CN114657772A - Bionic scale super wear-resistant agent for textile leather - Google Patents
Bionic scale super wear-resistant agent for textile leather Download PDFInfo
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- CN114657772A CN114657772A CN202210282943.2A CN202210282943A CN114657772A CN 114657772 A CN114657772 A CN 114657772A CN 202210282943 A CN202210282943 A CN 202210282943A CN 114657772 A CN114657772 A CN 114657772A
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- water
- silicon dioxide
- wear
- nanosheet powder
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 69
- 239000010985 leather Substances 0.000 title claims abstract description 27
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 27
- 239000004753 textile Substances 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000002135 nanosheet Substances 0.000 claims abstract description 90
- 239000000843 powder Substances 0.000 claims abstract description 66
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 64
- -1 polysiloxane Polymers 0.000 claims abstract description 47
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 44
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims description 39
- 239000006185 dispersion Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 235000011837 pasties Nutrition 0.000 claims description 9
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 8
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 4
- 230000003592 biomimetic effect Effects 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- GJFNRSDCSTVPCJ-UHFFFAOYSA-N 1,8-bis(dimethylamino)naphthalene Chemical compound C1=CC(N(C)C)=C2C(N(C)C)=CC=CC2=C1 GJFNRSDCSTVPCJ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
-
- 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
- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/01—Stain or soil resistance
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a bionic scale super wear-resistant agent for textile leather, which is a silicon dioxide nanosheet grafted water-soluble polysiloxane particle brush and comprises silicon dioxide nanosheet powder; and the water-soluble polysiloxane is chemically grafted on the surface of the silicon dioxide nanosheet powder. The particle brush structure of water-soluble polysiloxane is chemically grafted on the surface of the silicon dioxide nanosheet, and after the super wear-resistant agent is applied, a bionic scale structure can be formed on the surface of the textile leather, so that the textile leather is endowed with excellent wear resistance, glossiness, dry and wet rubbing resistance and flexibility, and also has excellent adhesive force and waterproof and anti-pollution capacity, and meanwhile, the hand feeling of the product can be increased, and the product is softer, more natural, smooth and finer.
Description
Technical Field
The invention belongs to the technical field of nano materials for textile leather, and particularly relates to a bionic scale super wear-resistant agent for textile leather, and a preparation method of the bionic scale super wear-resistant agent.
Background
With the application of textile leather, in order to improve the wear resistance of the textile leather, a certain proportion of wear-resistant agent is usually added into the textile leather. If common high-hardness wear-resistant materials such as inorganic oxide powder, silicon oxide, aluminum oxide or titanium oxide powder are directly used as a wear-resistant agent, the wear resistance of the materials is not good; if the oxide wear-resistant powder is reacted with the coupling agent to prepare the water-soluble wear-resistant agent, most of products are emulsion, other components react in the using process to generate instability and limitation, and simultaneously, groups in the coupling agent which are not completely reacted may react with yarns in the textile leather to cause incomplete desizing; in addition, if the wear-resistant powder reacts with chemical substances with low surface energy, the obtained wear-resistant agent is water-insoluble, and the weather resistance of the wear-resistant agent is greatly reduced due to weak acting force with textile leather caused by low water solubility of the wear-resistant agent.
Aiming at the problems, the current effective solution is to perform physical or chemical action on wear-resistant powder and a high polymer material to form an organic-inorganic composite wear-resistant agent. For example, chinese patent application publication No. CN108221398A discloses a silicone rubber leather with good wear resistance and a coating process thereof, but the wear resistance effect can be achieved only by using a large amount of the silicone rubber leather in the application of the scheme; also, for example, chinese patent application publication No. CN113529408A discloses a novel aqueous anti-wear agent and its application, but the reaction conditions are severe, the force between the polymer and the inorganic portion is weak, and the weather resistance is poor.
In conclusion, the existing scheme has the problems of harsh reaction conditions or complex process, poor wear resistance and easy pollution caused by adopting some volatile prepolymers.
Disclosure of Invention
In view of the above, the invention needs to provide a bionic flake super wear-resistant agent for textile leather, which is a silicon dioxide nanosheet grafted water-soluble polysiloxane particle brush structure, a thin-layer silicon dioxide nanosheet modified by double bonds is used as a main wear-resistant filler, and water-soluble polysiloxane is grafted on the surface of the silicon dioxide nanosheet.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a bionic scale super wear-resistant agent for textile leather, which is a silicon dioxide nanosheet grafted water-soluble polysiloxane particle brush and comprises the following components:
silicon dioxide nanosheet powder;
and the water-soluble polysiloxane is chemically grafted on the surface of the silicon dioxide nanosheet powder.
In a further scheme, the thickness of the silicon dioxide nanosheet is 3-100nm, and the size of the silicon dioxide nanosheet is 0.5-50 μm.
Further, the molecular weight of the water-soluble polysiloxane is 100-4000.
The invention further provides a preparation method of the super wear-resistant agent for the textile leather, which comprises the following steps:
providing silicon dioxide nanosheet powder and liquid mercapto-terminated water-soluble polysiloxane;
obtaining double-bond modified silicon dioxide nanosheet powder particles;
and mixing the double-bond modified silica nanosheet powder particles into the liquid mercapto-terminated water-soluble polysiloxane, adding an ultraviolet initiator, uniformly mixing, performing ultraviolet treatment, and performing click chemical reaction to obtain the pasty wear-resisting agent.
In a further scheme, the preparation method of the double-bond modified silica nanosheet powder particle comprises the following steps:
dispersing silicon dioxide nanosheet powder in an alcohol-water mixed solution with the pH value of 8-12 to form a dispersion liquid;
adding a silane coupling agent containing double bonds into the dispersion liquid, and reacting and modifying the silicon dioxide nanosheet powder at room temperature to obtain the double-bond modified silicon dioxide nanosheet powder particles.
In the further scheme, the volume ratio of alcohol to water in the alcohol-water mixed solution is 1-20, and the alcohol is water-soluble low molecular weight alcohol with the molecular weight of 46-1000.
In a further scheme, the adding amount of the double-bond-containing silane coupling agent is 0.1-20% of the mass of the silica nanosheet powder;
the double-bond-containing silane coupling agent is one or more than two of gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, vinyl trimethoxysilane and vinyl tri (b-methoxyethoxy) silane.
In a further scheme, the addition amount of the liquid mercapto-terminated water-soluble polysiloxane is 30-400% of the mass of the silica nanosheet powder, wherein the molecular weight Mn of the water-soluble polysiloxane is 100-4000.
In a further scheme, the addition amount of the ultraviolet initiator is 10-40% of the molar amount of the liquid mercapto-terminated water-soluble polysiloxane;
the ultraviolet initiator is one or more than two of isopropyl thia-anthraquinone, 4-methyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1-hydroxy-cyclohexyl-phenyl ketone.
In the further scheme, in the step of ultraviolet light treatment, the power of ultraviolet light is 35-100W, and the time is 1-24 h.
Compared with the prior art, the invention has the following beneficial effects:
the bionic scale super wear-resistant agent is a silicon dioxide nanosheet grafted polysiloxane particle brush, and the whole flaky structure enables the adhesion of the bionic scale super wear-resistant agent to be stronger than that of a spherical wear-resistant agent of the same type, and the bionic scale super wear-resistant agent is not easy to fall off and has a wide application range; the wear-resistant agent has a pearlescent effect due to the micron-sized large-size sheet structure and the material with small refractive index, and the glossiness can be effectively increased without adding other substances; the silica nanosheet is thin in thickness, soft in mechanical property and high in wear resistance. And the super wear-resisting agent can be adhered to the coating surface to form a bionic scale structure, and the super wear-resisting agent has lubricating components, so that the friction coefficient can be effectively reduced, and the super wear-resisting agent is more wear-resistant.
The super wear-resistant agent is prepared by selecting water-soluble polysilane, so that the super wear-resistant agent has dry-wet rub resistance and flexibility; the particle brush with the scale-shaped structure has strong barrier property and waterproof and anti-pollution capacity on the basis of moisture permeability due to the structural particularity.
The raw materials for preparing the super wear-resistant agent have low price, the preparation process is simple, the energy consumption is low, and the pollution is small; the adopted click chemical grafting method has high atom utilization rate and no solvent pollution.
Drawings
FIG. 1 is a schematic view of a preparation process of a bionic scale super wear-resistant agent in the invention;
FIG. 2 is a schematic diagram of the principle of the bionic scale super wear-resistant agent of the invention;
FIG. 3 is an SEM picture of silica nanosheet powder employed in examples 1-3 of the present invention;
FIG. 4 is an SEM image of the biomimetic scale super abrasive made in example 1;
FIG. 5 is an SEM image of bionic scale super wear-resistant agent prepared in example 2 after being applied to the surface of leather;
FIG. 6 is an SEM image of bionic scale super wear-resistant agent prepared in example 3 after being applied to the surface of textile fibers.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a bionic scale super wear-resistant agent for textile leather, which is a silicon dioxide nanosheet grafted water-soluble polysiloxane particle brush, and specifically comprises silicon dioxide nanosheet powder; and the water-soluble polysiloxane is chemically grafted on the surface of the silicon dioxide nanosheet powder particle. The structure enables the whole body to be flaky, the adhesion is stronger than that of a spherical wear-resistant agent of the same type, the super wear-resistant agent is not easy to fall off and has wide application range, and the bionic scale super wear-resistant agent forms a structure similar to a scale animal body surface sheet A after being coated on the surface of a material, so that the bionic scale super wear-resistant agent has a high wear-resistant effect; in addition, the bionic scale super wear-resistant agent has good affinity with a high polymer material and self-contains a lubricating component, so that the friction coefficient is reduced, and the wear-resistant effect is improved.
In a further scheme, the size of the silica nanosheet in the silica nanosheet powder can be adjusted or selected according to actual conditions, and in one or more embodiments of the present invention, the silica nanosheet has a thickness of 3-100nm and a size of 0.5-50 μm; preferably, the silica nanosheets are 5nm in thickness and 0.5-1 μm in size.
According to the further scheme, water-soluble polysiloxane is grafted on the surface of the silicon dioxide nanosheet, so that the super wear-resistant agent is endowed with dry-wet rubbing resistance and flexibility. In some embodiments of the present invention, the molecular weight of the water-soluble polysiloxane is preferably 100-4000, since the molecular weight results in high viscosity and increases the handling difficulty, and the water-soluble polysiloxane within this molecular weight range can further increase the adhesion of the super anti-wear agent.
The second aspect of the invention provides a preparation method of a bionic scale super wear-resistant agent for textile leather, which is combined with figure 1 and mainly comprises the following steps:
providing silica nanosheet powder and liquid mercapto-terminated water-soluble polysiloxane
The thickness of the silicon dioxide nanosheet powder is 3-100nm, and the size is 0.5-50 mu m; preferably, the thickness of the silicon dioxide nanosheet is 5nm, the size of the silicon dioxide nanosheet is 0.5-1 μm, and the silicon dioxide nanosheet can be selected according to actual conditions; the liquid hydrosulfuryl-terminated water-soluble polysiloxane is that hydrosulfuryl is contained in the terminal group of the water-soluble polysiloxane, thereby providing the basis for the subsequent reaction.
Preparation of double-bond modified silicon dioxide nanosheet powder particle
And preparing double-bond modified silica nanosheet powder particles, so that the surface of the silica nanosheet is provided with unsaturated bonds, and the subsequent reaction with the liquid mercapto-terminated water-soluble polysiloxane is realized.
The double-bond modified silica nanosheet powder particles can be prepared by first dispersing silica nanosheet powder in an alcohol-water mixed solution having a pH of 8-12, preferably a pH of 9-11, to form a dispersion according to embodiments of the present invention using methods conventional in the art; and then adding a double-bond-containing silane coupling agent into the dispersion liquid, and reacting and modifying the silicon dioxide nanosheet powder at room temperature to prepare the double-bond modified silicon dioxide nanosheet powder particle. Wherein, in the alcohol-water mixed solution, the volume ratio of alcohol to water is 1-20, the alcohol is water-soluble small molecular alcohol with molecular weight of 46-1000, and specific examples include but are not limited to ethanol, ethylene glycol, butanediol and the like; the pH control of the alcohol-water mixed solution can be realized by adding an alkali, which is an organic alkali or an inorganic alkali, and is a conventional composition in the art, for example, the organic alkali can be one selected from ethylenediamine, triethylamine, triethanolamine, tetraethylenepentamine, diethylenetriamine, triethylenetetramine, tris (hydroxymethyl) aminomethane, tetrahydroxyethylethylenediamine, tetrahydroxypropylethylenediamine, tetraethylethylenediamine, 1, 8-bis-dimethylamino-naphthalene, and imidazole, and the inorganic alkali is one selected from ammonia, sodium hydroxide, and potassium hydroxide, and it is understood that the concentration and the amount of the alkali are not particularly limited, as long as the purpose of adjusting the pH of the system to the required range can be achieved.
Further, the double bond-containing silane coupling agent of the present invention is selected from gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltris (b-methoxyethoxy) silane, etc., preferably gamma-methacryloxypropyltriethoxysilane; the amount of the double bond-containing silane coupling agent can be adjusted according to the amount of the silica nanosheet powder and the amount of the polysiloxane, and is not particularly limited, and in one or more embodiments of the present invention, the amount of the double bond-containing silane coupling agent added is 0.1-20% of the mass of the silica nanosheet powder particles.
Preparation of silica nanosheet grafted water-soluble polysiloxane particle brush
And mixing the prepared double-bond modified silicon dioxide nanosheet powder particles into liquid mercapto-terminated water-soluble polysiloxane, adding an ultraviolet initiator, uniformly mixing, carrying out ultraviolet treatment, and carrying out click chemical reaction to obtain the pasty wear-resistant agent. Specifically, because the surface of the silicon dioxide nanosheet powder particle contains unsaturated bond-double bond, under the initiation of ultraviolet initiator and ultraviolet light, the sulfydryl contained in the end group of the water-soluble polysiloxane and the double bond are subjected to click chemical reaction, so that the polysiloxane is grafted on the surface of the silicon dioxide nanosheet to form a particle brush structure, the particle brush is integrally flaky, the thickness of the particle brush is 3-100nm, and the size of the particle brush is 0.5-4 μm,
further, the addition amount of the water-soluble polysiloxane in the present invention can be adjusted according to actual needs, and in some specific embodiments of the present invention, the addition amount of the liquid mercapto-terminated water-soluble polysiloxane is 30% to 400% of the mass of the silica nanosheet powder, wherein the molecular weight Mn of the water-soluble polysiloxane is 100-4000.
It is to be understood that the uv initiator is conventionally selected in the art, and the amount thereof may be adjusted according to the reaction conditions, and thus is not particularly limited. In one or more embodiments of the invention, the uv initiator is added in an amount of 10% to 40% by mole based on the liquid mercapto-terminated water-soluble polysiloxane; examples of the ultraviolet initiator that may be specifically mentioned include, but are not limited to, one or two or more of isopropyl thiaanthraquinone, 4-methylbenzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxy-cyclohexyl-phenyl ketone.
Further, the super wear-resistant agent is prepared by ultraviolet light treatment, the specific parameters of which are not particularly limited, and according to the embodiment of the invention, in the step of ultraviolet light treatment, the power of the ultraviolet light is 35-100W, and the time is 1-24 h.
The function principle of the super wear-resistant agent with the bionic scales prepared by the invention is shown in figure 2, the super wear-resistant agent with the particle brush structure is applied to the surface of the material to form the bionic scales structure, and the wear-resistant material has good affinity (intersolubility) with an adhesive material (high polymer material) from the mechanism of the wearability, has lubricating components, reduces the friction coefficient and can obviously improve the wear-resistant effect. The super wear-resistant agent can be efficiently prepared by a simple preparation method, the obtained super wear-resistant agent can form a bionic scale structure on the coating surface because the self-assembly of the nano sheets tends to the minimum interface energy form, and the super wear-resistant agent not only has excellent wear resistance, excellent glossiness, dry and wet rubbing resistance and flexibility, but also has excellent adhesive force and waterproof and anti-pollution capacity, and can increase the hand feeling of a product, so that the product is softer, more natural, smoother and finer.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and reagents and materials used therein are commercially available, unless otherwise specified, and conditions or steps thereof are not specifically described.
Example 1
Dispersing 1g of silicon dioxide nanosheet powder in a mixed solution of 100mL of ethanol and 30mL of water, and adding ammonia water to adjust the pH value to 10 to form a dispersion A;
adding 0.2g of gamma-methacryloxypropyl triethoxysilane into the dispersion liquid A, reacting at room temperature, and performing suction filtration to obtain double-bond modified silicon dioxide nanosheet powder particles;
mixing double-bond modified silicon dioxide nanosheet powder particles into 2g of hydrosoluble polysiloxane (with the molecular weight of 200) terminated by sulfydryl, adding 0.2g of 1-hydroxy-cyclohexyl-phenyl ketone, and uniformly mixing to form a dispersion liquid B;
and treating the mixture for 24 hours by using 35W ultraviolet light to form the dispersion liquid B into a pasty anti-wear agent.
Fig. 3 shows an SEM picture of the silica nanosheet powder in the present embodiment, and it can be seen that the microstructure of the silica nanosheet powder is nanosheet, and the SEM characterization result of the super wear-resistant agent in the present embodiment is shown in fig. 4, and it can be seen from comparison between fig. 4 and fig. 3 that the dispersibility is increased after the silica nanosheet is grafted with the water-soluble polysiloxane particle brush, and the phenomenon of stacking of the nanosheets in fig. 3 does not occur, but the edge resolution of the nanosheet is reduced due to the deterioration of the conductivity of the silica nanosheet after the surface is grafted with the polymer.
Example 2
Dispersing 2g of silicon dioxide nanosheet powder in a mixed solution of 100mL of ethanol and 30mL of water, and adding ammonia water to adjust the pH value to 10 to form a dispersion liquid A;
adding 0.4g of gamma-methacryloxypropyl triethoxysilane into the dispersion liquid A, reacting at room temperature, and performing suction filtration to obtain double-bond modified silicon dioxide nanosheet powder particles;
mixing double-bond modified silicon dioxide nanosheet powder particles into 2g of hydrosoluble polysiloxane (with the molecular weight of 200) terminated by sulfydryl, adding 0.2g of 1-hydroxy-cyclohexyl-phenyl ketone, and uniformly mixing to form a dispersion liquid B;
and treating the mixture for 24 hours by using 35W ultraviolet light to form the dispersion liquid B into a pasty anti-wear agent.
The SEM of the coating obtained after the super abrasion-resistant agent in this example was applied to the leather surface showed that the result is shown in fig. 5, and it can be seen from fig. 5 that the abrasion-resistant agent forms an abrasion-resistant layer of a continuous biomimetic scale structure on the leather surface.
Example 3
Dispersing 1g of silicon dioxide nanosheet powder in a mixed solution of 100mL of ethanol and 30mL of water, and adding ammonia water to adjust the pH value to 10 to form a dispersion A;
adding 0.2g of gamma-methacryloxypropyltriethoxysilane into the dispersion liquid A, reacting at room temperature, and performing suction filtration to obtain double-bond modified silicon dioxide nanosheet powder particles;
mixing double-bond modified silicon dioxide nanosheet powder particles into 2g of hydrosoluble polysiloxane (with the molecular weight of 400) terminated by sulfydryl, adding 0.2g of 1-hydroxy-cyclohexyl-phenyl ketone, and uniformly mixing to form a dispersion liquid B;
and treating the mixture for 24 hours by using 35W ultraviolet light to form the dispersion liquid B into a pasty anti-wear agent.
The SEM results of the coating obtained after the super abrasion-resistant agent in this example was applied to the surface of the textile fiber show that the results are shown in fig. 6, and it can be seen from fig. 6 that the abrasion-resistant agent can also form an abrasion-resistant coating with a complete biomimetic scale structure on a rough surface similar to the textile fiber.
Example 4
Dispersing 1g of silicon dioxide nanosheet powder in a mixed solution of 100mL of ethanol and 30mL of water, and adding ammonia water to adjust the pH value to 10 to form a dispersion A;
adding 0.2g of gamma-methacryloxypropyltriethoxysilane into the dispersion liquid A, reacting at room temperature, and performing suction filtration to obtain double-bond modified silicon dioxide nanosheet powder particles;
mixing double-bond modified silicon dioxide nanosheet powder particles into 2g of hydrosoluble polysiloxane (molecular weight 200) terminated by sulfydryl, adding 0.1g of 1-hydroxy-cyclohexyl-phenyl ketone, and uniformly mixing to form a dispersion liquid B;
and treating the mixture for 24 hours by using 35W ultraviolet light to form the dispersion liquid B into a pasty anti-wear agent.
Example 5
Dispersing 1g of silica nanosheet powder in a mixed solution of 90mL of ethanol and 40mL of water, and adding ammonia water to adjust the pH to 11 to form a dispersion A;
adding 0.2g of gamma-methacryloxypropyltriethoxysilane into the dispersion liquid A, reacting at room temperature, and performing suction filtration to obtain double-bond modified silicon dioxide nanosheet powder particles;
mixing double-bond modified silicon dioxide nanosheet powder particles into 2g of hydrosoluble polysiloxane (with the molecular weight of 400) terminated by sulfydryl, adding 0.2g of 1-hydroxy-cyclohexyl-phenyl ketone, and uniformly mixing to form a dispersion liquid B;
and treating the mixture for 24 hours by using 35W ultraviolet light to form the dispersion liquid B into a pasty anti-wear agent.
Example 6
Dispersing 4g of silicon dioxide nanosheet powder in a mixed solution of 100mL of ethanol and 30mL of water, and adding ammonia water to adjust the pH value to 10 to form a dispersion liquid A;
adding 0.8g of gamma-methacryloxypropyltriethoxysilane into the dispersion liquid A, reacting at room temperature, and performing suction filtration to obtain double-bond modified silicon dioxide nanosheet powder particles;
mixing double-bond modified silicon dioxide nanosheet powder particles into 5g of hydrosoluble polysiloxane (molecular weight is 1000) terminated by sulfydryl, adding 0.4g of 4-methylbenzophenone, and uniformly mixing to form a dispersion liquid B;
and treating the mixture for 24 hours by using 35W ultraviolet light to form the dispersion liquid B into a pasty anti-wear agent.
Comparative example 1
The same embodiment as in example 1 was used except that: the silicon dioxide powder adopts spherical silicon dioxide nano particles, and the particle size of the silicon dioxide nano particles is between 80 and 100 nm.
Comparative example 2
The same procedure as in example 2 was followed, except that: a mercapto-terminated, water-insoluble polysilane (molecular weight 200) was used.
Comparative example 3
Comparative example 3 is a commercially available leather abrasion resistance agent.
Test example
The abrasion resistant agents of examples 1 to 3 and comparative examples 1 to 3 were applied to the leather sample cut with scissors using an applicator, and the abrasion resistance of the finished leather was measured, and the results are shown in Table 1.
TABLE 1 abrasion resistance agent Performance test results
Note: the test methods of the test items in table 1 are respectively:
(1) wear resistance: QB/T2726-;
(2) water vapor permeability: QB/T1811-93.
As can be seen from the test results in table 1, silica as an abrasion resistant material can effectively increase the hardness of the abrasion resistant agent; 2. compared with spherical particles, the bionic scale-shaped structure formed in the invention can improve the adhesion; 3. the water-based polyoxosilane effectively increases the wear resistance and the water vapor permeability of the wear-resisting agent.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The utility model provides a bionical scale super abrasive resistance for textile leather which is characterized in that, it is the water-soluble polysiloxane particle brush of silica nanosheet grafting, includes:
silicon dioxide nanosheet powder;
and the water-soluble polysiloxane is chemically grafted on the surface of the silicon dioxide nanosheet powder.
2. The biomimetic scale super abrasive resistant agent according to claim 1, wherein the silica nanosheet has a thickness of 3-100nm and a size of 0.5-50 μm.
3. The super wear-resistant agent with bionic scales as claimed in claim 1, wherein the molecular weight of the water-soluble polysiloxane is 100-4000.
4. A preparation method of a bionic scale super wear-resistant agent for textile leather is characterized by comprising the following steps:
providing silicon dioxide nanosheet powder and liquid mercapto-terminated water-soluble polysiloxane;
obtaining double-bond modified silicon dioxide nanosheet powder particles;
and mixing the double-bond modified silica nanosheet powder particles into the liquid mercapto-terminated water-soluble polysiloxane, adding an ultraviolet initiator, uniformly mixing, performing ultraviolet treatment, and performing click chemical reaction to obtain the pasty wear-resisting agent.
5. The preparation method according to claim 4, wherein the double-bond-modified silica nanosheet powder particle is prepared by:
dispersing silicon dioxide nanosheet powder in an alcohol-water mixed solution with the pH value of 8-12 to form a dispersion liquid;
adding a silane coupling agent containing double bonds into the dispersion liquid, and reacting and modifying the silicon dioxide nanosheet powder at room temperature to obtain the double-bond modified silicon dioxide nanosheet powder particles.
6. The method according to claim 5, wherein the alcohol-water mixed solution has a volume ratio of alcohol-water of 1 to 20, and the alcohol is a water-soluble low molecular weight alcohol having a molecular weight of 46 to 1000.
7. The preparation method of claim 5, wherein the amount of the double-bond-containing silane coupling agent added is 0.1-20% of the mass of the silica nanosheet powder;
the double-bond-containing silane coupling agent is one or more than two of gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, vinyl trimethoxysilane and vinyl tri (b-methoxyethoxy) silane.
8. The preparation method of claim 4, wherein the amount of the liquid mercapto-terminated water-soluble polysiloxane added is 30-400% of the mass of the silica nanosheet powder, and the molecular weight Mn of the water-soluble polysiloxane is 100-4000.
9. The preparation method of claim 4, wherein the amount of the ultraviolet photoinitiator added is 10 to 40 percent of the molar amount of the liquid mercapto-terminated water-soluble polysiloxane;
the ultraviolet initiator is one or more than two of isopropyl thia-anthraquinone, 4-methyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1-hydroxy-cyclohexyl-phenyl ketone.
10. The method according to claim 4, wherein the ultraviolet light treatment step is carried out at a power of 35 to 100W for a time of 1 to 24 hours.
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