CN102766244A - Sulfonate-type hydrophilic chain extender and preparation method thereof - Google Patents
Sulfonate-type hydrophilic chain extender and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sulfonate-type hydrophilic chain extender and a preparation method thereof. The preparation method comprises the following steps of: adding cyanuric chloride and ice water to a vessel, controlling the temperature of a reaction solution between 0 to 5 DEG C, dropwise adding a sodium paminobenzene sulfonate solution under stirring, using a NaOH solution to adjust the system pH, and then reacting; heating, dropewise adding the sodium paminobenzene sulfonate solution, using the NaOH solution to adjust the system pH, and then reacting; heating, dropwise adding diethanolamine, using the NaOH solution to adjust the system pH, and the reaction being finished; cooling the mixture to room temperature, concentrating under reduced pressure and drying to remove moisture, and then being dissolved in anhydrous ethanol, keeping stand, and separating NaCl and unreacted sodium paminobenzene sulfonate; and finally, removing ethanol by atmospheric distillation to obtain a pale yellow solid, i.e., the sulfonate-type hydrophilic chain extender. A waterborne polyurethane dispersing agent prepared by using the hydrophilic chain extender as a raw material has higher solid content and can be stably stored in a wider pH range, and a coating has higher tensile strength.
Description
Technical field
The invention belongs to the chemical materials synthesis technical field, be specifically related to a kind of sulfonate type hydrophilic chain extender and preparation method thereof.
Background technology
Urethane can be divided into solvent-borne type and water-based two big classes.In preparation aqueous polyurethane (WPU) process, solvent load is few, toxicity is low, and the noxious odor of generation is few, and low toxic and environment-friendly is simple to operate.The aqueous polyurethane product has had superior application performance under optimum conditions, in fields such as coating, textile finishing, pigment printing, coating, sizing agent, leather, is bringing into play more and more important effect.
Hydrophilic chain extender is a material of when the base polyurethane prepolymer for use as that contains isocyanate terminated base is carried out chain extension, introducing hydrophilic radical.Common dimethylol propionic acid (DMPA), dihydroxyl half ester, diethylenetriamine, the methyldiethanolamine etc. of mainly containing.This type chainextender is the special raw material that uses in the aqueous polyurethane preparation, often contains carboxyl or secondary amine.
With the sulfonate type hydrophilic chain extender is that the aqueous polyurethane of feedstock production is the sulfonate type aqueous polyurethane.At present, the exploitation of sulfonate type hydrophilic chain extender has become current aqueous polyurethane hot research fields.
In October, 2006, Zuo Haili, Wu Xiaoqing etc. are raw material with epoxy chloropropane (ECH), sodium sulfite anhy 96 and soda ash light, have synthesized 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium (DHPA), and proved product structure with Fourier infrared spectrum and fusing point appearance.In June, 2009, the Kangping is flat, and Song Wensheng etc. adopt quadrol (EDA) and 2-chloroethene sodium sulfonate to react synthesis of ethylenediamine base ethyl sulfonic acid sodium, with ir spectra (FTIR), nucleus magnetic hydrogen spectrum (
1H NMR) and carbon spectrum (
13CNMR), means such as X-ray diffraction (XRD), ultimate analysis have characterized the structure and the characteristic of product.In April, 2011, Song Wensheng, Xu Cuicui, Zheng Yingli etc. are with the synthetic N of diethylolamine and 2-chloroethyl sodium sulfonate reaction, N-two (2-hydroxyethyl)-2-aminoethyl sulfonic acid sodium (BES sodium salt), with nucleus magnetic hydrogen spectrum (
1H NMR) and carbon spectrum (
13C NMR), ir spectra (FT-IR), X-ray diffraction means such as (XRD) have characterized the structure and the characteristic of synthetic product, and have optimized the best synthesis technique of having confirmed the BES sodium salt.
Publication number is the preparation method that the patent of CN 101240057A discloses a kind of sulfonic acid type hydrophilic chain extender: polyamine is dissolved in the appropriate solvent; Add the olefin sulfonic acid salt brine solution after being warming up to 40～100 ℃; Insulation reaction 4～30 hours; Through removal of impurities, operation such as stability processings etc., obtaining outward appearance has light yellow, the oily of muddiness, thick liquid.
With the aqueous polyurethane dispersing liquid of carboxylic acid type hydrophilic chain extender preparation can only stable existence under higher pH condition, and solid content is not high.Above-mentioned quadrol base ethyl sulfonic acid sodium and the disclosed sulfonate type hydrophilic chain extender of patent CN 101240057A are the chain extending reaction group with amino all, and reactive behavior is higher, is easy to generate gel, difficult control.1 of investigator's preparation; 2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium (DHPA) and N; N-two (2-hydroxyethyl)-2-aminoethyl sulfonic acid sodium (BES sodium salt) is the chain extending reaction group with the alcoholic extract hydroxyl group; Its chain extending reaction is gentle, and all only contains a sulfonate radical in the molecule, and is still lower with the polyaminoester emulsion solid content of its preparation.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art; The object of the present invention is to provide a kind of sulfonate type hydrophilic chain extender and preparation method thereof; With this hydrophilic chain extender is that the aqueous polyurethane dispersing liquid solid content of feedstock production is higher; Can under wider pH range of condition, stablize and preserve, and the tensile strength of filming is higher.
In order to achieve the above object, the present invention takes following technical scheme:
A kind of sulfonate type hydrophilic chain extender, molecular structure is:
Wherein, R is C
2～C
3Alkyl, m equals 1 or 2, n equals 1 or 2.
Its preparation feedback formula is represented as follows:
Its preparation method may further comprise the steps:
In container, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir the mass concentration 10% aniline sulfonic acid sodium salt solution that drips 195.1～297.3 parts of mass fractions down; NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 1.5～2.0h; Be warmed up to 35～45 ℃, drip the aniline sulfonic acid sodium salt solution of the mass concentration 10% of 195.1～297.3 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5～3.0h; Be warming up to 75～85 ℃, drip 10.51～13.32 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.5, adds afterreaction 2.5～3.0h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender;
Described aniline sulfonic acid sodium salt is Sodium sulfanilate, aniline-2,4-sodium disulfonate and aniline-2, a kind of in the 5-sodium disulfonate;
Described glycol amine is a kind of in diethylolamine and the HSDB 338.
The present invention has the following advantages:
1. the present invention as reaction solvent, had not only saved cost but also low-carbon environment-friendly with water.
2. the aqueous polyurethane of the present invention's preparation is with containing more hydrophilic radical in the hydrophilic chain extender molecule.Contain 2～4mol sulfonate radical and 2mol alcoholic extract hydroxyl group in this hydrophilic chain extender molecule of 1mol, it has better water-solubility, can be applicable in the wider environment of pH, and chain extending reaction speed is moderate, and is more easy to control.
3. the hydrophilic chain extender with the present invention preparation is a raw material synthesis of polyurethane aqueous dispersions, and its solid content is high, and performances such as heat-resisting and acid and alkali-resistance are excellent more.Because this chainextender has high charge value, the median size of particle is littler in the polyurethane aqueous dispersion, and it is bigger and elongation at break is littler that it processes the tensile strength of film.
Embodiment
Through embodiment the present invention is specifically described below; It is important to point out that embodiment only is used for the present invention is further specified; Can not be interpreted as restriction to protection domain of the present invention, those skilled in the art according to the present invention content make some nonessential improvement and adjustment also belongs to protection scope of the present invention.
Embodiment one: preparation chainextender 1
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir the mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions down; NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 1.5h; Be warmed up to 35～40 ℃, drip the Sodium sulfanilate solution of the mass concentration 10% of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.5, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender.
The molecular structure of this chainextender is following:
Embodiment two: preparation chainextender 2
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 4-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip the Sodium sulfanilate solution of the mass concentration 10% of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 80～85 ℃, drip 13.32 parts of mass fraction HSDB 338s, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 3.0h, and reaction finishes; Concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature; Remove moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature, use anhydrous alcohol solution again, leave standstill; Divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt; Ethanol is removed in last air distillation, obtains faint yellow solid, is the sulfonate type hydrophilic chain extender.
The molecular structure of this hydrophilic chain extender is following:
Embodiment three: preparation chainextender 3
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 5-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 40～45 ℃, drip mass concentration 10% aniline-2 of 297.3 parts of mass fractions, 5-sodium disulfonate solution, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender.
The molecular structure of this hydrophilic chain extender is following:
Embodiment four: preparation chainextender 4
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 5-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip the mass concentration 10% Sodium sulfanilate solution of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender.
The molecular structure of this hydrophilic chain extender is following:
Embodiment five: preparation chainextender 5
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 4-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip mass concentration 10% aniline-2 of 297.3 parts of mass fractions, 5-sodium disulfonate solution, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender.
The molecular structure of this hydrophilic chain extender is following:
Embodiment six: preparation chainextender 6
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir the mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions down; NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 1.5h; Be warmed up to 35～40 ℃, drip the mass concentration 10% Sodium sulfanilate solution of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 13.32 parts of mass fraction HSDB 338s, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.0～7.5, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender.
The molecular structure of this hydrophilic chain extender is following:
Embodiment seven: preparation chainextender 7
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 4-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip mass concentration 10% aniline-2 of 297.3 parts of mass fractions, 4-sodium disulfonate solution, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.0～7.5, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender.
The molecular structure of this hydrophilic chain extender is following:
Preliminary Applications test and result
With tolylene diisocyanate (TDI), polyoxypropyleneglycol (N210) and seven kinds of hydrophilic chain extenders is that main raw material is prepared eight kinds of polyurethane aqueous dispersions, has measured index of correlation.Wherein, the polyurethane aqueous dispersion of making hydrophilic chain extender with dimethylol propionic acid (DMPA) is a control group, and all the other are experimental group.Control group and experimental group synthesis technique are following:
Control group: in the four-hole boiling flask that TM, condensation cocurrent flow pipe and whisking appliance are housed; With a certain amount of polyoxypropyleneglycol (N210) in 110 ℃ of vacuum hydro-extraction 2h; Be cooled to 30 ℃ of logical people's nitrogen, add metering TDI (n (NCO)/n (OH)=2.2) and a small amount of dibutyl tin laurate, be warmed up to 70～75 ℃ of reactions extremely-NCO content is about 3%; With an amount of, a spot of acetone adjustment system viscosity, judge reaction end with the Di-n-Butyl Amine volumetry.Be cooled to 60 ℃, (DMPA) is dissolved in minor N with dimethylol propionic acid, in the dinethylformamide (DMF), in system, slowly adds DMF solution then, in 70 ℃ of reaction 1.5h.Again reaction system is cooled to 30 ℃, and in system, slowly adds quantitative, minimum Pottasium Hydroxide deionized water solution, under intense stirring condition, carry out emulsification, promptly get the polyurethane aqueous dispersion of high solids content low-viscosity.
Test group: in the four-hole boiling flask that TM, condensation cocurrent flow pipe and whisking appliance are housed; With a certain amount of polyoxypropyleneglycol (N210) in 110 ℃ of vacuum hydro-extraction 2h; Be cooled to 30 ℃ of logical people's nitrogen, add metering TDI (n (NCO)/n (OH)=2.2) and a small amount of dibutyl tin laurate, be warmed up to 70～75 ℃ of reactions extremely-NCO content is about 3%; With an amount of, a spot of acetone adjustment system viscosity, judge reaction end with the Di-n-Butyl Amine volumetry.Be cooled to 60 ℃, hydrophilic chain extender is dissolved in minor N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan (NMP), in system, slowly add nmp solution then, in 70 ℃ of reaction 1.5h.Again reaction system is cooled to 30 ℃, and in system, slowly adds quantitative, minimum deionized water, under intense stirring condition, carry out emulsification, promptly get the polyurethane aqueous dispersion of high solids content low-viscosity.
The relevant nature of table 1 polyurethane aqueous dispersion
Annotate: consider that the molecular weight of chainextender is far longer than DMPA in the experimental group, in application, suitably enlarge the consumption of experimental group chainextender.
Claims (9)
1. a sulfonate type hydrophilic chain extender is characterized in that, molecular structure is:
Wherein, R is C
2～C
3Alkyl, m equals 1 or 2, n equals 1 or 2.
2. a kind of sulfonate type hydrophilic chain extender according to claim 1 is characterized in that the preparation method may further comprise the steps:
In container, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir the mass concentration 10% aniline sulfonic acid sodium salt solution that drips 195.1～297.3 parts of mass fractions down; NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 1.5～2.0h; Be warmed up to 35～45 ℃, drip the aniline sulfonic acid sodium salt solution of the mass concentration 10% of 195.1～297.3 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5～3.0h; Be warming up to 75～85 ℃, drip 10.51～13.32 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.5, adds afterreaction 2.5～3.0h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again; Leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender;
Described aniline sulfonic acid sodium salt is Sodium sulfanilate, aniline-2,4-sodium disulfonate and aniline-2, a kind of in the 5-sodium disulfonate;
Described glycol amine is a kind of in diethylolamine and the HSDB 338.
3. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that the preparation method may further comprise the steps:
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir the mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions down; NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 1.5h; Be warmed up to 35～40 ℃, drip the Sodium sulfanilate solution of the mass concentration 10% of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.5, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again, leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt; Ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender
The molecular structure of this chainextender is following:
4. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that the preparation method may further comprise the steps:
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 4-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip the Sodium sulfanilate solution of the mass concentration 10% of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 80～85 ℃, drip 13.32 parts of mass fraction HSDB 338s, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 3.0h, and reaction finishes; Concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature, uses anhydrous alcohol solution again; Leave standstill; Divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt, ethanol is removed in last air distillation, obtains faint yellow solid; Be the sulfonate type hydrophilic chain extender
The molecular structure of this hydrophilic chain extender is following:
5. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that the preparation method may further comprise the steps:
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 5-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 40～45 ℃, drip mass concentration 10% aniline-2 of 297.3 parts of mass fractions, 5-sodium disulfonate solution, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again, leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt; Ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender
The molecular structure of this hydrophilic chain extender is following:
6. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that the preparation method may further comprise the steps:
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 5-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip the mass concentration 10% Sodium sulfanilate solution of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again, leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt; Ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender
The molecular structure of this hydrophilic chain extender is following:
7. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that the preparation method may further comprise the steps:
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 4-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip mass concentration 10% aniline-2 of 297.3 parts of mass fractions, 5-sodium disulfonate solution, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.5～8.0, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again, leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt; Ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender
The molecular structure of this hydrophilic chain extender is following:
8. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that the preparation method may further comprise the steps:
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir the mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions down; NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 1.5h; Be warmed up to 35～40 ℃, drip the mass concentration 10% Sodium sulfanilate solution of 195.1 parts of mass fractions, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 2.5h; Be warming up to 75～80 ℃, drip 13.32 parts of mass fraction HSDB 338s, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.0～7.5, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again, leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt; Ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender
The molecular structure of this hydrophilic chain extender is following:
9. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that the preparation method may further comprise the steps:
In four-hole boiling flask, add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water; 0～5 ℃ of control reacting liquid temperature; Stir mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions down, 4-sodium disulfonate solution is with the NaOH solution regulation system potential of hydrogen of mass concentration 10%; Make it to be stabilized in pH6.0～7.0, add afterreaction 2.0h; Be warmed up to 35～40 ℃, drip mass concentration 10% aniline-2 of 297.3 parts of mass fractions, 4-sodium disulfonate solution, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH6.0～7.0, adds afterreaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethylolamine, the NaOH solution regulation system potential of hydrogen with mass concentration 10% makes it to be stabilized in pH7.0～7.5, adds afterreaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, and concentrating under reduced pressure under vacuum tightness 0.1MPa, 55 ℃ of conditions of temperature is removed moisture in vacuum tightness 0.1MPa, 40 ℃ of dryings of temperature; Use anhydrous alcohol solution again, leave standstill, divide and remove NaCl, unreacted amino Phenylsulfonic acid sodium salt; Ethanol is removed in last air distillation; Obtain faint yellow solid, be the sulfonate type hydrophilic chain extender
The molecular structure of this hydrophilic chain extender is following:
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665292A (en) * | 2013-11-29 | 2014-03-26 | 陕西科技大学 | Sulfonic acid type water-based polyurethane chain extender and preparation method thereof |
| CN104358119A (en) * | 2014-10-23 | 2015-02-18 | 广东溢达纺织有限公司 | Reaction type anionic modifier and preparation method thereof |
| CN110938186A (en) * | 2019-10-24 | 2020-03-31 | 江汉大学 | High-solid-content polyurethane emulsion and preparation method thereof |
| CN115340814A (en) * | 2022-09-22 | 2022-11-15 | 刘翔 | Preparation and application of cationic polyurethane antibacterial coating |
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| CN101240057A (en) * | 2008-03-18 | 2008-08-13 | 北京林氏精化新材料有限公司 | Sulfonic acid type hydrophilic chain extender and preparation method thereof |
| US8148462B2 (en) * | 2006-07-07 | 2012-04-03 | Tosoh Corporation | Aqueous polyurethane fluid dispersion and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8148462B2 (en) * | 2006-07-07 | 2012-04-03 | Tosoh Corporation | Aqueous polyurethane fluid dispersion and method for producing the same |
| CN101240057A (en) * | 2008-03-18 | 2008-08-13 | 北京林氏精化新材料有限公司 | Sulfonic acid type hydrophilic chain extender and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665292A (en) * | 2013-11-29 | 2014-03-26 | 陕西科技大学 | Sulfonic acid type water-based polyurethane chain extender and preparation method thereof |
| CN103665292B (en) * | 2013-11-29 | 2015-06-03 | 陕西科技大学 | Sulfonic acid type water-based polyurethane chain extender and preparation method thereof |
| CN104358119A (en) * | 2014-10-23 | 2015-02-18 | 广东溢达纺织有限公司 | Reaction type anionic modifier and preparation method thereof |
| CN104358119B (en) * | 2014-10-23 | 2016-09-21 | 广东溢达纺织有限公司 | A kind of anion-modified dose of response type and preparation method thereof |
| CN110938186A (en) * | 2019-10-24 | 2020-03-31 | 江汉大学 | High-solid-content polyurethane emulsion and preparation method thereof |
| WO2021077793A1 (en) * | 2019-10-24 | 2021-04-29 | 江汉大学 | High-solid-content polyurethane emulsion and preparation method therefor |
| CN115340814A (en) * | 2022-09-22 | 2022-11-15 | 刘翔 | Preparation and application of cationic polyurethane antibacterial coating |
| CN115340814B (en) * | 2022-09-22 | 2023-08-01 | 苏州邦得纳米涂层科技有限公司 | Preparation and application of cationic polyurethane antibacterial coating |
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