CN109553746B - Preparation method of tetrasulfosilsesquioxane modified waterborne polyurethane color fixing agent - Google Patents
Preparation method of tetrasulfosilsesquioxane modified waterborne polyurethane color fixing agent Download PDFInfo
- Publication number
- CN109553746B CN109553746B CN201811430243.3A CN201811430243A CN109553746B CN 109553746 B CN109553746 B CN 109553746B CN 201811430243 A CN201811430243 A CN 201811430243A CN 109553746 B CN109553746 B CN 109553746B
- Authority
- CN
- China
- Prior art keywords
- tetramercaptosilsesquioxane
- waterborne polyurethane
- preparing
- modified
- fixing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of waterborne polyurethane modified by tetramercaptosilsesquioxane, which comprises the following steps: firstly, mixing oligomer polyol and diisocyanate for reaction to obtain a prepolymer, then adding a hydrophilic chain extender for reaction to further increase the molecular weight of the prepolymer, adding self-made tetrasulfosilsesquioxane to increase the crosslinking degree of the system, finally adding a neutralizer, adding water after the reaction is finished, stirring and emulsifying to obtain the tetrasulfosilsesquioxane modified waterborne polyurethane emulsion. According to the invention, a cage-shaped structure is introduced into the system by using the tetramercaptosilsesquioxane, the tetramercaptosilsesquioxane is used as a crosslinking point, so that the waterborne polyurethane has a more compact network distribution, the polyurethane emulsion can more effectively wrap the dye when being used as a color fixing agent, the color fixing performance is improved, and the stability of the emulsion system is good.
Description
Technical Field
The invention relates to the technical field of color fixing agents, and particularly relates to a preparation method of a tetramercapto silsesquioxane modified waterborne polyurethane color fixing agent.
Background
In recent years, the water-based polyurethane color fixing agent is paid attention to by people, has the advantages of safety, no toxicity, no pollution and the like, can bring some additional surface properties to fabrics besides color fixing, has a large molecular weight of polyurethane molecules, has a cross-linked network structure, can cover dyes and coat water-soluble groups of the dyes, adheres and seals the dyes in a transparent thin layer form, greatly improves the color fastness of washing, and has a good color fixing effect, not only is suitable for the water-soluble dyes, but also has a good effect on disperse dyes and the like.
However, the pure waterborne polyurethane has many defects, such as poor film-forming property, poor adhesion to fabric, poor water resistance, poor thermal stability, poor hand feeling of the finished fabric and the like, so that the improvement of the comprehensive performance of the waterborne polyurethane color fixing agent has become a research hotspot at present.
Chinese patent publication No. CN105113255A describes a preparation method for fixing color of organosilicon modified polyurethane, which introduces polysiloxane chain segments into polyurethane molecules to properly improve the hand feeling of the finished fabric. Chinese patent publication No. CN101824135A reports preparation and application of a blocked cationic waterborne polyurethane color fixing agent, in the method, a target product is prepared through polyurethane prepolymerization, blocking by a blocking agent, acid neutralization and ionization reaction, partial active groups are reserved by a method of blocking the active groups, so that the active groups can be released to react with fabrics when the fabrics are baked at high temperature, the adhesion of polyurethane to the fabrics is improved, but the stability, particularly the thermal stability of emulsion is influenced by the existence of the active groups.
Chinese patent (CN108034349A) discloses a preparation method of octa-nitro silsesquioxane modified two-component waterborne polyurethane emulsion, wherein octa-nitro silsesquioxane is used for modifying waterborne polyurethane, so that the water resistance, transparency and mechanical properties of the waterborne polyurethane are improved; chinese patent (CN102827340A) discloses that amino-containing ladder-shaped polysilsesquioxane modifies polyurethane to improve the hardness and heat resistance of the polyurethane; the present invention relates to a method for modifying waterborne polyurethane with N-butyl-aminopropyl polysilsesquioxane POSS, which can improve the heat resistance, mechanical properties and water contact angle of polyurethane, but is used as a color fixing agent commonly used in the field, how to modify waterborne polyurethane to improve the color fixing effect of the color fixing agent, and the prior art does not have a good solution. Yuangang et al, thermoset resins, vol.30, No. 4) and Leili et al, "Synthesis and characterization of mercapto-functionalized silsesquioxanes," journal of the university of chemical Beijing (Nature sciences edition, vol.36, No. 6), all disclose the preparation of mercapto-functionalized silsesquioxanes, but the prior art does not have any report on the modification of polyurethanes with mercapto-silsesquioxanes to improve the effect of polyurethane fixatives.
Disclosure of Invention
The invention aims to improve the comprehensive performance of the waterborne polyurethane color fixing agent, and provides a preparation method of the waterborne polyurethane color fixing agent modified by the tetrasulfosiloxane.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the preparation method of the waterborne color fixing agent modified by the tetramercaptosilsesquioxane is characterized by comprising the following steps of firstly preparing the tetramercaptosilsesquioxane, and then modifying polyurethane by using the prepared tetramercaptosilsesquioxane as a crosslinking additive in the synthetic process of the waterborne polyurethane:
step one, preparing tetramercaptosilsesquioxane: adding 3-mercaptopropyltrimethoxysilane and octyltriethoxysilane into a flask equipped with a magnetic stirrer and a condenser according to a certain proportion, simultaneously adding a certain amount of concentrated hydrochloric acid and methanol, reacting the mixture at a certain temperature for a sufficient time under stirring to ensure completion of hydrosilylation, then cooling, removing the methanol solvent, washing the crude product with cold methanol for multiple times to remove redundant oligomeric silsesquioxane, and performing vacuum drying to obtain viscous liquid tetramercaptosilsesquioxane;
step two, preparing a waterborne polyurethane prepolymer: uniformly stirring and mixing oligomer polyol and diisocyanate in a solvent with the total mass of 40-50% according to the ratio of the R value of 1.5-2, and reacting at 60-70 ℃ for 2-3 hours, wherein the R value refers to the molar ratio of isocyanate-NCO to hydroxyl-OH in the polyol. Then adding a hydrophilic chain extender accounting for 3-4% of the total mass of the polyol and the diisocyanate, heating to 70-75 ℃, and reacting for 1-1.5 hours to obtain a waterborne polyurethane prepolymer;
step three, preparing the waterborne polyurethane modified by the tetramercaptosilsesquioxane: adding 0.5-1% of multi-mercapto-time siloxane, based on the total mass of the polyol, the diisocyanate and the chain extender, into the waterborne polyurethane prepolymer, reacting at 70-75 ℃ for 0.5-1 hour, cooling to 30-40 ℃, adding a neutralizing agent for reacting for half an hour, cooling to normal temperature, adding water, stirring and emulsifying to obtain the tetra-mercapto-silsesquioxane modified waterborne polyurethane emulsion.
Further, in the first step, the molar ratio of the 3-mercaptopropyltrimethylsilane to the octyltriethoxysilane is 1: 1; the volume ratio of the oligomeric silsesquioxane to concentrated hydrochloric acid and methanol is 10-20: 20-40: 240-480; the stirring reaction temperature is 80-90 ℃, and the stirring reaction time is 36-60 hours.
Further, in the first step, the structural formula of the tetramercaptosilsesquioxane is as follows:
R1represents:
R2represents:
further, in the second step, the oligomer polyol is one or a blend of two or more selected from polyoxyethylene glycol, polyoxypropylene glycol, polytetrahydrofuran glycol, polyoxypropylene triol, polyethylene glycol adipate glycol, polyhexamethylene adipate glycol and polyhexamethylene phthalate.
In the second step, the diisocyanate is selected from one or a blend of two or more of toluene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate.
In the second step, the solvent is selected from any one of 1-methyl-2-pyrrolidone and N, N-dimethyl amide butanone; the hydrophilic chain extender is selected from one of dimethylolpropionic acid, 1, 2-propanediol-3-sodium sulfonate and N-methyldiethanolamine.
Further, in the third step, the neutralizing agent is selected from one of triethylamine, triethanolamine and N, N-dimethylethanolamine.
The invention has the beneficial effects that:
introducing cage type multi-mercapto silsesquioxane as a crosslinking point in a polyurethane molecule, wherein mercapto reacts with isocyanic acid radicals, so that the polyurethane molecule has more compact network distribution, the dye can be better wrapped, and the adhesiveness of a polyurethane film to a fabric is improved, so that the color fastness of the fabric to dry and wet friction after fixation treatment is improved, and meanwhile, because of the space size effect of the cage type multi-mercapto silsesquioxane and the hydrogen bond bonding effect between the mercapto and water molecules, the polyurethane emulsion modified by the multi-mercapto silsesquioxane has better suspension performance, does not settle within 24 hours, and can be used for a longer time.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Any modifications that can be easily made by a person skilled in the art to the present invention without departing from the technical solutions of the present invention will fall within the scope of the claims of the present invention.
Example 1
Synthesis of waterborne polyurethane modified by tetrasulfosilsesquioxane (the weight of the tetrasulfosilsesquioxane accounts for 0.5 percent of the total weight of the polyol, the diisocyanate and the chain extender)
(1) Preparation of Tetramercaptosilsesquioxane: 3-mercaptopropyltrimethoxysilane (Guangzhou Shuangtao Fine chemical Co., Ltd.) and 27.64g octyltriethoxysilane (Suzhou Si Su. The mixture was reacted at 90 ℃ for 36 hours with stirring, followed by cooling, removal of the methanol solvent, washing of the crude product with cold methanol several times to remove excess oligomeric silsesquioxane, and vacuum drying to give viscous liquid tetrasulfosilsesquioxane.
(2) Synthesizing the waterborne polyurethane modified by the tetramercaptosilsesquioxane: 100g of polyethylene glycol 1000, 31.32g of toluene diisocyanate and 52.5g of 1-methyl-2-pyrrolidone are added into a four-neck flask, the mixture is reacted for 2 hours at 70 ℃, then the temperature is raised to 75 ℃, 3.94g of dimethylolpropionic acid is added, the reaction is carried out for 1 hour, 0.68g of tetramercaptosilsesquioxane is added, the reaction is continued for 1 hour, the temperature is lowered to 40 ℃, 3g of triethylamine is added, the neutralization reaction is carried out for half an hour, 85.5g of water is slowly added, and the stirring is carried out while adding, so that the tetramercaptosilsesquioxane modified waterborne polyurethane emulsion is obtained.
Example 2
Synthesis of waterborne polyurethane modified by tetrasulfosilsesquioxane (the weight of the tetrasulfosilsesquioxane accounts for 0.8 percent of the total mass of the polyol, the diisocyanate and the chain extender)
(1) Preparation of Tetramercaptosilsesquioxane: 19.6g of 3-mercaptopropyltrimethoxysilane and 27.64g of octyltriethoxysilane were added to a flask equipped with magnetic stirring and a condenser, while adding 100ml of concentrated hydrochloric acid and 1200ml of methanol. The mixture was reacted at 90 ℃ for 36 hours with stirring, followed by cooling, removal of the methanol solvent, washing of the crude product with cold methanol several times to remove excess oligomeric silsesquioxane, and vacuum drying to give viscous liquid tetrasulfosilsesquioxane.
(2) Synthesizing the waterborne polyurethane modified by the tetramercaptosilsesquioxane: 100g of polyethylene glycol 1000, 31.32g of toluene diisocyanate and 52.5g of 1-methyl-2-pyrrolidone are added into a four-neck flask, the mixture is reacted for 2 hours at 70 ℃, then the temperature is raised to 75 ℃, 3.94g of dimethylolpropionic acid is added, the reaction is carried out for 1 hour, 1.08g of tetramercaptosilsesquioxane is added, the reaction is continued for 1 hour, the temperature is lowered to 40 ℃, 3g of triethylamine is added, the neutralization reaction is carried out for half an hour, 85.5g of water is slowly added, and the stirring is carried out while adding, so that the tetramercaptosilsesquioxane modified waterborne polyurethane emulsion is obtained.
Example 3
Synthesis of waterborne polyurethane modified by tetrasulfosilsesquioxane (the weight of the tetrasulfosilsesquioxane accounts for 1% of the total mass of the polyol, the diisocyanate and the chain extender)
(1) Preparation of Tetramercaptosilsesquioxane: 19.6g of 3-mercaptopropyltrimethoxysilane and 27.64g of octyltriethoxysilane were added to a flask equipped with magnetic stirring and a condenser, while adding 100ml of concentrated hydrochloric acid and 1200ml of methanol. The mixture was reacted at 90 ℃ for 36 hours with stirring, followed by cooling, removal of the methanol solvent, washing of the crude product with cold methanol several times to remove excess oligomeric silsesquioxane, and vacuum drying to give viscous liquid tetrasulfosilsesquioxane.
(2) Synthesizing the waterborne polyurethane modified by the tetramercaptosilsesquioxane: 100g of polyethylene glycol 1000, 31.32g of toluene diisocyanate and 52.5g of 1-methyl-2-pyrrolidone are added into a four-neck flask, the mixture is reacted for 2 hours at 70 ℃, then the temperature is raised to 75 ℃, 3.94g of dimethylolpropionic acid is added, the reaction is carried out for 1 hour, 1.38g of tetramercaptosilsesquioxane is added, the reaction is continued for 1 hour, the temperature is lowered to 40 ℃, 3g of triethylamine is added, the neutralization reaction is carried out for half an hour, 85.5g of water is slowly added, and the stirring is carried out while adding, so that the tetramercaptosilsesquioxane modified waterborne polyurethane emulsion is obtained.
Comparative example 1
Synthesis of unmodified waterborne polyurethane:
100g of polyethylene glycol 1000 (Hubei Xingying river chemical Co., Ltd.), 31.32g of toluene diisocyanate (Nanjing Shuntai chemical Co., Ltd.), 52.5g of 1-methyl-2-pyrrolidone (Weifang Haimai chemical Co., Ltd.) were added into a four-necked flask, and reacted at 70 ℃ for 2 hours, then heated to 75 ℃, 3.94g of dimethylolpropionic acid (Guangzhou Xinpu Tai chemical Co., Ltd.) was added, reacted for 1 hour, cooled to 40 ℃, 3g of triethylamine (Nantong Yiyi chemical Co., Ltd.) was added, and neutralized for half an hour, 85.5g of water was slowly added, and the aqueous polyurethane emulsion was obtained by stirring while adding.
Comparative example 2
According to the preparation method in example 1 of CN106977688A, the tetramercaptosilsesquioxane in step 1 was replaced with Methacryloxypropylsilsesquioxane (MASSQ).
Methacryloxypropylsilsesquioxane (MASSQ) was synthesized by the following steps:
1) in a 100mL three-necked flask, 40.0g (0.161mol) of 3-methacryloxypropyltrimethoxysilane (MAPTMS) was weighed, and then a thermometer, a mechanical stirring and a constant pressure dropping funnel were installed on each of three necks of the three-necked flask; in addition, 8.792g of 0.1mol/L dilute hydrochloric acid (the amount of water substance is 0.485mol) and 14.8g of ethanol were weighed in a 50mL beaker, stirred uniformly with a glass rod to obtain a colorless reaction solution, and then transferred to a constant pressure dropping funnel; at the moment, the molar ratio of water to MAPTMS is 3: 1;
2) under the conditions of room temperature and mechanical stirring, a constant-pressure dropping funnel is started to drop the reactant solution into MAPTMS, and the dropping speed is controlled to ensure that the reactant solution is completely dropped within 30 minutes; after finishing dropping, quickly replacing the constant-pressure dropping funnel with a reflux condenser tube and keeping mechanical stirring, heating the reaction mixture to 60 ℃, and maintaining the temperature for 4 hours to obtain a colorless solution;
in the synthesis step, a solution of water, hydrochloric acid and ethanol is dropped into 3-methacryloxypropyltrimethoxysilane (MAPTMS) to generate hydrolysis reaction, and acid is used as a catalyst. The condensation reaction also occurs simultaneously with the increase of the silicon hydroxyl groups occurring by hydrolysis. The step is an obvious exothermic process, and reactants need to be slowly dripped in order to control the reaction rate and prevent local reaction from being too fast.
3) Pouring the colorless solution obtained in the step 2) into a 100mL round-bottom flask, carrying out reduced pressure rotary evaporation, heating in a water bath to 80 ℃, keeping the vacuum degree at 0.095MPa for 4 hours, and removing volatile alcohols and water in the colorless solution to obtain a colorless and transparent oily substance, namely a first intermediate Methacryloxypropylsilsesquioxane (MASSQ), which is marked as a sample MASSQ-1.
Comparative example 3
Same as example 1 except substituting tetramercaptosilsesquioxane in step 1 with octaaminophenylsilsesquioxane (prepared according to example 1 of CN 106832387A).
And (3) carrying out a color fixing experiment and an emulsion stability test on the products obtained in the comparative examples and the commercially available waterborne polyurethane color fixing agent. The stability test method comprises the following steps: 100ml of sample was added to a 100ml graduated cylinder, the cylinder was inverted 10 times 2 seconds each time, the cylinder was left to stand in a water bath at 30 ℃ for 24 hours, the amount of milk product at the bottom of the emulsion was recorded and the volume was recorded. The test results were as follows:
the above table shows that compared with the commercially available polyurethane wet rubbing fastness improving agent, the synthesized tetra-mercapto silsesquioxane modified waterborne polyurethane color fixing agent has the dry rubbing fastness improved by 1-1.5 levels, the wet rubbing fastness can be improved by 1-2 levels, and the effect is obviously improved; compared with the silsesquioxane commonly used in other patents, the dry rubbing fastness is improved by 1-1.5 levels, the wet rubbing fastness can be improved by 1-1.5 levels, the emulsion stability is better, and 24 hours of emulsion does not settle.
The above are only typical examples of the present invention, and besides, the present invention may have other embodiments, and all the technical solutions formed by equivalent substitutions or equivalent changes are within the scope of the present invention as claimed.
Claims (7)
1. A preparation method of a waterborne color fixing agent modified by tetramercaptosilsesquioxane is characterized by comprising the following steps of firstly preparing the tetramercaptosilsesquioxane, and then modifying polyurethane by using the prepared tetramercaptosilsesquioxane as a crosslinking additive in the synthetic process of waterborne polyurethane:
step one, preparing tetramercaptosilsesquioxane: adding 3-mercaptopropyltrimethoxysilane and octyltriethoxysilane into a flask equipped with a magnetic stirrer and a condenser according to a certain proportion, simultaneously adding a certain amount of concentrated hydrochloric acid and methanol, reacting the mixture at a certain temperature for a sufficient time under stirring to ensure completion of hydrosilylation, then cooling, removing the methanol solvent, washing the crude product with cold methanol for multiple times to remove redundant oligomeric silsesquioxane, and performing vacuum drying to obtain viscous liquid tetramercaptosilsesquioxane;
step two, preparing a waterborne polyurethane prepolymer: uniformly stirring and mixing oligomer polyol and diisocyanate in a solvent with the total mass of 40-50% according to the ratio of the R value of 1.5-2, reacting at 60-70 ℃ for 2-3 hours, wherein the R value refers to the molar ratio of isocyanate-NCO to hydroxyl-OH in the oligomer polyol, adding hydrophilic chain extender with the total mass of 3-4% of the oligomer polyol and the diisocyanate, heating to 70-75 ℃, and reacting for 1-1.5 hours to obtain a waterborne polyurethane prepolymer;
step three, preparing the waterborne polyurethane modified by the tetramercaptosilsesquioxane: adding the tetra-mercapto silsesquioxane with the total mass of oligomer polyol, diisocyanate and chain extender of 0.5-1% into the waterborne polyurethane prepolymer, reacting at 70-75 ℃ for 0.5-1 hour, cooling to 30-40 ℃, adding a neutralizer for reacting for half an hour, cooling to normal temperature, adding water, stirring and emulsifying to obtain the tetra-mercapto silsesquioxane modified waterborne polyurethane emulsion.
2. The method for preparing the tetramercaptosilsesquioxane modified aqueous fixing agent of claim 1, wherein in step one, the molar ratio of the 3-mercaptopropyltrimethylsilane to the octyltriethoxysilane is 1: 1; the volume ratio of the oligomeric silsesquioxane to concentrated hydrochloric acid and methanol is 10-20: 20-40: 240-480; the stirring reaction temperature is 80-90 ℃, and the stirring reaction time is 36-60 hours.
3. The method for preparing the waterborne color fixing agent modified by the tetramercaptosilsesquioxane of claim 1, wherein in the first step, the tetramercaptosilsesquioxane has a structural formula:
R1represents:
R2represents:
。
4. the method for preparing the tetramercaptosilsesquioxane modified aqueous color fixative of claim 1, wherein in step two, the oligomer polyol is selected from one or a blend of two or more of polyoxyethylene glycol, polyoxypropylene glycol, polytetrahydrofuran glycol, polyoxypropylene triol, polyethylene adipate glycol, polyhexamethylene adipate glycol, and polyhexamethylene phthalate.
5. The method for preparing the waterborne color fixing agent modified by tetramercaptosilsesquioxane of claim 1, wherein in the second step, the diisocyanate is one or a blend of two or more of toluene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate.
6. The method for preparing the tetramercaptisosilsesquioxane-modified aqueous color fixing agent, as claimed in claim 1, wherein in step two, the solvent is selected from any one of 1-methyl-2-pyrrolidone and N, N-dimethylamide butanone; the hydrophilic chain extender is selected from one of dimethylolpropionic acid, 1, 2-propanediol-3-sodium sulfonate and N-methyldiethanolamine.
7. The method for preparing the waterborne color fixing agent modified by tetramercaptosilsesquioxane of claim 1, wherein in step three, the neutralizing agent is one selected from triethylamine, triethanolamine and N, N-dimethylethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811430243.3A CN109553746B (en) | 2018-11-27 | 2018-11-27 | Preparation method of tetrasulfosilsesquioxane modified waterborne polyurethane color fixing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811430243.3A CN109553746B (en) | 2018-11-27 | 2018-11-27 | Preparation method of tetrasulfosilsesquioxane modified waterborne polyurethane color fixing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109553746A CN109553746A (en) | 2019-04-02 |
| CN109553746B true CN109553746B (en) | 2020-12-11 |
Family
ID=65867459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811430243.3A Active CN109553746B (en) | 2018-11-27 | 2018-11-27 | Preparation method of tetrasulfosilsesquioxane modified waterborne polyurethane color fixing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109553746B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255624A (en) * | 2012-02-10 | 2013-08-21 | 恒源祥（集团）有限公司 | Treatment technology for POSS containing fabric |
| CN103467693A (en) * | 2013-09-25 | 2013-12-25 | 江苏华夏制漆科技有限公司 | Preparation method of waterborne polyurethane with excellent freeze-thawing stability |
| CN106832387A (en) * | 2017-01-09 | 2017-06-13 | 淮阴工学院 | A kind of obdurability polymer/caged silsesquioxane hybrid aerogel and its preparation method and application |
-
2018
- 2018-11-27 CN CN201811430243.3A patent/CN109553746B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255624A (en) * | 2012-02-10 | 2013-08-21 | 恒源祥（集团）有限公司 | Treatment technology for POSS containing fabric |
| CN103467693A (en) * | 2013-09-25 | 2013-12-25 | 江苏华夏制漆科技有限公司 | Preparation method of waterborne polyurethane with excellent freeze-thawing stability |
| CN106832387A (en) * | 2017-01-09 | 2017-06-13 | 淮阴工学院 | A kind of obdurability polymer/caged silsesquioxane hybrid aerogel and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| "POSS化学改性聚氨酯的研究进展";赵欣 等;《当代化工》;20180728;第47卷(第7期);1481-1484 * |
| "Synthesis of waterborne polyurethane containing alkoxysilane side groups: Study on spacer linkages";Qi Li 等;《Journal of Applied Polymer Science》;20180920;1-10 * |
| "八氨丙基POSS的合成及棉织物的阻燃整理";范宝养 等;《印染》;20160915(第18期);37-45 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109553746A (en) | 2019-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021109371A1 (en) | Method for preparing polyether modified polyorganosiloxane | |
| Naghash et al. | RETRACTED: Synthesis of a silicone containing allylic monomer and its uses in the waterborne polyurethane/vinyl acetate–acrylic hybrid emulsion copolymers | |
| CN106049069B (en) | One kind has branched structure free-floride fabric water repellent agent and preparation method thereof | |
| CN107266648A (en) | A kind of waterborne polyurethane resin from delustring and preparation method thereof | |
| BRPI1107157B1 (en) | POLYSILOXANES WITH GROUPS CONTAINING NITROGEN, ITS PREPARATION PROCESS, COMPOSITIONS AND ITS USE | |
| WO2020062970A1 (en) | Organosilicon modified polyether polyol as well as preparation method therefor and application thereof | |
| CN110105535A (en) | A kind of preparation method of silane coupling agent graft modified aqueous polyurethane | |
| CN107915820A (en) | The preparation method of polyurethane-modified organosilicon | |
| CN104558494A (en) | Highly moisture permeable modified polyurethane and preparation method thereof | |
| CN103484008A (en) | Organic silicon modified water-based polyurethane paint and preparation method | |
| CN110156997A (en) | It is a kind of can moisture solidification organic silicon block copolymer and preparation method thereof | |
| Ge et al. | Synthesis of a novel UV crosslinking waterborne siloxane–polyurethane | |
| CN106715120A (en) | Laminated film and method for producing same | |
| CN109880107A (en) | The polysiloxane compound and its preparation and application that polyethers and quaternary ammonium cation are modified | |
| CN115286799A (en) | Triblock polysiloxane quaternary ammonium salt and preparation method thereof | |
| CN102399372B (en) | Method for forming curing laminated film of siloxane resin compound | |
| CN109553746B (en) | Preparation method of tetrasulfosilsesquioxane modified waterborne polyurethane color fixing agent | |
| KR102470706B1 (en) | Method of preparing condensation cross-linked particles | |
| CN107189035B (en) | A kind of preparation method of solvent-free hyperbranched silicone softening agent | |
| CN103937001A (en) | Method for preparing water-dispersible alkyl/polyether amino-silicon resin | |
| WO2015118158A1 (en) | Surface treatment | |
| CN113956434B (en) | Hyperbranched organic amino silicon post-chain extension modified waterborne polyurethane and preparation method thereof | |
| CN114182535B (en) | Organic silicon finishing agent with thermal stability | |
| CN116102706B (en) | Preparation method of organic silicon modified flame-retardant aqueous polyurethane emulsion | |
| Luo et al. | Synthesis and properties of a hydrolysis resistant cationic trisiloxane surfactant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |