CN107266650B - Water pressure resistant waterproof polyurethane fabric finishing agent and preparation method thereof - Google Patents
Water pressure resistant waterproof polyurethane fabric finishing agent and preparation method thereof Download PDFInfo
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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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/428—Lactides
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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
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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Abstract
The invention discloses a water pressure resistant waterproof polyurethane fabric finishing agent and a preparation method thereof, wherein the finishing agent is prepared by the following steps: reacting the macrodiol I, the macrodiol II and diisocyanate at 90-100 ℃ for 2-4 h to obtain a polyurethane prepolymer a1(ii) a To polyurethane prepolymer a1Adding a micromolecular chain extender, a hydrophilic chain extender I, a solvent and a catalyst, and reacting for 3-6 h at the temperature of 60-80 ℃ to obtain the waterborne polyurethane prepolymer a2(ii) a To an aqueous polyurethane prepolymer a2Adding a solvent and a hydrophilic chain extender II, and reacting at 50-60 ℃ for 0.5-1 h to obtain a waterborne polyurethane prepolymer a3(ii) a To an aqueous polyurethane prepolymer a3Adding a solvent, adding a salt forming agent under high-speed shearing, stirring for 1-5 min, adding water, dispersing and emulsifying at high speed for 5-10 min, and removing the solvent under vacuum to obtain the high-performance water-based emulsion. The process is simple, the preparation process is easy to control, and the prepared water pressure resistant waterproof polyurethane fabric finishing agent has high hydrostatic pressure resistance and excellent waterproof moisture permeability.
Description
Technical Field
The invention relates to the field of fabric finishing agents, in particular to a water pressure resistant waterproof polyurethane fabric finishing agent and a preparation method thereof.
Background
The waterproof fabric is a functional textile developed in the middle of the 70 th age in the 20 th century, is widely applied to the fields of military affairs, sports, medicine and the like, and means that a polymer film or a coating does not allow liquid such as water drops and the like to permeate, but can allow water vapor to freely permeate, so that the aims of water resistance and moisture permeability are fulfilled. At present, the waterproof coatings used for textiles are mainly polyurethanes which are divided into solvent type polyurethane and water-based polyurethane, but the hydrostatic pressure resistance and the waterproof moisture permeability of the two types of polyurethane are not ideal, so that the application of waterproof fabrics is influenced.
Disclosure of Invention
In view of the above, the present invention aims to provide a water-resistant waterproof polyurethane fabric finishing agent and a preparation method thereof, which have excellent hydrostatic pressure resistance and waterproof moisture permeability.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a water pressure resistant waterproof polyurethane fabric finishing agent comprises the following steps:
a) reacting the macrodiol I, the macrodiol II and diisocyanate at 90-100 ℃ for 2-4 h to obtain a polyurethane prepolymer a1；
b) To the polyurethane prepolymer a obtained in step a)1Adding a micromolecular chain extender, a hydrophilic chain extender I, a solvent and a catalyst, and reacting for 3-6 h at the temperature of 60-80 ℃ to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding a solvent and a hydrophilic chain extender II, and reacting at 50-60 ℃ for 0.5-1 h to obtain a waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding a solvent, adding a salt forming agent under high-speed shearing, stirring for 1-5 min, adding water, dispersing and emulsifying at high speed for 5-10 min, and removing the solvent under vacuum to obtain the water pressure resistant waterproof polyurethane fabric finishing agent.
Preferably, the macromolecular polyol I is selected from one or two of phthalic anhydride polyester diol and dimer acid polyester diol;
preferably, the macromolecular polyol II is polyester diol obtained by ring-opening polymerization of D, L-lactide with polyethylene glycol.
Preferably, the hydrophilic chain extender I is dimethylolpropionic acid or dimethylolbutyric acid;
the hydrophilic chain extender II is ethylenediamine sodium sulfonate.
Preferably, the diisocyanate is toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, 4 '-diphenylmethane diisocyanate or 4,4' -dicyclohexylmethane diisocyanate.
Preferably, the small-molecule chain extender is diethylene glycol, 1, 4-butanediol, 3-methyl-1, 5-pentanediol or polyethylene glycol 200.
Preferably, the catalyst is selected from one or more of stannous octoate, n-butyltin dilaurate, organic Bi salt catalyst and organic Zn salt catalyst.
Preferably, the salt forming agent is triethylamine, N dimethylethanolamine, sodium hydroxide or potassium hydroxide.
Preferably, in step b) and step c), the solvent is independently selected from acetone or butanone.
A water pressure resistant waterproof polyurethane fabric finishing agent is prepared by adopting the preparation method of the water pressure resistant waterproof polyurethane fabric finishing agent.
The invention provides a water pressure resistant waterproof polyurethane fabric finishing agent and a preparation method thereof, wherein the finishing agent is prepared by the following steps: a) reacting the macrodiol I, the macrodiol II and diisocyanate at 90-100 ℃ for 2-4 h to obtain a polyurethane prepolymer a1(ii) a b) To the polyurethane prepolymer a obtained in step a)1Adding a micromolecular chain extender, a hydrophilic chain extender I, a solvent and a catalyst, and reacting for 3-6 h at the temperature of 60-80 ℃ to obtain the waterborne polyurethane prepolymer a2(ii) a c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding a solvent and a hydrophilic chain extender II, and reacting at 50-60 ℃ for 0.5-1 h to obtain a waterborne polyurethane prepolymer a3(ii) a d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding a solvent, adding a salt forming agent under high-speed shearing, stirring for 1-5 min, adding water, dispersing and emulsifying at high speed for 5-10 min, and removing the solvent under vacuum to obtain the water pressure resistant waterproof polyurethane fabric finishing agent. The invention has simple process and easy control of the preparation process, and the prepared water pressure resistant waterproof polyurethaneThe ester fabric finishing agent has high hydrostatic pressure resistance and excellent waterproof moisture permeability.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
The invention provides a preparation method of a water pressure resistant waterproof polyurethane fabric finishing agent, which comprises the following steps:
a) reacting the macrodiol I, the macrodiol II and diisocyanate at 90-100 ℃ for 2-4 h to obtain a polyurethane prepolymer a1；
b) To the polyurethane prepolymer a obtained in step a)1Adding a micromolecular chain extender, a hydrophilic chain extender I, a solvent and a catalyst, and reacting for 3-6 h at the temperature of 60-80 ℃ to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding a solvent and a hydrophilic chain extender II, and reacting at 50-60 ℃ for 0.5-1 h to obtain a waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding a solvent, adding a salt forming agent under high-speed shearing, stirring for 1-5 min, adding water, dispersing and emulsifying at high speed for 5-10 min, and removing the solvent under vacuum to obtain the water pressure resistant waterproof polyurethane fabric finishing agent.
In the technical scheme, the process is simple, the preparation process is easy to control, and the prepared water-pressure-resistant waterproof polyurethane fabric finishing agent has high hydrostatic pressure resistance and excellent waterproof moisture permeability.
Reacting the macrodiol I, the macrodiol II and diisocyanate at 90-100 ℃ for 2-4 h to obtain a polyurethane prepolymer a1。
In the embodiment of the invention, the macromolecular polyol I is selected from one or two of phthalic anhydride polyester diol and dimer acid polyester diol; in other embodiments, the relative molecular weight of macrodiol I is 1000-2000; in a further embodiment, the macrodiol has a relative molecular weight of 2000.
In the embodiment of the invention, the macromolecular polyol II is polyester dihydric alcohol obtained by polyethylene glycol ring-opening polymerization of D, L-lactide, in other embodiments, the relative molecular weight of the macromolecular polyol II is 1000-8000, and in other embodiments, the relative molecular weight of the macromolecular polyol II is 4000.
Wherein, the relative molecular weight of the polyethylene glycol is 400,600,800,1000 or 2000; in the examples of the present invention, the polyethylene glycol has a relative molecular weight of 800.
In the examples of the present invention, the diisocyanate is toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, 4 '-diphenylmethane diisocyanate or 4,4' -dicyclohexylmethane diisocyanate.
Obtaining a polyurethane prepolymer a1Then adding a micromolecular chain extender, a hydrophilic chain extender I, a solvent and a catalyst, and reacting for 3-6 h at the temperature of 60-80 ℃ to obtain the waterborne polyurethane prepolymer a2。
In the embodiment of the invention, the small-molecule chain extender is diethylene glycol, 1, 4-butanediol, 3-methyl-1, 5-pentanediol or polyethylene glycol 200; in other embodiments, the small molecule chain extender is polyethylene glycol 200.
In the embodiment of the present invention, the hydrophilic chain extender I is dimethylolpropionic acid or dimethylolbutyric acid; in other embodiments, the hydrophilic chain extender is dimethylolpropionic acid.
In the embodiment of the invention, the catalyst is selected from one or more of stannous octoate, n-butyltin dilaurate, organic Bi salt catalyst and organic Zn salt catalyst; in other embodiments, the organic Bi salt catalyst is bismuth isooctanoate, bismuth laur acid or bismuth neodecanoate; the organic Zn salt catalyst is dimethyl zinc or diethyl zinc.
In an embodiment of the invention, in step b), the solvent is acetone or butanone.
The obtained waterborne polyurethane prepolymer a2Then adding a solvent and a hydrophilic chain extender II into the mixture, reacting for 0.5 to 1 hour at the temperature of between 50 and 60 ℃,obtaining the waterborne polyurethane prepolymer a3。
In the embodiments of the present invention, the solvent is the same as described above, and is not described herein again.
In an embodiment of the present invention, the hydrophilic chain extender II is sodium ethylene diamine sulfonate.
Obtaining the waterborne polyurethane prepolymer a3Then adding a solvent into the mixture, adding a salt forming agent under high-speed shearing, stirring for 1-5 min, adding water, dispersing and emulsifying at high speed for 5-10 min, and removing the solvent under vacuum to obtain the waterborne polyurethane
In the embodiments of the present invention, the solvent is the same as described above, and is not described herein again.
In embodiments of the invention, the salt forming agent is triethylamine, N dimethylethanolamine, sodium hydroxide or potassium hydroxide; in other embodiments, the salt-forming agent is triethylamine.
In the embodiment of the invention, the mass ratio of the macromolecular diol I, the macromolecular diol II, the diisocyanate, the micromolecular chain extender, the hydrophilic chain extender I, the catalyst, the hydrophilic chain extender II, the salt forming agent and water is (10-20): (10-40): (15-30): (2-10): (2-8): (0.1-0.3): (1-5): (0.8-5): (80-100).
In the embodiment of the invention, the mass ratio of the solvent in the step b), the solvent in the step c) and the solvent in the step d) to the diisocyanate is (2-3): (0.8-1.2): (0.6-2.8): 1.
the invention also provides a water pressure resistant waterproof polyurethane fabric finishing agent prepared by adopting the preparation method.
The water-resistant waterproof polyurethane fabric finishing agent provided by the invention has high hydrostatic pressure resistance and excellent waterproof moisture permeability, but can easily permeate water vapor.
The water-resistant and water-proof polyurethane fabric finishing agent and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
a) The relative molecular weight of the polyester diol of phthalic anhydride with the relative molecular weight of 1000 and the relative componentReacting macromolecular polyol II with the molecular weight of 1000 with isophorone diisocyanate at 90 ℃ for 4h to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 400;
b) to the polyurethane prepolymer a obtained in step a)1Adding diethylene glycol, dimethylol propionic acid, acetone and stannous octoate, and reacting for 3h at 60 ℃ to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 50 ℃ for 1h to obtain the waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding butanone, adding N, N-dimethylethanolamine under high-speed shearing, stirring for 5min, adding water, dispersing and emulsifying at high speed for 7min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of phthalic anhydride polyester dihydric alcohol, macromolecular polyalcohol II, isophorone diisocyanate, diethylene glycol, dimethylolpropionic acid, stannous octoate, sodium ethylene diamine sulfonate, N dimethylethanolamine to water is 10: 40: 15: 2: 2: 0.3: 1: 3.5: 80.
in the examples of the present invention, the mass ratio of acetone in step b), acetone in step c), butanone and diisocyanate in step d) is 2: 0.8: 0.6: 1.
example 2
a) Reacting a dimer acid polyester diol with a relative molecular weight of 2000, a macromolecular polyol II with a relative molecular weight of 3000 and 4,4' -dicyclohexylmethane diisocyanate at 100 ℃ for 2h to obtain a polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 800;
b) to the polyurethane prepolymer a obtained in step a)1Adding 1, 4-butanediol, dimethylolbutyric acid, butanone and n-butyltin dilaurate, and reacting at 80 deg.C for 4 hr to obtain aqueous polymerUrethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 60 deg.C for 0.5h to obtain aqueous polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding acetone, adding sodium hydroxide under high-speed shearing, stirring for 1min, adding water, dispersing and emulsifying at high speed for 5min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of dimer acid polyester diol, macromolecular polyol II, 4' -dicyclohexylmethane diisocyanate, 1, 4-butanediol, dimethylolbutyric acid, n-butyltin dilaurate, sodium ethylenediamine sulfonate, sodium hydroxide and water is 12: 35: 20: 4: 4: 0.25: 2: 4: 100.
in the examples of the present invention, the mass ratio of methyl ethyl ketone in step b), acetone in step c), and acetone to diisocyanate in step d) was 3: 1.2: 2.8: 1.
example 3
a) Reacting polyester diol with a relative molecular weight of 2000, macromolecular polyol II with a relative molecular weight of 8000 and 1, 6-hexamethylene diisocyanate at 100 ℃ for 3h to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 800;
b) to the polyurethane prepolymer a obtained in step a)1Adding 3-methyl-1, 5-pentanediol, dimethylol propionic acid, acetone, bismuth isooctanoate and dimethyl zinc, and reacting for 5 hours at 70 ℃ to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding butanone and ethylenediamine sodium sulfonate, and reacting at 60 ℃ for 1h to obtain the waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding butanone, adding potassium hydroxide under high speed shearing, stirring for 3min, adding water, dispersing and emulsifying at high speed for 10min, and vacuum emulsifyingRemoving the solvent in the air to obtain the water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of phthalic anhydride polyester dihydric alcohol, macromolecular polyalcohol II, 1, 6-hexamethylene diisocyanate, 3-methyl-1, 5-pentanediol, dimethylol propionic acid, bismuth isooctanoate, dimethyl zinc, sodium ethylene diamine sulfonate, potassium hydroxide and water is 14: 20: 25: 5: 6: 0.1: 0.1: 3.5: 5: 90.
in the examples of the present invention, the mass ratio of acetone in step b), butanone in step c), butanone in step d) to diisocyanate was 2.5: 1: 1: 1.
example 4
a) Reacting dimer acid polyester diol with the relative molecular weight of 2000, macromolecular polyol II with the relative molecular weight of 5000 and isophorone diisocyanate at 90 ℃ for 3h to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 1000;
b) to the polyurethane prepolymer a obtained in step a)1Adding polyethylene glycol 200, dimethylolbutyric acid, butanone and diethyl zinc, and reacting at 80 ℃ for 6h to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding butanone and ethylenediamine sodium sulfonate, and reacting at 50 deg.C for 0.8 hr to obtain aqueous polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding butanone, adding triethylamine under high-speed shearing, stirring for 4min, adding water, dispersing and emulsifying at high speed for 5min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric coating agent;
the mass ratio of dimer acid polyester diol, macromolecular polyol II, isophorone diisocyanate, polyethylene glycol 200, dimethylolbutyric acid, diethyl zinc, sodium ethylene diamine sulfonate, triethylamine and water is 16: 20: 27: 8: 7: 0.15: 4: 2: 85.
in the examples of the present invention, the mass ratio of butanone in step b), butanone in step c), butanone in step d) and diisocyanate was 2.3: 0.9: 1.5: 1.
example 5
a) Reacting dimer acid polyester diol with the relative molecular weight of 2000, macromolecular polyol II with the relative molecular weight of 4000 and toluene diisocyanate at 100 ℃ for 3 hours to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 1000;
b) to the polyurethane prepolymer a obtained in step a)1Adding polyethylene glycol 200, dimethylol propionic acid, acetone and bismuth neodecanoate, and reacting at 70 ℃ for 6h to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 50 deg.C for 0.8 hr to obtain aqueous polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding acetone, adding triethylamine under high-speed shearing, stirring for 3min, adding water, dispersing and emulsifying at high speed for 8min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of dimer acid polyester dihydric alcohol, macromolecular polyalcohol II, toluene diisocyanate, polyethylene glycol 200, dimethylolpropionic acid, bismuth neodecanoate, sodium ethylene diamine sulfonate, triethylamine and water is 20: 10: 30: 10: 8: 0.1: 5: 0.8: 95.
in the examples of the present invention, the mass ratio of acetone in step b), acetone in step c), acetone and diisocyanate in step d) was 2.7: 1.1: 2: 1.
example 6
a) Phthalic anhydride polyester dihydric alcohol with the relative molecular weight of 2000, dimer acid polyester dihydric alcohol with the relative molecular weight of 4000, macromolecular polyol II with the relative molecular weight of 3000 and 4,4' -diphenylmethane diisocyanate react for 4 hours at the temperature of 90 ℃ to obtain polyurethane prepolymer a1The macromolecular polyol II is polyester diol obtained by ring-opening polymerization of D, L-lactide with polyethylene glycol, wherein the relative molecular weight of the polyethylene glycolIs 800;
b) to the polyurethane prepolymer a obtained in step a)1Adding polyethylene glycol 200, dimethylol propionic acid, acetone and bismuth laur , and reacting at 80 ℃ for 6h to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 60 ℃ for 1h to obtain the waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding acetone, adding triethylamine under high-speed shearing, stirring for 5min, adding water, dispersing and emulsifying at high speed for 7min, and removing the solvent under vacuum to obtain the water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of phthalic anhydride polyester diol, dimer acid polyester diol, macromolecular polyol II, 4' -diphenylmethane diisocyanate, polyethylene glycol 200, dimethylolpropionic acid, bismuth laur , sodium ethylene diamine sulfonate, triethylamine and water is 7.5: 7.5: 25: 22.5: 6: 5: 0.2: 3: 2.9: 90.
in the examples of the present invention, the mass ratio of acetone in step b), acetone in step c), acetone and diisocyanate in step d) is 2.5: 1: 1.7: 1.
finishing the water-pressure-resistant waterproof polyurethane fabric finishing agent prepared in the embodiment 1-6 on cotton, terylene and chinlon fabrics according to the GB/T4744 1997 textile fabric water impermeability determination hydrostatic pressure test and the GB/T12704,2-2009 textile fabric moisture permeability test method part 2: the hydrostatic pressure resistance and the waterproof moisture permeability of the product are tested by an evaporation method, and the results are shown in a table 1.
TABLE 1 Experimental results for examples 1 to 6
The water-resistant and waterproof polyurethane fabric finishing agent and the preparation method thereof provided by the present invention are described in detail above, and the principle and the embodiment of the present invention are illustrated herein by using specific examples, and the description of the above examples is only for helping to understand the method of the present invention and the core idea thereof, it should be noted that, for those skilled in the art, the present invention can be modified and modified without departing from the principle of the present invention, and the modified and modified aspects also fall within the protection scope of the claims of the present invention.
Claims (1)
1. A preparation method of a water pressure resistant waterproof polyurethane fabric finishing agent is characterized by comprising the following steps:
a) reacting polyester diol with the relative molecular weight of 1000, macromolecular polyol II with the relative molecular weight of 1000 and isophorone diisocyanate at 90 ℃ for 4h to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 400;
b) to the polyurethane prepolymer a obtained in step a)1Adding diethylene glycol, dimethylol propionic acid, acetone and stannous octoate, and reacting for 3h at 60 ℃ to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 50 ℃ for 1h to obtain the waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding butanone, adding N, N-dimethylethanolamine under high-speed shearing, stirring for 5min, adding water, dispersing and emulsifying at high speed for 7min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of phthalic anhydride polyester dihydric alcohol, macromolecular polyalcohol II, isophorone diisocyanate, diethylene glycol, dimethylolpropionic acid, stannous octoate, sodium ethylene diamine sulfonate, N dimethylethanolamine to water is 10: 40: 15: 2: 2: 0.3: 1: 3.5: 80;
the mass ratio of acetone in the step b), acetone in the step c) and butanone and diisocyanate in the step d) is 2: 0.8: 0.6: 1;
or a) the relative molecular weight is adjusted to2000 dimer acid polyester diol, macromolecular polyol II with the relative molecular weight of 3000 and 4,4' -dicyclohexyl methane diisocyanate react for 2 hours at 100 ℃ to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 800;
b) to the polyurethane prepolymer a obtained in step a)1Adding 1, 4-butanediol, dimethylolbutyric acid, butanone and n-butyltin dilaurate, and reacting at 80 ℃ for 4h to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 60 deg.C for 0.5h to obtain aqueous polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding acetone, adding sodium hydroxide under high-speed shearing, stirring for 1min, adding water, dispersing and emulsifying at high speed for 5min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of dimer acid polyester diol, macromolecular polyol II, 4' -dicyclohexylmethane diisocyanate, 1, 4-butanediol, dimethylolbutyric acid, n-butyltin dilaurate, sodium ethylenediamine sulfonate, sodium hydroxide and water is 12: 35: 20: 4: 4: 0.25: 2: 4: 100, respectively;
the mass ratio of butanone in the step b), acetone in the step c) and acetone to diisocyanate in the step d) is 3: 1.2: 2.8: 1;
or a) reacting polyester diol with the relative molecular weight of 2000 phthalic anhydride, macromolecular polyol II with the relative molecular weight of 8000 and 1, 6-hexamethylene diisocyanate at 100 ℃ for 3h to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 800;
b) to the polyurethane prepolymer a obtained in step a)1Adding 3-methyl-1, 5-pentanediol, dimethylol propionic acid, acetone, bismuth isooctanoate and dimethyl zinc, and reacting for 5 hours at 70 ℃ to obtain the waterborne polyurethane prepolymera2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding butanone and ethylenediamine sodium sulfonate, and reacting at 60 ℃ for 1h to obtain the waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding butanone into the mixture, adding potassium hydroxide under high-speed shearing, stirring for 3min, adding water, dispersing and emulsifying at high speed for 10min, and removing the solvent under vacuum to obtain the water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of phthalic anhydride polyester dihydric alcohol, macromolecular polyalcohol II, 1, 6-hexamethylene diisocyanate, 3-methyl-1, 5-pentanediol, dimethylol propionic acid, bismuth isooctanoate, dimethyl zinc, sodium ethylene diamine sulfonate, potassium hydroxide and water is 14: 20: 25: 5: 6: 0.1: 0.1: 3.5: 5: 90, respectively;
the mass ratio of acetone in the step b), butanone in the step c) and butanone to diisocyanate in the step d) is 2.5: 1: 1: 1;
or a) reacting dimer acid polyester diol with the relative molecular weight of 2000, macromolecular polyol II with the relative molecular weight of 5000 and isophorone diisocyanate at 90 ℃ for 3h to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 1000;
b) to the polyurethane prepolymer a obtained in step a)1Adding polyethylene glycol 200, dimethylolbutyric acid, butanone and diethyl zinc, and reacting at 80 ℃ for 6h to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding butanone and ethylenediamine sodium sulfonate, and reacting at 50 deg.C for 0.8 hr to obtain aqueous polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding butanone, adding triethylamine under high-speed shearing, stirring for 4min, adding water, dispersing and emulsifying at high speed for 5min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric coating agent;
the mass ratio of dimer acid polyester diol, macromolecular polyol II, isophorone diisocyanate, polyethylene glycol 200, dimethylolbutyric acid, diethyl zinc, sodium ethylene diamine sulfonate, triethylamine and water is 16: 20: 27: 8: 7: 0.15: 4: 2: 85 parts by weight;
the mass ratio of butanone in the step b), butanone in the step c) and butanone to diisocyanate in the step d) is 2.3: 0.9: 1.5: 1;
or a) reacting dimer acid polyester dihydric alcohol with the relative molecular weight of 2000, macromolecular polyol II with the relative molecular weight of 4000 and toluene diisocyanate at 100 ℃ for 3 hours to obtain polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 1000;
b) to the polyurethane prepolymer a obtained in step a)1Adding polyethylene glycol 200, dimethylol propionic acid, acetone and bismuth neodecanoate, and reacting at 70 ℃ for 6h to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 50 deg.C for 0.8 hr to obtain aqueous polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding acetone, adding triethylamine under high-speed shearing, stirring for 3min, adding water, dispersing and emulsifying at high speed for 8min, and removing solvent under vacuum to obtain water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of dimer acid polyester dihydric alcohol, macromolecular polyalcohol II, toluene diisocyanate, polyethylene glycol 200, dimethylolpropionic acid, bismuth neodecanoate, sodium ethylene diamine sulfonate, triethylamine and water is 20: 10: 30: 10: 8: 0.1: 5: 0.8: 95;
the mass ratio of acetone in step b), acetone in step c) and acetone to diisocyanate in step d) is 2.7: 1.1: 2: 1;
or a) mixing phthalic anhydride polyester diol with a relative molecular weight of 2000, dimer acid polyester diol with a relative molecular weight of 4000, macromolecular polyol II with a relative molecular weight of 3000 and 4,4' -diphenylmethane diisocyanateThe ester is reacted for 4 hours at 90 ℃ to obtain a polyurethane prepolymer a1The macromolecular polyalcohol II is polyester dihydric alcohol obtained by ring-opening polymerization of polyethylene glycol D, L-lactide, wherein the relative molecular weight of the polyethylene glycol is 800;
b) to the polyurethane prepolymer a obtained in step a)1Adding polyethylene glycol 200, dimethylol propionic acid, acetone and bismuth laur , and reacting at 80 ℃ for 6h to obtain the waterborne polyurethane prepolymer a2；
c) B) adding the aqueous polyurethane prepolymer a obtained in step b)2Adding acetone and sodium ethylene diamine sulfonate, and reacting at 60 ℃ for 1h to obtain the waterborne polyurethane prepolymer a3；
d) Adding the aqueous polyurethane prepolymer a obtained in the step c)3Adding acetone, adding triethylamine under high-speed shearing, stirring for 5min, adding water, dispersing and emulsifying at high speed for 7min, and removing the solvent under vacuum to obtain the water pressure resistant waterproof polyurethane fabric finishing agent;
the mass ratio of phthalic anhydride polyester diol, dimer acid polyester diol, macromolecular polyol II, 4' -diphenylmethane diisocyanate, polyethylene glycol 200, dimethylolpropionic acid, bismuth laur , sodium ethylene diamine sulfonate, triethylamine and water is 7.5: 7.5: 25: 22.5: 6: 5: 0.2: 3: 2.9: 90, respectively;
the mass ratio of acetone in step b), acetone in step c) and acetone to diisocyanate in step d) is 2.5: 1: 1.7: 1.
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| CN109897524A (en) * | 2019-04-02 | 2019-06-18 | 上海金狮化工有限公司 | A kind of high adhesion force finishing agent and preparation method thereof |
| CN110684172A (en) * | 2019-11-12 | 2020-01-14 | 东莞市米儿塑胶原料有限公司 | Water-pressure-resistant water-based polyurethane resin |
| CN112227083A (en) * | 2020-09-30 | 2021-01-15 | 京准化工技术(上海)有限公司 | Fabric water pressure resistance improver and preparation method thereof |
| CN114437307B (en) * | 2020-10-30 | 2024-01-26 | 长兴化学工业(中国)有限公司 | Aqueous polyurethane dispersion, coating composition and application thereof |
| CN112480352A (en) * | 2020-11-24 | 2021-03-12 | 桐乡市正嵘纺织助剂有限公司 | Aqueous polyurethane textile coating agent |
| CN113265901B (en) * | 2021-05-13 | 2023-03-31 | 南京林业大学 | Dimer acid-based waterborne polyurethane surface sizing agent and preparation method and application thereof |
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Address after: Room 618, building G5, No. 31, Kefeng Road, Huangpu District, Guangzhou City, Guangdong Province Patentee after: Guangzhou dolphin New Material Co.,Ltd. Address before: Room 618, building G5, No. 31, Kefeng Road, Huangpu District, Guangzhou City, Guangdong Province Patentee before: Guangzhou dolphin Polyurethane Technology Service Co., Ltd |