Polypropylene carbonate polyol and preparation method and application thereof
By using amine compounds to convert propylene carbonate in the production of polypropylene carbonate polyols, the problem of difficulty in separation of by-products is solved, the production process is simplified, the cost is reduced, and the product performance is improved.
Patent Information
- Application Number
- CN202411987134.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-11
AI Technical Summary
Propylene carbonate, the by-product produced during the copolymerization of carbon dioxide and propylene oxide, is difficult to separate, resulting in high temperature, high vacuum and long-term production of polypropylene carbonate polyols, which increases energy consumption and cannot be completely removed, thereby increasing production costs.
By reacting propylene oxide, carbon dioxide with the starting agent under the action of the catalyst, polypropylene carbonate polyol containing propylene carbonate was obtained, and amine compounds were added to the reaction. After the reaction, the propylene carbonate was converted into carbamate polyol, avoiding the subsequent removal process.
This method simplifies the production process, reduces energy consumption and production costs, ensures that the product does not contain cyclic propylene carbonate, and improves the mechanical properties of the polyurethane.
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Figure CN119798637A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polymer compounds, and in particular relates to a polypropylene carbonate polyol and a preparation method and application thereof. Background Art
[0002] In the context of increasingly obvious carbon reduction trends, the use of carbon dioxide and propylene oxide to prepare polycarbonate polyols has always been a hot topic in industry research. Polypropylene carbonate polyols are a low-cost, excellent performance, environmentally friendly polyurethane raw material. Currently, it is mainly used as a polyurethane soft segment in polyurethane leather resins, hot melt adhesives, coatings and other industries.
[0003] In the process of regulating the copolymerization of carbon dioxide and propylene oxide, in addition to obtaining polypropylene carbonate polyol, a certain amount of by-products will be produced, that is, carbon dioxide and propylene oxide will react to form cyclic propylene carbonate. In the downstream applications of polypropylene carbonate polyol, propylene carbonate (PC) has a great impact on the synthesis of polyurethane materials and product performance, such as affecting the mechanical properties and surface dryness of leather resin. Studies have shown that under the catalysis of triethylamine (TEA), isocyanate and PC can undergo a ring-opening reaction to form an alternating copolymer with amide and ester as units. When the isocyanate in the reaction system is excessive, a hyperbranched amorphous structure with side chains and partial cross-linking will be formed. This amorphous structure will cause the product performance to be unstable during the polyurethane synthesis process. In addition, studies have found that when propylene carbonate is cured in water-based polyurethane, a ring-opening reaction will occur, resulting in cross-linking, which increases the cross-linking degree of the product.
[0004] Therefore, in the industrial application of polypropylene carbonate polyol, propylene carbonate usually needs to be removed. Propylene carbonate is a high boiling point solvent with a high boiling point, and polypropylene carbonate polyol has a high viscosity, which makes it difficult to separate propylene carbonate in industrial production. It generally needs to be distilled at 120-150°C under vacuum and a flow rate of about 1 ton / hour. Therefore, in industrial production, high temperature, high vacuum and long time all cause energy consumption, and it is often impossible to completely remove it. The removal process is prone to lead to the degradation of polypropylene carbonate polyol, and also increases energy consumption and production time, thereby increasing production costs.
[0005] Therefore, it is of great significance to develop a production process for polypropylene carbonate polyols that can effectively reduce the content of by-product propylene carbonate. Summary of the invention
[0006] The purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and provide a polypropylene carbonate polyol and a preparation method and application thereof.
[0007] The present invention is achieved through the following technical solutions:
[0008] In a first aspect, the present invention provides a method for preparing polypropylene carbonate polyol, comprising the following steps:
[0009] (1) Under the action of a catalyst, propylene oxide, carbon dioxide and an initiator react to obtain a polypropylene carbonate polyol containing propylene carbonate;
[0010] (2) adding an amine compound to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) to react, thereby obtaining the polypropylene carbonate polyol;
[0011] The amine compound includes at least one of a diamine and a triamine.
[0012] The invention discloses a method for preparing polypropylene carbonate polyol, wherein an amine compound is used as a consuming agent of propylene carbonate in the production of polypropylene carbonate polyol, and propylene carbonate is converted after the reaction to obtain polypropylene carbonate polyol containing carbamate polyol. The polypropylene carbonate polyol does not need to undergo a next step of cyclic propylene carbonate removal process, is simple and controllable, has lower cost, can ensure that no cyclic propylene carbonate remains, and when the obtained polypropylene carbonate polyol containing carbamate polyol is used to synthesize polyurethane, the carbamate polyol contains strongly polar carbamate, which can greatly improve the performance of polyurethane.
[0013] Preferably, the amine compound includes at least one of ethylenediamine (EDA), isophoronediamine (IPDA), and diethylenetriamine (DETA).
[0014] In the present invention, the reaction mechanism of ethylenediamine, isophoronediamine, diethylenetriamine and propylene carbonate is as follows:
[0015]
[0016] From the above mechanism, it can be known that ethylenediamine, isophoronediamine, diethylenetriamine and propylene carbonate can react to obtain carbamate polyol, and when the product is used to synthesize polyurethane, it can effectively improve the performance of polyurethane.
[0017] Preferably, in step (1), the catalyst comprises a liquid bimetallic catalyst; more preferably, the liquid bimetallic catalyst is a chelated cyanide of any two metals selected from zinc, cadmium, cobalt, aluminum, tin, lanthanum and mercury.
[0018] Preferably, in step (1), the initiator is at least one of polyols, polyphenols, polycarboxylic acids, and polyhydroxy-containing polymers; preferably, the molecular weight Mn of the polyhydroxy-containing polymer is ≥400.
[0019] Preferably, the specific operation of step (1) is: mixing carbon dioxide and propylene oxide in a container, adding a catalyst, continuing to introduce carbon dioxide to a pressure of 1Mpa-10Mpa, and reacting at a constant pressure until the solid content reaches 90%-99%, thereby obtaining polypropylene carbonate polyol (PCD) containing propylene carbonate.
[0020] Preferably, in step (2), the flow rate of the amine compound when added is 0.1 L / h-30 L / h.
[0021] More preferably, in the step (2), the flow rate of the amine compound when added is 10 L / h-20 L / h.
[0022] Preferably, in step (2), the reaction temperature is 50°C-80°C, and the reaction time is 0.5h-2h.
[0023] Preferably, in step (2), the reaction is carried out under stirring at a stirring speed of 500 r / min-1000 r / min.
[0024] Preferably, in the step (2), the molar ratio of the amine compound to the propylene carbonate in the polypropylene carbonate polyol containing propylene carbonate is 1:(1.5-2).
[0025] More preferably, in the step (2), the molar ratio of the amine compound to the propylene carbonate in the polypropylene carbonate polyol containing propylene carbonate is 1:(1.7-1.85).
[0026] In a second aspect, the present invention provides polypropylene carbonate polyol (PCD) prepared by a method for preparing polypropylene carbonate polyol.
[0027] In a third aspect, the present invention provides a polyurethane, wherein the raw material of the polyurethane includes the polypropylene carbonate polyol.
[0028] The polypropylene carbonate polyol obtained by the preparation method of the present invention can convert the byproduct propylene carbonate into carbamate polyol to obtain the polypropylene carbonate polyol containing carbamate polyol, which can be further applied to polyurethane to improve the performance of polyurethane.
[0029] The present invention has the following beneficial effects: (1) The preparation method of the present invention is simple and controllable, takes a short time, and has a low production cost; (2) The polypropylene carbonate polyol obtained by the preparation method of the present invention does not contain cyclic propylene carbonate; (3) When the polypropylene carbonate polyol containing urethane polyol obtained by the present invention is used to prepare polyurethane products, the mechanical properties of the product are greatly improved. (4) No by-products are generated in the production process of the polypropylene carbonate polyol of the present invention, and no investment is required to build by-product distillation equipment, thereby significantly reducing production and investment costs. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 The infrared spectra of the polypropylene carbonate polyols obtained in Examples 1, 5 and 6, wherein PCD-EDA is Example 1, PCD-DETA is Example 5, and PCD-IPDA is Example 6;
[0031] Figure 2 The H-NMR spectra of the polypropylene carbonate polyols obtained in Examples 1, 5, and 6, wherein (a) is for Example 1, (b) is for Example 6, and (c) is for Example 5. DETAILED DESCRIPTION
[0032] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be understood by those skilled in the art that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
[0033] Unless otherwise specified, the experimental methods used in the examples are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.
[0034] In the following examples and comparative examples, the liquid bimetallic catalyst is a cadmium-chromium bimetallic catalyst, which is prepared with reference to patent CN201410108262.X.
[0035] Example 1
[0036] A method for preparing polypropylene carbonate polyol (PCD) comprises the following steps:
[0037] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%;
[0038] (2) At 80° C., 7.36 kg of ethylenediamine (EDA) (the molar ratio of ethylenediamine to propylene carbonate is 1:2) is added to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) through a booster pump, the flow rate is controlled to be 10 L / h, the stirring speed is controlled to be 500 r / min, and the reaction is carried out at 80° C. for 1 hour to obtain the polypropylene carbonate polyol (PCD-EDA).
[0039] Example 2
[0040] A method for preparing polypropylene carbonate polyol comprises the following steps:
[0041] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%;
[0042] (2) adding 20.85 kg of isophorone diamine (IPDA) (the molar ratio of isophorone diamine to propylene carbonate is 1:2) to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) at 80° C. through a booster pump, controlling the flow rate to 10 L / h and the stirring speed to 500 r / min. After adding the materials, react at 80° C. for 1 hour to obtain the polypropylene carbonate polyol.
[0043] Example 3
[0044] A method for preparing polypropylene carbonate polyol comprises the following steps:
[0045] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%;
[0046] (2) At 80° C., 12.63 kg of diethylenetriamine (DETA) (the molar ratio of diethylenetriamine to propylene carbonate is 1:2) is added to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) through a booster pump, the flow rate is controlled to be 10 L / h, the stirring speed is controlled to be 500 r / min, and the reaction is carried out at 80° C. for 1 hour to obtain the polypropylene carbonate polyol.
[0047] Example 4
[0048] A method for preparing polypropylene carbonate polyol comprises the following steps:
[0049] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%;
[0050] (2) At 80° C., 12.63 kg of diethylenetriamine (DETA) (the molar ratio of diethylenetriamine to propylene carbonate is 1:2) is added to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) through a booster pump, the flow rate is controlled to 30 L / h, the stirring speed is controlled to 500 r / min, and the reaction is carried out at 80° C. for 1 hour to obtain the polypropylene carbonate polyol.
[0051] Example 5
[0052] A method for preparing polypropylene carbonate polyol comprises the following steps:
[0053] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%;
[0054] (2) At 50° C., 12.63 kg of diethylenetriamine (DETA) (the molar ratio of diethylenetriamine to propylene carbonate is 1:2) is added to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) through a booster pump, the flow rate is controlled to 0.1 L / h, the stirring speed is controlled to 1000 r / min, and the reaction is carried out at 50° C. for 0.5 h to obtain the polypropylene carbonate polyol (PCD-DETA).
[0055] Example 6
[0056] A method for preparing polypropylene carbonate polyol comprises the following steps:
[0057] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%;
[0058] (2) At 70° C., 23.7 kg of isophorone diamine (IPDA) (the molar ratio of isophorone diamine to propylene carbonate is 1:1.8) is added to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) through a booster pump, the flow rate is controlled to 15 L / h, the stirring speed is controlled to 700 r / min, and the reaction is carried out at 70° C. for 2 h to obtain the polypropylene carbonate polyol (PCD-IPDA).
[0059] Comparative Example 1
[0060] A method for preparing polypropylene carbonate polyol comprises the following steps:
[0061] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. Then, 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%.
[0062] Comparative Example 2
[0063] A method for preparing polypropylene carbonate polyol comprises the following steps:
[0064] (1) First, carbon dioxide is introduced into the reactor until the pressure reaches 1 MPa, 600 kg of propylene oxide is added, and the mixture is stirred for 1 hour. 100 kg of initiator polyoxypropylene glycol (PPG-600) is added, and 0.1 kg of liquid bimetallic catalyst is added. Carbon dioxide is continued to be introduced until the pressure reaches 5 MPa. After a constant temperature and pressure reaction for 100 hours, the solid content of the system is detected. When the solid content reaches 98%, unreacted propylene oxide and carbon dioxide are separated by vacuum decompression to obtain 1000 kg of polypropylene carbonate polyol containing propylene carbonate; the content of cyclic propylene carbonate in the detection system is 2.5 wt%;
[0065] (2) At 80° C., 11.4 kg of aniline (the molar ratio of aniline to propylene carbonate is 1:2) is added to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) through a booster pump, the flow rate is controlled to be 10 L / h, the stirring speed is controlled to be 500 r / min, and the reaction is carried out at 80° C. for 1 hour to obtain the polypropylene carbonate polyol.
[0066] Characterization Tests:
[0067] 1. The polypropylene carbonate polyols obtained in Examples 1, 5 and 6 were characterized by infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy. The characterization results are as follows: Figure 1 and Figure 2 As shown. Figure 1 , Figure 2 It can be seen from the infrared and nuclear magnetic characterization diagrams that EDA, IPDA, and DETA react with propylene carbonate in polypropylene carbonate polyol to generate carbamate polyol, indicating that the preparation method of the present invention can effectively remove propylene carbonate in polypropylene carbonate polyol.
[0068] 2. The polypropylene carbonate polyols prepared in the examples and comparative examples were prepared into polyurethanes, and the properties of the polyurethanes were tested to evaluate the polypropylene carbonate polyols prepared in the examples and comparative examples.
[0069] The preparation method of the polyurethane is as follows: 330 kg of isophorone diisocyanate (IPDI), 50 kg of 2,2-dihydroxymethylpropionic acid (DMPA), and 50 kg of N,N-dimethylformamide (DMF) are added to the polypropylene carbonate polyol prepared in the embodiment and the comparative example, and the mixture is reacted at 85° C. for 2 hours with a stirring speed of 1000 r / min, and then the temperature is lowered to 35° C., 37.6 kg of triethylamine (TEA) is added, and the mixture is reacted for 15 minutes, the temperature is lowered to 5° C., a mixed solution of water and diethylamine (EDA) (7 kg of diethylamine and 3000 kg of water) is added, and the speed of the agitator is adjusted to 3000 r / min, and the mixture is stirred at high speed for 15 minutes, and the DMF solvent is removed to obtain an aqueous polyurethane emulsion.
[0070] The performance of the aqueous polyurethane emulsions prepared in each embodiment and comparative example was tested, and the test standards were as follows:
[0071] 1. Tensile strength: ASTM D 412;
[0072] 2. Water absorption: ASTM D 570;
[0073] 3. Contact angle: contact angle tester;
[0074] 4. Adhesion: ASTM D 3359;
[0075] 5. Hardness: ASTM D 3363;
[0076] The test results are shown in Table 1.
[0077] Table 1 Performance test results of waterborne polyurethane emulsions prepared in Examples and Comparative Examples
[0078]
[0079] It can be seen from the test results of Table 1 that the polypropylene carbonate polyol obtained by the preparation method of the present invention does not contain propylene carbonate, which can effectively improve the mechanical properties of polyurethane. In Comparative Example 1, propylene carbonate in the polypropylene carbonate polyol was not removed, resulting in a significant decrease in the mechanical properties and adhesion of the polyurethane. In Comparative Example 2, monoamine (aniline) was used to react with propylene carbonate, and the results showed that the mechanical properties were not significantly improved. Therefore, in the production process, diamine or triamine was used to remove propylene carbonate in the polypropylene carbonate polyol to further improve its performance.
[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.
Claims
1. A method for preparing polypropylene carbonate polyol, characterized in that: The following steps are involved: (1) Under the action of a catalyst, propylene oxide, carbon dioxide and an initiator react to obtain a polypropylene carbonate polyol containing propylene carbonate; (2) adding an amine compound to the polypropylene carbonate polyol containing propylene carbonate obtained in step (1) to react, thereby obtaining the polypropylene carbonate polyol; The amine compound includes at least one of a diamine and a triamine.
2. The method for preparing polypropylene carbonate polyol according to claim 1, characterized in that: The amine compound includes at least one of ethylenediamine, isophoronediamine and diethylenetriamine.
3. The method for preparing polypropylene carbonate polyol according to claim 1, characterized in that: In the step (1), the catalyst comprises a liquid bimetallic catalyst; and / or the initiator is at least one of polyols, polyphenols, polycarboxylic acids, and polyhydroxy-containing polymers.
4. The method for preparing polypropylene carbonate polyol according to claim 1, characterized in that: In the step (2), the flow rate of the amine compound when added is 0.1 L / h-30 L / h.
5. The method for preparing polypropylene carbonate polyol according to claim 4, characterized in that: In the step (2), the flow rate of the amine compound when added is 10L / h-20L / h.
6. The method for preparing polypropylene carbonate polyol according to claim 1, characterized in that: In the step (2), the reaction temperature is 50°C-80°C and the reaction time is 0.5h-2h.
7. The method for preparing polypropylene carbonate polyol according to claim 1, characterized in that: In the step (2), the molar ratio of the amine compound to the propylene carbonate in the polypropylene carbonate polyol containing propylene carbonate is 1:(1.5-2).
8. The method for preparing polypropylene carbonate polyol according to claim 7, characterized in that: In the step (2), the molar ratio of the amine compound to the propylene carbonate in the polypropylene carbonate polyol containing propylene carbonate is 1:(1.7-1.85).
9. Polypropylene carbonate polyol prepared by the preparation method of polypropylene carbonate polyol according to any one of claims 1 to 8.
10. A polyurethane, characterized in that: The raw material of the polyurethane includes the polypropylene carbonate polyol.
Citation Information
Patent Citations
Production process of polypropylene carbonate polyalcohol
CN103865052A