Carbon dioxide-based polyol for polyurethane and preparation method thereof

Abstract

The invention relates to the technical field of carbon dioxide-based polyols, in particular to a carbon dioxide-based polyols for polyurethane and a preparation method thereof, and the preparation raw materials at least comprise a bimetallic catalyst, ethylene oxide, carbon dioxide and a solvent; the addition amount of the bimetallic catalyst is 0.01-1% of the mass of ethylene oxide, the bimetallic catalyst is selected from at least one of a zinc-cobalt bimetallic catalyst, a zinc-iron bimetallic catalyst or a zinc-nickel bimetallic catalyst, ethylene oxide (EO) is used as a raw material, and the addition amount of the bimetallic catalyst is 0.01-1% of the mass of ethylene oxide. The carbon dioxide-based polyol with high added value is synthesized by optimizing the matching of other raw materials in the system and the control of process conditions, and is decomposed into polyol with proper molecular weight, so that the polyurethane with excellent mechanical property, low odor and environmental protection is synthesized, and the application field of the polyurethane is widened.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of carbon dioxide-based polyols, in particular to a carbon dioxide-based polyol for polyurethane and a preparation method thereof. BACKGROUND

[0002] With increasing emphasis on environmental protection and the concept of "carbon neutralization", biodegradable materials are attracting more and more attention. How to reduce carbon dioxide emissions has become a major consideration for industrial investment. Polycarbonate polyol (PPC) synthesized from carbon dioxide and propylene oxide (PO) is the most mature carbon dioxide-based polyol at present. However, the performance of PPC is not outstanding, the odor of the hard foam polyurethane synthesized by using PPC as raw material is heavy, the cell is not fine, the mechanical properties need to be improved, and the overall cost is high. Therefore, the promotion is still limited. Chinese patent application (publication number CN 118255977 A) discloses a preparation method of high-activity carbon dioxide-based diol. The catalyst, carboxylic acid chain transfer agent, propylene oxide and ethylene oxide are copolymerized with carbon dioxide to improve the selectivity and primary hydroxyl content of the product. However, the subsequent application effect needs to be further improved. SUMMARY

[0003] In order to solve the above problems, the application provides a carbon dioxide-based polyol for polyurethane and a preparation method thereof. The carbon dioxide-based polyol with high added value is synthesized by using ethylene oxide (EO) as raw material, optimizing the cooperation of other raw materials in the system and controlling the process conditions, and then decomposed into polyol with appropriate molecular weight. The polyurethane product with excellent mechanical properties, low odor and environmental protection is synthesized subsequently, thereby widening the use field.

[0004] In one aspect, the application provides a carbon dioxide-based polyol for polyurethane, which is prepared from at least the following raw materials: a bimetallic catalyst, ethylene oxide, carbon dioxide and a solvent. The solvent is at least one selected from toluene, dimethylbenzene, trimethylbenzene or chloroform, and the bimetallic catalyst at least includes a bimetallic cyanide complex catalyst.

[0005] In one embodiment, the addition amount of the bimetallic catalyst is 0.01-1% of the mass of ethylene oxide.

[0006] In one embodiment, the addition amount of the bimetallic catalyst is 0.1-0.3% of the mass of ethylene oxide.

[0007] The application realizes the copolymerization of EO and carbon dioxide to prepare carbon dioxide-based polyols by optimizing the selection of bimetallic catalyst and solvent in the reaction system, fully utilizes carbon dioxide, reduces the overall cost, and better meets the actual application requirements of polyurethane. Further, by optimizing the addition amount of bimetallic catalyst in the system and the control of reaction temperature, the mass ratio of carbon dioxide in the carbon dioxide-based polyol is improved while the product yield is ensured, and the mechanical properties of the subsequent polyurethane are improved.

[0008] In an embodiment, the mass ratio of the ethylene oxide to the solvent is 1: (0.8-1.5).

[0009] In an embodiment, the mass ratio of the ethylene oxide to the solvent is 1:1.

[0010] The application further provides a preparation method of carbon dioxide-based polyols for polyurethane, which at least comprises the following steps: adding a solvent and a bimetallic catalyst into a reaction container, introducing carbon dioxide into the reaction container to replace the pressure for 4-6 times after the reaction container is vacuumized to maintain a slight positive pressure in the reaction container; adding ethylene oxide into the reaction container, and supplementing carbon dioxide to the reaction pressure under stirring to obtain carbon dioxide-based polyols by heating reaction.

[0011] In an embodiment, the stirring speed is 300-800 r / min.

[0012] In an embodiment, the stirring speed is 400-500 r / min.

[0013] In an embodiment, the reaction pressure is 1-8 MPa.

[0014] In an embodiment, the reaction pressure is 3-6 MPa.

[0015] In an embodiment, the heating reaction temperature is 40-90℃.

[0016] In an embodiment, the heating reaction temperature is 60-70℃.

[0017] In an embodiment, the heating reaction time is 24-120 h.

[0018] In an embodiment, the heating reaction time is 48-72 h.

[0019] Further, the application adds carbon dioxide to a reaction pressure of 3-6 MPa, and reacts at 60-70℃ for 48-72 h, so that the mass ratio of carbon dioxide in the provided carbon dioxide-based polyol is 30-35%, and the content of by-product EC in the carbon dioxide-based polyol can be effectively controlled to ensure the subsequent application performance of the product.

[0020] In an embodiment, the mass percentage of carbon dioxide in the carbon dioxide-based polyol is 20-40%.

[0021] In an embodiment, the mass percentage of carbon dioxide in the carbon dioxide-based polyol is 30-35%.

[0022] In an embodiment, the average molecular weight of the carbon dioxide-based polyol is 30000-200000.

[0023] The carbon dioxide-based polyol provided by the application is decomposed into a polyol with a molecular weight of 900-1100 by a chain transfer agent, and the synthesized polyurethane has good degradability, biocompatibility, and moisture and gas resistance, and is widely used in medical fields, agricultural fields, and hard foam, leather, waterproofing, etc.

[0024] The method provided by the application has low raw material cost of the carbon dioxide-based polyol, simple preparation method, and the obtained carbon dioxide-based polyol can be used in subsequent applications through simple processing, and is easy to realize large-scale industrial production.

[0025] Advantages 1. The application provides a carbon dioxide-based polyol for polyurethane and a preparation process thereof, wherein ethylene oxide (EO) is used as a raw material, other raw materials in the system are optimized, and process conditions are controlled to synthesize a carbon dioxide-based polyol with high added value, which is then decomposed into a polyol with a suitable molecular weight, and a polyurethane product with excellent mechanical properties, low odor, and environmental protection is synthesized, thereby widening the application field.

[0026] 2. The application realizes the copolymerization of EO and carbon dioxide to prepare a carbon dioxide-based polyol by optimizing the selection of a double metal catalyst and a solvent in the reaction system, fully utilizes carbon dioxide, reduces the overall cost, and better meets the actual application requirements of polyurethane.

[0027] 3. The application increases the mass percentage of carbon dioxide in the carbon dioxide-based polyol while ensuring the yield of the product by optimizing the addition amount of the double metal catalyst in the system and the control of the reaction temperature, thereby improving the mechanical properties of the subsequent polyurethane.

[0028] 4. The carbon dioxide-based polyol provided by the application is decomposed into a polyol with a molecular weight of 900-1100 by a chain transfer agent, and the synthesized polyurethane has good degradability, biocompatibility, and moisture and gas resistance, and is widely used in medical fields, agricultural fields, and hard foam, leather, waterproofing, etc.

[0029] 5. The method provided by this invention has low raw material cost for carbon dioxide-based polyols, simple preparation method, and the obtained carbon dioxide-based polyols can be applied after simple processing, making it easy to achieve large-scale industrial production. Detailed Implementation

[0030] Example 1 Example 1 of the present invention provides a process for preparing carbon dioxide-based polyols for polyurethanes, comprising the following steps: Solvent and bimetallic catalyst were added to the reaction vessel. After the reaction vessel was evacuated, carbon dioxide was introduced to replenish the pressure. The pressure was replaced 5 times to maintain a slight positive pressure inside the reaction vessel. 500g of ethylene oxide was added to the reaction vessel, and carbon dioxide was added to the reaction pressure under stirring. The temperature was raised to obtain carbon dioxide-based polyol.

[0031] The mass ratio of ethylene oxide to solvent is 1:1, and the solvent is toluene.

[0032] The amount of the bimetallic catalyst added is 0.1% of the mass of ethylene oxide.

[0033] The bimetallic catalyst is a bimetallic cyanide complex catalyst (DMC catalyst), sourced from Huai'an Bad Polyurethane Technology Co., Ltd.

[0034] The stirring speed is 500 r / min.

[0035] The reaction pressure is 3 MPa.

[0036] The temperature of the heating reaction is 70°C.

[0037] The heating reaction time is 48 hours.

[0038] Example 2 Example 2 of the present invention provides a preparation process for carbon dioxide-based polyols for polyurethanes. The specific implementation method is the same as that of Example 1, except that the bimetallic catalyst is replaced with a zinc-iron bimetallic catalyst, model XFL14, which is from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0039] Example 3 Example 3 of the present invention provides a preparation process for carbon dioxide-based polyols for polyurethanes. The specific implementation method is the same as that of Example 1, except that the bimetallic catalyst is replaced by a nickel-cobalt bimetallic catalyst, model XF337, which is from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0040] Example 4 Embodiment 4 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the solvent is replaced by xylene.

[0041] Embodiment 5 Embodiment 5 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the solvent is replaced by acetonitrile.

[0042] Embodiment 6 Embodiment 6 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the solvent is replaced by dichloromethane.

[0043] Embodiment 7 Embodiment 7 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the solvent is replaced by trichloromethane.

[0044] Embodiment 8 Embodiment 8 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the addition amount of the bimetallic catalyst is 0.01% of the mass of ethylene oxide.

[0045] Embodiment 9 Embodiment 9 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the addition amount of the bimetallic catalyst is 0.05% of the mass of ethylene oxide.

[0046] Embodiment 10 Embodiment 10 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the addition amount of the bimetallic catalyst is 0.15% of the mass of ethylene oxide.

[0047] Embodiment 11 Embodiment 11 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the addition amount of the bimetallic catalyst is 0.2% of the mass of ethylene oxide.

[0048] Embodiment 12 Embodiment 12 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Embodiment 1, except that the addition amount of the bimetallic catalyst is 0.3% of the mass of ethylene oxide.

[0049] Example 13 Example 13 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the temperature of the temperature-raising reaction is 40℃.

[0050] Example 14 Example 14 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the temperature of the temperature-raising reaction is 50℃.

[0051] Example 15 Example 15 of the present application provides a preparation process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the temperature of the temperature-raising reaction is 60℃.

[0052] Example 16 Example 16 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the temperature of the temperature-raising reaction is 80℃.

[0053] Example 17 Example 17 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the temperature of the temperature-raising reaction is 90℃.

[0054] Example 18 Example 18 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the reaction pressure is 1 MPa.

[0055] Example 19 Example 19 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the reaction pressure is 2 MPa.

[0056] Example 20 Example 20 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the reaction pressure is 4 MPa.

[0057] Example 21 Example 21 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyol for polyurethane, the specific implementation of which is the same as that of Example 1, except that the reaction pressure is 5 MPa.

[0058] Example 22 Example 22 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyols for polyurethane, the specific embodiment of which is the same as that of Example 1, except that the reaction pressure is 6 MPa.

[0059] Example 23 Example 23 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyols for polyurethane, the specific embodiment of which is the same as that of Example 1, except that the reaction pressure is 7 MPa.

[0060] Example 24 Example 24 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyols for polyurethane, the specific embodiment of which is the same as that of Example 1, except that the reaction pressure is 8 MPa.

[0061] Example 25 Example 25 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyols for polyurethane, the specific embodiment of which is the same as that of Example 1, except that the time of the temperature rising reaction is 24 h.

[0062] Example 26 Example 26 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyols for polyurethane, the specific embodiment of which is the same as that of Example 1, except that the time of the temperature rising reaction is 72 h.

[0063] Example 27 Example 27 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyols for polyurethane, the specific embodiment of which is the same as that of Example 1, except that the time of the temperature rising reaction is 96 h.

[0064] Example 28 Example 28 of the present application provides a hydrogenation treatment process of carbon dioxide-based polyols for polyurethane, the specific embodiment of which is the same as that of Example 1, except that the time of the temperature rising reaction is 120 h.

[0065] Performance test The amount of carbon dioxide-based polyols for polyurethane provided by Examples 1-28 is shown in Table 1, and the content of carbon dioxide and the content of by-product EC (ethylene carbonate) of each carbon dioxide-based polyol are analyzed, and the results are shown in Table 1.

[0066] Table 1

[0067] From the data of Table 1, it can be seen that the cooperation of catalyst, solvent, reaction pressure, temperature-rising reaction time and temperature-rising reaction temperature in the comprehensive control system can ensure the yield of carbon dioxide-based polyols while obtaining products with high carbon dioxide content and low EC content, better meeting the subsequent polyurethane application requirements.

Claims

1. A preparation process for carbon dioxide-based polyols for polyurethane, characterized in that, The raw materials for preparation include at least: a bimetallic catalyst, ethylene oxide, carbon dioxide, and a solvent; the solvent is selected from at least one of toluene, xylene, trimethylbenzene, or chloroform, and the bimetallic catalyst includes at least a bimetallic cyanide complex catalyst.

2. The preparation process of carbon dioxide-based polyol for polyurethane according to claim 1, characterized in that, The amount of the bimetallic catalyst added is 0.01-1% of the mass of ethylene oxide.

3. The preparation process of carbon dioxide-based polyol for polyurethane according to claim 1, characterized in that, The amount of the bimetallic catalyst added is 0.1-0.3% of the mass of ethylene oxide.

4. The preparation process of carbon dioxide-based polyol for polyurethane according to claim 1, characterized in that, The mass ratio of the ethylene oxide to the solvent is 1:(0.8-1.5).

5. A method for preparing a carbon dioxide-based polyol for polyurethane according to any one of claims 1-4, characterized in that, The process includes at least the following steps: adding solvent and bimetallic catalyst to a reaction vessel, evacuating the reaction vessel and then introducing carbon dioxide to replenish the pressure, purging 4-6 times to maintain a slight positive pressure inside the reaction vessel; adding ethylene oxide to the reaction vessel, adding carbon dioxide to the reaction pressure under stirring, and heating the reaction to obtain carbon dioxide-based polyols.

6. The method for preparing carbon dioxide-based polyols for polyurethane according to claim 5, characterized in that, The stirring speed is 300-800 r / min.

7. The method for preparing carbon dioxide-based polyols for polyurethane according to claim 5, characterized in that, The reaction pressure is 1-8 MPa.

8. The method for preparing carbon dioxide-based polyols for polyurethane according to claim 5, characterized in that, The temperature of the heating reaction is 40-90℃.

9. The method for preparing carbon dioxide-based polyols for polyurethane according to claim 5, characterized in that, The heating reaction time is 24-120 hours.

10. The method for preparing carbon dioxide-based polyols for polyurethane according to claim 5, characterized in that, The carbon dioxide-based polyol contains 20-40% carbon dioxide by mass.

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