A method for preparing high heat resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride

Abstract

The application relates to the technical field of high polymer synthesis, and discloses a method for preparing high-heat-resistant aliphatic polycarbonate diol by copolymerization of naphthalene anhydride, which comprises the following steps: under the action of a nonmetallic catalyst, polypropylene oxide, naphthalene anhydride and a chain transfer agent are subjected to a polymerization reaction by inputting carbon dioxide gas to obtain polycarbonate diol; the nonmetallic catalyst comprises triethyl boron and bis-(triphenyl phosphine) ammonium chloride; and the molar ratio of polypropylene oxide and naphthalene anhydride is 260:1-10. Through the technical scheme, the problem of low heat resistance of polycarbonate diol in the related art is solved.

Description

Technical Field

[0001] This invention relates to the field of polymer synthesis technology, specifically to a method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride. Background Technology

[0002] Carbon dioxide-based polycarbonate diols (PPCDL) are polycarbonate diols with molecular weights ranging from 1000 to 3000, produced by polymerizing carbon dioxide and propylene oxide under the action of a catalyst. As an important class of polymers, the development of polycarbonate diols is closely linked to many factors. Traditional polyester diols and polyether diols have revealed some limitations in applications. While polyester diols possess good mechanical properties, their hydrolysis resistance is poor, and they are prone to degradation in humid environments, leading to material performance deterioration. Polyether diols have improved hydrolysis resistance, but their oxidation resistance and weather resistance are insufficient; their performance gradually declines under light or high-temperature aerobic environments. PPCDL contains carbonate groups in its molecular backbone, which allows it to retain some of the excellent properties of polyester diols and polyether diols while possessing better hydrolysis resistance and chemical stability. Furthermore, because its synthesis raw materials include carbon dioxide, it significantly reduces dependence on traditional petroleum-based raw materials, aligning with the principles of green chemistry and sustainable development.

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

[0004] This invention proposes a method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene 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:

[0006] This invention proposes a method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride, comprising the following steps: propylene oxide, naphthalene anhydride, and a chain transfer agent are subjected to a polymerization reaction by introducing carbon dioxide gas under the action of a non-metallic catalyst to obtain polycarbonate diols; the non-metallic catalyst includes triethylboron and bis-(triphenylphosphine)ammonium chloride; the molar ratio of propylene oxide to naphthalene anhydride is 260:1~10.

[0007] As a further technical solution, the molar ratio of propylene oxide to naphthalene anhydride is 260:5~7.

[0008] In this invention, by limiting the molar ratio of propylene oxide to naphthalene anhydride to 260:5~7, the yield of aliphatic polycarbonate diol is improved.

[0009] As a further technical solution, the molar ratio of the triethylboron and the bis-(triphenylphosphine)ammonium chloride is 5~12:1.

[0010] As a further technical solution, the triethylboron is a 1 mol / L triethylboron tetrahydrofuran solution.

[0011] As a further technical solution, the chain transfer agent is 1,4-butanediol.

[0012] As a further technical solution, the pressure of the carbon dioxide is 1.0~1.2MPa.

[0013] As a further technical solution, the polymerization reaction temperature is 40~45℃ and the polymerization reaction time is 10~20h.

[0014] As a further technical solution, the molar ratio of propylene oxide, chain transfer agent, triethylboron, and bis-(triphenylphosphine)ammonium chloride is 2600:40~60:5~12:1.

[0015] As a further technical solution, nitrogen gas is introduced to replace the air before the carbon dioxide gas is introduced.

[0016] As a further technical solution, the post-treatment of the polycarbonate diol includes washing with water and drying.

[0017] The working principle and beneficial effects of this invention are as follows:

[0018] In this invention, using carbon dioxide and propylene oxide as raw materials, and under the action of a non-metallic catalyst composed of triethylboron and bis-(triphenylphosphine)ammonium chloride, naphthalene anhydride is added, and the molar ratio of propylene oxide to naphthalene anhydride is limited to 260:1~10, a polycarbonate diol is prepared, which has high heat resistance and solves the problem of low heat resistance of polycarbonate diol. Attached Figure Description

[0019] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0020] Figure 1 The NMR spectrum of the polycarbonate diol in Example 2;

[0021] Figure 2 The DSC spectra of polycarbonate diols in Example 4 and Comparative Example 1 are shown. Detailed Implementation

[0022] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0023] Example 1

[0024] 75.4 g of propylene oxide, 2.71 g of 1,4-butanediol, 1 g of naphthalene anhydride, 2.5 mL of triethylboron (1 mol / L triethylboron tetrahydrofuran solution), and 0.287 g of bis-(triphenylphosphine)ammonium chloride were placed in a polymerization reactor under N2 conditions. The reactor temperature was set to 40 °C, and the carbon dioxide pressure was 1.0 MPa. After reacting for 20 h, the product was washed with water and dried to obtain polycarbonate diol (molecular weight 2100).

[0025] Example 2

[0026] A method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride includes the following steps:

[0027] 75.4 g of propylene oxide, 2.3 g of 1,4-butanediol, 1 g of naphthalene anhydride, 4 mL of triethylboron (1 mol / L triethylboron tetrahydrofuran solution), and 0.287 g of bis-(triphenylphosphine)ammonium chloride were placed in a polymerization reactor under N2 conditions. The reactor temperature was set to 40 °C, and the carbon dioxide pressure was 1.0 MPa. After reacting for 20 h, the product was washed with water and dried to obtain polycarbonate diol (molecular weight 2112).

[0028] The NMR spectrum of the polycarbonate diol obtained in this embodiment is as follows: Figure 1 As shown.

[0029] Example 3

[0030] A method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride includes the following steps:

[0031] 75.4 g of propylene oxide, 1.81 g of 1,4-butanediol, 1 g of naphthalene anhydride, 6 mL of triethylboron (1 mol / L triethylboron tetrahydrofuran solution), and 0.287 g of bis-(triphenylphosphine)ammonium chloride were placed in a polymerization reactor under N2 conditions. The reactor temperature was set to 45 °C, and the carbon dioxide pressure was 1.2 MPa. After reacting for 10 h, the product was washed with water and dried to obtain polycarbonate diol (molecular weight 2131).

[0032] Example 4

[0033] The only difference between this embodiment and Example 2 is that the amount of naphthalene anhydride added is 9.9g; resulting in polycarbonate diol (molecular weight 2126).

[0034] Example 5

[0035] The only difference between this embodiment and Example 2 is that the amount of naphthalene anhydride added is 5g; thus, polycarbonate diol (molecular weight 2118) is obtained.

[0036] Example 6

[0037] The only difference between this embodiment and Example 2 is that the amount of naphthalene anhydride added is 6g; thus, polycarbonate diol (molecular weight 2113) is obtained.

[0038] Example 7

[0039] The only difference between this embodiment and Example 2 is that the amount of naphthalene anhydride added is 7g; thus, polycarbonate diol (molecular weight 2120) is obtained.

[0040] Comparative Example 1

[0041] The only difference between this comparative example and Example 4 is that naphthalene anhydride was not added.

[0042] Experimental Example 1

[0043] The glass transition temperature of the polycarbonate diols prepared in Example 4 and Comparative Example 1 was tested, and the test results are as follows: Figure 2 As shown, the results are recorded in Table 1.

[0044] Table 1. Glass transition temperature test results

[0045]

[0046] Compared with Comparative Example 1, the glass transition temperature of the polycarbonate diol prepared in Example 4 was higher than that of Comparative Example 1, indicating that adding naphthalene anhydride to the preparation of polycarbonate diol can improve the heat resistance of polycarbonate diol.

[0047] Experiment Example 2

[0048] The conversion rates of propylene oxide in Examples 1-7 are recorded in Table 2.

[0049] Table 2 Results of propylene oxide conversion test

[0050]

[0051] As shown in Table 2, the polycarbonate diol propylene oxide prepared in Examples 1-7 has a high conversion rate, thereby improving the efficiency in industrial production and showing broad application prospects.

[0052] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride, characterized in that, Includes the following steps: Polycarbonate diol is obtained by polymerizing propylene oxide, naphthalene anhydride, and a chain transfer agent under the action of a non-metallic catalyst and passing carbon dioxide gas through the catalyst. The non-metallic catalyst includes triethylboron and bis-(triphenylphosphine)ammonium chloride. The molar ratio of propylene oxide to naphthalene anhydride is 260:5~7. The molar ratio of propylene oxide, chain transfer agent, triethylboron, and bis-(triphenylphosphine)ammonium chloride is 2600:40~60:5~12:

1. The molar ratio of the triethylboron to the bis-(triphenylphosphine)ammonium chloride is 5~12:

1.

2. The method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride according to claim 1, characterized in that, The chain transfer agent is 1,4-butanediol.

3. The method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride according to claim 1, characterized in that, The pressure of the carbon dioxide is 1.0~1.2 MPa.

4. The method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride according to claim 1, characterized in that, The polymerization reaction is carried out at a temperature of 40-45°C for 10-20 hours.

5. The method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride according to claim 1, characterized in that, Before introducing carbon dioxide gas, nitrogen gas is first introduced to replace the air.

6. The method for preparing high heat-resistant aliphatic polycarbonate diols by copolymerization of naphthalene anhydride according to claim 1, characterized in that, The post-treatment of the polycarbonate diol includes washing and drying.

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