Cyclic carbonate crown ether ester as well as preparation method and application thereof

Abstract

The invention relates to cyclic carbonate crown ether ester as well as a preparation method and application thereof, and mainly solves the problems that traditional crown ether is small in aperture, cannot be complexed with metal atoms with larger sizes and is poor in complexing effect in the prior art. The novel cyclic carbonate crown ether ester is prepared by mixing polycarbonate polyether polyol and dicarboxylic acid according to a molar ratio of 1: (1-1.05); according to the technical scheme, the problems in the prior art are well solved, and the cyclic carbonate crown ether ester can be applied to a catalyst for preparing an adhesive.

Description

Technical Field

[0001] The invention relates to a cyclic carbonate crown ether ester, a preparation method and application thereof. Background Art

[0002] Macrocyclic compounds and their derivatives have specific cavities due to their structural characteristics and can play an important role in host-guest chemistry. Among various cyclic compounds, crown ether esters are flexible macrocyclic compounds containing both carbonyl groups and ether bonds. KHALID and MAHER gave a comprehensive introduction to the performance of crown ethers and their Schiff base derivatives as supramolecular catalysts, extractants, and probes in "Crown Ether Schiff bases and their Complexes", but there is less introduction to compounds with crown ether ester structures.

[0003] The biggest feature of crown ethers is that they can complex with positive ions, especially metal ions, and they can complex with different metal ions depending on the size of the ring. For example, 12-crown-4 complexes with lithium ions but not with sodium or potassium ions; 18-crown-6 complexes not only with potassium ions but also with diazonium salts, but not with lithium or sodium ions. (Note here: In fact, 18-crown-6 can complex with sodium ions, but its interaction force is not as strong as that of potassium ions. It is also not as strong as that of 15-crown-5 with sodium ions.) This property of crown ethers is extremely useful in synthesis, allowing many reactions that are difficult to react or even do not occur under traditional conditions to proceed smoothly. Crown ethers complex with positive ions in reagents, making the positive ions soluble in organic solvents, and the corresponding negative ions also enter the organic solvents. Crown ethers do not complex with negative ions, making free or exposed negative ions highly reactive and able to react quickly. In this process, the crown ether brings the reagent into the organic solvent, which is called a phase transfer agent or phase transfer catalyst. The reaction that occurs in this way is called a phase transfer catalytic reaction. This type of reaction has a fast rate, simple conditions, easy operation, and high yield. Summary of the invention

[0004] One of the technical problems to be solved by the present invention is that the pore size of the traditional crown ether in the prior art is too small to complex with metal atoms of larger size and the complexing effect is poor. A cyclic carbonate crown ether ester is provided. Compared with the traditional crown ether, the cyclic carbonate crown ether ester can provide both an ether group and a carbonyl group, and can better complex with metal ions with larger atomic diameters to form a more stable complex at room temperature. It has the advantages of delaying the curing speed in polyurethane foam and polyurethane adhesive and providing a longer open time. The second technical problem to be solved by the present invention is to provide a preparation method for the cyclic carbonate crown ether ester corresponding to the one of the technical problems to be solved. The third technical problem to be solved by the present invention is to provide an application of the cyclic carbonate crown ether ester corresponding to the one of the technical problems to be solved.

[0005] In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a cyclic carbonate crown ether ester, whose structural formula is as follows:

[0006]

[0007] Among them, n=2~4, m=9~12.

[0008] To solve the second of the above technical problems, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing the aforementioned cyclic carbonate crown ether ester comprises the following preparation steps:

[0010] S1: mixing polycarbonate polyether polyol and dicarboxylic acid in a molar ratio of 1:1 to 1.05;

[0011] S2: reacting at 100-120°C under alkali metal catalysis for 8-12 hours to obtain a cyclic carbonate crown ether ester;

[0012] In the above technical solution, preferably, the polycarbonate polyether polyol is selected from a group having a molecular weight of 300 to 3500 and a functionality of 2.

[0013] In the above technical solution, preferably, the dicarboxylic acid is one or more of oxalic acid, malonic acid or succinic acid.

[0014] In the above technical solution, preferably, the alkali metal catalyst is selected from at least one of lithium hydroxide and cesium hydroxide.

[0015] In the above technical solution, preferably, the amount of the alkali metal used is 1 / 10,000 to 5 / 10,000 of the total mass of the cyclic carbonate crown ether ester.

[0016] To solve the third of the above technical problems, the technical solution adopted by the present invention is as follows:

[0017] The aforementioned cyclic carbonate crown ether ester is used in the synthesis of metal complex catalysts.

[0018] The present invention provides a cyclic carbonate crown ether ester similar to a crown ether structure, which can synthesize crown ether esters of different calibers by screening polycarbonate polyethers of different molecular weights. Compared with traditional crown ethers, cyclic carbonate crown ether esters can provide both ether groups and carbonyl groups, and can better complex with metal ions with larger atomic diameters to form more stable complexes at room temperature. The metal complexes can be used in polyurethane foams and polyurethane adhesives to delay the curing speed and provide a longer open time, thereby achieving better technical effects. DETAILED DESCRIPTION

[0019] The present invention is further described below in conjunction with examples and comparative examples. These examples are only typical descriptions of the present invention, but the present invention is not limited thereto. The test methods used in the following examples and comparative examples are conventional methods unless otherwise specified, and the raw materials, reagents, etc. used are raw materials and reagents that can be obtained from conventional commercial sources such as commercial purchases, etc. unless otherwise specified.

[0020] Table 1 List of raw materials

[0021] raw material factory Remark PCE220S Hangzhou Puli Molecular weight 2100 PCE230D Hangzhou Puli Molecular weight 3300 Oxalic acid Comeo Analytical grade Malonic acid Comeo Analytical grade Succinic acid Comeo Analytical grade Lithium hydroxide Sinopharm Reagents Analytical grade Cesium Hydroxide Sinopharm Reagents Analytical grade Ferric chloride Maclean Analytical grade Dibutyltin dilaurate Evonik Industrial Grade Modified isocyanate 8018 Wanhua Industrial Grade CC968 Ultrafine Calcium Carbonate Powder Guangxi Hezhou Kelong Industrial Grade

[0022] [Example 1]

[0023] 3300 g (1 mol) PCE-230D, 90 g (1 mol) oxalic acid and 0.39 g lithium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 8 hours to obtain a cyclic carbonate crown ether ester product.

[0024] Weigh 20 g of the product and 1 g of dibutyltin dilaurate, stir and complex at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain an orange-yellow transparent complex catalyst.

[0025] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0026] The reaction equation of cyclic carbonate crown ether ester is:

[0027]

[0028]

[0029] [Example 2]

[0030] 3300 g (1 mol) PCE-230D, 109 g (1.05 mol) malonic acid and 0.39 g lithium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 10 hours to obtain a cyclic carbonate crown ether ester product.

[0031] Weigh 20 g of the product and 1 g of dibutyltin dilaurate, stir and complex at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain an orange-yellow transparent complex catalyst.

[0032] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0033] [Example 3]

[0034] 3300 g (1 mol) PCE-230D, 118 g (1 mol) succinic acid and 0.52 g lithium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 12 hours to obtain a cyclic carbonate crown ether ester product.

[0035] Weigh 20 g of the product and 1 g of dibutyltin dilaurate, stir at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain an orange-yellow transparent complex catalyst.

[0036] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0037] [Example 4]

[0038] 2100 g (1 mol) PCE-220S, 90 g (1 mol) oxalic acid and 0.98 g lithium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 10 hours to obtain a cyclic carbonate crown ether ester product.

[0039] Weigh 20 g of the product and 1 g of dibutyltin dilaurate, stir and complex at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain an orange-yellow transparent complex catalyst.

[0040] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0041] [Example 5]

[0042] 2100 g (1 mol) PCE-220S, 118 g (1 mol) succinic acid and 0.62 g cesium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 12 hours to obtain a cyclic carbonate crown ether ester product.

[0043] Weigh 20 g of the product and 1 g of dibutyltin dilaurate, stir and complex at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain an orange-yellow transparent complex catalyst.

[0044] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0045] [Example 6]

[0046] 2100 g (1 mol) PCE-220S, 109 g (1.05 mol) malonic acid and 0.75 g cesium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 8 hours to obtain a cyclic carbonate crown ether ester product.

[0047] Weigh 20 g of the product and 1 g of dibutyltin dilaurate, stir at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain a brown transparent complex catalyst.

[0048] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0049] [Example 7]

[0050] 2100 g (1 mol) PCE-220S, 104 g (1 mol) malonic acid and 0.75 g cesium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 8 hours to obtain a cyclic carbonate crown ether ester product.

[0051] Weigh 20 g of the product and 1 g of ferric chloride, stir at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain a brown transparent complex catalyst.

[0052] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0053] [Example 8]

[0054] 2100 g (1 mol) PCE-220S, 104 g (1 mol) malonic acid and 0.75 g cesium hydroxide were added to a three-necked flask connected to a condenser in sequence, and the mixture was heated to 110±5° C. and kept for reaction for 8 hours to obtain a cyclic carbonate crown ether ester product.

[0055] Weigh 20 g of the product and 1 g of nickel chloride, stir at 50±5° C. for 3 hours, and then stand at room temperature for 48 hours to obtain a brown transparent complex catalyst.

[0056] 0.1 g of the above complex catalyst was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0057] [Comparative Example 1]

[0058] 0.005 g of dibutyltin dilaurate was weighed and mixed with 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0059] [Comparative Example 2]

[0060] 0.005 g of ferric chloride was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0061] [Comparative Example 3]

[0062] 0.005 g of nickel chloride was weighed and mixed in 100 g of modified isocyanate 8018 and 100 g of dehydrated ultrafine calcium carbonate powder and dispersed evenly. The open time and storage stability were evaluated. The test results are shown in Table 2.

[0063] Table 2 Test results of products of Examples 1 to 8 and Comparative Examples 1 to 3

[0064]

[0065] Note: The open time test environment is standard conditions (temperature 23±2℃) (humidity 50%±5); storage stability judgment rules (viscosity change of more than 15% is considered unstable, otherwise it is considered qualified).

[0066] It can be seen from Table 2 Comparative Example 1 and Examples 1 to 8 that, under the premise of the effective amount of metal catalyst added, the open time of the modified isocyanate after complexation with the cyclic carbonate crown ether ester at room temperature is much longer than that of the catalyst that has not been complexed; there is almost no significant difference in the deep solidification speed and shear strength at high temperature, indicating that the metal catalyst after complexation can completely release the original activity of the original metal catalyst at high temperature. It is generally hoped that the open time of the prepared glue can be long, and the operation time thereof can be increased. The cyclic carbonate crown ether ester prepared in the present invention can be complexed with metal ions such as tin, iron, and nickel.

[0067] From the comparison of the application test data of Examples 1 to 8 in Table 2, it can be seen that the complex metal catalyst can coexist with the modified isocyanate in a friendly manner and will not significantly affect the stability of the modified isocyanate.

[0068] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims without affecting the essential content of the present invention.

Claims

1. A cyclic carbonate crown ether ester, the structural formula of which is as follows: in, n=2~4,m=9~12.

2. A method for preparing the cyclic carbonate crown ether ester according to claim 1, comprising the following preparation steps: S1: mixing polycarbonate polyether polyol and dicarboxylic acid in a molar ratio of 1:1 to 1.05; S2: react at 100-120°C under alkali metal catalysis for 8-12 hours to obtain a cyclic carbonate crown ether ester.

3. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized in that: The polycarbonate polyether polyol is selected from polyols with a molecular weight of 300 to 3500 and a functionality of 2.

4. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized in that: The dicarboxylic acid is one or more of oxalic acid, malonic acid or succinic acid.

5. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized in that: The alkali metal catalyst is selected from at least one of lithium hydroxide and cesium hydroxide.

6. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized in that: The amount of the alkali metal used is 1 / 10,000 to 5 / 10,000 of the total mass of the cyclic carbonate crown ether ester.

7. Use of the cyclic carbonate crown ether ester according to claim 1 in the synthesis of metal complex catalysts.

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