Single-ended vinyl hyperbranched polyether macromonomer and preparation method thereof

Abstract

The invention provides a preparation method of a single-ended vinyl hyperbranched polyether macromonomer, which can be applied to the technical field of hyperbranched polyether synthesis. The method comprises the following steps: carrying out ring-opening polymerization reaction on any one of an epoxy group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer or a carboxyl group-containing vinyl monomer and glycidol in the presence of a catalyst and a polymerization inhibitor to form the single-ended vinyl hyperbranched polyether macromonomer with an amino group, ester group or ether group structure. The invention also provides a single-ended vinyl hyperbranched polyether macromonomer product.

Description

Technical Field

[0001] The present disclosure relates to the field of hyperbranched polyether synthesis, and more specifically, to a single-end vinyl hyperbranched polyether macromonomer and a preparation method thereof. Background Art

[0002] Compared to traditional polymers, hyperbranched polymers possess unique molecular structures, including controllable relative molecular mass, highly symmetrical structural units, and numerous terminal groups. These structures offer advantages such as excellent solubility, low melt (or solution) viscosity, and ease of processing and molding. Furthermore, hyperbranched polymers can be synthesized in a single step and have broad application prospects in biomedical fields such as coatings, nanocatalysts, polymer processing, surface modification, and sustained-release drug formulations. Because hyperbranched polymers contain a large number of easily modifiable terminal groups, such as hydroxyl, carboxyl, and epoxy groups, they can also be modified to produce polymeric additives tailored to their performance.

[0003] Hyperbranched polymers are commonly modified in two ways: first, synthesizing the polymer and then modifying its end groups; second, adding a modifier later in the synthesis. End group modification creates new functional groups within the molecular structure, expanding the range of hyperbranched polymers and enabling their potential applications in diverse fields. Summary of the Invention

[0004] In view of the above problems, the present disclosure provides a single-end vinyl hyperbranched polyether macromonomer and its preparation method. The monomer can be further modified through free radical polymerization to form a polymer additive that meets various needs.

[0005] According to the first aspect of the present disclosure, a method for preparing a single-end vinyl hyperbranched polyether macromonomer is provided, comprising: carrying out a ring-opening polymerization reaction with glycidol in the presence of a catalyst and a polymerization inhibitor using any one of an epoxy group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, or a carboxyl group-containing vinyl monomer to form a single-end vinyl hyperbranched polyether macromonomer having an amino group, an ester group, or an ether group structure.

[0006] Among them, the vinyl monomer containing an amino group or an ester group is obtained by reacting glycidyl methacrylate or glycidyl acrylate with diethanolamine, diisopropanolamine, dihydroxymethylpropionic acid or dihydroxymethylbutyric acid; the vinyl monomer containing a hydroxyl group includes any one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate or allyl alcohol; the vinyl monomer containing a carboxyl group includes any one of methacrylic acid, acrylic acid, vinylphosphonic acid, p-vinylbenzoic acid or p-vinylbenzenesulfonic acid.

[0007] According to an embodiment of the present application, the polymerization inhibitor includes phenol, hydroquinone, p-methoxyphenol, diphenyl-2-nitrophenylhydrazine and a variable valence metal compound;

[0008] The variable valence metal compound comprises at least one of ferric chloride and cuprous chloride.

[0009] According to an embodiment of the present application, the catalyst includes at least one of potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, an organic tin compound, a Lewis acid, and an organic base; the organic tin compound includes stannous octoate or tin cyclohexane; the Lewis acid includes at least one of boron trifluoride, aluminum trioxide, and tin tetrachloride; and the organic base includes at least one of triethylamine, triethylenediamine, or 1,8-diazabicycloundec-7-ene.

[0010] According to an embodiment of the present application, the amount of the catalyst used is 0.2% to 5% of the total weight of other monomers.

[0011] According to an embodiment of the present application, the reaction temperature of the ring-opening polymerization reaction is 100-200°C.

[0012] According to an embodiment of the present application, the ring-opening polymerization reaction is carried out under solvent-free conditions, and can also be carried out in a polar aprotic solvent, wherein the polar aprotic solvent includes at least one of dioxane, tetrahydrofuran, dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide or N-methylpyrrolidone.

[0013] According to an embodiment of the present application, the reaction time of the ring-opening polymerization reaction is 1 to 10 hours.

[0014] According to the embodiments of the present application, it is prepared by any one of the above methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The above contents and other objects, features and advantages of the present disclosure will become more apparent through the following description of the embodiments of the present disclosure with reference to the accompanying drawings, in which:

[0016] Figure 1 This is the infrared spectrum of the single-end vinyl hyperbranched polyether macromonomer synthesized in Example 1.

[0017] Figure 2 This is the infrared spectrum of the single-end vinyl hyperbranched polyether macromonomer synthesized in Example 2.

[0018] Figure 3 This is the infrared spectrum of the single-end vinyl hyperbranched polyether macromonomer synthesized in Example 3. DETAILED DESCRIPTION

[0019] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present disclosure. In the detailed description below, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present disclosure. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present disclosure.

[0020] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The terms "comprise," "include," etc. used herein indicate the presence of the features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0021] All terms (including technical and scientific terms) used herein have the meanings commonly understood by those skilled in the art unless otherwise defined. It should be noted that the terms used herein should be interpreted as having a meaning consistent with the context of this specification and should not be interpreted in an idealized or overly rigid manner.

[0022] When expressions such as "at least one of A, B and C, etc." are used, they should generally be interpreted in accordance with the meaning of the expression commonly understood by those skilled in the art (for example, "a system having at least one of A, B and C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.).

[0023] The embodiment of the present application provides a method for preparing a single-end vinyl hyperbranched polyether macromonomer, comprising: carrying out a ring-opening polymerization reaction with glycidol in the presence of a catalyst and a polymerization inhibitor using any one of a vinyl monomer containing an amino group or an ester group, a vinyl monomer containing a hydroxyl group, or a vinyl monomer containing a carboxyl group to form a single-end vinyl hyperbranched polyether macromonomer having an amino group, an ester group, or an ether group structure.

[0024] The vinyl monomer containing an amino group or an ester group is obtained by reacting glycidyl methacrylate or glycidyl acrylate with diethanolamine, diisopropanolamine, dimethylolpropionic acid or dimethylolbutyric acid.

[0025] For example, in some embodiments, a single-end vinyl hyperbranched polyether having an amino group and an ether group structure is formed by reacting glycidyl methacrylate or glycidyl acrylate with diethanolamine and then performing a ring-opening polymerization reaction with glycidyl ether in the presence of a catalyst, and the structure thereof is shown in Formula (1). Formula (1) has a symmetrical structural unit and multiple terminal groups, and is a third-generation hyperbranched polyether single-end vinyl macromonomer.

[0026]

[0027] In the present application, R or R1 is a methyl group or a hydrogen group.

[0028] For example, in some embodiments, a single-end vinyl hyperbranched polyether macromonomer having an ester and ether structure is formed by reacting glycidyl methacrylate or glycidyl acrylate with dimethylol propionic acid, followed by a ring-opening reaction with glycidyl ether in the presence of a catalyst, and its structure is shown in Formula 2. The structural unit of Formula (2) is symmetrical and has multiple terminal groups, and is a third-generation hyperbranched polyether single-end vinyl macromonomer.

[0029]

[0030] For example, in some embodiments, a single-end vinyl hyperbranched polyether macromonomer having an amino group and an ether group structure is formed by reacting glycidyl acrylate or glycidyl methacrylate with dimethylolbutyric acid, followed by a ring-opening reaction with glycidyl ether in the presence of a catalyst, and has a structure as shown in Formula (3). The structural unit of Formula (3) is symmetrical and has multiple terminal groups, representing a third-generation hyperbranched polyether single-end vinyl macromonomer.

[0031]

[0032] The vinyl monomer containing a hydroxyl group includes any one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate or allyl alcohol.

[0033] For example, in some embodiments, a single-end vinyl hyperbranched polyether macromonomer having an amino group and an ether group structure is formed by a ring-opening reaction of hydroxyethyl acrylate, hydroxyethyl methacrylate, or hydroxypropyl methacrylate with glycidyl ether in the presence of a catalyst, and its structure is shown in Formula (4). The structural unit of Formula (4) is symmetrical and has multiple terminal groups, and it is a third-generation hyperbranched polyether single-end vinyl macromonomer.

[0034]

[0035] The carboxyl group-containing vinyl monomer includes any one of methacrylic acid, acrylic acid, vinylphosphonic acid, p-vinylbenzoic acid or p-vinylbenzenesulfonic acid.

[0036] It should be pointed out that the above only illustrates the structure of the third-generation single-end vinyl polyether macromonomer. However, according to the requirements of material synthesis, the molar ratio of propylene oxide to the initiator (such as acrylic acid, hydroxyethyl acrylate, etc.) can also be adjusted to generate first-generation, second-generation, fourth-generation and fifth-generation single-end vinyl polyether macromonomers.

[0037] For example, in some embodiments, a single-end vinyl hyperbranched polyether macromonomer is formed by ring-opening polymerization of acrylic acid or methacrylic acid with glycidyl ether in the presence of a catalyst. Its structure is shown in Formula (5). Formula (5) has symmetrical structural units and multiple terminal groups, representing a third-generation hyperbranched polyether single-end vinyl macromonomer.

[0038]

[0039] In some embodiments of the present application, the polymerization inhibitor includes phenol, hydroquinone, p-methoxyphenol, diphenyl-2-nitrophenylhydrazine and a variable valence metal compound; the variable valence metal compound includes at least one of ferric chloride and cuprous chloride.

[0040] In some embodiments of the present application, the catalyst includes at least one of potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, an organic tin compound, a Lewis acid, and an organic base; the organic tin compound includes stannous octoate or tin cyclohexane; the Lewis acid includes at least one of boron trifluoride, aluminum trioxide, and tin tetrachloride; and the organic base includes at least one of triethylamine, triethylenediamine, or 1,8-diazabicycloundec-7-ene.

[0041] In some embodiments of the present application, the amount of the catalyst is 0.2% to 5% of the total weight of the other monomers. For example, the amount of the catalyst is 0.2% of the total weight of the other monomers. The amount of the catalyst can also be 5%, or 1%, 2%, 3%, or 4% of the total weight of the other monomers.

[0042] In some embodiments of the present application, the reaction temperature of the ring-opening polymerization reaction is 100-200° C. The reaction temperature of the ring-opening polymerization reaction can be maintained at 100° C., the reaction can also be maintained at 200° C., the reaction temperature can also be maintained at 120, 150 or 180° C. The reaction temperature can also vary between 100 and 200, but not exceed this range.

[0043] In some embodiments of the present application, the ring-opening polymerization reaction can be carried out in the absence of a solvent or in a polar aprotic solvent, wherein the polar aprotic solvent includes at least one of dioxane, tetrahydrofuran, dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide, or N-methylpyrrolidone. For example, dioxane can be used alone as the solvent, or a mixed solvent of tetrahydrofuran and dimethyl sulfoxide, or a mixed solvent of dimethyl sulfoxide, diethyl sulfoxide, and dimethylformamide.

[0044] In some embodiments of the present application, the reaction time of the ring-opening polymerization reaction is 1 to 10 hours. For example, the reaction time can be 1, 5 or 10 hours.

[0045] The following will further illustrate the embodiments of the present application with reference to more detailed examples. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present application are purchased from the market.

[0046] Example 1

[0047] Operation 1.1.

[0048] The reaction materials and amounts used in operation 1.1 are shown in the following table.

[0049] substance weight Glycidyl methacrylate (GMA) 71 grams Diethanolamine 52.6 grams p-Methoxyphenol 0.037 g

[0050] Add GMA and p-methoxyphenol to the reaction flask, heat to 80°C, and add diethanolamine dropwise at this temperature over 2 hours. After the addition is complete, continue the reaction at 80°C for 1 hour.

[0051] Operation 1.2.

[0052] The reaction materials and amounts used in operation 1.2 are shown in the following table.

[0053] substance weight Product of Operation 1.1 9.92 grams Glycidol 36.96 grams Potassium methoxide 0.19 g p-Hydroxyanisole 1.5 grams

[0054] Place the product from step 1.1 and potassium methoxide in a reaction flask, heat to 150°C, add glycidol dropwise, and continue the reaction for 3 hours after the addition is complete over 5 hours. Remove the flask and store in the refrigerator.

[0055] The infrared spectrum of the single-end vinyl hyperbranched polyether macromonomer synthesized in Example 1 is as follows: Figure 1 shown.

[0056] Figure 1 The medium wave number is 3383.17 cm -1 It is a typical hydroxyl stretching vibration absorption peak, 1716.74cm -1 is the carbonyl absorption peak, 1639.51 cm -1 is the stretching vibration absorption peak of vinyl, 1115.34cm -1 It should be the typical stretching vibration absorption peak of ether group, 2976.31cm -1 The broad peaks at the bottom are the stretching vibration absorption peaks of methyl and methine. These all indicate that the synthesized substance is the target product.

[0057] Example 2

[0058] The reaction materials and amounts used in Example 2 are shown in the following table.

[0059] substance weight acrylic acid 7.3 g (0.1 mol) Glycidol 53.5 g (0.7 mol) p-Hydroxyanisole 0.2 g Triethylenediamine 0.33 g (0.5%)

[0060] Place acrylic acid and triethylenediamine in a reaction flask, heat to 150°C, add glycidol dropwise, add for 5 hours, and continue to react for 3 hours. Remove from the flask and store in a refrigerator.

[0061] The infrared spectrum of the monomer synthesized in Example 2 is as follows: Figure 2 shown.

[0062] The wave number in the figure is 3392.38cm -1 It is a typical hydroxyl stretching vibration absorption peak, 1727.87cm -1 is the carbonyl absorption peak, 1649.50 cm -1 is the stretching vibration absorption peak of vinyl, 1111.11cm -1 It should be the typical stretching vibration absorption peak of ether group, 2918.96cm -1 The group of peaks at 37° are the stretching vibration absorption peaks of methyl and methine. These all indicate that the synthesized substance is the target product.

[0063] Example 3

[0064] The reaction materials and amounts used in Example 3 are shown in the following table.

[0065]

[0066]

[0067] Add hydroxyethyl acrylate and triethylene diamine into a reaction flask, heat to 150 degrees, add glycidol dropwise, add for 5 hours, and continue to react for 3 hours. Remove and store in the refrigerator.

[0068] The infrared spectrum of the single-end vinyl polyether macromonomer synthesized in Example 3 is as follows: Figure 3 shown.

[0069] Figure 3 The medium wave number is 3382.63cm -1 It is a typical hydroxyl stretching vibration absorption peak, 1731.54cm -1 is the carbonyl absorption peak, 1650.99 cm -1 is the stretching vibration absorption peak of vinyl, 1115.23cm -1 It should be the typical stretching vibration absorption peak of ether group, 2917.47cm -1 The broad peaks at the bottom are the stretching vibration absorption peaks of methyl and methine. These all indicate that the synthesized substance is the target product.

[0070] Those skilled in the art will appreciate that the features described in the various embodiments of the present disclosure may be combined and / or coupled in various ways, even if such combinations or couplings are not explicitly described in the present disclosure. In particular, the features described in the various embodiments of the present disclosure may be combined and / or coupled in various ways without departing from the spirit and teachings of the present disclosure. All such combinations and / or couplings fall within the scope of the present disclosure.

[0071] The embodiments of the present disclosure are described above. However, these embodiments are for illustrative purposes only and are not intended to limit the scope of the present disclosure. Although each embodiment has been described separately above, this does not mean that the measures in each embodiment cannot be used in combination to advantage. The scope of the present disclosure is defined by the appended claims and their equivalents. Without departing from the scope of the present disclosure, those skilled in the art may make various substitutions and modifications, which should all fall within the scope of the present disclosure.

Claims

1. A method for preparing a single-end vinyl hyperbranched polyether macromonomer, characterized in that: include: A vinyl monomer containing an amino group or an ester group, a vinyl monomer containing a hydroxyl group, or a vinyl monomer containing a carboxyl group is subjected to a ring-opening polymerization reaction with glycidol in the presence of a catalyst and a polymerization inhibitor to form a single-end vinyl hyperbranched polyether macromonomer having an amino group, an ester group, or an ether group structure; Wherein, the vinyl monomer containing an amino group or an ester group is obtained by reacting glycidyl methacrylate or glycidyl acrylate with diethanolamine, diisopropanolamine, dimethylolpropionic acid or dimethylolbutyric acid; The vinyl monomer containing a hydroxyl group includes any one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate or allyl alcohol; The carboxyl group-containing vinyl monomer includes any one of methacrylic acid, acrylic acid, vinylphosphonic acid, p-vinylbenzoic acid or p-vinylbenzenesulfonic acid.

2. The method according to claim 1, characterized in that The polymerization inhibitor includes phenol, hydroquinone, p-methoxyphenol, diphenyl-2-nitrophenylhydrazine and a variable valence metal compound; The variable valence metal compound comprises at least one of ferric chloride and cuprous chloride.

3. The method according to claim 1, characterized in that The catalyst comprises at least one of potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, an organic tin compound, a Lewis acid, and an organic base; The organotin compound includes stannous octoate or tin naphthenate; The Lewis acid comprises at least one of boron trifluoride, aluminum trioxide, and tin tetrachloride; The organic base includes at least one of triethylamine, triethylenediamine or 1,8-diazabicycloundec-7-ene.

4. The method according to claim 3, characterized in that The amount of the catalyst used is 0.2% to 5% of the total weight of other monomers.

5. The method according to claim 1, wherein The reaction temperature of the ring-opening polymerization reaction is 100-200°C.

6. The method according to claim 1, characterized in that The ring-opening polymerization reaction is carried out in a solvent-free condition or in a polar aprotic solvent, wherein the polar aprotic solvent includes at least one of dioxane, tetrahydrofuran, dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide or N-methylpyrrolidone.

7. The method according to claim 1, characterized in that The reaction time of the ring-opening polymerization reaction is 1 to 10 hours.

8. A single-end vinyl hyperbranched polyether macromonomer, characterized in that: Prepared by any one of the methods described in claims 1 to 6.

9. A single-end vinyl hyperbranched polyether macromonomer, characterized in that: Its structural formula is any one of the following formulas (1) to (5); Wherein, R or R1 is a methyl group or a hydrogen group.

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