CN112940262A - Preparation method of high-flash-point polyether epoxy silicone oil - Google Patents
Preparation method of high-flash-point polyether epoxy silicone oil Download PDFInfo
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- CN112940262A CN112940262A CN202110362485.9A CN202110362485A CN112940262A CN 112940262 A CN112940262 A CN 112940262A CN 202110362485 A CN202110362485 A CN 202110362485A CN 112940262 A CN112940262 A CN 112940262A
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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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Abstract
The invention provides a preparation method of polyether epoxy silicone oil with high flash point, which adopts hydrogen-terminated silicone oil and allyl epoxy polyether as raw materials, adds catalyst, solvent and solubilizer, and obtains the polyether epoxy silicone oil with transparent and stable storage after complete silicon-hydrogen reaction; the solvent adopts high flash point alcohol ether, and takes high flash point polyol as a solubilizer, and the structure of the solubilizer is as follows: HO-R2- (OH) m, R2 is a divalent hydrocarbon group of 3 to 10 carbon atoms, straight or branched, which may be interrupted or substituted by oxygen atoms. The invention adopts a high flash point solvent in the synthetic process, has good solubility to the silicone oil, and can complete the hydrosilylation reaction even if the addition amount is as little as 1 percent. Not only reduces the generation and the emission of low-boiling-point substances, is environment-friendly and safe, but also has high safety to people and crops and good safety in the processes of production, storage and transportation and use.
Description
Technical Field
The invention relates to the technical field of silicone oil synthesis, in particular to a preparation method of high-flash-point polyether epoxy silicone oil.
Background
In recent years, the ternary block silicone oil is developed rapidly, compared with the traditional side chain amino silicone oil, the block polyether silicone oil introduces a polyether chain segment on the main chain, can improve the hydrophilic performance of the fabric, and can keep certain soft performance. One of the block silicone oil synthesis methods is to perform hydrosilylation on hydrogen-terminated silicone oil and allyl epoxy polyether and then perform amination reaction, but the process needs to perform hydrosilylation by using an isopropanol solvent, the solvent has a low flash point (12 ℃), potential safety hazards exist in the processes of production, transportation, storage and use, and the environmental pollution is large. Even if the isopropanol is removed in vacuum and replaced by the high-flash-point solvent, the safety risk can be reduced in the processes of transportation, storage and use, but the potential safety hazard still exists in the production process, and the replacement of the solvent also causes the increase of the production cost. At present, no method for preparing polyether epoxy silicone oil by using a high flash point solvent is found.
Disclosure of Invention
The invention aims to provide a preparation method of high flash point polyether epoxy silicone oil, which reduces the safety risk in the processes of transportation, storage and production and overcomes the defects of the prior art.
The technical scheme for solving the technical problem is as follows: a preparation method of high flash point polyether epoxy silicone oil is characterized by comprising the following steps: adopting hydrogen-terminated silicone oil and allyl epoxy polyether as raw materials, adding a catalyst, a solvent and a solubilizer, and completely carrying out a hydrosilation reaction to obtain transparent and stably-stored polyether epoxy silicone oil; the solvent adopts high flash point alcohol ether, and takes high flash point polyalcohol as solubilizer; the structural formula of the hydrogen-terminated silicone oil is shown as follows,
wherein Z is an integer of 50-300;
the structural formula of the allyl epoxy polyether is shown as follows,
wherein the value of (X + Y) is an integer of 10-30, and R1 is a saturated hydrocarbon group with 1-3 carbon atoms, and is straight-chain or branched;
the solubilizer is a polyalcohol solvent and has the following structure:
HO-R2-(OH)m，
wherein R2 is a divalent hydrocarbon group of 3 to 10 carbon atoms, straight or branched, which may be interrupted or substituted by oxygen atoms.
Further, the catalyst is a platinum group metal or a platinum group compound or a platinum group complex.
Further, the catalyst is selected from one or more of platinum supported on silica or alumina or activated carbon, or a platinum tetrachloride compound, or a hexachloroplatinic acid hexahydrate compound, or a platinum-alcohol complex, or a platinum-alkoxide complex, or a platinum-ether complex, or a platinum-vinylsiloxane complex.
Further, the amount of the catalyst is 1-50ppm based on the total weight of the raw materials calculated by platinum element.
Furthermore, the amount of the catalyst is 2-20ppm by weight calculated by platinum element as the total weight of the raw materials.
Further, the solvent is one or more of ethylene glycol butyl ether and diethylene glycol butyl ether.
Further, the solubilizer HO-R2- (OH) m, R2 is a divalent hydrocarbon group of 4-8 carbon atoms, and m is 1 or 2.
Further, the solubilizer includes one or more of propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1, 3-propanediol, dimethyl-1, 3-propanediol, butylene glycol, methyl-1, 3-butanediol, dimethyl-1, 2-butanediol, pentanediol, methyl-2, 4-pentanediol, dimethyl-2, 4-pentanediol, methoxy-1, 2-propanediol, triethylene glycol, methyl-1, 3, 5-pentanetriol.
Further, the solubilizer employs a glycol.
The invention has the beneficial effects that:
the preparation method of the high flash point polyether epoxy silicone oil belongs to a one-step method direct synthesis process, does not need to remove a solvent, and has a simple flow. In the synthesis process, a high flash point solvent is adopted, so that the silicon oil has good solubility, and the hydrosilylation reaction can be completed even if the addition amount is as small as 1%. Not only reduces the generation and the emission of low-boiling-point substances, is environment-friendly and safe, but also has high safety to people and crops and good safety in the processes of production, storage and transportation and use.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, but not limiting, of the invention.
The invention adopts hydrogen-terminated silicone oil and allyl epoxy polyether as raw materials, high-flash-point alcohol ether as a solvent, and high-flash-point polyol as a solubilizer, and can replace a low-flash-point isopropanol solvent to carry out hydrosilylation reaction to obtain the high-flash-point polyether epoxy silicone oil by a one-step method. The high flash point solubilizer selects polyhydric alcohol with stronger dissolving capacity, and the structure of the high flash point solubilizer contains a lipophilic alkyl chain segment and a hydrophilic hydroxyl/ether-based chain segment, so that the high flash point solubilizer can dissolve hydrophobic organic silicon compounds and hydrophilic allyl epoxy polyether. The method comprises the following steps:
firstly, hydrogen-terminated silicone oil (structure is as follows)
Wherein the content of the first and second substances,
z = 50-300, an integer;
allyl epoxy polyether (structure as follows):
wherein the content of the first and second substances,
x + Y = 10-30, an integer;
r1 is a saturated hydrocarbon group with 1-3 carbon atoms, straight chain or branched;
the molar ratio of the two is 1: (2.0-2.5), adding a catalyst, a solvent (the solvent accounts for 1-20% of the weight of the reactants) and a solubilizer (the solvent accounts for 1-20% of the weight of the reactants), heating to 70-120 ℃, and reacting for 2-12h to obtain the transparent and stable polyether epoxy silicone oil.
Wherein the content of the first and second substances,
the catalyst is preferably a platinum group metal or compound or complex, including platinum supported on silica, alumina or activated carbon, platinum tetrachloride, hexachloroplatinic acid hexahydrate compounds, platinum-alcohol complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-vinylsiloxane complexes,
the amount of the platinum-based catalyst is 1-50ppm, preferably 2-20ppm, calculated by platinum element;
the solvent is one or more of ethylene glycol butyl ether and diethylene glycol butyl ether;
the solubilizer is a polyalcohol solvent and has the following structure:
HO-R2-(OH)m
r2 is a divalent hydrocarbon group of 3 to 10 carbon atoms, straight or branched, possibly interrupted or substituted by oxygen atoms, preferably a divalent hydrocarbon group of 4 to 8 carbon atoms; m is 1 or 2.
The polyhydric alcohol solvent comprises one or more of propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1, 3-propanediol, dimethyl-1, 3-propanediol, butanediol, methyl-1, 3-butanediol, dimethyl-1, 2-butanediol, pentanediol, methyl-2, 4-pentanediol, dimethyl-2, 4-pentanediol, methoxy-1, 2-propanediol, triethylene glycol, methyl-1, 3, 5-pentanetriol, and preferably dihydric alcohol.
Hereinafter, a plurality of specific embodiments will be described by way of examples.
Example 1
100 g of hydrogen-terminated silicone oil (z = 175) and 9.1g of allyl polyether E500 (x =10, y = 0) are added into a four-neck flask provided with a thermometer and a reflux condenser, 0.22 g of hexachloroplatinic acid isopropyl alcohol solution (with platinum element concentration of 5000 ppm), 20.0g of ethylene glycol butyl ether and 10.0g of butyl-1, 3-butanediol serving as a solubilizer are added under the condition of stirring, and the mixture is stirred and reacted at 90 ℃ for 8 hours, so that the silicon-hydrogen reaction is complete, and the transparent and stable polyether epoxy silicone oil is obtained.
Example 2
100 g of hydrogen-terminated silicone oil (z = 50) and 86.4g of allyl polyether E1500 (x =15, y = 15) are added into a four-neck flask provided with a thermometer and a reflux condenser, 0.07 g of hexachloroplatinic acid isopropyl alcohol solution (with platinum element concentration of 5000 ppm), 1.0g of ethylene glycol butyl ether and 1.0g of solubilizer methoxy-1, 2-propylene glycol are added under the condition of stirring, and the mixture is stirred and reacted for 2 hours at 70 ℃, and the silicon-hydrogen reaction is completed, so that the transparent polyether epoxy silicone oil with stable storage is obtained.
Example 3
100 g of hydrogen-terminated silicone oil (z = 300) and 6.5g of allyl polyether E550 (x =7, y = 3) are added into a four-neck flask provided with a thermometer and a reflux condenser, 0.43 g of hexachloroplatinic acid isopropyl alcohol solution (with platinum element concentration of 5000 ppm), 20.0g of ethylene glycol butyl ether and 5.0g of dipropylene glycol as a solubilizer, and 10.0g of methoxy-1, 2-propanediol are added under stirring, and the stirring reaction is carried out for 12 hours at 120 ℃, so that the hydrosilation reaction is complete, and the transparent and stable polyether epoxy silicone oil is obtained.
Example 4
100 g of hydrogen-terminated silicone oil (z = 150) and 20.6g of allyl polyether E1000 (x =15, y = 5) are added into a four-neck flask provided with a thermometer and a reflux condenser, 0.24 g of hexachloroplatinic acid isopropyl alcohol solution (with platinum element concentration of 5000 ppm), 10.0g of ethylene glycol butyl ether and 5.0g of solubilizer methyl-2, 4-pentanediol are added under the condition of stirring, and the mixture is stirred and reacted at 80 ℃ for 8 hours, so that the silicon-hydrogen reaction is complete, and the transparent polyether epoxy silicone oil with stable storage is obtained.
Example 5
100 g of hydrogen-terminated silicone oil (z = 270) and 7.8g of allyl polyether E700 (x =10, y = 3) are added into a four-neck flask provided with a thermometer and a reflux condenser, 0.32 g of hexachloroplatinic acid isopropyl alcohol solution (with platinum element concentration of 5000 ppm), 5.0g of ethylene glycol butyl ether and 20.0g of solubilizer butanediol are added under the condition of stirring, and the stirring reaction is carried out for 8 hours at 80 ℃, so that the silicon-hydrogen reaction is complete, and the transparent polyether epoxy silicone oil with stable storage is obtained.
Comparative example
100 g of hydrogen-terminated silicone oil (z = 150) and 20.6g of allyl polyether E1000 (x =15, y = 5) were charged into a four-necked flask equipped with a thermometer and a reflux condenser, 0.24 g of an isopropyl alcohol hexachloroplatinate solution (platinum element concentration: 5000 ppm) and 15.0g of butyl cellosolve were added under stirring, and the mixture was stirred at 80 ℃ for 8 hours to complete the hydrosilation reaction, thereby obtaining a turbid reaction product, which was allowed to stand and separate into layers.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of high flash point polyether epoxy silicone oil is characterized by comprising the following steps: adopting hydrogen-terminated silicone oil and allyl epoxy polyether as raw materials, adding a catalyst, a solvent and a solubilizer, and completely carrying out a hydrosilation reaction to obtain transparent and stably-stored polyether epoxy silicone oil; the solvent adopts high flash point alcohol ether, and takes high flash point polyalcohol as solubilizer; the structural formula of the hydrogen-terminated silicone oil is shown as follows,
wherein Z is an integer of 50-300;
the structural formula of the allyl epoxy polyether is shown as follows,
wherein the value of (X + Y) is an integer of 10-30, and R1 is a saturated hydrocarbon group with 1-3 carbon atoms, and is straight-chain or branched;
the solubilizer is a polyalcohol solvent and has the following structure:
HO-R2-(OH)m，
wherein R2 is a divalent hydrocarbon group of 3 to 10 carbon atoms, straight or branched, which may be interrupted or substituted by oxygen atoms.
2. The method for preparing high flash point polyether epoxy silicone oil according to claim 1, wherein the catalyst is platinum group metal or platinum group compound or platinum group complex.
3. The method for preparing high flash point polyether epoxy silicone oil according to claim 2, wherein the catalyst is selected from one or more of platinum supported on silica or alumina or activated carbon, or a platinum tetrachloride compound, or a hexachloroplatinic acid compound, or a platinum-alcohol complex, or a platinum-alkoxide complex, or a platinum-ether complex, or a platinum-vinylsiloxane complex.
4. The method for preparing high flash point polyether epoxy silicone oil according to claim 3, wherein the amount of the catalyst is 1 to 50ppm based on the total weight of the raw materials, calculated as platinum element.
5. The method for preparing high flash point polyether epoxy silicone oil according to claim 4, wherein the amount of the catalyst is 2 to 20ppm by weight based on the total weight of the raw materials.
6. The method for preparing high flash point polyether epoxy silicone oil according to claim 1, wherein the solvent is one or more of ethylene glycol butyl ether and diethylene glycol butyl ether.
7. The process for preparing high flash point polyether epoxy silicone oil according to any one of claims 1 to 6, wherein the solubilizer HO-R2- (OH) m, R2 is a divalent hydrocarbon group of 4-8 carbon atoms, and m is 1 or 2.
8. The method of claim 7, wherein the solubilizer comprises one or more of propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1, 3-propanediol, dimethyl-1, 3-propanediol, butanediol, methyl-1, 3-butanediol, dimethyl-1, 2-butanediol, pentanediol, methyl-2, 4-pentanediol, dimethyl-2, 4-pentanediol, methoxy-1, 2-propanediol, triethylene glycol, and methyl-1, 3, 5-pentanetriol.
9. The method for preparing the high flash point polyether epoxy silicone oil according to claim 8, wherein the solubilizer is glycol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109256A (en) * | 2021-12-29 | 2022-09-27 | 浙江传化功能新材料有限公司 | Preparation method of block silicone oil with high flash point and low solvent content |
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| CN109485856A (en) * | 2018-11-27 | 2019-03-19 | 黄天宝 | Glycine betaine modified polyether epoxy silicon oil and its preparation method and application |
| CN109535428A (en) * | 2018-12-04 | 2019-03-29 | 江西蓝星星火有机硅有限公司 | A kind of poly- ammonium modified polyether silicone oil and its preparation method and application |
| CN112194797A (en) * | 2020-11-25 | 2021-01-08 | 佛山市顺德区德美瓦克有机硅有限公司 | High-flash-point quaternized polyether block silicone oil and preparation method thereof |
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- 2021-04-02 CN CN202110362485.9A patent/CN112940262A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108276581A (en) * | 2017-12-22 | 2018-07-13 | 浙江雀屏纺织化工股份有限公司 | A kind of synthetic method of low solvent block silicone oil and the hand feel finishing agent for including the low solvent block silicone oil |
| CN109485856A (en) * | 2018-11-27 | 2019-03-19 | 黄天宝 | Glycine betaine modified polyether epoxy silicon oil and its preparation method and application |
| CN109535428A (en) * | 2018-12-04 | 2019-03-29 | 江西蓝星星火有机硅有限公司 | A kind of poly- ammonium modified polyether silicone oil and its preparation method and application |
| CN112194797A (en) * | 2020-11-25 | 2021-01-08 | 佛山市顺德区德美瓦克有机硅有限公司 | High-flash-point quaternized polyether block silicone oil and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115109256A (en) * | 2021-12-29 | 2022-09-27 | 浙江传化功能新材料有限公司 | Preparation method of block silicone oil with high flash point and low solvent content |
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