CN111072974B - Method for preparing polyether modified polysiloxane - Google Patents
Method for preparing polyether modified polysiloxane Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract
The invention provides a method for preparing polyether modified polysiloxane, which comprises the steps of firstly preparing end azido-terminated polysiloxane and end alkynyl polyether polyol, and then obtaining polyether modified silicone oil with a hyperbranched structure by using a Click Chemistry technology. The organic silicon defoamer prepared by the method has smaller grain diameter, better stability and more excellent defoaming and foam inhibiting performance.
Description
Technical Field
The invention belongs to the technical field of surfactants and preparation thereof, and particularly relates to a method for preparing polyether modified polyorganosiloxane by click chemistry.
Background
The polyether modified polysiloxane is formed by connecting a polyether chain segment and a polysiloxane chain segment through chemical bonds. The hydrophilic polyether chain segment endows the polyether chain segment with water solubility, the hydrophobic polysiloxane chain segment endows the polysiloxane chain segment with low surface tension, a series of polyether modified polyorganosiloxanes with different HLB values can be prepared by changing the proportion of ethylene oxide and propylene oxide in the polyether chain segment, selecting polysiloxane chain segments with different hydrogen contents and adjusting the molar mass or the molar proportion of the polyether chain segment and the polysiloxane chain segment, the polyether modified polyorganosiloxanes have a series of functions of emulsification, wetting, foaming, defoaming, solubilization and the like, and are widely used in the fields of emulsifiers, water-soluble lubricants, polyurethane foam homogenizing agents, silicone defoamers, paint leveling agents, fabric hydrophilicity and the like.
At present, polyether modified polysiloxane has 2 structures of Si-O-C type and Si-C type, wherein the Si-C type is a main variety of the polyether modified polysiloxane, and Si-C type polyether modified silicone oil is prepared by hydrosilylation reaction of Si-H bond of polymethylhydrosiloxane and C ═ C bond of polyether terminal vinyl segment under the catalysis of platinum complex. This conventional method has the following disadvantages: 1) the hydrosilylation reaction product contains products of Markov rules and anti-Markov rules, which is not beneficial to researching the relationship between the performance and the product result; 2) the reaction catalyst metal platinum is expensive and difficult to remove in the purification process, which not only influences the product performance but also limits the application of the reaction catalyst in the fields of biological medicine and the like; 3) the platinum catalytic reaction conditions are harsh, and generally an anhydrous and oxygen-free environment is required; 4) the hydrosilation reaction belongs to a strong exothermic reaction, the temperature is not easy to control in industrial production, the heat preservation temperature is higher, and the energy consumption cost is increased. Therefore, it is imperative to find a new method for atom economy, green environmental protection to replace the traditional hydrosilation reaction. The common branched chain type and crosslinking type polyether modified silicone oil prepared by the traditional method has low emulsifying performance, and is difficult to emulsify high-viscosity silicone grease in the defoaming agent industry. Therefore, it is imperative to prepare polyether-modified polyorganosiloxanes with high emulsifying properties.
"click chemistry" was first proposed by Sharpless, the Nobel prize-winning Chemie, 2001, to rapidly and reliably synthesize diverse compounds via small unit molecules via carbon-heteroatom bonds (C-X-C). The representative reaction of click chemistry is copper-catalyzed azide-alkynyl cycloaddition reaction (CuAAC), has the advantages of mild reaction conditions, high conversion rate, low cost, high selectivity, better functional group tolerance and the like, and is widely applied to the fields of biology, medicine and the like at present. CN103342814A aromatic ring derivative diyne monomer and perfluor cyclobutyl azide monomer or perfluor cyclobutyl diyne monomer and aromatic ring derivative azide monomer or perfluor cyclobutyl diyne monomer and perfluor cyclobutyl azide monomer react in solvent to obtain the short fluorocarbon chain coating finishing agent with excellent water and oil repellent effect. CN105330834A utilizes the azido-terminated polycarboxylic acid water reducer to carry out click chemical reaction with alkynyl-terminated benzene-pyridine derivatives, and prepares a polycarboxylic acid mud-resistant water reducer with benzene-pyridine derivatives as side chain end groups. However, there has been no literature report or patent application on the preparation of polyether-modified polyorganosiloxanes by the azide-alkynyl click chemistry method.
Disclosure of Invention
The preparation method comprises the steps of firstly preparing terminal azido-terminated polysiloxane and terminal alkynyl polyether polyol, and then obtaining polyether modified silicone oil with a hyperbranched structure by using a Click Chemistry (Click Chemistry) technology. The organic silicon defoamer prepared by the method has smaller grain diameter, better stability and more excellent defoaming and foam inhibiting performance.
A method for preparing polyether modified polysiloxane comprises the following steps: (1) adding the terminal azido-terminated polysiloxane, the terminal alkynyl polyether polyol and a solvent into a reactor, uniformly dispersing the added reactants, and then adding a catalyst and a ligand at the temperature of 60-120 ℃; (2) reacting the mixture obtained in the step (1) at the temperature of 60-120 ℃ for 0.5-5h under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polysiloxane.
Wherein component A (I): azido terminated polysiloxanes
The preparation method comprises the following steps: 1) dissolving dihydroxytetramethyldisiloxane in 150ml of dichloromethane, and cooling to 0 ℃; continuously adding acyl chloride compound and pyridine, slowly dripping organic amine while stirring, and reacting for 0.5-5.0 h; washing the crude product with saline water, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain the bis-p-methylsulfonyl end-capped tetramethyldisiloxane; 2) adding the tetramethyl disiloxane terminated by the diacyl chloride compound and the siloxane ring body prepared in the step 1) into a dry round-bottom flask, pre-stirring for 10-20min at room temperature, then slowly adding an acid catalyst, and keeping the reaction temperature at 20-120 ℃ for 1-48 h. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined diacyl chloride compound-terminated polyorganosiloxane; 3) dissolving the diacyl chloride compound-terminated polyorganosiloxane prepared in the step 2) into 20ml of tetrahydrofuran, then adding 10ml of dimethylformamide, adding azide salt at room temperature, then heating to 20-120 ℃, and reacting for 1-48 h. And diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain the refined azido-terminated polysiloxane.
The molar ratio of the dihydroxytetramethyldisiloxane to the acyl chloride compound to the organic amine in the step (1) is as follows: 1: 1-5: 0.1-0.5: 5.0-15.0; in the step (2), the molar ratio of the bis-p-methylsulfonyl terminated tetramethyldisiloxane to the siloxane ring body to the acid catalyst is as follows: 1: 10-200: 0.5-5.0; the molar ratio of the bis-p-methylsulfonyl terminated polyorganosiloxane in the step (3) to the azide salt is as follows: 1: 1.0-4.0.
The dihydroxytetramethyldisiloxane is 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane, 1, 3-bis (3-hydroxyisobutyl) tetramethyldisiloxane and 1, 3-bis (3-hydroxypropyl) -1,1,3, 3-tetramethyldisiloxane; the organic solvent is dichloromethane, trichloromethane or tetrachloromethane; the acyl chloride compound is p-methylsulfonyl chloride, 4-toluenesulfonyl chloride, chloromethanesulfonyl chloride, thionyl chloride or trichloromethylsulfonyl chloride; the organic amine is methylamine, ethylamine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, urea, ethanolamine, 1, 3-propylenediamine, tripropylamine, triethanolamine, butylamine, isobutylamine, tert-butylamine, hexylamine and octylamine; the siloxane ring body is one or a combination of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6); the acid catalyst is concentrated sulfuric acid, concentrated nitric acid, solid acid and the like; the azide salt is sodium azide, potassium azide, cesium azide, ammonium azide, calcium azide or copper azide.
A (II): terminal alkynyl polyether polyol:
the preparation method comprises the following steps: weighing a certain amount of polyether polyol, adding the polyether polyol into a dry 250ml high vacuum bottle, weighing 150ml-200ml of dried anhydrous tetrahydrofuran, adding the anhydrous tetrahydrofuran into the high vacuum bottle, and dissolving the polyether polyol at the temperature of 40-60 ℃. And (3) cooling the system to room temperature, adding a specified amount of sodium hydride powder, reacting at room temperature, and stirring for 10-15 h. After the reaction is finished, adding a specified amount of the propyne bromine solution into the reaction system. After the reaction is carried out for 20-25h, unreacted sodium hydride and byproduct salt in the reaction system are removed through a neutral alumina column, the obtained solution is subjected to rotary evaporation to remove tetrahydrofuran, the residual solution is precipitated in ether for multiple times, and the polyether polyol with alkynyl at two ends is obtained through filtration and vacuum drying.
Wherein the polyether polyol is polyethylene glycol (molecular weight 200-; the molar ratio of sodium hydride to polyether polyol is 1:1-4: 1; the molar ratio of the propyne bromide to the polyether polyol is 1:1-4: 1.
A (III): solvent:
the solvent is a polar or non-polar solvent, preferably a polar solvent selected from tetrahydrofuran, toluene, N-dimethylformamide, N-dimethylacetamide, pyridine and triethylamine.
A (IV): catalyst:
the catalyst is a copper-based, iron-based or rhenium-based catalyst.
A (V): ligand:
the ligand is a polydentate ligand containing nitrogen and is selected from N, N, N' -pentamethyldiethylenetriamine, 1, 4, 7, 10, 10-hexamethyltriethylenetetramine and tri (N, N-dimethylaminoethyl) amine, N-hexyl-2-pyridylcarboxamide and tetramethylethylenediamine.
The mol ratio of the azido-terminated polysiloxane to the alkynyl-terminated polyether polyol is 3:2-6: 2; the mass usage of the catalyst is 0.1-5% of the total mass of the azido-terminated polysiloxane and the alkynyl-terminated polyether polyol; the ratio of the molar weight of the ligand to the molar weight of the catalyst is 1: 1-10: 1; the mass ratio of the mass of the solvent to the total mass of the azido-terminated polyorganosiloxane and the alkynyl-terminated polyether polyol is 4.5: 1-9: 1.
the method prepares the polyether modified polysiloxane with regular specific structure under the action of a catalyst at a certain temperature by the number and the positions of polymer chain connecting points of click chemistry, and overcomes the defect that the structure of the traditional polyether modified polysiloxane preparation is difficult to control. The raw material end azido group end capped polyether polyol structure for synthesizing the network structure contains azido groups with functionality not less than 3 and the end alkynyl group polyorganosiloxane structure contains alkynyl groups with functionality not less than 2, so that a compact space network structure can be formed, the compact space network structure can be fully mixed with highly crosslinked organosilicon active substances, and a stable emulsion system can be formed.
Examples of alkynyl-terminated polyether polyols
Example 1
100g of polyethylene glycol (molecular weight 1000) is weighed and added into a dry 250ml high vacuum bottle, 150ml of dried anhydrous tetrahydrofuran is weighed and added into the high vacuum bottle, and the polyethylene glycol (molecular weight 1000) is dissolved at 50 ℃. After the system is cooled to room temperature, 8.88g of sodium hydride powder is added, and the mixture is reacted at the normal temperature and stirred for 10 hours. After the reaction is finished, 8ml of propyne bromine solution is added into the reaction system. After the reaction is carried out for 20 hours, unreacted sodium hydride and byproduct salt in the reaction system are removed by passing through a neutral alumina column, the obtained solution is subjected to rotary evaporation to remove tetrahydrofuran, the residual liquid is precipitated in ether for a plurality of times, and the polyether polyol A (II) -1 with alkynyl at two ends is obtained by filtering and vacuum drying.
Example 2
100g of polyethylene glycol (molecular weight 200) is weighed and added into a dry 250ml high vacuum bottle, 200ml of dried anhydrous tetrahydrofuran is weighed and added into the high vacuum bottle, and the polyethylene glycol (molecular weight 200) is dissolved at 40 ℃. And (3) after the system is cooled to room temperature, adding 24g of sodium hydride powder, reacting at room temperature and stirring for 15 h. After the completion of the reaction, 78ml of a bromopropyne solution was added to the reaction system. After reacting for 25h, removing unreacted sodium hydride and byproduct salt in the reaction system by a neutral alumina column, removing tetrahydrofuran by rotary evaporation of the obtained solution, precipitating the residual liquid in diethyl ether for multiple times, filtering and drying in vacuum to obtain polyether polyol A (II) -2 with alkynyl at two ends. Example 3
100g of polyethylene glycol (molecular weight 2000) is weighed and added into a dry 250ml high vacuum bottle, 180ml of dry anhydrous tetrahydrofuran is weighed and added into the high vacuum bottle, and the polyethylene glycol (molecular weight 2000) is dissolved at the temperature of 60 ℃. And (3) after the system is cooled to room temperature, adding 3.6g of sodium hydride powder, reacting at normal temperature and stirring for 13 hours. After the reaction was completed, 14ml of a solution of propyne bromide was added to the reaction system. After reacting for 21h, removing unreacted sodium hydride and byproduct salt in the reaction system by a neutral alumina column, removing tetrahydrofuran by rotary evaporation of the obtained solution, precipitating the residual liquid in diethyl ether for multiple times, filtering and drying in vacuum to obtain polyether polyol A (II) -3 with alkynyl at two ends.
Example 4
100g of polypropylene glycol (molecular weight 200) was weighed and charged into a dry 250ml high vacuum flask, 190ml of dry anhydrous tetrahydrofuran was weighed and charged into the high vacuum flask, and the polypropylene glycol (molecular weight 200) was dissolved at 40 ℃. And (3) cooling the system to room temperature, adding 48g of sodium hydride powder, reacting at room temperature and stirring for 14 h. After the completion of the reaction, 78ml of a bromopropyne solution was added to the reaction system. After 24 hours of reaction, removing unreacted sodium hydride and byproduct salt in the reaction system through a neutral alumina column, removing tetrahydrofuran by rotary evaporation of the obtained solution, precipitating the residual liquid in diethyl ether for multiple times, filtering and drying in vacuum to obtain polyether polyol A (II) -4 with alkynyl at two ends.
Example 5
100g of polypropylene glycol (molecular weight 1000) was weighed into a dry 250ml high vacuum flask, 170ml of dry anhydrous tetrahydrofuran was weighed into the high vacuum flask, and the polypropylene glycol (molecular weight 1000) was dissolved at 50 ℃. After the system is cooled to room temperature, 2.4g of sodium hydride powder is added, and the mixture is reacted at the normal temperature and stirred for 12 hours. After the reaction was completed, 8ml of a solution of propyne bromide was added to the reaction system. After reacting for 21h, removing unreacted sodium hydride and byproduct salt in the reaction system by a neutral alumina column, removing tetrahydrofuran by rotary evaporation of the obtained solution, precipitating the residual liquid in diethyl ether for multiple times, filtering and drying in vacuum to obtain polyether polyol A (II) -5 with alkynyl at two ends.
Example 6
100g of polypropylene glycol (molecular weight 2000) was weighed into a dry 250ml high vacuum flask, 170ml of dry anhydrous tetrahydrofuran was weighed into the high vacuum flask, and the polypropylene glycol (molecular weight 2000) was dissolved at 60 ℃. After the system is cooled to room temperature, 2.4g of sodium hydride powder is added, and the mixture is reacted at room temperature and stirred for 13 hours. After the reaction was completed, 16ml of a solution of propyne bromide was added to the reaction system. After reacting for 22h, removing unreacted sodium hydride and byproduct salt in the reaction system by a neutral alumina column, removing tetrahydrofuran by rotary evaporation of the obtained solution, precipitating the residual liquid in diethyl ether for multiple times, filtering and drying in vacuum to obtain polyether polyol A (II) -6 with alkynyl at two ends.
Examples of azido-terminated polysiloxanes
Example 1
1) 8.36g of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane was dissolved in 150ml of chloroform and cooled to 0 ℃; continuously adding 8.60g of p-methylsulfonyl chloride and 0.73g of 4-dimethylaminopyridine, slowly dropwise adding 30.3g of triethylamine while stirring, and reacting for 1 h; washing the crude product with saline water, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain the bis-p-methylsulfonyl end-capped tetramethyldisiloxane; 2) 1.45g of bis-p-methylsulfonyl-terminated tetramethyldisiloxane prepared in 1) and 18.78g of D4 were added to a dry round-bottom flask, stirred at room temperature for 10min, and then 0.27g of concentrated sulfuric acid was added slowly, maintaining the reaction temperature at 20 ℃ and the reaction time at 48 h. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined bis-p-methylsulfonyl terminated polysiloxane; 3) 6.07g of bis-p-methylsulfonyl terminated polyorganosiloxane prepared in 2) was dissolved in 20ml of tetrahydrofuran, 10ml of dimethylformamide was added, and 0.13g of sodium azide was added at room temperature for 48 hours while maintaining the reaction temperature at 20 ℃. The crude product is diluted by cyclohexane, extracted, washed by brine, dried by anhydrous sodium sulfate, concentrated and purified to obtain the refined azido-terminated polysiloxane A (I) -1.
Example 2
1) 8.36g of 1, 3-bis (3-hydroxyisobutyl) tetramethyldisiloxane are dissolved in 150ml of dichloromethane and cooled to 0 ℃; continuing to add 11.18g of chloromethanesulfonyl chloride and 1.4g of 2-methylpyridine, slowly dropwise adding 27.49g of ethanolamine while stirring, and reacting for 0.5 h; washing the crude product with brine, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain dichloromethanesulfonyl chloride-terminated tetramethyldisiloxane; 2) 1.69g of bischloromethanesulphonyl chloride-terminated tetramethyldisiloxane prepared in 1) and 12.38 siloxane ring D5 were introduced into a dry round-bottomed flask, stirred at room temperature for 20min, then 0.11g of concentrated nitric acid was added slowly, the reaction temperature was maintained at 100 ℃ and the reaction time was 1 h. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined chloromethane sulfonyl chloride terminated polysiloxane; 3) 4.21g of bischloromethanesulphonyl chloride-terminated polyorganosiloxane prepared in 2) was dissolved in 20ml of tetrahydrofuran, then 10ml of dimethylformamide was added, 0.32g of potassium azide was added at room temperature, and then the temperature was raised to 120 ℃ for 1 hour. Diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain the refined azido-terminated polysiloxane A (I) -2.
Example 3
1) 8.36g of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane are dissolved in 150ml of dichloromethane and cooled to 0 ℃; continuously adding 14.3g of 4-tosyl chloride and 0.32g of 2, 4-lutidine, slowly dropwise adding 21.94g of tripropylamine while stirring, and reacting for 5.0 h; washing the crude product with brine, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain bis 4-tosyl chloride terminated tetramethyldisiloxane; 2) 1.96g of bis 4-tosyl chloride-terminated tetramethyldisiloxane prepared in 1) and 148.60g of siloxane ring body D3 were added to a dry round-bottom flask, stirred at room temperature for 10min, and then 1.64g of concentrated sulfuric acid was slowly added thereto, maintaining the reaction temperature at 120 ℃ and the reaction time at 1 hour. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined bis 4-tosyl chloride terminated polyorganosiloxane; 3) 45.08g of bis 4-tosyl chloride-terminated polyorganosiloxane prepared in 2) was dissolved in 20ml of tetrahydrofuran, and then 10ml of dimethylformamide was added, and 0.35g of cesium azide was added at room temperature, maintaining the temperature at 120 ℃ and reacting for 1 hour. Diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain the refined azido-terminated polysiloxane A (I) -3.
Example 4
1) 8.36g of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane are dissolved in 150ml of dichloromethane and cooled to 0 ℃; continuously adding 3.57 g of thionyl chloride and 0.73g of 2, 4.6-trimethylpyridine, slowly dropwise adding 21.94g of butylamine while stirring, and reacting for 3 hours; washing the crude product with brine, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain the tetramethyl disiloxane terminated by the dichlorosulfoxide; 2) 1.47g of bistrichlorosulfonyl terminated tetramethyldisiloxane prepared in 1) and 75.30g of siloxane ring body D4 were added to a dry round-bottom flask, stirred for 15min at room temperature, and then 0.65g of concentrated sulfuric acid was added slowly, maintaining the reaction temperature at 60 ℃ and the reaction time at 20 h. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined bis-thionyl chloride terminated polyorganosiloxane; 3) 22.99g of the bis thionyl chloride-terminated polyorganosiloxane prepared in 2) were dissolved in 20ml of tetrahydrofuran, then 10ml of dimethylformamide was added, 0.13g of sodium azide was added at room temperature, and then the temperature was raised to 100 ℃ for 15 hours. Diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain the refined azido-terminated polysiloxane A (I) -4.
Example 5
1) 8.36g of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane are dissolved in 150ml of dichloromethane and cooled to 0 ℃; continuously adding 16.34 g of trichloromethylsulfonyl and 0.56g of methylpyridine, slowly dropwise adding 18.03g of ethylenediamine while stirring, and reacting for 2 hours; washing the crude product with saline water, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain bis (trichloromethyl sulfonyl) terminated tetramethyldisiloxane; 2) 2.14g of bistrichloromethylamide-terminated tetramethyldisiloxane prepared in 1) and 18.78g of siloxane ring body D4 were introduced into a dry round-bottomed flask, stirred at room temperature for 18min, and then 0.27g of concentrated sulfuric acid was slowly added thereto, maintaining the reaction temperature at 60 ℃ and the reaction time at 20 h. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined bis (trichloromethyl sulfonyl) terminated polyorganosiloxane; 3) 22.99g of the bistrichloromethylsulfonyl-terminated polyorganosiloxane prepared in 2) were dissolved in 20ml of tetrahydrofuran, 10ml of dimethylformamide was then added, 0.065g of sodium azide was added at room temperature, and the reaction time was 15 hours at 100 ℃. Diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain the refined azido-terminated polysiloxane A (I) -5.
Example 6
1) 8.36g of 1, 3-bis (3-hydroxyisobutyl) tetramethyldisiloxane are dissolved in 150ml of dichloromethane and cooled to 0 ℃; continuously adding 8.6g of p-methylsulfonyl chloride and 0.73g of 4-dimethylaminopyridine, slowly dropwise adding 30.3g of triethylamine while stirring, and reacting for 2 hours; washing the crude product with brine, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain the bis-p-methylsulfonyl chloride terminated tetramethyldisiloxane; 2) 1.45g of bis-p-methylsulfonyl chloride-terminated tetramethyldisiloxane prepared in 1) and 18.78g of siloxane ring body D4 were added to a dry round-bottomed flask, stirred at room temperature for 18min, and then 0.27g of concentrated sulfuric acid was added slowly, maintaining the reaction temperature at 60 ℃ and the reaction time at 20 h. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined bis (trichloromethyl sulfonyl) terminated polyorganosiloxane; 3) 6.07g of bis-p-methylsulfonyl chloride-terminated polyorganosiloxane prepared in 2) was dissolved in 20ml of tetrahydrofuran, 10ml of dimethylformamide was added, 0.13g of sodium azide was added at room temperature, and the reaction time was 15 hours while elevating the temperature to 100 ℃. Diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain the refined azido-terminated polysiloxane A (I) -6.
Example 7
1) 7.51g of 1, 3-bis (3-hydroxypropyl) -1,1,3, 3-tetramethyldisiloxane were dissolved in 150ml of dichloromethane and cooled to 0 ℃; continuously adding 8.6g of p-methylsulfonyl chloride and 0.73g of 4-dimethylaminopyridine, slowly dropwise adding 30.3g of triethylamine while stirring, and reacting for 2 hours; washing the crude product with brine, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain the bis-p-methylsulfonyl chloride terminated tetramethyldisiloxane; 2) 1.36g of bis-p-methylsulfonyl chloride-terminated tetramethyldisiloxane prepared in 1) and 18.78g of siloxane ring body D4 were added to a dry round-bottomed flask, stirred at room temperature for 18min, and then 0.27g of concentrated sulfuric acid was added slowly, maintaining the reaction temperature at 60 ℃ and the reaction time at 20 h. Diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined bis (trichloromethyl sulfonyl) terminated polyorganosiloxane; 3) 6.04g of bis-p-methylsulfonyl chloride-terminated polyorganosiloxane prepared in 2) was dissolved in 20ml of tetrahydrofuran, 10ml of dimethylformamide was then added, 0.13g of sodium azide was added at room temperature, and then the temperature was raised to 100 ℃ for 15 hours. Diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain the refined azido-terminated polysiloxane A (I) -7.
Examples of polyether-modified polyorganosiloxanes
Example 1
(1) 17.88g of azido terminated polysiloxane A (I) -1, 2.09g of alkynyl terminated polyether polyol A (II) -1, 89.87g of toluene solvent were added to the reactor to disperse the added reactants uniformly, and then 0.2g of cuprous bromide catalyst and 0.0014mol of ligand N, N, N' -pentamethyldiethylenetriamine were added at 60 ℃; (2) reacting the mixture obtained in the step (1) at the temperature of 60 ℃ for 0.5h under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polyorganosiloxane B1.
Example 2
(1) 16.14g of azido terminated polysiloxane A (I) -2, 0.49g of alkynyl terminated polyether polyol A (II) -2 and 83.15g of toluene solvent are added into a reactor, after the added reactants are dispersed evenly, 0.017g of cuprous bromide catalyst and 0.00036mol of ligand N, N, N' -pentamethyldiethylenetriamine are added at the temperature of 80 ℃; (2) reacting the mixture obtained in the step (1) for 1.5h at the temperature of 80 ℃ under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polyorganosiloxane B2.
Example 3
(1) 268.92g of azido-terminated polysiloxane A (I) -3, 4.09g of alkynyl-terminated polyether polyol A (II) -3 and 2457.09g of solvent N, N-dimethylformamide are added into a reactor, so that the added reactants are uniformly dispersed, and then 13.66g of catalyst cuprous bromide and 0.954mol of ligand N, N, N' -pentamethyldiethylenetriamine are added at a temperature of 120 ℃; (2) reacting the mixture obtained in the step (1) at the temperature of 120 ℃ for 5h under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polyorganosiloxane B3.
Example 4
(1) 114.38g of azido-terminated polysiloxane A (I) -4, 0.49g of alkynyl polyether polyol A (II) -4 and 918.96g of pyridine solvent are added into a reactor, so that the added reactants are uniformly dispersed, and then 4.59g of catalyst CuI and 0.2169mol of ligand 1,1, 4, 7, 10, 10-hexamethylene triethylene tetramine and tris (N, N-dimethylaminoethyl) amine are added at the temperature of 70 ℃; (2) reacting the mixture obtained in the step (1) at the temperature of 70 ℃ for 2.5 hours under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polyorganosiloxane B4.
Example 5
(1) 27.76g of azido-terminated polysiloxane A (I) -5, 4.09g of alkynyl polyether polyol A (II) -5 and 222.95g of toluene solvent were added to a reactor to uniformly disperse the added reactants, and 0.96g of catalyst CuSO was added at 90 deg.C4And 0.03mol of ligand N-N-hexyl-2 pyridylcarboxamide; (2) reacting the mixture obtained in the step (1) at 90 ℃ for 2h under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polyorganosiloxane B5.
Example 6
(1) 26.82g of azido-terminated polysiloxane A (I) -6, 4.09g of alkynyl polyether polyol A (II) -6 and 247.28g of pyridine solvent are added into a reactor, after the added reactants are uniformly dispersed, 0.93g of catalyst CuI and 0.0392mol of ligand 1,1, 4, 7, 10, 10-hexamethyltriethylenetetramine and tris (N, N-dimethylaminoethyl) amine are added at the temperature of 70 ℃; (2) reacting the mixture obtained in the step (1) at the temperature of 70 ℃ for 2.5 hours under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polyorganosiloxane B6.
Example 7
(1) 29.66g of azido-terminated polysiloxane A (I) -7, 2.09g of alkynyl polyether polyol A (II) -1 and 222.25g of tetrahydrofuran solvent are added into a reactor, so that the added reactants are uniformly dispersed, and then 1.28g of catalyst CuSO is added at the temperature of 90 DEG C4And 0.04mol of ligand N-N-hexyl-2 pyridylcarboxamide; (2) reacting the mixture obtained in the step (1) at 90 ℃ for 2h under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction; (3) and (3) filtering and concentrating the initial product obtained in the step (2) to obtain the polyether modified polyorganosiloxane B7.
Comparative example 1
Reference is made to the preparation of polyether-modified polyorganosiloxane B6 (modified polyorganosiloxane obtained by reacting hydrogen-containing polyorganosiloxane, unsaturated polyether and alpha-olefin) according to the preparation method of patent CN104130879A
Comparative example 2
Reference is made to the preparation of polyether-modified polyorganosiloxane B7 (modified polyorganosiloxane obtained by reacting hydrogen-containing polyorganosiloxane, unsaturated polyether and divinyl-terminated polyorganosiloxane) prepared by the preparation method described in patent CN104130879A
Comparative example 3
Reference is made to the preparation of polyether-modified polyorganosiloxane B8 (obtained by reacting a high-viscosity hydrogen-containing silicone oil with an unsaturated polyether) from patent CN101298027A
Preparation of Silicone emulsion examples
The emulsions prepared using the polyether-modified polyorganosiloxanes of examples 1 to 7 and comparative examples 1 to 3 were prepared as follows:
(1) refer to patent CN104784980B for example 1 method to prepare defoaming composition;
(2) at room temperature, fully mixing 30 parts of defoaming composition, 12 parts of oleic acid polyoxyethylene (20) ether and 18 parts of polyether modified polysiloxane for 20min under stirring, raising the temperature of the system to 80 ℃, keeping the temperature of the system, slowly adding 40 parts of water, increasing the stirring speed to change the water-in-oil emulsion into an oil-in-water emulsion, continuously adding 20 parts of water until the mass concentration of the emulsion is 50%, further emulsifying the crude emulsion through a colloid mill, and finally diluting the crude emulsion to an emulsion S1-S10 with a polyacrylic acid thickener aqueous solution until the solid content is 10%.
Testing of Silicone emulsion stability
The stability of the sample is tested by using a formula/Turbiscan Tower/multiple light scattering stability analyzer, the testing temperature is 40 ℃, the sample dosage is 20g, and the smaller the TSI index in the testing result, the better the sample stability.
Measurement of defoaming and defoaming Properties
The silicone emulsion was added to the liquid laundry detergent in an amount of 0.5% and 50.1g of detergent mixed with the defoamer composition and 10Kg of water were added to a Wangmen tumbler washing machine, the test procedure was a jean procedure, the total machine wash time was 35min and the machine wash temperature was 30 ℃. The window of the washing machine is marked with 0-100% measurement marks which are respectively 0, 25%, 50%, 75% and 100% of the height of the window. "0" is the start, meaning no foam, and "100%" means full foam. Foam height was recorded 35min after machine washing. The larger the value, the higher the foam scale value in the washing machine, the worse the foam inhibition; the lower the foam scale value in the same time, the better the foam inhibition performance of the product.
Claims (6)
1. A method for preparing polyether modified polyorganosiloxane, which is characterized in that the method comprises the following steps:
(1) adding azido-terminated polysiloxane A (I), alkynyl polyether polyol A (II) and solvent A (III) into a reactor, uniformly dispersing the added reactants, and adding catalyst A (IV) and ligand A (V) at the temperature of 60-120 ℃;
(2) reacting the mixture obtained in the step (1) at the temperature of 60-120 ℃ for 0.5-5h under the protection of nitrogen, and obtaining a primary product through alkynyl-azide cycloaddition reaction;
(3) filtering and concentrating the primary product obtained in the step (2) to obtain the polyether modified polysiloxane;
the mole ratio of the azido-terminated polysiloxane A (I) to the alkynyl-terminated polyether polyol A (II) is 3:2-6: 2; the mass of the catalyst A (IV) is 0.1-5% of the total mass of the azido-terminated polysiloxane A (I) and the alkynyl-terminated polyether polyol A (II); the ratio of the molar amount of the ligand A (V) to the molar amount of the catalyst A (IV) is 1: 1-10: 1; the mass ratio of the mass of the solvent A (III) to the total mass of the azido-terminated polysiloxane A (I) and the alkynyl-terminated polyether polyol A (II) is 4.5: 1-9: 1;
the preparation method of the azido-terminated polysiloxane A (I) comprises the following steps of 1) dissolving dihydroxytetramethyldisiloxane in 150ml of organic solvent, and cooling to 0 ℃; continuously adding acyl chloride compound and pyridine, slowly dripping organic amine while stirring, and reacting for 0.5-5.0 h; washing the crude product with saline water, drying the crude product with anhydrous sodium sulfate, concentrating and purifying to obtain the bis-p-methylsulfonyl end-capped tetramethyldisiloxane; 2) adding the bis-p-methylsulfonyl end-capped tetramethyldisiloxane and the siloxane ring body prepared in the step 1) into a dry round-bottom flask, pre-stirring for 10-20min at room temperature, then slowly adding an acid catalyst, and maintaining the reaction temperature at 20-120 ℃ for 1-48 h; diluting the crude product with cyclohexane, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined diacyl chloride compound-terminated polyorganosiloxane; 3) dissolving the diacyl chloride compound-terminated polysiloxane prepared in the step 2) into 20ml of tetrahydrofuran, then adding 10ml of dimethylformamide, adding azide salt at room temperature, then heating to 20-120 ℃, and reacting for 1-48 h; diluting the crude product with cyclohexane, extracting, washing with brine, drying with anhydrous sodium sulfate, concentrating and purifying to obtain refined azido-terminated polysiloxane;
the preparation method of the terminal alkynyl polyether polyol A (II) comprises the steps of weighing a certain amount of polyether polyol, adding the polyether polyol into a dry 250ml high vacuum bottle, weighing 150ml-200ml of anhydrous tetrahydrofuran, adding the anhydrous tetrahydrofuran into the high vacuum bottle, and dissolving the polyether polyol at the temperature of 40-60 ℃; after the system is cooled to room temperature, adding a specified amount of sodium hydride powder, reacting at room temperature and stirring for 10-15 h; after the reaction is finished, adding a specified amount of propargyl bromide solution into a reaction system, after the reaction is carried out for 20-25h, removing unreacted sodium hydride and byproduct salt in the reaction system through a neutral alumina column, removing tetrahydrofuran by rotary evaporation of the obtained solution, precipitating the residual solution in diethyl ether for multiple times, filtering and vacuum-drying to obtain alkynyl-terminated polyether polyol with alkynyl at two ends;
the solvent A (III) is a polar solvent selected from tetrahydrofuran, toluene, N-dimethylformamide, N-dimethylacetamide, pyridine and triethylamine.
2. The method of claim 1, wherein the mole ratio of the bishydroxy tetramethyldisiloxane, the acid chloride compound, the pyridine and the organic amine in step (1) in the preparation method of the azido terminated polysiloxane A (I) is: 1: 1-5: 0.1-0.5: 5.0-15.0; in the step (2), the molar ratio of the bis-p-methylsulfonyl terminated tetramethyldisiloxane to the siloxane ring body to the acid catalyst is as follows: 1: 10-200: 0.5-5.0; the molar ratio of the bis-p-methylsulfonyl terminated polyorganosiloxane in the step (3) to the azide salt is as follows: 1: 1.0-4.0.
3. The method of claim 1, wherein the bis-hydroxy-tetramethyldisiloxane is 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane, 1, 3-bis (3-hydroxyisobutyl) tetramethyldisiloxane, 1, 3-bis (3-hydroxypropyl) -1,1,3, 3-tetramethyldisiloxane; the organic solvent is dichloromethane, trichloromethane or tetrachloromethane; the acyl chloride compound is p-methylsulfonyl chloride, chloromethanesulfonyl chloride, thionyl chloride or trichloromethylsulfonyl chloride; the organic amine is methylamine, ethylamine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, urea, ethanolamine, 1, 3-propylenediamine, tripropylamine, triethanolamine, butylamine, isobutylamine, tert-butylamine, hexylamine and octylamine; the siloxane ring body is one or a combination of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6); the acid catalyst is concentrated sulfuric acid, concentrated nitric acid and solid acid; the azide salt is sodium azide, potassium azide, cesium azide, ammonium azide, calcium azide or copper azide.
4. The method as claimed in claim 1, wherein the preparation method of the terminal alkynyl polyether polyol A (II) comprises the steps of preparing the terminal alkynyl polyether polyol A (II), wherein the polyether polyol is polyethylene glycol with molecular weight of 200-; the molar ratio of sodium hydride to polyether polyol is 1:1-4: 1; the molar ratio of the propyne bromide to the polyether polyol is 1:1-4: 1.
5. The method of claim 1, wherein the catalyst A (IV) is a copper, iron or rhenium catalyst.
6. The method of claim 1, wherein the ligand A (V) is a nitrogen-containing polydentate ligand selected from the group consisting of N, N, N', N ", N" -pentamethyldiethylenetriamine, 1, 4, 7, 10, 10-hexamethyltriethylenetetramine, tris (N, N-dimethylaminoethyl) amine, N-N-hexyl-2-pyridylcarboxamide, and tetramethylethylenediamine.
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| CN111841438B (en) * | 2020-07-23 | 2022-02-22 | 吉林大学 | Solubilizing material for restoring PCE pollution in underground environment and preparation method thereof |
| CN113024818B (en) * | 2021-03-01 | 2022-07-08 | 浙江润禾有机硅新材料有限公司 | Preparation method of high-purity low-byproduct polyether modified siloxane |
| CN113603891A (en) * | 2021-08-31 | 2021-11-05 | 李先明 | Preparation method of nonionic polyether modified tetrasiloxane surfactant |
| CN113856247B (en) * | 2021-10-22 | 2022-08-30 | 西安热工研究院有限公司 | Method for adding fire-resistant oil defoaming agent |
| CN114015005B (en) * | 2021-11-19 | 2023-04-18 | 合肥安利聚氨酯新材料有限公司 | Organic silicon leveling assistant for polyurethane and preparation method thereof |
| CN114477788B (en) * | 2022-01-27 | 2023-08-22 | 常州大学 | Simple preparation method of super-smooth surface material with multilayer porous structure and prepared super-smooth surface material |
| CN114805818B (en) * | 2022-06-21 | 2023-04-07 | 南京瑞思化学技术有限公司 | Preparation method of organic silicon emulsifier |
| CN115322382B (en) * | 2022-08-08 | 2023-05-12 | 佛山市南海大田化学有限公司 | Organosilicon emulsifier with special structure and preparation method and application thereof |
| CN115353629B (en) * | 2022-09-27 | 2024-01-23 | 唐山三友硅业股份有限公司 | Process for preparing epoxy organopolysiloxane |
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