPa, modulus 2GPa, toughness 30MJm-3。
Embodiment 2.
Loofah fiber is cleaned, sheared, one group of average diameter is obtained for 0.5~1mm, length is fine for 1cm luffa
Dimension.Then loofah fiber be placed in mass concentration be 1wt% NaOH solution in, soak 80h, take out, with ethanol and go from
Sub- water cleaning, dries, obtains the fiber A1 with exposed nanofibrillar structure and nano flower clustering architecture at room temperature.Then fibre
Dimension A1 is put into the CS that mass concentration is 10wt%, impregnates 50h, is taken out, is dried at room temperature.Finally carried out with Geniposide at crosslinking
Reason, that is, obtain the single green composite fibre of high-strength light high-ductility.As a result find, tensile strength of fiber 60MPa, modulus 5.1GPa,
Toughness 10MJm-3。
Embodiment 3.
Lotus leaf fasciated fiber is cleaned, sheared, one group of average diameter is obtained for 0.05mm, length is 2cm~3cm lotus leaf stem
Fiber.Then lotus leaf fasciated fiber is placed in the H that mass concentration is 10wt%2O2In, 2h is soaked, is taken out, with ethanol and deionized water
Cleaning, dries, obtains the fiber A1 with exposed nanofibrillar structure at room temperature.Then H2O2Fiber after processing is put into
Mass concentration is taken out, dried at room temperature in 15wt% PLA, to impregnate 20h.Crosslinking Treatment finally is carried out with heating, that is, is obtained
The single green composite fibre of high-strength light high-ductility.Result of the test shows, tensile strength of fiber 560MPa, modulus 7.2GPa, toughness
50MJ·m-3。
Embodiment 4.
Coir fibre is cleaned, sheared, one group of average diameter is obtained for 0.01~0.21mm, length is 2cm~3cm coconut palm
Case fibre.Then coir fibre is placed in the NaClO solution that mass concentration is 2wt%, soaks 10h, taken out, with ethanol and going
Ionized water is cleaned, and is dried at room temperature, and then fiber is put into the PU that mass concentration is 5wt%, 100h is impregnated, taken out, room temperature
Under dry, obtain with the fiber of surface porosity being made up of fibril.Finally heated carry out crosslinking Treatment, that is, obtain lightweight
The single green composite fibre of high-strength and high ductility.As a result find, tensile strength of fiber 750MPa, modulus 10GPa, toughness 100MJm-3。
Claims (8)
1. a kind of preparation method of the single green composite fibre of high-strength light high-ductility, it is characterised in that：Comprise the following steps,
The first step, the selection of raw material：
Natural fiber is cleaned, sheared, a diameter of 0.01mm~1mm is obtained, length is 1cm~3cm natural fiber A；
Second step, fiber pretreatment：
The natural fiber A obtained in the first step is placed in the solution B that mass concentration is 0.5wt%~20wt%, processing 1h~
80h, takes out, is cleaned, dried at room temperature with ethanol and deionized water, obtain the fiber A1 with diverse microcosmic structure；Described
Solution B is NaOH, NaClO or H2O2In one kind；
3rd step, it is polymer impregnated with being crosslinked：
Fiber A1 is put into the polymer solution C that mass concentration is 1wt%~20wt%, impregnates 10h~100h, taken out, done
It is dry, crosslinking Treatment is then carried out, the single green composite fibre A2 of high-strength light high-ductility is obtained；Described polymer solution C is poly-
One kind in vinyl alcohol PVA, polyurethane PU, polylactic acid PLA or chitosan CS；The single green of described high-strength light high-ductility is compound
A diameter of 0.01mm~the 1mm of fiber A2；Intensity is 60MPa~750MPa, and modulus is 2GPa~10GPa, and toughness is 10MJm-3
~100MJm-3；Described lightweight refers to that fiber is microcosmic in loose structure, and density range is 0.5g/cm3~2.15g/cm3。
2. a kind of preparation method of the single green composite fibre of high-strength light high-ductility according to claim 1, its feature exists
In：Described natural fiber A is one kind in luffa, coir fibre or lotus leaf stem silk.
3. a kind of preparation method of the single green composite fibre of high-strength light high-ductility according to claim 1, its feature exists
In：The mass concentration of described solution B is 1wt%~10wt%, and processing time is 2h~10h.
4. a kind of preparation method of the single green composite fibre of high-strength light high-ductility according to claim 1, its feature exists
In：Described polymer solution C mass concentration is 1wt%~15wt%, and dip time is 10h~50h.
5. a kind of preparation method of the single green composite fibre of high-strength light high-ductility according to claim 1, its feature exists
In：Described diverse microcosmic structure include exposed nanofibrillar structure, nanometer flowers, fibril composition surface porosity with
And pore space structure.
6. a kind of preparation method of the single green composite fibre of high-strength light high-ductility according to claim 1, its feature exists
In：The method of described crosslinking Treatment is heating, adds glutaraldehyde or Geniposide crosslinking agent.
7. a kind of single green composite fibre of high-strength light high-ductility, it is characterised in that：The described single green of high-strength light high-ductility
A diameter of 0.01mm~the 1mm of composite fibre；Intensity is 60MPa~750MPa, and modulus is 2GPa~10GPa, and toughness is 10MJ
m-3~100MJm-3；Described lightweight refers to that fiber is microcosmic in loose structure, and density range is 0.5g/cm3~2.15g/cm3。
8. the single green composite fibre of a kind of high-strength light high-ductility according to claim 7, it is characterised in that：The lightweight
The single green a diameter of 0.05mm~0.5mm of composite fibre of high-strength and high ductility.
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| CN105948594B (en) * | 2016-05-31 | 2018-03-30 | 华北水利水电大学 | A kind of method for preparing enhancing anticracking cement mortar using modified coir fibre |
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