CN113683747B - High-solid-content self-extinction aqueous polyurethane dispersion and preparation method thereof - Google Patents

High-solid-content self-extinction aqueous polyurethane dispersion and preparation method thereof Download PDF

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CN113683747B
CN113683747B CN202110673624.XA CN202110673624A CN113683747B CN 113683747 B CN113683747 B CN 113683747B CN 202110673624 A CN202110673624 A CN 202110673624A CN 113683747 B CN113683747 B CN 113683747B
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chain extender
prepolymer
organic solvent
stirring
catalyst
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CN113683747A (en
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姚红涛
司园精
吴后胜
张崇照
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Xiamen Winlight Optical Coating Technology Co ltd
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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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3206—Polyhydroxy compounds aliphatic
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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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
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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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
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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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers

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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of waterborne polyurethane resin, in particular to a high-solid-content self-extinction waterborne polyurethane dispersion and a preparation method thereof. The raw materials comprise the following components in percentage by weight: 15-40% of polymer polyol, 10-30% of isocyanate, 0.1-3% of first chain extender, 0.3-15% of second chain extender, 0.01-0.2% of catalyst, 5-30% of organic solvent and the balance of water; the first chain extender is a dihydroxysulfonic acid amine salt compound. According to the invention, 1, 2-dihydroxy-propanesulfonic acid amine salt is used as a preparation raw material of polyurethane, and the amine salt and substances such as specific polymer polyol act together, so that the solid content of the waterborne polyurethane is obviously improved, and the production, storage and transportation costs are low; the method adopts the low-boiling-point organic solvent to carry out smooth reaction, avoids the problems of high danger coefficient and the like caused by the introduction of the high-boiling-point solvent, has simple and convenient integral process and safe reaction process, and is suitable for wide popularization in the field of waterborne polyurethane.

Description

High-solid-content self-extinction aqueous polyurethane dispersion and preparation method thereof
Technical Field
The invention relates to the technical field of waterborne polyurethane resin, in particular to a high-solid-content self-extinction waterborne polyurethane dispersion and a preparation method thereof.
Background
The traditional delustering resin is prepared by dispersing a delustering agent into base material emulsion under the action of shearing force and adding an auxiliary agent with the functions of preventing sedimentation, thickening and the like; after the film is formed, a surface material with high roughness can be formed, so that light rays are subjected to diffuse reflection and scattering, and the extinction effect is achieved. Common matting agents can be classified into organic matting agents and inorganic matting agents 2; the organic flatting agent mainly comprises metal soap, wax and tung oil; the inorganic flatting agent mainly comprises diatomite, kaolin, talcum powder and silicon dioxide. The extinction resin has obvious extinction effect, but the addition of the extinction agent can cause the problems of increased brittleness, poor hand feeling, poor adhesive force, easy breaking and falling and the like of the coating. The precipitation of the matting material results in poor storage stability, which causes differences in gloss of the coating; poor polishing resistance of the coating, low transparency of the coating film and the like. The self-extinction waterborne polyurethane emulsion generates a micro-nano rough surface after emulsion particles with large particle size and high strength are solidified on the surface of a base material, and enhances the scattering and refraction of light, thereby achieving the extinction effect. The method not only solves the defects of the coating caused by the use of the traditional flatting agent, but also has excellent emulsion stability.
In the prior art, most of self-extinction aqueous polyurethane emulsion has low solid content (20-40 percent), and the product packaging, storage and transportation cost is increased. The high-solid content self-extinction waterborne polyurethane (the solid content is more than or equal to 50%) has low water content, so the drying and film-forming time is shortened, the production efficiency of the high-solid content self-extinction waterborne polyurethane is higher than that of the low-solid content waterborne polyurethane, and the storage and transportation cost is low, so the high-solid content quantitative development of the waterborne polyurethane becomes a hot research subject in the field. Chinese patent CN109206588A discloses a high-solid content large-particle size self-extinction aqueous polyurethane emulsion, which achieves the effect of improving extinction degree by the reaction of polyester polyol mixture, hydrophilic sulfonate oligomer dihydric alcohol, diisocyanate and other raw materials, but the solid content of a polyurethane product obtained by the prior art is only 43.6 percent at most; it is difficult to give consideration to the multiple effect promotion of polyurethane extinction degree and solid content. Based on the above, the research of the waterborne polyurethane with high solid content, strong extinction property and strong operability becomes an urgent problem to be solved in the field.
Disclosure of Invention
The invention provides the self-extinction aqueous polyurethane dispersion with high solid content, solves the problems of high brittleness, poor hand feeling, poor adhesive force, easy breakage and falling and the like of a coating caused by the traditional extinction agent, and overcomes the defect of low solid content of the self-extinction polyurethane, and realizes the aqueous polyurethane with high solid content, strong extinction property and strong operability.
The invention provides a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following raw materials in percentage by weight: 15-40% of polymer polyol, 10-30% of isocyanate, 0.1-3% of first chain extender, 0.3-15% of second chain extender, 0.01-0.2% of catalyst, 5-30% of organic solvent and the balance of water;
the first chain extender is a dihydroxysulfonic acid amine salt compound.
In a preferred embodiment, the raw materials comprise, by weight: 20-30% of polymer polyol, 12-20% of isocyanate, 0.5-2% of first chain extender, 0.4-11% of second chain extender, 0.04-0.1% of catalyst, 12-18% of organic solvent and the balance of water.
In a preferred embodiment, the polymer polyol comprises a combination of one or more of adipic acid-based polyester polyols, phthalic anhydride polyester polyols, polycaprolactone polyols, polycarbonate polyols, dimer acid polyester polyols, polyether-polyester polyols, polylactic acid polyols.
In a preferred embodiment, the polymer polyol has an average molecular weight of 500 to 10000.
In a preferred embodiment, the isocyanate includes hexamethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, toluidine diisocyanate, diphenylmethane diisocyanate, and combinations based on one or more of the foregoing isocyanate derivatives.
In a preferred embodiment, the second chain extender comprises a combination of one or more of a carboxylic acid compound, a polyol, and a polyamine.
In a preferred embodiment, the catalyst comprises an organotin-based catalyst and/or an organobismuth-based catalyst.
In a preferred embodiment, the organic solvent has a boiling point of 30 to 85 ℃.
The second aspect of the invention provides a preparation method of a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting to generate a first prepolymer;
s2, adding a first chain extender, an organic solvent and a catalyst into the first prepolymer, and reacting to obtain a second prepolymer;
s3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, and stirring to obtain a finished product;
the second chain extender is added in at least 1 step of S1, S2, S3.
In a preferred embodiment, the stirring speed of the stirring operation in the step S3 is 1500-4000r/min, and the stirring time is 30-150min.
Has the advantages that:
the high-solid-content self-extinction aqueous polyurethane dispersion prepared by the invention has the following advantages:
(1) According to the invention, 1, 2-dihydroxy-propanesulfonic acid amine salt is used as a preparation raw material of polyurethane, and the amine salt and substances such as specific polymer polyol act together, so that the solid content of the waterborne polyurethane is obviously improved, the product drying speed is high, and the production, storage and transportation costs are low;
(2) The method adopts the low-boiling-point organic solvent to carry out smooth reaction, avoids the problems of high risk coefficient and the like caused by the introduction of the high-boiling-point solvent, has simple and convenient integral process and safe and controllable reaction process, and is suitable for wide popularization in the field of waterborne polyurethane.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
As used herein, the term "consisting of 8230; preparation" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 8230comprises" excludes any non-specified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of 8230title" appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; no other elements are excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein in the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes equivalent parts that are acceptable for use in a generic sense without departing from the spirit and scope of the invention. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.
In order to solve the above problems, the invention provides, in a first aspect, a high-solid content self-extinction aqueous polyurethane dispersion, which comprises the following raw materials in percentage by weight: 15-40% of polymer polyol, 10-30% of isocyanate, 0.1-3% of first chain extender, 0.3-15% of second chain extender, 0.01-0.2% of catalyst, 5-30% of organic solvent and the balance of water;
the first chain extender is a dihydroxysulfonic acid amine salt compound.
Further preferably, the raw materials comprise, by weight: 20-30% of polymer polyol, 12-20% of isocyanate, 0.5-2% of first chain extender, 0.4-11% of second chain extender, 0.04-0.1% of catalyst, 12-18% of organic solvent and the balance of water.
In some preferred embodiments, the dihydroxysulfonate amine salt compound is obtained by reacting dihydroxysulfonic acid and a tertiary amine compound.
Preferably, the dihydroxy amine carboxylate compound is prepared by acidifying dihydroxy carboxylate with an acid gas, and purifying with enamel thin film evaporation and short path molecular distillation equipment to obtain pure dihydroxy carboxylic acid; then reacting with tertiary amine compound to obtain the dihydroxysulfonate amine salt compound finished product. The above dihydroxy carboxylic acid and dihydroxy carboxylic acid amine salt compounds are commercially available, for example, xiamen optical coating technology, inc.
Examples of the above-mentioned dihydroxysulfonate amine salt compounds include, but are not limited to, 1, 2-dihydroxy-propanesulfonate triethylamine salt, 1, 2-dihydroxy-propanesulfonate tripropylamine salt, and 1, 2-dihydroxy-propanesulfonate tributylamine salt.
In some preferred embodiments, the polymer polyol comprises a combination of one or more of adipic acid-based polyester polyols, phthalic anhydride polyester polyols, polycaprolactone polyols, polycarbonate polyols, dimer acid polyester polyols, polyether-polyester polyols, polylactic acid polyols.
In some preferred embodiments, the polymer polyol has an average molecular weight of 500 to 10000.
Further preferably, the polymer polyol has an average molecular weight of 500 to 5000.
In some preferred embodiments, the isocyanate includes at least one isocyanate having a functionality of 2; the isocyanate having a functionality of 2 includes hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, toluidine diisocyanate, diphenylmethane diisocyanate, and combinations based on one or more of the foregoing isocyanate derivatives.
Examples of the cyclohexyl diisocyanate include, but are not limited to, 1, 4-cyclohexyl diisocyanate.
In some preferred embodiments, the second chain extender comprises a combination of one or more of a carboxylic acid compound, a polyol, and a polyamine.
Further preferably, the second chain extender comprises one or more of a combination of a polyol and a polyamine.
Examples of polyols include, but are not limited to, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol, trimethylolpropane, triethanolamine, glycerol, dimethylolbutyric acid, castor oil polyols.
As examples of polyamines. Including but not limited to ethylenediamine, isophoronediamine, hydrazine hydrate, N- (. Beta. -aminoethyl) -gamma-aminopropyltrimethoxysilane (KH 792), 4-diphenylmethanediamine, N- (. Beta. -aminoethyl) -gamma-aminopropylmethyldimethoxysilane (KH 602), hexamethylenediamine, pentamethylenediamine.
In some preferred embodiments, the catalyst comprises an organotin-based catalyst and/or an organobismuth-based catalyst.
Examples of the organotin-based catalyst include, but are not limited to, stannous octoate, dibutyltin dilaurate, dibutyltin bis (dodecylthio) diacetate, and dibutyltin diacetate.
Examples of the organic bismuth-based catalyst include, but are not limited to, bismuth neodecanoate, bismuth isooctanoate, and bismuth oxide.
In some preferred embodiments, the organic solvent has a boiling point of 30 to 85 ℃.
Further preferably, the boiling point of the organic solvent is 50 to 80 ℃.
Still more preferably, the organic solvent is acetone with a boiling point of 56.3 ℃.
The second aspect of the invention provides a preparation method of a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting to generate a first prepolymer;
s2, adding a first chain extender, an organic solvent and a catalyst into the first prepolymer, and reacting to obtain a second prepolymer;
s3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, and stirring to obtain a finished product;
the second chain extender is added in at least 1 step of S1, S2, S3.
In some preferred embodiments, the reaction temperature of the step S1 is 60-95 ℃ and the reaction time is 1-3h.
More preferably, the reaction temperature of the step S1 is 90 ℃ and the reaction time is 2h.
In some preferred embodiments, the reaction temperature of the S2 step is 30 to 80 ℃ and the reaction time is 0.5 to 6 hours.
Further preferably, the reaction temperature of the step S2 is 50-75 ℃, and the reaction time is 1-5h.
In some preferred embodiments, the stirring speed of the stirring operation in the step S3 is 1500-4000r/min, and the stirring time is 30-150min.
Further preferably, the stirring speed of the stirring operation in the step S3 is 2000-3000r/min, and the stirring time is 60-120min.
More preferably, the stirring speed of the stirring operation in the step S3 is 2500r/min, and the stirring time is 80-120min.
The invention adopts the specially-made dihydroxysulfonate amine salt compound as the chain extender of the polyurethane synthesis reaction, and the dihydroxysulfonate amine salt compound reacts with polymer polyol and diisocyanate to obtain the polyurethane dispersoid with high solid content. Particularly, 1, 2-dihydroxy-propanesulfonic acid amine salt is added into a raw material system for reaction, so that a polyurethane dispersion with the solid content of more than 50 percent can be obtained; meanwhile, the second chain extender is used for acting together, so that the electrostatic repulsion among polymer molecular chains is weakened, the hard segments and the soft segments are alternately combined to form cross-linked and entangled dispersion particles, and the waterborne polyurethane has the characteristic of high solid content and has higher microscopic molecular particle size; when the second chain extender is carboxylic acid compound, polyamine, polyalcohol or combination thereof, the aggregation degree of dispersion particles is obviously improved, the particle size of the product is increased to more than 1000nm, the extinction effect of the polyurethane dispersion is strong, the glossiness of the cured product is obviously reduced, and the solid content is still kept at a higher level of more than 50%. Compared with the existing self-extinction aqueous polyurethane dispersion, the invention has the core of the concept that the extinction characteristic of the polyurethane dispersion is improved, the solid content of the aqueous polyurethane is improved, the drying speed of the product is high, the subsequent processing is convenient, the production cost and the storage and transportation cost are low, and the application range of the polyurethane in industrial production is widened.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the raw materials are commercially available and the extraction methods of the extract are all conventional extraction methods, if not otherwise specified.
Example 1.
The embodiment provides a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following raw materials in percentage by weight: 26% of polymer polyol, 16% of isocyanate, 1% of a first chain extender, 1% of a second chain extender, 0.1% of a catalyst, 17% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology company Limited.
The polymer polyol is polybutylene adipate diol, has an average molecular weight of 1000, and is purchased from Suguan plastic raw material Co.
The isocyanate is isophorone diisocyanate.
The second chain extender is a polyol, specifically trimethylolpropane.
The catalyst is an organic tin catalyst, and specifically is dibutyltin dilaurate.
The organic solvent is acetone, and the boiling point is 56.3 ℃.
The preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol, isocyanate and trimethylolpropane into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 60 ℃, adding a first chain extender and a catalyst into the first prepolymer, reacting for 4 hours at 60 ℃, then cooling to 55 ℃, adding an organic solvent, and stirring for 0.5 hour to obtain a second prepolymer;
and S3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, stirring for 120min at a speed of 2500r/min, and distilling and purifying a product to obtain a finished product.
Example 2.
The embodiment provides a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following raw materials in percentage by weight: 21% of polymer polyol, 16% of isocyanate, 1% of a first chain extender, 3.4% of a second chain extender, 0.1% of a catalyst, 18% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology company Limited.
The polymer polyol was polyoxypropylene triol with an average molecular weight of 3000, purchased from Chengdubble Chemicals, inc.
The isocyanate is isophorone diisocyanate.
The second chain extender is polyalcohol and polyamine; the polyhydric alcohol is dimethylol butyric acid and diethylene glycol, and the polyamine is ethylenediamine; the weight ratio of the dimethylolbutyric acid, the diethylene glycol and the ethylenediamine is 1:2:0.4.
the catalyst is an organic tin catalyst, and specifically is dibutyltin dilaurate.
The organic solvent is acetone, and the boiling point is 56.3 ℃.
The preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 70 ℃, adding dimethylolbutyric acid, diethylene glycol and a catalyst into the first prepolymer, stirring for 3 hours at 70 ℃, then cooling to 60 ℃, adding an organic solvent and a first chain extender, and stirring for 0.5 hour to obtain a second prepolymer;
s3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding ethylenediamine, stirring for 90min at the speed of 2500r/min, and distilling and purifying a product to obtain a finished product;
example 3.
The embodiment provides a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following raw materials in percentage by weight: 24% of polymer polyol, 16% of isocyanate, 1% of a first chain extender, 3% of a second chain extender, 0.1% of a catalyst, 16% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology Co.
The polymer polyol is polybutylene adipate glycol, has an average molecular weight of 1000, and is purchased from Suguan plastic raw materials Co.
The isocyanate is isophorone diisocyanate.
The second chain extender is polyalcohol and polyamine, the polyalcohol is trimethylolpropane and dimethylolbutyric acid specifically, and the polyamine is hydrazine hydrate specifically; the weight ratio of the trimethylolpropane to the dimethylolbutyric acid to the hydrazine hydrate is 1:1:1.
the catalyst is an organic tin catalyst, and specifically is dibutyltin dilaurate.
The organic solvent is acetone, and the boiling point is 56.3 ℃.
The preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol, isocyanate and trimethylolpropane into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 60 ℃, adding dimethylolbutyric acid, a first chain extender and a catalyst into the first prepolymer, reacting for 4 hours at the temperature of 60 ℃, then cooling to 55 ℃, adding an organic solvent, and stirring for 0.5 hour to obtain a second prepolymer;
and S3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding hydrazine hydrate, stirring for 60min at the speed of 2500r/min, and distilling and purifying a product to obtain a finished product.
Example 4.
The embodiment provides a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following raw materials in percentage by weight: 25% of polymer polyol, 13% of isocyanate, 1% of a first chain extender, 2% of a second chain extender, 0.1% of a catalyst, 17% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology Co.
The polymer polyol is polycaprolactone diol, has an average molecular weight of 1000, and is purchased from Jiangsu Jiaren chemical Co.
The isocyanate is isophorone diisocyanate.
The second chain extender is polyalcohol and polyamine, the polyalcohol is trimethylolpropane specifically, and the polyamine is ethylenediamine specifically; the weight ratio of the dimethylolbutyric acid to the ethylenediamine is 1:1.
the catalyst is an organic tin catalyst, and specifically is dibutyltin dilaurate.
The organic solvent is acetone, and the boiling point is 56.3 ℃.
The preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 60 ℃, adding dimethylolbutyric acid, a first chain extender and a catalyst into the first prepolymer, reacting for 4 hours at the temperature of 60 ℃, then cooling to 55 ℃, adding an organic solvent, and stirring for 0.5 hour to obtain a second prepolymer;
and S3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding ethylenediamine, stirring for 60min at the speed of 2500r/min, and distilling and purifying a product to obtain a finished product.
Example 5.
The embodiment provides a high-solid-content self-extinction aqueous polyurethane dispersion, which comprises the following raw materials in percentage by weight: 23% of polymer polyol, 15% of isocyanate, 1% of a first chain extender, 4% of a second chain extender, 0.1% of a catalyst, 15% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology Co.
The polymer polyol is polycaprolactone triol, has the average molecular weight of 3000, and is purchased from Jiangsu Runfeng synthetic technology Co., ltd.
The isocyanate is isophorone diisocyanate.
The second chain extender is polyalcohol and polyamine, the polyalcohol is dimethylolbutyric acid and 1, 4-butanediol, and the polyamine is N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane (CAS number is 3069-29-2); the weight ratio of the dimethylolbutyric acid, the 1, 4-butanediol and the N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane is 1:2:1.
the catalyst is an organic tin catalyst, and specifically is dibutyltin dilaurate.
The organic solvent is acetone, and the boiling point is 56.3 ℃.
The preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 70 ℃, adding dimethylolbutyric acid, 1, 4-butanediol and a catalyst into the first prepolymer, stirring for 3 hours at 70 ℃, then cooling to 60 ℃, adding an organic solvent and a first chain extender, reacting for 4 hours at 60 ℃, then cooling to 55 ℃, adding the organic solvent, and stirring for 0.5 hour to obtain a second prepolymer;
s3, transferring the second prepolymer into a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silicon, stirring for 90min at the speed of 2500r/min, and distilling and purifying a product to obtain a finished product.
Performance test method
Solid content:
taking the same amount (M) 0 ) The aqueous polyurethane dispersions obtained in examples 1 to 5 were placed in a clean and dry weighing cup, placed in an oven at 120 ℃ for 2 hours, transferred to a dryer for 2 hours, and then weighed (M) 1 ) (ii) a Calculating the solid content of the aqueous polyurethane dispersion; solid content = (M) 0 -M 1 )/M 0 X 100%. Each set of example samples was evaluated in 10 replicates.
Particle size:
the particle size of the aqueous polyurethane dispersions obtained in examples 1 to 5 was measured using a Sympatec NAPOPHOX nanoscopic laser particle sizer, germany. Each set of example samples was averaged 10 times in parallel.
Glossiness:
the aqueous polyurethane dispersions obtained in examples 1 to 5 were tested for gloss using a cusshijia photovoltaic apparatus co. Each set of example samples was evaluated in 10 replicates.
Performance test data
TABLE 1 Performance test results
Figure BDA0003120208620000111
Finally, it is pointed out that the foregoing examples are illustrative only, serving to explain some of the characteristics of the process according to the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Where the claims recite a range of values, such ranges are intended to include all sub-ranges subsumed therein, and variations within the ranges are intended to be encompassed by the claims as appended hereto where possible.

Claims (4)

1. A high-solid content self-extinction aqueous polyurethane dispersion is characterized by comprising the following raw materials in percentage by weight: 21% of polymer polyol, 16% of isocyanate, 1% of a first chain extender, 3.4% of a second chain extender, 0.1% of a catalyst, 18% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology company Limited;
the polymer polyol is polyoxypropylene triol, has an average molecular weight of 3000, and is purchased from Doctorite chemical technology, inc.;
the isocyanate is isophorone diisocyanate;
the second chain extender is polyalcohol and polyamine; the polyhydric alcohol is dimethylol butyric acid and diethylene glycol, and the polyamine is ethylenediamine; the weight ratio of the dimethylolbutyric acid, the diethylene glycol and the ethylenediamine is 1:2:0.4;
the catalyst is dibutyltin dilaurate;
the organic solvent is acetone, and the boiling point is 56.3 ℃;
the preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 70 ℃, adding dimethylolbutyric acid, diethylene glycol and a catalyst into the first prepolymer, stirring for 3 hours at 70 ℃, then cooling to 60 ℃, adding an organic solvent and a first chain extender, and stirring for 0.5 hour to obtain a second prepolymer;
and S3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding ethylenediamine, stirring for 90min at the speed of 2500r/min, and distilling and purifying a product to obtain a finished product.
2. A high-solid content self-extinction aqueous polyurethane dispersion is characterized by comprising the following raw materials in percentage by weight: 24% of polymer polyol, 16% of isocyanate, 1% of a first chain extender, 3% of a second chain extender, 0.1% of a catalyst, 16% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology Co., ltd;
the polymer polyol is poly butylene adipate glycol, has an average molecular weight of 1000 and is purchased from Suguan plastic raw material Co., ltd, dongguan city;
the isocyanate is isophorone diisocyanate;
the second chain extender is polyalcohol and polyamine, the polyalcohol is trimethylolpropane and dimethylolbutyric acid, and the polyamine is hydrazine hydrate; the weight ratio of the trimethylolpropane to the dimethylolbutyric acid to the hydrazine hydrate is 1:1:1;
the catalyst is dibutyltin dilaurate;
the organic solvent is acetone, and the boiling point is 56.3 ℃;
the preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol, isocyanate and trimethylolpropane into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 60 ℃, adding dimethylolbutyric acid, a first chain extender and a catalyst into the first prepolymer, reacting for 4 hours at 60 ℃, then cooling to 55 ℃, adding an organic solvent, and stirring for 0.5 hour to obtain a second prepolymer;
and S3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding hydrazine hydrate, stirring for 60min at the speed of 2500r/min, and distilling and purifying a product to obtain a finished product.
3. A high-solid content self-extinction aqueous polyurethane dispersion is characterized by comprising the following raw materials in percentage by weight: 25% of polymer polyol, 13% of isocyanate, 1% of a first chain extender, 2% of a second chain extender, 0.1% of a catalyst, 17% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology company Limited;
the polymer polyol is polycaprolactone diol, has the average molecular weight of 1000, and is purchased from Jiangsu Jiaren chemical Co., ltd;
the isocyanate is isophorone diisocyanate;
the second chain extender is polyalcohol and polyamine, the polyalcohol is specifically dimethylolbutyric acid, and the polyamine is specifically ethylenediamine; the weight ratio of the dimethylolbutyric acid to the ethylenediamine is 1:1;
the catalyst is dibutyltin dilaurate;
the organic solvent is acetone, and the boiling point is 56.3 ℃;
the preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 60 ℃, adding dimethylolbutyric acid, a first chain extender and a catalyst into the first prepolymer, reacting for 4 hours at the temperature of 60 ℃, then cooling to 55 ℃, adding an organic solvent, and stirring for 0.5 hour to obtain a second prepolymer;
and S3, transferring the second prepolymer to a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding ethylenediamine, stirring for 60min at the speed of 2500r/min, and distilling and purifying the product to obtain the finished product.
4. The high-solid-content self-extinction aqueous polyurethane dispersion is characterized by comprising the following raw materials in percentage by weight: 23% of polymer polyol, 15% of isocyanate, 1% of a first chain extender, 4% of a second chain extender, 0.1% of a catalyst, 15% of an organic solvent and the balance of water;
the first chain extender is 1, 2-dihydroxy-propanesulfonic acid triethylamine salt and is sourced from Xiamen Bright optical coating technology company Limited;
the polymer polyol is polycaprolactone triol, has the average molecular weight of 3000 and is purchased from Jiangsu Runfeng synthetic science and technology company Limited;
the isocyanate is isophorone diisocyanate;
the second chain extender is polyalcohol and polyamine, the polyalcohol is dimethylolbutyric acid and 1, 4-butanediol, and the polyamine is N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane; the weight ratio of the dimethylolbutyric acid, the 1, 4-butanediol and the N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane is 1:2:1;
the catalyst is dibutyltin dilaurate;
the organic solvent is acetone, and the boiling point is 56.3 ℃;
the preparation method of the high-solid-content self-extinction aqueous polyurethane dispersion comprises the following specific preparation steps:
s1, adding polymer polyol and isocyanate into a reaction kettle, and reacting for 2 hours at 90 ℃ to generate a first prepolymer;
s2, cooling to 70 ℃, adding dimethylolbutyric acid, 1, 4-butanediol and a catalyst into the first prepolymer, stirring for 3 hours at 70 ℃, then cooling to 60 ℃, adding an organic solvent and a first chain extender, reacting for 4 hours at 60 ℃, then cooling to 55 ℃, adding the organic solvent, and stirring for 0.5 hour to obtain a second prepolymer;
and S3, transferring the second prepolymer into a high-speed emulsifying machine, adding water, stirring for 20min at the speed of 2500r/min, adding N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, stirring for 90min at the speed of 2500r/min, and distilling and purifying the product to obtain the finished product.
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