CN112062935A - Preparation method and application of odorless water-dispersible polyisocyanate - Google Patents
Preparation method and application of odorless water-dispersible polyisocyanate Download PDFInfo
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- CN112062935A CN112062935A CN202010923543.6A CN202010923543A CN112062935A CN 112062935 A CN112062935 A CN 112062935A CN 202010923543 A CN202010923543 A CN 202010923543A CN 112062935 A CN112062935 A CN 112062935A
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
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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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
The invention relates to the field of preparation of polyisocyanates, in particular to a preparation method and application of odorless water-dispersible polyisocyanate. According to the invention, sulfonic acid and phosphoric acid are mixed and modified, so that the modified polyisocyanate has smaller particle size after being emulsified in water, better compatibility with water-based resin and better gloss and fullness of a prepared paint film; compared with nonionic modified and common sulfonic acid modified polyisocyanates, better water dispersion performance can be obtained by using fewer modified substances by controlling the process of sulfonic acid modification and phosphoric acid modification, so that the resistance is further improved, the difficulty that sulfonate is difficult to be grafted to polyisocyanate in the presence of the same amount of tertiary amine is solved, and the problems that the conventional sulfonic acid modified polyisocyanate in the market has more residual amine, has larger smell and influences performance are solved.
Description
Technical Field
The invention relates to the field of preparation of polyisocyanates, in particular to a preparation method and application of odorless water-dispersible polyisocyanate.
Background
Along with the stricter environmental regulations and the gradually strengthened environmental awareness of people, more and more oily coatings and adhesives are replaced by corresponding water-based materials; water-dispersible polyisocyanates are also gaining increasing attention as important crosslinking components in aqueous coatings. The current processes for the preparation of water-dispersible polyisocyanates can be largely divided into anionic and nonionic types.
The non-ionic type means that the polyisocyanate is modified by polyether, ether bond is introduced, hydrophilicity is increased, and the polyisocyanate can be emulsified and dispersed in water, so that the polyisocyanate and the water-based hydroxyl component can be uniformly mixed for use; because a large amount of polyether groups are introduced to ensure sufficient water dispersibility, better gloss is obtained, but because a large amount of polyether is grafted, NCO groups are consumed too much, the effective NCO content is greatly reduced, the functionality is also greatly reduced, the crosslinking density is low, and the coating resistance and physical properties are not good; secondly, a large number of ether bonds are present in the coating, resulting in poor water resistance and hardness of the coating. The anionic water dispersible polyisocyanate generally means that carboxyl or sulfonic acid groups are introduced into the polyisocyanate, and then neutralization and salt formation are carried out to endow the polyisocyanate with hydrophilic performance, so that the polyisocyanate can be emulsified and dispersed in water, and the performances such as water resistance, hardness and the like of a coating prepared by using the anionic water dispersible polyisocyanate are improved to a certain extent compared with a nonionic type.
The carboxylate ionic water-dispersible polyisocyanate is usually prepared by introducing DMPA or DMBA into molecules and neutralizing with ammonia to form salts, so that the resistance of the polyisocyanate is greatly improved compared with that of nonionic type, but because DMPA and DMBA are bifunctional molecules, the molecular weight of the product is greatly improved, the viscosity is very high, the water-dispersible performance of the product is poor, and the current industrial products are few.
The sulfonate ionic water dispersible polyisocyanate is usually prepared by introducing sulfamate into polyisocyanate and neutralizing with ammonia to form salt, and because sulfonate has stronger hydrophilicity, less sulfonate groups can be introduced to obtain better water dispersible performance compared with nonionic, so that the resistance and physical properties are greatly improved compared with nonionic. At present, sulfonate type water dispersible polyisocyanates are distributed in the market as mainstream products, but because more hydrophilic groups are introduced into molecules and the particle size after water dispersion is not fine enough, the defects of resistance, gloss and oil resistance still exist.
In addition, the reaction conditions for introducing the sulfamate into the polyisocyanate are harsh, ammonia is needed as a catalyst and a neutralizing agent to catalyze the reaction at high temperature, the hundreds of percent of the sulfamate cannot be completely grafted into the polyisocyanate for a long reaction time, and a small amount of free neutralized amine is remained in the product after the reaction, so that the odor, the storage stability, the resistance after film formation and the hardness of the product are adversely affected.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a method for preparing a neat water dispersible polyisocyanate, comprising the steps of:
(1) mixing polyisocyanate, sulfamic acid and a neutralization catalyst, and reacting to obtain sulfonic acid modified polyisocyanate;
(2) adding modified phosphoric acid into sulfonic acid modified polyisocyanate, and reacting to obtain water dispersible polyisocyanate;
the modified phosphoric acid contains hydroxyl or amino.
In a preferred embodiment of the present invention, the molar ratio of the total molar amount of the sulfamic acid and the modified phosphoric acid to the molar amount of the neutralization catalyst is (1-1.1): 1.
in a preferred embodiment of the present invention, the molar ratio of the sulfamic acid to the modified phosphoric acid is 1: (0.1 to 3).
In a preferable technical scheme of the invention, the molar ratio of the total molar weight of the sulfamic acid and the modified phosphoric acid to the molar weight of the isocyanate in the polyisocyanate is (0.005-0.05): 1.
As a preferable technical scheme of the invention, the reaction temperature in the step (1) is 70-110 ℃.
As a preferable technical scheme of the invention, the reaction temperature in the step (2) is 65-100 ℃.
In a preferred embodiment of the present invention, the polyisocyanate is one selected from the group consisting of isocyanurate polyisocyanate, biuret polyisocyanate, carbodiimide polyisocyanate, uretonimine polyisocyanate, uretdione polyisocyanate, allophanate polyisocyanate, urethane polyisocyanate, and iminooxadiazinedione polyisocyanate.
In a preferred embodiment of the present invention, the sulfamic acid is aliphatic sulfamic acid or alicyclic sulfamic acid.
In a preferred embodiment of the present invention, the neutralization catalyst is selected from the group consisting of trimethylamine, triethylamine, isomeric tripropylamines and tributylamines, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylisopropylamine, N-dimethylbutylamine, N-dimethylisobutylamine, N-dimethyloctylamine, N-dimethyl-2-ethylhexylamine, N-dimethyllaurylamine, N-diethylmethylamine, N-diethylpropylamine, N-diethylbutylamine, N-diethylhexylamine, N-diethyloctylamine, N-diethyl-2-ethylhexylamine, N-diethyllaurylamine, N-tributylamine, N-dimethylisopropylamine, N-dimethyloctylamine, N-dimethyllaurylamine, N-dimethyldodecylamine, N-dimethyllaurylamine, N-dimethyllaur, N, N-diisopropylmethylamine, N-diisopropylethylamine, N-diisopropylbutylamine, N-diisopropyl-2-ethylhexylamine, N-dioctylmethylamine, N-dimethylallylamine, N-dimethylbenzylamine, N-diethylbenzylamine, N-dibenzylmethylamine, tribenzylamine, N-dimethyl-4-methylbenzylamine, N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-dicyclohexylmethylamine, N-dicyclohexylethylamine, tricyclohexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-diisopropylbutylamine, N-diisopropylhexylamine, N-dibenzylmethylamine, tribenzylamine, N-dimethyl-4-methylbenzylamine, N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-methylpyrrolidine, N-ethylp, One or more of N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-methylmorpholine, N-ethylmorpholine, N-propylmorpholine, N-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-isobutyl morpholine and quinuclidine.
In a second aspect, the invention provides the use of the process for the preparation of said odorless water-dispersible polyisocyanate for aqueous coatings.
Compared with the prior art, the invention has the following beneficial effects:
1. the sulfonic acid and the phosphoric acid are mixed and modified, so that the modified polyisocyanate has smaller particle size after being emulsified in water, better compatibility with water-based resin and better luster and fullness of a prepared paint film.
2. Compared with nonionic modified and common sulfonic acid modified polyisocyanates, the process of modifying by sulfonic acid and then modifying by phosphoric acid can obtain better water dispersion performance by using fewer modified substances, so that the resistance is further improved.
3. The process of firstly modifying excessive tertiary amine by sulfonic acid and then modifying the excessive tertiary amine by phosphoric acid and neutralizing the excessive tertiary amine is adopted, the difficulty that sulfonate is difficult to be grafted on polyisocyanate in the presence of the same amount of tertiary amine is solved (sulfamic acid can be easily grafted on under relatively mild conditions in the presence of large excessive tertiary amine), and the excessive tertiary amine can be completely neutralized by modifying the excessive tertiary amine by phosphoric acid, so that the product is basically tasteless, and the problems that the conventional sulfonic acid modified polyisocyanate in the market has more residual amine, has larger smell and influences the performance are solved.
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.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, 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 …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. 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.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
In a first aspect, the present invention provides a process for the preparation of an odorless water-dispersible polyisocyanate, comprising the steps of:
(1) mixing polyisocyanate, sulfamic acid and a neutralization catalyst, and reacting to obtain sulfonic acid modified polyisocyanate;
(2) adding modified phosphoric acid into sulfonic acid modified polyisocyanate, and reacting to obtain water dispersible polyisocyanate; the modified phosphoric acid contains hydroxyl or amino.
Step (1)
The polyisocyanate is obtained by addition of diisocyanate monomers. Suitable diisocyanate monomers are any diisocyanates which are available in various ways, for example by phosgenation in the liquid or gas phase or by phosgene-free routes, for example by thermal urethane cleavage. Preferred diisocyanates are those having aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups in the molecular weight range from 140 to 400, such as, for example, 1, 4-butanediisocyanate, 1, 5-Pentanediisocyanate (PDI), 1, 6-Hexanediisocyanate (HDI), 2-methyl-1, 5-pentanediisocyanate, 1, 5-diisocyanato-2, 2-dimethylpentane, 2, 4-or 2,4, 4-trimethyl-1, 6-hexanediisocyanate, 1, 10-decanediisocyanate, m-xylylene isocyanate (XDI), 1, 3-and 1, 4-cyclohexane diisocyanate, 1, 3-and 1, 4-bis (isocyanatomethyl) cyclohexane, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4' -dicyclohexylmethane diisocyanate, 1-isocyanato-1-methyl-4 (3) isocyanatomethylcyclohexane, bis (isocyanatomethyl) norbornane, 1, 3-and 1, 4-bis (2-isocyanatoprop-2-yl) benzene (TMXDI), 2, 4-and 2, 6-Toluene Diisocyanate (TDI), 2,4' -and 4,4' -diphenylmethane diisocyanate (MDI), 1, 5-naphthalene diisocyanate or any mixture of such diisocyanates; preferably, HDI, IPDI, TDI, MDI, XDI, HMDI or TMXDI; particularly preferably, HDI.
Suitable polyisocyanates are any polyisocyanates having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure prepared by modification of simple aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates; preferably, isocyanurate polyisocyanates, biuret polyisocyanates, carbodiimide polyisocyanates, uretonimine polyisocyanates, uretdione polyisocyanates, allophanate polyisocyanates, urethane polyisocyanates, iminooxadiazinedione polyisocyanates; particularly preferred is isocyanurate polyisocyanate.
The applicant has found that by modifying the polyisocyanate with sulphamic acid, a sulphonate-containing polyisocyanate is obtained, providing high shear forces, promoting the dispersibility of the polyisocyanate in water; suitable sulfamic acids may be aliphatic or alicyclic sulfamic acids, such as 2-aminoethane sulfonic acid, 3-aminopropane-1-sulfonic acid, 4-aminobutane-1-sulfonic acid, 3-amino-2-methylpropane-1-sulfonic acid, 4-aminobutane-2-sulfonic acid, 2-methylaminoethane-1-sulfonic acid, 2-ethylaminoethane-1-sulfonic acid, 2-propylaminoethane-1-sulfonic acid, 2-isopropylaminoethane-1-sulfonic acid, 2-n-butylaminoethane-1-sulfonic acid, 2- (tert-butyl) aminoethane-1-sulfonic acid, 2-pentylaminoethane-1-sulfonic acid, 2-hexylaminoethane-1-sulfonic acid, 2-octylaminoethane-1-sulfonic acid, 2-anilinoethane-1-sulfonic acid, 2-cyclopropylaminoethane-1-sulfonic acid, 2-cyclobutylaminoethane-1-sulfonic acid, 2-cyclopentylaminoethane-1-sulfonic acid, 2-cyclohexylaminoethane-1-sulfonic acid, isomeric 2- (methylcyclohexyl) aminoethane-1-sulfonic acid, 2- (2, 3-dimethylcyclohexyl) aminoethane-1-sulfonic acid, 2- (3,3, 5-trimethylcyclohexylaminoethane-1-sulfonic acid, 2- (4-tert-butylcyclohexyl) aminoethane-1-sulfonic acid, and mixtures thereof, 2-cycloheptylaminoethane-1-sulfonic acid, 2-cyclooctylaminoethane-1-sulfonic acid, 2- (2-norbornyl) aminoethane-1-sulfonic acid, 2- (1-adamantyl) aminoethane-1-sulfonic acid, 2- (3, 5-dimethyl-1-adamantyl) aminoethane-1-sulfonic acid, 3-methylaminopropane-1-sulfonic acid, 3-ethylaminopropane-1-sulfonic acid, 3-propylaminopropane-1-sulfonic acid, 3-isopropylaminopropane-1-sulfonic acid, 3-n-butylaminopropane-1-sulfonic acid, 3- (tert-butyl) aminopropane-1-sulfonic acid, sodium salt, potassium salt, sodium salt, 3-pentylaminopropane-1-sulfonic acid, 3-hexylaminopropane-1-sulfonic acid, 3-octylaminopropane-1-sulfonic acid, 3-anilinopropane-1-sulfonic acid, 3-cyclopropylaminopropane-1-sulfonic acid, 3-cyclobutylaminopropane-1-sulfonic acid, 3-cyclopentylaminopropane-1-sulfonic acid, 3-cyclohexylaminopropane-1-sulfonic acid, the isomeric 3- (methylcyclohexyl) aminopropane-1-sulfonic acids, 3- (2, 3-dimethylcyclohexyl) aminopropane-1-sulfonic acid, 3- (3,3, 5-trimethylcyclohexylaminopropane-1-sulfonic acid, 3- (4-tert-butylcyclohexyl) aminopropane-1-sulfonic acid, and mixtures thereof, 3-cycloheptylaminopropane-1-sulfonic acid, 3-cyclooctylaminopropane-1-sulfonic acid, 3- (2-norbornyl) aminopropane-1-sulfonic acid, 3- (1-adamantyl) aminopropane-1-sulfonic acid, 3- (3, 5-dimethyl-1-adamantyl) aminopropane-1-sulfonic acid, 3-methylaminobutane-1-sulfonic acid, 3-ethylaminobutane-1-sulfonic acid, 3-propylaminobutane-1-sulfonic acid, 3-isopropylaminobutane-1-sulfonic acid, 3-n-butylaminobutane-1-sulfonic acid, 3- (tert-butyl) aminobutane-1-sulfonic acid, and mixtures thereof, 3-pentylaminobutane-1-sulfonic acid, 3-hexylaminobutane-1-sulfonic acid, 3-octylaminobutane-1-sulfonic acid, 3-anilinobutane-1-sulfonic acid, 3-cyclopropylaminobutane-1-sulfonic acid, 3-cyclobutylaminobutane-1-sulfonic acid, 3-cyclopentylaminobutane-1-sulfonic acid, 3-cyclohexylaminobutane-1-sulfonic acid, the isomeric 3- (methylcyclohexyl) aminobutane-1-sulfonic acid, 3- (2, 3-dimethylcyclohexyl) aminobutane-1-sulfonic acid, 3- (3,3, 5-trimethylcyclohexylaminobutane-1-sulfonic acid, 3- (4-tert-butylcyclohexyl) aminobutane-1-sulfonic acid, the salts thereof, and the salts thereof, 3-cycloheptylaminobutane-1-sulfonic acid, 3-cyclooctylaminobutane-1-sulfonic acid, 3- (2-norbornyl) aminobutane-1-sulfonic acid, 3- (1-adamantyl) aminobutane-1-sulfonic acid, 3- (3, 5-dimethyl-1-adamantyl) aminobutane-1-sulfonic acid, 4-methylaminobutane-1-sulfonic acid, 4-ethylaminobutane-1-sulfonic acid, 4-propylaminobutane-1-sulfonic acid, 4-isopropylaminobutane-1-sulfonic acid, 4-n-butylaminobutane-1-sulfonic acid, 4- (tert-butyl) aminobutane-1-sulfonic acid, sodium chloride, 4-pentylaminobutane-1-sulfonic acid, 4-hexylaminobutane-1-sulfonic acid, 4-octylaminobutane-1-sulfonic acid, 4-anilinobutane-1-sulfonic acid, 4-cyclopropylaminobutane-1-sulfonic acid, 4-cyclobutylaminobutane-1-sulfonic acid, 4-cyclopentylaminobutane-1-sulfonic acid, 4-cyclohexylaminobutane-1-sulfonic acid, the isomeric 4- (methylcyclohexyl) aminobutane-1-sulfonic acid, 4- (2, 3-dimethylcyclohexyl) aminobutane-1-sulfonic acid, 4- (3,3, 5-trimethylcyclohexylaminobutane-1-sulfonic acid, 4- (4-tert-butylcyclohexyl) aminobutane-1-sulfonic acid, the salts thereof, and the salts thereof, 4-cycloheptylaminobutane-1-sulfonic acid, 4-cyclooctylaminobutane-1-sulfonic acid, 4- (2-norbornyl) aminobutane-1-sulfonic acid, 4- (1-adamantyl) aminobutane-1-sulfonic acid, 4- (3, 5-dimethyl-1-adamantyl) aminobutane-1-sulfonic acid, 3-methylamino-2-methylpropane-1-sulfonic acid, 3-ethylamino-2-methylpropane-1-sulfonic acid, 3-propylamino-2-methylpropane-1-sulfonic acid, 3-isopropylamino-2-methylpropane-1-sulfonic acid, 3-n-butylamino-2-methylpropane-1-sulfonic acid, 4- (2-norbornyl) aminobutane-1-sulfonic acid, 4- (2-norbornanyl), 3- (tert-butyl) amino-2-methylpropane-1-sulfonic acid, 3-pentylamino-2-methylpropane-1-sulfonic acid, 3-hexylamino-2-methylpropane-1-sulfonic acid, 3-octylamino-2-methylpropane-1-sulfonic acid, 3-anilino-2-methylpropane-1-sulfonic acid, 3-cyclopropylamino-2-methylpropane-1-sulfonic acid, 3-cyclobutylamino-2-methylpropane-1-sulfonic acid, 3-cyclopentylamino-2-methylpropane-1-sulfonic acid, 3-cyclohexylamino-2-methylpropane-1-sulfonic acid, and mixtures thereof, The isomers 3- (methylcyclohexyl) amino-2-methylpropane-1-sulfonic acid, 3- (2, 3-dimethylcyclohexyl) amino-2-methylpropane-1-sulfonic acid, 3- (3,3, 5-trimethylcyclohexylamino-2-methylpropane-1-sulfonic acid, 3- (4-tert-butylcyclohexyl) amino-2-methylpropane-1-sulfonic acid, 3-cycloheptylamino-2-methylpropane-1-sulfonic acid, 3-cyclooctylamino-2-methylpropane-1-sulfonic acid, 3- (2-norbornanyl) amino-2-methylpropane-1-sulfonic acid, 3- (1-adamantyl) amino-2-methylpropane-1-sulfonic acid Sulfonic acid, 3- (3, 5-dimethyl-1-adamantyl) amino-2-methylpropane-1-sulfonic acid, 3-methylaminobutane-2-sulfonic acid, 3-ethylaminobutane-2-sulfonic acid, 3-propylaminobutane-2-sulfonic acid, 3-isopropylaminobutane-2-sulfonic acid, 3-n-butylaminobutane-2-sulfonic acid, 3- (tert-butyl) aminobutane-2-sulfonic acid, 3-pentylaminobutane-2-sulfonic acid, 3-hexylaminobutane-2-sulfonic acid, 3-octylaminobutane-2-sulfonic acid, 3-anilinobutane-2-sulfonic acid, sodium chloride, sodium, 3-cyclopropylaminobutane-2-sulfonic acid, 3-cyclobutylaminobutane-2-sulfonic acid, 3-cyclopentylaminobutane-2-sulfonic acid, 3-cyclohexylaminobutane-2-sulfonic acid, the isomeric 3- (methylcyclohexyl) aminobutane-2-sulfonic acids, 3- (2, 3-dimethylcyclohexyl) aminobutane-2-sulfonic acid, 3- (3,3, 5-trimethylcyclohexylaminobutane-2-sulfonic acid, 3- (4-tert-butylcyclohexyl) aminobutane-2-sulfonic acid, 3-cycloheptylaminobutane-2-sulfonic acid, 3-cyclooctylaminobutane-2-sulfonic acid, 3- (2-norbornyl) aminobutane-2-sulfonic acid, 3-cyclopentylaminobutane-2-sulfonic acid, 3- (1-adamantyl) amino-2-sulfonic acid and 3- (3, 5-dimethyl-1-adamantyl) aminobutane-2-sulfonic acid; preferably, 2-propylaminoethane-1-sulfonic acid, 2-isopropylaminoethane-1-sulfonic acid, 2-cyclohexylaminoethane-1-sulfonic acid, the isomeric 2- (methylcyclohexyl) aminoethane-1-sulfonic acid, 3-cyclohexylaminopropane-1-sulfonic acid, the isomeric 3- (methylcyclohexyl) aminopropane-1-sulfonic acid, 4-cyclohexylaminobutane-1-sulfonic acid, the isomeric 4- (methylcyclohexyl) aminobutane-1-sulfonic acid, the isomeric 3- (methylcyclohexyl) amino-2-methylpropane-1-sulfonic acid; particularly preferred are 2-isopropylaminoethane-1-sulfonic acid, 2-cyclohexylaminoethane-1-sulfonic acid, 3-cyclohexylaminopropane-1-sulfonic acid, the isomeric 3- (methylcyclohexyl) aminopropane-1-sulfonic acids, 4-cyclohexylaminobutane-1-sulfonic acid, the isomeric 4- (methylcyclohexyl) aminobutane-1-sulfonic acids.
The applicant finds that the sulfamic acid and the polyisocyanate have poor solubility, two-phase reaction occurs, the sulfamic acid is difficult to graft on the polyisocyanate, and the neutralization catalyst, especially the neutralization catalyst of tertiary amine, is added to not only have good compatibility with the polyisocyanate, but also have certain solubility on sulfonic acid monomers, so that the double effects of catalysis and neutralization are exerted, and the reactivity and the speed of the amino group and the isocyanic acid radical in the sulfamic acid and the polyisocyanate can be obviously promoted. Suitable sulfamic acids may be trimethylamine, triethylamine, tripropylamine, the isomeric tripropylamines and tributylamines, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylisopropylamine, N-dimethylbutylamine, N-dimethylisobutylamine, N-dimethyloctylamine, N-dimethyl-2-ethylhexylamine, N-dimethyllaurylamine, N-diethylmethylamine, N-diethylpropylamine, N-diethylbutylamine, N-diethylhexylamine, N-diethyloctylamine, N-diethyl-2-ethylhexylamine, N-diethyllaurylamine, N-diisopropylmethylamine, N-diisopropylmethylamine, N, N-diisopropylethylamine, N-diisopropylbutylamine, N-diisopropyl-2-ethylhexylamine, N-dioctylmethylamine, N-dimethylallylamine, N-dimethylbenzylamine, N-diethylbenzylamine, N-dibenzylmethylamine, tribenzylamine, N-dimethyl-4-methylbenzylamine, N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-dicyclohexylmethylamine, N-dicyclohexylethylamine, tricyclohexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpyrrolidine, N-butylpyrrolidine, N-ethylpiperidine, N-diisopropylethylamine, N-2-ethylhexylamine, N-dioctylmethylamine, N-dimethylcyclohexylamine, N-dibenzylamine, N, n-propylpiperidine, N-butylpiperidine, N-methylmorpholine, N-ethylmorpholine, N-propylmorpholine, N-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-isobutyl morpholine and quinuclidine; preferably, trimethylamine, triethylamine, tripropylamine, tributylamine, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylisopropylamine, N-dimethylbutylamine, N-dimethylisobutylamine, N-dimethylcyclohexylamine, N-diethylcyclohexylamine; particularly preferred are trimethylamine, triethylamine, tripropylamine, tributylamine, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylbutylamine, N-dimethylcyclohexylamine.
Step (2)
Suitable modified phosphoric acids are those containing hydroxyl, amino, etc. groups that are reactive with isocyanates, and in one embodiment, the modified phosphoric acids of the present invention contain hydroxyl or amino groups.
Suitable hydroxyl-containing modified phosphoric acids may be organic hydroxyl-containing phosphoric acids having a hydroxyl group, for example, hydroxyethylidene diphosphonic acid, 2-hydroxyethyl phosphoric acid, di (2-ethylhexyl) phosphoric acid, 3-hydroxypropyl phosphoric acid, 2-hydroxybutyl phosphoric acid, 2-hydroxyoctyl phosphoric acid, 2-hydroxylauryl phosphoric acid; preferred are hydroxyethylidene diphosphonic acid, 2-hydroxyethyl phosphoric acid, di (2-ethylhexyl) phosphoric acid, 3-hydroxypropyl phosphoric acid, 2-hydroxybutyl phosphoric acid.
Suitable amino group-containing modified phosphoric acids may be organic amino phosphoric acids having an amino group, for example, ethylenediamine-N, N ' -bis (methylenephosphinic acid), ethylenediamine tetra (methylenephosphinic acid), nitriloacetic acid-bis (methylenephosphorous acid), nitrilodiacetic acid- (methylenephosphorous acid), nitriloacetic acid-beta-propionic acid-methylenephosphonic acid, nitrilotris (methylenephosphonic acid), cyclohexanediaminetetra (methylenephosphonic acid), ethylenediamine-N, N ' -diacetic acid-N, N ' -bis (methylenephosphonic acid), ethylenediamine tetra (methylenephosphonic acid), polymethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), carbamylphosphoric acid, 1-aminopropylphosphoric acid, 3-aminopropylphosphonic acid, 1-aminobutyl phosphoric acid, (1-amino-3-methylbutyl) phosphoric acid, 4-aminobutyl phosphoric acid, 1-aminoheptyl phosphoric acid, 1-aminooctyl phosphoric acid; preferably, carbamyl phosphoric acid, 1-aminopropyl phosphoric acid, 3-aminopropyl phosphonic acid, 1-aminobutyl phosphoric acid, (1-amino-3-methylbutyl) phosphoric acid, 4-aminobutyl phosphoric acid, 1-aminoheptyl phosphoric acid, 1-aminooctyl phosphoric acid; particularly preferred are carbamyl phosphate, 1-aminopropyl phosphate and 1-aminobutyl phosphate.
The applicant finds that by controlling the total molar amount of sulfamic acid and modified phosphoric acid and the molar ratio of the catalyst, the catalyst can be controlled to be completely neutralized by the sulfonic acid and the phosphoric acid and grafted to the polyisocyanate to obtain the polyisocyanate containing sulfonic acid ammonium salt and phosphoric acid ammonium salt branched chains, so that the influence of residual organic amine on the smell, the stability, the resistance and the hardness of the coating after film forming is avoided; in one embodiment, the molar ratio of the total molar amount of sulfamic acid and modified phosphoric acid, and the molar amount of neutralization catalyst, in the present invention, is (1-1.1): 1; preferably, the molar ratio of the total molar amount of sulfamic acid and modified phosphoric acid, and the molar amount of neutralization catalyst, according to the present invention, is 1.05: 1.
the applicant finds that by adopting sulfonic acid and phosphoric acid to graft to isocyanate, the modified isocyanate has better dispersibility and smaller particle size after being emulsified in water compared with the modified isocyanate which is grafted by using the sulfonic acid and the phosphoric acid alone, which is probably because the different emulsifying property and the dissociation property of the sulfonate and the phosphate grafted on the surface of the polyisocyanate promote the dissolution in water and simultaneously avoid the self-thickening and the increase of the particle size caused by too high intermolecular force, thereby further promoting the dispersibility and the increase of the resistance of the coating; preferably, the molar ratio of the sulfamic acid and the modified phosphoric acid is 1: (0.1 to 3); preferably, the molar ratio of the sulfamic acid and the modified phosphoric acid is 1: (1-2).
The applicant has found that when a proper amount of sulfamic acid and modified phosphoric acid is added, the dispersion and curing properties of the polyisocyanate are improved, when the amount of the sulfonic acid and the phosphoric acid is too low, the water dispersibility is poor, and when the amount of the sulfonic acid and the phosphoric acid is too high, the residual amount of isocyanate groups is adversely affected, the curing properties are affected, and the physical properties, the resistance, the stability and the like of the coating are affected. More preferably, the molar ratio of the total molar amount of the sulfamic acid and the modified phosphoric acid in the invention to the molar amount of the isocyanate in the polyisocyanate is (0.005-0.05): 1; further, the molar ratio of the total molar weight of the sulfamic acid and the modified phosphoric acid to the molar weight of the isocyanate in the polyisocyanate is (0.01-0.03): 1; further, the molar ratio of the total molar amount of the sulfamic acid and the modified phosphoric acid in the invention to the molar amount of the isocyanate group in the polyisocyanate is 0.021: 1.
the applicant has found that by adding the sulphonic acid and excess catalyst first, the reaction of the sulphamic acid with the polyisocyanate under mild conditions can be further promoted, promoting the completion of the reaction of the sulphamic acid. Further preferably, the reaction temperature in the step (1) is 70-110 ℃; further preferably, the reaction temperature in the step (1) is 80-90 ℃; furthermore, in the step (1), polyisocyanate, sulfamic acid and a neutralization catalyst are mixed at 55-65 ℃, and the temperature is raised to 80-90 ℃ for reaction, so that the sulfonic acid modified polyisocyanate is obtained.
Applicants have found that modified phosphoric acid and polyisocyanate are more reactive than sulfamic acid and are reactive at lower temperatures; more preferably, the reaction temperature in the step (2) is 65-100 ℃; still more preferably, the reaction temperature in the step (2) of the present invention is 75 to 80 ℃.
In a second aspect, the present invention provides the use of a process for the preparation of an odorless water-dispersible polyisocyanate as described above for an aqueous coating.
Coatings using water as a solvent or as a dispersion medium may be referred to as waterborne coatings.
Examples
The present invention will be specifically described below by way of examples. 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.
Example 1
This example provides a process for preparing an odorless water dispersible polyisocyanate comprising the steps of:
(1) at 60 ℃, adding isocyanurate polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 4-cyclohexylaminobutane-1-sulfonic acid (0.008mol) into a three-neck flask, adding N, N-dimethylbutylamine (0.02mol), mixing, heating to 85 ℃, and reacting for 2 hours until the solution becomes completely clear to obtain sulfonic acid modified polyisocyanate;
(2) cooling the sulfonic acid modified polyisocyanate to 76 ℃, adding 2-hydroxyethyl phosphoric acid (0.013mol), reacting for 2 hours, and cooling to room temperature to obtain the water dispersible polyisocyanate.
The isocyanurate polyisocyanate is available from Desmodur N3300, kosa.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Example 2
This example provides a process for preparing an odorless water dispersible polyisocyanate comprising the steps of:
(1) at 60 ℃, adding biuret polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 3-cyclohexylaminopropane-1-sulfonic acid (0.005mol) into a three-neck flask, adding N, N-dimethylethylamine (0.01mol), mixing, heating to 85 ℃, and reacting for 1.5 hours until the solution becomes completely clear to obtain sulfonic acid modified polyisocyanate;
(2) cooling the sulfonic acid modified polyisocyanate to 76 ℃, adding hydroxyethylidene diphosphonic acid (0.005mol), reacting for 1.5 hours, and cooling to room temperature to obtain the water dispersible polyisocyanate.
The biuret polyisocyanate was purchased from Desmodur N100, kossian.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Example 3
This example provides a process for preparing an odorless water dispersible polyisocyanate comprising the steps of:
(1) at 60 ℃, adding isocyanurate polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 4-cyclohexylaminobutane-1-sulfonic acid (0.01mol) into a three-neck flask, adding N, N-dimethylbutylamine (0.029mol), mixing, heating to 85 ℃, and reacting for 3 hours until the solution becomes completely clear to obtain sulfonic acid modified polyisocyanate;
(2) cooling the sulfonic acid modified polyisocyanate to 76 ℃, adding carbamyl phosphoric acid (0.02mol), reacting for 3 hours, and cooling to room temperature to obtain the water dispersible polyisocyanate.
The isocyanurate polyisocyanate is available from Desmodur N3300, kosa.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Example 4
This example provides a process for preparing an odorless water dispersible polyisocyanate comprising the steps of:
(1) at 60 ℃, adding isocyanurate polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 4-cyclohexylaminobutane-1-sulfonic acid (0.008mol) into a three-neck flask, adding N, N-dimethylbutylamine (0.02mol), mixing, heating to 85 ℃, and reacting for 2 hours until the solution becomes completely clear to obtain sulfonic acid modified polyisocyanate;
(2) cooling the sulfonic acid modified polyisocyanate to 76 ℃, adding 1-aminopropyl phosphoric acid (0.013mol), reacting for 2 hours, and cooling to room temperature to obtain the water dispersible polyisocyanate.
The isocyanurate polyisocyanate is available from Desmodur N3300, kosa.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Example 5
This example provides a process for preparing an odorless water dispersible polyisocyanate comprising the steps of:
(1) at 60 ℃, adding isocyanurate polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 4-cyclohexylaminobutane-1-sulfonic acid (0.008mol) into a three-neck flask, adding N, N-dimethylbutylamine (0.02mol), mixing, heating to 85 ℃, and reacting for 2 hours until the solution becomes completely clear to obtain sulfonic acid modified polyisocyanate;
(2) cooling the sulfonic acid modified polyisocyanate to 76 ℃, adding 1-aminooctyl phosphoric acid (0.013mol), reacting for 2 hours, and cooling to room temperature to obtain the water dispersible polyisocyanate.
The isocyanurate polyisocyanate is available from Desmodur N3300, kosa.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Comparative example 1
This example provides a process for preparing a water dispersible polyisocyanate comprising the steps of:
at 80 ℃, adding isocyanurate polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 4-cyclohexylaminobutane-1-sulfonic acid (0.03mol) into a three-neck flask, adding N, N-dimethylbutylamine (0.03mol), mixing, heating to 100 ℃, and reacting for 8 hours until the solution becomes completely clear to obtain the water dispersible polyisocyanate.
The isocyanurate polyisocyanate is available from Desmodur N3300, kosa.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Comparative example 2
This example provides a process for preparing a water dispersible polyisocyanate comprising the steps of:
at 80 ℃, adding isocyanurate polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 4-cyclohexylaminobutane-1-sulfonic acid (0.02mol) into a three-neck flask, adding N, N-dimethylbutylamine (0.02mol), mixing, heating to 100 ℃, and reacting for 5 hours until the solution becomes completely clear to obtain the water dispersible polyisocyanate.
The isocyanurate polyisocyanate is available from Desmodur N3300, kosa.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Comparative example 3
This example provides a process for preparing a water dispersible polyisocyanate comprising the steps of:
at 65 ℃, adding isocyanurate polyisocyanate (the molar weight of isocyanic acid radical is 1mol) and 2-hydroxyethyl phosphoric acid (0.02mol) into a three-neck flask, adding N, N-dimethylbutylamine (0.02mol), mixing, heating to 85 ℃, and reacting for 3.5 hours until the solution becomes completely clear, thereby obtaining the water dispersible polyisocyanate.
The isocyanurate polyisocyanate is available from Desmodur N3300, kosa.
The water-dispersible polyisocyanate obtained in this example was a colorless, clear and transparent liquid.
Evaluation of Performance
The following experiments were performed as experimental groups provided in the examples.
1. NCO content: the NCO content of the water-dispersible polyisocyanates given in the examples was determined by the di-n-butylamine-hydrochloric acid titration method and the results are given in Table 1.
2. Viscosity: the water-dispersible polyisocyanates provided in the examples were tested for viscosity by viscometer and the results are given in Table 1.
3. Particle size of emulsion in water: the water-dispersible polyisocyanate provided in example was diluted 100 times with water, and the emulsified particle size was measured by a particle size analyzer, and the results are shown in Table 1.
4. Odor: the odor of the water-dispersible polyisocyanate provided in example was subjected to sensory evaluation, and the presence or absence of an ammonia odor was judged, and the results are shown in Table 1.
5. Coating film glossiness: the water dispersible polyisocyanate provided in the example and YL-MY7138 resin (3.8% aqueous hydroxypropyl dispersion) were mixed at a ratio of 1: 4, and curing at normal temperature to obtain a coating film, and testing the 60-degree gloss of the coating film, wherein the results are shown in table 1.
6. Water resistance: the water dispersible polyisocyanate provided in the example and YL-MY7138 resin (3.8% aqueous hydroxypropyl dispersion) were mixed at a ratio of 1: 4, curing at normal temperature, curing for 7 days to obtain a coating film, testing to obtain the water resistance of the coating film after soaking in water at normal temperature for 240 hours, and evaluating according to whether the surface of the coating film has blistering and cracking, wherein the results are shown in table 1.
7. Hardness: the water dispersible polyisocyanate provided in the example and YL-MY7138 resin (3.8% aqueous hydroxypropyl dispersion) were mixed at a ratio of 1: 4, curing at normal temperature, curing for 7 days to obtain a coating film, and testing the pencil hardness of the coating film, wherein the results are shown in table 1.
Table 1 performance characterization test
As can be seen from the test results in Table 1, the water-dispersible polyisocyanate prepared by the preparation method of odorless water-dispersible polyisocyanate provided by the invention has the advantages of high effective NCO value, low viscosity, better dispersion, no odor and small emulsified particle size, and a coating film obtained by using the water-dispersible polyisocyanate prepared by the invention as a curing agent has good glossiness, tolerance and physical properties.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present 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. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A method for preparing odorless water dispersible polyisocyanate, which is characterized by comprising the following steps:
(1) mixing polyisocyanate, sulfamic acid and a neutralization catalyst, and reacting to obtain sulfonic acid modified polyisocyanate;
(2) adding modified phosphoric acid into sulfonic acid modified polyisocyanate, and reacting to obtain water dispersible polyisocyanate;
the modified phosphoric acid contains hydroxyl or amino.
2. The method for preparing the odorless water dispersible polyisocyanate according to claim 1, wherein the molar ratio of the total molar amount of the sulfamic acid and the modified phosphoric acid to the molar amount of the neutralization catalyst is (1-1.1): 1.
3. the process for the preparation of neat water dispersible polyisocyanates according to claim 1, wherein the molar ratio of said sulfamic acid and modified phosphoric acid is 1: (0.1 to 3).
4. The method of claim 1, wherein the molar ratio of the total molar amount of sulfamic acid and modified phosphoric acid to the molar amount of isocyanate groups in the polyisocyanate is (0.005-0.05): 1.
5. The method for preparing the odorless water-dispersible polyisocyanate according to claim 1, wherein the reaction temperature in the step (1) is 70-110 ℃.
6. The method for preparing the odorless water-dispersible polyisocyanate according to claim 1, wherein the reaction temperature in the step (2) is 65-100 ℃.
7. The method of any one of claims 1 to 6, wherein the polyisocyanate is selected from one of isocyanurate polyisocyanates, biuret polyisocyanates, carbodiimide polyisocyanates, uretonimine polyisocyanates, uretdione polyisocyanates, allophanate polyisocyanates, urethane polyisocyanates, iminooxadiazinedione polyisocyanates.
8. The method for producing the odorless water-dispersible polyisocyanate according to any one of claims 1 to 6, wherein the sulfamic acid is an aliphatic sulfamic acid or an alicyclic sulfamic acid.
9. The process according to any one of claims 1 to 6, wherein the neutralizing catalyst is selected from the group consisting of trimethylamine, triethylamine, isomeric tripropylamine and tributylamine, N-dimethylethylamine, N-dimethylpropylamine, N-dimethylisopropylamine, N-dimethylbutylamine, N-dimethylisobutylamine, N-dimethyloctylamine, N-dimethyl-2-ethylhexylamine, N-dimethyllaurylamine, N-diethylmethylamine, N-diethylpropylamine, N-diethylbutylamine, N-diethylhexylamine, N-diethyloctylamine, N-diethyl-2-ethylhexylamine, N-diethylhexylamine, N-diethyloctylamine, N-diethyl-2-ethylhexylamine, N, N-diethyllaurylamine, N-diisopropylmethylamine, N-diisopropylethylamine, N-diisopropylbutylamine, N-diisopropyl-2-ethylhexylamine, N-dioctylmethylamine, N-dimethylallylamine, N-dimethylbenzylamine, N-diethylbenzylamine, N-dibenzylmethylamine, tribenzylamine, N-dimethyl-4-methylbenzylamine, N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-dicyclohexylmethylamine, N-dicyclohexylethylamine, tricyclohexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, One or more of N-butylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-methylmorpholine, N-ethylmorpholine, N-propylmorpholine, N-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-isobutyl morpholine and quinuclidine.
10. Use of the process according to any one of claims 1 to 9 for the preparation of an odorless water-dispersible polyisocyanate for a water-borne coating.
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| CN115466201B (en) * | 2021-06-11 | 2024-05-03 | 万华化学集团股份有限公司 | Sulfonic acid modified polyisocyanate and preparation method thereof |
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