CN116575240A - Super-flexible polyphenylene sulfide fiber aerogel elastomer and preparation method and application thereof - Google Patents
Super-flexible polyphenylene sulfide fiber aerogel elastomer and preparation method and application thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 127
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 126
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 126
- 239000004964 aerogel Substances 0.000 title claims abstract description 98
- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 239000000806 elastomer Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
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- 238000002156 mixing Methods 0.000 claims abstract description 11
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- 238000007710 freezing Methods 0.000 claims abstract description 9
- 230000008014 freezing Effects 0.000 claims abstract description 9
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- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims abstract description 8
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 21
- 229920001410 Microfiber Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 11
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- 230000008569 process Effects 0.000 claims description 9
- 239000012774 insulation material Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000002074 melt spinning Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
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- 239000002052 molecular layer Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 239000011540 sensing material Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009998 heat setting Methods 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
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- 238000001000 micrograph Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005489 elastic deformation Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 238000001914 filtration Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- 239000011343 solid material Substances 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
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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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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- 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
- D06M13/10—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
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
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- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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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
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- Artificial Filaments (AREA)
Abstract
A preparation method of an ultra-flexible polyphenylene sulfide fiber aerogel elastomer comprises the following steps: dispersing 0.5-5mm of polyphenylene sulfide superfine fibers into a hydroxymethyl cellulose aqueous solution according to a proportion to obtain a polyphenylene sulfide superfine fiber dispersion liquid, wherein the mass fractions of the polyphenylene sulfide superfine fibers with the fiber lengths of 0.5-1mm, 1-2mm and 2-5mm are respectively 0-30%, 50-100% and 0-30%; mixing and hydrolyzing the organic siloxane containing the hydrophobic group with an acid-containing aqueous solution, then mixing with the polyphenylene sulfide superfine fiber aqueous dispersion, stirring, freezing, vacuum freeze-drying, and dehydrating and polycondensing after drying to obtain the aerogel elastomer. The preparation process is simple and convenient, does not need to use an organic solvent, is suitable for large-scale production, regulates and controls the polyphenylene sulfide fiber aerogel, improves the flexibility and rebound resilience of the aerogel, and the prepared super-flexible polyphenylene sulfide fiber aerogel elastomer has excellent rebound resilience, flexibility, high porosity, low thermal conductivity, thermal stability and good flame retardance.
Description
Technical Field
The invention relates to the technical field of fiber manufacturing, in particular to an ultra-flexible polyphenylene sulfide fiber aerogel elastomer, and a preparation method and application thereof.
Background
The aerogel is used as a solid material of a three-dimensional porous network structure, and the characteristics of low density, high porosity and large specific surface area make the aerogel possible to be applied to the fields of flame retardance, heat insulation, filtration and adsorption, shock absorption, sound absorption and the like. In order to meet the requirements of the aerogel in the fields of national defense, aerospace and civil use, the aerogel not only needs excellent comprehensive performance, thermal stability and low thermal conductivity, but also needs to pursue a preparation method which is flexible, high in elasticity, simple and convenient, can be produced in a large scale and the like. The traditional inorganic aerogel is easy to break due to poor mechanical strength, high brittleness and stress, so that the application of the inorganic aerogel in the field of high-performance flexibility is greatly limited. However, organic aerogels (polyurethane, polyurea, chitosan aerogels) suffer from the disadvantage of poor thermal stability. Thus, it remains a challenging problem in the art to design a new aerogel that has excellent mechanical properties, good thermal stability, low thermal conductivity, good flexibility, and good resilience.
Polyphenylene Sulfide (PPS) is a polymer with a main chain containing p-phenylene sulfide repeating structural units, is a novel functional engineering plastic, has good heat resistance, excellent chemical corrosion resistance and flame retardance, and can be widely applied to the fields of high-temperature filtration, special protective clothing, heat insulation materials, battery diaphragms and the like. At present, no polyphenylene sulfide fiber aerogel is reported, and the main reason is that the aerogel prepared from the polyphenylene sulfide fibers is difficult to mold, or after molding, the aerogel has high heat conductivity and poor rebound resilience and flexibility, so that the application is limited, and the application requirements cannot be met.
Disclosure of Invention
Based on the above, the invention provides an ultra-flexible polyphenylene sulfide fiber aerogel elastomer, and a preparation method and application thereof, so as to solve the technical problem that the prior art cannot well manufacture micro/nano fibers from polyphenylene sulfide materials and use the micro/nano fibers as aerogel.
In order to achieve the above purpose, the invention provides a preparation method of an ultra-flexible polyphenylene sulfide fiber aerogel elastomer, which comprises the following steps:
s1, dispersing 0.5-5mm of polyphenylene sulfide superfine fiber into a hydroxymethyl cellulose aqueous solution according to a proportion to obtain a polyphenylene sulfide superfine fiber dispersion liquid, wherein the mass fraction of the polyphenylene sulfide superfine fiber with the length of 0.5-1mm is 0-30%, the mass fraction of the polyphenylene sulfide superfine fiber with the length of 1-2mm is 50-100%, and the mass fraction of the polyphenylene sulfide superfine fiber with the length of 2-5mm is 0-30%;
s2, mixing and hydrolyzing the organic siloxane containing the hydrophobic group with an acid-containing aqueous solution, then mixing with the polyphenylene sulfide superfine fiber aqueous dispersion, stirring, freezing, freeze-drying in vacuum, and dehydrating and polycondensing after drying to obtain the super-flexible polyphenylene sulfide fiber aerogel elastomer.
As a further preferable technical scheme of the invention, the polyphenylene sulfide superfine fiber in the step S1 is prepared by taking a mixture of polyphenylene sulfide and alkali-soluble polyester as a raw material, carrying out melt spinning on islands in the sea, then carrying out drafting heat setting, and then carrying out alkali hydrolysis and cutting.
As a further preferable embodiment of the present invention, the polyphenylene sulfide ultrafine fiber produced in the step S1 has a diameter of 0.5 to 1.5. Mu.m, and the fiber is round.
As a further preferable technical scheme of the invention, the organic siloxane containing the hydrophobic group in the step S2 is at least one of methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane and propyltrimethoxysilane; the acid-containing aqueous solution is acetic acid, oxalic acid or hydrochloric acid with the concentration of 0.01-6 mmol/L.
As a further preferable technical scheme of the invention, in the step S2, the hydrolysis time is 15-30 min; stirring for 1-3 h; freezing is freezing in liquid nitrogen; the process conditions of vacuum freeze drying are as follows: freeze drying and polymerizing for 2-3 days in vacuum environment with vacuum degree lower than 30 Pa; the treatment temperature of the drying, dehydrating and condensing treatment is 40-90 ℃ and the time is 8-48 h.
As a further preferable technical scheme of the invention, the step S2 is to add the mixture of the polyphenylene sulfide superfine fiber aqueous dispersion liquid: the mass fraction of the polyphenylene sulfide superfine fiber is 35% -90%, the mass fraction of the organopolysiloxane is 9% -64%, and the mass fraction of the hydroxymethyl cellulose is 0.1% -1%.
According to another aspect of the present invention, the present invention further provides an ultra-flexible polyphenylene sulfide fiber aerogel elastomer, which is prepared by the preparation method of the ultra-flexible polyphenylene sulfide fiber aerogel elastomer, and the ultra-flexible polyphenylene sulfide fiber aerogel elastomer is an organic-inorganic hybrid fiber using a polyphenylene sulfide ultrafine fiber as a base material and an organopolysiloxane nano layer as a coating layer.
According to still another aspect of the present invention, the present invention also provides an application of the super-flexible polyphenylene sulfide fiber aerogel elastomer, which is applied to a thermal insulation material, a sound insulation material, a vibration absorption material, a catalytic material, an oil absorption material, a flexible functional material three-dimensional skeleton, a pressure sensing material or a magnetic response material.
The super-flexible polyphenylene sulfide fiber aerogel elastomer and the preparation method and application thereof can achieve the following beneficial effects by adopting the technical scheme:
1) The invention utilizes the good heat resistance, excellent chemical corrosion resistance and flame retardance of polyphenylene sulfide (PPS), and the sea-island type polyphenylene sulfide fiber aerogel prepared by alkaline hydrolysis, dispersion and full stirring with organic siloxane after melt sea-island composite spinning and finally freezing and freeze drying has the performances of excellent rebound resilience, flexibility, thermal stability, chemical stability and the like, and the preparation process is simple and convenient, does not need an organic solvent, and is suitable for large-scale production;
2) According to the invention, the polyphenylene sulfide superfine fiber with the diameter of 0.5-1.5 mu m can be prepared through island melt composite spinning, and the flexibility and rebound resilience of the polyphenylene sulfide fiber aerogel are improved through hybridization of the organosiloxane and the polyphenylene sulfide superfine fiber;
3) The super-flexible polyphenylene sulfide fiber aerogel elastomer has the advantages of excellent rebound resilience, flexibility, high porosity, low heat conductivity and the like, has excellent heat stability and flame retardance, can meet the use requirements of the aerogel in various environments, has better flexibility than the aerogel elastomer in the prior art, can be repeatedly folded without breaking or cracking, has wider application range, and can be applied to more fields.
In summary, the preparation method of the super-flexible polyphenylene sulfide fiber aerogel elastomer provided by the invention has the advantages that the preparation process is simple and convenient, an organic solvent is not required, the preparation method is suitable for large-scale production, the polyphenylene sulfide fiber aerogel is regulated and controlled, the flexibility and the rebound resilience of the aerogel are improved, and the prepared super-flexible polyphenylene sulfide fiber aerogel elastomer has excellent rebound resilience, flexibility, high porosity, low thermal conductivity, thermal stability, flame retardance and the like.
In addition, the super-flexible polyphenylene sulfide fiber aerogel elastomer prepared by the preparation method is suitable for the fields of heat insulation, sound absorption, oil absorption, heat preservation and the like.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a scanning electron microscope image of an island-in-sea polyphenylene sulfide ultrafine fiber prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the super-flexible polyphenylene sulfide fiber aerogel elastomer prepared in example 1 of the present invention;
FIG. 3 is a graph showing the physical and flexibility properties of the super-flexible polyphenylene sulfide fiber aerogel elastomer prepared in example 1 of the present invention;
FIG. 4 is an elastic deformation curve of the super flexible polyphenylene sulfide fiber aerogel elastomer prepared in example 1 of the present invention;
FIG. 5 is a graph showing the contact angle of the aerogel elastomer of the super flexible polyphenylene sulfide fiber prepared in example 1 of the present invention;
FIG. 6 is a graph showing the mass change with temperature of the super-flexible polyphenylene sulfide fiber aerogel elastomer prepared in the example of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The invention will be further described with reference to the drawings and detailed description. The terms such as "upper", "lower", "left", "right", "middle" and "a" in the preferred embodiments are merely descriptive, but are not intended to limit the scope of the invention, as the relative relationship changes or modifications may be otherwise deemed to be within the scope of the invention without substantial modification to the technical context.
Examples 1 to 6
Examples 1-6 are respectively preparation methods of super-flexible polyphenylene sulfide fiber aerogel elastomers, the technological parameters in the preparation process are shown in table 1, and the specific preparation process comprises the following steps:
s1, preparing polyphenylene sulfide superfine fibers:
firstly, drying polyphenylene sulfide particles/powder (PPS) and alkali-soluble Polyester (PET) with a melt index of 10-50g/10min at 80-160 ℃ for 12-24 hours, mixing the materials in a mass ratio of 2:8-8:2, and carrying out island melt spinning to obtain round polyphenylene sulfide superfine fiber filaments with a diameter of 0.5-1.5 mu m; the screw extrusion temperature is 315-325 ℃ in the melt spinning process, the screw melt pressure is 60-120bar, the spinning box temperature is 315-325 ℃, the spinning component pressure is less than 60kgf/cm < 2 >, the spinning speed is 600-1000m/min, and the draft multiple is 3.6-4.3 times;
then dissolving the polyphenylene sulfide superfine fiber filaments in sodium hydroxide solution to remove PET components, wherein the dissolving concentration is 5-15%, the time is 60-300min, the temperature is 60-90 ℃, and then cutting to obtain the polyphenylene sulfide superfine fiber with the fiber length of 0.5-5 mm;
s2, preparing a polyphenylene sulfide superfine fiber dispersion liquid:
and dispersing the polyphenylene sulfide superfine fibers which are cut into 0.5-5mm into a hydroxymethyl cellulose aqueous solution according to the distribution proportion of different lengths to obtain a polyphenylene sulfide superfine fiber dispersion liquid, wherein the solid content of the polyphenylene sulfide superfine fibers is 0.2-0.6%, and the concentration of the hydroxymethyl cellulose dispersing agent is 0.1-1%.
S3, preparing the super-flexible polyphenylene sulfide fiber aerogel:
mixing and hydrolyzing organic siloxane containing hydrophobic groups with an acid-containing aqueous solution with the concentration of 0.01-6 mmol/L, then mixing with a polyphenylene sulfide superfine fiber aqueous dispersion, wherein the mass fraction of the polyphenylene sulfide superfine fiber is 35-90%, the mass fraction of the organic polysiloxane is 9-64%, the mass fraction of the hydroxymethyl cellulose is 0.1-1%, and then stirring, freezing, freeze-drying, dehydrating and polycondensing to obtain the super-flexible polyphenylene sulfide fiber aerogel elastomer.
TABLE 1 Process parameters in the preparation of the ultra-flexible polyphenylene sulfide fiber aerogel elastomer of EXAMPLES 1-6
The super-flexible polyphenylene sulfide fiber aerogel elastomer prepared by the preparation method has specific performance indexes shown in table 2.
TABLE 2 Performance index of the ultra-flexible polyphenylene sulfide fiber aerogel elastomers prepared in examples 1-6
As is clear from Table 2, the super-flexible polyphenylene sulfide fiber aerogel elastomers prepared in examples 1 to 6 have a porosity of 90 to 95%, a contact angle of 140 to 164 degrees, a thermal conductivity of less than 0.032W/(m.K), a recovery elastic deformation of 86 to 96%, and a thermal stability of more than 320 ℃. The aerogel has high porosity, is favorable for being applied to the fields of heat insulation, sound absorption, heat preservation and the like, and the super-hydrophobic property is favorable for absorbing oil of the aerogel. In addition, the polyphenylene sulfide fiber aerogel was repeatedly foldable, indicating excellent flexibility.
The polyphenylene sulfide superfine fiber is used as an aerogel framework material, the surface of the polyphenylene sulfide superfine fiber is coated with an organopolysiloxane nano inorganic layer, the aerogel is endowed with good flexibility by the high length-diameter ratio of the polyphenylene sulfide superfine fiber, and the inorganic hybridization layer and the surface coating endow the aerogel with excellent heat resistance, so that the flame resistance of the aerogel can be greatly improved.
The following tests were carried out, taking the product of example 1 as an example:
the scanning electron microscope image of the polyphenylene sulfide ultrafine fiber prepared in example 1 is shown in fig. 1, and the diameter of the polyphenylene sulfide ultrafine fiber is measured to be between 0.5 and 1.5 μm. FIG. 2 is a scanning electron microscope image of the super flexible polyphenylene sulfide fiber aerogel elastomer in example 1, which has the structure as follows; the organosiloxane forms a sheet layer, and the fibers are coated or inserted into the sheet layer, so that the rebound resilience of the polyphenylene sulfide fiber aerogel is improved; FIG. 3 is a physical diagram of the super-flexible polyphenylene sulfide fiber aerogel elastomer of example 1, as can be seen from FIG. 3, the aerogel elastomer of various shapes in (a) is repeatedly folded according to the method of (b), and the polyphenylene sulfide aerogel elastomer can be completely folded without breaking, which indicates that the polyphenylene sulfide fiber aerogel elastomer has good flexibility; FIG. 4 is an elastic deformation curve of the super-flexible polyphenylene sulfide fiber aerogel elastomer of example 1, which can be seen that the polyphenylene sulfide aerogel can be completely recovered after 30%,60%,80% compression, indicating excellent rebound resilience; FIG. 5 is a contact angle of the super-flexible polyphenylene sulfide fiber aerogel elastomer of example 1, which is greater than 150 °, showing super-hydrophobic properties; fig. 6 is a graph showing the variation of the quality of the super flexible polyphenylene sulfide fiber aerogel elastomer of example 1 with temperature, and it can be seen from fig. 6 that the quality of the super flexible polyphenylene sulfide fiber aerogel elastomer starts to be significantly reduced after exceeding 500 ℃, showing excellent thermal stability.
In order to further study the characteristics of the super-flexible polyphenylene sulfide fiber aerogel elastomer of the present invention, examples 7 to 10 were presented according to the same preparation method and process parameters as in example 1, only the distribution of the lengths of the polyphenylene sulfide ultrafine fibers was different (i.e., the contents of the polyphenylene sulfide ultrafine fibers of different lengths were different), and the specific process parameters and the corresponding product performance indexes are shown in table 3.
When the fiber length is 100% distributed in the range of 0.5 to 1mm according to the fiber length, as in example 7, the fiber is well dispersed and easily molded, but the flexibility of the aerogel is poor and the rebound resilience effect is also poor due to poor entanglement forces between the fibers; when the fiber length is 100% distributed in the range of 1 to 2mm, as in example 8, entanglement forces between fibers are enhanced, rebound resilience and flexibility become good, and thermal conductivity is reduced; when the fiber length is 100% distributed in 2 to 5mm, as in example 9, entanglement between fibers is serious, dispersion in the dispersion liquid is not uniform, and aerogel can not be produced by molding, and finally an aerogel elastomer can not be obtained; when the distribution of the fibers is 0.5 to 1mm (25%), 1 to 2mm (50%), 2 to 5mm (25%), as in example 10, the short fibers are advantageous for dispersion, the long fibers are advantageous for entanglement, the intermediate length fibers are used as the skeleton of the aerogel, the rebound resilience and flexibility are better, the thermal conductivity is further lowered (smaller heat insulation effect is better), indicating that the structure is more reasonable, and the prepared aerogel is excellent in various properties. In addition, tests were carried out in which the prepared aerogel exhibited no flexibility and rebound resilience when the fiber length was 100% distributed below 0.5 mm; while the fiber length is 100% distributed over 5mm, the aerogel cannot be prepared by molding.
Table 3 examples 7-9 Process parameters in the preparation of the ultra-flexible polyphenylene sulfide fiber aerogel elastomer
From this, it can be seen that the content distribution of the polyphenylene sulfide ultrafine fibers with different lengths mainly affects rebound resilience, flexibility and thermal conductivity, and the aerogel prepared by three kinds of blending has better effect than that of the single-component length fibers. The aerogel elastomer prepared by mixing the polyphenylene sulfide ultrafine fibers with different lengths has better rebound resilience and higher thermal conductivity, and the reason is that too many long fibers have poor dispersibility and poor molding, so that the performance is poor; too many short fibers have good dispersibility, but have poor entanglement ability, resulting in deterioration of rebound resilience. Experiments show that the optimal choice is to mix and pair three length types of polyphenylene sulfide ultrafine fibers.
In order to investigate the influence of the component content of the organopolysiloxane on the product properties, examples 10 to 12 were presented according to the same preparation method and process parameters as in example 1, and only the content of the polyphenylene sulfide ultrafine fiber and the component content of the organopolysiloxane were changed, and the specific process parameters and the corresponding product performance index are shown in table 4.
Table 4 examples 10-12 process parameters in the preparation of the ultra-flexible polyphenylene sulfide fiber aerogel elastomer
From this, it is clear that the organosiloxane concentration is critical for the stability of the aerogel structure, that its concentration is reduced, that its rebound resilience is poor, that the structure collapses, and that the thermal conductivity is increased (the insulation effect is poor).
The invention also provides a super-flexible polyphenylene sulfide fiber aerogel elastomer, which is prepared by the preparation method of the super-flexible polyphenylene sulfide fiber aerogel elastomer in any embodiment, wherein the super-flexible polyphenylene sulfide fiber aerogel elastomer is an organic-inorganic hybrid fiber which takes polyphenylene sulfide ultrafine fibers as a base material and takes an organopolysiloxane nano layer as a coating layer, and the polyphenylene sulfide ultrafine fibers are connected with the organopolysiloxane through hydrogen bond interaction and chemical bonding.
The invention also provides application of the super-flexible polyphenylene sulfide fiber aerogel elastomer, which is applied to heat preservation and insulation materials, sound insulation materials, vibration absorption materials, catalytic materials, oil absorption materials, flexible functional material three-dimensional frameworks, pressure sensing materials or magnetic response materials.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (8)
1. The preparation method of the super-flexible polyphenylene sulfide fiber aerogel elastomer is characterized by comprising the following steps of:
s1, dispersing 0.5-5mm of polyphenylene sulfide superfine fiber into a hydroxymethyl cellulose aqueous solution according to a proportion to obtain a polyphenylene sulfide superfine fiber dispersion liquid, wherein the mass fraction of the polyphenylene sulfide superfine fiber with the length of 0.5-1mm is 0-30%, the mass fraction of the polyphenylene sulfide superfine fiber with the length of 1-2mm is 50-100%, and the mass fraction of the polyphenylene sulfide superfine fiber with the length of 2-5mm is 0-30%;
s2, mixing and hydrolyzing the organic siloxane containing the hydrophobic group with an acid-containing aqueous solution, then mixing with the polyphenylene sulfide superfine fiber aqueous dispersion, stirring, freezing, freeze-drying in vacuum, and dehydrating and polycondensing after drying to obtain the super-flexible polyphenylene sulfide fiber aerogel elastomer.
2. The method for preparing the super-flexible polyphenylene sulfide fiber aerogel elastomer according to claim 1, wherein the polyphenylene sulfide superfine fiber in the step S1 is prepared by taking a mixture of polyphenylene sulfide and alkali-soluble polyester as a raw material, carrying out melt spinning on islands in the sea, then carrying out drafting heat setting, and then carrying out alkali hydrolysis and chopping.
3. The method for preparing an aerogel elastomer of a super-flexible polyphenylene sulfide fiber according to claim 1, wherein the diameter of the polyphenylene sulfide super-fine fiber prepared in the step S1 is 0.5-1.5 μm, and the fiber is round.
4. The method for preparing the super flexible polyphenylene sulfide fiber aerogel elastomer according to claim 1, wherein the organosiloxane containing the hydrophobic groups in the step S2 is at least one of methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane and propyltrimethoxysilane; the acid-containing aqueous solution is acetic acid, oxalic acid or hydrochloric acid with the concentration of 0.01-6 mmol/L.
5. The method for preparing the super-flexible polyphenylene sulfide fiber aerogel elastomer according to claim 1, wherein in the step S2, the hydrolysis time is 15-30 min; stirring for 1-3 h; freezing is freezing in liquid nitrogen; the process conditions of vacuum freeze drying are as follows: freeze drying and polymerizing for 2-3 days in vacuum environment with vacuum degree lower than 30 Pa; the treatment temperature of the drying, dehydrating and condensing treatment is 40-90 ℃ and the time is 8-48 h.
6. The method for preparing an aerogel elastomer of a super-flexible polyphenylene sulfide fiber according to claim 1, wherein step S2 is performed in a mixture after adding an aqueous dispersion of a polyphenylene sulfide super-fine fiber: the mass fraction of the polyphenylene sulfide superfine fiber is 35% -90%, the mass fraction of the organopolysiloxane is 9% -64%, and the mass fraction of the hydroxymethyl cellulose is 0.1% -1%.
7. The super-flexible polyphenylene sulfide fiber aerogel elastomer is characterized by being prepared by the preparation method of the super-flexible polyphenylene sulfide fiber aerogel elastomer in any one of claims 1-6, wherein the super-flexible polyphenylene sulfide fiber aerogel elastomer is an organic-inorganic hybrid fiber taking polyphenylene sulfide ultrafine fibers as a base material and an organopolysiloxane nano layer as a coating layer.
8. The use of the super-flexible polyphenylene sulfide fiber aerogel elastomer as claimed in claim 7, wherein the super-flexible polyphenylene sulfide fiber aerogel elastomer is used as a thermal insulation material, a sound insulation material, a vibration absorption material, a catalytic material, an oil absorption material, a flexible functional material three-dimensional skeleton, a pressure sensing material or a magnetic response material.
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