CN102634987A - Fluoroalkyl carboxy polysiloxane/nano particle super-hydrophobic composite membrane and preparation method thereof - Google Patents
Fluoroalkyl carboxy polysiloxane/nano particle super-hydrophobic composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a fluoroalkyl carboxy polysiloxane/nano particle super-hydrophobic composite membrane and a preparation method thereof. By using a strong static acting force between -COO- of fluoroalkyl carboxy modified polysiloxane in a solution and protonized amino on the surface of a nano particle, a self-assembling aggregate is formed, and a certain positive charge on the surface of the aggregate is regulated; and then the aggregate is loaded on the surface of a natural cotton fiber fabric effectively by adopting a solution immersion method, and a fluoroalkyl carboxy modified polysiloxane/nano silica super-hydrophobic composite membrane is prepared by adopting baking and curing processes. The preparation method of the super-hydrophobic composite membrane on the surface of the cotton fabric has a strong actual application value.
Description
Technical field
The present invention relates to a kind of fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane and preparation method thereof.
Background technology
The natural cotton fiber of biomimetic super hydrophobic also is a frontier in the chemical simulation biosystem in recent years owing to performances such as its excellent antisticking, antifouling, automatically cleaning enjoy people's welcome, the preparation of bionical super-hydrophobic fabric and performance study.
At present, biomimetic super hydrophobic process for making such fabric emerge in multitude mainly contains that sol-gel process, template, particle-filled method, CNT method, laser/plasma etching, electricity are spun, solution soaks method and self assembly etc.Wherein big numerator self-assembly technique is because preparation technology's simple and fast; Do not need special membrane equipment; Overcome the defective such as complicated process of preparation, condition harshness of common synthetic method; Nano particle distributes controlled, is easy to large tracts of land system film, and particularly this method does not rely on kind, size and the surface configuration of film carrier matrix; Can be on complex matrices film forming (like on-plane surface matrix, flexible fibre substrate), become in recent years one type of effectively important channel of preparation macromolecule and nano particle compound system.
It is more to adopt macromolecule and nano particle to form the research report of aggregation of micro-nano-scale space structure high-sequential through non-covalent bonding under certain condition in the at present big molecule self assembly, and the copolymer or the macromolecule-nano particle compound system of the unique construction that mainly can common common synthetic method is difficult to prepare because of the method through the static combination come true; This preparation method of what is more important can effectively regulate and control the specific region that nano particle is distributed in assembly, and this is vital to the compound final properties.
At present, construct the existing certain report of research of functional macromolecule assembly based on electrostatic force.CN1610013A will contain golden nanometer particle and 8 third ammoniums, eight siloxanes to carry out the stratiform assembling and has made a kind of ultrathin conductive membrane with optics and electric conductivity.CN101747512A has reported bionic super-molecule assembling body of a kind of static driven and preparation method thereof, and this bionic super-molecule assembling body is made up of like hydrophilic polymer and the surperficial nano particle that contains positive charge of holding carboxyl polystyrene or end carboxyl polymethyl methacrylate, end to contain amino the carboxylic hydrophobic polymer of end.The research group of Vincent M.Rotello is to surface-functionalized Au nano particle or surface-functionalized SiO
2Nano particle and high molecular static self-assembling method have been carried out very distinctive work; These macromolecules mainly have polyamide-amide dendrimer, [styrene-aminomethyl phenyl ethene-methoxy styrene] copolymer of positively charged; And these assemblies are mainly as efficient catalyst; Referring to Acc.Chem.Res. (2003,36,549).J.Am.Chem.Soc. (2004; 126:15938) also reported the compound system that gathers (N-NIPA) and polyacrylic copolymer aquagel microballoon and Au nanometer rods based on electrostatic interaction; This complex microsphere has and can change through the contraction-swelling that loads laser radiation control " switch ", for realizing that triggering property drug is significant.AATCC Review (2010,2:45) reported that amino silicones and carboxyl polysiloxanes are assembled in the cotton fabric surface through supermolecule, obtained the fabric of unique hand feeling and surface property, and from microcosmic, the pattern of supermolecule film has been studied.
Summary of the invention
The object of the present invention is to provide a kind of fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane and preparation method thereof, this super-hydrophobicity composite membrane can give cotton fiber matrix good ultra-hydrophobicity.
For achieving the above object, the present invention has adopted following technical scheme.
A kind of fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane, this super-hydrophobicity composite membrane is made up of fluoroalkyl carboxylic alkyl modified polyorganosiloxane and ammonia alkyl modified Nano particle.
Said super-hydrophobicity composite membrane forms aggregation through the electrostatic interaction between amino and the carboxyl by fluoroalkyl carboxylic alkyl modified polyorganosiloxane and ammonia alkyl modified Nano particle in solution, adopt infusion process to make aggregation load on the cotton fabric surface then.
Said fluoroalkyl carboxylic alkyl modified polyorganosiloxane is a pectinate texture, and molecular structure is suc as formula (I):
In the formula (I): R
fRepresent the fluoro aliphatic group, R
1=CH
3～C
18H
37Or trifluoro propyl, R
2=methyl or methoxy, A=CH
2CH
2Or CH=CH, m=3～50, n=2～20, p=10～100, q=0～300.
Said fluoroalkyl carboxylic alkyl modified polyorganosiloxane at room temperature viscosity scope is 500～10000mPas, and carboxylic value scope is 0.2～0.8mmol/g.
Said ammonia alkyl modified Nano particle is ammonia alkyl modified manometer silicon dioxide, ammonia alkyl modified nano-titanium dioxide or the aminopropyl modification polyhedral oligomeric silsesquioxane with 1～8 functional group; The average grain diameter of ammonia alkyl modified Nano particle is 20～200nm; The ammonia alkyl is aminopropyl, N-β-aminoethyl-γ-aminopropyl or N; N-dimethylaminoethyl, aminopropyl modification polyhedral oligomeric silsesquioxane are octa-aminopropyl eight siloxanes.
A kind of method for preparing above-mentioned fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane may further comprise the steps:
1) fluoroalkyl carboxylic alkyl modified polyorganosiloxane is dissolved in to be mixed with mass percent concentration in the oxolane be 0.01～1% solution A;
2) be dissolved in the oxolane ammonia alkyl modified Nano particle to such an extent that mass percent concentration is 0.001～0.3% solution B;
3) with solution A and solution B according to 1～20: 1 mass ratio mix mixed liquor; Regulating the pH of mixed value is 6～6.5; Then cotton fabric is immersed and flood 1～30 minute in the mixed liquor; Cotton fabric behind the dipping in 100 ℃ of baking 5min, is solidified 2min at 160 ℃ again, promptly make the super-hydrophobicity composite membrane on the cotton fiber surface.
The preparation method of said fluoroalkyl carboxylic alkyl modified polyorganosiloxane is:
(1) preparation of fluoroalkyl ammonia alkyl polysiloxanes:
Add monomer in the three-neck flask successively; Said monomer comprises 9.8～19g γ-aminopropyl methyl dimethoxysilane, 25.5～25.6g long-chain perfluoroalkyl silane, 30～140g 1,3,5-three (methyl trifluoro propyl) cyclotrisiloxane or long chain alkyl silane and 59.2～64.64g octamethylcy-clotetrasiloxane; Lead to nitrogen after adding monomer; Heat up after stirring, in 90～100 ℃ of catalyst TMAHs that add monomer gross masses 0.06～0.08%, uncovered reaction is warming up to 110～120 ℃ again after 0.5～1 hour; The HMDO that adds monomer gross mass 0.5～1%; Insulation reaction 6h, system is warming up to 135～140 ℃ of reaction 0.5h decomposition catalysts then, and system is cooled to 120 ℃ behind the decomposition catalyst; At pressure is to carry out decompression distillation 0.5h under the 0.075Mpa to remove low-boiling-point substance, gets the transparence thick liquid and is fluoroalkyl ammonia alkyl polysiloxanes;
(2) carboxylation reaction of fluoroalkyl ammonia alkyl polysiloxanes and organic acid anhydride prepares product:
Fluoroalkyl ammonia alkyl polysiloxanes is cooled to 60～125 ℃, loads onto reflux, add 6.2～11.4g organic acid anhydride then in batches, insulation reaction 1～2h gets product fluoroalkyl carboxylic alkyl modified polyorganosiloxane (poly-COOH).
Said long-chain perfluoroalkyl silane is 13 fluoro octyl group trimethoxy silanes or 13 fluoro octyltri-ethoxysilane.
Said organic acid anhydride comprises maleic anhydride or succinyl oxide.
Said ammonia alkyl modified Nano particle (●-NH
2) the preparation method be: 10～20g nano silicon or titanium dioxide and 5～9g aminopropyl trialkoxy silane are dispersed in the ethanol of 50～100g purity 95%; After fully being uniformly dispersed; Be warming up to 70～80 ℃ of back flow reaction 3～4h, be cooled to room temperature then, again filtration under diminished pressure; Use washing with acetone, dry then.
Fluoroalkyl carboxylic alkyl polysiloxanes according to the invention/nano particle super-hydrophobicity composite membrane utilizes fluoroalkyl carboxylic alkyl polysiloxanes-COO
-Form the self assembly aggregation with protonated amino strong electrostatic force in solution of nanoparticle surface; And the adjusting aggregate surface contains certain positive charge; Adopt solution dipping method that aggregation is loaded on the natural cotton fiber fabric face then; Again through baking curing process; Make fluoroalkyl carboxylic alkyl modified polyorganosiloxane/nano particle super-hydrophobicity composite membrane, this super-hydrophobicity composite membrane has good ultra-hydrophobicity, can be applied at aspects such as snow defence/Rain-proof garment, camping tent, military fighting uniform, diving suit, medical protective garments.
Fluoroalkyl carboxylic alkyl modified polyorganosiloxane of the present invention adopts two-step reaction to make; At first adopt the alkaline equilibrium reaction with complete (containing) fluorine monomer of hydrophobicity such as long-chain perfluoroalkyl silane, 1; 3; 5-three (methyl trifluoro propyl) cyclotrisiloxane with (or) hydrophobicity long chain alkyl silane, octamethylcy-clotetrasiloxane (reducing the product cost) and functional monomer γ-aminopropyl methyl dimethoxysilane copolymerization, make the fluoroalkyl ammonia alkyl polysiloxanes intermediate of pectinate texture; And then the reaction of itself and organic acid anhydride made a kind of fluoroalkyl carboxylic alkyl modified polyorganosiloxane of pectinate texture.This pectinate texture helps silicon fiml the aligning of fabric face, and promptly hydrophobic group such as long-chain perfluoroalkyl, trifluoro propyl and chain alkyl stretch to air, effectively reduce the surface energy of fabric; In addition, fluoroalkyl carboxylic alkyl modified polyorganosiloxane carboxyl anion (COO in solution
-) can with a large amount of amino cation (NH that exist in modified manometer silicon dioxide surface
3 +) form aggregation through electrostatic interaction, through solution dipping method it is loaded on fabric surface again, make a kind of fluoroalkyl carboxylic alkyl modified polyorganosiloxane/nano silicon super-hydrophobicity composite membrane.Through-COO
-With-NH
3 +Between electrostatic interaction, effectively improved the durability of nano particle at fabric face.
The specific embodiment
Through embodiment the present invention is further described below.
Embodiment 1
(1) with 140g1,3,5-three (methyl trifluoro propyl) cyclotrisiloxane D
3 F, 19g γ-aminopropyl methyl dimethoxysilane KH-551,25.6g 13 fluoro octyl group trimethoxy silanes; And the 64.64g octamethylcy-clotetrasiloxane places device that the three-necked bottle of thermometer, reflux condenser is arranged, and logical nitrogen is heated to 95 ℃ after stirring and mixing; Add 0.16g TMAH THMA; Uncovered reaction 0.5 hour, system is muddy shape, general faint blue light; Add that then reflux continues to be warming up to 115 ℃, system gradually becomes transparence, when viscosity obviously becomes big, adds the 1.7g HMDO, insulation reaction 6 hours; System continues to be warming up to 140 ℃; Remove reflux; Insulation reaction 0.5h is cooled to 120 ℃ with system at last, is to carry out decompression distillation 30min under the 0.075Mpa to remove low-boiling-point substance at pressure; Get transparent, sticky shape liquid, i.e. γ-aminopropyl/fluoroalkyl modified polyorganosiloxane (ammonia value: 0.613mmol/g); Reaction system is cooled to 65 ℃, adds the 11.4g maleic anhydride in batches, insulation reaction 2 hours, fluoroalkyl carboxylic alkyl modified polyorganosiloxane (formula 1, m=5.5, n=12, p=90, q=87), carboxylic value: 0.58mmol/g, viscosity: 9400mPa.s (25 ℃); (2) preparation of aminopropyl modified manometer silicon dioxide: 10g nano silicon (average grain diameter 110nm), 5g aminopropyl trimethoxysilane and 80g 95% ethanol fully are mixed and heated to 80 ℃; Reaction down 4 hours refluxes; System is cooled to room temperature; Decompress filter again, and with washing with acetone twice, after the drying the aminopropyl modified manometer silicon dioxide;
(3) fluoroalkyl carboxylic alkyl modified polyorganosiloxane is dissolved in to process mass fraction in the oxolane be 0.3% weak solution A; The aminopropyl modified manometer silicon dioxide is dissolved in to process mass fraction in the oxolane be 0.03% weak solution B; Then with weak solution A and weak solution B according to mass ratio blend in 10: 1 and to regulate the pH value be 6.5; (size: 10cm * 10cm) immerse static self assembly 10min in this blend solution takes out cloth specimen then, at 100 ℃ of baking 5min with clean natural pure cotton appearance again; Solidify 2min at 160 ℃ again, the final water contact angle that on COTTON FABRIC, obtains is fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane of 168 °.
Formula 1
Embodiment 2
(1) with 59.2g octamethylcy-clotetrasiloxane, 93.7g 1,3,5-three (methyl trifluoro propyl) cyclotrisiloxane D
3 F, 9.8g γ-aminopropyl methyl dimethoxysilane KH-551 and 25.5g 13 fluoro octyltri-ethoxysilane place device that the three-necked bottle of thermometer, reflux condenser is arranged; Logical nitrogen; Be heated to 95 ℃ after stirring and mixing, add 0.17g TMAH THMA, uncovered reaction 0.5 hour; System is muddy shape, general faint blue light; Add that then reflux continues to be warming up to 115 ℃, system gradually becomes transparence, when viscosity obviously becomes big, adds 2g HMDO, insulation reaction 6 hours; System continues to be warming up to 140 ℃; Remove reflux; Insulation reaction 0.5h is cooled to 120 ℃ with system at last, is to carry out decompression distillation 30min under the 0.075Mpa to remove low-boiling-point substance at pressure; Get transparent, sticky shape liquid, i.e. γ-aminopropyl/fluoroalkyl modified polyorganosiloxane (ammonia value: 0.361mmol/g); Temperature of reaction system is transferred to 120 ℃, add the 6.2g succinyl oxide in batches, insulation reaction 1.5 hours gets fluoroalkyl carboxylic alkyl modified polyorganosiloxane (formula 2; M=4.4, n=4.9, p=49; Q=65), carboxylic value: 0.355mmol/g, viscosity: 8200mPa.s (25 ℃);
(2) preparation of aminopropyl modified nano-titanium dioxide: 20g nano titanium oxide (average grain diameter 40nm), 9g aminopropyl trimethoxysilane and 80g 95% ethanol fully are mixed and heated to 75 ℃; Reaction down 4 hours refluxes; System is cooled to room temperature; Decompress filter again, and with washing with acetone twice, after the drying the aminopropyl modified nano-titanium dioxide;
(3) be dissolved in the oxolane fluoroalkyl carboxylic alkyl modified polyorganosiloxane to such an extent that mass fraction is 0.1% weak solution A; Be dissolved in the oxolane aminopropyl modified nano-titanium dioxide to such an extent that mass fraction is 0.05% weak solution B; Then with weak solution A and weak solution B according to mass ratio blend in 20: 1 and to regulate the pH value be 6.5; Again clean natural pure cotton appearance is immersed in this blend solution and take out cloth specimen behind the assembling 10min; At 100 ℃ of baking 5min, solidify 2min at 160 ℃ again, the final water contact angle that on COTTON FABRIC, obtains is fluoroalkyl carboxylic alkyl polysiloxanes/nano particle self assembly super-hydrophobicity composite membrane of 164 °.
Formula 2
Embodiment 3
(1) with 30g methyl dodecyl dimethoxy silane, 18g γ-aminopropyl methyl dimethoxysilane KH-551,25.6g 13 fluoro octyl group trimethoxy silane; And the 64g octamethylcy-clotetrasiloxane places device that the three-necked bottle of thermometer, reflux condenser is arranged, and logical nitrogen is heated to 90 ℃ after stirring and mixing; Add 0.14g TMAH THMA; Uncovered reaction 1 hour, system is muddy shape, general faint blue light; Add that then reflux continues to be warming up to 110 ℃, system gradually becomes transparence, when viscosity obviously becomes big, adds 1.188g HMDO, insulation reaction 6 hours; System continues to be warming up to 135 ℃; Remove reflux; Insulation reaction 0.5h is cooled to 120 ℃ with system at last, is to carry out decompression distillation 30min under the 0.075Mpa to remove low-boiling-point substance at pressure; Get transparent, sticky shape liquid, i.e. γ-aminopropyl/fluoroalkyl modified polyorganosiloxane (ammonia value: 0.8mmol/g); Reaction system is cooled to 70 ℃, adds the 10g maleic anhydride in batches, insulation reaction 1 hour, fluoroalkyl carboxylic alkyl modified polyorganosiloxane (formula 3, carboxylic value: 0.74mmol/g, m=7.5, n=15, p=15, q=118);
(2) preparation of aminopropyl modified manometer silicon dioxide: 12g nano silicon (average grain diameter 200nm), 6g aminopropyl trimethoxysilane and 50g 95% ethanol fully are mixed and heated to 70 ℃; Reaction down 3 hours refluxes; System is cooled to room temperature; Decompress filter again, and with washing with acetone twice, after the drying the aminopropyl modified manometer silicon dioxide;
(3) fluoroalkyl carboxylic alkyl modified polyorganosiloxane is dissolved in to process mass fraction in the oxolane be 1% weak solution A; The aminopropyl modified manometer silicon dioxide is dissolved in to process mass fraction in the oxolane be 0.001% weak solution B; Then with weak solution A and weak solution B according to mass ratio blend in 1: 1 and to regulate the pH value be 6; (size: 10cm * 10cm) immerse static self assembly 1min in this blend solution takes out cloth specimen then, at 100 ℃ of baking 5min with clean natural pure cotton appearance again; Solidify 2min at 160 ℃ again, the final water contact angle that on COTTON FABRIC, obtains is fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane of 168 °.
Formula 3
Embodiment 4
(1) with 60g octamethylcy-clotetrasiloxane, 95g 1,3,5-three (methyl trifluoro propyl) cyclotrisiloxane D
3 F, 10g γ-aminopropyl methyl dimethoxysilane KH-551 and 25.5g 13 fluoro octyl group trimethoxy silanes place device that the three-necked bottle of thermometer, reflux condenser is arranged; Logical nitrogen; Be heated to 100 ℃ after stirring and mixing, add 0.15g TMAH THMA, uncovered reaction 1 hour; System is muddy shape, general faint blue light; Add that then reflux continues to be warming up to 120 ℃, system gradually becomes transparence, when viscosity obviously becomes big, adds 1.905g HMDO, insulation reaction 6 hours; System continues to be warming up to 135 ℃; Remove reflux; Insulation reaction 0.5h is cooled to 120 ℃ with system at last, is to carry out decompression distillation 30min under the 0.075Mpa to remove low-boiling-point substance at pressure; Get transparent, sticky shape liquid, i.e. γ-aminopropyl/fluoroalkyl modified polyorganosiloxane (ammonia value: 0.32mmol/g); Temperature of reaction system is transferred to 115 ℃, add the 7g succinyl oxide in batches, insulation reaction 1 hour, (structure is seen formula 4, m=4.6, n=5.2, p=51, q=68.6, carboxylic value: 0.31mmol/g) to get fluoroalkyl carboxylic alkyl modified polyorganosiloxane;
(2) preparation of aminopropyl modified nano-titanium dioxide: 16g nano titanium oxide (average grain diameter 20nm), 8g aminopropyl trimethoxysilane and 100g 95% ethanol fully are mixed and heated to 70 ℃; Reaction down 3 hours refluxes; System is cooled to room temperature; Decompress filter again, and with washing with acetone twice, after the drying the aminopropyl modified nano-titanium dioxide.
(3) be dissolved in the oxolane fluoroalkyl carboxylic alkyl modified polyorganosiloxane to such an extent that mass fraction is 0.01% weak solution A; Be dissolved in the oxolane aminopropyl modified nano-titanium dioxide to such an extent that mass fraction is 0.3% weak solution B; Then with weak solution A and weak solution B according to mass ratio blend in 5: 1 and to regulate the pH value be 6; Again clean natural pure cotton appearance is immersed in this blend solution and take out cloth specimen behind the assembling 30min; At 100 ℃ of baking 5min, solidify 2min at 160 ℃ again, the final water contact angle that on COTTON FABRIC, obtains is fluoroalkyl carboxylic alkyl polysiloxanes/nano particle self assembly super-hydrophobicity composite membrane of 164 °.
Claims (10)
1. fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane, it is characterized in that: this super-hydrophobicity composite membrane is made up of fluoroalkyl carboxylic alkyl modified polyorganosiloxane and ammonia alkyl modified Nano particle.
2. according to the said a kind of fluoroalkyl carboxylic alkyl polysiloxanes of claim 1/nano particle super-hydrophobicity composite membrane; It is characterized in that: said super-hydrophobicity composite membrane forms aggregation through the electrostatic interaction between amino and the carboxyl by fluoroalkyl carboxylic alkyl modified polyorganosiloxane and ammonia alkyl modified Nano particle in solution, adopt infusion process to make aggregation load on the cotton fabric surface then.
3. according to the said a kind of fluoroalkyl carboxylic alkyl polysiloxanes of claim 1/nano particle super-hydrophobicity composite membrane, it is characterized in that: said fluoroalkyl carboxylic alkyl modified polyorganosiloxane is a pectinate texture, and molecular structure is suc as formula (I):
In the formula (I): R
fRepresent the fluoro aliphatic group, R
1=CH
3～C
18H
37Or trifluoro propyl, R
2=methyl or methoxy, A=CH
2CH
2Or CH=CH, m=3～50, n=2～20, p=10～100, q=0～300.
4. according to the said a kind of fluoroalkyl carboxylic alkyl polysiloxanes of claim 3/nano particle super-hydrophobicity composite membrane; It is characterized in that: said fluoroalkyl carboxylic alkyl modified polyorganosiloxane at room temperature viscosity scope is 500～10000mPas, and carboxylic value scope is 0.2～0.8mmol/g.
5. according to the said a kind of fluoroalkyl carboxylic alkyl polysiloxanes of claim 1/nano particle super-hydrophobicity composite membrane; It is characterized in that: said ammonia alkyl modified Nano particle is ammonia alkyl modified manometer silicon dioxide, ammonia alkyl modified nano-titanium dioxide or the aminopropyl modification polyhedral oligomeric silsesquioxane with 1～8 functional group; The average grain diameter of ammonia alkyl modified Nano particle is 20～200nm; The ammonia alkyl is aminopropyl, N-β-aminoethyl-γ-aminopropyl or N; N-dimethylaminoethyl, aminopropyl modification polyhedral oligomeric silsesquioxane are octa-aminopropyl eight siloxanes.
6. one kind prepares the method for fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane according to claim 1, it is characterized in that: may further comprise the steps:
1) fluoroalkyl carboxylic alkyl modified polyorganosiloxane is dissolved in to be mixed with mass percent concentration in the oxolane be 0.01～1% solution A;
2) be dissolved in the oxolane ammonia alkyl modified Nano particle to such an extent that mass percent concentration is 0.001～0.3% solution B;
3) with solution A and solution B according to 1～20: 1 mass ratio mix mixed liquor; Regulating the pH of mixed value is 6～6.5; Then cotton fabric is immersed and flood 1～30 minute in the mixed liquor; Cotton fabric behind the dipping in 100 ℃ of baking 5min, is solidified 2min at 160 ℃ again, promptly make the super-hydrophobicity composite membrane on the cotton fiber surface.
7. according to the said a kind of method for preparing fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane of claim 6, it is characterized in that: the preparation method of said fluoroalkyl carboxylic alkyl modified polyorganosiloxane is:
(1) preparation of fluoroalkyl ammonia alkyl polysiloxanes:
Add monomer in the three-neck flask successively; Said monomer comprises 9.8～19g γ-aminopropyl methyl dimethoxysilane, 25.5～25.6g long-chain perfluoroalkyl silane, 30～140g 1,3,5-three (methyl trifluoro propyl) cyclotrisiloxane or long chain alkyl silane and 59.2～64.64g octamethylcy-clotetrasiloxane; Lead to nitrogen after adding monomer; Heat up after stirring, in 90～100 ℃ of catalyst TMAHs that add monomer gross masses 0.06～0.08%, uncovered reaction is warming up to 110～120 ℃ again after 0.5～1 hour; The HMDO that adds monomer gross mass 0.5～1%; Insulation reaction 6h, system is warming up to 135～140 ℃ of reaction 0.5h decomposition catalysts then, and system is cooled to 120 ℃ behind the decomposition catalyst; At pressure is to carry out decompression distillation 0.5h under the 0.075Mpa to remove low-boiling-point substance, gets the transparence thick liquid and is fluoroalkyl ammonia alkyl polysiloxanes;
(2) carboxylation reaction of fluoroalkyl ammonia alkyl polysiloxanes and organic acid anhydride prepares product:
Fluoroalkyl ammonia alkyl polysiloxanes is cooled to 60～125 ℃, loads onto reflux, add 6.2～11.4g organic acid anhydride then in batches, insulation reaction 1～2h gets product fluoroalkyl carboxylic alkyl modified polyorganosiloxane.
8. according to the said a kind of method for preparing fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane of claim 7, it is characterized in that: said long-chain perfluoroalkyl silane is 13 fluoro octyl group trimethoxy silanes or 13 fluoro octyltri-ethoxysilane.
9. according to the said a kind of method for preparing fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane of claim 7, it is characterized in that: said organic acid anhydride comprises maleic anhydride or succinyl oxide.
10. according to the said a kind of method for preparing fluoroalkyl carboxylic alkyl polysiloxanes/nano particle super-hydrophobicity composite membrane of claim 6; It is characterized in that: the preparation method of said ammonia alkyl modified Nano particle is: 10～20g nano silicon or titanium dioxide and 5～9g aminopropyl trialkoxy silane are dispersed in the ethanol of 50～100g purity 95%, after being uniformly dispersed, are warming up to 70～80 ℃ of back flow reaction 3～4h; Be cooled to room temperature then; Filtration under diminished pressure is used washing with acetone again, and is dry then.
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| CN103276596B (en) * | 2013-05-29 | 2015-07-01 | 上海师范大学 | Preparation method of quaternized halamine antibacterial cotton fiber |
| WO2015051780A1 (en) * | 2013-10-08 | 2015-04-16 | Martin-Luther-Universität Halle-Wittenberg | Method for producing plant fibres doped with nanoparticles |
| CN105601939A (en) * | 2015-12-28 | 2016-05-25 | 广州希森美克新材料科技有限公司 | Preparation method for nano SiO2 hybrid comb organic fluorine-silicon copolymer as well as product and application of copolymer |
| CN105601939B (en) * | 2015-12-28 | 2018-06-15 | 广州希森美克新材料科技有限公司 | Nano-meter SiO_22The preparation method and its product of hydridization pectination organic fluorinated silicone copolymer and application |
| CN107059409A (en) * | 2017-02-06 | 2017-08-18 | 陕西科技大学 | Environment-friendly type polysilsesquioxane nano hybridization super-hydrophobic coating material and preparation method thereof |
| CN107059409B (en) * | 2017-02-06 | 2019-06-14 | 陕西科技大学 | Environment-friendly type polysilsesquioxane nano hybridization super-hydrophobic coating material and preparation method thereof |
| CN108192405A (en) * | 2017-12-04 | 2018-06-22 | 苏州吉人高新材料股份有限公司 | A kind of Organic-inorganic composite fluorescent powder and preparation method thereof |
| CN109137476A (en) * | 2018-09-11 | 2019-01-04 | 南通大学 | One kind being based on TiO2The preparation method of the bionic super-hydrophobic cotton fabric of nanotube |
| CN114656642A (en) * | 2022-04-26 | 2022-06-24 | 宁波辉宏新材料有限公司 | Organic fluorine-silicon emulsion release agent and preparation method thereof |
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