KR20130059493A - Environment-friendly plasticizers prepared with vegetable oil and preparation method thereof - Google Patents

Abstract

PURPOSE: A manufacturing method of a plasticizer is provided to have similar physical properties to a phthalate plasticizer, and to manufacture a large amount of environment-friendly plasticizers with a high reaction yield. CONSTITUTION: A manufacturing method of a plasticizer using vegetable oil comprises a step of epoxidizing the vegetable oil under an acid condition(S1); and a step of reacting the vegetable oil with an alcohol-based solvent and alkali. The epoxidization step uses 20-85% hydroperoxide solution, peracetic acid, perfomic acid, or perbenzoic acid at 0-50 deg. C for 3-24 hours under the presence of an organic solvent or not. [Reference numerals] (AA) Comparative example; (BB) Example 21; (CC) Example 22; (DD) Example 15; (EE) Example 11

Description

Eco-friendly plasticizer manufactured using vegetable oil and manufacturing method thereof {ENVIRONMENT-FRIENDLY PLASTICIZERS PREPARED WITH VEGETABLE OIL AND PREPARATION METHOD THEREOF}

The present invention relates to an environment-friendly plasticizer prepared using vegetable oil and a method for producing the same, more specifically soybean oil, soybean oil, edible and waste edible oil, palm oil, sunflower oil, rapeseed oil, rapeseed oil, jatropha oil, flax oil and the like. The present invention relates to an environment-friendly plasticizer manufactured by using the same as having a physical property equal to or higher than that of a phthalate plasticizer and harmless to a human body, and a method of manufacturing the same.

Plasticizer is a compound used in large quantities around the world to increase the polymer processability, flexibility, adhesion and productability of PVC and the like since the development of PVC. Around 1968, the addition of camphor to nitrocellulose significantly increased the plasticity of celluloid.

Examples of plasticizers include phthalate plasticizers containing alcohols of C ₄ -C ₁₃ , epoxide plasticizers using unsaturated natural fats, esters of dicarboxylic acid series, phosphate plasticizers added with aliphatic or aromatic alcohols, and polyester plasticizers. In addition to these, trimellitic anhydride esters and aliphatic or aromatic hydrocarbon-based plasticizers have been used for special purposes. Among the plasticizers used, phthalate plasticizers such as DOP, DEHP, DBP, DINP, BBP, and DIDP are the most used. As of 2011, more than 700,000 tons are produced and used in Korea.

Phthalate plasticizers, however, can damage human fertility, and are attracting attention as hazardous chemicals that adversely affect liver, kidney, lungs, blood, etc. in animal experiments, and high-risk substances (SVHC) in the REACH regulation. Substances of Very High Concern (DNOP, DEHP, DIDP, DINP, DBP, BBP, etc.) are classified as regulated substances in most countries, so production is likely to be banned in the near future. This is a situation that is greatly highlighted.

In order to solve this problem, Korean Patent Laid-Open Publication No. 2008-0011884 relates to a secondary plasticizer for PVC, a PVC sol composition containing the same, and a product thereof, having a distillation range of 285 to 340 ° C, an aromatic content of 1 wt% or less, and a kinematic viscosity. Is a dearomatic product having 4 to 8 cSt and containing 55 to 80% of paraffinic carbon atoms, and a secondary plasticizer for PVC is disclosed. However, the plasticizer disclosed in Korean Patent Laid-Open Publication No. 2008-0011884 is a plasticizer which reduces harmful aromatic components compared to conventional plasticizers, but has a limitation in that it contains a small amount of aromatics.

Citric acid derived from the biodegradable citric acid in the US (Morflex), benzoflex (Velsicol) in the benzoic acid derivatives, instead of phthalic anhydride used in the manufacture of phthalate plasticizers, Dupont's polycaprolactone-polycarbonate by ELVALOY, an olefinic copolymer resin consisting of ethulene, vinyl acetate and other polar monomers, and the Royal Institute of Technology in Sweden Although polycaprolactone-polycarbonate copolymers have been developed and used, it is difficult to meet the physical and chemical properties required by economics or the market.

Accordingly, the inventors of the present invention have tried to develop a new eco-friendly plasticizer harmless to the human body that can overcome the above-mentioned general problems, and as a result, an eco-friendly plasticizer and a manufacturing method thereof that can satisfy the economic and market demanded properties It has been developed to complete the present invention.

An object of the present invention is to provide an environmentally friendly plasticizer that can replace the harmful phthalate plasticizer, has physical properties equal to or higher than that of the phthalate plasticizer, harmless to the human body, and is applied to polymers such as PVC.

It is another object of the present invention to provide a method for producing an environmentally friendly plasticizer that can produce a large amount of environmentally friendly plasticizers having equivalent or more physical properties and harmless to a human body and applied to a polymer such as PVC.

In order to achieve the above object, the present invention is a method for producing a plasticizer using vegetable oil, the step of epoxidizing the vegetable oil under acidic conditions (S1) and the epoxidized vegetable oil alcohol solvent and alkali It provides a method for producing a plasticizer, comprising the step of reacting with (S2).

In one embodiment of the present invention, in the step S1, the vegetable oil is 20 to 20 hours for 3 to 24 hours at an temperature of 0 to 50 ℃ under an acidic condition using formic acid, acetic acid, phosphoric acid or sulfuric acid in an organic solvent or without an organic solvent. The epoxidation can be carried out using 85% hydrogen peroxide solution, peracetic acid, performic acid or perbenzoic acid.

In the present invention, the vegetable oil may include soybean oil, soybean oil, edible oil, edible oil, palm oil, sunflower oil, rapeseed oil, rapeseed oil, jatropha oil, linseed oil, and the like.

In the present invention, as the alcohol solvent, methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isopropyl alcohol, isobutanol, isopentanol, C5-C10 alcohol, and the like can be used. Potassium hydroxide, lithium hydroxide, etc. can be used.

When preparing plasticizers using vegetable oils according to the invention, epoxy methyl ester mixtures, epoxy ethyl ester mixtures, epoxy propyl ester mixtures, epoxy butyl ester mixtures, epoxy isopropyl ester mixtures, epoxy isobutyl ester mixtures and epoxy isopentyl An environmentally friendly plasticizer selected from the group consisting of ester mixtures can be obtained.

In addition, the present invention is a method for preparing a plasticizer using glycerol, selected from the group consisting of 1 equivalent of lauric acid, palmitic acid, stearic acid, oleic acid, epoxy oleic acid, linoleic acid and epoxy linoleic acid in glycerol. It provides a method for producing a plasticizer comprising the step of removing water after the reaction by adding an acid and reacting the reactant from which water is removed with 2 equivalents of acetic acid to remove water.

In the method for preparing a plasticizer using the glycerol of the present invention, the acid may be selected from the group consisting of lauric acid, palmitic acid, stearic acid, oleic acid, epoxy oleic acid, linoleic acid and epoxy linoleic acid, and phosphoric acid, It can be used by mixing one selected from the group consisting of hydrochloric acid and sulfuric acid.

In one embodiment of the invention, the reaction of each step in the process of preparing a plasticizer using glycerol is 50 ~ 130 ℃ The temperature may be performed for 3 to 24 hours.

When preparing a plasticizer using the glycerol according to the present invention, diacetyl lauryl glycerol, diacetyl palmityl glycerol, diacetyl stearyl glycerol, diacetyl oleic glycerol, diacetyl epoxy oleic glycerol, diacetyl linoleic glycerol And a diacetyl epoxy linoleic glycerol can be obtained an environmentally friendly plasticizer selected from the group consisting of.

The plasticizer of the present invention prepared according to the above can be used in the production of various products using PVC.

The present invention provides an eco-friendly plasticizer which has physical properties equivalent to or higher than that of phthalate plasticizer, which can replace harmful phthalate plasticizer, is harmless to human body, and is applied to polymers such as PVC, and has high reaction yield and economical efficiency. It can provide a method for producing an eco-friendly plasticizer that can mass-produce the eco-friendly plasticizer.

1 is a photograph photographing a comparison of the PVC sheet prepared in Examples and Comparative Examples in Test Example 1 of the present invention.
Figure 2 is a photograph of the roller used to extrude the PVC sheet in the embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

In order to prepare a plasticizer using the vegetable oil according to the present invention, the vegetable oil is first epoxidized under acidic conditions (step S1).

In the present invention, it is possible to provide an environment-friendly plasticizer by using vegetable oils harmless to the human body such as soybean oil, waste soybean oil, edible oil, waste cooking oil, palm oil, sunflower oil, rapeseed oil, rapeseed oil, jatropha oil, flax oil and the like.

In the step S1 of the present invention, using vegetable oil in an acidic condition using formic acid, acetic acid, phosphoric acid or sulfuric acid, using 20-85% hydrogen peroxide solution, peracetic acid, performic acid or perbenzoic acid at a temperature of 0 to 50 ° C. The epoxidation reaction can be carried out by stirring for a time.

The epoxidation reaction of the vegetable oil in the present invention can be carried out under or without other organic solvents such as benzene, toluene.

In the present invention, after carrying out the epoxidation reaction, it is neutralized with a basic solution, the benzene layer can be extracted, and the drying, filtration and distillation steps may be further performed by methods well known in the art.

Next, the vegetable oil epoxidized in step S1 is reacted with an alcohol solvent and an alkali (step S2).

The vegetable oil epoxidized in the step S2 is alcohol solvents such as methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isopropyl alcohol, isobutanol, isopentanol, C5-C10 alcohol, sodium hydroxide, hydroxide After mixing with alkali such as potassium and lithium hydroxide, The reaction is carried out with heating and stirring at a temperature for 3 to 24 hours.

In the present invention, the epoxidized vegetable oil as described above in step S2 is reacted by heating and stirring with an alcohol solvent and an alkali, and then the reaction is neutralized with an acidic solution such as 1M aqueous hydrochloric acid solution, and the like with benzene, toluene or xylene. Extraction, drying, filtration and distillation steps may be further performed.

Epoxy methyl ester mixtures, epoxy ethyl ester mixtures, epoxy propyl ester mixtures, epoxy butyl ester mixtures, epoxy isopropyl ester mixtures, epoxy isobutyl ester mixtures, epoxy when carrying out steps S1 and S2 for vegetable oils as described above. Isopentyl ester mixtures can be prepared.

In addition, the present invention is a method for producing a plasticizer using glycerol, the glycerol is selected from the group consisting of lauric acid, palmitic acid, stearic acid, oleic acid, epoxy oleic acid, linoleic acid and epoxy linoleic acid It provides a method of producing a plasticizer comprising the step of removing water after the reaction by adding an acid and the reaction by removing the water and the acetic acid to remove the water.

Phosphoric acid to one acid selected from the group consisting of lauric acid, palmitic acid, stearic acid, oleic acid, epoxy oleic acid, linoleic acid and epoxy linoleic acid in the method for preparing a plasticizer using glycerol according to the present invention. , One selected from the group consisting of hydrochloric acid and sulfuric acid is mixed and used as a catalyst.

In one embodiment of the present invention, by adding 1 equivalent of acid to the glycerol and reacting to remove water, and reacting the water is removed with 2 equivalents of acetic acid to remove the water to prepare a plasticizer using glycerol Can be.

When preparing a plasticizer using glycerol as described above, diacetyl lauryl glycerol, diacetyl palmityl glycerol, diacetyl stearyl glycerol, diacetyl oleic glycerol, diacetyl epoxy oleic glycerol, diacetyl linoleic glycerol And diacetyl epoxy linoleic glycerol.

The present invention provides a PVC product prepared using a plasticizer prepared as described above.

In one embodiment of the present invention, PVC-related products or PVC sheets and the like may be manufactured using 10 to 50 parts by weight of the plasticizer and 3 to 10 parts by weight of the plasticizer based on 100 parts by weight of PVC.

In another embodiment of the present invention, PVC related products or PVC using 10 to 50 parts by weight of the plasticizer, 3 to 10 parts by weight of stabilizer, 1 to 20 parts by weight of triacetin and PEG 1 to 20, based on 100 parts by weight of PVC. A sheet etc. can be manufactured.

Hereinafter, preferred embodiments and test examples of the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments, test examples, and drawings described herein are preferred embodiments of the present invention, and do not represent all of the technical idea of the present invention, and thus, various equivalents and modifications may be substituted for them at the time of the present application. Can be.

Example

Example  One: Soybean oil  Used epoxy Methyl ester  Preparation of mixtures

(One) Soybean oil  Used epoxy Soybean oil  Produce

217.7 g of soybean oil and 43.8 g of formic acid were added to 500 mL of benzene, followed by stirring for 3 hours. 35% hydrogen peroxide (123.9 g) was added thereto, followed by stirring at room temperature for about 5 hours. After the reaction was completed, neutralized by adding saturated sodium bicarbonate, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain epoxidized soybean oil.

Yield: 98%; ¹ H-NMR (CDCl ₃ )? 5.11 (m, 1H), 4.13 (m, 1H), 3.97 (m, , 1.34-1. 10 (m, 75H), 0.69 (m, 9H).

(2) epoxy Methyl ester  Preparation of mixtures

250 g of epoxidized soybean oil, 43 g of methanol and 1.5 g of sodium hydroxide were added to 500 mL of benzene, and the mixture was heated and stirred at 60 ° C. for 4 hours. The mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired compound.

Yield: 90%; ¹ H-NMR (CDCl ₃ ) δ 3.61 (s, 3H), 2.95-2.85 (m, 2H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 0.81 (m, 3H).

Example  2: Waste soybean oil  Used epoxy Methyl ester  Preparation of mixtures

(One) Waste soybean oil  Used epoxy Soybean oil  Produce

217.7 g of spent soybean oil and 43.8 g of formic acid were added to 500 mL of benzene, followed by stirring for 3 hours, followed by 123.9 g of 35% hydrogen peroxide, followed by stirring at room temperature for 5 hours. After the reaction was completed, neutralized by adding saturated sodium bicarbonate, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain epoxidized soybean oil.

Yield 91%; ¹ H-NMR (CDCl ₃ ) δ 5.11 (m, 1H), 4.13 (m, 1H), 3.97 (m, 1H), 2.93 (m, 4H), 2.78 (m, 5H), 2.1 (m, 6H) , 1.34-1.10 (m, 75H), 0.69 (m, 9H)

(2) epoxy Methyl ester  Preparation of mixtures

250 g of epoxidized soybean oil, 43 g of methanol and 1.5 g of sodium hydroxide were added to 500 mL of benzene, and the mixture was heated and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield 94%; ¹ H-NMR (CDCl ₃ ) δ 3.61 (s, 3H), 2.95-2.85 (m, 2H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 0.81 (m, 3H)

Example  3: epoxy Soybean oil  Preparation of Epoxy Isopropyl Ester Mixtures Using

250 g of the epoxidized soybean oil, 80.4 g of isopropanol, and 1.5 g of sodium hydroxide were added to 500 mL of benzene, and the mixture was heated and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield 93%; ¹ H-NMR (CDCl ₃ ) δ 4.31 (m, 1H), 2.95-2.85 (m, 2H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 1.35 (m, 6H), 0.82 ( m, 3H).

Example  4: From waste soybean oil  Manufactured Epoxy Soybean oil  Preparation of Epoxy Isopropyl Ester Mixtures Using

250 g of benzene epoxidized soybean oil, 80.4 g of isopropanol, and 1.5 g of sodium hydroxide were added to 500 mL of benzene, and the mixture was heated and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield: 89%; ¹ H-NMR (CDCl ₃ ) δ 4.30 (m, 1H), 2.95-2.85 (m, 2H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 1.35 (m, 6H), 0.82 ( m, 3H).

Example  5: epoxy Soybean oil  Preparation of Epoxy Ethyl Ester Mixtures Using

250 g of the epoxidized soybean oil, 59.0 g of ethanol, and 1.5 g of sodium hydroxide were added to 500 mL of benzene, and the mixture was heated and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield: 95%; ¹ H-NMR (CDCl ₃ ) δ 4.12 (q, 2H), 2.95-2.85 (m, 2H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 1.30 (t, 3H), 0.82 ( m, 3H).

Example  6: From waste soybean oil  Manufactured Epoxy Soybean oil  Preparation of Epoxy Ethyl Ester Mixtures Using

 In 500 mL of benzene, 250 g of epoxidized soybean oil, 59.0 g of ethanol, and 1.5 g of sodium hydroxide were added and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield: 98%; ¹ H-NMR (CDCl ₃ ) δ 4.10 (q, 2H), 2.95-2.85 (m, 2H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 1.30 (t, 3H), 0.82 ( m, 3H).

Example  7: epoxy Soybean oil  Preparation of Epoxy Isobutyl Ester Mixtures Using

250 g of epoxidized soybean oil, 99.2 g of isobutanol, and 1.5 g of sodium hydroxide were added to 500 mL of benzene, and the mixture was heated and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield: 88%; ¹ H-NMR (CDCl ₃ ) δ 4.04 (d, 2H), 2.95-2.85 (m, 2H), 2.43 (m, 1H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 1.01 ( d, 6H), 0.80 (m, 3H).

Example  8: From waste soybean oil  Manufactured Epoxy Soybean oil  Preparation of Epoxy Isobutyl Ester Mixtures Using

250 g of epoxidized soybean oil, 99.2 g of isobutanol, and 1.5 g of sodium hydroxide were added to 500 mL of benzene, and the mixture was heated and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was neutralized with 1M aqueous hydrochloric acid solution, the benzene layer was extracted, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield: 89%; ¹ H-NMR (CDCl ₃ ) δ 4.04 (d, 2H), 2.95-2.85 (m, 2H), 2.43 (m, 1H), 2.25 (m, 2H), 1.69-1.21 (m, 27H), 1.01 ( d, 6H), 0.80 (m, 3H).

Example  9: using glycerol Diacetyl Lauryl  Preparation of Glycerol

Stirring 217.7g of lauric acid and 1.5g of sulfuric acid in 100g of glycerol for 8 hours at 80 ℃ to remove water formed during the reaction using a Dean-Stark apparatus. 130.4 g of acetic acid was added to the reaction mixture, which was stirred at 80 ° C. for 8 hours to remove water formed during the reaction. Thereafter, 600 g of toluene was added to the obtained compound, neutralized with saturated aqueous sodium bicarbonate solution, the organic layer was separated, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield 90%; ¹ H-NMR (CDCl ₃ ) δ 4.3 (m, 1H), 4.2 (m, 1H), 2.3 (m, 2H), 2.1 (d, 6H), 1.6 (m, 2H), 1.6-1.1 (m, 19H), 0.9 (m, 3H).

Example  10: with glycerol Diacetyl Epoxy Oleic  Preparation of Glycerol

324.4 g of epoxy oleic acid and 1.5 g of sulfuric acid were stirred in 80 g of glycerol at 80 ° C. for 8 hours, and water formed during the reaction was removed using a Dean-Stark apparatus. 130.4 g of acetic acid was added to the reaction mixture and stirred at 80 ° C. for 8 hours to remove water formed during the reaction. Thereafter, 600 g of toluene was added to the obtained compound, neutralized with saturated aqueous sodium bicarbonate solution, the organic layer was separated, dried over anhydrous magnesium sulfate, filtered and distilled to obtain a desired mixture.

Yield 97%; ¹ H-NMR (CDCl ₃ ) δ 4.3 (m, 1H), 4.2 (m, 1H), 2.6 (m, 1H), 2.3 (m, 2H), 2.1 (d, 6H), 1.6 (m, 2H) , 1.4-1.0 (m, 28H), 0.87 (m, 3H).

Example  11: From soybean oil Derived  Epoxy Methyl ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy methyl ester mixture which is an environmentally friendly plasticizer (preferably 180 ℃) Preheated) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  12: From waste soybean oil Derived  Epoxy Methyl ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy methyl ester mixture which is eco-friendly plasticizer (preferably 180 ℃) Preheated) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  13: From soybean oil Derived  Epoxy Isopropyl Ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy isopropyl ester mixture, an environmentally friendly plasticizer (preferably 180) Preheated to < 0 > C) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  14: From waste soybean oil Derived  Epoxy Isopropyl Ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy isopropyl ester mixture, an environmentally friendly plasticizer (preferably 180) Preheated to < 0 > C) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  15: From soybean oil Derived  Epoxy Ethyl ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy ethyl ester mixture, an environmentally friendly plasticizer (preferably 180 ℃) Preheated) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  16: From waste soybean oil Derived  Epoxy Ethyl ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy ethyl ester mixture, an environmentally friendly plasticizer (preferably 180 ℃) Preheated) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  17: From soybean oil Derived  Epoxy Isobutyl Ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy isobutyl ester mixture, an environmentally friendly plasticizer (preferably 180) Preheated to < 0 > C) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  18: From waste soybean oil Derived  Epoxy Isobutyl Ester  With mixture PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of epoxy isobutyl ester mixture, an environmentally friendly plasticizer (preferably 180) Preheated to < 0 > C) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  19: From soybean oil Derived  Epoxy Methyl ester  Mixture and PEG Using PVC  Manufacture of sheets

100g of PVC powder (Hanhwa, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer), 20g of epoxy methyl ester mixture, eco-friendly plasticizer, and 10g of PEG (molecular weight 200) are used to extrude PVC sheet. It was put into a roller (preheated preferably to 180 ° C.) and processed into a sheet. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  20: From soybean oil Derived  Epoxy Methyl ester  mixture, Triacetin  And PEG Using PVC  Manufacture of sheets

PVC sheet was mixed by mixing 100 g of PVC powder (Hanhwa, 1000 molecular weight), 3 g of stabilizer (BZ-205T, barium, zinc PVC stabilizer), 20 g of epoxy methyl ester mixture, 5 g of triacetin, and 5 g of PEG (molecular weight 200). It was put into the roller (preheated at 180 degreeC) used for extrusion, and processed into the sheet | seat. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  21: Triacetin  Used PVC  Manufacture of sheets

100 g of PVC powder (Hanhwa, molecular weight 1000), 3 g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30 g of triacetin are mixed into a roller (preheated to 180 ° C.), which is used to extrude the PVC sheet. The sheet was processed. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  22: Diacetyl Lauryl  Glycerol as a plasticizer PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of diacetyl lauryl glycerol, an environmentally friendly plasticizer (preferably 180) Preheated to ° C) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Example  23: Diacetyl Epoxy Oleic  Glycerol as a plasticizer PVC  Manufacture of sheets

Roller used to extrude PVC sheet by mixing 100g of PVC powder (Hanhwa product, molecular weight 1000), 3g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30g of diacetyl epoxyoleic glycerol, an environmentally friendly plasticizer (preferably Preheated to 180 ° C.) and processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Comparative example

100 g of PVC powder (Hanhwa, molecular weight 1000), 3 g of stabilizer (BZ-205T, barium, zinc PVC stabilizer) and 30 g of phthalate plasticizer DOP are mixed on a roller (preheated to 180 ° C. preferably). The sheet was processed into sheets. The degree of visual processing was compared to DOP and the transition to the sheet surface was observed.

Test Example : Example  And In the comparative example  Manufactured PVC  Visual observation of the sheet

Table 11 shows the PVC sheets prepared in Example 11, Example 15, Example 21, Example 22, and Comparative Examples prepared with the compositions shown in Table 1, and are shown in FIG. 1.

1, it can be seen that the PVC sheet manufactured using the eco-friendly plasticizer according to the present invention was well prepared without any difference from the PVC sheet manufactured using the phthalate plasticizer harmful to the human body. In addition, in most examples, the phenomenon that the plasticizer migrated to the sheet surface was not observed and the workability was very good.

ingredient Example 11 Example 15 Example 21 Example 22 Comparative example PVC powder (g) 100 100 100 100 100 DOP (g) - - - - 30 Synthetic epoxy methyl ester
Mixture (g) 30 - - - - Synthetic epoxy ethyl ester
Mixture (g) - 30 - - - Triacetin
(triacetin) (g) - - 30 - - Diacetyl lauric glycerol (g) - - - 30 - PEG
(Molecular weight 200) (g) - - 5 - - stabilizator
(BZ-205T) (g) 3 3 3 3 3

Claims (14)

As a method of preparing a plasticizer using vegetable oil,
Epoxidizing vegetable oil under acidic conditions (S1) and reacting the epoxidized vegetable oil with an alcohol-based solvent and an alkali (S2).
The method according to claim 1,
20-85% hydrogen peroxide solution, peracetic acid, performic acid or perbenzoic acid for 3 to 24 hours at an temperature of 0-50 ° C. under acidic conditions using formic acid, acetic acid, phosphoric acid or sulfuric acid in an organic solvent or without an organic solvent. Method for producing a plasticizer, characterized in that the epoxidation reaction using.
The method according to claim 1,
The vegetable oil is a manufacturing method of a plasticizer, characterized in that selected from the group consisting of soybean oil, soybean oil, edible oil, waste edible oil, palm oil, sunflower oil, rapeseed oil, rapeseed oil, jatropha oil and linseed oil.
The method according to claim 1,
Neutralizing to basic solution after the epoxidation reaction in the step S1, extracting the benzene layer, drying, filtration and distillation method of producing a plasticizer, characterized in that further carried out.
The method according to claim 1,
The vegetable oil epoxidized in step S2 is reacted with an alcohol solvent and an alkali by heating and stirring, and then neutralized with an acidic solution, extracted with benzene, toluene or xylene, and further dried, filtered and distilled. Method of producing a plasticizer.
The method according to claim 1,
The alcohol solvent is methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isopropyl alcohol, isobutanol, isopentanol and C5 ~ C10 method of producing a plasticizer, characterized in that selected from the group consisting of alcohol.
The method according to claim 1,
The alkali is a method of producing a plasticizer, characterized in that selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
As a method of preparing a plasticizer using glycerol,
A method of preparing a plasticizer comprising the steps of removing water after the reaction by adding acid to glycerol and reacting the reaction product from which the water is removed with acetic acid to remove water.
The method according to claim 8,
Wherein said acid is selected from the group consisting of lauric acid, palmitic acid, stearic acid, oleic acid, epoxy oleic acid, linoleic acid and epoxy linoleic acid.
The method according to claim 9,
The acid selected from the group consisting of phosphoric acid, hydrochloric acid and sulfuric acid as a catalyst to one selected from the group consisting of lauric acid, palmitic acid, stearic acid, oleic acid, epoxy oleic acid, linoleic acid and epoxy linoleic acid as the acid Method for producing a plasticizer, characterized in that the addition and use.
The method according to claim 8,
The reaction is 50 ~ 130 ℃ Method for producing a plasticizer, characterized in that carried out for 3 to 24 hours at a temperature.
It is prepared according to the process according to any one of claims 1 to 7, wherein the epoxy methyl ester mixture, epoxy ethyl ester mixture, epoxy propyl ester mixture, epoxy butyl ester mixture, epoxy isopropyl ester mixture, epoxy isobutyl ester mixture and epoxy iso Plasticizer, characterized in that selected from the group consisting of pentyl ester mixture.
Prepared according to the process according to any one of claims 8 to 11, diacetyl lauryl glycerol, diacetyl palmityl glycerol, diacetyl stearyl glycerol, diacetyl oleic glycerol, diacetyl epoxy oleic glycerol, diacetyl linol Plasticizer, characterized in that it is selected from the group consisting of lake glycerol and diacetyl epoxy linoleic glycerol.
PVC products made using the plasticizer according to claim 12.

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