Method for preparing high-heat-resistance aliphatic polycarbonate diol through naphthalene anhydride copolymerization

Abstract

The invention relates to the technical field of polymer synthesis, and provides a method for preparing high-heat-resistance aliphatic polycarbonate diol through anhydride naphthalene copolymerization, which comprises the following steps: under the action of a non-metal catalyst, introducing carbon dioxide gas to carry out polymerization reaction to obtain polycarbonate diol, the non-metal catalyst comprises triethyl boron and bis-(triphenylphosphine) ammonium chloride; the molar ratio of the epoxypropane to the anhydride naphthalene is 260: (1-10). According to the technical scheme, the problem of low heat resistance of polycarbonate diol in related technologies is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer synthesis, and specifically, to a method for preparing high heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride. Background Art

[0002] Carbon dioxide-based polycarbonate diol (abbreviated as PPCDL) is a polycarbonate diol with a molecular weight of 1000 - 3000, which is polymerized from carbon dioxide and propylene oxide under the action of a catalyst. As an important class of polymers, the development background of polycarbonate diol is closely related to many factors. Traditional polyester diols and polyether diols have shown some limitations in applications. Although polyester diols have good mechanical properties, they have poor hydrolysis resistance and are prone to degradation in a humid environment, resulting in deterioration of material properties. The hydrolysis resistance of polyether diols has been improved, however, their oxidation resistance and weather resistance are insufficient, and their properties will gradually decline under light or high-temperature aerobic environments. The molecular main chain of PPCDL contains carbonate groups, which enables it to have better hydrolysis resistance and chemical stability while retaining some excellent properties of polyester diols and polyether diols. At the same time, since its synthesis raw materials include carbon dioxide, it greatly reduces the dependence on traditional petroleum-based raw materials, which is in line with the concepts of green chemistry and sustainable development.

[0003] However, due to the lack of rigid groups in polycarbonate diol and its low glass transition temperature, the polyurethane materials made from polycarbonate diol are prone to softening or deformation at high temperatures. Therefore, improving the heat resistance of polycarbonate diol is a problem that needs to be solved currently. Summary of the Invention

[0004] The present invention provides a method for preparing high heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride, which solves the problem of low heat resistance of polycarbonate in related technologies.

[0005] The technical solution of the present invention is as follows: The present invention provides a method for preparing high heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride, comprising the following steps: polymerizing propylene oxide, naphthalic anhydride, and a chain transfer agent under the action of a non-metallic catalyst by introducing carbon dioxide gas to obtain polycarbonate diol; the non-metallic catalyst includes triethylboron and bis-(triphenylphosphonium) ammonium chloride; the molar ratio of propylene oxide to naphthalic anhydride is 260:1 - 10.

[0006] As a further technical solution, the molar ratio of propylene oxide to naphthalic anhydride is 260:5 - 7.

[0007] In the present invention, by limiting the molar ratio of propylene oxide to naphthalic anhydride to 260:5 - 7, the yield of aliphatic polycarbonate diol is increased.

[0008] As a further technical solution, the molar ratio of the triethylborane and the bis-(triphenylphosphonium) ammonium chloride is 5 to 12:1.

[0009] As a further technical solution, the triethylborane is a 1 mol / L triethylborane tetrahydrofuran solution.

[0010] As a further technical solution, the chain transfer agent is 1,4-butanediol.

[0011] As a further technical solution, the pressure of the carbon dioxide is 1.0 to 1.2 MPa.

[0012] As a further technical solution, the temperature of the polymerization reaction is 40 to 45 °C, and the time of the polymerization reaction is 10 to 20 h.

[0013] As a further technical solution, the molar ratio of the propylene oxide, the chain transfer agent, the triethylborane, and the bis-(triphenylphosphonium) ammonium chloride is 2600:40 to 60:5 to 12:1.

[0014] As a further technical solution, before the carbon dioxide gas is introduced, nitrogen is first introduced to displace the air.

[0015] As a further technical solution, the post-treatment of the polycarbonate diol includes washing with water and drying.

[0016] The working principle and beneficial effects of the present invention are as follows: In the present invention, using carbon dioxide and propylene oxide as raw materials, under the action of a non-metallic catalyst composed of triethylborane and bis-(triphenylphosphonium) ammonium chloride, by adding naphthalic anhydride and limiting the molar ratio of propylene oxide to naphthalic anhydride to 260:1 to 10, the prepared polycarbonate diol has high heat resistance and solves the problem of low heat resistance of polycarbonate diol. Description of the Drawings

[0017] The present invention will be further described in detail below with reference to the drawings and specific embodiments.

[0018] Figure 1 It is the nuclear magnetic spectrum of the polycarbonate diol in Example 2; Figure 2 It is the DSC spectra of the polycarbonate diols in Example 4 and Comparative Example 1. Specific Embodiments

[0019] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0020] Example 1 Put 75.4 g of propylene oxide, 2.71 g of 1,4-butanediol, 1 g of naphthalic anhydride, 2.5 mL of triethylboron (1 mol / L triethylboron tetrahydrofuran solution), and 0.287 g of bis-(triphenylphosphonium) ammonium chloride into a polymerization kettle under N2 conditions. Set the temperature of the polymerization kettle to 40 °C, introduce carbon dioxide with a pressure of 1.0 MPa, and after reacting for 20 h, polycarbonate diol (with a molecular weight of 2100) is obtained after washing with water and drying.

[0021] Example 2 A method for copolymerizing naphthalic anhydride to prepare a highly heat-resistant aliphatic polycarbonate diol, comprising the following steps: Put 75.4 g of propylene oxide, 2.3 g of 1,4-butanediol, 1 g of naphthalic anhydride, 4 mL of triethylboron (1 mol / L triethylboron tetrahydrofuran solution), and 0.287 g of bis-(triphenylphosphonium) ammonium chloride into a polymerization kettle under N2 conditions. Set the temperature of the polymerization kettle to 40 °C, introduce carbon dioxide with a pressure of 1.0 MPa, and after reacting for 20 h, polycarbonate diol (with a molecular weight of 2112) is obtained after washing with water and drying.

[0022] The nuclear magnetic resonance spectrum of the polycarbonate diol prepared in this example is as Figure 1 shown.

[0023] Example 3 A method for copolymerizing naphthalic anhydride to prepare a highly heat-resistant aliphatic polycarbonate diol, comprising the following steps: Put 75.4 g of propylene oxide, 1.81 g of 1,4-butanediol, 1 g of naphthalic anhydride, 6 mL of triethylboron (1 mol / L triethylboron tetrahydrofuran solution), and 0.287 g of bis-(triphenylphosphonium) ammonium chloride into a polymerization kettle under N2 conditions. Set the temperature of the polymerization kettle to 45 °C, introduce carbon dioxide with a pressure of 1.2 MPa, and after reacting for 10 h, polycarbonate diol (with a molecular weight of 2131) is obtained after washing with water and drying.

[0024] Example 4 Compared with Example 2, the difference in this example is only that the addition amount of naphthalic anhydride is 9.9 g; polycarbonate diol (with a molecular weight of 2126) is obtained.

[0025] Example 5 This example is only different from Example 2 in that the addition amount of naphthalic anhydride is 5 g; polycarbonate diol (molecular weight is 2118) is obtained.

[0026] Example 6 This example is only different from Example 2 in that the addition amount of naphthalic anhydride is 6 g; polycarbonate diol (molecular weight is 2113) is obtained.

[0027] Example 7 This example is only different from Example 2 in that the addition amount of naphthalic anhydride is 7 g; polycarbonate diol (molecular weight is 2120) is obtained.

[0028] Comparative Example 1 This comparative example is only different from Example 4 in that naphthalic anhydride is not added.

[0029] Experimental Example 1 The glass transition temperature of the polycarbonate diol prepared in Example 4 and Comparative Example 1 was tested, and the test results are as Figure 2 shown, and the shown results are recorded in Table 1.

[0030] Table 1 Glass Transition Temperature Test Results

[0031] Compared with Comparative Example 1, the glass transition temperature of the polycarbonate diol prepared in Example 4 is higher than that of Comparative Example 1, indicating that adding naphthalic anhydride in the preparation of polycarbonate diol can improve the heat resistance of polycarbonate diol.

[0032] Experimental Example 2 The conversion rates of propylene oxide in Examples 1 to 7 are recorded in Table 2.

[0033] Table 2 Propylene Oxide Conversion Rate Test Results

[0034] As can be seen from Table 2, the conversion rates of propylene oxide of the polycarbonate diols prepared in Examples 1 to 7 are relatively high, thus improving the efficiency in industrial production and having a broad application prospect.

[0035] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a high heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride, characterized in that, It includes the following steps: Propylene oxide, naphthalic anhydride, and a chain transfer agent are polymerized with carbon dioxide gas under the action of a non-metallic catalyst to obtain polycarbonate diol; the non-metallic catalyst includes triethyl borane and bis-(triphenylphosphonium) chloride; the molar ratio of propylene oxide to naphthalic anhydride is 260:1 to 10.

2. The method for preparing a highly heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride according to claim 1, characterized in that The molar ratio of propylene oxide to naphthalic anhydride is 260:5 to 7.

3. The method for preparing a highly heat-resistant aliphatic polycarbonate diol by copolymerizing naphthalic anhydride according to claim 1, characterized in that, The molar ratio of triethyl borane to bis-(triphenylphosphonium) chloride is 5 to 12:

1.

4. A method for preparing a highly heat-resistant aliphatic polycarbonate diol by copolymerizing naphthalic anhydride according to claim 1, characterized in that, The chain transfer agent is 1,4-butanediol.

5. A method for preparing a highly heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride according to claim 1, characterized in that, The pressure of carbon dioxide is 1.0 to 1.2 MPa.

6. A method for preparing a high heat-resistant aliphatic polycarbonate diol by copolymerizing naphthalic anhydride according to claim 1, characterized in that, The temperature of the polymerization reaction is 40 to 45 °C, and the time of the polymerization reaction is 10 to 20 h.

7. A method for preparing a highly heat-resistant aliphatic polycarbonate diol by copolymerizing naphthalic anhydride according to claim 1, characterized in that, The molar ratio of propylene oxide, chain transfer agent, triethyl borane, and bis-(triphenylphosphonium) chloride is 2600:40 to 60:5 to 12:

1.

8. A method for preparing a highly heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride according to claim 1, characterized in that, Before introducing the carbon dioxide gas, nitrogen is introduced to displace the air.

9. A method for preparing a high heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalic anhydride according to claim 1, characterized in that, The post-treatment of the polycarbonate diol includes washing with water and drying.

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