Oleic acid VP copolymer as well as preparation method and application thereof

Abstract

The invention provides an oleic acid VP copolymer and a preparation method and application thereof.The oleic acid VP copolymer is obtained through copolymerization of oleic acid and N-vinyl pyrrolidone, and the oleic acid VP copolymer has the ionization characteristic of oleic acid carboxyl and can be combined with some dyes or pigments; the amide group of the VP has certain water solubility, so that the copolymerization product can be widely applied.

Description

Technical Field

[0001] The invention belongs to the technical field of biomaterial preparation, and relates to an oleic acid VP copolymer and a preparation method and application thereof. Background Art

[0002] Unsaturated fatty acids refer to fatty acids that contain at least one double bond. They are a type of fatty acid that makes up body fat and are essential for human metabolism. They are of great significance to human health. Unsaturated fatty acids are divided into two types, monounsaturated fatty acids and polyunsaturated fatty acids, depending on the number of double bonds. Unsaturated fatty acids are found in large quantities in vegetable oils, nuts, fish, and seafood. For example, common 18-carbon unsaturated fatty acids, such as monoenoic acid (oleic acid), dienoic acid (linoleic acid), and trienoic acid (α-linolenic acid), are mostly found in natural oils and fats. Marine animal oils and fats often contain long-chain unsaturated fatty acids with four or more double bonds.

[0003] Oleic acid is the most abundant unsaturated fatty acid, generally present in the form of esters in animal and vegetable oils. The chemical molecule of oleic acid is C18H34O2, and its structural formula is CH 3 (CH 2 ) 7 CH=CH(CH 2 ) 7 COOH, oleic acid is insoluble in water, but miscible with organic solvents such as ethanol and ether. In addition to being a necessity for human health, oleic acid also has a wide range of uses. In industry, 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. From the structure, it can be seen that oleic acid contains double bonds and has the ability to polymerize, but because the double bond is in the middle of the molecule, its steric hindrance is very large, and its double bond activity is very weak. Conventional polymerization methods are difficult to obtain high molecular weight polymers, and generally only dimers or trimers can be obtained.

[0004] Macromolecular substances often have some unique functional characteristics compared with smaller molecular substances, so they are widely studied. However, due to the particularity of its structure, oleic acid is less studied as a polymerization monomer both at home and abroad. However, with the continuous increase in the production of agricultural genetically modified soybeans, the preparation of macromolecular substances by copolymerization of oleic acid and other monomers has received attention. Patent CN110294821A discloses a dispersant and its preparation method and application, discloses a dispersant, a dispersant prepared under the condition of oleic acid and maleic anhydride as an initiator, the dispersant can promote the uniform dispersion of reinforcing materials in polypropylene matrices with different surface energies, improve the thermodynamic spontaneous tendency of reinforcing materials to be uniformly dispersed in plastic matrices, reduce the tendency of reinforcing materials to condense in polypropylene matrices, and improve the interface properties of reinforcing materials and matrices at the same time, meet the mechanical properties of the materials, thereby effectively improving the toughening and strengthening effect of fillers on polypropylene matrices. Patent CN112745455A discloses an oleic acid copolymer dispersion resin and its preparation method and application. The dispersion resin is prepared by copolymerizing oleic acid, acrylic monomers, electron-rich olefin monomers, initiators and semi-blocked isocyanates. The dispersion resin has good wetting and dispersing effects on commonly used pigments and fillers and wide versatility. It also has good cross-linking and curing properties and can reduce the negative impact on paint film performance. Summary of the invention

[0005] In view of the deficiencies of the prior art, the purpose of the present invention is to provide an oleic acid VP copolymer and its preparation method and application. PVP is a very important water-soluble high molecular polymer, which has good water solubility, is safe and non-toxic, can be miscible or complexed with a variety of high and low molecular weights, and has excellent adsorption, film-forming, adhesion and thermal stability. The product of the copolymerization of oleic acid and VP has the ionization characteristics 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 copolymerization product more widely used.

[0006] To achieve this object, the present invention adopts the following technical solutions:

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

[0008] Preferably, the copolymerization is 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 has a boiling point of 130-160°C (eg, 130°C, 135°C, 140°C, 145°C, 150°C or 160°C).

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

[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 of dicumyl peroxide, di-tert-butyl diisopropylbenzene peroxide or di-tert-butyl peroxide, or a combination of at least two thereof.

[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] In another aspect, the present invention provides a method for preparing an oleic acid VP copolymer, the preparation method comprising the following steps:

[0018] Oleic acid and VP (N-vinyl pyrrole) 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°C, for example 130°C, 135°C, 140°C, 145°C or 150°C, and the reaction time is 8h-24h, for example 8h, 10h, 12h, 16h, 18h, 20h, 22h or 24h.

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

[0021] Place oleic acid and solvent in a four-necked flask, purge with nitrogen, heat the oil bath to 120℃ and keep warm for 1h, remove trace moisture in the system, weigh a certain amount of refined VP monomer and remove moisture and inhibitor by vacuum drying, add the treated VP monomer to the four-necked flask of oleic acid and solvent, continue to heat to 130-150℃, protect with nitrogen, add half of the initiator to initiate polymerization, and then add 1 / 3 of the remaining initiator every 2h until all the initiators are added, continue to react for 2h, cool down to stop the reaction. After the temperature drops to room temperature, remove the solvent by vacuum distillation, then add acetone and agent to wash and remove unreacted oleic acid and other impurities, stand and separate to remove most of the acetone agent to leave a viscous liquid, and finally remove acetone and other solvents by vacuum distillation to obtain the finished product.

[0022] In another aspect, the present invention provides use of the oleic acid VP copolymer as described above in cosmetics.

[0023] In another aspect, the present invention provides the use of the oleic acid VP copolymer as an antistatic agent or lubricant for fibers.

[0024] Oleic acid and VP raw materials are harmless to the human body. Oleic acid has a carboxyl group and a long-chain hydrocarbon group that has a good dispersing effect on oily dyes. The amide group of VP also has a good adsorption effect on certain dyes and has good water solubility. Its copolymer can be used in makeup removers in the cosmetics industry to disperse the oily dyes in cosmetics and clean them with water, so that no harmful chemicals will remain on the face. Oleic acid copolymers can also be used as fiber antistatic agents or lubricants.

[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 property of the oleic acid carboxyl group and can be combined with certain dyes or pigments, and the amide group of VP has certain water solubility, so that the copolymer product has a wider application. DETAILED DESCRIPTION

[0027] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0028] Example 1

[0029] Weigh 75g of VP monomer and remove moisture and inhibitor by vacuum drying for later use, weigh 75g of oleic acid and 150g of isoamyl alcohol, and heat in an oil bath at 120°C for 1h under nitrogen protection, then add the treated VP monomer to the mixture of oleic acid and isoamyl alcohol, add 0.75g of di-tert-butyl peroxide, continue to heat the oil bath to 140°C for reaction, add 0.25g of di-tert-butyl peroxide for 2h to continue the reaction, then add 0.25g of di-tert-butyl peroxide every 2h until 0.75g of initiator is added, continue the reaction for 2h, stop the reaction and cool down, take samples in the middle to track the oleic acid content by liquid phase to determine the degree of reaction. After the temperature drops to room temperature, remove isoamyl alcohol by vacuum distillation, then add xylene solvent for washing to remove unreacted oleic acid and other impurities, stand and separate to remove most of the acetone solvent to leave a viscous liquid, finally remove acetone and other solvents by vacuum distillation to obtain the finished product, and take samples to calculate the yield.

[0030] Example 2

[0031] Weigh 45g VP monomer and remove moisture and inhibitor by vacuum drying for later use, weigh 105g oleic acid, 120g ethylene glycol butyl ether, oil bath 120℃, keep warm for 1h under nitrogen protection, then add the treated VP monomer to the mixture of oleic acid and ethylene glycol butyl ether, add 1.12g diisopropyl ditert-butyl peroxide, continue to heat the oil bath to 150℃, react for 2h, add 0.38g diisopropyl ditert-butyl peroxide to continue the reaction, add 0.38g diisopropyl ditert-butyl peroxide every 2h until 1.13g initiator is added, continue the reaction for 2h, stop the reaction and cool down, take samples in the middle to track the oleic acid content by liquid phase to determine the degree of reaction. After the temperature drops to room temperature, remove isoamyl alcohol by vacuum distillation, add xylene solvent to wash and remove unreacted oleic acid and other impurities, stand and separate to remove most of the acetone solvent to leave a viscous liquid, finally remove acetone and other solvents by vacuum distillation to obtain the finished product, take samples to calculate the yield.

[0032] Example 3

[0033] Weigh 60g VP monomer and remove moisture and inhibitor by vacuum drying for later use, weigh 90g oleic acid, 130g ethylene glycol butyl ether, oil bath 120℃, keep warm for 1h under nitrogen protection, then add the treated VP monomer to the mixture of oleic acid and ethylene glycol butyl ether, add weighed 0.45g diisopropylbenzene peroxide, continue to heat the oil bath to 130℃ for reaction, add 0.15g diisopropylbenzene peroxide to continue the reaction after 2h, then add 0.15g diisopropylbenzene peroxide every 2h until 0.45g initiator is added, continue the reaction for 2h, stop the reaction and cool down, take samples in the middle to track the oleic acid content by liquid phase to determine the degree of reaction. After the temperature drops to room temperature, remove ethylene glycol butyl ether by vacuum distillation, then add acetone solvent to wash and remove unreacted oleic acid and other impurities, stand and separate to remove most of the acetone solvent to leave a viscous liquid, finally remove xylene and other solvents by vacuum distillation to obtain the finished product, take samples to calculate the yield.

[0034] Example 4

[0035] Weigh 50g VP monomer and remove moisture and inhibitor by vacuum drying for later use, weigh 70g oleic acid, 100g ethylene glycol butyl ether, oil bath 120℃, keep warm for 1h under nitrogen protection, then add the treated VP monomer to the mixture of oleic acid and ethylene glycol butyl ether, add weighed 0.6g diisopropylbenzene peroxide, continue to heat the oil bath to 130℃ for reaction, add 0.15g diisopropylbenzene peroxide to continue the reaction after 2h, then add 0.15g diisopropylbenzene peroxide every 2h until 0.45g initiator is added, continue the reaction for 2h, stop the reaction and cool down, take samples in the middle to track the oleic acid content by liquid phase to determine the degree of reaction. After the temperature drops to room temperature, remove ethylene glycol butyl ether by vacuum distillation, then add xylene solvent to wash and remove unreacted oleic acid and other impurities, stand and separate to remove most of the acetone solvent to leave a viscous liquid, finally remove acetone and other solvents by vacuum distillation to obtain the finished product, take samples to calculate the yield.

[0036] Example 5

[0037] Weigh 30g VP monomer and remove moisture and inhibitor by vacuum drying for later use, weigh 50g oleic acid, 80g ethylene glycol butyl ether, oil bath 120℃, keep warm for 1h under nitrogen protection, then add the treated VP monomer to the mixture of oleic acid and n-butanol, add 0.75g diisopropylbenzene peroxide, continue to heat the oil bath to 130℃, react for 2h, add 0.15g diisopropylbenzene peroxide to continue the reaction, then add 0.15g diisopropylbenzene peroxide every 2h until 0.5g initiator is added, continue the reaction for 2h, stop the reaction and cool down, take samples in the middle to track the oleic acid content by liquid phase to determine the degree of reaction. After the temperature drops to room temperature, remove n-butanol by vacuum distillation, then add xylene solvent to wash and remove unreacted oleic acid and other impurities, stand and separate to remove most of the acetone solvent to leave a viscous liquid, finally remove acetone and other solvents by vacuum distillation to obtain the finished product, take samples to calculate the yield.

[0038] Comparative Example 1

[0039] Weigh 15g VP monomer and remove moisture and inhibitor by vacuum drying for later use, weigh 85g oleic acid, 150g isoamyl alcohol, oil bath 120℃, keep warm for 1h under nitrogen protection, then add the treated VP monomer to the mixture of oleic acid and isoamyl alcohol, add weighed 0.65g di-tert-butyl peroxide, continue to heat the oil bath to 140℃, react for 2h, add 0.2g di-tert-butyl peroxide to continue the reaction, then add 0.2g di-tert-butyl peroxide every 2h until 0.6g initiator is added, continue the reaction for 2h, stop the reaction and cool down, take samples in the middle to track the oleic acid content by liquid phase to determine the degree of reaction. After the temperature drops to room temperature, remove isoamyl alcohol by vacuum distillation, then add xylene solvent to wash and remove unreacted oleic acid and other impurities, stand and separate to remove most of the acetone solvent to leave a viscous liquid, finally remove acetone and other solvents by vacuum distillation to obtain the finished product, take samples to calculate the yield.

[0040] Table 1

[0041]

[0042]

[0043] The copolymer prepared in the example was subjected to performance testing, and the testing method was as follows:

[0044] Common oil-soluble red was smeared on a white cloth, and then rinsed with clean water as a blank sample. The above-prepared sample was used to scrub it, and then rinsed with a large amount of clean water. The K / S value was measured by 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 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 the amount of VP is too small, resulting in no copolymerization product between oleic acid and VP, and more oleic acid dimer has a poor cleaning effect on dyes.

[0048] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the oleic acid VP copolymer and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An oleic acid VP copolymer, characterized in that: The oleic acid VP copolymer is obtained by copolymerizing oleic acid and N-vinyl pyrrolidone.

2. The oleic acid VP copolymer according to claim 1, characterized in that The copolymerization is solution polymerization.

3. The oleic acid VP copolymer according to claim 1 or 2, characterized in that The mass ratio of oleic acid to N-vinylpyrrole is 50-70:30-50.

4. The oleic acid VP copolymer according to any one of claims 1 to 3, characterized in that The polymerization is carried out in a solvent; Preferably, the solvent is a solvent with a boiling point of 130-160°C; Preferably, the solvent is selected from any one of n-pentanol, isopentanol, n-hexanol, methyl isobutyl carbinol, ethylene glycol butyl ether or DMF, or a combination of at least two thereof.

5. The oleic acid VP copolymer according to claim 4, characterized in that The mass ratio of the solvent to oleic acid is 80-100:30-50.

6. The oleic acid VP copolymer according to any one of claims 1 to 5, characterized in that The polymerization is carried out under the initiation of an initiator; Preferably, the initiator is selected from any one of dicumyl peroxide, di-tert-butyl diisopropylbenzene peroxide or di-tert-butyl peroxide, or a combination of at least two thereof.

7. The oleic acid VP copolymer according to claim 6, characterized in that The mass ratio of the initiator to oleic acid is 0.6-1.5:50-70.

8. A method for preparing the oleic acid VP copolymer according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: Oleic acid and N-vinyl pyrrole are polymerized in a solvent under the initiation of an initiator to obtain the oleic acid VP copolymer; Preferably, the polymerization reaction temperature is 130-150° C., and the reaction time is 8 h-24 h.

9. Use of the oleic acid VP copolymer according to any one of claims 1 to 7 in cosmetics.

10. Use of the oleic acid VP copolymer according to any one of claims 1 to 7 as an antistatic agent or lubricant for fibers.

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