CN113416310A - Preparation method of organic silicon modified acrylate - Google Patents
Preparation method of organic silicon modified acrylate Download PDFInfo
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Abstract
The invention relates to the technical field of acrylate modification, in particular to a preparation method of organic silicon modified acrylate. The preparation method of the organic silicon modified acrylate provided by the invention comprises the following steps: (1) mixing allyl methacrylate, a catalyst and a polymerization inhibitor, and then carrying out first preheating to obtain a preheated mixed raw material; (2) carrying out second preheating on the hydrogen-terminated silicone oil to obtain preheated hydrogen-terminated silicone oil; (3) introducing the preheated mixed raw material and hydrogen silicone oil at the preheated end into a microchannel reactor to carry out hydrosilylation reaction to obtain organosilicon modified acrylate; the step (1) and the step (2) have no chronological order. According to the invention, through carrying out hydrosilylation in the microchannel reactor, the heat transfer efficiency and the mass transfer efficiency can be improved, the raw materials do not self-polymerize, and the large-scale production of the organic silicon modified acrylate can be realized.
Description
Technical Field
The invention relates to the technical field of acrylate modification, in particular to a preparation method of organic silicon modified acrylate.
Background
The acrylate polymer is a saturated compound and has excellent ultraviolet resistance and oxidation resistance, but the molecule contains polar ester groups, so that the water resistance of the acrylate polymer is poor, a coating film is easy to turn white after absorbing water, and the ester groups are even decomposed under certain conditions, so that the product performance is influenced. Meanwhile, acrylate polymers, particularly linear polymers, are prone to high temperature tack, have reduced stain resistance, become brittle at low temperatures, and have poor toughness. The organic silicon has good performances of heat resistance, weather resistance, gloss retention, water resistance, chalking resistance, ultraviolet light resistance and the like due to the characteristics of molecular structures, but cannot be self-dried at normal temperature, has poor film forming property and poor adhesion to base materials. The main chain of the organic silicon is flexible, and the intermolecular action force of the organic silicon is much weaker than that of hydrocarbon, so that the organic silicon has lower viscosity, weaker surface tension, smaller surface energy and stronger film forming capability than that of hydrocarbon with the same molecular weight. This low surface tension and low surface energy are the main reasons for its versatile use: excellent performances such as hydrophobicity, defoaming, foam stability, anti-sticking, lubrication, glazing and the like. Therefore, the organosilicon component is utilized to modify the acrylic resin, and the organosilicon modified acrylic resin with the advantages of the organosilicon component and the acrylic resin can be prepared.
Chemical synthesis of silicone-modified acrylate resins is generally produced by the hydrosilylation process. The hydrosilylation reaction is a strong exothermic reaction, the influence of heat and mass transfer on the reaction is great, at present, an intermittent kettle type reactor is generally adopted at home and abroad for preparation, and the specific steps are approximately as follows: firstly, adding an ester raw material into a reaction kettle, and adding a catalyst and a polymerization inhibitor; secondly, hydrogen-terminated silicone oil is slowly added in a dropwise adding mode, and the reaction temperature is controlled by adopting a jacket and coil cooling method, so that the reaction temperature is ensured to be as stable as possible in the reaction process, and the influence of overtemperature on the color and performance of the product is avoided; and thirdly, after reacting for 3-5 hours, completely converting hydrogen-terminated silicone oil to obtain the organic silicon modified acrylate resin. However, the intermittent kettle type reactor has the advantages that the heat exchange area is small in heat transfer, a large amount of reaction heat generated in the process of dropwise adding the hydrogen-terminated silicone oil cannot be timely removed, local overtemperature is caused, and the requirement on the dropwise adding rate is high; in the aspect of mass transfer, the traditional batch kettle type reactor adopts mechanical stirring, and the type, size, position and rotating speed of a stirrer influence the reaction efficiency. In addition, the intermittent kettle type reactor has the defects of long reaction time, low production capacity and the like due to the dropwise adding process; in addition, during the production process, the ester raw materials are easy to generate self-polymerization reaction to generate macromolecular polymers, so that the yield and the production efficiency of the hydrosilylation product are reduced.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing organosilicon modified acrylate, wherein the hydrosilylation reaction is performed in a microchannel reactor, the heat transfer efficiency and the mass transfer efficiency can be improved, the yield is high, the raw materials are not self-polymerized, and the production efficiency is high.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of organic silicon modified acrylate, which comprises the following steps:
(1) mixing allyl methacrylate, a platinum-containing catalyst and a polymerization inhibitor, and then carrying out first preheating to obtain a preheated mixed raw material;
(2) carrying out second preheating on the hydrogen-terminated silicone oil to obtain preheated hydrogen-terminated silicone oil;
(3) introducing the preheated mixed raw material and hydrogen silicone oil at the preheated end into a microchannel reactor to carry out a silicon-hydrogen addition reaction to obtain organosilicon modified acrylate;
the step (1) and the step (2) have no chronological order.
Preferably, the ratio of platinum to the total mass of the allyl methacrylate and the hydrogen-terminated silicone oil in the platinum-containing catalyst is 1-100 μ g/g.
Preferably, the hydrogen-terminated silicone oil comprises one or more of tetramethyldisiloxane, hexamethylcyclotrisiloxane and 3, 3-diphenyl-1, 1,5, 5-tetramethyltrisiloxane.
Preferably, the mol ratio of the allyl methacrylate to the hydrogen-terminated silicone oil is (2-4): 1.
preferably, the polymerization inhibitor comprises one or more of hydroquinone, phenothiazine, p-hydroxyanisole, p-benzoquinone, 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical and phosphite ester.
Preferably, the mass ratio of the polymerization inhibitor to the allyl methacrylate is Wie 50-10000 [ mu ] g/g.
Preferably, the temperature of the first preheating and the second preheating is 30-100 ℃ independently.
Preferably, the temperature of the hydrosilylation reaction is 50-120 ℃, the time is 1-350 s, and the pressure is less than or equal to 5 MPa.
The invention provides a preparation method of organic silicon modified acrylate, which comprises the following steps: (1) mixing allyl methacrylate, a platinum-containing catalyst and a polymerization inhibitor, and then carrying out first preheating to obtain a preheated mixed raw material; (2) carrying out second preheating on the hydrogen-terminated silicone oil to obtain preheated hydrogen-terminated silicone oil; (3) introducing the preheated mixed raw material and hydrogen silicone oil at the preheated end into a microchannel reactor to carry out hydrosilylation reaction to obtain organic silicon modified acrylate; the step (1) and the step (2) have no chronological order. The invention adopts the microchannel reactor, reduces the process step of dripping the raw materials in the traditional batch kettle type reactor, has short reaction time, avoids the self-polymerization of the raw materials and obviously improves the reaction efficiency; the microchannel has large specific surface area, the reaction raw materials are fully contacted and uniformly mixed in the microchannel reactor, the back mixing of the materials can be reduced, the mass transfer effect is good, the selectivity of the organic silicon modified acrylate is improved, and the production cost is saved; the microchannel reactor has large specific surface and very large heat transfer coefficient, greatly enhances the heat transfer in the hydrosilylation reaction process, simultaneously removes the reaction heat in time, improves the safety, ensures the constant reaction temperature in the process, improves the quality of products, realizes the continuous production of the organic silicon modified acrylate, and is suitable for industrial production.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for preparing silicone-modified acrylate according to an embodiment of the present invention;
wherein, 1 is a raw material preparation unit, 11 is a mixed raw material preparation tank, 111 is a first stirrer, 112 is a first liquid level control pneumatic valve, 113 is a first liquid level meter, 114 is a first valve, 115 is a second valve, 116 is a second liquid level control pneumatic valve, 117 is a second liquid level meter, and 118 is a first sample injection pump; 12 is a hydrogen-terminated silicone oil preparation tank, 121 is a second stirrer, 122 is a third liquid level control pneumatic valve, 123 is a third liquid level meter, 124 is a fourth liquid level control pneumatic valve, 125 is a fourth liquid level meter, and 126 is a second sample injection pump; 13 is an allyl methacrylate metering tank, 14 is a catalyst metering tank, 15 is a polymerization inhibitor metering tank, and 16 is a hydrogen-terminated silicone oil metering tank; 2 is a micro-channel reactor; and 3, an organic silicon modified acrylate storage tank.
Detailed Description
The invention provides a preparation method of organic silicon modified acrylate, which comprises the following steps:
mixing allyl methacrylate, a platinum-containing catalyst and a polymerization inhibitor, and then carrying out first preheating to obtain a preheated mixed raw material;
carrying out second preheating on the hydrogen-terminated silicone oil to obtain preheated hydrogen-terminated silicone oil;
and introducing the preheated mixed raw material and hydrogen-containing silicone oil at the preheating end into a microchannel reactor to carry out a hydrosilylation reaction, thereby obtaining the organosilicon modified acrylate.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the preparation of the silicone-modified acrylate is preferably performed in a silicone-modified acrylate production apparatus, as shown in fig. 1, comprising a raw material preparation unit 1 and a microchannel reactor 2.
In the invention, the organosilicon modified acrylate preparation device comprises a raw material preparation unit 1, wherein the raw material preparation unit 1 comprises a mixed raw material preparation tank 11, a hydrogen-terminated silicone oil preparation tank 12, an allyl methacrylate metering tank 13, a catalyst metering tank 14, a polymerization inhibitor metering tank 15 and a hydrogen-terminated silicone oil metering tank 16.
In the present invention, a first stirrer 111 is provided in the mixed material preparation tank 11.
In the present invention, the top of the mixed raw material preparation tank 11 is provided with an allyl methacrylate inlet, a catalyst inlet, a polymerization inhibitor inlet, and a vent. In the invention, the allyl methacrylate inlet is communicated with the outlet of the allyl methacrylate metering tank 13 through a first pipeline, and a first liquid level control pneumatic valve 112 is arranged on the first pipeline; the mixed raw material preparation tank 11 is also provided with a first liquid level meter 113, and the first liquid level meter 113 extends into the mixed raw material preparation tank 11; the first level gauge 113 is in communication with the first level control pneumatic valve 112; the first level control pneumatic valve 112 and the second level meter 113 are used for correctly measuring the volume or weight of the tank body (namely, the liquid level measurement is used for metering and economic accounting), monitoring the liquid level of the tank body, and giving an alarm to the allowable upper limit and lower limit of the liquid level, thereby continuously monitoring production and adjusting. In the present invention, the catalyst inlet is communicated with the outlet of the catalyst metering tank 14 through a second pipeline, and the second pipeline is provided with a first valve 114 for metering the adding amount of the catalyst. In the present invention, the polymerization inhibitor inlet is communicated with the outlet of the polymerization inhibitor metering tank 15 through a third pipe, and the third pipe is provided with a second valve 115. In the invention, a preheated mixed raw material outlet is arranged at the bottom of the mixed raw material preparation tank 11, the preheated mixed raw material outlet is communicated with the microchannel reactor 2 through a fourth pipeline, a second liquid level control pneumatic valve 116, a second liquid level meter 117 and a first sample injection pump 118 are arranged on the fourth pipeline, the second liquid level control pneumatic valve 116 and the second liquid level meter 117 are used for cutting, adjusting and throttling mixed raw materials, the mixed raw materials are opened during feeding, and the feeding is closed after finishing feeding.
In the invention, the mixed raw material preparation tank 11 has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure; the heat exchange medium is preferably water vapor or process water, the water vapor is used for heating the raw materials, and the process water is used for cooling; the heat exchange medium flows in the interlayer of the mixed raw material preparation tank 11 and is used for preheating the mixed raw material of allyl methacrylate and the catalyst.
In the invention, a second stirrer 121 is arranged in the hydrogen-terminated silicone oil preparation tank 12.
In the invention, a hydrogen-terminated silicone oil inlet is arranged at the top of the hydrogen-terminated silicone oil preparation tank 12, the hydrogen-terminated silicone oil inlet is communicated with an outlet of the hydrogen-terminated silicone oil metering tank 16 through a fifth pipeline, and a third liquid level control pneumatic valve 122 is arranged on the fifth pipeline; the hydrogen-terminated silicone oil preparation tank 12 is further provided with a second liquid level meter 123, and the second liquid level meter 123 extends into the hydrogen-terminated silicone oil preparation tank 12; the second level gauge 123 communicates with the third level control pneumatic valve 122; the third level control pneumatic valve 122 and the third level meter 123 are used for correctly measuring the volume or weight of the tank body (i.e. the purpose of the level measurement is for metering and economic accounting), monitoring the level of the tank body, and alarming the allowable upper and lower limits of the level, thereby continuously monitoring production and adjusting. In the invention, a preheating end hydrogen-silicone oil outlet is arranged at the bottom of the end hydrogen-silicone oil preparation tank 12, the preheating end hydrogen-silicone oil outlet is communicated with the microchannel reactor 2 through a sixth pipeline, a fourth liquid level control pneumatic valve 124, a fourth liquid level meter 125 and a second sample injection pump 126 are arranged on the sixth pipeline, the fourth liquid level control pneumatic valve 124 and the fourth liquid level meter 125 are used for realizing the cutting, adjustment and throttling of the preheating end hydrogen-silicone oil, the preheating end hydrogen-silicone oil preparation tank is opened during feeding, and the feeding is closed after finishing feeding.
In the invention, the hydrogen-terminated silicone oil preparation tank 12 has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure; the heat exchange medium is preferably water vapor or process water, the water vapor is used for heating the raw materials, and the process water is used for cooling; the heat exchange medium flows in the interlayer of the hydrogen-terminated silicone oil preparation tank 12 and is used for preheating the hydrogen-terminated silicone oil.
In the present invention, the silicone-modified acrylate production apparatus includes a microchannel reactor 2. In the invention, the microchannel reactor 2 is provided with a preheating mixed raw material inlet, a preheating end hydrogen-silicone oil inlet and a reaction liquid outlet, the preheating mixed raw material inlet is communicated with a preheating mixed raw material outlet of the mixed raw material preparation tank 11, the preheating end hydrogen-silicone oil inlet is communicated with a preheating end hydrogen-silicone oil outlet of the end hydrogen-silicone oil preparation tank 12, and the reaction liquid outlet is communicated with the post-processing unit 3.
In the invention, the microchannel reactor 2 has a double-layer side wall structure, and a heat exchange medium is filled in an interlayer formed by the double-layer side wall structure; the heat exchange medium is preferably water vapor or process water, the water vapor is used for heating the raw materials, and the process water is used for cooling; the heat exchange medium flows in the interlayer of the microchannel reactor 2 and is used for controlling the temperature of the hydrosilylation reaction.
In the invention, the microchannel reactor 2 is provided with microchannels, and is preferably provided with microchannel reaction sheets; the shape of the microchannel preferably comprises an umbrella structure, a T structure, a Y structure, a cross structure or a co-flow structure, and more preferably is an umbrella structure; the length of the micro-channel is preferably 0.8-1 m, and more preferably 0.85 m; the depth of the micro-channel is preferably 0.5-0.6 mm, and more preferably 0.55 mm.
In the invention, the microchannel reactor is provided with microchannel reaction plates, and the number of the reaction plates in the microchannel reactor is preferably 5-20, and more preferably 10. In the invention, the liquid holdup of each microchannel reaction plate is independently preferably 0.5-2 mL, more preferably 1-1.5 mL, and most preferably 1.18 mL. In the present invention, the material of the reaction sheet is preferably 316L stainless steel.
In the present invention, the apparatus for preparing silicone-modified acrylate preferably further comprises a silicone-modified acrylate storage tank 3 communicating with the reaction liquid outlet of the microchannel reactor 2.
According to the invention, allyl methacrylate, a platinum-containing catalyst and a polymerization inhibitor are mixed and then are preheated for the first time, so that a preheated mixed raw material is obtained.
In the invention, the platinum-containing catalyst preferably comprises a Speier catalyst (namely chloroplatinic acid/isopropanol catalyst) and/or a Karstedt catalyst (namely platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane), and the content of platinum in the Speier catalyst and the Karstedt catalyst is independently preferably 1-100 ppm, more preferably 5-50 ppm, and most preferably 10-20 ppm. In the present invention, the polymerization inhibitor preferably comprises one or more of hydroquinone, phenothiazine, p-hydroxyanisole, p-benzoquinone, 2,6, 6-tetramethyl-4-hydroxy nitroxide radical (ZJ-701) and phosphite ester (ZJ-705). In the present invention, the mass ratio of the polymerization inhibitor to the allyl methacrylate is 50 to 10000. mu.g/g, more preferably 100 to 5000. mu.g/g, and most preferably 500 to 1000. mu.g/g.
In the present invention, the allyl methacrylate, the platinum-containing catalyst and the polymerization inhibitor are preferably mixed by stirring; in the present invention, the speed and time of the stirring and mixing are not particularly limited, and allyl methacrylate and a platinum-containing catalyst may be mixed uniformly. In the invention, the temperature of the first preheating is preferably 30-100 ℃, more preferably 40-80 ℃, and most preferably 50-70 ℃.
According to the invention, the hydrogen-terminated silicone oil is subjected to secondary preheating to obtain the preheated hydrogen-terminated silicone oil. In the invention, the hydrogen-terminated silicone oil preferably comprises one or more of tetramethyldisiloxane, hexamethylcyclotrisiloxane and 3, 3-diphenyl-1, 1,5, 5-tetramethyltrisiloxane. In the invention, the mol ratio of the allyl methacrylate to the hydrogen-terminated silicone oil is preferably (2-4): 1, more preferably (2.2 to 3.6): 1, most preferably (2.5-3): 1. in the invention, the ratio of the mass of platinum in the platinum-containing catalyst to the total mass of the allyl methacrylate and the preheating terminal hydrogen silicone oil is 1-100 mu g/g, more preferably 5-50 mu g/g, and most preferably 20-30 mu g/g. In the invention, the second preheating temperature is preferably 30-100 ℃, more preferably 40-80 ℃, and most preferably 50-70 ℃.
After the preheating mixed raw material and the preheating end hydrogen silicone oil are obtained, the preheating mixed raw material and the preheating end hydrogen silicone oil are subjected to hydrosilylation reaction in a microchannel reactor to obtain the organic silicon modified acrylic ester.
In the invention, the temperature of the hydrosilylation reaction is preferably 50-120 ℃, more preferably 60-100 ℃, and most preferably 70-90 ℃; the time of the hydrosilylation reaction is preferably 1-350 s, more preferably 50-300 s, and most preferably 30-180 s; the pressure of the hydrosilylation reaction was atmospheric pressure. In the present invention, the time (i.e., residence time) for the hydrosilylation reaction is preferably the time from when the feed enters the microchannel reactor to when it exits the microchannel reactor.
The microchannel reactor adopted by the invention can cut the flowing reaction raw material fluid, realizes the mixing and heat exchange of the reaction raw material fluid with the space-time size of micron or even smaller, and can improve the reaction yield. The microchannel reactor adopted by the invention has small characteristic size of the microchannel inside, the generated direct advantage strengthens the processes of mass transfer and heat transfer, the diffusion time of the raw materials is short, the allyl methacrylate is beneficial to fully contacting with hydrogen silicone oil at the preheating end, the mixing process of the reaction raw materials is fast, the back mixing of the reaction raw materials is eliminated, the proportion of the reaction raw materials is accurate, the occurrence of side reaction is avoided, and the selectivity of the product is improved; the reaction yield and selectivity are improved, the time of the ring-opening addition reaction is shortened from the traditional hours to minutes, and the reaction efficiency is improved; moreover, the micro-channel reactor has large specific surface area, greatly enhances the heat transfer in the chemical process, simultaneously removes the reaction heat in time, avoids the self-polymerization of the raw materials, improves the safety and is suitable for industrial production.
The following describes a specific method for preparing organic silicon modified acrylate by using an organic silicon modified acrylate preparation device with reference to fig. 1, comprising the following steps:
(1) adding allyl methacrylate metered by an allyl methacrylate metering tank 13, a polymerization inhibitor metered by a polymerization inhibitor metering tank 15 and a catalyst metered by a catalyst metering tank 14 into a mixed raw material preparation tank 11, stirring and mixing, and preheating the obtained mixed raw material under the heating action of a heat exchange medium flowing in an interlayer of the mixed raw material preparation tank 11 to obtain a preheated mixed raw material;
(2) adding the end hydrogen silicone oil metered by the end hydrogen silicone oil metering tank 16 into the end hydrogen silicone oil preparation tank 12, and preheating the end hydrogen silicone oil under the heating action of a heat exchange medium flowing in an interlayer of the end hydrogen silicone oil preparation tank 12 to obtain preheated end hydrogen silicone oil;
(3) pumping the preheated and mixed raw material into the microchannel reactor 2 through a preheated and mixed raw material inlet by a first sample injection pump 118, simultaneously pumping the hydrogen silicone oil at the preheated end into the microchannel reactor 2 through a second sample injection pump 126, and carrying out hydrosilylation reaction under the heating action of a heat exchange medium flowing in an interlayer of the microchannel reactor 2 to obtain the organic silicon modified acrylate.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention.
Example 1
The preparation of the silicone-modified acrylate was carried out using the silicone-modified acrylate preparation apparatus shown in fig. 1:
(1) 504g of allyl methacrylate metered by an allyl methacrylate metering tank 13, 0.11g of hydroquinone metered by a polymerization inhibitor metering tank 15 and 4.6g of Karstedt catalyst metered by a catalyst metering tank 14 are added into a mixed raw material preparation tank 11 to be stirred and mixed, and the obtained mixed raw material is preheated to 60 ℃ under the heating action of a heat exchange medium flowing in an interlayer of the mixed raw material preparation tank 11 to obtain a preheated mixed raw material;
(2) 268g of tetramethyldisiloxane metered by a hydrogen-terminated silicone oil metering tank 16 is added into a hydrogen-terminated silicone oil preparation tank 12, and the hydrogen-terminated silicone oil is preheated to 60 ℃ under the heating action of a heat exchange medium flowing in an interlayer of the hydrogen-terminated silicone oil preparation tank 12 to obtain preheated hydrogen-terminated silicone oil;
(3) pumping the preheated and mixed raw material into a microchannel reactor 2 through a preheated and mixed raw material inlet by a first sampling pump 118, simultaneously pumping hydrogen silicone oil at a preheated end into the microchannel reactor 2 through a second sampling pump 126, and carrying out hydrosilylation reaction for 120s at 80 ℃ and under normal pressure by the heating action of a heat exchange medium flowing in an interlayer of the microchannel reactor 2 to obtain organic silicon modified acrylate, wherein the microchannel is an umbrella-shaped channel, the length of the microchannel is 0.85m, the depth of the microchannel is 0.55mm, the number of reaction plates is 10, the liquid holding capacity of a single reaction plate is 1.18mL, and the material is 316L stainless steel;
analyzing the organic silicon modified acrylate obtained in the step (3) by using gas chromatography, wherein the gas chromatography conditions are as follows: the model of a gas chromatograph is GC9800, the gas chromatograph is detected by a hydrogen flame ionization detector, the quantitative analysis is carried out by an area normalization method, the chromatographic column is an elastic quartz capillary column (30m multiplied by 0.25mm), the column temperature is 100 ℃, the detector temperature is 260 ℃, the vaporization chamber temperature is 260 ℃, the temperature programming rate is 10 ℃/min, the final temperature is 280 ℃, the retention time is 10min, the sample injection amount is 0.2 mu L, and the test results are shown in Table 1.
Examples 2 to 8
The organosilicon modified acrylate was prepared and tested according to the method of example 1, the reaction conditions and the product test results of examples 2 to 8 are shown in table 1, and the preparation conditions not listed in table 1 are the same as those of example 1.
TABLE 1 EXAMPLES 1-8 reaction conditions and results of product testing
Comparative example 1
454g of allyl methacrylate, 0.09g of hydroquinone serving as a polymerization inhibitor and 8.6g of Karstedt catalyst are added into a 1000mL four-mouth bottle provided with a mechanical stirrer, a reflux condenser and a thermometer which are mechanically sealed, the stirrer is started, the temperature is increased to 80 ℃, 201g of tetramethyldisiloxane is dropwise added, the reaction temperature is controlled to be 90-100 ℃, the reaction is carried out for 4 hours, and after the reaction is finished, a product is analyzed by gas chromatography, wherein the conversion rate of the tetramethyldisiloxane is 95.2%.
Comparative example 2
Adding 567g of allyl methacrylate, 0.09g of polymerization inhibitor phenothiazine and 9.2g of Karstedt catalyst into a 1000mL four-mouth bottle provided with a mechanical stirrer, a reflux condenser and a thermometer which are mechanically sealed, starting the stirrer, raising the temperature to 80 ℃, dropwise adding 201g of tetramethyldisiloxane, controlling the reaction temperature to be 90-100 ℃, and allowing the tetramethyldisiloxane to self-polymerize after reacting for 3 hours.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of organic silicon modified acrylate is characterized by comprising the following steps:
(1) mixing allyl methacrylate, a platinum-containing catalyst and a polymerization inhibitor, and then carrying out first preheating to obtain a preheated mixed raw material;
(2) carrying out second preheating on the hydrogen-terminated silicone oil to obtain preheated hydrogen-terminated silicone oil;
(3) introducing the preheated mixed raw material and hydrogen silicone oil at the preheated end into a microchannel reactor to carry out hydrosilylation reaction to obtain organosilicon modified acrylate;
the step (1) and the step (2) have no chronological order.
2. The production method according to claim 1, wherein the ratio of the mass of platinum in the platinum-containing catalyst to the total mass of the allyl methacrylate and hydrogen-terminated silicone oil is 1 to 100 μ g/g.
3. The preparation method according to claim 1, wherein the hydrogen-terminated silicone oil comprises one or more of tetramethyldisiloxane, hexamethylcyclotrisiloxane and 3, 3-diphenyl-1, 1,5, 5-tetramethyltrisiloxane.
4. The production method according to claim 1 or 3, wherein the molar ratio of the allyl methacrylate to the hydrogen-terminated silicone oil is (2 to 4): 1.
5. the method according to claim 1, wherein the polymerization inhibitor comprises one or more of hydroquinone, phenothiazine, p-hydroxyanisole, p-benzoquinone, 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide radical and phosphite.
6. The production method according to claim 1 or 5, wherein the mass ratio of the polymerization inhibitor to the allyl methacrylate is 50 to 10000. mu.g/g.
7. The production method according to claim 1,3 or 5, wherein the temperatures of the first preheating and the second preheating are independently 30 to 100 ℃.
8. The method according to claim 1,3 or 5, wherein the hydrosilylation reaction is carried out at a temperature of 50 to 120 ℃ for 1 to 350 seconds and under a pressure of 5MPa or less.
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| CN115232312A (en) * | 2022-08-05 | 2022-10-25 | 华诺森（武汉）生物医药技术有限公司 | Organic silicon macromonomer for orthokeratology lens and preparation method thereof |
| CN115636845A (en) * | 2022-11-21 | 2023-01-24 | 黄河三角洲京博化工研究院有限公司 | Preparation method of organic silicon pesticide spreading agent |
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| CN108178834A (en) * | 2017-12-07 | 2018-06-19 | 江苏奥斯佳材料科技股份有限公司 | A kind of preparation method of graft modification silicone oil |
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| CN110407582A (en) * | 2019-08-05 | 2019-11-05 | 衢州学院 | A kind of silicon carbide microreactor preparation method based on gel forming |
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| CN114736374A (en) * | 2022-04-07 | 2022-07-12 | 华诺森（武汉）生物医药技术有限公司 | High oxygen permeable silica hydrogel raw material for orthokeratology lens and preparation method thereof |
| CN115011260A (en) * | 2022-04-20 | 2022-09-06 | 河源然生新材料有限公司 | Low-refractive-index UV adhesive and preparation method and application thereof |
| CN115011260B (en) * | 2022-04-20 | 2023-11-17 | 河源然生新材料有限公司 | Low-refractive-index UV adhesive and preparation method and application thereof |
| CN115232312A (en) * | 2022-08-05 | 2022-10-25 | 华诺森（武汉）生物医药技术有限公司 | Organic silicon macromonomer for orthokeratology lens and preparation method thereof |
| CN115636845A (en) * | 2022-11-21 | 2023-01-24 | 黄河三角洲京博化工研究院有限公司 | Preparation method of organic silicon pesticide spreading agent |
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