CN113024818B - Preparation method of high-purity low-byproduct polyether modified siloxane - Google Patents
Preparation method of high-purity low-byproduct polyether modified siloxane Download PDFInfo
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Abstract
The invention belongs to the field of organosilicon synthesis, and particularly relates to a preparation method of polyether modified siloxane with high purity and low by-product. The preparation method comprises the steps of adding a stabilizing auxiliary agent into allyl polyether, then adding the hydrogen-containing siloxane and the alkenyl polyether added with the stabilizing auxiliary agent into a reactor, then adding a certain amount of antioxidant, introducing nitrogen for protection, reacting at 30-150 ℃ for 1-10 hours in the presence of a platinum catalyst, stopping the reaction after no residual hydrogen exists through infrared detection, and filtering the synthesized product to obtain the product with light color, high purity, less impurities, good performance and stable quality.
Description
Technical Field
The invention belongs to the field of organosilicon synthesis, and particularly relates to a preparation method of polyether modified siloxane with high purity and low by-product.
Background
Hydrosilylation refers to a process in which a Si-H containing hydrogen-containing siloxane and an unsaturated organic compound undergo an addition reaction to give a modified organosilicon compound. Unsaturated organic compounds commonly used in hydrosilylation include alkenyl polyethers, unsaturated olefins, olefinic acid esters, olefinic alcohols, and the like. The polyether modified siloxane is an important organosilicon surfactant and is widely applied to the industries such as coating industry, polyurethane, pesticide, daily chemical industry and the like. The pesticide organosilicon synergist is widely applied and researched due to the unique wettability.
The pesticide synergist can obviously improve the wetting, spreading, dispersing and penetrating performances, and the action mechanism mainly inhibits or weakens the detoxification and phytotoxicity prevention effects of targets (pests, weeds, germs and the like) on the pesticide activity, delays the metabolism speed of the pesticide in a control object, and further increases the biological control effect.
At present, the most efficient and common pesticide synergist is an organosilicon surfactant, and particularly, the polyether modified heptamethyltrisiloxane organosilicon surfactant is the most widely and mature type in agriculture at present. The polyether modified heptamethyltrisiloxane silicone surfactant can obviously reduce the surface tension of water, has the advantages of good wettability, strong adhesiveness, excellent wetting and spreading properties, high air pore permeability, good rain erosion resistance and the like, is suitable for various herbicides, insecticides, bactericides, plant growth regulators, biological pesticides and leaf fertilizers as a pesticide synergist, and can save the pesticide consumption by more than 40% and save water by more than 1/3.
The silicone surfactants are different from most common surfactants in linear structure, and the chemical structure of the silicone surfactants is a T-shaped structure, and methylated siloxane forms a framework to form a hydrophobic part. One or more polyether segments are suspended from the backbone to form the hydrophilic portion, and the properties of the surfactant may vary greatly depending on the polyether structure.
The conventional production and synthesis mode adopts a stirring type reaction kettle for reaction, for example, patent CN 101690878A, but the reaction temperature is difficult to control in the reaction process and the temperature flushing phenomenon is serious because the hydrosilylation of allyl polyether and heptamethyltrisiloxane is strongly exothermic, and the allyl polyether and the heptamethyltrisiloxane are difficult to timely and fully remove through a jacket outside the reaction kettle, so that local hot spots are formed, unnecessary side reactions are caused, the product is often rich in impurities, high in viscosity and deep in color, and the final synergistic effect is greatly reduced.
Disclosure of Invention
In order to solve the technical problems of insufficient reaction, difficult temperature control, more side reactions and environmental pollution in the prior art, the application aims to provide the preparation method of the polyether modified siloxane with high purity and low by-product.
In order to achieve the above object, the present application adopts the following technical solutions:
a preparation method of polyether modified siloxane with high purity and low byproduct comprises the following steps: 1) synthesizing hydrogen-containing siloxane, 2) synthesizing polyether modified siloxane; adding hydrogen-containing siloxane and alkenyl polyether added with a stabilizing auxiliary agent into a reactor in the step 2), adding an antioxidant, introducing nitrogen for protection, reacting for 1-10 hours at 30-150 ℃ in the presence of a metal catalyst, stopping the reaction after no residual hydrogen is detected, and filtering the synthesized product to obtain polyether modified siloxane; the stabilizing additive is at least one of alkali metal salt or alkaline earth metal salt, and the addition amount of the stabilizing additive is 1-2000 ppm; the antioxidant comprises at least one of peroxide decomposition type antioxidant, free radical scavenging type antioxidant and metal deactivation type antioxidant, and the addition amount of the antioxidant is 1-5000 ppm.
Preferably, the polyether modified siloxane has the following structural formula:
wherein: m =0-4, n =1-3, x =2-4, a =4-20, b =0-10, R = H or CH3CO-or CyH2y+1，y=1-9。
Preferably, the mass ratio of the hydrogen-containing siloxane to the allyl polyether in the step 2) is 50-100: 50-500.
Preferably, the addition amount of the stabilizing additive in the step 2) is 100-1500 ppm; the amount of the antioxidant added was 100-2000 ppm.
Preferably, the metal catalyst in the step 2) is a complex containing palladium, rhodium or platinum, and the addition amount of the metal catalyst is 1-1000 ppm; more preferably, the amount of the catalyst added is 1-300 ppm.
Preferably, the metal catalyst in the step 2) is a platinum metal catalyst, and is at least one of chloroplatinic acid isopropanol solution, platinum-divinyldisiloxane Karstedt platinum catalyst, platinum-allyl polyether Karstedt catalyst and supported solid platinum catalyst.
Preferably, the stabilizing auxiliary agent in step 2) comprises at least one of sodium salt, potassium salt, calcium salt and barium salt, and is preferably NaCl and Na2SO4、Na3PO4、KCl、K2SO4、K3PO4、CaCl2、CaSO4、Ca3（PO4）2、BaCl2、BaSO4、Ba3（PO4）2At least one of them.
Preferably, the antioxidant in step 2) includes at least one of zinc dialkyldithiophosphate, zinc dialkyldithiocarbamate, N-phenyl- α -naphthylamine, alkylphenothiazine, benzotriazole derivatives, mercaptobenzothiazole derivatives, 2, 6-di-tert-butyl-p-cresol, 3,4, 5-trihydroxybenzoic acid, tocopherol, and the like.
Preferably, the synthesis of the hydrosiloxane in step 1) comprises the following steps:
1) hexamethyldisiloxane, dimethyl mixed cyclosiloxane or octamethylcyclotetrasiloxane, and methyl hydrogen mixed cyclosiloxane or tetramethylcyclotetrasiloxane are mixed according to the mass ratio of 14: 0-50: 1-30 and an acid catalyst are added into a reaction vessel, the temperature is controlled to be 10-80 ℃, the reaction is carried out for 3-16 hours, the acid catalyst is treated, and then the hydrogen-containing siloxane is obtained by rectification and purification, wherein the hydrogen-containing siloxane has the following structure:
wherein m =0-4, n = 1-3;
the acidic catalyst protonic acid or strong acidic ion exchange resin is preferably any one of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated phosphoric acid, trifluoromethanesulfonic acid and strong acidic ion exchange resin.
The preparation method comprises the steps of putting hydrogen-containing siloxane and alkenyl polyether into a four-neck flask, adding a stabilizer and an antioxidant, introducing nitrogen, stirring, heating to 30-150 ℃ in the presence of a metal catalyst, reacting for 1-12 hours, stopping the reaction after no Si-H residue is detected, and adsorbing and filtering by using activated carbon to obtain a finished product.
Further, the application also discloses polyether modified siloxane prepared by the method, and the detection viscosity of the polyether modified siloxane is 30-60mm20.1 wt% aqueous solution with surface tension of 20-24mN/m, and wetting 20 μ L of 0.1% aqueous solution on polyethylene filmWet area of 30-100mm2。
By adopting the technical scheme, the preparation method disclosed by the invention does not use a solvent, does not generate toxic raw materials, does not generate waste gas or waste water, effectively controls reaction heat release by adding the stabilizer and the antioxidant, reduces side reactions, and has high product purity and stable quality. The invention has simple process, can circularly react and can realize continuous production.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a hydrosiloxane of the present application.
FIG. 2 is a schematic diagram of the hydrosilylation reaction scheme.
Detailed Description
Example 1
1) Preparation of hydrogen-containing siloxanes
135g of hexamethyldisiloxane, 50g of tetramethylcyclotetrasiloxane and 1g of cation exchange resin are added into a 500mL four-neck flask, the temperature is controlled at 30 ℃ under stirring, the reaction is carried out for 5h, the cation exchange resin is removed by filtration, and then the material is rectified and purified to obtain 74g of hydrogenous trisiloxane (MD' M) with the content of 99 percent.
2) Hydrosilylation reaction
Adding 50g of 99% hydrogen-containing trisiloxane and 135g of allyl polyether (x =3, a =10, b =0, R = H) into a 500mL four-neck flask, adding 1000ppm NaCl and 1000ppm BHT antioxidant, stirring and heating to 80 ℃ by introducing nitrogen, adding 5ppm chloroplatinic acid isopropanol solution, continuously heating to 100 ℃ for heat preservation, heating to 105 ℃ by heat release and flushing, sampling uninterruptedly by infrared, and no Si-H residue exists in 3H to indicate complete reaction, stopping the reaction, and filtering to obtain light yellow transparent liquid. The detected viscosity is 35.8mm2(ii)/s, surface tension (0.1% by weight aqueous solution) of 20.2mN/m, and a wet area of 20. mu.L of 0.1% strength aqueous solution on a polyethylene film of 80mm2。
Comparative example 1
1) Preparation of hydrogen-containing siloxanes
135g of hexamethyldisiloxane, 50g of tetramethylcyclotetrasiloxane and 1g of cation exchange resin are added into a 500mL four-neck flask, the temperature is controlled at 30 ℃ under stirring, the reaction is carried out for 5h, the cation exchange resin is removed by filtration, and then the material is rectified and purified to obtain 74g of hydrogenous trisiloxane (MD' M) with the content of 99 percent.
2) Hydrosilylation reaction
Adding 50g of 99% hydrogen-containing trisiloxane and 135g of allyl polyether (x =3, a =10, b =0, R = H) into a 500mL four-neck flask, introducing nitrogen, stirring and heating to 80 ℃, adding 5ppm of chloroplatinic acid isopropanol solution, continuously heating to 100 ℃, keeping the temperature, heating to 130 ℃, continuously sampling by infrared, and filtering to obtain light yellow transparent liquid when no Si-H remains in 6 hours, which indicates that the reaction is complete. The detected viscosity is 50.2mm2(ii)/s, surface tension (0.1% by weight aqueous solution) of 20.8mN/m, and a wet area of 65mm on a polyethylene film from 20. mu.L of a 0.1% strength aqueous solution2。
Comparative example 2
1) Preparation of hydrogen-containing siloxanes
81g of hexamethyldisiloxane, 37g of dimethyl mixed cyclosiloxane, 30g of tetramethylcyclotetrasiloxane and 1g of concentrated sulfuric acid are added into a 500mL four-neck flask, the temperature is controlled at 20 ℃ under stirring, the mixture reacts for 12 hours, sulfuric acid is neutralized by sodium carbonate, neutralized salts are removed by filtration, and then the material is rectified and purified to obtain 59.2g of hydrosiloxane (MDD' M) with the content of 95%.
2) Hydrosilylation reaction
40g of 95% hydrosiloxane and 146g of vinyl polyether (x =2, a =5, b =3, R = H) are added into a 500mL four-neck flask, 1000ppm of K3PO4 is added, 10ppm of Pt-divinyl disiloxane Karstedt catalyst is added when the temperature is raised to 80 ℃ by stirring through nitrogen, the temperature is continuously heated to 100 ℃ and is kept, the temperature is raised to 110 ℃ by heat release, infrared uninterrupted sampling is carried out, no Si-H is left when 4 hours exist, the reaction is complete, the reaction is stopped, and light yellow transparent liquid is obtained by filtration. The detected viscosity is 65.1mm2(ii)/s, surface tension (0.1% by weight aqueous solution) of 21.3mN/m, and a wet area of 53mm on a polyethylene film from 20. mu.L of a 0.1% strength aqueous solution2。
Comparative example 3
1) Preparation of hydrogen-containing siloxanes
81g of hexamethyldisiloxane, 37g of dimethyl mixed cyclosiloxane, 30g of tetramethylcyclotetrasiloxane and 1g of concentrated sulfuric acid are added into a 500mL four-neck flask, the temperature is controlled at 20 ℃ under stirring, the mixture reacts for 12 hours, sulfuric acid is neutralized by sodium carbonate, neutralized salts are removed by filtration, and then the material is rectified and purified to obtain 59.2g of hydrosiloxane (MDD' M) with the content of 95%.
2) Hydrosilylation reaction
Adding 40g of 95% hydrosiloxane and 146g of vinyl polyether (x =2, a =5, b =3, R = H) into a 500mL four-neck flask, adding 100ppm of antioxidant 3,4, 5-trihydroxybenzoic acid, stirring and heating to 80 ℃ by introducing nitrogen, adding 10ppm of Pt-divinyl disiloxane Karstedt catalyst, continuously heating to 100 ℃ for heat preservation, heating to 130 ℃ by heat release and flushing, sampling without interruption by infrared, and obtaining a light yellow transparent liquid after filtering when no Si-H remains in 6H, which indicates that the reaction is complete. The detected viscosity is 78.9mm2(ii)/s, surface tension (0.1% by weight aqueous solution) of 22.0mN/m, and a wetted area of 20. mu.L of 0.1% strength aqueous solution on a polyethylene film of 41mm2。
Example 2
1) Preparation of hydrogen-containing siloxanes
81g of hexamethyldisiloxane, 81.4g of octamethylcyclotetrasiloxane, 66.8g of methylhydrogen cyclosiloxane mixture and 0.1g of trifluoromethanesulfonic acid were placed in a 500mL four-necked flask, the temperature was controlled at 10 ℃ with stirring, the reaction was carried out for 8 hours, trifluoromethanesulfonic acid was neutralized with sodium carbonate, the neutralized salts were removed by filtration, and the material was purified by rectification to obtain 80.1g of a hydrosiloxane (MD 2D' 2M) having a content of 80%.
2) Hydrosilylation reaction
Adding 30g of 95% hydrosiloxane and 152g of methyl allyl polyether (x =4, a =10, b =4, R = CH 3) into a 500mL four-neck flask, adding 500ppm of mCaSO4 and 300ppm of antioxidant tocopherol, introducing nitrogen, stirring, heating to 80 ℃, adding 3ppm of platinum-allyl polyether catalyst, continuously heating to 110 ℃, keeping the temperature, heating to 108 ℃, continuously sampling by infrared, and obtaining a light yellow transparent liquid after filtering, wherein no Si-H residue exists in 4H and indicates that the reaction is complete. The detected viscosity is 58.3mm2(ii)/s, surface tension (0.1% wt aqueous solution) 23.2mN/m, 20. mu.L 0.1% concentrationThe wetting area of the aqueous solution on the polyethylene film was 32mm2。
Comparative example 4
1) Preparation of hydrogen-containing siloxanes
81g of hexamethyldisiloxane, 81.4g of octamethylcyclotetrasiloxane, 66.8g of methylhydrogen cyclosiloxane mixture and 0.1g of trifluoromethanesulfonic acid were placed in a 500mL four-necked flask, the temperature was controlled at 10 ℃ with stirring, the reaction was carried out for 8 hours, trifluoromethanesulfonic acid was neutralized with sodium carbonate, the neutralized salts were removed by filtration, and the material was purified by rectification to obtain 80.1g of a hydrosiloxane (MD 2D' 2M) having a content of 80%.
2) Hydrosilylation reaction
Adding 30g of 95% hydrosiloxane and 152g of methyl allyl polyether (x =4, a =10, b =4, R = CH 3) into a 500mL four-neck flask, adding 100ppm of MecASO 4 and 300ppm of antioxidant tocopherol, introducing nitrogen, stirring, heating to 80 ℃, adding 3ppm of platinum-allyl polyether catalyst, continuously heating to 110 ℃, keeping the temperature, heating to 120 ℃, continuously sampling by infrared, and obtaining a light yellow transparent liquid after filtering, wherein no Si-H remains in 4H and indicates that the reaction is complete. The detected viscosity is 75.2mm2(ii)/s, surface tension (0.1% by weight aqueous solution) of 24.5mN/m, and a wet area of 20. mu.L of 0.1% strength aqueous solution on a polyethylene film of 10mm2。
Example 3
1) Preparation of hydrogen-containing siloxanes
121.5g of hexamethyldisiloxane, 90g of tetramethylcyclotetrasiloxane and 1g of concentrated phosphoric acid are added into a 500mL four-neck flask, the temperature is controlled at 40 ℃ under stirring, the reaction is carried out for 10h, the concentrated phosphoric acid is neutralized by sodium carbonate, the neutralized salt is removed by filtration, and then the material is rectified and purified to obtain 63.5g of hydrosiloxane (MD' 2M) with the content of 98 percent.
2) Hydrosilylation reaction
Adding 30g of 98% hydrosiloxane and 161g of allyl polyether (x =3, a =9, b =3, R = CH3 COO) into a 500mL four-neck flask, adding 200ppm of BaCl2 and 500ppm of BHT antioxidant, stirring and heating to 80 ℃ by introducing nitrogen, adding 20ppm of supported platinum catalyst, continuing to heat to 120 ℃, keeping the temperature, heating to 132 ℃ by heat release and flushing, and carrying out infrared ray treatmentSampling is carried out continuously, no Si-H residue exists in 5 hours, the reaction is complete, the reaction is stopped, and light yellow transparent liquid is obtained by filtering. The detected viscosity was 49mm2(ii)/s, surface tension (0.1% by weight aqueous solution) of 22.4mN/m, and a wet area of 40mm on a polyethylene film from 20. mu.L of a 0.1% strength aqueous solution2。
Comparative example 5
1) Preparation of hydrogen-containing siloxanes
121.5g of hexamethyldisiloxane, 90g of tetramethylcyclotetrasiloxane and 1g of concentrated phosphoric acid are added into a 500mL four-neck flask, the temperature is controlled at 40 ℃ under stirring, the reaction is carried out for 10h, the concentrated phosphoric acid is neutralized by sodium carbonate, the neutralized salt is removed by filtration, and then the material is rectified and purified to obtain 63.5g of hydrosiloxane (MD' 2M) with the content of 98 percent.
2) Hydrosilylation reaction
30g of 98% hydrosiloxane and 161g of allyl polyether (x =3, a =9, b =3, R = CH3 COO) are added into a 500mL four-neck flask, 200ppm of BaCl2 is added, the mixture is stirred by introducing nitrogen and heated to 80 ℃, 20ppm of supported platinum catalyst is added, the mixture is continuously heated to 120 ℃ for heat preservation, the temperature is raised to 145 ℃ by heat release and flushing, infrared uninterrupted sampling is carried out, no Si-H residue exists in 7H, the reaction is complete, the reaction is stopped, and a light yellow transparent liquid is obtained by filtration. The detected viscosity is 63mm2(ii)/s, surface tension (0.1% by weight aqueous solution) of 23.8mN/m, and a wet area of 28mm on a polyethylene film from 20. mu.L of a 0.1% strength aqueous solution2。
The process conditions of the examples and comparative examples of the present application are as follows:
TABLE 1
The product properties of the examples and comparative examples of the present application are as follows in table 2:
TABLE 2
| Viscosity (mm)2/s） | Surface tension (mN/m) | Wetted area (mm)2） | |
| Example 1 | 35 | 20.2 | 80 |
| Comparative example 1 | 50 | 20.8 | 65 |
| Comparative example 2 | 65 | 21.3 | 53 |
| Comparative example 3 | 78 | 22.0 | 41 |
| Example 2 | 58 | 23.2 | 32 |
| Comparative example 4 | 75 | 24.5 | 10 |
| Example 3 | 49 | 22.4 | 40 |
| Comparative example 5 | 63 | 23.8 | 28 |
Continuous production device includes:
storage tank: for storing the raw material;
a metering pump: a conveying device for conveying the raw materials in proportion;
circulating pump: a material conveying device of the circulating intermediate tank;
a preheater: heating the raw materials;
a packed tower: the inside is provided with a load type catalyst to ensure the hydrosilylation reaction;
packed tower temperature sensor: feeding back the exothermic condition of the reaction, and adjusting the conveying flow of the raw materials in time;
a filtering device: the interior is filled with active carbon.
Hydrogen-containing siloxane is put into the storage tank 1, alkenyl polyether is put into the storage tank 2, and an antioxidant and a stabilizer are added into the storage tank 2 and are uniformly mixed with the alkenyl polyether.
The set temperature of the preheater is 20-180 ℃, and the conveying speed of the storage tank 1 and the storage tank 2 is (10-10000): (10-10000) Kg/h, which is determined by the structures and molecular weights of hydrosiloxane and alkenyl polyether.
The conventional kettle type stirrer is omitted in the conveying device, so that the phenomenon of uneven reaction caused by material layering in the conveying process after mixing is avoided, and the materials are directly conveyed to the platinum catalyst packed tower in proportion through the feeding pump; the packed tower is provided with a temperature sensing device, so that the feeding temperature can be effectively controlled by displaying the temperature for different formulas, and the stable reaction is ensured; the device is provided with a circulating intermediate pump, wherein the circulating intermediate pump can be used for storing intermediate products, and two materials which are not completely reacted are conveyed to a platinum catalyst packed tower to carry out secondary reaction to multiple times of reaction for remediation, so that unqualified products caused by insufficient reaction are effectively avoided; and (3) performing activated carbon adsorption filtration treatment on the material which is completely reacted to obtain a product with lighter color and higher appearance quality.
One specific embodiment is as follows:
the preparation method comprises the steps of putting allyl polyether with the molecular weight of 400 into a storage tank 2, adding 1000ppm K3PO4 and 1000ppm BHT antioxidant into the storage tank, putting hydrogen-containing trisiloxane (MD' M) into a storage tank 1, setting the temperature of a preheater to be 100 ℃, simultaneously and proportionally conveying two raw materials by a metering pump at the same time, wherein the conveying speed of the hydrogen-containing trisiloxane is 100Kg/H, the conveying speed of the allyl polyether is 210Kg/H, feeding the materials passing through the preheater into a reaction device filled with a supported platinum catalyst, continuously conveying the materials upwards from the bottom by the pressure of the pump, fully contacting the platinum catalyst, displaying the temperature by a temperature sensing device to be 103 ℃, sampling from the top, detecting by infrared rays, and filtering the materials by an activated carbon filtering device to obtain a finished product which is colorless and transparent liquid. The detected viscosity is 36.3mm2Pt-Co color 20, surface tension (0.1% wt aqueous solution) 20.1mN/m, and wet area of 20. mu.L of 0.1% aqueous solution on polyethylene film 80mm2。
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, including any reference to the above-mentioned embodiments. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of polyether modified siloxane with high purity and low byproduct comprises the following steps: 1) synthesizing hydrogen-containing siloxane, 2) synthesizing polyether modified siloxane; the method is characterized in that hydrogen-containing siloxane and alkenyl polyether added with a stabilizing auxiliary agent in the step 2) are added into a reactor, then antioxidant is added, nitrogen is introduced for protection, the reaction is carried out for 1 to 10 hours at 30 to 150 ℃ in the presence of a metal catalyst, the reaction is stopped after no residual hydrogen is detected, and the synthesized product is filtered to obtain polyether modified siloxane; the stabilizing additive is at least one of alkali metal salt or alkaline earth metal salt, and the addition amount of the stabilizing additive is 1-2000 ppm; the antioxidant comprises at least one of peroxide decomposition type antioxidant, free radical scavenging type antioxidant and metal deactivation type antioxidant, and the addition amount of the antioxidant is 1-5000 ppm;
the polyether modified siloxane has the following structural formula:
wherein: m =0-4, n =1-3, x =2-4, a =4-20, b =0-10, R = H or CH3CO-or CyH2y+1，y=1-9；
The stabilizing auxiliary agent comprises NaCl and Na2SO4、Na3PO4、KCl、K2SO4、K3PO4、CaCl2、CaSO4、Ca3（PO4）2、BaCl2、BaSO4And Ba3（PO4）2At least one of (1);
the antioxidant comprises at least one of zinc dialkyl dithiophosphate, zinc dialkyl dithiocarbamate, N-phenyl-alpha-naphthylamine, alkyl phenothiazine, 2, 6-di-tert-butyl-p-cresol, 3,4, 5-trihydroxy benzoic acid and tocopherol.
2. The method for preparing high-purity low-byproduct polyether modified siloxane according to claim 1, wherein the mass ratio of the hydrogen-containing siloxane to the allyl polyether in the step 2) is 50-100: 50-500.
3. The method for preparing high purity low by-product polyether modified siloxane as claimed in claim 1, wherein the amount of the stabilizing additive added in step 2) is 100-1500 ppm; the amount of the antioxidant added was 100-2000 ppm.
4. The method for preparing polyether modified siloxane with high purity and low byproduct according to claim 1, wherein the metal catalyst in step 2) is a complex containing palladium, rhodium or platinum, and the addition amount of the metal catalyst is 1-1000 ppm.
5. The method for preparing a high purity low by-product polyether modified siloxane according to claim 4, wherein the amount of the metal catalyst added in step 2) is 1-300 ppm.
6. The method for preparing high-purity low-byproduct polyether modified siloxane according to claim 1, wherein the metal catalyst in the step 2) is a platinum metal catalyst.
7. The method for preparing high-purity low-byproduct polyether modified siloxane according to claim 6, wherein the metal catalyst is at least one of chloroplatinic acid isopropanol solution, platinum-divinyl disiloxane Karstedt platinum catalyst, platinum-allyl polyether Karstedt catalyst and supported solid platinum catalyst.
8. The method for preparing high-purity polyether-modified siloxane with low byproduct according to claim 1, wherein the synthesis of the hydrosiloxane in step 1) comprises the following steps:
1) hexamethyldisiloxane, dimethyl mixed cyclosiloxane or octamethylcyclotetrasiloxane, and methyl hydrogen mixed cyclosiloxane or tetramethylcyclotetrasiloxane are mixed according to the mass ratio of 14: 0-50: 1-30 and an acidic catalyst are added into a reaction vessel, the temperature is controlled to be 10-80 ℃, the reaction lasts for 3-16 hours, the acidic catalyst is treated, and then the rectification and purification are carried out to obtain the needed hydrogen-containing siloxane, wherein the hydrogen-containing siloxane has the following structure:
wherein m =0-4, n = 1-3;
the acidic catalyst is protonic acid or strong acidic ion exchange resin.
9. The method according to claim 8, wherein the acidic catalyst is any one of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated phosphoric acid, trifluoromethanesulfonic acid, and strongly acidic ion exchange resin.
10. The polyether modified siloxane prepared by the method of any one of claims 1 to 9, wherein the polyether modified siloxane has a viscosity of 30 to 60mm20.1% by weight aqueous solution having a surface tension of 20-24mN/m, and 20. mu.L of a 0.1% strength aqueous solution having a wetting area of 30-100mm on a polyethylene film2。
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