CN111072972A - Preparation method of epoxy-terminated silicone oil and application of epoxy-terminated silicone oil in amino silicone oil - Google Patents
Preparation method of epoxy-terminated silicone oil and application of epoxy-terminated silicone oil in amino silicone oil 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
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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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
- 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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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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
- 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
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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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
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
Abstract
The invention discloses a preparation method of terminal epoxy silicone oil and application thereof in amino silicone oil, which comprises the following steps of taking double-end hydrogen-containing silicone oil as a reaction monomer, adding allyl glycidyl ether as an epoxy end-capping agent, carrying out hydrosilylation reaction under the action of a chlorine-free zero-valent platinum catalyst, filtering to obtain the terminal epoxy silicone oil after the hydrosilylation reaction is finished, wherein the chlorine-free zero-valent platinum catalyst is prepared by the following steps of dissolving ① parts by weight of chloroplatinic acid in 1000 parts by weight of ethanol, stirring for 1 hour, adding ② parts by weight of tetramethyl divinyl disiloxane into the mixture, carrying out equilibrium reaction for 5 hours at the temperature of 40-70 ℃, adding ③ parts by weight of sodium bicarbonate to remove chlorine and acid, and filtering to obtain a colorless and transparent chlorine-free zero-valent platinum ethanol solution.
Description
Technical Field
The invention relates to the technical field of silicone oil preparation, in particular to a preparation method of epoxy-terminated silicone oil and application of the epoxy-terminated silicone oil in amino silicone oil.
Background
Silicone oil generally refers to a linear polysiloxane product that remains in a liquid state at room temperature. Generally, the modified silicone oil is divided into methyl silicone oil and modified silicone oil, and commonly used modified silicone oil comprises terminal hydrogen-containing silicone oil, terminal epoxy silicone oil and amino silicone oil.
The epoxy-terminated silicone oil is prepared by taking hydrogen-terminated silicone oil as a raw material through a hydrosilylation reaction. The epoxy-terminated silicone oil has high reaction activity, can react with hydroxyl, amino, carboxyl and the like on the surface of fiber as a finishing agent of the fiber fabric, endows the fiber fabric with a durable softening effect, and the finished fabric is washable and does not turn yellow.
The amino silicone oil can be prepared by taking epoxy-terminated silicone oil as a raw material through polymerization reaction. The amino silicone oil is a basic component of a softening finishing agent specially used for textiles, and has optimal adsorbability, compatibility and easy emulsibility. Different amines and terminal epoxy silicone oils can be polymerized to form amino silicone oils with different ammonia values, which can change the softness, smoothness and elasticity of the amino silicone oils to suit different fabrics.
The prior epoxy-terminated silicone oil is mainly prepared by taking hydrogen-containing silicone oil and allyl glycidyl ether as raw materials and taking chloroplatinic acid as a catalyst to carry out hydrosilylation. In the prior art, an invention patent application publication No. CN106432735A discloses a double-end epoxy silicone oil and a preparation method thereof, and the preparation method comprises the following steps: 450kg of double-end hydrogen-containing silicone oil 350 and 8-20 kg of allyl glycidyl ether are put into an enamel kettle or a stainless steel reaction kettle, the temperature is raised to 70-95 ℃ after stirring, an isopropanol solution of chloroplatinic acid as a catalyst is added, the temperature is raised to 90-120 ℃ after reaction for 15min, the solution is continuously reacted for 1-2h at 90-120 ℃ after being reacted to be transparent and clear, and finally, low-boiling-point substances such as the participating allyl glycidyl ether and the like are removed at 130 ℃ under the condition of 100 and 130 ℃ for 30-90min under the reduced pressure condition, so that the double-end epoxy silicone oil is obtained.
The chloroplatinic acid is used as a catalyst in the preparation of the epoxy-terminated silicone oil, and has the advantages of more usage amount, higher cost and lower reaction rate in the reaction process.
The Chinese invention patent with application publication number CN110465313A discloses a chlorine-containing zero-valent platinum compound, a preparation method thereof and application thereof in hydrosilylation. The chlorine-containing zero-valent platinum compound takes block copolymer or macrocyclic polyether containing silicon-oxygen groups and hydrophilic polymers as a protective agent, takes a platinum compound in a high oxidation state as a precursor, and uses a reducing agent and water in the synthesis process. The synthesized chlorine-containing zero-valent platinum compound used in the hydrosilylation reaction has far better catalytic activity than that of the traditional platinum catalyst (a platinum compound containing a double-bond ligand and a heterogeneous platinum catalyst), and the catalyst has long service life and high selectivity (for terminal unsaturated hydrocarbon, a terminal addition product can be obtained with high activity and high selectivity). The prior chlorine-containing zero-valent platinum compound for catalyzing hydrosilylation has the characteristics of mild conditions, safety, high activity, long service life, high selectivity and easy preparation of the catalyst.
Although the chlorine-containing zero-valent platinum catalyst can improve the catalytic activity, in the production of epoxy terminated silicone oil and the subsequent amino silicone oil, chlorine exists and H in the solution is increased+And further, the acidity is high. The epoxy-terminated silicone oil and the amino silicone oil are alkalescent products, and the acidity can influence the performance of the epoxy-terminated silicone oil and the amino silicone oil products, so that the chlorine-free zero-valent platinum catalyst is more suitable for synthesis of the epoxy-terminated silicone oil.
Disclosure of Invention
The invention aims to provide a preparation method of epoxy-terminated silicone oil and application of the epoxy-terminated silicone oil in amino silicone oil.
The purpose of the invention is realized by the following technical scheme:
the epoxy-terminated silicone oil has chlorine-free zero-valent platinum as catalyst, and has greatly reduced catalyst consumption, lowered production cost and raised reaction rate.
A preparation method of epoxy-terminated silicone oil comprises the following steps of taking hydrogen-terminated silicone oil as a reaction monomer, adding allyl glycidyl ether as an epoxy end-capping agent, carrying out hydrosilylation reaction under the action of a chlorine-free zero-valent platinum catalyst, and filtering to obtain the epoxy-terminated silicone oil, wherein the chlorine-free zero-valent platinum catalyst is prepared by the following steps of dissolving ① parts by weight of chloroplatinic acid 100 parts in 1000 parts of ethanol, stirring for 1 hour, adding ② parts of tetramethyldivinyldisiloxane into the solution, carrying out equilibrium reaction for 5 hours at the temperature of 40-70 ℃, adding ③ parts of sodium bicarbonate to remove chlorine and acid, and filtering to obtain a colorless and transparent chlorine-free zero-valent platinum ethanol solution.
By adopting the technical scheme, the allyl glycidyl ether has small molecular weight, so the reaction activity is high, when the allyl glycidyl ether and the hydrogen-containing silicone oil at the double ends are subjected to hydrosilylation, an exothermic phenomenon can occur, and the hydrosilylation reaction is easy to carry out. The chlorine-free zero-valent platinum is used as the catalyst in the catalytic equilibrium method, so that the use amount of the catalyst is reduced, the production cost is reduced, and the reaction rate is improved.
Further, the synthesis steps of the epoxy-terminated silicone oil are as follows:
s1, taking 1000 parts of 1500-part double-end hydrogen-containing silicone oil and 30-80 parts of allyl glycidyl ether by weight, stirring, heating to 80-85 ℃, adding 0.13-0.2 part of chlorine-free zero-valent platinum catalyst, and continuing stirring for 1-3 hours to perform hydrosilylation reaction;
and S2, after the hydrosilylation reaction is finished, removing low-boiling-point substances by a vacuum pump, cooling, and filtering by a filter to obtain the epoxy-terminated silicone oil.
Further, the synthesis steps of the epoxy-terminated silicone oil are as follows:
s1, taking 1000 parts by weight of hydrogen-containing silicone oil at both ends and 60 parts by weight of allyl glycidyl ether, stirring, heating to 83 ℃, adding 0.2 part of chlorine-free zero-valent platinum catalyst, and continuing stirring for 2.5 hours to perform hydrosilylation reaction;
and S2, after the hydrosilylation reaction is finished, removing low-boiling-point substances by a vacuum pump, cooling, and filtering by a filter to obtain the epoxy-terminated silicone oil.
By adopting the technical scheme, although the traditional chloroplatinic acid has good catalytic action on the hydrosilylation reaction of the terminal epoxy silicone oil, the consumption of the chloroplatinic acid is larger than that of a chlorine-free zero-valent platinum catalyst; every 15 kg of epoxy terminated silicone oil is obtained, the chloroplatinic acid needs to contain 7ppm of platinum to complete the reaction, and the chlorine-free zero-valent platinum only needs to contain 1ppm of platinum to complete the reaction.
Further, the filter in step 2 was a 0.1 μm bag filter.
By adopting the technical scheme and adopting the bag filter with the diameter of 0.1 mu m, bubbles and solid particles mixed in the silicone oil can be removed in the filtering process, and homogeneous silicone oil can be obtained.
Further, the stirring speed in step 1 is 100-200 r/min.
By adopting the technical scheme, the hydrogen-containing silicone oil, the allyl glycidyl ether and the chlorine-free zero-valent platinum catalyst can be uniformly mixed at the speed of 100-200r/min, so that the catalytic efficiency of the chlorine-free zero-valent platinum catalyst is improved.
The second purpose of the invention is realized by the following technical scheme:
the epoxy-terminated silicone oil is applied to amino silicone oil synthesis, and amino silicone oil is synthesized by selecting the epoxy-terminated silicone oil synthesized by using chlorine-free zero-valent platinum as a catalyst as a raw material.
Use of the epoxy-terminated silicone oil according to any one of claims 1 to 3 in amino silicone oil synthesis, specifically comprising the following steps: (1) taking 800-; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
Further, the method is used for synthesizing amino silicone oil and comprises the following specific steps: (1) taking 1000 parts by weight of epoxy-terminated silicone oil and 400 parts by weight of isopropanol, stirring, adding 40 parts by weight of N, N-diethyl propylene diamine, heating to reflux temperature, reacting for 2 hours, and fully polymerizing the N, N-diethyl propylene diamine on the epoxy-terminated silicone oil; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
Further, the N, N-diethylpropanediamine in said step 1 may be replaced with any one of ethanolamine, tetramethylhexanediamine, 3-methoxypropylamine and polyetheramine.
By adopting the technical scheme, different amines and the epoxy-terminated silicone oil are selected for carrying out polymerization reaction, amino silicone oil with different styles can be obtained, and soft, smooth or fluffy amino silicone oil can be obtained according to specific requirements.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. the chlorine-free zero-valent platinum is used as the catalyst in the catalytic equilibrium method, so that the use amount of the catalyst is reduced, the production cost is reduced, and the reaction rate is improved;
2. different amines and epoxy terminated silicone oil are used for polymerization reaction, amino silicone oil with different styles can be obtained, and the amino silicone oil can be soft, smooth or fluffy according to specific requirements.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Preparation example of chlorine-free zero-valent platinum catalyst
Preparation example of chlorine-free zero-valent platinum catalyst 1: ① 1000g of chloroplatinic acid was dissolved in 10kg of ethanol, stirred for 1 hour, ② g of tetramethyldivinyldisiloxane was added, equilibrium reaction was carried out at 55 ℃ for 5 hours, ③ g of sodium bicarbonate was added to remove chlorine, colorless transparent chlorine-free zero-valent platinum ethanol solution was obtained after filtration, and the volume of the chlorine-free zero-valent platinum ethanol solution was determined to be 100ppm of platinum content.
Preparation example 2 of a chlorine-free zero-valent platinum catalyst ① 1000g of chloroplatinic acid was dissolved in 10kg of ethanol, stirred for 1 hour, ② g of tetramethyldivinyldisiloxane was added, equilibrium reaction was carried out at 55 ℃ for 5 hours, ③ g of sodium bicarbonate was added to remove chlorine, and after filtration, a colorless transparent chlorine-free zero-valent platinum ethanol solution was obtained, and the volume of the chlorine-free zero-valent platinum ethanol solution was adjusted to 70ppm of platinum content.
Preparation example 3 of a chlorine-free zero-valent platinum catalyst ① 1000g of chloroplatinic acid was dissolved in 10kg of ethanol, stirred for 1 hour, ② g of tetramethyldivinyldisiloxane was added, equilibrium reaction was carried out at 70 ℃ for 5 hours, ③ g of sodium bicarbonate was added to remove chlorine, and after filtration, a colorless and transparent chlorine-free zero-valent platinum ethanol solution was obtained, and the volume of the chlorine-free zero-valent platinum ethanol solution was adjusted to 50ppm of platinum content.
Preparation example of chlorine-free zero-valent platinum catalyst ① 1000g of chloroplatinic acid was dissolved in 10kg of ethanol, stirred for 1 hour, ② g of tetramethyldivinyldisiloxane was added, equilibrium reaction was carried out at 40 ℃ for 5 hours, ③ g of sodium bicarbonate was added to remove chlorine, and after filtration, a colorless transparent chlorine-free zero-valent platinum ethanol solution was obtained, and the volume of the chlorine-free zero-valent platinum ethanol solution was adjusted to 100ppm of platinum content.
Preparation examples of Hydrogen-containing Silicone oils at both ends
Preparation example 1 of hydrogen-containing silicone oil at both ends: 1) taking 36kg of 1,1,3, 3-tetramethyl dihydrodisiloxane and 1900kg of octamethylcyclotetrasiloxane, adding 10kg of activated clay catalyst while stirring, heating to 80 ℃, and keeping the temperature for 8 hours to perform polymerization reaction; 2) and after the polymerization reaction is finished, adding 10kg of diatomite filter aid, performing circulating filtration until the filtrate is clear and transparent, and collecting clear and transparent liquid to obtain the hydrogen-containing silicone oil.
Preparation example 2 of hydrogen-containing silicone oil at both ends: 1) taking 29kg of 1,1,3, 3-tetramethyl dihydrodisiloxane and 1900kg of octamethylcyclotetrasiloxane, adding 10kg of activated clay catalyst while stirring, heating to 80 ℃, and preserving heat for 8-12 hours to perform polymerization reaction; 2) and after the polymerization reaction is finished, adding 10kg of diatomite filter aid, performing circulating filtration until the filtrate is clear and transparent, and collecting clear and transparent liquid to obtain the hydrogen-containing silicone oil.
Preparation example 3 of hydrogen-containing silicone oil at both ends: 1) taking 75kg of 1,1,3, 3-tetramethyl dihydrodisiloxane and 1900kg of octamethylcyclotetrasiloxane, adding 10kg of activated clay catalyst while stirring, heating to 80 ℃, and keeping the temperature for 12 hours to perform polymerization reaction; 2) and after the polymerization reaction is finished, adding 10kg of modified diatomite filter aid, performing circulating filtration until the filtrate is clear and transparent, and collecting clear and transparent liquid to obtain the hydrogen-containing silicone oil.
Preparation of epoxy-terminated silicone oil
Example 1:
s1, taking 1500kg of double-ended hydrogen-containing silicone oil (selected from preparation example 1 of the double-ended hydrogen-containing silicone oil) and 60kg of allyl glycidyl ether, stirring at the rotating speed of 100-200r/min, heating to 80-85 ℃, adding 156g of chlorine-free zero-valent platinum catalyst (selected from preparation example 1 of the chlorine-free zero-valent platinum catalyst) with the platinum concentration of 100ppm, and continuing stirring for 1-3 hours to perform hydrosilylation reaction;
and S2, after the hydrosilylation reaction is finished, removing low-boiling-point substances such as allyl glycidyl ether and the like by a vacuum pump, cooling, and filtering by a bag filter of 0.1 mu m to obtain the epoxy-terminated silicone oil.
Example 2:
s1, taking 1500kg of double-ended hydrogen-containing silicone oil (selected from preparation example 1 of the double-ended hydrogen-containing silicone oil) and 70kg of allyl glycidyl ether, stirring at the rotating speed of 100-200r/min, heating to 80-85 ℃, adding 220g of chlorine-free zero-valent platinum catalyst (preparation example 2 of the chlorine-free zero-valent platinum catalyst) with the platinum concentration of 70ppm, and continuing stirring for 1-3 hours to perform hydrosilylation reaction;
and S2, after the hydrosilylation reaction is finished, removing low-boiling-point substances such as allyl glycidyl ether and the like by a vacuum pump, cooling, and filtering by a bag filter of 0.1 mu m to obtain the epoxy-terminated silicone oil.
Example 3: the epoxy-terminated silicone oil is prepared by the following method:
s1, taking 1000kg of double-end hydrogen-containing silicone oil (selected from preparation example 2 of the double-end hydrogen-containing silicone oil) and 60kg of allyl glycidyl ether, stirring at the rotating speed of 100-200r/min, heating to 80-85 ℃, adding 300g of chlorine-free zero-valent platinum catalyst (preparation example 1 of the chlorine-free zero-valent platinum catalyst) with the platinum concentration of 50ppm, and continuing stirring for 1-3 hours to perform hydrosilylation reaction;
and S2, after the hydrosilylation reaction is finished, removing low-boiling-point substances such as allyl glycidyl ether and the like by a vacuum pump, cooling, and filtering by a bag filter of 0.1 mu m to obtain the epoxy-terminated silicone oil.
Fourthly, amino silicone oil prepared by adopting the epoxy-terminated silicone oil
Example 4:
(1) taking 1000kg of terminal epoxy silicone oil (the terminal epoxy silicone oil obtained in example 1) and 400kg of isopropanol, adding 40kg of N, N-diethyl propylene diamine while stirring, heating to the reflux temperature, and reacting for 2 hours to ensure that the N, N-diethyl propylene diamine is fully polymerized on the terminal epoxy silicone oil; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
Example 5:
(1) taking 1000kg of epoxy-terminated silicone oil obtained in example 1) and 400kg of isopropanol in parts by weight, adding 21kg of ethanolamine while stirring, heating to reflux temperature, and reacting for 3 hours to ensure that the ethanolamine is fully polymerized on the epoxy-terminated silicone oil; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
Example 6:
(1) taking 1000kg of epoxy-terminated silicone oil (the epoxy-terminated silicone oil obtained in example 1) and 400kg of isopropanol, adding 53kg of tetramethylhexamethylenediamine while stirring, heating to reflux temperature, and reacting for 3 hours to ensure that the tetramethylhexamethylenediamine is fully polymerized on the epoxy-terminated silicone oil; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
Example 7:
(1) taking 1000kg of epoxy-terminated silicone oil (the epoxy-terminated silicone oil obtained in example 1) and 400kg of isopropanol, adding 28kg of 3-methoxypropylamine while stirring, heating to the reflux temperature, and reacting for 3 hours to ensure that the 3-methoxypropylamine is fully polymerized on the epoxy-terminated silicone oil; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
Example 8:
(1) taking 1000kg of epoxy-terminated silicone oil (the epoxy-terminated silicone oil obtained in example 1) and 400kg of isopropanol in parts by weight, adding 100kg of polyetheramine while stirring, heating to a reflux temperature, and reacting for 3 hours to ensure that the polyetheramine is fully polymerized on the epoxy-terminated silicone oil; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
Fifth, comparative example
Comparative example 1: the epoxy terminated silicone oil is prepared by the following method: 1500kg of double-ended hydrogen-containing silicone oil (selected from preparation example 1 of double-ended hydrogen-containing silicone oil) and 60kg of allyl glycidyl ether are put into an enamel kettle or a stainless steel reaction kettle, the temperature is raised to 85 ℃ after stirring, 156g of isopropanol solution of chloroplatinic acid with platinum concentration of 100ppm is added, the temperature is raised to 115 ℃ after reaction for 15 minutes, the solution continues to react for 1 hour at 115 ℃ after reaction is transparent and clear, and finally, residual low-boiling-point substances such as allyl glycidyl ether and the like are removed for 30-60min under the conditions of 110 ℃ and 120 ℃ and reduced pressure, so that double-ended epoxy silicone oil is obtained.
Comparative example 2: this comparative example is different from example 1 in that the chlorine-free zero-valent platinum catalyst was prepared from preparation example 3 of the chlorine-free zero-valent platinum catalyst.
Comparative example 3: this comparative example is different from example 1 in that the chlorine-free zero-valent platinum catalyst was prepared from preparation example 4 of the chlorine-free zero-valent platinum catalyst.
Comparative example 4: this comparative example differs from example 4 in that 40kg of N, N-diethylpropanediamine was changed to 30kg of N, N-diethylpropanediamine.
Comparative example 5: this comparative example differs from example 4 in that 40kg of N, N-diethylpropanediamine was changed to 50kg of N, N-diethylpropanediamine.
Sixthly, performance test
1. End epoxy silicone oil performance testing
Epoxy-terminated silicone oils were prepared by the methods of examples 1 to 3 and comparative examples 1 to 3, respectively, and the hand feeling of the epoxy-terminated silicone oils obtained without the preparation method was tested.
Comparing examples 1 to 3 in Table 1 with comparative example 1, the results show that the yield of the epoxy terminated silicone oil obtained using chloroplatinic acid as a catalyst is lower than that of example 1 and is also inferior in softness and smoothness. The results show that the catalytic performance of chloroplatinic acid with the same platinum content is lower than that of chlorine-free zero-valent platinum.
The chlorine-free zero-valent platinum catalyst of comparative example 2 was prepared from preparation example 3 of a platinum-valent catalyst, and the difference from preparation example 1 of the chlorine-free zero-valent platinum catalyst was that the reaction temperature was increased from 55 ℃ to 70 ℃, and the test results showed that the softness and smoothness of the terminal epoxy silicone oil prepared in comparative example 2 were reduced. The result shows that the chlorine-free zero-valent platinum catalyst prepared at the temperature of 55 ℃ has higher catalytic activity.
The chlorine-free zero-valent platinum catalyst in comparative example 3 was prepared from preparation example 4 of the chlorine-free zero-valent platinum catalyst, and the difference from preparation example 1 of the chlorine-free zero-valent platinum catalyst was that the reaction temperature was lowered from 55 ℃ to 40 ℃, and the test results showed that the softness and smoothness of the terminal epoxy silicone oil prepared in comparative example 3 were lowered. The result shows that the chlorine-free zero-valent platinum catalyst prepared at the temperature of 55 ℃ has higher catalytic activity.
TABLE 1 epoxy terminated Silicone oils Performance test
2. Amino silicone oil Performance testing
The amino silicone oil prepared by the epoxy-terminated silicone oil of the invention is used for testing the hand feeling of the amino silicone oil prepared by different preparation methods.
Comparing the values in table 2, the reaction of the epoxy-terminated silicone oil with different amines can obtain amino silicone oils with different handfeels, and the requirements of different fabrics can be met according to the different handfeels.
The amount of N, N-diethylpropanediamine added in comparative example 4 was lower than that of N, N-diethylpropanediamine in example 4, and the softness and smoothness of the amino silicone oil in comparative example 4 were reduced and the hydrophilicity was improved, and the test results showed that increasing the content of amine can improve the softness and smoothness of the amino silicone oil.
The amount of N, N-diethylpropanediamine added in comparative example 5 is higher than that of N, N-diethylpropanediamine in example 4, and the softness, smoothness and hydrophilicity of the amino silicone oil of comparative example 5 are hardly changed as compared with example 4, and the test results show that the polymerization of epoxy-terminated silicone oil with amine has a linear line and the polymerization is not continued after a certain amount of amine has been polymerized. And the yellowing degree of the amino silicone oil can be increased by increasing the content of the amine.
TABLE 2 amino silicone oil Performance testing
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. A preparation method of epoxy-terminated silicone oil is characterized by comprising the following steps of taking hydrogen-terminated silicone oil as a reaction monomer, adding allyl glycidyl ether as an epoxy end-capping agent, carrying out hydrosilylation reaction under the action of a chlorine-free zero-valent platinum catalyst, and filtering to obtain the epoxy-terminated silicone oil after the hydrosilylation reaction is finished, wherein the chlorine-free zero-valent platinum catalyst is prepared by the following steps of dissolving ① parts by weight of chloroplatinic acid in 1000 parts by weight of ethanol, stirring for 1 hour, adding ② parts by weight of tetramethyldivinyldisiloxane into the solution, carrying out equilibrium reaction for 5 hours at the temperature of 40-70 ℃, adding 50 parts by weight of sodium bicarbonate to remove chlorine and acid, and filtering to obtain a colorless and transparent chlorine-free zero-valent platinum ethanol solution.
2. The preparation method of the epoxy-terminated silicone oil and the application of the epoxy-terminated silicone oil in amino silicone oil according to claim 1 are characterized in that: the synthesis steps of the epoxy-terminated silicone oil are as follows:
s1, taking 1000 parts of 1500-part double-end hydrogen-containing silicone oil and 30-80 parts of allyl glycidyl ether by weight, stirring, heating to 80-85 ℃, adding 0.13-0.2 part of chlorine-free zero-valent platinum catalyst, and continuing stirring for 1-3 hours to perform hydrosilylation reaction;
and S2, after the hydrosilylation reaction is finished, removing low-boiling-point substances by a vacuum pump, cooling, and filtering by a filter to obtain the epoxy-terminated silicone oil.
3. The preparation method of the epoxy-terminated silicone oil and the application of the epoxy-terminated silicone oil in amino silicone oil according to claim 1 are characterized in that: the synthesis steps of the epoxy-terminated silicone oil are as follows:
s1, taking 1000 parts by weight of hydrogen-containing silicone oil at both ends and 60 parts by weight of allyl glycidyl ether, stirring, heating to 83 ℃, adding 0.2 part of chlorine-free zero-valent platinum catalyst, and continuing stirring for 2.5 hours to perform hydrosilylation reaction;
and S2, after the hydrosilylation reaction is finished, removing low-boiling-point substances by a vacuum pump, cooling, and filtering by a filter to obtain the epoxy-terminated silicone oil.
4. The preparation method of the epoxy-terminated silicone oil and the application thereof in amino silicone oil according to claim 2 or 3, characterized in that: the filter in step 2 is a 0.1 μm bag filter.
5. The preparation method of the epoxy-terminated silicone oil and the application thereof in amino silicone oil according to claim 2 or 3, characterized in that: the stirring speed in the step 1 is 100-200 r/min.
6. Use of the epoxy-terminated silicone oil according to any one of claims 1 to 3 in amino silicone oils, characterized in that: the method is used for synthesizing amino silicone oil and comprises the following steps: (1) taking 800-; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
7. Use of the silicone oil according to claim 6 in amino silicone oils, characterized in that: the method is used for synthesizing amino silicone oil and comprises the following steps: (1) taking 1000 parts by weight of epoxy-terminated silicone oil and 400 parts by weight of isopropanol, stirring, adding 40 parts by weight of N, N-diethyl propylene diamine, heating to reflux temperature, reacting for 2 hours, and fully polymerizing the N, N-diethyl propylene diamine on the epoxy-terminated silicone oil; (2) and removing the isopropanol solvent under vacuum reduced pressure to obtain the amino silicone oil.
8. Use of the silicone oil according to claim 7 in amino silicone oils, characterized in that: the N, N-diethylpropanediamine in said step 1 may be replaced with any one of ethanolamine, tetramethylhexanediamine, 3-methoxypropylamine and polyetheramine.
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