JP2016173328A - Method for quantitative analysis of additives contained in polyolefins - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an accurate and simple method for the quantitative analysis of an additive, specifically an antioxidant, included in polyolefin, which simply and efficiently extracts an additive, specifically an antioxidant, analyzes it with a high extraction rate, and does not cause the extraction rates of other additives to decline either.SOLUTION: Provided is the method for the quantitative analysis of the additive included in polyolefin, the method characterized in that it includes an operation for impregnating a polyolefin sample in a mixed solvent and extracting it, the mixed solvent including a non-polar solvent (A) whose SP value (solubility parameter) is 6-10 and dielectric constant (20°C) is 0-4.5 or less or dipolar moment is less than 1 and a micropolar solvent (B) whose SP value is 6-10 and dielectric constant (20°C) is 4.5 or greater or dipolar moment is 1 or greater.SELECTED DRAWING: None

Description

  The present invention relates to a method for quantitative analysis of an additive contained in a polyolefin, and more specifically, a polyolefin characterized in that an additive such as an antioxidant contained in a polyolefin can be quantitatively analyzed accurately and rapidly. The present invention relates to a method for quantitative analysis of additives contained therein.

  In general, polyolefins such as polyethylene and polypropylene are filled with antioxidants, antistatic agents, ultraviolet absorbers, nucleating agents, flame retardants, lubricants, colorants, and fillers to improve various physical properties and prevent deterioration over time. Various additives such as an agent are added. Among these, antioxidants and ultraviolet absorbers provide important functions for preventing deterioration over time.

  Therefore, the quality of polyolefins is greatly influenced by the types and amounts of these additives. Therefore, obtaining correct information on the types and amounts of additives contained in polyolefins is important in improving and producing polyolefins. Indispensable for quality control.

In order to obtain correct information on the types and amounts of additives contained in polyolefins, quantitative analysis of the additives contained in polyolefins is required. In general, such additives are extracted from polyolefins. And the operation of analyzing the type and content of the additive.
Conventionally, so-called Soxhlet extraction method and reprecipitation method are used as such analytical operations, but Soxhlet extraction method applies siphon's principle to circulate a solvent and extract additives in polyolefin. This method is disadvantageous in that it requires refluxing for 5 hours or more in order to obtain a high extraction rate, which requires a lot of time.
The reprecipitation method is a method in which the polyolefin sample is completely dissolved in a solvent and then mixed with another solvent to lower the solubility, and the additive is separated from the solution to precipitate the target product. The analytical operation is complicated and requires a great amount of time and a large amount of solvent.

  Furthermore, specifically, in the quantitative analysis of the antioxidant that is an additive of polyolefin, a mixed solvent of cyclohexane and 2-propanol (mixing ratio) is used as an alternative solvent for chloroform, which is a conventional extraction solvent for antioxidants. 1: 1) was reported (Non-Patent Document 1), and in quantitative analysis of phenolic antioxidants in polyethylene packaging bags (plastic bags), cyclohexane-2-propanol was used as an extraction solvent for antioxidants. A method for analysis by HPLC (high performance liquid chromatography) using a mixed solvent has been reported (Non-patent Document 2). In addition, a special analytical instrument system using liquid carbon dioxide as a mobile phase is also known as an instrumental analysis chromatography method (Non-patent Document 3).

  However, in these conventional antioxidant quantitative analysis methods, the analytical operation is complicated, the extraction rate is insufficient, and even if the extraction rate is high, the extraction rate of other additives is reduced. There was a problem.

Tokyo Metropolitan Institutes of Health Research Annual Report No. 55, 179-182 (2004) “Examination of the Extraction Solvent and Stability of Antioxidants in Food Plastics” Fukuoka City Institute of Health and Environmental Science No. 34, 141-144 (2008) “A Survey of Antioxidants in Plastic Bags” Japan waters homepage "UPC2 system (application of UPC2 analysis to extract analysis)"

In the conventional quantitative analysis of additives contained in polyolefins, as described above in the background art, the analytical operation is complicated and takes a lot of time. Especially, the quantitative analysis of antioxidants has an insufficient extraction rate. In addition, even if the extraction rate is high, there is a problem that the extraction rate of other additives decreases.
Therefore, the object of the present invention, that is, the problem to be solved by the present invention, is to easily and efficiently extract additives, particularly antioxidants, contained in polyolefin, and to analyze additives, particularly antioxidants, at a high extraction rate. Another object of the present invention is to provide an accurate and simple quantitative analysis method for additives, particularly antioxidants, which does not reduce the extraction rate of other additives.

In order to solve the above-mentioned problems of the invention, the present inventors searched for a new extraction method in quantitative analysis of additives contained in polyolefins, particularly antioxidants, examined the extraction solvents widely, and dissolved the properties of polyolefins. In consideration of (SP value; solubility parameter), the polarities and combinations of the solvents were examined, and a quantitative analysis method for additives, particularly antioxidants, contained in the polyolefin, which can solve the above problems, was obtained.
As a result, the ultrasonic solvent extraction method is adopted as a new extraction method, the SP value and polarity of the solvent are defined, and the above-mentioned problems can be solved by combining such solvents. New quantitative analysis methods for additives, particularly antioxidants, can be found, and the present invention has been created.

  That is, the present invention is a quantitative analysis method using a specific and specific solvent in a quantitative analysis method of an additive, particularly an antioxidant contained in a polyolefin, and particularly a quantitative analysis method using an ultrasonic solvent extraction method. As a basic feature, the solubility characteristics (SP value), the polar performance, etc. are defined, and such solvents are used in combination.

  Specifically, as a basic invention, the present invention provides a polyolefin sample having an SP value of 6 to 10 and a relative dielectric constant (20 ° C.) of 0 to less than 4.5 or a dipole moment of less than 1. Or two or more kinds of nonpolar solvents (A), one or two or more kinds of micropolarities having an SP value of 6 to 10 and a relative dielectric constant (20 ° C.) of 4.5 or more or a dipole moment of 1 or more. It is the quantitative analysis method of the additive contained in polyolefin comprised from operation which impregnates and extracts in the mixed solvent containing a solvent (B).

  In contrast to the basic invention described above (the invention of the independent claim of claim 1), as an accompanying embodiment invention (each invention of the dependent claims), the additive to be analyzed is specified as an antioxidant. (Claims 2 and 3), a nonpolar solvent is identified (Claim 4), a micropolar solvent is identified (Claim 5), and the extraction operation is identified by the ultrasonic solvent extraction method (Claim 6), and mixing is performed. The volume ratio of the solvent is specified (Claim 7), and the quantitative analysis method is used for the polyolefin production method and quality control method (Claims 8 and 9).

In the present invention, as described above, in the quantitative analysis method of additives, particularly antioxidants, contained in polyolefin, the solvent extraction method using a specific and specific solvent, particularly the ultrasonic solvent extraction method is used. As a specific solvent, the solubility characteristics (SP value), polar performance, etc. are defined, and the basic feature is that these solvents are used in combination. Easy and efficient extraction and analysis of additives, especially antioxidants, with a high extraction rate, and does not reduce the extraction rate of other additives, accurate and simple quantitative analysis method of additives, especially antioxidants, and Become.
Such a unique and novel configuration cannot be found in a small amount from the prior art literature.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described in general. Here, the overall configuration of the present invention will be summarized and summarized in the following [1]. ] To [9].
Here, the peculiar analysis method in [1] is configured as the basic invention [1], and [2] each of the following inventions adds an additional requirement to the basic invention or indicates an embodiment thereof. It is.

[1] In a method for quantitative analysis of additives contained in polyolefin, a polyolefin sample is obtained with an SP value (solubility parameter) of 6 to 10 and a relative dielectric constant (20 ° C.) of less than 0 to 4.5 or a dipole moment. Is one or two or more nonpolar solvents (A) having an SP value of less than 1, an SP value of 6 to 10, a relative dielectric constant (20 ° C.) of 4.5 or more, or a dipole moment of 1 or more Or a method for quantitative analysis of an additive contained in a polyolefin, comprising an operation of impregnating and extracting a mixed solvent containing two or more kinds of micropolar solvents (B).

[2] The method for quantitative analysis of an additive contained in a polyolefin according to [1], wherein the additive is a phenol-based antioxidant.
[3] The polyolefin according to [2], wherein the phenolic antioxidant is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Quantitative analysis method for additives contained.

[4] The method for quantitative analysis of an additive contained in a polyolefin according to any one of [1] to [3], wherein the nonpolar solvent (A) is a hydrocarbon nonpolar solvent.
[5] The quantitative analysis of the additive contained in the polyolefin according to any one of [1] to [4], wherein the micropolar solvent (B) is a heteroatom-containing hydrocarbon micropolar solvent Method.

[6] The extraction operation is an ultrasonic solvent extraction operation using an extraction solvent in a temperature range of 40 to 70 ° C., and included in the polyolefin according to any one of [1] to [5] Quantitative analysis method for additives.
[7] Determination of additive contained in polyolefin in any one of [1] to [6], wherein the mixing volume ratio of the nonpolar solvent to the micropolar solvent is 99 to 0.1 times Analysis method.

[8] A step of obtaining a difference between a standard value of the amount of the additive to be blended in the polyolefin and an analytical value of the amount of the additive obtained by the method in any one of [1] to [7]; A method for producing a polyolefin resin, comprising a feedback step of adjusting the amount of additive to be blended accordingly.
[9] A step of comparing the standard value of the amount of additive blended in the polyolefin with the analytical value of the amount of additive determined by the method in any one of [1] to [7], and selling the polyolefin A quality control method for polyolefin resin, comprising the step of determining whether or not.

In the quantitative analysis method for additives contained in polyolefins of the present invention, additives, especially antioxidants, contained in polyolefins can be extracted easily and efficiently, and additives, particularly antioxidants, can be extracted at a high extraction rate. The effect of the invention is achieved that is an accurate and simple quantitative analysis method for additives, particularly antioxidants, which does not reduce the extraction rate of other additives.
In the present invention, the amount of additives, particularly antioxidants, can be analyzed with high accuracy, so that the production of defective products that deviate from the standard value of the amount of additives can be suppressed. It is possible to suppress the distribution of defective products that deviate from the standard value to the market, and the effect of the invention that the customer satisfaction can be enhanced is also achieved.

(I) Basic Configuration The present invention is basically a method for quantitatively analyzing additives contained in polyolefin, and the polyolefin sample is measured with an SP value of 6 to 10 and a relative dielectric constant (20 ° C.) of 0 to 4. One or two or more non-polar solvents (A) having a dipole moment of less than 5 or less than 1, an SP value of 6 to 10 and a relative dielectric constant (20 ° C.) of 4.5 or more, or a dipole moment of It is a quantitative analysis method for an additive contained in a polyolefin, comprising an operation of impregnating and extracting a mixed solvent containing one or more micropolar solvents (B), which is one or more.
In the present invention, in particular, it relates to an antioxidant as an additive, and an ultrasonic solvent extraction method is used as an extraction method.

(II) Quantitative Analysis by Solvent Extraction Method (1) Basic Operation A method for quantitative analysis by the solvent extraction method is generally performed by the following operation.
(I) [Sample preparation operation]
The sample polyolefin is made into a film or powder.
(Ii) [Extraction operation]
The target substance to be quantified is extracted and separated from the sample prepared in (i) to obtain an extracted sample.
(Iii) [Quantitative operation]
The target substance is quantitatively detected from the extracted sample obtained in (ii).

(2) Sample Preparation Operation First, an operation for preparing a sample (sample preparation operation) is performed. The shape of the sample is preferably a film or a powder.
The sample can be made into a film by hot pressing or the like. In order to increase the surface area, the film may be cut finely. The thickness of the film is preferably 100 μm or less in order to improve the extraction efficiency.
The press temperature can be determined in consideration of the melting point of the sample, deterioration of the sample, decomposition of the additive, and the like. For example, when the sample is polypropylene, the press temperature is preferably about 190 to 250 ° C. If the press pressure is too low, the thickness of the film will not be sufficiently reduced. If the press pressure is too high, the press apparatus will fail. For example, when the sample is polypropylene, the press pressure is preferably about 5 to 20 MPa.
If the press time is too short, the thickness of the film will not be sufficiently thin because the sample will not melt sufficiently, and if it is too long, it will cause deterioration of the sample and decomposition of the additive. For example, if the sample is polypropylene, The pressing time is preferably about 30 to 300 seconds.

The sample can be made into powder by freeze-grinding. It can grind | pulverize directly from the state of a pellet etc., and can also grind | pulverize from the state of a film or the cut | disconnected film.
The particle size of the powder is preferably 1 mm or less and more preferably 100 μm or less in order to improve the extraction efficiency.

(3) Extraction operation Next, an extraction operation is performed to extract and separate the target substance to be quantified from the sample to obtain an extracted sample. A sample prepared by the sample preparation operation (2) can be used as the sample.
As a conventional technique for the extraction operation, a Soxhlet method, a reprecipitation method and the like are known. However, there are problems such as a long extraction time and poor work efficiency. The Soxhlet extraction method is a method in which the principle of siphon is applied to circulate the solvent and extract the additives in the polyolefin. To obtain a high extraction rate, reflux for 5 hours or more is required, which requires a lot of time. Presents the drawbacks. The reprecipitation method is a method in which a polyolefin sample is completely dissolved in a solvent and then mixed with another solvent to lower the solubility of the additive, and the additive is separated from the solution to precipitate the target product. In addition, the analytical operation is complicated, requiring a lot of time and a large amount of solvent.
In the present invention, by using the ultrasonic solvent extraction method, the extraction time is ½ or less and the workability is remarkably improved as compared with the Soxhlet method or the reprecipitation method.

In the present invention, the sample to be analyzed is preferably extracted by the following procedure using an ultrasonic solvent extraction method.
Here, the ultrasonic solvent elution method performs extraction by irradiating a container containing a sample and a solvent with ultrasonic waves from an ultrasonic generator. By performing solvent extraction while applying ultrasonic waves, a high extraction rate can be achieved in a short time, which is efficient.
If the extraction time is too short, the additive compound to be quantified cannot be extracted in its entirety. If it is too long, the additive compound may be decomposed, resulting in a lower quantitative value. The extraction time is preferably about 30 to 120 minutes, more preferably 60 to 90 minutes. The extraction temperature is preferably 40 to 70 ° C, and more preferably in the range of 50 to 65 ° C.
By setting the temperature of the extraction solvent to not more than the upper limit of the above range, the antioxidant can be selectively extracted without completely dissolving the sample. By setting the temperature of the extraction solvent to be equal to or higher than the lower limit value in the above range, the sample swells into the solvent, and the extraction rate can be further increased.

  Specifically, the polyolefin sample is placed in a container such as a flask together with the extraction solvent, and fixed to an ultrasonic extractor. In this state, ultrasonic extraction is performed for the time required for extraction, and the polyolefin is filtered off using filter paper or the like, and the extract is collected in a container such as an eggplant flask. An extraction sample is obtained by completely removing the extraction solvent from the extract with an evaporator or the like.

Here, if the absolute amount of the sample is too small, the concentration of the additive to be extracted is thin, which is less than the limit of quantification of the analyzer, and the quantification may be lacking. Moreover, if the amount of the sample is relatively large or the amount of the extraction solvent is too small, the sample film may not be sufficiently immersed in the extraction solvent, and the extraction rate may be lowered. Moreover, when there is too much absolute amount of an extraction solvent, there exists a possibility that the time of solvent removal after extraction may be long and efficiency may worsen.
Therefore, the amount of the sample is preferably 0.5 to 3 g, and the amount of the extraction solvent is preferably 30 to 100 ml.

(4) Quantitative operation A quantitative operation is performed in which an additive such as an antioxidant is quantitatively detected using the extracted sample. The detection method is not particularly limited, and an ordinary quantitative analysis method is used. GC (gas chromatography), GC-MS (combination of GC and MS (mass spectrum)), HPLC (high performance liquid chromatography), LC (liquid Chromatography), LC-MS (combination of LC and MS) or NMR (nuclear magnetic resonance spectrum) is preferred.
Prepare a standard sample containing a specified amount of additive in advance, statistically prepare the extracted sample, detect these samples, and perform quantitative detection of the extracted sample by comparing the detection results of the standard sample and the extracted sample .

(III) Extraction solvent of the present invention In the method for quantitative analysis of additives in polyolefins of the present invention, by using a specific solvent consisting of a combination of a nonpolar solvent and a slightly polar solvent, Specific additives, particularly antioxidants such as the phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IR1010) without impairing the extraction rate It became possible to extract the whole quantity.

(1) SP value (dissolution parameter)
In order to extract an additive such as an antioxidant from a polyolefin at a high extraction rate, it is considered necessary to swell the polyolefin to a preferable state. In the present invention, focusing on the solubility parameter (SP value) As a result of the examination, by setting the SP value of the extraction solvent within a predetermined range that approximates the SP value of the polyolefin, it is possible to obtain a preferable swelling state, thereby facilitating the extraction of additives such as antioxidants. found.

The extraction solvent used in the present invention preferably has an SP value close to that of polyolefin (7.7 to 9.1). Therefore, the extraction solvent used in the present invention has an SP value of 6 to 10 and more preferably 6.6 to 9.5.
The SP value is known as a solubility parameter that is a measure of the solubility of the binary solution, and can be determined according to the method described in “POLYMER HANDBOOK FOURTH EDITION (ISBN0-471-16628-6)”.

(2) Nonpolar and slightly polar solvents Furthermore, it is considered that the extraction of the phenolic antioxidant (particularly IR1010) can be promoted by swelling the polyolefin in a more preferable state.
For this reason, as a result of detailed investigation focusing on the polarity of the solvent, the solvent (A) is a nonpolar solvent, and the relative permittivity and the dipole moment of the solvent (A) related to the polarity of the solvent are within a predetermined range. Thus, it was found that the polyolefin can be swelled more preferably and the phenolic antioxidant can be extracted at a high extraction rate.

The relative permittivity (20 ° C.) of the extraction solvent A used in the present invention is defined as 0 to less than 4.5 or the dipole moment is less than 1, and the relative permittivity is less than 0 to 2.5 or the dipole moment is Preferably it is less than 0.5.
The relative dielectric constant is known as the ratio between the dielectric constant of the substance and the dielectric constant of the vacuum, and can be determined according to the method described in “Chemical Handbook Basic Edition, Rev. 5 (ISBN 4-621-07341-9 C3543)”. it can.

Furthermore, as a method for extracting a wide variety of additives at a high extraction rate, the present invention focuses on the dipole interaction between the additive and the extraction solvent.
And as a result of examining in detail, by using the solvent (B) with respect to the solvent (A) and setting the relative dielectric constant or dipole moment of the solvent (B) within a predetermined range, the additive, the extraction solvent, It has been found that a variety of additives can be extracted at a high extraction rate by further dipolar interaction.
The relative permittivity (20 ° C.) of the extraction solvent (B) used in the present invention is specified to be 4.5 or more or the dipole moment is 1 or more, the relative permittivity is 4.8 or more, or the dipole moment is 1 to 3. Preferably there is.

  The extraction solvent used in the present invention is used in combination with the solvent (A) and the solvent (B) in order to extract various additives at a high extraction rate, and has an SP value of 6 to 10 and a relative dielectric constant of 0 to 0. A nonpolar solvent (A) having a value less than 4.5 or a dipole moment of less than 1 and a micropolar solvent (B) having an SP value of 6 to 10 and a relative dielectric constant of 4.5 or more or a dipole moment of 1 or more The extraction solvent is preferably included.

(3) Specific examples of extraction solvent The extraction solvent used in the present invention is typically a hydrocarbon nonpolar solvent as the nonpolar solvent (A), and a heteroatom-containing hydrocarbon micropolar solvent as the micropolar solvent (B). As mentioned. As the mixed solvent of the present invention, a mixed solvent of these solvents is used.

Examples of the nonpolar solvent (A) include pentane, hexane, heptane, cyclopentane, cyclohexane and the like, and hexane is preferable.
Examples of the slightly polar solvent (B) include chloroform, tetrahydrofuran, acetone, and the like. Chloroform and tetrahydrofuran are preferable, and chloroform is particularly preferable.
Solvents (A) and (B) are not limited to the above representative examples, and (A) and (B) may be used alone or in combination of two or more.

  The amount of the nonpolar solvent (A) used is preferably 99 to 0.1 times, more preferably 9 to 1 times the volume of the micropolar solvent (B) such as chloroform.

(IV) Polyolefin The object of quantitative analysis of the additive of the present invention is a polyolefin, and is not particularly limited, but is preferably a polyolefin having crystallinity.
Examples thereof include polyethylene, polypropylene, polybutene, block polypropylene which is a mixture of polypropylene and an ethylene-propylene copolymer, or a mixture of these resins.

(V) Additive The additive that is the object of the quantitative analysis of the present invention is not particularly limited, but various types such as an antioxidant, an antistatic agent, an ultraviolet absorber, a nucleating agent, a flame retardant, a lubricant, a colorant, and a filler. Additives are targeted and are particularly useful for quantitative analysis of antioxidants.

  Examples of the antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, trade name Irganox 1010), tris (2,4- Di-t-butylphenyl) phosphite (manufactured by BASF Japan Ltd., trade name Irgafos 168), UV absorber, for example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5 Chlorobenzotriazole (manufactured by BASF Japan Ltd., trade name Tinuvin 326), as a lubricant, for example, erucic acid amide (manufactured by Lion Specialty Chemicals Co., Ltd., trade name Armoslip E), and as a flame retardant, for example, bis (3,5-dibromo-4-dibromopropyloxyphenyl) Hong (Maruhishiyu Kogyo Co., Ltd. under the trade name Non'nen PR-2) and the like.

(VI) Use of quantitative analysis By using the quantitative analysis method of the present invention, it becomes possible to accurately and quickly analyze the amount of additives in polyolefin resin products. It can be applied to product quality control.

(1) Process control As an example of process control of a method for producing a polyolefin resin, the difference between the standard value of the amount of various additives blended in the polyolefin and the analytical value of the amount of additive determined by the above method is obtained. There is a manufacturing method including a step and a feedback step of adjusting the amount of additive to be blended according to the magnitude of this difference.

  In the manufacturing method of the present invention, the standard value is, for example, a value that is experimentally and artificially determined in advance so that a desired reforming width can be stably obtained. And / or a numerical range having a lower limit.

Determine whether the amount of additive in the sample meets the specified value by providing a step to determine the difference between the specified value and the analytical value of the additive amount determined by the above method for a representative sample of polyolefin resin can do. When obtaining the difference, a bias (a margin value / deviation value) may be provided. When it is determined that the standard value is not satisfied, the amount of additive to be blended can be adjusted according to the magnitude of the difference by feedback.
The representative sample of the polyolefin resin is preferably sampled so that the analytical value is statistically a representative value. In the production method of the present invention, the difference may be a ratio or a numerical value.

(2) Quality control As an example of a method for quality control of polyolefin resin, a step of comparing the standard value of the amount of additive blended in the polyolefin with the analytical value of the amount of additive determined by the above method, and the like And a step of determining whether or not to sell the polyolefin based on the comparison.
Since the modification range of the physical properties of polyolefin depends on the addition amount, the addition amount is generally standardized so that a desired modification range can be stably obtained.

  In the quality control method of the present invention, the standard value is, for example, a value determined experimentally and artificially in advance so that a desired reforming width can be stably obtained. It may be a numerical range having a value and / or a lower limit. It is determined whether or not the amount of the additive in the sample satisfies the standard value by providing a step for comparing the standard value with the analytical value of the additive amount obtained by the above method for the representative sample of the polyolefin resin. be able to. A bias may be provided for comparison.

  If it is determined that the standard value is not satisfied, it can be determined that the desired modification range cannot be stably obtained, and it can be determined that the polyolefin resin is not sold, and it is determined that the standard value is satisfied. In such a case, it can be determined that the desired modification width can be stably obtained and the polyolefin resin is sold. The representative sample of the polyolefin resin is preferably sampled so that the analytical value is statistically a representative value. Such quality control can increase customer satisfaction.

  The present invention will be described in more detail by the following examples and comparative examples. However, the present invention is not limited to these, and demonstrates the rationality, significance and usefulness of the configuration of the present invention and the superiority over the prior art. To do.

The sample, solvent, and analysis conditions used in the experiment are described below. The SP value (cal / cm ³ ) ^1/2 of the solvent is the value described in “POLYMER HANDBOOK 4th (ISBN 0-471-16628-6)”, relative dielectric constant (20 ° C.), dipole moment and boiling point. "CRC HANDBOOK OF CHEMISTRY and PHYSICS 88th (ISBN-0-849-0488-1)" or "CRC CHEMISTRY and PHYSICS 73rd (ISBN-0-8493-0473-3)" ISBN 4-621-07341-9 C35
The values listed in 43) were used.

(1) Sample Sample 1: Polyethylene to which 0.04% by weight of antioxidant A (IR1010), 0.10% by weight of antioxidant B, and 0.10% by weight of lubricant C were added Sample 2: Antioxidation Polypropylene with 0.13% by weight of Agent A (IR1010) and 0.16% by weight of Antioxidant B Antioxidant A (IR1010): Pentaerythritol tetrakis [3- (3,5-di-tert-butyl -4-hydroxyphenyl) propionate] (trade name Irganox 1010, manufactured by BASF Japan Ltd.)
Antioxidant B: Tris (2,4-di-t-butylphenyl) phosphite Lubricant C: Erucamide

(2) Extraction solvent Solvent 1: Hexane / chloroform = 4/6 (volume ratio) mixed solvent Hexane: SP value 7.3, relative dielectric constant 1.89, boiling point 68.7 ° C., dipole moment≈0 Chloroform: SP value 9.3, relative dielectric constant 4.81, boiling point 61.1 ° C., dipole moment 1.04
Solvent 2: Mixed solvent of hexane / chloroform = 1/9 (volume ratio) Solvent 3: Mixed solvent of cyclohexane / chloroform = 1/9 (volume ratio) cyclohexane: SP value 8.2, relative dielectric constant 2.02, boiling point 80.7 ° C, dipole moment ≒ 0
Solvent 4: Mixed solvent of hexane / tetrahydrofuran = 9/1 (volume ratio) Tetrahydrofuran: SP value 9.1, relative dielectric constant 7.6, boiling point 65 ° C., dipole moment 1.75
Solvent 5: Hexane Solvent 6: Cyclohexane Solvent 7: Chloroform Solvent 8: Mixed solvent of chloroform / tetrahydrofuran = 9/1 (volume ratio) Solvent 9: Mixed solvent 2- of cyclohexane / 2-propanol = 1/1 (volume ratio) Propanol: SP value 11.5, relative permittivity 20.18, boiling point 82.3 ° C, dipole moment 1.56
Solvent 10: Mixed solvent of chloroform / acetone = 6/4 (volume ratio) Acetone: SP value 9.9, relative permittivity 21.01, boiling point 56 ° C., dipole moment 2.88

(3) Analysis conditions A solution obtained by adding 50 ml of extraction solvent to 1 g of a sample and extracting the additive by ultrasonic extraction is collected in an eggplant flask. After completely removing the solvent of the extract with an evaporator, 10 ml of chloroform is added to prepare a sample solution.
The sample solution is filtered through a 0.2 μm syringe filter, and the antioxidant is measured and quantified under the conditions of liquid chromatography shown in Table 1, and the lubricant C is measured under the conditions of gas chromatography shown in Table 2.

（ＧＲ：グラジエント溶出 ＩＳＯ：アイソクラティック溶出）

(GR: gradient elution ISO: isocratic elution)

[Example 1] 0.04% by weight of antioxidant A (IR1010) and 0.1% of antioxidant B
Polyethylene (sample 1) to which 0% by weight and 0.10% by weight of lubricant C were added was formed into a film having a thickness of about 80 μm using a hot press.
1 g of this film was collected in an Erlenmeyer flask together with 50 ml of solvent 1 and fixed to an ultrasonic extractor in which a hot water bath was set at 60 ° C. The temperature of the extraction solvent was 60 ° C. In this state, ultrasonic extraction is carried out for 1 hour and 30 minutes, followed by filtration using # 5 filter paper, and the extract is recovered in an eggplant flask. The solvent of the extract was completely removed with an evaporator, and 10 ml of a mixed solvent of chloroform / acetone = 1/9 (volume ratio) was added to the eggplant flask to obtain a sample solution.

  A solution prepared by dissolving 15 mg of antioxidant A or antioxidant B or lubricant C in 100 ml of a mixed solvent of chloroform / acetone = 1/99 (volume ratio) was used as a standard solution. Sample solution and standard solution were measured by liquid chromatography and gas chromatography, respectively, and the peak area and standard attributed to antioxidant A (IR1010), antioxidant B, and lubricant C in the chromatogram of the sample solution were measured. The liquid chromatogram was quantitated using antioxidant A (IR1010), antioxidant B, and the peak area of lubricant C.

[Example 2] Sample 1 was used as a sample, and solvent 2 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Example 3] Sample 1 was used as a sample, and solvent 3 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Example 4] Sample 1 was used as a sample, and solvent 4 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Example 5] Sample 2 was used as a sample, and solvent 2 was used as an extraction solvent. Antioxidant A and antioxidant B were extracted under the same conditions as in Example 1, and measured and quantified.

[Comparative Example 1] Sample 1 was used as a sample, and solvent 5 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Comparative Example 2] Sample 1 was used as a sample, and solvent 6 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Comparative Example 3] Sample 1 was used as a sample, and solvent 7 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Comparative Example 4] Sample 1 was used as a sample, and solvent 8 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Comparative Example 5] Sample 1 was used as a sample, and solvent 9 was used as an extraction solvent. Antioxidant A, antioxidant B, and lubricant C were extracted under the same conditions as in Example 1, and measured and quantified. .
[Comparative Example 6] Sample 2 was used as a sample, and solvent 10 was used as an extraction solvent. Antioxidant A and antioxidant B were extracted under the same conditions as in Example 5 for measurement and quantification.
The quantitative values of antioxidant A, antioxidant B, and lubricant C of each sample are as shown in Table 3.

Table 4 below describes the reasons for selecting the examples and comparative examples.

[Consideration of results of Examples and Comparative Examples]
As is clear from Tables 3 and 4, in the quantitative analysis of each example by the method of the present invention using various extraction solvents, antioxidants A and B and lubricant C were extracted at a high rate of 90% or more. Has been. These results have been demonstrated for both polyethylene and polypropylene.
On the other hand, in the case of each comparative example not using the method of the present invention, in comparative examples 1 and 2 using only the solvent (A), the extraction rate of the lubricant C is low, and in comparative example 3 using only the solvent (B). In Comparative Example 4 where the extraction rate of the antioxidant A is low and only the solvent (B) is used, the extraction rates of the antioxidant A and the lubricant C are low. In Comparative Example 5 using the solvent of the conventional extraction method, the extraction rate of the antioxidant A and the lubricant C is low, and in Comparative Example 6 using only the solvent (B) in HPP, the extraction rate of the antioxidant A is low.
Therefore, the rationality, significance and usefulness of the composition of the present invention and the superiority over the prior art are proved.

  Thus, in the present invention, the additives contained in the polyolefin, particularly antioxidants, are extracted easily and efficiently, and the additives, particularly antioxidants, are analyzed with a high extraction rate, and the extraction rate of other additives The effect of the invention that it is an accurate and simple quantitative analysis method for additives, particularly antioxidants, is experimentally clarified.

According to the present invention, since the additive contained in the polyolefin can be efficiently extracted at a high extraction rate, it becomes a more accurate and simple quantitative analysis method for the additive, particularly the antioxidant, compared to the conventional method. And since this quantitative analysis method can be utilized for management and quality control of the manufacturing process of polyolefin, it is very useful in the industry of polyolefin manufacture.

Claims (9)

In a method for quantitative analysis of additives contained in polyolefin, a polyolefin sample is obtained with an SP value (solubility parameter) of 6 to 10 and a relative dielectric constant (20 ° C.) of less than 0 to 4.5 or a dipole moment of less than 1. One or two or more kinds of nonpolar solvents (A), an SP value of 6 to 10 and a relative dielectric constant (20 ° C.) of 4.5 or more, or a dipole moment of 1 or more The quantitative analysis method of the additive contained in polyolefin characterized by including operation which impregnates and extracts in the mixed solvent containing the above micropolar solvent (B). The method for quantitative analysis of an additive contained in a polyolefin according to claim 1, wherein the additive is a phenol-based antioxidant. The phenolic antioxidant is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], contained in a polyolefin according to claim 2, characterized in that Quantitative analysis method for additives. The method for quantitative analysis of an additive contained in a polyolefin according to any one of claims 1 to 3, wherein the nonpolar solvent (A) is a hydrocarbon nonpolar solvent. The method for quantitative analysis of an additive contained in a polyolefin according to any one of claims 1 to 4, wherein the micropolar solvent (B) is a heteroatom-containing hydrocarbon-based micropolar solvent. The additive contained in the polyolefin according to any one of claims 1 to 5, wherein the extraction operation is an ultrasonic solvent extraction operation using an extraction solvent in a temperature range of 40 to 70 ° C. Quantitative analysis method. The method for quantitative analysis of an additive contained in a polyolefin according to any one of claims 1 to 6, wherein the mixing volume ratio of the nonpolar solvent to the micropolar solvent is 99 to 0.1 times. . A step of obtaining a difference between a standard value of the amount of additive to be blended in the polyolefin and an analytical value of the amount of additive obtained by the method according to any one of claims 1 to 7, and blending according to the magnitude of the difference A method for producing a polyolefin resin, comprising a feedback step of adjusting the amount of additive used. A step of comparing the standard value of the amount of additive blended in the polyolefin with the analytical value of the amount of additive determined by the method according to any one of claims 1 to 7, and whether or not to sell the polyolefin And a step of determining the quality control method of the polyolefin resin.