CN111807927B - Production device and preparation method of organic sodium alkoxide - Google Patents
Production device and preparation method of organic sodium alkoxide Download PDFInfo
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Abstract
The invention discloses a production preparation method of organic sodium alkoxide, which comprises a kettle reverse rectification device, wherein metal sodium is added into the kettle reverse rectification device, then nitrogen is replaced, a vacuum device is started to pump a reactor to-0.1 MPa, organic alcohol is added into the reactor, and the reaction is carried out under the conditions of certain temperature and negative pressure to obtain a certain solid content organic sodium alkoxide solution. According to the preparation method of the organic sodium alkoxide, the boiling point of the organic alcohol is reduced through vacuum rectification, the evaporated organic alcohol flows back to the reaction system again, direct heat exchange between the material and the backflow material can be promoted, the temperature of the reaction system is reduced, and the problems that metal sodium is heated and melted into a spherical shape due to high boiling point of the organic alcohol, the intensity of reaction is increased, and reaction is out of control are solved.
Description
Technical Field
The invention relates to a preparation method of organic alcohol alkali metal salt, in particular to a production device and a preparation method of organic sodium alkoxide, belonging to the field of application of fine chemical engineering technology.
Background
The polycarboxylate water reducer is a high-efficiency water reducer represented by first-generation lignosulfonate, second-generation naphthalene sulfonate, aliphatic sulfonate and the like, and a third-generation high-performance water reducer developed recently has the characteristics of high water reducing rate, good slump retention and the like, is popularized and applied in large scale in the fields of capital construction engineering, civil buildings, nuclear power, hydropower and the like, is a water reducer product with the largest domestic application amount at present, and accounts for about 80 percent of the market share of the concrete water reducer.
The polyether macromonomer is a main raw material for synthesizing the polycarboxylate water reducer, accounts for 80-90% of the mass of the polycarboxylate water reducer, the polyether macromonomer used for synthesizing the polycarboxylate water reducer in the year reaches about 240 ten thousand tons, and the effective content of the polyether macromonomer has obvious influence on the performance of the finally prepared polycarboxylate water reducer.
The catalysts currently used for polyether synthesis are classified into acid catalysts, coordination catalysts and base catalysts. The acid catalyst is common concentrated sulfuric acid, concentrated hydrochloric acid, boron trifluoride diethyl etherate, lewis acid and the like [ Zyguoguo et al, ring-opening polymerization of ethylene oxide and propylene oxide [ J ], chemical progress, 2007,19 (1), 145-152]. The polyether prepared by using the acid catalyst has low molecular weight and has cyclic byproducts, and the cyclic byproducts are only used in a few polyether products; the coordination catalyst is mainly a bimetallic catalyst, DMC or MMC for short, which is developed by American general tire rubber company and aims at the polymerization of polyether polyol, and the DMC or MMC catalyst is particularly suitable for the polymerization working condition of propylene oxide, and has high polymerization rate and low polyether molecular weight distribution. When ethylene oxide is used to participate in the polymerization, the efficiency of the DMC catalyst is significantly reduced and the polyether molecular weight distribution is significantly broadened. Therefore, the current application range of DMC is limited to the production of polyether polyol prepared by propylene oxide [ Tangsiqing et al, production by using bimetallic catalyst [ C ], proceedings of the eleventh year meeting of the Chinese polyurethane industry Association, 2002,102-104]; the alkali catalyst is common metal sodium, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium hydride, potassium tert-butoxide, alkaline earth metal and the like, is suitable for ethylene oxide polymerization, has low polymerization efficiency on propylene oxide, easily generates allyl byproducts and causes the unsaturation degree of polyether to be increased. At present, the catalyst used in the polyether macromonomer industry is mainly an alkali catalyst, and the type of the catalyst is gradually changed from sodium hydroxide and sodium methoxide at the beginning to sodium hydride or metallic sodium with better reaction activity and higher purity.
The procedure of adding catalyst in the production process of polyether macromonomer is mainly to prime with unsaturated alcohol, then add metallic sodium or sodium hydride into the unsaturated alcohol, and transfer the materials into a polyether reactor to produce polyether macromonomer after full reaction. The safety risk of the prior process is high, on one hand, the boiling point of unsaturated alcohol is high, the reaction process with metal sodium or sodium hydride is violent and accompanied with hydrogen generation, so that the metal sodium is easy to melt into a spherical shape, and the hydrogen is easy to explode or ignite; on the other hand, various companies do not have good treatment methods for the reaction of unsaturated alcohol and metallic sodium or sodium hydride at present, the risk is avoided by adopting an open-air catalyst adding mode, and the requirement on occupational quality of operators is high.
In conclusion, the polyether macromonomer is a main raw material of the polycarboxylate superplasticizer, and the synthesis of the polyether macromonomer is mainly performed by using metallic sodium or sodium hydride as a catalyst at home. Because the boiling point of the unsaturated alcohol is generally above 100 ℃, the melting point of the metal sodium is reached or exceeded, in the reaction process of the unsaturated alcohol and the metal sodium, the metal sodium is easily heated, heated and melted into a spherical shape, and the reaction rate is further aggravated to further cause safety accidents, in addition, the reaction process is accompanied with hydrogen generation, and fire or explosion is easily caused when the hydrogen is not removed in time; the specific surface area of sodium hydride is far greater than that of metal sodium, hydrogen is generated in the reaction process of the sodium hydride and unsaturated alcohol, the reaction is very violent, the sodium hydride can be added into the unsaturated alcohol only for a few times, the working procedure time is obviously prolonged, and the solvent kerosene and water of the sodium hydride are insoluble, so that the polymerization effect is adversely affected when the carboxylic acid water reducing agent is prepared. Based on the method, the invention provides a safe and efficient preparation method of the organic sodium alkoxide.
Disclosure of Invention
The invention aims to solve the problems and provide a production device and a preparation method of organic sodium alkoxide.
The invention achieves the above purpose through the following technical scheme, and a production device and a preparation method of organic sodium alkoxide comprise a kettle reverse rectification device, wherein the kettle reverse rectification device comprises a tower kettle, a tower kettle outer jacket capable of heating and cooling is fixed on the tower kettle, a stirrer is sleeved in the tower kettle, the top end of the tower kettle is communicated with a rectification column, the surface of the rectification column is fixed with a steam heating heat retainer, the bottom of the tower kettle is communicated with a finished product tank, the rectification column is communicated with a full reflux condenser, the bottom of the full reflux condenser is communicated with a receiving tank, the receiving tank is respectively communicated with a material reflux pump and a vacuum pump, and the bottom of the material reflux pump is communicated with the rectification column, and the preparation method comprises the following steps:
(1) Adding metal sodium into the tower kettle, sealing the tower kettle, replacing nitrogen for 3 times, starting a vacuum pump, and pumping the pressure in the tower kettle to-0.1 MPa;
(2) Opening a feeding valve of a tower kettle to suck organic alcohol dissolved with a polymerization inhibitor into the tower kettle, starting a stirrer, keeping a vacuum pipeline of a vacuum pump in an open state, starting jacket steam of the tower kettle to heat the tower kettle to a preset temperature, starting a steam heating heat retainer of a rectifying tower column, starting a circulating cooling water or chilled water valve of a total reflux condenser, starting a feeding pipeline valve and a discharging pipeline valve of a receiving tank, starting a material reflux pump to pump materials back into the rectifying tower column when a liquid level meter in the receiving tank shows that 25% of liquid level is displayed, forming stable rectification-reflux circulation, controlling the temperature of the tower kettle to be 50-90 ℃, controlling the pressure of a reaction system to be-0.1 MPa, and carrying out heat preservation reaction for 5-10 hours;
(3) After the reaction is finished, light yellow or light brown yellow viscous liquid is obtained, nitrogen is used for pressing the materials in the tower kettle into a finished product tank, and the organic sodium alkoxide is obtained and stored for later use.
Preferably, the volume of the tower kettle is 5-10 m 3 。
Preferably, the rectifying column is a plate column or a packed column, the diameter d of the column is =10 cm-30 cm, the height L of the column is =100 cm-500 cm, the packing of the packed column is made of stainless steel and is in the shape of a cylinder, a saddle, a ripple, a theta and the like, and the packing is filled in the packed column in a random manner.
Preferably, the total reflux condenser is of a shell and tube or disc structure, materials are fed in a pipeline or an interlayer, and circulating cooling water or chilled water is fed outside the pipeline or the interlayer.
Preferably, the vacuum pump is one of a roots vacuum pump, a water ring vacuum pump, a vacuum oil pump and the like, wherein the water ring vacuum pump is provided with an anti-reverse adsorption piece.
Preferably, the metal sodium is sodium rods directly delivered from a factory, the specification of the sodium rods is 1.5 Kg/root, the sodium rods are directly piled in a tower kettle after being wiped by oil absorption paper, and the mass feeding ratio of the metal sodium to the organic alcohol is 1: (10-40), the adding sequence is that the metallic sodium is added firstly and then the organic alcohol is added.
Preferably, the organic alcohol is mainly a starter for synthesizing polyether macromonomer for polycarboxylic acid water reducing agent, and comprises unsaturated alcohol and saturated alcohol, wherein the unsaturated alcohol comprises one of allyl alcohol, methallyl alcohol, 3-methyl-3 butene-1-ol, ethylene glycol vinyl ether, 7-octene-1-ol, 3, 7-dimethyl-7-octenol and other unsaturated alcohols, and the saturated alcohol comprises one of methanol, ethanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, isopropanol, n-butanol, cyclohexanol, isooctanol and other saturated alcohols.
Preferably, the polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butylcatechol and the like, and the dosage of the polymerization inhibitor is 0.01-0.05% of the mass of the organic alcohol.
Preferably, the reaction of the metal sodium and the organic alcohol does not need heating in the reaction process, the reaction temperature is controlled to be 50-90 ℃ by means of heat release and temperature rise of the reaction of the metal sodium and the organic alcohol.
The invention has the beneficial effects that:
(1) According to the preparation method of the organic sodium alkoxide, the boiling point of the organic alcohol is reduced through vacuum rectification, the evaporated organic alcohol flows back to the reaction system again, direct heat exchange between the material and the backflow material can be promoted, the temperature of the reaction system is reduced, and the problems that metal sodium is heated and melted into a spherical shape due to high boiling point of the organic alcohol, the intensity of reaction is increased, and reaction is out of control are solved.
(2) The preparation method of the organic sodium alkoxide well solves the problem of hydrogen enrichment generated by the reaction of the organic alcohol and the metal sodium, and quickly removes the hydrogen in the reaction system out of the system through rectification under reduced pressure.
(3) According to the preparation method of the organic sodium alkoxide, the purity of the produced organic sodium alkoxide is high, the reaction system is in a vacuum state, the time of rectification under reduced pressure is short, and the reduction of the purity of the organic sodium alkoxide caused by the reaction of moisture in air and carbon dioxide with the organic sodium alkoxide is avoided.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a tank reverse rectification apparatus of the present invention.
In the figure: 1. the device comprises a tower kettle, 2 parts of a stirrer, 3 parts of a rectifying tower column, 4 parts of a total reflux condenser, 5 parts of a receiving tank, 6 parts of a material reflux pump, 7 parts of a vacuum pump, 8 parts of a finished product tank, 9 parts of a tower kettle outer jacket, and 10 parts of a steam heating heat retainer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner" and "outer" indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; the connection may be direct or indirect through an intermediate medium, and the connection may be internal to the two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art can, in light of the present disclosure, vary the reagents, and reaction process conditions within the scope of the invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
All chemical reagents in the invention are commercial industrial-grade purity products, and the use amount of each raw material is mass parts. The determination of the sodium organylalkoxide content described in the present invention was carried out by titration, with reference to the method specified in standard HG/T2561-2014. The molecular weight of the polyether macromonomer is tested by a hydroxyl value method specified in JC/T2033-2018 polyether for concrete admixture and derivatives thereof; high performance liquid testing method test reported in effective content reference of polyether macromonomer (Xiliana et al, high performance liquid chromatography determination of polyethylene glycol mass fraction [ J ],2016,33 (6), 53-60) in polycarboxylic acid water reducer macromonomer; the molecular weight distribution of the polyether macromonomer was measured using aqueous phase high performance Gel Permeation Chromatography (GPC).
Referring to fig. 1, a production device and a preparation method of organic sodium alkoxide include a kettle reverse rectification device, the kettle reverse rectification device includes a tower kettle 1, a tower kettle external jacket 9 capable of heating and cooling is fixed on the tower kettle 1, a stirrer 2 is sleeved in the tower kettle 1, the top end of the tower kettle 1 is connected to an inlet at the lower end of a rectification tower column 3, a steam heating heat retainer 10 is arranged on the outer surface of the rectification tower column 3, the bottom of the tower kettle 1 is communicated with a finished product tank 8, a top outlet of the rectification tower column 3 is connected to an inlet of a total reflux condenser 4, a bottom outlet of the total reflux condenser 4 is connected to a top inlet of a receiving tank 5, a bottom outlet of the receiving tank 5 is respectively communicated with a material reflux pump 6 and a vacuum pump 7, a bottom outlet of the material reflux pump 6 is connected to the middle upper part of the rectification tower column 3, and the preparation method includes the following steps:
(1) Adding metal sodium into the tower kettle 1, sealing the tower kettle 1, replacing with nitrogen for 3 times, and starting a vacuum pump 7 to pump the pressure in the tower kettle 1 to-0.1 MPa;
(2) Opening a feeding valve of a tower kettle 1, sucking organic alcohol dissolved with a polymerization inhibitor into the tower kettle 1, starting a stirrer 2, keeping a vacuum pipeline of a vacuum pump 7 in an open state, starting jacket steam of the tower kettle 1 to heat the tower kettle 1 to a preset temperature, starting a steam heating heat retainer 10 of a rectifying tower column 3, wherein the heat retaining temperature is the same as the temperature of the tower kettle, starting a circulating cooling water or chilled water valve of a total reflux condenser 4, starting a feeding pipeline valve and a discharging pipeline valve of a receiving tank 5, and when 25% of liquid level in the receiving tank 5 is displayed, starting a material reflux pump 6 to pump the material back into the rectifying tower column 3 to form stable rectifying-reflux circulation, controlling the temperature of the tower kettle 1 to be 50-90 ℃, controlling the pressure of a reaction system to be-0.1 MPa, and carrying out heat retaining reaction for 5-10 hours;
(3) After the reaction is finished, light yellow or light brown yellow viscous liquid is obtained, nitrogen is used for pressing the materials in the tower kettle 1 into a finished product tank 8, and the organic sodium alkoxide is obtained and stored for later use.
The volume of the tower kettle 1 is 5-10 m 3 。
The rectifying column 3 is a plate column or a packed column, the column diameter d =10 cm-30 cm, the column height L =100 cm-500 cm, wherein the packed column packing is made of stainless steel materials and is in the shape of a cylinder, a saddle, a ripple, a theta and the like, and the packing is filled in the packed column in a random manner.
The total reflux condenser 4 is of a tube array type or disc type structure, materials are fed in a pipeline or an interlayer, and circulating cooling water or chilled water is fed outside the pipeline or the interlayer.
The vacuum pump 7 is one of a Roots vacuum pump, a water ring vacuum pump, a vacuum oil pump and the like, wherein the water ring vacuum pump is provided with an anti-reverse adsorption piece.
The sodium metal is sodium rods directly delivered from a factory, the specification of the sodium rods is 1.5 Kg/root, the sodium rods are directly placed in a tower kettle 1 in a messy manner after being wiped by oil absorption paper, and the mass feed ratio of the sodium metal to the organic alcohol is 1: (10-40), the adding sequence is that the metallic sodium is added firstly and then the organic alcohol is added.
The organic alcohol is mainly an initiator synthesized by polyether macromonomer for a polycarboxylic acid water reducing agent, and comprises unsaturated alcohol and saturated alcohol, wherein the unsaturated alcohol comprises one of unsaturated alcohols such as allyl alcohol, methallyl alcohol, 3-methyl-3-butene-1-ol, ethylene glycol vinyl ether, 7-octene-1-ol and 3, 7-dimethyl-7-octenol, and the saturated alcohol comprises one of saturated alcohols such as methanol, ethanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, isopropanol, n-butanol, cyclohexanol and isooctanol.
The polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butyl catechol and the like, and the dosage of the polymerization inhibitor is 0.01-0.05 percent of the mass of the organic alcohol.
The reaction of the metal sodium and the organic alcohol is carried out, after the reaction is preheated in the initial stage, the subsequent reaction process does not need to be heated, the reaction temperature is controlled to be 50-90 ℃ by means of the exothermic temperature rise of the reaction of the metal sodium and the organic alcohol.
Example 1
Weighing 1 part of sodium metal, adding the sodium metal into a tower kettle 1, replacing the sodium metal with nitrogen for 3 times, opening a vacuum device 7, pumping the pressure in the reactor to-0.1 MPa, adding 0.01% hydroquinone into allyl alcohol, and sucking 30 parts of allyl alcohol into the tower kettle 1 in a vacuum state. The stirrer 2 is switched on, keeping the vacuum line of the vacuum pump 7 switched on. And (3) starting a jacket of the tower kettle 1 for steam heating, raising the temperature to 50 ℃, stopping steam heating, and controlling the temperature of the tower kettle 1 to be 50 +/-5 ℃. Allyl alcohol steam enters a total reflux condenser 4 through a rectifying tower 3, is condensed into liquid and then enters a receiving tank 5, when the liquid level of a liquid level meter of the receiving tank 5 reaches 25%, a material reflux pump 6 is started, the liquid level of the liquid level meter in the receiving tank 5 is kept unchanged, and other materials are pumped back to the rectifying tower. The temperature of the tower kettle 1 in the reaction is controlled to be 50 +/-5 ℃, the reaction pressure is-0.1 MPa, and the reaction time is 5 hours through the allyl alcohol cooling material entering the tower kettle 1 by backflow and the jacket heating and cooling functions of the tower kettle 1. After the reaction, nitrogen was added to the reaction mixture under atmospheric pressure. A sample is taken from the tower bottom 1 to obtain a light yellow viscous liquid, and the content of the organic sodium alkoxide is 11.5 percent by a titration method. And (3) pressing the residual materials in the residual tower kettle 1 to a finished product tank 8 by using nitrogen, wherein the sodium allyl alcohol prepared by the reaction of the allyl alcohol and the metal sodium is named as C-1.
In the same way, according to the same working procedures and flow, the following organic sodium alkoxide is prepared:
sodium organoalkoxide C-2: 2 parts of metal sodium, 25 parts of methallyl alcohol and 0.02% of polymerization inhibitor hydroquinone, wherein the using amount of the methallyl alcohol is 0.02%, the reaction temperature of a tower kettle 1 is 70 ℃, the reaction pressure is-0.1 MPa, the reaction time is 8.0h, after the reaction is finished, nitrogen is pressurized to normal pressure, a sample is taken from the tower kettle 1 to obtain light yellow viscous liquid, the content of the organic sodium alkoxide is 30.3% through a titration method, and the name of the liquid is C-2.
Sodium organoalkoxide C-3: 1 part of metal sodium, 20 parts of 3-methyl-3 butene-1-ol, 0.04 percent of the dosage of 3-methyl-3 butene-1-ol of polymerization inhibitor p-benzoquinone, 80 ℃ of reaction temperature in a tower kettle 1, 0.1MPa of reaction pressure and 8.0 hours of reaction time, after the reaction is finished, nitrogen is supplemented to normal pressure, a light yellow viscous liquid is obtained by sampling in the tower kettle 1, the content of organic sodium alkoxide is determined by a titration method to be 22.4 percent, and the name is C-3.
Sodium organoalkoxide C-4: 1 part of sodium metal, 40 parts of ethylene glycol vinyl ether and 0.05 percent of the dosage of ethylene glycol vinyl ether serving as polymerization inhibitor phenothiazine, wherein the reaction temperature of a tower kettle 1 is 90 ℃, the reaction pressure is-0.1 MPa, the reaction time is 10.0h, the nitrogen pressure is supplemented to the normal pressure after the reaction is finished, a light brown yellow viscous liquid is obtained by sampling in the tower kettle 1, the content of organic sodium alkoxide is 11.7 percent through a titration method, and the name of the liquid is C-4.
Organic sodium alkoxide C-5: 1 part of metal sodium, 30 parts of 3, 7-dimethyl-7-octenol, 0.01 percent of the consumption of 3, 7-dimethyl-7-octenol serving as a polymerization inhibitor, 70 ℃ of reaction temperature in a tower kettle 1, 0.1MPa of reaction pressure and 9.0h of reaction time, supplementing nitrogen to normal pressure after the reaction is finished, sampling in the tower kettle 1 to obtain light brown yellow viscous liquid, and determining the content of organic sodium alkoxide by a titration method to be 24.9 percent, wherein the name of the liquid is C-5.
Sodium organylalkoxide C-6: 1 part of sodium metal, 10 parts of methanol, the reaction temperature of a tower kettle 1 is 40 ℃, the reaction pressure is-0.1 MPa, the reaction time is 6.0h, the nitrogen pressure is supplemented to the normal pressure after the reaction is finished, a light yellow viscous liquid is obtained by sampling in the tower kettle 1, the content of the sodium alkoxide is 21.3 percent through the titration method, and the name is C-6.
Sodium organoalkoxide C-7: 1 part of sodium metal, 15 parts of ethylene glycol monomethyl ether, the reaction temperature of a tower kettle 1 is 50 ℃, the reaction pressure is-0.1 MPa, the reaction time is 8.0h, the nitrogen is supplemented to the normal pressure after the reaction is finished, a light yellow viscous liquid is obtained by sampling the tower kettle 1, the content of the sodium alkoxide is determined to be 26.6 percent by a titration method, and the sodium alkoxide is named as C-7.
Sodium organoalkoxide C-8: 1 part of sodium metal, 11 parts of isopropanol, 60 ℃ of reaction temperature in a tower kettle 1, -0.1MPa of reaction pressure and 7.0h of reaction time, supplementing nitrogen to normal pressure after the reaction is finished, sampling in the tower kettle 1 to obtain light yellow viscous liquid, and determining the content of organic sodium alkoxide by a titration method to be 29.7 percent, wherein the name of the liquid is C-8.
Sodium organoalkoxide C-9: 1 part of sodium metal, 20 parts of cyclohexanol, the reaction temperature of a tower kettle 1 is 70 ℃, the reaction pressure is-0.1 MPa, the reaction time is 5.0h, the nitrogen pressure is supplemented to the normal pressure after the reaction is finished, a light yellow viscous liquid is obtained by sampling the tower kettle 1, the content of organic sodium alkoxide is measured by a titration method and is named as C-9, and the content of the organic sodium alkoxide is 25.2%.
Example 2
Weighing 52.8 parts of allyl alcohol and 53.3 parts of catalyst C, adding into the polyether reaction kettle, replacing with nitrogen for 3 times, and pumping the polyether reaction kettle to-0.1 MPa again. Starting a heating device to raise the temperature of the polyether reaction kettle to 100 ℃, opening an ethylene oxide feeding valve, firstly introducing 1 part of ethylene oxide, continuing to introduce 4032 parts of ethylene oxide when polymerization of the ethylene oxide in the polyether reaction kettle begins (temperature rises and pressure drops), controlling the reaction temperature to be 120 +/-5 ℃, controlling the reaction pressure to be less than or equal to 0.4MPa, finishing introduction of the ethylene oxide, continuing to perform heat preservation reaction for 30min, cooling the polyether reaction kettle to 50 ℃, then performing vacuum degassing to-0.1 MPa, and finally performing pressure supplementing by nitrogen to normal pressure for discharging. 4100 parts of a light brown yellow viscous liquid, designated PEG-1, were obtained. The weight average molecular weight is 2390 measured by a hydroxyl value method; the molecular weight distribution of the polyether is 1.01 by GPC; the effective content of polyether is 99.2% by HPLC test.
In the same way, the following polyether macromonomer is prepared according to the same process flow:
polyether macromonomer PEG-2: 86.6 parts of methallyl alcohol, 2.2 parts of catalyst C, 3230 parts of ethylene oxide, 120 +/-5 ℃ of reaction temperature, less than or equal to 0.4MPa of reaction pressure and 30min of heat preservation reaction time to obtain 3300 parts of light brown yellow viscous liquid, which is named as PEG-2. The weight average molecular weight is 2387 measured by hydroxyl value method; the molecular weight distribution of the polyether is 1.01 by GPC; the effective content of polyether is 99.5% by HPLC test.
Polyether macromonomer PEG-3: 80.7 parts of 3-methyl-3-butene-1-ol, 324.9 parts of catalyst C, 2690 parts of ethylene oxide, 120 +/-5 ℃ of reaction temperature, less than or equal to 0.4MPa of reaction pressure and 30min of heat preservation reaction time to obtain 2790 parts of light brown yellow viscous liquid, which is named as PEG-3. The weight average molecular weight is 2405 through a hydroxyl value method test; the molecular weight distribution of the polyether is 1.02 through GPC test; the effective content of polyether is 98.8% by HPLC test.
Polyether macromonomer PEG-4: 58.1 parts of ethylene glycol vinyl ether, 47.5 parts of catalyst C-4, 2630 parts of ethylene oxide, 120 +/-5 ℃ of reaction temperature, less than or equal to 0.4MPa of reaction pressure and 30min of heat preservation reaction time to obtain 2710 part of light brown yellow viscous liquid which is named as PEG-4. The weight average molecular weight is 2389 measured by hydroxyl value method; the molecular weight distribution of the polyether is 1.01 by GPC; the effective content of polyether is 98.5% by HPLC test.
Polyether macromonomer PEG-5: 85.1 parts of 3, 7-dimethyl-7-octenol, 85.8 parts of catalyst C-519.8 parts, 1440 parts of ethylene oxide, 120 +/-5 ℃ of reaction temperature, less than or equal to 0.4MPa of reaction pressure, and 30min of heat preservation reaction time to obtain 1540 parts of light brown yellow viscous liquid which is named as PEG-5. The weight average molecular weight is 2393 measured by hydroxyl value method; the molecular weight distribution of the polyether is 1.01 by GPC; the effective content of polyether is 99.2% by HPLC test.
Polyether macromonomer PEG-6: 72.3 parts of methanol, 35.2 parts of catalyst C-6, 7400 parts of ethylene oxide, 120 +/-5 ℃ of reaction temperature, less than or equal to 0.4MPa of reaction pressure and 30min of heat preservation reaction time to obtain 7500 parts of light brown yellow viscous liquid, which is named as PEG-6. The weight average molecular weight is 2412 by a hydroxyl value method; the molecular weight distribution of the polyether is 1.02 through GPC test; the effective content of polyether is 99.5% by HPLC test.
Polyether macromonomer PEG-7: 84.2 parts of ethylene glycol monomethyl ether, 21.5 parts of catalyst C-7.5 parts, 3100 parts of ethylene oxide, reaction temperature of 120 +/-5 ℃, reaction pressure of less than or equal to 0.4MPa, and reaction time of 30min under heat preservation to obtain 3160 parts of light brown yellow viscous liquid, which is named as PEG-7. The weight average molecular weight is 2408 through a hydroxyl value method; the molecular weight distribution of the polyether is 1.01 by GPC; the effective content of polyether is 99.4% by HPLC test.
Polyether macromonomer PEG-8: 86.1 parts of isopropanol, 19.8 parts of catalyst C-8, 3800 parts of ethylene oxide, 120 +/-5 ℃ of reaction temperature, less than or equal to 0.4MPa of reaction pressure and 30min of heat preservation reaction time to obtain 3870 parts of light brown yellow viscous liquid, which is named as PEG-8. The weight average molecular weight is 2386 measured by a hydroxyl value method; the molecular weight distribution of the polyether is 1.02 through GPC test; the effective content of polyether is 98.6% by HPLC test.
Polyether macromonomer PEG-9: 83.9 parts of cyclohexanol, 21.5 parts of catalyst C-9, 2300 parts of ethylene oxide, 120 +/-5 ℃ of reaction temperature, less than or equal to 0.4MPa of reaction pressure and 30min of heat preservation reaction time to obtain 2400 parts of light brown yellow viscous liquid which is named as PEG-9. The weight average molecular weight is 2391 measured by hydroxyl value method; the molecular weight distribution of the polyether is 1.01 by GPC; the effective content of polyether is 99.3% by HPLC test.
Comparative example 1
Weighing 100 parts of methallyl alcohol and 4.5 parts of sodium methoxide, adding into a polyether reaction kettle, replacing with nitrogen for 3 times, and pumping the polyether reaction kettle to-0.1 MPa again. Starting a heating device to raise the temperature of the polyether reaction kettle to 100 ℃, opening an ethylene oxide feeding valve, firstly introducing 1 part of ethylene oxide, continuing introducing 3250 parts of ethylene oxide when polymerization of ethylene oxide in the polyether reaction kettle begins (temperature rises and pressure drops), controlling the reaction temperature to be 120 +/-5 ℃, controlling the reaction pressure to be less than or equal to 0.4MPa, finishing the introduction of ethylene oxide, continuing heat preservation reaction for 30min, cooling the polyether reaction kettle to 50 ℃, then vacuum degassing to-0.1 MPa, and finally supplementing pressure with nitrogen to normal pressure for discharging. 3300 parts of a light brown yellow viscous liquid, designated PEG-10, were obtained. The weight average molecular weight is 2215 through a hydroxyl value method; the molecular weight distribution of the polyether is 1.03 by GPC; the effective content of polyether is 94.7% by HPLC test.
Comparative example 2
100 parts of 3-methyl-3-butene-1-ol and 2.2 parts of sodium hydride (60%) are weighed and added into a polyether reaction kettle, nitrogen is replaced for 3 times, and the polyether reaction kettle is pumped to-0.1 MPa again. Starting a heating device to raise the temperature of the polyether reaction kettle to 100 ℃, opening an ethylene oxide feeding valve, firstly introducing 1 part of ethylene oxide, continuing introducing 2650 parts of ethylene oxide when polymerization of the ethylene oxide in the polyether reaction kettle starts (temperature rises and pressure drops), controlling the reaction temperature to be 120 +/-5 ℃, controlling the reaction pressure to be less than or equal to 0.4MPa, finishing the introduction of the ethylene oxide, continuing heat preservation reaction for 30min, cooling the polyether reaction kettle to 50 ℃, then carrying out vacuum degassing to-0.1 MPa, and finally supplementing pressure with nitrogen to normal pressure for discharging. 2750 parts of a tan viscous liquid is obtained and is named as PEG-11. The weight-average molecular weight is 2198 by a hydroxyl value method; the molecular weight distribution of the polyether is 1.05 by GPC; the effective content of polyether is 95.2% by HPLC test.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A production preparation method of organic sodium alkoxide is characterized in that: comprises a kettle reverse rectification device, the kettle reverse rectification device comprises a tower kettle (1), a tower kettle outer jacket (9) capable of heating and cooling is fixed on the tower kettle (1), a stirrer (2) is sleeved in the tower kettle (1), the top end of the tower kettle (1) is communicated with a rectification tower column (3), a steam heating heat retainer (10) is fixed on the surface of the rectification tower column (3), a finished product tank (8) is communicated with the bottom of the tower kettle (1), a total reflux condenser (4) is communicated with the rectification tower column (3), a receiving tank (5) is communicated with the bottom of the total reflux condenser (4), a material reflux pump (6) and a vacuum pump (7) are respectively communicated with the receiving tank (5), the bottom of the material reflux pump (6) is communicated with the rectification tower column (3),
the production and preparation method of the organic sodium alkoxide comprises the following steps,
(1) Adding metal sodium into the tower kettle (1), sealing the tower kettle (1), replacing nitrogen for 3 times, starting a vacuum pump (7) to pump the pressure in the tower kettle (1) to-0.1 MPa;
(2) Opening a feeding valve of a tower kettle (1), sucking organic alcohol dissolved with a polymerization inhibitor into the tower kettle (1), starting a stirrer (2), keeping a vacuum pipeline of a vacuum pump (7) in an open state, starting jacket steam of the tower kettle (1) to heat the tower kettle (1) to a preset temperature, starting a steam heating heat retainer (10) of a rectifying tower column (3), starting a circulating cooling water or freezing water valve of a total reflux condenser (4), starting a feeding pipeline valve and a discharging pipeline valve of a receiving tank (5), starting a material reflux pump (6) to pump a material back into the rectifying tower column (3) when a liquid level meter in the receiving tank (5) displays 25% of liquid level, forming stable rectifying-reflux circulation, controlling the temperature of the tower kettle (1) to be 50-90 ℃, controlling the pressure of a reaction system to be-0.1 MPa, and carrying out heat preservation reaction for 5-10 hours;
(3) And after the reaction is finished, obtaining light yellow or light brown yellow viscous liquid, pressing the materials in the tower kettle (1) into a finished product tank (8) by using nitrogen, namely the organic sodium alkoxide, and storing for later use.
2. The method for preparing sodium organoalkoxide according to claim 1, wherein: the volume of the tower kettle (1) is 5 to 10m 3 。
3. The method for preparing sodium organoalkoxide according to claim 1, wherein: the rectifying tower column (3) is a plate tower or a packed tower, the diameter d of the tower is =10 cm-30 cm, the height L of the tower is =100 cm-500 cm, the packed tower packing is made of stainless steel and is cylindrical, saddle-shaped, corrugated or theta-shaped, and the packing is filled in the packed tower in a random manner.
4. The method for preparing sodium organoalkoxide according to claim 1, wherein: the total reflux condenser (4) is of a tube array type or disc type structure, materials are fed in a pipeline or an interlayer, and circulating cooling water or chilled water is fed outside the pipeline or the interlayer.
5. The method for preparing sodium organoalkoxide according to claim 1, wherein: the vacuum pump (7) is one of a Roots vacuum pump, a water ring vacuum pump and a vacuum oil pump vacuum pump, wherein the water ring vacuum pump is provided with an anti-reverse adsorption piece.
6. The method for preparing sodium organoalkoxide according to claim 1, wherein: the sodium metal is sodium rods directly delivered from a factory, the specification of the sodium rods is 1.5 Kg/root, the sodium rods are directly placed in a tower kettle (1) in a random stack after being wiped by oil absorption paper, and the mass feed ratio of the sodium metal to the organic alcohol is 1: (10-40), the adding sequence is that the metallic sodium is added firstly and then the organic alcohol is added.
7. The method for preparing sodium organoalkoxide according to claim 1, wherein: the organic alcohol is mainly an initiator synthesized by polyether macromonomer for a polycarboxylic acid water reducing agent, and comprises unsaturated alcohol and saturated alcohol, wherein the unsaturated alcohol comprises one of allyl alcohol, methallyl alcohol, 3-methyl-3 butene-1-ol, ethylene glycol vinyl ether, 7-octene-1-ol and 3, 7-dimethyl-7-octenol unsaturated alcohol, and the saturated alcohol comprises one of methanol, ethanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, isopropanol, n-butanol, cyclohexanol and isooctanol saturated alcohol.
8. The method for preparing sodium organoalkoxide according to claim 1, wherein: the polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine and p-tert-butyl catechol, and the dosage of the polymerization inhibitor is 0.01-0.05% of the mass of the organic alcohol.
9. The method for preparing sodium organoalkoxide according to claim 1, wherein: the reaction of the metal sodium and the organic alcohol does not need heating in the reaction process, the reaction temperature is controlled to be 50-90 ℃ by means of the exothermic temperature rise of the reaction of the metal sodium and the organic alcohol.
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