CN102766244B - 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 the large class of water-based two.In preparing 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 the 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 to introduce the material of hydrophilic radical when the base polyurethane prepolymer for use as to containing isocyanate terminated base carries out chain extension.Common dimethylol propionic acid (DMPA), dihydroxyl half ester, diethylenetriamine, the methyldiethanolamine etc. of mainly containing.This class chainextender is the special raw material used in the aqueous polyurethane preparation, often contains carboxyl or secondary amine.
Aqueous polyurethane prepared as raw material by the sulfonate type hydrophilic chain extender of take is the sulfonate type aqueous polyurethane.At present, the exploitation of sulfonate type hydrophilic chain extender has become the study hotspot in current aqueous polyurethane field.
In October, 2006, Zuo Haili, it is raw material that Wu Xiaoqing etc. be take epoxy chloropropane (ECH), sodium bisulfite and anhydrous sodium carbonate, has synthesized 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium (DHPA), and has proved product structure with Fourier infrared spectrum and melting point apparatus.In June, 2009, Kangping is flat, and Song Wensheng etc. adopt quadrol (EDA) and 2-chloroethene sodium sulfonate reaction synthesis of ethylenediamine base ethyl sulfonic acid sodium, use infrared spectra (FTIR), nucleus magnetic hydrogen spectrum (
1h NMR) and carbon spectrum (
13cNMR), the means such as X-ray diffraction (XRD), ultimate analysis have characterized structure and the characteristic of product.In April, 2011, Song Wensheng, Xu Cuicui, Zheng Yingli etc. react with 2-chloroethyl sodium sulfonate and synthesize N with diethanolamine, N-bis-(2-hydroxyethyl)-2-aminoethyl sulfonic acid sodium (BES sodium salt), with nucleus magnetic hydrogen spectrum (
1h NMR) and carbon spectrum (
13c NMR), the means such as infrared spectra (FT-IR), X-ray diffraction (XRD) have characterized the structure and characteristics of synthetic product, and have optimized the best synthesis technique of having determined the BES sodium salt.
The patent that publication number is CN 101240057A discloses a kind of preparation method of sulfonic acid type hydrophilic chain extender: polyamine is dissolved in appropriate solvent, add the olefin sulfonic acid salt brine solution after being warming up to 40～100 ℃, insulation reaction 4～30 hours, through operations such as removal of impurities, disposal of stabilities, obtaining outward appearance has muddy light yellow, oily, thick liquid.
The aqueous polyurethane dispersing liquid prepared with the carboxylic acid type hydrophilic chain extender 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 all be take amino as the chain extending reaction group, and reactive behavior is higher, easily produces gel, more difficult control.The investigator prepare 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium (DHPA) and N, N-bis-(2-hydroxyethyl)-2-aminoethyl sulfonic acid sodium (BES sodium salt) be take alcoholic extract hydroxyl group as the chain extending reaction group, its chain extending reaction is gentleer, and all only containing a sulfonate radical in molecule, the polyaminoester emulsion solid content prepared with it is still lower.
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, take this hydrophilic chain extender as aqueous polyurethane dispersing liquid solid content prepared by raw material higher, can under wider pH range of condition, stablize preservation, 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 equal 1 or 2, n equal 1 or 2.
Its preparation feedback formula is expressed as follows:
Its preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in container, control 0～5 ℃ of reacting liquid temperature, stir the lower mass concentration 10% aniline sulfonic acid sodium salt solution that drips 195.1～297.3 parts of mass fractions, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5～3.0h; Be warming up to 75～85 ℃, drip 10.51～13.32 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.5, adds rear reaction 2.5～3.0h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 diethanolamine and diisopropanolamine (DIPA).
The present invention has the following advantages:
1. the present invention is usingd water as reaction solvent, has not only saved cost but also low-carbon environment-friendly.
2. the aqueous polyurethane that prepared by the present invention 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-soluble, can be applicable in the wider environment of pH, and chain extending reaction speed is moderate, more easy to control.
3. hydrophilic chain extender prepared by the present invention of take is raw material synthesis of polyurethane aqueous dispersions, and its solid content is high, and the performances such as heat-resisting and acid and alkali-resistance are more excellent.Because this chainextender has high charge value, in polyurethane aqueous dispersion, the median size of particle is less, and its tensile strength of making film is larger and elongation at break is less.
Embodiment
Below by embodiment, the present invention is specifically described; it is important to point out that embodiment only is used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, those skilled in the art according to the present invention content make some nonessential improvement and adjust and also belong to protection scope of the present invention.
Embodiment mono-: prepare chainextender 1
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir the lower mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.5, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
Embodiment bis-: prepare chainextender 2
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 4-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 80～85 ℃, drip 13.32 parts of mass fraction diisopropanolamine (DIPA), the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 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 again anhydrous alcohol solution, standing, 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 as follows:
Embodiment tri-: prepare chainextender 3
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 5-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
Embodiment tetra-: prepare chainextender 4
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 5-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
Embodiment five: prepare chainextender 5
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 4-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
Embodiment six: prepare chainextender 6
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir the lower mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 13.32 parts of mass fraction diisopropanolamine (DIPA), the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.0～7.5, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
Embodiment seven: prepare chainextender 7
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 4-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.0～7.5, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
Preliminary Applications test and result
Take tolylene diisocyanate (TDI), polyoxypropyleneglycol (N210) and seven kinds of hydrophilic chain extenders prepares eight kinds of polyurethane aqueous dispersions as main raw material, has measured index of correlation.Wherein, the polyurethane aqueous dispersion that the dimethylol propionic acid (DMPA) of take is made hydrophilic chain extender is control group, and all the other are experimental group.Control group and experimental group synthesis technique are as follows:
Control group: in the four-hole boiling flask that thermometer, condensation cocurrent flow pipe and agitator are housed, by a certain amount of polyoxypropyleneglycol (N210) in 110 ℃ of vacuum hydro-extraction 2h, be cooled to 30 ℃ of logical people's nitrogen, add the TDI(n (NCO) of metering/n (OH)=2.2) and a small amount of dibutyl tin laurate, be warmed up to 70～75 ℃ of reactions to-NCO content and be about 3%, with appropriate, a small amount of acetone adjustment system viscosity, with Di-n-Butyl Amine volumetry judgement reaction end.Be cooled to 60 ℃, dimethylol propionic acid (DMPA) is dissolved in a small amount of DMF (DMF), then in system, slowly add DMF solution, in 70 ℃ of reaction 1.5h.Reaction system is cooled to 30 ℃ again, and slowly adds quantitative, minimum potassium hydroxide deionized water solution in system, carry out emulsification under the condition of vigorous stirring, obtain the polyurethane aqueous dispersion of high solids content low-viscosity.
Test group: in the four-hole boiling flask that thermometer, condensation cocurrent flow pipe and agitator are housed, by a certain amount of polyoxypropyleneglycol (N210) in 110 ℃ of vacuum hydro-extraction 2h, be cooled to 30 ℃ of logical people's nitrogen, / n(-OH)=2.2) and a small amount of dibutyl tin laurate the TDI(n(-NCO that adds metering), be warmed up to 70～75 ℃ of reactions to-NCO content and be about 3%, with appropriate, a small amount of acetone adjustment system viscosity, with Di-n-Butyl Amine volumetry judgement reaction end.Be cooled to 60 ℃, hydrophilic chain extender is dissolved in a small amount of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (NMP), then in system, slowly add nmp solution, in 70 ℃ of reaction 1.5h.Reaction system is cooled to 30 ℃ again, and slowly adds quantitative, minimum deionized water in system, carry out emulsification under the condition of vigorous stirring, obtain the polyurethane aqueous dispersion of high solids content low-viscosity.
The relevant nature of table 1 polyurethane aqueous dispersion
Annotate: consider that in experimental group, the molecular weight of chainextender is far longer than DMPA, suitably enlarge the consumption of experimental group chainextender in application.
Claims (9)
1. a sulfonate type hydrophilic chain extender, is characterized in that, molecular structure is:
Wherein, R is C
2～C
3alkyl, m equal 1 or 2, n equal 1 or 2.
2. a kind of sulfonate type hydrophilic chain extender according to claim 1, is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in container, control 0～5 ℃ of reacting liquid temperature, stir the lower mass concentration 10% aniline sulfonic acid sodium salt solution that drips 195.1～297.3 parts of mass fractions, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5～3.0h; Be warming up to 75～85 ℃, drip 10.51～13.32 parts of mass fraction glycol amine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.5, adds rear reaction 2.5～3.0h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 diethanolamine and diisopropanolamine (DIPA).
3. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir the lower mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.5, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
4. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 4-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 80～85 ℃, drip 13.32 parts of mass fraction diisopropanolamine (DIPA), the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 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 again anhydrous alcohol solution, standing, 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 as follows:
5. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 5-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
。
6. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 5-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
7. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 4-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.5～8.0, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
。
8. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir the lower mass concentration 10% Sodium sulfanilate solution that drips 195.1 parts of mass fractions, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 2.5h; Be warming up to 75～80 ℃, drip 13.32 parts of mass fraction diisopropanolamine (DIPA), the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.0～7.5, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
9. according to claim 1 and 2 described a kind of sulfonate type hydrophilic chain extenders, it is characterized in that, the preparation method comprises the following steps:
Add 18.45 parts of mass fraction cyanuric chlorides and 30 portions of mass fraction frozen water in four-hole boiling flask, control 0～5 ℃ of reacting liquid temperature, stir lower mass concentration 10% aniline-2 that drips 297.3 parts of mass fractions, 4-sodium disulfonate solution, NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH6.0～7.0, add rear reaction 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 by mass concentration 10%, make it to be stabilized in pH6.0～7.0, adds rear reaction 3.0h; Be warming up to 75～80 ℃, drip 10.51 parts of mass fraction diethanolamine, the NaOH solution regulation system potential of hydrogen by mass concentration 10%, make it to be stabilized in pH7.0～7.5, adds rear reaction 2.5h, and reaction finishes; Mixture is cooled to room temperature, 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 again anhydrous alcohol solution, standing, 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 as follows:
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