CN117777447A - Method for preparing methylphenyl silicone oil by one-pot process - Google Patents
Method for preparing methylphenyl silicone oil by one-pot process Download PDFInfo
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- CN117777447A CN117777447A CN202311840390.9A CN202311840390A CN117777447A CN 117777447 A CN117777447 A CN 117777447A CN 202311840390 A CN202311840390 A CN 202311840390A CN 117777447 A CN117777447 A CN 117777447A
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Abstract
The invention provides a method for preparing methyl phenyl silicone oil by a one-pot method, which comprises the following steps: s100, carrying out hydrolysis reaction on phenyl dialkoxysilane selected from methyl phenyl dimethoxy silane and diphenyl dimethoxy silane and chain extender selected from dimethyl cyclosiloxane and alpha, omega-dihydroxy polydimethylsiloxane at the temperature of 40-90 ℃ and in the presence of water and a first catalyst, and carrying out first de-ironing treatment; s200, adding a second catalyst, and reacting at 70-160 ℃; s300, performing second low-removal treatment to obtain methyl phenyl silicone oil; wherein the first catalyst and the second catalyst are each independently selected from the group consisting of tetramethylammonium hydroxide silicon alkoxide, potassium hydroxide silicon alkoxide; the method further comprises the steps of: the capping agent is added before the hydrolysis reaction in step S100 or before the second catalyst is added in step S200.
Description
Technical Field
The invention belongs to the technical field of organic silicon, and particularly relates to a method for preparing methyl phenyl silicone oil by a one-pot method.
Background
The methylphenyl silicone oil can be prepared by adopting a hydrolysis route, and generally comprises the procedures of hydrolysis, neutralization, water washing, layering, concentration, polycondensation, neutralization, low-pressure removal and the like. The hydrolysis is generally carried out by putting raw materials such as methyl phenyl dichloro silane (or methyl phenyl dimethoxy silane), diphenyl dichloro silane (or diphenyl dimethoxy silane) and the like into a hydrolysis kettle, neutralizing under toluene solvent and acidic condition (adding hydrochloric acid, dilute sulfuric acid, acid clay and the like), transferring the materials into a layering tank for layering, standing for layering, taking out an upper layer oil layer or a lower layer oil layer according to the density of the hydrolyzed materials, transferring the upper layer oil layer or the lower layer oil layer into a concentration kettle for further concentration, transferring the concentrated upper layer oil layer or the lower layer oil layer into a polycondensation kettle for polycondensation reaction under alkaline condition (adding KOH alkaline gel or ammonia gel and the like), adding a proper amount of neutralizing agent for neutralization (ammonia gel is removed after medium breaking at about 150 ℃), removing low-boiling substances through a removing procedure, and removing color through filtration or activated carbon adsorption.
For example, zhou Yiwen et al disclose high viscosity benzyl silicone oils and methods of making them (high viscosity benzyl silicone oil preparation and performance control research [ D ]. Shanghai application university, 2017), gong Yugui et al disclose methylphenyl vinyl silicone oils and methods of making them (methylphenyl vinyl silicone oil preparation and performance [ J ]. Organosilicon materials, 2017,31 (01): 6-9), sun Dawei et al disclose vinyl-terminated methylphenyl silicone oils and methods of making them (vinyl-terminated methylphenyl silicone oil preparation and performance characterization [ J ]. Bonding, 2011,32 (05): 58-60), zhang Chaodeng et al disclose methyl diphenyl-terminated benzyl silicone oils and methods of making them (methyl diphenyl-terminated benzyl silicone oil synthesis research [ J ]. University of Hangzhou university (Nature science edition), 2017,16 (01): 39-45).
Therefore, in the scheme of preparing the methylphenyl silicone oil by the existing hydrolysis route, the process is complicated (comprising the procedures of hydrolysis, neutralization, layering separation, concentration, polycondensation and the like), the reaction device comprises at least four main devices of water (a decomposing kettle, a standing layering device, a concentrating kettle, a polycondensation kettle and the like), and the input cost is high.
Disclosure of Invention
In view of the above, the invention aims to overcome the defects of the prior art and provide a method for preparing methyl phenyl silicone oil by a one-kettle method.
The aim of the invention is achieved by the following technical scheme.
The invention provides a method for preparing methyl phenyl silicone oil by a one-pot method, which comprises the following steps:
s100, carrying out hydrolysis reaction on phenyl dialkoxysilane selected from methyl phenyl dimethoxy silane and diphenyl dimethoxy silane and chain extender selected from dimethyl cyclosiloxane and alpha, omega-dihydroxy polydimethylsiloxane at the temperature of 40-90 ℃ and in the presence of water and a first catalyst to obtain hydrolysis reaction mixed solution, and carrying out first abatement treatment on the hydrolysis reaction mixed solution to obtain hydrolysate;
s200, adding a second catalyst into the hydrolysate, reacting at 70-160 ℃, and stopping the reaction to obtain a polycondensate;
s300, carrying out second low-pressure removal treatment on the polycondensate to obtain methyl phenyl silicone oil;
wherein the first catalyst and the second catalyst are each independently selected from tetramethylammonium hydroxide silicon alkoxide, potassium hydroxide silicon alkoxide, and the amount of the first catalyst is 20 to 1000ppm based on the total weight of the phenyldialkoxysilane and the chain extender, and the ratio of the amount of the second catalyst to the amount of the first catalyst is (1 to 10): 1, a step of;
and wherein the method further comprises: the capping agent is added before the hydrolysis reaction in step S100 or before the second catalyst is added in step S200.
In the invention, specific phenyl dialkoxysilane and a chain extender are used as raw materials, hydrolysis reaction is carried out in the presence of water and a specific first catalyst, operations such as water washing, neutralization, filtration and the like are not needed, and after the temperature is raised, the hydrolyzed product after the removal of the low content is directly subjected to polycondensation in the presence of a second catalyst, so that the methylphenyl silicone oil is prepared. The method reduces the process of preparing the methyl phenyl silicone oil to two processes of hydrolysis and polycondensation, realizes the effect of preparing the methyl phenyl silicone oil by a one-kettle method, and has the advantages of low input cost of production equipment and the like.
According to the method provided by the invention, the properties, particularly the refractive index, of the methylphenyl silicone oil can be adjusted by controlling the phenyl dialkoxysilane and the chain extender. Meanwhile, the viscosity of the methylphenyl silicone oil can be regulated by controlling the dosage of the chain extender. Typically, the amount of chain extender used is positively correlated with the viscosity of the methylphenyl silicone oil.
In some embodiments, the phenyl dialkoxysilane comprises diphenyl dimethoxy silane or a mixture of methyl phenyl dimethoxy silane and diphenyl dimethoxy silane. In the mixture of the methylphenyl dimethoxy silane and the diphenyl dimethoxy silane, the weight ratio of the methylphenyl dimethoxy silane to the diphenyl dimethoxy silane can be (0.5-2): 1, preferably (0.8 to 1.2): 1.
in some embodiments, the weight ratio of the phenyl dialkoxysilane to the chain extender may be (0.1-5): 1. for example, the weight ratio of the phenyl dialkoxysilane to the chain extender may be 0.1: 1. 0.2: 1. 0.4: 1. 0.5: 1. 0.8: 1. 1: 1. 1.2: 1. 1.5: 1.2: 1. 2.5: 1. 3:1. 4: 1.5:1 or a range of compositions thereof. In some embodiments, the weight ratio of the phenyl dialkoxysilane to the chain extender may be (0.4-3): 1, preferably (0.4 to 2.5): 1.
the method according to the invention is provided in which the dimethylcyclosiloxane can be octamethyltetrasiloxane (D4) or a dimethylsiloxane hybrid ring (DMC), in particular a mixture of octamethyltetrasiloxane, decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). The proportion of D4, D5 and D6 in the dimethylsiloxane hybrid ring is not particularly limited in the present invention, and DMC known in the art may be used.
The method according to the invention provides wherein the alpha, omega-dihydroxypolydimethylsiloxane has a viscosity of 50 to 140mpa.s, for example 80 to 120mpa.s, at 25 ℃.
The process according to the invention provides, in step S100, a molar ratio of water to phenyldialkoxysilane of (0.1 to 0.3): 1, preferably of (0.15 to 0.25): 1.
The process according to the invention is provided wherein the first catalyst may be used in an amount of 40 to 500ppm, preferably 40 to 300ppm, based on the total weight of the phenyldialkoxysilane and the chain extender.
According to the method provided by the invention, wherein, the end-capping agent is selected from hexamethyldisiloxane (CAS No. 107-46-0), low viscosity methyl silicone oil, 1, 3-dimethyl-1, 3-tetraphenyldisiloxane (CAS No. 807-28-3) 1, 5-tetraphenyl-1, 3, 5-tetramethyltrisiloxane (CAS number 3982-82-9) and 1, 3-diphenyl-1, 3-tetramethyldisiloxane (CAS number 56-33-7).
In the invention, the viscosity of the low-viscosity methyl silicone oil at 25 ℃ can be 1-10 mm 2 Preferably 5 to 8mm 2 And/s. According to the method provided by the invention, the viscosity of the methylphenyl silicone oil can be adjusted by controlling the dosage of the end-capping agent. Typically, the amount of blocking agent used is inversely related to the viscosity of the methylphenyl silicone oil.
In some embodiments, the capping agent is used in an amount of 1 to 20 parts by weight, preferably 1.5 to 17.5 parts by weight, based on 100 parts by weight total of the phenyldialkoxysilane and the chain extender.
The method provided by the invention, wherein the conditions of the hydrolysis reaction in the step S100 comprise: the temperature is 50-70 ℃; and/or for a time of 1 to 12 hours, preferably 1 to 3 hours.
The method provided by the invention, wherein the conditions of the first abatement process in step S100 include: the vacuum degree is-0.03 to-0.099 MPa, and is preferably-0.03 to-0.08 MPa; the time is 1 to 12 hours, preferably 1 to 3 hours.
The vacuum degree used in the first pull-down process in step S100 may be determined according to the kind of the chain extender. In some embodiments, the chain extender is dimethylcyclosiloxane and the vacuum employed in the first stripping treatment may be from-0.03 MPa to-0.04 MPa. At such vacuum, dimethyl cyclosiloxanes such as D4 or DMC can be prevented from being pulled off with methanol.
According to the method provided by the invention, in the step S100, after hydrolysis, methanol generated in the hydrolysis process can be carried out through the first low-removal treatment (concentration), so that the balance of the reaction is pushed to the right.
In the present invention, it may be judged that the hydrolysis and the first delighting process in step S100 have been completed in the following manner:
mode I: no bubbles are emitted in the reactor, and the condensation pipe for condensing the first stripping gas is no longer dripped; and/or the number of the groups of groups,
mode II: sampling from the reactor, mixing the sample with water according to a mass ratio of 1:1, standing for 10min, and if an oil layer after oil-water separation is free of white turbidity.
According to the method provided by the invention, the hydrolysis reaction and the first stripping treatment in the step S100 can be carried out once or repeatedly, for example, 2 to 5 times, preferably 2 to 3 times.
In some embodiments, water may be added during the second or more hydrolysis reactions and the first removal of the lower portion. The weight ratio of the water to the phenyl dialkoxysilane is (0.1-0.3): 1.
According to the method provided by the invention, the amount of the second catalyst can be determined according to the reaction rate (viscosity increase rate). For example, after the addition of the second catalyst, if the reaction rate is slower, the second catalyst may be supplemented, for example, by a dosage of 50 to 60 ppm. Specifically, if the viscosity does not significantly climb, it is considered that no additional catalyst is required, whereas if the amount of the second catalyst previously added is considered to be insufficient, resulting in a lower reaction rate.
In some embodiments, the second catalyst is used in an amount of 50 to 1000ppm, preferably 50 to 500ppm, based on the total weight of the phenyl dialkoxysilane and the chain extender.
According to the method provided by the invention, the ratio of the dosage of the first catalyst to the dosage of the second catalyst can be 1: 1. 1.2: 1. 3:1. 4: 1.5: 1. 6: 1. 7: 1. 8: 1. 9: 1. 10:1 or a composition range thereof, preferably (1.2 to 6): 1.
the method provided by the invention, wherein the dosage of the first catalyst is the same as the species of the second catalyst. For example, both the first catalyst and the second catalyst are basic or neutral.
The method provided by the invention, wherein the reaction conditions in the step S200 comprise: the reaction temperature is 90-160 ℃; and/or the reaction time is 1 to 10 hours, preferably 2 to 6 hours.
According to the method provided by the invention, in the step S200, the reaction end point can be determined by the following method, and the termination reaction is performed: every 1h, samples were taken, the viscosity of the samples was measured using a kinematic viscometer or a Bohler fly-rotor viscometer, and when the viscosity increase of 2 samples in succession was less than 3%, the end point of the reaction was reached.
The method according to the present invention, wherein, in step S200, the reaction is terminated by:
s210, heating to 150 ℃ to perform medium breaking reaction for 1-2 h; or alternatively
S220, adding a neutralizing agent, and neutralizing for 1-2 h.
In some embodiments, the neutralizing agent is selected from the group consisting of silicone phosphates such as K 2 CO 3 And Na (Na) 2 CO 3 Is a strong base and weak acid salt.
In some embodiments, the first catalyst and the second catalyst are tetramethyl ammonium hydroxide silicon alkoxide, and the reaction conditions in step S200 include: the temperature is 90-120 ℃; the reaction time is 5-6 h; and heating to 150 ℃ to perform medium breaking reaction for 1-2 h. Further, the reaction in step S200 may be performed under a vacuum condition, thereby accelerating the reaction rate. Preferably, the vacuum degree can be-0.04 to-0.05 MPa.
In some embodiments, the first catalyst and the second catalyst are potassium hydroxide silicon alkoxides and the neutralizing agent is a siloxane phosphate; the reaction conditions in step S200 include: the temperature is 140-160 ℃; the reaction time is 6-10 h; the reaction is terminated by adding a neutralizing agent and neutralizing at a temperature of 40 to 150 ℃ for 1 to 2 hours. In addition, the reaction in step S200 may be performed for 1 to 2 hours and then vacuum-drawn, thereby increasing the reaction rate. Preferably, the vacuum degree can be-0.04 to-0.05 MPa.
In some embodiments, the weight sum ratio of the neutralizing agent to the first catalyst and the second catalyst is from 1.5 to 4:1, preferably 2 to 3:1.
the method provided by the invention, wherein the conditions of the second low-removal treatment in the step S300 include: the temperature is 160-180 ℃; the vacuum degree is-0.05 to-0.099 MPa; the time is 1-4 h.
In the present invention, the second lowering treatment in step S300 may be performed under stirring or nitrogen bubbling, or may be performed directly, and the present invention is not particularly limited thereto.
The method provided by the invention, wherein step S300 may further include: the product of the second reduction treatment was filtered to obtain transparent methylphenyl silicone oil. The invention can adopt diatomite and active carbon for filtering.
According to the method provided by the invention, the structure of the methylphenyl silicone oil can be shown as a formula I:
in the formula I, ra and Rb are each independently a capping agent residue, x is more than or equal to 1, y is more than or equal to 0, z is more than or equal to 0, and y+z is more than or equal to 1.
Formula I shows by way of example that the methylphenyl silicone oil prepared according to the invention may contain dimethylsiloxane units (repeating units), methylphenylsiloxane units (repeating units), diphenylsiloxane units (repeating units), but does not mean that the three repeating units are arranged in the order shown. The present invention has no special requirement on the arrangement sequence (position) of three chain links (repeating units). In general, the methylphenyl silicone oil prepared by the method of the invention can be a mixture of different arrangement structures.
For example, the methylphenyl silicone oil of formula I also includes a structure of formula II or formula III:
in the formulas II and III, ra and Rb are each independently a capping agent residue, x is greater than or equal to 1, y is greater than or equal to 0, z is greater than or equal to 0, and y+z is greater than or equal to 1. In some embodiments, ra and Rb are selected from:
the method provided by the invention, wherein the viscosity of the methylphenyl silicone oil at 25 ℃ can be 40-20000 mm 2 /s。
In addition, the methylphenyl silicone oil prepared by the method can be colorless or pale yellow liquid with the chromaticity less than 60 hazen.
The method of the invention has the following advantages:
(1) In the prior art, in the way of adopting dilute hydrochloric acid as a hydrolysis catalyst, water-soluble hydrogen ions and chloride ions are introduced and need to be removed by a water washing mode, but a small amount of hydrogen ions still remain after water washing, a neutralization process is generally added, the time is long, for example, excessive ammonium bicarbonate is added for neutralization, and after the neutralization, the excessive ammonium bicarbonate is heated to be removed.
In the method, specific phenyl dialkoxysilane and a chain extender are used as raw materials, hydrolysis reaction is carried out in the presence of water and a specific first catalyst, operations such as washing, neutralization and filtration are not needed, and after the temperature is raised, the hydrolysate after the removal of the low temperature is directly subjected to polycondensation in the presence of a second catalyst to prepare the methylphenyl silicone oil, so that the process of preparing the methylphenyl silicone oil is reduced to two processes of hydrolysis and polycondensation, the effect of preparing the methylphenyl silicone oil by a one-pot method is realized, and the method has the advantages of low input cost of production equipment and the like.
(2) In the method, tetramethyl ammonium hydroxide silicon alkoxide or potassium hydroxide silicon alkoxide is adopted as a first catalyst and a second catalyst, and is mutually soluble with a chain extender, a blocking agent and phenyl dialkoxysilane, toluene or other organic solvents are not required in the hydrolysis process of the step S100, and the repeated water washing process and the standing layering process are not required after the hydrolysis; the hydrolysis, the first stripping treatment, the polycondensation and other procedures are all completed in the same reactor. The invention can realize the effects of procedures such as hydrolysis, concentration, polycondensation and the like by only one reaction kettle, has the effects of simple production, safe production, no methoxy residue, environmental protection and the like, and has less equipment investment and high production efficiency.
(3) The methyl phenyl silicone oil prepared by the method can be used as raw materials of vacuum diffusion pump oil, high-temperature heating oil, additives in daily chemical industry, soft finishing agents in textile industry, lubricating oil in electronic and electric industry, self-oil-seepage liquid silicone rubber, gas chromatographic carrier, high-temperature lubricating oil, lubricating grease and heat-conducting silicone grease, and has wide application prospect.
Drawings
FIG. 1 is a methyl phenyl silicone oil prepared in example 1 1 H-NMR spectrum;
FIG. 2 is a methyl phenyl silicone oil prepared in example 2 1 H-NMR spectrum.
Detailed Description
The raw materials involved in each of the examples and comparative examples of the present invention include:
methyl phenyl dimethoxy silane, diphenyl dimethoxy silane, jiangxi Hongbai New Material Co., ltd;
tetramethyl ammonium hydroxide silicon alkoxide catalyst, 3% in content, jiangxi blue star fire organosilicon company, inc.;
potassium hydroxide silicon alkoxide 15%, jiangxi blue star fire organic silicon limited company;
silicon-based phosphate with a content of 15%, jiangxi blue Starfire organic silicon Co., ltd;
d4 and DMC, jiangxi blue starfire silicone limited;
low viscosity alpha, omega-dihydroxy polydimethylsiloxane, jiangxi blue Starfire organosilicon Co., ltd;
1, 3-dimethyl-1, 3-tetraphenyldisiloxane, anhui Ai Yaoda silicone oil Co., ltd;
1, 5-tetraphenyl-1, 3, 5-tetramethyltrisiloxane, dakaning.
In addition, the reagents or apparatus used in the present application are not intended to be manufacturer specific and may be purchased or self-made by a regular channel.
Example 1
(1) 127.4g of methyl phenyl dimethoxy silane, 122.2g of diphenyl dimethoxy silane, 100g of octamethyl cyclotetrasiloxane (D4) and 60g of 1, 5-tetraphenyl-1, 3, 5-tetramethyl trisiloxane are added into a reactor, and the temperature is raised to 50 ℃ to obtain a premix;
(2) Adding 51.84g of deionized water and 0.683g of tetramethyl ammonium hydroxide silicon alkoxide (ammonia gum) catalyst into the premix, and hydrolyzing for 3 hours to obtain hydrolysis reaction mixed solution; vacuumizing and reducing the hydrolysis reaction mixed solution for 1h, wherein the vacuum degree is-0.03 MPa, so as to obtain hydrolysate;
(3) Heating to 90 ℃, adding 4.1g of tetramethyl ammonium hydroxide silicon alkoxide catalyst into the hydrolysate, polycondensing for 5 hours, heating to 150 ℃, and carrying out medium breaking reaction for 1 hour to obtain a polycondensate;
(4) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Example 2
(1) 232g of diphenyl dimethoxy silane, 94g of octamethyl cyclotetrasiloxane (D4) and 17g of 1, 3-dimethyl-1, 3-tetraphenyl disiloxane are added into a reactor, and the temperature is raised to 70 ℃ to obtain a premix;
(2) Adding 41.08 deionized water and 0.573g of tetramethyl ammonium hydroxide silicon alkoxide catalyst into the premix, and hydrolyzing for 3 hours to obtain hydrolysis reaction mixed solution; vacuumizing and reducing the hydrolysis reaction mixed solution for 1h, wherein the vacuum degree is-0.03 MPa, so as to obtain hydrolysate;
(3) Heating to 90 ℃, adding 3.43g of tetramethyl ammonium hydroxide silicon alkoxide catalyst into the hydrolysate, polycondensing for 5 hours, heating to 150 ℃, and carrying out medium breaking reaction for 1 hour to obtain a polycondensate;
(4) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Example 3
(1) 127.4g of methyl phenyl dimethoxy silane, 122.2g of diphenyl dimethoxy silane, 100g of octamethyl cyclotetrasiloxane (D4) and 60g of 1, 5-tetraphenyl-1, 3, 5-tetramethyl trisiloxane are added into a reactor, and the temperature is raised to 60 ℃ to obtain a premix;
(2) Adding 46.84g of deionized water and 0.533g of KOH silicon alkoxide catalyst, and hydrolyzing for 3 hours to obtain a hydrolysis reaction mixed solution; vacuumizing and reducing the hydrolysis reaction mixed solution for 1h, wherein the vacuum degree is-0.03 MPa, so as to obtain hydrolysate;
(3) Heating to 160 ℃, adding 0.667g of KOH silicon alkoxide catalyst into the hydrolysate, and carrying out polycondensation for 5h; 3.6g of a silicon-based phosphate was added and neutralized for 1 hour to obtain a polycondensate.
(4) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Example 4
(1) 53g of diphenyldimethoxysilane, 120g of a polymer having a viscosity of 96mm, were added to the reactor 2 Alpha, omega-dihydroxydimethicone of/s, 3g viscosity 5mm 2 Methyl silicone oil per s; heating to 50 ℃ to obtain premix;
(2) Adding 9.37g of deionized water and 0.047g of KOH silicon alkoxide catalyst into the premix, hydrolyzing for 3 hours to obtain a hydrolysis reaction mixed solution, and vacuumizing and reducing the hydrolysis reaction mixed solution for 1 hour, wherein the vacuum degree is-0.04 MPa to obtain hydrolysate;
(3) Heating to 160 ℃, adding 0.067g of KOH silicon alkoxide catalyst into the hydrolysate, and carrying out polycondensation for 5h; adding 0.34g of silicon-based phosphate, and neutralizing for 1h to obtain a polycondensate;
(4) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Comparative example 1
(1) 127.4g of methyl phenyl dimethoxy silane and 122.2g of diphenyl dimethoxy silane are added into a reactor, a condensing reflux mode is adopted, the temperature is raised to 70 ℃, and 30g of toluene is continuously added to obtain a premix;
(2) Slowly dripping 5g of 7 per mill hydrochloric acid and 50g of deionized water into the reactor, and raising the temperature to 80 ℃ to carry out hydrolysis reaction for 5 hours;
(3) Stopping heating, transferring the materials in the reactor in the step (2) into a separating funnel, standing for 5 hours, layering, and taking out the lower layer hydrolysate;
(4) Transferring the hydrolysate in the step (3) to a water washing kettle for washing for 5 times, adding 2g of 1% ammonia water solution, heating to 30 ℃, and neutralizing for 1h;
(5) After the temperature is raised to 60 ℃, starting a vacuum pump, and carrying out low-pressure treatment for 1h under the vacuum degree of minus 0.08MPa;
(6) Transferring the material obtained in the step (5) into a polycondensation kettle, heating to 90 ℃, adding 100g of D4 (tetracyclic body of octamethyl siloxane) and 60g of 1, 5-tetraphenyl-1, 3, 5-tetramethyl trisiloxane, adding 4.1g of tetramethyl ammonium hydroxide silicon alkoxide, reacting for 5 hours, heating to 150 ℃, and breaking medium to react for 1 hour to obtain a polycondensate;
(7) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Comparative example 2
(1) 232g of diphenyl dimethoxy silane is added into a reactor, a condensing reflux mode is adopted, the temperature is raised to 70 ℃, and 30g of toluene is continuously added to obtain a premix;
(2) Slowly dripping 5g of 7 per mill hydrochloric acid and 40g of deionized water into the reactor, and raising the temperature to 80 ℃ to carry out hydrolysis reaction for 5 hours;
(3) Stopping heating, transferring the materials in the reactor in the step (2) into a separating funnel, standing for 5 hours, layering, and taking out the lower layer hydrolysate;
(4) Transferring the hydrolysate in the step (3) to a water washing kettle for washing for 5 times, adding 2g of 1% ammonia water, heating to 30 ℃, and neutralizing for 1h;
(5) Heating to 60 ℃, and then carrying out dehydration treatment for 1h under the vacuum degree of-0.08 MPa;
(6) Transferring the material obtained in the step (5) into a polycondensation kettle, heating to 90 ℃, adding 94g of D4 (tetracyclic body of octamethylsiloxane) and 17g of 1, 3-dimethyl-1, 3-tetraphenyldisiloxane, adding 3.43g of tetramethylammonium hydroxide silicon alkoxide, reacting for 5 hours, heating to 150 ℃, and carrying out medium breaking reaction for 1 hour to obtain a polycondensate;
(7) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Comparative example 3
(1) 127.4g of methyl phenyl dimethoxy silane and 122.2g of diphenyl dimethoxy silane are added into a reactor, a condensing reflux mode is adopted, the temperature is raised to 70 ℃, and 30g of toluene is continuously added to obtain a premix;
(2) Slowly dripping 5g of 7 per mill hydrochloric acid and 43g of deionized water into the reactor, and raising the temperature to 80 ℃ to carry out hydrolysis reaction for 5 hours;
(3) Stopping heating, transferring the materials in the reaction kettle in the step (2) into a separating funnel, standing for 5 hours, layering, and taking out the lower layer hydrolysate;
(4) Transferring the hydrolysate in the step (3) to a water washing kettle for washing for 5 times, adding 2g of 1% ammonia water, heating to 30 ℃, and neutralizing for 1h;
(5) Heating to 60 ℃, and then carrying out dehydration treatment for 1h under the vacuum degree of-0.08 MPa;
(6) Transferring the material obtained in the step (5) into a polycondensation kettle, heating to 160 ℃, adding 100g of D4 (tetracyclic body of octamethylsiloxane) and 60g of 1, 5-tetraphenyl-1, 3, 5-tetramethyltrisiloxane, adding 0.667g of KOH silicon alkoxide catalyst, and reacting for 5 hours;
(7) 2.0g of phosphosiloxane is added to neutralize for 1h;
(8) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Comparative example 4
(1) 53g of diphenyl dimethoxy silane is added into a reactor, a condensing reflux mode is adopted, the temperature is raised to 70 ℃, and 7g of toluene is continuously added to obtain a premix;
(2) Slowly dripping 1.5g of 7%o hydrochloric acid and 9.38g of deionized water into the reactor, and raising the temperature to 80 ℃ to carry out hydrolysis reaction for 5 hours;
(3) Stopping heating, transferring the materials in the reactor in the step (2) into a separating funnel, standing for 5 hours, layering, and taking out the lower layer hydrolysate;
(4) Transferring the hydrolysate in the step (3) to a water washing kettle for washing for 5 times, adding 0.5g of 1% ammonia water solution, heating to 30 ℃, and neutralizing for 1h;
(5) Removing the waste water from the reactor for 1h under the vacuum degree of-0.08 MPa;
(6) Condensation reaction: transferring the material obtained in the step (5) into a polycondensation kettle, heating to 160 ℃, and adding 120g of the material with the viscosity of 96mm 2 Alpha, omega-dihydroxydimethicone per second and 3g viscosity 5mm 2 Methyl silicone oil per second, adding 0.067g of KOH silicon alkoxide catalyst, and reacting for 5 hours;
(7) Adding 0.20g of phosphosiloxane ester, and neutralizing for 1h;
(8) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Comparative example 5
(1) 127.4g of methyl phenyl dimethoxy silane, 122.2g of diphenyl dimethoxy silane, 100g of octamethyl cyclotetrasiloxane (D4) and 60g of 1, 5-tetraphenyl-1, 3, 5-tetramethyl trisiloxane are added into a reactor, and the temperature is raised to 50 ℃ to obtain a premix;
(2) Adding 0.683g of tetramethyl ammonium hydroxide silicon alkoxide catalyst into the premix, and reacting for 3 hours to obtain a reaction mixed solution; vacuumizing and removing the reaction mixture for 1h, wherein the vacuum degree is-0.03 MPa, so as to obtain a reaction mixture;
(3) Heating to 90 ℃, adding 4.1g of tetramethyl ammonium hydroxide silicon alkoxide catalyst into the reaction mixture, polycondensing for 5 hours, heating to 150 ℃, and carrying out medium breaking reaction for 1 hour to obtain a polycondensate;
(4) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Comparative example 6
(1) 127.4g of methyl phenyl dimethoxy silane, 122.2g of diphenyl dimethoxy silane, 100g of octamethyl cyclotetrasiloxane (D4) and 60g of 1, 5-tetraphenyl-1, 3, 5-tetramethyl trisiloxane are added into a reactor, and the temperature is raised to 50 ℃ to obtain a premix;
(2) Adding 51.84g of deionized water and 4.783g of tetramethylammonium hydroxide silicon alkoxide catalyst, and hydrolyzing for 3 hours to obtain a hydrolysis reaction mixed solution; vacuumizing and reducing the hydrolysis reaction mixed solution for 1h, wherein the vacuum degree is-0.03 MPa, so as to obtain hydrolysate;
(3) Heating to 90 ℃, continuing to react for 5 hours, heating to 150 ℃, and carrying out medium breaking reaction for 1 hour to obtain a polycondensate;
(4) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Comparative example 7
(1) 127.4g of methyl phenyl dimethoxy silane, 122.2g of diphenyl dimethoxy silane, 100g of octamethyl cyclotetrasiloxane (D4) and 60g of 1, 5-tetraphenyl-1, 3, 5-tetramethyl trisiloxane are added into a reactor, and the temperature is raised to 50 ℃ to obtain a premix;
(2) Adding 51.84g of deionized water and 3.189g of tetramethylammonium hydroxide silicon alkoxide catalyst, and hydrolyzing for 3 hours to obtain a hydrolysis reaction mixed solution; vacuumizing and reducing the hydrolysis reaction mixed solution for 1h, wherein the vacuum degree is-0.04 MPa, so as to obtain hydrolysate;
(3) Heating to 90 ℃, adding 1.594g of tetramethyl ammonium hydroxide silicon alkoxide catalyst into the hydrolysate, polycondensing for 4 hours, heating to 150 ℃, and carrying out medium breaking reaction for 1 hour to obtain a polycondensate;
(4) Heating to 180 ℃, vacuumizing to below-0.095 MPa, and removing low pressure for 1h to obtain the methylphenyl silicone oil.
Product characterization
AVANCE AV400MHZ Nuclear magnetic resonance Using Bruce, germanyThe instrument characterizes the product, FIG. 1 shows the 1H-NMR spectrum of the sample of example 1, FIG. 2 shows the sample of example 2 1 H-NMR spectrum. As can be seen from FIGS. 1-2, the target product was obtained, wherein the sample of example 1 had nuclear magnetic information of H atoms of methyl groups having methylphenyl segments in a range of 0.2 to 0.6, whereas the product of example 2 did not contain the nuclear magnetic information. In a similar manner to that described above, 1 the H-NMR spectrum showed that the target products were also prepared in examples 3 to 4.
The refractive index, kinematic viscosity, and chromaticity of each example product were measured, and the results are shown in table 1. In addition, by mixing the sample with deionized water according to 1:1 weight ratio for 30min, then standing for 30min, and observing whether the layering is turbid or not to evaluate the quality, and the result is shown in Table 1.
TABLE 1 Methylphenyl Silicone oil Properties
With reference to table 1, it can be seen from examples 1 to 4 and comparative examples 1 to 4 that the method of the present invention does not require washing, neutralization, filtration, etc., and after the temperature is raised, the hydrolyzed product after the removal of the low temperature is directly polycondensed in the presence of the second catalyst to prepare the methylphenyl silicone oil, thereby reducing the process of preparing the methylphenyl silicone oil to two processes of hydrolysis and polycondensation, obviously reducing the material conversion times, realizing the effect of preparing the methylphenyl silicone oil by the one-pot method, and having the characteristic of low input cost of production equipment.
As is clear from the combination of example 1 and comparative example 5, in the absence of water, substantially no hydrolysis was performed in step (2), the polycondensation in step (3) was incomplete, the sample viscosity was low, and after delamination by mixing with water, the sample became cloudy, a large amount of small molecules were present, and the chromaticity was high; whereas the catalyst was used in a 2: when added in a proportion of 1 or more (comparative examples 6 and 7), the hydrolysis rate is too high, gel, even precipitate, occurs after polycondensation, filtration is required, and after delamination by mixing with water, turbidity is brought about, a large number of small molecules are present, and chromaticity is high.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art. The generic principles defined herein may be applied to 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 method for preparing methyl phenyl silicone oil by a one-pot method, wherein the method comprises the following steps:
s100, carrying out hydrolysis reaction on phenyl dialkoxysilane selected from methyl phenyl dimethoxy silane and diphenyl dimethoxy silane and chain extender selected from dimethyl cyclosiloxane and alpha, omega-dihydroxy polydimethylsiloxane at the temperature of 40-90 ℃ and in the presence of water and a first catalyst to obtain hydrolysis reaction mixed solution, and carrying out first abatement treatment on the hydrolysis reaction mixed solution to obtain hydrolysate;
s200, adding a second catalyst into the hydrolysate, reacting at 70-160 ℃, and stopping the reaction to obtain a polycondensate;
s300, carrying out second low-pressure removal treatment on the polycondensate to obtain methyl phenyl silicone oil;
wherein the first catalyst and the second catalyst are each independently selected from tetramethylammonium hydroxide silicon alkoxide, potassium hydroxide silicon alkoxide, and the amount of the first catalyst is 20 to 1000ppm based on the total weight of the phenyldialkoxysilane and the chain extender, and the ratio of the amount of the second catalyst to the amount of the first catalyst is (1 to 10): 1, a step of;
and wherein the method further comprises: the capping agent is added before the hydrolysis reaction in step S100 or before the second catalyst is added in step S200.
2. The method of claim 1, wherein the phenyl dialkoxysilane comprises diphenyl dimethoxy silane or a mixture of methyl phenyl dimethoxy silane and diphenyl dimethoxy silane; preferably, in the mixture of the methylphenyl dimethoxy silane and the diphenyl dimethoxy silane, the weight ratio of the methylphenyl dimethoxy silane to the diphenyl dimethoxy silane is (0.5-2): 1, preferably (0.8 to 1.2):
and/or the dimethylcyclosiloxane is an octamethyltetrasiloxane or a mixed ring of dimethylsiloxanes, for example, a mixture of octamethyltetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane;
and/or the alpha, omega-dihydroxy polydimethylsiloxane has a viscosity of 50 to 140mpa.s, preferably 80 to 120mpa.s, at 25 ℃;
and/or the weight ratio of the phenyl dialkoxysilane to the chain extender is (0.1-5): 1, preferably (0.4 to 3): 1, more preferably (0.4 to 2.5): 1.
3. the process according to claim 1 or 2, wherein in step S100 the molar ratio of water to phenyl dialkoxysilane is (0.1-0.3): 1, preferably (0.15-0.25): 1.
4. The method according to claim 1 to 3, wherein, the end-capping agent is selected from hexamethyldisiloxane, low viscosity methyl silicone oil, 1, 3-dimethyl-1, 3-tetraphenyl disiloxane 1, 5-tetraphenyl-1, 3, 5-tetramethyltrisiloxane and 1, 3-diphenyl-1, 3-tetramethyldisiloxane;
preferably, the viscosity of the low-viscosity methyl silicone oil at 25 ℃ is 1-10 mm 2 Preferably 5 to 8mm 2 /s；
And/or the end-capping agent is used in an amount of 1 to 20 parts by weight, preferably 1.5 to 17.5 parts by weight, based on 100 parts by weight of the total amount of the phenyldialkoxysilane and the chain extender.
5. The method according to any one of claims 1 to 4, wherein the conditions of the hydrolysis reaction in step S100 include: the temperature is 50-70 ℃; and/or for a time of 1 to 12 hours, preferably 1 to 3 hours.
6. The method according to any one of claims 1 to 5, wherein the conditions of the first abatement process in step S100 include: the vacuum degree is-0.03 to-0.099 MPa, preferably-0.03 to-0.08 MPa, and more preferably-0.03 to-0.04 MPa; the time is 1 to 12 hours, preferably 1 to 3 hours.
7. The process according to any one of claims 1 to 6, wherein the first catalyst is used in an amount of 40 to 500ppm, preferably 40 to 300ppm, based on the total weight of phenyl dialkoxysilane and chain extender;
and/or the second catalyst is used in an amount of 50 to 1000ppm, preferably 50 to 500ppm, based on the total weight of the phenyldialkoxysilane and the chain extender;
and/or the ratio of the amount of the second catalyst to the amount of the first catalyst is (1.2 to 6): 1.
8. the method according to any one of claims 1 to 7, wherein in step S200, the reaction is terminated by:
s210, heating to 150 ℃ to perform medium breaking reaction for 1-2 h; or alternatively
S220, adding a neutralizing agent, and neutralizing for 1-2 h;
preferably, the neutralizing agent is selected from the group consisting of silicone phosphates;
preferably, the weight sum ratio of the neutralizing agent to the first catalyst and the second catalyst is 1.5 to 4:1, preferably 2 to 3:1.
9. the method according to any one of claims 1 to 8, wherein the conditions of the second abatement process in step S300 include: the temperature is 160-180 ℃; the vacuum degree is-0.05 to-0.099 MPa; the time is 1-4 h.
10. The process according to any one of claims 1 to 9, wherein the viscosity of the methylphenyl silicone oil at 25 ℃ can be 40 to 20000mm 2 /s。
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| CN118580495A (en) * | 2024-08-06 | 2024-09-03 | 辽宁新邦新材料有限公司 | Phenyl dimethyl end-capped or triphenyl end-capped methylphenyl silicone oil and preparation method thereof |
| CN119735812A (en) * | 2024-12-31 | 2025-04-01 | 江西蓝星星火有机硅有限公司 | A kind of production method of diphenyl silicone oil |
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