CN117003986A - Aqueous polyurethane dispersion and preparation method and application thereof - Google Patents

Aqueous polyurethane dispersion and preparation method and application thereof Download PDF

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Publication number
CN117003986A
CN117003986A CN202311051618.6A CN202311051618A CN117003986A CN 117003986 A CN117003986 A CN 117003986A CN 202311051618 A CN202311051618 A CN 202311051618A CN 117003986 A CN117003986 A CN 117003986A
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polyol
parts
aqueous polyurethane
prepolymer
polyurethane dispersion
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李伽宁
刘文杰
邱贵森
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Mojia Shanghai Biotechnology Co ltd
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Mojia Shanghai Biotechnology Co ltd
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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
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

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

Abstract

The application provides an aqueous polyurethane dispersion, which is prepared from the following raw materials in parts by weight: 7-15 parts of isocyanate, 25-43 parts of polyol and 0.2-2 parts of reactive internal emulsifier, wherein the isocyanate comprises 1, 5-pentamethylene diisocyanate; the mass percentage of the 1, 5-pentamethylene diisocyanate in the isocyanate is more than or equal to 30 percent, the viscosity of the aqueous polyurethane dispersion is less than 800 (23 ℃ C., mPa.s), the light transmittance is more than 89 percent, and the water absorption is less than 4 percent.

Description

Aqueous polyurethane dispersion and preparation method and application thereof
Technical Field
The application belongs to the technical field of polyurethane, and particularly relates to a waterborne polyurethane dispersoid and a preparation method and application thereof.
Background
The aqueous polyurethane dispersion (PUD) is a common film forming agent and is widely applied to the fields of paint, adhesives, textiles and the like. The film component can provide excellent mechanical properties and excellent surface decoration properties such as water resistance, wear resistance, weather resistance and the like.
In the conventional aqueous polyurethane dispersion, low-boiling point solvents such as acetone, methyl ethyl ketone and the like are required to be added in the preparation process to reduce the viscosity of the prepolymer, so that the prepolymer can be rapidly dispersed in water, and meanwhile, the low-boiling point solvents in the dispersion are removed by adopting a reduced pressure distillation mode after the dispersion is finished, so that the aqueous polyurethane dispersion with low solvent residues is prepared. However, this process requires not only a large amount of the solvent of class a but also a high energy-consuming process such as distillation and rectification.
There are also a number of aqueous polyurethane dispersions employing high boiling water-soluble aprotic solvents such as: n-methylpyrrolidone, N-ethylpyrrolidone, dipropylene glycol dimethyl ether and the like are used as solvents in the prepolymerization reaction, and the solvents remain as one component of the PUD after the completion of the preparation of the PUD. The high boiling point solvent not only reduces the viscosity of the prepolymer, but also can remain in the dispersion to improve the film forming property, glossiness and other properties of the dispersion. However, the PUD prepared by the process has the disadvantages of high VOC, long drying time, possible toxicity of high boiling point solvents, and the like.
CN113039322a prepared an aqueous polyurethane dispersion that was completely free of solvent. The process uses a special emulsification process, and requires high-speed dispersion to prepare stable PUD when the prepolymer is mixed with an emulsifier and the mixture is emulsified, and the emulsifier solution is easy to react when the emulsifier solution is mixed with the prepolymer, so that the viscosity rises, and gel is initiated.
CN113302221a disperses a prepolymer containing a hydrophilic group into an aqueous solution containing a polyaminosulfonate, and an alkali metal hydroxide or a nonvolatile organic tertiary amine as a neutralizing agent and other components, to prepare a high-solid PUD substantially free of volatile organic compounds. The preparation method has the advantages of simple process, high emulsion solid content, extremely low TVOC and the like. However, the PUD prepared by the process uses the carboxyl as a neutralizing agent, and the carboxyl still exists in the form of carboxylate after film formation, so that the water resistance of a coating film can be greatly reduced, and simultaneously, the crosslinking agent containing epoxy, aziridine, carbodiimide and the like and capable of reacting with the carboxyl can not be crosslinked, so that the application range of the resin is greatly reduced.
Because the aqueous polyurethane dispersoid in the prior art has the problems of organic solvent, poor light transmittance, poor water resistance, high viscosity and the like in the preparation process. Therefore, development of an aqueous polyurethane dispersion which has low viscosity, does not require an organic solvent, has high light transmittance and low water absorption rate is a problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the application aims to provide an aqueous polyurethane dispersion, a preparation method and application thereof, wherein the content of 1, 5-Pentamethylene Diisocyanate (PDI) in the prepolymer isocyanate component of the aqueous polyurethane dispersion is more than 30 percent, the viscosity is less than 800 (23 ℃, mPa.s), the light transmittance is more than 89 percent, and the water absorption is less than 4 percent.
To achieve the purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides an aqueous polyurethane dispersion, the preparation raw materials of the aqueous polyurethane dispersion comprising a combination of a prepolymer, a chain extender and an external emulsifier, the preparation raw materials of the prepolymer comprising, in parts by weight: 7-15 parts of isocyanate (for example, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 13 parts, 15 parts, and specific point values between the above point values are not exhaustive of the specific point values included in the range, for reasons of space and brevity), 25-43 parts of polyol (for example, 25 parts, 26 parts, 28 parts, 30 parts, 35 parts, 40 parts, 43 parts, and specific point values between the above point values are not exhaustive of the specific point values included in the range, for reasons of space and brevity), 0.2-2 parts of reactive internal emulsifier (for example, 0.2 parts, 0.3 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, and specific point values between the above point values are not exhaustive, for reasons of space and brevity, the specific point values included in the range are not exhaustive), and the isocyanate comprises 1, 5-pentamethylene diisocyanate; the mass percent of 1, 5-pentamethylene diisocyanate in the isocyanate is more than or equal to 30 percent (for example, 30 percent, 35 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 100 percent, and the specific point values among the above point values are limited in space and for the sake of brevity, the application is not intended to exhaustively list the specific point values included in the range.
Preferably, the isocyanate further comprises any one or a combination of at least two of isophorone diisocyanate, hexamethylene Diisocyanate (HDI) or dicyclohexylmethane diisocyanate.
PDI is a special linear odd-carbon diisocyanate having lower crystallinity than HDI, and when used in the preparation of a prepolymer of an aqueous polyurethane dispersion, it can reduce the viscosity of the prepolymer due to its relatively lower crystallinity, and at the same time, its low crystallinity can prevent the prepolymer from being structured into gel form during emulsification, resulting in emulsification failure. Meanwhile, the PDI has higher reactivity compared with other aliphatic diisocyanates, the reactivity of the PDI with water is close to that of the aromatic diisocyanate, and the emulsion particles can be quickly formed during phase inversion due to the high reactivity of the PDI.
Preferably, the polyol comprises any one or a combination of at least two of a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polyethylene oxide polyol, a polypropylene oxide polyol, an ethylene oxide-propylene oxide copolyol, a polytetrahydrofuran polyol, a poly 1, 3-propylene glycol ether polyol, a vegetable oil polyol, a polyesteramide polyol, a polythioether polyol, a polyacetal polyol, a polyolefin polyol, or a polysiloxane polyol.
Preferably, the polyol comprises any one or a combination of at least two of polycarbonate diol, ethylene oxide propylene oxide co-diol, polypropylene oxide diol, polytetrahydrofuran diol, polycaprolactone diol, polybutylene adipate diol, or polyethylene oxide diol.
Preferably, the polyols have a number average molecular weight of 300-5000, and may be, for example, 300, 400, 500, 1000, 2000, 3000, 4000, 5000, and specific point values between the above point values, although for brevity and for simplicity, the application is not intended to be exhaustive of the specific point values encompassed by the described ranges.
Preferably, the reactive internal emulsifier includes a hydrophilic polyol type internal emulsifier and a water-soluble polyamine type internal emulsifier.
Preferably, the reactive internal emulsifier comprises any one or a combination of at least two of dimethylolpropionic acid, dimethylolbutyric acid or polyethylene glycol monomethyl ether, sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate, lysine, 3- (2-aminoethylamino) propane-1-sulfonic acid or sodium N- (2-aminoethyl) -beta-alaninate.
Preferably, the preparation raw materials of the prepolymer further comprise 0-2000ppm of catalyst in parts by weight, for example, 1ppm, 5ppm, 10ppm, 100ppm, 500ppm, 1000ppm, 2000ppm, and specific point values among the above point values, and the present application is not exhaustive of the specific point values included in the range for the sake of brevity and conciseness.
Preferably, the catalyst comprises an organobismuth catalyst.
Preferably, the prepolymer has an NCO group content of 5 to 10% by mass, for example 5%, 6%, 7%, 8%, 9%, 10% and specific point values between the above point values, and the application is not intended to be exhaustive of the specific point values included in the range given for reasons of space and for reasons of simplicity.
Preferably, the preparation raw materials of the aqueous polyurethane dispersion further comprise a neutralizing agent.
Preferably, the preparation raw materials of the aqueous polyurethane dispersion comprise the following components in parts by weight: 40 parts of prepolymer, 1.4-2.5 parts of chain extender (e.g., 1.4 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, and specific point values between the above point values, limited in space and for brevity, the application is not exhaustive of the specific point values included in the ranges), 0.1-0.8 parts of neutralizing agent (e.g., 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.6 parts, 0.7 parts, 0.8 parts, and specific point values between the above point values, limited in space and for brevity, the present application is not intended to be exhaustive list of the specific point values included in the range), 0.2 to 1 part of external emulsifier (e.g., may be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, and specific point values between the above point values), 38 to 60 parts of water (e.g., may be 38 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, and specific point values between the above point values), is not intended to be exhaustive list of the specific point values included in the range for brevity and conciseness.
Preferably, the chain extender comprises any one or a combination of at least two of hydrazine hydrate, ethylenediamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, piperazine, 2-methylpiperazine, 5-amino-1, 3-trimethyl-cyclohexanemethyl amine or diethylenetriamine.
Preferably, the neutralizing agent comprises any one or a combination of at least two of alkali metal hydroxide, alkali metal carbonate, organic tertiary amine, alcohol amine, 2-amino-2-methyl-1-propanol, methyldiethanolamine, dimethylethanolamine, diethylethanolamine, triisopropanolamine, aqueous ammonia, or triethylamine.
Preferably, the external emulsifier comprises any one or a combination of at least two of anionic surfactant, cationic surfactant, nonionic surfactant, polyvinyl alcohol or water-soluble cellulose.
Preferably, the external emulsifier comprises any one or a combination of at least two of fatty alcohol ether sodium sulfate, succinic acid alkyl polyoxyethylene ether monoester disodium sulfonate or dodecyl benzene sulfonate.
In a second aspect, the present application provides a process for the preparation of an aqueous polyurethane dispersion according to the first aspect, the process comprising:
(1) Mixing isocyanate, polyalcohol and a reactive internal emulsifier, and reacting to obtain a prepolymer;
(2) And (3) mixing the prepolymer obtained in the step (1), a chain extender and an external emulsifier, and reacting to obtain the aqueous polyurethane dispersion.
Preferably, the preparation method specifically comprises the following steps:
(1) Mixing isocyanate, polyalcohol, a reactive internal emulsifier and a catalyst, and reacting to obtain a prepolymer;
(2) And (3) mixing the prepolymer obtained in the step (1), a chain extender, a neutralizing agent and an external emulsifier, and reacting to obtain the aqueous polyurethane dispersion.
Preferably, the temperature of the reaction in step (1) is 50-100 ℃, for example 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, and specific values between the above values, the application not being exhaustive of the specific values included in the range for reasons of space and for reasons of simplicity.
Preferably, the reaction time in step (1) is 2-10h, for example, 2h, 3h, 5h, 8h, 10h, and the specific point values between the above point values, are limited in space and for the sake of brevity, the present application is not exhaustive of the specific point values included in the range.
Preferably, the mixing of step (2) is performed with stirring.
Preferably, the stirring rate is 200-800rpm, for example, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, and specific point values between the above point values, are limited in space and for the sake of brevity, the present application is not exhaustive of the specific point values included in the ranges.
Preferably, the temperature of the reaction in step (2) is 15-40 ℃, for example, 15 ℃, 16 ℃,20 ℃, 25 ℃, 30 ℃, 35 ℃, 38 ℃, 40 ℃, and specific values between the above values, are limited in space and for the sake of brevity, and the present application is not exhaustive of the specific values included in the range.
Preferably, the reaction time in step (2) is 40-120min, for example, 40min, 42min, 45min, 50min, 60min, 62min, 65min, 70min, 75min, 80min, 90min, 100min, 110min, 120min, and specific point values among the above point values, which are limited in space and for brevity, the present application is not exhaustive.
The hydrophilic groups are introduced into the polyurethane chain segments to endow the polyurethane with certain water dispersibility, and the polyurethane is realized by adding the reactive internal emulsifier. The reactive internal emulsifier may be added in the form of a hydrophilic polyol in the prepolymer stage or in the form of a water-soluble polyamine in the post-chain extension stage.
The preparation method specifically comprises the following steps:
(1) Reacting polyisocyanate, polyol and hydrophilic polyol type internal emulsifier at 50-100 ℃ to prepare a polyurethane prepolymer containing PDI, wherein the prepolymer has lower viscosity;
(2) Slowly adding the polyurethane prepolymer prepared by the method into other added water mixtures containing chain extender, neutralizer, water-soluble polyamine internal emulsifier, external emulsifier and the like with the dispersion speed of 200-800rpm within 40-120min, controlling the reaction temperature below 40 ℃ through a jacket and the dropping speed of the prepolymer until the prepolymer is completely dropped, then continuously controlling the temperature and dispersing for more than 60min, and finally filtering and discharging.
In a third aspect, the application provides the use of an aqueous polyurethane dispersion according to the first aspect in coatings, adhesives, textiles.
Compared with the prior art, the application has the following beneficial effects:
according to the aqueous polyurethane dispersion, the preparation method and the application thereof, when the PDI content in the isocyanate component of the prepolymer is more than or equal to 30%, and the polyurethane prepolymer prepared by adopting high NCO/OH ratio and having higher content of free isocyanate NCO% (5% -10%), has lower viscosity at a lower temperature (50-100 ℃), and is easy to disperse. The obtained emulsion has lower viscosity and particle size, and when the solid content is 39.98-44.6%, the particle size of the emulsion is 68-102nm, and the viscosity is 217-463mPa.s; when the solid content is 55.09-59.3%, the particle size of the emulsion is 186-201nm, the viscosity is 677-792 Pa.s, when the PDI content in the prepolymer isocyanate component is more than or equal to 30%, the water absorption rate of the adhesive film is 2.2-3.8%, the light transmittance is more than 89%, and the light transmittance is 89.1-92.1%. When the PDI content is more than or equal to 70% and less than or equal to 90%, the light transmittance is more than 91%, and can reach 91.1-92.1%.
Detailed Description
The technical scheme of the application is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and are not to be construed as a specific limitation thereof.
The experimental materials used in the examples and comparative examples of the present application are as follows:
(1) Polycarbonate diol, brand, UH200, manufacturer, department of Yu;
(2) Polypropylene oxide diol, brand, PPG2000, manufacturer, national chemistry;
(3) Polytetrahydrofuran diol, brand, PTMG2000, manufacturer, BASF;
(4) Polycaprolactone diol, brand, CAPA2101A, manufacturer, injevelet; brand CAPA2201A, manufacturer, injevelet;
(5) Polybutylene adipate glycol, trade mark, XCP-44, manufacturer, chuangchuang chemical;
(6) Polyethylene oxide glycol, brand, PEG1000, manufacturer, eastern chemistry;
(7) Dimethylolpropionic acid, manufacturer, pascals;
(8) Linear difunctional polyethylene glycol monomethyl ether, trade name, ymerN120, manufacturer, pascals;
(9) Isophorone diisocyanate, manufacturer, scientific;
(10) Dicyclohexylmethane diisocyanate, manufactured by manufacturers, created by science;
(11) 1, 6-hexamethylene diisocyanate, manufacturer, scientific creation;
(12) 85% hydrazine hydrate solution, manufacturer, national drug reagent;
(13) 95% 2-amino-2-methyl-1-propanol solution, trade mark, AMP-95, manufacturer, angust;
(14) An aqueous solution of succinic acid alkyl polyoxyethylene ether monoester disodium sulfonate, the brand of which is AEROSOL A-102, manufacturer, sorvol;
(15) Triethylamine, manufacturer, national medicine reagent;
(16) Acetone, manufacturer, national drug reagent;
(17) Butanediol BDO, manufacturers, national drug agents;
(18) Sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate, vestamina95 (50% active ingredient), manufacturer, earned.
Example 1
The embodiment provides an aqueous polyurethane dispersion and a preparation method thereof, wherein the preparation raw materials of the aqueous polyurethane dispersion comprise: 100g of polycarbonate diol UH200, 300g of polytetrahydrofuran ether glycol PTMEG2000, 10g of dimethylolpropionic acid DMPA, 0.5g of organobismuth catalyst Valikat Bi2010, 70g of 1, 5-pentamethylene diisocyanate PDI, 30g of isophorone diisocyanate IPDI, 16.26g of 85% hydrazine hydrate, 6.65g of neutralizer AMP-95, 8g of AEROSOL A102 and 500g of deionized water.
The preparation method comprises the following steps:
adding polycarbonate dihydric alcohol UH200, polytetrahydrofuran ether glycol PTMEG2000, dimethylolpropionic acid DMPA and an organic bismuth catalyst Valikat Bi2010 into a flask provided with a thermometer and mechanical stirring, heating to 80 ℃ and uniformly stirring, then adding 1, 5-pentamethylene diisocyanate PDI and isophorone diisocyanate IPDI, uniformly stirring, slowly heating to 93-97 ℃, measuring NCO content less than 5.8% by using a di-n-butylamine method, obtaining a prepolymer, and cooling to 80 ℃;
uniformly mixing 85% hydrazine hydrate, a neutralizer AMP-95, AEROSOL 102 and deionized water, controlling the temperature of the mixed solution at 18 ℃, slowly adding 400g of the prepared prepolymer into the mixed solution within 60min at a dispersion speed of 450rpm, and controlling the temperature of the mixed solution below 40 ℃; after the prepolymer is added dropwise, continuing to disperse for 60min, and filtering by a 200-mesh filter screen to obtain the aqueous polyurethane dispersoid.
Examples 2 to 9
Examples 2 to 9 provide an aqueous polyurethane dispersion and a method for producing the same, the raw materials for producing the aqueous polyurethane dispersion being different from example 1 as shown in table 1, and the method for producing the same being the same as example 1.
TABLE 1
Comparative example 1
The comparative example provides an aqueous polyurethane dispersion and a preparation method thereof, wherein the preparation raw materials of the aqueous polyurethane dispersion comprise: 100g of polycarbonate diol UH200, 300g of polytetrahydrofuran ether glycol PTMEG2000, 10g of dimethylolpropionic acid DMPA, 0.5g of organobismuth catalyst Valikat Bi2010, 30g of 1, 5-pentamethylene diisocyanate PDI, 90g of isophorone diisocyanate IPDI, 16.11g of 85% hydrazine hydrate, 6.65g of neutralizer AMP-95, 8g of AEROSOL A102 and 500g of deionized water.
The preparation method comprises the following steps:
adding polycarbonate dihydric alcohol UH200, polytetrahydrofuran ether glycol PTMEG2000, dimethylolpropionic acid DMPA and an organic bismuth catalyst Valikat Bi2010 into a flask provided with a thermometer and mechanical stirring, heating to 80 ℃ and uniformly stirring, then adding 1, 5-pentamethylene diisocyanate PDI and isophorone diisocyanate IPDI, uniformly stirring, slowly heating to 93-97 ℃, measuring NCO content to 5.8% by a di-n-butylamine method, completing preparation of a prepolymer, and cooling to 80 ℃;
uniformly mixing 85% hydrazine hydrate, a neutralizer AMP-95, AEROSOL 102 and deionized water, controlling the temperature of the mixed solution at 18 ℃, slowly adding 400g of the prepared prepolymer into the mixed solution within 60min at a dispersion speed of 450rpm, and controlling the temperature of the mixed solution below 40 ℃; after the prepolymer is added dropwise, continuing to disperse for 60min, and filtering by a 200-mesh filter screen to obtain the aqueous polyurethane dispersoid.
Comparative examples 2 to 5
Comparative examples 2 to 5 provide an aqueous polyurethane dispersion, the raw materials for the preparation of which are different from those of comparative example 1 as shown in table 2, and a preparation method thereof, which is the same as that of comparative example 1.
TABLE 2
The aqueous polyurethane dispersions provided in examples 1-9 and comparative examples 1-5 were subjected to performance testing as follows:
(1) Viscosity: a Brookfield DV2T assay is used;
(2) Particle size: measuring by using a Markov laser particle size analyzer;
(3) Water absorption rate: immersing the dried and weighed adhesive film in water for 1H, and then measuring the water absorption capacity of the adhesive film;
and (3) preparation of an adhesive film: applying the dispersion to a glass sheet at a thickness of 400-600 μm, then drying at room temperature for 24 hours, and then drying in an oven at 80 ℃ for 8 hours to prepare a film having a dry film thickness of about 300 μm;
(4) Transmittance: the method is adopted for measurement by a GB/T2410-2008 method;
(5) Solid content: measured by GB-T1725-2007.
The aqueous polyurethane dispersions provided in examples 1-9 and comparative examples 1-5 were subjected to performance tests, and the test results are shown in tables 3-4:
TABLE 3 Table 3
TABLE 4 Table 4
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From the data in tables 3 to 4, examples 1 to 9 show that at a solids content of 39.98 to 49.83%, the particle size distribution of the emulsion is 68 to 118nm and the viscosity is 217 to 632mPa.s; the emulsion has a particle size distribution of 136-201nm at a solid content of 50.42-59.3%, a viscosity of 677-792 Pa.s, and when the PDI content in the prepolymer isocyanate component is more than or equal to 30% and less than 90%, the light transmittance of the adhesive film gradually increases from 89% to 92% and has the highest light transmittance of 92.1% at a PDI content of 75%, and the water absorption of the adhesive film rapidly decreases and is stabilized at a lower level with the increase of the PDI content. When PDI is not added in the formula, the particle size of the comparative example 1 is larger, the viscosity of the comparative example 2 is too large, the fluidity is not available, the prepolymer of the comparative example 3 is large in viscosity and cannot be dispersed, and when about 50% of the prepolymer of the comparative example 4 is added in the emulsification process, the emulsion gel fails; the amount of the internal emulsifier used in comparative example 5 was outside the preferred range, and no external emulsifier was added, and the obtained particle size was large, the water absorption was high, and the light transmittance was low. The linear odd-numbered 1, 5-pentamethylene diisocyanate used in the PUD of the present application has low crystallinity compared to even-numbered 1, 6-hexamethylene diisocyanate, and has higher crystallinity and shorter molecular segments compared to isophorone diisocyanate and dicyclohexylmethane diisocyanate; the shorter molecular chain segments and low crystallinity can help the emulsion form smaller particle size and lower viscosity at the same solid content, and the smaller particle size and proper crystallinity can greatly improve the film forming compactness of the resin, thereby obtaining higher water resistance. When the PDI content is less than 30%, the phase inversion speed becomes slow, resulting in a larger emulsion particle size. Compared with PDI, HDI has high viscosity due to severe crystallization phenomenon in the preparation process of the prepolymer caused by too high crystallinity, and when the prepolymer containing a large amount of HDI is dispersed, the prepolymer cannot be phase-inverted due to too high crystallinity, so that gel occurs.
The applicant states that the present application is illustrated by the above examples as an aqueous polyurethane dispersion of the present application and a method for preparing the same and applications thereof, but the present application is not limited to the above examples, i.e., it does not mean that the present application must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present application, equivalent substitution of raw materials for the product of the present application, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present application and the scope of disclosure.

Claims (10)

1. The preparation raw materials of the aqueous polyurethane dispersion comprise a combination of a prepolymer, a chain extender and an external emulsifier, and the preparation raw materials of the prepolymer comprise the following components in parts by weight: 7-15 parts of isocyanate, 25-43 parts of polyol and 0.2-2 parts of reactive internal emulsifier, wherein the isocyanate comprises 1, 5-pentamethylene diisocyanate; the mass percentage of the 1, 5-pentamethylene diisocyanate in the isocyanate is more than or equal to 30 percent.
2. The aqueous polyurethane dispersion according to claim 1, wherein said isocyanate further comprises any one or a combination of at least two of isophorone diisocyanate, hexamethylene diisocyanate, or dicyclohexylmethane diisocyanate;
preferably, the polyol comprises any one or a combination of at least two of a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polyethylene oxide polyol, a polypropylene oxide polyol, an ethylene oxide-propylene oxide copolyol, a polytetrahydrofuran polyol, a poly 1, 3-propylene glycol ether polyol, a vegetable oil polyol, a polyesteramide polyol, a polythioether polyol, a polyacetal polyol, a polyolefin polyol, or a polysiloxane polyol;
preferably, the polyol comprises any one or a combination of at least two of polycarbonate diol, ethylene oxide propylene oxide co-diol, polypropylene oxide diol, polytetrahydrofuran diol, polycaprolactone diol, polybutylene adipate diol, or polyethylene oxide diol;
preferably, the polyol has a number average molecular weight of 300 to 5000;
preferably, the reactive internal emulsifier comprises any one or a combination of at least two of dimethylolpropionic acid, dimethylolbutyric acid, polyethylene glycol monomethyl ether, sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate, lysine, 3- (2-aminoethylamino) propane-1-sulfonic acid or sodium N- (2-aminoethyl) -beta-alanine;
preferably, the preparation raw materials of the prepolymer also comprise 0-2000ppm of catalyst in parts by weight;
preferably, the catalyst comprises an organobismuth catalyst;
preferably, the mass percentage of NCO groups in the prepolymer is 5-10%.
3. The aqueous polyurethane dispersion according to claim 1 or 2, wherein the raw materials for preparing the aqueous polyurethane dispersion further comprise a neutralizing agent and a solvent;
preferably, the preparation raw materials of the aqueous polyurethane dispersion comprise the following components in parts by weight: 40 parts of prepolymer, 1.4-2.5 parts of chain extender, 0.1-0.8 part of neutralizer, 0.2-1 part of external emulsifier and 38-60 parts of water;
preferably, the chain extender comprises any one or a combination of at least two of hydrazine hydrate, ethylenediamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, piperazine, 2-methylpiperazine, 5-amino-1, 3-trimethyl-cyclohexanemethyl amine or diethylenetriamine;
preferably, the neutralizing agent comprises any one or a combination of at least two of alkali metal hydroxide, alkali metal carbonate, organic tertiary amine, alcohol amine, 2-amino-2-methyl-1-propanol, methyldiethanolamine, dimethylethanolamine, diethylethanolamine, triisopropanolamine, aqueous ammonia, or triethylamine.
4. The aqueous polyurethane dispersion according to any one of claims 1 to 3, wherein the external emulsifier comprises any one or a combination of at least two of anionic surfactant, cationic surfactant, nonionic surfactant, polyvinyl alcohol or water-soluble cellulose;
preferably, the external emulsifier comprises any one or a combination of at least two of fatty alcohol ether sodium sulfate, succinic acid alkyl polyoxyethylene ether monoester disodium sulfonate or dodecyl benzene sulfonate.
5. A process for the preparation of an aqueous polyurethane dispersion according to any one of claims 1 to 4, comprising:
(1) Mixing isocyanate, polyalcohol and a reactive internal emulsifier, and reacting to obtain a prepolymer;
(2) And (3) mixing the prepolymer obtained in the step (1), a chain extender and an external emulsifier, and reacting to obtain the aqueous polyurethane dispersion.
6. The preparation method according to claim 5, characterized in that it comprises in particular:
(1) Mixing isocyanate, polyalcohol, a reactive internal emulsifier and a catalyst, and reacting to obtain a prepolymer;
(2) And (3) mixing the prepolymer obtained in the step (1), a chain extender, a neutralizing agent and an external emulsifier, and reacting to obtain the aqueous polyurethane dispersion.
7. The process according to claim 5 or 6, wherein the temperature of the reaction in step (1) is 50-100 ℃;
preferably, the reaction time of step (1) is 2-20 hours.
8. The method of any one of claims 5-7, wherein the mixing of step (2) is performed with stirring;
preferably, the stirring is at a rate of 200-800rpm.
9. The method of any one of claims 5-8, wherein the temperature of the reaction of step (2) is 15-40 ℃;
preferably, the reaction time of step (2) is 40-120min.
10. Use of the aqueous polyurethane dispersion according to any of claims 1 to 4 in coatings, adhesives, textiles.
CN202311051618.6A 2023-08-21 2023-08-21 Aqueous polyurethane dispersion and preparation method and application thereof Pending CN117003986A (en)

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