Continuous synthesis method of organosilicon polyether copolymer

Abstract

The invention relates to a continuous synthesis method of an organosilicon polyether copolymer. The continuous synthesis method comprises the following steps: mixing, hydrosilylation and epoxy ring-opening polymerization. The invention solves the problems of high risk, low safety factor, low product conversion, low purity and the like in the production process. Compared with a traditional process of firstly polymerizing and then adding, the process of firstly adding and then polymerizing has the advantages that the reaction is more controllable, and the product quality is more stable. The preparation method is simple in process, mild in reaction condition and high in conversion rate. In addition, the prepared organosilicon polyether copolymer is good in wetting and dispersing performance and low in raw material cost, and the organosilicon polyether copolymer has good application prospects in the aspects of defoaming, wetting, leveling, emulsifying and the like. The invention can be widely applied to defoaming agents, paints, high-temperature semiconductors, crystalline silicon cutting and the like.

Description

Technical Field

[0001] The invention relates to the technical field of silicone polyether, and in particular to a continuous synthesis method of an organosilicon polyether copolymer. Background Art

[0002] Silicone polyether copolymer combines the advantages of silicone and polyether on the basis of silicone and polyether. Silicone, as a hydrophobic group, makes the product have low surface tension and excellent chemical stability, electrical insulation, anti-aging and other properties; polyether, as a hydrophilic group, makes the product have good surface activity. The type, quantity and position of polyether can effectively adjust the hydrophilicity and lipophilicity of the copolymer, thereby obtaining different properties such as foam stabilization, defoaming, lubrication and emulsification.

[0003] Silicone polyether copolymers can replace the Span Tween series of non-ionic emulsifiers, solving the problem of easy foaming and high temperature resistance of the series of non-ionic emulsifiers. Silicone polyether copolymers can be used in various industrial fields, such as defoamers, chemicals, food processing, pharmaceuticals, textiles, plastics, coatings, polyurethanes, printing inks, oil extraction and other industries.

[0004] The existing processes for synthesizing organosilicon polyether copolymers mostly use traditional kettle reactors, which have high reaction temperatures, high pressures, high risks, and problems such as low conversion rates and low product purity. Summary of the invention

[0005] In view of the above problems, the present invention provides a continuous synthesis method of an organosilicon polyether copolymer, which uses a microchannel reactor as the main reaction equipment, hydrogen-containing silicone oil and enol oligomers as the main raw materials, and the reactor is modified to facilitate the addition of a catalyst, and then the reaction pressure, temperature, ratio, flow rate, and time conditions are further adjusted to prepare an intermediate. The intermediate is then polymerized with an epoxy compound to produce an organosilicon polyether copolymer.

[0006] The specific method of the present invention is:

[0007] A continuous synthesis method of an organosilicon polyether copolymer, using a microchannel reactor as a reaction device, the microchannel reactor comprising a first temperature zone and a second temperature zone connected in series, the first temperature zone and the second temperature zone both comprising a plurality of reaction modules connected in series, the specific steps are as follows:

[0008] S1, mixing: adding the catalyst into the hydrogen-containing silicone oil and mixing evenly;

[0009] S2, hydrosilylation: pumping the hydrogenated silicone oil catalyst mixed liquid reaction liquid and the enolate oligomer into the first temperature zone of the microchannel reactor at the same time, mixing and completing the hydrosilylation reaction; the molar ratio of the hydrogenated silicone oil to the enolate oligomer is 1.0-1.5:1, the temperature is 60-130°C, and the residence time of the hydrosilylation in the first temperature zone is 0.5min-2min, to obtain an intermediate reaction liquid;

[0010] S3, epoxy ring-opening polymerization: the intermediate reaction liquid of step S2 continues to flow to the second temperature zone of the microchannel reactor, and the epoxide is pumped into the second temperature zone at the same time, mixed and the epoxy ring-opening polymerization reaction is completed; the molar ratio of the intermediate reaction liquid of S2 to the epoxide is 1.03-1.3:1, the temperature is 80-150° C., the residence time in the second temperature zone is 1-3 min, the reaction liquid flows out of the microchannel reactor, and the silicone polyether copolymer is obtained after cooling.

[0011] Wherein, the structural formula of the enol in the enol oligomer is

[0012] Where R is C 1-6 alkyl.

[0013] More preferably, the enol oligomer is one or more of oligopropylene alcohol, butenol, pentenol, methylpropylene alcohol or methylbutenol.

[0014] Wherein, the epoxy compound is one or both of ethylene oxide and propylene oxide.

[0015] The catalyst dosage is 20-80 μg / g.

[0016] More preferably, the catalyst is two or three of nano-scale palladium, silver, platinum, gold, isopropanol solution of chloroplatinic acid, silicone oil solution of potassium hydroxide, and DMC bimetallic catalyst.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] 1. The microchannel continuous production process solves the problems of high risk, low safety factor, low product conversion and low purity in the production process compared to the traditional kettle reaction. Compared with the traditional process of polymerization before addition, the first addition and then polymerization process has a more controllable reaction and more stable product quality. The preparation method has a simple process, mild reaction conditions and high conversion rate.

[0019] 2. The organosilicon polyether copolymer prepared by the present invention has good wetting and dispersing properties and low raw material cost. The organosilicon polyether copolymer shows good application prospects in defoaming, wetting, leveling, emulsification, etc. It is widely used in defoaming agents, paints and coatings, high-temperature semiconductors, crystalline silicon cutting, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic diagram of the microchannel reactor process. DETAILED DESCRIPTION

[0021] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0022] The raw materials used in the examples of this application are all commercially available.

[0023] Unless otherwise specified, the following materials are measured by mass.

[0024] Example 1

[0025] S1, mixing: adding 0.1 parts of nano silver and 0.1 parts of isopropanol solution of chloroplatinic acid to 50 parts of hydrogen-containing silicone oil and mixing evenly;

[0026] S2, hydrosilylation: pump the hydrogenated silicone oil catalyst mixed liquid reaction liquid and 50 parts of propylene alcohol oligomer into the first temperature zone of the microchannel reactor at the same time, mix and complete the hydrosilylation reaction, the temperature is 60° C., the residence time of the hydrosilylation in the first temperature zone is 0.5 min, and an intermediate reaction liquid is obtained;

[0027] S3, epoxy ring-opening polymerization: the intermediate reaction liquid of step S2 continues to flow to the second temperature zone of the microchannel reactor, and 100 parts of ethylene oxide are pumped into the second temperature zone at the same time, mixed and the epoxy ring-opening polymerization reaction is completed, the temperature is 80°C, and the residence time in the second temperature zone is 1 minute. The reaction liquid flows out of the microchannel reactor and is cooled to obtain the silicone polyether copolymer.

[0028] Example 2

[0029] S1, mixing: adding 0.1 parts of nano-gold and 0.2 parts of potassium hydroxide in a silicone oil solution to 70 parts of hydrogen-containing silicone oil and mixing evenly;

[0030] S2, hydrosilylation: pump the hydrogenated silicone oil catalyst mixed liquid reaction liquid and 50 parts of propylene alcohol oligomer into the first temperature zone of the microchannel reactor at the same time, mix and complete the hydrosilylation reaction, the temperature is 100° C., the residence time of the hydrosilylation in the first temperature zone is 1 min, and the intermediate reaction liquid is obtained;

[0031] S3, epoxy ring-opening polymerization: the intermediate reaction liquid of step S2 continues to flow to the second temperature zone of the microchannel reactor, and 120 parts of propylene oxide are pumped into the second temperature zone at the same time, mixed and completed epoxy ring-opening polymerization reaction, the temperature is 100°C, the residence time in the second temperature zone is 1.5 minutes, the reaction liquid flows out of the microchannel reactor, and the silicone polyether copolymer is obtained after cooling.

[0032] Example 3

[0033] S1, mixing: adding 0.3 parts of nano silver and 0.2 parts of potassium hydroxide in a silicone oil solution to 100 parts of hydrogen-containing silicone oil and mixing evenly;

[0034] S2, hydrosilylation: pump the hydrogenated silicone oil catalyst mixed liquid reaction liquid and 50 parts of butenol oligomers into the first temperature zone of the microchannel reactor at the same time, mix and complete the hydrosilylation reaction, the temperature is 120° C., the residence time of the hydrosilylation in the first temperature zone is 1.5 min, and an intermediate reaction liquid is obtained;

[0035] S3, epoxy ring-opening polymerization: the intermediate reaction liquid of step S2 continues to flow to the second temperature zone of the microchannel reactor, and 100 parts of ethylene oxide are pumped into the second temperature zone at the same time, mixed and the epoxy ring-opening polymerization reaction is completed, the temperature is 120°C, and the residence time in the second temperature zone is 1.8 minutes. The reaction liquid flows out of the microchannel reactor and is cooled to obtain the silicone polyether copolymer.

[0036] Example 4

[0037] S1, mixing: adding 0.4 parts of nano-palladium and 0.2 parts of DMC bimetallic catalyst to 80 parts of hydrogen-containing silicone oil and mixing evenly;

[0038] S2, hydrosilylation: pump the hydrogenated silicone oil catalyst mixed liquid reaction liquid and 100 parts of pentenol oligomers into the first temperature zone of the microchannel reactor at the same time, mix and complete the hydrosilylation reaction, the temperature is 70° C., the residence time of the hydrosilylation in the first temperature zone is 2 min, and the intermediate reaction liquid is obtained;

[0039] S3, epoxy ring-opening polymerization: the intermediate reaction liquid of step S2 continues to flow to the second temperature zone of the microchannel reactor, and 200 parts of propylene oxide are pumped into the second temperature zone at the same time, mixed and the epoxy ring-opening polymerization reaction is completed, the temperature is 140°C, and the residence time in the second temperature zone is 2 minutes. The reaction liquid flows out of the microchannel reactor and is cooled to obtain the silicone polyether copolymer.

[0040] Example 5

[0041] S1, mixing: adding 0.3 parts of nano-platinum and 0.2 parts of potassium hydroxide in a silicone oil solution to 100 parts of hydrogen-containing silicone oil and mixing evenly;

[0042] S2, hydrosilylation: pump the hydrogenated silicone oil catalyst mixed liquid reaction liquid and 80 parts of methyl propylene alcohol oligomer into the first temperature zone of the microchannel reactor at the same time, mix and complete the hydrosilylation reaction, the temperature is 130° C., the residence time of the hydrosilylation in the first temperature zone is 2 minutes, and the intermediate reaction liquid is obtained;

[0043] S3, epoxy ring-opening polymerization: the intermediate reaction liquid of step S2 continues to flow to the second temperature zone of the microchannel reactor, and 150 parts of ethylene oxide are pumped into the second temperature zone at the same time, mixed and the epoxy ring-opening polymerization reaction is completed, the temperature is 150° C., and the residence time in the second temperature zone is 3 minutes. The reaction liquid flows out of the microchannel reactor and is cooled to obtain the silicone polyether copolymer.

[0044] Comparative Example 1

[0045] Polyether-modified silicone oil prepared by the reaction of allyl polyether and methyl hydrogen-containing silicone oil. Put the short-chain hydrogen-containing silicone oil and terminal allyl polyether into a reactor, heat it to 130°C, stir it quickly, add 1ppm of chloroplatinic acid isopropanol as a catalyst, naturally heat it to 130°C, the reaction system gradually changes from turbid to transparent, react for 3h, and then remove low-boiling substances by decompression to obtain the desired polyether-modified silicone oil.

[0046] Comparative Example 2

[0047] Silicone block polyether was synthesized with hydrogen-terminated silicone oil and allyl polyoxyethylene ether as raw materials under chloroplatinic acid catalysis. The synthesis conditions were n (hydrogen-terminated silicone oil): n (allyl polyoxyethylene ether) = 1: 2.2, reaction temperature 120 ° C, reaction time 3.5h, catalyst dosage 2g / kg,

[0048] Sample No. Conversion rate Example 1 82.5％ Example 2 85.6％ Example 3 88.3％ Example 4 86.4％ Example 5 84.9％ Comparative Example 1 67.8％ Comparative Example 2 69.1％

[0049] It can be seen from the above results that the conversion rate of the microchannel continuous production process of the present invention is significantly higher than that of the traditional process, the process is simple, the reaction conditions are mild, and compared with the traditional process of polymerization followed by addition, the reaction is more controllable and the product quality is more stable.

Claims

1. A continuous synthesis method of an organosilicon polyether copolymer, characterized in that: A microchannel reactor is used as a reaction device, wherein the microchannel reactor comprises a first temperature zone and a second temperature zone connected in series, and each of the first temperature zone and the second temperature zone comprises a plurality of reaction modules connected in series. The specific steps are as follows: S1, mixing: adding the catalyst into the hydrogen-containing silicone oil and mixing evenly; S2, hydrosilylation: pumping the hydrogenated silicone oil catalyst mixed liquid reaction liquid and the enol oligomer into the first temperature zone of the microchannel reactor at the same time, mixing and completing the hydrosilylation reaction, the molar ratio of the hydrogenated silicone oil to the enol oligomer is 1.0-1.5:1, the temperature is 60-130° C., and the residence time of the hydrosilylation in the first temperature zone is 0.5 min-2 min, to obtain an intermediate reaction liquid; S3, epoxy ring-opening polymerization: the intermediate reaction liquid of step S2 continues to flow to the second temperature zone of the microchannel reactor, and the epoxide is pumped into the second temperature zone at the same time, mixed and the epoxy ring-opening polymerization reaction is completed, the molar ratio of the intermediate reaction liquid of S2 to the epoxide is 1.03-1.3:1, the temperature is 80-150°C, the residence time in the second temperature zone is 1-3min, the reaction liquid flows out of the microchannel reactor, and the silicone polyether copolymer is obtained after cooling.

2. The continuous synthesis method of a silicone polyether copolymer according to claim 1, characterized in that: The structural formula of the enol in the enol oligomer is Where R is C 1-6 alkyl.

3. The method for continuous synthesis of an organosilicon polyether copolymer according to claim 2, characterized in that: The enol oligomer is one or more of low polypropylene alcohol, butenol, pentenol, methylpropylene alcohol or methylbutenol.

4. The method for continuous synthesis of an organosilicon polyether copolymer according to claim 1, characterized in that: The epoxy compound is one or both of ethylene oxide and propylene oxide.

5. The method for continuous synthesis of an organosilicon polyether copolymer according to claim 1, characterized in that: The amount of catalyst in S1 is 20-80 μg / g.

6. The method for preparing an organosilicon polyether copolymer according to claim 5, characterized in that: The catalyst is two or three of nano-scale palladium, silver, platinum, gold, isopropanol solution of chloroplatinic acid, silicone oil solution of potassium hydroxide, and DMC bimetallic catalyst.

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