CN113862998A - Nano graphite fluoride modified organic silicone oil water repellent finishing agent and preparation method thereof - Google Patents
Nano graphite fluoride modified organic silicone oil water repellent finishing agent and preparation method thereof Download PDFInfo
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- CN113862998A CN113862998A CN202111191749.5A CN202111191749A CN113862998A CN 113862998 A CN113862998 A CN 113862998A CN 202111191749 A CN202111191749 A CN 202111191749A CN 113862998 A CN113862998 A CN 113862998A
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- graphite fluoride
- nano graphite
- water repellent
- silicone oil
- finishing agent
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- 239000005871 repellent Substances 0.000 title claims abstract description 57
- 230000002940 repellent Effects 0.000 title claims abstract description 56
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 48
- 239000011737 fluorine Substances 0.000 claims abstract description 48
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000003921 oil Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 10
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 5
- 229920013822 aminosilicone Polymers 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 239000004744 fabric Substances 0.000 abstract description 32
- 229920000742 Cotton Polymers 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 9
- 238000009736 wetting Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- -1 perfluorooctyl sulfonyl compounds Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical class OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007730 finishing process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011881 graphite nanoparticle Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002759 woven fabric Substances 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
- 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
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a nano graphite fluoride modified organic silicone oil water repellent finishing agent and a preparation method thereof, wherein the preparation method comprises the following steps: s1, mixing amino organic silicon and fluorine-containing graphite oxide, adding a proper amount of isopropanol, stirring at a high speed for reaction for 0.2-1 h, heating to 65-75 ℃, and continuing to react for 4-6 h to obtain semitransparent viscous liquid, namely nano graphite fluoride modified organic silicon oil; s2, mixing an emulsifier and the nano graphite fluoride modified organic silicone oil prepared in the step S1 in a weight ratio of (1-3): stirring and mixing the materials in water according to the proportion of 100, adjusting the pH value to be neutral, heating to 60-85 ℃, and stirring for 0.5-1.5 hours to obtain the nano graphite fluoride modified organic silicone oil functional finishing agent. The nano graphite fluoride modified organic silicone oil water repellent finishing agent provided by the invention is used for water repellent finishing of cotton fabrics or natural fabrics, so that the fabrics have soft and smooth handfeel, and meanwhile, the water repellent effect of the cotton fabrics after finishing is very excellent.
Description
Technical Field
The invention belongs to the technical field of textile auxiliaries, and particularly relates to a nano graphite fluoride modified organic silicone oil water repellent finishing agent and a preparation method thereof.
Background
However, with the development of science and technology and the increase of the living and scientific research demands of people, how to make cotton fabrics with good hygroscopicity have stronger water repellency becomes one of the important research directions in the functional finishing of textiles.
The fluorine-containing finishing agent has the most obvious water repellent effect, but perfluorooctyl sulfonyl compounds (PFOS) and perfluorooctanoic acid compounds (PFOA) are the most indispensable raw material sources of the fluorine-containing water repellent agent, and because the use of the fluorine-containing water repellent agent is bound to be limited due to international ban on the application of PFOS and PFOA, the search for the type of water repellent finishing auxiliary agent becomes an important research subject in the industry.
The Chinese patent application with the application number of CN201810597996.7 discloses a fluoride-free water repellent which mainly comprises inorganic SiO2Modified acrylate emulsion and water-repellent small molecule filler; the application number of CN201910194368.9 in the invention is CN201910194368.9, which discloses a fluorine-free water repellent finishing method for polyester fabric, dipping mercapto group modified polyester fabric in POSS solution or mixed solution of POSS and long chain alkyl mercaptan, and ultraviolet curing. However, all of these alternatives fluorine-containing water repellent finishing agents and/or finishing methods exist in one or more places which need to be perfected, for example, some fabrics after water repellent finishing have poor hand feeling, some fabrics are not breathable, the wearing experience is poor, some water-washing resistance needs to be improved, some fabrics have unsatisfactory water repellent effect, some fabrics are too complicated in finishing process, and the like.
The organic silicon water repellent is a green environment-friendly water repellent, has good water repellency and air permeability, is the water repellent which is the most widely used water repellent in the water repellency field except for organic fluorine water repellent at present, and fluorine materials have incomparable water repellency and are incomparable with all other materials. In practical application, the water repellent effect of the organosilicon water repellent agent is not ideal, and the water repellent performance of organosilicon can be improved through modification, so that the organosilicon water repellent agent has the water repellent effect of the fluorine-containing water repellent agent as far as possible and has durability, which becomes a research focus.
Disclosure of Invention
The invention provides a nano graphite fluoride modified organic silicone oil water repellent finishing agent and a preparation method thereof, which can solve the defects in the prior art.
The invention provides a preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent, which comprises the following steps:
s1, mixing amino organic silicon and fluorine-containing graphite oxide, adding a proper amount of isopropanol, stirring at a high speed for reaction for 0.2-1 h, heating to 65-75 ℃, and continuing to react for 4-6 h to obtain semitransparent viscous liquid, namely nano graphite fluoride modified organic silicon oil;
s2, mixing an emulsifier and the nano graphite fluoride modified organic silicone oil prepared in the step S1 in a weight ratio of (1-3): stirring and mixing the materials in water according to the proportion of 100, adjusting the pH value to be neutral, heating to 60-85 ℃, and stirring for 0.5-1.5 hours to obtain the nano graphite fluoride modified organic silicone oil functional finishing agent.
In nature, it is observed that the leaf surfaces of a large number of plants are super-hydrophobic, and their constitution lies in the so-called "lotus effect" principle, i.e., the low surface energy chemical composition and the coarse structure of the material are two important factors affecting the water repellency thereof, and a similar water repellency effect can be achieved by adjusting the chemical composition and the microstructure of the material surface. According to the invention, the fluorine-containing graphite nanoparticles and the modified organic silicon are covalently bonded together by utilizing the ring-opening addition reaction of amino groups in amino organic silicon and epoxy groups in fluorine-containing graphite oxide, so that the nano graphite fluoride composite organic silicon oil finishing agent is prepared, the nano graphite fluoride in the finished coating not only can be combined with micron-sized grooves in cotton fibers to construct a cotton fabric surface with a bionic hydrophobic micro-nano structure, but also contains a large amount of fluorine elements, and the nano graphite fluoride particles have extremely excellent hydrophobicity, can be synergistically acted with an organic silicon oil film and a rough structure, and further improve the water repellency of the finished fabric.
Preferably, in step S1, the mass ratio of the amino silicone to the fluorine-containing graphite oxide is 1: (0.1-0.5).
Specifically, in step S1, the cyclic amino silicone is prepared by the following steps:
reacting an octamethylcyclotetrasiloxane linear body, an ammonia type coupling agent, an end-capping agent and a strong basic catalyst aqueous solution at the temperature of 100-110 ℃ for 4-8 hours to obtain a transparent viscous liquid, then cooling to room temperature, and carrying out reduced pressure distillation to remove low-boiling-point substances to obtain amino organosilicon; wherein the mass ratio of the octamethylcyclotetrasiloxane linear body to the ammonia-type coupling agent to the end-capping agent to the strong basic catalyst is (30-50): 2-10): 0.1-0.6): 0.1-1. By introducing reactive amino groups into the side chains of the organosilicon, the polymer and the nano-microspheres are bonded together by utilizing the reactive groups in the modified organosilicon and the fluorine-containing graphite oxide.
Preferably, the ammonia-type coupling agent is at least one selected from the group consisting of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and gamma-aminopropylmethyldimethoxysilane.
Preferably, the blocking agent is selected from at least one of hexamethyldisiloxane and pentamethyldisiloxane.
Preferably, the strongly basic catalyst is selected from at least one of an inorganic base potassium hydroxide and an organic base tetramethylammonium hydroxide.
Specifically, in step S1, the fluorine-containing graphite oxide is prepared by a modified Hummers method, which specifically includes the following steps: after the nano graphite fluoride is oxidized at low temperature, medium temperature and high temperature, the nano graphite fluoride is cleaned and centrifuged for a plurality of times, and after vacuum heating and concentration, a proper amount of isopropanol is added to obtain the fluorine-containing graphite oxide.
Preferably, the particle size of the nano graphite fluoride is 200-800 nm, and the fluorine content of the nano graphite fluoride is 20-60%.
Further preferably, the particle size of the nano graphite fluoride is 400nm, and the fluorine content of the nano graphite fluoride is 40%.
The invention provides a nano graphite fluoride modified organic silicon oil water repellent finishing agent, which is prepared by adopting the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the embodiment of the invention provides a preparation method of a nano graphite fluoride modified organic silicon oil water repellent finishing agent, which has simple process and convenient operation, adopts an alkaline catalytic organic silicon monomer to introduce reactive amino into an organic silicon side chain, utilizes reactive groups in modified organic silicon and fluorine-containing graphite oxide to bond a polymer and nano microspheres together, and water is emulsified to obtain the water repellent finishing agent.
2. According to the preparation method of the nano graphite fluoride modified organic silicone oil water repellent finishing agent provided by the embodiment of the invention, a large number of unreacted active groups such as epoxy groups, carboxyl groups and the like are contained on the surface of nano graphite fluoride particles, and can react with hydroxyl groups on cotton fibers during post-finishing baking, so that the binding power with cotton fabrics is increased, a film can be formed on the surface of the cotton fibers after finishing, the washability of the finished fabrics can be improved, and meanwhile, the nano graphite fluoride modified organic silicone oil water repellent finishing agent has good air permeability.
3. In the preparation method of the nano graphite fluoride modified organic silicone oil water repellent finishing agent provided by the embodiment of the invention, the application of C8 materials is effectively avoided, and meanwhile, a fluorine-containing material with excellent water repellency is introduced, so that the water repellency effect of the finished fabric is excellent; in addition, the graphite fluoride particles have better conductivity, so the finished fabric still can keep better antistatic property.
4. When the nano graphite fluoride modified organic silicon oil water repellent finishing agent prepared by the preparation method provided by the embodiment of the invention is used for water repellent finishing of fabrics, the finishing process is simple, the finished fabrics have soft and smooth hand feeling similar to those of the fabrics finished by the organic silicon softening agent, and the water repellent effect, the water washability and the air permeability of the fabrics are improved.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
FIG. 1 is an infrared spectrum of fluorine-containing graphite oxide obtained in example 1;
FIG. 2 is a surface topography of fibers after the cotton fabrics are finished by the nano graphite fluoride modified organic silicone oil water repellent finishing agent prepared in example 2.
Detailed Description
In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.
Example 1
The preparation method of the nano fluorine-containing graphite oxide by using the improved Hummers method comprises the following specific steps:
1. oxidation of nano-scale fluorine-containing graphite
(1) And (3) low-temperature stage: adding 70ml of concentrated sulfuric acid into a dry beaker in an ice bath, sequentially adding 3g of nano-scale graphite fluoride powder (with the specification of D50 and the fluorine content of 20%) and 1.5g of sodium nitrate into the beaker, stirring at a high speed to ensure that the nano-scale fluorine-containing graphite is completely wetted and fully pre-oxidized by the concentrated sulfuric acid, wherein the reaction system is gray black turbid liquid, the stirring speed is reduced after 1.5 hours, 12g of potassium permanganate is slowly added, the adding is completed within about 1 hour, the rotating speed is properly increased, stirring is continued for 4 hours, the color of the reaction liquid is changed from gray black to dark green, and the temperature at a low-temperature stage is controlled to be 0-5 ℃;
(2) a medium temperature stage: raising the temperature of the water bath to 35 ℃, and continuing stirring for 2 hours;
(3) and (3) high-temperature stage: and removing the water bath, keeping stirring, slowly adding 140ml of deionized water, raising the temperature of the reaction system to 90-98 ℃, and keeping the reaction liquid in a gray black state for about 40 min. After the temperature of the reaction solution is naturally cooled to room temperature, 500ml of deionized water is added for dilution, after the temperature of the reaction solution is cooled to room temperature again, 25ml of hydrogen peroxide is added dropwise, a large amount of gray black foam is generated at the moment, the reaction solution is black, and finally 3ml of hydrochloric acid (5 wt%) is added, fully stirred and then kept stand.
2. Post-treatment of nano-scale fluorine-containing graphite oxide
(1) Cleaning: after 24 hours of full standing, the reaction solution is divided into an upper layer and a lower layer, wherein the upper layer is gray foam, the middle layer is clear transparent liquid, and the lower layer is black mud slurry solid. Removing the middle layer clear liquid, respectively taking the upper layer product and the lower layer product, and washing the products for 8-10 times by vacuum filtration;
(2) centrifuging: respectively carrying out repeated centrifugal washing on the washed upper and lower layer products by using deionized water at the rotating speed of 10000r/min for 15min until the pH value of the supernatant liquid is close to neutral;
(3) vacuum heating and concentrating, adding a proper amount of isopropanol to obtain the nano fluorine-containing graphite oxide with the fluorine content of 20%. Wherein, the function of the isopropanol is a dispersion medium, and the specific dosage is adjusted according to the dispersion and wetting condition of the nano fluorine-containing graphite oxide.
In addition, the present embodiment also provides another preparation method of nano-scale fluorine-containing graphite oxide, which has only one difference from the above preparation method: the specification of the adopted nano-scale graphite fluoride powder is D50, the fluorine content is 40%, and finally the nano-scale fluorine-containing graphite oxide with the fluorine content of 40% is obtained.
FIG. 1 is an IR spectrum of a nanoscale fluorine-containing graphite oxide prepared in this example, wherein curve (a) is a nanometer prepared from nanoscale graphite fluoride powder containing 40% fluorineThe infrared spectrogram of the graphite fluoride powder has a curve (a) of the infrared spectrogram of the nano-scale graphite fluoride powder prepared by the nano-scale graphite fluoride powder with 20 percent of fluorine content, and the two curves are positioned at 3417cm-1、1730cm-1、1630cm-1、1220cm-1The absorption peaks of (a) correspond to hydroxyl (-OH), carboxylic acid (-COOH), carbonyl (C ═ O), and fluorocarbon bond (C — F), respectively. In addition, FIG. 2.4b at 1056cm-1And 874cm-1The absorption peaks at the two positions respectively correspond to the characteristic peaks of a carbon-oxygen single bond (C-O) and an epoxy group, and the appearance of the characteristic peaks of an oxygen-containing functional group indicates that oxygen is successfully introduced into the product.
Example 2
The embodiment provides a preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent, which comprises the following steps: 72.61g of octamethylcyclotetrasiloxane linear body, 9.68g of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 0.8g of hexamethyldisiloxane and 0.9g of potassium hydroxide aqueous solution are reacted for 6 hours at the temperature of 110 ℃ to obtain transparent viscous liquid, the temperature is reduced to room temperature, reduced pressure distillation is carried out to remove low-boiling-point substances to obtain amino organosilicon, then 16.1g of fluorine-containing graphite oxide (40 percent F) prepared in example 1 and a proper amount of isopropanol (wherein the function of the isopropanol is a dispersion medium, the specific dosage of the isopropanol is adjusted according to the dispersion and wetting conditions of the nano-scale fluorine-containing graphite oxide) are added, the mixture is stirred for half an hour at the rotating speed of 5000r/min (here, the stirring function is to fully and uniformly mix the amino organosilicon, the fluorine-containing graphite oxide and the isopropanol), the temperature is heated to 70 ℃, the reaction is continued for 6 hours, and finally, adding 1.68g of sodium dodecyl sulfate and 300mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour (wherein the stirring effect is to ensure that the nano graphite fluoride composite organic silicon oil and the sodium dodecyl sulfate fully react) to obtain the nano graphite fluoride composite organic silicon oil finishing agent.
Example 3
The embodiment provides a preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent, which comprises the following steps: 75.62g of octamethylcyclotetrasiloxane linear body, 7.56g of gamma-aminopropylmethyldimethoxysilane, 0.9g of hexamethyldisiloxane and 0.85g of potassium hydroxide aqueous solution are reacted for 6 hours at the temperature of 110 ℃ to obtain transparent viscous liquid, the temperature is reduced to room temperature, low-boiling-point substances are removed by reduced pressure distillation, then 15.13g of fluorine-containing graphite oxide (40 percent F) prepared in example 1 and a proper amount of isopropanol are added, the mixture is stirred for half an hour at the rotating speed of 5000r/min, the temperature is heated to 70 ℃, and the reaction is continued for 6 hours to obtain the nano graphite fluoride composite organic silicone oil. And finally, adding 1.66g of sodium dodecyl benzene sulfonate and 300mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the nano graphite fluoride composite organic silicon oil finishing agent.
Example 4
The embodiment provides a preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent, which comprises the following steps: 57.35g of octamethylcyclotetrasiloxane linear body, 10.75g of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 1.1g of hexamethyldisiloxane and 0.92g of potassium hydroxide aqueous solution are reacted for 6 hours at the temperature of 110 ℃ to obtain transparent viscous liquid, the temperature is reduced to room temperature, reduced pressure distillation is carried out to remove low-boiling-point substances, then 28.67g of fluorine-containing graphite oxide (40 percent F) prepared in example 1 and a proper amount of isopropanol are added, the mixture is stirred for half an hour at the rotating speed of 5000r/min, the temperature is raised to 70 ℃, and the reaction is continued for 6 hours to obtain the nano graphite fluoride composite organic silicon oil. And finally, adding 3.23g of sodium dodecyl sulfate and 300mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the nano graphite fluoride composite organic silicon oil finishing agent.
Example 5
The embodiment provides a preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent, which comprises the following steps: 65.52g of octamethylcyclotetrasiloxane linear body, 10.08g of gamma-aminopropylmethyldimethoxysilane, 0.85g of hexamethyldisiloxane and 0.85g of potassium hydroxide aqueous solution are reacted for 6 hours at the temperature of 110 ℃ to obtain transparent viscous liquid, the temperature is reduced to room temperature, low-boiling-point substances are removed by reduced pressure distillation, then 20.16g of fluorine-containing graphite oxide (40 percent F) prepared in example 1 and a proper amount of isopropanol are added, the mixture is stirred for half an hour at the rotating speed of 5000r/min, the temperature is heated to 70 ℃, and the reaction is continued for 6 hours to obtain the nano graphite fluoride composite organic silicone oil. And finally, adding 4.23g of sodium dodecyl benzene sulfonate and 300mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the nano graphite fluoride composite organic silicon oil finishing agent.
Example 6
The embodiment provides a preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent, which comprises the following steps: 74.07g of octamethylcyclotetrasiloxane linear body, 5.56g of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 0.8g of hexamethyldisiloxane and 0.9g of potassium hydroxide aqueous solution are reacted for 6 hours at the temperature of 110 ℃ to obtain transparent viscous liquid, the temperature is reduced to room temperature, reduced pressure distillation is carried out to remove low-boiling-point substances, then 18.52g of fluorine-containing graphite oxide (40 percent F) prepared in example 1 and a proper amount of isopropanol are added, the mixture is stirred for half an hour at the rotating speed of 5000r/min, the temperature is raised to 70 ℃, and the reaction is continued for 6 hours to obtain the nano graphite fluoride composite organic silicon oil. And finally, adding 1.85g of sodium dodecyl sulfate and 300mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the nano graphite fluoride composite organic silicon oil finishing agent.
Example 7
The embodiment provides a preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent, which comprises the following steps: 62.83g of octamethylcyclotetrasiloxane linear body, 10.58g of gamma-aminopropylmethyldimethoxysilane, 0.9g of hexamethyldisiloxane and 0.95g of potassium hydroxide aqueous solution are reacted for 6 hours at the temperature of 110 ℃ to obtain transparent viscous liquid, the temperature is reduced to room temperature, low-boiling-point substances are removed by reduced pressure distillation, then 23.15g of fluorine-containing graphite oxide (40 percent F) prepared in example 1 and a proper amount of isopropanol are added, the mixture is stirred for half an hour at the rotating speed of 5000r/min, the temperature is heated to 70 ℃, and the reaction is continued for 6 hours to obtain the nano graphite fluoride composite organic silicon oil. And finally, adding 3.44g of sodium dodecyl benzene sulfonate and 300mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the nano graphite fluoride composite organic silicon oil finishing agent.
Test examples
The nano graphite fluoride composite organic silicon oil finishing agent prepared in the embodiments 2 to 7 is subjected to water repellency effect detection, the nano graphite fluoride composite organic silicon oil finishing agent is diluted to 100g/L, then plain woven fabric of pure cotton is subjected to the traditional two-dipping two-rolling process treatment in the diluted finishing liquid, the rolling residual rate is 65-75%, and then the nano graphite fluoride composite organic silicon oil finishing agent is pre-dried at 100 ℃ for 6 minutes, baked at 180 ℃ for 3 minutes and cooled to the room temperature.
The initial and 10 wash cycles of the sample prepared above were followed by a water spray test according to AATCC 22-2010 standard. After the wash cycle, the fabrics were drum dried prior to spray testing. Typical drum drying temperatures are 60-65 ℃ for 30 minutes. According to the spray test rating chart, a rating of 100 means no adhesion or wetting of the surface of the fabric, a rating of 90 means slight random adhesion or wetting of the surface of the fabric, a rating of 80 means surface wetting of the fabric at the spray point, a rating of 70 means partial wetting of the surface of the fabric beyond the spray point, and a rating of 50 means complete wetting of the entire surface of the fabric.
TABLE 1 comparison of the Properties of the fabrics finished with the nano-graphite fluoride-modified silicone oil water repellent finish obtained in examples 2 to 7
| Finishing agent | Hand feeling | Initial | 10 washing cycles |
| Not finished | Difference (D) | 50 | 50 |
| Example 2 | Softness | 100 | 80 |
| Example 3 | Softness | 100 | 80 |
| Example 4 | Softness | 100 | 90 |
| Example 5 | Softness | 100 | 80 |
| Example 6 | Softness | 100 | 80 |
| Example 7 | Softness | 100 | 90 |
As can be seen from Table 1, after the nano graphite fluoride composite organic silicon oil finishing agent prepared by the preparation method disclosed by the invention is used for finishing plants, the water repellency grade is high, a better washing resistant effect can be still kept after 10 times of cyclic washing, and meanwhile, the textile fabric has better softness and smoothness and has a hand feeling effect similar to that of the organic silicon softening agent after the textile fabric is finished.
As can be seen from FIG. 2, after the nano graphite fluoride modified organosilicon water repellent agent prepared by the preparation method of the invention is finished, the rough structure of the surface of cotton fiber is obviously improved, and the surface of the cotton fiber has obvious convex shape of particles, and the particles are tightly coated on the surface of the fiber with micron scale, so that the special surface structure of the cotton fabric is realized.
The foregoing disclosure discloses only the preferred embodiments of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
Claims (9)
1. A preparation method of a nano graphite fluoride modified organic silicone oil water repellent finishing agent is characterized by comprising the following steps:
s1, mixing amino organic silicon and fluorine-containing graphite oxide, adding a proper amount of isopropanol, stirring at a high speed for reaction for 0.2-1 h, heating to 65-75 ℃, and continuing to react for 4-6 h to obtain semitransparent viscous liquid, namely nano graphite fluoride modified organic silicon oil;
s2, mixing an emulsifier and the nano graphite fluoride modified organic silicone oil prepared in the step S1 in a weight ratio of (1-3): stirring and mixing the materials in water according to the proportion of 100, adjusting the pH value to be neutral, heating to 60-85 ℃, and stirring for 0.5-1.5 hours to obtain the nano graphite fluoride modified organic silicone oil functional finishing agent.
2. The method for preparing the nano graphite fluoride-modified silicone oil water repellent finishing agent according to claim 1, wherein in step S1, the mass ratio of the amino silicone to the fluorine-containing graphite oxide is 1: (0.1-0.5).
3. The preparation method of the nano graphite fluoride modified silicone oil water repellent finishing agent according to claim 1, wherein in step S1, the cyclic amino silicone is prepared by the following steps:
reacting an octamethylcyclotetrasiloxane linear body, an ammonia type coupling agent, an end-capping agent and a strong basic catalyst aqueous solution at the temperature of 100-110 ℃ for 4-8 hours to obtain a transparent viscous liquid, then cooling to room temperature, and carrying out reduced pressure distillation to remove low-boiling-point substances to obtain amino organosilicon; wherein the mass ratio of the octamethylcyclotetrasiloxane linear body to the ammonia-type coupling agent to the end-capping agent to the strong basic catalyst is (30-50): 2-10): 0.1-0.6): 0.1-1.
4. The preparation method of the nano graphite fluoride modified silicone oil water repellent finishing agent as claimed in claim 3, wherein the ammonia type coupling agent is at least one selected from N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and gamma-aminopropylmethyldimethoxysilane.
5. The preparation method of the nano graphite fluoride modified silicone oil water repellent finishing agent according to claim 3, wherein the end-capping agent is at least one selected from hexamethyldisiloxane and pentamethyldisiloxane.
6. The preparation method of the nano graphite fluoride modified silicone oil water repellent finishing agent according to claim 3, wherein the strong basic catalyst is at least one selected from inorganic alkali potassium hydroxide and organic alkali tetramethyl ammonium hydroxide.
7. The preparation method of the nano graphite fluoride modified silicone oil water repellent finishing agent according to claim 2, wherein in step S1, the fluorine-containing graphite oxide is prepared by adopting a modified Hummers method, and the method specifically comprises the following steps: after the nano graphite fluoride is oxidized at low temperature, medium temperature and high temperature, the nano graphite fluoride is cleaned and centrifuged for a plurality of times, and after vacuum heating and concentration, a proper amount of isopropanol is added to obtain the fluorine-containing graphite oxide.
8. The preparation method of the nano graphite fluoride-modified silicone oil water repellent finishing agent according to claim 7, characterized in that the particle size of the nano graphite fluoride is 200-800 nm, and the fluorine content of the nano graphite fluoride is 20-60%.
9. The nano graphite fluoride modified organic silicone oil water repellent finishing agent prepared by the preparation method of any one of claims 1 to 8.
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