Sebacic acid polycarbonate polyether polyol and production process thereof

Abstract

The invention provides sebacic acid polycarbonate polyether polyol and a production process thereof, and relates to the technical field of chemical engineering. The production process is carried out in a tubular reaction device, and raw materials are premixed and then fed into a reaction pipeline for polymerization reaction at one time. In the polymerization reaction process, the residual sebacic acid can be effectively reduced by performing refined temperature control, replenishing the catalyst in the middle and rear sections of the reaction and increasing the circulating flow rate, the acid value of the obtained product is lower than 0.3 mgKOH / g, the molecular difference index is smaller than 3%, and the application scene of the polyhydric alcohol is greatly expanded. The production process is carried out in a tubular reaction device, so that reaction conditions and parameters are easy to control, and the method can be suitable for large-scale industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of chemistry and chemical engineering, and in particular to a sebacic acid polycarbonate polyether polyol and a production process thereof. Background Art

[0002] Polycarbonate polyether polyols are a type of polyols with carbonate groups in the molecule and hydroxyl groups at the ends of the molecular chain, which can be obtained by copolymerization of carbon dioxide and epoxy compounds. Carbon dioxide, as one of the raw materials, is cheap and easy to obtain, non-toxic and non-flammable, has a clear carbon dioxide chemical fixation effect, and the temperature required for the reaction is not high, the energy consumption is low, and the copolymerization method of carbon dioxide and epoxy compounds has broad application prospects and high industrial value. Polycarbonate polyether polyols have high modulus, high hydrogen bond density, high weather resistance and wear resistance brought by carbonate bonds, as well as fluidity and flexibility brought by ether bonds, and are widely used in polyurethane applications. Polyurethane coatings, adhesives, foams and other application products prepared with this type of polyol have more excellent product performance. The market prospect of this polyol is broad, and the synthesis research and industrial production of polycarbonate polyether polyols have been widely and deeply studied worldwide.

[0003] Sebacic acid polycarbonate polyether polyol is a polyol synthesized by polymerization of carbon dioxide and propylene oxide with DMC catalyst, using sebacic acid as a small molecule initiator. However, when sebacic acid is used as an initiator, it is easy to cause the acid value of the product (the mass of KOH consumed by the acidic component in each gram of sample) to be too high. In the prior art, the acid value of sebacic acid products is basically around 1.5 mgKOH / g. A higher acid value often limits the use of polyols in the synthesis of polyurethanes, causing synthesis difficulties and affecting its downstream applications. In the preparation process, the acid value of the sebacic acid product needs to be controlled below 0.3 mgKOH / g to make it easy and widespread for downstream applications. Therefore, controlling the residual amount of sebacic acid and synthesizing a sebacic acid product with a low acid value has become a current technical difficulty.

[0004] In addition, since sebacic acid is a flaky crystal, easily soluble in propylene oxide, and has a slow reaction rate, a higher reaction temperature is required when using sebacic acid as an initiator compared to other initiators. For example, bisphenol A polycarbonate polyether polyol reacts at 80°C, while sebacic acid polycarbonate polyether polyol needs to react at 90°C. This reaction is an exothermic reaction, which releases a large amount of heat during the reaction and the temperature rises sharply. Due to the increase in reaction temperature, the risk of uncontrollable explosion of the reaction increases, resulting in a high molecular weight difference index, poor batch stability, and easy to produce amplification effect. The amplification effect refers to the research results obtained by using small equipment to conduct chemical process (i.e. small-scale) experiments (such as laboratory scale). The results obtained under the same operating conditions are often very different from those obtained by large-scale production equipment (such as industrial scale). The impact of these differences is called the amplification effect. Summary of the invention

[0005] The object of the present invention is to provide a production process of sebacic acid polycarbonate polyether polyol, which adopts a special tube-in-tube reaction device to improve the heat exchange and temperature control capabilities, ensure the gas-liquid mass transfer and solid-liquid-gas mixing efficiency of the reactants, heat and dissipate heat sufficiently, and effectively avoid implosion. The production process has no amplification effect, is suitable for industrial large-scale production of sebacic acid polycarbonate polyether polyol, can solve the problem of too high acid value of the product, effectively improve the total conversion rate and safety, reduce production costs, and improve the ability to be directly used in different applications of polyurethane.

[0006] The present invention provides a production process of sebacic acid polycarbonate polyether polyol, which is carried out in a tube-in-tube reaction device, and the tube-in-tube reaction device includes a premixing kettle, a reaction pipeline and a circulation pump. The production process includes: adding an epoxy compound, sebacic acid and a catalyst into the premixing kettle, and introducing CO2 for mixing to obtain a premix; introducing the premix into the reaction pipeline at one time, and introducing 2-6MPa of CO2; heating the material in the reaction pipeline to a preset reaction temperature of 80-95°C, and circulating the material in the reaction pipeline at a first circulation flow rate to perform a polymerization reaction; during the polymerization reaction, monitoring the material temperature and material density in the reaction pipeline, and performing the following steps: when it is monitored that the CO2 consumption value in the reaction pipeline is greater than 0.1MPa, and the material temperature rises by more than 2°C above the preset reaction temperature, the heat exchange medium temperature of the reaction pipeline is reduced to 70-80°C, until it is monitored that the material in the reaction pipeline is reduced to the preset reaction temperature, the heat exchange medium temperature is raised to 80-95°C; when it is monitored that the material density reaches 1g / cm 3When the reaction is completed, the catalyst is added to the reaction pipeline and the material is adjusted to a second circulation flow rate, wherein the second circulation flow rate is greater than the first circulation flow rate, and the amount of the catalyst added is 5-10% of the mass of the catalyst in the premixing kettle; the sebacic acid polycarbonate polyether polyol separated after the reaction satisfies: an acid value of less than 0.3 mgKOH / g, a molecular difference index ΔM of less than 3%, and a batch stability coefficient Q of less than 5.

[0007] Specifically, the acid value of the product is determined according to the method in GB / T 12008.5-2010 "Plastic polyether polyols Part 5: Determination of acid value".

[0008] The molecular weight difference index ΔM is used to characterize the difference between the theoretical molecular weight of the product calculated according to the feed ratio and the actual molecular weight of the product measured after the reaction. The smaller the molecular weight difference index, the smaller the difference between the actual product molecular weight and the theoretical molecular weight, indicating that the controllability of the production device and process is better, the yield of the target product is higher, and the product quality is higher. The molecular weight difference index ΔM can be calculated using the following formula (1): ΔM=|g 实际 -g 理论 | / g 理论 ×100% (1); In formula (1), g 实际 Represents the measured number average molecular weight of the product, g 理论 represents the theoretical molecular weight, which is calculated as follows (2): g 理论 =A×B+D formula (2); Wherein, in formula (2), A is the average chain segment molecular weight, which is calculated as shown in the following formula (3); B is the number of chain segments, which is calculated as shown in the following formula (4); and D is the initiator molecular weight.

[0009] A=X×102+Y×58 (3); Wherein, in formula (3), X is the proportion of ester segments in the product, and Y is the proportion of ether segments in the product.

[0010] B = K × C × (1-Z) (4); Wherein, in formula (4), K is the molar ratio of the initiator feed, C is the conversion rate, and Z is the mass percentage of polypropylene carbonate.

[0011] Specifically, in the embodiment of the present invention, the calculation formula of the batch stability coefficient Q is shown in the following formula (5): Q = E × H (5); Among them, in formula (5), E is the fluctuation coefficient, and its calculation method is shown in the following formula (6); H is the average difference, and its calculation method is shown in the following formula (7); E = (g 最大 -g 最小 ) / g 理论中值 (6); In formula (6), g 最大 is the maximum actual molecular weight of all batches, g 最小 is the minimum actual molecular weight among all batches. g理论中值 Refers to the theoretical molecular weight (g 理论1 , g 理论2 ……g 理论n ), n is the number of batches; H = √ (1 / n (g1-g 理论1 ) 2 + (g2-g 理论2 ) 2 + (g3-g 理论3 ) 2 +...(g n -g 理论n ) 2 )) (7) In formula (7), g1, g2, g3, ..., gn are the actual molecular weights of each batch; g 理论1 , g 理论2 , g 理论3 ……g 理论n is the theoretical molecular weight in each batch.

[0012] In an exemplary embodiment of the present invention, the rate of the second circulation flow rate is 1.2 to 2 times of the first circulation flow rate.

[0013] In an exemplary embodiment of the present invention, in the premixing kettle, the catalyst is a DMC catalyst; the molar ratio of the epoxy compound to the sebacic acid is 15:1 to 70:1, and the mass of the catalyst is 0.04% to 0.09% of the mass of the epoxy compound. More preferably, the mass of the catalyst is 0.054% to 0.07% of the mass of the epoxy compound.

[0014] In an exemplary embodiment of the present invention, in the premixing step, the method of introducing CO2 is: using CO2 to slowly bubble from the bottom, the bubbling rate is 40-60 bubbles / min; the pressure in the premixing kettle is 0.1~2MPa; the premixing temperature is 0~40°C, and the premixing time is 1~2h; preferably, the pressure in the premixing kettle is 0.1~0.5MPa, the premixing temperature is 40°C, and the premixing time is 1h.

[0015] In an exemplary embodiment of the present invention, the reaction pipeline is connected to a circulation pump, and the material is circulated through the circulation pump.

[0016] In an exemplary embodiment of the present invention, the tube-in-tube reaction device is provided with a plurality of the reaction pipes arranged in parallel, and each of the reaction pipes has the same material circulation path formed by the connecting pipe and the circulation pump.

[0017] In an exemplary embodiment of the present invention, the reaction pipeline includes a dispersion sheet, a gas-liquid mixing heat conduction zone and a solid-liquid mixing zone arranged in sequence, the dispersion sheet is used to disperse and control the material in the gas-liquid mixing heat conduction zone to be dispersed into liquid droplets for mass transfer and heat transfer without contacting the pipeline wall; the solid-liquid mixing zone is used to achieve real-time mixing and polymerization reaction of the catalyst and the epoxy compound; after the material in the reaction pipeline is dispersed by the dispersion sheet, it flows from the gas-liquid mixing heat conduction zone to the solid-liquid mixing zone, and then flows back to the gas-liquid mixing heat conduction zone through the dispersion sheet.

[0018] In an exemplary embodiment of the present invention, the reaction pipe has a feed end and a discharge end, and the reaction mixture product flowing through the discharge end of the reaction pipe is circulated to the feed end of the reaction pipe via a circulation pump, and passes through the dispersion plate, the gas-liquid mixing heat conduction zone and the solid-liquid mixing zone of the reaction pipe to reach the discharge end for one cycle. The first circulation flow rate is to control the circulation pump to complete a cycle in 10-15 minutes; or, control the circulation pump to complete a cycle in 10 minutes.

[0019] In an exemplary embodiment of the present invention, the plurality of reaction pipes are independent of each other and are each provided with independently controllable valves.

[0020] In an exemplary embodiment of the present invention, when the premixture is introduced into the reaction pipe at one time, the reaction pipe is controlled to meet the following conditions: the temperature is 35-45° C., and the CO 2 pressure is 0.1-2 MPa.

[0021] In an exemplary embodiment of the present invention, a temperature sensor and a density meter are provided in the reaction pipe, and the temperature of the material in the reaction pipe is determined by the temperature sensor, and the density of the material is determined by the density meter.

[0022] In an exemplary embodiment of the present invention, when the density of the reaction product reaches 1.1-1.3 g / cm 3 , and the change is less than 0.01g / cm within 5min 3 The reaction is terminated.

[0023] In an exemplary embodiment of the present invention, the metal elements of the catalyst are only two metal elements, zinc and cobalt, except for impurities; the catalyst is obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent, and the water-soluble metal salt of cobalt is a cyanide salt of cobalt; the catalyst is modified by a mixed acid during synthesis, and the mixed acid contains 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 butanetetracarboxylic acid, and the molar ratio of the water-soluble inorganic acid to the organic acid is 1:10 to 10:1.

[0024] According to a second aspect of the present invention, there is provided a sebacic acid polycarbonate polyether polyol prepared according to any one of the production processes described above, wherein the sebacic acid polycarbonate polyether polyol has a structural formula represented by Formula I: Formula I; Wherein, in formula I, R1 and R2 are selected from formula II or OH; Formula II; Wherein, in formula II, m / (m+n)+n / (m+n)=1, 0.1<n / (m+n)<0.9, * represents the connection position; The number average molecular weight of the sebacic acid polycarbonate polyether polyol is 1500-4000 g / mol, the molecular weight polydispersity index PDI≤1.5, the hydroxyl value is 30-60 mgKOH / g, and the carbonate segment ratio F CO2 ≥45%.

[0025] Specifically, the polydispersity index PDI is measured by gel permeation chromatography (GPC). The smaller the PDI value, the narrower the molecular weight distribution and the more uniform the product quality.

[0026] Specifically, the carbonate chain ratio F CO2 Used to characterize the ester content of the product, F CO2 The higher the F, the better the carbon dioxide fixation effect. CO2 With the help of 1 H-NMR was used to determine the product 1 The integral area of ​​the H-NMR spectrum and its related proton peaks is used to calculate the carbonate chain ratio (molar ratio) F in the copolymerization reaction. CO2 , the specific calculation method is: F CO2 =(A 5.0 +A 4.2 -2×A 4.6 ) / [(A 5.0 +A 4.2 -2×A4.6 )+A 3.5 ]×100%; among which, A 5.0 represents the integrated area of ​​the peak at 5.0 ppm, A 4.2 represents the integrated area of ​​the peak at 4.2 ppm; A 4.6 represents the integrated area of ​​the peak at 4.6 ppm, and A 3.5 It represents the proton peak at 3.5ppm; 5.0ppm and 4.2ppm belong to the proton peaks of the methine and methylene on the polycarbonate chain segment; 4.9ppm, 4.6ppm, 4.5ppm and 4.1ppm belong to the proton peaks of the methine and methylene in the five-membered ring carbonate, and 3.5-3.8ppm belongs to the proton peak of the ether chain segment.

[0027] The beneficial effects of the production process of the sebacic acid polycarbonate polyether polyol according to the embodiment of the present invention are: (1) Compared with the traditional process, the production process provided by the present invention supplements the catalyst in the middle and later stages of the reaction, and controls and adjusts the reaction process, so that the residual acid value of the obtained product is low, not exceeding 0.3 mgKOH / g, and no additional post-processing steps are required, simplifying the production process. The obtained sebacic acid product can be used in downstream products such as the synthesis of polyurethane, and has broad application prospects.

[0028] (2) During the reaction process, the reaction temperature is finely controlled according to the temperature rise and CO2 consumption, which can effectively avoid the occurrence of explosion reaction and the problem of product quality degradation caused by temperature runaway. The molecular difference index of the obtained product is less than 3%.

[0029] (3) The present invention uses a special tube-in-tube reaction device to react, so that the materials react in multiple reaction pipes and are continuously mixed with each other through a circulating pump, which can accurately control the temperature rise and fall of each reaction pipe without causing large differences in the products of each pipe, making the reaction milder and reducing the risk of implosion. Through a suitable reaction time, the ester content is within a suitable range. In addition, through the special structure of the reaction pipe, the materials can undergo sufficient gas-liquid heat conduction and gas-liquid-solid mixing in the reaction pipe, effectively improving the product quality.

[0030] (4) The molecular weight distribution of the product obtained by the present invention is narrow, and there is no amplification effect. The product molecular weight is highly controllable, the production between batches is stable, and the product quality is high. At the same time, the production process is safe, does not produce explosion, and has no amplification effect, which is suitable for industrial large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings herein are incorporated into the specification and constitute a part of the specification, illustrate embodiments consistent with the present disclosure, and together with the specification are used to explain the principles of the present disclosure. Obviously, the accompanying drawings described below are only some embodiments of the present disclosure, and for ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without creative work.

[0032] Figure 1 A schematic structural diagram of a tube-in-tube reaction device for producing sebacic acid polycarbonate polyether polyol provided in an embodiment of the present invention.

[0033] Icons: M- agitator; 101- premixing kettle; 102- carbon dioxide inlet; 103- catalyst feeding tank; 104- feed mixer; 105- upper dispersion plate; 106- jacket; 107- static mixer; 108- lower dispersion plate; 109- reaction pipeline; 110- circulation pump; 111- separation unit; 112- refining unit; 113- distillation unit. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0035] The following is a detailed description of the sebacic acid polycarbonate polyether polyol and its production process according to the embodiment of the present invention. The embodiment of the present invention provides a production process of sebacic acid polycarbonate polyether polyol, specifically, the sebacic acid polycarbonate polyether polyol is synthesized by using sebacic acid as a small molecule initiator, an epoxy compound and CO2 under the action of a DMC catalyst.

[0036] The structural formula of the sebacic acid polycarbonate polyether polyol in the embodiment of the present invention is represented by Formula I: Formula I; Wherein, in formula I, R1 and R2 are selected from formula II or OH; Formula II; Wherein, in formula II, m / (m+n)+n / (m+n)=1, 0.1<n / (m+n)<0.9, * represents the connection position; The actual number average molecular weight of the sebacic acid polycarbonate polyether polyol is 2000-3000 g / mol, the molecular weight polydispersity index PDI is not more than 1.5, and the carbonate chain segment ratio F CO2Greater than 55%, acid value less than 0.3mgKOH / g, molecular difference index ΔM less than 3%, batch stability coefficient Q less than 5.

[0037] This production process is carried out in a shell-and-tube reaction device. By adopting a special shell-and-tube reaction device and finely controlling the temperature and CO2 pressure of the reaction process, the heat exchange and temperature control capabilities are improved, the solid-liquid-gas mixing efficiency is improved, and problems such as explosion and polymerization are avoided. Sebacic acid polycarbonate polyether polyol is synthesized in one step without amplification effect, which is suitable for large-scale industrial production, solves the problem of excessively high acid value of the product, effectively improves the overall conversion rate and safety, and reduces production costs.

[0038] It should be noted that the one-step synthesis of sebacic acid polycarbonate polyether polyol means that all the reaction raw materials, epoxy compound and sebacic acid, are put into the reaction device at one time, and no epoxy compound and sebacic acid are added in the subsequent reaction process. Among them, 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, the epoxy compound is selected from propylene oxide.

[0039] Furthermore, the DMC catalyst used in this embodiment is a mixed acid modified zinc-cobalt double metal cyanide catalyst, wherein the metal elements of the catalyst are only two metal elements, zinc and cobalt, except for impurities; the catalyst is obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent, wherein the water-soluble metal salt of cobalt is a cyanide salt of cobalt; the catalyst is modified by a mixed acid during synthesis, wherein 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 butanetetracarboxylic acid, and the molar ratio of the water-soluble inorganic acid to the organic acid is 1:10 to 10:1.

[0040] Specifically, see Figure 1In a preferred embodiment, the tube-in-tube reaction device includes a premixing kettle 101, a reaction pipeline 109, a circulation pump 110 and a carbon dioxide gas replenishment port 102. A stirrer M is provided in the premixing kettle 101, and a plurality of reaction pipelines 109 are provided, and the plurality of reaction pipelines 109 are arranged in parallel. A jacket 106 is provided on the outside of each reaction pipeline 109, and the temperature of the reaction pipeline 109 is controlled by passing steam, water, heat transfer oil and other media into the jacket 106. The space between the plurality of reaction pipelines 109 is filled with a heat transfer medium, and an insulation layer is provided on the outside of the heat transfer medium. The carbon dioxide gas replenishment port 102 is connected to the reaction pipeline 109 for replenishing carbon dioxide into the reaction pipeline 109. The lower discharge ends of the plurality of reaction pipelines 109 intersect through a connecting pipeline, reach the top liquid distributor through a circulation pump 110, and then are dispersed into each reaction pipeline to complete the cycle.

[0041] Further preferably, each reaction pipeline 109 has the same material circulation path formed by the connecting pipeline and the circulation pump 110. The number of reaction pipelines 109 is 2 to 8, for example, 4, 6, etc. The multiple reaction pipelines 109 are independent of each other and are provided with independently controllable valves. By independently controlling each reaction pipeline 109, when the local temperature of a certain reaction pipeline 109 is too high or other undesirable conditions occur, it can be controlled separately in time to avoid affecting the entire reaction process.

[0042] Further preferably, through the circulation system, the interior of the reaction pipe 109 can be divided into an upper gas-liquid mixed heat conduction zone and a lower solid-liquid mixed zone. An upper dispersion sheet 105 and a lower dispersion sheet 108 are provided in the reaction pipe 109, and the upper dispersion sheet 105 is used to disperse and control the material to be dispersed into liquid beads in the gas-liquid mixed heat conduction zone for mass transfer and heat transfer. The solid-liquid mixed zone is used to achieve real-time mixing and polymerization reaction of the catalyst and the epoxy compound. After the material in the reaction pipe 109 is dispersed by the upper dispersion sheet 105, it flows from the gas-liquid mixed heat conduction zone to the solid-liquid mixed zone, and then flows back to the gas-liquid mixed heat conduction zone through the lower dispersion sheet 108 and the upper dispersion sheet 105. The upper dispersion sheet 105, the CO2 space at the top of the reaction pipe 109 and the loop between the circulating pump 110 together constitute a gas-liquid mixed heat conduction path, so that the mixed material with a low CO2 content in the reaction pipe 109 re-dissolves CO2, and heat exchange is performed in the gas-liquid mixed heat conduction zone. A static mixer 107 is provided in the solid-liquid mixing area. The loop between the static mixer 107, the reaction pipe 109 and the circulating pump 110 together constitutes a solid-liquid mixing path. The lower dispersion sheet 108 is used to fix the static mixer 107 and further disperse and mix the products flowing down. The solid catalyst is evenly dispersed in the epoxy compound through the solid-liquid mixing path, and the reaction heat generated is dispersed at the same time, reducing the temperature difference between the center temperature in the reaction pipe 109 and the pipe wall, and avoiding the generation of explosion points.

[0043] Further preferably, the upper dispersion sheet 105 is arranged at a position of 10 to 50 mm near the top of the reaction pipe 109, and the lower dispersion sheet 108 is arranged at a position of 10 to 50 mm near the bottom of the reaction pipe 109, and the upper dispersion sheet 105 and the lower dispersion sheet 108 are both provided with a plurality of dispersion holes. More preferably, the plurality of dispersion holes are arranged in an array, for example, in a rectangular array or an annular array. By arranging the upper dispersion sheet 105 and the lower dispersion sheet 108, the reaction materials can be evenly dispersed, and flow down in a water droplet shape at the end, increasing the mass transfer and heat transfer area. The static mixer 107 and the circulating pump 110 built in the coordinated reaction pipe 109, the entire circulating dispersion system can replace the traditional stirring process to continuously mix the reaction materials during the circulation process, and can effectively make the reaction materials in the gas region for better gas-liquid mass transfer and release excess heat.

[0044] Further preferably, a temperature sensor is provided inside the reaction pipe 109, and a density meter is provided at the outlet, and the temperature sensor measures the material temperature in the reaction pipe 109, and the density meter measures the material density. The temperature of the jacket 106 is adjusted according to the material density and the internal temperature of the reactor to control the reaction rate.

[0045] The production process of sebacic acid polycarbonate polyether polyol provided in the embodiment of the present invention comprises the following steps: (1) At a temperature of 0-40°C, add an epoxy compound, sebacic acid and a catalyst into a premixing kettle 101 at one time, and introduce CO2 for mixing to obtain a premix. Specifically, in the premixing kettle 101, carbon dioxide is provided by a carbon dioxide storage tank or carbon dioxide recovered and purified by a carbon dioxide purification device, and is introduced into the premixing kettle 101 through a carbon dioxide gas supply port 102, and the propylene oxide raw material enters the premixing kettle 101 in a carbon dioxide atmosphere through a metering pump. A fixed amount of sebacic acid and a catalyst are added to the premixing kettle 101 using a weighing bucket. After the raw materials are mixed in the premixing kettle 101, a premix is ​​obtained. Preferably, the temperature of the premixing kettle 101 is 0-40°C, the pressure is 0.1-2MPa, and the premixing time is 1-2h. More preferably, the temperature of the premixing kettle 101 is 30-40°C, the pressure is 0.1-0.5MPa, and the premixing time is 1h.

[0046] (2) The premix is ​​fed into the reaction pipe 109 at one time. When the raw materials enter the reaction pipe 109, the reaction pipe 109 is controlled to meet the following conditions: the temperature of the reaction pipe 109 is 35-45°C, and the CO2 pressure is 0.1-2MPa. More preferably, during the feeding process, the temperature is relatively low to prevent the initiator from decomposing into small molecules.

[0047] (3) When the raw materials have completely entered the reaction pipe 109, the feeding is completed. Carbon dioxide is added through the carbon dioxide gas inlet 102 until the pressure in the reaction pipe 109 is 2-6 MPa. More preferably, the pressure in the reaction pipe 109 is 3 MPa. When the pressure is too low, a solenoid valve is used to automatically introduce carbon dioxide from the carbon dioxide gas inlet 102 to supplement the pressure.

[0048] (4) Turn on the circulation pump 110 and adjust the temperature of the medium in the jacket 106 to raise the temperature of the reaction pipe 109 to a preset reaction temperature of 80-95°C for reaction. For example, the preset reaction temperature is 90°C and the temperature is raised to 90°C for reaction. During the reaction, the circulation pump 110 is maintained at a first circulation flow rate, and the first circulation flow rate is preferably such that the material completes one cycle in 1-20 minutes. During the entire reaction process, the reaction temperature and material density in the reaction pipe 109 are monitored by a temperature sensor and a density meter.

[0049] When it is monitored that the CO2 consumption value in the reaction pipe 109 is greater than 0.1MPa, and the material temperature rise value in the reaction pipe 109 exceeds 2°C, the medium temperature in the jacket 106 is reduced to 70-80°C, for example, the medium temperature is reduced to 80°C, until the material temperature in the reaction pipe 109 is monitored to be reduced to 80-95°C, for example, when the material temperature is reduced to 80°C, the medium temperature in the jacket 106 is increased to 80-95°C, for example, the heating medium is increased to 80°C. Since the reaction temperature required by the sebacic acid product itself is relatively high, it is judged that the reaction rate may be too fast through the CO2 consumption value and the increase in the reaction temperature, and the temperature is controlled in time to avoid the risk of implosion.

[0050] When the material density reaches 1g / cm 3 When the catalyst is added from the catalyst adding tank 103 to the reaction pipe 109 through the feed mixer 104, the rate of the circulation pump 110 is increased from the first circulation flow rate to the second circulation flow rate, and the rate of the second circulation flow rate is greater than the first circulation flow rate. Further preferably, the second circulation flow rate is 1.2 to 2 times the first circulation flow rate. The amount of the added catalyst is 5 to 10% of the mass of the catalyst in step (1). The material density reaches 1 g / cm 3 When the reaction reaches the middle and later stages, by adding a certain amount of catalyst and increasing the circulation flow rate, the efficient conversion of sebacic acid can be accelerated and the acid value of the product can be reduced.

[0051] When the material density reaches the reaction end point, the reaction is terminated. The reaction end point is: the material density is 1.1~1.3 g / cm 3 , and / or, the fluctuation value of material density within 5 minutes is not greater than 0.01g / cm 3 .

[0052] Further preferably, in the above-mentioned reaction process, the reaction mixture product at the discharge end of the reaction pipeline 109 converges on the circulation pump 110 via one end connecting pipeline, and intersects with the liquid distributor at the top of the reaction pipeline 109 through the circulation pump 110 and the connecting pipeline at the other end, and then passes through the upper dispersion sheet 105, the gas-liquid mixing heat conduction zone, the solid-liquid mixing zone and the lower dispersion sheet 108 of the reaction pipeline 109 to reach the discharge end, completing a cycle. The first circulation flow rate is to control the circulation pump 110 to complete a cycle within 1 to 20 minutes. Further preferably, the first circulation flow rate is to control the circulation pump 110 to complete a cycle within 10 to 15 minutes. By regulating the circulation flow rate of the circulation pump 110, it is ensured that the reaction process is fully carried out. Heat conduction, gas-liquid mass transfer and solid-liquid mixing processes, ensure that the reaction process is stable, and improve the quality and production efficiency of the product.

[0053] (5) After the reaction is completed, the reaction product is a mixture containing polycarbonate polyether polyol, cyclic carbonate and unreacted raw material propylene oxide, which flows out from the discharge port. The single discharge of the discharge port is not more than 80% of the volume of the reaction pipe 109. The reaction product is then passed into the separation unit 111 in the post-treatment area, and the separation unit 111 separates the propylene oxide and dissolved CO2 in the mixture to obtain a crude product, and adjusts the viscosity of the crude product at the same time. The crude product is passed into the refining unit 112, and a refining agent is added for adsorption treatment. After filtering, a crude product with a catalyst metal content of less than 5 ppm is obtained. The refined crude product is passed into the distillation unit 113 to separate the main product polycarbonate polyether polyol and the by-product cyclic carbonate, that is, a polycarbonate polyether polyol product is obtained.

[0054] It should be noted that the above-mentioned premixing kettle 101, separation unit 111, refining unit 112, distillation unit 113, etc. can all refer to existing structures and will not be described in detail here.

[0055] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0056] Example 1 This embodiment provides a sebacic acid polycarbonate polyether polyol, using the above-mentioned tube-in-tube reaction device, the reaction process is as follows: 8L propylene oxide, 4g DMC catalyst, and 660g sebacic acid were added to the premixing kettle 101 respectively, and 0.4MPa of carbon dioxide was introduced and mixed and stirred at a temperature of 40°C. After stirring for 1h, the mixture was pressed into an 8L×2 tubular reactor, wherein the diameter of a single reaction pipe 109 was 100mm, and the length of the reaction pipe 109 was 1000mm. After all the mixture was pressed into the rear reaction pipe 109, carbon dioxide was introduced to 3MPa and the pressure was maintained. The circulation pump 110 was turned on, and the flow rate was controlled to complete a cycle in 10min (the first circulation flow rate, the flow rate of the circulation pump 110 was about 600g / min), and the temperature of the heat exchange medium in the jacket 106 of the reaction pipe 109 was controlled, and the temperature of the reaction pipe 109 was raised to the preset reaction temperature of 90°C to carry out the polymerization reaction.

[0057] During the reaction, the material temperature and density are monitored and the following steps are performed: (1) When the material temperature in the reaction pipe 109 is monitored to be higher than 92°C (increased by more than 2°C) and the CO2 consumption is greater than 0.1MPa, the temperature of the heat exchange medium is reduced to 80°C to reduce the material temperature. When the material temperature drops to 90°C, the temperature in the jacket 106 is adjusted to 85°C.

[0058] (2) When the material density reaches 1.0 g / cm 3 When the reaction entered the middle and late stages, 0.2 g of DMC catalyst was added. The flow rate of the circulating pump 110 was adjusted to 16.5 min to complete a cycle (the second circulation flow rate, the flow rate of the circulating pump was about 900 g / min). After reacting for 3 hours at a temperature of 90 ° C, the density was uniformly increased to 1.12 g / cm 3 The reaction was maintained for 5 minutes, at which time the reaction was completed, and the temperature was lowered to take out the product. After the catalyst was removed by the catalyst filter, the main and by-products were separated using a scraper evaporator.

[0059] The DMC catalyst is a zinc-cobalt double metal cyanide complex catalyst obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent. The specific preparation method is as follows: potassium hexacyanocobaltate and zinc bromide in a molar ratio of 1:4 are weighed, dissolved in an aqueous solvent containing water and tert-butyl alcohol, and stirred continuously, and the total mass of the metal salt (i.e., cobalt salt and zinc salt) and the mass ratio of the aqueous solvent are 1:5. Inorganic acid and organic acid are added, the inorganic acid is dilute hydrochloric acid, the pH value is 2, the organic acid is glutaric acid, the molar ratio of the inorganic acid to the organic acid is 5:1, and the total molar number of the metal salt to the molar number of the acid is 4:1. Stir for several hours at a temperature of 10-100°C, and precipitate is continuously generated. The above precipitate is filtered and dried to obtain a filter cake. The filter cake is re-slurried and washed with an aqueous solvent at a temperature of 10-100°C, specifically, the washing temperature is 100°C, washing for 3 minutes, stirring for several hours, and then filtered and dried to obtain a filter cake, and the above slurrying, washing, and drying steps are repeated for multiple times at a temperature of 10-100°C until the system liquid pH is 6-7, specifically, the temperature is 60°C, and each time for 6 minutes. The solid product is further dried under vacuum conditions at 80-100°C to obtain the final catalyst, and the catalyst is processed into powder particles by mechanical grinding under anhydrous drying conditions before use.

[0060] The purified product is sampled and analyzed. Specifically, the polymerization reaction product (polycarbonate-polyether polyol and cyclic propylene carbonate and unreacted propylene oxide) is sampled and collected in a container, and the polymerization reaction product sample is characterized by nuclear magnetic resonance hydrogen spectrum to calculate the ratio of polymer to cyclic small molecules in the crude product. After the polymer is purified, nuclear magnetic resonance hydrogen spectrum test is performed again to calculate the ratio of polycarbonate chain segments to polyether chain segments on the polymer main chain. There are only two structures, polycarbonate chain segments and polyether chain segments, on the polymer main chain, and the sum of the two percentages is 100%.

[0061] With the help of 1 The amount of carbon dioxide introduced in the obtained polycarbonate polyether polyol (carbonate segment content) and the ratio of propylene carbonate (cyclic carbonate) to polycarbonate polyether polyol were determined by H-NMR (Bruker, DPX400, 400 MHz; pulse program zg30, waiting time d1:10 s, 64 scans). In each case, the sample was dissolved in deuterated chloroform. 1 The relevant resonant proton peaks in H-NMR (based on TMS=0ppm) are as follows: Among them, 5.0ppm and 4.2ppm belong to the proton peaks of the methine and methylene on the polycarbonate chain, 4.9ppm, 4.5ppm and 4.1ppm belong to the proton peaks of the methine and methylene in the five-membered ring carbonate, and 3.5-3.8ppm belong to the proton peak of the ether chain. The capital letter A plus a numerical subscript represents the integrated area of ​​the peak at a certain ppm on the nuclear magnetic resonance hydrogen spectrum, for example, A 5.0represents the integrated area of ​​the peak at 5.0 ppm. 1 The integral area of ​​the H-NMR spectrum and its related proton peaks is used to calculate the carbonate chain ratio (molar ratio) F in the copolymerization reaction. CO2 and cyclic carbonate content mass fraction W PC , the amount of carbon dioxide embedded M CO2 , the specific calculation method is as follows: F CO2 =(A 5.0 +A 4.2 -2×A 4.6 ) / [(A 5.0 +A 4.2 -2×A 4.6 )+A 3.5 ]×100%; W PC =102×A 1.5 / [102×(A 5.0 +A 4.2 -2×A 4.6 +A1.5)+58×A 3.5 ]×100%; M CO2 =44×F CO2 / [102×F CO2 +58×(1-F CO2 )]×100%.

[0062] The coefficient 44 is the molar mass of carbon dioxide, the coefficient 58 is the molar mass of PO (propylene oxide), and the coefficient 102 is the sum of the molar masses of carbon dioxide (molar mass 44 g / mol) and PO (molar mass 58 g / mol).

[0063] The formula for calculating the product conversion rate n is n=m×(1-M CO2 ) / (Mm×M CO2 ), wherein m is the mass of the product after removing propylene oxide, and M is the total sample mass containing propylene oxide.

[0064] The polymer number average molecular weight (Mn) and polymer molecular weight polydispersity index (PDI) were determined by gel permeation chromatography (GPC).

[0065] The molecular weight difference index ΔM is used to characterize the difference between the theoretical molecular weight of the product calculated according to the feed ratio and the actual molecular weight of the product measured after the reaction. The smaller the molecular weight difference index is, the smaller the difference between the actual product molecular weight and the theoretical molecular weight is, indicating that the controllability of the production equipment and process is better, the yield of the target product is higher, and the product quality is higher. The molecular weight difference index ΔM can be calculated using the following formula: ΔM=|g 实际-g 理论 | / g 理论 ×100%, where g 实际 Represents the measured number average molecular weight of the product, g 理论 represents the theoretical molecular weight.

[0066] The acid value is determined according to the method in GB / T 12008.5-2010 "Plastic polyether polyols Part 5: Determination of acid value".

[0067] The hydroxyl value (OHV) is obtained by GB / T 12008.3-2009 Plastic polyether polyols Part 3: Determination of hydroxyl value.

[0068] Embodiment 2~6 Referring to the preparation method and test method of Example 1, the material parameters and process parameters are shown in Table 1, and the performance test table is shown in Table 2.

[0069] Table 1 project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Propylene oxide: Sebacic acid (molar ratio) 35:1 35:1 35:1 35:1 35:1 35:1 Sebacic acid (g) 660 413 1450 9900 1320 2640 Propylene oxide (L) 8 5 17.6 120 16 32 Catalyst (g) 4 2.5 8.8 60 8 16 Catalyst addition amount (g) 0.2（5%） 0.125（5%） 0.44（5%） 5.4（5%） 0.56（5%） 1.6（5%） Premix temperature (℃) 40 40 40 40 30 40 Premix pressure (MPa) 0.4 0.4 0.4 0.4 0.1 0.4 Premixing time (h) 2 2 2 2 1 2 Bubble speed, bubbles / min 40-60 40-60 40-60 40-60 40-60 40-60 Reaction pressure (MPa) 3 3 3 3 3 3 Preset reaction temperature (℃) 80 92 91 93 95 90 First cycle flow rate (time to complete one cycle, min) 10 10 10 10 10 10 Second cycle flow rate (time to complete one cycle, min) 16.5 16.5 13.2 22 13.2 16.5

[0070] The test results of Examples 1 to 6 are shown in Table 2 below: Table 2

[0071] As can be seen from Tables 1 and 2, the method of additionally adding a catalyst in the second half of the reaction of the production process, combined with temperature control and reaction cycle rate control, can stabilize the synthetic product, and the acid value of the product is stabilized below 0.3 mgKOH / g, and the requirements for the application of synthetic polyurethane can be met without subsequent treatment.

[0072] Among them, Examples 3 to 6 performed an amplified reaction, and when the reaction was amplified, it was achieved by adding parallel reaction pipes 109, for example, the reaction pipe 109 was replaced by 8L×2 to 8L×8, and the flow rate of the circulating pump 110 was correspondingly increased, and no other adjustments were required. It can be seen from Tables 1 and 2 that when the reaction was amplified, after the catalyst was added, the molecular weight, molecular weight distribution and conversion rate of the polymer did not fluctuate significantly, the molecular weight difference index was small and the molecular weight distribution was narrow, and it can be seen that the production process provided in this embodiment has no amplification effect and is suitable for industrial production.

[0073] Example 7 Batch stability experiment: The experiment was repeated with the same preparation method and reaction apparatus as in Example 1. The products obtained were denoted as 7-1, 7-2, 7-3, and 7-4. The performance parameters are shown in Table 3.

[0074] Among them, the calculation formula of batch stability coefficient Q is: Q=E×H Where E is the volatility coefficient, which is calculated as: E = (g 最大 -g 最小 ) / g 理论中值 where g 理论中值 Refers to the theoretical molecular weight (g 理论1、 g 理论2 ……g 理论n ), H is the mean difference, which is calculated as: H = √ (1 / n (g1-g 理论1 ) 2 + (g2-g 理论2 ) 2 + (g3-g 理论3 ) 2 +...(g n -g 理论n ) 2 )), where g 最大 is the maximum actual molecular weight of all batches, g 最小 is the minimum actual molecular weight of all batches, g1, g2, g3...g n is the actual molecular weight of each batch, g 理论1 , g 理论2 , g 理论3 ……g 理论n is the theoretical molecular weight in each batch.

[0075] Table 3

[0076] It can be seen from the data in Table 3 that the batch stability coefficient Q of Example 7 calculated by the formula is 0.25, that is, when the same product is synthesized in different batches, the product batches obtained by the device and process provided by the embodiment of the present invention have small differences, good stability, high conversion rate, and narrow molecular weight distribution, which reduces the quality instability and application difficulty caused by batch differences in downstream applications.

[0077] Comparative Example 1 This comparative example provides a sebacic acid polycarbonate polyether polyol, using the same tubular reaction device as in Example 1, and the difference from the reaction process in Example 1 is that no additional catalyst is added in the middle and late stages of the reaction, and the circulating pump 110 is always maintained at the first circulation flow rate during the reaction process. Three batches of products are obtained, which are recorded as: CK1-1, CK1-2, and CK1-3, and the performance parameters are shown in Table 4.

[0078] Comparative Example 2 This comparative example provides a sebacic acid polycarbonate polyether polyol, using the same tubular reaction device as in Example 1, and the difference from the reaction process in Example 1 is that after the catalyst is added, the circulation flow rate of the circulation pump 110 remains unchanged. Three batches of products are obtained, which are recorded as: CK2-1, CK2-2, and CK2-3, and the performance parameters are shown in Table 4.

[0079] Comparative Example 3 This comparative example provides a sebacic acid polycarbonate polyether polyol, using the same tubular reaction device as in Example 1, and the difference from the reaction process in Example 1 is that the amount of catalyst added is 0.6 g (15%). Three batches of products are obtained, which are recorded as: CK3-1, CK3-2, and CK3-3, and the performance parameters are shown in Table 4.

[0080] Comparative Example 4 This comparative example provides a sebacic acid polycarbonate polyether polyol, using the same tubular reaction device as in Example 1, and the difference from the reaction process in Example 1 is that the medium temperature in the jacket 106 is always maintained at 90°C, and no temperature control is performed, and the reaction temperature during the reaction is 90-100°C. Three batches of products are obtained, which are recorded as: CK4-1, CK4-2, and CK4-3, and the performance parameters are shown in Table 4.

[0081] Table 4

[0082] The difference between Comparative Example 1 and Example 1 is that the catalyst is not added in the middle and late stages of the reaction, and the reaction is not sufficient, resulting in excessive residual sebacic acid and a high acid value of the product.

[0083] Compared with Example 1, in Comparative Example 2, the circulation flow rate was not adjusted after the catalyst was added. The addition of catalyst will change the reaction rate in the reaction system. If the flow rate is not adjusted at this time, it will cause uneven internal reaction and excessive reaction rate in some areas, which will reduce the ester content. In addition, due to the uneven reaction, the acid value was not reduced below the target value.

[0084] The only difference between Comparative Example 3 and Example 1 is that the amount of added catalyst exceeds 15%. The excessive addition of catalyst causes the reaction rate to be too fast and uncontrollable, so that the ester content is further reduced, and there is a risk of explosion.

[0085] Compared with Example 1, Comparative Example 4 does not perform temperature control, but always maintains the temperature of the jacket 106 at the reaction temperature. Maintaining only the temperature of the jacket 106 at the reaction temperature will cause the temperature inside the reaction pipe 109 to be unable to be effectively transmitted in a timely manner, so that when a large amount of heat is released during a rapid reaction, the material cannot be maintained at the reaction temperature, which will cause explosion and polymerization, produce a large amount of polyether, and the molecular weight distribution will be very high.

[0086] From the above embodiments and comparative examples, it can be seen that the tubular reaction device provided in the embodiment of the present invention uniformly mixes the raw materials at one time through the premixing kettle 101, and is combined with the gas-liquid mixing heat conduction zone and the solid-liquid mixing zone in the reaction pipe 109, so as to achieve full mixing of the materials and provide better reaction conditions. During the reaction process, the refined temperature control and the batch addition of the catalyst are used to synergistically improve the degree of reaction, so that the residual amount of sebacic acid is small, the acid value of the prepared sebacic acid-type polycarbonate polyether polyol is low, the molecular weight distribution is narrow, the actual product molecular weight is small compared with the target theoretical value, the molecular weight of the products of different batches is stable, the production process is safe, no implosion occurs, and there is no amplification effect, which is suitable for industrial large-scale production.

[0087] The embodiments described above are part of the embodiments of the present invention, rather than all of the embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A production process for sebacic acid polycarbonate polyether polyol, characterized in that: The process is carried out in a tube-in-tube reaction device, which includes a premixing kettle, a reaction pipeline and a circulation pump; the production process includes: Adding epoxy compound, sebacic acid and catalyst into a premixing kettle, and introducing CO2 for mixing to obtain a premixing mixture; The premixture is introduced into the reaction pipe at one time, and 2-6 MPa of CO2 is introduced; the material in the reaction pipe is heated to a preset reaction temperature of 80-95° C., and the material is circulated in the reaction pipe at a first circulation flow rate to perform a polymerization reaction; During the polymerization reaction, the material temperature and material density in the reaction pipe are monitored, and the following steps are performed: When the CO2 consumption value in the reaction pipeline is monitored to be greater than 0.1MPa, and the material temperature rises by more than 2°C above the preset reaction temperature, the temperature of the heat exchange medium in the reaction pipeline is reduced to 70-80°C, until the material in the reaction pipeline is monitored to drop to the preset reaction temperature, the temperature of the heat exchange medium is raised back to 80-95°C; When the material density reaches 1g / cm 3 When the catalyst is added to the reaction pipeline, the material is adjusted to a second circulation flow rate, wherein the second circulation flow rate is greater than the first circulation flow rate, and the amount of the catalyst added is 5-10% of the mass of the catalyst in the premixing kettle; The sebacic acid polycarbonate polyether polyol separated after the reaction meets the following requirements: acid value is less than 0.3 mgKOH / g, molecular difference index ΔM is less than 3%, and batch stability coefficient Q is less than 5.

2. The production process of sebacic acid polycarbonate polyether polyol according to claim 1, characterized in that: The first circulation flow rate is 1 to 20 minutes to complete one cycle, and the second circulation flow rate is 1.2 to 2 times of the first circulation flow rate.

3. The production process of sebacic acid polycarbonate polyether polyol according to claim 2, characterized in that: The first circulation flow rate is such that one cycle is completed in 10 to 15 minutes.

4. The production process of sebacic acid polycarbonate polyether polyol according to claim 1, characterized in that: In the premixing kettle, the molar ratio of the epoxy compound to the sebacic acid is 15:1 to 70:

1.

5. The production process of sebacic acid polycarbonate polyether polyol according to claim 1, characterized in that: In the premixing kettle, the mass of the catalyst is 0.04% to 0.09% of the mass of the epoxy compound.

6. The production process of sebacic acid polycarbonate polyether polyol according to claim 1, characterized in that: The method of introducing CO2 into the premixing kettle is: using CO2 to bubble slowly from the bottom, the bubbling speed is 40-60 bubbles / min; the pressure in the premixing kettle is 0.1~2MPa; the premixing temperature is 0~40℃, and the premixing time is 1~2h.

7. The production process of sebacic acid polycarbonate polyether polyol according to claim 1, characterized in that: The reaction pipeline is connected to the circulation pump, and the material is circulated by the circulation pump, wherein the reaction pipeline has a feed end and a discharge end, and the reaction mixture product flowing through the discharge end of the reaction pipeline is circulated to the feed end of the reaction pipeline via the circulation pump, and passes through the dispersion sheet, gas-liquid mixing heat conduction zone and solid-liquid mixing zone of the reaction pipeline to reach the discharge end, which is one cycle.

8. The production process of sebacic acid polycarbonate polyether polyol according to claim 1, characterized in that: When the premixture is introduced into the reaction pipe at one time, the reaction pipe is controlled to meet the following conditions: the temperature is 35-45°C and the CO2 pressure is 0.1-2MPa; a temperature sensor and a density meter are provided in the reaction pipe, the temperature of the material in the reaction pipe is determined by the temperature sensor, and the density of the material is determined by the density meter; when the density of the reaction product reaches 1.1-1.3 g / cm 3 , and the change is less than 0.01g / cm within 5min 3 The reaction is terminated.

9. The production process of sebacic acid polycarbonate polyether polyol according to claim 2, characterized in that: The metal elements of the catalyst are only zinc and cobalt except impurities; the catalyst is obtained by reacting water-soluble metal salts of zinc and cobalt in a water-soluble solvent, and the water-soluble metal salt of cobalt is a cyanide salt of cobalt; the catalyst is modified by a mixed acid during synthesis, and the mixed acid contains 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 butanetetracarboxylic acid, and the molar ratio of the water-soluble inorganic acid to the organic acid is 1:10 to 10:

1.

10. A sebacic acid polycarbonate polyether polyol prepared according to the production process according to any one of claims 1 to 9, characterized in that: The structural formula of the sebacic acid polycarbonate polyether polyol is as follows: Formula I; Wherein, in formula I, R1 and R2 are selected from formula (2) or OH; Formula II; Wherein, in formula II, m / (m+n)+n / (m+n)=1, 0.1<n / (m+n)<0.9, * represents the connection position; The number average molecular weight of the sebacic acid polycarbonate polyether polyol is 1500-4000 g / mol, the molecular weight polydispersity index PDI≤1.5, the hydroxyl value is 30-60 mgKOH / g, and the carbonate segment ratio F CO2 ≥45%.

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