The method of obtaining epoxydecane vegetable oils

 

(57) Abstract:

The invention relates to a method for epoxydecane vegetable oils, which are used as plasticizers stabilizers of polyvinyl chloride, various polymer non-toxic compositions. Describes how to obtain epoxydecane vegetable oils by oxidation, and the oxidation of oils or waste carried out in air with UV light for 6 h with simultaneous cooling to 6 to 10oC. the Technical result in the use of this invention is to simplify the process, the absence of expensive and hazardous reagents, lack of wastewater. table 2.

The invention relates to methods for epoxydecane vegetable oils used as plasticizers and stabilizers of polyvinyl chloride, various polymer non-toxic compositions.

Known epoxidation of vegetable oils held peracetic or naturalyou acids in two ways. One of these methods at the beginning of the organic acid or its anhydride and 30% hydrogen peroxide are nagkalat, then it is used for epoxidation vegetable oil epoxidised nagkalat at the time of its formation /A. C. Danyushevsky, A. F. Vorob'ev, A. N. Sergeeva research in the field of stabilization of polyvinyl chloride", "Plastic" N 11, S. 20-23, 1960/.

The obstacles to achieve the desired technical result is that required large quantities of such chemicals as hydrogen peroxide, formic or acetic acid, and then after the epoxidation reaction, the washing water received product from nagkalat.

A method of obtaining epoxydecane esters of fatty acids by epoxidation of esters of unsaturated fatty acids in the environment plasticizers mixture of formic acid and hydrogen peroxide at 70-75oC /A. S. USSR N 794009, MKI 07 D 301/12, From 08 To 5/15, 1981/. The obstacles to achieve the desired technical result is that epoxydecane soybean oil contains dioctylphthalate. Total time epoxidation is very significant - 12 hours, the temperature of the epoxidation is 70 - 75oC. For epoxidation used significant quantities of expensive reagents. 300 kg of soybean oil using 150 g of dioctylphthalate, 380 kg of hydrogen peroxide (30%), 60 kg of formic acid (85%). After carrying out epoxidation produce a assertion re the organic layer is then reloaded in the vacuum evaporation apparatus and distilled impurities and filtered from mechanical impurities. Thus, this method is multistage and costly reagents and, therefore, ethnological.

A known method of producing epoxypolyester epoxidation of vegetable oils organic nagkakamali in the moment of their formation of organic acids and hydrogen peroxide in the presence of a catalyst is sulfuric acid in the medium of organic solvent. /A. S. USSR N 1068432, MKI 07 D 301/16, C 07 D 303/16, 1984). The obstacles to achieve the desired technical result is that the multi-stage process: after receiving epoxyether raw, it is washed with water, then carry out the neutralization of the aqueous alkali solution followed by rinsing with water and distilled off the solvent (benzene), water, filtered with the separation of the target product. The distillation of the solvent and water are in the presence of 0.1 to 5.0% (wt.) from the mass of epoxyether raw mixture of soda ash and montmorillonite clay at a ratio of 1:(1-10) and accordingly the temperature of 130-170oC and the pressure 20-760 mm RT.article This process also uses a large number of reagents: 200 g of soybean oil, 200 g of benzene, 35,52 g of acetic acid, 181,9 g hydrogen peroxide (30%) with 1 g of the stabilizer of trinatriyfosfat, 2,55 g Catania epoxidation. The total duration of 15 hours. In addition, the implementation of this method is accompanied by large quantities of wastewater. Thus the disadvantages of this method is the complexity of the process due to its mnogostadiinost and duration.

Closest to the claimed is a method for epoxydecane vegetable oils or peracetic naturalyou acids /M. F., Sorokin, H. A. Kochneva, L., soda. "Chemistry and technology of film-forming substances), Chemistry, 1989, S. 415 - 416/. The obstacles to achieve the desired technical result is that this process consists of the following main stages:

1) epoxidation of vegetable oils in the form of a toluene solution;

2) rinse epoxidizing vegetable oil water;

3) drying oils and distillation of toluene.

As a result, this method requires high cost of reagents: hydrogen peroxide, formic acid or acetic acid, toluene, and obtained a large amount of wastewater is difficult in hardware design, long time.

The task of the invention is to develop effective ecologie forming wastewater.

The technical result obtained using the present invention is to simplify technology. The technical result is achieved by the fact that the oxidation of vegetable oils or waste carried out in air with UV light for 6 hours while cooling them to 6-10oC.

A thin film of vegetable oil reacts with oxygen of air at the lighting of fluorescent lamp

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Were used, such oil as well as sunflower and mustard, as well as waste mustard and sunflower oils having the same composition as that according to GOST 8807-74, but with increased acidity, component of 14.0 mg NaOH/g, and edible mustard oil must have an acidity of not more than 3 mg NaOH/g

Processing of vegetable oils or waste carried out in a laboratory setup. The reactor of large diameter was cooled with a mixture of ice with salt and lit from above fluorescent lamp (60, 4000-7000 angstroms). After lighting a thin layer of vegetable oil with UV light in the air are formed in the active particles of oxygen and ozone, which interact with molecules of triglycerides nanalysis or their waste.

This double bonds in triglycerides of unsaturated carboxylic acids interact with the active particles of oxygen or ozone to form epoxypropyl, also there is an increase in acid number due to the formation of free carboxylic groups.

Due to the absence of any moving parts, dosing devices and mixers this method of obtaining epoxydecane vegetable oils has increased reliability, along with good technological and economic indicators makes it very promising. In addition, the production is waste. The effectiveness of the proposed method stems from the fact that when illuminated with UV light to form the active particles of oxygen and ozone, which together constitute a valid factor in the initiation of radical reactions oxidation of vegetable oils (triglycerides of unsaturated carboxylic acids), resulting in epoxydecane vegetable oils of high purity (containing no moisture or residual solvent).

Given the applicant's analysis of the prior art, including the search for patent materials and scientific and technological sources informalities not found similar, characterized by signs, identical to all the essential features of the claimed invention. The definition from the list of identified unique prototype, as the closest solutions to the totality of symptoms, revealed a set of essential towards perceived by the applicant to the technical result of the distinctive features in the claimed object set forth in the claims. Therefore, the claimed invention meets the requirement of "Novelty" by applicable law.

To verify compliance of the claimed invention to the requirement of "Inventive step", the applicant conducted an additional search of the known solutions in order to identify characteristics that match the distinctive features of the prototype of the characteristics of the claimed invention, the results of which showed that the claimed invention to a person skilled not obvious from the prior art.

Therefore, the claimed invention meets the requirement of "Inventive step".

The method of epoxidation of vegetable oils is as follows. In the reactor of large diameter glass is placed a thin layer of vegetable oil over the surface is formed, and the temperature of the vegetable oil in it does not exceed 10oC, depending on the requirements of the experience of changing the thickness of the oil layer and the dwell time of the oil under UV light. And depending on trebovani experience vegetable oil or waste is treated within the required time, that is required to reduce the iodine value, as well as to the required number of epoxy groups.

After conducting relevant experiments performed research on the composition epoxydecane vegetable oils or waste. Determined by the standard method GOST 5475-69 iodine number and the number of epoxy groups of THE 6-10-722-86.

Here is an example of a specific implementation of the method:

Example 1.

As the object use mustard oil, having the following composition according to GOST 8807-74 (wt.% in terms of fatty acids)

Saturated fatty acids 4-7%

Oleic 17,9-20,3

Linoleic 20,0-26,7

Linolenic 9,0-10,5

Erucic 26,7-32,5

Pour into the reactor with a thin film thickness of 0.6 mm mustard oil in a quantity of 50 ml 46,00 g and illuminate the fluorescent lamp (4000-7000 angstroms), while cooling to a 6-10oC. Process air oxidation is performed 6 hours, get 46,98 g epoxidizing oil, which at room the content of epoxy groups of 6.8% and the iodine value, mg J2/1 g was 9.33.

Example 2.

The experiment is carried out according to the method of example 1 with the difference that the film thickness is 1.2 mm, receive and 47.0 g epoxidizing mustard oil with iodine number, mg J2/1 g of 18.4, content of epoxy groups of 5.83%.

Example 3.

The experiment is carried out according to the method of example 1 with the difference that the film thickness is 1.8 mm Get to 46.8 g epoxidizing mustard oil with iodine number, mg J2/1 g 25,3. The content of epoxy groups was 4.6%.

Example 4.

Unlike example 1 as the object of use of the non-conforming waste mustard oil. The qualitative composition of mustard oil and its waste are identical, the difference is that substandard oil has inflated acid number (>2 mg NaOH/g), and this determines its unsuitability for food purposes. Received and 47.0 g epoxidizing mustard oil with iodine number, mg J2/1 g of 8,9, content of epoxy groups of 7.2%.

Example 5.

The experiment is carried out according to the method of example 4 with the difference that the film thickness is 1.2 mm Obtain 47 g epoxidizing mustard oil with iodine number, mg J2/1 g - 17,6; the content of the epoxy GRI is 1.8 mm Get 48 g epoxidizing mustard oil with iodine number, mg J2/ 1 g 19,8, content of epoxy groups 5,0%.

Example 7.

Unlike example 1 as the object used sunflower oil having the following composition according to GOST 8807-74.

(wt.% in terms of fatty acids)

Linoleic 59%

Linolenic 2%

Alanova 29%

Saturated 17%

The process of oxidation by oxygen in the air spend 6 hours when cooled to 6-8oC. Receive and 47.5 g epoxidizing sunflower oil, which at room temperature is a colorless homogeneous liquid which does not change during storage. According to the analysis of the content of epoxy groups is 5.0% and the iodine value of 20.7.

Example 8.

Unlike example 7, the film thickness of sunflower oil is 1.2 mm. Receive 48,0 g epoxidizing sunflower oil containing epoxy groups 4,33% and the iodine value mg J2/1 g 32,6.

Example 9.

Unlike example 7, the film thickness of sunflower oil is 1.8 mm Get to 48.5 g epoxidizing sunflower oil containing epoxy groups of 3.6% and the iodine value is, mg J2/1 g 40,5.

The best conditions will be the temperature of 6-10oC, time epoxidation 6 hours. In the case of sunflower oil - temperature better support 5-7oC, because the presence of double bonds separated by a simple relationship increases the reactivity of apachegroup and interact oxide with a carboxylic acid.

The process proceeded, and the oxidation reaction occurs at the interface, so the thinner the film, the better is the oxidation.

Thus, the above data confirm that the implementation of the use of the claimed invention the following cumulative conditions:

1) the method embodying the claimed invention in its implementation is intended for use epoxydecane vegetable oils as a non-toxic plasticizer - stabilizers of different polymer compositions;

2) for the claimed invention in the form as it is described in the independent clause following claims, confirmed the possibility of its implementation using the above described in the application or known before the priority date methods and techniques;

3) the method embodying the claimed invention in its implementation, retina meets the requirements of "Industrial applicability" under the current law.

The method of obtaining epoxydecane vegetable oils by oxidation, characterized in that the oxidation of oils or waste carried out in air with UV light for 6 h while cooling to 6 to 10oC.

 

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