Cyclic carbonate crown ether esters, methods of preparation and uses thereof

Abstract

The present application relates to a kind of cyclic carbonate crown ether ester, preparation method and its use, mainly solve the problems of existing technology in the prior art, traditional crown ether aperture is small, cannot complex larger size metal atom, complex effect is poor.The present application is by using a new cyclic carbonate crown ether ester, including the mixing of polycarbonate polyether polyol and dibasic carboxylic acid according to mole ratio 1:1~1.05;Under the condition of alkali metal catalysis, 100~120 ℃ is reacted for 8~12h, and the technical scheme of cyclic carbonate crown ether ester is obtained, which preferably solves the problem, and can be used in the catalyst for adhesive preparation.

Description

TECHNICAL FIELD

[0001] The present application relates to a cyclic carbonate crown ether ester, a preparation method and use thereof. BACKGROUND

[0002] Due to the structural characteristics, macrocyclic compounds and their derivatives have specific cavities and can play an important role in host-guest chemistry. Among various cyclic compounds, crown ether ester is a flexible macrocyclic compound containing both carbonyl and ether bonds. KHALID, MAHER introduced the performance of crown ether and its Schiff base derivatives as supramolecular catalysts, extractants, probes in Crown Ether Schiff bases and their Complexes, but there are few introductions to crown ether ester compounds.

[0003] The biggest feature of crown ether is that it can complex with positive ions, especially metal ions, and different metal ions are complexed with different sizes of rings. For example, 12-crown-4 complexes with lithium ions but not with sodium or potassium ions; 18-crown-6 not only complexes with potassium ions, but also with diazonium salts, but not with lithium or sodium ions. (Note: 18-crown-6 can actually complex with sodium ions, but the force is not as strong as potassium ions. It is also not as strong as the interaction between 15-crown-5 and sodium ions.) This property of crown ether is extremely useful in synthesis, enabling many reactions that are difficult or even impossible under traditional conditions to proceed smoothly. Crown ether complexes with positive ions in reagents, allowing the positive ion to be dissolved in organic solvents, while the corresponding negative ion also enters the organic solvent. Crown ether does not complex with negative ions, making the free or naked negative ions highly reactive and able to react quickly. In this process, crown ether brings reagents into organic solvents, known as phase transfer agents or phase transfer catalysts. Such reactions are fast, simple, easy to operate, and have high yield. SUMMARY

[0004] One of the technical problems to be solved by the present application is that the existing technology has the problem of small pore size of traditional crown ether, which cannot complex with large-sized metal atoms, and the complexing effect is poor. The present application provides a cyclic carbonate crown ether ester. Compared with traditional crown ether, the cyclic carbonate crown ether ester can not only provide ether groups, but also provide carbonyl groups, which can better complex with metal ions with larger atomic diameters, and form more stable complexes 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 application is to provide a preparation method for preparing a cyclic carbonate crown ether ester corresponding to the first technical problem. The third technical problem to be solved by the present application is to provide an application of a cyclic carbonate crown ether ester corresponding to the first technical problem.

[0005] To solve one of the above technical problems, the technical solution adopted by the present application is as follows: A cyclic carbonate crown ether ester has the following structural formula:

[0006]

[0007] Wherein, n = 2-4, m = 9-12.

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

[0009] A preparation method of the aforementioned cyclic carbonate crown ether ester, comprising the following preparation steps:

[0010] S1: mixing polycarbonate polyether polyol with dicarboxylic acid according to a molar ratio of 1:1-1.05;

[0011] S2: reacting at 100-120℃ under alkali metal catalysis for 8-12h to obtain the cyclic carbonate crown ether ester;

[0012] In the above technical solution, preferably, the polycarbonate polyether polyol is selected from one or more of the following: a molecular weight of 300-3500, 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 or cesium hydroxide.

[0015] In the above technical solution, preferably, the amount of alkali metal is 0.01-0.05% 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 application is as follows:

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

[0018] The present application provides a cyclic carbonate crown ether ester similar to the structure of crown ether, which can be synthesized into crown ether ester of different caliber by screening polycarbonate polyether of different molecular weight. Compared with traditional crown ether, the cyclic carbonate crown ether ester can not only provide ether group, but also provide carbonyl group, which can better complex with metal ions with larger atomic diameter, form more stable complex at room temperature, and the metal complex can be used in polyurethane foam and polyurethane adhesive to delay the curing speed, provide longer open time, and achieve good technical effect. DETAILED DESCRIPTION

[0019] The present application will be further described in connection with the following examples and comparative examples. These examples are merely typical of the application and do not limit the application 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 conventional commercially available raw materials and reagents unless otherwise specified.

[0020] Table 1 Raw material list

[0021] Raw materials Factory Remark PCE220S Hangzhou Puli Molecular weight 2100 PCE230D Hangzhou Puli Molecular weight 3300 Oxalic acid Kemio Analytically pure Malonic acid Kemio Analytically pure Succinic acid Kemio Analytically pure Lithium hydroxide National Reagent Analytically pure Cesium hydroxide National Reagent Analytically pure Iron chloride Macklin Analytically pure Dibutyltin dilaurate Yingchuan Industrial grade Modified isocyanate 8018 Wanhua Industrial grade CC968 ultrafine calcium carbonate powder Guangxi Hezhou Kelong Industrial grade

[0022] Example 1

[0023] Into a three-necked flask with a condenser, 3300 g (1 mol) of PCE-230D and 90 g (1 mol) of oxalic acid and 0.39 g of lithium hydroxide were sequentially added, heated to 110±5°C for 8 hours to obtain a cyclic carbonate crown ether ester product.

[0024] After 20 g of the product was weighed and mixed with 1 g of dibutyltin dilaurate and stirred at 50±5°C for 3 hours to complex, it was left to stand at room temperature for 48 hours to obtain an orange yellow transparent complex catalyst.

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

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

[0027]

[0028]

[0029] Example 2

[0030] Into a three-necked flask with a condenser, 3300 g (1 mol) of PCE-230D and 109 g (1.05 mol) of malonic acid and 0.39 g of lithium hydroxide were sequentially added, heated to 110±5°C for 10 hours to obtain a cyclic carbonate crown ether ester product.

[0031] After 20 g of the product was weighed and mixed with 1 g of dibutyltin dilaurate and stirred at 50±5°C for 3 hours to complex, it was left to stand at room temperature for 48 hours to obtain an orange yellow transparent complex catalyst.

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

[0033] Example 3

[0034] In a three-necked flask with a condenser, 3300 g (1 mol) of PCE-230D and 118 g (1 mol) of succinic acid and 0.52 g of lithium hydroxide were sequentially added, heated to 110±5°C for 12 hours to obtain a cyclic carbonate crown ether ester product.

[0035] 20 g of the product and 1 g of dibutyltin dilaurate were weighed and stirred at 50±5°C for complexation for 3 hours, and then left to 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 and dispersed in 100 g of modified isocyanate 8018 and 100 g of dehydrated superfine calcium carbonate powder, and the open time and storage stability were evaluated, and the test results are shown in Table 2.

[0037] Example 4

[0038] In a three-necked flask with a condenser, 2100 g (1 mol) of PCE-220S and 90 g (1 mol) of oxalic acid and 0.98 g of lithium hydroxide were sequentially added, heated to 110±5°C for 10 hours to obtain a cyclic carbonate crown ether ester product.

[0039] 20 g of the product and 1 g of dibutyltin dilaurate were weighed and stirred at 50±5°C for complexation for 3 hours, and then left to 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 and dispersed in 100 g of modified isocyanate 8018 and 100 g of dehydrated superfine calcium carbonate powder, and the open time and storage stability were evaluated, and the test results are shown in Table 2.

[0041] Example 5

[0042] In a three-necked flask with a condenser, 2100 g (1 mol) of PCE-220S and 118 g (1 mol) of succinic acid and 0.62 g of cesium hydroxide were sequentially added, heated to 110±5°C for 12 hours to obtain a cyclic carbonate crown ether ester product.

[0043] 20 g of the product and 1 g of dibutyltin dilaurate were weighed and stirred at 50±5°C for complexation for 3 hours, and then left to 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 and dispersed in 100 g of modified isocyanate 8018 and 100 g of dehydrated superfine calcium carbonate powder, and the open time and storage stability were evaluated, and the test results are shown in Table 2.

[0045] Example 6

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

[0047] 20 g of the product and 1 g of dibutyltin dilaurate were weighed and stirred at 50±5°C for complexation for 3 hours, and then left to stand at room temperature for 48 hours to obtain a brownish 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 superfine calcium carbonate powder to disperse uniformly, and the open time and storage stability were evaluated. The test results are shown in Table 2.

[0049]

Example 7

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

[0051] 20 g of the product and 1 g of ferric chloride were weighed and stirred at 50±5°C for complexation for 3 hours, and then left to stand at room temperature for 48 hours to obtain a brownish 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 superfine calcium carbonate powder to disperse uniformly, and the open time and storage stability were evaluated. The test results are shown in Table 2.

[0053]

Example 8

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

[0055] 20 g of the product and 1 g of nickel chloride were weighed and stirred at 50±5°C for complexation for 3 hours, and then left to stand at room temperature for 48 hours to obtain a brownish 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 superfine calcium carbonate powder to disperse uniformly, and the open time and storage stability were evaluated. The test results are shown in Table 2.

[0057]

Comparative Example 1

[0058] Take 0.005 g of dibutyltin dilaurate and mix it evenly in 100 g of modified isocyanate 8018 and 100 g of dehydrated superfine calcium carbonate powder, evaluate the open time and storage stability, the test results are shown in Table 2.

[0059]

Comparative Example 2

[0060] Take 0.005 g of iron trichloride and mix it evenly in 100 g of modified isocyanate 8018 and 100 g of dehydrated superfine calcium carbonate powder, evaluate the open time and storage stability, the test results are shown in Table 2.

[0061]

Comparative Example 3

[0062] Take 0.005 g of nickel chloride and mix it evenly in 100 g of modified isocyanate 8018 and 100 g of dehydrated superfine calcium carbonate powder, evaluate the open time and storage stability, the test results are shown in Table 2.

[0063] Table 2 Product test results of Examples 1-8 and Comparative Examples 1-3

[0064]

[0065] Note: The open time test environment is standard condition (temperature 23±2℃) (humidity 50%±5); the storage stability judgment rule (viscosity change more than 15% is judged as unstable, otherwise judged as qualified).

[0066] From Table 2, Comparative Example 1 and Examples 1-8, under the premise of effective metal catalyst addition amount, the open time of modified isocyanate after being complexed by cyclic carbonate crown ether ester at room temperature is much longer than that of the catalyst without complexing treatment; the deep solidification speed and shear strength at high temperature have no obvious difference, which shows that the complexed metal catalyst can completely release the original activity of the metal catalyst at high temperature. Generally, it is hoped that the open time of the prepared glue can be long, which can increase the operation time. The cyclic carbonate crown ether ester prepared in the present application can be complexed with metal ions such as tin, iron and nickel.

[0067] From the application test data comparison of Table 2, Examples 1-8, the complexed metal catalyst can coexist with the modified isocyanate, and does not significantly affect the stability of the modified isocyanate.

[0068] The specific embodiments of the present application are described above, it should be understood that the present application is not limited to the above specific embodiments, those skilled in the art can make various modifications or modifications within the scope of the claims, and do not affect the essential content of the present application.

Claims

1. A cyclic carbonate crown ether ester, having the following structural formula: ###0001### wherein n = 2-4, m = 9-12. ； wherein 2. A method for preparing the cyclic carbonate crown ether ester of claim 1, comprising the following steps: S1: mixing polycarbonate polyether polyol with dicarboxylic acid according to a molar ratio of 1:1-1.05; S2: reacting at 100-120°C under alkali metal catalysis for 8-12h to obtain the cyclic carbonate crown ether ester. The polycarbonate polyether polyol is selected from the group consisting of molecular weight of 300-3500, functionality of 2. The dicarboxylic acid is oxalic acid. The alkali metal catalyst is selected from at least one of lithium hydroxide or cesium hydroxide.

3. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized by, The amount of alkali metal is 0.01-0.05% of the total mass of the cyclic carbonate crown ether ester.

4. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized by, 7. The cyclic carbonate crown ether ester of claim 1 for use in the synthesis of metal complex catalysts.

5. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized by, ​ 6. The method for preparing a cyclic carbonate crown ether ester according to claim 2, characterized by, ​ ​

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