CN110713705A - Water-based polyurethane emulsion with interpenetrating network structure and preparation method and application thereof - Google Patents
Water-based polyurethane emulsion with interpenetrating network structure and preparation method and application thereof Download PDFInfo
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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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- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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Abstract
The invention belongs to the technical field of new polymer materials, and particularly relates to an interpenetrating network structure aqueous polyurethane emulsion, and a preparation method and application thereof. According to the invention, the polypropylene carbonate dihydric alcohol, the diisocyanate and the reactive monomer are adopted as main raw materials, and the interpenetrating network structure is introduced through molecular design, so that the waterborne polyurethane emulsion with the interpenetrating network structure has more excellent water resistance, hardness and tensile strength, has good comprehensive performance, and can solve the problems of low hardness, no scratch resistance, poor water resistance and the like of the existing waterborne polyurethane emulsion. In addition, the raw materials of the water-based polyurethane emulsion with the interpenetrating network structure do not need organic solvents, acetone does not need to be used as a solvent in the preparation process to reduce the system viscosity, the reactive monomer can reduce the system viscosity, the use of the organic solvents is avoided, the discharge problem of VOC is further solved, and the pollution to the environment and the harm to the health are reduced.
Description
Technical Field
The invention belongs to the technical field of new polymer materials, and particularly relates to an interpenetrating network structure aqueous polyurethane emulsion, and a preparation method and application thereof.
Background
The attention on environmental protection is a common trend of social development, and new environment-friendly materials such as ultraviolet light curing polyurethane paint and the like gradually replace the traditional solvent type polyurethane material to enter the market for application and gradually replace the traditional product. In addition, because the ultraviolet light curing polyurethane coating has the characteristics of high efficiency and energy conservation such as quick curing, no need of heating and baking and the like, the ultraviolet light curing polyurethane coating is very suitable for assembly line operation, the market development of the ultraviolet light curing polyurethane coating is gradually increased year by year, the ultraviolet light curing polyurethane coating is more and more applied to the industrial production of commodities, and a new revolution is brought to the whole surface coating industry.
The water-based ultraviolet curing system combines a plurality of advantages of the traditional photocuring coating and the water-based coating, and compared with the traditional solvent type polyurethane material, the water-based ultraviolet curing coating has low VOC content and little smell, and belongs to an environment-friendly material. However, the solid content of the existing water-based polyurethane material on the market is generally about 305-35%, and the water-based system has the defects of low curing speed, poor paint film performance and the like in the use process due to high moisture content. The traditional ultraviolet light curing waterborne polyurethane mainly takes isocyanate and polymer polyol as raw materials, wherein the most commonly used polymer polyol is polyester polyol and polyether polyol. However, ester bonds of polyester-based waterborne polyurethanes are easily hydrolyzed and have poor water resistance; the polyether type waterborne polyurethane has low strength and hardness, is not scratch-resistant and has poor product performance.
Therefore, how to improve the water resistance, hardness and scratch resistance of the waterborne polyurethane becomes a technical problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides an aqueous polyurethane emulsion with an interpenetrating network structure, and a preparation method and an application thereof, which are used for improving the water resistance, hardness and scratch resistance of the aqueous polyurethane.
The specific technical scheme of the invention is as follows:
the water-based polyurethane emulsion with the interpenetrating network structure comprises the following raw materials: the preparation method comprises the following steps of (1) poly (propylene carbonate) dihydric alcohol, diisocyanate, hydrophilic functional monomers, a catalyst, a chain extender, reactive monomers, a neutralizer, an initiator and deionized water;
the reactive monomer is selected from one or more of methyl methacrylate, butyl acrylate, styrene, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylate.
According to the invention, the polypropylene carbonate dihydric alcohol, the diisocyanate and the reactive monomer are adopted as main raw materials, an interpenetrating network structure is introduced through molecular design, the polyurethane prepolymer is obtained through the polypropylene carbonate dihydric alcohol, the diisocyanate, the hydrophilic functional monomer and the chain extender to form a first polymer network, then the reactive monomer is swelled in the polyurethane prepolymer, and the reactive monomer is initiated to form a second polymer network through adding the initiator and the like, so that an interpenetrating network polymer is formed, the aqueous polyurethane emulsion with the interpenetrating network structure has more excellent water resistance, hardness and tensile strength, has good comprehensive performance, and can solve the problems of low hardness, no scratch resistance, poor water resistance and the like of the existing aqueous polyurethane emulsion. In addition, the raw materials of the water-based polyurethane emulsion with the interpenetrating network structure do not need organic solvents, acetone does not need to be used as a solvent in the preparation process to reduce the system viscosity, the reactive monomer can reduce the system viscosity, the use of the organic solvents is avoided, the discharge problem of VOC is further solved, and the pollution to the environment and the harm to the health are reduced.
Preferably, the raw materials comprise, by mass: 60 parts of polypropylene carbonate dihydric alcohol, 30-150 parts of diisocyanate, 2-10 parts of hydrophilic functional monomer, 0.12-0.36 part of catalyst, 2-10 parts of chain extender, 10-50 parts of reactive monomer, 2-10 parts of neutralizer, 0.2-0.8 part of initiator and 100-400 parts of deionized water.
More preferably, the raw materials comprise, by mass: 60 parts of polypropylene carbonate dihydric alcohol, 30 parts of diisocyanate, 6.5 parts of hydrophilic functional monomer, 0.12 part of catalyst, 2 parts of chain extender, 30 parts of reactive monomer, 4.9 parts of neutralizer, 0.3 part of initiator and 250 parts of deionized water.
Preferably, the molecular weight of the polypropylene carbonate dihydric alcohol is 1000-3000;
the hydroxyl functionality of the polypropylene carbonate dihydric alcohol is 2-3;
the mole fraction of carbonate groups in the molecule of the polypropylene carbonate dihydric alcohol is 0.3-0.4.
More preferably, the polypropylene carbonate diol has a molecular weight of 2000 and a hydroxyl functionality of 2.
According to the invention, the poly (propylene carbonate) polyol is synthesized by taking carbon dioxide as an initial raw material, adding an initiator and carrying out catalytic copolymerization with propylene oxide, has good mechanical properties and low cost, can relieve the greenhouse effect by consuming carbon dioxide gas in large-scale production, saves energy sources such as petroleum and the like, and has great significance for environmental protection, energy conservation and emission reduction.
In the invention, the diisocyanate is aliphatic diisocyanate, so that the yellowing resistance of the film photocured by the water-based polyurethane emulsion with the interpenetrating network structure is better than that of the film photocured by the aromatic water-based polyurethane emulsion, and the chain extender is a non-hydrophilic chain extender.
Preferably, the diisocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate, and more preferably isophorone diisocyanate;
the hydrophilic functional monomer is selected from one or more of dimethylol propionic acid, dimethylol butyric acid, pyromellitic dianhydride, 1, 2-propylene glycol-3-sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt, and is preferably dimethylol propionic acid;
the catalyst is selected from one or more of stannous octoate, di-n-butyltin dilaurate and tin acetate, and is more preferably stannous octoate;
the chain extender is one or more selected from ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, glycerol, trimethylolpropane, ethylenediamine, 1, 6-hexamethylenediamine, ethanolamine and diethanolamine. More preferably, the chain extender is a mixture of 1, 4-butanediol, trimethylolpropane and ethylenediamine, and the mass ratio of the 1, 4-butanediol, the trimethylolpropane and the ethylenediamine is 1-3: 0.1-1: 1 to 3.
Preferably, the neutralizing agent is selected from one or more of triethylamine, tripropylamine, tributylamine, sodium hydroxide and ammonia water, more preferably triethylamine;
the initiator is selected from one or more of azodiisobutyronitrile, azodiisoheptadecylne, ammonium persulfate and potassium persulfate.
The invention also provides a preparation method of the waterborne polyurethane emulsion with the interpenetrating network structure, which comprises the following steps:
a) carrying out a first reaction on polypropylene carbonate dihydric alcohol, diisocyanate and a hydrophilic functional monomer under the action of a catalyst to obtain an intermediate;
b) adding a chain extender into the intermediate to carry out a second reaction to obtain a polyurethane prepolymer;
c) adding a reactive monomer into the polyurethane prepolymer, adding a neutralizer for neutralization reaction, adding deionized water for emulsification, and adding a chain extender for chain extension reaction to obtain a waterborne polyurethane emulsion;
d) adding an initiator into the aqueous polyurethane emulsion to carry out a third reaction, and then adding a reactive monomer to carry out a fourth reaction to obtain an aqueous polyurethane emulsion with an interpenetrating network structure;
wherein the reactive monomer is selected from one or more of methyl methacrylate, butyl acrylate, styrene, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylate.
The preparation method of the invention enables the polyurethane resin and the acrylate resin to form an interpenetrating network structure, effectively combines the excellent performances of the two resins, combines the soft and hard structures of the two materials, enables the water-based polyurethane emulsion with the interpenetrating network structure to have better film-forming property, enables the film cured by the water-based polyurethane emulsion with the interpenetrating network structure to have good hardness, wear resistance, tolerance and the like, and improves the practical application value of the material.
In the invention, the reactive monomer added in the step c) can reduce the viscosity of the system, and the reactive monomer reacts with the subsequently added reactive monomer to obtain the water-based polyurethane emulsion with the interpenetrating network structure. The mass ratio of the reactive monomer in the step c) to the reactive monomer in the step d) is (0.5-1.5): (1-5), more preferably 1: 2.
preferably, the temperature of the first reaction in the step a) is 70-90 ℃, the time of the first reaction is 2-6 h, more preferably, the temperature of the first reaction is 85 ℃, and the time is 4 h;
the temperature of the second reaction in the step b) is 70-80 ℃, the time of the second reaction is 1-2 h, and more preferably, the temperature of the second reaction is 70 ℃ and the time is 1 h.
Preferably, the temperature of the neutralization reaction in the step c) is 10-40 ℃, and the time of the neutralization reaction is 5-30 min;
the emulsifying temperature is 10-25 ℃, and the emulsifying time is 10-60 min;
the temperature of the chain extension reaction is 10-25 ℃, and the time of the chain extension reaction is 10-60 min.
Preferably, the temperature of the third reaction in the step d) is 60-70 ℃, the time of the third reaction is 1-2 h, and more preferably, the temperature of the third reaction is 70 ℃ and the time is 1 h;
the temperature of the fourth reaction is 60-80 ℃, and the time of the fourth reaction is 4-6 h. More preferably, the fourth reaction comprises: reacting for 2 to 3 hours at the temperature of between 60 and 80 ℃, and then cooling to react for 2 to 3 hours at the temperature of between 60 and 70 ℃. More preferably, the reaction is carried out at 80 ℃ for 3h, and then the temperature is reduced to 70 ℃ for 2 h.
The invention also provides the application of the waterborne polyurethane emulsion with the interpenetrating network structure in the technical scheme and/or the waterborne polyurethane emulsion with the interpenetrating network structure prepared by the preparation method in the technical scheme as a coating.
In summary, the invention provides an aqueous polyurethane emulsion with an interpenetrating network structure, and the raw materials of the aqueous polyurethane emulsion with the interpenetrating network structure comprise: the preparation method comprises the following steps of (1) poly (propylene carbonate) dihydric alcohol, diisocyanate, hydrophilic functional monomers, a catalyst, a chain extender, reactive monomers, a neutralizer, an initiator and deionized water; the reactive monomer is selected from one or more of methyl methacrylate, butyl acrylate, styrene, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylate. According to the invention, the polypropylene carbonate dihydric alcohol, the diisocyanate and the reactive monomer are adopted as main raw materials, and the interpenetrating network structure is introduced through molecular design, so that the waterborne polyurethane emulsion with the interpenetrating network structure has more excellent water resistance, hardness and tensile strength, has good comprehensive performance, and can solve the problems of low hardness, no scratch resistance, poor water resistance and the like of the existing waterborne polyurethane emulsion. In addition, the raw materials of the water-based polyurethane emulsion with the interpenetrating network structure do not need organic solvents, acetone does not need to be used as a solvent in the preparation process to reduce the system viscosity, the reactive monomer can reduce the system viscosity, the use of the organic solvents is avoided, the discharge problem of VOC is further solved, and the pollution to the environment and the harm to the health are reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a flow chart of the preparation of example 1 of the present invention.
Detailed Description
The invention provides an interpenetrating network structure aqueous polyurethane emulsion, a preparation method and application thereof, which are used for improving the water resistance, hardness and scratch resistance of aqueous polyurethane.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, a flow chart of the preparation of the aqueous polyurethane emulsion with interpenetrating network structure in this embodiment of the invention is shown, which includes the following steps:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000, the hydroxyl functionality of 2 and the mole fraction of carbonate groups of 0.34, dehydrating in vacuum at high temperature, adding 30 parts of isophorone diisocyanate, 6.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 0.45 part of chain extender trimethylolpropane into the intermediate, and carrying out a second reaction for 1 hour under the heat preservation condition to obtain the polyurethane prepolymer.
3) And (2) cooling to 40 ℃, adding 10 parts of methyl methacrylate into the polyurethane prepolymer, adding 4.9 parts of triethylamine serving as a neutralizing agent, performing neutralization reaction for 10 minutes, adding 250 parts of deionized water, performing emulsion reaction for 30 minutes at 15 ℃, and adding 1.55 parts of ethylene diamine serving as a chain extender, performing chain extension reaction for 30 minutes to obtain the waterborne polyurethane emulsion.
4) And heating to 70 ℃, dropwise adding 0.3 part of ammonium persulfate into the aqueous polyurethane emulsion, preserving heat for carrying out a third reaction for 1 hour, then adding 10 parts of methyl methacrylate, preserving heat for reacting for 3 hours at 80 ℃, cooling to 70 ℃, and preserving heat for reacting for 2 hours to obtain the aqueous polyurethane emulsion with the interpenetrating network structure.
Example 2
In this embodiment, the preparation of the aqueous polyurethane emulsion with an interpenetrating network structure includes the following steps:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000, the hydroxyl functionality of 2 and the mole fraction of carbonate groups of 0.34, dehydrating in vacuum at high temperature, adding 30 parts of isophorone diisocyanate, 6.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 0.45 part of chain extender trimethylolpropane into the intermediate, and carrying out a second reaction for 1 hour under the heat preservation condition to obtain the polyurethane prepolymer.
3) And (2) cooling to 40 ℃, adding 10 parts of methyl methacrylate into the polyurethane prepolymer, adding 4.9 parts of triethylamine serving as a neutralizing agent, performing neutralization reaction for 10 minutes, adding 250 parts of deionized water, performing emulsion reaction for 30 minutes at 15 ℃, and adding 1.55 parts of ethylene diamine serving as a chain extender, performing chain extension reaction for 30 minutes to obtain the waterborne polyurethane emulsion.
4) And heating to 70 ℃, dropwise adding 0.3 part of ammonium persulfate into the aqueous polyurethane emulsion, preserving heat for carrying out a third reaction for 1 hour, then adding 20 parts of methyl methacrylate, preserving heat for reacting for 3 hours at 80 ℃, cooling to 70 ℃, and preserving heat for reacting for 2 hours to obtain the aqueous polyurethane emulsion with the interpenetrating network structure.
Example 3
In this embodiment, the preparation of the aqueous polyurethane emulsion with an interpenetrating network structure includes the following steps:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000, the hydroxyl functionality of 2 and the mole fraction of carbonate groups of 0.34, dehydrating in vacuum at high temperature, adding 30 parts of isophorone diisocyanate, 6.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 0.45 part of chain extender trimethylolpropane into the intermediate, and carrying out a second reaction for 1 hour under the heat preservation condition to obtain the polyurethane prepolymer.
3) And (2) cooling to 40 ℃, adding 10 parts of methyl methacrylate into the polyurethane prepolymer, adding 4.9 parts of triethylamine serving as a neutralizing agent, performing neutralization reaction for 10 minutes, adding 250 parts of deionized water, performing emulsion reaction for 30 minutes at 15 ℃, and adding 1.55 parts of ethylene diamine serving as a chain extender, performing chain extension reaction for 30 minutes to obtain the waterborne polyurethane emulsion.
4) And heating to 70 ℃, dropwise adding 0.3 part of ammonium persulfate into the aqueous polyurethane emulsion, preserving heat for carrying out a third reaction for 1 hour, then adding 30 parts of methyl methacrylate, preserving heat for reacting for 3 hours at 80 ℃, cooling to 70 ℃, and preserving heat for reacting for 2 hours to obtain the aqueous polyurethane emulsion with the interpenetrating network structure.
Example 4
In this embodiment, the preparation of the aqueous polyurethane emulsion with an interpenetrating network structure includes the following steps:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000, the hydroxyl functionality of 2 and the mole fraction of carbonate groups of 0.34, dehydrating in vacuum at high temperature, adding 30 parts of isophorone diisocyanate, 6.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 0.45 part of chain extender trimethylolpropane into the intermediate, and carrying out a second reaction for 1 hour under the heat preservation condition to obtain the polyurethane prepolymer.
3) And (2) cooling to 40 ℃, adding 10 parts of methyl methacrylate into the polyurethane prepolymer, adding 4.9 parts of triethylamine serving as a neutralizing agent, performing neutralization reaction for 10 minutes, adding 250 parts of deionized water, performing emulsion reaction for 30 minutes at 15 ℃, and adding 1.55 parts of ethylene diamine serving as a chain extender, performing chain extension reaction for 30 minutes to obtain the waterborne polyurethane emulsion.
4) And heating to 70 ℃, dropwise adding 0.3 part of ammonium persulfate into the aqueous polyurethane emulsion, preserving heat for carrying out a third reaction for 1 hour, then adding 40 parts of methyl methacrylate, preserving heat for reacting for 3 hours at 80 ℃, cooling to 70 ℃, and preserving heat for reacting for 2 hours to obtain the aqueous polyurethane emulsion with the interpenetrating network structure.
Comparative example 1
The comparative example was carried out to prepare an aqueous polyurethane emulsion comprising the steps of:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000, the hydroxyl functionality of 2 and the mole fraction of carbonate groups of 0.34, dehydrating in vacuum at high temperature, adding 30 parts of isophorone diisocyanate, 6.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 0.45 part of chain extender trimethylolpropane into the intermediate, and carrying out a second reaction for 1 hour under the heat preservation condition to obtain the polyurethane prepolymer.
3) And cooling to 40 ℃, adding 4.9 parts of triethylamine serving as a neutralizing agent into the polyurethane prepolymer, carrying out neutralization reaction for 10 minutes, adding 250 parts of deionized water, carrying out emulsion reaction for 30 minutes at 15 ℃, adding 1.55 parts of ethylenediamine serving as a chain extender, and carrying out chain extension reaction for 30 minutes to obtain the waterborne polyurethane emulsion.
Comparative example 2
1) Taking 60 parts by mass of polyether diol with the molecular weight of 2000 and the hydroxyl functionality of 2, dehydrating the polyether diol at high temperature in vacuum, adding 30 parts of isophorone diisocyanate, 6.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 0.45 part of chain extender trimethylolpropane into the intermediate, and carrying out a second reaction for 1 hour under the heat preservation condition to obtain the polyurethane prepolymer.
3) And (2) cooling to 40 ℃, adding 10 parts of methyl methacrylate into the polyurethane prepolymer, adding 4.9 parts of triethylamine serving as a neutralizing agent, performing neutralization reaction for 10 minutes, adding 250 parts of deionized water, performing emulsion reaction for 30 minutes at 15 ℃, and adding 1.55 parts of ethylene diamine serving as a chain extender, performing chain extension reaction for 30 minutes to obtain the waterborne polyurethane emulsion.
4) And heating to 70 ℃, dropwise adding 0.3 part of initiator into the aqueous polyurethane emulsion, carrying out heat preservation for carrying out a third reaction for 1 hour, then adding 10 parts of methyl methacrylate, carrying out heat preservation reaction for 3 hours at 80 ℃, cooling to 70 ℃, and carrying out heat preservation reaction for 2 hours to obtain the aqueous polyurethane emulsion with the interpenetrating network structure.
Example 5
In the embodiment, the aqueous polyurethane emulsion with the interpenetrating network structures in the embodiments 1 to 4, the aqueous polyurethane emulsion in the comparative example 1 and the aqueous polyurethane emulsion with the interpenetrating network structure in the comparative example 2 are subjected to performance tests, including storage stability test and emulsion particle size test, the storage stability test is that the emulsions are filled into plastic bottles according to the test method of GBT23999-2009, the plastic bottles are sealed and then placed in a constant-temperature oven at 50 ℃ and taken out after 7 days, and the emulsions are stirred without agglomeration, so that the storage is considered to be abnormal. Emulsion particle size test the emulsion was tested by diluting it to 0.05% with deionized water using a ZETA potentiostat from beckmann coulter.
Uniformly spreading the waterborne polyurethane emulsion with the interpenetrating network structures of the embodiments 1-4, the waterborne polyurethane emulsion of the comparative example 1 and the waterborne polyurethane emulsion with the interpenetrating network structure of the comparative example 2 in an HDPE film, fully drying the film after film formation to obtain a cured film, and carrying out a water resistance test, a pendulum hardness test, a tensile strength test and an elongation at break test on the cured film.
Testing the water resistance of the adhesive film: the cured film was cut into 2cm by 2cm area samples, weighed with an analytical balance and recorded as dry film weight m1Putting the weighed dry film into enough tap water, removing bubbles attached to two sides of the film to enable the film to be fully soaked in the water, taking out the film after 24 hours, weighing the film again by using a balance, and recording as the wet film weight m 2. Calculating the water absorption rate s according to the formula 1-1:
testing the hardness of the oscillating bar: testing a swing rod hardness tester, wherein the number of standard swing rods is n, and adjusting the swing rod hardness tester to enable n to be within an interval of 250 +/-10. The prepared latex sample for the pendulum bar was placed on a glass plate, the test result was recorded as n1, the hardness ratio was calculated as R, and the hardness ratio was calculated according to the following formula 1-2:
tensile strength and elongation at break test: and cutting the film paved on the HDPE board into a dumbbell shape, measuring the thickness by using a thickness gauge, and testing the tensile strength and the elongation at break of the adhesive film at room temperature according to GB/T1040.3-2006. The test temperature was 25 ℃ and the drawing speed was 200 mm/min.
The results shown in table 1 show that, compared with the aqueous polyurethane emulsion of comparative example 1 and the aqueous polyurethane emulsion of comparative example 2, the aqueous polyurethane emulsion of the interpenetrating network structure of examples 1 to 4 has more excellent water resistance, hardness and tensile strength after film formation, and can be used in the aqueous coating industry. According to the invention, an interpenetrating network structure is introduced through molecular design, and the waterborne polyurethane emulsion with the interpenetrating network structure has good comprehensive performance, so that the problems of low hardness, scratch resistance, poor water resistance and the like in the existing waterborne coating industry can be well improved.
TABLE 1 Performance test results of the aqueous polyurethane emulsions of examples 1 to 4 interpenetrating network structures, the aqueous polyurethane emulsion of comparative example 1, and the aqueous polyurethane emulsion of comparative example 2 interpenetrating network structure
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The water-based polyurethane emulsion with the interpenetrating network structure is characterized in that the water-based polyurethane emulsion with the interpenetrating network structure comprises the following raw materials: the preparation method comprises the following steps of (1) poly (propylene carbonate) dihydric alcohol, diisocyanate, hydrophilic functional monomers, a catalyst, a chain extender, reactive monomers, a neutralizer, an initiator and deionized water;
the reactive monomer is selected from one or more of methyl methacrylate, butyl acrylate, styrene, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylate.
2. The aqueous polyurethane emulsion with an interpenetrating network structure according to claim 1, wherein the raw materials comprise, in parts by mass: 60 parts of polypropylene carbonate dihydric alcohol, 30-150 parts of diisocyanate, 2-10 parts of hydrophilic functional monomer, 0.12-0.36 part of catalyst, 2-10 parts of chain extender, 10-50 parts of reactive monomer, 2-10 parts of neutralizer, 0.2-0.8 part of initiator and 100-400 parts of deionized water.
3. The aqueous polyurethane emulsion with an interpenetrating network structure according to claim 1, wherein the molecular weight of the polypropylene carbonate diol is 1000 to 3000;
the hydroxyl functionality of the polypropylene carbonate dihydric alcohol is 2-3;
the mole fraction of carbonate groups in the molecule of the polypropylene carbonate dihydric alcohol is 0.3-0.4.
4. The aqueous polyurethane emulsion of an interpenetrating network structure of claim 1, wherein the diisocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate;
the hydrophilic functional monomer is selected from one or more of dimethylol propionic acid, dimethylol butyric acid, pyromellitic dianhydride, 1, 2-propylene glycol-3-sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt;
the catalyst is selected from one or more of stannous octoate, di-n-butyltin dilaurate and tin acetate;
the chain extender is one or more selected from ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, glycerol, trimethylolpropane, ethylenediamine, 1, 6-hexamethylenediamine, ethanolamine and diethanolamine.
5. The aqueous polyurethane emulsion with an interpenetrating network structure according to claim 1, wherein the neutralizing agent is one or more selected from triethylamine, tripropylamine, tributylamine, sodium hydroxide and ammonia water;
the initiator is selected from one or more of azodiisobutyronitrile, azodiisoheptadecylne, ammonium persulfate and potassium persulfate.
6. A preparation method of an interpenetrating network structure aqueous polyurethane emulsion is characterized by comprising the following steps:
a) carrying out a first reaction on polypropylene carbonate dihydric alcohol, diisocyanate and a hydrophilic functional monomer under the action of a catalyst to obtain an intermediate;
b) adding a chain extender into the intermediate to carry out a second reaction to obtain a polyurethane prepolymer;
c) adding a reactive monomer into the polyurethane prepolymer, adding a neutralizer for neutralization reaction, adding deionized water for emulsification, and adding a chain extender for chain extension reaction to obtain a waterborne polyurethane emulsion;
d) adding an initiator into the aqueous polyurethane emulsion to carry out a third reaction, and then adding a reactive monomer to carry out a fourth reaction to obtain an aqueous polyurethane emulsion with an interpenetrating network structure;
wherein the reactive monomer is selected from one or more of methyl methacrylate, butyl acrylate, styrene, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylate.
7. The preparation method according to claim 6, wherein the temperature of the first reaction in the step a) is 70-90 ℃, and the time of the first reaction is 2-6 h;
the temperature of the second reaction in the step b) is 70-80 ℃, and the time of the second reaction is 1-2 h.
8. The preparation method according to claim 6, wherein the temperature of the neutralization reaction in the step c) is 10-40 ℃, and the time of the neutralization reaction is 5-30 min;
the emulsifying temperature is 10-25 ℃, and the emulsifying time is 10-60 min;
the temperature of the chain extension reaction is 10-25 ℃, and the time of the chain extension reaction is 10-60 min.
9. The preparation method according to claim 6, wherein the temperature of the third reaction in step d) is 60-70 ℃, and the time of the third reaction is 1-2 h;
the temperature of the fourth reaction is 60-80 ℃, and the time of the fourth reaction is 4-6 h.
10. Use of the aqueous polyurethane emulsion of an interpenetrating network structure according to any one of claims 1 to 5 and/or the aqueous polyurethane emulsion of an interpenetrating network structure prepared by the preparation method according to any one of claims 6 to 9 as a coating.
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