CN108264622A - Aqueous polyurethane and its prepare intermediate and preparation method - Google Patents

Aqueous polyurethane and its prepare intermediate and preparation method Download PDF

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CN108264622A
CN108264622A CN201611262006.1A CN201611262006A CN108264622A CN 108264622 A CN108264622 A CN 108264622A CN 201611262006 A CN201611262006 A CN 201611262006A CN 108264622 A CN108264622 A CN 108264622A
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preparation
aqueous polyurethane
formula
alkyl
weight
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CN108264622B (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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    • C08G18/08—Processes
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    • 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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    • C07C309/42—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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    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • 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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    • C08G18/72—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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    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
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  • Chemical & Material Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of aqueous polyurethane and its prepare intermediate with and preparation method thereof.Wherein the preparation method of aqueous polyurethane includes S1, prepares the intermediate with the structure as shown in following formula I, S2, under the conditions of prepolymerization reaction, promote the intermediate and the organic carboxyl acid haptoreaction contained there are two hydroxyl of polyalcohol, the first polyisocyanates and number-average molecular weight less than 250g/mol, form performed polymer；S3, under emulsification condition, to the performed polymer carry out emulsification treatment, under the conditions of chain extension, to through emulsification treatment performed polymer carry out chain extension processing.This method can prepare the relatively low prepolymer of viscosity, without organic solvent by adding the intermediate with structure shown in formula I during prepolymerization reaction, you can direct emulsification prepares the aqueous polyurethane of high solids content.

Description

Aqueous polyurethane and its prepare intermediate and preparation method
Technical field
The present invention relates to aqueous polyurethane production fields, and in particular, to a kind of aqueous polyurethane is used to prepare aforementioned water The preparation method for preparing intermediate and aforementioned aqueous polyurethane of property polyurethane.
Background technology
Aqueous polyurethane is as the new polyurethane system of decentralized medium using water instead of organic solvent, and also referred to as moisture dissipates poly- Urethane, aqueous polyurethane or water-based polyurethane.Aqueous polyurethane has pollution-free, safe and reliable, mechanical performance using water as solvent Excellent, the advantages that compatibility is good, easily modified.It has been widely used in leather finish, painting dressing automobiles, fiber treatment, paper maker The fields such as industry auxiliary agent, coating and adhesive.
The preparation method of aqueous polyurethane has two kinds of outer emulsion process and self-emulsification, and outer emulsion process is using additional emulsification Agent, the forced emulsification for being dispersed in water base polyurethane prepolymer for use as in the presence of high shear force, emulsion particle diameter obtained by the method compared with (0.7-3 μm) greatly, storage stability is bad.And due to the use of more emulsifier, hydrophilic small molecules emulsifier it is residual The deterioration in physical properties of polyurethane film can be caused by staying.Therefore at present aqueous polyurethane preparation based on ionic self-emulsification, Suitable hydrophilic radical is introduced on polymer chain, thermoplastic polymer forms lotion under certain condition.Self-emulsification can divide again For acetone method, pre-polymer process, melting dispersion method and ketimine.In aforementioned self-emulsification with acetone method and Pre-polymer process is more mature, wherein：
Acetone method is by the way that the high viscosity performed polymer that end group is NCO first is made with polyalcohol and di-isocyanate reaction, adds Entering low boiling point such as acetone reduces viscosity, then with hydrophilic monomer chain extension, is evaporated under reduced pressure after adding in water, dispersion under high velocity agitation It goes out acetone (can recycle).
Pre-polymer process：Synthesis is using NCO as the performed polymer of end group, when relative molecular mass is less big and viscosity is smaller When, a small amount of solvent is not added with or added in, first with hydrophilic monomer part chain extension, is dispersed in water under high velocity agitation, then with instead Answer activity high and amine substance progress chain extension.
Wherein the chain extending reaction of acetone method carries out in homogeneous system, easily operated, reproducible, and quality of the emulsion is high, fits Ying Xingguang, but a large amount of solvents are consumed, and low production efficiency, energy consumption are big, cost is higher.The advantages of pre-polymer process is to save Organic solvent can prepare the polyaminoester emulsion of the degree of branching, and emulsion intercalation method is preferable, convenient for industrializing continuous production, but Chain extender need to be diffused into prepolymer ion from water phase to be reacted with-NCO, it is impossible to be carried out by stoichiometric mode, be influenced to produce The quality and reproducibility of product.
Invention content
The object of the present invention is to provide a kind of aqueous polyurethane and its intermediate and preparation method are prepared, in aqueous polyurethane Preparation process in without solvent (acetone), and the reproducibility of preparation method is preferable.
For this purpose, according to the first aspect of the invention, providing a kind of preparation method of aqueous polyurethane, this method includes：
S1, the intermediate with the structure as shown in following formula I is prepared,
R in formula I1To have the structural unit of the structure as shown in any in following formula II, formula III and formula IV, R2Selected from C5-C9 Alkyl, C5-C9Cycloalkyl or C6-C10Any one of aryl；X is oxygen, NH or NR3, wherein R3For C3-C6Alkyl or C3-C6Cycloalkanes Base；Z is (CH2)nOr C6H4, n is the integer in 1-12；M is selected from Na+、K+、NH4 +Or NR '4 +, R ' is C1-C4Alkyl；
Wherein, R4For C1-C3Alkyl；
S2, under the conditions of prepolymerization reaction, promote the intermediate and polyalcohol, the first polyisocyanates and number-average molecular weight The organic carboxyl acid haptoreaction contained there are two hydroxyl less than 250g/mol, forms performed polymer；
S3, under emulsification condition, to the performed polymer carry out emulsification treatment, under the conditions of chain extension, to it is described through emulsification at The performed polymer of reason carries out chain extension processing.
According to the second aspect of the invention, a kind of aqueous polyurethane as prepared by the above method is provided.
According to the third aspect of the invention we, provide a kind of aqueous polyurethane prepares intermediate, before which has State structure shown in formula I.
According to the fourth aspect of the invention, a kind of aqueous polyurethane is additionally provided, such as following formula is contained in the aqueous polyurethane Structural unit shown in VI,
R in formula VI1For the structural unit with shown structure any in previously described formula II, formula III and formula IV, R2To be selected from C5-C9Alkyl, C5-C9Cycloalkyl or C6-C10Any one of aryl；X is oxygen, NH or NR3, wherein R3For C3-C6Alkyl or C3- C6Cycloalkyl；Z is (CH2)nOr C6H4, n is the integer in 1-12, and M is selected from Na+、K+、NH4 +Or NR '4 +, R ' is C1-C4Alkyl.
Using above-mentioned technical proposal of the present invention, by during the prepolymerization reaction addition have in structure shown in formula I Mesosome can prepare the relatively low prepolymer of viscosity, without organic solvent, you can direct emulsification prepares high solids content Aqueous polyurethane emulsion, and process is simple, easily operated, reproducible, wide adaptability.This method is because wherein without adding in Solvent reduces the viscosity of prepolymer, and not only almost organic solvent zero-emission, does not have the problem of environmental pollution；And without follow-up Removed under reduced pressure solvent the step of, can reduce energy loss, improve efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to the first aspect of the invention, a kind of preparation method of aqueous polyurethane is provided, this method includes：
S1, the intermediate with the structure as shown in following formula I is prepared,
R in formula I1To have the structural unit of the structure as shown in any in following formula II, formula III and formula IV, R2Selected from C5-C9 Alkyl, C5-C9Cycloalkyl or C6-C10Any one of aryl；X is oxygen, NH or NR3, wherein R3For C3-C6Alkyl or C3-C6Cycloalkanes Base；Z is (CH2)nOr C6H4, n is the integer in 1-12；M is selected from Na+、K+、NH4 +Or NR '4 +, R ' is C1-C4Alkyl,
Wherein, R4For C1-C3Alkyl；
S2, under the conditions of prepolymerization reaction, promote the intermediate and polyalcohol, the first polyisocyanates and dihydroxymethyl carboxylic Sour haptoreaction forms performed polymer；
S3, under emulsification condition, to the performed polymer carry out emulsification treatment, under the conditions of chain extension, to it is described through emulsification at The performed polymer of reason carries out chain extension processing.
According to the present invention, the C in above-mentioned intermediate1-C3Alkyl can be straight chain or branch.The C1- C3The example of alkyl can include but is not limited to methyl, ethyl or propyl.
According to the present invention, the C in above-mentioned intermediate5-C9Alkyl (preferably C5-C6Alkyl) can be straight chain, it can also It is branch.The C5-C6The example of alkyl can include but is not limited to 1,6- hexylidenes or 1,5- pentylidene.
According to the present invention, the C in above-mentioned intermediate5-C9Cycloalkyl (preferably C5-C6Cycloalkyl) it can be with or without The cycloalkyl of substituent group.The C5-C6The example of alkyl can include but is not limited to cyclohexyl, cyclopenta or 3- methylene -3, 5,5- trimethylcyclohexyls.
According to the present invention, the C in above-mentioned intermediate6-C10Aryl (preferably C6Aryl or C10Aryl) can be containing or not Aryl containing substituent group.The C6The example of alkyl can be 2,4- methylphenylenes；C10The example of alkyl can be 1,5- Naphthylene.
The preparation method of the above-mentioned aqueous polyurethane of the present invention will be described in detail step by step below
(1) being prepared about the step S1 in the preparation method of above-mentioned aqueous polyurethane has in the structure as shown in following formula I Mesosome.Wherein can there is no particular/special requirement for the preparation method of the centre, as long as forming the intermediate of structure shown in above-mentioned formula I .
Under preferable case, preparing, there is the method for the intermediate of structure as shown in following formula I to include：In polymeric reaction condition Under, by the second polyisocyanates with the structure as shown in following formula V in terms of NCO group with the sulfonate containing reactive group with anti- Group meter is answered according to molar ratio 3：1 haptoreaction, the reactive group are OH, NH2Or NH, the intermediate is obtained,
R in formula V1To have the structural unit of the structure as shown in any in following formula II, formula III and formula IV, R2Selected from C5- C9Alkyl, C5-C9Cycloalkyl or C6-C10Any one of aryl；Wherein about R2Selected from C5-C9Alkyl, C5-C9Cycloalkyl or C6- C10The explanation of any one of aryl is with reference to the description of front, and details are not described herein.
In the second polyisocyanates of structure shown in formula V, as R in formula V1For the knot with structure shown in previously described formula II During structure unit, which is HDI trimer or IPDI tripolymers, and (hexamethylene diisocyanate base gathers the HDI Isocyanates) tripolymer can be commercially available from Beyer Co., Ltd N3300 or the HT-600 commercially available from Wan Hua companies；The IPDI (isophorone diisocyanate) tripolymer can be the IPDI trimer curing agents commercially available from Beyer Co., Ltd.
In the second polyisocyanates of structure shown in formula V, as R in formula V1For the knot with structure shown in previously described formula III During structure unit, which is HDI-TMP addition products, the addition product can synthesize by the following method：By HDI with TMP (trimethylolpropane) is with 9:1 molar ratio is reacted at 60-90 DEG C, until the NCO content of system no longer changes, is stopped Reaction, decompression steam excessive HDI, and product is HDI-TMP addition products, and wherein HDI can be the N3300 commercially available from Beyer Co., Ltd Or the HT-600 commercially available from Wan Hua companies.
In the second polyisocyanates of structure shown in formula V, as R in formula V1For the knot with structure shown in previously described formula IV During structure unit, which is HDI biuret polymer.The HDI biurets polymer can be commercially available from Bayer The N100 of company.
According to the present invention, can there is no particular/special requirement for the sulfonate, as long as wherein containing OH, NH2Or NH groups, And contain sulfonate radical.Under preferable case, the cation of the sulfonate can select to be selected from Na+、K+、NH4 +Or NR '4 +In Any, R ' is C1-C4Alkyl (such as any one of direct-connected or indirectly connected methane, ethane, propane and butane).It is more excellent In the case of choosing, the sulfonate is sodium isethionate, sodium hydroxymethane sulfonate, 4- hydroxybutyls sodium sulfonate, p-aminobenzene sulfonic acid One or more of sodium, 2- aminoethylsulfonic acids sodium and Cyclohexylamino ethylsulfonic acid sodium.
According to the present invention, for the polymeric reaction condition with the intermediate of structure shown in formula I, can be wanted without special It asks, is referred to popular response condition known in the field, under preferable case, the polymeric reaction condition includes：Temperature is 60-90 DEG C, it is stirred to react 1-4h.
(2) performed polymer is formed about the step S2 in the preparation method of above-mentioned aqueous polyurethane.Wherein for used There is no particular/special requirements for polyalcohol and the first polyisocyanates, are referred to the conventional selection of this field.
In a kind of embodiment according to the present invention, the polyalcohol includes polymer polyatomic alcohol and monomeric polyols, and On the basis of 100 parts by weight of polyalcohol, the content of the polymer polyatomic alcohol is 95-100 weight %, the monomeric polycarboxylic The content of alcohol is 0-5 weight %.
Under preferable case, the number-average molecular weight of the polymer polyatomic alcohol is 500-10000g/mol, more preferable 1000- 5000g/mol；The example of the polymer polyatomic alcohol for example includes but unlimited polyester polyol, polyether polyol and polyether ester are more One or more of first alcohol, wherein the example of the polyester polyol includes but not limited to polyadipate 1,4-butanediol ester, Polyethylene glycol adipate, poly adipate succinic acid ester, polybutyleneadipate neopentyl glycol ester and polyadipate hexylene glycol ester One or more of；The example of the polyether polyol includes but not limited to polyethylene glycol, polypropylene glycol, PolyTHF two One or more of first alcohol, polytetramethylene ether diol, polyoxypropylene glycol and polyoxypropylene three；The polyethers The example of ester polyol includes but not limited to one kind or several in polydiethylene glycol adipate and polyadipate dipropylene glycol ester Kind.
Under preferable case, the monomeric polyols are with monomeric form rather than polymer form presence, including dihydric alcohol And/or trihydroxylic alcohol；It is preferred that the number-average molecular weight of the monomeric polyols is less than 200g/mol, example includes but not limited to second two One or more of alcohol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol and trimethylolpropane.It is added in polyalcohol Monomeric polyols are conducive to improve dry film strength and the viscosity of performed polymer.In practical operation, lead in commercially available polyalcohol The step of often containing water, vacuum dehydration processing further included before feeding intake for this polyalcohol containing water, such as will be described polynary Alcohol vacuum dehydration at a temperature of 100-120 DEG C handles 0.5-2h.
According to the present invention, the example of first polyisocyanates includes but not limited to hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), '-diphenylmethane diisocyanate (MDI), HDI trimer, benzene dimethylene diisocyanate (XDI) and one kind in hydrogenation benzene dimethylene diisocyanate (HXDI) or It is several, preferably hexamethylene diisocyanate (HDI) and the composition of isophorone diisocyanate (IPDI), more preferable two The molar ratio of person is 3:1-1:3.
According to the present invention, can there is no particular/special requirement for the organic carboxyl acid of the used hydroxyl containing there are two, as long as its In simultaneously including two hydroxyls and a carboxylic acid, and number average molecular weight is met the requirements.It is described contain it is organic there are two hydroxyl The example of carboxylic acid includes but not limited to dimethylolpropionic acid (DMBA) or dihydromethyl propionic acid (DMPA) etc..
In the case of, according to the invention it is preferred to, contained by intermediate described in the S2 and first polyisocyanates NCO group and the molar ratio of OH groups contained in polyalcohol and organic carboxyl acid are (1.5-2.4)：1.
In the case of, according to the invention it is preferred to, the additive amount of organic carboxyl acid described in the S2 is done for the aqueous polyurethane The 1-4wt% of weight.The dosage of organic carboxyl acid is controlled in the range of this, in the presence of having sulfonate radical, is conducive to Simplify emulsification difficulty, and improve as the tensile strength and anti-hydrolytic performance of the membrane material prepared by this aqueous polyurethane.
In the case of, according to the invention it is preferred to, contained sulfonate radical and the dihydroxymethyl carboxylic acid in intermediate in the S2 The molar ratio of middle carboxylate radical is (0.25-4)：1, preferably (0.5-2)：1, and with the dry weight of prepared aqueous polyurethane On the basis of, the total weight of the carboxylate radical and sulfonate radical is 1-1.5 weight %.The content of sulfonate radical and carboxylate radical is controlled above-mentioned In the range of, be conducive to be further simplified emulsification difficulty, and improve strong as the stretching of the membrane material prepared by this aqueous polyurethane Degree and anti-hydrolytic performance.
According to the present invention, in the step of forming performed polymer, addition catalyst is to promote catalytic generation.Wherein for The selection of catalyst can not have particular/special requirement, be referred to conventional catalyst known in the field, under preferable case, institute It is selected from one or more of organotin, organo-bismuth, organic zinc and organic amine to state catalyst；The example of the organotin includes But it is not limited to one or more of two neodecanoic acid tin of dibutyl tin dilaurate, two stannous octoates and dimethyl；It is described organic The example of bismuth includes but not limited to one or more of Bismuth Octoate and lauric acid bismuth；The example of the organic zinc includes but unlimited In zinc Isoocatanoate；The example of the organic amine includes but not limited to triethylene diamine and 1,8- diazabicyclos [5.4.0] 11 Carbon -7- alkene (DBU)；Under preferable case, the dosage of the catalyst is the intermediate, polyalcohol, the first polyisocyanates and The 0.01-0.1 weight % of dihydroxymethyl carboxylic acid total weight.
According to the present invention, can there is no particular/special requirement for prepolymerization reaction condition, be referred to known in the field normal Reaction condition is advised, under preferable case, the polymeric reaction condition includes：Temperature is 60-90 DEG C, is stirred to react 1 hour or more, excellent Choosing is stirred to react 1-4h.
According to the present invention, the prepared performed polymer in the S2, wherein by intermediate of the introducing with sulfonate radical, energy The performed polymer of viscosity relative reduction is enough prepared, to be conducive to, in the case where additionally not adding organic solvent, directly be emulsified Processing.Under preferable case, the viscosity of the performed polymer is 2000-50000mPa.s, more preferably 5000-20000mPa.s. The viscosity of performed polymer is to measure to obtain by GB-T2794-1995 methods in the present invention.
(3) emulsification treatment and chain extension processing are formed about the step S3 in the preparation method of above-mentioned aqueous polyurethane.For Emulsification treatment and the method for chain extension processing are referred to the conventional method of this field.
It in the case of, according to the invention it is preferred to, before emulsification treatment, is additionally included at a temperature of 50-70 DEG C, in the performed polymer The step of middle addition neutralizer carries out neutralization reaction, the carboxylate radical in the neutralizer and performed polymer that are added in this step occurs Reaction, the reaction time is preferably 10-30min.It is preferred that the neutralizer is in selection triethylamine, sodium hydroxide and sodium bicarbonate It is one or more of.It is preferred that the equivalent proportion of the neutralizer and organic carboxyl acid (molar ratio of reactive group) is 0.99-1.01：1.
According to the present invention, for emulsification treatment the step of can not have particular/special requirement, wherein organic solvent need not be added, it can With with reference to conventional method known in the field.Under preferable case, the emulsification treatment condition includes：In the presence of water, 50-70 DEG C temperature, emulsification treatment 15-30min.Under preferable case, the dosage of water added in the emulsification treatment step is causes The solid content of prepared aqueous polyurethane is the dosage of 20-50wt%.
According to the present invention, hydrophilic chain extender is added in the step of chain extension is handled；Under preferable case, the hydrophilic chain extender In contained NH2And/or 50-80% of the molal quantity of NH groups for the molal quantity of activity NCO contained by performed polymer before the chain extension.
According to the present invention, the selection of hydrophilic chain extender added in chain extension processing procedure can be wanted without special It asks, is referred to raw material known in the field.Under preferable case, the chain extender includes diamine and/or polyamine, described Diamine and/or polyamine are selected from ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, cyclohexyl diamine and different Fo Er One or more of ketone diamines；The chain extender can also include monoamine, and the dosage of the monoamine is the chain extender The 0-30 weight % of total weight, preferably described monoamine are diethanol amine or ethanol amine.
According to the present invention, can there is no particular/special requirement for the condition of chain extension processing, be referred to known in the field Common process condition, under preferable case, the condition of the chain extension processing includes：In the presence of hydrophilic chain extender, temperature for room temperature- 70 DEG C of chain extensions handle 15-30min.
According to the second aspect of the invention, a kind of aqueous polyurethane as prepared by the above method is provided.
According to the third aspect of the invention we, provide a kind of aqueous polyurethane prepares intermediate, before which has State structure shown in formula I.Explanation reference foregoing description of the present invention for the intermediate, details are not described herein.
According to the fourth aspect of the invention, additionally provide a kind of aqueous polyurethane prepares prepolymer, which is characterized in that institute The structural unit shown in containing previously described formula VI is stated in prepolymer,
R in formula VI1For structural unit (wherein formula II, formula III with shown structure any in formula II, formula III and formula IV With the structural unit shown in formula IV with reference to foregoing description of the present invention, details are not described herein), R2To be selected from C5-C9Alkyl, C5-C9Ring Alkyl or C6-C10Any one of aryl；X is oxygen, NH or NR3, wherein R3For C3-C6Alkyl or C3-C6Cycloalkyl；Z is (CH2)n Or C6H4, n is the integer in 1-12；M is selected from Na+、K+、NH4 +Or NR '4 +, R ' is C1-C4Alkyl.
According to the present invention, containing carboxylate radical and sulfonate radical in the aqueous polyurethane, the carboxylate radical and sulfonate radical rub You are than being (0.25-4)：1, preferably (0.5-2)：1, and on the basis of the dry weight of the aqueous polyurethane, the carboxylate radical and The total weight of sulfonate radical is 1-1.5 weight %.
It is further illustrated the present invention below with reference to specific preparation example, comparison preparation example, embodiment and comparative example aqueous poly- Urethane and preparation method thereof
Raw material is described as follows used by following preparation example and comparison preparation example：
Sodium isethionate：Commercially available from the MW148 of Aladdin Reagent Company；
Containing NH2The sulfonate of group：Commercially available from the MW195 of the sodium sulfanilate of Aladdin company；
Cyclohexylamino ethylsulfonic acid sodium：Commercially available from the MW229 of carat Ma Er chemical reagents corporations；
HDI trimer (has structure shown in previously described formula II)：Commercially available from the HDI trimer HT-600 of Wan Hua group companies, NCO content 23wt%；
HDI-TMP addition products (have structure shown in previously described formula III)：By HDI (commercially available from Wan Hua group companies and TMP (quotient Co., Ltd is melted into purchased from TCI Shanghai) with 9：1 molar ratio is reacted at 80 DEG C, until the NCO content of system no longer changes, Stop reaction, decompression steams excessive HDI, and product is HDI-TMP addition products, NCO content 20wt%；
HDI biurets polymer (has structure shown in previously described formula V), commercially available from the N100 of Beyer Co., Ltd, NCO content 22wt%；
Dimethylolpropionic acid：Commercially available from Aladdin Reagent Company.
Hereinafter intermediate and its preparation side are prepared by further illustrate the present invention aqueous polyurethane by preparation example 1-3 Method.
Preparation example 1
By sodium isethionate (hydroxyl) and HDI trimer (HT-600) by nOH/nNCO=1：3 mixing, are heated to 80 DEG C, 1.5h is stirred to react, obtains intermediate A 1, NCO group content is 12.1wt% in the intermediate A 1.The intermediate A 1 Structural formula is as follows：
Preparation example 2
By Sodium p-aminobenzene sulfonat and HDI biuret polymer (Bayer N100) by nOH/nNCO=1：3 mixing, is heated to 60 DEG C, 1.5h is stirred to react, obtains intermediate A 2, NCO group content is 11.2wt% in the intermediate A 1.The intermediate A 2 Structural formula is as follows：
Preparation example 3
Cyclohexylamino ethylsulfonic acid sodium and HDI-TMP addition products are pressed into nOH/nNCO=1：3 ratio mixing, is heated to 60 DEG C, 1.5h is stirred to react, obtains intermediate A 3, NCO group content is 9.7wt% in the intermediate A 3.The intermediate A 3 Structural formula is as follows：
Raw material employed in following examples and comparative is described as follows：
Polyether polyol：Commercially available from polypropylene glycol PPG (number-average molecular weight 2000g/mol, the hydroxyl of Dong great blue stars company Content is 56mgKOH/g), commercially available from the polytetramethylene ether diol (number-average molecular weight of Hangzhou company of Zhao Yuan Chemical Co., Ltd.s For 2000g/mol, hydroxy radical content 56mgKOH/g)；
Polyester polyol：Commercially available from the polyadipate hexylene glycol ester of Huada Chemical Group Co., Ltd., number-average molecular weight is 2000g/mol, hydroxy radical content 56mgKOH/g；
HDI：Commercially available from Wan Hua chemical companies, NCO group content 50wt%；
IPDI：Commercially available from BASF AG, NCO group content 37.8wt%；
Organotin catalysts：Commercially available from the dibutyl tin laurate (T12) of Xin Dian chemical companies；
Triethylamine (neutralizer), ethylenediamine (diamine chain extenders), hexamethylene diamine (diamine chain extenders) and ethanol amine (unitary Amine chainextender)：Commercially available from Aladdin Reagent Company.
In following examples and comparative, with reference to GB/T 10247-2008 methods rotary viscosity measuring prepolymer Viscosity, with reference to the solid content of coating solids test volume test aqueous polyurethane in GB1725-79.
To aqueous polyurethane and preparation method thereof be further illustrated the present invention by embodiment 1-4 and comparative example 1-2 below.
Embodiment 1
For illustrating aqueous polyurethane of the present invention and preparation method thereof, specific method is as follows：
The polypropylene glycol PPG (wherein hydroxy radical content is 56mgKOH/g) of 60g is added in into reactor, is taken off under 120 DEG C of vacuum Water 30 minutes, is then cooled to 80 DEG C, add in 1.48g dimethylolpropionic acid (pre-prepared aqueous polyurethane dry weight 1.8wt%), stirring after five minutes, add in 4g intermediate A 1 (wherein NCO group content be 0.012mol, the content of sulfonate radical For 0.0069mol), (wherein NCO group contains by the HDI (wherein NCO group content is 0.11mol) of 9.23g and the IPDI of 6.18g Measure as 0.056mol), the dibutyl tin laurate (T12) of 0.08g reacts 2 hours, prepares the performed polymer B1 (viscosity of 80.9g For 12000mPa.S, wherein NCO group content is 5.1wt%)；
Performed polymer B1 is cooled to 60 DEG C, the triethylamine for adding in 1g neutralizes, and is subsequently added into the deionized water of 84g in high-speed stirring It mixes constant temperature under condition (3000RPM) and emulsifies 15min；It adds in 1.5g ethylenediamine chain extender constant temperature and is stirred to react 15min, 167g is made Aqueous polyurethane S1 (solid content 50wt%).The molar ratio of carboxylate radical and sulfonate radical is 1.45 in the aqueous polyurethane：1, and On the basis of the dry weight of the aqueous polyurethane, the total weight of the carboxylate radical and sulfonate radical is 1.2 weight %.
Embodiment 2
For illustrating aqueous polyurethane of the present invention and preparation method thereof, specific method is as follows：
By the PTMEG (hydroxy radical content 56mgKOH/g) of 75g, reactor is added in, in 120 DEG C of dehydrated under vacuum 30 minutes, drop Temperature adds in the dimethylolpropionic acid (1.7wt% of pre-prepared aqueous polyurethane dry weight) of 1.8g to 70 DEG C, stirs 5 minutes Afterwards, intermediate A 2 (wherein NCO group content is 0.014mol, and sulfonic acid radical content is 0.01mol), the 11.76g of 5.32g is added in HDI (wherein NCO group content is 0.14mol) and 7.77g IPDI (wherein NCO group content is 0.07mol), 0.1g's Dibutyl tin laurate (T12) reacts 3 hours, prepares performed polymer B2 (the viscosity 8000mPa.S, wherein NCO of 101.6g Group content is 5.2wt%)；
Performed polymer B2 is cooled to 50 DEG C, the triethylamine for adding in 1.22g neutralizes；The deionized water of 110g is added in high-speed stirring It mixes constant temperature under condition (3000RPM) and emulsifies 15min；The ethylenediamine constant temperature chain extension 15min of 1.8g is added in, the aqueous poly- ammonia of 215g is made Ester S2 (solid content 49wt%).The molar ratio of carboxylate radical and sulfonate radical is 1.2 in the aqueous polyurethane:1, and with described aqueous On the basis of the dry weight of polyurethane, the total weight of the carboxylate radical and sulfonate radical is 1.3 weight %.
Embodiment 3
For illustrating aqueous polyurethane of the present invention and preparation method thereof, specific method is as follows：
By the PBA2000 (hydroxy radical content 56mgKOH/g) of 50g, reactor is added in, in 120 DEG C of dehydrated under vacuum 30 minutes, 90 DEG C are cooled to, adds in the dimethylolpropionic acid (the 1.72% of pre-prepared aqueous polyurethane dry weight) of 1.21g, stirs 5 points Zhong Hou, add in 3.42g intermediate A 3 (, wherein NCO group content is 0.0079mol, and the content of sulfonate radical is 0.005mol), The IPDI (wherein NCO group content is 0.048mol) of the HDI (wherein NCO group content is 0.095mol) of 8g, 5.29g, The dibutyl tin laurate (T12) of 0.06g, react 1.5 hours, prepare 68g performed polymer B3 (viscosity 15000mPa.S, Wherein NCO group content is 5.1wt%)；
Performed polymer B3 is cooled to 70 DEG C, the triethylamine for adding in 0.83g neutralizes；The deionized water of 76g is added in high-speed stirring It mixes constant temperature under condition (3000RPM) and emulsifies 15min；1.25g ethylenediamine constant temperature chain extension 15min are added in, the aqueous poly- ammonia of 146g is made Ester S3 (solid content 48wt%).The molar ratio of carboxylate radical and sulfonate radical is 1.7 in the aqueous polyurethane：1, and with described aqueous On the basis of the dry weight of polyurethane, the total weight of the carboxylate radical and sulfonate radical is 1.1 weight %.
Embodiment 4
For illustrating aqueous polyurethane of the present invention and preparation method thereof, specific method is as follows：
By the PPG (number-average molecular weight 2000g/mol, hydroxy radical content 56mgKOH/g) of 64g, reactor is added in, 120 DEG C dehydrated under vacuum 30 minutes, is cooled to 80 DEG C, add in 0.9g 1,4-butanediol (hydroxy radical content 1244mgKOH/g) and The dimethylolpropionic acid (0.016wt% of pre-prepared aqueous polyurethane dry weight) of 1.48g, stirring after five minutes, add in 4g's Intermediate A 1 (wherein NCO group content is 0.011mol, and the content of sulfonate radical is 0.0069mol), 11.59g HDI (wherein NCO group content is 0.14mol) and 7.66g IPDI (wherein NCO group content be 0.069mol), the tin dilaurate of 0.08g Dibutyl tin (T12) reacts 2 hours, and preparing 89g performed polymers B4, (viscosity 17900mPa.S, wherein NCO group content are 5.4wt%)；
Performed polymer B4 is cooled to 60 DEG C, the triethylamine for adding in 1g neutralizes；100g deionized waters are added in high-speed stirred item Constant temperature emulsifies 15min under part (3000RPM)；The ethylenediamine constant temperature chain extension for adding in 1.5g is stirred to react 15min, and it is aqueous that 192g is made Polyurethane S1 (solid content 48wt%).The molar ratio of carboxylate radical and sulfonate radical is 1.45 in the aqueous polyurethane：1, and with institute On the basis of the dry weight for stating aqueous polyurethane, the total weight of the carboxylate radical and sulfonate radical is 1.2 weight %.
Comparative example 1
Illustrate aqueous polyurethane of the present invention and preparation method thereof for reference, specific method is as follows：
The polyether polyol PPG2000 of 60g is needed before experiment in 110 DEG C of oil bath temperature, vacuum dehydration 1h；It is cooled to The IPDI (wherein NCO group content is 0.072mol) of 8g is added in after 80 DEG C, (wherein NCO group content is the HDI of 16g 0.19mol) react 2h；The dihydromethyl propionic acid DMPA of 4g is added in, and using acetone control viscosity as 3000mPa.S, the reaction was continued 2h is cooled to 40 DEG C, adds in the triethylamine of 3.03g, reacts 15min；The distilled water of 170g is added in, high speed dispersion 20min is added in The ethylenediamine chain extension of 1.5g, vacuum distillation remove acetone, obtain the aqueous polyurethane emulsion (solid content 35wt%) of 262g.
Comparative example 2
Illustrate aqueous polyurethane of the present invention and preparation method thereof for reference, specific method is as follows：
The polyether polyol PPG2000 of 60g is needed before experiment in 110 DEG C of oil bath temperature, vacuum dehydration 1h；It is cooled to The IPDI (wherein NCO group content is 0.072mol) of 8g is added in after 80 DEG C, (wherein NCO group content is the HDI of 16g 0.19mol) react 2h；1g dihydromethyl propionic acid DMPA are added in, add in 40ml acetone, the reaction was continued 2h is cooled to 25 DEG C, adds in The triethylamine of 3.03g reacts 15min；Add in 2- amino-ethyl b sodium salts solution (50wt% aqueous solutions) reaction 10 of 4g Minute, the distilled water of 170g is added in, high speed dispersion 20min adds in the ethylenediamine chain extension of 1.5g, is evaporated under reduced pressure, removes acetone, obtain To the aqueous polyurethane emulsion (solid content 35wt%) of 262g.
Test case：
Aqueous polyurethane prepared by embodiment 1 to 4 and comparative example 1 and 2 is tested as follows：
(1) average grain diameter of aqueous polyurethane：Laser particle analyzer measures lotion average grain diameter；
(2) storage stability of aqueous polyurethane：15mL lotions is taken to be placed in a centrifuge, are centrifuged with the rotating speed of 3000RPM Precipitation production has been seen whether after 15min, if being generated without precipitation, has illustrated that lotion storage stability is more than 6 months；
(3) glued membrane water absorption rate：The preparation method of glued membrane is to pour into lotion in glass guide channel, at room temperature placement one day, so After be put into baking oven be baked at 60 DEG C it is dry to get glued membrane；The measuring method of water absorption rate is big for sample is cut into 2cm × 2cm It is small, it is 24 hours dry under vacuum, weight (W1) is weighed, then sample is dipped in deionized water, its weight is claimed after 24 hours (W2), water absorption rate is calculated as follows：η=(W2-W1)/W1 × 100%；
(4) glued membrane tensile strength：For the preparation method of glued membrane referring to (3), the measuring method of tensile strength is with reference to GB/T 1040-92 plastic tensile performance measurement methods.
(5) measurement result：As shown in table 1.
Table 1.
As data in table 1 it is found that compared with according to the aqueous polyurethane D1-D2 prepared by comparative example, according to institute of the present invention The good combination property of the aqueous polyurethane S1-S4 of preparation, moreover, the system of the aqueous polyurethane S1-S4 according to prepared by the present invention By intermediate of the introducing with specific structure in standby technique, the performed polymer of modest viscosity can be prepared, it is organic without adding Solvent not only reduces cost of material, and also improves industrial production safety, environmentally protective, is more suitable for extensive life Production.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (20)

1. a kind of preparation method of aqueous polyurethane, which is characterized in that the method includes：
S1, the intermediate with the structure as shown in following formula I is prepared,
R in formula I1To have the structural unit of the structure as shown in any in following formula II, formula III and formula IV, R2Selected from C5-C9Alkyl, C5-C9Cycloalkyl or C6-C10Any one of aryl；X is oxygen, NH or NR3, wherein R3For C3-C6Alkyl or C3-C6Cycloalkyl；Z For (CH2)nOr C6H4, n is the integer in 1-12；M is selected from Na+、K+、NH4 +Or NR '4 +, R ' is C1-C4Alkyl；
R in formula III4For C1-C3Alkyl；
S2, under the conditions of prepolymerization reaction, the intermediate is promoted to be less than with polyalcohol, the first polyisocyanates and number-average molecular weight The organic carboxyl acid haptoreaction contained there are two hydroxyl of 250g/mol, forms performed polymer；
S3, under emulsification condition, to the performed polymer carry out emulsification treatment, then under the conditions of chain extension, to it is described through emulsification at The performed polymer of reason carries out chain extension processing.
2. preparation method according to claim 1, wherein, the centre with the structure as shown in following formula I is prepared in the S1 The method of body includes：Under the polymerization conditions, by the second polyisocyanates with the structure as shown in following formula V with NCO group Meter with the sulfonate containing reactive group in terms of reactive group according to molar ratio 3：1 haptoreaction, the reactive group are OH, NH2 Or NH,
R in formula V1For the structural unit with shown structure any in the formula II, the formula III and the formula IV, R2It is selected from C5-C9Alkyl, C5-C9Cycloalkyl or C6-C10Any one of aryl.
3. preparation method according to claim 2, wherein, the cation of the sulfonate is selected from Na+、K+、NH4 +Or NR′4 +Any one of, R ' is C1-C4Alkyl；It is preferably selected from sodium isethionate, sodium hydroxymethane sulfonate, 4- hydroxybutyl sulfonic acid One or more of sodium, sodium sulfanilate, 2- aminoethylsulfonic acids sodium and Cyclohexylamino ethylsulfonic acid sodium.
4. preparation method according to claim 2, wherein, the polymeric reaction condition includes：At a temperature of 60-90 DEG C, It is stirred to react 1-4h.
5. preparation method according to claim 2, wherein, in the S2,
Contained NCO group and OH contained in polyalcohol and organic carboxyl acid in the intermediate and first polyisocyanates The molar ratio of group is (1.5-2.4)：1；
Preferably, the additive amount of the organic carboxyl acid is the 1-4wt% of the aqueous polyurethane dry weight；
Preferably, the molar ratio of carboxylate radical is (0.25-4) in contained sulfonate radical and the organic carboxyl acid in the intermediate： 1, preferably (0.5-2)：1, and on the basis of the dry weight of prepared aqueous polyurethane, the carboxylate radical and sulfonate radical Total weight is 1-1.5 weight %.
6. preparation method according to claim 1, wherein, polyalcohol includes polymer polyatomic alcohol in the S2 and monomer is more First alcohol, and on the basis of 100 parts by weight of polyalcohol, the content of the polymer polyatomic alcohol is 95-100 weight %, described The content of monomeric polyols is 0-5 weight %；It is preferred that the polymer polyatomic alcohol be selected from polyester polyol, polyether polyol and It is one or more in polyester ether polylol, and the number-average molecular weight of the polymer polyatomic alcohol is 500-10000g/mol, more It is preferred that 1000-5000g/mol；It is preferred that the number-average molecular weight of the monomeric polyols is less than 200g/mol.
7. preparation method according to claim 1, wherein, the first polyisocyanates described in the S2 is selected from hexa-methylene Diisocyanate, isophorone diisocyanate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, HDI trimer, benzene One or more of dimethylene diisocyanate and hydrogenation benzene dimethylene diisocyanate.
8. preparation method according to claim 1, wherein, organic carboxyl acid described in the S2 for dimethylolpropionic acid and/ Or dihydromethyl propionic acid.
9. preparation method according to claim 1, wherein, in the step of S2 forms performed polymer, addition catalyst with Promote catalytic generation；It is preferred that the catalyst in organotin, organo-bismuth, organic zinc and organic amine one kind or It is several；It is preferred that the dosage of the catalyst is the intermediate, polyalcohol, the first polyisocyanates and organic carboxyl acid total weight 0.01-0.1 weight %.
10. preparation method according to claim 1, wherein, prepolymerization reaction condition includes in the S2：Exist in catalyst Under, at a temperature of 60-90 DEG C, it is stirred to react 1-4h.
11. preparation method according to claim 1, wherein, the viscosity of performed polymer is 2000- formed in the S2 50000mPa.S preferably 5000-20000mPa.S.
12. preparation method according to claim 1, wherein, in the S3 before emulsification treatment, it is additionally included in 50-70 DEG C At a temperature of, the step of neutralizer carries out neutralization reaction is added in the performed polymer, preferably described neutralizer is triethylamine, hydrogen-oxygen The equivalent proportion of change one or more of sodium and sodium bicarbonate, preferably described neutralizer and the organic carboxyl acid is 0.99-1.01： 1。
13. preparation method according to claim 1, wherein, emulsification treatment condition includes in the S3：In the presence of water, 50-70 DEG C of temperature, emulsification treatment 15-30min.
14. preparation method according to claim 1, wherein, in the S3, added in the step of carrying out chain extension processing hydrophilic Chain extender, contained NH in preferably described hydrophilic chain extender2And/or the total mole number of NH groups is the pre-polymerization before the chain extension The 50-80% of the molal quantity of NCO group in body.
15. preparation method according to claim 14, wherein, the chain extender includes diamine and/or polyamine,
Preferably, the chain extender is preferably selected from ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, cyclohexyl diamine One or more of with isophorone diamine；
Preferably, the chain extender further includes monoamine, and the dosage of the monoamine is the 0.1-30 of the chain extender total weight Weight %；
It is highly preferred that the monoamine is diethanol amine and/or ethanol amine.
16. preparation method according to claim 1, wherein, the condition of the chain extension processing includes：It is deposited in hydrophilic chain extender Under, -70 DEG C of chain extension processing 15-30min of room temperature.
17. the aqueous polyurethane that a kind of preparation method as described in any one in claim 1 to 16 prepares, preferably institute It states and contains carboxylate radical and sulfonate radical in aqueous polyurethane, the molar ratio of the carboxylate radical and sulfonate radical is (0.25-4)：1, preferably For (0.5-2)：1, and on the basis of the dry weight of the aqueous polyurethane, the total weight of the carboxylate radical and sulfonate radical is 1-1.5 Weight %.
18. a kind of aqueous polyurethane prepares intermediate, which is characterized in that the intermediate has structure shown in formula I,
R in formula I1To have the structural unit of the structure as shown in any in following formula II, formula III and formula IV, R2Selected from C5-C9Alkyl, C5-C9Cycloalkyl or C6-C10Any one of aryl；X is oxygen, NH or NR3, wherein R3For C3-C6Alkyl or C3-C6Cycloalkyl；Z For (CH2)nOr C6H4, n is the integer in 1-12；M is selected from Na+、K+、NH4 +Or NR '4 +, R ' is C1-C4Alkyl；
R in formula III4For C1-C3Alkyl.
19. a kind of aqueous polyurethane, which is characterized in that in the aqueous polyurethane containing formula VI shown in structural unit；
R in formula VI1To have the structural unit of the structure as shown in any in following formula II, formula III and formula IV, R2To be selected from C5-C9Alkane Base, C5-C9Cycloalkyl or C6-C10Any one of aryl；X is oxygen, NH or NR3, wherein R3For C3-C6Alkyl or C3-C6Cycloalkanes Base；Z is (CH2)nOr C6H4, n is the integer in 1-12；M is selected from Na+、K+、NH4 +Or NR '4 +, R ' is C1-C4Alkyl；
R in formula III4For C1-C3Alkyl.
20. aqueous polyurethane according to claim 19, wherein, carboxylate radical and sulfonic acid are contained in the aqueous polyurethane The molar ratio of root, the carboxylate radical and sulfonate radical is (0.25-4)：1, preferably (0.5-2)：1, and with the aqueous polyurethane Dry weight on the basis of, the total weight of the carboxylate radical and sulfonate radical is 1-1.5 weight %.
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CN109251300A (en) * 2018-08-24 2019-01-22 湘潭大学 A kind of salt polyaminoester emulsion of cross-linking type sulfoacid carboxylic acid and preparation method thereof
CN111040426A (en) * 2019-12-27 2020-04-21 安徽匠星联创新材料科技有限公司 Nano zinc oxide modified waterborne polyurethane emulsion and preparation method thereof
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CN111393613A (en) * 2020-04-29 2020-07-10 广东巴德富新材料有限公司 Easily-dispersible self-extinction waterborne polyurethane curing agent and preparation method thereof
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CN109251300A (en) * 2018-08-24 2019-01-22 湘潭大学 A kind of salt polyaminoester emulsion of cross-linking type sulfoacid carboxylic acid and preparation method thereof
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CN112679687A (en) * 2020-12-24 2021-04-20 华南理工大学 Hydroxysulfonic acid hydrophilic monomer and preparation method and application thereof
CN112679687B (en) * 2020-12-24 2022-06-21 华南理工大学 Hydroxysulfonic acid hydrophilic monomer and preparation method and application thereof

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