Method for preparing polycarbonate polyol by means of organocatalyzed irreversible polycondensation

Abstract

The present invention relates to the technical field of polymer synthesis and depolymerization. Disclosed is a method for preparing a polycarbonate polyol by mean of organocatalyzed irreversible polycondensation. The method comprises the following step: preparing a diol substrate and diphenyl carbonate into a polycarbonate polyol under the action of an organic catalyst by means of polycondensation of a carbonic ester. In the present invention, a polycarbonate polyol having a high added value can be efficiently synthesized by means of the catalytic system. Compared with catalysis by using inorganic matters and metal organic matters in the prior art, the present invention has the characteristics of a high selectivity, wide application, etc. The polycarbonate polyol is a material having good hydrolysis resistance, light resistance, oxidation degradation resistance and heat resistance, can be used for preparing elastomers, paints, coatings or adhesives, has a high strength, good weather resistance, chemical stability, etc., and has a great commercial application potential in the fields of microelectronics industry, chip packaging, buildings, medical treatment, etc.

Description

Preparation method of polycarbonate polyol by organic catalytic non-reversible polycondensation TECHNICAL FIELD

[0001] The present application relates to the field of polymer synthesis and depolymerization, in particular to a preparation method of polycarbonate polyol by organic catalytic non-reversible polycondensation. BACKGROUND

[0002] Catalytic polycondensation of polycarbonate polyols is widely used in the preparation of polyurethane materials, and is an important synthesis method. Polycarbonate polyols have excellent hydrolysis resistance, light resistance, oxidation resistance and heat resistance, and can be used to prepare elastomers, paints, coatings or adhesives, and have been widely used in microelectronics, chip packaging, construction, medical and other fields. The traditional synthesis method of polycarbonate polyol requires the use of toxic metal organic solvents, which has caused certain impact on the environment. Therefore, the research on catalytic polycondensation of polycarbonate polyols has attracted widespread attention.

[0003] At present, some important achievements have been made in the research on catalytic polycondensation of polycarbonate polyols. First of all, the research on catalyst is the key. Researchers have found that different types of catalysts have different catalytic effects on the synthesis of polycarbonate polyols. Commonly used catalysts include organic metal compounds, ionic liquids and biological catalysts [Dazhong Fertilizer. 2022, 45, 128-132]. Second, the optimization of reaction conditions is an important factor to improve the synthesis efficiency and product quality. Researchers have realized the high selectivity and high yield synthesis of polycarbonate polyols by adjusting the reaction temperature, time, catalyst dosage and other conditions. In addition, some novel catalyst design and reaction mechanism research also provide new ideas and methods for the catalytic polycondensation of polycarbonate polyols.

[0004] However, there are still some challenges and problems in the catalytic polycondensation of polycarbonate polyols at present. The key to the synthesis of polycarbonate polyols is the selection of catalysts, among which organic titanium compounds are the most studied catalysts, such as tetrabutyl titanate (Ti(OC4H9)4) [Polymer Materials Science and Engineering, 2010, 26, 12-15], titanium isopropyl titanate (Ti(OC3H7)4) and titanium acetylacetone (Ti(acac)4) [Polymer Materials Science and Engineering. 2011, 27, 8-10] have been reported, but due to the residual metal catalyst, it cannot be used in high value-added fields, including microelectronics industry, chip packaging, construction, medical and other fields, therefore, the development of new organic catalysts is still the focus of current research. First of all, the stability and life of the catalyst are the key to its application, some catalysts are easy to deactivate during long-term use, and need to be further improved and optimized. How to improve the selectivity and yield of the reaction is also one of the focuses of current research. TECHNICAL PROBLEM

[0005] In view of the problems existing in the prior art of the preparation method of polycarbonate polyols by organic catalysis and non-reversible condensation polymerization, the present application is proposed.

[0006] Therefore, the problem to be solved by the present application is how to provide a preparation method of polycarbonate polyols by organic catalysis and non-reversible condensation polymerization. Solution

[0007] To solve the above technical problems, the present application provides the following technical solutions: a preparation method of polycarbonate polyols by organic catalysis and non-reversible condensation polymerization, comprising the following steps,

[0008] The diol substrate is subjected to carbonate condensation polymerization with diphenyl carbonate under the action of an organic catalyst to generate polycarbonate polyols, and the molecular formula of the polycarbonate polyols is shown in Formula 1:

[0009] Formula 1;

[0010] In Formula 1, R is a functional group, and the diol substrate contains R.

[0011] As a preferred scheme of the preparation method of polycarbonate polyols by organic catalysis and non-reversible condensation polymerization, wherein: the diol substrate comprises,

[0012] Formula 2

[0013] Formula 3

[0014] Formula 4

[0015] Formula 5

[0016] Formula 6

[0017] Formula 7

[0018] Formula 8

[0019] Formula 9

[0020] Formula 10

[0021] Formula 11

[0022] Formula 12

[0023] Formula 13

[0024] Formula 14

[0025] Formula 15

[0026] Formula 16

[0027] Formula 17.

[0028] As a preferred scheme of the preparation method of the organic catalytic irreversible polycondensation polycarbonate polyol according to the application, wherein: the organic catalyst is one or any combination of methyl sulfonic acid, p-toluene sulfonic acid, 3-aminobenzenesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid, amidine, guanidine or imidazole.

[0029] As a preferred scheme of the preparation method of the organic catalytic irreversible polycondensation polycarbonate polyol according to the application, wherein: the carbonate is diphenyl carbonate.

[0030] As a preferred scheme of the preparation method of the organic catalytic irreversible polycondensation polycarbonate polyol according to the application, wherein: the molar ratio of the diol substrate, carbonate and organic catalyst is 1:0.9-0.1:0.0001-30.

[0031] As a preferred scheme of the preparation method of the organic catalytic irreversible polycondensation polycarbonate polyol according to the application, wherein: the reaction temperature is 40-200℃, and the reaction time is 2-8 hours.

[0032] The application has the beneficial effect that: the above-mentioned catalytic system can efficiently synthesize polycarbonate polyol with high added value, compared with the inorganic and metal organic catalysis in the prior art, it has high selectivity and wide application, etc. Polycarbonate polyol is a material with good hydrolysis resistance, light resistance, oxidation resistance and heat resistance, which can be used to prepare elastomers, paints, coatings or adhesives, has high strength, good weather resistance and chemical stability, etc. It has great commercial application potential in the fields of microelectronics industry, chip packaging, construction, medical treatment, etc. BRIEF DESCRIPTION OF DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort based on these drawings.

[0034] Figure 1 is a hydrogen spectrum of the carbonate product in Example 1.

[0035] Figure 2 is a hydrogen spectrum of the carbonate product in Example 2.

[0036] Figure 3 is a hydrogen spectrum of the carbonate product in Example 3.

[0037] Figure 4 is a hydrogen spectrum of the carbonate product in Example 4.

[0038] Figure 5 is a hydrogen spectrum of the carbonate product in Example 5.

[0039] Figure 6 is a hydrogen spectrum of the carbonate product in Example 6.

[0040] Figure 7 is a hydrogen spectrum of the carbonate product in Example 7.

[0041] Figure 8 is a hydrogen spectrum of the carbonate product in Example 8. Best Mode for Carrying Out the Invention

[0042] In order to make the above objectives, features and advantages of the present application more apparent, the specific embodiments of the present application will be described in detail below with reference to the accompanying drawings.

[0043] In the following description, a lot of specific details are set forth in order to provide a thorough understanding of the present application, however, the present application can be practiced in other different manners than those described herein, and those skilled in the art can make similar generalization without departing from the spirit of the present application, therefore, the present application is not limited to the specific embodiments disclosed below.

[0044] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the present application. The "in one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is the embodiment alone or alternatively mutually exclusive with other embodiments. Embodiments

[0045] Referring to Figure 1, the first embodiment of the present application provides a preparation method of organic catalytic non-reversible polycondensation polycarbonate polyol, the preparation method of organic catalytic non-reversible polycondensation polycarbonate polyol comprises the following steps,

[0046] The diol substrate is reacted with diphenyl carbonate in the presence of an organic catalyst to produce polycarbonate polyols by carbonate polycondensation, wherein the carbonate is diphenyl carbonate, the reaction temperature is 40-200 DEG C, and the reaction time is 2-8 hours. The polycarbonate polyols have a molecular formula as shown in Formula 1:

[0047] Formula 1

[0048] In Formula 1, R is a functional group, and the diol substrate contains R.

[0049] The diol substrate includes,

[0050] Formula 2

[0051] Formula 3

[0052] Formula 4

[0053] Formula 5

[0054] Formula 6

[0055] Formula 7

[0056] Formula 8

[0057] Formula 9

[0058] Formula 10

[0059] Formula 11

[0060] Formula 12

[0061] Formula 13

[0062] Formula 14

[0063] Formula 15

[0064] Formula 16

[0065] Formula 17.

[0066] Further, the organic catalyst is one or any combination of methyl sulfonic acid, p-toluene sulfonic acid, 3-amino benzene sulfonic acid, sulfamic acid, trifluoromethanesulfonic acid, amidine, guanidine or imidazole.

[0067] Preferably, the molar ratio of the diol substrate, carbonate and organic catalyst is 1:0.9-0.1:0.0001-30.

[0068] The present application includes the following advantages:

[0069] (1) The present application can efficiently synthesize polycarbonate polyols with high added value, which has high selectivity and wide application compared to the prior art using inorganic and metal organic catalysts. Polycarbonate polyols are a material with good hydrolysis resistance, light resistance, oxidation resistance and heat resistance, which can be used to prepare elastomers, paints, coatings or adhesives, and has high strength, good weather resistance and chemical stability, etc., and has great potential for commercial application in the fields of microelectronics industry, chip packaging, construction, medical treatment, etc.

[0070] (2) The preparation method of the present application is used to prepare polycarbonate polyols, and the catalyst has no metal residue, which is green and environmentally friendly compared to known technologies, and the obtained polycarbonate polyols can be used in the medical field.

[0071] (3) The diol, carbonate and catalyst used in the present application are easy to obtain and widely available, and do not need to use solvents, which is conducive to reducing production cost and has obvious economic advantage.

[0072] (4) The by-product phenol in the present application can be reused, which is conducive to reducing production cost and has significant economic advantage.

[0073] In summary, the present application has obvious advantages of high efficiency, easy preparation, green and environmentally friendly compared to other existing catalytic systems. Embodiment of the present application

[0074] Example 2

[0075] Referring to FIG. 1, this example provides a method for the preparation of organocatalytic non-reversible polycondensation of polycarbonate polyols, specifically: To a reaction flask was added methanesulfonic acid (20 µl, 0.1 mmol, 0.01 equiv), 1,4-butanediol (0.90 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv). The reaction was placed in a heating mantle at 140 °C for 4 hours. The resulting product was an orange red clear liquid, the product was purified by distillation under reduced pressure with a yield of 85%. The hydrogen spectrum of the product is shown in FIG. 1, (NMR hydrogen spectrum, 400Hz, CDCl3). The spectrum data is:

[0076] 1H NMR (400 MHz, Chloroform-d) δ 4.16 (s, 1H), 1.77 (s, 1H).

[0077] Example 3

[0078] Referring to FIG. 2, this example provides a method for the preparation of organocatalytic non-reversible polycondensation of polycarbonate polyols, specifically: To a reaction flask was added methanesulfonic acid (19.4 µl, 0.1 mmol, 0.01 equiv), 1,5-pentanediol (1.0 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv). The reaction was placed in a heating mantle at 140 °C for 4 hours. The resulting product was an orange red clear liquid, the product was purified by distillation under reduced pressure with a yield of 81%. The hydrogen spectrum of the product is shown in FIG. 2, (NMR hydrogen spectrum, 400Hz, CDCl3). The spectrum data is:

[0079] 1H NMR (400 MHz, Chloroform-d) δ 4.13 (s, 1H), 1.71 (s, 1H), 1.47 (s, 1H).

[0080] Example 4

[0081] Referring to FIG. 3, this example provides a method for the preparation of an organocatalytic non-reversible polycondensation to polycarbonate polyols, specifically: to a reaction flask was added methanesulfonic acid (19 μΐ, 0.1 mmol, 0.01 equiv), 1,6-hexanediol (1.18 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv). The reaction was placed in a heating block at 140 °C for 4 hours. The resulting product was an orange red clear liquid, the product was purified by distillation under reduced pressure with a yield of 92%. The hydrogen spectrum of the product is shown in FIG. 3, (proton nuclear magnetic resonance, 400 Hz, CDC13). The spectral data is:

[0082] 1H NMR (400 MHz, Chloroform-d) δ 4.12 (s, 1H), 1.68 (s, 1H), 1.41 (s, 1H).

[0083] Example 5

[0084] Referring to FIG. 4, this example provides a method for the preparation of an organocatalytic non-reversible polycondensation to polycarbonate polyols, specifically: to a reaction flask was added methanesulfonic acid (18.5 μΐ, 0.1 mmol, 0.01 equiv), 1,7-heptanediol (1.32 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv). The reaction was placed in a heating block at 140 °C for 4 hours. The resulting product was an orange red clear liquid, the product was purified by distillation under reduced pressure with a yield of 94%. The hydrogen spectrum of the product is shown in FIG. 4, (proton nuclear magnetic resonance, 400 Hz, CDC13). The spectral data is:

[0085] 1H NMR (400 MHz, Chloroform-d) δ 4.11 (s, 1H), 1.66 (s, 1H), 1.37 (s, 2H).

[0086] Example 6

[0087] Referring to FIG. 5, this embodiment provides a method for preparing polycarbonate polyols via organocatalytic non-reversible polycondensation, specifically: adding methanesulfonic acid (17.9 μΐ, 0.1 mmol, 0.01 equiv), 1,8-octanediol (1.46 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv) into a reaction bottle. The reaction was carried out in a heating oven at 140 °C for 4 hours. The obtained product was an orange-red clear liquid, and the product was purified by distillation under reduced pressure with a yield of 95%. The hydrogen spectrum of the product is shown in FIG. 5 (400Hz, CDC13). The spectrum data is:

[0088] 1H NMR (400 MHz, Chloroform-d) δ 4.10 (s, 1H), 1.65 (s, 1H), 1.32 (s, 2H).

[0089] Example 7

[0090] Referring to FIG. 6, this embodiment provides a method for preparing polycarbonate polyols via organocatalytic non-reversible polycondensation, specifically: adding methanesulfonic acid (17.2 μΐ, 0.1 mmol, 0.01 equiv), 1,9-nonanediol (1.60 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv) into a reaction bottle. The reaction was carried out in a heating oven at 140 °C for 4 hours. The obtained product was an orange-red clear liquid, and the product was purified by distillation under reduced pressure with a yield of 89%. The hydrogen spectrum of the product is shown in FIG. 6 (400Hz, CDC13). The spectrum data is:

[0091] 1H NMR (400 MHz, Chloroform-d) δ 4.11 (s, 1H), 1.66 (s, 1H), 1.30 (s, 3H).

[0092] Example 8

[0093] Referring to FIG. 7, this example provides a method for the preparation of an organocatalytic non-reversible polycondensation to make polycarbonate polyols, specifically: To a reaction flask was added methanesulfonic acid (16.6 µl, 0.1 mmol, 0.01 equiv), 1,10-decanediol (1.74 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv). The reaction was placed in a heating block at 140 °C for 4 hours. The resulting product was an orange red clear liquid, the product was purified by distillation under reduced pressure with a yield of 85%. The hydrogen spectrum of the product is shown in FIG. 7, (NMR hydrogen spectrum, 400Hz, CDCl3). The spectrum data is:

[0094] 1H NMR (400 MHz, Chloroform-d) δ 4.11 (s, 1H), 1.66 (s, 1H), 1.28 (s, 3H).

[0095] Example 9

[0096] Referring to FIG. 8, this example provides a method for the preparation of an organocatalytic non-reversible polycondensation to make polycarbonate polyols, specifically: To a reaction flask was added methanesulfonic acid (16 µl, 0.1 mmol, 0.01 equiv), neopentyl glycol (1 g, 10 mmol, 1.0 equiv), 1,4-cyclohexanedimethanol (1.40 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (2.14 g, 10 mmol, 1.0 equiv). The reaction was placed in a heating block at 140 °C for 4 hours. The resulting product was an orange red clear liquid, the product was purified by distillation under reduced pressure with a yield of 81%. The hydrogen spectrum of the product is shown in FIG. 8, (NMR hydrogen spectrum, 400Hz, CDCl3). The spectrum data is:

[0097] 1H NMR (400 MHz, Chloroform-d) δ 4.12 – 3.97 (m, 14H), 3.52 (d, J = 4.9 Hz, 1H), 1.99 (s, 1H), 1.68 – 1.53 (m, 15H), 1.48 (s, 1H), 1.35 (d, J = 24.8 Hz, 12H).

[0098] Example 10

[0099] Specifically: To the reaction bottle was added methylsulfonic acid (16.6 μΐ, 0.1 mmol, 0.01 equiv), 1,10-decanediol (1.74 g, 10 mmol, 1.0 equiv), and dimethyl carbonate (1.92 g, 9 mmol, 0.9 equiv). The molecular weight was determined by GPC, and the molecular weight obtained in each reaction of dimethyl carbonate was 1300 g / mol, 1450 g / mol, 1610 g / mol. To the reaction bottle was added methylsulfonic acid (16.6 μΐ, 0.1 mmol, 0.01 equiv), 1,10-decanediol (1.74 g, 10 mmol, 1.0 equiv), and diphenyl carbonate (1.92 g, 9 mmol, 0.9 equiv). The molecular weight was determined by GPC, and the molecular weight obtained in each reaction of diphenyl carbonate was 2000 g / mol, 1980 g / mol, 2050 g / mol. The reproducibility of the molecular weight obtained in each reaction of dimethyl carbonate was poor, and the reproducibility of the reaction of diphenyl carbonate was good.

[0100] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present application, and they should be covered in the scope of the claims of the present application.

Claims

A method for the production of polycarbonate polyols by organocatalytic non-reversible polycondensation, characterized in that comprising the steps of, reacting a diol substrate with diphenyl carbonate in the presence of an organic catalyst to form a polycarbonate polyol by carbonate polycondensation, the polycarbonate polyol having a molecular formula as shown in Formula 1: Formula 1 In Formula 1, R is a functional group, and the diol substrate contains R. The method for producing a polycarbonate polyol by organocatalytic non-reversible polycondensation according to claim 1, characterized in that: The diol substrate includes, Formula 2 Formula 3 Formula 4 Formula 5 Formula 6 Formula 7 Formula 8 Formula 9 Formula 10 Formula 11 Formula 12 Formula 13 Formula 14 Formula 15 Formula 16 Formula 17. Process for the preparation of a polycarbonate polyol organocatalytically non-reversibly polycondensed as claimed in claim 1 or 2, characterized in that: The organic catalyst is one or any combination of methyl sulfonic acid, p-toluene sulfonic acid, 3-aminobenzenesulfonic acid, sulfamic acid, trifluoromethanesulfonic acid, amidine, guanidine, or imidazole. The method for producing a polycarbonate polyol by organocatalytic non-reversible polycondensation according to claim 3, characterized in that The carbonate is diphenyl carbonate. The method for producing a polycarbonate polyol by organocatalytic non-reversible polycondensation according to claim 4, characterized in that The molar ratio of the diol substrate, the carbonate, and the organic catalyst is 1:0.9-0.1:0.0001-30. The method for producing a polycarbonate polyol by organocatalytic non-reversible polycondensation according to claim 5, characterized in that: The reaction temperature is 40-200℃, and the reaction time is 2-8 hours.

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