CN116496499B - Preparation method of hydroxyl silicone oil and hydroxyl silicone oil - Google Patents
Preparation method of hydroxyl silicone oil and hydroxyl silicone oil Download PDFInfo
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- CN116496499B CN116496499B CN202310394667.3A CN202310394667A CN116496499B CN 116496499 B CN116496499 B CN 116496499B CN 202310394667 A CN202310394667 A CN 202310394667A CN 116496499 B CN116496499 B CN 116496499B
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 134
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000012670 alkaline solution Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- -1 cyclic siloxane Chemical class 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 56
- 238000006460 hydrolysis reaction Methods 0.000 description 51
- 230000007062 hydrolysis Effects 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000007142 ring opening reaction Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003929 acidic solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The application provides a preparation method of hydroxyl silicone oil and the hydroxyl silicone oil, relates to the technical field of the hydroxyl silicone oil, and solves the technical problems of high production cost and high recovery difficulty of anhydride in the existing method for preparing the hydroxyl silicone oil with high hydroxyl content and low viscosity by increasing the using amount of anhydride. The preparation method of the hydroxyl silicone oil comprises the following steps: mixing cyclic siloxane, acetic anhydride and a catalyst to obtain a first product; mixing the first product with an alkaline solution at a first preset temperature; heating to a second preset temperature to prepare hydroxyl silicone oil; wherein the first preset temperature is less than or equal to 0 ℃.
Description
Technical Field
The application relates to the technical field of hydroxyl silicone oil, in particular to a preparation method of hydroxyl silicone oil and the hydroxyl silicone oil.
Background
The hydroxyl silicone oil can react with various groups as a modified silicone oil with stronger activity, has wide application field, and particularly has higher hydroxyl content and lower viscosity.
At present, an anhydride hydrolysis method is a relatively common method for preparing hydroxyl silicone oil. In order to obtain the hydroxyl silicone oil with higher hydroxyl content and lower viscosity, the usage amount of anhydride is generally increased to obtain more ring-opened products capped by acetoxy, so that the hydroxyl silicone oil with higher hydroxyl content and lower viscosity can be obtained after further hydrolysis.
The method for preparing the hydroxyl silicone oil with high hydroxyl content and low viscosity by increasing the using amount of the anhydride has the problems of high production cost, increased anhydride recovery difficulty and the like.
Disclosure of Invention
The application provides a preparation method of hydroxyl silicone oil and the hydroxyl silicone oil, which can be used for solving the technical problems of high production cost and high recovery difficulty of anhydride in the current mode of preparing hydroxyl silicone oil with high hydroxyl content and low viscosity by increasing the using amount of anhydride.
In a first aspect, an embodiment of the present application provides a method for preparing hydroxyl silicone oil, where the preparation method includes:
Mixing cyclic siloxane, acetic anhydride and a catalyst to obtain a first product;
mixing the first product with an alkaline solution at a first preset temperature;
Heating to a second preset temperature to prepare hydroxyl silicone oil;
Wherein the first preset temperature is less than or equal to 0 ℃.
Optionally, in one embodiment, the first preset temperature is-20 ℃ to 0 ℃.
Optionally, in one embodiment, said mixing said first product with an alkaline solution at a first preset temperature comprises:
Mixing the first product with an alkaline solution at a first preset temperature and for a first preset period of time;
Wherein the first preset time period is greater than or equal to 1h.
Optionally, in an embodiment, the first preset duration is 1h to 2h.
Optionally, in one embodiment, the cyclic siloxane comprises dimethylsiloxane and/or hexamethylcyclotrisiloxane.
Optionally, in one embodiment, the catalyst comprises a first catalyst and a second catalyst;
The first catalyst comprises a strong acid; the second catalyst comprises acetic acid.
Optionally, in one embodiment, the alkaline solution comprises a sodium carbonate solution and/or a sodium bicarbonate solution.
Optionally, in an embodiment, the heating to the second preset temperature prepares hydroxyl silicone oil, including:
heating to a second preset temperature, and controlling the reaction time to be 6-8 hours to prepare the hydroxyl silicone oil; wherein the second preset temperature is 60-80 ℃.
Optionally, in one embodiment, the mixing of the cyclic siloxane, acetic anhydride, and catalyst results in a first product comprising:
and mixing cyclic siloxane, acetic anhydride and a catalyst, and controlling the temperature to be 100-160 ℃ for reaction for 4-6 hours to obtain the first product.
In a second aspect, an embodiment of the present application provides a hydroxyl silicone oil, where the hydroxyl silicone oil is prepared according to the preparation method of the hydroxyl silicone oil provided in the first aspect of the present application.
The embodiment of the application has the following beneficial effects:
By adopting the scheme provided by the embodiment of the application, the preparation method of the hydroxyl silicone oil comprises the following steps: mixing cyclic siloxane, acetic anhydride and a catalyst to obtain a first product; mixing the first product with an alkaline solution at a first preset temperature; heating to a second preset temperature to prepare hydroxyl silicone oil; wherein the first preset temperature is less than or equal to 0 ℃. By controlling the mixing process of the first product and the alkaline solution to be carried out at low temperature, a large amount of heat released by the neutralization reaction and the hydrolysis reaction in the mixing stage can be transferred in time, and further polymerization of silicone oil can be avoided. Thus, even if the using amount of the anhydride is small, the hydroxyl silicone oil with higher hydroxyl content and lower viscosity can be prepared. Furthermore, the input amount of the anhydride can be reduced, so that the production cost and the recovery difficulty of the anhydride can be reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. In the drawings:
FIG. 1 is a schematic flow chart of a preparation method of hydroxyl silicone oil according to an embodiment of the present application;
Fig. 2 is a schematic flow chart of another preparation method of hydroxyl silicone oil according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below with reference to specific embodiments of the present application and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
As described in the background of the application, the anhydride hydrolysis method is a relatively common method for preparing hydroxyl silicone oil, and mainly comprises a ring opening stage and a hydrolysis stage. In the ring opening stage, the acid anhydride is added to end the ring-opened product, so that the repolymerization of the ring-opened product can be avoided. In the hydrolysis stage, the blocked ring-opened product is easy to carry out hydrolysis grafting hydroxyl reaction; and it is difficult to carry out the reaction of hydrolytically grafting hydroxyl groups after repolymerization of the ring-opened product which is not blocked. Based on this, in order to obtain a hydroxyl silicone oil having a higher hydroxyl group content and a lower viscosity, it is common practice to increase the amount of acid anhydride used to obtain a more ring-opened product terminated with an acetoxy group and to reduce the case of repolymerization of the ring-opened product. In the hydrolysis stage, more materials can be subjected to hydrolysis grafting hydroxyl reaction, so that the hydroxyl silicone oil with high hydroxyl content and low viscosity can be obtained. In practical application, the method for preparing the hydroxyl silicone oil with high hydroxyl content and low viscosity by increasing the using amount of the anhydride has the problems that the production cost is high due to the increased anhydride input amount, the recycling amount of the anhydride is increased, the recycling difficulty is increased and the like.
In view of the above, the embodiment of the application provides a preparation method of hydroxyl silicone oil, which can be used for preparing hydroxyl silicone oil with high hydroxyl content and low viscosity. Wherein, the hydroxyl silicone oil with high hydroxyl content and low viscosity can be specifically hydroxyl silicone oil with 5-15% of hydroxyl content and 5mm 2/s～50mm2/s of viscosity.
As shown in fig. 1, the preparation method of hydroxyl silicone oil provided by the embodiment of the application may include the following steps:
Step 101, mixing cyclic siloxane, acetic anhydride and a catalyst to obtain a first product.
The cyclic siloxane may include, among other things, dimethylsiloxane and/or hexamethylcyclotrisiloxane. When dimethylsiloxane is selected as cyclic siloxane, octamethyltetrasiloxane D4 may be specifically selected.
The catalyst may be an acidic catalyst. In order that the cyclic siloxane may be smoothly ring-opened, and the ring-opening efficiency may be improved, the catalyst may include a first catalyst and a second catalyst. Wherein the first catalyst can be used as a main catalyst and the second catalyst can be used as a cocatalyst. Further, the main catalyst may include strong acids such as concentrated sulfuric acid, acid clay, acid resin, sulfonic acid, and the like. The promoter may comprise acetic acid. By using acetic acid and strong acid in a combined way, the method is more beneficial to smooth ring opening and improvement of reaction efficiency compared with the method using single strong acid as a catalyst.
The cyclic siloxane can obtain an acetoxy-terminated ring-opening product under the action of acetic anhydride and a catalyst. The first product may be an acidic solution comprising an acetoxy terminated ring opened product.
Step 102, mixing the first product with an alkaline solution at a first preset temperature, wherein the first preset temperature is less than or equal to 0 ℃.
Wherein the alkaline solution may comprise sodium carbonate solution and/or sodium bicarbonate solution.
The inventors have found that the hydrolysis stage also affects the hydroxyl content and viscosity of the final hydroxyl silicone oil. On the one hand, when the alkaline solution is mixed with the acidic solution obtained after the ring opening stage, a neutralization reaction can occur to release a large amount of heat, and the local heat is too high to easily cause silicone oil polymerization, so that the hydroxyl content is reduced and the viscosity is increased. On the other hand, in the mixing stage of the alkaline solution and the acidic solution, the partial acetoxy-terminated ring-opened product also undergoes hydrolysis reaction, and in the mixing stage, the hydrolysis reaction of the solution also releases a large amount of heat to cause polymerization of silicone oil due to the fact that the hydrolysis reaction is in a meta-acid or meta-base environment (if the acidic solution is added to the alkaline solution, then in a meta-acid environment, if the alkaline solution is added to the acidic solution), so that the hydroxyl content is reduced and the viscosity is increased. It will be appreciated that although the related art has adopted an increase in the amount of anhydride used to increase the hydroxyl content and decrease the viscosity of the hydroxyl silicone oil, for the reasons described above, there is still some polymerization of the silicone oil during the hydrolysis stage which affects the hydroxyl content and viscosity of the final hydroxyl silicone oil.
In step 102 of the embodiment of the present application, the temperature is controlled to be less than or equal to 0 ℃ when the first product is mixed with the alkaline solution, that is, the mixing process of the first product and the alkaline solution is controlled to be performed at a low temperature. Therefore, a large amount of heat released by the neutralization reaction and the hydrolysis reaction in the mixing stage can be timely transferred, and further polymerization of the silicone oil can be avoided. By means of the low-temperature control of the hydrolysis stage to prevent the silicone oil from polymerizing, even if the anhydride is used in an amount smaller than that in the related art, the hydroxy silicone oil with higher hydroxy content and lower viscosity can be prepared.
In order to enable further timely heat transfer and not to affect the mixing of the first product with the alkaline solution, the first preset temperature may be set at-20 to 0 ℃. In particular, the first preset temperature may be-20 ℃, -15 ℃, -10 ℃, -5 ℃,0 ℃ or any temperature between the listed temperature values.
And step 103, heating to a second preset temperature to prepare the hydroxyl silicone oil.
The second preset temperature is higher than the first preset temperature, and is a temperature suitable for hydrolysis reaction. The second preset temperature may be 60-80 deg.c. Specifically, the second preset temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any temperature between the listed temperature values.
After the temperature is raised to the second preset temperature, most of the acetoxy-terminated ring-opened product undergoes hydrolysis at this stage.
In the embodiment of the application, the hydrolysis stage is divided into two sub-stages, wherein the first sub-stage is a stage of mixing the first product with the alkaline solution in a low-temperature control manner, and the second sub-stage is a stage of raising the temperature to a second preset temperature for hydrolysis. In this way, the first product and the alkaline solution are mixed before the temperature is raised to the second preset temperature for hydrolysis, the solution is nearly neutral, and the hydrolysis reaction in the second sub-stage is in a nearly neutral environment, so that a large amount of heat is not generated. Thereby, further polymerization of the silicone oil in the second sub-stage can also be avoided.
It can be understood that the preparation method of the hydroxyl silicone oil provided by the embodiment of the application comprises the following steps: mixing cyclic siloxane, acetic anhydride and a catalyst to obtain a first product; mixing the first product with an alkaline solution at a first preset temperature; heating to a second preset temperature to prepare hydroxyl silicone oil; wherein the first preset temperature is less than or equal to 0 ℃. By controlling the mixing process of the first product and the alkaline solution to be carried out at low temperature, a large amount of heat released by the neutralization reaction and the hydrolysis reaction in the mixing stage can be transferred in time, and further polymerization of silicone oil can be avoided. Thus, even if the using amount of the anhydride is small, the hydroxyl silicone oil with higher hydroxyl content and lower viscosity can be prepared. Furthermore, the input amount of the anhydride can be reduced, so that the production cost and the recovery difficulty of the anhydride can be reduced. Meanwhile, the hydroxyl silicone oil has higher hydroxyl content and lower viscosity, so that the dispersing effect is better, and the stability of the hydroxyl silicone oil is better.
On the other hand, in the related art, an acidic solution obtained by mixing an alkaline solution with an acidic solution obtained after a ring opening stage in a heated environment is mostly adopted, and the heated environment is favorable for hydrolysis reaction of an acetoxy-terminated ring opening product, so that a large amount of acetoxy-terminated ring opening product is hydrolyzed in the mixing stage, a large amount of heat is released, and silicone oil is polymerized. In the preparation method of the hydroxyl silicone oil provided by the embodiment of the application, the hydrolysis stage is divided into two sub-stages, wherein the first sub-stage is a stage of mixing a first product with an alkaline solution under low temperature control, and the second sub-stage is a stage of raising the temperature to a second preset temperature for hydrolysis. Therefore, the hydrolysis reaction strain of the hydrolysis in the first sub-stage is less, and the heat released by the hydrolysis reaction in the second sub-stage is also less, so that the heat released by the hydrolysis reaction in the whole hydrolysis stage can be reduced, the polymerization of silicone oil is reduced, the hydroxyl content of hydroxyl silicone oil is further improved, and the viscosity is reduced.
In addition, the use of the acid anhydride increases the use amount of the alkaline solution in the related art, and the generated wastewater is also increased. By adopting the preparation method of the hydroxyl silicone oil provided by the embodiment of the application, the hydroxyl silicone oil with higher hydroxyl content and lower viscosity can be prepared even if the using amount of the anhydride is small. Thus, the amount of acid anhydride to be added can be reduced, and the amount of alkaline solution to be used and the amount of waste water to be produced can be reduced accordingly.
In practical applications, to avoid mixing the first product with the alkaline solution too quickly to cause local heating too quickly to transfer heat in time, step 102, in one embodiment, mixes the first product with the alkaline solution at a first preset temperature, comprising: mixing the first product with an alkaline solution at a first preset temperature and for a first preset period of time; the first preset time period is greater than or equal to 1h.
Wherein, in a first preset period of time, the first product is mixed with the alkaline solution, which can be understood as: and (3) dropwise adding the first product into the alkaline solution until the first product is completely added, wherein the adding duration is the first preset duration. Or dropwise adding the alkaline solution into the first product until the alkaline solution is completely dropwise added, wherein the dropwise adding duration is the first preset duration.
It can be appreciated that by adopting the above scheme, the first product and the alkaline solution are mixed by controlling the first preset time period, so that the first product and the alkaline solution can be slowly mixed, the heat release speed can be slowed down, and the heat can be transferred in time.
Further, in one embodiment, the first preset duration is 1h to 2h. Specifically, the first preset duration may be 1h, 1.2h, 1.5h, 1.8h, 2h, or any duration between the listed duration values.
It can be understood that the first preset time length is controlled to be 1-2 hours, so that the heat release speed can be slowed down, and meanwhile, the production efficiency of the hydroxyl silicone oil can be considered.
In addition, the acetic anhydride can be recovered before the first product is mixed with the alkaline solution, thereby realizing the recycling.
In order to complete the mixing of the first product and the alkaline solution before the temperature is raised to the second preset temperature for hydrolysis, the solution is nearly neutral, and the second sub-stage hydrolysis reaction can be in a nearly neutral environment, in one embodiment, after the first product is mixed with the alkaline solution at the first preset temperature in step 102, and before the temperature is raised to the second preset temperature in step 103, the preparation method of the hydroxyl silicone oil provided in the embodiment of the present application further includes: the mixture obtained after mixing the first product with the alkaline solution is stirred for 0.5h-1h. Then, the mixture is heated to a second preset temperature. Wherein, stirring is carried out for 0.5h-1h, which can be 0.5h, 0.8h, 1h or any time period between the stirring time periods.
In practice, to allow for smooth ring opening and capping of the cyclic siloxane, in one embodiment, step 101 mixes the cyclic siloxane, acetic anhydride, and catalyst to obtain a first product comprising: and mixing cyclic siloxane, acetic anhydride and a catalyst, and controlling the temperature to be 100-160 ℃ for reaction for 4-6 hours to obtain the first product.
Specifically, the reaction may be conducted at 100 ℃,110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, or at any temperature between the values of the temperatures listed. The reaction time length of 4 h-6 h can be specifically 4h, 4.5h, 5h, 5.5h and 6h, or any time length among the listed time length values.
To enable sufficient hydrolysis of the acetoxy terminated ring-opened product during the hydrolysis stage, in one embodiment, step 103 is warmed to a second predetermined temperature to produce a hydroxy silicone oil comprising: heating to a second preset temperature, and controlling the reaction time to be 6-8 hours to prepare the hydroxyl silicone oil.
The reaction time period of 6 h-8 h can be specifically 6h, 6.5h, 7h, 7.5h and 8h, or any time period among the listed time period values.
In order to reduce impurities in the hydroxyl silicone oil and improve the transparency of the hydroxyl silicone oil, after the temperature is raised to a second preset temperature and the reaction time is controlled to be 6-8 hours, the reaction product can be further subjected to phase separation, dehydration, decoloration and other treatments, so that the hydroxyl silicone oil final product with high hydroxyl content and low viscosity is prepared.
In one embodiment, to increase the yield of hydroxy silicone oil, in one embodiment, the starting materials are prepared from: octamethyl cyclotetrasiloxane, acetic anhydride, concentrated sulfuric acid, acetic acid and sodium carbonate solution; the weight portions are as follows: 195-205 parts of octamethyl cyclotetrasiloxane, 70-80 parts of acetic anhydride, 5-6 parts of concentrated sulfuric acid, 10-15 parts of acetic acid and 800-1200 parts of sodium carbonate solution. Wherein the mass fraction of the sodium carbonate solution is 20%.
Wherein, the octamethyl cyclotetrasiloxane can take any value of 195-205, the acetic anhydride can take any value of 70-80, the concentrated sulfuric acid can take any value of 5-6, the acetic acid can take any value of 10-15, and the sodium carbonate solution can take any value of 800-1200.
Based on the preparation method of the hydroxyl silicone oil provided in the above embodiment of the present application, the embodiment of the present application further provides a more specific preparation method of the hydroxyl silicone oil, as shown in fig. 2, the preparation method may include:
Step 201, mixing octamethyl cyclotetrasiloxane, acetic anhydride, concentrated sulfuric acid and acetic acid, and controlling the temperature to be 100-160 ℃ for reaction for 4-6 hours to obtain a first product.
Step 202, dripping the first product into a sodium carbonate solution at the temperature of-20 ℃ to 0 ℃ for 1h to 2h, and stirring for 0.5h to 1h after the dripping is completed to obtain a mixture.
And 203, heating the mixture to 60-80 ℃, and controlling the reaction time to be 6-8 hours to prepare the hydroxyl silicone oil.
It can be understood that by adopting the preparation method of hydroxyl silicone oil provided by the embodiment of the application, a large amount of heat released by the neutralization reaction and the hydrolysis reaction in the mixing stage can be timely transferred by controlling the mixing process of the first product and the alkaline solution to be carried out at low temperature, so that further polymerization of silicone oil can be avoided. Thus, even if the using amount of the anhydride is small, the hydroxyl silicone oil with higher hydroxyl content and lower viscosity can be prepared. Furthermore, the input amount of the anhydride can be reduced, so that the production cost and the recovery difficulty of the anhydride can be reduced.
On the other hand, in the preparation method of the hydroxyl silicone oil provided by the embodiment of the application, the hydrolysis stage is divided into two sub-stages, wherein the first sub-stage is a stage of mixing a first product with an alkaline solution under low temperature control, and the second sub-stage is a stage of raising the temperature to a second preset temperature for hydrolysis. Therefore, the hydrolysis reaction strain of the hydrolysis in the first sub-stage is less, and the heat released by the hydrolysis reaction in the second sub-stage is also less, so that the heat released by the hydrolysis reaction in the whole hydrolysis stage can be reduced, the polymerization of silicone oil is reduced, the hydroxyl content of hydroxyl silicone oil is further improved, and the viscosity is reduced.
In addition, the embodiment of the application also provides hydroxyl silicone oil, which can be prepared according to the preparation method of the hydroxyl silicone oil provided by any embodiment of the application.
In order to facilitate the explanation of the preparation method and the effects achieved by the hydroxyl silicone oil provided in the examples of the present application, the following description will be made with reference to specific examples and comparative examples.
Example 1
200G of octamethyl cyclotetrasiloxane, 77g of acetic anhydride, 5.5g of concentrated sulfuric acid and 12.5g of acetic acid were weighed and reacted at 110℃for 6 hours.
The reaction solution was then added dropwise to the Na 2CO3 solution over 1h at a temperature of 0℃and stirred for 1h.
Gradually returning to room temperature, stirring at 80 ℃ for reaction for 6 hours, and then carrying out phase separation, dehydration, decoloration and other treatments to obtain the hydroxyl silicone oil.
The hydroxyl silicone oil obtained in example 1 has a hydroxyl group content of 5.5% and a viscosity of 38mm 2/s, as measured.
Example 2
200G of octamethyl cyclotetrasiloxane, 77g of acetic anhydride, 5.5g of concentrated sulfuric acid and 12.5g of acetic acid were weighed and reacted at 110℃for 6 hours.
Then, the reaction solution was added dropwise to the Na 2CO3 solution over 1 hour at a temperature of-5℃and stirred for 1 hour.
Gradually returning to room temperature, stirring at 80 ℃ for reaction for 6 hours, and then carrying out phase separation, dehydration, decoloration and other treatments to obtain the hydroxyl silicone oil.
The hydroxyl silicone oil obtained in example 2 was found to have a hydroxyl group content of 7.2% and a viscosity of 33mm 2/s.
Example 3
200G of octamethyl cyclotetrasiloxane, 77g of acetic anhydride, 5.5g of concentrated sulfuric acid and 12.5g of acetic acid were weighed and reacted at 110℃for 6 hours.
Then, the reaction solution was added dropwise to the Na 2CO3 solution over 1 hour at a temperature of-10℃and stirred for 1 hour.
Gradually returning to room temperature, stirring at 80 ℃ for reaction for 6 hours, and then carrying out phase separation, dehydration, decoloration and other treatments to obtain the hydroxyl silicone oil.
The hydroxyl silicone oil obtained in example 3, as tested, has a hydroxyl content of: 8.9% and a viscosity of 25mm 2/s.
Comparative example 1
200G of octamethyl cyclotetrasiloxane, 77g of acetic anhydride, 5.5g of concentrated sulfuric acid and 12.5g of acetic acid were weighed and reacted at 110℃for 6 hours.
The reaction solution was then added dropwise to the Na 2CO3 solution over 1h at room temperature and stirred for 1h.
Then stirring and reacting for 6 hours at 80 ℃, and then carrying out treatments such as phase separation, dehydration, decoloration and the like to prepare the hydroxyl silicone oil.
The hydroxyl silicone oil obtained in comparative example 1 was found to have a hydroxyl group content of 3.2% and a viscosity of 75mm 2/s.
Comparative example 2
200G of octamethyl cyclotetrasiloxane, 77g of acetic anhydride, 5.5g of concentrated sulfuric acid and 12.5g of acetic acid were weighed and reacted at 110℃for 6 hours.
The reaction solution was then added dropwise to the Na 2CO3 solution at 60℃over 1h, and stirred for 1h.
Then stirring and reacting for 6 hours at 80 ℃, and then carrying out treatments such as phase separation, dehydration, decoloration and the like to prepare the hydroxyl silicone oil.
The hydroxyl silicone oil prepared in comparative example 2 has the following hydroxyl content by detection: 0.8% and a viscosity of 135mm 2/s.
As can be seen from the examples and comparative examples, by adopting the preparation method of hydroxyl silicone oil provided by the above examples of the present application, by controlling the mixing process of the first product and the alkaline solution to be performed at a low temperature, a large amount of heat released by the neutralization reaction and the hydrolysis reaction in the mixing stage can be transferred in time, and further, silicone oil can be prevented from further polymerization. Thus, the hydroxyl silicone oil with higher hydroxyl content and lower viscosity can be prepared. Meanwhile, the hydrolysis stage is divided into two sub-stages, wherein the first sub-stage is a stage of mixing the first product and the alkaline solution in a low-temperature control manner, and the second sub-stage is a stage of raising the temperature to a second preset temperature for hydrolysis. Therefore, the hydrolysis reaction strain of the hydrolysis in the first sub-stage is less, and the heat released by the hydrolysis reaction in the second sub-stage is also less, so that the heat released by the hydrolysis reaction in the whole hydrolysis stage can be reduced, the polymerization of silicone oil is reduced, the hydroxyl content of hydroxyl silicone oil is further improved, and the viscosity is reduced.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises the element.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various combinations, modifications, and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are to be included in the scope of the claims of the present application.
Claims (8)
1. A preparation method of hydroxyl silicone oil, which is characterized by comprising the following steps: mixing cyclic siloxane, acetic anhydride and a catalyst to obtain a first product; mixing the first product with an alkaline solution at a first preset temperature; heating to a second preset temperature to prepare hydroxyl silicone oil; wherein the first preset temperature is less than or equal to 0 ℃, and the first preset time period is greater than or equal to 1h.
2. The method for preparing hydroxyl silicone oil according to claim 1, wherein the first preset temperature is-20 ℃ to 0 ℃.
3. The method for preparing hydroxyl silicone oil according to claim 1, wherein the first preset time period is 1h to 2h.
4. A method of preparing a hydroxy silicone oil according to claim 1, wherein the cyclic siloxane comprises dimethyl siloxane and/or hexamethyl cyclotrisiloxane.
5. The method for preparing hydroxyl silicone oil according to claim 1, wherein the catalyst comprises a first catalyst and a second catalyst; the first catalyst comprises a strong acid; the second catalyst comprises acetic acid.
6. The method for preparing hydroxyl silicone oil according to claim 1, wherein the alkaline solution comprises sodium carbonate solution and/or sodium bicarbonate solution.
7. The method for preparing hydroxyl silicone oil according to claim 1, wherein the heating to the second preset temperature prepares hydroxyl silicone oil, comprising: heating to a second preset temperature, and controlling the reaction time to be 6-8 hours to prepare the hydroxyl silicone oil; wherein the second preset temperature is 60-80 ℃.
8. The method for preparing hydroxyl silicone oil according to claim 1, wherein the mixing of cyclic siloxane, acetic anhydride and catalyst to obtain a first product comprises: and mixing cyclic siloxane, acetic anhydride and a catalyst, and controlling the temperature to be 100-160 ℃ for reaction for 4-6 hours to obtain the first product.
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