Oleic acid vp copolymer, process for its preparation and use thereof

Abstract

This invention provides an oleic acid VP copolymer, its preparation method, and its application. The oleic acid VP copolymer is obtained by copolymerizing oleic acid and N-vinylpyrrolidone. The oleic acid VP copolymer of this invention has the ionization characteristics of the oleic acid carboxyl group, which can be combined with certain dyes or pigments. The amide group of VP has a certain water solubility, which makes the copolymer product more widely used.

Description

Technical Field

[0001] This invention belongs to the field of biomaterial preparation technology, and relates to an oleic acid VP copolymer, its preparation method and application. Background Technology

[0002] Unsaturated fatty acids are fatty acids containing at least one double bond. They are a type of fatty acid that constitutes body fat and are essential for human metabolism, playing a vital role in human health. Unsaturated fatty acids are classified into monounsaturated fatty acids and polyunsaturated fatty acids based on the number of double bonds. Unsaturated fatty acids are abundant in vegetable oils, nuts, fish, and seafood. For example, common 18-carbon unsaturated fatty acids, such as monoenoic acid (oleic acid), diallyl acid (linoleic acid), and trienoic acid (alpha-linolenic acid), are predominantly found in natural oils. Marine animal oils often contain long-chain unsaturated fatty acids with four or more double bonds.

[0003] Oleic acid is the most abundant unsaturated fatty acid, generally existing in the form of oleic esters in animal and vegetable oils. The chemical formula of oleic acid is C18H34O2, and its structural formula is CH3(CH2)7CH=CH(CH2)7COOH. Oleic acid is insoluble in water but miscible with organic solvents such as ethanol and ether. Besides being essential for human health, oleic acid has a wide range of applications. Industrially, it is an important raw material for surfactants, an emulsifier and dispersant in the cosmetics industry, and a cosolvent and stabilizer in the pharmaceutical industry. As can be seen from its structure, oleic acid contains double bonds, giving it the ability to polymerize. However, due to the large steric hindrance caused by the double bonds in the middle of the molecule, its double bond activity is very weak. Conventional polymerization methods rarely yield high molecular weight polymers; generally, only dimers or trimers are obtained.

[0004] Polymers often possess unique functional properties compared to smaller molecules, leading to their widespread research. However, due to the unique structure of oleic acid, its study as a polymerization monomer has been relatively limited both domestically and internationally. Nevertheless, with the continuous increase in the yield of genetically modified soybeans, the preparation of polymers using oleic acid copolymerized with other monomers has gained attention. Patent CN110294821A discloses a dispersant, its preparation method, and its application. This dispersant, prepared using oleic acid and maleic anhydride under peroxide initiation conditions, promotes the uniform dispersion of reinforcing materials in polypropylene matrices with different surface energies. It enhances the thermodynamic spontaneous dispersion tendency of reinforcing materials in the plastic matrix, reduces the tendency for reinforcing materials to aggregate in the polypropylene matrix, and improves the interfacial properties between the reinforcing material and the matrix, satisfying the material's mechanical properties. This effectively enhances the toughening and reinforcing effect of the filler on the polypropylene matrix. Patent CN112745455A discloses an oleic acid copolymer dispersion resin, its preparation method and application. The dispersion resin is prepared by copolymerization of oleic acid, acrylic monomers, electron-rich olefin monomers, initiators and semi-blocked isocyanates. The dispersion resin has good wetting and dispersion effects on commonly used pigments and fillers and is widely applicable. At the same time, it has good crosslinking and curing properties, which can reduce the negative impact on the performance of the coating film. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an oleic acid-VP copolymer, its preparation method, and its applications. VP is a very important water-soluble polymer with good water solubility, safety, and non-toxicity. It is miscible or can complex with various polymers and low molecular weights, and possesses excellent adsorption, film-forming, adhesive, and thermal stability. The copolymerization product of oleic acid and VP combines the ionization properties of the oleic acid carboxyl groups, enabling it to bind with certain dyes or pigments, with the amide groups of VP exhibiting a certain degree of water solubility, thus broadening the applications of the copolymer.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] On one hand, the present invention provides an oleic acid VP copolymer, which is obtained by copolymerizing oleic acid and VP (N-vinylpyrrole).

[0008] Preferably, the copolymerization is a solution polymerization.

[0009] Preferably, the mass ratio of oleic acid to N-vinylpyrrole is 50-70:30-50, for example, 50:30, 50:33, 50:35, 50:38, 50:40, 50:45, 50:48, 50:50, 55:30, 58:30, 60:30, 65:30, 68:30, 70:30, 55:35, 58:35, 60:35, 65:35, 68:35, 70:35, 55:40, 58:40, 60:40, 65:40, 68:40, 70:40, 55:50, 58:50, 60:50, 65:50, 68:50, or 70:50, etc.

[0010] Preferably, the polymerization is carried out in a solvent.

[0011] Preferably, the solvent is a solvent with a boiling point of 130-160°C (e.g., 130°C, 135°C, 140°C, 145°C, 150°C or 160°C).

[0012] Preferably, the solvent is selected from any one or a combination of at least two of n-pentanol, isoamyl alcohol, n-hexanol, methyl isobutyl methanol, ethylene glycol butyl ether, or DMF.

[0013] Preferably, the mass ratio of the solvent to oleic acid is 80-100:30-50, for example 80:30, 80:35, 80:40, 80:45, 80:50, 90:30, 90:35, 90:38, 90:40, 90:45, 90:50, 100:30, 100:35, 100:38, 100:40, 100:45, or 100:50.

[0014] Preferably, the polymerization is carried out under the initiation of an initiator.

[0015] Preferably, the initiator is selected from any one or a combination of at least two of dicumyl peroxide, di-tert-butyl peroxide, or di-tert-butyl peroxide.

[0016] Preferably, the mass ratio of the initiator to oleic acid is 0.6-1.5:50-70, for example, 0.6:50, 0.8:50, 1:50, 1.3:50, 1.5:50, 0.6:55, 0.8:55, 1:55, 1.3:55, 1.5:55, 0.6:60, 0.8:60, 1:60, 1.3:60, 1.5:60, 0.6:70, 0.8:70, 1:70, 1.3:70, 1.5:70.

[0017] On the other hand, the present invention provides a method for preparing an oleic acid VP copolymer, the method comprising the following steps:

[0018] Oleic acid and VP (N-vinylpyrrole) are polymerized in a solvent under the initiation of an initiator to obtain the oleic acid-VP copolymer.

[0019] Preferably, the polymerization reaction temperature is 130-150℃, for example 130℃, 135℃, 140℃, 145℃ or 150℃, and the reaction time is 8h-24h, for example 8h, 10h, 12h, 16h, 18h, 20h, 22h or 24h.

[0020] In this invention, as a preferred technical solution, the preparation method specifically includes the following steps:

[0021] Oleic acid and solvent were placed in a four-necked flask, purged with nitrogen, and heated in an oil bath to 120°C and held for 1 hour to remove trace amounts of moisture. A measured amount of purified VP monomer was weighed and dried under vacuum to remove moisture and polymerization inhibitor. The treated VP monomer was added to the four-necked flask containing oleic acid and solvent, and the temperature was further increased to 130-150°C under nitrogen protection. Half of the initiator was added to initiate polymerization, and the remaining 1 / 3 of the initiator was added every 2 hours until all the initiator was added. The reaction was continued for another 2 hours, and then the temperature was lowered to stop the reaction. After the temperature dropped to room temperature, the solvent was removed by vacuum distillation. Acetone and solvent were then added to wash away unreacted oleic acid and other impurities. After standing and separating, most of the acetone was removed, leaving a viscous liquid. Finally, the acetone and other solvents were removed by vacuum distillation to obtain the final product.

[0022] On the other hand, the present invention provides the application of the oleic acid VP copolymer as described above in cosmetics.

[0023] On the other hand, the present invention provides the application of the oleic acid VP copolymer fiber antistatic agent or lubricant as described above.

[0024] Both oleic acid and VP are harmless to the human body. Oleic acid, with its carboxyl group and long-chain hydrocarbon group, has excellent dispersing properties for oil-based dyes. VP's amide group also has good adsorption effects on certain dyes and excellent water solubility. Their copolymers can be used in makeup removers in the cosmetics industry, effectively dispersing oil-based dyes in cosmetics and allowing for easy rinsing with water, leaving no harmful chemical residues on the face. Oleic acid copolymers can also be used as antistatic agents or lubricants for fibers.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The oleic acid VP copolymer of the present invention has the ionization properties of the oleic acid carboxyl group, which can be combined with certain dyes or pigments, and the amide group of VP has a certain water solubility, which makes the copolymer product more widely used. Detailed Implementation

[0027] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0028] Example 1

[0029] 75g of VP monomer was weighed and dried under vacuum to remove moisture and polymerization inhibitor. 75g of oleic acid and 150g of isoamyl alcohol were weighed and heated in an oil bath at 120℃ under nitrogen protection for 1 hour. The treated VP monomer was then added to the mixture of oleic acid and isoamyl alcohol, followed by 0.75g of di-tert-butyl peroxide. The oil bath temperature was increased to 140℃, and the reaction was continued for 2 hours. Then, 0.25g of di-tert-butyl peroxide was added, and the reaction continued. Subsequently, 0.25g of di-tert-butyl peroxide was added every 2 hours until all 0.75g of initiator was added. The reaction was continued for another 2 hours, then stopped and cooled. Interim samples were taken and the oleic acid content was monitored using liquid chromatography to determine the degree of reaction. After cooling to room temperature, isoamyl alcohol was removed by vacuum distillation. Xylene solvent was then added for washing to remove unreacted oleic acid and other impurities. After standing and separation to remove most of the acetone solvent, a viscous liquid remained. Finally, acetone and other solvents were removed by vacuum distillation to obtain the final product. Samples were taken and the yield was calculated.

[0030] Example 2

[0031] 45g of VP monomer was weighed and dried under vacuum to remove moisture and polymerization inhibitor. 105g of oleic acid and 120g of ethylene glycol butyl ether were weighed and heated in an oil bath at 120℃ under nitrogen protection for 1 hour. The treated VP monomer was then added to the mixture of oleic acid and ethylene glycol butyl ether, followed by 1.12g of bis(tert-butylperoxide)diisopropylbenzene. The oil bath temperature was increased to 150℃, and the reaction was continued for 2 hours. Then, 0.38g of bis(tert-butylperoxide)diisopropylbenzene was added, and the reaction was continued. Subsequently, 0.38g of bis(tert-butylperoxide)diisopropylbenzene was added every 2 hours until 1.13g of initiator was added. The reaction was continued for another 2 hours, then stopped and cooled. Intermediate samples were taken and the oleic acid content was monitored using liquid chromatography to determine the degree of reaction. After the temperature dropped to room temperature, isoamyl alcohol was removed by vacuum distillation. Xylene solvent was added for washing to remove unreacted oleic acid and other impurities. After standing and separation, most of the acetone solvent was removed, leaving a viscous liquid. Finally, acetone and other solvents were removed by vacuum distillation to obtain the final product. The yield was calculated by sampling.

[0032] Example 3

[0033] 60g of VP monomer was weighed and dried under vacuum to remove moisture and polymerization inhibitor. 90g of oleic acid and 130g of ethylene glycol butyl ether were weighed and heated in an oil bath at 120℃ under nitrogen protection for 1 hour. The treated VP monomer was then added to the mixture of oleic acid and ethylene glycol butyl ether, followed by 0.45g of cumene peroxide. The oil bath temperature was raised to 130℃, and the reaction was continued for 2 hours. Then, 0.15g of cumene peroxide was added, and the reaction continued. Subsequently, 0.15g of cumene peroxide was added every 2 hours until the 0.45g initiator was completely added. The reaction was continued for another 2 hours, then stopped and cooled. Interim samples were taken and the oleic acid content was monitored using liquid chromatography to determine the degree of reaction. After cooling to room temperature, ethylene glycol butyl ether was removed by vacuum distillation. Acetone was then added to wash away unreacted oleic acid and other impurities. After standing and separation to remove most of the acetone solvent, a viscous liquid remained. Finally, xylene and other solvents were removed by vacuum distillation to obtain the final product. Samples were taken and the yield was calculated.

[0034] Example 4

[0035] 50g of VP monomer was weighed and dried under vacuum to remove moisture and polymerization inhibitor. 70g of oleic acid and 100g of ethylene glycol butyl ether were weighed and heated in an oil bath at 120℃ under nitrogen protection for 1 hour. The treated VP monomer was then added to the mixture of oleic acid and ethylene glycol butyl ether, followed by 0.6g of weighed dicumyl peroxide. The oil bath temperature was increased to 130℃, and the reaction was continued for 2 hours. Then, 0.15g of dicumyl peroxide was added, and the reaction continued. Subsequently, 0.15g of dicumyl peroxide was added every 2 hours until 0.45g of initiator was added, and the reaction was continued for another 2 hours before stopping and cooling. Intermediate samples were taken, and the oleic acid content was monitored using liquid chromatography to determine the degree of reaction. After cooling to room temperature, ethylene glycol butyl ether was removed by vacuum distillation. Xylene solvent was added for washing to remove unreacted oleic acid and other impurities. After standing and separation to remove most of the acetone solvent, a viscous liquid remained. Finally, acetone and other solvents were removed by vacuum distillation to obtain the final product. Samples were taken and the yield was calculated.

[0036] Example 5

[0037] 30g of VP monomer was weighed and dried under vacuum to remove moisture and polymerization inhibitor. 50g of oleic acid and 80g of ethylene glycol butyl ether were weighed and incubated in an oil bath at 120℃ under nitrogen protection for 1 hour. The treated VP monomer was then added to a mixture of oleic acid and n-butanol, followed by 0.75g of cumene peroxide. The oil bath temperature was increased to 130℃, and the reaction continued for 2 hours. Then, 0.15g of cumene peroxide was added, and the reaction continued. Subsequently, 0.15g of cumene peroxide was added every 2 hours until 0.5g of initiator was added, and the reaction was continued for another 2 hours before stopping and cooling. Intermediate samples were taken and the oleic acid content was monitored using liquid chromatography to determine the degree of reaction. After cooling to room temperature, n-butanol was removed by vacuum distillation. Xylene solvent was then added for washing to remove unreacted oleic acid and other impurities. After standing and separation to remove most of the acetone solvent, a viscous liquid remained. Finally, acetone and other solvents were removed by vacuum distillation to obtain the final product. Samples were taken and the yield was calculated.

[0038] Comparative Example 1

[0039] 15g of VP monomer was weighed and dried under vacuum to remove moisture and polymerization inhibitor. 85g of oleic acid and 150g of isoamyl alcohol were weighed and heated in an oil bath at 120℃ under nitrogen protection for 1 hour. The treated VP monomer was then added to the mixture of oleic acid and isoamyl alcohol, followed by 0.65g of di-tert-butyl peroxide. The oil bath temperature was increased to 140℃, and the reaction was continued for 2 hours. Then, 0.2g of di-tert-butyl peroxide was added, and the reaction continued. Subsequently, 0.2g of di-tert-butyl peroxide was added every 2 hours until 0.6g of initiator was completely added. The reaction was continued for another 2 hours, then stopped and cooled. Intermediate samples were taken and the oleic acid content was monitored using liquid chromatography to determine the degree of reaction. After cooling to room temperature, isoamyl alcohol was removed by vacuum distillation. Xylene solvent was then added for washing to remove unreacted oleic acid and other impurities. After standing and separation to remove most of the acetone solvent, a viscous liquid remained. Finally, acetone and other solvents were removed by vacuum distillation to obtain the final product. Samples were taken and the yield was calculated.

[0040] Table 1

[0041]

[0042]

[0043] The copolymers prepared in the examples were subjected to performance testing, and the testing methods are as follows:

[0044] Apply common oil-soluble red to a white cloth, rinse with water to serve as a blank sample, wipe with the sample prepared above, rinse with plenty of water, and measure the K / S value using a spectrophotometer. The results are shown in Table 2 below.

[0045] Table 2

[0046] sample K / S 520nm blank 2.86 Example 1 0.32 Example 2 0.43 Example 3 0.35 Example 4 1.02 Example 5 1.32 Comparative Example 1 1.85

[0047] Table 2 shows that the oleic acid-VP copolymer has a good cleaning effect on oily dyes, and the higher the VP ratio, the better the cleaning effect. Comparative Example 1 shows that too little VP content resulted in oleic acid not forming a copolymer with VP, and more importantly, the oleic acid dimer had a poor cleaning effect on the dye.

[0048] The applicant declares that this invention illustrates the oleic acid VP copolymer, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. An oleic acid VP copolymer, characterized in that, The oleic acid VP copolymer is obtained by copolymerizing oleic acid and N-vinylpyrrolidone; The copolymerization is a solution polymerization; The polymerization is carried out under the initiation of an initiator; The initiator is selected from any one or a combination of at least two of dicumyl peroxide, di-tert-butyl peroxide, or di-tert-butyl peroxide. The mass ratio of oleic acid to N-vinylpyrrolidone is 50-70:30-50; The mass ratio of the initiator to oleic acid is 0.6-1.5:50-70.

2. The oleic acid VP copolymer according to claim 1, characterized in that, The polymerization is carried out in a solvent.

3. The oleic acid VP copolymer according to claim 2, characterized in that, The solvent is a solvent with a boiling point of 130-160℃.

4. The oleic acid VP copolymer according to claim 3, characterized in that, The solvent is selected from any one or a combination of at least two of n-pentanol, isopentanol, n-hexanol, methyl isobutyl methanol, ethylene glycol butyl ether, or DMF.

5. The oleic acid VP copolymer according to claim 2, characterized in that, The mass ratio of the solvent to oleic acid is 80-100:30-50.

6. A method for preparing the oleic acid VP copolymer according to any one of claims 1-5, characterized in that, The preparation method includes the following steps: Oleic acid and N-vinylpyrrolidone are polymerized in a solvent under the initiation of an initiator to obtain the oleic acid VP copolymer.

7. The preparation method according to claim 6, characterized in that, The polymerization reaction is carried out at a temperature of 130-150℃ for 8-24 hours.

8. The use of the oleic acid VP copolymer according to any one of claims 1-5 in cosmetics.

9. The use of the oleic acid VP copolymer according to any one of claims 1-5 as a fiber antistatic agent or lubricant.

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