CN119285920A - A bisphenol A type low molecular weight polycarbonate polyether polyol and its production process - Google Patents
A bisphenol A type low molecular weight polycarbonate polyether polyol and its production process Download PDFInfo
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Abstract
The invention provides bisphenol A type low molecular weight polycarbonate polyether polyol and a production process thereof, and relates to the technical field of chemistry and chemical engineering. The production process is carried out in an integrated tubular reactor, and comprises premixing an epoxy compound, CO 2, bisphenol A and a catalyst, and then putting the premixed epoxy compound, CO 2, bisphenol A and the catalyst into a reaction pipeline for polymerization reaction at one time. During the polymerization reaction, the slow temperature rise control and gas pressurization compensation are performed so that the molecular weight polydispersity index PDI of the bisphenol a low molecular weight polycarbonate polyether polyol is no more than 1.5, the carbonate linkage ratio F CO2 is greater than 55%, and in the color system of lxab, the value of b is no more than 0.1. The problem of yellowing of the product generated in the one-step preparation process of the bisphenol A type low molecular weight polycarbonate polyether polyol can be solved through the regulation and control process, and the production efficiency is high. The prepared product has narrow molecular weight distribution, does not generate explosion polymerization and amplification effect, and is suitable for industrialized mass production.
Description
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to bisphenol A type low molecular weight polycarbonate polyether polyol and a production process thereof.
Background
Bisphenol A type low molecular weight polycarbonate polyether polyol is polycarbonate polyether polyol with molecular weight smaller than 3000, is mainly synthesized from a small molecular initiator, carbon dioxide and an epoxy compound through a bimetallic complex catalyst, and takes propylene oxide as an example, CO 2 and propylene oxide are synthesized into main products under the action of the small molecular initiator and DMC catalyst, wherein the main products comprise polycarbonate polyether polyol and byproduct carbonic acid acrylic ester, and the synthetic route is as follows:
Bisphenol A is used as an initiator to obtain bisphenol A type polycarbonate polyether polyol, and the aromatic ring and the carbon-oxygen chain structure in the molecule of the bisphenol A type polycarbonate polyether polyol respectively endow specific rigidity and toughness to the material, so that the structure and the property of a polymer are effectively improved, the good mechanical property and the thermal stability of a downstream product are endowed, and the bisphenol A type polycarbonate polyether polyol has an important role in the fields of adhesives, rubber, surfactants and the like.
The prior art CN115785435A discloses a method for preparing polyether polyol by a one-step method, which comprises the steps of adding an epoxy compound, an initiator and a catalyst into a reaction device at one time at room temperature to carry out polymerization reaction, and adding no reaction raw materials in the reaction process, so that the reaction efficiency is obviously improved.
The inventors have found that yellowing of the obtained product is serious when bisphenol a is used as an initiator to prepare bisphenol a-type polycarbonate polyether polyol by a one-step method, probably because the rapid increase in temperature (for example, 5 ℃ in 1 min) is easily induced in a short time during the polymerization reaction due to the one-time input of all the raw materials when the product is prepared by a one-step method. Bisphenol A is susceptible to thermal decomposition under conditions of high temperature for a long period of time, for example, decomposition into several small molecules according to the position of the broken line in the following formula:
;
The decomposition products of bisphenol A are liable to react with intermediate products, byproducts, etc. of polymerization reaction to form yellow substances, such as small molecular substances of dimethyl phthalate or quinoid structures with chromophoric groups, etc., thereby causing yellowing of the products and affecting downstream applications of the products.
Disclosure of Invention
The invention aims to provide bisphenol A type low molecular weight polycarbonate polyether polyol and a production process thereof, which are suitable for industrialized mass production of bisphenol A type low molecular weight polycarbonate polyether polyol, can solve the problem of yellowing of products caused in the production process of a one-step method, effectively improve the total conversion rate and the safety, and reduce the production cost.
According to a first aspect of the present invention there is provided a process for the production of bisphenol a type low molecular weight polycarbonate polyether polyol in an integrated tubular reactor apparatus having at least one reaction conduit, the process comprising:
Introducing a premix into the reaction pipeline at one time, and introducing CO 2 with a first pressure value, wherein the premix is obtained by introducing CO 2 into all the epoxy compound, bisphenol A and the catalyst for premixing;
Heating and circulating the premix in a reaction pipeline to perform polymerization reaction, and separating to obtain bisphenol A type low molecular weight polycarbonate polyether polyol, wherein during the polymerization reaction, slow temperature rise control and gas pressurization compensation are performed so that the molecular weight polydispersity index PDI of the bisphenol A type low molecular weight polycarbonate polyether polyol is not more than 1.5, the carbonate chain unit ratio F CO2 is more than 55%, and in an Lxa-b-type color system, the b-value is not more than 0.1.
Specifically, the polydispersity index PDI is determined by Gel Permeation Chromatography (GPC). The smaller the value of PDI, the narrower the molecular weight distribution, and the more uniform the product quality. More preferably, the molecular weight polydispersity index PDI of the product can be controlled between 1.1 and 1.2 under the cooperative control of slow temperature rise and gas pressurization compensation.
Specifically, the value of the color system of l×a×b×b may be obtained by a color difference meter, where the coordinate l×a×b indicates color brightness, l=0 indicates black, and l=100 indicates white. The coordinates a indicate the position between red/magenta and green, a negative value indicating green and a positive value indicating magenta. The coordinates b indicate a position between yellow and blue, b indicates blue with negative values and positive values indicates yellow. The larger the b value, the more severe the yellowing of the sample. Further, the product obtained by the examples of the present invention has a value of a less than 0.1 and b less than 0.1, and the product is nearly colorless.
In the embodiment of the invention, the slow temperature rise control comprises the steps of controlling the temperature difference between the heating temperature of a reaction pipeline and the temperature of materials in the reaction pipeline to be not more than 3-5 ℃ and carrying out polymerization reaction after the materials in the reaction pipeline are heated to 75-85 ℃.
In the embodiment of the invention, the gas pressurization compensation comprises the steps of introducing CO 2 gas with a second pressure value into a reaction pipeline when the temperature of the material in the reaction pipeline is suddenly increased in the polymerization reaction process until the temperature of the material in the reaction pipeline is reduced to 75-85 ℃, wherein the judgment index of the sudden increase of the temperature of the material is that the temperature increase is not less than 5 ℃ within 1min, and the second pressure value is 4-8 MPa and is larger than the first pressure value.
In an exemplary embodiment of the present invention, when the gas pressurization compensation is performed, the temperature of the CO 2 gas is controlled to be 50-65 ℃.
In an exemplary embodiment of the present invention, the first pressure value is 2 to 6mpa, and the second pressure value is 4 to 8mpa. For example, in one embodiment, the first pressure value is 3MPa and the second pressure value is 4MPa. For another example, in another embodiment, the first pressure value is 5MPa and the second pressure value is 7MPa.
In the exemplary embodiment of the invention, a heat exchange medium circularly flows outside the reaction pipeline to control the temperature of the materials, and the method further comprises the step of controlling the temperature of the heat exchange medium to be approximately equal to the temperature of the materials in the reaction pipeline in the polymerization process so as to keep the temperature of the materials in the reaction pipeline at 75-85 ℃.
In an exemplary embodiment of the invention, the integrated tubular reaction device comprises a premixing unit and a reaction unit, wherein the premixing is obtained by premixing the premixing unit, the reaction unit comprises a circulating pump and a plurality of reaction pipelines, the circulating pump is used for enabling materials to circularly flow in the plurality of reaction pipelines, and the circulating flow rate of the circulating pump is 10-15 min to finish one cycle. Or the circulation flow rate of the circulation pump is 10min to finish one circulation.
In an exemplary embodiment of the invention, a plurality of reaction pipelines are arranged in parallel, the feed end of each reaction pipeline is intersected with a liquid distributor through a connecting pipeline, the discharge end of each reaction pipeline is converged with the circulating pump through the connecting pipeline, one end of each liquid distributor is provided with a feed inlet communicated with the premixing unit, the other end of each liquid distributor is communicated with the circulating pump, each reaction pipeline is provided with a gas supplementing port for CO 2 to enter, the mixed products flowing out of the plurality of reaction pipelines are converged with the circulating pump together, and after being pumped into the liquid distributor through the circulating pump, the mixed products are dispersed into a plurality of reaction pipelines and then reach the discharge end through the reaction pipelines, so that one cycle is completed.
In an exemplary embodiment of the invention, in the polymerization reaction process, the gas-liquid volume ratio in the reaction pipeline is controlled to be 1:1-4.
In an exemplary embodiment of the invention, the temperature of the pre-mixing unit is controlled to be 0-40 ℃, the pressure is controlled to be 0.1-2 MPa, the pre-mixing time is controlled to be 1-2 h in the mixing process of the pre-mixing unit, the temperature of the reaction pipeline is controlled to be 35-45 ℃ when materials of the pre-mixing unit are put into the reaction unit, and the reaction is terminated when the density of a reaction product reaches 1.1-1.3 g/cm 3 and the change in the density is less than 0.01g/cm 3 in 5 min.
In an exemplary embodiment of the invention, the metal elements of the catalyst are only two metal elements of zinc and cobalt except impurities, the catalyst is obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent, the water-soluble metal salts of cobalt are cyanide salts of cobalt, the catalyst is modified by mixed acid during synthesis, the mixed acid comprises at least one organic acid and at least one water-soluble inorganic acid, wherein the water-soluble inorganic acid is selected from dilute sulfuric acid and dilute hydrochloric acid, the pH value is between 0 and 5, the organic acid is selected from any one or more of succinic acid, glutaric acid, phthalic acid, iminodiacetic acid, pyromellitic acid and butane tetracarboxylic acid, and the molar ratio of the water-soluble inorganic acid to the organic acid is 1:10-10:1.
According to a second aspect of the present invention, there is provided a bisphenol a type low molecular weight polycarbonate polyether polyol produced according to the production process as described in any one of the above, the structural formula of the bisphenol a type low molecular weight polycarbonate polyether polyol being represented by formula (1):
formula (1);
Wherein in formula (1), R 1、R2 is selected from formula (2) or OH,
Formula (2);
Wherein in the formula (2), n is not less than 1 and not more than 22, m is not less than 1 and not more than 39, and the connection position is represented by x;
The bisphenol A type low molecular weight polycarbonate polyether polyol has a number average molecular weight of 1000-3000 g/mol, a molecular weight polydispersity index PDI of less than or equal to 1.5, a hydroxyl value of 35-110 mgKOH/g and a carbonate chain unit ratio F CO2 of more than or equal to 45%.
Specifically, the carbonate chain segment ratio F CO2 was determined by means of 1 H-NMR, and the carbonate chain segment ratio (molar ratio) F CO2 in the copolymerization reaction was calculated from the 1 H-NMR spectrum of the product and the integral area of the proton peak associated therewith, specifically by ：FCO2=(A5.0+A4.2-2×A4.6)/[(A5.0+A4.2-2×A4.6)+A3.5]×100%; wherein A 5.0 represents the integral area of the peak at 5.0ppm, A 4.2 represents the integral area of the peak at 4.2ppm, A 4.6 represents the integral area of the peak at 4.6ppm, and A 3.5 represents the integral area of the peak at 3.5ppm, 5.0ppm and 4.2ppm belong to the integral areas of the proton peaks on the methine and methylene groups on the polycarbonate chain segments, 4.9ppm, 4.6ppm, 4.5ppm and 4.1ppm then belong to the proton peaks on the methine and methylene groups in the five-membered ring carbonate, and 3.5 to 3.8ppm then belong to the proton peaks of the ether chain segments.
The bisphenol A type low molecular weight polycarbonate polyether polyol and the production process thereof have the beneficial effects that:
(1) Compared with the traditional process, the embodiment of the invention has the advantages that the reaction time is effectively shortened, the production efficiency is improved, the problem of yellowing of the product caused by decomposition of bisphenol A is solved based on rapid temperature rise introduced in the process of preparing the product by a one-step method, the temperature-sensitive bisphenol A is protected from decomposition and influencing the polymerization reaction by refined slow temperature rise control and gas pressurization compensation, particularly, when the temperature rises, the carbon dioxide gas with a larger pressure value is timely fed in the process of rapidly rising the reaction temperature, and the polymerization reaction process is cooperatively controlled by the two aspects, so that the PDI of the obtained polyol product is not more than 1.5 and the b value is not more than 0.1, the product is nearly colorless, the product quality is effectively improved, and the technical blank of synthesizing bisphenol A type polycarbonate polyether polyol by a one-step method is filled.
(2) The production process is carried out in an integrated tubular reactor, materials continuously circulate, and through designing the structures and parameters of a specific premixing unit and a specific reaction unit, the full gas-liquid heat conduction and gas-liquid-solid mixing in the polymerization reaction process are ensured, and the materials are cooperatively matched with reaction control parameters (temperature control, circulation speed control and gas compensation control), so that the molecular weight distribution of the obtained product is narrow, no amplification effect exists, the molecular weight controllability of the product is strong, the production among batches is stable, the production quality is high, meanwhile, the production process is safe, the explosion polymerization is not generated, the amplification effect is not generated, and the production process is suitable for industrial large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure. It will be apparent to those of ordinary skill in the art that the drawings in the following description are merely examples of the disclosure and that other drawings may be derived from them without undue effort.
Fig. 1 is a schematic diagram of an integrated tubular reactor for producing bisphenol a type low molecular weight polycarbonate polyether polyol according to an embodiment of the present invention, wherein a black arrow is a raw material flowing direction, a green arrow is a gas entering direction, a blue arrow is a circulating direction in a pipeline reactor, and a red arrow is a product flowing direction.
FIG. 2 is a schematic structural view of a reaction unit of the reaction apparatus of FIG. 1, wherein a green part represents a gas-liquid mixed heat conduction region and a red part represents a solid-liquid mixed region.
The icons are 001-propylene oxide, 002-catalyst, 003-small molecule initiator, 004-CO 2 gas supply device, 005-premixing unit, 006-reaction unit, 007-circulating pump, 008-separation unit, 009-refining unit, 010-rectifying unit, 101-liquid distributor, 102-carbon dioxide gas supplementing port, 103-dispersing tablet, 104-static mixer, 105-jacket and 106-reaction pipeline.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The bisphenol A type low molecular weight polycarbonate polyether polyol and the production process thereof according to the examples of the present invention are specifically described below. The embodiment of the invention provides a production process of bisphenol A type low molecular weight polycarbonate polyether polyol, in particular to bisphenol A type low molecular weight polycarbonate polyether polyol which is synthesized by taking bisphenol A as a small molecular initiator and propylene oxide and CO 2 under the action of DMC catalyst.
In the examples of the present invention, the structural formula of bisphenol A type low molecular weight polycarbonate polyether polyol is represented by formula (1):
formula (1);
Wherein in formula (1), R 1、R2 is selected from formula (2) or OH,
Formula (2);
Wherein in the formula (2), n is not less than 1 and not more than 22, m is not less than 1 and not more than 39, and the connection position is represented by x;
The bisphenol a type low molecular weight polycarbonate polyether polyol has a number average molecular weight of less than 3000.
The embodiment of the invention provides a process for producing the bisphenol A type low molecular weight polycarbonate polyether polyol, which is carried out in an integrated tubular reaction device, referring to FIG. 1, wherein the integrated reaction device comprises a premixing unit 005, a reaction unit 006 and a post-treatment area.
The one-step synthesis of bisphenol a polycarbonate polyether polyol means that all the epoxy compound, bisphenol a and catalyst are put into a reaction device at one time, and raw materials are not added except for introducing CO 2 in the subsequent reaction process. Wherein the epoxy compound is selected from one or more of ethylene oxide, propylene oxide, 2-butylene oxide, 1, 4-butylene oxide and epichlorohydrin. Preferably, in this embodiment, propylene oxide is used as the epoxy compound.
Further, the DMC catalyst used in the embodiment is a mixed acid modified zinc-cobalt double metal cyanide catalyst, metal elements of the catalyst are only two metal elements of zinc and cobalt except impurities, the catalyst is obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent, the water-soluble metal salts of cobalt are cyanide salts of cobalt, the catalyst is modified by a mixed acid during synthesis, and the mixed acid comprises at least one organic acid and at least one water-soluble inorganic acid. The water-soluble inorganic acid is selected from dilute sulfuric acid and dilute hydrochloric acid, the pH value is 0-5, the organic acid is selected from any one or more of succinic acid, glutaric acid, phthalic acid, iminodiacetic acid, pyromellitic acid and butane tetracarboxylic acid, and the molar ratio of the water-soluble inorganic acid to the organic acid is 1:10-10:1.
Referring to fig. 1 and 2, the premixing unit is provided with a premixing device, which may be, for example, a premixing kettle, into which the raw materials are fed into the premixing unit for premixing. The premixed raw materials are introduced into the reaction unit 006, and after the reaction is finished, the reaction product is introduced into the next step for post-treatment.
Specifically, in a preferred embodiment, the reaction unit 006 includes a reaction pipe 106, a liquid distributor 101, a circulation pump 007, a carbon dioxide gas supply port 102, a dispersion sheet 103, and a jacket 105. The reaction pipelines 106 are provided with a plurality of reaction pipelines 106 which are arranged in parallel. The outer side of each reaction pipeline 106 is provided with a jacket 105, and heat exchange media such as steam, water, heat conducting oil and the like are introduced into the jacket 105 to regulate and control the temperature of the reaction pipeline 106. The spaces between the plurality of reaction tubes 106 are filled with a heat exchange medium, and an insulating layer is provided outside the heat exchange medium. The feed ends of the plurality of reaction tubes 106 meet the liquid distributor 101 through connecting tubes, and the discharge ends meet the circulation pump 007 through connecting tubes. The reaction mixture flowing out of the discharge end of the reaction tube 106 enters from the feed end of the reaction tube 106 via the circulation pump 007, passes through the reaction tube 106 to the discharge end, and completes one cycle.
Specifically, each reaction tube 106 is provided with a carbon dioxide gas supply port 102 for the entry of CO 2. Each reaction tube 106 is identical to the material circulation path formed by the connecting tube and the circulation pump 007.
Further preferably, the number of the reaction tubes 106 is 2 to 8, for example, 4, 6, etc. The reaction pipes 106 are independent of each other and are provided with valves that can be controlled independently. By independently controlling each reaction pipeline 106, when the local temperature of one reaction pipeline 106 is too high or other adverse conditions occur, the independent control can be timely performed, and the whole reaction process is prevented from being influenced.
It is further preferred that the center-to-center distance between two adjacent reaction tubes 106 is less than or equal to 2 times the inner diameter of the reaction tubes 106. Further preferably, the aspect ratio of the reaction tube 106 is 10.ltoreq.L.ltoreq.d.ltoreq.40. In the production process of bisphenol A type low molecular weight polycarbonate polyether polyol, a tubular reaction device is adopted, if the length-diameter ratio of a reaction pipeline is too large, the reaction heat generated by scattering is not facilitated, the decomposition of polyester chain links is easy to cause, and the yellowing of the product occurs. If the length-diameter ratio of the reaction pipeline is too small, the center position is too far from the pipeline wall position, and a larger temperature difference is formed, so that the molecular weight distribution is widened. Meanwhile, the reaction process continuously generates heat, the temperature of a reaction system can be increased, the reactor needs to timely release the heat generated in materials, and when the flow rate is fixed, the liquid needs to complete circulation within a specified time to release the heat and conduct gas-liquid mass transfer. By the length and center-to-center distance of the reaction tube 106, a sufficient heating reaction time is ensured during the reaction process, and the requirement of production efficiency is met.
Further preferably, referring to fig. 2, the reaction tube 106 includes a dispersion plate 103, a gas-liquid mixed heat conduction region (green part in fig. 2), and a solid-liquid mixed region (red part in fig. 2). The dispersion sheet 103 is used for dispersing and controlling the material to be dispersed into liquid beads in the gas-liquid mixed heat conduction area for mass and heat transfer without contacting the pipe wall. The solid-liquid mixing zone is used for realizing the real-time mixing and polymerization reaction of the catalyst and the epoxy compound. After the materials in the reaction pipeline 106 are dispersed by the dispersing pieces 103, the materials flow from the gas-liquid mixed heat conduction region to the solid-liquid mixed region, and then circulate to the dispersing pieces 103 through an external circulating pump to flow back to the gas-liquid mixed heat conduction region. A static mixer 104 is provided in the solid-liquid mixing zone, and the static mixer 104 has a portion extending to the gas-liquid mixing heat transfer zone. The dispersion plate 103, the gas-liquid mixed heat conduction region, and the loop among the static mixer part, the reaction pipeline 106 and the circulating pump 007 in the region together form a gas-liquid mixed heat conduction path, so that the mixed material with low CO 2 content in the reaction unit redissolves CO 2, and heat exchange is carried out in the gas-liquid mixed heat conduction region. The loop among the static mixer 104, the reaction pipeline 106 and the circulating pump 007 together form a solid-liquid mixing path so as to uniformly disperse the solid catalyst into the epoxy compound, and meanwhile, disperse the generated reaction heat, reduce the temperature difference between the central temperature and the pipe wall in the reaction pipeline and avoid the generation of explosion points.
Further preferably, the length of the gas-liquid mixed heat conduction region accounts for 20% -50% of the length of the reaction pipeline, so that sufficient gas-liquid mass transfer efficiency is ensured.
Further preferably, during the polymerization reaction, the volume ratio of the gas to the liquid in the reaction pipeline 106 is controlled to be 1:1-4. For example, the gas-liquid volume ratio of the reaction pipeline is 1:1, 1:2, 1:4, etc. It will be appreciated that for example, the volume of the reaction conduit is 8L and 4L of material is fed, the gas-liquid volume ratio is 1:1. Through controlling the gas-liquid volume ratio in the reaction pipeline, the proper ratio of gas and liquid is ensured, the gas-liquid ratio is too low, the mass transfer and heat transfer efficiency in the CO 2 area is deteriorated, the ester content is reduced, the color is changed to yellow, the generated heat of the materials is easily increased during the reaction, the temperature control difficulty is increased, and the explosion polymerization is extremely easy.
Further preferably, the dispersion sheet 103 is disposed at a position of 10 to 50mm near the top of the reaction tube 106, and a plurality of dispersion holes are formed therein. By providing the dispersion sheet 103, the reaction material can be uniformly dispersed and flow down in a bead shape at the end, and the mass and heat transfer area can be increased. The static mixer 104 and the circulating pump 007 are arranged in the cooperative reaction pipeline 106, and the whole circulating dispersion system can replace the traditional stirring process to continuously mix the reaction materials in the circulating process. Meanwhile, the dispersing tablets 103 can effectively enable the reactant materials to perform better gas-liquid mass transfer in a gas area and release redundant heat.
Further preferably, a temperature sensor is arranged in the reaction pipeline 106, a density detector is arranged at the outlet, the temperature of the jacket is adjusted according to the density of the materials and the temperature in the reactor, and the reaction rate is controlled. Specifically, in one embodiment, temperature sensors are provided at the middle and bottom of the reaction tube 106 to more fully monitor the temperature within the reaction tube 106.
The production process of the bisphenol A type low molecular weight polycarbonate polyether polyol provided by the embodiment of the invention comprises the following steps:
(1) At the temperature of 0-40 ℃, all the epoxy compound, bisphenol A and catalyst are added into the premixing unit 005 at one time, and CO 2 is introduced into the premixing unit for mixing, so as to obtain a premix. Specifically, firstly, propylene oxide 001 is added into a premixing kettle, secondly, quantitative small molecular initiator 003 and DMC catalyst 002 are added into the premixing kettle, and then carbon dioxide is supplemented into the premixing kettle through a CO 2 air supply device 004. Preferably, the temperature of the premixing unit is 40 ℃, the pressure of carbon dioxide is 0.1-2 MPa, and the premixing time is 1-2 h. More preferably, the premixing time is 1h.
(2) The pre-mixture is fed through the feed lines into each of the reaction lines 106 in the reaction unit at one time. When the raw materials enter the reaction pipeline 106, the reaction unit is controlled to be satisfied that the temperature of the reaction pipeline 106 is 35-45 ℃ and the pressure of carbon dioxide is 0.1-0.5MPa. In the feeding process, the temperature is lower, and the raw materials are prevented from being decomposed.
(3) After the raw materials completely enter the reaction unit, the feeding is completed. Carbon dioxide is supplemented through the carbon dioxide supplementing port 102, and the pressure value of CO 2 is controlled to be 2-6 MPa, and more preferably, the pressure value of CO 2 is controlled to be 3MPa. A solenoid valve is used to automatically vent the carbon dioxide make-up pressure from the carbon dioxide make-up port 102 when the pressure is too low.
(4) The circulation pump 007 is turned on, the temperature of the heat exchange medium in the jacket 105 is adjusted, and the temperature is slowly raised to raise the temperature of the material in the reaction pipeline 106 to the reaction temperature of 80+/-5 ℃. For example, the reaction temperature is 80 ℃, 78 ℃, etc. Specifically, the slow temperature rise process comprises the step of controlling the temperature difference between the heat exchange medium in the jacket 105 and the material in the reaction pipeline 106 to be not more than 3-5 ℃. Preferably, the temperature difference between the heat exchange medium temperature in the jacket 105 and the temperature of the reaction tube 106 is controlled to be 3 ℃ to slowly raise the temperature of the reaction tube 106 until the temperature of the reaction tube 106 reaches 80+/-5 ℃. More preferably, the temperature measurement value of the temperature sensor installed at the middle of the reaction tube 106 is taken as the temperature of the reaction tube 106 during the temperature rising process. By the control of slow temperature rise, bisphenol A can be prevented from being decomposed into small molecules due to excessively fast temperature rise of materials, and the polymerization effect and the product quality are prevented from being influenced.
(5) After the temperature is raised to 80+/-5 ℃, the polymerization reaction is carried out, the circulating pump 007 is kept in an open state, the temperature in the reaction pipeline 106 is monitored, when the temperature of the reaction pipeline 106 is raised, the temperature of a heat exchange medium in the jacket 105 is correspondingly lowered, and the lowering temperature of the medium in the jacket 105 is approximately equal to the raising or lowering temperature of the reaction pipeline 106, so that the temperature of materials is kept at 80+/-5 ℃. Specifically, in the above process, the temperature measurement value of the temperature sensor installed at the bottom of the reaction tube 106 is taken as the temperature of the reaction tube 106. The temperature in the reaction pipeline 106 is always increased due to exothermic heat of the raw material reaction, and the temperature of the reaction system is kept relatively constant by reducing the temperature of the heat exchange medium of the jacket 105 during the temperature increase.
Meanwhile, the gas pressurization compensation control is performed in the polymerization reaction process. The gas pressurization compensation control step comprises the step of introducing CO 2 gas with a second pressure value into the reaction pipeline 106 when the temperature of the material in the reaction pipeline 106 is rapidly increased in the polymerization reaction process until the temperature of the material in the reaction pipeline 106 is reduced to 80+/-5 ℃, wherein the temperature increase of the material in 1min is not less than 5 ℃ as a judgment index of the rapid temperature increase of the material, and the second pressure value is 4-8 MPa and is larger than the first pressure value.
In particular, when the polymerization reaction occurs more severely, or when the local area reaction rate is too fast, a sharp rise in the material temperature may result. When the rapid temperature rise in the reaction pipeline is monitored, purified CO 2 gas provided by the carbon dioxide purification unit is fed into the reaction pipeline 106 through the carbon dioxide gas supplementing port 102 until the temperature of the materials in the reaction pipeline 106 is reduced to 80+/-5 ℃. Wherein, the judgment index of the rapid rise of the material temperature is that the temperature rise is not less than 5 ℃ within 1 min. Preferably, when the purified CO 2 gas is fed, the temperature of the CO 2 gas is 50-65 ℃, for example, the temperature of the fed CO 2 gas is 50 ℃,55 ℃, 60 ℃ and the like. For example, in one embodiment, where the reaction temperature is 80 ℃, the temperature of the material in the reaction conduit is raised to over 85 ℃ within 1 minute, CO 2 purified gas at 60 ℃ is fed until the temperature in the reaction conduit is reduced to 80 ℃. The material can be rapidly cooled by supplementing low-temperature high-pressure CO 2 gas, so that the explosion risk is reduced. And because CO 2 gas with higher pressure is fed in, the gas-liquid mass transfer degree in the pipeline is greatly increased, and the step is controlled in cooperation with the slow temperature rise program, so that the occurrence of yellowing of the product is effectively avoided.
Further preferably, in the reaction process, the reaction is terminated when the density reaches 1.1 to 1.3 g/cm 3 and the variation is less than 0.01g/cm 3 within 5 minutes by taking the density as the reaction end point.
Further, in the polymerization reaction process, one cycle is completed by controlling the circulation flow rate of the circulation pump 007 to be 10 to 15 minutes. More preferably, the circulation pump 007 has a circulation flow rate of 10 minutes to complete one cycle. By regulating the circulation flow rate of the circulation pump 007, the processes of heat conduction, gas-liquid mass transfer, solid-liquid mixing and the like are guaranteed to be fully carried out in the reaction process, the stable performance of the reaction process is guaranteed, and the quality and the production efficiency of the product are improved.
(6) After the reaction, the reaction product is a mixture containing polycarbonate polyether polyol, cyclic carbonate and unreacted raw material propylene oxide. The reaction product flows out from the discharge port. The single discharge of the discharge port is not more than 80% of the volume of the reaction pipeline 106. The reaction product is then passed to a separation unit 008 in a post-treatment step, the separation unit 008 separating propylene oxide and dissolved CO 2 in the mixture to obtain a crude product while adjusting the viscosity of the crude product. And introducing the crude product into a refining unit 009, adding a refining agent for adsorption treatment, and filtering to obtain the crude product with the catalyst metal content lower than 10 ppm. And (3) introducing the refined crude product into a rectifying unit 010, separating the main product polycarbonate polyether polyol and the byproduct cyclic carbonate to obtain a polycarbonate polyether polyol product, and then filling.
Note that, the above-mentioned premixing unit 005, separation unit 008, refining unit 009, rectifying unit 010, etc. may refer to the conventional structure, and will not be described here again.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol using the above-mentioned integrated reaction apparatus, the reaction process is as follows:
Adding 8L of propylene oxide, 4gDMC of catalyst and 520g of bisphenol A into a premixing kettle respectively, introducing 0.4MPa of carbon dioxide, mixing and stirring at 40 ℃, pressing the mixture into an 8L multiplied by 2 integrated tubular reactor after stirring for 1h, wherein the diameter of a single reaction pipeline is 100mm, the length of the reaction pipeline is 1000mm, introducing the carbon dioxide into the reaction pipeline to 3MPa after all pressing, and maintaining the pressure. The circulation pump is started, the temperature is raised to 80 ℃ to carry out polymerization reaction, and the reaction is controlled for 10min to complete one cycle (the flow rate of the circulation pump is about 600 g/min). In the heating process, the temperature difference between the temperature of the heat exchange medium in the jacket and the temperature in the reaction pipeline is controlled to be 3 ℃, the temperature of the materials in the reaction pipeline is slowly increased until the temperature of the raw materials in the reaction pipeline is increased to 80 ℃, and the polymerization reaction is carried out.
During the polymerization, temperature monitoring was performed and the following steps were performed:
(1) When the temperature of the temperature sensor in the middle of the reaction pipeline (namely, the temperature of the material) is higher than 80 ℃, the temperature of the heat exchange medium in the jacket is reduced, and the reduced temperature of the heat exchange medium is equal to the difference value of the temperature sensor which is higher than 80 ℃, so that the temperature of the material is kept balanced at 80 ℃.
(2) When the temperature of the material in the reaction pipeline is monitored to rise above 85 ℃, introducing CO 2 gas into a carbon dioxide gas supplementing port by a CO 2 purification system, wherein the gas temperature is 60 ℃, supplementing the pressure of CO 2 to 4MPa, and reducing the temperature of a heat exchange medium in a jacket, wherein the reducing temperature of the heat exchange medium is the difference between the temperature of the material and 80 ℃ until the temperature of the material is reduced to 80 ℃.
After 3 hours of reaction, the density is evenly increased to 1.12g/cm 3 and is stable (the change in 5min is less than 0.01g/cm 3), at the moment, the reaction is finished, the temperature is reduced, and the product is taken out. After the catalyst is removed by the catalyst filtering device, a scraper evaporator is used for separating main byproducts.
The DMC catalyst is zinc-cobalt double metal cyanide complex catalyst obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent. The preparation method comprises the steps of weighing potassium hexacyanocobaltate and zinc bromide in a molar ratio of 1:4, dissolving in an aqueous solvent containing water and tertiary butanol, and continuously stirring, wherein the mass ratio of the total mass of the metal salt (namely cobalt salt and zinc salt) to the aqueous solvent is 1:5. Adding inorganic acid and organic acid, wherein the inorganic acid is dilute hydrochloric acid, the pH value is 2, the organic acid is glutaric acid, the mol ratio of the inorganic acid to the organic acid is 5:1, the mol ratio of the total mol number of the metal salt to the mol number of the acid is 4:1, and stirring for several hours at the temperature of 10-100 ℃ continuously generates precipitate. And (3) carrying out suction filtration on the precipitate, and drying to obtain a filter cake. Reslurrying and washing the filter cake with an aqueous solvent at the temperature of 10-100 ℃, specifically, washing at the temperature of 100 ℃ for 3 minutes, stirring for several hours, and then carrying out suction filtration and drying to obtain the filter cake, and repeating the steps of slurrying, washing and drying at the temperature of 10-100 ℃ for a plurality of times until the pH value of the system liquid is 6-7, specifically, the temperature is 60 ℃ for 6 minutes each time. And further drying the filter cake at the temperature of 80-100 ℃ under vacuum condition to obtain a final catalyst, and processing the catalyst into powder particles under anhydrous drying condition by mechanical grinding before use.
Sampling and analyzing the purified product, namely sampling and collecting a polymerization reaction product (polycarbonate-polyether polyol, cyclic propylene carbonate and unreacted propylene oxide) in a container, performing nuclear magnetic resonance spectrum characterization on the polymerization reaction product sample to calculate the ratio of a polymer to cyclic micromolecules in the crude product, purifying the polymer, performing nuclear magnetic resonance spectrum test on the polymer, and calculating to obtain the ratio of polycarbonate chain links to polyether chain links on a polymer main chain, wherein the polymer main chain is provided with only two structures of polycarbonate chain links and polyether chain links, and the percentage of the two structures is added to be 100%.
The amount of carbon dioxide introduced (carbonate chain link content) and the ratio of propylene carbonate (cyclic carbonate) to polycarbonate polyether polyol in the polycarbonate polyether polyol obtained were determined by means of 1 H-NMR (Bruker, DPX400,400MHz; pulse program zg30, waiting time d1:10s,64 scans). In each case the sample was dissolved in deuterated chloroform. 1 The relevant resonance proton peaks in H-NMR (based on tms=0 ppm) are as follows:
Wherein 5.0ppm and 4.2ppm belong to proton peaks on the methylene and the methylene of the polycarbonate chain units, 4.9ppm, 4.5ppm and 4.1ppm belong to proton peaks on the methylene and the methylene of the five-membered ring carbonate, and 3.5-3.8ppm belong to proton peaks of the ether chain units. The integrated area of a peak at some ppm on the nuclear magnetic hydrogen spectrum is represented by capital letter a plus a numerical subscript, e.g., a 5.0 represents the integrated area of a peak at 5.0 ppm. According to 1 H-NMR spectrum of the copolymerization crude product and integral area of relevant proton peak, calculating the embedding amount M CO2 of carbon dioxide of carbonate chain link ratio (molar ratio) F CO2 and cyclic carbonate content mass fraction W PC、 in the copolymerization reaction, wherein the specific calculation method is as follows:
FCO2=(A5.0+A4.2-2×A4.6)/[(A5.0+A4.2-2×A4.6)+A3.5]×100%;
WPC=102×A1.5/[102×(A5.0+A4.2-2×A4.6+A1.5)+58×A3.5]×100%;
MCO2=44×FCO2/[102×FCO2+58×(1-FCO2)]×100%。
Coefficient 44 is the molar mass of carbon dioxide, coefficient 58 is the molar mass of PO (propylene oxide), and coefficient 102 is the sum of the molar mass of carbon dioxide (44 g/mol) and the molar mass of PO (58 g/mol).
The calculation formula of the product conversion rate n is n=mX (1-M CO2)/(M-m×MCO2), wherein M is the mass of the product after removing propylene oxide, and M is the total sample mass containing propylene oxide.
The polymer number average molecular weight (Mn) and the polymer molecular weight polydispersity index (PDI) are determined by Gel Permeation Chromatography (GPC).
The hydroxyl number (OHV) was determined from the test of GB/T12008.3-2009 plastics polyether polyol part 3 hydroxyl number.
And (3) performing chromaticity test on the final product, taking 5g of the object to be tested, placing the cuvette in a dark environment, and reducing the influence of a light source on the test to cause errors. The test was performed using an NR10QC color instrument, and the test data included three basic indices L, a, b.
Where the value of L represents the color brightness, l=0 indicates black, l=100 indicates white.
Where a denotes the position between red/magenta and green, a is negative indicating green, and a is positive indicating magenta.
Where b denotes the position between yellow and blue, b denotes blue with negative values and b denotes yellow with positive values.
The smaller the absolute values of the a and b values, the better the smaller the approach to colorless.
The test results are shown in table 1 below:
TABLE 1
As can be seen from Table 1, the production process provided by the embodiment of the invention can fully react the raw materials at 80 ℃, the molecular weight distribution of the prepared polycarbonate polyether polyol is narrower and is about 1.1, the b value is smaller than 0.1 and is close to 0, i.e. the product is not yellowing, the proportion of carbonate chain links is higher, i.e. the carbon dioxide fixation rate is high, more than 55%. And the reaction time is very short, only 3 hours are needed to reach the given conversion rate, and the energy consumption is relatively less.
Example 2
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
the raw materials were added in the amounts of 32L of propylene oxide, 16gDMC of catalyst, 2080g of bisphenol A, and an 8L X8 integrated tube reactor was used. The circulation flow rate was controlled to complete one cycle at 10min (the flow rate of the circulation pump was about 2400 g/min).
Example 3
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
The raw materials were added in an amount of 300L of propylene oxide, 150gDMC of catalyst, 19500g of bisphenol A, and a 240L X2 integrated tube reactor was used. The diameter of the reaction pipeline is 220mm, the length is 8600mm, the circulating pump is started when the liquid in the reaction pipeline is more than 10%, and the circulating flow rate is controlled to be 10min to complete one cycle (the flow rate of the circulating pump is about 22500 g/min).
Example 4
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
The gas-liquid specific volume is 1:4.
Example 5
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
the aspect ratio of the reaction pipeline is 40:1.
Example 6
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
The reaction temperature was 70 ℃.
Example 7
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
the reaction temperature was 85 ℃.
Example 8
This example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
the circulation flow rate was controlled to be 15min to complete one cycle (the flow rate of the circulation pump was about 900 g/min).
The products obtained in examples 2 to 8 were tested according to the method in example 1, and the test results are shown in table 2 below.
TABLE 2
Example 2 and example 3 were scaled up in production with respect to example 1. As can be seen from Table 2, the molecular weight, molecular weight distribution, conversion and other indices of the polymers obtained in example 2 and example 3 were not significantly fluctuated. In examples 4 to 8, relative to example 1, there was no significant fluctuation in the molecular weight, molecular weight distribution, conversion, etc. of the compound by changing one condition alone within a certain range by adjusting the gas-liquid ratio and the reaction temperature and the liquid circulation rate. The integrated tubular reactor provided by the embodiment of the invention can not influence indexes such as molecular weight, molecular weight distribution, conversion rate and the like of the polymer after being amplified, has no obvious amplification effect, and can reduce energy consumption while carrying out production while amplifying and sharing a set of heating equipment by the same parallel reaction pipelines.
Comparative example 1
This comparative example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
The pressure of CO 2 is always 3MPa, and CO 2 pressurization compensation is not performed when the temperature rises sharply.
Comparative example 2
This comparative example provides a bisphenol a type low molecular weight polycarbonate polyether polyol, which differs from example 1 in the production process of reference example 1 in that:
during the temperature rise, the temperature of the heat exchange medium in the jacket 105 of the reaction tube was controlled to 80 ℃ until the reaction temperature in the reaction tube was raised to 80 ℃.
Comparative example 3
This comparative example provides a bisphenol a low molecular weight polycarbonate polyether polyol which differs from that of example 1 in that:
The liquid circulation flow rate in the reaction unit was 25min to complete one cycle, and the remaining reaction conditions were the same as in example 1.
Comparative example 4
This comparative example provides a bisphenol a low molecular weight polycarbonate polyether polyol which differs from that of example 1 in that:
When the polymerization reaction is carried out after the temperature rise is finished, temperature monitoring is not carried out in the polymerization reaction process, and the temperature of the heat exchange medium in the jacket is always kept at 80 ℃.
Comparative example 5
This comparative example provides a bisphenol a low molecular weight polycarbonate polyether polyol which differs from that of example 1 in that:
the volume ratio of gas to liquid in the reaction pipeline is 1:5, namely, the reaction raw materials are added, and the rest reaction conditions are kept consistent with those of the example 1.
Comparative example 6
This comparative example provides a bisphenol A type low molecular weight polycarbonate polyether polyol, the reaction apparatus is different from example 1 in that a dispersion sheet and a gas-liquid mixed heat conduction region are not provided in a reaction pipe, and a liquid circulation pump in a reaction unit is replaced with a gas booster pump. The reaction process is as follows:
Adding 8L of propylene oxide, 4gDMC of catalyst and 520g of bisphenol A into a premixing kettle respectively, introducing 0.4MPa of carbon dioxide, mixing and stirring at 40 ℃, pressing the mixture into an 8L multiplied by 2 reactor array after stirring for 1h, wherein the diameter of a single reaction pipeline is 100mm, the length of the reaction pipeline is 1000mm, introducing carbon dioxide into the reaction pipeline after all pressing to 3MPa, maintaining the pressure, compressing the carbon dioxide at the upper part of the pipeline by using a booster pump, introducing the carbon dioxide from the bottom of the pipeline, so that the materials in the pipeline fully dissolve the carbon dioxide, the booster ratio is 25:1, uniformly increasing the density to 1.12g/cm 3 after reacting for 3h at 80 ℃ and stabilizing, and taking out the product after the reaction is finished and the temperature is reduced. After the catalyst is removed by the catalyst filtering device, a scraper evaporator is used for separating main byproducts.
The products obtained in comparative examples 1 to 6 were tested in accordance with the method in example 1, and the test results are shown in Table 3 below.
TABLE 3 Table 3
Compared with the embodiment 1, the temperature of the reaction unit is controlled by directly utilizing the heating jacket, and the low-temperature CO 2 is not supplemented, so that the method is easy to cause that when the reaction is severe, the temperature change is large, the supplementation of low-temperature CO 2 is needed to be matched to stabilize the temperature of materials in a reaction pipeline, the color of a product is changed to yellow, meanwhile, the rate of consumption of CO 2 in liquid materials is increased, excessive supplementation of CO 2 is avoided, the dissolution rate of CO 2 cannot keep up with the consumption rate, the PDI is excessively high, and the ester content is relatively low.
Compared with the embodiment 1, the temperature of the reaction pipeline is directly increased by a heat exchange medium with higher temperature during temperature increase, and the temperature increase process is not finely regulated, so that the method can cause uneven heating, the temperature of materials close to the pipe wall is increased quickly, the local quick reaction releases heat, the local temperature is overhigh, the molecular weight distribution is widened, and the value of a product b is increased, namely the color is yellow.
Comparative example 3 reduced the liquid circulation rate compared to example 1, and the lower circulation rate caused the temperature build-up of the reacted material, resulting in popping and high temperature oxidation of bisphenol a leading to yellowing of the product.
Comparative example 4, in contrast to example 1, does not have temperature control during the polymerization reaction, which causes temperature aggregation of the reaction mass, resulting in high temperature oxidation of bisphenol A, which results in yellowing of the product.
Compared with the embodiment 1, the comparative example 5 reduces the gas-liquid ratio, and the reduction of the gas-liquid ratio not only causes the deterioration of the mass and heat transfer efficiency in the CO 2 area, reduces the ester content and the color to yellow, but also increases the heat generated by the materials during the reaction, increases the temperature control difficulty and is extremely easy to burst.
Compared with the method in the embodiment 1 without a gas-liquid mixed heat conduction area, the method has the advantages that gas is adopted to circulate in a pipeline to complete gas-liquid mass transfer, the actual conversion rate is lower, the molecular weight distribution (PDI) is wider, the reaction speed is higher, the generated heat is more difficult to release and remove in a short time due to the fact that no liquid circulation is used for continuously mixing materials and releasing heat, the color is yellow, and the explosion polymerization is easier.
By combining the above examples and comparative examples, the bisphenol A type low molecular weight polycarbonate polyether polyol production process of the invention is carried out in an integrated tubular reactor with a special structure, materials can flow circularly in a reaction pipeline for polymerization, and a specific process control program is matched, so that the PDI of the obtained product is small, the carbon dioxide conversion rate is high, the product is nearly white, the problem of yellowing of the product caused in the one-step production process in the prior art is effectively solved, the molecular weight distribution of the product is narrow, the amplification effect is avoided, the molecular weight controllability of the product is strong, the production between batches is stable, and the yield is high. Meanwhile, the production process is safe and controllable, explosion polymerization is not easy to generate, no amplification effect is generated, and the method is suitable for industrial large-scale production.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. A process for the production of bisphenol a type low molecular weight polycarbonate polyether polyols in an integrated tubular reactor having at least one reaction conduit, said process comprising:
Introducing a premix into the reaction pipeline at one time, and introducing CO 2 with a first pressure value, wherein the premix is obtained by introducing CO 2 into all the epoxy compound, bisphenol A and the catalyst for premixing;
Heating and circulating the premix in a reaction pipeline to perform polymerization reaction, and separating to obtain bisphenol A type low molecular weight polycarbonate polyether polyol, wherein during the polymerization reaction, slow temperature rise control and gas pressurization compensation are performed so that the molecular weight polydispersity index PDI of the bisphenol A type low molecular weight polycarbonate polyether polyol is not more than 1.5, and in an Lxa x b x color system, the b x value is not more than 0.1;
The slow temperature rise control comprises the steps of controlling the temperature difference between the heating temperature of the reaction pipeline and the temperature of the materials in the reaction pipeline to be not more than 3-5 ℃ so that the materials in the reaction pipeline are heated to 75-85 ℃ and then subjected to polymerization reaction, and the gas pressurization compensation comprises the steps of introducing CO 2 gas with a second pressure value into the reaction pipeline when the temperature of the materials in the reaction pipeline is rapidly increased in the polymerization reaction process until the temperature of the materials in the reaction pipeline is reduced to 75-85 ℃, wherein the judgment index of the rapid increase of the temperature of the materials is that the temperature is increased to be not less than 5 ℃ within 1min, and the second pressure value is larger than the first pressure value.
2. The process for producing bisphenol a type low molecular weight polycarbonate polyether polyol according to claim 1, wherein the temperature of the CO 2 gas is controlled to be 50-65 ℃ when the gas pressurization compensation is performed.
3. The process according to claim 1, wherein a heat exchange medium is circulated outside the reaction tube to control the temperature of the material, and the process further comprises controlling the temperature of the heat exchange medium to be substantially equal to the temperature of the material in the reaction tube during the polymerization reaction to maintain the temperature of the material in the reaction tube at 75-85 ℃.
4. The process for producing bisphenol a type low molecular weight polycarbonate polyether polyol according to claim 1, wherein the first pressure value is 2 to 6mpa and the second pressure value is 4 to 8mpa.
5. The production process of the bisphenol A type low molecular weight polycarbonate polyether polyol according to claim 1, wherein the integrated tubular reaction device comprises a premixing unit and a reaction unit, wherein the premixing unit is obtained by premixing the premix, the reaction unit comprises a circulating pump and a plurality of reaction pipelines, the circulating pump is used for enabling materials to circularly flow in the plurality of reaction pipelines, the circulating pump has a circulating flow rate of 10-15 min to finish one cycle, or the circulating pump has a circulating flow rate of 10min to finish one cycle.
6. The process for producing bisphenol A type low molecular weight polycarbonate polyether polyol according to claim 5, wherein a plurality of reaction pipelines are arranged in parallel, the feed end of each reaction pipeline is intersected with a liquid distributor through a connecting pipeline, the discharge end of each reaction pipeline is converged with the circulating pump through the connecting pipeline, one end of each liquid distributor is provided with a feed inlet communicated with the premixing unit, the other end of each liquid distributor is communicated with the circulating pump, each reaction pipeline is provided with a gas supplementing port for CO 2 to enter, the mixed products flowing out of the reaction pipelines are converged with the circulating pump together, are dispersed into a plurality of reaction pipelines after being pumped into the liquid distributor through the circulating pump, and then reach the discharge end through the reaction pipelines to complete one cycle.
7. The process for producing bisphenol A type low molecular weight polycarbonate polyether polyol according to claim 5, wherein the gas-liquid volume ratio in the reaction pipeline is controlled to be 1:1-4 in the polymerization reaction process.
8. The process for producing bisphenol A type low molecular weight polycarbonate polyether polyol according to claim 5, wherein the temperature of the pre-mixing unit is controlled to be 0-40 ℃, the pressure is controlled to be 0.1-2 MPa, the pre-mixing time is controlled to be 1-2 hours during the mixing of the pre-mixing unit, the temperature of the reaction pipeline is controlled to be 35-45 ℃ when the pre-mixture of the pre-mixing unit is put into the reaction unit, and the reaction is terminated when the density of the reaction product reaches 1.1-1.3 g/cm 3 and the variation within 5min is less than 0.01g/cm 3.
9. The process for producing bisphenol a type low molecular weight polycarbonate polyether polyol according to claim 1, wherein the metal elements of the catalyst are only two metal elements of zinc and cobalt except impurities, the catalyst is obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent, the water-soluble metal salts of cobalt are cyanide salts of cobalt, the catalyst is modified by a mixed acid during synthesis, the mixed acid comprises at least one organic acid and at least one water-soluble inorganic acid, wherein:
the water-soluble inorganic acid is selected from dilute sulfuric acid and dilute hydrochloric acid, and the pH value is between 0 and 5;
The organic acid is selected from any one or more of succinic acid, glutaric acid, phthalic acid, iminodiacetic acid, pyromellitic acid and butane tetracarboxylic acid, and the molar ratio of the water-soluble inorganic acid to the organic acid is 1:10-10:1.
10. A bisphenol a low molecular weight polycarbonate polyether polyol produced according to any one of claims 1 to 9, wherein the structural formula of the bisphenol a low molecular weight polycarbonate polyether polyol is represented by formula (1):
formula (1);
Wherein in formula (1), R 1、R2 is selected from formula (2) or OH,
Formula (2);
Wherein in the formula (2), n is not less than 1 and not more than 22, m is not less than 1 and not more than 39, and the connection position is represented by x;
The bisphenol A type low molecular weight polycarbonate polyether polyol has a number average molecular weight of 1000-3000 g/mol, a molecular weight polydispersity index PDI of less than or equal to 1.5, a hydroxyl value of 35-110 mgKOH/g and a carbonate chain unit ratio F CO2 of more than or equal to 45%.
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