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CN108264622B - Waterborne polyurethane, preparation intermediate and preparation method thereof - Google Patents

Waterborne polyurethane, preparation intermediate and preparation method thereof Download PDF

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Publication number
CN108264622B
CN108264622B CN201611262006.1A CN201611262006A CN108264622B CN 108264622 B CN108264622 B CN 108264622B CN 201611262006 A CN201611262006 A CN 201611262006A CN 108264622 B CN108264622 B CN 108264622B
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preparation
polyol
sulfonate
prepolymer
formula
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CN108264622A (en
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黄少华
徐学峰
张秀峰
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BYD Co Ltd
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BYD Co Ltd
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C07C309/15—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton the nitrogen atom of at least one of the amino groups being part of any of the groups, X being a hetero atom, Y being any atom
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    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
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    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • 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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    • 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
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses waterborne polyurethane, a preparation intermediate thereof and a preparation method thereof. The preparation method of the waterborne polyurethane comprises the following steps of S1, preparing an intermediate with a structure shown in the following formula I, S2, under the condition of prepolymerization reaction, promoting the intermediate to contact and react with polyol, first polyisocyanate and organic carboxylic acid containing two hydroxyl groups and having the number average molecular weight of less than 250g/mol to form prepolymer; and S3, carrying out emulsification treatment on the prepolymer under an emulsification condition, and carrying out chain extension treatment on the emulsified prepolymer under a chain extension condition. According to the method, the intermediate with the structure shown in the formula I is added in the prepolymerization reaction process, so that the prepolymer with relatively low viscosity can be prepared, and the high-solid-content waterborne polyurethane can be directly prepared by emulsification without adopting an organic solvent.

Description

Waterborne polyurethane, preparation intermediate and preparation method thereof
Technical Field
The invention relates to the field of production of waterborne polyurethane, in particular to waterborne polyurethane, a preparation intermediate for preparing the waterborne polyurethane and a preparation method of the waterborne polyurethane.
Background
Aqueous polyurethanes are new polyurethane systems in which water is used as the dispersion medium instead of an organic solvent, and are also referred to as water-dispersed polyurethanes, aqueous polyurethanes, or water-based polyurethanes. The waterborne polyurethane takes water as a solvent, and has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like. Has been widely applied to the fields of leather finishing, automobile coating, fiber treatment, auxiliary agents in the paper industry, coatings, adhesives and the like.
The preparation method of the waterborne polyurethane comprises an external emulsification method and a self-emulsification method, wherein the external emulsification method adopts a forced emulsification method of dispersing a polyurethane prepolymer in water by using an external emulsifier in the presence of high shearing force, and the emulsion obtained by the method has larger particle size (0.7-3 mu m) and poor storage stability. And the physical properties of the polyurethane film are deteriorated due to the residue of the hydrophilic small-molecular emulsifier since a large amount of the emulsifier is used. Therefore, the preparation of the existing waterborne polyurethane mainly adopts an ionic self-emulsification method, namely, a proper amount of hydrophilic groups are introduced on a polymer chain, and the hydrophilic groups are spontaneously dispersed to form emulsion under a certain condition. The self-emulsification method can be classified into an acetone method, a prepolymer dispersion method, a melt dispersion method, and a ketimine/ketazine method. The self-emulsification method is mature in an acetone method and a prepolymer dispersion method, wherein:
the acetone method is that polyol and diisocyanate react to produce high viscosity NCO prepolymer, which is added with low boiling point acetone to lower viscosity, hydrophilic monomer is used to chain extend, water is added while stirring at high speed, and after dispersion, acetone is distilled out under reduced pressure for recovery.
Prepolymer dispersion method: synthesizing a prepolymer with NCO as a terminal group, when the relative molecular mass is not too large and the viscosity is small, adding no or a small amount of solvent, firstly extending the chain by using a hydrophilic monomer part, dispersing the chain in water under high-speed stirring, and then extending the chain by using amine substances with high reaction activity.
The chain extension reaction of the acetone method is carried out in a homogeneous system, the operation is easy, the repeatability is good, the emulsion quality is high, the adaptability is wide, but a large amount of solvent is consumed, the production efficiency is low, the energy consumption is high, and the cost is high. The prepolymer dispersion method has the advantages of saving organic solvent, being capable of preparing polyurethane emulsion with branching degree, having better stability and being convenient for industrial continuous production, but the chain extender needs to diffuse into prepolymer ions from water phase to react with-NCO and can not be carried out according to a chemical quantitative mode, thereby influencing the quality and the reproducibility of products.
Disclosure of Invention
The invention aims to provide waterborne polyurethane, a preparation intermediate and a preparation method thereof, wherein a solvent (acetone) is not required to be adopted in the preparation process of the waterborne polyurethane, and the preparation method has good reproducibility.
To this end, according to a first aspect of the present invention, there is provided a method for producing an aqueous polyurethane, the method comprising:
s1, preparing an intermediate with a structure shown in the following formula I,
Figure BDA0001199964940000021
in the formula I, R1Is a structural unit having a structure represented by any one of the following formulas II, III and IV, R2Is selected from C5-C9Alkyl radical, C5-C9Cycloalkyl or C6-C10Any of aryl groups; x is oxygen, NH or NR3Wherein R is3Is C3-C6Alkyl or C3-C6A cycloalkyl group; z is (CH)2)nOr C6H4N is an integer of 1 to 12; m is selected from Na+、K+、NH4 +Or NR'4 +R' is C1-C4An alkyl group;
Figure BDA0001199964940000022
wherein R is4Is C1-C3An alkyl group;
s2, under the condition of prepolymerization reaction, promoting the intermediate to contact and react with polyol, first polyisocyanate and organic carboxylic acid containing two hydroxyl groups and having the number average molecular weight of less than 250g/mol to form a prepolymer;
and S3, carrying out emulsification treatment on the prepolymer under an emulsification condition, and carrying out chain extension treatment on the emulsified prepolymer under a chain extension condition.
According to a second aspect of the present invention, there is provided an aqueous polyurethane prepared by the above process.
According to a third aspect of the invention, an intermediate for preparing the waterborne polyurethane is provided, and the intermediate has a structure shown in the formula I.
According to the fourth aspect of the invention, the invention also provides a waterborne polyurethane, which contains a structural unit shown as the following formula VI,
Figure BDA0001199964940000031
r in formula VI1Is a structural unit having a structure represented by any one of the aforementioned formulas II, III and IV, R2Is selected from C5-C9Alkyl radical, C5-C9Cycloalkyl or C6-C10Any of aryl groups; x is oxygen, NH or NR3Wherein R is3Is C3-C6Alkyl or C3-C6A cycloalkyl group; z is (CH)2)nOr C6H4N is an integer of 1 to 12, M is selected from Na+、K+、NH4 +Or NR'4 +R' is C1-C4An alkyl group.
By applying the technical scheme of the invention, the intermediate with the structure shown in the formula I is added in the prepolymerization process, the prepolymer with relatively low viscosity can be prepared, and the high-solid-content waterborne polyurethane emulsion can be directly prepared by emulsification without adopting an organic solvent. The method does not need to add a solvent to reduce the viscosity of the prepolymer, so that the method has almost zero emission of the organic solvent and no problem of environmental pollution; and the subsequent step of removing the solvent under reduced pressure is not needed, so that the energy loss can be reduced, and the efficiency is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a method for producing an aqueous polyurethane, the method comprising:
s1, preparing an intermediate with a structure shown in the following formula I,
Figure BDA0001199964940000041
in the formula I, R1Is a structural unit having a structure represented by any one of the following formulas II, III and IV, R2Is selected from C5-C9Alkyl radical, C5-C9Cycloalkyl or C6-C10Any of aryl groups; x is oxygen, NH or NR3Wherein R is3Is C3-C6Alkyl or C3-C6A cycloalkyl group; z is (CH)2)nOr C6H4N is an integer of 1 to 12; m is selected from Na+、K+、NH4 +Or NR'4 +R' is C1-C4An alkyl group, a carboxyl group,
Figure BDA0001199964940000042
wherein R is4Is C1-C3Alkyl groups of (a);
s2, under the condition of prepolymerization reaction, promoting the intermediate to contact and react with polyol, first polyisocyanate and dimethylolcarboxylic acid to form a prepolymer;
and S3, carrying out emulsification treatment on the prepolymer under an emulsification condition, and carrying out chain extension treatment on the emulsified prepolymer under a chain extension condition.
According to the invention, in the above-mentioned intermediates C1-C3The alkyl group may be linear or branched. Said C is1-C3Examples of alkyl groups may include, but are not limited to, methyl, ethyl, or propyl.
According to the invention, in the above-mentioned intermediates C5-C9Alkyl (preferably C)5-C6Alkyl) may be linear or branched. Said C is5-C6Examples of alkyl groups may include, but are not limited to, 1, 6-hexylene or 1, 5-pentylene.
According to the invention, in the above-mentioned intermediates C5-C9Cycloalkyl (preferably C)5-C6Cycloalkyl) may or may not contain a substituent. Said C is5-C6Examples of the alkyl group of (a) may include, but are not limited to, cyclohexyl, cyclopentyl or 3-methylene-3, 5, 5-trimethylcyclohexyl.
According to the invention, in the above-mentioned intermediates C6-C10Aryl (preferably C)6Aryl or C10Aryl) may be aryl with or without substituents. Said C is6Examples of the alkyl group may be a2, 4-methylphenylene group; c10An example of an alkyl group may be 1, 5-naphthylene.
The preparation method of the above aqueous polyurethane of the present invention will be described in detail in steps
(1) Step S1 in the above-mentioned method for producing an aqueous polyurethane produces an intermediate having a structure represented by the following formula I. Wherein there is no particular requirement for the intermediate preparation process, as long as an intermediate having the structure shown in formula I above is formed.
Preferably, the process for preparing an intermediate having a structure represented by formula i below comprises: under the condition of polymerization reaction, theA second polyisocyanate having a structure represented by formula v below in a molar ratio of NCO groups to reactive group-containing sulfonate salts of 3:1, the reaction group is OH and NH2Or NH to give the intermediate,
Figure BDA0001199964940000051
in the formula V, R1Is a structural unit having a structure represented by any one of the following formulas II, III and IV, R2Is selected from C5-C9Alkyl radical, C5-C9Cycloalkyl or C6-C10Any of aryl groups; wherein with respect to R2Is selected from C5-C9Alkyl radical, C5-C9Cycloalkyl or C6-C10The description of any of the aryl groups is referred to the previous description and will not be repeated here.
In the second polyisocyanate of the structure of formula V, when R in formula V1In the case of a structural unit having a structure represented by the aforementioned formula II, the second polyisocyanate is an HDI trimer or an IPDI trimer, and the HDI (hexamethylene diisocyanate polyisocyanate) trimer may be N3300 commercially available from Bayer or HT-600 commercially available from Waals; the IPDI (isophorone diisocyanate) trimer can be an IPDI trimer curing agent commercially available from bayer corporation.
In the second polyisocyanate of the structure of formula V, when R in formula V1In the case of a structural unit having a structure represented by the aforementioned formula III, the second polyisocyanate is an HDI-TMP adduct which can be synthesized by the following method: HDI and TMP (trimethylolpropane) are reacted at a molar ratio of 9:1 at 60-90 ℃ until the NCO content of the system is not changed any more, the reaction is stopped, and excess HDI is distilled off under reduced pressure, namely a HDI-TMP adduct, wherein HDI can be N3300 commercially available from Bayer or HT-600 commercially available from Wanhua company.
In the second polyisocyanate of the structure of formula V, when R in formula V1When the structural unit has the structure shown in the formula IV, the secondThe polyisocyanate is an HDI biuret polymer. The HDI biuret polymer may be N100 commercially available from bayer corporation.
According to the present invention, there may be no particular requirement for the sulfonate as long as it contains OH, NH2Or NH group and contains sulfonate. Preferably, the cation of the sulfonate salt is selected from the group consisting of Na+、K+、NH4 +Or NR'4 +R' is C1-C4Alkyl (e.g., any of directly or indirectly linked methane, ethane, propane, and butane). More preferably, the sulfonate is one or more of sodium isethionate, sodium methylolsulfonate, sodium 4-hydroxybutyl sulfonate, sodium sulfanilate, sodium 2-aminoethyl sulfonate and sodium cyclohexylaminoethyl sulfonate.
According to the present invention, there is no particular requirement for the polymerization conditions of the intermediate having the structure represented by formula i, and reference may be made to conventional reaction conditions known in the art, and preferably, the polymerization conditions include: the temperature is 60-90 ℃, and the stirring reaction is carried out for 1-4 h.
(2) Step S2 in the above-described method for producing an aqueous polyurethane forms a prepolymer. There is no particular requirement for the polyol and the first polyisocyanate employed, and reference may be made to conventional selections in the art.
In one embodiment of the present invention, the polyol includes a polymer polyol and a monomer polyol, and the polymer polyol is contained in an amount of 95 to 100% by weight and the monomer polyol is contained in an amount of 0 to 5% by weight, based on 100 parts by weight of the polyol.
Preferably, the number average molecular weight of the polymer polyol is 500-10000g/mol, more preferably 1000-5000 g/mol; examples of the polymer polyol include, for example, but are not limited to, one or more of polyester polyol, polyether polyol and polyether ester polyol, wherein examples of the polyester polyol include, but are not limited to, one or more of 1, 4-butanediol adipate, ethylene glycol adipate, butanediol adipate, neopentyl glycol adipate and hexanediol adipate; examples of the polyether polyol include, but are not limited to, one or more of polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, polytetramethylene ether glycol, polypropylene oxide ether glycol, and polypropylene oxide ether tri; examples of the polyetherester polyol include, but are not limited to, one or more of polydiethylene glycol adipate and polydipropylene glycol adipate.
Preferably, the monomeric polyol is present in monomeric, rather than polymeric, form, including diols and/or triols; preferably, the monomeric polyol has a number average molecular weight of less than 200g/mol, examples including, but not limited to, one or more of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and trimethylolpropane. The addition of the monomeric polyol in the polyol is beneficial to improving the strength of a dry film and the viscosity of a prepolymer. In practice, commercially available polyols usually contain water, and a vacuum dehydration treatment step is also included before charging such water-containing polyols, for example, the polyol is subjected to vacuum dehydration treatment at a temperature of 100 ℃ and 120 ℃ for 0.5 to 2 hours.
According to the present invention, examples of the first polyisocyanate include, but are not limited to, one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), HDI trimer, Xylylene Diisocyanate (XDI) and Hydrogenated Xylylene Diisocyanate (HXDI), preferably a composition of Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI), more preferably in a molar ratio of 3:1 to 1: 3.
According to the present invention, there may be no particular requirement for the organic carboxylic acid having two hydroxyl groups to be used, as long as two hydroxyl groups and one carboxylic acid are included therein at the same time and the data molecular weight satisfies the requirements. Examples of the organic carboxylic acid having two hydroxyl groups include, but are not limited to, dimethylolbutanoic acid (DMBA) or dimethylolpropanoic acid (DMPA), and the like.
According to the present invention, it is preferable that the molar ratio of NCO groups contained in the intermediate and the first polyisocyanate in S2 to OH groups contained in the polyol and the organic carboxylic acid is (1.5 to 2.4): 1.
according to the present invention, it is preferable that the amount of the organic carboxylic acid added in S2 is 1 to 4 wt% based on the dry weight of the aqueous polyurethane. The adding amount of the organic carboxylic acid is controlled within the range, under the condition that a sulfonic acid group exists, the emulsifying difficulty is facilitated to be simplified, and the tensile strength and hydrolysis resistance of a film material prepared from the waterborne polyurethane are improved.
According to the present invention, it is preferable that the molar ratio of the sulfonate group contained in the intermediate in S2 to the carboxylate group in the dimethylolcarboxylic acid is (0.25 to 4): 1, preferably (0.5-2): 1, and the total weight of the carboxylate and sulfonate groups is 1-1.5 wt% based on the dry weight of the prepared aqueous polyurethane. The content of the sulfonate and the carboxylate is controlled within the range, so that the emulsifying difficulty is further simplified, and the tensile strength and hydrolysis resistance of the membrane material prepared from the waterborne polyurethane are improved.
According to the present invention, in the step of forming the prepolymer, a catalyst is added to promote the contact reaction. Wherein, there is no special requirement for the selection of the catalyst, and the conventional catalyst known in the art can be referred to, and preferably, the catalyst is one or more selected from organic tin, organic bismuth, organic zinc and organic amine; examples of such organotin include, but are not limited to, one or more of dibutyl tin dilaurate, stannous dioctoate, and dimethyl tin dineodecanoate; examples of the organic bismuth include, but are not limited to, one or more of bismuth octoate and bismuth laurate; examples of the organic zinc include, but are not limited to, zinc isooctanoate; examples of such organic amines include, but are not limited to, triethylenediamine and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU); preferably, the catalyst is used in an amount of 0.01 to 0.1% by weight based on the total weight of the intermediate, the polyol, the first polyisocyanate and the dimethylolcarboxylic acid.
According to the present invention, there may be no particular requirement for the prepolymerization reaction conditions, and conventional reaction conditions known in the art may be referred to, and preferably, the polymerization reaction conditions include: the temperature is 60-90 ℃, the stirring reaction is carried out for more than 1 hour, and the stirring reaction is preferably carried out for 1-4 hours.
According to the present invention, the prepolymer prepared in S2, in which an intermediate having a sulfonate group is introduced, can be prepared to have a relatively reduced viscosity, so as to facilitate direct emulsification treatment without additional addition of an organic solvent. Preferably, the viscosity of the prepolymer is 2000-50000mPa.s, more preferably 5000-20000 mPa.s. The viscosity of the prepolymer in the present invention is measured by the method of GB-T2794-1995.
(3) Step S3 in the above-described method for producing an aqueous polyurethane forms an emulsification treatment and a chain extension treatment. For the method of the emulsification treatment and the chain extension treatment, a conventional method in the art may be referred to.
According to the present invention, it is preferable that the method further comprises a step of adding a neutralizing agent to the prepolymer at a temperature of 50 to 70 ℃ for neutralization reaction before the emulsification treatment, wherein the neutralizing agent added in the step reacts with carboxylate radicals in the prepolymer, and the reaction time is preferably 10 to 30 min. Preferably, the neutralizing agent is one or more selected from triethylamine, sodium hydroxide and sodium bicarbonate. Preferably, the equivalent ratio of the neutralizing agent to the organic carboxylic acid (molar ratio of reactive groups) is from 0.99 to 1.01: 1.
according to the present invention, there may be no particular requirement for the step of emulsification treatment, wherein no organic solvent is added, and reference may be made to conventional methods known in the art. Preferably, the emulsification treatment conditions include: emulsifying at 50-70 deg.C for 15-30min in the presence of water. Preferably, the amount of water added in the emulsification treatment step is such that the solid content of the aqueous polyurethane produced is 20 to 50 wt%.
According to the invention, a hydrophilic chain extender is added in the step of chain extension treatment; preferably, NH contained in the hydrophilic chain extender2And/or the mole number of the NH group is 50-80% of the mole number of the active NCO contained in the prepolymer before chain extension.
There may be no particular requirement for the choice of hydrophilic chain extender to be added during the chain extension treatment according to the present invention, and reference may be made to starting materials known in the art. Preferably, the chain extender comprises diamine and/or polyamine, and the diamine and/or polyamine is one or more selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, cyclohexyldiamine and isophoronediamine; the chain extender may also include a monoamine, which is used in an amount of 0 to 30% by weight based on the total weight of the chain extender, preferably the monoamine is diethanolamine or ethanolamine.
According to the present invention, there may be no particular requirement for the conditions of the chain extension treatment, and conventional process conditions known in the art may be referred to, and preferably, the conditions of the chain extension treatment include: and carrying out chain extension treatment for 15-30min at the room temperature of-70 ℃ in the presence of a hydrophilic chain extender.
According to a second aspect of the present invention, there is provided an aqueous polyurethane prepared by the above process.
According to a third aspect of the invention, an intermediate for preparing the waterborne polyurethane is provided, and the intermediate has a structure shown in the formula I. The description of the intermediate refers to the previous description of the invention and is not repeated here.
According to the fourth aspect of the invention, the invention also provides a prepolymer for preparing the waterborne polyurethane, which is characterized in that the prepolymer contains the structural unit shown in the formula VI,
Figure BDA0001199964940000101
r in formula VI1For structural units having a structure represented by any one of formulas II, III and IV (wherein the structural units represented by formulas II, III and IV refer to the description of the invention, and are not repeated), R2Is selected from C5-C9Alkyl radical, C5-C9Cycloalkyl or C6-C10Any of aryl groups; x is oxygen, NH or NR3Wherein R is3Is C3-C6Alkyl or C3-C6A cycloalkyl group; z is (CH)2)nOr C6H4N is an integer of 1 to 12; m is selected from Na+、K+、NH4 +Or NR'4 +R' is C1-C4An alkyl group.
According to the invention, the waterborne polyurethane contains carboxylate and sulfonate, and the molar ratio of the carboxylate to the sulfonate is (0.25-4): 1, preferably (0.5-2): 1, and the total weight of the carboxylate and sulfonate groups is 1-1.5 wt.%, based on the dry weight of the aqueous polyurethane.
The aqueous polyurethane of the present invention and the process for producing the same will be further described below with reference to specific preparation examples, comparative preparation examples, examples and comparative examples
The starting materials used in the following preparations and comparative preparations are illustrated below:
sodium isethionate: MW148 commercially available from alatin reagent company;
containing NH2Sulfonate of the group: MW195 of sodium sulfanilate commercially available from alatin;
sodium cyclohexylaminoethyl sulfonate: MW229 commercially available from krama chemical company;
HDI trimer (having the structure shown in the formula II): HDI trimer HT-600, commercially available from the Wanhua group corporation, having an NCO content of 23% by weight;
HDI-TMP adduct (having the structure shown in formula III above): HDI (commercially available from Wanhua group company and TMP (commercially available from TCI Shanghai formation Co., Ltd.) was reacted at 80 ℃ in a molar ratio of 9:1 until the NCO content of the system did not change any more, the reaction was stopped, excess HDI was distilled off under reduced pressure, and the product was an HDI-TMP adduct having an NCO content of 20 wt%;
HDI biuret polymer (having the structure of formula V described above), N100, commercially available from Bayer corporation, with an NCO content of 22 wt%;
dimethylolbutyric acid: commercially available from alatin reagent.
The intermediate for the production of the aqueous polyurethane of the present invention and the production method thereof will be further described below by way of production examples 1 to 3.
Preparation example 1
Dissolving hydroxyethyl sulfonic acidSodium (hydroxyl) and HDI trimer (HT-600) in the formula of nOH/nNCO1:3, heating to 80 ℃, and stirring for reaction for 1.5h to obtain an intermediate A1, wherein the NCO group content of the intermediate A1 is 12.1 wt%. The structural formula of the intermediate A1 is as follows:
Figure BDA0001199964940000121
preparation example 2
Mixing sodium aminobenzenesulfonate and HDI biuret polymer (Bayer N100) according to NOH/nNCO1:3, heated to 60 ℃, and stirred for 1.5h to obtain intermediate a2 having an NCO group content of 11.2 wt% in intermediate a 1. The structural formula of the intermediate A2 is as follows:
Figure BDA0001199964940000122
preparation example 3
Addition product of sodium cyclohexylaminoethyl sulfonate and HDI-TMP as nOH/nNCO1:3, heated to 60 ℃, and stirred for reaction for 1.5h to obtain an intermediate A3, wherein the NCO group content of the intermediate A3 is 9.7 wt%. The structural formula of the intermediate A3 is as follows:
Figure BDA0001199964940000131
the starting materials used in the following examples and comparative examples are illustrated below:
polyether polyol: PPG (number average molecular weight of 2000g/mol, hydroxyl group content of 56mgKOH/g) commercially available from Todar blue, polytetramethylene ether glycol (number average molecular weight of 2000g/mol, hydroxyl group content of 56mgKOH/g) commercially available from Hangzhou SHOWAY CHEMICAL CORPORATION;
polyester polyol: polyadipic acid hexanediol ester, commercially available from Huada chemical group, Inc., having a number average molecular weight of 2000g/mol and a hydroxyl group content of 56 mgKOH/g;
HDI: commercially available from Vanhua chemical company, having an NCO group content of 50% by weight;
IPDI: commercially available from BASF corporation, NCO group content 37.8 wt.%;
organotin catalyst: dibutyltin dilaurate (T12) commercially available from newcastle chemical company;
triethylamine (neutralizer), ethylenediamine (diamine chain extender), hexamethylenediamine (diamine chain extender) and ethanolamine (monoamine chain extender): commercially available from alatin reagent.
In the following examples and comparative examples, the viscosity of the prepolymer was measured with a rotational viscometer with reference to the GB/T10247-2008 method, and the solid content of the aqueous polyurethane was tested with reference to the paint solid content test quantity in GB 1725-79.
The aqueous polyurethane of the present invention and the production method thereof will be further described below by examples 1 to 4 and comparative examples 1 to 2.
Example 1
The waterborne polyurethane and the preparation method thereof are illustrated by the following specific methods:
60g of polypropylene glycol PPG (with a hydroxyl group content of 56mgKOH/g) was charged into a reactor, and dehydrated under vacuum at 120 ℃ for 30 minutes, followed by cooling to 80 ℃ and addition of 1.48g of dimethylolbutyric acid (1.8% by weight based on the dry weight of the aqueous polyurethane prepared), and after stirring for 5 minutes, 4g of intermediate A1 (with an NCO group content of 0.012mol and a sulfonate content of 0.0069mol), 9.23g of HDI (with an NCO group content of 0.11mol) and 6.18g of IPDI (with an NCO group content of 0.056mol), 0.08g of dibutyltin dilaurate (T12) were added, and reacted for 2 hours to prepare 80.9g of prepolymer B1 (with a viscosity of 12000mPa.S and an NCO group content of 5.1% by weight);
cooling prepolymer B1 to 60 ℃, adding 1g of triethylamine for neutralization, then adding 84g of deionized water, and emulsifying at constant temperature for 15min under the condition of high-speed stirring (3000 RPM); 1.5g of ethylenediamine chain extender is added, stirred and reacted for 15min at constant temperature, and 167g of waterborne polyurethane S1 (the solid content is 50 wt%) is prepared. The molar ratio of the carboxylate to the sulfonate in the aqueous polyurethane is 1.45: 1, and the total weight of the carboxylate and sulfonate groups is 1.2 wt.%, based on the dry weight of the aqueous polyurethane.
Example 2
The waterborne polyurethane and the preparation method thereof are illustrated by the following specific methods:
75g of PTMEG (hydroxyl group content 56mgKOH/g) was charged into a reactor, dehydrated under vacuum at 120 ℃ for 30 minutes, cooled to 70 ℃, added with 1.8g of dimethylolbutyric acid (1.7% by weight based on the dry weight of the aqueous polyurethane prepared previously), stirred for 5 minutes, added with 5.32g of intermediate A2 (wherein the NCO group content was 0.014mol and the sulfonate content was 0.01mol), 11.76g of HDI (wherein the NCO group content was 0.14mol) and 7.77g of IPDI (wherein the NCO group content was 0.07mol), 0.1g of dibutyltin dilaurate (T12), and reacted for 3 hours to prepare 101.6g of prepolymer B2 (viscosity 8000mPa.S and NCO group content of 5.2% by weight);
cooling prepolymer B2 to 50 ℃, and adding 1.22g of triethylamine for neutralization; adding 110g of deionized water, and emulsifying at constant temperature for 15min under the condition of high-speed stirring (3000 RPM); adding 1.8g of ethylenediamine for chain extension at constant temperature for 15min to obtain 215g of waterborne polyurethane S2 (the solid content is 49 wt%). The molar ratio of the carboxylate groups to the sulfonate groups in the aqueous polyurethane is 1.2:1, and the total weight of the carboxylate groups and the sulfonate groups is 1.3 wt% based on the dry weight of the aqueous polyurethane.
Example 3
The waterborne polyurethane and the preparation method thereof are illustrated by the following specific methods:
50g of PBA2000 (hydroxyl group content 56mgKOH/g) were charged into a reactor, dehydrated at 120 ℃ for 30 minutes under vacuum, cooled to 90 ℃, and added with 1.21g of dimethylolbutyric acid (1.72% of the dry weight of the aqueous polyurethane prepared) and stirred for 5 minutes, then 3.42g of intermediate A3 (wherein NCO group content was 0.0079mol and sulfonate content was 0.005mol), 8g of HDI (wherein NCO group content was 0.095mol), 5.29g of IPDI (wherein NCO group content was 0.048mol), 0.06g of dibutyltin dilaurate (T12) were added and reacted for 1.5 hours to prepare 68g of prepolymer B3 (viscosity 15000mPa.S, wherein NCO group content was 5.1 wt%);
cooling prepolymer B3 to 70 ℃, and adding 0.83g of triethylamine for neutralization; adding 76g of deionized water, and emulsifying at constant temperature under high-speed stirring (3000RPM) for 15 min; adding 1.25g of ethylenediamine for chain extension at constant temperature for 15min to obtain 146g of waterborne polyurethane S3 (the solid content is 48 wt%). The molar ratio of the carboxylate to the sulfonate in the aqueous polyurethane is 1.7: 1, and the total weight of the carboxylate and sulfonate groups is 1.1 wt.%, based on the dry weight of the aqueous polyurethane.
Example 4
The waterborne polyurethane and the preparation method thereof are illustrated by the following specific methods:
64g of PPG (number average molecular weight 2000g/mol, hydroxyl group content 56mgKOH/g) was charged into a reactor, dewatered under vacuum at 120 ℃ for 30 minutes, cooled to 80 ℃, charged with 0.9g of 1, 4-butanediol (hydroxyl group content 1244mgKOH/g) and 1.48g of dimethylolbutyric acid (0.016% by weight of the dry weight of the aqueous polyurethane prepared), stirred for 5 minutes, charged with 4g of intermediate A1 (NCO group content 0.011mol, sulfonate content 0.0069mol), 11.59g of HDI (NCO group content 0.14mol) and 7.66g of IPDI (NCO group content 0.069mol), 0.08g of dibutyltin dilaurate (T12), reacted for 2 hours to give 89g of prepolymer B4 (viscosity 17900mPa.S, NCO group content 5.4% by weight);
cooling prepolymer B4 to 60 ℃, and adding 1g of triethylamine for neutralization; adding 100g of deionized water, and emulsifying at constant temperature under high-speed stirring (3000RPM) for 15 min; adding 1.5g of ethylenediamine, carrying out constant-temperature chain extension and stirring reaction for 15min to obtain 192g of waterborne polyurethane S1 (the solid content is 48 wt%). The molar ratio of the carboxylate to the sulfonate in the aqueous polyurethane is 1.45: 1, and the total weight of the carboxylate and sulfonate groups is 1.2 wt.%, based on the dry weight of the aqueous polyurethane.
Comparative example 1
The reference description of the waterborne polyurethane and the preparation method thereof is as follows:
60g of polyether polyol PPG2000 is dehydrated for 1h in vacuum at the oil bath temperature of 110 ℃ before the experiment; after cooling to 80 ℃ 8g of IPDI (with an NCO group content of 0.072mol) and 16g of HDI (with an NCO group content of 0.19mol) were added and reacted for 2 h; adding 4g of dimethylolpropionic acid DMPA, controlling the viscosity to be 3000mPa.S by using acetone, continuously reacting for 2h, cooling to 40 ℃, adding 3.03g of triethylamine, and reacting for 15 min; 170g of distilled water was added, high-speed dispersion was carried out for 20min, 1.5g of ethylenediamine was added for chain extension, and distillation under reduced pressure was carried out to remove acetone, thereby obtaining 262g of an aqueous polyurethane emulsion (solid content: 35 wt%).
Comparative example 2
The reference description of the waterborne polyurethane and the preparation method thereof is as follows:
60g of polyether polyol PPG2000 is dehydrated for 1h in vacuum at the oil bath temperature of 110 ℃ before the experiment; after cooling to 80 ℃ 8g of IPDI (with an NCO group content of 0.072mol) and 16g of HDI (with an NCO group content of 0.19mol) were added and reacted for 2 h; adding 1g of dimethylolpropionic acid DMPA, adding 40ml of acetone, continuing to react for 2 hours, cooling to 25 ℃, adding 3.03g of triethylamine, and reacting for 15 min; 4g of a sodium 2-aminoethylethanesulfonate salt solution (50 wt% aqueous solution) was added thereto and reacted for 10 minutes, 170g of distilled water was added thereto and dispersed at a high speed for 20 minutes, 1.5g of ethylenediamine was added thereto for chain extension, and acetone was removed therefrom by distillation under reduced pressure to obtain 262g of an aqueous polyurethane emulsion (having a solid content of 35 wt%).
Test example:
the aqueous polyurethanes prepared in examples 1 to 4 and comparative examples 1 and 2 were tested as follows:
(1) average particle size of aqueous polyurethane: measuring the average particle size of the emulsion by a laser particle sizer;
(2) storage stability of aqueous polyurethane: placing 15mL of emulsion in a centrifuge, centrifuging for 15min at the rotating speed of 3000RPM, and observing whether a precipitate is produced or not, wherein if no precipitate is generated, the storage stability of the emulsion is more than 6 months;
(3) the water absorption of the adhesive film is measured by cutting a sample into 2cm multiplied by 2cm, drying for 24 hours in vacuum, weighing the weight (W1), soaking the sample in deionized water for 24 hours, weighing the weight (W2), and calculating the water absorption according to the following formula of η - (W2-W1)/W1 multiplied by 100%;
(4) tensile strength of the adhesive film: the preparation method of the adhesive film is shown in (3), and the measurement method of the tensile strength refers to the measurement method of GB/T1040-92 plastic tensile property.
(5) And (3) measuring results: as shown in table 1.
Table 1.
Figure BDA0001199964940000171
As can be seen from the data in Table 1, compared with the waterborne polyurethane D1-D2 prepared according to the comparative example, the waterborne polyurethane S1-S4 prepared according to the invention has good comprehensive performance, and the prepolymer with moderate viscosity can be prepared by introducing the intermediate with a specific structure in the preparation process of the waterborne polyurethane S1-S4 prepared according to the invention, so that the organic solvent is not required to be added, the raw material cost is reduced, the safety of industrial production is improved, the polyurethane is green and environment-friendly, and the polyurethane is more suitable for large-scale production.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (34)

1. A preparation method of waterborne polyurethane is characterized in that the method does not need to adopt a solvent, and the method comprises the following steps:
s1, preparing an intermediate with a structure shown in the following formula I,
Figure FDA0002433863540000011
in the formula I, R1Is a structural unit having a structure represented by any one of the following formulas II, III and IV, R2Is selected from C5-C9Alkyl radical, C5-C9Cycloalkyl or C6-C10Any of aryl groups; x is oxygen, NH or NR3Wherein R is3Is C3-C6Alkyl or C3-C6A cycloalkyl group; z is (CH)2)nOr C6H4N is an integer of 1 to 12; m is selected from Na+、K+、NH4 +Or NR'4 +R' is C1-C4An alkyl group;
Figure FDA0002433863540000012
formula II formula III formula IV formula II,
in the formula III, R4Is C1-C3An alkyl group;
s2, under the condition of prepolymerization reaction, promoting the intermediate to contact and react with polyol, first polyisocyanate and organic carboxylic acid containing two hydroxyl groups and having the number average molecular weight of less than 250g/mol to form a prepolymer;
s3, carrying out emulsification treatment on the prepolymer under an emulsification condition, and then carrying out chain extension treatment on the emulsified prepolymer under a chain extension condition;
the method for preparing the intermediate with the structure shown as the following formula I in S1 comprises the following steps: under polymerization conditions, a second polyisocyanate having a structure represented by the following formula V is reacted with a reactive group-containing sulfonate in a molar ratio of 3 in terms of NCO groups: 1, the reaction group is OH and NH2Or a combination of NH and hydrogen, or a combination of NH,
Figure FDA0002433863540000021
formula V.
2. The method according to claim 1, wherein the cation of the sulfonate is Na+、K+、NH4 +Or NR'4 +R' is C1-C4An alkyl group.
3. The preparation method according to claim 2, wherein the sulfonate is selected from one or more of sodium isethionate, sodium methylolsulfonate, sodium 4-hydroxybutyl sulfonate, sodium sulfanilate, sodium 2-aminoethyl sulfonate and sodium cyclohexylaminoethyl sulfonate.
4. The production method according to claim 1, wherein the polymerization reaction conditions include: stirring and reacting for 1-4h at the temperature of 60-90 ℃.
5. The production method according to claim 1, wherein in S2, the molar ratio of NCO groups contained in the intermediate and the first polyisocyanate to OH groups contained in the polyol and the organic carboxylic acid is (1.5 to 2.4): 1.
6. the production method according to claim 1, wherein the organic carboxylic acid is added in an amount of 1 to 4 wt% based on the dry weight of the aqueous polyurethane in S2.
7. The preparation method according to claim 1, wherein in S2, the molar ratio of the sulfonate contained in the intermediate to the carboxylate in the organic carboxylic acid is (0.25-4): 1, and the total weight of the carboxylate and sulfonate groups is 1-1.5 wt% based on the dry weight of the prepared aqueous polyurethane.
8. The preparation method according to claim 7, wherein in S2, the molar ratio of the sulfonate contained in the intermediate to the carboxylate in the organic carboxylic acid is (0.5-2): 1.
9. the method according to claim 1, wherein the polyol in S2 includes a polymer polyol and a monomer polyol, and the polymer polyol is contained in an amount of 95 to 100 wt% and the monomer polyol is contained in an amount of 0 to 5 wt% based on 100 parts by weight of the polyol.
10. The preparation method according to claim 9, wherein in the S2, the polymer polyol is one or more selected from polyester polyol, polyether polyol and polyether ester polyol, and the number average molecular weight of the polymer polyol is 500-10000 g/mol.
11. The production method as claimed in claim 10, wherein the polymer polyol has a number average molecular weight of 1000-5000 g/mol.
12. The method of claim 9, wherein the monomeric polyol has a number average molecular weight of less than 200 g/mol.
13. The preparation method of claim 1, wherein the first polyisocyanate in S2 is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, HDI trimer, xylylene diisocyanate and hydrogenated xylylene diisocyanate.
14. The production method according to claim 1, wherein the organic carboxylic acid in S2 is dimethylolbutanoic acid and/or dimethylolpropanoic acid.
15. The method according to claim 1, wherein in the step of forming a prepolymer in S2, a catalyst is added to promote the contact reaction.
16. The preparation method of claim 15, wherein the catalyst is one or more selected from the group consisting of organotin, organobismuth, organozinc, and organoamine.
17. The method of claim 15, wherein the catalyst is used in an amount of 0.01 to 0.1 wt% based on the total weight of the intermediate, the polyol, the first polyisocyanate, and the organic carboxylic acid.
18. The preparation method of claim 1, wherein the prepolymerization reaction conditions in the S2 comprise: stirring and reacting for 1-4h at the temperature of 60-90 ℃ in the presence of a catalyst.
19. The method as claimed in claim 1, wherein the viscosity of the prepolymer formed in S2 is 2000-50000 mPa.S.
20. The method as claimed in claim 19, wherein the viscosity of the prepolymer formed in S2 is 5000-.
21. The method according to claim 1, wherein the step of neutralizing the prepolymer with a neutralizing agent at 50 to 70 ℃ is further included in S3 before the emulsification.
22. The preparation method of claim 21, wherein the neutralizing agent is one or more of triethylamine, sodium hydroxide and sodium bicarbonate.
23. The method of claim 21, wherein the equivalent ratio of the neutralizing agent to the organic carboxylic acid is from 0.99 to 1.01: 1.
24. the preparation method according to claim 1, wherein the emulsification treatment conditions in S3 include: emulsifying at 50-70 deg.C for 15-30min in the presence of water.
25. The production method according to claim 1, wherein in S3, a hydrophilic chain extender is added in the step of performing chain extension treatment.
26. The production method according to claim 25, wherein NH contained in the hydrophilic chain extender2And/or the total mole number of NH groups is 50-80% of the mole number of NCO groups in the prepolymer before chain extension.
27. The method of claim 25, wherein the chain extender comprises a diamine and/or a polyamine.
28. The preparation method of claim 27, wherein the chain extender is one or more selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, cyclohexyldiamine, and isophoronediamine.
29. A method of making as set forth in claim 25 wherein the chain extender further comprises a monoamine present in an amount of from 0.1 to 30% by weight of the total weight of the chain extender.
30. The production method according to claim 29, wherein the monoamine is diethanolamine and/or ethanolamine.
31. The production method according to claim 1, wherein the conditions of the chain extension treatment include: chain extension treatment is carried out for 15-30min at room temperature of-70 ℃ in the presence of a hydrophilic chain extender.
32. An aqueous polyurethane obtained by the production method according to any one of claims 1 to 31.
33. The aqueous polyurethane according to claim 32, wherein the aqueous polyurethane contains carboxylate and sulfonate groups, and the molar ratio of the carboxylate to the sulfonate groups is (0.25-4): 1, and the total weight of the carboxylate and sulfonate groups is 1-1.5 wt.%, based on the dry weight of the aqueous polyurethane.
34. The aqueous polyurethane of claim 33, wherein the molar ratio of carboxylate and sulfonate is (0.5-2): 1.
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