Epoxy palm oil-based acrylate and preparation method thereof

Abstract

A preparation method of epoxy palm oil-based acrylate relates to the technical field of acrylate preparation, and comprises the following steps: S1, preparing epoxy palm oil; s2, enabling the epoxy palm oil prepared in S1 to react with acrylic acid, 4-methoxyphenol and triphenylphosphine at 110-120 DEG C for 5-6 hours, and purifying to obtain an epoxy palm oil-based acrylate crude product; s3, carrying out reduced pressure distillation on the epoxy palm oil-based acrylate crude product prepared in S2 at 70-80 DEG C to obtain epoxy palm oil-based acrylate; the preparation process is simple and easy to implement, the reaction time is short, the conditions are mild, and continuous and large-scale production of the epoxy palm oil-based acrylate is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of acrylate preparation, and in particular to epoxy palm oil-based acrylate and a preparation method thereof. Background Art

[0002] Petroleum-based acrylates are a class of chemical substances prepared from petroleum extracts, mainly products obtained by esterification of acrylic acid (extracted from petrochemical product propylene) and various alcohols. Such compounds are widely used in coatings, adhesives, plastics, textiles and paper, and have advantages such as good transparency, weather resistance and water resistance; however, petroleum-based acrylates rely on non-renewable petroleum resources and cause certain environmental pollution during production and degradation. Therefore, in recent years, more and more research has been devoted to the development of more environmentally friendly alternatives, such as bio-based acrylates extracted from vegetable oils (such as palm oil and soybean oil).

[0003] Epoxidized palm oil is a derivative prepared by epoxidation of palm oil. It is mainly used as a plasticizer and stabilizer added to plastics such as polyvinyl chloride to enhance its flexibility, impact resistance and weather resistance, and also improve the heat resistance and aging resistance of plastics; by reacting epoxy palm oil with acrylate, the acrylate material has better flexibility, impact resistance and environmental stability. Therefore, the use of epoxy palm oil to modify polyacrylate has a wide range of application prospects, but there is little record of the above modification method in the prior art. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides an epoxy palm oil-based acrylate and a preparation method thereof, which solves the problem in the prior art of how to modify polyacrylate with epoxy palm oil.

[0005] A method for preparing epoxy palm oil-based acrylate comprises the following steps:

[0006] S1. preparing epoxidized palm oil;

[0007] S2, reacting the epoxy palm oil prepared in S1 with acrylic acid, 4-methoxyphenol and triphenylphosphine at 110-120° C. for 5-6 hours, and obtaining a crude epoxy palm oil-based acrylate after purification;

[0008] S3. The crude product of epoxy palm oil-based acrylate obtained in S2 is subjected to reduced pressure distillation at 70-80° C. to obtain epoxy palm oil-based acrylate.

[0009] Preferably, in step S2, in parts by mass, the epoxy palm oil is 50 to 70 parts, the acrylic acid is 4.8 to 9.6 parts, the 4-methoxyphenol is 0.10 to 0.14 parts, and the triphenylphosphine is 0.75 to 1.05 parts.

[0010] Preferably, in step S2, the specific operation of purification is to add dichloromethane to the reaction-completed mixture to dissolve it, then add sodium bicarbonate solution to wash it and separate the liquids, and finally wash it with pure water to obtain the crude product of epoxy palm oil-based acrylate.

[0011] Preferably, the mass concentration of the sodium bicarbonate solution is 1%.

[0012] Preferably, in step S1, the method for preparing epoxidized palm oil comprises the following steps:

[0013] S11, taking hydrogen peroxide, formic acid and concentrated sulfuric acid according to the amount, and mixing the three to prepare an epoxidizing agent;

[0014] S12, taking palm oil according to the amount, heating the palm oil to raise the temperature, and then dropwise adding the epoxidizing agent prepared in S11 thereto, stirring evenly and reacting for a certain time;

[0015] S13. The mixture prepared in S12 is first washed with a sodium hydroxide solution, then washed with deionized water, and then distilled under reduced pressure to obtain epoxy palm oil.

[0016] Preferably, in step S11, in parts by mass, the hydrogen peroxide is 86 parts, the formic acid is 12 parts, and the concentrated sulfuric acid is 0.6 parts, wherein the mass concentration of the hydrogen peroxide is 30%.

[0017] Preferably, in step S12, the amount of palm oil is 60 parts by mass.

[0018] Preferably, in step S12, the reaction temperature is 60° C. and the reaction time is 6 h.

[0019] Preferably, the mass concentration of the sodium hydroxide solution in step S13 is 0.5%.

[0020] The invention also provides an epoxy palm oil-based acrylate, which is prepared by the preparation method.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The present invention activates the epoxy group by triphenylphosphine, which, as a Lewis acid, forms a coordination bond with the oxygen atom of the epoxy group to activate the epoxy group. In this process, the empty orbit of the phosphorus atom forms a coordination bond with the lone pair of electrons of the oxygen atom, which changes the electron cloud distribution of the epoxy group and reduces its reactivity threshold.

[0023] 2. The oxygen atom in the carboxyl group of acrylic acid can attack the activated epoxy group as a nucleophile due to its high electronegativity. Under the catalysis of triphenylphosphine, the lone pair of electrons of the oxygen atom forms a new covalent bond with the activated epoxy group. At the same time, the original covalent bond is broken, releasing a molecule of water. The carbon-carbon double bond in acrylic acid is still retained, and a stable ester bond is finally formed.

[0024] 3. The formed acrylate can continue to react with more acrylic acid molecules to form longer ester chains through a similar mechanism, i.e., polymerization. In this process, 4-methoxyphenol acts as an inhibitor and reacts with free radicals to prevent the chain from growing too fast or forming unnecessary by-products.

[0025] 4. The process of preparing epoxy palm oil-based acrylate according to the present invention is simple and easy, has a short reaction time and mild conditions, and is conducive to the continuous and large-scale production of epoxy palm oil-based acrylate.

[0026] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is the synthesis formula of epoxidized palm oil.

[0028] Figure 2 It is the synthesis formula of epoxy palm oil based acrylate.

[0029] Figure 3 This is the infrared image of epoxy palm oil-based acrylate.

[0030] Figure 4 This is the effect of time on the acid value in Example 1.

[0031] Figure 5 The figure is a relationship diagram between the acid value and the yield of epoxy palm oil-based acrylate in each example. DETAILED DESCRIPTION

[0032] In order to make the technical means, creative features, objectives and functions of the present invention clearer and easier to understand, the present invention is further described below in conjunction with the accompanying drawings and specific embodiments:

[0033] Example 1

[0034] S1. Weigh 60 parts of palm oil, 86 parts of hydrogen peroxide, 12 parts of formic acid, and 0.6 parts of concentrated sulfuric acid;

[0035] S2, mix hydrogen peroxide, formic acid and concentrated sulfuric acid, and then pour them into a constant pressure dropping funnel;

[0036] S3, after heating the palm oil to 65°C, slowly drip a mixture of hydrogen peroxide, formic acid and concentrated sulfuric acid into the palm oil, stir evenly and react for 6 hours;

[0037] S4, adding a sodium hydroxide solution with a mass concentration of 0.5% to the mixture prepared in S3 for washing, then adding deionized water for washing and then distilling under reduced pressure to obtain epoxy palm oil;

[0038] S5, reacting 50 parts of epoxy palm oil, 4.8 parts of acrylic acid, 0.10 parts of 4-methoxyphenol and 0.75 parts of triphenylphosphine at 120° C. for 6 hours, then adding dichloromethane to dissolve, then adding sodium bicarbonate with a mass concentration of 1% to wash and separate the liquids, and then washing with pure water to obtain a crude epoxy palm oil-based acrylate;

[0039] S6. The crude product of epoxy palm oil-based acrylate obtained in S5 is subjected to reduced pressure distillation at 70° C. to obtain epoxy palm oil-based acrylate.

[0040] Example 2

[0041] S1. Weigh 60 parts of palm oil, 86 parts of hydrogen peroxide, 12 parts of formic acid, and 0.6 parts of concentrated sulfuric acid;

[0042] S2, mix hydrogen peroxide, formic acid and concentrated sulfuric acid, and then pour them into a constant pressure dropping funnel;

[0043] S3, after heating the palm oil to 65°C, slowly drip a mixture of hydrogen peroxide, formic acid and concentrated sulfuric acid into the palm oil, stir evenly and react for 6 hours;

[0044] S4, adding a sodium hydroxide solution with a mass concentration of 0.5% to the mixture prepared in S3 for washing, then adding deionized water for washing and then distilling under reduced pressure to obtain epoxy palm oil;

[0045] S5, reacting 55 parts of epoxy palm oil, 6 parts of acrylic acid, 0.11 parts of 4-methoxyphenol and 0.82 parts of triphenylphosphine at 120° C. for 5 hours, then adding dichloromethane to dissolve, then adding sodium bicarbonate with a mass concentration of 1% to wash and separate the liquids, and then washing with pure water to obtain a crude epoxy palm oil-based acrylate;

[0046] S6. The crude product of epoxy palm oil-based acrylate obtained in S5 is subjected to reduced pressure distillation at 75° C. to obtain epoxy palm oil-based acrylate.

[0047] Example 3

[0048] S1. Weigh 60 parts of palm oil, 86 parts of hydrogen peroxide, 12 parts of formic acid, and 0.6 parts of concentrated sulfuric acid;

[0049] S2, mix hydrogen peroxide, formic acid and concentrated sulfuric acid, and then pour them into a constant pressure dropping funnel;

[0050] S3, after heating the palm oil to 65°C, slowly drip a mixture of hydrogen peroxide, formic acid and concentrated sulfuric acid into the palm oil, stir evenly and react for 6 hours;

[0051] S4, adding a sodium hydroxide solution with a mass concentration of 0.5% to the mixture prepared in S3 for washing, then adding deionized water for washing and then distilling under reduced pressure to obtain epoxy palm oil;

[0052] S5, reacting 60 parts of epoxy palm oil, 7.2 parts of acrylic acid, 0.12 parts of 4-methoxyphenol and 0.9 parts of triphenylphosphine at 110° C. for 6 hours, then adding dichloromethane to dissolve, then adding sodium bicarbonate with a mass concentration of 1% to wash and separate the liquids, and then washing with pure water to obtain a crude epoxy palm oil-based acrylate;

[0053] S6. The crude product of epoxy palm oil-based acrylate prepared in S5 is subjected to reduced pressure distillation at 80° C. to obtain epoxy palm oil-based acrylate.

[0054] Example 4

[0055] S1. Weigh 60 parts of palm oil, 86 parts of hydrogen peroxide, 12 parts of formic acid, and 0.6 parts of concentrated sulfuric acid;

[0056] S2, mix hydrogen peroxide, formic acid and concentrated sulfuric acid, and then pour them into a constant pressure dropping funnel;

[0057] S3, after heating the palm oil to 65°C, slowly drip a mixture of hydrogen peroxide, formic acid and concentrated sulfuric acid into the palm oil, stir evenly and react for 6 hours;

[0058] S4, adding a sodium hydroxide solution with a mass concentration of 0.5% to the mixture prepared in S3 for washing, then adding deionized water for washing and then distilling under reduced pressure to obtain epoxy palm oil;

[0059] S5, reacting 65 parts of epoxy palm oil, 8.4 parts of acrylic acid, 0.13 parts of 4-methoxyphenol and 0.98 parts of triphenylphosphine at 115° C. for 6 hours, then adding dichloromethane to dissolve, then adding sodium bicarbonate with a mass concentration of 1% to wash and separate the liquids, and then washing with pure water to obtain a crude epoxy palm oil-based acrylate;

[0060] S6. The crude product of epoxy palm oil-based acrylate prepared in S5 is subjected to reduced pressure distillation at 80° C. to obtain epoxy palm oil-based acrylate.

[0061] Example 5

[0062] S1. Weigh 60 parts of palm oil, 86 parts of hydrogen peroxide, 12 parts of formic acid, and 0.6 parts of concentrated sulfuric acid;

[0063] S2, mix hydrogen peroxide, formic acid and concentrated sulfuric acid, and then pour them into a constant pressure dropping funnel;

[0064] S3, after heating the palm oil to 65°C, slowly drip a mixture of hydrogen peroxide, formic acid and concentrated sulfuric acid into the palm oil, stir evenly and react for 6 hours;

[0065] S4, adding a sodium hydroxide solution with a mass concentration of 0.5% to the mixture prepared in S3 for washing, then adding deionized water for washing and then distilling under reduced pressure to obtain epoxy palm oil;

[0066] S5, reacting 70 parts of epoxy palm oil, 9.6 parts of acrylic acid, 0.14 parts of 4-methoxyphenol and 1.05 parts of triphenylphosphine at 115° C. for 5 hours, then adding dichloromethane to dissolve, then adding sodium bicarbonate with a mass concentration of 1% to wash and separate the liquids, and then washing with pure water to obtain a crude epoxy palm oil-based acrylate;

[0067] S6. The crude product of epoxy palm oil-based acrylate obtained in S5 is subjected to reduced pressure distillation at 70° C. to obtain epoxy palm oil-based acrylate.

[0068] like Figure 3 As shown in the infrared spectrum of epoxy palm oil acrylate, at 810 cm -1 The absorption peak at 1617 cm is caused by the vinyl part of the acrylic acid group (CH2=CH-R). -1 -1640cm -1 The absorption band is also caused by the vinyl part of the acrylic acid group (CH2=CH-R), 3500cm -1 There is a broad hydroxyl (-OH) absorption band around 1725cm -1 The absorption peak of (-C=O) further proves the formation of acrylate group and the successful preparation of epoxy palm oil-based acrylate.

[0069] like Figure 4 As shown, it is shown that the optimal reaction time for generating epoxy palm oil-based acrylate is 5-6h.

[0070] like Figure 5 As shown, by measuring the initial acid value and terminal acid value of the epoxy palm oil-based acrylate in Examples 1-5, The calculation formula is as follows: The yield of epoxy palm oil-based acrylate in Examples 1-5 is calculated as follows:

[0071] Yield % Example 1 89.03 Example 2 89.28 Example 3 85.25 Example 4 85.85 Example 5 84.21

[0072] It can be seen from the above table that the yield of epoxy palm oil-based acrylate in Example 2 is the best.

[0073] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution of the present invention, which should be included in the scope of the claims of the present invention.

Claims

1. A method for preparing epoxy palm oil-based acrylate, characterized in that: The following steps are involved: S1. preparing epoxidized palm oil; S2, reacting the epoxy palm oil prepared in S1 with acrylic acid, 4-methoxyphenol and triphenylphosphine at 110-120° C. for 5-6 hours, and obtaining a crude epoxy palm oil-based acrylate after purification; S3. The crude product of epoxy palm oil-based acrylate obtained in S2 is subjected to reduced pressure distillation at 70-80° C. to obtain epoxy palm oil-based acrylate.

2. The method for preparing epoxy palm oil-based acrylate according to claim 1, characterized in that: In step S2, the epoxy palm oil is 50 to 70 parts by mass, the acrylic acid is 4.8 to 9.6 parts by mass, the 4-methoxyphenol is 0.10 to 0.14 parts by mass, and the triphenylphosphine is 0.75 to 1.05 parts by mass.

3. The method for preparing epoxy palm oil-based acrylate according to claim 1, characterized in that: In step S2, the specific operation of purification is to add dichloromethane to the reaction-completed mixture to dissolve it, then add sodium bicarbonate solution to wash and separate the liquids, and finally wash with pure water to obtain a crude product of epoxy palm oil-based acrylate.

4. The method for preparing epoxy palm oil-based acrylate according to claim 3, characterized in that: The mass concentration of the sodium bicarbonate solution is 1%.

5. The method for preparing epoxy palm oil-based acrylate according to claim 1, characterized in that: In step S1, the method for preparing epoxidized palm oil comprises the following steps: S11, taking hydrogen peroxide, formic acid and concentrated sulfuric acid according to the amount, and mixing the three to prepare an epoxidizing agent; S12, taking palm oil according to the amount, heating the palm oil to raise the temperature, and then dropwise adding the epoxidizing agent prepared in S11 thereto, stirring evenly and reacting for a certain time; S13. The mixture prepared in S12 is first washed with a sodium hydroxide solution, then washed with deionized water, and then distilled under reduced pressure to obtain epoxy palm oil.

6. The method for preparing epoxy palm oil-based acrylate according to claim 5, characterized in that: In step S11, by weight, the hydrogen peroxide is 86 parts, the formic acid is 12 parts, and the concentrated sulfuric acid is 0.6 parts, wherein the mass concentration of the hydrogen peroxide is 30%.

7. The method for preparing epoxy palm oil-based acrylate according to claim 5, characterized in that: In step S12, the palm oil is 60 parts by mass.

8. The method for preparing epoxy palm oil-based acrylate according to claim 5, characterized in that: In step S12, the reaction temperature is 60° C. and the reaction time is 6 h.

9. The method for preparing epoxy palm oil-based acrylate according to claim 5, characterized in that: The mass concentration of the sodium hydroxide solution in step S13 is 0.5%.

10. An epoxy palm oil-based acrylate, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

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