CN111848921A - Waterborne polyurethane resin for coating and preparation method thereof - Google Patents
Waterborne polyurethane resin for coating and preparation method thereof Download PDFInfo
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- CN111848921A CN111848921A CN202010714903.1A CN202010714903A CN111848921A CN 111848921 A CN111848921 A CN 111848921A CN 202010714903 A CN202010714903 A CN 202010714903A CN 111848921 A CN111848921 A CN 111848921A
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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
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
Abstract
The invention relates to the technical field of high polymer materials, in particular to a waterborne polyurethane resin for paint and a preparation method thereof. The waterborne polyurethane resin for the coating is prepared by carrying out prepolymerization on isocyanate and dihydric alcohol and then respectively carrying out chain extension under the action of a hydrophilic functional component and diamine as chain extenders. Compared with the prior art, the hydrophilic polyurethane resin provided by the invention enables polyurethane to be waterborne by introducing the hydrophilic chain extender, and has excellent emulsifying capacity. The waterborne polyurethane resin provided by the invention is matched with an isocyanate HDI trimer for use, so that the emulsion is good; the activation period is long, and the field construction is facilitated; the surface of the coating film is dried quickly, and the coating film has high hardness and good adhesive force and flexibility.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a waterborne polyurethane resin for paint and a preparation method thereof.
Background
Compared with a polyurethane structure, the stability of a C-N bond in the polyurea structure is larger than that of a C-O bond in the polyurea structure, the polarity of carbamido is large, so that the molecular structure of polyurea is more stable, the polyurea has excellent corrosion resistance, acid and alkali resistance, aging resistance and good mechanical properties, the polyurea can be cured at low temperature, and a coating is continuous and compact.
At present, water-based coatings are a research hotspot and have unique advantages: water can be used as a diluent, so that the use of an organic solvent is reduced, the toxicity and the irritation are reduced, and the environment-friendly effect is realized on the human body and the environment; the coating can be thinly coated, the requirements of more places are met, and the cost is reduced; the construction mode is not limited, and the construction equipment is easy to clean.
The viscosity of the oil polyurethane used in the conventional polyurethane coating is high, and the field construction is inconvenient. In addition, the traditional waterborne polyurethane has poor performance, and cannot have good adhesion and flexibility while having good hardness.
Disclosure of Invention
Aiming at the technical problems, hydrophilic groups are introduced into the polyurethane-polyurea structure, so that the polyurethane-polyurea structure has certain hydrophilicity, and the synthesized polyurea modified waterborne polyurethane resin has considerable performance and application prospect.
In particular, the first aspect of the invention provides aAn aqueous polyurethane resin having the following structural formula:
as a preferable technical scheme of the invention, R in the structural formula of the waterborne polyurethane resin1A combination of one or more selected from the following structural formulae:
as a preferable technical scheme of the invention, X in the structural formula of the aqueous polyurethane resin is selected from one or more of the following structural formulas:
as a preferable technical scheme of the invention, R in the structural formula of the waterborne polyurethane resin is
As a preferable technical scheme of the invention, R in the structural formula of the waterborne polyurethane resin3Is a straight-chain alkyl group with the carbon number of 1-10.
The second aspect of the present invention provides a method for producing the aqueous polyurethane resin as described above, comprising the steps of:
(1) under the protection of nitrogen, adding diisocyanate into a reaction bottle, controlling the temperature to be 50-70 ℃, dropwise adding dihydric alcohol to react with the diisocyanate, and stopping the reaction when the-NCO value reaches a theoretical value to obtain a compound A;
(2) under the protection of nitrogen, adding the compound A into a reaction bottle, controlling the temperature to be 60-80 ℃, dropwise adding an N-methyl pyrrolidone solution of dimethylolpropionic acid to react with the compound A, and stopping the reaction when the detected-NCO value reaches a theoretical value to obtain a compound B;
(3) and (3) under the protection of nitrogen and in a dark condition, adding excessive diamine with the weight of 5-20% into a reaction bottle, dropwise adding the compound B to react with the diamine at room temperature, detecting no-NCO group, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin.
As a preferable technical scheme of the invention, the diamine is an addition product of alicyclic diamine and maleic acid diester.
In a preferred embodiment of the present invention, the cycloaliphatic diamine is selected from one or more of methylcyclohexanediamine, diaminomethylcyclohexylmethane, isophoronediamine, diaminodicyclohexylmethane, diaminomethylcyclohexane, and diaminocyclohexane.
As a preferred embodiment of the present invention, the maleic acid diester is selected from one or more of dimethyl maleate, diethyl maleate, dibutyl maleate, and dioctyl maleate.
The third aspect of the present invention provides the use of the aqueous polyurethane resin as described above in the field of coatings.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waterborne polyurethane resin provided by the invention enables polyurethane to be waterborne by introducing the hydrophilic chain extender, and has excellent emulsifying capacity.
(2) The waterborne polyurethane resin provided by the invention is matched with an isocyanate HDI trimer for use, and is well emulsified; the activation period is long, and the field construction is facilitated; the surface of the coating film is dried quickly, and the coating film has high hardness and good adhesive force and flexibility.
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 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.
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.
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 words "preferred", "preferably", "further", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The first aspect of the present invention provides an aqueous polyurethane resin having the following structural formula:
in some embodiments, R in the structural formula of the aqueous polyurethane resin1A combination of one or more selected from the following structural formulae:
in some embodiments, X in the structural formula of the aqueous polyurethane resin is selected from the group consisting of one or more of the following structural formulas:
preferably, R in the above formula2Is a hydrogen atom or a methyl group.
In some embodiments, R in the structural formula of the waterborne polyurethane resin is
Preferably, R in the above formula0Is a hydrogen atom or a methyl group.
In some embodiments, R in the structural formula of the aqueous polyurethane resin3Is a straight-chain alkyl group with the carbon number of 1-20.
Preferably, R in the structural formula of the waterborne polyurethane resin3Is a straight-chain alkyl group with the carbon number of 1-10.
The second aspect of the present invention provides a method for producing the aqueous polyurethane resin as described above, comprising the steps of:
(1) under the protection of nitrogen, adding diisocyanate into a reaction bottle, controlling the temperature to be 50-70 ℃, dropwise adding dihydric alcohol to react with the diisocyanate, and stopping the reaction when the-NCO value reaches a theoretical value to obtain a compound A;
(2) under the protection of nitrogen, adding the compound A into a reaction bottle, controlling the temperature to be 60-80 ℃, dropwise adding an N-methyl pyrrolidone solution of dimethylolpropionic acid (DMPA) to react with the compound A, and stopping the reaction when the-NCO value reaches a theoretical value to obtain a compound B;
(3) and (3) under the protection of nitrogen and in a dark condition, adding excessive diamine with the weight of 5-20% into a reaction bottle, dropwise adding the compound B to react with the diamine at room temperature, detecting no-NCO group, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin.
In some embodiments, the reaction time of step (1), step (2) and step (3), independently, is 3 to 5 hours.
In some embodiments, the diisocyanate is selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate in any one or more combinations.
Preferably, the diisocyanate is isophorone diisocyanate (IPDI).
In some embodiments, the diol is a polyether diol.
Preferably, the polyether glycol is polyethylene glycol and/or polypropylene glycol.
Preferably, the number average molecular weight of the polyethylene glycol or the polypropylene glycol is 200-3000.
Preferably, the number average molecular weight of the polyethylene glycol or the polypropylene glycol is 200-2000.
In some embodiments, the diamine is an addition product of a cycloaliphatic diamine and a maleic diester.
Further, the alicyclic diamine is selected from one or more of methyl cyclohexane diamine, diaminomethyl cyclohexyl methane, isophorone diamine, diaminodicyclohexyl methane, diaminomethyl cyclohexane and diaminocyclohexane.
Preferably, the diamine is diaminodicyclohexylmethane.
In some embodiments, the maleic acid diester is selected from the group consisting of dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, in combination with one or more thereof.
Preferably, the maleic acid diester is diethyl maleate.
In some preferred embodiments, the method for preparing the diamine comprises the steps of:
under the protection of nitrogen, weighing a certain amount of diester maleate, adding the diester maleate into a reaction bottle, controlling the temperature to be 60-80 ℃, slowly adding the alicyclic diamine to react with the diester maleate, keeping the temperature for reaction for 3-5 days, and detecting that primary amine does not exist, namely cooling and stopping the reaction to obtain the diamine.
Preferably, the mole ratio of the maleic acid diester to the cycloaliphatic diamine is 2: 1.
in some embodiments, a certain amount of catalyst may be added in step (1), step (2) and step (3) of the preparation method of the aqueous polyurethane resin.
Furthermore, the dosage of the catalyst is 0.05-2% of the weight of the dihydric alcohol, the dimethylolpropionic acid and the diamine respectively.
Preferably, dibutyltin dilaurate is used as the catalyst.
In the preparation process of traditional polyurethane, diisocyanate and polyether/polyester polyol are generally required to react to prepare a prepolymer, and then the prepolymer and diol or diamine are used as a chain extender to prepare the final polyurethane resin. However, the polyurethane resin has a structure in which the hydrophilic group content is too small, and the whole is oily, and thus it is necessary to use the polyurethane resin after dissolving the polyurethane resin in an organic solvent such as acetone to form a solution. Of course, in the prior art, a specific emulsifier is adopted to prepare the water-based polyurethane, so that the use of an organic solvent is successfully avoided, but the problems of short activation period and to-be-improved comprehensive performance exist. According to the method, on one hand, after a prepolymer is prepared, an NMP solution of dimethylolpropionic acid (DMPA) is adopted, the isocyanate-terminated prepolymer is reacted with dihydric alcohol containing carboxyl, carboxyl containing strong hydrophilicity is introduced to a molecular chain structure of the prepolymer, and then diamine obtained by modifying maleic acid diester and alicyclic diamine is added to be used as a final chain extender to carry out chain extension to prepare the waterborne polyurethane. Because the polyurethane has a stronger hydrophilic carboxyl group in the molecular structure, the hydrophilic polyurethane is beneficial to improving the hydrophilicity of the aqueous polyurethane and has excellent emulsifying capacity. On the other hand, triethylamine is used as a neutralizing agent in the method, so that a salt is formed between the hydrophilic carboxyl with negative charges in the molecular chain of the polyurethane resin and the alkaline tertiary amine, the hydrophilicity and the stability in water of the polyurethane resin are further improved, and the emulsifying capacity in water is improved. In addition, the structure of diisocyanate, the use amount of alkoxy ether, maleic acid diester modified cycloaliphatic diamine and dimethylolpropionic acid are adjusted, the molecular design is carried out on the waterborne polyurethane, so that the waterborne polyurethane has excellent hardness, good adhesive force, flexibility and excellent activation period, and the construction application of the waterborne polyurethane is obviously improved.
The third aspect of the present invention provides the use of the aqueous polyurethane resin as described above in the field of coatings.
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.
Examples
Example 1: an aqueous polyurethane resin is provided, which has the following structural formula:
the preparation method of the waterborne polyurethane resin comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 300g of PEG200 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A1 is obtained;
(2) under the protection of nitrogen, 580g of compound A1 is weighed and added into a reaction bottle, the temperature is controlled to be 70 +/-5 ℃, 60.3g of NMP solution of DMPA is slowly dripped to react with the compound A1, and the reaction is stopped when the detected-NCO value reaches the theoretical-NCO value to obtain a compound B1;
(3) weighing 548.5g of diamine, adding into a reaction flask under the protection of nitrogen, slowly dropwise adding 640.3g of compound B1 at room temperature to react with the diamine, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin WPU 1.
The preparation method of the diamine comprises the following steps:
under the protection of nitrogen, 344g of diethyl maleate is weighed and added into a reaction bottle, the temperature is controlled to be 70 +/-5 ℃, 210g of diaminodicyclohexylmethane is slowly added to react with the diethyl maleate, the temperature is kept for reaction for 3-5 days, and when no primary amine exists, the temperature is reduced and the reaction is stopped to obtain the diamine.
HDI tripolymer and WPU1 are mixed according to the mass ratio of 10: 54, adding a certain amount of deionized water, stirring to form emulsion, coating the emulsion on tinplate, curing at room temperature to form a film, and performing performance detection on the film. The performance data are shown in Table 1.
Example 2: an aqueous polyurethane resin is provided, which has the following structural formula:
the preparation method of the waterborne polyurethane resin comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 600g of PEG400 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A2 is obtained;
(2) under the protection of nitrogen, 760g of the compound A2 is weighed and added into a reaction bottle, the temperature is controlled to be 70 +/-5 ℃, 60.3g of NMP solution of DMPA is slowly dripped to react with the compound A2, and the reaction is stopped when the detected-NCO value reaches the theoretical-NCO value to obtain a compound B2;
(3) weighing 548.5g of diamine, adding the diamine into a reaction bottle, slowly dropwise adding 820.3g of compound B2 at room temperature to react with the diamine under the protection of nitrogen, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin WPU 2.
Wherein the diamine was prepared as in example 1.
HDI tripolymer and WPU2 are mixed according to the mass ratio of 10: 62, adding a certain amount of deionized water, stirring to form emulsion, coating the emulsion on tinplate, curing at room temperature to form a film, and carrying out performance detection on the film. The performance data are shown in Table 1.
Example 3: an aqueous polyurethane resin is provided, which has the following structural formula:
the preparation method of the waterborne polyurethane resin comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 900g of PEG600 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A3 is obtained;
(2) under the protection of nitrogen, 940g of the compound A3 is weighed and added into a reaction bottle, the temperature is controlled to be 70 +/-5 ℃, 60.3g of NMP solution of DMPA is slowly dripped to react with the compound A3, and the reaction is stopped when the detected-NCO value reaches the theoretical-NCO value to obtain a compound B3;
(3) weighing 548.5g of diamine, adding the diamine into a reaction bottle, slowly dropwise adding 1000.3g of compound B3 at room temperature to react with the diamine under the protection of nitrogen, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin WPU 3.
Wherein the diamine was prepared as in example 1.
HDI tripolymer and WPU3 are mixed according to the mass ratio of 10: 70, adding a certain amount of deionized water, stirring to form emulsion, coating the emulsion on tinplate, curing at room temperature to form a film, and performing performance detection on the film. The performance data are shown in Table 1.
Example 4: an aqueous polyurethane resin is provided, which has the following structural formula:
the preparation method of the waterborne polyurethane resin comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 1200g of PEG800 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A4 is obtained;
(2) weighing 1120g of the compound A4 and adding the compound A4 into a reaction bottle under the protection of nitrogen, controlling the temperature to be 70 +/-5 ℃, slowly dripping 60.3g of NMP solution of DMPA to react with the compound A4, and stopping the reaction when the detected-NCO value reaches the theoretical-NCO value to obtain a compound B4;
(3) weighing 548.5g of diamine, adding the diamine into a reaction bottle, slowly dropwise adding 1180.3g of compound B4 at room temperature to react with the diamine under the protection of nitrogen, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin WPU 4.
Wherein the diamine was prepared as in example 1.
HDI tripolymer and WPU4 are mixed according to the mass ratio of 10: 78, adding a certain amount of deionized water, stirring to form emulsion, coating the emulsion on tinplate, curing at room temperature to form a film, and carrying out performance detection on the film. The performance data are shown in Table 1.
Example 5: an aqueous polyurethane resin is provided, which has the following structural formula:
the preparation method of the waterborne polyurethane resin comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 1500g of PEG1000 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A5 is obtained;
(2) weighing 1300g of the compound A5 and adding into a reaction bottle under the protection of nitrogen, controlling the temperature to be 70 +/-5 ℃, slowly dripping 60.3g of NMP solution of DMPA to react with the compound A5, and stopping the reaction when the detected-NCO value reaches the theoretical-NCO value to obtain a compound B5;
(3) weighing 548.5g of diamine, adding the diamine into a reaction bottle, slowly dropwise adding 1360.3g of compound B5 at room temperature to react with the diamine under the protection of nitrogen, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin WPU 5.
Wherein the diamine was prepared as in example 1.
HDI tripolymer and WPU5 are mixed according to the mass ratio of 10: 86, adding a certain amount of deionized water, stirring to form emulsion, coating the emulsion on tinplate, curing at room temperature to form a film, and performing performance detection on the film. The performance data are shown in Table 1.
Example 6: an aqueous polyurethane resin is provided, which has the following structural formula:
the preparation method of the waterborne polyurethane resin comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 3000g of PEG2000 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A6 is obtained;
(2) weighing 2200g of the compound A6 under the protection of nitrogen, adding into a reaction bottle, controlling the temperature to be 70 +/-5 ℃, slowly dripping 60.3g of NMP solution of DMPA to react with the compound A6, and stopping the reaction when the detected-NCO value reaches the theoretical-NCO value to obtain a compound B6;
(3) weighing 548.5g of diamine, adding the diamine into a reaction bottle, slowly dropwise adding 2260.3g of compound B6 at room temperature to react with the diamine under the protection of nitrogen, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin WPU 6.
Wherein the diamine was prepared as in example 1.
HDI tripolymer and WPU6 are mixed according to the mass ratio of 10: 125, adding a certain amount of deionized water, stirring, and having poor emulsifying effect and no emulsion formation.
Comparative example 1: provides an oil-based polyurethane resin, and the preparation method comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 600g of PEG400 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A2 is obtained;
(2) weighing 548.5g of diamine, adding into a reaction bottle under the protection of nitrogen, slowly dropwise adding 380.1g of compound A2 at room temperature to react with the diamine, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize, thus obtaining the oil-based polyurethane resin PU 2.
Wherein the diamine was prepared as in example 1.
Mixing HDI tripolymer and PU2 according to the mass ratio of 10: 40, adding 30 +/-5 wt% of acetone for dilution, coating the mixture on tinplate, curing at room temperature to form a film, and carrying out performance detection on the film. The performance data are shown in Table 1.
Comparative example 2: provides an oil-based polyurethane resin, and the preparation method comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 900g of PEG600 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A3 is obtained;
(2) weighing 548.5g of diamine, adding into a reaction bottle under the protection of nitrogen, slowly dropwise adding 470g of compound A3 at room temperature to react with the diamine, detecting no-NCO group, and adding a corresponding amount of triethylamine to neutralize to obtain the oil-based polyurethane resin PU 3.
Wherein the diamine was prepared as in example 1.
Mixing HDI tripolymer and PU3 according to the mass ratio of 10: 45, adding 30 +/-5 wt% of acetone for dilution, coating the mixture on tinplate, curing the mixture at room temperature to form a film, and then carrying out performance detection on the film. The performance data are shown in Table 1.
Comparative example 3: provides an oil-based polyurethane resin, and the preparation method comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 1500g of PEG1000 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A5 is obtained;
(2) weighing 548.5g of diamine, adding into a reaction bottle under the protection of nitrogen, slowly dropwise adding 650g of compound A5 at room temperature to react with the diamine, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize, thus obtaining the oil-based polyurethane resin PU 5.
Wherein the diamine was prepared as in example 1.
Mixing HDI tripolymer and PU5 according to the mass ratio of 10: 52, adding 30 +/-5 wt% of acetone for dilution, coating the mixture on tinplate, curing the mixture at room temperature to form a film, and then carrying out performance detection on the film. The performance data are shown in Table 1.
Comparative example 4: provides a waterborne polyurethane resin, and the preparation method comprises the following steps:
(1) under the protection of nitrogen, 666.8g of IPDI is weighed and added into a reaction bottle, the temperature is controlled to be 60 +/-5 ℃, 600g of PEG400 is slowly dripped to react with the IPDI, and the reaction is stopped when the-NCO value reaches the theoretical-NCO value, so that a compound A2 is obtained;
(2) under the protection of nitrogen, 760g of the compound A2 is weighed and added into a reaction bottle, the temperature is controlled to be 70 +/-5 ℃, 60.3g of NMP solution of DMPA is slowly dripped to react with the compound A2, and the reaction is stopped when the detected-NCO value reaches the theoretical-NCO value to obtain a compound B2;
(3) and (2) weighing 208.2g of diaminodicyclohexylmethane under the protection of nitrogen, adding into a reaction bottle, slowly dropwise adding 820.3g of compound B2 at room temperature to react with the diaminodicyclohexylmethane, detecting that no-NCO group exists, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin PU 21.
Mixing HDI tripolymer and PU21 according to the mass ratio of 10: 45, adding a certain amount of deionized water, stirring to form emulsion, coating the emulsion on tinplate, curing at room temperature to form a film, and carrying out performance detection on the film. The performance data are shown in Table 1.
Performance testing
The applicant carried out the following performance tests on the aqueous/oily polyurethane materials of the above examples and comparative examples:
(1) adhesion force: according to the regulations of the national standard GB/T9286.
(2) Surface drying time: the drying time is regulated according to the national standard GB/T1728.
(3) Hardness: according to the regulations of the national standard GB/T6739.
(4) Flexibility: according to the regulations of the national standard GB/T1731.
Further, tests of the solid content, the pot life and the emulsifying ability were carried out according to the conventional methods, and the test results are shown in table 1.
TABLE 1 test results
As can be seen from the performance test results in table 1, the waterborne polyurethane resin provided by the embodiment of the present invention and the HDI trimer are matched to form a film, and compared with the oil-based polyurethane resin having the same main structure, the waterborne polyurethane resin has the advantages of maintaining higher hardness and better adhesion and flexibility, and greatly prolonging the activation period, so as to be more beneficial to actual construction; the waterborne polyurethane resin has certain hydrophilicity, can be diluted by adding water when in use, and reduces the harm to human bodies and the environment.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content disclosed above into an equivalent embodiment with equivalent changes, but all those simple modifications, equivalent changes and modifications made on the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. An aqueous polyurethane resin, characterized in that it has the following structural formula:
2. the aqueous polyurethane resin according to claim 1, wherein R in the structural formula of the aqueous polyurethane resin is represented by1A combination of one or more selected from the following structural formulae:
3. the aqueous polyurethane resin according to claim 1, wherein X in the structural formula of the aqueous polyurethane resin is selected from one or more of the following structural formulas:
4. the aqueous polyurethane resin according to claim 1, wherein R in the structural formula of the aqueous polyurethane resin is
Wherein R is0Is a hydrogen atom or a methyl group.
5. The aqueous polyurethane resin according to any one of claims 1 to 4, wherein R in the structural formula of the aqueous polyurethane resin is3Is a straight-chain alkyl group with the carbon number of 1-10.
6. The method for producing the aqueous polyurethane resin according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) under the protection of nitrogen, adding diisocyanate into a reaction bottle, controlling the temperature to be 50-70 ℃, dropwise adding dihydric alcohol to react with the diisocyanate, and stopping the reaction when the-NCO value reaches a theoretical value to obtain a compound A;
(2) under the protection of nitrogen, adding the compound A into a reaction bottle, controlling the temperature to be 60-80 ℃, dropwise adding an N-methyl pyrrolidone solution of dimethylolpropionic acid to react with the compound A, and stopping the reaction when the detected-NCO value reaches a theoretical value to obtain a compound B;
(3) and (3) under the protection of nitrogen and in a dark condition, adding excessive diamine with the weight of 5-20% into a reaction bottle, dropwise adding the compound B to react with the diamine at room temperature, detecting no-NCO group, and adding a corresponding amount of triethylamine to neutralize to obtain the waterborne polyurethane resin.
7. The method for producing an aqueous polyurethane resin according to claim 6, wherein the diamine is an addition product of a cycloaliphatic diamine and a maleic diester.
8. The method for producing an aqueous polyurethane resin according to claim 7, wherein the cycloaliphatic diamine is one or more selected from the group consisting of methylcyclohexanediamine, diaminomethylcyclohexylmethane, isophoronediamine, diaminodicyclohexylmethane, diaminomethylcyclohexane, and diaminocyclohexane.
9. The method for preparing the aqueous polyurethane resin according to claim 7, wherein the maleic acid diester is selected from one or more of dimethyl maleate, diethyl maleate, dibutyl maleate and dioctyl maleate.
10. The use of the aqueous polyurethane resin according to any one of claims 1 to 5 in the field of coatings.
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