CN110964200A - Preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate - Google Patents
Preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate Download PDFInfo
- Publication number
- CN110964200A CN110964200A CN201911313502.9A CN201911313502A CN110964200A CN 110964200 A CN110964200 A CN 110964200A CN 201911313502 A CN201911313502 A CN 201911313502A CN 110964200 A CN110964200 A CN 110964200A
- Authority
- CN
- China
- Prior art keywords
- polysiloxane
- distillate
- hydroxyl
- temperature
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The invention provides a preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate, which comprises the following steps: carrying out air tightness inspection on the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out high-temperature vacuum condensation, reflux and dewatering for later use; adding tetrachloroethane into a reaction kettle, performing constant temperature protection by using inert gas, adding phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution; adding trifluoromethanesulfonic acid into tetrachloroethane, mixing uniformly, dripping into phosphorus pentachloride mixed solution, stirring at constant temperature, adding titanium dioxide sol, and stirring at constant temperature to obtain complex catalyst solution; adding a complex catalyst solution into the polysiloxane distillate, slowly heating, keeping the temperature, continuously heating, and stirring in vacuum to obtain polysiloxane distillate subjected to ring opening treatment; adding the flaky graphene into polysiloxane distillate subjected to ring opening treatment, uniformly stirring, adding an end-capping reagent, and reacting to obtain the hydroxyl end-capped polysiloxane based on the polysiloxane distillate.
Description
Technical Field
The invention belongs to the technical field of siloxane, and particularly relates to a preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate.
Background
In recent years, with the development of economy, silicone sealants and silicone rubber products are increasingly used in daily life and industrial fields. The hydrolysis and polycondensation of monomer and linear body as material to produce polydimethyl siloxane polymer is important basic material and technological process for all silicone products. The hydrolysis and polycondensation of monomer and linear body as material to produce polydimethyl siloxane polymer is important basic material and technological process for all silicone products. 6-membered or more cyclic bodies are inevitably generated or remained in the polymerization process of polydimethylsiloxane by the currently used acid method or alkali method, the cyclic bodies are removed by high-temperature vacuum in the final polysiloxane finished product, and the proportion of the removed distillate is generally 13-17%. The removed distillate can be reused, but the energy consumption for generation is increased, and the distillate which is generally treated for more than 3 times is used as industrial waste, so that the environment is polluted and wasted.
The trifluoromethanesulfonic acid (CF3SO3H) is the strongest organic acid, has stable performance, can replace the traditional inorganic acids such as the traditional sulfuric acid, hydrochloric acid and the like, and plays a role in optimizing and improving the process, and the derivative of the trifluoromethanesulfonic acid refers to the trifluoromethanesulfonic acid
Atoms or atomic groups in molecules, mainly hydrogen atoms, are replaced by other atoms or atomic groups to form a series of compounds. The trifluoromethanesulfonic acid and its derivatives both contain parent CF3SO 3-polyatomic group, and the CF3SO 3-polyatomic group has extremely strong thermodynamic and chemical stability, and fluorine ions cannot be liberated even in the presence of a strong nucleophile, SO that the trifluoromethanesulfonic acid and its derivatives play an important role in the industries such as medicine, chemical engineering and the like.
Catalytic systems based on derivatives of trifluoromethanesulfonic acid or its homologues have been used for the polymerization of cyclosiloxane monomers. Chinese patent CN109384928A discloses a polysiloxane elastomer based on aryl disulfide bond and imine bond and a preparation method thereof, which comprises the steps of uniformly dispersing polysiloxane and diamino diphenyl disulfide in a solvent to form a first mixed solution; uniformly dispersing 1, 3, 5-triphenylformaldehyde and a catalyst in a solvent to form a second mixed solution; adding the second mixed solution into the first mixed solution, reacting under the conditions of inert protective gas atmosphere and continuous stirring, and crosslinking through condensation reaction of aldehyde group and amino group to simultaneously introduce two dynamic covalent bonds of aryl disulfide bond and imine bond into polysiloxane; after the reaction in the step 2, putting the reaction solution in the step 2 into a mould for solvent volatilization and drying. Wherein the catalyst is a triflate salt, such as zinc triflate, europium triflate, yttrium triflate, scandium triflate, or ytterbium triflate. Chinese patent CNCN1414991 discloses a process for the preparation of polyorganosiloxanes by polymerization catalyzed by a catalyst system based on trifluoromethanesulfonic acid or on trifluoromethanesulfonic acid derivatives, which will be characterized by the use of at least one catalyst of the following general formula (I): (I) (CmF2m +1SO2) nA wherein: Δ m is an integer greater than or equal to 1, preferably 1. ltoreq. m.ltoreq.100, still more preferably 1. ltoreq. m.ltoreq.10 and most particularly m.ltoreq.1; Δ n is an integer equal to 1 or 2 and a represents OH, NH2 or NH: (i) n ═ 1 and a ═ OH, (ii) n ═ 1 and a ═ NH2 or (iii) n ═ 2 and a ═ NH; the Δ condition is based on: when this catalyst corresponds to the general formula I (i), it is supported on an inert material, preferably carbon black, in an amount of mass QM expressed as% by weight relative to the total mass of (a) monosilane and/or acyclic siloxane or (b) starting siloxane compound: QM.ltoreq.1.5, preferably QM.ltoreq.1, more preferably 0.01. ltoreq.QM.ltoreq.1. This particular group of catalysts of general formula (I) makes it possible, with high kinetics, to obtain polydiorganosiloxanes and in particular polydimethylsiloxanes having the desired degree of polymerization. It is known from the prior art that polydimethylsiloxane having more excellent performance and a more simplified preparation process can be expected to be obtained by modifying a catalyst system of trifluoromethanesulfonic acid or a trifluoromethanesulfonic acid derivative.
The invention takes trifluoromethanesulfonic acid and phosphorus pentachloride as main raw materials to form a catalyst system, and takes the distillate of siloxane as the raw material to prepare the polydimethylsiloxane with low cost and excellent performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate, wherein trifluoromethanesulfonic acid and phosphorus pentachloride are used as main raw materials to form a catalyst system, and a small amount of flaky graphene is added after ring-opening treatment is carried out on the polysiloxane distillate, so that polydimethylsiloxane with low cost and excellent performance is prepared.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a process for the preparation of a polysiloxane distillate based hydroxy-terminated polysiloxane, characterized in that: the method comprises the following steps:
(1) carrying out air tightness inspection on the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out high-temperature vacuum condensation, reflux and dewatering for later use;
(2) adding tetrachloroethane into the reaction kettle prepared in the step (1), protecting by inert gas at constant temperature, adding phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution;
(3) adding trifluoromethanesulfonic acid into tetrachloroethane, mixing uniformly, adding dropwise into the phosphorus pentachloride mixed solution prepared in step (2), stirring at constant temperature, adding titanium dioxide sol, and stirring at constant temperature continuously to obtain a complex catalyst solution;
(4) adding the complex catalyst solution prepared in the step (3) into the polysiloxane distillate, slowly heating, keeping the temperature, continuously heating, and stirring in vacuum to obtain polysiloxane distillate subjected to ring opening treatment;
(5) adding the flaky graphene into the polysiloxane distillate subjected to the ring-opening treatment prepared in the step (4), uniformly stirring, adding an end-capping reagent, and reacting to obtain the hydroxyl end-capped polysiloxane based on the polysiloxane distillate.
Preferably, the temperature of the high temperature in the step (1) is 105-110 ℃, and the time is 5-30 min.
Preferably, the constant temperature in the step (2) is 25 to 35 ℃.
Preferably, in the step (3), the mass ratio of the trifluoromethanesulfonic acid to the phosphorus pentachloride is 20-25:13-16, the trifluoromethanesulfonic acid accounts for 7-8% of the total system by mass, and the mass ratio of the trifluoromethanesulfonic acid to the titanium dioxide gel is 1.2-1.6: 1.
Preferably, in the step (3), the concentration of the complexing catalyst solution is 10 to 15%.
Preferably, in the step (4), the polysiloxane distillate is a product obtained by stepwise heating distillation of polysiloxane under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃.
Preferably, in the step (4), the amount of the complex catalyst used in the complex catalyst solution is 15 to 18 ppm.
Preferably, in the above technical solution, the temperature raising process in the step (4) is: heating to 40-45 deg.C at a rate of 3-5 deg.C/min, maintaining for 1-2h, heating to 80-85 deg.C at a rate of 6-8 deg.C/min, and reacting under-0.1 MPa for 1-4 days.
Preferably, the viscosity of the polysiloxane distillate subjected to ring opening treatment in the step (4) is 40-45 ten thousand.
Preferably, in the above technical solution, the mass ratio of the flake graphene added to the silicone distillate subjected to ring opening treatment in step (5) is 100: 1-5.
Compared with the prior art, the invention has the following beneficial effects:
(1) the hydroxyl-terminated polysiloxane based on the polysiloxane distillate is prepared by mainly selecting trifluoromethanesulfonic acid and phosphorus pentachloride as main raw materials, mainly reacting to generate trifluoromethanesulfonic anhydride, adding titanium dioxide sol in the reaction process, so that the trifluoromethanesulfonic anhydride and the titanium dioxide mutually permeate to form a complex catalyst, and the acidity and hydrogenation catalyst of the complex catalyst prepared by the method further improves the ring opening effect of more than six rings remained in the polysiloxane distillate, realizes the utilization rate of the polysiloxane distillate, reduces the production cost of the polysiloxane, and after ring opening treatment is carried out on the polysiloxane distillate, a small amount of flaky graphene is added, so that the existence of the flaky graphene is beneficial to forming a layered structure in polydimethylsiloxane, and further, the process of forming the ring body by back biting of a wire body is avoided, therefore, the polydimethylsiloxane with excellent performance is prepared while the cyclic utilization of the polysiloxane distillate is realized and the production cost is reduced.
(2) The polysiloxane byproduct used in the invention is prepared by taking D4 and HMM as main raw materials, uniformly mixing, and heating to about 140 ℃ in stages from 72 ℃ under a vacuum condition to obtain the polysiloxane distillate accounting for about 13-17% of the total amount, wherein the polysiloxane distillate contains special 6-membered and 8-membered ring bodies, has high purity and good ring opening effect, is subjected to ring opening treatment and then is polymerized to generate polysiloxane, and the method belongs to resource recycling and is beneficial to reduction of production cost.
(3) The preparation method is simple and strong in controllability, and the prepared polysiloxane distillate subjected to ring-opening treatment is used with various end-capping agents, so that the preparation method is strong in applicability, wide in application range, good in industrial application value and good in economical efficiency.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at a high temperature of 105 ℃ for 5min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, protecting at a constant temperature of 25 ℃ in an inert gas atmosphere, adding 200g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, adding 130g of trifluoromethanesulfonic acid into 1000g of tetrachloroethane, uniformly mixing, then dropwise adding into the phosphorus pentachloride mixed solution at the speed of 10mL/min, stirring at the constant temperature of 50 ℃ for 2-3 days, adding titanium dioxide sol with the content of 29% according to the mass ratio of the trifluoromethanesulfonic acid to the titanium dioxide gel of 1.2:1, and continuously stirring at the constant temperature for 3 days to obtain a 10% complex catalyst solution.
(4) Adding a complex catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the usage amount of the complex catalyst is 15ppm, firstly raising the temperature to 40 ℃ at the speed of 3 ℃/min, preserving the temperature for 1h, then raising the temperature to 80 ℃ at the usage rate of 6 ℃/min, and stirring and reacting for 1 day under the vacuum pressure of-0.1 MPa to obtain the polysiloxane distillate subjected to ring opening treatment and having the viscosity of 40 ten thousand.
(5) Adding the flaky graphene into the polysiloxane distillate subjected to the ring opening treatment according to the mass ratio of 100:1, uniformly stirring the flaky graphene and the polysiloxane distillate subjected to the ring opening treatment, adding a hydroxyl silicone oil end-capping agent, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Example 2:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at a high temperature of 110 ℃ for 30min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, protecting at the constant temperature of 35 ℃ in an inert gas atmosphere, adding 250g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, 160g of trifluoromethanesulfonic acid is added into 1000g of tetrachloroethane and uniformly mixed, then the mixture is added into the phosphorus pentachloride mixed solution in a dropwise manner at the speed of 10mL/min, the mixture is stirred at the constant temperature of 60 ℃ for 3 days, titanium dioxide sol with the content of 30% is added according to the mass ratio of the trifluoromethanesulfonic acid to the titanium dioxide gel of 1.6:1, and the mixture is continuously stirred at the constant temperature for 4 days, so that 15% of complex catalyst solution is obtained.
(4) Adding a complexing catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the using amount of the complexing catalyst is 18ppm, firstly raising the temperature to 45 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, then raising the temperature to 85 ℃ at the using rate of 8 ℃/min, and stirring and reacting for 4 days under the vacuum pressure of-0.1 MPa to obtain the polysiloxane distillate subjected to ring opening treatment and having the viscosity of 40-45 ten thousand.
(5) Adding the flaky graphene into the polysiloxane distillate subjected to the ring opening treatment according to the mass ratio of 100:5, uniformly stirring the flaky graphene and the polysiloxane distillate subjected to the ring opening treatment, adding a hydroxyl silicone oil end-capping agent, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Example 3:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at a high temperature of 108 ℃ for 10min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, protecting at constant temperature of 30 ℃ in an inert gas atmosphere, adding 240g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, 150g of trifluoromethanesulfonic acid is added into 1000g of tetrachloroethane and uniformly mixed, then the mixture is added into the phosphorus pentachloride mixed solution in a dropwise manner at the speed of 10mL/min, the mixture is stirred at the constant temperature of 55 ℃ for 2.5 days, titanium dioxide sol with the content of 20 percent is added according to the mass ratio of the trifluoromethanesulfonic acid to the titanium dioxide gel of 1.4:1, and the mixture is continuously stirred at the constant temperature for 3.5 days, so that a 13 percent complex catalyst solution is obtained.
(4) Adding a complexing catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the using amount of the complexing catalyst is 17ppm, firstly heating to 43 ℃ at the speed of 3.5 ℃/min, preserving heat for 1.5h, then heating to 83 ℃ at the using rate of 6-8 ℃/min, and stirring and reacting for 3 days under the vacuum pressure of-0.1 MPa to obtain the polysiloxane distillate subjected to ring opening treatment and with the viscosity of 43 ten thousand.
(5) Adding the flaky graphene into the polysiloxane distillate subjected to the ring opening treatment according to the mass ratio of 100:3, uniformly stirring the flaky graphene and the polysiloxane distillate subjected to the ring opening treatment, adding a hydroxyl silicone oil end-capping agent, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Example 4:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at the high temperature of 109 ℃ for 30min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, under the atmosphere of inert gas, protecting at the constant temperature of 29 ℃, adding 220g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, 150g of trifluoromethanesulfonic acid is added into 1000g of tetrachloroethane and uniformly mixed, then the mixture is added into the phosphorus pentachloride mixed solution in a dropwise manner at the speed of 10mL/min, the mixture is stirred at the constant temperature of 56 ℃ for 2-3 days, titanium dioxide sol with the content of 24% is added according to the mass ratio of the trifluoromethanesulfonic acid to the titanium dioxide gel of 1.5:1, and the mixture is continuously stirred at the constant temperature for 3.7 days, so that a 13% complex catalyst solution is obtained.
(4) Adding a complexing catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the using amount of the complexing catalyst is 16ppm, firstly raising the temperature to 42 ℃ at the speed of 4 ℃/min, preserving the temperature for 3h, then raising the temperature to 83 ℃ at the using rate of 7 ℃/min, and carrying out stirring reaction for 2 days under the vacuum pressure of-0.1 MPa to obtain the polysiloxane distillate subjected to ring opening treatment and having the viscosity of 40-45 ten thousand.
(5) Adding the flaky graphene into the polysiloxane distillate subjected to the ring opening treatment according to the mass ratio of 100:4, uniformly stirring the flaky graphene and the polysiloxane distillate subjected to the ring opening treatment, adding a hydroxyl silicone oil end-capping agent, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Example 5:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at a high temperature of 105 ℃ for 30min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, under the atmosphere of inert gas, protecting at the constant temperature of 25 ℃, adding 250g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, adding 130g of trifluoromethanesulfonic acid into 1000g of tetrachloroethane, uniformly mixing, then dropwise adding into the phosphorus pentachloride mixed solution at the speed of 10mL/min, stirring at the constant temperature of 60 ℃ for 2 days, adding titanium dioxide sol with the content of 20-30% according to the mass ratio of the trifluoromethanesulfonic acid to the titanium dioxide gel of 1.6:1, and continuously stirring at the constant temperature for 3 days to obtain a 15% complex catalyst solution.
(4) Adding a complexing catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the using amount of the complexing catalyst is 18ppm, firstly raising the temperature to 40 ℃ at the speed of 3 ℃/min, preserving the temperature for 1h, then raising the temperature to 83 ℃ at the using rate of 7.3 ℃/min, and stirring and reacting for 4 days under the vacuum pressure of-0.1 MPa to obtain the ring-opening treated polysiloxane distillate with the viscosity of 44 ten thousand.
(5) Adding the flaky graphene into the polysiloxane distillate subjected to the ring opening treatment according to the mass ratio of 100:4, uniformly stirring the flaky graphene and the polysiloxane distillate subjected to the ring opening treatment, adding a hydroxyl silicone oil end-capping agent, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Example 6:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at a high temperature of 110 ℃ for 5min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, protecting at the constant temperature of 35 ℃ in an inert gas atmosphere, adding 200g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, 160g of trifluoromethanesulfonic acid is added into 1000g of tetrachloroethane and uniformly mixed, then the mixture is added into the phosphorus pentachloride mixed solution in a dropwise manner at the speed of 10mL/min, the mixture is stirred at the constant temperature of 50 ℃ for 3 days, titanium dioxide sol with the content of 30% is added according to the mass ratio of the trifluoromethanesulfonic acid to the titanium dioxide gel of 1.2:1, and the mixture is continuously stirred at the constant temperature for 3 days, so that a 15% complex catalyst solution is obtained.
(4) Adding a complex catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the usage amount of the complex catalyst is 15ppm, firstly raising the temperature to 40 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, then raising the temperature to 85 ℃ at the usage rate of 6 ℃/min, and stirring and reacting for 1 day under the vacuum pressure of-0.1 MPa to obtain the polysiloxane distillate subjected to ring opening treatment and having the viscosity of 45 ten thousand.
(5) Adding the flaky graphene into the polysiloxane distillate subjected to the ring opening treatment according to the mass ratio of 100:3, uniformly stirring the flaky graphene and the polysiloxane distillate subjected to the ring opening treatment, adding a hydroxyl silicone oil end-capping agent, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Comparative example 1:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at a high temperature of 108 ℃ for 10min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, protecting at constant temperature of 30 ℃ in an inert gas atmosphere, adding 240g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, 150g of trifluoromethanesulfonic acid is added into 1000g of tetrachloroethane and uniformly mixed, then the mixture is added into the phosphorus pentachloride mixed solution in a dropwise manner at the speed of 10mL/min, and the mixture is stirred at the constant temperature of 55 ℃ for 5 days to obtain a 12% complex catalyst solution.
(4) Adding a complexing catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the using amount of the complexing catalyst is 17ppm, firstly heating to 43 ℃ at the speed of 3.5 ℃/min, preserving heat for 1.5h, then heating to 83 ℃ at the using rate of 6-8 ℃/min, and stirring and reacting for 3 days under the vacuum pressure of-0.1 MPa to obtain the polysiloxane distillate subjected to ring opening treatment and with the viscosity of 43 ten thousand.
(5) Adding the flaky graphene into the polysiloxane distillate subjected to the ring opening treatment according to the mass ratio of 100:3, uniformly stirring the flaky graphene and the polysiloxane distillate subjected to the ring opening treatment, adding a hydroxyl silicone oil end-capping agent, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Comparative example 2:
(1) and (3) checking the air tightness of the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out vacuum condensation reflux dewatering treatment at a high temperature of 108 ℃ for 10min for later use.
(2) Adding 1000g of tetrachloroethane into a reaction kettle, protecting at constant temperature of 30 ℃ in an inert gas atmosphere, adding 240g of phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution.
(3) Under the inert gas atmosphere, 150g of trifluoromethanesulfonic acid is added into 1000g of tetrachloroethane and uniformly mixed, then the mixture is added into the phosphorus pentachloride mixed solution in a dropwise manner at the speed of 10mL/min, and the mixture is stirred at the constant temperature of 55 ℃ for 3 days to obtain a 10% complex catalyst solution.
(4) Adding a complexing catalyst solution into polysiloxane distillate subjected to segmented temperature rise distillation under the vacuum pressure of-0.1 MPa and the temperature of 72-140 ℃, wherein the using amount of the complexing catalyst is 17ppm, firstly heating to 43 ℃ at the speed of 3.5 ℃/min, preserving heat for 1.5h, then heating to 83 ℃ at the using rate of 6-8 ℃/min, and stirring and reacting for 3 days under the vacuum pressure of-0.1 MPa to obtain the polysiloxane distillate subjected to ring opening treatment and with the viscosity of 43 ten thousand.
(5) Adding a hydroxyl silicone oil end-capping agent into the polysiloxane distillate subjected to the ring opening treatment, and reacting to obtain hydroxyl end-capped polysiloxane based on the polysiloxane distillate, wherein the viscosity of the prepared polysiloxane can be determined by the water content.
Upon examination, the appearance, viscosity and yield results for the silicone distillate-based hydroxyl-terminated polysiloxanes of examples 1-6, the silicone distillate-based hydroxyl-terminated polysiloxanes prepared in comparative examples 1-2, and the existing hydroxyl-terminated polysiloxanes are as follows:
as can be seen from the table above, the hydroxyl-terminated polysiloxane based on the polysiloxane distillate prepared by the invention has good appearance, viscosity and yield, can completely meet the use requirements, and has good market application prospect.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A process for the preparation of a polysiloxane distillate based hydroxy-terminated polysiloxane, characterized in that: the method comprises the following steps:
(1) carrying out air tightness inspection on the reaction kettle, replacing, drying and dewatering by using nitrogen, rinsing the reaction kettle by tetrachloroethane, and carrying out high-temperature vacuum condensation, reflux and dewatering for later use;
(2) adding tetrachloroethane into the reaction kettle prepared in the step (1), protecting by inert gas at constant temperature, adding phosphorus pentachloride, and uniformly stirring to obtain a phosphorus pentachloride mixed solution;
(3) adding trifluoromethanesulfonic acid into tetrachloroethane, mixing uniformly, adding dropwise into the phosphorus pentachloride mixed solution prepared in step (2), stirring at constant temperature, adding titanium dioxide sol, and stirring at constant temperature continuously to obtain a complex catalyst solution;
(4) adding the complex catalyst solution prepared in the step (3) into the polysiloxane distillate, slowly heating, keeping the temperature, continuously heating, and stirring in vacuum to obtain polysiloxane distillate subjected to ring opening treatment;
(5) adding the flaky graphene into the polysiloxane distillate subjected to the ring-opening treatment prepared in the step (4), uniformly stirring, adding an end-capping reagent, and reacting to obtain the hydroxyl end-capped polysiloxane based on the polysiloxane distillate.
2. The method for preparing hydroxyl-terminated polysiloxane based on polysiloxane distillate according to claim 1, characterized in that the temperature of the high temperature in step (1) is 105-110 ℃ and the time is 5-30 min.
3. The method for preparing a polysiloxane distillate based hydroxyl-terminated polysiloxane according to claim 1, wherein the constant temperature in the step (2) is 25-35 ℃.
4. The method for preparing hydroxyl-terminated polysiloxane based on polysiloxane distillate according to claim 1, wherein the mass ratio of trifluoromethanesulfonic acid to phosphorus pentachloride in step (3) is 20-25:13-16, the content of trifluoromethanesulfonic acid in the total system is 7-8% by mass, and the mass ratio of trifluoromethanesulfonic acid to titanium dioxide gel is 1.2-1.6: 1.
5. The method for preparing a polysiloxane distillate based hydroxyl-terminated polysiloxane according to claim 1, wherein the concentration of the complexing catalyst solution in the step (3) is 10-15%.
6. The method for preparing a polysiloxane distillate-based hydroxyl-terminated polysiloxane according to claim 1, wherein the polysiloxane distillate in the step (4) is a product of stepwise temperature rise distillation of polysiloxane under a vacuum pressure of-0.1 MPa and at a temperature of 72-140 ℃.
7. The method for preparing a polysiloxane distillate based hydroxyl-terminated polysiloxane according to claim 1, characterized in that the amount of the complex catalyst used in the complex catalyst solution in the step (4) is 15-18 ppm.
8. The method for preparing the polysiloxane distillate-based hydroxyl-terminated polysiloxane according to claim 1, wherein the temperature raising process in the step (4) is as follows: heating to 40-45 deg.C at a rate of 3-5 deg.C/min, maintaining for 1-2h, heating to 80-85 deg.C at a rate of 6-8 deg.C/min, and reacting under-0.1 MPa for 1-4 days.
9. The method for preparing the hydroxyl-terminated polysiloxane based on the polysiloxane distillate, according to claim 1, characterized in that the viscosity of the polysiloxane distillate subjected to ring opening treatment in the step (4) is 40-45 ten thousand.
10. The preparation method of the hydroxyl-terminated polysiloxane based on the polysiloxane distillate, which is characterized in that the mass ratio of the added sheet graphene to the polysiloxane distillate subjected to ring opening treatment in the step (5) is 100: 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911313502.9A CN110964200A (en) | 2019-12-19 | 2019-12-19 | Preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911313502.9A CN110964200A (en) | 2019-12-19 | 2019-12-19 | Preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110964200A true CN110964200A (en) | 2020-04-07 |
Family
ID=70035075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911313502.9A Pending CN110964200A (en) | 2019-12-19 | 2019-12-19 | Preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110964200A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333846A (en) * | 2020-04-13 | 2020-06-26 | 新纳奇材料科技江苏有限公司 | Preparation method of single-end alkoxy and single-end methyl polydimethylsiloxane |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0087532A1 (en) * | 1981-11-12 | 1983-09-07 | Imperial Chemical Industries Plc | Production of aromatic polyketones |
| JP2000053631A (en) * | 1998-08-05 | 2000-02-22 | Central Glass Co Ltd | Purification of trifluoromethanesulfonic acid anhydride |
| CN101225170A (en) * | 2008-01-26 | 2008-07-23 | 中国船舶重工集团公司第七二五研究所 | Method for synthesizing short-chain hydroxyl silicone oil |
| WO2013066734A1 (en) * | 2011-10-31 | 2013-05-10 | Merck Sharp & Dohme Corp. | Process and intermediates for the preparation of 3-amino-4-cyclobutyl-2-hydroxybutanamide and salts thereof |
| CN104204083A (en) * | 2012-02-02 | 2014-12-10 | 巴斯夫欧洲公司 | Thermoplastic pom material |
| CN105308038A (en) * | 2013-04-30 | 2016-02-03 | 葛兰素史密斯克莱知识产权（第2号）有限公司 | Enhancer of zeste homolog 2 inhibitors |
| CN105755864A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Method for preparing printing coating adhesive |
| CN108484452A (en) * | 2018-03-22 | 2018-09-04 | 东北师范大学 | A kind of preparation method of oroalkane sulfonyl hydrazone |
| CN110483458A (en) * | 2018-05-15 | 2019-11-22 | 万华化学集团股份有限公司 | Lactone aromatic derivative and preparation method and side chain liquid crystalline polymer and the preparation method and application thereof containing liquid crystal unit |
-
2019
- 2019-12-19 CN CN201911313502.9A patent/CN110964200A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0087532A1 (en) * | 1981-11-12 | 1983-09-07 | Imperial Chemical Industries Plc | Production of aromatic polyketones |
| JP2000053631A (en) * | 1998-08-05 | 2000-02-22 | Central Glass Co Ltd | Purification of trifluoromethanesulfonic acid anhydride |
| CN101225170A (en) * | 2008-01-26 | 2008-07-23 | 中国船舶重工集团公司第七二五研究所 | Method for synthesizing short-chain hydroxyl silicone oil |
| WO2013066734A1 (en) * | 2011-10-31 | 2013-05-10 | Merck Sharp & Dohme Corp. | Process and intermediates for the preparation of 3-amino-4-cyclobutyl-2-hydroxybutanamide and salts thereof |
| CN104204083A (en) * | 2012-02-02 | 2014-12-10 | 巴斯夫欧洲公司 | Thermoplastic pom material |
| CN105308038A (en) * | 2013-04-30 | 2016-02-03 | 葛兰素史密斯克莱知识产权（第2号）有限公司 | Enhancer of zeste homolog 2 inhibitors |
| CN105755864A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Method for preparing printing coating adhesive |
| CN108484452A (en) * | 2018-03-22 | 2018-09-04 | 东北师范大学 | A kind of preparation method of oroalkane sulfonyl hydrazone |
| CN110483458A (en) * | 2018-05-15 | 2019-11-22 | 万华化学集团股份有限公司 | Lactone aromatic derivative and preparation method and side chain liquid crystalline polymer and the preparation method and application thereof containing liquid crystal unit |
Non-Patent Citations (5)
| Title |
|---|
| 张健: "二（三氟甲磺酰）亚胺锂和苯氧菌酯的合成工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 章基凯: "《有机硅材料》", 31 October 1999, 中国物资出版社 * |
| 陈冠荣: "《化工百科全书 第7卷》", 30 September 1994, 化学工业出版社 * |
| 魏文德: "《有机化工原料大全 中》", 31 January 1999, 化学工业出版社 * |
| 黄汉生: "三氟甲烷磺酸及其衍生物的开发与应用", 《有机氟工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333846A (en) * | 2020-04-13 | 2020-06-26 | 新纳奇材料科技江苏有限公司 | Preparation method of single-end alkoxy and single-end methyl polydimethylsiloxane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106432728B (en) | A kind of pheiiyldimetliyl siloxy cage-type silsesquioxane silicone rubber crosslinking agent and preparation method thereof | |
| CN108034051A (en) | A kind of vinyl polysiloxane and preparation method and application | |
| CN110964200A (en) | Preparation method of hydroxyl-terminated polysiloxane based on polysiloxane distillate | |
| CN109306059A (en) | A kind of preparation method of high activity tetramethylammonium hydroxide organosilicon alkali glue | |
| CN100471898C (en) | Method of preparing star-type multi-arm silicon oil | |
| CN113896893A (en) | Preparation method of high-conversion low-cycle-content simethicone | |
| CN113185689B (en) | Low-water-absorption copolymerized nylon resin and preparation method thereof | |
| CN101665571A (en) | Polyphenyl methylsiloxane modified epoxy resin and manufacturing method of high performance electronic packaging material thereof | |
| CN110684199A (en) | Organic siloxane-polyoxypropylene segmented copolymer and preparation method thereof, and prepared bi-component LED (light-emitting diode) pouring sealant and preparation method thereof | |
| CN102604101B (en) | Synthesis method for phenyl organosilicon copolymer with uniformly distributed phenyl units | |
| CN109535427A (en) | A kind of preparation method of ethenyl blocking fluorosilicon oil | |
| CN103172866B (en) | The preparation method of the hydroxyl endblocked polydimethylsiloxane that a kind of viscosity is controlled | |
| EP0484120B1 (en) | Hydrogenpolysiloxanes and methods of making them | |
| CN115286796A (en) | Ring-opening continuous polymerization process for cyclosiloxane anion | |
| CN102659831A (en) | Synthesis method of gamma-thiopropyl trimethoxy silane | |
| CN114316272A (en) | Preparation process of structure control agent | |
| CN110305297B (en) | Preparation method and application of thermosetting epoxy resin shape memory polymer | |
| CN111072967A (en) | Method for preparing organic silicon by hydrolyzing and condensing chlorosilane in isopropanol | |
| CN105885052A (en) | Preparation method of vinyl-terminated polymethyl ethyl siloxane | |
| CN115819769B (en) | Catalyst for organic silicon and preparation method thereof | |
| CN110903482B (en) | Production process of end sealing agent | |
| CN110387054B (en) | Preparation method of low-cost transparent hybrid silicone rubber | |
| CN115490863B (en) | High-temperature-resistant organic silicon elastomer and preparation method thereof | |
| CN107216456A (en) | Silicone hydroxyl blocks the preparation method of dimethione | |
| CN113004523B (en) | Epoxy-organic silicon resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200407 |