Composition

Abstract

Provided is a composition which contains a polymerizable compound, has high storage stability, and is capable of suppressing metal corrosion during storage. The composition contains an unsaturated compound represented by formula (1) and an organic halide, and the content of the organic halide in terms of halogen elements is 1-10,000 ppm by mass (inclusive) based on the content of the unsaturated compound. In formula (1), R1, R2, R3, R4, R5, and R6 are each independently a hydrogen atom or an alkyl group having 1-10 carbon atoms. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to compositions. Background Art

[0002] 2-Methylene-1,3-propanediol diacetate (hereinafter also referred to as "MPDAc") is used as a modifier (comonomer) of ethylene-vinyl alcohol copolymer (hereinafter also referred to as "EVOH"), etc. (see Patent Document 1). MPDAc-modified EVOH obtained by saponifying a copolymer of ethylene, vinyl ester and MPDAc can maintain good barrier properties and improve molding processability compared to non-modified EVOH. The same effect can be exerted when using a compound in which a part of the atoms in MPDAc are substituted. Hereinafter, MPDAc and a compound in which a part of the atoms in MPDAc are substituted are also collectively referred to as "MPDAc, etc."

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-34647 Summary of the invention

[0006] Problems to be solved by the invention

[0007] As mentioned above, MPDAc and the like are polymerizable compounds, and during storage, a polymerization inhibitor is added to inhibit the polymerization reaction. Before using MPDAc and the like for polymerization, the added polymerization inhibitor needs to be removed. However, the boiling point of MPDAc and the like is as high as 200°C or more. Therefore, in order to remove the polymerization inhibitor from MPDAc and the like at a low temperature, a vacuum distillation device needs to be used, which has low production efficiency.

[0008] In contrast, the present inventors have found that: during storage, the organic halide acts as a polymerization inhibitor for MPDAc, etc., and on the other hand, even if the organic halide is not removed at a relatively high temperature at which the polymerization reaction of MPDAc, etc. proceeds, a good polymerization reaction of MPDAc, etc. occurs. In addition, compositions containing a large amount of organic halide may sometimes cause corrosion of metal containers during storage.

[0009] The present invention has been made based on such circumstances, and an object of the present invention is to provide a composition containing a polymerizable compound, the composition having high storage stability and capable of suppressing metal corrosion during storage.

[0010] Means used to solve problems

[0011] The above object is achieved by providing the following technical solutions.

[0012] [1] A composition comprising 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 is 1 mass ppm or more and 10,000 mass ppm or less based on the content of the unsaturated compound;

[0013] [Chemistry 1]

[0014]

[0015] (In the above formula (1), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

[0016] [2] The composition according to [1], wherein the content of the unsaturated compound is 95% by mass or more;

[0017] [3] The composition according to [1] or [2], wherein the content of the inorganic halide in terms of halogen element is 10 ppm by mass or less based on the content of the unsaturated compound;

[0018] [4] The composition according to any one of [1] to [3], wherein the organic halide comprises a compound represented by the following formula (2);

[0019] [Chemistry 2]

[0020]

[0021] (In the above formula (2), X is a halogen atom. R 7 and R 8 Any one of the following conditions A, B, and C is satisfied.

[0022] Condition A: R 7 CR 9 R 10 =CR 11 -(R 9 , R 10 and R 11 Each of them is independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group). 8 It is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

[0023] Condition B: R 7 is a monovalent secondary hydrocarbon group or a monovalent tertiary hydrocarbon group, or a monovalent secondary halogenated hydrocarbon group or a monovalent tertiary halogenated hydrocarbon group. 8It is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

[0024] Condition C: R 7 and R 8 Each is independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.)

[0025] [5] The composition according to [4], wherein R in the above formula (2) 7 and R 8 Satisfy the above condition A;

[0026] [6] The composition according to any one of [1] to [5], wherein the organic halide comprises a compound having a carbon-carbon unsaturated double bond;

[0027] [7] The composition according to any one of [1] to [6], wherein the organic halide comprises a compound represented by C4H5X3 (X is a halogen atom);

[0028] [8] The composition according to any one of [1] to [7], which is used for synthesizing a polymer.

[0029] Effects of the Invention

[0030] According to the present invention, there is provided a composition containing a polymerizable compound, the composition having high storage stability and capable of suppressing metal corrosion during storage. DETAILED DESCRIPTION

[0031] 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)"), wherein the content of the organic halide (B) in terms of halogen element is greater than 1 mass ppm and less than 10,000 mass ppm based on the content of the unsaturated compound (A).

[0032] [Chemistry 3]

[0033]

[0034] In the above formula (1), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0035] The composition of the present invention is a composition containing a polymerizable compound, which has high storage stability and can also inhibit metal corrosion during storage. The reason is still uncertain, but it can be inferred that it is because: the organic halide (B) functions as an inhibitor when the unsaturated compound (A) is stored, and there is no excessive organic halide (B) that causes metal corrosion. In addition, in the composition, when the composition is supplied to a polymerization reaction without performing a refining operation such as distillation (removal operation of the organic halide (B)), a good polymerization reaction will occur. It can be considered that this is because: the organic halide (B) fully exerts the effect of inhibiting the polymerization reaction of the unsaturated compound (A) at the temperature of a general storage environment (e.g., room temperature), but at a temperature of, for example, 80°C or above for the polymerization reaction, it hardly exerts the effect of inhibiting the polymerization reaction. The reason for this is presumably that, at the temperature of a general storage environment, at least a portion of the organic halide (B) exists in the form of highly stable free radicals, and functions as a polymerization inhibitor by capturing free radicals of the unsaturated compound (A) generated by heat, light, oxygen, etc. However, at high temperatures, the stability of the free radicals of the organic halide (B) becomes relatively low.

[0036] Hereinafter, each component of the composition of the present invention will be described in detail.

[0037] (Unsaturated compound (A))

[0038] The unsaturated compound (A) is a compound represented by the above formula (1). 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0039] As 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 include methyl group, ethyl group, n-propyl group, isopropyl group, etc. As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms is preferred.

[0040] R in the above formula (1) 1 , R 2 , R 3 and R 4 It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0041] R in the above formula (1)5 and R 6 Each of them is 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 still more preferably a methyl group.

[0042] R in the above formula (1) 1 , R 2 , R 3 and R 4 is a hydrogen atom, R 5 and R 6 When the unsaturated compound (A) is a methyl group, it is 2-methylene-1,3-propanediol diacetate (MPDAc). The unsaturated compound (A) may be used alone or in combination of two or more.

[0043] The content of the unsaturated compound (A) in the composition of the present invention is not particularly limited, for example, it can be 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, preferably 95% by mass or more, more preferably 99% by mass or more, further preferably 99.5% by mass or more, and particularly preferably 99.9% by mass or more. When the unsaturated compound (A) occupies most of the composition of the present invention, the composition can be particularly suitably used as a monomer raw material. The content of the unsaturated compound (A) in the composition can be 99.9999% by mass or less, or 99.999% by mass or less, or 99.99% by mass or less.

[0044] The unsaturated compound (A) can be produced by a conventionally known method. Specifically, the unsaturated compound (A) can be synthesized by reacting 2-methylene-1,3-propanediol with acetic anhydride, reacting β-methylallyl acetate with acetic acid in the presence of a metal catalyst and an oxygen atmosphere, or the like.

[0045] (Organic halide (B))

[0046] The organic halide (B) is not particularly limited as long as it is an organic substance containing halogen. As the halogen possessed by the organic halide (B), fluorine, chlorine, bromine, iodine, etc. can be listed, preferably chlorine. That is, the organic halide (B) is preferably an organic chloride. The organic halide (B) can be composed of, for example, carbon atoms, hydrogen atoms and halogen atoms, or can be composed of carbon atoms, hydrogen atoms and chlorine atoms.

[0047] 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 (XCH: X is a halogen atom). In such a structure, the dissociation energy of the CH bond is low. Therefore, free radicals are easily generated from the organic halide (B) having such a structure, and the stability of the generated free radicals is high, so that the storage stability is further improved.

[0048] The organic halide (B) preferably includes a compound represented by the following formula (2), and more preferably includes a compound represented by the following formula (2).

[0049] [Chemistry 4]

[0050]

[0051] In the above formula (2), X is a halogen atom. 7 and R 8 Any one of the following conditions A, B, and C is satisfied.

[0052] Condition A: R 7 CR 9 R 10 =CR 11 -(R 9 , R 10 and R 11 Each of them is independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group). 8 It is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

[0053] Condition B: R 7 is a monovalent secondary hydrocarbon group or a monovalent tertiary hydrocarbon group, or a monovalent secondary halogenated hydrocarbon group or a monovalent tertiary halogenated hydrocarbon group. 8 It is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

[0054] Condition C: R 7 and R 8 Each is independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

[0055] In the above formula (2), X and R 8 , R 9 , R 10 and R 11 Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is preferred.

[0056] As R in the above formula (2) 7 , R 8 , R 9 , R 10 and R 11The monovalent hydrocarbon group shown in the figure may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, etc., preferably alkyl or alkenyl, more preferably alkyl. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, etc. Examples of the alkenyl group include vinyl, propenyl, etc. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 6, and more preferably 1 to 4.

[0057] As R in the above formula (2) 7 , R 8 , R 9 , R 10 and R 11 The monovalent halogenated hydrocarbon group shown in the above-mentioned monovalent hydrocarbon group includes a group in which at least one hydrogen atom possessed by the above-mentioned monovalent hydrocarbon group is 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.

[0058] As R in the above formula (2) 7 The monovalent secondary hydrocarbon group or monovalent tertiary hydrocarbon group shown in the formula (a) may include secondary aliphatic hydrocarbon groups or tertiary aliphatic hydrocarbon groups such as secondary alkyl groups or tertiary alkyl groups, secondary alkenyl groups or tertiary alkenyl groups, preferably secondary alkyl groups or tertiary alkyl groups. Examples of secondary alkyl groups include isopropyl groups and secondary butyl groups. Examples of tertiary alkyl groups include tertiary butyl groups and tertiary amyl groups. The number of carbon atoms in the monovalent secondary hydrocarbon group or the monovalent tertiary hydrocarbon group is preferably 3 to 6.

[0059] As R in the above formula (2) 7 The monovalent secondary halogenated hydrocarbon group or monovalent tertiary halogenated hydrocarbon group shown in the above-mentioned monovalent secondary hydrocarbon group or monovalent tertiary hydrocarbon group may be a group in which at least one hydrogen atom possessed by the above-mentioned monovalent secondary hydrocarbon group or monovalent tertiary hydrocarbon group is substituted by a halogen atom (preferably a chlorine atom). The number of carbon atoms of the monovalent secondary halogenated hydrocarbon group or monovalent tertiary halogenated hydrocarbon group is preferably 3 to 6.

[0060] In the above formula (2), R 7 and R 8 Multiple of the above-mentioned conditions A, B and C may be satisfied.

[0061] The organic halide (B) satisfying the above condition A is a compound that generates an allyl radical when H (hydrogen atom) is dissociated from the structure of XCH. Since the allyl radical is highly stable, the use of the organic halide (B) in this form can improve the storage stability.

[0062] In the form that satisfies the above condition A, R 8 Preferably it is a hydrogen atom. 9 and R 10 It is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom or a chlorine atom. 11It is preferably a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, more preferably an alkyl group or a halogenated alkyl group, further preferably a methyl group or a halogenated methyl group, and still more preferably a methyl group or a chloromethyl group. 11 The number of carbon atoms in is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0063] Examples of the organic halide (B) satisfying the above condition 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-propene, 3-chloro-1-butene, 1,1,3-trichloro-1-butene, 1,3,4-trichloro-1-butene, and 1,3,3-trichloro-2-butene.

[0064] The organic halide (B) satisfying the above condition B is a compound having a carbon radical generated when H (hydrogen atom) is dissociated from the structure of XCH and a bulky monovalent secondary hydrocarbon group or monovalent tertiary hydrocarbon group, or a monovalent secondary halogenated hydrocarbon group or a monovalent tertiary halogenated hydrocarbon group (R 7 ) is adjacent to this structure. The carbon free group is sterically hindered and is difficult to react with other compounds. Therefore, when using this form of organic halide (B), the storage stability can also be improved.

[0065] In the form that satisfies the above condition B, R 7 Preferably, it is a monovalent secondary hydrocarbon group or a monovalent secondary halogenated hydrocarbon group. 7 It is also preferably a monovalent secondary halogenated hydrocarbon group or a monovalent tertiary halogenated hydrocarbon group. 7 More preferably, it is a secondary haloalkyl group or a secondary haloalkenyl group, and more preferably, it is a secondary haloalkyl 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 further preferably 3. 8 Preferred is a hydrogen atom.

[0066] Examples of the organic halide (B) satisfying the above condition B include 1,2,3-trichloro-2-methylpropane, 1-chloro-2-methylpropane, 1-chloro-2,2-dimethylpropane, 1-chloro-2-ethylbutane, 2-vinyl-1-chloropentane, 1,1,3-trichloro-2-methyl-1-propene, and 3-chloro-2-chloromethyl-1-propene.

[0067] The organic halide (B) satisfying the above condition C is a compound that generates a secondary radical when H (hydrogen atom) is dissociated from the structure of XCH. The stability of the secondary radical is also sufficiently high, and therefore, by using the organic halide (B) in this form, the storage stability can be improved.

[0068] In the form that satisfies the above condition C, R 7 and R 8It is preferably an alkyl group or a halogenated alkyl group, and more preferably an alkyl group or a chlorinated alkyl group. 7 and R 8 The number of carbon atoms in the moiety is preferably 1 to 3, more preferably 1 or 2.

[0069] Examples of the organic halide (B) satisfying the above condition C include 2-chlorobutane, 2-chloro-2-methylbutane, 2-chloropropane, 3-chloropentane, and 3-chloro-1-pentene.

[0070] Among these, the organic halide (B) is preferably a compound represented by the above formula (2) in which R 7 and R 8 A compound satisfying the above condition A. The organic halide (B) may satisfy the above condition B, and more preferably satisfies both the above condition A and the above condition B.

[0071] The organic halide (B) also preferably includes a compound having a carbon-carbon unsaturated double bond. Such an organic halide can also exhibit good storage stability due to the high stability of the generated free radicals. As a compound having a carbon-carbon unsaturated double bond, among the compounds represented by the above formula (2), except for the compound having a carbon-carbon unsaturated double bond (typically, R 7 and R 8 In addition to the compound satisfying the above condition A), there can be mentioned 4-chloro-1-butene, 1,4-dichloro-1-butene, 4-chloro-1,3-butadiene, vinyl chloride, and the like.

[0072] The organic halide (B) also preferably includes a compound represented by C4H5X3 (X is a halogen atom), and is also preferably a compound represented by C4H5X3. By using such an organic halide (B), the effect of the present invention that the storage stability is high and metal corrosion during storage can be suppressed is particularly well exerted. Examples of such an organic halide include 1,1,3-trichloro-2-methyl-1-propylene, 1,1,3-trichloro-1-butene, 1,3,4-trichloro-1-butene, and 1,3,3-trichloro-2-butene.

[0073] In the composition of the present invention, the content of the halogen element converted to the organic halide (B) 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 above-mentioned halide (B) is sometimes preferably 10 mass ppm, more preferably 30 mass ppm, further preferably 50 mass ppm, and further preferably 100 mass ppm, 200 mass ppm, 300 mass ppm, 400 mass ppm or 500 mass ppm. By making the content of the halide (B) above the lower limit, the storage stability of the composition can be improved. The upper limit of the content of the above-mentioned halide (B) is sometimes preferably 5,000 mass ppm, more preferably 3,000 mass ppm, further preferably 2,500 mass ppm, further preferably 2,200 mass ppm, 2,000 mass ppm, 1,600 mass ppm, 1,300 mass ppm or 1,000 mass ppm. By making the content of the halide (B) below the above upper limit, the corrosion of the metal (metal container, etc.) during storage of the composition can be suppressed. In addition, when the content of the halide (B) is below the above upper limit, there is also an advantage that the odor of the composition is reduced and the handling property is improved.

[0074] As the total content of the unsaturated compound (A) and the organic halide (B) in the composition of the present invention, it is preferably 95% by mass or more, more preferably 99% by mass or more, further 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 can be 100% by mass, or it can be 99.9999% by mass or less, 99.999% by mass or less, or 99.99% by mass or less. In this case, the composition can be particularly suitably used as a monomer raw material.

[0075] The organic halide (B) can be produced by a conventionally known method. A commercially available organic halide (B) can be used. One or more organic halide (B) can be used.

[0076] (Other ingredients)

[0077] 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 solvents, inorganic halide, water, and the like.

[0078] As inorganic halides, chlorine, hydrochloric acid, sodium chloride, etc. can be cited. Among them, in the composition of the present invention, the content of the halogen element conversion of the inorganic halide based on the content of the unsaturated compound (A) is preferably 10 mass ppm or less, more preferably 3 mass ppm or less, further preferably 1 mass ppm or less, and can be substantially 0 mass ppm. In the composition of the present invention, it is preferred that no inorganic halide is contained. Like this, when the content of the inorganic halide is small, the corrosion of the metal is further reduced.

[0079] In addition, in the composition of the present invention, the content of water 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, carboxylic acid is sometimes generated due to the hydrolysis reaction of the unsaturated compound (A), and part of the organic halide (B) is decomposed to generate chloride ions that may cause metal corrosion. Therefore, when the content of water is below the above upper limit, metal corrosion is further reduced.

[0080] (Preparation method)

[0081] 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).

[0082] (Purpose, etc.)

[0083] The composition of the present invention can be used for various purposes known as MPDAc, etc. In particular, the composition can be suitably used for synthesizing polymers. That is, it can be used as a polymerizing material using the unsaturated compound (A) contained in the composition as a monomer. The composition can be a polymerization composition. In particular, the composition can be suitably used as a material (polymerization composition) when manufacturing a modified ethylene-vinyl ester copolymer (modified EVOH). When the composition is used for synthesizing polymers, even if the content of the organic halide (B) is not reduced by a refining operation, a good polymerization reaction will occur. Therefore, the productivity of the method for manufacturing a polymer using the composition is also high.

[0084] Modified EVOH can be obtained by, for example, a manufacturing method having the following steps, the steps being: a step of copolymerizing the unsaturated compound (A), ethylene and vinyl ester contained in the composition of the present invention; and a step of saponifying the obtained copolymer. This modified EVOH has the characteristics of being able to maintain good barrier properties and improving stretchability and shrinkage compared to non-modified EVOH. In addition, the modified EVOH obtained by this manufacturing method does not contain chlorine atoms in the polymer. Therefore, there is also an advantage that no hydrochloric acid is generated when the modified EVOH is melt-kneaded and reused, and it is easy to reuse. Regarding the modified EVOH manufactured using a composition containing the unsaturated compound (A) of the present invention and the organic halide (B) in a specified ratio, there is no chlorine atom in the polymer or even if it contains chlorine atoms, it is extremely small, so there is a characteristic of excellent recyclability in melt kneading.

[0085] Example

[0086] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0087] The compounds used in Examples and Comparative Examples are shown below.

[0088] Unsaturated compounds (A)

[0089] MPDAc: a compound represented by the following formula (A1)

[0090] Organic halides (B)

[0091] B1: 1,1,3-trichloro-2-methyl-1-propene (a compound represented by the following formula (B1): R in the above formula (2) 7 CCl2=C(CH3)-, R 8 is a hydrogen atom and X is a chlorine atom)

[0092] B2: 3-chloro-2-chloromethyl-1-propene (a compound represented by the following formula (B2): R in the above formula (2) 7 is CH2=C(CH2Cl)-, R 8 is a hydrogen atom and X is a chlorine atom)

[0093] B3: 1,2,3-trichloro-2-methylpropane (a compound represented by the following formula (B3): R in the above formula (2) 7 is CH2Cl-CCl(CH3)-, R 8 is a hydrogen atom and X is a chlorine atom)

[0094] B4: 2-chlorobutane (a compound represented by the following formula (B4): R in the above formula (2) 7 CH3-, R8 is CH3CH2-, X is a chlorine atom)

[0095] [Chemistry 5]

[0096]

[0097] [Chemistry 6]

[0098]

[0099] The organic halide (B1) used was one produced according to a method described in a known document (title of doctoral dissertation: INVESTIGATION OF THERECTIONS OF 1,1,3-TRICHLORO-2-METHYL-1-PROPENE AND RELATED COMPOUNDS WITH CERTAIN AROMATICS, 1955, author: HDEIPLEDGER, JR.).

[0100] As the organic halide (B2) and the organic halide (B4), reagents sold by Tokyo Chemical Industry Co., Ltd. were used.

[0101] The organic halide (B3) used is a compound produced according to a known document (title: Identification of the higher-boiling products resulting from chlorination of isobutylene) Chemicke Zvesti, Vol. 27, No. 3, pp. 355-358 (1973).

[0102] In addition, MPDAc and the organic halides (B1) to (B4) were used in each of the Examples and Comparative Examples after the water content was reduced to 10 ppm or less using nitrogen bubbling or molecular sieve 3A.

[0103] [Example 1]

[0104] (1) Storage stability test at 40°C for 1 month

[0105] A solution obtained by diluting MPDAc 100 times with acetonitrile was injected into a gas chromatograph (analytical equipment: GC-2014 (manufactured by Shimadzu Corporation), detector: FID (hydrogen flame ionization detector), column: Rxi-5ms (length 30 m, film thickness 0.25 μm, inner diameter 0.25 mm, manufactured by RESTEK), analysis conditions: vaporizer 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. Next, 99.90 parts by mass of MPDAc and 0.10 parts by mass of an organic halide (B1) were mixed in air at 23° C. to obtain a mixed solution (composition) of Example 1. The halogen element-converted content of the organic halide (B1) in the obtained mixed solution based on the content of MPDAc is 673 mass ppm. A portion of the mixed solution is taken out and diluted in the same manner, and the diluted solution is injected into a gas chromatograph to measure the peak area of ​​MPDAc. The MPDAc content of the mixed solution is determined based on the peak area ratio (MPDAc peak area of ​​the mixed solution / MPDAc peak area of ​​the MPDAc single solution). The MPDAc content of the mixed solution before storage is shown in Table 1. Next, the mixed solution is sealed in a 100 mL glass bottle. It should be noted that 1 mL of the mixed solution is taken out before sealing, and the MPDAc content of the mixed solution before the above storage is measured. The mixed solution sealed in the glass bottle is stored in a constant temperature bath at 40°C for 1 month. After storage, it is restored to 23°C and the mixed solution is diluted under the same conditions. The diluted solution is injected into a gas chromatograph to measure the peak area of ​​MPDAc. The MPDAc content after storage at 40°C for one month was determined based on the peak area ratio (MPDAc peak area of ​​the mixed solution after storage / MPDAc peak area of ​​the MPDAc single solution without 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 undecomposed MPDAc. The results are shown in Table 1. As shown in Table 1, the ratio of undecomposed MPDAc was high even after storage at 40°C for one month.

[0106] (2) Corrosion resistance test of iron containers

[0107] To 100 parts by mass of the mixed solution of MPDAc and an organic halide prepared by the above (1), 0.2 parts by mass of water is further added, and the mixture is stored in a 20L iron barrel at 40°C for 1 month. 0.5 g of the mixed solution after storage for 1 month is put into a Teflon (registered trademark) pressure vessel, 5 mL of concentrated nitric acid is added thereto, and it is decomposed at room temperature for 30 minutes. Thereafter, the lid is closed, and the mixture is heated at 150°C for 10 minutes using a wet decomposition device (manufactured by ACTAC: "MWS-2"), and then heated at 180°C for 5 minutes to decompose the mixture, and then cooled to room temperature. The treated liquid is transferred to a 50 mL volumetric flask (manufactured by TPX) and fixed to volume with pure water. The solution is analyzed for iron content using an ICP emission spectrometer ("OPTIMA4300DV" manufactured by PerkinElmer). Corrosion resistance is evaluated according to the following criteria based on the iron content.

[0108] A: less than 5ppm

[0109] B: 5ppm or more and less than 10ppm

[0110] C: 10ppm or more

[0111] The results are shown in Table 1. The iron content in the mixed liquid was less than 5 ppm, and corrosion of iron was not observed.

[0112] (3) Aggregation evaluation

[0113] (3-1) Synthesis of modified ethylene-vinyl acetate copolymer

[0114] 99.90 parts by mass of MPDAc and 0.10 parts by mass of an organic halide (B-1) were mixed to prepare an MPDAc mixed solution (composition). 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 above MPDAc mixed solution were added to a 250 L pressurized reaction tank equipped with a jacket, a stirrer, a nitrogen inlet, an ethylene inlet, and an initiator addition port. After the temperature was raised to 60° C., nitrogen was bubbled for 30 minutes to replace the inside of the reaction tank with nitrogen. Next, ethylene was introduced so that the pressure in the reaction tank (ethylene pressure) became 4.9 MPa. After adjusting the temperature in the reaction tank to 60° C., 60 g of 2,2'-azobis(2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator was added in the form of a methanol solution to start 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 polymerization rate of VAc reached 45%, the polymerization was stopped by cooling. The reaction tank was opened and deethylene was carried out, and nitrogen was blown in to completely deethylene. Then, after removing unreacted VAc under reduced pressure, MeOH was added to the modified ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as modified EVAc) into which the structural unit derived from MPDAc was introduced by copolymerization to prepare a 20 mass % MeOH solution.

[0115] (3-2) Saponification of modified EVAc

[0116] A 20 mass % MeOH solution of the modified EVAc obtained in (3-1) was added to a 500 L reaction tank equipped with a jacket, a stirrer, a nitrogen inlet, a reflux condenser and a solution addition port. While blowing nitrogen into the solution, the temperature was raised to 60°C, and 0.5 equivalents of sodium hydroxide were added in the form of a 2 equivalent MeOH solution relative to the vinyl acetate unit in the modified EVAc. After the addition of the sodium hydroxide MeOH solution was completed, the temperature in the system was maintained at 60°C, and the methyl acetate and MeOH were distilled off while stirring for 2 hours to carry out a saponification reaction. Thereafter, acetic acid was added to stop the saponification reaction. Thereafter, ion exchange water was added while heating and stirring at 60 to 80°C, so that MeOH was distilled out of the reaction tank, and the modified ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as modified EVOH) was precipitated. The precipitated modified EVOH was collected and crushed using a stirrer. The obtained modified EVOH powder was put into a 1g / L acetic acid aqueous solution (bath ratio of 20: the ratio of aqueous solution to 1kg of powder is 20L), stirred and washed for 2 hours. It was dehydrated and further put into a 1g / L acetic acid aqueous solution (bath ratio of 20), stirred and washed for 2 hours. After dehydration, it was put into ion exchange water (bath ratio of 20), stirred and washed for 2 hours and dehydrated, and the operation was repeated 3 times for purification. Then, after being stirred and immersed in 10L of an aqueous solution containing 0.5g / L acetic acid and 0.1g / L sodium acetate for 4 hours, the liquid was removed and dried at 60°C for 16 hours to obtain a crude dried modified EVOH. The melt flow rate (MFR) of the obtained modified EVOH (190°C, 2160g load) is 8.0g / 10min.

[0117] (3-3) Content of each structural unit in modified EVAc

[0118] The ethylene unit content, the content of the structural unit derived from vinyl acetate, and the content of the structural unit derived from MPDAc in the modified EVAc were determined by 1 H-NMR measurement was used for calculation. First, a small amount of the MeOH solution of the modified EVAc obtained in (3-1) was sampled and the modified EVAc was precipitated in ion exchange water. The precipitate was collected and dried at 60°C under vacuum to obtain a dried product of the modified EVAc. Next, the dried product of the modified EVAc was dissolved in dimethyl sulfoxide (DMSO)-d6 containing tetramethylsilane as an internal standard substance and the product was analyzed using a 500 MHz 1 H-NMR (manufactured by NEC Corporation:

[0119] "GX-500") was measured at 80°C.

[0120] Modified EVAc 1Each peak in the H-NMR spectrum is assigned as follows.

[0121] 0.6~1.0ppm: Methylene protons (4H) of the terminal ethylene unit

[0122] 1.0 to 1.85 ppm: methylene protons (4H) of the middle ethylene unit, main chain methylene protons (2H) of the structural unit derived from MPDAc, and methylene protons (2H) of the vinyl acetate unit

[0123] 1.85 to 2.1 ppm: Methyl protons (6H) of the structural unit derived from MPDAc and methyl protons (3H) of the vinyl acetate unit

[0124] 3.7 to 4.1 ppm: Methylene protons (4H) in the side chain of the structural unit derived from MPDAc

[0125] 4.4 to 5.3 ppm: Methylene protons (1H) of vinyl acetate units

[0126] According to the above attribution, when the integral value of 0.6 to 1.0 ppm is set as x, the integral value of 1.0 to 1.85 ppm is set as y, the integral value of 3.7 to 4.1 ppm is set as z, and the integral value of 4.4 to 5.3 ppm is set 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.

[0127] a=(2x+2y-z-4w) / (2x+2y+z+4w)×100

[0128] b=8w / (2x+2y+z+4w)×100

[0129] c=2z / (2x+2y+z+4w)×100

[0130] The results calculated by the above method are as follows: the content of ethylene units in the modified EVAc (a) is 38.0 mol%, the content of vinyl ester units (b) is 60.5 mol%, and the content of structural units derived from MPDAc (c) is 1.5 mol%. The values ​​of a, b, and c in the modified EVAc are the same as those in the modified EVOH after saponification.

[0131] (4) Saponification degree of modified EVOH

[0132] The same process is also performed on the modified EVOH after saponification. 1H-NMR measurement: The crude dried product of the modified EVOH obtained in (3-2) above was dissolved in dimethyl sulfoxide (DMSO)-d6 containing tetramethylsilane as an internal standard substance and tetrafluoroacetic acid (TFA) as an additive, and the product was measured using a 500 MHz 1 H-NMR (manufactured by JEOL Ltd.: "GX-500") was used for measurement at 80°C. 1 The results of H-NMR measurement clearly show that since the peak intensity of 1.85 to 2.1 ppm is greatly reduced, the ester groups derived from vinyl acetate in the modified EVOH are saponified, and the ester groups contained in the structural units derived from MPDAc are also saponified to form hydroxyl groups. The saponification degree is calculated based on the peak intensity ratio of the methyl protons of the vinyl acetate unit (1.85 to 2.1 ppm) and the methine protons of the vinyl alcohol unit (3.15 to 4.15 ppm). The saponification degree of the modified EVOH of Example 1 is 99.9 mol% or more.

[0133] From the above results, it was confirmed that modified EVOH can be obtained by using a mixed solution (composition) containing a small amount of an organic halide relative to MPDAc.

[0134] [Examples 2 to 7, Comparative Examples 1 and 2]

[0135] In the composition of the mixed solution (composition) of MPDAc and the organic halide, the type of organic halide and the mixing ratio of MPDAc and the organic halide were changed as shown in Table 1, and the storage stability test and the corrosion resistance test were carried out in the same manner as in Example 1. No organic halide was used in Comparative Example 1. The results are shown in Table 1.

[0136] In addition, in each of the mixed solutions (compositions) of Examples 1 to 7 and Comparative Examples 1 and 2, the content of the inorganic halide calculated as the halogen element based on the content of MPDAc was 0 mass ppm.

[0137]

[0138] As shown in Table 1, in each of the mixed solutions (compositions) of Examples 1 to 7, the ratio of undecomposed MPDAc after storage was as high as 96.5 mass % or more, and the storage stability was high. In addition, in each of the mixed solutions (compositions) of Examples 1 to 7, metal corrosion during storage was also suppressed. On the other hand, the storage stability of MPDAc in Comparative Example 1 containing no organic halide was low. In addition, in the mixed solution of Comparative Example 2 having an excessive content of organic halide, metal corrosion occurred during storage.

Claims

1. A composition comprising an unsaturated compound represented by the following formula (1) and an organic halide, The halogen element-converted content of the organic halide based on the content of the unsaturated compound is 1 mass ppm or more and 10,000 mass ppm or less, [Chemistry 1] In the formula (1), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents 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% by mass or more.

3. The composition according to claim 1 or 2, 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 any one of claims 1 to 3, wherein The organic halide comprises a compound represented by the following formula (2): [Chemistry 2] In the formula (2), X is a halogen atom; R 7 and R 8 Satisfy any of the following conditions A, B and C, Condition A: R 7 CR 9 R 10 =CR 11 - shown in the group, wherein 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, R 8 is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group; Condition B: R 7 is a monovalent secondary hydrocarbon group or a monovalent tertiary hydrocarbon group, or a monovalent secondary halogenated hydrocarbon group or a monovalent tertiary halogenated hydrocarbon group, R 8 is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group; Condition C: R 7 and R 8 Each is independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group.

5. The composition according to claim 4, wherein In the formula (2), R 7 and R 8 The condition A is satisfied.

6. The composition according to any one of claims 1 to 5, wherein The organic halide includes a compound having a carbon-carbon unsaturated double bond.

7. The composition according to any one of claims 1 to 6, wherein The organic halide comprises a compound represented by C4H5X3, wherein X is a halogen atom.

8. The composition according to any one of claims 1 to 7, which is used for synthesizing a polymer.

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