CN112322169A - Waterborne polyurethane emulsion, preparation method, coating solution and PVC functional film - Google Patents
Waterborne polyurethane emulsion, preparation method, coating solution and PVC functional film Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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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
- C08G18/70—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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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Abstract
The invention belongs to the technical field of coatings, and particularly relates to a waterborne polyurethane emulsion, a preparation method thereof, a coating solution and a PVC functional film. The preparation method of the waterborne polyurethane emulsion comprises the following steps: prepolymerization, namely forming a prepolymer by polycarbonate polyol and isophorone diisocyanate; carrying out reflux reaction; carrying out neutralization reaction; dispersing and emulsifying; chain extension reaction; cooling to prepare the aqueous polyurethane emulsion. The PVC film has the advantages of wear resistance, toughness, high glossiness, difficult yellowing and stain resistance, can be used for plastic packaging or preparing PVC functional films with the effects of scratch resistance, stain resistance, high gloss and the like, is applied to surface veneers of furniture and home decoration, effectively solves the problem of environmental protection, improves the qualification rate of products and reduces the overall cost.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a waterborne polyurethane emulsion, a preparation method thereof, a coating solution and a PVC functional film.
Background
The PVC highlight scratch-resistant stain-resistant functional film is mainly applied to the fields of surface veneering of furniture and home decoration and the like. The common PVC decorative film has the defects of easy scratch, insufficient glossiness and no cleaning after the surface is stained by ball pens, marking pens and other articles. Products in the market achieve the effects of high gloss, scratch resistance and stain resistance through the ultraviolet curing of the oily coating, but the phenomenon of cracking of materials can be formed at the bent part in the plastic suction process; the water-based coating on the surface of the middle bending part hardly has the characteristics of high light and scratch resistance and has no stain resistance.
Disclosure of Invention
The invention provides a waterborne polyurethane emulsion, a preparation method thereof, a coating solution and a PVC functional film.
In order to solve the technical problems, the invention provides a preparation method of an aqueous polyurethane emulsion, which comprises the following steps: prepolymerization, namely forming a prepolymer by polycarbonate polyol and isophorone diisocyanate; carrying out reflux reaction; carrying out neutralization reaction; dispersing and emulsifying; chain extension reaction; cooling to prepare the aqueous polyurethane emulsion.
In a second aspect, the invention also provides an aqueous polyurethane emulsion, which comprises the following raw materials: polycarbonate polyol, isophorone diisocyanate and modified fluorine materials.
In a third aspect, the invention also provides a coating solution, which comprises the following raw materials in parts by mass: 45-50 parts of a water-based polyurethane emulsion; 3-4 parts of a crosslinking agent; 0.5-1 part of a defoaming agent; 0.5-1 part of a wetting agent; 0.2-5 parts of a drier; and 40-45 parts of a solvent.
In a fourth aspect, the present invention also provides a method for synthesizing a coating solution, comprising: sequentially adding the aqueous polyurethane emulsion, the wetting agent and the defoaming agent, and stirring and mixing; adding a drier and increasing the stirring speed; adding a cross-linking agent and a solvent, and reducing the stirring speed; and filtering to obtain a coating solution.
In a fifth aspect, the present invention also provides a PVC functional film, including: the functional coating is positioned on the surface of the substrate.
In a sixth aspect, the present invention further provides a spraying process, including: spraying the coating solution onto the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue between 35 and 45g per square meter; drying at 55-65 ℃.
The invention has the beneficial effects that the waterborne polyurethane emulsion, the preparation method, the coating solution, the synthesis method, the functional film and the spraying process prepare the waterborne polyurethane emulsion from the polycarbonate polyol, the isophorone diisocyanate and the modified fluorine material through prepolymerization, reflux reaction, neutralization reaction, dispersion and emulsification, chain extension reaction and cooling, has the advantages of wear resistance, toughness and high glossiness, is not easy to yellow and stain resistant, can be used for plastic packaging or preparing a PVC functional film with the effects of scratch resistance, stain resistance, high gloss and the like, and can be applied to surface veneering of furniture and home furnishings, so that the environmental protection problem is effectively solved, the qualification rate of products is improved, and the overall cost is reduced.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a process for preparing an aqueous polyurethane emulsion of the present invention;
FIG. 2 is a flow chart of a process for preparing the coating solution of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. 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.
A first part: elucidating the specific technical scheme
Aiming at the defects that the water-based coating in the prior art is difficult to have high light, scratch resistance and stain resistance, the phenomenon that a material is cracked at a bent part is particularly caused in the plastic suction process. Referring to fig. 1, the invention provides a preparation method of an aqueous polyurethane emulsion, comprising the following steps: prepolymerization, namely forming a prepolymer by polycarbonate polyol and isophorone diisocyanate; carrying out reflux reaction; carrying out neutralization reaction; dispersing and emulsifying; chain extension reaction; cooling to prepare the aqueous polyurethane emulsion.
As an alternative to prepolymerization.
At normal temperature and normal pressure, mixing polycarbonate polyol and isophorone diisocyanate according to a molar ratio of 1: 1.2-1.5, pumping into a polyurethane resin reaction kettle, starting a stirring device to stir the materials, and enabling polycarbonate polyol and isophorone diisocyanate to form a prepolymer.
Optionally, the molecular formula of the polycarbonate polyol is shown in the specification
(n is 6 to 9); wherein HO-R-OH is such as but not limited to 1, 4-Butanediol (BDO), 1, 6-Hexanediol (HDO), diethylene glycol, 1, 5-hexanediol, triethylene glycol, low molecular weight polyester glycol and the like, and has the advantages of excellent scratch resistance, good toughness, high glossiness and the like.
Optionally, the molecular formula of the isophorone diisocyanate is
As an alternative embodiment of the reflux reaction.
The reflux reaction comprises the following steps: adding an auxiliary agent and a catalyst into the prepolymer, and carrying out reflux reaction for 3-5 hours at the temperature of 60 ℃; wherein the additives comprise butanediol and a rheological additive: the catalyst comprises: dibutyltin dilaurate; can improve the purity, improve the reaction degree and reduce the content of the small molecular monomer.
As an alternative embodiment of the neutralization reaction.
The neutralization reaction comprises the following steps: when the content of isocyanic acid radical reaches the specified value (generally less than 0.5 per thousand), the product of the reflux reaction is cooled to 30-40 ℃; transferring the mixture into a high-speed dispersion machine, and adding triethylamine for neutralization. Can adjust the pH value to be alkalescent.
As an alternative to dispersion emulsification.
The dispersion and emulsification comprises the following steps: adding the modified fluorine material for dispersion at low temperature (15 +/-5 ℃), and then adding deionized water for emulsification so as to better disperse the modified fluorine material and the polyurethane particles in water; wherein the molecular formula of the modified fluorine material is
Is a modified fluorine material with hydroxyl.
The conventional fluorine materials (such as Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluoroolefin-vinyl ether copolymer (FEVE) and the like) have good hydrophobicity, so that the conventional fluorine materials cannot be well compatible with water, and further influence synthetic resins, so that the conventional fluorine materials are difficult to be used for dispersion and emulsification in the scheme. Compared with the conventional fluorine material, the fluorine material is modified by the scheme, so that the fluorine material has lower surface energy and extremely low friction coefficient, and has good compatibility with the aqueous polyurethane main body.
The specific dispersing and emulsifying process is as follows: adding the modified fluorine material while stirring at high speed, adding deionized water after 1.5 hours for emulsification, and dispersing the prepolymer in water under the action of shearing force. The dispersion process must be carried out at low temperatures in order to reduce the reactivity of the-NCO with water.
As an alternative embodiment of the chain extension reaction.
The chain extension reaction comprises the following steps: adding a chain extender to enable the dispersed and emulsified product to generate high molecular weight waterborne polyurethane; wherein the chain extender comprises at least one of ethylenediamine and dimethylolbutyric acid. The ethylene diamine and the dimethylolbutyric acid with high reaction activity are subjected to chain extension in water, so that the chain extension reaction can be rapidly promoted, and the high-molecular-weight waterborne polyurethane is generated.
As an alternative to cooling.
When the polymer reaches a certain viscosity (the general viscosity range is 20-50cps), introducing cooling water into the jacket to cool the materials to 40 ℃, opening a nitrogen control valve to introduce nitrogen (0.3MPa) into the reaction kettle, opening a kettle bottom valve, filtering impurities of the materials by a stainless steel filter screen, and pressing the materials into a 200Kg plastic bucket to obtain the waterborne polyurethane emulsion.
In the scheme, the preparation method of the aqueous polyurethane emulsion also needs to be combined with corresponding production equipment to control the following preparation process conditions:
(1) the liquid material ensures the pipeline to be closely conveyed.
(2) Polyester polyol is matched with heat conducting oil and a cooling water coil; the polyurethane resin reaction kettle is provided with a jacket, steam and cooling water can be introduced, the temperature is controlled by DCS, when the temperature does not reach a set value, a steam valve is opened for heating, when the temperature is too high, a valve at a steam inlet is closed, and a cooling water valve is opened for cooling the reaction kettle.
(3) The nitrogen flow is manually controlled and needs to be measured by a nitrogen flow meter.
(4) The quality control of polyester polyol uses nitrogen atmosphere to prevent oxidation reaction.
(5) The reaction kettle is provided with a condenser, and the condenser is provided with a discharge pipe connected with the receiving barrel to ensure the collection and treatment of waste gas in the preparation process.
(6) The polyester polyol is directly conveyed into a tank through a pipeline for storage for standby use, and N is used for finished product packaging and material pressing2。
Further, the invention also provides a waterborne polyurethane emulsion, which comprises the following raw materials: polycarbonate polyol, isophorone diisocyanate and modified fluorine materials.
The raw materials can be prepared into the aqueous polyurethane emulsion by the preparation method of the aqueous polyurethane emulsion and combining with a chain extender, an auxiliary agent, a catalyst and the like. The dosage and the adding process of each component can be referred to the relevant description in the preparation method of the aqueous polyurethane emulsion.
Further, the invention also provides a coating solution which comprises the following raw materials in parts by weight: 45-50 parts of a water-based polyurethane emulsion; 3-4 parts of a crosslinking agent; 0.5-1 part of a defoaming agent; 0.5-1 part of a wetting agent; 0.2-5 parts of a drier; and 40-45 parts of solvent (such as deionized water).
Optionally, the coating solution comprises the following raw materials in parts by mass: 48 parts of a water-based polyurethane emulsion; 3.5 parts of a crosslinking agent; 0.8 part of defoaming agent; 0.7 part of wetting agent; 2 parts of a drier; and 45 parts of a solvent.
Further, referring to fig. 2, the present invention also provides a method for synthesizing a coating solution, comprising: sequentially adding the aqueous polyurethane emulsion, the wetting agent and the defoaming agent, and stirring and mixing; adding a drier and increasing the stirring speed; adding a cross-linking agent and a solvent, and reducing the stirring speed; and filtering to obtain a coating solution. Specifically, when the drier is added, the stirring speed can be increased to 2000r/min, which is beneficial to the dispersion and more uniformity of the mixture; after the cross-linking agent and the solvent are added, the stirring speed can be reduced to 200r/min, and the water is prevented from foaming too much.
Further, the invention also provides a PVC functional film, which comprises: the functional coating is positioned on the surface of the substrate.
Optionally, the substrate is, for example but not limited to, a rigid transparent PVC film, and the thickness of the substrate is 0.06-0.07 mm.
Further, the invention also provides a spraying process, which comprises the following steps: spraying the coating solution onto the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue between 35 and 45g per square meter; drying at 55-65 ℃.
Specifically, the coating solution is sprayed to the surface of a substrate through a micro-concave coating head, and the coating weight of wet glue is between 35 and 45g per square meter; and (3) drying the sprayed substrate by 15 groups of 6-meter drying ovens, controlling the temperature to be 55-65 ℃ and the speed to be 35 m/min.
A second part: some examples are given below
Example 1
(1) Preparation of aqueous polyurethane emulsion
Mixing polycarbonate polyol and isophorone diisocyanate according to a molar ratio of 1: 1.2, pumping the mixture into a polyurethane resin reaction kettle, and starting a stirring device to stir the materials. And adding an auxiliary agent, a catalyst and the like into the prepolymer, and carrying out reflux reaction for 3.5 hours at the temperature of 60 ℃. When the content of the isocyanic acid radical reaches a specified value, cooling to 38 +/-2 ℃, transferring to a high-speed dispersion machine, and adding triethylamine at a medium speed for neutralization. Adding the modified fluorine material while stirring at a high speed, and adding deionized water for emulsification after 1.5 hours to disperse the prepolymer in water under the action of shearing force. The dispersion process is carried out at low temperature to reduce the reactivity of-NCO and water, the water participating in the reaction is used as a chain extender, and then the ethylene diamine and dimethylolbutyric acid with high reactivity are used for chain extension in water to rapidly promote the chain growth reaction to generate the waterborne polyurethane with high molecular weight. And (3) introducing cooling water into the jacket to cool the materials to 40 ℃ after the polymer reaches a certain viscosity, opening a nitrogen control valve to introduce nitrogen (0.3MPa) into the reaction kettle, opening a kettle bottom valve, filtering impurities of the materials through a stainless steel filter screen, and pressing the materials into a 200Kg plastic bucket for packaging to obtain the finished product of the waterborne polyurethane emulsion.
(2) Preparation of coating solution
Sequentially adding 50 parts of waterborne polyurethane emulsion, 0.8 part of wetting agent and 0.8 part of defoaming agent, and stirring and mixing; adding 0.4 part of drier and increasing the stirring speed; adding 3 parts of cross-linking agent and 45 parts of solvent, and reducing the stirring speed; and filtering to obtain a coating solution.
(3) Spraying of paint
Spraying the coating solution to the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue at 35 g/square meter; drying at 55-60 ℃ to obtain the PVC functional film.
Example 2
(1) Preparation of aqueous polyurethane emulsion
Mixing polycarbonate polyol and isophorone diisocyanate according to a molar ratio of 1: 1.5, pumping the mixture into a polyurethane resin reaction kettle, and starting a stirring device to stir the materials. And adding an auxiliary agent, a catalyst and the like into the prepolymer, and carrying out reflux reaction for 5 hours at the temperature of 60 ℃. When the content of the isocyanic acid radical reaches a specified value, cooling to 32 +/-2 ℃, transferring to a high-speed dispersion machine, and adding triethylamine at a medium speed for neutralization. Adding the modified fluorine material while stirring at a high speed, and adding deionized water for emulsification after 1.5 hours to disperse the prepolymer in water under the action of shearing force. The dispersion process is carried out at low temperature to reduce the reactivity of-NCO and water, the water participating in the reaction is used as a chain extender, and then the ethylene diamine and dimethylolbutyric acid with high reactivity are used for chain extension in water to rapidly promote the chain growth reaction to generate the waterborne polyurethane with high molecular weight. And (3) introducing cooling water into the jacket to cool the materials to 40 ℃ after the polymer reaches a certain viscosity, opening a nitrogen control valve to introduce nitrogen (0.3MPa) into the reaction kettle, opening a kettle bottom valve, filtering impurities of the materials through a stainless steel filter screen, and pressing the materials into a 200Kg plastic bucket for packaging to obtain the finished product of the waterborne polyurethane emulsion.
(2) Preparation of coating solution
Sequentially adding 50 parts of waterborne polyurethane emulsion, 1 part of wetting agent and 1 part of defoaming agent, and stirring and mixing; adding 4 parts of drier and increasing the stirring speed; adding 4 parts of cross-linking agent and 40 parts of solvent, and reducing the stirring speed; and filtering to obtain a coating solution.
(3) Spraying of paint
Spraying the coating solution to the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue at 45 g/square meter; drying at 60-65 ℃ to obtain the PVC functional film.
Example 3
(1) Preparation of aqueous polyurethane emulsion
Mixing polycarbonate polyol and isophorone diisocyanate according to a molar ratio of 1: 1.3, pumping the mixture into a polyurethane resin reaction kettle, and starting a stirring device to stir the materials. And adding an auxiliary agent, a catalyst and the like into the prepolymer, and carrying out reflux reaction for 4 hours at the temperature of 60 ℃. When the content of the isocyanic acid radical reaches a specified value, cooling to 36 +/-2 ℃, transferring to a high-speed dispersion machine, and adding triethylamine at a medium speed for neutralization. Adding the modified fluorine material while stirring at a high speed, and adding deionized water for emulsification after 1.5 hours to disperse the prepolymer in water under the action of shearing force. The dispersion process is carried out at low temperature to reduce the reactivity of-NCO and water, the water participating in the reaction is used as a chain extender, and then the ethylene diamine and dimethylolbutyric acid with high reactivity are used for chain extension in water to rapidly promote the chain growth reaction to generate the waterborne polyurethane with high molecular weight. And (3) introducing cooling water into the jacket to cool the materials to 40 ℃ after the polymer reaches a certain viscosity, opening a nitrogen control valve to introduce nitrogen (0.3MPa) into the reaction kettle, opening a kettle bottom valve, filtering impurities of the materials through a stainless steel filter screen, and pressing the materials into a 200Kg plastic bucket for packaging to obtain the finished product of the waterborne polyurethane emulsion.
(2) Preparation of coating solution
Adding 49 parts of aqueous polyurethane emulsion, 0.8 part of wetting agent and 0.7 part of defoaming agent in sequence, and stirring and mixing; adding 1 part of drier and increasing the stirring speed; adding 3.5 parts of cross-linking agent and 45 parts of solvent, and reducing the stirring speed; and filtering to obtain a coating solution.
(3) Spraying of paint
Spraying the coating solution to the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue at 38 g/square meter; drying at 56-61 deg.c to obtain the functional PVC film.
Example 4
(1) Preparation of aqueous polyurethane emulsion
Mixing polycarbonate polyol and isophorone diisocyanate according to a molar ratio of 1: 1.4, pumping the mixture into a polyurethane resin reaction kettle, starting a stirring device to stir the materials, adding an auxiliary agent, a catalyst and the like into the prepolymer, and carrying out reflux reaction for 4.5 hours at the temperature of 60 ℃. When the content of the isocyanic acid radical reaches a specified value, cooling to 34 +/-2 ℃, transferring to a high-speed dispersion machine, and adding triethylamine at a medium speed for neutralization. Adding the modified fluorine material while stirring at a high speed, and adding deionized water for emulsification after 1.5 hours to disperse the prepolymer in water under the action of shearing force. The dispersion process is carried out at low temperature to reduce the reactivity of-NCO and water, the water participating in the reaction is used as a chain extender, and then the ethylene diamine and dimethylolbutyric acid with high reactivity are used for chain extension in water to rapidly promote the chain growth reaction to generate the waterborne polyurethane with high molecular weight. And (3) introducing cooling water into the jacket to cool the materials to 40 ℃ after the polymer reaches a certain viscosity, opening a nitrogen control valve to introduce nitrogen (0.3MPa) into the reaction kettle, opening a kettle bottom valve, filtering impurities of the materials through a stainless steel filter screen, and pressing the materials into a 200Kg plastic bucket for packaging to obtain the finished product of the waterborne polyurethane emulsion.
(2) Preparation of coating solution
Adding 48 parts of aqueous polyurethane emulsion, 0.9 part of wetting agent and 0.9 part of defoaming agent in sequence, stirring and mixing; 2.4 parts of drier is added, and the stirring speed is increased; adding 3.8 parts of cross-linking agent and 44 parts of solvent, and reducing the stirring speed; and filtering to obtain a coating solution.
(3) Spraying of paint
Spraying the coating solution to the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue at 42 g/square meter; drying at 58-63 ℃ to obtain the PVC functional film.
Comparative example 1
(1) Preparation of aqueous polyurethane emulsion
Mixing polycarbonate polyol and isophorone diisocyanate according to a molar ratio of 1: 1.2, pumping the mixture into a polyurethane resin reaction kettle, and starting a stirring device to stir the materials. And adding an auxiliary agent, a catalyst and the like into the prepolymer, and carrying out reflux reaction for 3.5 hours at the temperature of 60 ℃. When the content of the isocyanic acid radical reaches a specified value, cooling to 38 +/-2 ℃, transferring to a high-speed dispersion machine, and adding triethylamine at a medium speed for neutralization. Adding conventional fluorine material (such as Polytetrafluoroethylene (PTFE)) while stirring at high speed, adding deionized water after 1.5 hours for emulsification, and dispersing the prepolymer in water under the action of shearing force. The dispersion process is carried out at low temperature to reduce the reactivity of-NCO and water, the water participating in the reaction is used as a chain extender, and then the ethylene diamine and dimethylolbutyric acid with high reactivity are used for chain extension in water to rapidly promote the chain growth reaction to generate the waterborne polyurethane with high molecular weight. And (3) introducing cooling water into the jacket to cool the materials to 40 ℃ after the polymer reaches a certain viscosity, opening a nitrogen control valve to introduce nitrogen (0.3MPa) into the reaction kettle, opening a kettle bottom valve, filtering impurities of the materials through a stainless steel filter screen, and pressing the materials into a 200Kg plastic bucket for packaging to obtain the finished product of the waterborne polyurethane emulsion.
(2) Preparation of coating solution
Sequentially adding 50 parts of waterborne polyurethane emulsion, 0.8 part of wetting agent and 0.8 part of defoaming agent, and stirring and mixing; adding 0.4 part of drier and increasing the stirring speed; adding 3 parts of cross-linking agent and 45 parts of solvent, and reducing the stirring speed; and filtering to obtain a coating solution.
(3) Spraying of paint
Spraying the coating solution to the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue at 35 g/square meter; drying at 55-60 ℃ to obtain the PVC functional film.
Comparative example 2
The aqueous polyurethane resin is prepared according to the technical scheme disclosed in CN 101033287A. The method comprises the following specific steps:
(1) reacting polyester polyol a1, polyether polyol a2, dihydric alcohol b1 and organic polyisocyanate c1 at 70-80 ℃ for 2-4 hours in the presence of dibutyltin dilaurate catalyst; wherein the molar ratio of a1 to a2 to c1 is c1 (a1+ a2) ═ 2.3-3.3: 1, a2: a1 is 0-70: 30-100, the mass of the dihydric fluoroalcohol is 0.1-2% of the total mass of the prepolymer, and the mass of the dibutyltin dilaurate is 0.01-0.1% of the total mass of the prepolymer;
(2) then adding a hydrophilic component accounting for 3.0-6.5% of the total mass of the prepolymer, a polyhydroxy-containing small molecular compound accounting for 0-2.5% of the total mass of the prepolymer and acetone accounting for 5-15% of the total mass of the prepolymer, and reacting at 65-70 ℃ for 2 hours to obtain a prepolymer;
(3) then, when the temperature is reduced to 40 ℃, triethylamine is added into the prepared prepolymer for neutralization, and the neutralization degree is controlled to be 60-110%; adding the neutralized polyurethane prepolymer into deionized water and low-molecular polyamine which account for 45-65% of the total mass of the aqueous polyurethane emulsion, stirring at a high speed for 0.5-1 hour, and simultaneously carrying out emulsification and chain extension reaction; wherein the molar consumption of the low molecular weight polyamine is 60-120% of the difference between the total mole number of-NCO and the total mole number of-OH in the raw materials, and finally, the acetone is evaporated under reduced pressure to prepare the aqueous polyurethane emulsion with the solid content of 35-55%; the hydrophilic component is 2, 2-dimethylolacetic acid, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid or 2, 2-dimethylolpentanoic acid; the polyhydroxy micromolecule compound is trimethylolpropane, 1, 4-butanediol, glycol or 1, 6-hexanediol; the low molecular weight polyamine has a molecular weight less than 300, and is ethylenediamine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, hydrazine or isophorone diamine. The polyester polyol is polyester dihydric alcohol, polylactone diol or polycarbonate diol, and the molecular weight is 600-5000. The organic polyisocyanate is one or a mixture of two of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate and diphenylmethane-4, 4' -diisocyanate. Comparative example 3
The waterborne polyurethane resin is prepared according to the technical scheme disclosed in CN101033287A, and the modified fluorine material is added into the waterborne polyurethane resin. The method comprises the following specific steps:
(1) reacting polyester polyol a1, polyether polyol a2, dihydric alcohol b1 and organic polyisocyanate c1 at 70-80 ℃ for 2-4 hours in the presence of dibutyltin dilaurate catalyst; wherein the molar ratio of a1 to a2 to c1 is c1 (a1+ a2) ═ 2.3-3.3: 1, a2: a1 is 0-70: 30-100, the mass of the dihydric fluoroalcohol is 0.1-2% of the total mass of the prepolymer, and the mass of the dibutyltin dilaurate is 0.01-0.1% of the total mass of the prepolymer;
(2) then adding a hydrophilic component accounting for 3.0-6.5% of the total mass of the prepolymer, a polyhydroxy-containing small molecular compound accounting for 0-2.5% of the total mass of the prepolymer and acetone accounting for 5-15% of the total mass of the prepolymer, and reacting at 65-70 ℃ for 2 hours to obtain a prepolymer;
(3) then, when the temperature is reduced to 40 ℃, triethylamine is added into the prepared prepolymer for neutralization, and the neutralization degree is controlled to be 60-110%; adding the neutralized polyurethane prepolymer into deionized water and low-molecular polyamine which account for 45-65% of the total mass of the aqueous polyurethane emulsion, adding the modified fluorine material, stirring at a high speed for 0.5-1 hour, and simultaneously performing emulsification and chain extension reaction; wherein the molar consumption of the low molecular weight polyamine is 60-120% of the difference between the total mole number of-NCO and the total mole number of-OH in the raw materials, and finally, the acetone is evaporated under reduced pressure to prepare the aqueous polyurethane emulsion with the solid content of 35-55%; the hydrophilic component is 2, 2-dimethylolacetic acid, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid or 2, 2-dimethylolpentanoic acid; the polyhydroxy micromolecule compound is trimethylolpropane, 1, 4-butanediol, glycol or 1, 6-hexanediol; the low molecular weight polyamine has a molecular weight less than 300, and is ethylenediamine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, hydrazine or isophorone diamine. The polyester polyol is polyester dihydric alcohol, polylactone diol or polycarbonate diol, and the molecular weight is 600-5000. The organic polyisocyanate is one or a mixture of two of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate and diphenylmethane-4, 4' -diisocyanate.
And a third part: comparative analysis of performance parameters
The PVC functional films prepared in examples 1 to 4 and the diaphragms prepared in comparative examples 1 to 3 were tested in this section, and the test results are shown in Table 1. Wherein the glossiness adopts a glossiness tester of 60 degrees, and the detection standard is GB 8807-1988; the scratch resistance adopts a multifunctional alcohol rubber friction tester, and the detection standard is FLTMBN 107-01; the pollution resistance adopts a coating pollution resistance tester, and is in accordance with BG/T9780-2013 standard.
TABLE 1 test results of the functional films
As shown in Table 1, the stain resistance of the PVC functional films prepared in examples 1-4 is far better than that of other comparative examples. In comparative example 1, which is the test data of the preparation method according to the present invention but adding the conventional fluorine material, the appearance problems of bright stripes, shrinkage cavities and the like occur during coating of the separator due to poor solution compatibility. Further as comparative example 2 is experimental data for the preparation according to the comparative patent (unmodified fluoro material), the membrane gloss is very poor and far from reaching the desired gloss of more than 95. In addition, as comparative example 3, the preparation method disclosed in the patent CN101033287A is followed, but the experimental data of adding the modified fluorine material in the present case shows that the scratch resistance effect of the membrane is not sufficient and the flexibility is poor.
In conclusion, the waterborne polyurethane emulsion, the preparation method, the coating solution, the synthesis method, the functional film and the spraying process of the invention prepare the waterborne polyurethane emulsion from the polycarbonate polyol, the isophorone diisocyanate and the modified fluorine material through prepolymerization, reflux reaction, neutralization reaction, dispersion emulsification, chain extension reaction and cooling, and have the advantages of wear resistance, toughness, high glossiness and difficult yellowing.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A preparation method of aqueous polyurethane emulsion is characterized by comprising the following steps:
prepolymerization, namely forming a prepolymer by polycarbonate polyol and isophorone diisocyanate;
carrying out reflux reaction;
carrying out neutralization reaction;
dispersing and emulsifying;
chain extension reaction;
cooling to prepare the aqueous polyurethane emulsion.
2. The aqueous polyurethane emulsion according to claim 1,
the reflux reaction comprises the following steps: adding an auxiliary agent and a catalyst into the prepolymer, and carrying out reflux reaction for 3-5 hours at the temperature of 60 ℃; wherein
The auxiliary agent comprises: butanediol and a rheology aid;
the catalyst comprises: dibutyltin dilaurate.
3. The production method according to claim 1,
the neutralization reaction comprises the following steps:
cooling the product of the reflux reaction to 30-40 ℃;
transferring the mixture into a high-speed dispersion machine, and adding triethylamine for neutralization.
4. The production method according to claim 1,
the dispersion and emulsification comprises the following steps: adding the modified fluorine material for dispersion at low temperature, and adding deionized water for emulsification; wherein
The molecular formula of the modified fluorine material is
5. The production method according to claim 1,
the chain extension reaction comprises the following steps: adding a chain extender to enable the dispersed and emulsified product to generate high molecular weight waterborne polyurethane; wherein
The chain extender comprises at least one of ethylenediamine and dimethylolbutyric acid.
6. The waterborne polyurethane emulsion is characterized by comprising the following raw materials:
polycarbonate polyol, isophorone diisocyanate and modified fluorine materials.
7. The coating solution is characterized by comprising the following raw materials in parts by mass:
45-50 parts of a water-based polyurethane emulsion;
3-4 parts of a crosslinking agent;
0.5-1 part of a defoaming agent;
0.5-1 part of a wetting agent;
0.2-5 parts of a drier; and
40-45 parts of a solvent.
8. A method of synthesizing a coating solution, comprising:
sequentially adding the aqueous polyurethane emulsion, the wetting agent and the defoaming agent, and stirring and mixing;
adding a drier and increasing the stirring speed;
adding a cross-linking agent and a solvent, and reducing the stirring speed;
and filtering to obtain a coating solution.
9. A functional film, comprising:
the functional coating is positioned on the surface of the substrate.
10. A spray coating process, comprising:
spraying the coating solution onto the surface of a substrate through a micro-concave coating head, and keeping the coating weight of wet glue between 35 and 45g per square meter;
drying at 55-65 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116218347A (en) * | 2022-06-24 | 2023-06-06 | 国家电投集团科学技术研究院有限公司 | Cavitation erosion resistant finish paint and preparation method and application thereof |
| CN116285646A (en) * | 2022-11-30 | 2023-06-23 | 广东邦固化学科技有限公司 | Water-based paint with excellent adhesive force to polypropylene film and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465565B1 (en) * | 2000-07-06 | 2002-10-15 | Omnova Solutions, Inc. | Anionic waterborne polyurethane dispersions containing polyfluorooxetanes |
| JP2006096893A (en) * | 2004-09-30 | 2006-04-13 | Sanyo Chem Ind Ltd | Polyurethane resin emulsion |
| JP2008156488A (en) * | 2006-12-25 | 2008-07-10 | Nippon Polyurethane Ind Co Ltd | Water-based polyurethane resin emulsion coating composition and method for production thereof |
| KR20080114371A (en) * | 2007-06-27 | 2008-12-31 | 주식회사 케이씨씨 | A method for preparing water dispersable and crosslinkable polyurethane resin containing inorganic compounds and an aqueous coating composition containing this resin |
| CN101838383A (en) * | 2010-04-06 | 2010-09-22 | 杭州之江有机硅化工有限公司 | Aqueous fluoro modified urethane resin and preparation of aqueous fluoro modified urethane resin paint |
| CN104059420A (en) * | 2014-05-22 | 2014-09-24 | 张扬 | Nano-paste, self-cleaning coating liquid and thermal insulating coating liquid as well as transparent substrates and preparation methods thereof |
| CN104530372A (en) * | 2014-12-25 | 2015-04-22 | 张家港康得新光电材料有限公司 | Water-based polyurethane and preparation method thereof, and composite film with water-based polyurethane |
-
2020
- 2020-11-17 CN CN202011286741.2A patent/CN112322169A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465565B1 (en) * | 2000-07-06 | 2002-10-15 | Omnova Solutions, Inc. | Anionic waterborne polyurethane dispersions containing polyfluorooxetanes |
| JP2006096893A (en) * | 2004-09-30 | 2006-04-13 | Sanyo Chem Ind Ltd | Polyurethane resin emulsion |
| JP2008156488A (en) * | 2006-12-25 | 2008-07-10 | Nippon Polyurethane Ind Co Ltd | Water-based polyurethane resin emulsion coating composition and method for production thereof |
| KR20080114371A (en) * | 2007-06-27 | 2008-12-31 | 주식회사 케이씨씨 | A method for preparing water dispersable and crosslinkable polyurethane resin containing inorganic compounds and an aqueous coating composition containing this resin |
| CN101838383A (en) * | 2010-04-06 | 2010-09-22 | 杭州之江有机硅化工有限公司 | Aqueous fluoro modified urethane resin and preparation of aqueous fluoro modified urethane resin paint |
| CN104059420A (en) * | 2014-05-22 | 2014-09-24 | 张扬 | Nano-paste, self-cleaning coating liquid and thermal insulating coating liquid as well as transparent substrates and preparation methods thereof |
| CN104530372A (en) * | 2014-12-25 | 2015-04-22 | 张家港康得新光电材料有限公司 | Water-based polyurethane and preparation method thereof, and composite film with water-based polyurethane |
Non-Patent Citations (2)
| Title |
|---|
| 李冠来等: ""水性自交联PCD改性聚氨酯的研制及在高抗刮性家具涂料中的应用"", 《涂料技术与文摘》 * |
| 汪立强等: ""环氧树脂_有机硅复合改性水性聚氨酯的研究"", 《杭州化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116218347A (en) * | 2022-06-24 | 2023-06-06 | 国家电投集团科学技术研究院有限公司 | Cavitation erosion resistant finish paint and preparation method and application thereof |
| CN116218347B (en) * | 2022-06-24 | 2024-02-06 | 国家电投集团科学技术研究院有限公司 | Cavitation erosion resistant finish paint and preparation method and application thereof |
| CN116285646A (en) * | 2022-11-30 | 2023-06-23 | 广东邦固化学科技有限公司 | Water-based paint with excellent adhesive force to polypropylene film and preparation method thereof |
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