CN109553746A - A kind of preparation method of four sulfydryls silsesquioxane modified aqueous polyurethane color fixing agent - Google Patents
A kind of preparation method of four sulfydryls silsesquioxane modified aqueous polyurethane color fixing agent Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of preparation methods with four sulfydryl silsesquioxane modified aqueous polyurethanes, it include: that oligomer polyol and diisocyanate hybrid reaction are first obtained into performed polymer, then the molecular weight that hydrophilic chain extender reaction further increases performed polymer is added, add homemade four sulfydryls silsesquioxane, the degree of cross linking of increase system, it is eventually adding neutralizer, reaction terminates to add water and stir emulsification, obtains four sulfydryl silsesquioxane modified aqueous polyurethane emulsions.The use of four sulfydryl silsesquioxanes in the present invention introduces cagelike structure into system, it makes aqueous polyurethane possess finer and close network distribution as crosslinking points, the polyaminoester emulsion be used as color fixing agent using when more effectively dyestuff can be wrapped up, fixing property is improved, and the stability of emulsion system is good.
Description
Technical field
The present invention relates to color fixing agent technical fields, and in particular to a kind of four sulfydryl silsesquioxane modified aqueous polyurethanes are solid
The preparation method of toner.
Background technique
Water-borne polyurethane color fixing agent is paid close attention to by people in recent years, have many advantages, such as it is safe and non-toxic, pollution-free, remove fixation
It can also carry out some additional surface propertys to webbing outside, the molecular weight of polyurethane molecular is larger, and has cross-linked network shape
Structure can cover dyestuff and coat the water soluble group of dyestuff, dyestuff is bonded and closed in the form of transparent lamina,
Washing will greatly improve, and colour fixation is applicable not only to water-soluble dye, also have good effect to disperse dyes etc.
Fruit.
But simple aqueous polyurethane have the shortcomings that it is more, as film forming is poor, water resistance poor to the adhesion of fabric
Difference, thermal stability are poor, arrange after fabric feeling it is bad etc., therefore the comprehensive performance of raising water-borne polyurethane color fixing agent has become
Current research hotspot.
China Patent Publication No. CN105113255A describes a kind of preparation method of organic silicon modified polyurethane fixation, should
Method introduces polysiloxanes segment into polyurethane molecular, suitably to be promoted the feel of fabric after arrangement.China Patent Publication No.
CN101824135A reports the preparation and application of a kind of terminated-type cation water-borne polyurethane color fixing agent, and this method passes through poly- ammonia
Ester pre-polymerization, blocking agent, acid neutralize, and ion reaction is made target product, passes through the method reserve part of closing activity group
Point active group enables it to discharge active group when high temperature bakes to react with fabric, raising polyurethane to the adhesion of fabric,
But the presence of active group will affect emulsion intercalation method especially thermal stability.
Chinese patent (CN108034349A) discloses a kind of eight modified bi-component aqueous polyurethane of nitro silsesquioxane
The preparation method of lotion is modified aqueous polyurethane using eight nitro silsesquioxanes, it is water-fast to improve aqueous polyurethane
Property, the transparency and mechanical property;Chinese patent (CN102827340A) discloses ladder-like polysiloxane containing amino to poly-
Urethane is modified, and improves the hardness and heat resistance of polyurethane;((" novel polysilsesquioxane (POSS) modified water such as Zhang Qunchao
Property polyurethane research ", " 2013 aqueous polyurethane industry annual meetings and the 11st water paint seminar ") propose a kind of N mono-
The method of one aminopropyl polysilsesquioxane POSS modified aqueous polyurethane of butyl, can be improved heat resistance, the mechanics of polyurethane
Performance and water contact angle.But as aqueous polyurethane emulsion as color fixing agent commonly used in the art, how to aqueous polyurethane
It is modified, improves the colour fixation of color fixing agent, in the prior art not good solution.Based on existing in the prior art
Above-mentioned deficiency, the invention discovery can be significantly improved solid by the silicone-modified water-borne polyurethane color fixing agent of four sulfydryls
Color effect.Although disclosing (" poly- times of sulfydryl of hydrosulphonyl functionalized silsesquioxane preparation method, such as Yuan Gang etc. in the prior art
The synthesis of half siloxanes influence factor ", Yuan Gang etc., " thermosetting resin ", the 4th phase of volume 30) and " hydrosulphonyl functionalized times of Zhang Lei etc.
The synthesis and characterization of half siloxanes " " Beijing University of Chemical Technology's journal (natural science edition ", the 6th phase of volume 36) it all discloses and prepares mercapto
Base functionalized silesquioxanes, but the prior art is not any to be modified polyurethane about using sulfydryl silsesquioxane
To improve the report of the effect of polyurethane color fixing agent.
Summary of the invention
It is an object of the invention to improve the comprehensive performance of water-borne polyurethane color fixing agent, four sulfydryl siloxanes of one kind are provided and are changed
Property water-borne polyurethane color fixing agent preparation method, using color fixing agent made from this method be applied to fabric fixation treatment, can
Effectively improve fabric dry and wet colorfastness to rubbing, and the excellent in stability of polyaminoester emulsion.
In order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
A kind of preparation of four sulfydryls silsesquioxane modified water-soluble color fixing agent, which is characterized in that four sulfydryl sesquialters are first made
Then siloxanes uses four sulfydryls silsesquioxane obtained to make as crosslinking additives in the synthesis process of aqueous polyurethane
It is modified with to polyurethane, the specific steps are as follows:
Step 1, the preparation of four sulfydryl silsesquioxanes: by 3-mercaptopropyi trimethoxy silane and octyl triethoxy
Silane is added according to a certain percentage in the flask equipped with magnetic agitation and condenser, while a certain amount of concentrated hydrochloric acid and first is added
Mixture is reacted time enough at a certain temperature under stiring to ensure to complete hydrosilylation by alcohol, and then cooling, is removed
Methanol solvate is removed, crude product is washed with cold methanol repeatedly removes extra oligomeric silsesquioxane, and vacuum drying obtains viscous fluid
Four sulfydryl silsesquioxane of body;
Step 2, the preparation of Waterborne Polyurethane Prepolymer: by oligomer polyol and diisocyanate by R value 1.5~2
Ratio uniform stirring in the solvent of the two gross mass 40~50% mixes, and reacts 2~3 hours at 60~70 DEG C, wherein R value
Refer to the molar ratio of isocyano-NCO and the hydroxyl-OH in polyvalent alcohol.Then polyvalent alcohol and the total matter of diisocyanate are added
The hydrophilic chain extender of amount 3~4% is warming up to 70~75 DEG C, reacts 1~1.5 hour, obtains Waterborne Polyurethane Prepolymer;
The preparation of four sulfydryl silsesquioxane modified aqueous polyurethanes: step 3 is put into hydrotropism's base polyurethane prepolymer for use as
More sulfydryl times siloxanes of polyvalent alcohol, diisocyanate and chain extender gross mass 0.5~1%, react 0.5 at 70~75 DEG C
~1 hour, 30~40 DEG C are cooled to, neutralizer is added and reacts half an hour, is finally down to room temperature and adds water and stirs emulsification, obtain four mercaptos
Base silsesquioxane modified aqueous polyurethane emulsion.
Further, in step 1, mole of the 3- mercaptopropyi trimethyl silane and octyltri-ethoxysilane
Than being 1: 1;The volume ratio of the oligomeric silsesquioxane and concentrated hydrochloric acid, methanol is 10~20: 20~40: 240~480;Institute
The temperature that is stirred to react stated is 80~90 DEG C, and the time that is stirred to react is 36~60 hours.
Further, in step 1, the structural formula of the four sulfydryls silsesquioxane are as follows:
R1It indicates:
R2It indicates:
Further, in step 2, the oligomer polyol is selected from polyoxyethylene glycol, polypropylene oxide binary
Alcohol, polytetrahydrofuran dihydric alcohol, polypropylene oxide triol, polyethylene glycol adipate glycol, polyhexamethylene adipate glycol,
One or both of poly- phthalic acid hexylene glycol ester and two or more blends.
Further, in step 2, the diisocyanate is selected from toluene di-isocyanate(TDI), isophorone diisocyanate
One or both of ester, '-diphenylmethane diisocyanate and two or more blends.
Further, in step 2, the solvent is in 1-Methyl-2-Pyrrolidone, N, N- dimethylformamide butanone
Any one;The hydrophilic chain extender is selected from dihydromethyl propionic acid, 1,2-PD -3- sodium sulfonate, N methyldiethanol amine
One of.
Further, in step 3, the neutralizer is in triethylamine, triethanolamine, N, N- dimethylethanolamine
It is a kind of.
The beneficial effects of the present invention are:
The more sulfydryl silsesquioxanes of cage modle are introduced into react as the crosslinking points in polyurethane molecular, sulfydryl and isocyano,
So that polyurethane molecular has finer and close network distribution, preferably dyestuff can be wrapped up, and improve polyurethane
Film is to fabric to adhesion, to be promoted after fixation treatment, fabric is to dry and wet colorfastness to rubbing, simultaneously because the more sulfydryls of cage modle
Hydrogenbond effect between the bulk effect and its sulfydryl and hydrone of silsesquioxane, so that more sulfydryl silsesquioxanes
The modified polyaminoester emulsion of alkane has better suspendability, does not settle within 24 hours, use that can be more permanent.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit the scope of the invention.Under the premise of without departing substantially from technical solution of the invention, the present invention is made
Those of ordinary skill in the art's any change easy to accomplish fall within scope of the presently claimed invention.
Embodiment 1
(four sulfydryl silsesquioxanes account for polyvalent alcohol, two different for the synthesis of four sulfydryl silsesquioxane modified aqueous polyurethanes
The 0.5% of cyanate and chain extender gross mass)
The preparation of (1) four sulfydryl silsesquioxane: by 19.6g3- mercaptopropyi trimethoxy silane, (double peaches are fine in Guangzhou
Chemical Co., Ltd.) and 27.64g octyltri-ethoxysilane (Suzhou Xi Suo new material Co., Ltd) be added be equipped with magnetic agitation
In the flask of condenser, while 100ml concentrated hydrochloric acid and 1200ml methanol is added.Mixture is reacted at 90 DEG C under stiring
It is 36 hours, then cooling, methanol solvate is removed, crude product is washed with cold methanol and repeatedly removes extra oligomeric silsesquioxane,
Vacuum drying obtains four sulfydryl silsesquioxane of thick liquid.
The synthesis of (2) four sulfydryl silsesquioxane modified aqueous polyurethanes: 100g polyethylene glycol is added into four-hole boiling flask
1000, toluene di-isocyanate(TDI) 31.32g, 1-Methyl-2-Pyrrolidone 52.5g react 2h at 70 DEG C, then heat to 75
DEG C, 3.94g dihydromethyl propionic acid is added, reacts 1h, adds tetra- sulfydryl silsesquioxane of 0.68g, the reaction was continued 1h is cooled to
40 DEG C, triethylamine 3g is added, neutralization reaction half an hour is slowly added to 85.5g water, stirring while adding to obtain four sulfydryl silsesquioxanes
Alkane modified aqueous polyurethane emulsion.
Embodiment 2
(four sulfydryl silsesquioxanes account for polyvalent alcohol, two different for the synthesis of four sulfydryl silsesquioxane modified aqueous polyurethanes
The 0.8% of cyanate and chain extender gross mass)
The preparation of (1) four sulfydryl silsesquioxane: by 19.6g3- mercaptopropyi trimethoxy silane and 27.64g octyl three
Ethoxysilane is added in the flask equipped with magnetic agitation and condenser, while 100ml concentrated hydrochloric acid and 1200ml methanol is added.?
Mixture is reacted 36 hours at 90 DEG C under stirring, it is then cooling, methanol solvate is removed, crude product is washed repeatedly with cold methanol
Extra oligomeric silsesquioxane is removed, vacuum drying obtains four sulfydryl silsesquioxane of thick liquid.
The synthesis of (2) four sulfydryl silsesquioxane modified aqueous polyurethanes: 100g polyethylene glycol is added into four-hole boiling flask
1000, toluene di-isocyanate(TDI) 31.32g, 1-Methyl-2-Pyrrolidone 52.5g react 2h at 70 DEG C, then heat to 75
DEG C, 3.94g dihydromethyl propionic acid is added, reacts 1h, adds tetra- sulfydryl silsesquioxane of 1.08g, the reaction was continued 1h is cooled to
40 DEG C, triethylamine 3g is added, neutralization reaction half an hour is slowly added to 85.5g water, stirring while adding to obtain four sulfydryl silsesquioxanes
Alkane modified aqueous polyurethane emulsion.
Embodiment 3
(four sulfydryl silsesquioxanes account for polyvalent alcohol, two different for the synthesis of four sulfydryl silsesquioxane modified aqueous polyurethanes
The 1% of cyanate and chain extender gross mass)
The preparation of (1) four sulfydryl silsesquioxane: by 19.6g3- mercaptopropyi trimethoxy silane and 27.64g octyl three
Ethoxysilane is added in the flask equipped with magnetic agitation and condenser, while 100ml concentrated hydrochloric acid and 1200ml methanol is added.?
Mixture is reacted 36 hours at 90 DEG C under stirring, it is then cooling, methanol solvate is removed, crude product is washed repeatedly with cold methanol
Extra oligomeric silsesquioxane is removed, vacuum drying obtains four sulfydryl silsesquioxane of thick liquid.
The synthesis of (2) four sulfydryl silsesquioxane modified aqueous polyurethanes: 100g polyethylene glycol is added into four-hole boiling flask
1000, toluene di-isocyanate(TDI) 31.32g, 1-Methyl-2-Pyrrolidone 52.5g react 2h at 70 DEG C, then heat to 75
DEG C, 3.94g dihydromethyl propionic acid is added, reacts 1h, adds tetra- sulfydryl silsesquioxane of 1.38g, the reaction was continued 1h is cooled to
40 DEG C, triethylamine 3g is added, neutralization reaction half an hour is slowly added to 85.5g water, stirring while adding to obtain four sulfydryl silsesquioxanes
Alkane modified aqueous polyurethane emulsion.
Comparative example 1
The synthesis of unmodified aqueous polyurethane:
100g cetomacrogol 1000 (the emerging milky way Chemical Co., Ltd. in Hubei) is added into four-hole boiling flask, toluene diisocynate
Ester 31.32g (Nanjing is along safe Chemical Co., Ltd.), 1-Methyl-2-Pyrrolidone 52.5g (Weifang Hai Meng Chemical Co., Ltd.),
2h is reacted at 70 DEG C, then heats to 75 DEG C, is added 3.94g dihydromethyl propionic acid (Guangzhou Xin Putai Chemical Co., Ltd.),
1h is reacted, is cooled to 40 DEG C, triethylamine 3g (the Nantong same Chemical Co., Ltd. of benefit) is added, neutralization reaction half an hour, is slowly added to
85.5g water, it is stirring while adding to obtain aqueous polyurethane emulsion.
Comparative example 2
According to the preparation method in the embodiment 1 of CN106977688A, four sulfydryl silsesquioxanes in step 1 are replaced
For methacryloxypropyl silsesquioxane (MASSQ).
Methacryloxypropyl silsesquioxane (MASSQ), synthesis step is as follows:
1) in the three-necked flask of a 100mL, 40.0g (0.161mol) 3- methacryloxypropyl front three is weighed
Oxysilane (MAPTMS) then installs thermometer, mechanical stirring and constant pressure addition on three bottlenecks of three-necked flask respectively
Funnel;In addition, successively weighing the dilute hydrochloric acid of the 0.1mol/L of 8.792g in the beaker of another 50mL, (amount of the substance of water is
It 0.485mol) with 14.8g ethyl alcohol, is stirred evenly with glass bar, obtains colourless reactant solution, be then transferred to constant pressure addition leakage
In bucket;At this point, the molar ratio of water and MAPTMS are 3: 1;
2) under conditions of room temperature and mechanical stirring, start constant pressure funnel dropwise reaction object solution into MAPTMS,
Reactant solution is added dropwise in 30 minutes completely in control rate of addition;After dripping off, constant pressure funnel is changed into reflux rapidly
Condenser pipe simultaneously keeps mechanical stirring, and reaction mixture is heated to 60 DEG C, and maintains 4 hours at this temperature, obtains colourless solution;
In the synthesis step, the solution of water and hydrochloric acid, ethyl alcohol is instilled into 3- methacryloxypropyl trimethoxy
In silane (MAPTMS), hydrolysis, acid as catalyst occurs.As the silicone hydroxyl that hydrolysis occurs increases, condensation reaction is also same
Shi Fasheng.The step is an apparent exothermic process, for control reaction rate, prevents local reaction too fast, reactant need to delay
It is slow to be added dropwise.
3) colourless solution obtained by step 2) is poured into a 100mL round-bottomed flask, depressurizes rotary evaporation, heating water bath is extremely
80 DEG C, vacuum degree reaches 0.095MPa, and keeps 4 hours at this temperature and pressure, thus by volatility in colourless solution
Alcohols and water remove, finally obtain colorless and transparent grease, as the first intermediate methacryloxypropyl silicon times
Half oxygen alkane (MASSQ) is labeled as sample MASSQ-1.
Comparative example 3
It is same as Example 1, in addition to four sulfydryl silsesquioxanes in step 1 are replaced with eight aminophenyl silsesquioxanes
Alkane (is prepared) according to the embodiment 1 of CN106832387A.
The obtained product of above-mentioned comparative example and embodiment and commercially available water-borne polyurethane color fixing agent are done into fixation experiment and cream
Liquid stability test.Stability test method: being added 100ml sample, turn upside down graduated cylinder 10 times in the graduated cylinder of 100ml, and every time 2
Second, graduated cylinder stands 24 hours in 30 DEG C of water-baths, and the cream analysis object amount of record lotion bottom records volume.Test result is as follows:
The four same commercial polyurethanes of sulfydryl silsesquioxane modified aqueous polyurethane color fixing agent synthesized as can be seen from the above table
Wet friction fastness improving agent comparison, dry fastness promote 1~1.5 grade, and fastness to wet rubbing can promote 1~2 grade, and effect has obviously
It improves;Compared with silsesquioxane common in other patents, dry fastness promotes 1~1.5 grade, and fastness to wet rubbing can be promoted
1~1.5 grade, stability of emulsion is more preferable, does not settle for 24 hours.
Certainly, above is representative instance of the invention, and in addition to this, the present invention can also have other a variety of specific implementations
Mode, all technical solutions formed using equivalent substitution or equivalent transformation, is all fallen within the scope of protection of present invention.
Claims (7)
1. a kind of preparation method of four sulfydryl silsesquioxane modified water-soluble color fixing agent, which is characterized in that four sulfydryls times are first made
Then half siloxanes uses four sulfydryls silsesquioxane obtained as crosslinking additives in the synthesis process of aqueous polyurethane
It is modified using to polyurethane, the specific steps are as follows:
Step 1, the preparation of four sulfydryl silsesquioxanes: by 3-mercaptopropyi trimethoxy silane and octyltri-ethoxysilane
It is added in the flask equipped with magnetic agitation and condenser according to a certain percentage, while a certain amount of concentrated hydrochloric acid and methanol is added,
Mixture is reacted to time enough at a certain temperature under stiring to ensure to complete hydrosilylation, then cooling removes
Methanol solvate, crude product is washed with cold methanol repeatedly removes extra oligomeric silsesquioxane, and vacuum drying obtains thick liquid
Four sulfydryl silsesquioxanes;
Step 2, the preparation of Waterborne Polyurethane Prepolymer: by oligomer polyol and diisocyanate in the ratio of R value 1.5~2
Uniform stirring mixes in the solvent of the two gross mass 40~50%, reacts 2~3 hours at 60~70 DEG C, wherein R value refers to different
The molar ratio of hydroxyl-OH in cyanate radical-NCO and polyvalent alcohol, then add polyvalent alcohol and diisocyanate gross mass 3~
4% hydrophilic chain extender is warming up to 70~75 DEG C, reacts 1~1.5 hour, obtains Waterborne Polyurethane Prepolymer;
The preparation of four sulfydryl silsesquioxane modified aqueous polyurethanes: step 3 is put into poly- more in hydrotropism's base polyurethane prepolymer for use as
More sulfydryl times siloxanes of first alcohol, diisocyanate and chain extender gross mass 0.5~1% react 0.5~1 at 70~75 DEG C
Hour, 30~40 DEG C are cooled to, neutralizer is added and reacts half an hour, is finally down to room temperature and adds water and stirs emulsification, obtain four sulfydryls
Silsesquioxane modified aqueous polyurethane emulsion.
2. the preparation method of four sulfydryls silsesquioxane modified water-soluble color fixing agent as described in claim 1, which is characterized in that step
In rapid one, the molar ratio of the 3- mercaptopropyi trimethyl silane and octyltri-ethoxysilane is 1: 1;Described oligomeric times
The volume ratio of half siloxanes and concentrated hydrochloric acid, methanol is 10~20: 20~40: 240~480;The temperature that is stirred to react is 80
~90 DEG C, the time that is stirred to react is 36~60 hours.
3. the preparation method of four sulfydryls silsesquioxane modified water-soluble color fixing agent as described in claim 1, which is characterized in that step
In rapid one, the structural formula of the four sulfydryls silsesquioxane are as follows:
R1It indicates:
R2It indicates:。
4. the preparation method of four sulfydryls silsesquioxane modified water-soluble color fixing agent as described in claim 1, which is characterized in that step
In rapid two, the oligomer polyol is selected from polyoxyethylene glycol, Polyoxypropylene diol, polytetrahydrofuran binary
Alcohol, polypropylene oxide triol, polyethylene glycol adipate glycol, polyhexamethylene adipate glycol, poly- phthalic acid oneself two
One or both of alcohol ester and two or more blends.
5. the preparation method of four sulfydryls silsesquioxane modified water-soluble color fixing agent as described in claim 1, which is characterized in that step
In rapid two, the diisocyanate is selected from toluene di-isocyanate(TDI), isophorone diisocyanate, '-diphenylmethane diisocyanate
One or both of and two or more blends.
6. the preparation method of four sulfydryls silsesquioxane modified water-soluble color fixing agent as described in claim 1, which is characterized in that step
In rapid two, the solvent is selected from 1-Methyl-2-Pyrrolidone, N, any one in N- dimethylformamide butanone;It is described hydrophilic
Chain extender is selected from one of dihydromethyl propionic acid, 1,2-PD -3- sodium sulfonate, N methyldiethanol amine.
7. the preparation method of four sulfydryls silsesquioxane modified water-soluble color fixing agent as described in claim 1, which is characterized in that step
In rapid three, the neutralizer is selected from triethylamine, triethanolamine, N, one of N- dimethylethanolamine.
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