Composition

Abstract

Provided is a composition that contains a compound having polymerizability, that has high storage stability, and that can suppress corrosion of metal during storage. This composition contains an unsaturated compound represented by formula (1) and an organic halide. The contained amount of the organic halide expressed as halogen elements is 1-10,000 mass ppm with respect to the contained amount of the unsaturated compound. In formula (1), R1, R2, R3, R4, R5, and R6 each independently represent a hydrogen atom or an alkyl group having 1-10 carbon atoms.

Description

composition

[0001] The present invention relates to a composition.

[0002] 2-Methylene-1,3-propanediol diacetate (hereinafter also referred to as "MPDAc") is used, for example, as a modifier (comonomer) for ethylene-vinyl alcohol copolymer (hereinafter also referred to as "EVOH") (see Patent Document 1). MPDAc-modified EVOH obtained by saponifying a copolymer of ethylene, a vinyl ester, and MPDAc has improved moldability while maintaining good barrier properties compared to unmodified EVOH. Similar effects can be achieved when a compound in which some atoms of MPDAc have been substituted is used. Hereinafter, MPDAc and compounds in which some atoms of MPDAc have been substituted will be collectively referred to as "MPDAc, etc."

[0003] JP 2014-34647 A

[0004] As described above, MPDAc and the like are polymerizable compounds, and a polymerization inhibitor is added to suppress polymerization reactions during storage. Before carrying out polymerization using MPDAc and the like, it is necessary to remove the added polymerization inhibitor. However, MPDAc and the like have a high boiling point of 200°C or higher. Therefore, in order to remove the polymerization inhibitor from MPDAc and the like at low temperatures, it is necessary to use reduced pressure distillation equipment, which reduces production efficiency.

[0005] In response to this, the inventors have found that the organic halide acts as a polymerization inhibitor for MPDAc, etc. during storage, and that at the relatively high temperatures at which the polymerization reaction of MPDAc, etc. occurs, a good polymerization reaction of MPDAc, etc. occurs even without removing the organic halide. Furthermore, compositions with a high content of organic halide may cause corrosion of metal containers during storage.

[0006] The present invention has been made based on the above circumstances, and an object of the present invention is to provide a composition containing a polymerizable compound, which has high storage stability and can also inhibit metal corrosion during storage.

[0007] The above object is to provide a composition comprising: [1] an unsaturated compound represented by the following formula (1) and an organic halide, wherein the content of the organic halide in terms of halogen element based on the content of the unsaturated compound is 1 ppm by mass or more and 10,000 ppm by mass or less; (In the above formula (1), R １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) [2] The composition of [1], in which the content of the unsaturated compound is 95% by mass or more; [3] The composition of [1] or [2], in which the content of the inorganic halide, calculated as a halogen element based on the content of the unsaturated compound, is 10 ppm by mass or less; [4] Any of the compositions of [1] to [3], in which the organic halide includes a compound represented by the following formula (2): (In the above formula (2), X is a halogen atom. R ７ and R ８ satisfies one of the following requirements A, B, and C. Requirement A: R ７ is CR ９ R １０ =CR １１ - (R ９ , R １０ and R １１ are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group. ８ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group. ７ R is a secondary or tertiary monovalent hydrocarbon group, or a secondary or tertiary monovalent halogenated hydrocarbon group. ８ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group. ７ and R ８ are each independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group. [5] R in the above formula (2) ７ and R ８[6] The composition according to any one of [1] to [5], wherein the organic halide contains a compound having a carbon-carbon unsaturated double bond; [7] The composition according to [4], wherein the organic halide contains a compound having a carbon-carbon unsaturated double bond; ４ H ５ X ３ (X is a halogen atom); [8] any one of the compositions [1] to [7] used in the synthesis of a polymer.

[0008] According to the present invention, it is possible to provide a composition containing a polymerizable compound, which has high storage stability and can inhibit metal corrosion during storage.

[0009] The composition of the present invention contains an unsaturated compound represented by the following formula (1) (hereinafter also referred to as "unsaturated compound (A)") and an organic halide (hereinafter also referred to as "organic halide (B)"), and the content of the organic halide (B) in terms of halogen element, based on the content of the unsaturated compound (A), is 1 ppm by mass or more and 10,000 ppm by mass or less.

[0010]

[0011] In the above formula (1), R １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0012] The composition of the present invention contains a polymerizable compound, has high storage stability, and can inhibit metal corrosion during storage. While the reason for this is unclear, it is presumed that the organic halide (B) functions as a polymerization inhibitor during storage of the unsaturated compound (A), and that the organic halide (B), which can cause metal corrosion, is not present in excess. Furthermore, even when the composition is subjected to a polymerization reaction without a purification procedure such as distillation (a procedure for removing the organic halide (B)), a satisfactory polymerization reaction occurs. This is thought to be due to the fact that the organic halide (B) is effective in inhibiting the polymerization reaction of the unsaturated compound (A) at temperatures typically encountered during storage (e.g., room temperature), but is barely effective at inhibiting the polymerization reaction at temperatures above 80°C. The reason for this is presumably that, under the temperature of a typical storage environment, at least a portion of the organic halide (B) exists as a highly stable radical, and functions as a polymerization inhibitor by capturing the radical of the unsaturated compound (A) generated by heat, light, oxygen, etc., but at high temperatures, the stability of the radical of the organic halide (B) becomes relatively low.

[0013] Each component of the composition of the present invention will be specifically described below.

[0014] (Unsaturated Compound (A)) The unsaturated compound (A) is a compound represented by the above formula (1). In the above formula (1), R １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0015] R in the above formula (1) １ , R ２ , R ３ , R ４ , R ５ and R ６ Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms is preferred.

[0016] R in the above formula (1) １ , R ２ , R ３ and R ４ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0017] R in the above formula (1) ５ and R ６ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0018] R in the above formula (1) １ , R ２ , R ３ and R ４ is a hydrogen atom, and R ５ and R ６ is a methyl group, the unsaturated compound (A) is 2-methylene-1,3-propanediol diacetate (MPDAc). One or more kinds of unsaturated compounds (A) can be used.

[0019] The content of the unsaturated compound (A) in the composition of the present invention is not particularly limited, and may be, for example, 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more, but is preferably 95% by mass or more, more preferably 99% by mass or more, even more preferably 99.5% by mass or more, and particularly preferably 99.9% by mass or more. When the unsaturated compound (A) accounts for the majority of the composition of the present invention, the composition is particularly suitable for use as a monomer raw material. The content of the unsaturated compound (A) in the composition may be 99.9999% by mass or less, or 99.999% by mass or less, or 99.99% by mass or less.

[0020] The unsaturated compound (A) can be produced by a conventionally known method, such as a method of reacting 2-methylene-1,3-propanediol with acetic anhydride or a method of reacting β-methallyl acetate with acetic acid in the presence of a metal catalyst and in an oxygen atmosphere.

[0021] (Organic Halide (B)) The organic halide (B) is not particularly limited as long as it is an organic substance containing a halogen. Examples of the halogen contained in the organic halide (B) include fluorine, chlorine, bromine, and iodine, with chlorine being preferred. That is, the organic halide (B) is preferably an organic chlorine compound. The organic halide (B) may be, for example, one composed of carbon atoms, hydrogen atoms, and halogen atoms, or one composed of carbon atoms, hydrogen atoms, and chlorine atoms.

[0022] The organic halide (B) preferably has a structure in which at least one hydrogen atom and at least one halogen atom (preferably a chlorine atom) are bonded to one carbon atom (X-C-H: X is a halogen atom). In such a structure, the dissociation energy of the C-H bond is low. Therefore, radicals are easily generated from the organic halide (B) having such a structure, and the generated radicals are relatively stable, resulting in improved storage stability.

[0023] The organic halide (B) preferably contains a compound represented by the following formula (2), and more preferably is a compound represented by the following formula (2).

[0024]

[0025] In the above formula (2), X is a halogen atom. ７ and R ８ satisfies one of the following requirements A, B, and C. Requirement A: R ７ is CR ９ R １０ =CR １１ - (R ９ , R １０ and R １１ are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group. ８ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group. ７R is a secondary or tertiary monovalent hydrocarbon group, or a secondary or tertiary monovalent halogenated hydrocarbon group. ８ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or a monovalent halogenated hydrocarbon group. ７ and R ８ are each independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

[0026] X and R in the above formula (2) ８ , R ９ , R １０ and R １１ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is preferred.

[0027] R in the above formula (2) ７ , R ８ , R ９ , R １０ and R １１ The monovalent hydrocarbon group represented by the formula (I) may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group, with an alkyl group or an alkenyl group being preferred, and an alkyl group being more preferred. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkenyl group include an ethenyl group and a propenyl group. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 6, and more preferably 1 to 4.

[0028] R in the above formula (2) ７ , R ８ , R ９ , R １０ and R １１ Examples of the monovalent halogenated hydrocarbon group represented by the formula (I) include groups in which at least one hydrogen atom of the above-mentioned monovalent hydrocarbon group has been substituted with a halogen atom (preferably a chlorine atom). The number of carbon atoms in the monovalent halogenated hydrocarbon group is preferably 1 to 6, and more preferably 1 to 4.

[0029] R in the above formula (2) ７Examples of the secondary or tertiary monovalent hydrocarbon group represented by the formula (I) include secondary or tertiary aliphatic hydrocarbon groups such as secondary or tertiary alkyl groups and secondary or tertiary alkenyl groups, with secondary or tertiary alkyl groups being preferred. Examples of secondary alkyl groups include an isopropyl group and a sec-butyl group. Examples of tertiary alkyl groups include a tert-butyl group and a tert-pentyl group. The number of carbon atoms in the secondary or tertiary monovalent hydrocarbon group is preferably 3 to 6.

[0030] R in the above formula (2) ７ Examples of the secondary or tertiary monovalent halogenated hydrocarbon group represented by the formula (I) include groups in which at least one hydrogen atom of the above-mentioned secondary or tertiary monovalent hydrocarbon group has been substituted with a halogen atom (preferably a chlorine atom). The number of carbon atoms in the secondary or tertiary monovalent halogenated hydrocarbon group is preferably 3 to 6.

[0031] R in the above formula (2) ７ and R ８ may satisfy two or more of the above requirements A, B, and C.

[0032] The organic halide (B) satisfying the above requirement A is a compound that generates an allyl radical when H (hydrogen atom) dissociates from the X—C—H structure. Because the allyl radical is highly stable, the use of such a form of organic halide (B) can improve storage stability.

[0033] In a form that satisfies the above requirement A, R ８ is preferably a hydrogen atom. ９ and R １０ is preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom or a chlorine atom. １１ is preferably a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, more preferably an alkyl group or a halogenated alkyl group, even more preferably a methyl group or a halogenated methyl group, and even more preferably a methyl group or a chloromethyl group. １１ The number of carbon atoms in the group is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0034] Examples of the organic halide (B) that satisfies the above requirement A include 1,1,3-trichloro-2-methyl-1-propene, 3-chloro-2-methyl-1-propene, 3-chloro-2-chloromethyl-1-propene, 3-chloro-1-propene, 3-chloro-1-butene, 1,1,3-trichloro-1-butene, 1,3,4-trichloro-1-butene, and 1,3,3-trichloro-2-butene.

[0035] The organic halide (B) that satisfies the above requirement B is a compound in which, when H (hydrogen atom) dissociates from the X—C—H structure, the resulting carbon radical contains a bulky secondary or tertiary monovalent hydrocarbon group, or a secondary or tertiary monovalent halogenated hydrocarbon group (R ７ ) are adjacent to each other. This carbon radical is unlikely to react with other compounds due to steric hindrance. Therefore, even when using an organic halide (B) in this form, storage stability can be improved.

[0036] In a configuration that satisfies the above requirement B, R ７ is preferably a secondary monovalent hydrocarbon group or a secondary monovalent halogenated hydrocarbon group. ７ It is also preferred that R is a secondary or tertiary monovalent halogenated hydrocarbon group. ７ is more preferably a secondary halogenated alkyl group or a secondary halogenated alkenyl group, and more preferably a secondary halogenated alkyl group or a secondary chlorinated alkenyl group. ７ The number of carbon atoms in R is preferably 3 to 6, more preferably 3 or 4, and even more preferably 3. ８ is preferably a hydrogen atom.

[0037] Examples of the organic halide (B) that satisfies the above requirement B include 1,2,3-trichloro-2-methylpropane, 1-chloro-2-methylpropane, 1-chloro-2,2-dimethylpropane, 1-chloro-2-ethylbutane, 2-ethenyl-1-chloropentane, 1,1,3-trichloro-2-methyl-1-propene, and 3-chloro-2-chloromethyl-1-propene.

[0038] The organic halide (B) that satisfies the above requirement C is a compound that generates a secondary radical when H (hydrogen atom) dissociates from the X—C—H structure. Because the secondary radical is also sufficiently stable, the use of such a form of organic halide (B) can improve storage stability.

[0039] In a form that satisfies the above requirement C, R ７ and R ８ is preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group or a chlorinated alkyl group. ７ and R ８ The number of carbon atoms is preferably 1 to 3, and more preferably 1 or 2.

[0040] Examples of the organic halide (B) that satisfies the above requirement C include 2-chlorobutane, 2-chloro-2-methylbutane, 2-chloropropane, 3-chloropentane, and 3-chloro-1-pentene.

[0041] Among these, from the viewpoint of exhibiting particularly good storage stability, the organic halide (B) is a compound represented by the above formula (2) in which R ７ and R ８ It is preferable that the organic halide (B) satisfies the above requirement A. The organic halide (B) may also satisfy the above requirement B, and it is more preferable that the organic halide (B) satisfies both the above requirement A and the above requirement B.

[0042] It is also preferable that the organic halide (B) contains a compound having a carbon-carbon unsaturated double bond. Such organic halides can also exhibit good storage stability due to the high stability of the radicals generated. The compound having a carbon-carbon unsaturated double bond is, for example, a compound represented by the above formula (2) having a carbon-carbon unsaturated double bond (typically, R ７ and R ８ satisfies the above requirement A), as well as 4-chloro-1-butene, 1,4-dichloro-1-butene, 4-chloro-1,3-butadiene, chloroethylene, etc.

[0043] The organic halide (B) is C ４ H ５X ３ (X is a halogen atom), ４ H ５ X ３ The use of such an organic halide (B) particularly satisfies the effects of the present invention, namely, high storage stability and suppression of metal corrosion during storage. Examples of such organic halide include 1,1,3-trichloro-2-methyl-1-propene, 1,1,3-trichloro-1-butene, 1,3,4-trichloro-1-butene, and 1,3,3-trichloro-2-butene.

[0044] In the composition of the present invention, the content of the organic halide (B) in terms of halogen element based on the content of the unsaturated compound (A) is 1 mass ppm or more and 10,000 mass ppm or less. The lower limit of the content of the halide (B) is preferably 10 mass ppm, more preferably 30 mass ppm, even more preferably 50 mass ppm, and in some cases even more preferably 100 mass ppm, 200 mass ppm, 300 mass ppm, 400 mass ppm or 500 mass ppm. By having the content of the halide (B) be equal to or more than the above lower limit, the storage stability of the composition can be improved. The upper limit of the content of the halide (B) is preferably 5,000 ppm by mass, more preferably 3,000 ppm by mass, even more preferably 2,500 ppm by mass, and in some cases even more preferably 2,200 ppm by mass, 2,000 ppm by mass, 1,600 ppm by mass, 1,300 ppm by mass, or 1,000 ppm by mass. When the content of the halide (B) is equal to or less than the upper limit, corrosion of metals (metal containers, etc.) during storage of the composition can be suppressed. In addition, when the content of the halide (B) is equal to or less than the upper limit, there are also advantages such as reduced odor of the composition and improved handleability.

[0045] The total content of the unsaturated compound (A) and the organic halide (B) in the composition of the present invention is preferably 95% by mass or more, more preferably 99% by mass or more, even more preferably 99.5% by mass or more, and particularly preferably 99.9% by mass or more. The total content of the unsaturated compound (A) and the organic halide (B) in the composition may be 100% by mass, or may be 99.9999% by mass or less, 99.999% by mass or less, or 99.99% by mass or less. In such a case, the composition is particularly suitable for use as a monomer raw material.

[0046] The organic halide (B) can be produced by a conventionally known method. A commercially available product can also be used as the organic halide (B). One or more organic halides (B) can be used.

[0047] (Other Components) The composition of the present invention may further contain other components in addition to the unsaturated compound (A) and the organic halide (B). Examples of other components include a solvent, an inorganic halide, and water.

[0048] Examples of inorganic halides include chlorine, hydrochloric acid, sodium chloride, etc. However, in the composition of the present invention, the content of inorganic halides in terms of halogen element based on the content of unsaturated compound (A) is preferably 10 mass ppm or less, more preferably 3 mass ppm or less, even more preferably 1 mass ppm or less, and may be substantially 0 mass ppm. It is preferable that the composition of the present invention does not contain inorganic halides. Thus, when the content of inorganic halides is low, metal corrosion is further reduced.

[0049] In addition, in the composition of the present invention, the water content is preferably 10,000 mass ppm or less, more preferably 2,000 mass ppm or less, 1,000 mass ppm or less, 500 mass ppm or less, 100 mass ppm or less, or 50 mass ppm or less. When the composition contains water, a carboxylic acid is generated by the hydrolysis reaction of the unsaturated compound (A), and a portion of the organic halide (B) is decomposed, which may generate chloride ions that cause metal corrosion. Therefore, when the water content is not more than the above upper limit, metal corrosion is further reduced.

[0050] (Preparation Method) The method for preparing the composition of the present invention is not particularly limited, and can be carried out by a conventionally known method. Typically, the composition can be prepared by adding a predetermined amount of an organic halide (B) to an unsaturated compound (A).

[0051] (Uses, etc.) The composition of the present invention can be used in various applications that are conventionally known for the use of MPDAc, etc. In particular, the composition is suitably used in the synthesis of a polymer. That is, the composition can be used as a polymerization material in which the unsaturated compound (A) contained in the composition is used as a monomer. The composition may be a polymerization composition. In particular, the composition can be suitably used as a material (polymerization composition) for producing a modified ethylene-vinyl ester copolymer (modified EVOH). When the composition is used in the synthesis of a polymer, a good polymerization reaction occurs even without reducing the content of the organic halide (B) through a purification procedure. Therefore, a method for producing a polymer using the composition also has high productivity.

[0052] Modified EVOH can be obtained, for example, by a production method comprising the steps of copolymerizing the unsaturated compound (A) contained in the composition of the present invention with ethylene and a vinyl ester, and saponifying the resulting copolymer. Such modified EVOH is characterized by enhanced stretchability and shrinkability while maintaining good barrier properties compared to unmodified EVOH. Furthermore, the modified EVOH obtained by such a production method does not contain chlorine atoms in the polymer. Therefore, when the modified EVOH is melt-kneaded and recycled, hydrochloric acid is not generated, making it easy to recycle. Modified EVOH produced using a composition containing the unsaturated compound (A) and the organic halide (B) in a certain ratio of the present invention also contains no chlorine atoms in the polymer, or only a very small amount of chlorine atoms, and is therefore characterized by excellent recyclability by melt-kneading.

[0053] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0054] The compounds used in the examples and comparative examples are as follows: Unsaturated compound (A) MPDAc: a compound represented by the following formula (A1) Organic halide (B) B1: 1,1,3-trichloro-2-methyl-1-propene (a compound represented by the following formula (B1): R in the above formula (2) ７ is CCl ２ =C(CH ３ ) -, R ８ is a hydrogen atom and X is a chlorine atom) B2: 3-chloro-2-chloromethyl-1-propene (a compound represented by the following formula (B2): ７ is CH ２ =C(CH ２ Cl)-, R ８ is a hydrogen atom and X is a chlorine atom) B3: 1,2,3-trichloro-2-methylpropane (a compound represented by the following formula (B3): ７ is CH ２ Cl-CCl(CH ３ ) -, R ８is a hydrogen atom and X is a chlorine atom) B4: 2-chlorobutane (a compound represented by the following formula (B4): a compound represented by the formula (2) above, ７ is CH ３ -, R ８ is CH ３ CH ２ -, compounds in which X is a chlorine atom)

[0055]

[0056]

[0057] The organic halide (B1) used was produced according to the method described in a known document (Doctoral thesis title: INVESTIGATION OF THE REACTIONS OF 1,1,3-TRICHLORO-2-METHYL-1-PROPENE AND RELATED COMPOUNDS WITH CERTAIN AROMATICS, 1955, author HDEI PLEDGER, JR.). The organic halide (B2) and the organic halide (B4) used were commercially available reagents from Tokyo Chemical Industry Co., Ltd. The organic halide (B3) was prepared according to a known document (title: Identification of the higher-boiling products resulting from chlorination of isobutylene) Chemikke Zvestii, Vol. 27, No. 3, pp. 355-358 (1973). MPDAc and the organic halides (B1) to (B4) were used in each of the Examples and Comparative Examples after their moisture contents were reduced to 10 ppm or less using nitrogen bubbling or a molecular sieve 3A.

[0058] [Example 1] (1) Storage stability test after 1 month at 40 ° C. A solution obtained by diluting MPDAc 100 times with acetonitrile was analyzed by gas chromatography (analytical equipment: GC-2014 (Shimadzu Corporation), detector: FID (flame ionization detector), column: Rxi-5ms (length 30 m, film thickness 0.25 μm, inner diameter 0.25 mm, manufactured by RESTEK), analytical conditions: vaporization chamber temperature: 230 ° C., detector temperature: 300 ° C., heating conditions: after holding at 50 ° C. for 3 minutes, heating to 250 ° C. at 10 ° C. / min, and then holding at 250 ° C. for 10 minutes)), and the peak area of ​​MPDAc detected at a retention time of 12.1 minutes was measured. Subsequently, 99.90 parts by mass of MPDAc and 0.10 parts by mass of organic halide (B1) were mixed in air at 23 ° C. to obtain the mixed solution (composition) of Example 1. The halogen element-equivalent content of organic halide (B1) based on the MPDAc content in the obtained mixed solution was 673 ppm by mass. A portion of this mixed solution was taken out and diluted in the same manner, and the diluted solution was injected into gas chromatography to measure the MPDAc peak area. The MPDAc content of the mixed solution was determined from the peak area ratio (MPDAc peak area of ​​the mixed solution / MPDAc peak area of ​​the MPDAc solution alone). The MPDAc content of the mixed solution before storage is shown in Table 1. The mixed solution was then sealed in a 100 mL glass bottle. Before sealing, 1 mL of the mixed solution was taken out and the MPDAc content of the mixed solution before storage was measured. The mixed solution sealed in the glass bottle was stored in a constant temperature bath at 40°C for one month. After storage, the temperature was returned to 23°C, and the mixed solution was diluted under the same conditions. The diluted solution was injected into gas chromatography to measure the MPDAc peak area. The MPDAc content after storage at 40°C for 1 month was determined from the peak area ratio (MPDAc peak area of ​​the mixed solution after storage / MPDAc peak area of ​​the MPDAc solution alone that was not subjected to a storage test). The MPDAc content of the mixed solution after storage is shown in Table 1. In addition, the percentage of the MPDAc content of the mixed solution after storage relative to the MPDAc content of the mixed solution before storage was calculated as the ratio of undegraded MPDAc. The results are shown in Table 1. As shown in Table 1, the ratio of undegraded MPDAc was high even after storage at 40°C for 1 month.

[0059] (2) Corrosion Resistance Test of Iron Containers 0.2 parts by mass of water was added to 100 parts by mass of the mixed solution of MPDAc and organic halide prepared in (1) above, and the mixture was stored at 40 ° C. in a 20 L iron pail for 1 month. 0.5 g of the mixed solution after 1 month of storage was placed in a Teflon (registered trademark) pressure vessel, and 5 mL of concentrated nitric acid was added thereto and decomposed at room temperature for 30 minutes. The vessel was then capped and heated at 150 ° C. for 10 minutes, then at 180 ° C. for 5 minutes using a wet decomposition apparatus (manufactured by Actac Co., Ltd.: "MWS-2"), followed by cooling to room temperature. This treated solution was transferred to a 50 mL measuring flask (manufactured by TPX) and diluted with pure water. The iron element content of this solution was analyzed using an ICP atomic emission spectrometer (manufactured by PerkinElmer, "OPTIMA 4300DV"). Corrosion resistance was evaluated based on the iron content using the following criteria. A: Less than 5 ppm B: 5 ppm or more and less than 10 ppm C: 10 ppm or more The results are shown in Table 1. The iron content in the mixed solution was less than 5 ppm, and no iron corrosion was confirmed.

[0060] (3) Polymerization Evaluation (3-1) Synthesis of Modified Ethylene-Vinyl Acetate Copolymer 99.90 parts by mass of MPDAc and 0.10 parts by mass of organic halide (B-1) were mixed to prepare an MPDAc mixed solution (composition). A 250 L pressurized reactor equipped with a jacket, a stirrer, a nitrogen inlet, an ethylene inlet, and an initiator addition port was charged with 100 kg of vinyl acetate (hereinafter sometimes referred to as VAc), 10 kg of methanol (hereinafter sometimes referred to as MeOH), and 2.9 kg of the MPDAc mixed solution. The temperature was raised to 60°C, and then nitrogen bubbling was performed for 30 minutes to replace the atmosphere inside the reactor with nitrogen. Ethylene was then introduced so that the reactor pressure (ethylene pressure) was 4.9 MPa. After adjusting the temperature inside the reaction vessel to 60°C, 60 g of 2,2'-azobis(2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.) was added as an initiator in the form of a methanol solution to initiate polymerization. During the polymerization, the ethylene pressure was maintained at 4.9 MPa, and the polymerization temperature was maintained at 60°C. After 6 hours, when the conversion of VAc reached 45%, the polymerization was terminated by cooling. The reaction vessel was opened to remove ethylene, and nitrogen gas was then bubbled through to completely remove ethylene. Next, unreacted VAc was removed under reduced pressure, and MeOH was added to a modified ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as "modified EVAc") into which structural units derived from MPDAc had been introduced by copolymerization to prepare a 20% by mass MeOH solution.

[0061] (3-2) Saponification of Modified EVAc A 500 L reaction vessel equipped with a jacket, a stirrer, a nitrogen inlet, a reflux condenser, and a solution addition port was charged with a 20% by mass MeOH solution of the modified EVAc obtained in (3-1). While blowing nitrogen into this solution, the temperature was raised to 60°C, and 0.5 equivalents of sodium hydroxide relative to the vinyl acetate units in the modified EVAc were added as a 2N MeOH solution. After the addition of the sodium hydroxide MeOH solution was completed, the temperature in the system was maintained at 60°C, and the saponification reaction was allowed to proceed for 2 hours while stirring and distilling off methyl acetate and MeOH. Thereafter, acetic acid was added to terminate the saponification reaction. Subsequently, while heating and stirring at 60 to 80°C, ion-exchanged water was added, and MeOH was distilled out of the reaction vessel, resulting in the precipitation of a modified ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as "modified EVOH"). The precipitated modified EVOH was collected and pulverized in a mixer. The resulting modified EVOH powder was placed in a 1 g / L aqueous acetic acid solution (bath ratio 20: 20 L of aqueous solution per 1 kg of powder) and washed with stirring for 2 hours. The powder was drained and then placed in a 1 g / L aqueous acetic acid solution (bath ratio 20) and washed with stirring for 2 hours. The drained powder was placed in ion-exchanged water (bath ratio 20) and washed with stirring for 2 hours, followed by draining. This process was repeated three times for purification. The powder was then immersed in 10 L of an aqueous solution containing 0.5 g / L of acetic acid and 0.1 g / L of sodium acetate with stirring for 4 hours, drained, and dried at 60°C for 16 hours to obtain a crude dried modified EVOH. The melt flow rate (MFR) of the resulting modified EVOH was 8.0 g / 10 min (190°C, under a load of 2160 g).

[0062] (3-3) Content of each structural unit in modified EVAc The content of ethylene units, the content of structural units derived from vinyl acetate, and the content of structural units derived from MPDAc in modified EVAc were determined by comparing the modified EVAc before saponification with the modified EVAc before saponification. １ The H-NMR was measured and calculated. First, a small amount of the MeOH solution of modified EVAc obtained in (3-1) was sampled, and the modified EVAc was precipitated in ion-exchanged water. The precipitate was collected and dried at 60°C under vacuum to obtain a dried product of modified EVAc. Next, the obtained dried product of modified EVAc was dissolved in dimethyl sulfoxide (DMSO)-d6 containing tetramethylsilane as an internal standard substance, and the H-NMR was measured at 500 MHz.１ Measurement was performed at 80°C using a H-NMR (manufactured by JEOL Ltd.: "GX-500").

[0063] Modified EVAc １ The peaks in the H-NMR spectrum are assigned as follows: 0.6 to 1.0 ppm: methylene protons (4H) of terminal ethylene units; 1.0 to 1.85 ppm: methylene protons (4H) of intermediate ethylene units, methylene protons (2H) of the main chain of structural units derived from MPDAc, and methylene protons (2H) of vinyl acetate units; 1.85 to 2.1 ppm: methyl protons (6H) of structural units derived from MPDAc and methyl protons (3H) of vinyl acetate units; 3.7 to 4.1 ppm: methylene protons (4H) of the side chain of structural units derived from MPDAc; 4.4 to 5.3 ppm: methine protons (1H) of vinyl acetate units.

[0064] According to the above attribution, when the integral value from 0.6 to 1.0 ppm is defined as x, the integral value from 1.0 to 1.85 ppm as y, the integral value from 3.7 to 4.1 ppm as z, and the integral value from 4.4 to 5.3 ppm as w, the content of ethylene units (a: mol %), the content of vinyl ester units (b: mol %), and the content of structural units derived from MPDAc (c: mol %) are calculated according to the following formulas: a = (2x + 2y - z - 4w) / (2x + 2y + z + 4w) × 100 b = 8w / (2x + 2y + z + 4w) × 100 c = 2z / (2x + 2y + z + 4w) × 100

[0065] As a result of calculation using the above method, the content of ethylene units (a) of the modified EVAc was 38.0 mol%, the content of vinyl ester units (b) was 60.5 mol%, and the content of structural units derived from MPDAc (c) was 1.5 mol%. The values ​​of a, b, and c in the modified EVAc are the same as the values ​​of a, b, and c in the modified EVOH after saponification.

[0066] (4) Degree of saponification of modified EVOH The same applies to the modified EVOH after saponification. １The crude dried modified EVOH obtained in (3-2) above was dissolved in dimethyl sulfoxide (DMSO)-d6 containing tetramethylsilane as an internal standard and tetrafluoroacetic acid (TFA) as an additive, and subjected to H-NMR measurement at 500 MHz. １ Measurement was performed at 80°C using a H-NMR (manufactured by JEOL Ltd.: "GX-500"). １ The H-NMR measurement results showed a significant decrease in peak intensity between 1.85 and 2.1 ppm, clearly indicating that in addition to the ester groups derived from vinyl acetate in the modified EVOH, the ester groups contained in the structural units derived from MPDAc were also saponified to hydroxyl groups. The degree of saponification was calculated from the peak intensity ratio of the methyl protons of the vinyl acetate units (1.85 to 2.1 ppm) to the methine protons of the vinyl alcohol units (3.15 to 4.15 ppm). The degree of saponification of the modified EVOH of Example 1 was 99.9 mol% or higher. These results confirmed that a modified EVOH could be obtained using a mixture (composition) containing a small amount of organic halide relative to MPDAc.

[0067] [Examples 2 to 7, Comparative Examples 1 and 2] Storage stability tests and corrosion resistance tests were conducted in the same manner as in Example 1, except that in the composition of the mixed liquid (composition) of MPDAc and organic halide, the type of organic halide and the mixing ratio of MPDAc to organic halide were changed as shown in Table 1. In Comparative Example 1, no organic halide was used. The results are shown in Table 1.

[0068] In each of the mixed liquids (compositions) of Examples 1 to 7 and Comparative Examples 1 and 2, the content of inorganic halides converted to halogen elements based on the content of MPDAc was 0 ppm by mass.

[0069]

[0070] As shown in Table 1, in each of the mixed solutions (compositions) of Examples 1 to 7, the proportion of undecomposed MPDAc after storage was as high as 96.5 mass% or more, and the storage stability was high. Furthermore, in each of the mixed solutions (compositions) of Examples 1 to 7, metal corrosion during storage was also suppressed. On the other hand, the MPDAc of Comparative Example 1, which did not contain an organic halide, had poor storage stability. Furthermore, in the mixed solution of Comparative Example 2, which contained too much organic halide, metal corrosion occurred during storage.

Claims

1. A composition containing an unsaturated compound represented by the following formula (1) and an organic halide, wherein the content of the organic halide in terms of halogen element based on the content of the unsaturated compound is 1 mass ppm or more and 10,000 mass ppm or less. 【Chemical 1】 In the above formula (1), R １ , R ２ , R ３ , R ４ , R ５ , and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

2. The composition according to Claim 1, wherein the content of the unsaturated compound is 95 mass% or more.

3. The composition according to Claim 1, wherein the content of the inorganic halide in terms of halogen element based on the content of the unsaturated compound is 10 mass ppm or less.

4. The composition according to Claim 1, wherein the organic halide contains a compound represented by the following formula (2). 【Chemical 2】 In the above formula (2), X is a halogen atom. R ７ and R ８ satisfy any one of the following requirements A, requirement B, and requirement C. Requirement A: R ７ is CR ９ R １０ = CR １１ -(R ９ 、R １０ and R １１ are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.) is a group represented by. R ８ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group. Requirement B: R ７ is a secondary or tertiary monovalent hydrocarbon group, or a secondary or tertiary monovalent halogenated hydrocarbon group. R ８ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group. Requirement C: R ７ and R ８ are each independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

5. R in the above formula (2) ７ and R ８ is the composition according to claim 4, which satisfies the above requirement A.

6. The composition according to Claim 1, wherein the organic halide contains a compound having a carbon-carbon unsaturated double bond.

7. The above organic halide is C ４ H ５ X ３ (X is a halogen atom.), The composition according to claim 1, comprising a compound represented by the formula:

8. The composition according to any one of Claims 1 to 7, which is used for the synthesis of a polymer.

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