CN116143993A - A kind of anti-staining water-based polyurethane emulsion and preparation method thereof - Google Patents
A kind of anti-staining water-based polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN116143993A CN116143993A CN202310163711.XA CN202310163711A CN116143993A CN 116143993 A CN116143993 A CN 116143993A CN 202310163711 A CN202310163711 A CN 202310163711A CN 116143993 A CN116143993 A CN 116143993A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- D06N3/146—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 characterised by the macromolecular diols used
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- 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
- D06N3/147—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 characterised by the isocyanates used
- D06N3/148—(cyclo)aliphatic polyisocyanates
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- 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
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
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- 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
- D06N2209/146—Soilproof, soil repellent
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- 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
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1685—Wear resistance
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Abstract
The invention discloses an anti-contamination aqueous polyurethane emulsion and a preparation method thereof, and particularly relates to the technical field of textile coatings. The emulsion is prepared from hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, aliphatic diamine sodium sulfonate, polycaprolactone polyol, micromolecular polyol, polycarbonate diol, organosilicon polyol, chain extender, emulsifier and deionized water through prepolymerization reaction, chain extension reaction, emulsification reaction and chain extension reaction. The invention adopts a post chain extension process, and adopts an amine chain extender to form urea bonds, thereby increasing rigidity, improving film forming strength and enhancing anti-fouling performance; the product of the invention has good process implementation, environmental protection and no pollution. The aqueous polyurethane emulsion disclosed by the invention is simple and convenient to produce, low in production cost, excellent in stain resistance, good in fastness, wear resistance and washing resistance, and environment-friendly in water.
Description
Technical Field
The invention relates to the technical field of textile coatings, in particular to an anti-contamination aqueous polyurethane emulsion and a preparation method thereof.
Background
With the rapid development of textile markets, functional textiles with different functions are becoming popular, and particularly, environmental protection functional products are becoming well accepted, however, the anti-staining fabrics on the markets are generally achieved by the following ways: on one hand, three-proofing arrangement belongs to fluorine-containing compounds, and is more and more limited; on the other hand, the solvent type coating is adopted, and harmful gas is discharged in the production and use processes, so that the environment and human body are damaged, the development of the water-based anti-contamination product is urgently needed, and the similar products are not found in the data record at present.
Disclosure of Invention
Therefore, the invention provides an anti-contamination aqueous polyurethane emulsion and a preparation method thereof, which are used for solving the problems that the existing anti-contamination fabric contains fluorine and is harmful to the environment and human body.
In order to achieve the above object, the present invention provides the following technical solutions:
according to the invention, the stain-resistant aqueous polyurethane emulsion is prepared from hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, aliphatic diamine sodium sulfonate, polycaprolactone polyol, micromolecular polyol, polycarbonate diol, organosilicon polyol, chain extender, emulsifier and deionized water through a prepolymerization reaction, a chain extension reaction, an emulsification reaction and a chain extension reaction.
Further, the emulsion is prepared from 60-80 parts of hydrogenated diphenylmethane diisocyanate, 20-40 parts of isophorone diisocyanate, 5-10 parts of aliphatic diamine sulfonic acid sodium salt, 10-15 parts of polycaprolactone polyol, 50-10 parts of micromolecular polyol, 80-100 parts of polycarbonate diol, 50-80 parts of organosilicon polyol, 5-15 parts of chain extender, 6-10 parts of emulsifier and 420-690 parts of deionized water through prepolymerization reaction, chain extension reaction, emulsification reaction and chain extension reaction.
Further, the aliphatic diamine sulfonic acid sodium salt equivalent 220; preferably degussa VESTAMINA and 95.
Further, the small molecular polyol is one or more of neopentyl glycol, 3-methyl 1, 5-pentanediol and trimethylolethane.
The micromolecular polyol adopts neopentyl glycol, 3-methyl 1,5 pentanediol and trimethylolethane for chain extension, and because the side chain methyl groups are contained, the intermolecular repulsive force of the product is increased, the viscosity of the emulsion is reduced, the realization of the product is achieved, and the water resistance, solvent resistance, wear resistance and contamination resistance are further increased.
Further, the polycaprolactone polyol is a trifunctional polyol having a molecular weight of 200-550.
Further, the silicone polyol is a difunctional, 3000 molecular weight polyol, preferably Tech-2176 from Shanghai Tegn Polymer technology Co.
The organosilicon polyol provides soft chain segments, and the siloxane structure has specificity and is a polymer with stable framework formed by silicon atoms and oxygen atoms alternately. The polysiloxane has a main chain-Si-O-Si-which belongs to an inorganic structure, the bond energy of the polysiloxane is far higher than that of a C-C bond, the bond energy of the Si-C bond is also higher, and the Si-O bond and the Si-C bond are difficult to break by simple thermal movement, so that the polysiloxane has good thermal stability. In addition, the main chain of the siloxane is composed of siloxane bonds, and the bond distance, bond angle and bond energy are large, so that the siloxane is very flexible, the viscous flow activation energy is small, and when the temperature is reduced to-136 ℃, the polydimethylsiloxane also has chain segment movement, and has excellent low temperature resistance and cold resistance. Secondly, the siloxane main chain has no unsaturated bond, and Si-O-Si bond is very stable to oxygen, ozone, ultraviolet rays and the like, so that the anti-aging agent has good weather resistance. The siloxane structure determines that the siloxane has excellent hydrophobicity, the contact angle of the siloxane structure to water is similar to that of paraffin, so the siloxane structure is widely used as a waterproof material, the water permeability and the water absorbability of the treated fabric are greatly reduced, the air permeability, the mechanical property and other properties of the treated fabric are not damaged, hydroxyl groups in the organosilicon polyol are connected with silicon atoms on a main chain through sigma bonds, the free rotating space volume is increased, hydrogen atoms of the hydroxyl groups and the hydrogen atoms of the water are mutually repelled, and water molecules are difficult to combine with hydrophilic oxygen, so the hydrophobic effect and the anti-fouling performance are provided, and in a product connected with organosilicon chain segments, organosilicon groups are directionally arranged on the outer layer of the coating in the drying process, so the anti-fouling performance of the coating is improved.
Further, the polycarbonate diol is selected from diols with a molecular weight of 1000-3000.
The ester bond in the common polyester is easy to hydrolyze, chain breakage is generated, and the product is unstable, while the polycarbonate polyol and polycaprolactone triol are selected and used in the invention, and the polycarbonate polyol and the polycaprolactone triol are known to have good hydrolysis resistance and excellent strength, so that the film forming compactness and waterproof and antifouling effects are realized.
The emulsifier is emulsifier ON-50, preferably product of Basoff company.
The anionic reactive sulfonate hydrophilic group and the nonionic emulsifier are selected for synergistic effect, so that the emulsion stability is further enhanced, the coating prepared by the product has better permeability and good binding fastness with cloth cover, and the washing resistance of the product is improved.
Further, the chain extender is one or more of ethylenediamine, isophorone diamine and triethylene diamine.
According to another aspect of the invention, a preparation method of the anti-contamination aqueous polyurethane emulsion comprises the following steps:
step one, prepolymerization
Adding hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, polycaprolactone polyol and polycarbonate diol into a reaction kettle, and heating for reaction;
step two, chain extension reaction
Adding micromolecular polyalcohol into the reaction kettle for reaction; adding organic silicon polyol, continuing to react, then adding aliphatic diamine sulfonic acid sodium salt, continuing to react, and cooling;
step three, emulsification reaction
Continuously adding an emulsifying agent and deionized water into the reaction kettle, and rapidly dispersing by using a high-speed dispersing machine to obtain a dispersion;
step four, chain extension reaction
Adding a chain extender into the dispersoid for reaction, and cooling to below 30 ℃ after the reaction is finished to obtain the aqueous polyurethane emulsion.
As an example, the preparation method is specifically as follows:
(1) Prepolymerization reaction: adding hydrogenated diphenylmethane diisocyanate (A), isophorone diisocyanate (IPDI), polycaprolactone polyol (D) and polycarbonate diol (F) into a reaction kettle, heating to 70-90 ℃ and reacting for 2-4 hours;
(2) Chain extension reaction: continuously adding (E) micromolecular polyalcohol into a reaction kettle to react for 2-3 hours at 70-90 ℃; adding (G) organosilicon polyol, reacting for 1-1.5 hours at 50-60 ℃, then adding (C) aliphatic diamine sulfonic acid sodium salt, continuously reacting for 0.5-1 hour, and cooling to 40+/-5 ℃;
(3) And (3) emulsification reaction: adding (J) an emulsifier ON-50 and (H) deionized water into the reaction kettle, rapidly dispersing by using a high-speed dispersing machine, keeping the temperature at 40+/-5 ℃, and dispersing uniformly to obtain a dispersion;
(4) Chain extension reaction: adding (H) chain extender into the dispersion, keeping the temperature at 50+/-5 ℃ for reaction for 2-3 hours, and cooling to below 30 ℃ to obtain the finished product.
The chemical indexes of the product are as follows:
appearance: a transparent emulsion;
ionic nature: a vagina;
pH value: 8+/-1;
the solid content: 35.+ -. 1%.
The invention has the following advantages:
the raw materials selected by the invention are hydrogenated diphenylmethane diisocyanate and isophorone diisocyanate, and the two isocyanate monomers are in synergistic reaction and all have a cyclic structure, the cyclic structure is stable in the synthesis process, and the polymer can still exist after being formed, so that the structure can increase the rigidity of the product, has good elasticity, and can improve the fluffy feel of the coating while enhancing the water resistance, solvent resistance, wear resistance and contamination resistance; in addition, isophorone diisocyanate has an isomeric structure, and the reaction speed of two isomeric isocyanate groups is different, so that the stability of the reaction process is improved.
The invention adopts a post chain extension process, and adopts an amine chain extender to form urea bond, thereby increasing rigidity, improving film forming strength and enhancing anti-fouling performance.
Different kinds of hydroxyl raw materials are selected in the synthesis process to improve the performances of wear resistance, washing resistance, contamination resistance and the like of the product. The product of the invention has good process implementation, environmental protection and no pollution.
The aqueous polyurethane emulsion disclosed by the invention is simple and convenient to produce, low in production cost, excellent in stain resistance, good in fastness, wear resistance and washing resistance, and environment-friendly in water.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw material sources are as follows:
sodium salt of aliphatic diamine sulfonic acid (equivalent 220) -VESTAMINA of degussa;
polycaprolactone polyols- -trifunctional polyols having a molecular weight of 200 to 550;
small molecule polyalcohol-one or more of neopentyl glycol, 3-methyl-1, 5-pentanediol and trimethylolethane;
organosilicon polyol, tech-2176 of Shanghai Tegn Polymer technology Co., ltd, is a difunctional, 3000 molecular weight polyol;
chain extender-one or more of ethylenediamine, isophorone diamine and triethylene diamine;
emulsifier- -emulsifier ON-50, product of Basoff company;
other raw materials are conventional raw materials, can be purchased directly, and are not particularly limited.
Example 1
The embodiment provides a preparation method of an anti-contamination aqueous polyurethane emulsion.
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 60 parts, (B) isophorone diisocyanate (IPDI) 30 parts, (C) aliphatic diamine sulfonic acid sodium salt (equivalent 220) 5 parts, (D) polycaprolactone polyol (molecular weight 500) 15 parts, (E) 3-methyl 1,5 pentanediol 10 parts, (F) polycarbonate diol (molecular weight 2000) 80 parts, (G) silicone polyol 60 parts, (H) isophorone diisocyanate 15 parts, (J) emulsifier ON-506 parts, (H) deionized water 520 parts preparation method:
(1) Prepolymerization reaction: hydrogenating the diphenylmethane diisocyanate (A) (H) 12 MDI) 60 parts, (B) isophorone diisocyanate (IPDI) 30 parts, (D) polycaprolactone polyol 15 parts, and (F) polycarbonate diol 80 parts are added into a reaction kettle, and the temperature is raised toReacting for 2-4 hours at 70-90 ℃;
(2) Chain extension reaction: adding 10 parts of (E) micromolecular polyol into the prepolymer, and reacting for 2-3 hours at 70-90 ℃; 60 parts of (G) organic silicon polyol is added to react for 1 to 1.5 hours at 50 to 60 ℃, then 5 parts of (c) aliphatic diamine sodium sulfonate (equivalent 220) is added to continue to react for 0.5 to 1 hour, and the temperature is reduced to 40+/-5 ℃;
(5) And (3) emulsification reaction: adding (J) emulsifier ON-506 parts and (H) deionized water 520 parts, rapidly dispersing by using a high-speed dispersing machine, and keeping the temperature at 40+/-5 ℃;
(6) Chain extension reaction: after the above-mentioned dispersion is uniform, 15 portions of (H) chain extender are added, and reacted for 2-3 hr at 50+ -5 deg.C, and cooled to below 30 deg.C so as to obtain the invented finished product with 35.5%.
Example 2
The embodiment provides a preparation method of an anti-contamination aqueous polyurethane emulsion.
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 61 parts, (B) isophorone diisocyanate (IPDI) 35 parts, (C) aliphatic diamine sulfonic acid sodium salt (equivalent 220) 8 parts, (D) polycaprolactone polyol (molecular weight 400) 12 parts, (E) neopentyl glycol 7 parts, (F) polycarbonate diol (molecular weight 3000) 80 parts, (G) silicone polyol 70 parts, (H) isophorone diamine 4 parts, ethylenediamine 8 parts, (J) emulsifier ON-507 parts, (H) deionized water 555 parts, the preparation method is the same as in example 1, and the product content is 35.3%.
Example 3
The embodiment provides a preparation method of an anti-contamination aqueous polyurethane emulsion.
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 68 parts, (B) isophorone diisocyanate (IPDI) 35 parts, (C) aliphatic diamine sulfonic acid sodium salt (equivalent 220) 7 parts, (D) polycaprolactone polyol (molecular weight 400) 12 parts, (E) trimethylolethane 14 parts, (F) polycarbonate diol (molecular weight 1000) 90 parts, (G) silicone polyol 75 parts, (H) triethylene diamine 5 parts, ethylenediamine 8 parts, (J) emulsifier ON-506.2 parts, and (H) deionized water 575 parts, the production method was the same as in example 1, and the product content was 35.2%.
Example 4
The embodiment provides a preparation method of an anti-contamination aqueous polyurethane emulsion.
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 70 parts, (B) isophorone diisocyanate (IPDI) 20 parts, (C) aliphatic diamine sulfonic acid sodium salt (equivalent 220) 7 parts, (D) polycaprolactone polyol (molecular weight 550) 12 parts, (E) neopentyl glycol 3 parts, trimethylolethane 6 parts, (F) polycarbonate diol (molecular weight 2000) 80 parts, (G) silicone polyol 65 parts, (H) isophorone diamine 10 parts, ethylenediamine 4.7 parts, (J) emulsifier ON-506.2 parts, and (H) deionized water 540 parts, the same preparation method as in example 1, and the product content is 34.9%.
Example 5
The embodiment provides a preparation method of an anti-contamination aqueous polyurethane emulsion.
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 80 parts, (B) 20 parts of isophorone diisocyanate (IPDI), (C) 6.3 parts of aliphatic diamine sulfonic acid sodium salt (equivalent 220), (D) 15 parts of polycaprolactone polyol (molecular weight 200), (E) 5 parts of 3-methyl 1,5 pentanediol, 5 parts of trimethylolethane, (F) 80 parts of polycarbonate diol (molecular weight 2000), 70 parts of organosilicon polyol, (H) 4 parts of isophorone diamine, 10 parts of triethylene diamine, J) emulsifier ON-506.8 parts of (H) deionized water, and the preparation method is the same as in example 1, to obtain a product with a content of 35.4%.
Example 6
The embodiment provides a preparation method of an anti-contamination aqueous polyurethane emulsion.
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 61 parts, (B) isophorone diisocyanate (IPDI) 35 parts, (C) aliphatic diamine sulfonic acid sodium salt (equivalent 220) 7 parts, (D) polycaprolactone polyol (molecular weight 400) 12 parts, (E) neopentyl glycol 4 parts, 3-methyl 1,5 pentanediol 11.7 parts, (F) polycarbonate diol (molecular weight 2500) 80 parts, (G) silicone polyol 65 parts, (H) ethylenediamine 7.2 parts, (J) emulsifier ON-506.2 parts, (H) deionized water 580 parts, the same preparation method as in example 1, and the product content was 35.1%.
Comparative example 1
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 61 parts, (B) isophorone diisocyanate (IPDI) 35 parts, (C) aliphatic diamine sulfonic acid sodium salt (equivalent 220) 7 parts, (D) polycaprolactone polyol (molecular weight 600) 15 parts, (E) neopentyl glycol 4 parts, 3-methyl 1,5 pentanediol 11.7 parts, (F) polycarbonate diol (molecular weight 2500) 80 parts, (G) silicone polyol 65 parts, (H) ethylenediamine 7.2 parts, (J) emulsifier ON-506.2 parts, (H) deionized water 591 parts, the preparation method was the same as in example 1, and the product content was 35.2%.
Comparative example 2
The weight ratio of the raw materials is as follows: (A) Hydrogenated diphenylmethane diisocyanate (H) 12 MDI) 61 parts, (B) isophorone diisocyanate (IPDI) 35 parts, (C) aliphatic diamine sulfonic acid sodium salt (equivalent 220) 7 parts, (D) polycaprolactone polyol (molecular weight 400) 12 parts, (E) neopentyl glycol 4 parts, 3-methyl 1,5 pentanediol 11.7 parts, (F) polycarbonate diol (molecular weight 3500) 100 parts, (G) silicone polyol 65 parts, (H) ethylenediamine 7.2 parts, (J) emulsifier ON-506.2 parts, (H) deionized water 617 parts, the preparation method is the same as in example 1, and the product content is 35.0%.
Experimental example
The application method of the stain-resistant aqueous polyurethane emulsion for fabric coating comprises the following steps: the emulsion is thickened by a thickener FS-300H, the viscosity reaches 5000+/-200 centipoise (25 ℃), a 2% aqueous formaldehyde-free cross-linking agent DF-819N is added, and then a coating machine is used for coating on fabrics, and the fabrics are dried for 2 minutes at 150-165 ℃.
Wherein the thickener FS-300H and the cross-linking agent 819N are all products produced by Liaoning fixed star fine chemical industry Co.
The test indexes are as follows:
1. solid content test: testing according to the determination of solid content of HG/T4266-2011 textile dyeing and finishing auxiliary;
2. washing fastness detection: GB/T8629-2001 household washing and drying program for textile testing; swan XPB55-518S washing machine;
3. anti-fouling performance test: an antifouling test is carried out according to AATCC130 standard;
4. and (3) abrasion resistance detection: the method for measuring the wear resistance of the coated fabric; fabric flat grinder FZ/T01011-91.
The comparative experiment results of the invention and similar products at home and abroad are shown in table 1.
Wherein, foreign sample: DLN-SD product of Kogyo Polymer (China).
Domestic sample: vanhua chemical group Co., ltd
3250 product.
TABLE 1
As can be seen from the test results in Table 1, the product of the invention has good wear resistance, good washing fastness and stain resistance which are obviously better than other products under the condition that the dry weight of the coating film is basically the same as that of the similar products, and meanwhile, compared with comparative example 1 and comparative example 2, the wear resistance and the stain resistance of the product of the invention are better.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (8)
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Country or region after: China Address after: 215500 Suzhou, Changshou City Province, South Ring Road No. 99, No., No. three Applicant after: Suzhou Institute of Technology Applicant after: LIAONING FIXED STAR FINE CHEMICAL Co.,Ltd. Applicant after: DANDONG UNIK TEXTILE CO.,LTD. Address before: 215556 Jiangsu Province, Suzhou City, Changshu City, Nan Sanhuan Road 99 Applicant before: CHANGSHU INSTITUTE OF TECHNOLOGY Country or region before: China Applicant before: LIAONING FIXED STAR FINE CHEMICAL Co.,Ltd. Applicant before: DANDONG UNIK TEXTILE CO.,LTD. |
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