Continuous production method and device for long-chain alkyl phenyl modified silicone oil with precisely controllable viscosity

Abstract

The invention provides a continuous production method and device for long-chain alkyl phenyl modified silicone oil with accurate and controllable viscosity. The continuous production method of the long-chain alkyl phenyl modified silicone oil is characterized by comprising the following steps: step 1, reacting hydrogen-containing silicone oil and a styrene monomer in a microchannel reactor to obtain a first reactant; and step 2, further reacting the first reactant with long-chain carbene in a dynamic tubular reactor to obtain the long-chain alkyl phenyl modified silicone oil.

Description

Technical Field

[0001] The invention relates to the field of organosilicon compound synthesis, and in particular to a continuous production method and device for long-chain alkylphenyl modified silicone oil with precisely controllable viscosity. Background Art

[0002] Long-chain alkylphenyl modified silicone oil refers to a modified silicone oil obtained by partially or completely replacing the methyl group of the side chain in methyl silicone oil with a long-chain alkyl group and a phenyl group. It is generally believed that long-chain alkyl modification can improve the hydrophobicity and lubricity of silicone oil, while phenyl modification can improve the high and low temperature resistance of silicone oil. Depending on the ratio of long-chain alkyl to phenyl in long-chain alkylphenyl modified silicone oil, the uniformity, and the chain length of the long-chain alkyl, long-chain alkylphenyl silicone oil will show different properties and is widely used as a release agent, etc.

[0003] An exemplary reaction for preparing long-chain alkylphenyl-modified silicone oil is shown below.

[0004]

[0005] Long-chain alkylphenyl modified silicone oil is generally a hydrosilicone oil with styrene monomers and carbenes under the catalysis of platinum catalysts for hydrosilylation reaction. This reaction has two characteristics, the first is high heat release, so in the literature (such as Chinese patent publication CN101402734A and Chinese patent publication CN111333845A), a kettle-type intermittent reaction is adopted, and the method of dripping hydrogenated silicone oil is adopted to control the heat release of the reaction; the second is that the reactivity of styrene monomers and carbenes with hydrogenated silicone oil is different, and the reactivity of carbenes is higher than that of styrene monomers, so the kettle-type intermittent reaction needs to control the different activities of the reactants. In Chinese patent publication CN101402734A, styrene and a small amount of long-chain carbenes are first reacted with hydrogenated silicone oil, and then the remaining carbenes are added for reaction. In Chinese patent publication CN111333845A, styrene and hydrogenated silicone oil are first reacted completely, and then reacted with carbenes.

[0006] However, in the intermittent reaction method, in order to control the high heat release of the reaction, it is necessary to adopt a process control method of dripping hydrogen-containing silicone oil, and this control method is the main reason for the reaction unevenness. This is because hydrogen-containing silicone oil has multiple reaction sites for reactive hydrogen, and the degree of reaction between the hydrogen-containing silicone oil dripped in the early stage and styrene must be much higher than the degree of reaction between the hydrogen-containing silicone oil dripped in the later stage, resulting in a wider molecular weight distribution of the reactants and a larger range of product viscosity. In addition, the process method of the intermittent reaction is prone to the side reaction of hydrogen-containing silicone oil decomposition and release of hydrogen due to poor heat transfer effect and high reaction temperature, and also leads to the occurrence of isomerization side reactions of the raw materials styrene and carbenes, resulting in a waste of raw materials.

[0007] As is known to all, microchannel reactors have very good heat and mass transfer effects and are often used in highly exothermic reactions that require efficient heat and mass transfer (e.g., Chinese patent publication CN105693753A). However, when the viscosity of the reaction materials in a microchannel reactor is high, it is easy to cause excessive system pressure. The viscosity of long-chain alkylphenyl silicone oil is generally 1000-2000Cp, so it is inappropriate to directly apply a microchannel reactor to the synthesis of long-chain alkylphenyl silicone oil.

[0008] Citation list

[0009] Patent Literature

[0010] Patent document 1: CN101402734A

[0011] Patent document 2: CN111333845A

[0012] Patent document 3: CN105693753A Summary of the invention

[0013] The present invention is completed in view of the problems existing in the above-mentioned prior art, and its purpose is to provide a continuous production method and device for long-chain alkylphenyl modified silicone oil. The method and device of the present invention can operate smoothly and continuously at a relatively low temperature, which can not only well solve the problems of high heat release and reaction uniformity in the synthesis of long-chain alkylphenyl silicone oil, but also reduce the impurity content in the reaction material.

[0014] Solutions for solving problems

[0015] The inventors have found through in-depth research that by appropriately combining a microchannel reactor and a dynamic tubular reactor, the reaction can be smoothly and continuously operated at a relatively low temperature, which can not only solve the problems of high heat release and reaction uniformity in the synthesis of long-chain alkylphenyl silicone oil, but also reduce the impurity content in the reaction materials, thereby completing the present invention.

[0016] Specifically, the present invention provides:

[0017] 1. A continuous production method for long-chain alkylphenyl modified silicone oil, characterized in that it comprises:

[0018] Step 1: reacting hydrogen-containing silicone oil and styrene-based monomers in a microchannel reactor to obtain a first reactant;

[0019] Step 2: The first reactant is further reacted with the long-chain carbene in a dynamic tubular reactor to obtain a long-chain alkylphenyl-modified silicone oil.

[0020] 2. The continuous production method of the long-chain alkylphenyl modified silicone oil described in 1 above, wherein:

[0021] The pore size of the microchannel reactor is 1mm-2mm; the dynamic tubular reactor is a vertical dynamic tubular reactor.

[0022] 3. The continuous production method of the long-chain alkylphenyl modified silicone oil described in 1 or 2 above, wherein the styrene monomer is α-C1-C 10 Alkylstyrene, preferably α-methylstyrene;

[0023] The long-chain carbene is a long-chain carbene having 4 to 18 carbon atoms, preferably 1-dodecene.

[0024] 4. The continuous production method of the long-chain alkylphenyl-modified silicone oil described in any one of 1 to 3 above, wherein a catalyst, preferably a platinum-based catalyst, can also be used in step 1.

[0025] 5. The continuous production method of the long-chain alkylphenyl modified silicone oil described in any one of 1 to 4 above, wherein

[0026] The molar ratio of the long-chain carbene to the hydrogen-containing silicone oil is 30-70:1, preferably 40-55:1, and more preferably 46-50:1;

[0027] The molar ratio of the styrene monomer to the hydrogen-containing silicone oil is 20-35:1, preferably 22-28:1, and more preferably 23-26:1.

[0028] 6. The continuous production method of the long-chain alkylphenyl modified silicone oil described in any one of 1 to 5 above, wherein

[0029] The heating temperature of the microchannel reactor and the dynamic tubular reactor is 60-140°C, preferably 90-120°C, more preferably 95-110°C;

[0030] The reaction pressure is 6-17 bar, preferably 8-16 bar, and more preferably 12-14 bar.

[0031] 7. The continuous production method of the long-chain alkylphenyl-modified silicone oil described in any one of 1 to 6 above, wherein:

[0032] The mass flow rate of the hydrogen-containing silicone oil is 6-10 g / min, preferably 7-9 g / min, and more preferably 7.5-8.5 g / min.

[0033] The mass flow rate of the styrene monomer is 3-8 g / min, preferably 4-7 g / min, more preferably 5.5-6.5 g / min,

[0034] The mass flow rate of the long-chain carbene is 12-26 g / min, preferably 14-20 g / min, and more preferably 15-17 g / min.

[0035] 8. A continuous production device for long-chain alkylphenyl modified silicone oil, comprising:

[0036] A microchannel reactor, which is used to receive hydrogen-containing silicone oil and styrene-based monomers and react them to obtain a first reactant;

[0037] The dynamic tubular reactor is connected to the microchannel reactor to receive the first reactant and has a feed port for feeding long-chain carbene so that the first reactant and the long-chain carbene can further react to obtain long-chain alkylphenyl modified silicone oil.

[0038] 9. The continuous production device for long-chain alkylphenyl-modified silicone oil described in 8 above, wherein:

[0039] The pore size of the microchannel reactor is 1mm-2mm; the dynamic tubular reactor is a vertical dynamic tubular reactor.

[0040] 10. The continuous production device of the long-chain alkylphenyl-modified silicone oil described in 8 or 9 above, wherein:

[0041] A control device is also provided, and the control device is used to control the temperature and pressure of each reactor and the mass flow rate of each raw material.

[0042] Effects of the Invention

[0043] According to the continuous production method and production device of the long-chain alkylphenyl modified silicone oil of the present invention, a microchannel reactor is first used to accurately control the reaction process, ensuring that materials with poor compatibility react fully and evenly and ensuring the degree of reaction; and then a dynamic tubular reactor is used to ensure that the raw materials react at a preset molar ratio, so that the product long-chain alkyl silicone oil accurately reaches the required viscosity. In addition, due to the low reaction temperature, there are fewer impurities caused by the isomerization of olefins. DETAILED DESCRIPTION

[0044] [Continuous production method of long-chain alkylphenyl modified silicone oil]

[0045] According to one aspect of the present invention, the present invention provides a continuous production method for long-chain alkylphenyl modified silicone oil (hereinafter, sometimes referred to as the production method of the present invention), which comprises: step 1: reacting hydrogenated silicone oil and styrene monomers in a microchannel reactor to obtain a first reactant; step 2: further reacting the first reactant with a long-chain carbene in a dynamic tubular reactor to obtain a long-chain alkylphenyl modified silicone oil.

[0046] In the present invention, the term "microchannel reactor" refers to a microreactor whose internal structure mainly includes micron-scale to millimeter-scale (usually 10-3000 μm, such as 0.5-3 mm) channels. As long as the microchannel reactor known in the art can be used in the present invention, there is no particular restriction on its material, pipeline layout, etc. For example, the pore (diameter) of the microchannel reactor can be 1 mm-2 mm; the channel can adopt a star structure. As microchannel reactors that can be used in the present invention, there can be listed: G1 reactor manufactured by Corning Reactor Technology Co., Ltd., microchannel reactor manufactured by Shandong Weijing Chemical Technology Co., Ltd., and microchannel reactor manufactured by Shandong Haomai Chemical Technology Co., Ltd. Among them, the G1 reactor manufactured by Corning Reactor Technology Co., Ltd. is preferred. When using Corning G1 reactor as the microchannel reactor of the present invention, the number of modules is preferably 1-10, more preferably 3-8, and further preferably 4-6. Here, the number of modules refers to the number of microchannel reaction units.

[0047] In the present invention, the term "dynamic tubular reactor" refers to a reaction device in which the reaction channel is cylindrical. It can be used for mass transfer by dynamic stirring, heat transfer in a variety of heat exchange cavities, and can use continuous flow and other technologies. The aspect ratio of the reaction channel is preferably ≥8. As long as it is a dynamic tubular reactor known in the art, it can be used in the present invention, and there is no particular restriction on its material, layout, length, capacity, etc. As a dynamic tubular reactor that can be used in the present invention, it can be listed: a dynamic tubular reactor manufactured by Shandong Weijing Chemical Technology Co., Ltd., a dynamic tubular reactor manufactured by Shandong Haomai Chemical Technology Co., Ltd., and a dynamic tubular reactor manufactured by Anhui Kexin Microflow Chemical Technology Co., Ltd. Among them, the dynamic tubular reactor manufactured by Shandong Weijing Chemical Technology Co., Ltd. is preferred, which is vertical, 0.5 liter capacity, and 316L material.

[0048] In the present invention, hydrogenated silicone oil refers to a hydrogenated silicone oil (hydrogenated polysiloxane) having at least two active hydrogens in one molecule that can be used to react with styrene monomers and long-chain carbenes, respectively. As long as the hydrogenated silicone oil is a hydrogenated silicone oil having at least two active hydrogens in one molecule, there is no particular restriction, for example, it can be a modified hydrogenated silicone oil containing other groups in the main chain and / or side chain, and as other groups, alkyl, aryl, carbon functional group, polyether chain can be listed. Its active hydrogen amount is preferably 1.40-1.70wt%, more preferably 1.50-1.65wt%, and further preferably 1.55-1.63wt%. If the active hydrogen amount is less than 1.40wt%, the number of units of phenyl and long-chain alkyl in the synthesized long-chain alkylphenyl modified silicone oil will be too low, thereby affecting the application of the product. If the active hydrogen amount is higher than 1.70wt%, the number of units of phenyl and long-chain alkyl in the synthesized long-chain alkylphenyl modified silicone oil will be too high, resulting in excessive viscosity, thereby affecting the application of the product.

[0049] As hydrogen-containing silicone oil, there can be mentioned silicone oils having the structural formula Me3SiO(SiMeHO) n The hydrogen-containing silicone oil represented by SiMe3, wherein Me represents a methyl group, and n represents the number of repeating units, which is an integer greater than 2, preferably 14-700, more preferably 24-268, and further preferably 36-120.

[0050] In the present invention, a styrene-based monomer refers to a styrene-based monomer having no other substituents at the carbon at the β position in the styrene structure. As long as the above structure is satisfied, there is no particular limitation. For example, α-C1-C 10 Alkylstyrene, preferably α-C1-C4 alkylstyrene, more preferably α-methylstyrene and α-ethylstyrene. The benzene ring of the styrene monomer may be further substituted with other groups. As other groups, alkyl, alkenyl, alkynyl, nitro, cyano, aryl, heteroaryl, aralkyl, and combinations thereof, having 1 to 20 carbon atoms, may be cited.

[0051] In the present invention, the long-chain carbene is preferably a long-chain carbene with a carbon number of 4 to 18, and more preferably a long-chain carbene with a carbon number of 8 to 16. In the long-chain carbene, the olefin bond is preferably at position 1, and preferably there is no other substituent at position 1. The long-chain carbene is most preferably 1-dodecene.

[0052] In the reaction of the above step 1, a catalyst may be added to promote the reaction. As the catalyst, a noble metal catalyst may be used, preferably a platinum catalyst. As the platinum catalyst, Karstedt catalyst, chloroplatinic acid, chloroplatinate, etc. may be cited. Karstedt catalyst is more preferred. When the catalyst is used, its concentration in the total reaction mass is 0.5-20 ppm, preferably 1-10 ppm, more preferably 1.5-3 ppm, based on the effective ingredient.

[0053] In the present invention, the molar ratio of the styrene monomer to the hydrogen-containing silicone oil may be 20-35:1, preferably 22-28:1, and more preferably 23-26:1.

[0054] In the present invention, the molar ratio of the long-chain carbene to the hydrogen-containing silicone oil may be 30-70:1, preferably 40-55:1, and more preferably 46-50:1.

[0055] In the present invention, hydrogenated silicone oil can be fed into the microchannel reactor as one material alone, styrene monomer and optional catalyst can be premixed in a batch reaction bottle in proportion and then fed into the microchannel reactor as one material, or styrene monomer and optional catalyst can be continuously fed into a static mixer in proportion and then fed into the microchannel reactor as one material. Long-chain carbenes can be fed into the dynamic tubular reactor as one material alone.

[0056] Preferably, the heating temperature of the microchannel reactor and the dynamic tubular reactor is controlled at 60-140°C, preferably 90-120°C, and more preferably 95-110°C.

[0057] Preferably, the system pressure is 6-17 bar, preferably 8-16 bar, more preferably 12-14 bar.

[0058] Preferably, the mass flow rate of the hydrogen-containing silicone oil is 6-10 g / min, preferably 7-9 g / min, and more preferably 7.5-8.5 g / min.

[0059] Preferably, the mass flow rate of the styrene monomer is 3-8 g / min, preferably 4-7 g / min, and more preferably 5.5-6.5 g / min.

[0060] Preferably, the mass flow rate of the long-chain carbene is 12-26 g / min, preferably 14-20 g / min, and more preferably 15-17 g / min.

[0061] By controlling the above reaction conditions, the molar ratio of hydrogen-containing silicone oil to styrene monomers and long-chain carbenes can be controlled within a required range, thereby achieving an effect of accurately controlling the viscosity.

[0062] [Continuous production device for long-chain alkylphenyl modified silicone oil]

[0063] According to one aspect of the present invention, the present invention provides a production device for the above production method, which includes: a microchannel reactor, which is used to receive hydrogenated silicone oil and styrene monomers and react them to obtain a first reactant; a dynamic tubular reactor, which is connected to the above microchannel reactor to receive the above first reactant and has a feed port for feeding long-chain carbenes, so that the above first reactant and the long-chain carbenes further react to obtain long-chain alkylphenyl modified silicone oil. The various components can be connected in sequence with PFA pipeline fittings. The production device can also include a delivery pump for conveying each material.

[0064] As the microchannel reactor, as described above, there can be cited: the G1 reactor manufactured by Corning Reactor Technology Co., Ltd., the microchannel reactor manufactured by Shandong Weijing Chemical Technology Co., Ltd., and the microchannel reactor manufactured by Shandong Haomai Chemical Technology Co., Ltd. Among them, the G1 reactor manufactured by Corning Reactor Technology Co., Ltd. is preferred. When the Corning G1 reactor is used as the microchannel reactor of the present invention, the number of modules is preferably 1-10, more preferably 3-8, and further preferably 4-6.

[0065] As the dynamic tubular reactor, as mentioned above, there can be listed: Shandong Weijing dynamic tubular reactor, dynamic tubular reactor manufactured by Shandong Haomai Chemical Technology Co., Ltd., and dynamic tubular reactor manufactured by Anhui Kexin Microflow Chemical Technology Co., Ltd., among which the dynamic tubular reactor manufactured by Shandong Weijing Chemical Technology Co., Ltd. is preferred, which is vertical, has a capacity of 0.5 liters, and is made of 316L material.

[0066] Furthermore, the production device of the present invention may also include a control device for controlling the temperature and pressure of each reactor and the mass flow rate of each raw material.

[0067] By using the production method and production device of the present invention, a long-chain alkylphenyl modified silicone oil can be obtained, which has a viscosity in the range of 1450-1600 Cp and a refractive index in the range of 1.43-1.49. The refractive index is one of the most important physical constants of organic compounds, which can be accurately and conveniently measured as a standard for the purity of a substance.

[0068] The long-chain alkylphenyl modified silicone oil of the present invention can be used in various technical fields such as die-casting release agent, water repellent, lubrication treatment of leather and synthetic leather, plastic additive, lubricant and coating additive.

[0069] The present invention aims at the problems in the prior art, that is, the intermittent reactor has poor heat and mass transfer effects, resulting in a wide viscosity range of the product long-chain alkylphenyl modified silicone oil, unstable product quality, and many by-products. A series of improvement methods are adopted: 1) a microchannel reactor is first used to carry out a continuous flow reaction on hydrogenated silicone oil and styrene monomers. Since the residence time of the reaction materials in the microchannel reactor is short, the reaction materials are evenly mixed, and the reaction process can be accurately controlled to ensure that the two materials with poor compatibility, hydrogenated silicone oil and styrene monomer, are fully and evenly reacted and the reaction degree is guaranteed; 2) a dynamic tubular reactor is then used to carry out a continuous flow reaction on the reaction materials and long-chain carbenes, and the long-chain carbenes react with the hydrogenated silicone oil until the reaction is complete, so as to ensure that the hydrogenated silicone oil, styrene monomers, and long-chain carbenes react in a pre-set molar ratio, so that the product long-chain alkyl silicone oil accurately reaches the required viscosity; 3) since the reaction temperature is relatively low, the impurity problem caused by the isomerization of olefins is less.

[0070] Example

[0071] The present invention is further described below in conjunction with the examples. It should be noted that the examples cannot be used as a limitation on the scope of protection of the present invention. Those skilled in the art will appreciate that any improvements and changes made on the basis of the present invention are within the scope of protection of the present invention.

[0072] Conventional chemical reagents used in the following examples are all commercially available, among which hydrogenated silicone oil H68 was purchased from Jiangxi Bluestar Starfire Silicone Co., Ltd., α-methylstyrene (purity>99%) was purchased from Shanghai MacLean Biochemical Technology Co., Ltd., 1-dodecene was purchased from Aladdin Reagent JD self-operated flagship store, and Karstedt catalyst (platinum content 10wt%) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. The microchannel reactor was Corning G1 reactor, and the dynamic tubular reactor was Shandong Weijing dynamic tubular reactor (vertical, 0.5L capacity, 316L material, operating pressure 0-2Mpa).

[0073] Preparation method

[0074] The preparation method of the present invention is carried out according to the following steps: (1) adding a catalyst to α-methylstyrene in a required proportion, stirring evenly, and setting aside as material A, hydrogenated silicone oil H68 as material B, and 1-dodecene as material C, (2) using a metering plunger pump to pump material solution A and material B into a microchannel reactor at a set flow rate, (3) raising the temperature of the reaction system to a set temperature through a high and low temperature integrated machine, (4) at the feed port of the dynamic tubular reactor, pumping material C and the reaction product from the microchannel reactor at the set flow rate, respectively, (4) after the flow rate, temperature, and pressure of the reaction system are stabilized, collecting the product at an appropriate outlet of the dynamic tubular reactor into a receiving reaction bottle.

[0075] Analytical methods

[0076] The active hydrogen residue of raw material H68 (chemical shift 4.75ppm) and the residue of raw material α-methylstyrene (chemical shift 2.07ppm) were determined by H NMR. The ratio of phenyl side chain to alkyl side chain in the product can be determined by the ratio of the integrated area of ​​the NMR peak representing the phenyl side chain (Si-CH2-, chemical shift 0.90ppm) to the integrated area of ​​the NMR peak representing the long-chain alkyl side chain (Si-CH2-, chemical shift 0.48ppm).

[0077] Refractive index determination method:

[0078] The refractive index determination method is carried out in accordance with GB / T614-2021 General method for determination of refractive index of chemical reagents. The determination instrument adopts Abbe refractometer.

[0079] Viscosity measurement method:

[0080] The viscosity determination method is carried out in accordance with the GB / T10247-2008 viscosity determination method standard. The instrument adopts a flat viscometer.

[0081] Example 1

[0082] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, and the microchannel reactor 8 modules were used. Material C was fed at the inlet of the dynamic tube, the flow rate of material C was 16.2g / min, the reaction temperature was 100°C, and the pressure of the reaction system was 15bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 58ppm, the residual α-methylstyrene of the raw material was less than 1%, and the ratio of phenyl side chain to alkyl side chain in the product was 47:82. After five samplings (2 hours apart), the viscosity of the product ranged from 1490-1560Cp and the refractive index was 1.466-1.469.

[0083] Example 2

[0084] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, and the microchannel reactor 8 modules were used. Material C was fed at the inlet of the dynamic tube, the flow rate of material C was 18.2g / min, the reaction temperature was 100°C, and the pressure of the reaction system was 14.6bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 26ppm, the raw material α-methylstyrene residue was less than 1%, and the ratio of phenyl side chain to alkyl side chain in the product was 47:83. After five samplings (2 hours apart), the viscosity of the product ranged from 1490-1560Cp and the refractive index was 1.471-1.478.

[0085] Example 3

[0086] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, and the microchannel reactor 8 modules were used. Material C was fed at the inlet of the dynamic tube, the flow rate of material C was 15.3g / min, the reaction temperature was 100°C, and the pressure of the reaction system was 15.9bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 119ppm, the raw material α-methylstyrene residue was less than 1%, and the ratio of phenyl side chain to alkyl side chain in the product was 47:81. After five samplings (2 hours apart), the product viscosity range was 1510-1600Cp, and the refractive index was 1.481-1.490.

[0087] Example 4

[0088] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, a microchannel reactor 6 module was used, material C was fed at the inlet of the dynamic tube, the flow rate of material C was 16.2g / min, the reaction temperature was 100°C, and the pressure of the reaction system was 14.8bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 67ppm, the raw material α-methylstyrene residue was less than 1.6%, the ratio of phenyl side chain to alkyl side chain in the product was 46:83, and after five samplings (2 hours apart), the product viscosity range was 1450-1530Cp, and the refractive index was 1.439-1.442.

[0089] Example 5

[0090] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 6ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, and the microchannel reactor 8 modules were used. Material C was fed at the inlet of the dynamic tube, the flow rate of material C was 16.2g / min, the reaction temperature was 100°C, and the pressure of the reaction system was 14.8bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 48ppm, the raw material α-methylstyrene residue was less than 0.8%, and the ratio of phenyl side chain to alkyl side chain in the product was 47:82. After five samplings (2 hours apart), the product viscosity ranged from 1490-1560Cp and the refractive index was 1.472-1.477.

[0091] Example 6

[0092] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, and the microchannel reactor 8 modules were used. Material C was fed at the inlet of the dynamic tube, the flow rate of material C was 16.2g / min, the reaction temperature was 110°C, and the pressure of the reaction system was 14.2bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 45ppm, the raw material α-methylstyrene residue was less than 0.9%, and the ratio of phenyl side chain to alkyl side chain in the product was 47:82. After five samplings (2 hours apart), the product viscosity ranged from 1490-1560Cp and the refractive index was 1.468-1.476.

[0093] Example 7

[0094] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, and the microchannel reactor 8 modules were used. Material C was fed at the inlet of the dynamic tube, the flow rate of material C was 16.2g / min, the reaction temperature was 120°C, and the pressure of the reaction system was 13.5bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 40ppm, the raw material α-methylstyrene residue was less than 0.9%, the ratio of phenyl side chain to alkyl side chain in the product was 47:82, and the product viscosity ranged from 1480-1540Cp and the refractive index was 1.467-1.473 after five samplings (2 hours apart).

[0095] Example 8

[0096] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, materials A and B were fed at the inlet of the microchannel reactor, and the microchannel reactor 8 modules were used. Material C was fed at the inlet of the dynamic tube, the flow rate of material C was 16.2g / min, the reaction temperature was 60°C, and the pressure of the reaction system was 16.1bar. After the product was deoxidized, the nuclear magnetic resonance hydrogen spectrum determined that the active hydrogen residue of the raw material H68 was 180ppm, the raw material α-methylstyrene residue was less than 2.1%, and the ratio of phenyl side chain to alkyl side chain in the product was 45:80. After five samplings (2 hours apart), the product viscosity ranged from 1450-1510Cp and the refractive index was 1.441-1.447.

[0097] Comparative Example 1

[0098] Add 570g of α-methylstyrene and 200g of 1-dodecene to the reaction bottle, and add about 2ppm of Karstedt platinum catalyst based on platinum metal. Heat to 120℃, slowly add 810g of H68 in about 3 hours, and control the temperature not to exceed 140℃. After the addition is completed, slowly add the remaining 1420g of 1-dodecene. After the addition is completed, continue the reaction for 1 hour. After decompression and removal of low boiling, the product is obtained. Five experimental measurements show that the product viscosity is 1430-1700Cp and the refractive index is 1.432-1.489.

[0099] Comparative Example 2

[0100] 570g of α-methylstyrene was added to the reaction bottle, and about 2ppm of Karstedt platinum catalyst was added based on platinum metal. The temperature was raised to 120°C, and 810g of H68 was slowly added dropwise over about 3 hours, and the temperature was controlled not to exceed 140°C. After the addition was completed, 1620g of dodecene was slowly added dropwise, and the reaction was continued for 1 hour after the addition was completed. The product was obtained after the low boiling point was removed by decompression. Five experiments were conducted to determine that the product viscosity was 1400-1700Cp and the refractive index was 1.467-1.498.

[0101] Comparative Example 3

[0102] Using microchannel reactor alone, the total number of reaction modules is 12:

[0103] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2ppm, the flow rate of material A was 5.7g / min, the flow rate of material B was 8.1g / min, and materials A and B were fed at the entrance of the microchannel reactor. Material C was fed at the entrance of reaction module 9, the flow rate of material C was 16.2g / min, the reaction temperature was 100°C, and the pressure of the reaction system exceeded 18bar. As a result, the reaction system was shut down due to exceeding the safety pressure, and the reaction could not proceed normally.

[0104] Comparative Example 4

[0105] Using the dynamic tube reactor alone:

[0106] The content of Karstedt platinum catalyst in the reaction system (in terms of platinum metal) was controlled to be 2 ppm, the flow rate of material A was 5.7 g / min, the flow rate of material B was 8.1 g / min, materials A and B were fed at the inlet of the dynamic tube, material C was fed at 40% of the dynamic tube, the flow rate of material C was 16.2 g / min, the reaction temperature was 100°C, the actual reaction temperature exceeded 140°C, the reaction temperature could not be effectively controlled, and the reaction could not proceed normally.

Claims

1. A continuous production method for long-chain alkylphenyl modified silicone oil, characterized in that: Include: Step 1: reacting hydrogen-containing silicone oil and styrene-based monomers in a microchannel reactor to obtain a first reactant; Step 2: The first reactant is further reacted with the long-chain carbene in a dynamic tubular reactor to obtain a long-chain alkylphenyl-modified silicone oil.

2. The continuous production method of the long-chain alkylphenyl modified silicone oil according to claim 1, wherein: The pore size of the microchannel reactor is 1 mm to 2 mm; the dynamic tubular reactor is a vertical dynamic tubular reactor.

3. The continuous production method of long-chain alkylphenyl modified silicone oil according to claim 1 or 2, wherein the styrene monomer is α-C1-C 10 Alkylstyrene, preferably α-methylstyrene; The long-chain carbene is a long-chain carbene having 4 to 18 carbon atoms, preferably 1-dodecene.

4. The continuous production method of long-chain alkylphenyl-modified silicone oil according to any one of claims 1 to 3, wherein a catalyst, preferably a platinum catalyst, can also be used in step 1.

5. The continuous production method of the long-chain alkylphenyl modified silicone oil according to any one of claims 1 to 4, wherein The molar ratio of the long-chain carbene to the hydrogen-containing silicone oil is 30-70:1, preferably 40-55:1, and more preferably 46-50:1; The molar ratio of the styrene monomer to the hydrogen-containing silicone oil is 20-35:1, preferably 22-28:1, and more preferably 23-26:

1.

6. The continuous production method of the long-chain alkylphenyl modified silicone oil according to any one of claims 1 to 5, wherein The heating temperature of the microchannel reactor and the dynamic tubular reactor is 60-140°C, preferably 90-120°C, more preferably 95-110°C; The reaction pressure is 6-17 bar, preferably 8-16 bar, and more preferably 12-14 bar.

7. The continuous production method of the long-chain alkylphenyl modified silicone oil according to any one of claims 1 to 6, wherein: The mass flow rate of the hydrogen-containing silicone oil is 6-10 g / min, preferably 7-9 g / min, and more preferably 7.5-8.5 g / min. The mass flow rate of the styrene monomer is 3-8 g / min, preferably 4-7 g / min, more preferably 5.5-6.5 g / min, The mass flow rate of the long-chain carbene is 12-26 g / min, preferably 14-20 g / min, and more preferably 15-17 g / min.

8. A continuous production device for long-chain alkylphenyl modified silicone oil, comprising: A microchannel reactor, which is used to receive hydrogen-containing silicone oil and styrene-based monomers and react them to obtain a first reactant; The dynamic tubular reactor is connected to the microchannel reactor to receive the first reactant and has a feed port for feeding long-chain carbene so that the first reactant and the long-chain carbene can further react to obtain long-chain alkylphenyl modified silicone oil.

9. The continuous production device of the long-chain alkylphenyl modified silicone oil according to claim 8, wherein: The pore size of the microchannel reactor is 1 mm to 2 mm; the dynamic tubular reactor is a vertical dynamic tubular reactor.

10. The continuous production device of long-chain alkylphenyl-modified silicone oil according to claim 8 or 9, wherein: A control device is also provided for controlling the temperature, pressure of each reactor and the mass flow rate of each raw material.

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