CN117306271A - Preparation method of water-based synthetic leather prepared based on organosilicon Pickering emulsion - Google Patents
Preparation method of water-based synthetic leather prepared based on organosilicon Pickering emulsion Download PDFInfo
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- CN117306271A CN117306271A CN202311268612.4A CN202311268612A CN117306271A CN 117306271 A CN117306271 A CN 117306271A CN 202311268612 A CN202311268612 A CN 202311268612A CN 117306271 A CN117306271 A CN 117306271A
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- synthetic leather
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- 239000000839 emulsion Substances 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002649 leather substitute Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 23
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 23
- 239000003921 oil Substances 0.000 claims abstract description 21
- 230000015271 coagulation Effects 0.000 claims abstract description 16
- 238000005345 coagulation Methods 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000012686 silicon precursor Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 229920001558 organosilicon polymer Polymers 0.000 abstract description 6
- 230000003373 anti-fouling effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005815 base catalysis Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
-
- 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
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic 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
- D06N3/0063—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
- D06N3/12—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
- D06N3/144—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 with polyurethane and polymerisation products, e.g. acrylics, PVC
-
- 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
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/142—Hydrophobic
-
- 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
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/145—Oleophobic
-
- 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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a preparation method of water-based synthetic leather based on organosilicon Pickering emulsion, which comprises the following steps: step (1), preparing organic silicon water emulsion; adding the organosilicon aqueous emulsion into the aqueous polyurethane emulsion, adding color paste and an auxiliary agent, and uniformly stirring to obtain a soaking liquid; step (3), pre-shrinking the base fabric to remove the surface oil agent, putting the base fabric into an impregnation tank, performing secondary impregnation and secondary padding with resin, respectively putting the base fabric into an acid coagulation tank for coagulation, putting the base fabric into an alkaline bath for condensation, and putting the base fabric into a water washing tank for washing; and (4) drying to obtain the water-based synthetic leather. According to the invention, the organosilicon tree precursor is used, the Pickering emulsion is prepared by emulsifying and adding the nano magnesium hydroxide powder, a stable emulsion system is formed, the precursor is reacted through the acid bath and the alkali bath in the forming process to form the organosilicon polymer, on one hand, the magnesium hydroxide is removed from the acid bath, and a gap is formed in the coating, and on the other hand, the formed organosilicon polymer can increase the effects of hydrophobicity, oleophobicity, antifouling and the like for the product.
Description
Technical Field
The invention belongs to the technical field of synthetic leather production, and particularly relates to a preparation method of water-based synthetic leather based on organosilicon Pickering emulsion.
Background
As an emerging technical product in the synthetic leather industry, many functions and processes are yet to be developed. The synthetic leather is used as a composite material, various functional materials can be added in the forming process so as to realize the functionalization of the synthetic leather, and the organic silicon modification is one of the functional materials.
Common organic silicon modification is to add adjuvants such as silicone resin or modified silicone oil into resin, thus achieve the functional effects of hydrophobic oleophobic, antifouling, etc., but silicone oil is directly added into aqueous system, its dilution stability is poor sometimes, often appear demulsification, etc. to the unfavorable phenomenon of product.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of water-based synthetic leather based on organosilicon Pickering emulsion. The organosilicon tree precursor is used, pickering emulsion is prepared by emulsifying and adding nano magnesium hydroxide powder, a stable emulsion system is formed, the precursor is reacted to form organosilicon polymer through acid bath and alkali bath in the synthetic leather forming process, on one hand, magnesium hydroxide is removed from the acid bath, gaps can be formed in the coating, and on the other hand, the formed organosilicon polymer can increase the effects of hydrophobicity, oleophobicity, antifouling and the like for the product.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of an aqueous synthetic leather based on organosilicon Pickering emulsion, which comprises the following steps:
step (1), preparing organic silicon water emulsion;
step (2), adding the organosilicon aqueous emulsion prepared in the step (1) into aqueous polyurethane emulsion, and then adding aqueous color paste and aqueous auxiliary agent, and uniformly stirring to obtain impregnation liquid;
step (3), pre-shrinking the base fabric, removing the surface oil agent, entering the impregnation tank prepared in the step (2), carrying out secondary soaking and secondary rolling on resin, respectively entering an acidic coagulation tank for coagulation, entering an alkaline bath for condensation, and entering a water washing tank for washing;
and (4) drying to obtain the water-based synthetic leather with the functions of water repellency and oleophobic property.
In the technical scheme, in the step (1), the specific steps for preparing the organosilicon water emulsion are as follows:
s1: the organic silicon precursor ethyl orthosilicate is used as an oil phase;
s2: adding the emulsifier and the nano magnesium hydroxide into water, and uniformly stirring to obtain a water phase;
s3: and (3) pouring the oil phase into the water phase, emulsifying for a certain time under the condition of high-speed stirring, and then stirring for 10-24 hours at a low speed to obtain Pickering emulsion of the organosilicon precursor, namely the organosilicon water emulsion.
In the above technical scheme, the aqueous phase: the mass ratio of the oil phase is 1:1-5:1, and the addition amount of the magnesium hydroxide is 0.1% -5% of the mass of the oil phase.
In the technical scheme, the grain diameter of the tetraethoxysilane in the organosilicon water emulsion is controlled to be 1-20 mu m.
In the technical scheme, the speed in emulsification is controlled to 8000-20000rpm/min, and the emulsification time is controlled to 5-10min.
In the technical proposal, in the step (3), caCl with the pH value less than or equal to 3 is regulated by formic acid in the acidic coagulating bath 3 And ammonium sulfate solution, wherein the alkaline bath is aqueous solution with pH value being more than or equal to 9 regulated by NaOH.
In the technical scheme, in the step (3), the temperature of the acidic coagulation bath is controlled to be 20-60 ℃, the temperature of the alkaline bath is controlled to be 20-50 ℃, and the temperature of the water washing tank is controlled to be 20-80 ℃.
In the above technical scheme, in the step (2), the aqueous auxiliary agent comprises an aqueous leveling agent and an aqueous defoaming agent, and the immersion liquid comprises the following components in parts by mass: 100 parts of aqueous polyurethane emulsion, 0.1-1 part of aqueous flatting agent, 0.1-0.5 part of aqueous defoamer, 3-20 parts of aqueous color paste and 1-20 parts of organic silicon aqueous emulsion.
The invention has the beneficial effects that:
1. the method uses the organosilicon tree precursor, prepares Pickering emulsion by emulsifying and adding nano magnesium hydroxide powder, forms a stable emulsion system, and enables the precursor to react to form organosilicon polymer through acid bath and alkali bath in the synthetic leather forming process, on one hand, magnesium hydroxide is removed from the acid bath, gaps can be formed in the coating, and on the other hand, the formed organosilicon polymer can increase the effects of hydrophobicity, oleophobicity, antifouling and the like for the product.
2. Most of common synthetic leather is prepared from solvent-based polyurethane, the waterborne synthetic leather provided by the invention is waterborne polyurethane, and raw materials used in the process of preparing the polyurethane synthetic leather are waterborne materials, so that the DMF content is effectively reduced, and the aim of environmental protection is achieved.
3. The added magnesium hydroxide is removed when the base fabric is solidified, so that the tetraethoxysilane is exposed, the reaction can be started by more fully contacting with the acid bath, meanwhile, the removed magnesium hydroxide can form columnar or other shaped cavities different from the traditional foam holes, the resin structure is not damaged by gas generation in the neutralization process, and the formed cavities can provide slippage space for fibers and provide good hand feeling for the base fabric.
4. The effect of adjusting the hydrophobicity and oleophobicity of the synthetic leather can be achieved by adjusting the addition amount of the organosilicon aqueous emulsion.
Detailed Description
The invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the invention. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
The invention provides a preparation method of an aqueous synthetic leather based on organosilicon Pickering emulsion, which comprises the following steps:
step (1), preparing an organosilicon aqueous emulsion: adding the organosilicon precursor ethyl orthosilicate serving as an oil phase, adding the emulsifier and the nano magnesium hydroxide into water, uniformly stirring to serve as a water phase, pouring the oil phase into the water phase, emulsifying for a certain time under the condition of high-speed stirring, and then stirring for 10-24 hours at a low speed to obtain Pickering emulsion of the organosilicon precursor, namely the organosilicon water emulsion, so as to be ready for use.
It should be noted that: in the prior art (for example 2019109522546), the precursor is simply added into an aqueous system, so that the oil phase cannot be well dispersed, and the stability is poor. According to the invention, by adding the nano magnesium hydroxide and the emulsifier, the shell-core structure can be formed while the tetraethoxysilane is uniformly dispersed, and the nano magnesium hydroxide is used as a wall material to play a role in stabilizing an oil phase.
Ethyl orthosilicate is purchased from commercial products commonly available on the market. The emulsifier is common industrial emulsifier in the market, including but not limited to sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, gum arabic, etc., and the addition amount is 0.1-10% of the mass of water. The particle size of the tetraethoxysilane in the organosilicon water emulsion is controlled to be 1-20 mu m, the smaller the particle size is, the better the particle size is, but the stability of the particle size to the nanometer level is poor, the dispersion in the aqueous polyurethane is not facilitated, and the optimal particle size is 1-5 mu m.
The nano magnesium hydroxide has the grain size less than or equal to 200nm, can be a common industrial product in the market, and can also be prepared by itself, and the preparation process is that MgCl is stirred at 50 DEG C 2 ·6H 2 Slowly dripping 2% NaOH solution into the O solution until precipitation is not generated, standing and precipitating for 30min, and filtering, cleaning and drying the precipitate to obtain the nano magnesium hydroxide powder. The nano magnesium hydroxide is used as a shell material in a Pickering emulsion, and has the function of being physically adsorbed on the surface of oil drops and undergoing a neutralization reaction with acid when passing through an acid coagulation bath in the synthetic leather. The magnesium hydroxide particles are uniformly dispersed, and the non-uniform phenomena such as agglomeration and the like cannot occur.
Aqueous phase: the mass ratio of the oil phase is 1:1-5:1, and the addition amount of the magnesium hydroxide is 0.1% -5% of the mass of the oil phase;
the speed is controlled to 8000-20000rpm/min during emulsification, and the emulsification time is controlled to 5-10min.
And (2) adding the organosilicon aqueous emulsion into the aqueous polyurethane emulsion, and then adding the corresponding color paste and the auxiliary agent, and uniformly stirring to obtain the impregnation liquid.
It should be noted that: the auxiliary agent comprises an aqueous leveling agent, an aqueous defoaming agent and the like. The aqueous polyurethane is preferably a polyether type aqueous polyurethane resin with the aliphatic solid content of 30-40%. The water-based leveling agent is preferably an organosilicon modified polyether-based leveling agent such as BYK-346 and BYK-348. The water-based defoamer is preferably an organosilicon modified bubble-inhibiting auxiliary agent such as BYK-024, BYK-054 and the like. The mass parts of each component of the impregnation liquid are shown in table 1.
TABLE 1 composition of the infusion
| Component (A) | Parts by weight |
| Aqueous polyurethane resin | 100 |
| Water-based leveling agent | 0.1-1 |
| Aqueous defoamer | 0.1-0.5 |
| Water-based color paste | 3-20 |
| Aqueous organosilicon emulsion | 1-20 |
| The viscosity is cps/25 DEG C | 100-500 |
| Liquid carrying rate% | 100-250 |
And (3) pre-shrinking the base fabric, removing the surface oil agent, entering an impregnation tank, performing secondary impregnation and secondary padding, respectively entering an acidic coagulation tank for coagulation, entering an alkaline bath for condensation, and entering a water washing tank for cleaning.
It should be noted that: the base fabric can be used with an oil agent in the manufacturing process, and if the base fabric is not cleaned, the sizing of the aqueous resin can be influenced, and meanwhile, oil spots can be generated. If the pre-shrinking treatment is not performed, the density distribution of the base fabric is uneven after the resin is coated.
If the tetraethoxysilane is used as a precursor for polycondensation into silicone resin, acid catalysis or base catalysis is needed, and the most widely used method is acid catalysis and base catalysis. The organic silicon aqueous emulsion prepared in the invention is not silicon resin, and is simply prepared by coating ethyl orthosilicate with nano magnesium hydroxide to prepare stable microcapsule emulsion, and in the synthetic leather forming process, the condensation reaction of the ethyl orthosilicate is promoted by an acid-base bath; meanwhile, the acidic coagulation tank can enable the aqueous polyurethane to be demulsified and coagulated.
The acidic coagulating bath is CaCl with pH less than or equal to 3 regulated by formic acid 3 And ammonium sulfate solution, wherein the alkaline bath is aqueous solution with pH value being more than or equal to 9 regulated by NaOH. The speed of the vehicle in the production process is controlled to be 1-20m/min; the temperature of the acidic coagulating bath is controlled to be 20-60 ℃, the temperature of the alkaline bath is controlled to be 20-50 ℃, and the temperature of the water washing tank is controlled to be 20-80 ℃.
The inorganic particles added in the base fabric impregnating resin are magnesium hydroxide with uniform fineness and particle size less than or equal to 200 nm. After the base fabric passes through the acidic coagulation bath, magnesium hydroxide is neutralized on the one hand, so that a space is provided for fiber slippage, and on the other hand, tetraethoxysilane is exposed to be fully contacted with acid to start reaction.
In addition to formic acid, the acidic coagulation bath contains calcium chloride and ammonium sulfate, and the three substances can play a role in demulsification and pre-coagulation of the aqueous polyurethane, and the formic acid can initiate polycondensation reaction of the tetraethoxysilane; the purpose of the alkaline bath is to allow the tetraethyl orthosilicate to undergo alkaline polycondensation. The acid and the base can catalyze the ethyl orthosilicate, the acid catalysis is mild, and the base catalysis speed is high.
Step (4): and drying to obtain the water-based synthetic leather with the functions of water repellency and oleophobic property.
It should be noted that: in the synthetic leather forming process, the hydrophobic and oleophobic functions of the synthetic leather are provided after the tetraethoxysilane is polycondensated into the silicone resin through acid-base catalysis. The water-based synthetic leather with different degrees of hydrophobic and oleophobic effects can be obtained by adjusting the addition amount of the organosilicon water emulsion.
The water-based synthetic leather prepared by the preparation method provided by the invention has the advantages that the contact angles of different organic silicon water emulsion addition amounts in the synthetic leather are changed, the test temperature is 25 ℃, and the air humidity is 65%. The specific test results are shown in table 2 below.
Table 2 experimental test results
| Numbering device | Organosilicon aqueous emulsion added parts | Contact angle/° | Time/s for water drop to infiltrate cloth cover |
| 1 | 0 | 68 | 15 |
| 2 | 3 | 73 | 45 |
| 3 | 7 | 78 | 60 |
| 4 | 11 | 85 | 70 |
| 5 | 15 | 85 | 75 |
| 6 | 20 | 91 | 80 |
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. The preparation method of the water-based synthetic leather based on the organosilicon Pickering emulsion is characterized by comprising the following steps of: the method comprises the following steps:
step (1), preparing organic silicon water emulsion;
step (2), adding the organosilicon aqueous emulsion prepared in the step (1) into aqueous polyurethane emulsion, and then adding aqueous color paste and aqueous auxiliary agent, and uniformly stirring to obtain impregnation liquid;
step (3), pre-shrinking the base fabric, removing the surface oil agent, entering the impregnation tank prepared in the step (2), carrying out secondary soaking and secondary rolling on resin, respectively entering an acidic coagulation tank for coagulation, entering an alkaline bath for condensation, and entering a water washing tank for washing;
and (4) drying to obtain the water-based synthetic leather with the functions of water repellency and oleophobic property.
2. The method of manufacture of claim 1, wherein: in the step (1), the specific steps for preparing the organosilicon aqueous emulsion are as follows:
s1: the organic silicon precursor ethyl orthosilicate is used as an oil phase;
s2: adding the emulsifier and the nano magnesium hydroxide into water, and uniformly stirring to obtain a water phase;
s3: and (3) pouring the oil phase into the water phase, emulsifying for a certain time under the condition of high-speed stirring, and then stirring for 10-24 hours at a low speed to obtain Pickering emulsion of the organosilicon precursor, namely the organosilicon water emulsion.
3. The preparation method according to claim 2, characterized in that: aqueous phase: the mass ratio of the oil phase is 1:1-5:1, and the addition amount of the magnesium hydroxide is 0.1% -5% of the mass of the oil phase.
4. The preparation method according to claim 2, characterized in that: the grain diameter of the tetraethoxysilane in the organosilicon water emulsion is controlled to be 1-20 mu m.
5. The preparation method according to claim 2, characterized in that: the speed is controlled to 8000-20000rpm/min during emulsification, and the emulsification time is controlled to 5-10min.
6. The method of manufacture of claim 1, wherein: in the step (3), caCl with pH less than or equal to 3 regulated by formic acid is used in the acidic coagulation bath 3 And ammonium sulfate solution, wherein the alkaline bath is aqueous solution with pH value being more than or equal to 9 regulated by NaOH.
7. The method of manufacture of claim 1, wherein: in the step (3), the temperature of the acidic coagulation bath is controlled to be 20-60 ℃, the temperature of the alkaline bath is controlled to be 20-50 ℃, and the temperature of the water washing tank is controlled to be 20-80 ℃.
8. The method of manufacture of claim 1, wherein: in the step (2), the aqueous auxiliary comprises an aqueous leveling agent and an aqueous defoaming agent, wherein the immersion liquid comprises the following components in parts by mass: 100 parts of aqueous polyurethane emulsion, 0.1-1 part of aqueous flatting agent, 0.1-0.5 part of aqueous defoamer, 3-20 parts of aqueous color paste and 1-20 parts of organic silicon aqueous emulsion.
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