WO2016070644A1 - 一种水性聚氨酯乳液的制备方法及其应用 - Google Patents

一种水性聚氨酯乳液的制备方法及其应用 Download PDF

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WO2016070644A1
WO2016070644A1 PCT/CN2015/083566 CN2015083566W WO2016070644A1 WO 2016070644 A1 WO2016070644 A1 WO 2016070644A1 CN 2015083566 W CN2015083566 W CN 2015083566W WO 2016070644 A1 WO2016070644 A1 WO 2016070644A1
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aqueous polyurethane
polyurethane emulsion
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agent
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French (fr)
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徐玉华
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江苏中科金龙化工有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • 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
    • 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
    • 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
    • C08G18/48—Polyethers
    • 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
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers

Definitions

  • the invention relates to a preparation method of an aqueous polyurethane emulsion and an application thereof in the field of coatings, and belongs to the field of waterborne polyurethane coatings.
  • Waterborne polyurethane is a polyurethane system that uses water as a dispersion medium instead of a solvent. It not only has a very low VOC, but also does not contain free -NCO. With the emphasis on environmental protection, waterborne polyurethane is now an important direction for the development of polyurethane. Water-based polyurethane is used to prepare coatings, which can greatly reduce the damage of solvents in the paint to the human body, reduce the cost, and has the advantages of scratch resistance, wear resistance and strong adhesion. Therefore, waterborne polyurethanes are increasingly used in coatings.
  • the invention adopts a novel composite polyol whose carbonate structure is a polypropylene carbonate structure, one or more mixed structures of polyethylene carbonate; the polyether segment is polyethylene oxide. a mixed structure of one or two kinds of polyoxypropylene; the polycarbonate structure and the polyether structure are both formed by polymerization of carbon dioxide and an epoxy compound; the novel polyol has flexibility of polyether And water resistance, and the rigidity and hydrolysis resistance of the polycarbonate polyol; the aqueous polyurethane hard emulsion prepared by using the polyol has both high hardness and impact resistance, and is resistant to water and scratches. Wear-resistant, long storage period, the most important thing is that this product is cheap and cost-effective.
  • CN201310347297.4 discloses the preparation of an internally crosslinked poly(propylene carbonate) aqueous polyurethane emulsion, which has improved performance, but there is still a big gap in the use of hard coatings; It is very practical to prepare a waterborne polyurethane hard coating which can meet the industrial requirements.
  • an object of the present invention to provide a process for the preparation of an aqueous polyurethane emulsion and its use in aqueous coatings, especially high hardness aqueous coatings.
  • the technical scheme adopted by the present invention is: a preparation method of an aqueous polyurethane emulsion, a mass ratio and an operation step: a first step, a composite polyol containing a polycarbonate structure and a polyether structure 50 to 100 parts, 0.05 to 0.2 parts of the catalyst is added to the reaction vessel, the temperature is raised to 50 to 60 ° C, and the mixture is uniformly stirred. 10 to 80 parts of isocyanate is added, and the temperature is raised to 70 to 85 ° C for 2 to 4 hours, and non-hydrophilic alcohol is added.
  • the composite polyol has a carbonate structure and an ether structure, and its molecular structural formula is:
  • the carbonate structure in the composite polyol is a polypropylene carbonate structure, one or more mixed structures of polyethylene carbonate; the polyether structure is one or two of polyethylene oxide and polypropylene oxide. Mixed structure; the polycarbonate structure and the polyether structure are both formed by polymerization of carbon dioxide and an epoxy compound; the polycarbonate structure in the composite polyol accounts for ⁇ 30% by mole;
  • the composite polyol described has an average molecular weight of between 500 and 5,000.
  • the isocyanates include, but are not limited to, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,6-hexyl diisocyanate (HDI), dicyclohexyl One or more of methane diisocyanate (HMDI).
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • HDI 1,6-hexyl diisocyanate
  • HMDI dicyclohexyl One or more of methane diisocyanate
  • the catalyst is dibutyltin dilaurate, stannous octoate, organic hydrazine, one or more of them.
  • the non-hydrophilic chain extender is an alcohol and an amine, including but not limited to: ethylene glycol, methyl propylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, 1, One or more of 6-hexanediol, neopentyl glycol, ethylenediamine, propylenediamine, di-n-butylamine, trimethylhexamethylenediamine, isophoronediamine, and hydrazine hydrate.
  • the hydrophilic chain extender includes, but is not limited to, dimethylolpropionic acid, dimethylolbutanoic acid or sodium N-(2-aminoethyl)-2-aminoethanesulfonate (AAS salt), One or more of 2,4-diaminobenzenesulfonic acid, sodium 2-sulfonate-1,4-butanediol.
  • the crosslinking agent includes, but not limited to, one or more of trimethylolpropane, triethanolamine, and diethylenetriamine.
  • the neutralizing agent includes one of ammonia water, triethylamine, triethanolamine, potassium hydroxide, and sodium hydroxide.
  • the filler includes, but is not limited to, one or more of titanium dioxide, talc, diatomaceous earth, kaolin, heavy calcium carbonate, light calcium carbonate, and montmorillonite.
  • the pigments are: water-soluble or water-dispersible toners and color pastes.
  • the auxiliaries include, but are not limited to, one or more of a leveling agent, a wetting agent, an antifoaming agent, a dispersing agent, a flash rust inhibitor, a light stabilizer, an antioxidant, a thickener, and a preservative.
  • a leveling agent e.g., one or more of a leveling agent, a wetting agent, an antifoaming agent, a dispersing agent, a flash rust inhibitor, a light stabilizer, an antioxidant, a thickener, and a preservative.
  • Waterborne polyurethane emulsions are used in waterborne metal coatings, waterborne wood coatings, waterborne glass coatings, and aqueous hard leather coatings.
  • the obtained water-based polyurethane emulsion can prepare a high-adhesive water-based paint, has good impact resistance at the same time of high hardness, and has good storage stability under the premise of good water resistance, and has low temperature formation. It has the characteristics of membrane properties and fast drying. It is widely used in waterborne metal coatings, waterborne wood coatings, waterborne glass coatings and waterborne hard leather coatings. It has excellent performance and cost performance.
  • a polycarbonate having a polycarbonate propylene structure of 55% by mole and a polyoxypropylene ether structure of 45% by mole of a complex polyol (molecular weight: 2,500, hydroxyl value: 45 mg (KOH)/g) 200 kg and octanoic acid 0.4Kg of tin was added to the reaction vessel and stirred uniformly at 50 ° C; 136 Kg of toluene diisocyanate was added, the temperature was raised to 70 ° C, and the reaction was carried out for 2 hours; 30 Kg of 1,4-butanediol was added, and the reaction was carried out at 80 ° C for 1 hour; 20Kg of methylpropionic acid, reacted at 80 ° C for 2 hours; cooled to 60 ° C, added 3Kg of trimethylolpropane and added The reaction was carried out in acetone 40Kg for 1.5 hours; the temperature was lowered to 50 ° C, 15Kg of
  • Mpa was removed from acetone; the material was filtered to obtain a translucent blue-colored aqueous polyurethane emulsion A.
  • 10Kg of deionized water is added to the batching tank, and 0.3Wg of wetting agent, 0.2Kg of pH adjuster, 0.3Kg of defoaming agent, 0.2Kg of leveling agent and 0.2Kg of leveling agent are added to the dispersion tank while stirring.
  • Test items testing method Test Results Exterior Visual inspection Good fullness Viscosity Iwata No. 2 Cup 24S luster 60° gloss meter 85° Adhesion Baige method Level 0 hardness Pencil hardness method 2H Water resistance Soak at room temperature No change for 48 hours Alcohol resistant 50° alcohol 4 hours without change Blocking resistance 500g, 60°C/4h by Wear resistance (750g/500r)/g ⁇ 0.02 Scratch resistance 100g Not scratched Stain resistance Vinegar, tea 2h by
  • a polycarbonate having a polycarbonate propylene structure of 70% by mole and a polyoxypropylene ether structure of 30% by mole of a composite polyol (molecular weight: 2000, hydroxyl value: 56 mg (KOH)/g) 200 Kg and two laurel 0.2Kg of dibutyltin acid was added to the reaction vessel and stirred uniformly at 60 ° C; 179 Kg of isophorone diisocyanate was added, the temperature was raised to 75 ° C, and the reaction was carried out for 2 hours; 38 kg of diethylene glycol was added, and the reaction was carried out at 80 ° C for 1 hour.
  • Test items testing method Test Results Exterior Visual inspection Good fullness Viscosity Iwata No. 2 Cup 26S luster 60° gloss meter 55° Adhesion Baige method Level 0 hardness Pencil hardness method 1-2H Water resistance Soak at room temperature No change for 48 hours Alcohol resistant 50° alcohol 4 hours without change Blocking resistance 500g, 60°C/4h by Wear resistance (750g/500r)/g ⁇ 0.02 Scratch resistance 100g Not scratched Stain resistance Vinegar, tea 5h by
  • the reaction was carried out for 1 hour; 20 kg of dimethylolpropionic acid was added, and the reaction was carried out at 80 ° C for 2 hours; the temperature was lowered to 50 ° C, and 2Kg of diethylenetriamine and 30Kg of acetone were added for 1 hour; the temperature was lowered to 40 ° C, 15Kg of triethylamine was added for 15 minutes; water was added at 761Kg, dispersed at high speed for 10 minutes; 12Kg of isophorone diamine was added, and dispersed at high speed 30 Minutes, the obtained emulsion was transferred to a desolvent kettle, heated to 55 ° C, and maintained at a vacuum of 0.09 MPa to remove acetone; the material was filtered to obtain a translucent blue-colored aqueous polyurethane emulsion C.
  • 10Kg of deionized water is added to the batching tank, and 0.2Wg of wetting agent, 0.2Kg of pH adjuster, 0.3Kg of antifoaming agent, 0.2Kg of leveling agent, and 25.4Kg of white surface pulp are uniformly stirred and stirred.
  • 0.2Wg of wetting agent, 0.2Kg of pH adjuster, 0.3Kg of antifoaming agent, 0.2Kg of leveling agent, and 25.4Kg of white surface pulp are uniformly stirred and stirred.
  • adding to the dispersion tank adding 61Kg of the above aqueous polyurethane emulsion C, stirring for 40 minutes, adding anti-flash rust agent 2Kg and 0.7Kg thickener with stirring, stirring for 10 minutes, filtering out the material to obtain bright water-based polyurethane metal topcoat C.
  • Test items testing method Test Results Exterior Visual inspection No bubbles, no pinholes Viscosity Iwata No. 2 Cup 32S luster 60° gloss meter 70° Adhesion GB/T 9286-1998 Level 0 hardness GB/T 1732-1993 1-2H Water resistance GB/T 1733-1993 24 hours no change Impact resistance GB/T 1732-1993 ⁇ 50cm Wear resistance (750g/500r)/g ⁇ 0.02 Scratch resistance GB/T1732-1993 500g not scratched
  • 10Kg of deionized water is added to the batching tank, and 0.3Kg of wetting agent, 0.2Kg of pH regulator, 0.3Kg of defoaming agent, 0.2Kg of leveling agent, 0.5Kg of dispersing agent, 0.5Kg of zinc phosphate, and 5Kg of zinc phosphate are added.
  • 3Kg of iron oxide red and 15Kg of talc powder were uniformly dispersed and added to the dispersion tank.
  • 63Kg of the above aqueous polyurethane emulsion D was added, stirred for 40 minutes, and 2Kg of anti-flash rust agent and 0.5Kg of thickener were added while stirring, and stirred for 10 minutes. , filtering and discharging to obtain an aqueous polyurethane rust-proof iron red metal primer D.
  • Test items testing method Test Results Exterior Visual inspection No bubbles, no pinholes Viscosity Iwata No. 2 Cup 32S luster 60° gloss meter 50° Adhesion GB/T 9286-1998 Level 0 hardness GB/T 1732-1993 1-2H Water resistance GB/T 1733-1993 24 hours no change Impact resistance GB/T 1732-1993 ⁇ 50cm Wear resistance (750g/500r)/g ⁇ 0.02 Scratch resistance GB/T1732-1993 500g not scratched Stain resistance Vinegar, tea 2h by
  • a polycarbonate having a polycarbonate propylene structure of 70% by mole and a polyoxypropylene ether structure of 30% by mole of a composite polyol (molecular weight: 2000, hydroxyl value: 56 mg (KOH)/g) 200 Kg and two laurel 0.1Kg of dibutyltin acid and 0.1kg of stannous octoate were added to the reaction vessel and stirred uniformly at 60 ° C; 210 Kg of 1,6-hexyl diisocyanate was added, the temperature was raised to 80 ° C, and the reaction was carried out for 2 hours; neopentyl glycol 43.4 Kg was added.
  • the reaction was carried out at 80 ° C for 1 hour; 24.8 Kg of dimethylolpropionic acid was added, and the reaction was carried out at 70 ° C for 3 hours; the temperature was lowered to 60 ° C, 1 kg of trimethylolpropane was added, and 20 kg of acetone was added for reaction for 2 hours; the temperature was lowered to 40 ° C.
  • the second step 8Kg of deionized water is added to the batching tank, and 0.2Wg of wetting agent, 0.2Kg of pH adjuster, 0.3Kg of defoaming agent, 0.2Kg of leveling agent and 0.2Kg of leveling agent are added while stirring, and then 90Kg of the above water is added.
  • the polyurethane emulsion E was stirred for 40 minutes, 0.7 kg of a thickener was added thereto with stirring, stirred for 10 minutes, and the material was filtered to obtain an aqueous polyurethane glass varnish E.
  • Test items testing method Test Results Exterior Visual inspection Good fullness Viscosity Iwata No. 2 Cup 28S luster 60° gloss meter 85° Adhesion Baige method Level 0 hardness Pencil hardness method 1-2H Water resistance Soak at room temperature No change for 48 hours Alcohol resistant Wipe with anhydrous alcohol 50 times without revealing Blocking resistance 500g, 60°C/4h by Wear resistance (750g/500r)/g ⁇ 0.02 Scratch resistance 200g Not scratched

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明公布了一种水性聚氨酯乳液的制备方法及其应用，主要成分包括:50～100份碳酸酯结构和醚结构的复合多元醇、0.05～0.2份催化剂、异氰酸酯10～80份、交联剂1～12份、亲水扩链剂2～10份、非亲水扩链剂0～15份、丙酮30-100份、中和剂1～12份、去离子水150～400份、填料0～25份、颜料0～30份、助剂0～15份。该硬性涂料具有低成膜温度(0℃以上)、干燥快、附着力强、耐划伤、抗冲击、铅笔硬度可达2H，可用于金属、木器、玻璃、塑料、皮革等材料的涂装，该涂料应用范围广，性价比高，具有广阔的市场前景。

Description

一种水性聚氨酯乳液的制备方法及其应用 技术领域
本发明涉及一种水性聚氨酯乳液的制备方法及其在涂料领域的应用，属于水性聚氨酯涂料领域。
技术背景
水性聚氨酯是以水作为分散介质代替了溶剂的聚氨酯体系，不仅具有极低的VOC，而且不含游离的-NCO，随着人们对环保的重视，水性聚氨酯目前成为聚氨酯发展的一个重要方向。水性聚氨酯用于制备涂料，可以大幅的降低涂料中溶剂对人体的伤害，降低了成本，而且具有耐划伤、耐磨、附着力强等优势。因此，水性聚氨酯用于涂料越来越受到青睐。
目前市场上单组份自干型水性聚氨酯应用于硬性涂料的不多，主要是由于用聚醚制备的水性聚氨酯硬度远远不够，而一般聚酯型水性聚氨酯其耐水解性较差，储存期较短。能用于木器、金属、玻璃、硬革上的水性聚氨酯自干漆，一般采用聚碳酸酯多元醇才能达到相应的性能，但是因为聚碳酸酯多元醇价格高昂，常温难以成膜，附着力也较差，导致水性聚氨酯硬性乳液失去了竞争优势。本发明采用的是一种新型复合多元醇，其碳酸酯结构为聚碳酸亚丙酯结构、聚碳酸亚乙酯的一种或一种以上的混合结构；所述聚醚链段为聚氧化乙烯、聚氧化丙烯的一种或两种的混合结构；所述聚碳酸酯结构和聚醚结构都是由二氧化碳和环氧化合物聚合过程中一起生成的；此新型多元醇既具有聚醚的柔韧性和耐水性，又有聚碳酸酯多元醇的刚性和耐水解性；用此多元醇制备的水性聚氨酯硬性乳液，既有高硬的特性，又有耐冲击的特性，而且耐水、耐划伤、耐磨，储存期长，最关键的是此产品价格便宜，性价比极高。
之前的专利中，申请号为CN201010565904.0的专利中提到了一种用聚碳酸亚丙酯多元醇制备的水性聚氨酯涂料，但其性能较差，应用也不清楚，制备工业涂料是有欠缺的；申请号为CN201110180540.9提到了一种用聚碳酸亚丙酯多元醇制备的一种水性聚氨酯防火涂料；申请号为CN201110180538.1提到了一种用聚碳酸亚丙酯多元醇制备的水性聚氨酯胶黏剂；申请号为CN201310347297.4专利中公开了一种内交联型聚碳酸亚丙酯水性聚氨酯乳液的制备，对性能有所改进，但用在硬性涂料中仍然有不小差距；因此，制备一种可以满足工业化要求的水性聚氨酯硬性涂料具有非常现实的意义。
发明内容
为了弥补现有技术的空白和克服现有技术的缺点，本发明目的是提供一种水性聚氨酯乳液的制备方法及其在水性涂料尤其是高硬度水性涂料中的应用。
为了达到上述目的，本发明采用的技术方案是：一种水性聚氨酯乳液的制备方法,按质量份数配比和操作步骤：第一步，将含有聚碳酸酯结构和聚醚结构的复合多元醇50～100份、催化剂0.05～0.2份加入反应釜中，升温至50～60℃搅拌均匀，加入异氰酸酯10～80份，升温至70～85℃反应2～4小时，加入非亲水醇类扩链剂0～30份，80～90℃反应1～2小时，加入亲水扩链剂2～10份，80～90℃反应1～3小时，降温至60～70℃；加入交联剂2～10份反应1～2小时，降温至50～60℃，加入丙酮10～100份、中和剂1～16份反应10～30分钟，加入去离子水150～800份，高速分散2～30分钟，加入非亲水胺类扩链剂0～20份，高速分散5-40分钟，出料至脱溶釜，升温至50～60℃，维持真空度0.09Mpa以上脱除丙酮，过滤出料得到水性聚氨酯乳液；第二步，向配料桶中加入5～30份去离子水，加入助剂0～10份，搅拌均匀，加入所需填料0～25份，加入颜料0～30份搅拌均匀；再加入第一步制备的水性聚氨酯乳液60～100份，转至分散桶或研磨机中，搅拌、分散研磨40～60分钟，加入助剂0～5份，搅拌15～30分钟，过滤出料包装得到水性聚氨酯涂料。
所述的一种复合多元醇，其结构中含有碳酸酯结构和醚结构，其分子结构式为：
Figure PCTCN2015083566-appb-000001
其中：R’＝H或CH3，f＝2或3，x≥1，y≥1；
复合多元醇中的碳酸酯结构为聚碳酸亚丙酯结构、聚碳酸亚乙酯的一种或一种以上的混合结构；所述聚醚结构为聚氧化乙烯、聚氧化丙烯的一种或两种的混合结构；所述聚碳酸酯结构和聚醚结构都是由二氧化碳和环氧化合物聚合过程中一起生成的；所述的复合多元醇中聚碳酸酯结构所占摩尔百分比≥30％；所述的复合多元醇的平均分子量为500～5000之间。
所述的异氰酸酯包括但不限于：甲苯二异氰酸酯(TDI),二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、1,6-己基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)中一种或几种。
所述的催化剂为二月桂酸二丁基锡、辛酸亚锡、有机铋，其中的一种或几种。所述的非亲水扩链剂有醇类和胺类，包括但不限于：乙二醇、甲基丙二醇、1,2-丙二醇、1,4-丁二醇、一缩二丙二醇、1,6-己二醇、新戊二醇、乙二胺、丙二胺、二正丁胺、三甲基己二胺、异佛尔酮二胺、水合肼中的一种或几种。
所述的亲水扩链剂包括但不限于：二羟甲基丙酸、二羟甲基丁酸或N-(2-氨基乙基)-2-氨基乙烷磺酸钠(AAS盐)、2,4-二氨基苯磺酸、2-磺酸钠-1,4-丁二醇中的一种或几种。
所述的交联剂包括但不限于：三羟甲基丙烷、三乙醇胺、二乙烯三胺中的一种或几种。
所述的中和剂包括：氨水、三乙胺、三乙醇胺、氢氧化钾、氢氧化钠中的一种。所述的填料包括但不限于：钛白粉、滑石粉、硅藻土、高岭土、重质碳酸钙、轻质碳酸钙、蒙脱土中的一种或几种。
所述的颜料为：水溶性或水分散型色粉及色浆。
所述的助剂包括但不限于：流平剂、润湿剂、消泡剂、分散剂、防闪锈剂、光稳定剂、抗氧剂、增稠剂、防腐剂中的一种或几种。
水性聚氨酯乳液的应用于水性金属涂料、水性木器涂料、水性玻璃涂料、水性硬革涂层中。
本发明具有以下的优点：得到的水性聚氨酯乳液可以制备高附着力的水性涂料，在高硬度的同时具备较好的耐冲击性，在耐水性好的前提下兼顾了储存稳定性，具有低温成膜特性，干燥快等特点，应用于水性金属涂料、水性木器涂料、水性玻璃涂料、水性硬革涂层中具备很好的综合性能，具有极高性价比。
具体实施方式
下面结合具体实施例对本发明作进一步详细描述。进一步证明和描述本发明的技术方案，下述实施例仅是为了更好地理解本发明，而不作为对本发明的限制。
实施例1
第一步，将聚碳酸酯亚丙酯结构占摩尔百分比55％、聚氧化丙烯醚结构占45％摩尔百分比的复合多元醇(分子量为2500，羟值45mg(KOH)/g)200Kg与辛酸亚锡0.4Kg加入到反应釜中，50℃下搅拌均匀；加入甲苯二异氰酸酯136Kg，升温到70℃，反应2小时；加入1,4-丁二醇30Kg，80℃下反应1小时；加入二羟甲基丙酸20Kg，80℃下反应2小时；降温至60℃，加入三羟甲基丙烷5Kg并加 入丙酮40Kg反应1.5小时；降温至50℃，加入三乙胺15Kg，反应15分钟；加入水700Kg，高速分散20分钟；得到的乳液转移至脱溶釜中，升温至50℃，维持真空度0.09Mpa脱除丙酮；过滤出料得到半透明带蓝光的水性聚氨酯乳液A。第二步，取去离子水10Kg加入配料桶中，边搅拌边加入润湿剂0.3Kg、PH调节剂0.2Kg、消泡剂0.3Kg、流平剂0.2Kg分散搅拌均匀后加入到分散桶中，加入上述水性聚氨酯乳液A 88.5Kg，搅拌40分钟，边搅拌边加入0.5Kg的增稠剂，搅拌10分钟，过滤出料，得到高光水性聚氨酯木器清漆A。
对水性聚氨酯木器漆A进行喷涂后，按照国标《GB/T 23999-2009室内装饰装修用水性木器涂料》的方法进行测试，结果如下：
检测项目 测试方法 测试结果
外观 目测 丰满度好
粘度 岩田2号杯 24S
光泽 60°光泽仪 85°
附着力 百格法 0级
硬度 铅笔硬度法 2H
耐水性 常温浸泡 48小时无变化
耐酒精 50°酒精 4小时无变化
抗粘连性 500g,60℃/4h 通过
耐磨性 (750g/500r)/g≤ 0.02
耐划伤性 100g 未划伤
耐污性 醋、茶2h 通过
实施例2
第一步，将聚碳酸酯亚丙酯结构占摩尔百分比70％、聚氧化丙烯醚结构占30％摩尔百分比的复合多元醇(分子量为2000，羟值56mg(KOH)/g)200Kg与二月桂酸二丁基锡0.2Kg加入到反应釜中，60℃下搅拌均匀；加入异氟尔酮二异氰酸酯179Kg，升温到75℃，反应2小时；加入一缩二乙二醇38Kg，80℃下反应1小时；加入二羟甲基丁酸22Kg，80℃下反应2小时；降温至60℃，加入三羟甲基丙烷3Kg并加入丙酮30Kg反应2小时；降温至40℃，加入三乙胺16.7Kg，反应15 分钟；加入水750Kg，高速分散10分钟；加入乙二胺10Kg，高速分散30分钟，得到的乳液转移至脱溶釜中，升温至55℃，维持真空度0.09Mpa脱除丙酮；过滤出料得到半透明带蓝光的水性聚氨酯乳液B。
第二步，取去离子水10Kg加入配料桶中，边搅拌边加入润湿剂0.2Kg、PH调节剂0.2Kg、消泡剂0.3Kg、流平剂0.2Kg、白面浆24Kg分散搅拌均匀后加入到分散桶中，加入64Kg上述水性聚氨酯乳液B，搅拌40分钟，边搅拌边加入0.7Kg的增稠剂，搅拌10分钟，过滤出料，得到半亚光水性聚氨酯木器白面漆B。
对水性聚氨酯木器漆B进行喷涂后，按照国标《GB/T 23999-2009室内装饰装修用水性木器涂料》的方法进行测试，结果如下：
检测项目 测试方法 测试结果
外观 目测 丰满度好
粘度 岩田2号杯 26S
光泽 60°光泽仪 55°
附着力 百格法 0级
硬度 铅笔硬度法 1-2H
耐水性 常温浸泡 48小时无变化
耐酒精 50°酒精 4小时无变化
抗粘连性 500g,60℃/4h 通过
耐磨性 (750g/500r)/g≤ 0.02
耐划伤性 100g 未划伤
耐污性 醋、茶5h 通过
实施例3
第一步，将聚碳酸酯亚丙酯结构占摩尔百分比63％、聚氧化丙烯醚结构占37％摩尔百分比的复合多元醇(分子量为3000，羟值38mg(KOH)/g)200Kg与二月桂酸二丁基锡0.1Kg,辛酸亚锡0.1Kg，加入到反应釜中，60℃下搅拌均匀；加入异氟尔酮二异氰酸酯162Kg，升温到80℃，反应1小时；加入乙二醇26Kg，80℃下反应1小时；加入二羟甲基丙酸20Kg，80℃下反应2小时；降温至50℃，加 入二乙烯三胺2Kg并加入丙酮30Kg反应1小时；降温至40℃，加入三乙胺15Kg，反应15分钟；加入水761Kg，高速分散10分钟；加入异氟尔酮二胺12Kg，高速分散30分钟，得到的乳液转移至脱溶釜中，升温至55℃，维持真空度0.09Mpa脱除丙酮；过滤出料得到半透明带蓝光的水性聚氨酯乳液C。
第二步，取去离子水10Kg加入配料桶中，边搅拌边加入润湿剂0.2Kg、PH调节剂0.2Kg、消泡剂0.3Kg、流平剂0.2Kg、白面浆25.4Kg分散搅拌均匀后加入到分散桶中，加入61Kg上述水性聚氨酯乳液C，搅拌40分钟，边搅拌边加入防闪锈剂2Kg和0.7Kg的增稠剂，搅拌10分钟，过滤出料，得到亮光水性聚氨酯金属面漆C。
对水性聚氨酯金属面漆C进行喷涂后，进行性能测试，结果如下：
检测项目 测试方法 测试结果
外观 目测 无气泡、无针孔
粘度 岩田2号杯 32S
光泽 60°光泽仪 70°
附着力 GB/T 9286-1998 0级
硬度 GB/T 1732-1993 1-2H
耐水性 GB/T 1733-1993 24小时无变化
抗冲击性 GB/T 1732-1993 ≥50cm
耐磨性 (750g/500r)/g≤ 0.02
耐划伤性 GB/T1732-1993 500g未划伤
实施例4
第一步，将聚碳酸酯亚丙酯结构占摩尔百分比55％、聚氧化丙烯醚结构占45％摩尔百分比的复合多元醇(分子量为2500，羟值45mg(KOH)/g)200Kg与辛酸亚锡0.1Kg，加入到反应釜中，50℃下搅拌均匀；加入甲苯二异氰酸酯82Kg，升温到75℃，反应1小时；加入1,6-己二醇18Kg，80℃下反应1小时；加入二羟甲基丙酸12Kg，80℃下反应2小时；降温至50℃，加入三羟甲基丙烷3.5Kg并加入丙酮40Kg反应1小时；降温至40℃，加入三乙胺9.5Kg，反应10分钟；加入水572Kg，高速分散5分钟；加入水合肼6Kg，高速分散30分钟，得到的乳液 转移至脱溶釜中，升温至50℃，维持真空度0.09Mpa脱除丙酮；过滤出料得到半透明带蓝光的水性聚氨酯乳液D。
第二步，取去离子水10Kg加入配料桶中，边搅拌边加入润湿剂0.3Kg、PH调节剂0.2Kg、消泡剂0.3Kg、流平剂0.2Kg、分散剂0.5Kg磷酸锌5Kg、氧化铁红3Kg、滑石粉15Kg分散搅拌均匀后加入到分散桶中，加入63Kg上述水性聚氨酯乳液D，搅拌40分钟，边搅拌边加入防闪锈剂2Kg和0.5Kg的增稠剂，搅拌10分钟，过滤出料，得到水性聚氨酯防锈铁红金属底漆D。
对水性聚氨酯防锈铁红金属底漆D进行喷涂后，进行性能测试，结果如下：
检测项目 测试方法 测试结果
外观 目测 无气泡、无针孔
粘度 岩田2号杯 32S
光泽 60°光泽仪 50°
附着力 GB/T 9286-1998 0级
硬度 GB/T 1732-1993 1-2H
耐水性 GB/T 1733-1993 24小时无变化
抗冲击性 GB/T 1732-1993 ≥50cm
耐磨性 (750g/500r)/g≤ 0.02
耐划伤性 GB/T1732-1993 500g未划伤
耐污性 醋、茶2h 通过
实施例5
第一步，将聚碳酸酯亚丙酯结构占摩尔百分比70％、聚氧化丙烯醚结构占30％摩尔百分比的复合多元醇(分子量为2000，羟值56mg(KOH)/g)200Kg与二月桂酸二丁基锡0.1Kg、辛酸亚锡0.1kg，加入到反应釜中，60℃下搅拌均匀；加入1,6-己基二异氰酸酯210Kg，升温到80℃，反应2小时；加入新戊二醇43.4Kg，80℃下反应1小时；加入二羟甲基丙酸24.8Kg，70℃下反应3小时；降温至60℃，加入三羟甲基丙烷1Kg并加入丙酮20Kg反应2小时；降温至40℃，加入三乙胺18.7Kg，反应15分钟；加入水700Kg，高速分散15分钟；加入三乙烯二胺5Kg，高速分散30分钟，得到的乳液转移至脱溶釜中，升温至55℃，维持真空度0.09Mpa 脱除丙酮；过滤出料得到半透明带蓝光的水性聚氨酯乳液E。
第二步，取去离子水8Kg加入配料桶中，边搅拌边加入润湿剂0.2Kg、PH调节剂0.2Kg、消泡剂0.3Kg、流平剂0.2Kg分散搅拌均匀后，加入90Kg上述水性聚氨酯乳液E，搅拌40分钟，边搅拌边加入0.7Kg的增稠剂，搅拌10分钟，过滤出料，得到水性聚氨酯玻璃清漆E。
对水性聚氨酯木器漆E进行喷涂后，进行测试，结果如下：
检测项目 测试方法 测试结果
外观 目测 丰满度好
粘度 岩田2号杯 28S
光泽 60°光泽仪 85°
附着力 百格法 0级
硬度 铅笔硬度法 1-2H
耐水性 常温浸泡 48小时无变化
耐酒精 无水酒精擦拭 50次不露底
抗粘连性 500g,60℃/4h 通过
耐磨性 (750g/500r)/g≤ 0.02
耐划伤性 200g 未划伤

Claims (10)

  1. 一种水性聚氨酯乳液的制备方法,其特征在于以下按质量份数配比和操作步骤：第一步，将含有聚碳酸酯结构和聚醚结构的复合多元醇50～100份、催化剂0.05～0.2份加入反应釜中，升温至50～60℃搅拌均匀，加入异氰酸酯10～80份，升温至70～85℃反应2～4小时，加入非亲水醇类扩链剂0～30份，80～90℃反应1～2小时，加入亲水扩链剂2～10份，80～90℃反应1～3小时，降温至60～70℃；加入交联剂2～10份反应1～2小时，降温至50～60℃，加入丙酮10～100份、中和剂1～16份反应10～30分钟，加入去离子水150～800份，高速分散2～30分钟，加入非亲水胺类扩链剂0～20份，高速分散5-40分钟，出料至脱溶釜，升温至50～60℃，维持真空度0.09Mpa以上脱除丙酮，过滤出料得到水性聚氨酯乳液；第二步，向配料桶中加入5～30份去离子水，加入助剂0～10份，搅拌均匀，加入所需填料0～25份，加入颜料0～30份搅拌均匀；再加入第一步制备的水性聚氨酯乳液60～100份，转至分散桶或研磨机中，搅拌、分散研磨40～60分钟，加入助剂0～5份，搅拌15～30分钟，过滤出料包装得到水性聚氨酯涂料。
  2. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的一种复合多元醇，其结构中含有聚碳酸酯结构和聚醚结构，其分子结构式为：
    Figure PCTCN2015083566-appb-100001
    其中：R’＝H或CH3，f＝2或3，x≥1，y≥1。
    复合多元醇中的聚碳酸酯结构为聚碳酸亚丙酯结构、聚碳酸亚乙酯的一种或一种以上的混合结构；所述聚醚结构为聚氧化乙烯、聚氧化丙烯的一种或两种的混合结构；所述聚碳酸酯结构和聚醚结构都是由二氧化碳和环氧化合物聚合过程中一起生成的；所述的复合多元醇中聚碳酸酯结构所占摩尔百分比≥30％；所述的复合多元醇的平均分子量为500～5000之间。
  3. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的异氰酸酯包括：甲苯二异氰酸酯(TDI),二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、1,6-己基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)中一种或几种。
  4. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的催化剂为二月桂酸二丁基锡、辛酸亚锡、有机铋中的一种或几种。
  5. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的非亲水扩链剂有醇类和胺类，包括：乙二醇、甲基丙二醇、1,2-丙二醇、1,4-丁二醇、一缩二丙二醇、1,6-己二醇、新戊二醇、乙二胺、丙二胺、二正丁胺、三甲基己二胺、异佛尔酮二胺、水合肼中的一种或几种。
  6. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的亲水扩链剂包括：二羟甲基丙酸、二羟甲基丁酸或N-(2-氨基乙基)-2-氨基乙烷磺酸钠(AAS盐)、2,4-二氨基苯磺酸、2-磺酸钠-1,4-丁二醇中的一种或几种。
  7. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的交联剂包括但不限于：三羟甲基丙烷、三乙醇胺、二乙烯三胺中的一种或几种。
  8. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的中和剂包括：氨水、三乙胺、三乙醇胺、氢氧化钾、氢氧化钠中的一种。
  9. 根据权利要求1所述的一种水性聚氨酯乳液的制备方法，其特征在于：所述的填料包括：钛白粉、滑石粉、硅藻土、高岭土、重质碳酸钙、轻质碳酸钙、蒙脱土中的一种或几种；所述的颜料为水溶性或水分散型色粉及色浆；所述的助剂包括：流平剂、润湿剂、消泡剂、分散剂、防闪锈剂、光稳定剂、抗氧剂、增稠剂、防腐剂中的一种或几种。
  10. 一种水性聚氨酯乳液的应用，用于水性金属涂料、水性木器涂料、水性玻璃涂料、水性硬革涂层中。
PCT/CN2015/083566 2014-11-07 2015-07-08 一种水性聚氨酯乳液的制备方法及其应用 WO2016070644A1 (zh)

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