CN107043466B - A kind of modification of chitosan-silicon dioxide composite aerogel material and its preparation method and application - Google Patents
A kind of modification of chitosan-silicon dioxide composite aerogel material and its preparation method and application Download PDFInfo
- Publication number
- CN107043466B CN107043466B CN201710341952.3A CN201710341952A CN107043466B CN 107043466 B CN107043466 B CN 107043466B CN 201710341952 A CN201710341952 A CN 201710341952A CN 107043466 B CN107043466 B CN 107043466B
- Authority
- CN
- China
- Prior art keywords
- chitosan
- solid
- modification
- silicon dioxide
- modified additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0065—Organic pigments, e.g. dyes, brighteners
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/142—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2201/00—Chemical constitution of the fibres, threads or yarns
- D06N2201/02—Synthetic macromolecular fibres
- D06N2201/0263—Polyamide fibres
Abstract
The present invention relates to a kind of modification of chitosan-silicon dioxide composite aerogel materials and its preparation method and application, modification of chitosan-the silicon dioxide composite aerogel is modified chitosan-silicon dioxide aeroge using the aeroge modified additive of the monomer structure containing fluorinated urethanes, it is reacted using the active hydroxyl groups on chitosan surface with the amino of modified additive, has the group of waterproof and oil preventing performance in the surface scion grafting of composite aerogel, keep the aperture of aeroge capped, no longer adsorb greasy dirt substance, and aerosil structure therein is but also with warmth retention property, the performance of breathable moisture permeability film can be formed using chitosan simultaneously, coating in homogeneous thickness is formed in textile surface, reach waterproof and oilproof, the warming comprehensive performance of moisture-inhibiting.
Description
Technical field
The invention belongs to after-finishing of textile products fields, have and are related to a kind of modification of chitosan-silicon dioxide composite aerogel
Material and preparation method thereof, applied to the final finishing of textile, warming in one layer of waterproof and oilproof of textile surface formation, moisture-inhibiting
Coating is used as water-proof jacket fabric.
Background technique
The major function of water-proof jacket is warming, but water-proof jacket currently on the market is mainly by adding warming lining
Mode achieve the effect that warming, and fabric does not have thermal property, causes more warming water-proof jacket lining thicker, it appears more swelling
It is swollen.
Aerosil is very widely used in building material industry at present as efficient thermal insulation material, heat insulation effect
Fabulous, thermal conductivity is lower than 0.013W/mK, therefore silica aerogel material is made into coating and is coated on fabric by someone,
High-efficiency insulated fabric is formed, although silica waterproof performance is preferable, but its pore structure is very easy to the non-pole of absorption
Property substance, that is, be easy oil suction, will lead to water-proof jacket fabric is very easy to dirty, reduces the practicability of clothes.
Simple silica aerogel material mechanical property is very low, cannot adhere in textile surface, therefore someone is logical
It crosses silica and composite aerogel is made in chitosan.As to disclose a kind of hydrophobicity shell poly- by Chinese patent CN104140553A
Sugar-silicon dioxide composite aerogel, the aeroge are prepared by the following method: will, chitosan solution is added in silicon source presoma
In, hydrolysis, condensation polymerization reaction gradually occurs, forms sticky complex sol, numerous hydroxyls and amino provide in chitosan
A large amount of active site participates in the formation of entire gel network structure as a kind of support frame, and further ageing makes network
Stable structure obtains plural gel, dries and removes the solvent in gel and obtains chitosan-silicon dioxide composite aerogel, using gas
Phase sedimentation carries out hydrophobically modified to it, and modifying agent steam is deposited on its surface at a constant temperature, finally obtains the compound gas of hydrophobicity
Gel.Although the composite aerogel improves mechanical property to a certain extent, which equally exists the suction to oil
Attached better performances are easy dirty problem.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of modification of chitosan-dioxy
SiClx aerogel composite and its preparation method and application.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is:
A kind of modification of chitosan-silicon dioxide composite aerogel material, includes aeroge modified additive, and the aeroge changes
The structural formula of property auxiliary agent are as follows:
One according to the present invention specific and preferred aspect, the modification of chitosan-silicon dioxide composite aerogel material
Raw material composition include following components: ethyl orthosilicate, chitosan, citric acid, water, the aeroge modified additive, it is described just
Mass ratio 2.63~2.71:0.71~0.80 of silester, chitosan, citric acid, water, the aeroge modified additive:
0.13~0.17:10:0.8~1.2.
The present invention takes another solution is that a kind of preparation method of above-mentioned aeroge modified additive, the aeroge
Modified additive is to carry out reacting obtained reactant under acidic catalyst effect by trifluoroethanol, carbonic acid；The reactant exists
Heating, which is reacted, in the presence of acetic anhydride and organic solvent is made solid A；The solid A reacts in the presence of solvent with benzene methanamine to be made
Solid B；The aeroge modified additive is made in the solid B roasting.
Preferably, the trifluoroethanol, carbonic acid, acidic catalyst mass ratio be 1:1~0.9:0.19~0.20, it is described
The reaction temperature reacted under acidic catalyst effect is 60~65 DEG C, and the acidic catalyst is sulfuric acid.
Preferably, the reaction temperature that reaction is heated in the presence of acetic anhydride and organic solvent is 80~85 DEG C.It is more excellent
Selection of land, the organic solvent are hexamethylene.
Preferably, the solid A, benzene methanamine mass ratio be 0.60~0.62:0.23~0.25, it is described solvent exist
The reaction temperature of lower reaction is 60~65 DEG C.It is highly preferred that.
Preferably, the solid A reacts in the presence of ethyl acetate with benzene methanamine.
Preferably, the temperature of the roasting is 190~210 DEG C.
In terms of a specific implementation according to the present invention: the preparation method of the aeroge modified additive includes following step
It is rapid:
It (1) is in mass ratio that 1:1~0.9:0.19~0.20 is mixed by trifluoroethanol, carbonic acid, sulfuric acid, in 60~65 DEG C of items
It is stirred to react 8~12h under part, filters, is added hexamethylene extraction in filtrate, acetic anhydride is added in upper solution in layering, in 80~
It is stirred to react 8~12h under the conditions of 85 DEG C, distills, obtains White crystalline solid A；
It (2) is in mass ratio that 0.60~0.62:0.23~0.25:1 is mixed by the solid A, benzene methanamine, ethyl acetate,
It is stirred to react 4~5h under the conditions of 60~65 DEG C, distills, obtains yellow needles solid B；
(3) make the yellow needles solid B in 190~210 DEG C of roastings to get the aeroge modified additive.
The another technical solution that the present invention takes: a kind of above-mentioned modification of chitosan-silicon dioxide composite aerogel material
Preparation method, the modification of chitosan-silicon dioxide composite aerogel material are by ethyl orthosilicate, chitosan, citric acid
It passes sequentially through and is stirred to react with water, be aged, freeze and gelatinous solid is made；The gelatinous solid and aeroge modification help
Agent ultrasonic disperse in the presence of the solvent, then removes solvent, and the compound airsetting of modification of chitosan-silica is made in freezing
Glue material.
Preferably, the ethyl orthosilicate, chitosan, citric acid, water be in mass ratio 2.63~2.71:0.71~
0.80:0.13~0.17:10, the reaction temperature being stirred to react are 80~85 DEG C, and the digestion time is 8~10h.
Preferably, the mass ratio of the aeroge modified additive and gelatinous solid is 2~2.5:8~9.
In terms of a specific implementation according to the present invention: the modification of chitosan-silicon dioxide composite aerogel material
Preparation method, comprising the following steps:
(A) preparation of aeroge modified additive: the aeroge modified additive is prepared according to the above method；
(B) modification of chitosan-silicon dioxide composite aerogel material preparation: by ethyl orthosilicate, chitosan, lemon
Acid, water are 2.63~2.71:0.71~0.80:0.13~0.17:10 mixing in mass ratio, are stirred to react in 80~85 DEG C, so
It is aged 8~10h afterwards, is washed with water and removes remaining citric acid, after vacuum filtration, gel is obtained after -10~15 DEG C of 1~2h of freezing
Shape solid；The aeroge modified additive and the gelatinous solid are added in cyclohexane, stirred evenly, ultrasonic disperse 2~
3h filters removal cyclohexane, with ethanol washing, then in -10~15 DEG C of 1~2h of freezing to get the modification of chitosan-dioxy
SiClx aerogel composite, wherein the mass ratio of the aeroge modified additive and gelatinous solid is 2~2.5:8~9.
The another technical solution again that the present invention takes is: above-mentioned modification of chitosan-silicon dioxide composite aerogel material
Application in textile industry.
The present invention take again another solution is that a kind of water proof anti-soil fabric, including base fabric and be formed in the base
Coating on the surface of cloth, the raw material of the coating include above-mentioned modification of chitosan-silicon dioxide composite aerogel material.
The base fabric is selected from Nylon Taffeta, specific as selected 30d, 350T circular hole Nylon Taffeta.
The preparation method of the water proof anti-soil fabric, comprising the following steps: the modification of chitosan-silica is compound
Aerogel material is that 1:1~1.5 are uniformly mixed with polyurethane in mass ratio, is coated on the surface of the base fabric, in 150~
Roll compacting is under the conditions of 160 DEG C and 8~10MPa to get the water proof anti-soil fabric.
It is of the invention again another solution is that a kind of water-proof jacket, is made of above-mentioned water proof anti-soil fabric.
Due to the utilization of above technical scheme, the present invention has the advantage that compared with prior art
The present invention changes chitosan-silicon dioxide aeroge using the modified additive of the monomer structure containing fluorinated urethanes
Property, it is reacted, is had in the surface scion grafting of composite aerogel anti-with the amino of modified additive using the active hydroxyl groups on chitosan surface
The group of water and oil preventing performance keeps the aperture of aeroge capped, no longer absorption greasy dirt substance, and silica gas therein
Gel structure can form using chitosan the performance of breathable moisture permeability film but also with warmth retention property, be formed in textile surface
Coating in homogeneous thickness reaches waterproof and oilproof, the comprehensive performance that moisture-inhibiting keeps warm.
Specific embodiment
The method comprises the steps of firstly, preparing the aeroge modified additives containing fluorinated urethanes monomer structure, then to chitosan-two
Silica aerogel is modified, and is reacted using the active hydroxyl groups on chitosan surface with the amino of modified additive, in compound airsetting
The surface scion grafting of glue has the group of waterproof and oil preventing performance, keeps the aperture of aeroge capped, no longer absorption greasy dirt substance,
And aerosil result therein is but also with warmth retention property, while the property of breathable moisture permeability film can be formed using chitosan
Can, coating in homogeneous thickness is formed in textile surface, reaches waterproof and oilproof, the comprehensive performance that moisture-inhibiting keeps warm.
The warming fabric coating of waterproof and oilproof, moisture-inhibiting can make water-proof jacket fabric have good thermal property, reduce
The use of warming lining, improves water-proof jacket comfort, no longer too fat to move.
The present invention is described in further details below in conjunction with specific embodiment.
Raw materials used substance is commercially available in following embodiment.Chitosan used in embodiment is raw using the green mind in Nantong
The relative molecular mass of object Engineering Co., Ltd production is 30000, the water soluble chitosan of deacetylation > 90%.In embodiment
Fabric select 30d, 350T circular hole Nylon Taffeta.
Embodiment 1
The present embodiment provides a kind of modification of chitosan-silicon dioxide composite aerogel materials, are prepared by following steps
It obtains:
(1) trifluoroethanol of 100g, 96g carbonic acid, 19.6g sulfuric acid are added in the three-necked flask of 500ml, agitating and heating
Reflux, keeping temperature is 60 DEG C, and after reacting 10h, then the hexamethylene extraction of 200ml is added in filtering in filtrate, will after extraction
10.2g acetic anhydride is added in upper solution, and after 80 DEG C of agitating and heatings flow back 8h, distillation obtains White crystalline solid A.
(2) 270g solid A, 108.16g benzene methanamine, 500ml ethyl acetate are added in the three-necked flask of 1000ml, in
After 60 DEG C of heating stirring reflux 5h, is distilled in 80 DEG C, obtain faint yellow needle-like solid B.
(3) solid B obtains solid C, i.e. aeroge modified additive in 200 DEG C of roasting 1h, and it is as follows to survey nuclear magnetic data:
1H-NMR (400Hz) δ (ppm) 4.22 (t, 2H), 4.60 (t, 2H), 7.06 (d, 2H), 7.07 (d, 1H), 7.14
(d, 2H), 8.0 (s, 1H).
(4) old by 93.5g ethyl orthosilicate, 25g chitosan, 5g citric acid and 350ml water in 80 DEG C of heating stirring 10h
It after changing 12h, is washed with water 3 times, removes remaining citric acid, after vacuum filtration, gelatinous solid D is obtained after -10 DEG C of freezing 2h.
(5) 22g solid C and 80g solid D is added in 100ml cyclohexane, after mixing evenly, ultrasonic disperse 3h, suction filtration is gone
It except cyclohexane, then uses ethanol washing 3 times, obtains gelatinous solid E, as modification of chitosan-two after freezing after -10 DEG C of freezing 2h
Silica aerogel composite.
10g gelatinous solid E is mixed with 12g polyurethane, after 100 DEG C of stirring 1h, blade coating on the surface of fabric, then at
150 DEG C, roll compacting 3 times under 9MPa, obtain waterproof, moisture-inhibiting, heat preservation fabric and detect its performance, results of property is referring to table 1.
Embodiment 2
The present embodiment provides a kind of chitosan-silicon dioxide aerogel composites, are prepared by following steps:
(1) 100g trifluoroethanol, 100g carbonic acid, 20g sulfuric acid are added in the three-necked flask of 500ml, agitating and heating is returned
Stream, keeping temperature is 65 DEG C, and after reacting 12h, then the hexamethylene extraction of 200ml is added in filtering in filtrate, will be upper after extraction
10.5g acetic anhydride is added in layer solution, and after 85 DEG C of agitating and heatings flow back 10h, distillation obtains White crystalline solid A.
(2) 280g solid A, 110g benzene methanamine, 500ml ethyl acetate are added in the three-necked flask of 1000ml, in 65
After DEG C heating stirring reflux 5h, is distilled in 85 DEG C, obtain faint yellow needle-like solid B.
(3) solid B is obtained into solid C, i.e. aeroge modified additive in 210 DEG C of roasting 1h.
(4) by 95g ethyl orthosilicate, 24g chitosan, 6g citric acid, 350ml water in 85 DEG C of heating stirring 10h, ageing
After 12h, be washed with water 3 times, remove remaining citric acid, after vacuum filtration, after -10 DEG C of freezing 2h gelatinous solid D.
(5) 25g solid C and 85g solid D is added in 100ml cyclohexane, after mixing evenly, ultrasonic disperse 3h, suction filtration is gone
It except cyclohexane, then uses ethanol washing 3 times, obtains gelatinous solid E, as modification of chitosan-two after freezing after -10 DEG C of freezing 2h
Silica aerogel composite.
10g gelatinous solid E is mixed with 15g polyurethane, after 120 DEG C of stirring 1h, blade coating on the surface of fabric, then at
160 DEG C, roll compacting 3 times under 10MPa, obtain waterproof, moisture-inhibiting, heat preservation fabric and detect its performance, results of property is referring to table 1.
Embodiment 3
The present embodiment provides a kind of chitosan-silicon dioxide aerogel composites, are prepared by following steps:
(1) 100g trifluoroethanol, 90g carbonic acid, 19g sulfuric acid are added in the three-necked flask of 500ml, agitating and heating is returned
Stream, keeping temperature is 60 DEG C, and after reacting 8h, then the hexamethylene extraction of 200ml is added in filtering in filtrate, will be upper after extraction
10g acetic anhydride is added in layer solution, and after 80 DEG C of agitating and heatings flow back 8h, distillation obtains White crystalline solid A.
(2) solid 270g solid A, 105g benzene methanamine, 500ml ethyl acetate are added in the three-necked flask of 1000ml,
After 60 DEG C of heating stirrings flow back 5h, is distilled in 80 DEG C, obtain faint yellow needle-like solid B.
(3) solid B is obtained into solid C, i.e. aeroge modified additive in 190 DEG C of roasting 1h.
(4) take 92g ethyl orthosilicate, 28g chitosan, 4.5g citric acid, 350ml water, in 80 DEG C of heating stirring 10h, it is old
It after changing 12h, is washed with water 3 times, removes remaining citric acid, after vacuum filtration, gelatinous solid D is obtained after -10 DEG C of freezing 2h.
(5) 20g solid C and 90g solid D is added in 100ml cyclohexane, after mixing evenly, ultrasonic disperse 2h, suction filtration is gone
It except cyclohexane, then uses ethanol washing 3 times, obtains gelatinous solid E, as modification of chitosan-two after freezing after -15 DEG C of freezing 2h
Silica aerogel composite.
10g gelatinous solid E is mixed with 10g polyurethane, after 90 DEG C of stirring 1h, blade coating on the surface of fabric, then at
145 DEG C, roll compacting 3 times under 8MPa, obtain waterproof, moisture-inhibiting, heat preservation fabric and detect its performance, results of property is referring to table 1.
Comparative example
This comparative example provides a kind of aerogel material, is prepared by following steps: take 93.5g ethyl orthosilicate,
25g chitosan, 5g citric acid, 350ml water are washed with water 3 times, remove remaining after being aged 12h in 80 DEG C of heating stirring 10h
Citric acid, after vacuum filtration, after -10 DEG C of freezing 2h aerogel material.
The relative molecular mass that wherein chitosan uses Nantong Lv Shen bioengineering Co., Ltd to produce is 30000, de- second
The water soluble chitosan of acyl degree > 90%.
10g aerogel material is mixed with 12g polyurethane, after mixing evenly, blade coating on the surface of fabric, then at 160 DEG C,
Roll compacting 3 times under 10MPa, obtain waterproof, moisture-inhibiting, heat preservation fabric and detect its performance, results of property is referring to table 1.
Table 1 is the performance test results of Examples 1 to 3 and comparative example
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example | |
| Water repellency (grade) | 5 grades | 5 grades | 5 grades | 5 grades |
| Oil repellent (grade) | 5 grades | 5 grades | 5 grades | 0 grade |
| Gas permeability (mm/s) | 1.5 | 1.7 | 1.6 | 1.6 |
| Penetrability (g/m2·24h) | 12315 | 12267 | 12304 | 12298 |
| Heat preservation rate (%) | 38 | 37 | 36 | 37 |
Above-mentioned the performance test results test to obtain by following test method:
According to national standard GBT 4745-2012, " detection and evaluation of textile water proof performance are stained with for the test of the water repellency of sample
Water law " it is tested.
According to national standard GB/T 19977-2014, " the anti-hydrocarbon of textile oil repellent is tried for the test of the oil repellent of sample
Test " it is tested.
The gas permeability of sample is tested according to national standard GB/T 5453-1997 " measurement of textile fabric gas permeability ".
The penetrability of sample is according to national standard GB/T 12704.1-2009 " textile fabric penetrability test method the 1st
Point: moisture absorption method " it is tested.
The heat preservation rate of sample can be " under textile physiological comfort limit hot according to professional standard GBT 11048-2008
The measurement of resistance and dampness " it is tested.
The present invention is described in detail above, the explanation of embodiment be merely used to help understand method of the invention and
Its core concept, its object is to allow the personage for being familiar with this field technology that can understand the contents of the present invention and be implemented, and
The protection scope that the present invention cannot be limited in this way, equivalent change or modification made by all Spirit Essences according to the present invention, is all answered
It is included within the scope of protection of the present invention.
Claims (10)
1. a kind of modification of chitosan-silicon dioxide composite aerogel material includes aeroge modified additive, which is characterized in that institute
State the structural formula of aeroge modified additive are as follows:
2. modification of chitosan according to claim 1-silicon dioxide composite aerogel material, which is characterized in that described to change
Property chitosan-silicon dioxide aerogel composite raw material composition include following components: ethyl orthosilicate, chitosan, lemon
Acid, water, the aeroge modified additive, the ethyl orthosilicate, chitosan, citric acid, water, the aeroge modified additive
Mass ratio is 2.63~2.71:0.71~0.80:0.13~0.17:10:0.8~1.2.
3. the preparation method of aeroge modified additive as described in claim 1, it is characterised in that: the aeroge modified additive
It is to carry out reacting obtained reactant under acidic catalyst effect by trifluoroethanol, carbonic acid；The reactant in acetic anhydride and
Heating, which is reacted, in the presence of organic solvent is made solid A；The solid A reacts in the presence of solvent with benzene methanamine is made solid B；Institute
It states solid B roasting and the aeroge modified additive is made.
4. the preparation method of aeroge modified additive according to claim 3, it is characterised in that: the trifluoroethanol, carbon
Sour, acidic catalyst mass ratio is 1:1~0.9:0.19~0.20, described to be reacted anti-under acidic catalyst effect
Answering temperature is 60~65 DEG C；The solid A, benzene methanamine mass ratio be 0.60~0.62:0.23~0.25, it is described to be deposited in solvent
It is 60~65 DEG C in the reaction temperature of lower reaction.
5. the preparation method of aeroge modified additive according to claim 3, it is characterised in that: the aeroge modification helps
The preparation method of agent the following steps are included:
It (1) is in mass ratio that 1:1~0.9:0.19~0.20 is mixed by trifluoroethanol, carbonic acid, sulfuric acid, under the conditions of 60~65 DEG C
It is stirred to react 8~12h, is filtered, hexamethylene extraction is added in filtrate, is layered, acetic anhydride is added in upper solution, in 80~85 DEG C
Under the conditions of be stirred to react 8~12h, distill, obtain White crystalline solid A；
It (2) is in mass ratio that 0.60~0.62:0.23~0.25:1 is mixed by the solid A, benzene methanamine, ethyl acetate, in 60
It is stirred to react 4~5h under the conditions of~65 DEG C, distills, obtains yellow needles solid B；
(3) make the yellow needles solid B in 190~210 DEG C of roastings to get the aeroge modified additive.
6. a kind of preparation method of modification of chitosan of any of claims 1 or 2-silicon dioxide composite aerogel material, special
Sign is: the modification of chitosan-silicon dioxide composite aerogel material be by ethyl orthosilicate, chitosan, citric acid and
Water, which passes sequentially through, to be stirred to react, and ageing freezes and gelatinous solid is made；The gelatinous solid and the aeroge modified additive
Ultrasonic disperse in the presence of the solvent, then removes solvent, and the modification of chitosan-silicon dioxide composite aerogel is made in freezing
Material.
7. modification of chitosan according to claim 6-silicon dioxide composite aerogel material preparation method, feature exist
In: the ethyl orthosilicate, chitosan, citric acid, water 2.63~2.71:0.71 in mass ratio~0.80:0.13~0.17:
10, the reaction temperature being stirred to react is 80~85 DEG C, and the digestion time is 8~10h.
8. modification of chitosan according to claim 6-silicon dioxide composite aerogel material preparation method, feature exist
In the preparation method comprises the following steps:
(A) preparation of aeroge modified additive: the preparation method of the aeroge modified additive is any in claim 3~5
Preparation method described in item claim；
(B) modification of chitosan-silicon dioxide composite aerogel material preparation: by ethyl orthosilicate, chitosan, citric acid, water
2.63~2.71:0.71 in mass ratio~0.80:0.13~0.17:10, mixing, is stirred to react in 80~85 DEG C, is then aged 8
~10h is washed with water and removes remaining citric acid, and after vacuum filtration, in -10~15 DEG C of 1~2h of freezing, it is solid that gel is made
Body；The aeroge modified additive and the gelatinous solid are added in cyclohexane, stirred evenly, 2~3h of ultrasonic disperse, is taken out
It filters off and removes cyclohexane, with ethanol washing, then in -10~15 DEG C of 1~2h of freezing to get the modification of chitosan-silica
Aerogel composite, wherein the mass ratio of the aeroge modified additive and gelatinous solid is 2~2.5:8~9.
9. a kind of water proof anti-soil fabric, including base fabric and the coating that is formed on the surface of the base fabric, it is characterised in that: described
The raw material of coating includes modification of chitosan of any of claims 1 or 2-silicon dioxide composite aerogel material.
10. a kind of water-proof jacket, it is characterised in that: be made of water proof anti-soil fabric as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341952.3A CN107043466B (en) | 2017-05-16 | 2017-05-16 | A kind of modification of chitosan-silicon dioxide composite aerogel material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341952.3A CN107043466B (en) | 2017-05-16 | 2017-05-16 | A kind of modification of chitosan-silicon dioxide composite aerogel material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107043466A CN107043466A (en) | 2017-08-15 |
| CN107043466B true CN107043466B (en) | 2019-03-15 |
Family
ID=59546254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710341952.3A Active CN107043466B (en) | 2017-05-16 | 2017-05-16 | A kind of modification of chitosan-silicon dioxide composite aerogel material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107043466B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108943272B (en) * | 2018-06-28 | 2020-01-14 | 台州中知英健机械自动化有限公司 | Processing method of bamboo rattan |
| CN109225150A (en) * | 2018-10-10 | 2019-01-18 | 烟台工程职业技术学院 | A kind of preparation method of the dioxide composite silica aerogel of adsorbable formaldehyde |
| CN110240730B (en) * | 2019-07-17 | 2022-03-04 | 哈尔滨工业大学 | CS-SiO modified by cellulose2Method for producing aerogels |
| CN110552197A (en) * | 2019-08-23 | 2019-12-10 | 唐雪金 | Breathable and warm-keeping aerogel composite fabric and preparation method thereof |
| CN112477333B (en) * | 2020-11-30 | 2023-11-10 | 浙江鑫海纺织有限公司 | Gel type wave-absorbing fabric and preparation method thereof |
| CN115161798B (en) * | 2022-06-29 | 2024-04-05 | 邦特云纤(青岛)新材料科技有限公司 | Breathable antistatic novel aerogel synthetic fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106575A (en) * | 1985-10-16 | 1987-04-22 | 阿托化学公司 | The fluoropropenes acid mono, by its derived polymers and be used for the processing of the water-repellancy and the grease proofness of different base |
| CN101094877A (en) * | 2004-12-28 | 2007-12-26 | 3M创新有限公司 | Water- and oil-repellent fluorourethanes and fluoroureas |
| CN101818454A (en) * | 2010-02-09 | 2010-09-01 | 广西大学 | Waterproof and oil-proof agent prepared by using fluorocarbon grated starch and preparation method thereof |
| CN103046382A (en) * | 2011-10-14 | 2013-04-17 | 东丽纤维研究所（中国）有限公司 | Waterproof and oilproof soil-release fabric and production method thereof |
| CN104140553A (en) * | 2014-07-18 | 2014-11-12 | 天津大学 | Hydrophobic chitosan-silicon dioxide composite aerogel and preparation method and oil absorption application thereof |
-
2017
- 2017-05-16 CN CN201710341952.3A patent/CN107043466B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106575A (en) * | 1985-10-16 | 1987-04-22 | 阿托化学公司 | The fluoropropenes acid mono, by its derived polymers and be used for the processing of the water-repellancy and the grease proofness of different base |
| CN101094877A (en) * | 2004-12-28 | 2007-12-26 | 3M创新有限公司 | Water- and oil-repellent fluorourethanes and fluoroureas |
| CN101818454A (en) * | 2010-02-09 | 2010-09-01 | 广西大学 | Waterproof and oil-proof agent prepared by using fluorocarbon grated starch and preparation method thereof |
| CN103046382A (en) * | 2011-10-14 | 2013-04-17 | 东丽纤维研究所（中国）有限公司 | Waterproof and oilproof soil-release fabric and production method thereof |
| CN104140553A (en) * | 2014-07-18 | 2014-11-12 | 天津大学 | Hydrophobic chitosan-silicon dioxide composite aerogel and preparation method and oil absorption application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107043466A (en) | 2017-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107043466B (en) | A kind of modification of chitosan-silicon dioxide composite aerogel material and its preparation method and application | |
| CN103214629B (en) | Antistatic agent for dacron textile and preparation method of antistatic agent | |
| CN110685170B (en) | Wool keratin/waterborne polyurethane composite emulsion coating agent with warm-keeping function and preparation method thereof | |
| CN105315507B (en) | A kind of method for preparing modified graphene chitosan laminated film | |
| CN111019332B (en) | Polyurethane waterproof moisture-permeable film and preparation method thereof | |
| CN106555248B (en) | The preparation method of moisture absorption acrylic fibers | |
| CN109591406A (en) | A kind of waterproof moisture-permeable composite fabric | |
| CN102031004A (en) | Fire resistant fiber molding environmental-friendly decorative material for wall and preparation method thereof | |
| CN110552197A (en) | Breathable and warm-keeping aerogel composite fabric and preparation method thereof | |
| CN106363926B (en) | A kind of high water pressure resistance, high ventilative, high moisture-inhibiting garment film preparation method | |
| CN103725252B (en) | A kind of Formaldehyde-free adhesive and its preparation method and application | |
| CN106188124B (en) | The preparation method of novel ester organosilicon quaternary ammonium salt | |
| CN106866074A (en) | A kind of high temperature resistant high-hardness water-proof wall covering and preparation method thereof | |
| CN105567119B (en) | A kind of chitosan system adhesive and its preparation method and application | |
| CN110863261B (en) | Phase-change temperature-regulating composite fiber with chitosan as matrix and preparation method thereof | |
| CN107141674B (en) | Polyvinyl alcohol and phosphoric acid compound blended film and preparation method thereof | |
| CN103524462B (en) | Modified alkyl ketene dimer and preparation method thereof | |
| CN116463784A (en) | Light warm-keeping wadding | |
| CN110565373A (en) | Temperature-adjusting textile and production method thereof | |
| CN108973301A (en) | A kind of preparation method of waterproof moisture permeating fabric | |
| CN107984849B (en) | Light cassimere composite material and preparation method thereof | |
| CN110029490B (en) | Preparation method of antifouling corrosion-resistant tablecloth material | |
| CN111979760A (en) | Waterproof non-woven fabric and preparation method thereof | |
| CN108546309B (en) | Preparation method of composite emulsion for paper surface modifier | |
| CN113024880A (en) | Preparation method of cellulose acetate nanofiber composite aerogel for heat preservation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |