CN116478338A - Nano modified waterborne polyurethane composition and preparation method thereof - Google Patents

Nano modified waterborne polyurethane composition and preparation method thereof Download PDF

Info

Publication number
CN116478338A
CN116478338A CN202310455836.XA CN202310455836A CN116478338A CN 116478338 A CN116478338 A CN 116478338A CN 202310455836 A CN202310455836 A CN 202310455836A CN 116478338 A CN116478338 A CN 116478338A
Authority
CN
China
Prior art keywords
nano
modified
waterborne polyurethane
mixture
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310455836.XA
Other languages
Chinese (zh)
Inventor
廖小龙
钱小强
葛明华
王俊
王荣平
谢锦祥
郜江勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Sunrising Chemical Co ltd
Original Assignee
Guangdong Sunrising Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Sunrising Chemical Co ltd filed Critical Guangdong Sunrising Chemical Co ltd
Priority to CN202310455836.XA priority Critical patent/CN116478338A/en
Publication of CN116478338A publication Critical patent/CN116478338A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a nano modified aqueous polyurethane composition and a preparation method thereof, belonging to the technical field of high polymer materials, and comprising a polyester precursor, modified nano filler, an aqueous reagent, sodium perborate, palladium salt, acrylic ester, sodium dodecyl sulfate and sodium isobutyryl peroxyacid, wherein the aqueous reagent is used as a solvent and does not contain an organic solvent, the VOC (volatile organic compound) emission is 0, the waste gas emission and the environmental pollution are greatly reduced, the international environmental protection standard is met, and meanwhile, the ozone consumption and the smoke formation are avoided; the product of the invention is nonionic water-based polyurethane, is easy to be degraded by microorganisms in the environment, and meanwhile, the acrylic ester also increases unsaturated bonds in molecules, thereby being beneficial to degradation, reducing the harm to the environment and improving the appearance color of the product by adding pigment.

Description

Nano modified waterborne polyurethane composition and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a nano modified waterborne polyurethane composition and a preparation method thereof.
Background
The paint has very large effect in production and life, can be widely applied to various fields, can play roles in decoration, protection and marking of objects, and most of the paint on the market at present is simple in manufacture, low in price and single in function, can be used as decoration simply, and in some special working environments, the simple paint cannot meet the needs of people.
Polyurethane has excellent corrosion resistance, adhesive force, chemical resistance and weather resistance, and can be widely applied in the fields of adhesives, coatings and the like. The existing polyurethane coating has the following defects: 1) The curing temperature is high, and the curing time is long; 2) The service life is short, and the durability is poor; 3) The coating layer of the polyurethane coating is uneven and has more flaws; 4) The temperature range suitable for curing the polyurethane coating is narrow; 5) The color and luster after solidification are not enough to be transparent to the atmosphere; 5) The polyurethane paint contains a large amount of solvents such as toluene, dimethylamide and the like, which cause serious environmental pollution; 6) The polyurethane paint is not easy to degrade and is not friendly to the environment.
Disclosure of Invention
In order to solve the problems, the invention provides a nano modified waterborne polyurethane composition and a preparation method thereof, and the specific contents are as follows:
the invention aims to provide a nano modified waterborne polyurethane composition, which is technically characterized by comprising 51.28-63.72wt% of polyester precursor with molecular weight of 8000-12000, 6-8wt% of modified nanofiller, 10-14wt% of waterborne reagent, 6-10wt% of sodium perborate, 0.1-0.3wt% of palladium salt, 10.1-10.3wt% of acrylic ester, 1.5-2.5 wt% of sodium dodecyl sulfate, 0.08-0.12wt% of sodium isobutyryl peroxide shown as the formula (I) and 2.5-3.5wt% of pigment;
in order to better realize the technical scheme, the polyester precursor in the nano modified aqueous polyurethane composition comprises a mixture of polycaprolactone and poly (internal plastic polyether) shown in a formula of a formula (II), wherein the mass ratio of the polycaprolactone to the poly (internal plastic polyether) is 7:3, a step of;
in order to better realize the technical scheme, the modified nano filler in the nano modified waterborne polyurethane composition is modified nano silicon dioxide.
In order to better realize the technical scheme, the modification method of the modified nano silicon dioxide in the nano modified waterborne polyurethane composition comprises the following steps:
firstly, placing 98.7-99.40wt% of silicon dioxide nano powder, 0.5-1wt% of acrylic acid and 0.1-0.3wt% of polyvinyl hydrazine shown as a molecular formula of a formula (III) into a roller rubber grinding layer in a three-roller machine for premixing to obtain a mixture A;
step two, then the mixture A is placed in ultrasonic treatment, so that acrylic acid, silicon dioxide nano powder and polyethylene hydrazine are fully reacted, and the surface of the mixture A is properly crosslinked to obtain a mixture B;
and thirdly, washing the mixture B with excessive water until the pH value reaches 7, and removing unbound acrylic acid and polyvinyl hydrazine to obtain the modified nano silicon dioxide.
In order to better realize the technical scheme, the aqueous reagent in the nano modified aqueous polyurethane composition is 2,2' - [ (4-aminophenyl) -imino ] diacetic acid shown in the molecular formula of the formula (IV);
in order to better realize the technical scheme, the palladium salt in the nano modified waterborne polyurethane composition is palladium (II) acetate.
In order to better realize the technical scheme, the acrylic ester in the nano modified waterborne polyurethane composition is methyl acrylate.
The invention also aims to provide a preparation method of the nano modified waterborne polyurethane, which is technically characterized by comprising the following steps:
firstly, adding polyester precursor, sodium dodecyl sulfate and sodium isobutyryl peroxide into a reaction kettle, and carrying out polymerization reaction at the temperature of 35-45 ℃ to generate polycaprolactone-poly (internal plastic polyether);
step two, adding the modified nano filler and the aqueous reagent based on the step one, and adding-NH in the aqueous reagent 2 The groups undergo Michael condensation reaction with the functional groups of the polyester precursor at a temperature of 30-40 ℃ to form amino-functional covalent bonds, yielding a partially water-soluble polyurethane;
step three, willB-OH groups in sodium perborate and-NH in unreacted aqueous reagent 2 The group z forms amide borate crosslinking points at the temperature of 20-50 ℃ under the catalysis of palladium salt to generate crosslinked polyurethane with a plastic network structure;
and step four, adding acrylic ester and cross-linked polyurethane on the basis of the step three, forming amide borate cross-linked points at the temperature of 30-40 ℃, adding pigment, and uniformly mixing to obtain the nano modified waterborne polyurethane with the molecular weight of 3000-5000.
Compared with the prior art, the nano modified waterborne polyurethane composition and the preparation method thereof can achieve the following beneficial effects:
1. the nano modified aqueous polyurethane composition provided by the invention comprises a polyester precursor, a modified nano filler, an aqueous reagent, sodium perborate, palladium salt, acrylic ester, sodium dodecyl sulfate and sodium isobutyryl peroxyacid, wherein the aqueous reagent is used as a solvent and does not contain an organic solvent, the VOC (volatile organic compound) emission is 0, the waste gas emission and the environmental pollution are greatly reduced, the international environmental protection standard is met, and meanwhile, ozone consumption and smoke formation are avoided; the product of the invention is nonionic water-based polyurethane, is easy to be degraded by microorganisms in the environment, and meanwhile, the acrylic ester also increases unsaturated bonds in molecules, thereby being beneficial to degradation, reducing the harm to the environment and improving the appearance color of the product by adding pigment.
2. The nano modified waterborne polyurethane is catalyzed by palladium salt, the crosslinking reaction is accelerated, high-temperature curing is not needed, the energy consumption and the carbon dioxide emission are greatly reduced, and the curing time is shortened to 3 minutes.
3. The molecular weight of the nano modified waterborne polyurethane is controlled to be 3000-5000 by acrylic ester copolymerization, so that the weather resistance, chemical resistance and mechanical strength are improved, meanwhile, the flexibility is also improved, and the applicable temperature range is expanded to 0-50 ℃.
4. According to the nano modified waterborne polyurethane, the emulsifier (sodium dodecyl sulfate) is added, so that the surface tension of the nano modified waterborne polyurethane is reduced, the fluidity and the coating performance are improved, the coating layer is uniform, and the defects are few.
5. According to the nano modified waterborne polyurethane, through modification measures, the mechanical strength and durability of the product are greatly improved, the recoating amount required per unit surface is reduced, the influence on the environment in the primary coating process is correspondingly reduced, the service life is prolonged, and the product is more environment-friendly and sustainable.
Detailed Description
A nano-modified aqueous polyurethane composition comprising:
the polyester precursor having a molecular weight of 8000-12000 and a mass fraction of 51.28-63.72wt%, further the polyester precursor of the present invention comprises a mass ratio of 7:3 and a poly (internal plastic polyether) of the formula (II),
the modified nanofiller according to the invention is preferably a modified nanofilica having a high surface activity and can be used to improve the aqueous and mechanical properties of polyurethanes, with a mass fraction of 6-8 wt%.
Further, the modification method of the modified nano silicon dioxide comprises the following steps:
step one, placing 98.7 to 99.40 weight percent of silicon dioxide nano powder, 0.5 to 1 weight percent of acrylic acid and 0.1 to 0.3 weight percent of polyethylenehydrazine shown as a molecular formula of a formula (III) in a roller rubber grinding layer in a three-roller machine for premixing to obtain a mixture A, wherein the preferable dosage of the acrylic acid is 0.75 weight percent, so that excessive quantity is avoided, and the physical properties of the silicon dioxide nano powder are influenced. The preferred amount of the polyvinyl hydrazine is 0.2wt percent, so that excessive amount is avoided, and the interaction of the silicon dioxide nano powder and the nonionic waterborne polyurethane is prevented. According to the invention, the surface defects of the silicon dioxide nano powder are increased by grinding of a three-roller machine, the specific surface area is increased, the number of hydrophilic groups on the surface is increased, and the dispersibility is improved.
Step two, then the mixture A is placed in ultrasonic treatment, so that acrylic acid, silicon dioxide nano powder and polyethylene hydrazine are fully reacted, and the surface of the mixture A is properly crosslinked to obtain a mixture B;
and thirdly, washing the mixture B with excessive water until the pH value reaches 7, and removing unbound acrylic acid and polyvinyl hydrazine to obtain the modified nano silicon dioxide.
In the method, the surface of the silicon dioxide nano powder is introduced with acrylic acid groups, and then the acrylic acid groups are generated by coupling reaction with the acrylic acid. By chiral interaction of acrylic groups, surface activity is enhanced and dispersibility is improved. By adding a proper amount of the polyvinyl hydrazine, a polyvinyl hydrazine-ethylene glycol ligand is generated, excessive aggregation of the silica nanoparticles is prevented, and stable dispersion in nonionic waterborne polyurethane is facilitated.
The surface modified silicon dioxide nano powder can show the following technical effects in nonionic water-based polyurethane:
1. the dispersion uniformity is remarkably improved. The modified silicon dioxide nano powder can be uniformly dispersed in a water phase, so that the dispersity of the non-ionic waterborne polyurethane is further improved, and high dispersion and high transparency are generated.
2. Improving mechanical strength. The surface density of the modified silicon dioxide nano powder is increased and the modified silicon dioxide nano powder is closely adhered, so that a tighter interface is formed with nonionic waterborne polyurethane, and the mechanical strength is further improved.
3. The hydrophobicity is improved. The modified silicon dioxide nano powder has high hydrophilic surface, is easier to react with water molecules, is favorable for the hydrophobic performance of products, and expands the application range.
4. Reducing the surface voltage. Proper surface modification can make the surface charge of the silicon dioxide nano powder more stable, is favorable for the fluidity and the coating property of the product in an aqueous medium, and achieves the unexpected effect of reducing the surface voltage of the ball.
5. Providing a richer color. The modified silica nano powder has more active surface and stronger pigment molecule adsorption capability, and provides richer and stable color through the action of SiO2 and pigment, thereby bringing stronger visual impact.
The aqueous reagent comprises 10-14wt% of aqueous reagent, and further the aqueous reagent is 2,2'- [ (4-aminophenyl) -imino ] diacetic acid shown in the formula (IV), and the 2,2' - [ (4-aminophenyl) -imino ] diacetic acid generates water-soluble polyurethane through the reaction with the soft functional group of the polyester precursor. The aqueous reagent of the invention replaces the use of the traditional organic solvent, thereby greatly reducing the exhaust emission and the environmental pollution.
Sodium perborate in an amount of 6-10wt% by mass, which produces a crosslinked structure by reacting with the amino groups of 2,2' - [ (4-aminophenyl) -imino ] diacetic acid, produces a curing effect.
The palladium salt of the invention is preferably palladium (II) acetate, which is used to catalyze the crosslinking reaction and reduce the curing time, in a mass fraction of 0.1 to 0.3 wt%.
The acrylic ester with the mass fraction of 10.1-10.3wt% is preferably methyl acrylate, the curing temperature can be controlled in the range of room temperature to 50 ℃, high-temperature curing is not needed, and the energy consumption and carbon dioxide emission are greatly reduced.
Sodium dodecyl sulfate with a mass fraction of 1.5-2.5% for improving flowability and coatability.
Sodium isobutyryl peroxide of formula (I) with mass fraction of 0.08-0.12wt% is used for limiting molecular weight and improving handling property.
The pigment with the mass fraction of 2.5-3.5wt% is preferably red pigment to improve the appearance and luster, and the invention can provide a colorful product series due to more flexible selection and addition of the aqueous polyurethane pigment, thereby overcoming the technical problems that the application of the pigment is influenced by an organic solvent and the color is single.
According to the formula, the preparation method of the nano modified waterborne polyurethane comprises the following steps:
firstly, adding polyester precursor, sodium dodecyl sulfate and sodium isobutyryl peroxide into a reaction kettle, and carrying out polymerization reaction at the temperature of 35-45 ℃ to generate polycaprolactone-poly (internal plastic polyether);
step two, adding the modified nano filler and the aqueous reagent based on the step one, and adding-NH in the aqueous reagent 2 The groups undergo Michael condensation reaction with the functional groups of the polyester precursor at a temperature of 30-40 ℃ to form amino-functional covalent bonds, yielding a partially water-soluble polyurethane;
step three, B-OH groups in sodium perborate are reacted with-NH in unreacted aqueous reagent 2 The group z forms amide borate crosslinking points at the temperature of 20-50 ℃ under the catalysis of palladium salt to generate crosslinked polyurethane with a plastic network structure;
the amount and effect of the palladium salt in this step is very important, and if the amount of palladium salt is too low, the catalytic effect will be insufficient to effectively drive the crosslinking reaction. The reaction will proceed very slowly, resulting in incomplete crosslinking and poor performance. More palladium salt is needed. If the palladium salt is used in an excessive amount, the excessive palladium salt may catalyze the reaction too severely, and the reaction may be accelerated too rapidly under severe conditions. This can lead to excessive crosslinking, creating a fragile and inflexible network. Some functional groups may also prematurely decompose due to overheating. Too much catalyst is detrimental to performance. Thus, the amount of palladium salt used has a significant effect on the kinetics and extent of crosslinking. An amount of the appropriate amount may result in desirable performance, while an amount that is too small or too large may impair performance.
Specifically, the purpose of adding palladium (II) acetate in the present invention is:
1. the curing time is reduced. Palladium (ii) acetate can effectively catalyze the amide borate crosslinking reaction between the aqueous reagent and sodium perborate. The crosslinking reaction can be carried out faster by catalysis of palladium (ii) acetate, resulting in a shorter cure time (e.g. 3 minutes) for the synthesis.
2. The crosslinking efficiency is improved. The catalysis of palladium (II) acetate may promote higher conversion of the crosslinking reaction, resulting in a higher degree of crosslinking in the final polymer network. This results in improved properties such as higher mechanical strength, better durability, etc.
3. Reducing side reactions. Without catalysis, the crosslinking reaction may proceed slowly and side reactions may compete, thereby producing unwanted byproducts. The palladium (II) acetate is used as a catalyst to help promote the forward development of the main reaction and inhibit the side reaction, so that the selectivity and purity of the product are improved.
4. Mild reaction conditions were allowed. Due to its high catalytic efficiency, palladium (ii) acetate allows the crosslinking reaction to be carried out under mild conditions (e.g., room temperature) rather than under severe conditions (high temperature). This helps to maintain the stability and performance of the functional groups in the polyurethane precursor.
And step four, adding acrylic ester and cross-linked polyurethane on the basis of the step three, forming amide borate cross-linked points at the temperature of 30-40 ℃, adding pigment, and uniformly mixing to obtain the nano modified waterborne polyurethane with the molecular weight of 3000-5000.
The aqueous polyurethane has higher biodegradability, so that the aqueous polyurethane is more suitable for application of coating garbage cans, ocean platforms and the like, and the pollution of the environment where the aqueous polyurethane is located due to long-term durability is prevented.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A nano-modified aqueous polyurethane composition comprising:
the mass fraction of the polyester precursor having a molecular weight of 10000 of 57.7wt%, and the further polyester precursor of the present invention comprises a mass ratio of 7:3 and a poly (internal plastic polyether) of the formula (II),
-7 wt% of modified nanofiller: preferably, the modified nano-filler is modified nano-silica, and further, the modification method of the modified nano-silica comprises the following steps:
firstly, placing 99.05wt% of silicon dioxide nano powder, 0.75wt% of acrylic acid and 0.5wt% of polyvinyl hydrazine shown as a molecular formula of a formula (III) into a roller rubber grinding layer in a three-roller machine for premixing to obtain a mixture A;
step two, then the mixture A is placed in ultrasonic treatment, so that acrylic acid, silicon dioxide nano powder and polyethylene hydrazine are fully reacted, and the surface of the mixture A is properly crosslinked to obtain a mixture B;
and thirdly, washing the mixture B with excessive water until the pH value reaches 7, and removing unbound acrylic acid and polyvinyl hydrazine to obtain the modified nano silicon dioxide.
The aqueous reagent comprises 12 weight percent of aqueous reagent, and further the aqueous reagent is 2,2' - [ (4-aminophenyl) -imino ] diacetic acid shown in the formula (IV);
-sodium perborate in a mass fraction of 8 wt%.
The palladium salt according to the invention is preferably palladium (II) acetate, with a mass fraction of 0.2% by weight of palladium salt.
The acrylate according to the invention is preferably methyl acrylate, with a mass fraction of 10% by weight.
-sodium dodecyl sulfate with a mass fraction of 2%.
0.1% by weight of sodium isobutyryl peroxo ate of formula (I),
the pigment according to the invention is preferably a red pigment, with a mass fraction of 3% by weight.
According to the formula, the preparation method of the nano modified waterborne polyurethane comprises the following steps:
firstly, adding polyester precursor, sodium dodecyl sulfate and sodium isobutyryl peroxide into a reaction kettle, and carrying out polymerization reaction at the temperature of 35-45 ℃ to generate polycaprolactone-poly (internal plastic polyether);
step two, adding the modified nano filler and the aqueous reagent based on the step one, and adding-NH in the aqueous reagent 2 The groups undergo Michael condensation reaction with the functional groups of the polyester precursor at a temperature of 30-40 ℃ to form amino-functional covalent bonds, yielding a partially water-soluble polyurethane;
step three, B-OH groups in sodium perborate are reacted with-NH in unreacted aqueous reagent 2 The group z forms amide borate crosslinking points at the temperature of 20-50 ℃ under the catalysis of palladium salt to generate crosslinked polyurethane with a plastic network structure;
and step four, adding acrylic ester and cross-linked polyurethane on the basis of the step three, forming amide borate cross-linked points at the temperature of 30-40 ℃, adding pigment, and uniformly mixing to obtain the nano modified waterborne polyurethane with the molecular weight of 4000.
Example 2
A nano-modified aqueous polyurethane composition comprising:
a mass fraction of 63.72 wt.% of a polyester precursor having a molecular weight of 8000, further polyester precursors of the invention comprising a mass ratio of 7:3 and a poly (internal plastic polyether) of the formula (II),
-6 wt% of modified nanofiller: preferably, the modified nano-filler is modified nano-silica, and further, the modification method of the modified nano-silica comprises the following steps:
firstly, placing 99.40wt% of silicon dioxide nano powder, 0.5wt% of acrylic acid and 0.1wt% of polyvinyl hydrazine shown as a molecular formula of a formula (III) into a roller rubber grinding layer in a three-roller machine for premixing to obtain a mixture A;
step two, then the mixture A is placed in ultrasonic treatment, so that acrylic acid, silicon dioxide nano powder and polyethylene hydrazine are fully reacted, and the surface of the mixture A is properly crosslinked to obtain a mixture B;
and thirdly, washing the mixture B with excessive water until the pH value reaches 7, and removing unbound acrylic acid and polyvinyl hydrazine to obtain the modified nano silicon dioxide.
The aqueous reagent comprises 10 weight percent of aqueous reagent, and further the aqueous reagent is 2,2' - [ (4-aminophenyl) -imino ] diacetic acid shown in the formula (IV);
-sodium perborate in a mass fraction of 6 wt%.
The palladium salt according to the invention is preferably palladium (II) acetate, with a mass fraction of 0.1% by weight of palladium salt.
The acrylate according to the invention is preferably methyl acrylate, with a mass fraction of 10.1% by weight.
Sodium dodecyl sulfate with a mass fraction of 1.5%.
0.08 wt.% sodium isobutyryl peroxo acid of formula (I),
the pigment according to the invention is preferably a red pigment, with a mass fraction of 2.5% by weight.
According to the formula, the preparation method of the nano modified waterborne polyurethane comprises the following steps:
firstly, adding polyester precursor, sodium dodecyl sulfate and sodium isobutyryl peroxide into a reaction kettle, and carrying out polymerization reaction at the temperature of 35-45 ℃ to generate polycaprolactone-poly (internal plastic polyether);
step two, adding the modified nano filler and the aqueous reagent based on the step one, and adding-NH in the aqueous reagent 2 The groups undergo Michael condensation reaction with the functional groups of the polyester precursor at a temperature of 30-40 ℃ to form amino-functional covalent bonds, yielding a partially water-soluble polyurethane;
step three, B-OH groups in sodium perborate are reacted with-NH in unreacted aqueous reagent 2 The groups form amide borate crosslinking points at the temperature of 20-50 ℃ under the catalysis of palladium salt to generate crosslinked polyurethane with a plastic network structure;
and step four, adding acrylic ester and cross-linked polyurethane on the basis of the step three, forming amide borate cross-linked points at the temperature of 30-40 ℃, adding pigment, and uniformly mixing to obtain the nano modified waterborne polyurethane with the molecular weight of 3000.
Example 3
A nano-modified aqueous polyurethane composition comprising:
a mass fraction of 51.28 wt.% of a polyester precursor having a molecular weight of 12000, further polyester precursors according to the invention comprising a mass ratio of 7:3 and a poly (internal plastic polyether) of the formula (II),
-8wt% of modified nanofiller: preferably, the modified nano-filler is modified nano-silica, and further, the modification method of the modified nano-silica comprises the following steps:
firstly, placing 98.7wt% of silicon dioxide nano powder, 1wt% of acrylic acid and 0.3wt% of polyvinyl hydrazine shown as a molecular formula of a formula (III) into a roller rubber grinding layer in a three-roller machine for premixing to obtain a mixture A;
step two, then the mixture A is placed in ultrasonic treatment, so that acrylic acid, silicon dioxide nano powder and polyethylene hydrazine are fully reacted, and the surface of the mixture A is properly crosslinked to obtain a mixture B;
and thirdly, washing the mixture B with excessive water until the pH value reaches 7, and removing unbound acrylic acid and polyvinyl hydrazine to obtain the modified nano silicon dioxide.
-14% by weight of an aqueous reagent according to the invention, further 2,2' - [ (4-aminophenyl) -imino ] diacetic acid of formula (iv);
-sodium perborate in a mass fraction of 10 wt%.
The palladium salt according to the invention is preferably palladium (II) acetate, with a mass fraction of 0.3% by weight of palladium salt.
The acrylate according to the invention is preferably methyl acrylate, with a mass fraction of 10.3% by weight.
-sodium dodecyl sulfate with a mass fraction of 2.5%.
0.12% by weight of sodium isobutyryl peroxo ate of formula (I),
the pigment according to the invention is preferably a red pigment, with a mass fraction of 3.5% by weight.
According to the formula, the preparation method of the nano modified waterborne polyurethane comprises the following steps:
firstly, adding polyester precursor, sodium dodecyl sulfate and sodium isobutyryl peroxide into a reaction kettle, and carrying out polymerization reaction at the temperature of 35-45 ℃ to generate polycaprolactone-poly (internal plastic polyether);
step two, adding the modified nano filler and the aqueous reagent based on the step one, and adding-NH in the aqueous reagent 2 The groups undergo Michael condensation reaction with the functional groups of the polyester precursor at a temperature of 30-40 ℃ to form amino-functional covalent bonds, yielding a partially water-soluble polyurethane;
step three, B-OH groups in sodium perborate are reacted with-NH in unreacted aqueous reagent 2 The group z forms amide borate crosslinking points at the temperature of 20-50 ℃ under the catalysis of palladium salt to generate crosslinked polyurethane with a plastic network structure;
and step four, adding acrylic ester and cross-linked polyurethane on the basis of the step three, forming amide borate cross-linked points at the temperature of 30-40 ℃, adding pigment, and uniformly mixing to obtain the nano modified waterborne polyurethane with the molecular weight of 5000.
Comparative example 1
The comparative example does not contain "7 wt% modified nanofiller" and "57.7 wt% polyester precursor having a molecular weight of 10000" in example 1 is "changed to" 64.7wt% polyester precursor having a molecular weight of 10000 ", and the other formulation and preparation method are the same as those of example 1.
Comparative example 2
The "mass fraction 57.7wt% of the polyester precursor having a molecular weight of 10000" in example 1 was changed to "mass fraction 67.7wt% of the polyester precursor having a molecular weight of 10000" without "10 wt% of the acrylic acid ester", and the other formulation and production method were the same as those in example 1.
Test examples
In order to verify whether the nano modified waterborne polyurethane prepared in the above embodiment achieves the beneficial effect, the nano modified waterborne polyurethane prepared in the embodiment 1-3 and the nano modified waterborne polyurethane prepared in the comparative embodiment 1-2 are respectively subjected to characterization test, the nano modified waterborne polyurethane prepared in the embodiment 1-3 and the nano modified waterborne polyurethane prepared in the comparative embodiment 1-2 are poured into a mold, are naturally air-dried and cured for 1-2 days at room temperature, are then put into a 50 ℃ oven for drying for more than 10 hours until the quality of the film is not changed, and are put into a dryer for standby performance test of the nano modified waterborne polyurethane after the film is removed, wherein the specific test method is as follows:
and (3) testing the emulsion stability of the nano modified waterborne polyurethane: the centrifugal machine is used for rotating at the speed of 3000 r.min -1 The nano modified waterborne polyurethane is continuously centrifuged for 15min under the condition, and if no precipitation or layering occurs, the nano modified waterborne polyurethane can be stably stored for more than 6 months.
Testing the viscosity of nano modified waterborne polyurethane: measuring the viscosity of each emulsion at 25 ℃ by using a rotary viscometer, and taking an average value after more than 5 times of measurement of each example/comparative example;
tensile properties of nano-modified waterborne polyurethane films: testing was performed with reference to GB/T16421-1996;
water absorption of nano modified aqueous polyurethane film: the test was performed with reference to GB/T1034-2008.
The test results are shown in Table 1 below:
TABLE 1
The foregoing is merely exemplary of the present invention and is not intended to limit the present invention. Various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are to be included in the scope of the claims of the present invention.

Claims (8)

1. A nano modified waterborne polyurethane composition is characterized by comprising 51.28-63.72wt% of polyester precursor with molecular weight of 8000-12000, 6-8wt% of modified nanofiller, 10-14wt% of aqueous reagent, 6-10wt% of sodium perborate, 0.1-0.3wt% of palladium salt, 10.1-10.3wt% of acrylic ester, 1.5-2.5 wt% of sodium dodecyl sulfate, 0.08-0.12wt% of sodium isobutyryl peroxyate with molecular formula shown in formula (I) and 2.5-3.5wt% of pigment;
2. the nano-modified waterborne polyurethane composition according to claim 1, wherein the polyester precursor comprises a mixture of polycaprolactone and a poly (internal plastic polyether) represented by the formula (II), and the mass ratio of the polycaprolactone to the poly (internal plastic polyether) is 7:3, a step of;
3. the nano-modified waterborne polyurethane composition according to claim 1, wherein the modified nano-filler is modified nano-silica.
4. A nano-modified waterborne polyurethane composition according to claim 3, wherein the modification method of the modified nano-silica is as follows:
firstly, placing 98.7-99.40wt% of silicon dioxide nano powder, 0.5-1wt% of acrylic acid and 0.1-0.3wt% of polyvinyl hydrazine shown as a molecular formula of a formula (III) into a roller rubber grinding layer in a three-roller machine for premixing to obtain a mixture A;
step two, then the mixture A is placed in ultrasonic treatment, so that acrylic acid, silicon dioxide nano powder and polyethylene hydrazine are fully reacted, and the surface of the mixture A is properly crosslinked to obtain a mixture B;
and thirdly, washing the mixture B with excessive water until the pH value reaches 7, and removing unbound acrylic acid and polyvinyl hydrazine to obtain the modified nano silicon dioxide.
5. The nano-modified waterborne polyurethane composition according to claim 1, wherein the waterborne agent is 2,2' - [ (4-aminophenyl) -imino ] diacetic acid shown in a molecular formula of a formula (IV);
6. the nano-modified waterborne polyurethane composition according to claim 1, wherein the palladium salt is palladium (II) acetate.
7. The nano-modified waterborne polyurethane composition according to claim 1, wherein the acrylic ester is methyl acrylate.
8. A process for the preparation of nano-modified waterborne polyurethane according to any of claims 1-7, comprising the steps of:
firstly, adding polyester precursor, sodium dodecyl sulfate and sodium isobutyryl peroxide into a reaction kettle, and carrying out polymerization reaction at the temperature of 35-45 ℃ to generate polycaprolactone-poly (internal plastic polyether);
step two, adding the modified nano filler and the aqueous reagent based on the step one, and adding-NH in the aqueous reagent 2 The groups undergo Michael condensation reaction with the functional groups of the polyester precursor at a temperature of 30-40 ℃ to form amino-functional covalent bonds, yielding a partially water-soluble polyurethane;
step three, B-OH groups in sodium perborate are reacted with-NH in unreacted aqueous reagent 2 The group z forms amide borate crosslinking points at the temperature of 20-50 ℃ under the catalysis of palladium salt to generate crosslinked polyurethane with a plastic network structure;
and step four, adding acrylic ester and cross-linked polyurethane on the basis of the step three, forming amide borate cross-linked points at the temperature of 30-40 ℃, adding pigment, and uniformly mixing to obtain the nano modified waterborne polyurethane with the molecular weight of 3000-5000.
CN202310455836.XA 2023-04-25 2023-04-25 Nano modified waterborne polyurethane composition and preparation method thereof Pending CN116478338A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310455836.XA CN116478338A (en) 2023-04-25 2023-04-25 Nano modified waterborne polyurethane composition and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310455836.XA CN116478338A (en) 2023-04-25 2023-04-25 Nano modified waterborne polyurethane composition and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116478338A true CN116478338A (en) 2023-07-25

Family

ID=87213447

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310455836.XA Pending CN116478338A (en) 2023-04-25 2023-04-25 Nano modified waterborne polyurethane composition and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116478338A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9101204D0 (en) * 1990-02-14 1991-02-27 Ici Plc Production of polyurethane polymers,the polymers so produced and compositions containing them
KR20040073698A (en) * 2003-02-14 2004-08-21 주식회사 금강고려화학 Composition for aqueous coating for plastic interior finish in automobile
CN1856594A (en) * 2003-09-02 2006-11-01 爱托特奇德国股份有限公司 Composition and process for improving the adhesion of a siccative organic coating compositions to metal substrates
CN115558384A (en) * 2022-11-02 2023-01-03 广东睿智环保科技有限责任公司 Low-temperature curing high-corner-coverage powder coating and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9101204D0 (en) * 1990-02-14 1991-02-27 Ici Plc Production of polyurethane polymers,the polymers so produced and compositions containing them
KR20040073698A (en) * 2003-02-14 2004-08-21 주식회사 금강고려화학 Composition for aqueous coating for plastic interior finish in automobile
CN1856594A (en) * 2003-09-02 2006-11-01 爱托特奇德国股份有限公司 Composition and process for improving the adhesion of a siccative organic coating compositions to metal substrates
CN115558384A (en) * 2022-11-02 2023-01-03 广东睿智环保科技有限责任公司 Low-temperature curing high-corner-coverage powder coating and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
张来新: "《有机合成化学》", 30 September 2003, 陕西科学技术出版社, pages: 73 - 75 *
曲家乐;王全杰;王闪闪;王玉洁;: "纳米二氧化硅改性水性聚氨酯", 皮革与化工, no. 01, 25 February 2013 (2013-02-25), pages 1 - 6 *
柳艳红;陈焕钦;: "水性聚氨酯涂料的改性研究进展", 化学建材, no. 03, 20 May 2008 (2008-05-20), pages 14 - 16 *

Similar Documents

Publication Publication Date Title
CN102993782B (en) Preparation method of polyurethane acrylate oligomer surface modified silica
CN101942192B (en) Method for preparing siloxane and nano silicon dioxide double modified ultraviolet curing aqueous polyurethane dispersion
CN109761834A (en) A kind of preparation method and application of the dispersible polyaspartic ester resin of water and aqueous carbamide paint
CN104592850B (en) The preparation method of ultra-hydrophilic transparent antifogging coating
CN101948561A (en) Organic/inorganic silicon hybrid resin for coating and preparation method thereof
CN101235148A (en) Multiple crosslinking ultraviolet light solidifying water polyurethane dispersoid and its preparation method and application
CN102336884A (en) Preparation method for macromonomer modified nanometer silica aqueous silica sol and light-cured aqueous polyurethane nanometer composite emulsion of same
CN113105605A (en) UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof
CN111944409A (en) Water-based two-component polyurethane coating and preparation method thereof
CN112048077B (en) Castor oil-based aqueous photocuring nonionic emulsion and preparation method and application thereof
CN107987244A (en) A kind of aqueous photosensitive supermolecule polyurethane resin and preparation method and application
CN103666241B (en) A kind of composite Nano waterborne UV coating and preparation method thereof
CN117126596B (en) High-strength wear-resistant water-based paint and preparation method thereof
CN114891183A (en) Waterborne polyurethane modified starch dispersion liquid and preparation method thereof
CN113512160B (en) Method for preparing antifouling surface by grafting organic-inorganic hybrid particle to lubricating oil
CN116478338A (en) Nano modified waterborne polyurethane composition and preparation method thereof
CN109575681A (en) A kind of water-based free radical-cationic hybrid light-curable ink and its application
CN112759995A (en) Amino-terminated polyether modified graphene oxide water-based high-corrosion-resistance coating and preparation method thereof
CN115232558B (en) Self-repairing waterproof coating and preparation method thereof
CN115011175B (en) Rare earth pigment photo-curing color paste and preparation method thereof
CN107501574B (en) UV-cured water-based composite emulsion and preparation method and application thereof
CN107163277A (en) A kind of method that ultraviolet light prepares hydrophobic polyurethane film
CN110055018B (en) Water-resistant water-based adhesive for cloth
CN110862491A (en) Preparation method of multi-chain cross network type waterborne polyurethane
CN114479583B (en) Preparation method of coating composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination