JP2010254685A - alpha-(UNSATURATED ALKOXYALKYL)ACRYLATE COMPOSITION, AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stabilized α-(unsaturated alkoxyalkyl)acrylate composition that can preserve an α-(unsaturated alkoxyalkyl)acrylate product for a long period maintaining high purity and can sufficiently prevent problems such as discoloring or gelling from arising during polymerization, and to provide a method for producing the α-(unsaturated alkoxyalkyl)acrylate composition industrially and safely obtainable of the highly pure α-(unsaturated alkoxyalkyl)acrylate. <P>SOLUTION: The α-(unsaturated alkoxyalkyl)acrylate composition comprising an antioxidant and an α-(unsaturated alkoxyalkyl)acrylate of a specific structure, is characterized by including the antioxidant in an amount of 0.03 to 0.5 mass% relative to 100 mass% of the α-(unsaturated alkoxyalkyl)acrylate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to an α- (unsaturated alkoxyalkyl) acrylate composition and a method for producing the same. More specifically, α- (unsaturated alkoxyalkyl) acrylates that can be suitably used as raw materials for producing curable resin compositions, colorant dispersion compositions, and the like in various fields such as engineering plastics, optical materials, and resist materials. The present invention relates to a composition and a method for producing the composition.

A polymer (resin) having a ring structure in the main chain or the like exhibits durability and particularly excellent heat resistance due to the ring structure, and therefore, technical fields that require such characteristics, such as engineering plastics, It attracts attention as a useful material expected to be used in various fields such as optical materials and resist materials.

Conventional methods for obtaining such resins include a method in which monomers having a ring structure are linked by polycondensation or addition polymerization, or a monomer having no ring structure is cyclized simultaneously with the addition polymerization. There is a method of polymerization. Above all, the method of obtaining a polymer having a ring structure by polymerizing while cyclizing simultaneously with addition polymerization provides a new production method different from the method of performing polymerization after preparing a monomer having a ring structure in advance. Therefore, the use of such a production method is expected in various technical fields in which a polymer having a ring structure is used. In any method, the method by addition polymerization is to polymerize a monomer having an unsaturated bond such as a double bond. However, it is generally easy to adjust the molecular weight, and under mild conditions. Since various vinyl monomers can be copolymerized, it is easy to adjust the physical properties and give various functions according to the application. Therefore, it has been studied as a method for synthesizing resins for applications such as optical materials and resist materials that require advanced and diverse functions.

By the way, the monomer which cyclizes at the time of superposition | polymerization is recognized as a special monomer unlike the monomer generally used for addition polymerization. As such a monomer, there is an α- (unsaturated alkoxyalkyl) acrylate having two unsaturated groups of an acryloyl group and an unsaturated alkoxy group in one molecule, for example, an allyl ether group as the unsaturated alkoxy group. An α- (allyloxymethyl) acrylate having the formula is exemplified. This special monomer has the structure _{-CH 2 -O-CH 2 -CH =} CH 2 is bonded to the carbon atom at position 2 in the double bond of an acryloyl group, the acryloyl group and an allyl ether group A cyclization reaction occurs during the polymerization to produce a polymer having a ring structure. As described above, α- (allyloxymethyl) acrylate and a monomer having a structure similar thereto, that is, α- (unsaturated alkoxyalkyl) acrylate is cyclopolymerized to form a polymer having a ring structure in the main chain or the like. It can be said that it is a useful monomer that can be given, but because it is a special monomer, there are very few documents that have studied its production method and characteristics.

Under such circumstances, a method for producing a corresponding allyl ether compound such as methyl α- (ethoxymethyl) acrylate by reacting methyl α- (hydroxymethyl) acrylate with ethyl alcohol or the like is disclosed. (For example, refer to Patent Document 1). In this method, an allyl ether compound having a structure in which ethoxymethyl or the like is bonded to the carbon atom at the 2-position in the double bond of the acryloyl group is produced, but α- (unsaturated alkoxyalkyl) acrylate is produced. There is no mention of that.

As a conventional method for producing α- (unsaturated alkoxyalkyl) acrylate represented by α- (allyloxymethyl) acrylate, for example, specific dialkyl 2,2 ′-[oxybis (methylene)] bisacrylates and activity A method for producing an α-substituted acrylate that reacts with a hydrogen group-containing compound is disclosed (for example, see Patent Document 2). Hydroxyl group-containing compounds are described as active hydrogen group-containing compounds, one of which is allyl alcohol. According to this, α- (allyloxymethyl) acrylate can be produced. Moreover, the manufacturing method of allyl ethers with which specific acrylic acid ester and a hydroxyl group containing compound are made to react is disclosed (for example, refer patent document 3).
In addition, although it is not a special monomer that forms a polymer having a ring structure, as a method for producing a monomer having an allyl ether structure, a specific α-allyl-ω-hydroxy-polyoxyalkylene and a specific fat are used. A method for producing an allyl ether ester monomer by esterification with an aromatic monocarboxylic acid is disclosed (for example, see Patent Document 4). Further, a method for producing α- (allyloxymethyl) acrylate by reacting halomethyl acrylate with allyl alcohol is disclosed (for example, see Non-Patent Document 1).

Patent No. 3943180 (first and third pages) JP 2005-239610 A (first and third pages) JP-A-8-325200 (pages 2 and 8) JP 3610331 (pages 1, 2, 15)

Robert D. Thompson et al., Macromolecules, (USA), American Chemical Society, 1992, Vol. 25, p. 6455-6459

The present inventors have stated that α- (unsaturated alkoxyalkyl) acrylate, which is a specific polymerization called cyclopolymerization, is a special monomer that is different from general acrylic monomers. It has been found that there has been almost no study of effective use as a free monomer, and that there are problems different from general acrylic monomers. That is, as described above, an α- (unsaturated alkoxyalkyl) acrylate having an acryloyl group and an unsaturated alkoxy group (allyl ether group or the like) in one molecule undergoes cyclopolymerization and has a ring structure in the main chain or the like. Although it can be said that it is a useful monomer capable of giving a polymer having, due to the special structure of having two different kinds of unsaturated groups, α- (allyloxymethyl) acrylate is particularly a molecule. Since it has an allyl ether group that is easily oxidized, the amount of peroxide produced tends to increase during production and storage. As a result, there has been a problem that the product is adversely affected such as coloring or gelation during polymerization.

In addition, α- (unsaturated alkoxyalkyl) acrylate has a special polymerization called cyclopolymerization, and therefore has a (meth) acryloyl group such as ordinary (meth) acrylate, especially for gelation during polymerization. Compared with acrylic monomers, it will be greatly affected. In addition, even if the α- (unsaturated alkoxyalkyl) acrylate product contains more than a certain amount of a nitrogen compound derived from the catalyst during production and an unsaturated alkyl ester (such as an allyl ester) as a by-product, the polymer It turned out that the coloring of this and gelation of a polymer have a big subject.

As described above, α- (unsaturated alkoxyalkyl) acrylate is a special monomer, and therefore, there are few literatures that have studied its production method and characteristics. Therefore, α- (allyloxymethyl) acrylate is representative. In order to effectively utilize the α- (unsaturated alkoxyalkyl) acrylate used as a raw material for cyclopolymerization, and to efficiently industrially produce a high-quality chemical product for cyclopolymerization, it was awaited. .

The present invention has been made in view of the above-described situation, and α- (unsaturated alkoxyalkyl) acrylate products such as α- (allyloxymethyl) acrylate can be stored with high purity for a long period of time. And the like, and a stabilized α- (unsaturated alkoxyalkyl) acrylate composition capable of sufficiently suppressing the occurrence of problems such as α- (allyloxymethyl) acrylate and the like. It is an object of the present invention to provide a method for producing an α- (unsaturated alkoxyalkyl) acrylate composition capable of industrially safely obtaining (unsaturated alkoxyalkyl) acrylate.

The inventors of the present invention have studied various means for solving the above-mentioned problems with respect to α- (unsaturated alkoxyalkyl) acrylate itself and the production method thereof, and as a result, a specific amount of oxidation with α- (unsaturated alkoxyalkyl) acrylate. If the composition contains an inhibitor, it effectively suppresses the amount of peroxide produced and can be stored with high purity for a long period of time, and suppresses problems such as coloring and gelation during polymerization. It has been found that the above problem can be solved brilliantly, and the present invention has been achieved. According to the present invention, α- (unsaturated alkoxyalkyl) acrylate can be obtained as a stabilized raw material monomer for cyclization polymerization, which is industrially significant and has an outstanding effect. Can be played.

Here, it is speculated that there are the following three gelling mechanisms. For example, as α- (unsaturated alkoxyalkyl) acrylate, α- (allyloxymethyl) acrylate will be described as an example. (1) Branch by uncyclization reaction, (2) Branch made of peroxide, 3) It is presumed that a branched structure is formed by branching with allyl esters, and this causes a reaction such as crosslinking, thereby generating a partially gelled structure and overall gelation. As a result, the molecular weight increases, the molecular weight distribution becomes wider, and finally gelation occurs.
The above (1) to (3) are exemplified as follows. In the following formula, R and R ′ represent a monovalent organic group.

It is speculated that the antioxidant is particularly useful for suppressing branching caused by the above (2) peroxide. In addition, branching due to the (1) uncyclization reaction can be suppressed by polymerizing in a chain transfer agent or a polar solvent, and that the branching due to the (3) allyl ester occurs in the polymer It is suppressed by reducing the content of allyl esters in the product. In other words, by using an antioxidant, branching caused by the above (2) peroxide is suppressed, so that problems such as gelation in polymerization can be solved, and it can be stored in high purity for a long time. Become. Furthermore, by reducing the amount of allyl esters in the composition, problems such as gelation in polymerization can be more fully solved.

On the other hand, the literature showing the state of the art describes that a polymerization inhibitor is used in order to prevent polymerization when producing a compound having a (meth) acryloyl group or the like. For example, Patent Document 1 describes p-methoxyphenol and the like, and Patent Document 2 also describes that compounds such as p-methoxyphenol and hydroquinone may be used as a polymerization inhibitor. Furthermore, Patent Document 4 also describes that compounds such as hydroquinone, butylhydroxytoluene, and triphenyl phosphite may be used. However, these prior art documents specify that a monomer having a special structure having two different unsaturated groups of the type α- (unsaturated alkoxyalkyl) acrylate is specified. There is no disclosure. Generally, it can be said that it is only disclosed that a polymerization inhibitor may be used when producing a monomer having a polymerizable double bond.

For example, Patent Document 1 and Patent Document 4 do not refer to α- (unsaturated alkoxyalkyl) acrylate, and thus the resulting monomer is cyclic during polymerization like α- (unsaturated alkoxyalkyl) acrylate. It can be said that it is completely different. Moreover, also in patent document 2, the raw material which can prepare (alpha)-(allyloxymethyl) acrylate is only mentioned as one illustration. Furthermore, if it is a common monomer (for example (meth) acrylic acid ester etc.), even if there is no antioxidant, it can be said that there was no great influence on coloring and gelation at the time of polymerization. Although Patent Documents 1, 2, and 4 describe that they may be used as polymerization inhibitors such as p-methoxyphenol and hydroquinone, for example, Patent Document 2 describes them in that document. In Example 1, it was considered that washing was performed as a purification step, and the polymerization inhibitor used during the production was substantially removed. Moreover, in patent document 3, washing | cleaning and extraction are performed as a refinement | purification process in Example 1 etc. which were described in the said literature, and the polymerization inhibitor used during manufacture is substantially removed also here.

That is, the present invention provides the following general formula (I):

(In the formula, R ¹ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 30 carbon atoms. .) And an α- (unsaturated alkoxyalkyl) acrylate represented by an antioxidant, and the content of the antioxidant is 100 masses of the α- (unsaturated alkoxyalkyl) acrylate. % Is an α- (unsaturated alkoxyalkyl) acrylate composition that is 0.03 to 0.5 mass%.

The present invention is also a method for producing a composition containing α- (unsaturated alkoxyalkyl) acrylate represented by the above general formula (I), wherein the production method comprises α- (hydroxymethyl) acrylate and The following general formula (III):

(In the formula, R ² , R ³ and R ⁴ are the same as the symbols in the general formula (I)), and the reaction is carried out by dropping the unsaturated alcohol. It is also a method for producing an α- (unsaturated alkoxyalkyl) acrylate composition including the step of causing the reaction.

The present invention further relates to a method for producing a composition containing α- (unsaturated alkoxyalkyl) acrylate represented by the above general formula (I), wherein the production method comprises crude α- (unsaturated alkoxyalkyl). ) An α- (unsaturated alkoxyalkyl) acrylate composition comprising a step of adding an antioxidant to the purified α- (unsaturated alkoxyalkyl) acrylate after the purification step of obtaining the purified α- (unsaturated alkoxyalkyl) acrylate from the acrylate It is also a manufacturing method.
The present invention is described in detail below.

[Α- (Unsaturated alkoxyalkyl) acrylate composition]
The α- (unsaturated alkoxyalkyl) acrylate composition of the present invention is a composition (also simply referred to as “composition”) containing an antioxidant together with α- (unsaturated alkoxyalkyl) acrylate.
The α- (unsaturated alkoxyalkyl) acrylate has two types of unsaturated groups such as an unsaturated alkoxy group such as an allyl ether group and an acryloyl group in one molecule, and is useful as a compound for cyclopolymerization. Then, it will be supplied and used as a monomer (monomer), but in the present invention, it will be supplied and used as a monomer composition containing an antioxidant. That is, strictly speaking, it is not the monomer itself, but the monomer itself contains an additive or the like and is generally referred to as “monomer” and supplied. Accordingly, the α- (unsaturated alkoxyalkyl) acrylate composition is a so-called monomer in which a small amount of an antioxidant and, if necessary, other additives are contained in the α- (unsaturated alkoxyalkyl) acrylate monomer. It may be supplied and used as a composition containing other monomers and compounds. If an antioxidant is contained together with α- (unsaturated alkoxyalkyl) acrylate in the entire composition, it corresponds to the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention. Become.

<Α- (Unsaturated alkoxyalkyl) acrylate>
The α- (unsaturated alkoxyalkyl) acrylate is a compound represented by the general formula (I). That is, an unsaturated alkoxyalkyl group (—CH ₂ —O—CH ₂ —C (R ² ) ═C (R ³ ) (R ⁴ )) is present on the α-position carbon atom constituting the double bond in the acrylate. A compound having a bonded structure.
In addition, the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention may include only one α- (unsaturated alkoxyalkyl) acrylate as the α- (unsaturated alkoxyalkyl) acrylate. And one or more of R ¹ , R ² , R ³ and R ⁴ may contain a plurality of different α- (unsaturated alkoxyalkyl) acrylates.

In the general formula (I), R ¹ is a group constituting an ester group and represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Above all, it is preferable that R ¹ represents an organic group having 1 to 30 carbon atoms.
The organic group may be linear, branched, or cyclic. The organic group preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and still more preferably 1 to 8. As the organic group, for example, a monovalent organic group consisting of a hydrocarbon skeleton or a hydrocarbon skeleton containing an ether bond is preferable, and a chain saturated hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Preferably there is. These groups may have a substituent, that is, a substituted chain saturated hydrocarbon group or a substituted alicyclic ring in which at least a part of the hydrogen atoms bonded to the carbon atoms constituting these groups are replaced with a substituent. It may be a formula hydrocarbon group or a substituted aromatic hydrocarbon group. Among these, a chain saturated hydrocarbon group which may have a substituent is preferable.
Examples of the monovalent organic group comprising a hydrocarbon skeleton containing an ether bond include oxygen to at least one carbon-carbon bond constituting the chain saturated hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group. Examples include structures with atoms inserted.
As said substituent, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a cyano group, a trimethylsilyl group, etc. are mentioned.

Examples of the chain saturated hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-amyl, s-amyl, t-amyl, neopentyl, n- Hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, Groups such as eicosyl, ceryl and melyl are preferred. Further, at least part of the hydrogen atoms bonded to the carbon atoms constituting the chain saturated hydrocarbon group may be substituted with a hydroxy group, a halogen atom, etc., for example, a hydroxy-substituted chain saturated hydrocarbon group Suitable examples include halogen-substituted chain saturated hydrocarbon groups.

Suitable examples of the hydroxy-substituted chain saturated hydrocarbon group include groups such as hydroxyethyl, hydroxypropyl, and hydroxybutyl.
As the halogen-substituted chain saturated hydrocarbon group, the halogen atom is preferably a fluorine atom or a chlorine atom. For example, a group such as fluoroethyl, difluoroethyl, chloroethyl, dichloroethyl, bromoethyl, dibromoethyl is preferable. Can be mentioned.

Examples of the alicyclic hydrocarbon group include cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentanyl, and dicyclopentenyl. These groups are preferred. Also about this, the substituted alicyclic hydrocarbon group which substituted at least one part of the hydrogen atom couple | bonded with the carbon atom which comprises with a hydroxyl group, a halogen atom, etc. may be sufficient.

Preferred examples of the aromatic hydrocarbon group include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, naphthyl, and anthranyl groups. Can be mentioned. Also about this, the substituted aromatic hydrocarbon group which replaced at least one part of the hydrogen atom couple | bonded with the carbon atom which comprises with an alkoxy group, a hydroxy group, a halogen atom, etc. may be sufficient.

The monovalent organic group composed of a hydrocarbon skeleton containing an ether bond includes at least the chain saturated hydrocarbon group, the chain unsaturated hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group. The structure is not particularly limited as long as it has a structure in which an oxygen atom is inserted into one carbon-carbon bond. For example, methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl Chain ether groups such as phenoxyethyl and phenoxyethoxyethyl: Cyclopentoxyethyl, cyclohexyloxyethyl, cyclopentoxyethoxyethyl, cyclohexyloxyethoxyethyl, dicyclopentenyloxyethyl and other alicyclic hydrocarbon groups Group with ether group: Phenoxyethyl Groups having both an aromatic hydrocarbon group and a chain ether group such as phenoxyethoxyethyl: glycidyl, β-methylglycidyl, β-ethylglycidyl, 3,4-epoxycyclohexylmethyl, 2-oxetanemethyl, 3-methyl-3- Preferred examples include cyclic ether groups such as oxetanemethyl, 3-ethyl-3-oxetanemethyl, tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropyranyl, dioxazolanyl, dioxanyl and the like.

In the general formula (I), R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ¹ is the same as the organic group having 1 to 30 carbon atoms that can be represented. Among these, R ² , R ³ and R ⁴ are preferably hydrogen atoms. In this case, the compound represented by the general formula (I) is a compound having a structure represented by an allyloxyalkyl group (—CH ₂ —O—CH ₂ —CH═CH ₂ ), that is, α- (allyloxy). Methyl) acrylate. Thus, the form in which the α- (unsaturated alkoxyalkyl) acrylate contains α- (allyloxymethyl) acrylate is also a preferred form of the present invention. As a result, the effects of the present invention are more remarkably exhibited.

As the α- (allyloxymethyl) acrylate, the following general formula (II):

(In the formula, R ^1, are similar to those for R ^1. In the above formula (I)) is suitably a compound represented by.
When the composition of the present invention contains α- (allyloxymethyl) acrylate as α- (unsaturated alkoxyalkyl) acrylate, the α- (allyloxymethyl) acrylate may be one kind. Alternatively, a plurality of α- (allyloxymethyl) acrylates having different R ¹ may be used.

Examples of the α- (allyloxymethyl) acrylate compound include the following compounds.
α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, n-propyl α-allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, α- N-butyl allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate s -Amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate neopentyl, α-allyloxymethyl acrylate n-hexyl, α-allyloxymethyl acrylate s-hexyl, α-allyloxymethyl N-heptyl acrylate, α-allyloxymethyl N-octyl crylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate capryl, α- Allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate acrylate, α-allyloxymethyl acrylate tridecyl, α-allyloxymethyl acrylate Myristyl, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate nonade Chain saturated hydrocarbon group-containing α- (allyloxymethyl) acrylates such as syl, α-allyloxymethyl acrylate eicosyl, α-allyloxymethyl ceryl acrylate, and melyl α-allyloxymethyl acrylate.

α- (allyloxymethyl) acrylates containing hydroxy-substituted chain saturated hydrocarbon groups such as hydroxyethyl α-allyloxymethyl acrylate, hydroxypropyl α-allyloxymethyl acrylate, hydroxybutyl α-allyloxymethyl acrylate; -Fluoroethyl allyloxymethyl acrylate, difluoroethyl α-allyloxymethyl acrylate, chloroethyl α-allyloxymethyl acrylate, dichloroethyl α-allyloxymethyl acrylate, bromoethyl α-allyloxymethyl acrylate, α-allyl Halogen-substituted chain-like saturated hydrocarbon group-containing α- (allyloxymethyl) acrylate such as dibromoethyl oxymethyl acrylate.

α-allyloxymethyl acrylate cyclopentyl, α-allyloxymethyl acrylate cyclopentyl methyl, α-allyloxymethyl acrylate cyclohexyl, α-allyloxymethyl acrylate acrylate methyl, α-allyloxymethyl acrylate 4-methylcyclohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxymethyl acryl Alicyclic hydrocarbon group-containing α- (allyloxymethyl) acrylates such as dicyclopentanyl acid and dicyclopentenyl α-allyloxymethyl acrylate; phenyl α-allyloxymethyl acrylate α-Allyloxymethyl acrylate methylphenyl, α-allyloxymethylacrylate dimethylphenyl, α-allyloxymethylacrylate trimethylphenyl, α-allyloxymethylacrylate 4-t-butylphenyl, α-allyloxymethylacrylic Acid benzyl, α-allyloxymethyl acrylate diphenylmethyl, α-allyloxymethyl acrylate diphenylethyl, α-allyloxymethyl acrylate triphenylmethyl, α-allyloxymethyl acrylate naphthyl, α-allyloxymethyl acrylate An α- (allyloxymethyl) acrylate containing an aromatic hydrocarbon group such as anthranyl.

methoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethoxyethyl α-allyloxymethyl acrylate, 3-methoxybutyl α-allyloxymethyl acrylate, α-allyloxymethyl Chain ether group-based saturated hydrocarbon group-containing α- such as ethoxyethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate (Allyloxymethyl) acrylate; cyclopentoxyethyl α-allyloxymethyl acrylate, cyclohexyloxylethyl α-allyloxymethyl acrylate, cyclopentoxy α-allyloxymethyl acrylate Α- (allyloxymethyl) acrylate having both an alicyclic hydrocarbon group and a chain ether group, such as toxiethyl, α-allyloxymethyl acrylate cyclohexyloxyethoxyethyl, α-allyloxymethyl acrylate dicyclopentenyloxyethyl; α- (allyloxymethyl) acrylate having both an aromatic hydrocarbon group and a chain ether group such as phenoxyethyl α-allyloxymethyl acrylate and phenoxyethoxyethyl α-allyloxymethyl acrylate; α-allyloxymethyl acrylic acid Glycidyl, α-allyloxymethyl acrylate β-methyl glycidyl, α-allyloxymethyl acrylate β-ethyl glycidyl, α-allyloxymethyl acrylate 3,4-epoxycyclohexylmethyl, α-allyloxymethyl acryl Acid 2-oxetanemethyl, α-allyloxymethyl acrylate 3-methyl-3-oxetanemethyl, α-allyloxymethyl acrylate 3-ethyl-3-oxetanemethyl, α-allyloxymethyl acrylate tetrahydrofuranyl, α- Cyclic ether group-based saturated hydrocarbon group-containing α- such as tetrahydrofurfuryl allyloxymethyl acrylate, tetrahydropyranyl α-allyloxymethyl acrylate, dioxazolanyl α-allyloxymethyl acrylate, dioxanyl α-allyloxymethyl acrylate (Allyloxymethyl) acrylate.

In the composition of the present invention, the content of α- (unsaturated alkoxyalkyl) acrylate is preferably 80% by mass or more in 100% by mass of the composition. This form is a form in which the concentration of α- (unsaturated alkoxyalkyl) acrylate is increased, and is suitable when α- (unsaturated alkoxyalkyl) acrylate itself is used. For example, it is suitable when a high-purity α- (unsaturated alkoxyalkyl) acrylate composition that produces a small amount of peroxide is used for cyclopolymerization as a so-called monomer.
The upper limit of the content of the α- (unsaturated alkoxyalkyl) acrylate is preferably 99.97% by mass or less. As a minimum, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more.

<Antioxidant>
The α- (unsaturated alkoxyalkyl) acrylate composition contains an antioxidant as an essential component. However, since the antioxidant changes after exhibiting the antioxidant action in the composition, it is not always necessary that the antioxidant itself is contained in the composition without changing at any time. That is, it is considered that the antioxidant gradually decreases after exhibiting the antioxidant action. Therefore, the composition of the present invention may be a composition to which an antioxidant is added. Although the content of the antioxidant for the composition may fall below the lower limit with the passage of time, the technical scope of the present invention as long as such a mode is one in which a specific amount of antioxidant is added. Is within.

The antioxidant may be added during the production of α- (unsaturated alkoxyalkyl) acrylate or after the production. If it is during production, it is preferable in that the action of the antioxidant can be exerted also in the reaction step and the purification step such as distillation. For example, it can be added during production so that the antioxidant remains after production, or the purification process so that the antioxidant used in the reaction process and purification process is not completely removed in the purification process. May be adjusted. After the production, it may be added after the reaction step or the purification step, or may be added at the time of storage. Preferably, as in the production method of the present invention to be described later, it is added after the purification step so as to have a predetermined concentration, and more preferably, the product as an α- (unsaturated alkoxyalkyl) acrylate composition is added. From the viewpoint of suppressing coloring and the amount of peroxide generated, it is preferable to add an antioxidant at a predetermined concentration early in the purification process.

In addition, when the raw material for producing α- (unsaturated alkoxyalkyl) acrylate contains an antioxidant, the compounds and monomers contained in the α- (unsaturated alkoxyalkyl) acrylate composition are oxidized. When it contains an antioxidant, the antioxidant contained therein can be used as the antioxidant in the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention. In such a case, the operation of adding the antioxidant itself to the α- (unsaturated alkoxyalkyl) acrylate composition is not performed, but in these cases, the composition containing the antioxidant is added. There is no change. However, it is preferable to add an antioxidant so as to have a predetermined concentration after the purification step, as in the production method of the present invention described later.

The antioxidant in the present invention is a compound that suppresses an oxidizing action on α- (unsaturated alkoxyalkyl) acrylate, and thereby a compound or composition that suppresses an increase in the amount of peroxide generated. Any one recognized by those skilled in the art as an antioxidant in the technical field using monomers may be used. In general, compounds and compositions recognized as radical polymerization inhibitors, radical chain inhibitors and the like can also be used as antioxidants in the present invention. However, in the present invention, since the effect varies greatly depending on the type of antioxidant and the like, it is preferable to select the antioxidant depending on the use of α- (unsaturated alkoxyalkyl) acrylate, the storage / use method, and the like. In addition, the fact that unsaturated alkoxy groups such as allyl ether groups are likely to be oxidized is considered to be one of the causes of the above problems, so it is effective against oxidation of unsaturated alkoxy groups such as allyl ether groups. It can be said that it is preferable to select what to do. A preferred embodiment of the antioxidant will be described later.

The α- (unsaturated alkoxyalkyl) acrylate composition contains an antioxidant in an amount of 0.03 to 0.5% by mass with respect to 100% by mass of α- (unsaturated alkoxyalkyl) acrylate. As described above, in the present invention, all of the antioxidant added to the α- (unsaturated alkoxyalkyl) acrylate does not remain unchanged, but gradually decreases after exhibiting the antioxidant action. It is thought to do. Therefore, when the antioxidant is contained in an amount of 0.03 to 0.5% by mass based on 100% by mass of α- (unsaturated alkoxyalkyl) acrylate, the oxidation added to α- (unsaturated alkoxyalkyl) acrylate The total amount of the inhibitor may be 0.03 to 0.5% by mass with respect to 100% by mass of α- (unsaturated alkoxyalkyl) acrylate. If the content of the antioxidant is less than the above range, the effect of adding the antioxidant may not be exhibited. If the content is more than the above range, the antioxidant becomes excessive, and the effect is appropriately achieved. There is a risk that it will be out of range. The lower limit is preferably 0.04% by mass or more. More preferably, it is 0.05 mass% or more. The upper limit is preferably 0.4% by mass or less. More preferably, it is 0.3 mass% or less, More preferably, it is 0.2 mass% or less. Especially preferably, it is 0.1 mass% or less.

Since the composition is intended to use α- (unsaturated alkoxyalkyl) acrylate as a monomer, the total amount of the antioxidant is contained within the above range during storage. Is preferred. Thus, if an antioxidant is added during the production of α- (unsaturated alkoxyalkyl) acrylate and removed in the purification process, the total amount of antioxidant in the α- (unsaturated alkoxyalkyl) acrylate composition at storage Does not include antioxidants removed in the purification process.

<A more preferable form of the composition>
Preferred forms of the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention include (1) a form in which the antioxidant contains a phenol-based antioxidant and / or a phosphorus-based antioxidant, and (2) an unsaturated alkyl. A form in which the ester content is 1% by mass or less based on 100% by mass of α- (unsaturated alkoxyalkyl) acrylate, (3) the nitrogen content is based on 100% by mass of α- (unsaturated alkoxyalkyl) acrylate (4) The amount of peroxide is 50 ppm or less with respect to 100% by mass of α- (unsaturated alkoxyalkyl) acrylate. These preferable forms (constituent requirements) may satisfy any one of the constituent requirements, or may satisfy two or more constituent requirements in combination.
Below, these preferable forms are demonstrated in order.

In the above (1) form in which the antioxidant includes (requires) a phenolic antioxidant and / or a phosphorus antioxidant, the oxidation inhibiting effect on α- (unsaturated alkoxyalkyl) acrylate, the peroxide The production amount suppressing effect is remarkable. In particular, it is considered to effectively act to suppress oxidation of unsaturated alkoxy groups such as allyl ether groups. The antioxidant is effective for both production and storage. When the antioxidant is added during production, it is preferable that the antioxidant is present even during storage. You may add the said antioxidant only at the time of a preservation | save.

As the phenolic antioxidant and the phosphorus antioxidant, either antioxidant may be used, or both antioxidants may be used, but a form using a phenolic antioxidant, particularly (1 (1) A form using a quinone-based antioxidant or a form (1-2) using a phenol-based antioxidant and a phosphorus-based antioxidant in combination is preferable. In the case of (1-2), the phenolic antioxidant is a primary antioxidant, that is, a radical chain inhibitor (radical scavenger), and the phosphorus antioxidant is a secondary antioxidant, that is, a peroxide generation amount. It is preferable to combine them as a peroxide decomposer for reducing the amount. Thereby, the gelatinization at the time of superposing | polymerizing using (alpha)-(unsaturated alkoxyalkyl) acrylate as a monomer can be suppressed effectively. As a mass ratio when combining a phenolic antioxidant and a phosphorus antioxidant, it is preferable that phenolic antioxidant: phosphorus antioxidant is 10 to 90: 90-10. More preferably, it is 25-75: 75-25. Particularly preferred is a form used substantially at 1: 1.

Here, the said antioxidant contains a phenolic antioxidant and / or a phosphorus antioxidant (it is essential) that a part or all of the antioxidant used in the present invention is a phenolic antioxidant and And / or a phosphorus-based antioxidant, preferably a phenol-based antioxidant and / or a phosphorus-based antioxidant as a main component of the antioxidant, more preferably substantially antioxidant. It is to use only a phenolic antioxidant and / or a phosphorus antioxidant as an agent.
The phenolic antioxidant and the phosphorus antioxidant can be used alone or in combination of two or more.

Examples of the phenol-based antioxidant include hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 2,2′-methylenebis (4 Quinone antioxidants such as -methyl-6-t-butylphenol) and 2,2'-methylenebis (4-ethyl-6-t-butylphenol); p-methoxyphenol, 2,6-di-t-butyl- 4-methylphenol, 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenol) butane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4-Butylidene-bis- (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydride Xylphenyl) propionate, tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane, triethylene glycol bis [3- (3-t-butyl-5-methyl) -4-hydroxyphenyl) propionate, N, N-bis-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionylhexamethylenediamine, 1,3,5-trimethyl-2, Alkylphenol antioxidants such as 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene are preferred.

As said phosphorus antioxidant, a phenyl phosphite type compound and other phosphorus atom containing compounds can be used, for example, triphenylphosphine, triphenyl phosphite (triphenyl phosphite), diphenylisodecyl phosphite. , Phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl ditridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), tris (nonylphenyl) phos Phyto, tris (mono and / or dinonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, di (2,4-di-tert-butylphenyl) -pentaerythritol diphosphite, 9,10-dihydro-9- Oxa-1 -Phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- Decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ether is preferred That.

The form in which the content of the unsaturated alkyl ester (2) is 1% by mass or less with respect to 100% by mass of α- (unsaturated alkoxyalkyl) acrylate is usually produced during the production of α- (unsaturated alkoxyalkyl) acrylate. This is because the content of the unsaturated alkyl ester, which is a by-product to be formed, in the product is suppressed. This also can effectively solve the problems in the present invention such as coloring of the polymer and gelation during polymerization.

In the present specification, the unsaturated alkyl ester that can be contained in the composition is one of the starting materials of α- (unsaturated alkoxyalkyl) acrylate, and is represented by the above general formula (III). It shall mean an ester of an alcohol and a raw material, product and / or by-product acrylate. Such unsaturated alkyl ester content (unsaturated alkyl ester content) refers to α- (hydroxymethyl) acrylate used as a raw material or an intermediate and the unsaturated compound represented by the above general formula (III) Esters with alcohols, esters of products α- (unsaturated alkoxyalkyl) acrylates with unsaturated alcohols represented by the above general formula (III), and by-products α- (alkoxyalkyls) It is the total amount of esters of acrylic acid and unsaturated alcohol. For example, when the α- (unsaturated alkoxyalkyl) acrylate is α- (allyloxymethyl) acrylate, α- (hydroxymethyl) acrylic acid which is an allyl ester of α- (hydroxymethyl) acrylate as a raw material or an intermediate The total amount of allyl, allyl ester α- (allyloxymethyl) acrylate, which is an allyl ester of the product, and allyl α- (alkoxymethyl) acrylate, which is a byproduct.
When the α- (unsaturated alkoxyalkyl) acrylate is α- (allyloxyalkyl) acrylate, the unsaturated alkyl ester corresponds to an allyl ester.

Here, the content of unsaturated alkyl ester in the product of α- (unsaturated alkoxyalkyl) acrylate is not found at all, but this value is deeply related to the problem in the present invention. It has been found.
In order to obtain such a form, a production method for obtaining α- (unsaturated alkoxyalkyl) acrylate is performed by using α- (hydroxymethyl) acrylate and an unsaturated alcohol represented by the general formula (III). May be produced by adding the unsaturated alcohol dropwise, or the unsaturated alkyl ester may be sufficiently removed in the purification step in the production of α- (unsaturated alkoxyalkyl) acrylate. Preferably, these two methods are used in combination.

Among the forms for reducing the unsaturated alkyl ester, in the method of dropping unsaturated alcohol dropwise, the amount of unsaturated alkyl ester generated can be increased by dropping dropwise the unsaturated alcohol instead of batch loading. It can be sufficiently suppressed. Thereby, a refinement | purification process can be simplified and it becomes possible to improve the refinement | purification yield of (alpha)-(unsaturated alkoxyalkyl) acrylate.

In addition, regarding the method for removing unsaturated alkyl ester in the purification step, since it is considered that the amount of unsaturated alkyl ester is not controlled in the usual purification step, in this preferred embodiment of the present invention, The unsaturated alkyl ester content is controlled to be within the above range (upper limit value). In order to achieve this unsaturated alkyl ester content, it is preferable to carry out distillation, and it is particularly preferable to carry out distillation using a distillation column having a number of stages. The upper limit is more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less. Regarding the lower limit, it is preferable that the content of the unsaturated alkyl ester is substantially 0 (zero). However, if it is within the above range (upper limit), the outstanding effect of the present invention is sufficiently obtained. It can be demonstrated.

The measurement time of the unsaturated alkyl ester content may be immediately after production after the purification step and / or storage after production, but in the normal storage state, the amount of unsaturated alkyl ester is substantially increased. Since it is considered that there is almost nothing, it may be at any point except when the amount of unsaturated alkyl ester is controlled as described above.

(3) The form in which the nitrogen content is 100 ppm or less with respect to 100% by mass of α- (unsaturated alkoxyalkyl) acrylate is an amine catalyst (usually used in the production of α- (unsaturated alkoxyalkyl) acrylate). And when the catalyst is chemically changed, the content of the compound having a nitrogen atom of the catalyst) in the product is suppressed. This can effectively solve the problems in the present invention such as coloring of the polymer and gelation during polymerization. Regarding the nitrogen content in the product of α- (unsaturated alkoxyalkyl) acrylate, there is no literature which examined it, but it has been found that this value is deeply related to the problem in the present invention. In order to obtain such a form, the amine catalyst may be sufficiently removed in the purification step in the production of α- (unsaturated alkoxyalkyl) acrylate. However, since it is considered that the nitrogen content is not controlled in the purification step that is usually performed, in the preferred embodiment of the present invention, the nitrogen content is within the above range (up to the upper limit). It will be controlled to become.

A particularly suitable purification condition for achieving the nitrogen content within the above range (below the upper limit) is to sufficiently remove the amine-based catalyst by washing with water before distillation purification. The upper limit of the nitrogen content is more preferably 80 ppm or less, still more preferably 50 ppm or less. As the lower limit, it is preferable that the nitrogen content is substantially 0 (zero), but if it is within the above range (below the upper limit), the outstanding effect of the present invention can be sufficiently exhibited. it can.
With respect to the measurement time of the nitrogen content, it may be immediately after production after the purification step and / or during storage after production, but in a normal storage state, the nitrogen content hardly increases substantially. Since it is considered, it may be at any time except when the nitrogen content is controlled as described above.

In the form in which the amount of the peroxide (4) is 50 ppm or less with respect to 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate, the amount of the peroxide generated is suppressed as described above, thereby Problems in the present invention such as coloring and gelation during polymerization can be effectively solved. Regarding the amount of peroxide in the product of α- (unsaturated alkoxyalkyl) acrylate, there is no literature that examined it, but it has been found that this value is deeply related to the problem in the present invention, This is technically significant for specifying the peroxide amount. The means for making such a form is to use an antioxidant for the α- (unsaturated alkoxyalkyl) acrylate, and to make it the preferred form described herein.

The upper limit of the peroxide amount is more preferably 50 ppm or less, still more preferably 30 ppm or less. As a lower limit, it is preferable that the amount of peroxide is substantially 0 (zero), but in reality, it is considered that a slight amount of peroxide is present. If it is in said range (below upper limit), the outstanding effect of this invention can fully be exhibited.
Examples of the time point for measuring the amount of the peroxide include production and / or storage after production, and α- (unsaturated alkoxyalkyl) acrylate is used as a monomer, and the polymer is colored or polymerized. From the viewpoint of suppressing gelation, it is preferable that the amount of peroxide is measured in the storage state and is within the above range (up to the upper limit value).
In the preferred form of the present invention, the measurement method used in the examples described later may be used for the measurement of unsaturated alkyl ester content, nitrogen content, and peroxide amount.

About the form of said (2)-(4), although the quality and state in the product of (alpha)-(unsaturated alkoxyalkyl) acrylate composition are specified, all these numerical ranges (upper limit) are polymers. Therefore, it is preferable to use a combination of two or more of them. For example, the above-mentioned (2) unsaturated alkyl ester content is 1% by mass or less and (3) the nitrogen content is preferably 100 ppm or less, and (4) the peroxide content is 50 ppm or less. It is more preferable to adopt a form that satisfies the above. Thus, in order to achieve the form in which any two or more of the above (2) to (4) are combined, the amount of peroxide is used by using an antioxidant for α- (unsaturated alkoxyalkyl) acrylate. In addition, the nitrogen content derived from the amine catalyst and the content of the unsaturated alkyl ester as a by-product are reduced within the above range (up to the upper limit). As a result, the α- (unsaturated alkoxyalkyl) acrylate composition is not only highly purified as a chemical product, but also has unprecedented properties of suppressing coloring of the polymer and gelation during polymerization. Will be demonstrated.

<Other ingredients>
The composition of the present invention may contain a compound other than α- (unsaturated alkoxyalkyl) acrylate and an antioxidant, for example, α- (unsaturated alkoxyalkyl) when used as a polymerization raw material. Another radical polymerizable monomer that polymerizes with acrylate (that is, a compound having a radical polymerizable double bond other than α- (unsaturated alkoxyalkyl) acrylate; hereinafter also referred to as “radical polymerizable monomer”). You may contain 1 type, or 2 or more types. These monomers are monomers having radically polymerizable unsaturated groups that are polymerized by irradiation with heat or active energy rays. What is necessary is just to select suitably the kind, usage-amount, etc. of another radically polymerizable monomer according to the characteristic of a polymer to manufacture, and a use. Moreover, you may contain 1 type, or 2 or more types of additives, such as a chain transfer agent.

Examples of the radical polymerizable monomer include various monomers. For example, (meth) acrylic acid esters, (meth) acrylamides, unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids. Acids, unsaturated monocarboxylic acids, unsaturated acid anhydrides, aromatic vinyls, N-substituted maleimides, macromonomers, conjugated dienes, vinyl esters in which the chain between the unsaturated group and the carboxyl group is extended It is preferable to use at least one selected from the group consisting of vinyl ethers, N-vinyl compounds and unsaturated isocyanates, and the following radical polymerizable monomers can be exemplified as industrially suitable.

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, T-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) Stearyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isovo (meth) acrylate Nyl, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ( Phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, (meth) acrylic acid (3 , 4-epoxycyclohexyl) methyl, (meth) acrylic acid N, - dimethylaminoethyl, alpha-hydroxymethyl acrylate methyl, (meth) acrylic acid esters such as alpha-hydroxymethyl acrylate.

(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; Unsaturated polycarboxylic acids such as acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; unsaturated groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate and carboxyl Unsaturated monocarboxylic acids having a chain extended between them; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene Methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, N-substituted maleimides such as nilmaleimide, benzylmaleimide, naphthylmaleimide; (meth) at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam Macromonomers having an acryloyl group; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether , Butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether Vinyl ethers such as ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl N-vinyl compounds such as morpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate.

As the chain transfer agent, for example, at least one selected from the group consisting of a compound having a mercapto group, disulfides, dithiocarbamates, monomer dimers, and alkyl halides is suitable.
Among them, compounds having a mercapto group are suitable, for example, mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-mercapto N-octyl propionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa Mercaptocarboxylic esters such as kiss (3-mercaptopropionate); ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoeta Alkyl mercaptans such as 2-mercaptoethanol, mercaptoalcohols such as 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol, 2-naphthalenethiol; Suitable examples include mercaptan chain transfer agents such as mercaptoisocyanurates such as (3-mercaptopropionyloxy) -ethyl] isocyanurate.

[Method for producing α- (unsaturated alkoxyalkyl) acrylate composition]
The present invention is also a method for producing a composition containing α- (unsaturated alkoxyalkyl) acrylate represented by the above general formula (I), wherein the production method comprises α- (hydroxymethyl) acrylate and , A method for producing an α- (unsaturated alkoxyalkyl) acrylate composition (hereinafter referred to as “an unsaturated alcohol”) comprising a step of reacting the unsaturated alcohol represented by the general formula (III) by dropping the unsaturated alcohol dropwise. Also referred to as “Production method 1”.). That is, it is preferable to add the unsaturated alcohols dropwise instead of adding them all at once, whereby the production amount of the unsaturated alkyl ester can be more sufficiently suppressed. In this way, by suppressing the production of unsaturated alkyl ester in the reaction step, the subsequent purification step can be simplified and the purification yield can be further improved. For example, in distillation purification, a high-purity α- (unsaturated alkoxyalkyl) acrylate will be obtained from a reaction solution containing a larger amount of unsaturated alkyl ester having a higher boiling point than the target α- (unsaturated alkoxyalkyl) acrylate. Then, since it is necessary to increase the reflux ratio or reduce the distillate amount, the efficiency cannot be improved, and the purification yield may not be sufficient.

Here, α- (hydroxymethyl) acrylate used in the step of reacting α- (hydroxymethyl) acrylate and unsaturated alcohol may be a raw material and / or an intermediate, that is, α- (unsaturated alkoxyalkyl). In the synthesis of acrylate, the present invention is applied to a production method via α- (hydroxymethyl) acrylate. A specific form of a method for obtaining an α- (unsaturated alkoxyalkyl) acrylate composition via α- (hydroxymethyl) acrylate will be described in detail later.

In the said manufacturing method 1, in the reaction process of (alpha)-(hydroxymethyl) acrylate and unsaturated alcohol, the said unsaturated alcohol will be dripped in, but what is necessary is just to set dripping time suitably with the usage-amount of a raw material etc. . For example, it is preferably 30 minutes to 8 hours, and more preferably 1 hour to 4 hours. In addition, it is suitable to perform an aging process after dropping unsaturated alcohol.
In the reaction step, the use amount (total amount) of the unsaturated alcohol is preferably 0.1 to 10 mol with respect to 1 mol of α- (hydroxymethyl) acrylate. More preferably, it is 1-5 mol.
Moreover, 10-150 degreeC is suitable for reaction temperature.

In the reaction step of the α- (hydroxymethyl) acrylate and the unsaturated alcohol, an amine catalyst is preferably used. That is, a form in which the production method includes a step of reacting in the presence of an amine-based catalyst is also a preferred form of the present invention. The details of the amine catalyst and the preferred range of the amount used are as described later.

The α- (unsaturated alkoxyalkyl) acrylate composition obtained by the production method including the production method 1 is preferably the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention described above, and includes an unsaturated alkyl ester. It is preferable that the amount of the α- (unsaturated alkoxyalkyl) acrylate composition is 1% by mass or less with respect to 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate. The suitable range of the upper limit and lower limit of the unsaturated alkyl ester content is as described above.
In order to obtain a suitable α- (unsaturated alkoxyalkyl) acrylate composition of the present invention, the method includes a step of removing the amine catalyst by washing with water after the production method 1, and a step of reducing the content of the unsaturated alkyl ester by distillation. The form is also one of the preferred forms of the present invention.

Examples of the α- (hydroxymethyl) acrylate include the following general formula (i):

It is preferable that it is represented by these. In Formula (i), the preferred form of R ¹ are the same as the preferred embodiment of R ¹ in general formula (I).

The unsaturated alcohol represented by the general formula (III) is not particularly limited as long as it has a structure represented by the general formula (III). Moreover, 1 type (s) or 2 or more types can be used for such unsaturated alcohol. Among these, it is preferable to use at least allyl alcohol. Thus, the form in which the unsaturated alcohol contains allyl alcohol is also a preferred form of the present invention.

The present invention further relates to a method for producing a composition containing α- (unsaturated alkoxyalkyl) acrylate represented by the above general formula (I), wherein the production method comprises crude α- (unsaturated alkoxyalkyl). ) An α- (unsaturated alkoxyalkyl) acrylate composition comprising a step of adding an antioxidant to the purified α- (unsaturated alkoxyalkyl) acrylate after the purification step of obtaining the purified α- (unsaturated alkoxyalkyl) acrylate from the acrylate (Hereinafter also referred to as “Production Method 2”). The α- (unsaturated alkoxyalkyl) acrylate composition obtained by such a production method is preferably the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention described above.
The production method of the present invention is particularly preferably a combination of the production method 1 and the production method 2, that is, the reaction step of the α- (hydroxymethyl) acrylate and the unsaturated alcohol, the purification step, and after the purification. It is a manufacturing method including the process of adding antioxidant.

In the said manufacturing method 2, after obtaining a crude product by the method mentioned later, in order to remove the catalyst and by-product which were used for manufacture, a refinement | purification process is performed. As will be described later, in the synthesis of α- (unsaturated alkoxyalkyl) acrylate, it is effective to use an amine-based catalyst, so that the nitrogen content can be reduced by the purification process, and by-products can be reduced. Certain unsaturated alkyl ester content can also be reduced and is effective to achieve the preferred form of the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention. On the other hand, in the synthesis of α- (unsaturated alkoxyalkyl) acrylate, it is effective to add a polymerization inhibitor or a chain inhibitor in order to prevent polymerization of the polymerizable unsaturated bond during the synthesis reaction. However, even if it acts as an antioxidant after production, it may be removed to the extent that it does not act effectively as an antioxidant in the purification process. If the purification process is sufficiently performed, the catalyst and by-products can be sufficiently removed, while those that act as an antioxidant when a polymerization inhibitor or chain transfer agent is added during production are also sufficient. It will be removed. When the purified α- (unsaturated alkoxyalkyl) acrylate obtained through such a purification process is stored as it is and used as a polymerization raw material, the amount of peroxide generated during storage increases, and the resulting polymer Coloring and gelation during polymerization cannot be suppressed. Conversely, when polymerization inhibitors, chain inhibitors, etc. are added during production and these act as antioxidants, when the purification process is not performed, or those that act as antioxidants act When the purification process is simplified so as to remain to such an extent that the catalyst is sufficiently exerted, the catalyst and by-products cannot be sufficiently removed.

In the said manufacturing method 2, the composition which contains antioxidant together with (alpha)-(unsaturated alkoxyalkyl) acrylate will be obtained by adding antioxidant after a refinement | purification process. Moreover, it can be said that such a manufacturing method is an effective means in order to achieve the preferable form of the composition of this invention mentioned above.

The said refinement | purification process should just be the process of implementing the purification method which can be used in the technical field of this invention, For example, the process of performing at least 1 of washing | cleaning, extraction, distillation, etc. is suitable. The purification conditions include impurities such as catalysts and by-products contained in the crude α- (unsaturated alkoxyalkyl) acrylate, and the type and amount of the solvent used in the reaction. What is necessary is just to set suitably according to whether an alkyl) acrylate is obtained. Preferably, the nitrogen content and the unsaturated alkyl ester content are within the above ranges (below the upper limit) so that the preferred form of the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention described above is obtained. The purification method and purification conditions may be set as appropriate.

In the step of adding an antioxidant to the purified α- (unsaturated alkoxyalkyl) acrylate, it is preferable to add an antioxidant as soon as possible after the purification step in order to suppress an increase in the amount of peroxide.
In addition, as above-mentioned, 1 type may be added and 2 or more types may be added for antioxidant. As an addition method, it may be added all at once or sequentially or continuously.

In the production method 1 and / or 2, as an example of a preferable method for obtaining α- (unsaturated alkoxyalkyl) acrylate, a form for obtaining α- (allyloxymethyl) acrylate represented by the above general formula (II) Will be described in detail. In addition, allyl alcohol used in the following reaction step (c) is a kind of unsaturated alcohol represented by the general formula (III). Α- (unsaturated alkoxyalkyl) acrylates other than α- (allyloxymethyl) acrylate can also be suitably obtained by appropriately changing the raw materials and the like in the following reaction steps (a) to (c).

As a method for obtaining the above α- (allyloxymethyl) acrylate, for example, a method of performing the following reaction steps (a), (b) and (c) is preferably exemplified. Moreover, it is preferable to use the amine catalyst mentioned later for these reaction processes.
(A) A step of reacting an acrylic ester with paraformaldehyde to obtain α- (hydroxymethyl) acrylate.
(B) A step of obtaining 2,2 ′-[oxybis (methylene)] bisacrylate from α- (hydroxymethyl) acrylate.
(C) A step of reacting 2,2 ′-[oxybis (methylene)] bisacrylate with allyl alcohol to produce α- (allyloxymethyl) acrylate and α- (hydroxymethyl) acrylate.

Among the reaction steps, the reaction step (b) and the reaction step (c) are combined, and α- (hydroxymethyl) acrylate is reacted with allyl alcohol to obtain α- (allyloxymethyl) acrylate and It is also preferable to perform the step of producing α- (hydroxymethyl) acrylate. That is, the production method (Production Method 2) preferably includes a step of reacting α- (hydroxymethyl) acrylate with the unsaturated alcohol represented by the general formula (III). In this case, it is more preferable to react the α- (hydroxymethyl) acrylate and the unsaturated alcohol by dropping the unsaturated alcohol in the same manner as in Production Method 1 described above. The preferable form of such a reaction process is as having mentioned above.
The method for obtaining the α- (allyloxymethyl) acrylate is also preferably based only on the reaction step (c).

When the reaction steps (a) to (c) are performed, or when the reaction steps (b) and (c) are performed, these steps may be performed as a continuous series of steps. It may be done separately. That is, in each step, α- (hydroxymethyl) acrylate or 2,2 ′-[oxybis (methylene)] bisacrylate may be produced and reacted as an intermediate, or added and reacted as a reaction raw material. Also good. In such a process, α- (hydroxymethyl) acrylate is used as a raw material and / or an intermediate, and 2,2 ′-[oxybis (methylene)] bisacrylate is used as a raw material and / or an intermediate. Will be used.
In the above reaction step, α- (hydroxymethyl) acrylate is produced together with α- (allyloxymethyl) acrylate, which is the target product. The α- (hydroxymethyl) acrylate is α- (allyloxymethyl) acrylate. Can be reused as a raw material for obtaining.

In the above reaction step, 2,2 ′-[oxybis (methylene)] bisacrylate in which the hydroxyl group of α- (hydroxymethyl) acrylate is dehydrated and condensed between molecules is produced from α- (hydroxymethyl) acrylate. , 2 '-[oxybis (methylene)] bisacrylate and allyl alcohol are reacted, but the hydroxyl group of α- (hydroxymethyl) acrylate is acetylated to form α- (acetoxymethyl) acrylate. A method of reacting α- (acetoxymethyl) acrylate with allyl alcohol is also suitable.

An example of the reaction steps (a) to (c) is shown in the following reaction formulas (a) to (c).
In this reaction formula, R ¹ is a methyl group as α- (hydroxymethyl) acrylate represented by the above general formula (i), and 1,4-diazabicyclo [2.2 .2] represents the case of using octane.

Regarding the reaction conditions in the above reaction steps (a) to (c), when these steps are carried out as a series of steps, when these steps are carried out separately, the molar ratio of the raw materials used, the type of catalyst and the mole The ratio, reaction temperature, time, and the like may be set as appropriate. An example of preferable reaction conditions is as follows.
Regarding the reaction step (a), the molar ratio of paraformaldehyde to methyl acrylate is preferably 0.05 to 20. The reaction temperature is preferably 10 to 150 ° C. in order to suppress the polymerization reaction of methyl acrylate or α- (hydroxymethyl) methyl acrylate. What is necessary is just to set reaction time suitably with the advancing speed of reaction.
Regarding the reaction step (b), the reaction temperature is preferably 10 to 150 ° C.
Regarding the reaction step (c), the amount of allyl alcohol used relative to methyl 2,2 ′-[oxybis (methylene)] bisacrylate is 2,2 ′-[oxybis (methylene)] methyl bisacrylate / allyl alcohol. The molar ratio is preferably 0.05-20. The reaction temperature is preferably 10 to 150 ° C.
The amount of amine catalyst used in these reaction steps will be described later.
In order to suppress polymerization of methyl acrylate, methyl α- (hydroxymethyl) acrylate, methyl 2,2 ′-[oxybis (methylene)] bisacrylate, methyl α- (allyloxymethyl) acrylate, It is preferable to use a polymerization inhibitor or molecular oxygen.

As a method for producing the α- (unsaturated alkoxyalkyl) acrylate, for example, a lower ester of α-allyloxymethylacrylic acid such as methyl α-allyloxymethylacrylate or ethyl α-allyloxymethylacrylate may be used. A method using a transesterification reaction is also suitable. In this case, for example, a lower ester of α- (unsaturated alkoxyalkyl) acrylic acid and an alcohol whose content of unsaturated alkyl ester, nitrogen content and / or peroxide is reduced to the above-mentioned preferred range by the above-described production method. The α- (unsaturated alkoxyalkyl) acrylate composition of the present invention is preferably subjected to a transesterification reaction using a transesterification catalyst, and further purified if necessary, and then added with an antioxidant after purification. Things can be obtained. Such a form is also one of the preferred forms of the present invention.

A preferred embodiment of the production method of the present invention is an embodiment of producing the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention and a preferred form thereof. (1) The antioxidant is a phenolic antioxidant and An aspect in which a phosphorus-based antioxidant is essential, and (2) a step of reacting α- (hydroxymethyl) acrylate with an unsaturated alcohol (allyl alcohol or the like) represented by the above general formula (III). Aspects and (3) an aspect including a step of reacting in the presence of an amine catalyst are particularly preferred aspects.
These preferable modes (constituent requirements) may satisfy any one of the constituent requirements, or may satisfy two or more constituent requirements in combination.

Regarding the aspect in which the (1) antioxidant is essentially a phenolic antioxidant and / or a phosphorus antioxidant, the phenolic antioxidant described in the α- (allyloxymethyl) acrylate composition of the present invention. And / or a preferred form relating to the phosphorus-based antioxidant.

(2) About the aspect including the process of making (alpha)-(hydroxymethyl) acrylate and an unsaturated alcohol react, in the said reaction process, (alpha)-(hydroxymethyl) acrylate is used as a reaction raw material and / or a reaction intermediate. It only has to react with the unsaturated alcohol.

About the aspect including the process made to react in the presence of said (3) amine catalyst, the said reaction process will be performed in presence of an amine catalyst.
Examples of the amine catalyst include a primary amine compound, a secondary amine compound, and a tertiary amine compound, and it is preferable to use a tertiary amine compound, that is, a tertiary amine catalyst in any of the above reaction steps. By using such an amine catalyst, side reactions can be reduced, and a highly pure α- (allyloxymethyl) acrylate composition can be efficiently produced.

Examples of the tertiary amine catalyst include monoamine compounds such as trimethylamine, triethylamine, tri-n-butylamine, dimethylethylamine, and dimethyln-butylamine; diamine compounds such as tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylbutylenediamine; , 4-diazabicyclo [2.2.2] octane, DBU (trade name, manufactured by San Apro), DBN (trade name, manufactured by San Apro), and other cyclic structure-containing amine compounds; Diaion WA-10 (trade name, Mitsubishi) Chemicals), weakly basic ion exchange resins such as Dowex MWA-1 (trade name, manufactured by Dow Chemical Company), Amberlite IRA-68 (trade name, manufactured by Rohm and Haas), etc. are suitable. It is mentioned as a thing. As these catalysts, those having a low boiling point such as trimethylamine may be used as a solution of water or an inert organic solvent, or only one kind may be used, or two or more kinds may be appropriately mixed. Of these, monoamine compounds and / or cyclic structure-containing amine compounds are preferred. More preferred is trimethylamine and / or 1,4-diazabicyclo [2.2.2] octane.

As the usage-amount of the said amine catalyst, it is preferable that it is 0.01-50 mol% with respect to 100 mol% of (alpha)-(hydroxymethyl) acrylate, for example. If it is less than 0.01 mol%, the catalytic activity is not sufficiently exhibited, the reaction time becomes too long, and α- (allyloxymethyl) acrylate may not be efficiently produced. On the other hand, if it exceeds 50 mol%, further improvement of the catalytic effect such as shortening of the reaction time in proportion to the increase in the amount of catalyst cannot be expected, and a part of the added catalyst may be wasted, which may be economically disadvantageous. is there. More preferably, it is 0.5-20 mol%.

In the above reaction steps (a) to (c), when these steps are carried out as a series of steps, the amount of amine catalyst used may be set as described above. In the case of carrying out, the optimum amount of the amine catalyst is preferably 0.01 to 50 mol% with respect to 100 mol% of paraformaldehyde in the reaction step (a). It is suitable that it is 0.01-50 mol% with respect to 100 mol% of (alpha)-(hydroxymethyl) acrylate in the said reaction process (b). It is suitable that it is 0.01-50 mol% with respect to 100 mol% of 2,2 '-[oxybis (methylene)] bisacrylate in the said reaction process (c).

[Suitable uses of α- (unsaturated alkoxyalkyl) acrylate composition, etc.]
The α- (unsaturated alkoxyalkyl) acrylate composition of the present invention and the composition obtained by the production method of the present invention have a cyclic structure such as a tetrahydrofuran ring (THF ring) as a main chain by cyclopolymerization. The ring structure-containing polymer is provided. Such a ring structure-containing polymer is excellent in heat resistance due to the ring structure, but exhibits high flexibility due to having a methylene group on both sides of the tetrahydrofuran ring, and is compatible with a solvent or solvent. It can exhibit the performance of excellent solubility.

Applications include adhesives, adhesives, dental materials, optical members, information recording materials, optical fiber materials, color filter resists, solder resists, plating resists, insulators, sealants, inkjet inks, printing inks, paints, Casting material, decorative plate, WPC (wood plastic combination), coating agent, photosensitive resin plate, dry film, lining agent, civil engineering and building material, putty, repair material, flooring material, paving material gel coat, overcoat, hand layup・ Spray-up, pultrusion, filament winding, molding materials such as SMC (sheet molding compound), BMC (bulk molding compound), polymer solid electrolyte, etc. Wide range of monomer compositions that give polymers It is those that can be used.

The α- (unsaturated alkoxyalkyl) acrylate composition of the present invention can be polymerized while cyclizing simultaneously with addition polymerization as described above to give a polymer having a ring structure in the main chain, etc. The cyclopolymerization is shown in the literature. For example, 1,6-dienes such as α- (allyloxymethyl) acrylate are polymerized by radical polymerization reaction to have a 5-membered ring, 6-membered ring structure, etc. A method for obtaining a polymer is shown. For example, Takashi Tsuda, Lon J. Mathias, POLYMER, 1994, Vol. 35, p3317-3328, Robert D. Thompson, William L. Jarrett (William L. Jarrett), Lon J. Mathias, Macromolecules, 1992, 25, p6455-659, Michio Urushisaki et al., Macro Macromolecules, 1999, Vol. 32, p322-327. In these documents, it can be said that the utility of the cyclopolymerizable monomer is shown.

Regarding the above cyclopolymerization, for example, in the case of α- (allyloxymethyl) acrylate, a polymer having a 5-membered ring and / or 6-membered ring structure in the main chain or the like as represented by the following reaction formula (d) (Α- (allyloxymethyl) acrylate polymer) will be provided. The mechanism of radical polymerization in the reaction formula is illustrated in parentheses in the following reaction formula (d).

The weight average molecular weight (Mw) of the α- (allyloxymethyl) acrylate polymer may be appropriately set according to the purpose and application, but for liquid applications such as radical curable resin compositions and colorant dispersion compositions. When used, in order to obtain good fluidity, it is preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 50000 or less. Moreover, in order for the characteristic as a polymer to fully be exhibited, it is preferable that it is 1000 or more, More preferably, it is 3000 or more.

The α- (allyloxymethyl) acrylate polymer preferably has a polydispersity (Mw / Mn) representing a molecular weight distribution of 5.0 or less, more preferably 4.0 or less, and still more preferably. Is 3.0 or less. In the production method of the present invention, it is considered that Mw / Mn can be reduced because branching of the polymer can be suppressed.
In addition, although it does not specifically limit about the measuring method of a weight average molecular weight (Mw) and polydispersity (Mw / Mn), For example, the measuring method used in the Example mentioned later can be used.

The α- (unsaturated alkoxyalkyl) acrylate composition of the present invention can store a product of α- (unsaturated alkoxyalkyl) acrylate such as α- (allyloxymethyl) acrylate with high purity for a long period of time. The occurrence of problems such as gelation is sufficiently suppressed and stabilized. Moreover, according to the manufacturing method of the α- (unsaturated alkoxyalkyl) acrylate composition of the present invention, α- (unsaturated alkoxyalkyl) acrylates such as high-purity α- (allyloxymethyl) acrylate are industrially safe. It is possible to achieve an outstanding effect that it can be obtained.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
Moreover, in the following example, unsaturated alkyl ester content, peroxide amount, and nitrogen content are methyl α- (allyloxymethyl) acrylate or methyl α- (crotyloxymethyl) acrylate contained in the product. Means the respective amount (% by mass) with respect to 100% by mass.

<Evaluation method>
(Reaction conversion and yield)
The conversion and yield of the reaction were as follows: gas chromatograph (GC-2010 (trade name), manufactured by Shimadzu Corporation, capillary column DB-WAX (trade name); length 30 m × inner diameter 0.25 mm, film thickness 0.25 μm. ) And determined using a calibration curve prepared in advance.

(Allyl ester content)
The content of allyl esters (α- (hydroxymethyl) acrylate, allyl α- (methoxymethyl) acrylate and allyl α- (allyloxymethyl) acrylate) is determined by gas chromatography (GC-2010 (trade name), ( It was measured using a capillary column DB-WAX (trade name) manufactured by Shimadzu Corporation; length 30 m × inner diameter 0.25 mm, film thickness 0.25 μm), and obtained using a calibration curve prepared in advance.
(Crotyl ester content)
The content of crotyl esters (crotyl α- (hydroxymethyl) acrylate, crotyl α- (methoxymethyl) acrylate and crotyl α- (crotyloxymethyl) acrylate) was also determined in the same manner.

(Peroxide amount)
The amount of peroxide was measured by an iodine quantification method in which potassium iodide was allowed to act on the sample to titrate the liberated iodine with sodium thiosulfate as a reducing agent.

(Nitrogen content)
The nitrogen content was measured using a trace total nitrogen analyzer (TN-100 type (trade name) manufactured by Mitsubishi Chemical Analytic Co., Ltd.).

(Polymerization conversion)
For the polymerization conversion rate, a gas chromatograph (GC-2010 (trade name), manufactured by Shimadzu Corporation, capillary column DB-17HT (trade name); length 30 m × inner diameter 0.25 mm, film thickness 0.15 μm) is used. Measured using a calibration curve prepared in advance.

(Weight average molecular weight and molecular weight distribution of polymer)
The weight average molecular weight and molecular weight distribution of the polymer were measured under the following conditions using a gel permeation chromatograph (GPC system, manufactured by Tosoh Corporation).
Column: Super HZM-M 6.0 × 150 (trade name, manufactured by Tosoh Corporation) × 2, column temperature: 40 ° C.
Developing solution: chloroform, flow rate: 0.6 ml / min, sample concentration: 1 mg / cc, injection volume: 20 μL
Detector: RI, calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)

(Hue)
The Hazen color number was used as an index. The Hazen color number was measured in accordance with the method described in JIS K0071-01 (1998).

Example 1-1
Process 1 (Reaction process)
In a 500 ml four-necked flask equipped with a stirrer, a condenser, a thermometer, a gas blowing tube and an oil bath, 203 g of methyl α- (hydroxymethyl) acrylate and 1,4-diazabicyclo [2.2.2] as a catalyst 10 g of octane, 0.20 g of hydroquinone monomethyl ether and 0.20 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor were charged. Thereafter, while blowing air into the reaction solution, the reaction solution was heated to 100 ° C. and reacted for 2 hours under a reduced pressure of 4 kPa while distilling off generated water. Then, under normal pressure, 152 g of allyl alcohol and 10 g of 1,4-diazabicyclo [2.2.2] octane as a catalyst were added dropwise over 2 hours and reacted for 12 hours. The conversion rate of methyl α- (hydroxymethyl) acrylate was 90 mol%, and the yield of methyl α- (allyloxymethyl) acrylate was 62 mol% based on methyl α- (hydroxymethyl) acrylate.

Step 2 (catalyst removal step)
The reaction solution was transferred to a separatory funnel and washed three times with 50 g of water to remove the catalyst 1,4-diazabicyclo [2.2.2] octane. The weight of the organic phase was 270 g, and the nitrogen content in the organic phase was 50 ppm.

Process 3 (Distillation process)
The reaction solution was transferred to a distillation apparatus (theoretical plate number: 13), and 0.27 g of hydroquinone monomethyl ether, 0.27 g of 2-t-butylhydroquinone and 0.27 g of triphenyl phosphite were added as polymerization inhibitors, Distillation was performed. After removing unreacted allyl alcohol at 7 kPa, 143 g of a mixture of methyl α- (hydroxymethyl) acrylate and methyl α- (allyloxymethyl) acrylate at 2.5 kPa and a tower top temperature of 81 ° C. I took it out. The composition of the obtained mixed liquid was 10.5% by mass of methyl α- (hydroxymethyl) acrylate and 89.5% by mass of methyl α- (allyloxymethyl) acrylate. The mixture was transferred to a separatory funnel, diluted with 30 g of hexane, washed 5 times with 30 g of water to remove methyl α- (hydroxymethyl) acrylate, hexane was removed under reduced pressure, and purified α- ( 122 g (M-1) of allyloxymethyl) methyl acrylate was obtained. The content of methyl α- (allyloxymethyl) acrylate is 99.3% by mass, the nitrogen content is 4 ppm, the peroxide amount is 2 ppm, and the allyl ester content corresponding to the unsaturated alkyl ester is 0.4% by mass. Met. Further, the content of methyl α- (hydroxymethyl) acrylate as a raw material was 0.2% by mass with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate.

Example 1-2
Process 1 (Reaction process)
The same operation as in Example 1-1 was performed.
Step 2 (catalyst removal step)
The distillation process was performed without performing the catalyst removal process.
Process 3 (Distillation process)
The same operation as in Example 1-1 was performed to obtain 98 g (M-2) of purified methyl α- (allyloxymethyl) acrylate. The content of methyl α- (allyloxymethyl) acrylate was 99.3% by mass, the nitrogen content was 120 ppm, the peroxide content was 5 ppm, and the allyl ester content was 0.4 mass%. Further, the content of methyl α- (hydroxymethyl) acrylate as a raw material was 0.2% by mass with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate.

Example 1-3
Process 1 (Reaction process)
The same operation as in Example 1-1 was performed.
Step 2 (catalyst removal step)
The same operation as in Example 1-1 was performed.
Process 3 (Distillation process)
Except having moved the reaction liquid to the simple distillation apparatus, operation similar to Example 1-1 was performed and 113 g (M-3) refine | purified methyl-alpha- (allyloxymethyl) acrylate was obtained. The content of methyl α- (allyloxymethyl) acrylate was 97.5% by mass, the nitrogen content was 8 ppm, the peroxide content was 5 ppm, and the allyl ester content was 2.3% by mass. Further, the content of methyl α- (hydroxymethyl) acrylate as a raw material was 0.2% by mass with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate.

Production example A
Process 1 (Reaction process)
Using the same reactor as in Example 1-1, 116 g of methyl α- (hydroxymethyl) acrylate, 87 g of allyl alcohol, 50 g of tungstophosphoric acid as a catalyst, 130 g of cyclohexane, 0.06 g of hydroquinone monomethyl ether as a polymerization inhibitor, 0.06 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl was charged. Thereafter, while blowing air into the reaction solution, the reaction solution was heated to 90 ° C. and reacted for 8 hours while refluxing cyclohexane. The conversion rate of methyl α- (hydroxymethyl) acrylate was 43 mol%, and the yield of methyl α- (allyloxymethyl) acrylate was 7 mol% based on methyl α- (hydroxymethyl) acrylate.
Step 2 (catalyst removal step)
The reaction mixture was transferred to a separatory funnel and washed twice with 50 g of water to remove the catalyst tungstophosphoric acid.
Process 3 (Distillation process)
The same operation as in Example 1-1 was performed to obtain 8 g (M-4) of purified methyl α- (allyloxymethyl) acrylate. The content of methyl α- (allyloxymethyl) acrylate was 99.6% by mass, the nitrogen content was 0 ppm, the peroxide content was 82 ppm, and the allyl ester content was 0% by mass. The content of methyl α- (hydroxymethyl) acrylate as a raw material was 0.3% by mass with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate.

Example 1-4
Process 1 (Reaction process)
In a 5 L four-necked flask equipped with a stirrer, a cooling tube, a thermometer, a gas blowing tube, and a decompressor, 2031.3 g of methyl α- (hydroxymethyl) acrylate and 1,4-diazabicyclo [2,2 as a catalyst , 2] 98.5 g of octane, 1.02 g of p-methoxyphenol and 1.02 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor were charged. Thereafter, while blowing an oxygen / nitrogen mixed gas (oxygen concentration 8%), the reaction solution was heated to 100 ° C. under a reduced pressure of 10 kPa, and reacted for 2 hours while distilling off generated water. The pressure was released and a solution prepared by dissolving 99.4 g of 1,4-diazabicyclo [2,2,2] octane in 1543.7 g of allyl alcohol at 100 ° C. under normal pressure was added dropwise over 2 hours and reacted for 12 hours. It was. After the reaction, when measured using gas chromatography, the yield of methyl α- (allyloxymethyl) acrylate was 62 mol% with respect to methyl α- (hydroxymethyl) acrylate, α- (hydroxymethyl) acrylic acid. The methyl conversion was 89 mol%, and the yield of allyl ester was 2 mol% based on methyl α- (hydroxymethyl) acrylate.

Process 2 (light boiling component removal process)
Next, the remaining allyl alcohol was distilled by simple distillation under reduced pressure (operating pressure: 7 kPa) to obtain 2766.8 g of a reaction solution. Further, 1629.6 g of methyl α- (allyloxymethyl) acrylate was contained in this reaction solution, and the content of allyl ester was 5.4 with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate. The content of methyl α- (hydroxymethyl) acrylate as a raw material was 12.1% by mass with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate.

Step 3 (α- (hydroxymethyl) methyl acrylate and catalyst removal step)
To the obtained reaction liquid, 927.9 g of 8 mass% sodium hydroxide solution was added and stirred at room temperature for 30 minutes and then allowed to stand for 30 minutes, followed by oil / water separation to obtain 2097.6 g of an organic phase. Further, 231.6 g of an 8% by mass sodium hydroxide solution was added to this organic phase, and the mixture was stirred at room temperature for 30 minutes and then allowed to stand for 30 minutes. Further, 1500.2 g of methyl α- (allyloxymethyl) acrylate was contained in this organic phase, and the content of allyl ester was 6.5 with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate. The content of methyl α- (hydroxymethyl) acrylate as a raw material was reduced to 0.8% by mass relative to 100% by mass of methyl α- (allyloxymethyl) acrylate. Subsequently, the obtained organic phase was washed with a 5% by mass aqueous sodium sulfate solution and subjected to oil / water separation. After performing this operation once again, 1916.7 g of organic phase was obtained.

Process 4 (distillation process)
To this organic phase, 1.92 g of hydroquinone monomethyl ether, 1.92 g of 2-tert-butylhydroquinone and 1.92 g of triphenyl phosphite are added as a polymerization inhibitor, and an oxygen / nitrogen mixed gas (oxygen concentration: 8 vol%) is blown into the organic phase. However, distillation was performed using a packed column (corresponding to 10 theoretical plates) packed with Dickson packing. After removing allyl alcohol remaining at 10 kPa, 1329.3 g (M-5) of methyl α- (allyloxymethyl) acrylate having a purity of 99.4% by mass at 2 kPa and a tower top temperature of 83 ° C. was obtained. Allyl ester was contained in an amount of 0.4% by mass, the nitrogen content was below the detection limit of the analyzer (less than 0.1 ppm), and the peroxide content was 1 ppm. Moreover, 0.1 mass% of α- (hydroxymethyl) methyl acrylate as a raw material was contained.

Production example B
(Synthesis of α-allyloxymethyl acrylate (CH-AMA))
Α- (allyloxymethyl) methyl acrylate (M-) synthesized in Example 1-4 in a reactor equipped with a stirrer, a temperature sensor, a gas introduction tube, a square tube, a cooling tube, and a distillate receiver 5) 74.6 g, cyclohexanol (CHOH) 24.04 g, dibutyltin oxide (IV) (DBTO) 6.0 g, p-methoxyphenol 1.5 g were charged and mixed with an oxygen / nitrogen mixed gas (oxygen concentration). The pressure in the reactor was gradually reduced until the pressure in the reactor reached 27 kPa. After reaching 27 kPa, temperature increase was started, the internal temperature was adjusted to 100 ° C., and the reaction was performed for 6.5 hours while distilling off the methanol generated by the transesterification reaction. After completion of the reaction, analysis by gas chromatography revealed that the area ratio of CH-AMA, M-5, and CHOH was 39:45:12. Then, after cooling once and reducing pressure to 800 Pa, CHOH and M-5 were distilled off until the internal temperature reached 100 ° C. Then, it cooled and decompressed.
The reaction solution was diluted with n-hexane, and further 4% NaOH aqueous solution was added to precipitate DBTO, which was removed by filtration. The filtrate was separated into oil and water, and the resulting oil layer was washed with 15% NaOH aqueous solution and separated into oil and water. This operation was repeated 5 times to remove residual M-5 and p-methoxyphenol. To the obtained organic phase, 5.0 g of an alkali adsorbent (KYOWARD 700SL, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, stirred for 1 hour at room temperature, and then filtered. The filtrate was charged into a reactor equipped with a stirrer, temperature sensor, gas inlet tube, G-shaped tube, cooling tube and distillate receiver, and mixed with oxygen / nitrogen mixed gas (oxygen concentration 8% by volume). Then, while heating so that the internal temperature becomes 25-30 ° C., n-hexane was removed by slowly reducing the pressure until the pressure reached 800 Pa. After reaching 800 Pa, the pressure was maintained for 20 minutes and then the pressure was released to obtain 26.4 g of purified cyclohexyl allyloxymethyl acrylate (CH-AMA). The content of cyclohexyl α-allyloxymethyl acrylate was 98.0% by mass, no allyl ester was contained, the nitrogen content was below the detection limit of the measuring apparatus, and the amount of peroxide was 2 ppm. Moreover, 0.6 mass% of α- (allyloxymethyl) methyl acrylate was contained.

Production Example C
(Synthesis of α-allyloxymethyl acrylate neopentyl (NP-AMA))
88.6 g of methyl α- (allyloxymethyl) acrylate (M-5) synthesized in Example 1-4 in a reactor equipped with a stirrer, a cooling tube, a thermometer, and a gas blowing tube, neopentyl alcohol (NPOH) ) 49.5 g, titanium tetraisopropoxide 8.1 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4H-TEMPO) 0.09 g was charged, and oxygen / nitrogen was stirred. While passing through the mixed gas (oxygen concentration: 8% by volume), the temperature was raised to 100 ° C. and reacted for 6 hours. After completion of the reaction, analysis by gas chromatography revealed that the area ratio of NP-AMA, M-5, and NPOH was 17: 8: 7. The reaction solution was diluted with n-hexane, water was added, and a titanium compound was precipitated and removed by filtration. After the filtrate was separated into oil and water, the organic phase and 4H-TEMPO were added to the reactor equipped with a stirrer, temperature sensor, gas inlet tube, bigrue, toroidal tube, cooling tube, fractionator, and distillate receiver. .46 g charged, stirred and passed through an oxygen / nitrogen mixed gas (oxygen concentration 8% by volume), the pressure in the reactor was reduced to 1333 Pa, the temperature was gradually raised, and n-hexane, residual NPOH, The remaining Me-AMA and NP-AMA were distilled in order and separated. The obtained NP-AMA was 37.1 g, and the final internal temperature was 110 ° C. The temperature of the gas phase during the NP-AMA distillation was 106 ° C. The obtained NP-AMA contained no allyl ester, the nitrogen content was also below the detection limit of the measuring device, and the peroxide content was 5 ppm.

Example 1-5
In a 200 ml four-necked flask equipped with a stirrer, a condenser, a thermometer, a gas blowing tube and an oil bath, 40.6 g of methyl α- (hydroxymethyl) acrylate and 1,4-diazabicyclo [2.2. 2] 1.96 g of octane, 0.02 g of hydroquinone monomethyl ether and 0.02 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor were charged. Thereafter, while blowing air into the reaction solution, the reaction solution was heated to 100 ° C. and reacted for 2 hours. Thereafter, 37.9 g of crotyl alcohol (produced by Tokyo Chemical Industry Co., Ltd., cis / trans mixture) and 1.96 g of 1,4-diazabicyclo [2.2.2] octane as a catalyst are added dropwise over 2 hours under normal pressure. Reacted for 12 hours. After the reaction, when measured using gas chromatography, the yield of methyl α- (crotyloxymethyl) acrylate was 60 mol% with respect to methyl α- (hydroxymethyl) acrylate, and α- (hydroxymethyl) acrylic. The conversion rate of methyl acid was 90 mol%, and the yield of crotyl ester corresponding to unsaturated alkyl ester was 1.9 mol% with respect to methyl α- (hydroxymethyl) acrylate.
Next, after the remaining crotyl alcohol was distilled by simple distillation under reduced pressure (operating pressure: 7 kPa), 18.4 g of an 8% by mass sodium hydroxide solution was added to the resulting reaction solution, and the mixture was stirred at room temperature for 30 minutes. After stirring, the mixture was allowed to stand for 30 minutes and separated into oil and water. Further, 4.6 g of an 8% by mass sodium hydroxide solution was added to this organic phase, and the mixture was stirred at room temperature for 30 minutes, allowed to stand for 30 minutes, and separated into oil and water to obtain an organic phase. Subsequently, the obtained organic phase was washed with a 5% by mass aqueous sodium sulfate solution and subjected to oil / water separation. After performing this operation once again, 53.9 g of organic phase was obtained. In the obtained organic phase, the raw material α- (hydroxymethyl) methyl acrylate was not contained.
To the organic phase, 0.05 g of hydroquinone monomethyl ether, 0.05 g of 2-t-butylhydroquinone and 0.05 g of triphenyl phosphite were added, and simple distillation was performed under reduced pressure. 27.4 g (M-6) of purified methyl α- (crotyloxymethyl) acrylate was obtained at 1.3 kPa and a tower top temperature of 93 ° C. The α- (crotyloxymethyl) methyl acrylate content was 97.1% by mass, the nitrogen content was below the detection limit, the peroxide content was 2 ppm, and the crotyl ester content corresponding to the unsaturated alkyl ester was 0.00. It was 8 mass%.

Example 2-1
To the purified methyl α- (allyloxymethyl) acrylate (M-1) obtained in Example 1-1, 500 ppm of 2-tert-butylhydroquinone was added as an antioxidant, and α- (allyloxymethyl) acrylic acid was added. A methyl composition was obtained. The Hazen color number of this composition was less than 10.
To a 200 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube and an oil bath, 20 g of the above α- (allyloxymethyl) methyl acrylate composition and 30 g of 2-butanone were added, and under a nitrogen atmosphere The temperature was raised to 80 ° C. When the temperature of the reaction solution reached 80 ° C., 0.010 g of azobisisobutyronitrile was added to initiate polymerization. Two hours after the start of polymerization, 16.7 g of 2-butanone was added, and the polymerization was stopped after 4 hours. The conversion rate of methyl α- (allyloxymethyl) acrylate was 83%, and the polymer obtained had a weight average molecular weight of 31,000 and a molecular weight distribution of 2.7. There was no change in hue before and after polymerization. The results are shown in Table 1.

Example 2-2
To the purified methyl α- (allyloxymethyl) acrylate (M-1) obtained in Example 1-1, 500 ppm of p-methoxyphenol and 500 ppm of triphenyl phosphite were added as antioxidants, and α- (allyloxy) was added. Methyl) methyl acrylate composition. The Hazen color number of this composition was less than 10.
Polymerization was conducted in the same manner as in Example 2-1, except that the above α- (allyloxymethyl) methyl acrylate composition was used. The conversion rate of methyl α- (allyloxymethyl) acrylate was 83%, and the obtained polymer had a molecular weight of 28500 and a molecular weight distribution of 2.8. There was no change in hue before and after polymerization. The results are shown in Table 1.

Example 2-3
To the purified methyl α- (allyloxymethyl) acrylate (M-2) obtained in Example 1-2, 500 ppm of 2-tert-butylhydroquinone was added as an antioxidant, and α- (allyloxymethyl) acrylic acid was added. A methyl composition was obtained. The Hazen color number of this composition was less than 10.
Polymerization was conducted in the same manner as in Example 2-1, except that the above α- (allyloxymethyl) methyl acrylate composition was used. The conversion of methyl α- (allyloxymethyl) acrylate was 83%, and the obtained polymer had a molecular weight of 33,000 and a molecular weight distribution of 3.3. The polymerization solution was pale yellow and the hue was 150. The results are shown in Table 1.

Example 2-4
To the purified methyl α- (allyloxymethyl) acrylate (M-3) obtained in Example 1-3, 500 ppm of 2-tert-butylhydroquinone was added as an antioxidant, and α- (allyloxymethyl) acrylic acid was added. A methyl composition was obtained. The Hazen color number of this composition was less than 10.
Polymerization was conducted in the same manner as in Example 2-1, except that the above α- (allyloxymethyl) methyl acrylate composition was used. The conversion rate of methyl α- (allyloxymethyl) acrylate is 80%. The resulting polymer has a molecular weight of 52,000 and a molecular weight distribution of 4.8, leading to the high molecular weight side and partially crosslinked. Polymer was produced. The results are shown in Table 1.

Example 2-5
To the purified methyl α- (allyloxymethyl) acrylate (M-4) obtained in Production Example A, 500 ppm of 2-tert-butylhydroquinone was added as an antioxidant, and α- (allyloxymethyl) methyl acrylate composition It was a thing. The Hazen color number of this composition was 30.
Polymerization was conducted in the same manner as in Example 2-1, except that the above α- (allyloxymethyl) methyl acrylate composition was used. The conversion rate of methyl α- (allyloxymethyl) acrylate is 72%, and the obtained polymer has a molecular weight of 65,000 and a molecular weight distribution of 6.1, which leads to the high molecular weight side, and is partially crosslinked. Polymer was produced. The results are shown in Table 1.

Example 2-6
To the purified α-allyloxymethyl acrylate (CH-AMA) obtained in Production Example B, 500 ppm of 2-tert-butylhydroquinone was added as an antioxidant, and α- (allyloxymethyl) cyclohexyl cyclohexyl composition did. The Hazen color number of this composition was 30.
Polymerization was carried out in the same manner as in Example 2-1, except that the above cyclohexyl composition of α- (allyloxymethyl) acrylate was used. The conversion of cyclohexyl α- (allyloxymethyl) acrylate was 82%, and the obtained polymer had a molecular weight of 33,000 and a molecular weight distribution of 2.6. Further, there was no change in hue before and after polymerization. The results are shown in Table 1.

Example 2-7
To the purified α-allyloxymethyl acrylate neopentyl (NP-AMA) obtained in Production Example C, 500 ppm of p-methoxyphenol and 500 ppm of triphenyl phosphite were added as antioxidants, and neopentyl α- (allyloxymethyl) acrylate was added. It was set as the composition. The Hazen color number of this composition was less than 10.
Polymerization was carried out in the same manner as in Example 2-1, except that 2-butanone was added 2 hours after the start of polymerization and the subsequent polymerization time was changed to 6 hours using the above-described neopentyl α- (allyloxymethyl) acrylate. went. The conversion of α- (allyloxymethyl) neopentyl acrylate was 86%, and the obtained polymer had a molecular weight of 21,000 and a molecular weight distribution of 2.7. Further, there was no change in hue before and after polymerization. The results are shown in Table 1.

Example 2-8
To the purified α- (crotyloxymethyl) methyl acrylate (M-6) obtained in Example 1-5, 500 ppm of 2-t-butylhydroquinone was added as an antioxidant, and α- (crotyloxymethyl) A methyl acrylate composition was obtained. The Hazen color number of this composition was less than 10.
Polymerization was carried out in the same manner as in Example 2-1, except that the above α- (crotyloxymethyl) methyl acrylate composition was used. The conversion rate of methyl α- (crotyloxymethyl) acrylate was 80%, and the obtained polymer had a molecular weight of 6800 and a molecular weight distribution of 2.6. There was no change in hue before and after polymerization. The results are shown in Table 1.

Reference example 1
Polymerization was conducted in the same manner as in Example 2-1, except that the purified α- (allyloxymethyl) methyl acrylate (M-1) obtained in Example 1-1 was used and no antioxidant was added. . Gelation occurred 2 hours after polymerization. Although it had been colored since the start of polymerization, Hazen could not be measured due to gelation. The results are shown in Table 1.

Examples 2-9 to 2-19, Reference Examples 2, 3
To the purified methyl α- (allyloxymethyl) acrylate (M-1) obtained in Example 1-1, the antioxidants shown in Table 2 were added. The Hazen color numbers of these compositions were all less than 10. This composition was transferred to a glass bottle, bubbled with air for 5 minutes, and then subjected to a storage stability test at 50 ° C. for 1 week. The compositions of Examples 2-9 to 19 had a Hazen color number of less than 10 even after one week. Further, the compositions of Reference Examples 2 and 3 had Hazen color number 20, and some coloring was confirmed. Table 2 shows the results (weight average molecular weight, molecular weight distribution, hue) of polymerization performed in the same manner as in Example 2-1 using the composition after the test. In Reference Examples 2 and 3, the color was further colored after polymerization, but the Hazen could not be measured due to gelation.

In Table 2 below, the trade names described in the column of the type of antioxidant mean the following compounds, respectively.
Antage DAH (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.); 2,5-di-tert-amylhydroquinone antage DBH (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.); 2,5-di-tert-butylhydroquinone antage W -400 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.); 2,2'-methylenebis (4-methyl-6-tert-butylphenol)
ADK STAB PEP24G (trade name, manufactured by ADEKA); di (2,4-di-tert-butylphenyl) pentaerythritol diphosphite IRGANOX1222 (trade name, manufactured by Ciba Specialty Chemicals); 3,5-di-tert -Butyl-4-hydroxybenzyl phosphate diethyl ether

Although Examples 2-1 to 2-8 are polymerized after the addition of the antioxidant, gelation is suppressed as compared with Reference Example 1 in which the antioxidant was not added. For this reason, coloring is further reduced.
In Examples 2-9 to 2-19, the content of the antioxidant is 500 ppm (0.05 mass%), 1000 ppm (0.1 mass%), or 2000 ppm (0.2 mass%). In the examples, a polymer is obtained without causing gelation, the weight average molecular weight (Mw) is 2.8 × 10 ^{4 to} 3.6 × 10 ⁴ , and the molecular weight distribution (Mw / Mn) is 2.8 to 3.4, and in both cases, the result is that there is no change in hue (Hazen). In contrast, in Reference Examples 2 and 3, in which the content of the antioxidant is lower than the lower limit of the present invention, that is, 0.03% by mass relative to 100% by mass of α- (unsaturated alkoxyalkyl) acrylate, Gelation occurs in 3 hours. In these reference examples, it is considered that gelation occurs as a result of insufficient antioxidant content and insufficient suppression of branching and crosslinking. In the examples described above, problems such as gelation are suppressed during polymerization and coloring is sufficiently suppressed. However, in the reference example, the problem of gelation occurs and coloring occurs.
In addition, when content of antioxidant exceeds the upper limit of this invention, ie, 0.5 mass% with respect to 100 mass% of (alpha)-(unsaturated alkoxyalkyl) acrylate, the quantity of antioxidant is appropriate. It doesn't mean that you're out of range and more effective.

Examples 3-1 and 3-2
To the purified methyl α- (allyloxymethyl) acrylate (M-5) obtained in Example 1-4, 500 ppm of 2-tert-butylhydroquinone was added as an antioxidant, and α- (allyloxymethyl) acrylic acid was added. A methyl composition was obtained. This composition was transferred to a glass or polyethylene container, and an oxygen / nitrogen mixed gas (oxygen concentration: 8% by volume) was bubbled for 5 minutes, and then a storage stability test was conducted at 50 ° C. for 30 weeks. In any composition of the container, no polymer was confirmed by GPC. The peroxide amounts were 2 ppm and 3 ppm, respectively. The results are shown in Table 3.

Reference examples 4 and 5
The purified α- (allyloxymethyl) methyl acrylate (M-5) obtained in Example 1-4 was transferred to a glass or polyethylene container without adding an antioxidant, and an oxygen / nitrogen mixed gas (oxygen concentration) 8% by volume) was bubbled for 5 minutes and then subjected to a storage stability test at 50 ° C. In any container, a polymer was confirmed after one week.

Examples 3-1 and 3-2 are examples in which an antioxidant was added to α- (unsaturated alkoxyalkyl) acrylate and a long-term storage stability test was performed, but by adding an antioxidant, It has been shown that even when stored for a long period of 30 weeks under severe conditions of 50 ° C., it can be stored for a long period of time with high purity without the formation of a polymer. On the other hand, Reference Examples 4 and 5 are examples in which no antioxidant was added, but it was shown that a polymer was formed after one week. These results show that α- (unsaturated alkoxyalkyl) acrylate can be stably stored with high purity for a long period of time by adding an antioxidant.

Example 4
To a 100 mL four-necked flask equipped with a stirrer, a condenser, a thermometer, a gas blowing tube and an oil bath, 34.8 g of methyl α- (hydroxymethyl) acrylate and 1,4-diazabicyclo [2,2 as a catalyst] , 2] 3.4 g of octane and 0.02 g of 4-hydroxy-2,2,6,6-tetramethyl-1-oxyl as a polymerization inhibitor were charged. Thereafter, the mixture was stirred, and the temperature was raised to 95 ° C. while blowing air into the reaction solution. 26.2 g of allyl alcohol was added dropwise over 8 hours, and the reaction was further continued for 8 hours. The conversion rate of methyl α- (hydroxymethyl) acrylate was 86 mol%, and the yields of methyl α- (allyloxymethyl) acrylate and allyl ester were 52. They were 2 mol% and 1.0 mol%. The allyl ester content was 2.2% by mass with respect to 100% by mass of methyl α- (allyloxymethyl) acrylate.

Reference Example 6
The procedure was the same as in Example 3-1, except that allyl alcohol was not dropped and was initially charged and reacted for 16 hours. The conversion rate of methyl α- (hydroxymethyl) acrylate was 86 mol%, and the yields of methyl α- (allyloxymethyl) acrylate and allyl ester were 52. They were 4 mol% and 3.7 mol%. The allyl ester content was 8.2% by mass relative to 100% by mass of methyl α- (allyloxymethyl) acrylate.

From the comparison between Example 4 and Reference Example 6 in Table 4, when reacting α- (hydroxymethyl) acrylate and unsaturated alcohol, allyl ester content was obtained by adding dropwise the unsaturated alcohol to react. It can be seen that In addition, although Example 1-1 to 1-3 mentioned above is also the form which dripped the unsaturated alcohol, the allyl ester content in the composition obtained also in these examples is reduced. Thus, it can be seen that the content of unsaturated alkyl ester (eg, allyl ester), which is one of the causes of gelation during polymerization, is reduced by dropping the unsaturated alcohol.

In the above-described examples and the like, α- (allyloxymethyl) acrylate or α- (crotyloxymethyl) acrylic which is a kind of α- (allyloxymethyl) acrylate is used as α- (unsaturated alkoxyalkyl) acrylate. Although methyl acid is prepared, an alkoxyalkyl group (—CH ₂ —O—CH ₂ —C (R ² ) ═C (R ³ ) () is attached to the α-position carbon atom constituting the double bond in the acrylate. As long as the compound has a structure in which R ⁴ ) is bonded, it is considered that the mechanism in which gelation occurs during polymerization due to the formation of a branched structure is the same. In particular, in the case of α- (allyloxymethyl) acrylate, the mechanism in which gelation occurs during polymerization due to the occurrence of a branched structure is the same as that of methyl α- (allyloxymethyl) acrylate. Therefore, the gelation problem can be sufficiently suppressed by containing a specific amount of the antioxidant to suppress the formation of the branched structure. Moreover, since the amount of peroxide generation can be sufficiently reduced by the antioxidant, coloring can also be prevented. Furthermore, in the form in which the antioxidant is essentially a phenolic antioxidant and / or phosphorus antioxidant, the form in which the peroxide amount, the nitrogen content, and the allyl ester content are in a specific range, the effect of the present invention Has been shown to be more effective.

Therefore, in the above-described Examples and the like, the α- (unsaturated alkoxyalkyl) acrylate composition containing the antioxidant in an amount of 0.03 to 0.5% by mass with respect to 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate. If it is a thing, it can fully suppress that problems, such as coloring and gelling, arise at the time of superposition | polymerization, and in the manufacturing method of such a composition, it was stabilized, highly purified alpha- ( It can be said that α- (unsaturated alkoxyalkyl) acrylates such as allyloxymethyl) acrylate have been shown to exhibit an advantageous effect that they can be obtained industrially safely. That is, an antioxidant is used for α- (unsaturated alkoxyalkyl) acrylate, more specifically, the antioxidant is added in an appropriate range to α- (unsaturated alkoxyalkyl) acrylate. It can be said that the relationship between the configuration and the effect of the present invention used is supported.

Claims (12)

The following general formula (I):

(In the formula, R ¹ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 30 carbon atoms. .) And an α- (unsaturated alkoxyalkyl) acrylate represented by an antioxidant,
The content of the antioxidant is 0.03 to 0.5% by mass with respect to 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate, and the α- (unsaturated alkoxyalkyl) acrylate is characterized in that Composition. The α- (unsaturated alkoxyalkyl) acrylate composition according to claim 1, wherein the α- (unsaturated alkoxyalkyl) acrylate includes α- (allyloxymethyl) acrylate. The α- (unsaturated alkoxyalkyl) acrylate composition according to claim 1, wherein the antioxidant essentially comprises a phenol-based antioxidant and / or a phosphorus-based antioxidant. 4. The composition according to claim 1, wherein the content of the unsaturated alkyl ester is 1% by mass or less with respect to 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate. An α- (unsaturated alkoxyalkyl) acrylate composition. 5. The α- (unsaturated) according to claim 1, wherein the composition has a nitrogen content of 100 ppm or less with respect to 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate. Saturated alkoxyalkyl) acrylate composition. The α- (unsaturated) according to claim 1, wherein the composition has a peroxide amount of 50 ppm or less with respect to 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate. Saturated alkoxyalkyl) acrylate composition. The following general formula (I):

(In the formula, R ¹ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 30 carbon atoms. A composition comprising an α- (unsaturated alkoxyalkyl) acrylate represented by:
The production method includes α- (hydroxymethyl) acrylate and the following general formula (III):

(In the formula, R ² , R ³ and R ⁴ are the same as the symbols in the general formula (I)), and the reaction is carried out by dropping the unsaturated alcohol. The manufacturing method of the alpha- (unsaturated alkoxyalkyl) acrylate composition characterized by including the process to make. The composition obtained by the manufacturing method has an unsaturated alkyl ester content of 1% by mass or less based on 100% by mass of the α- (unsaturated alkoxyalkyl) acrylate. A process for producing an α- (unsaturated alkoxyalkyl) acrylate composition. The following general formula (I):

(In the formula, R ¹ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 30 carbon atoms. A composition comprising an α- (unsaturated alkoxyalkyl) acrylate represented by:
The production method comprises a step of adding an antioxidant to the purified α- (unsaturated alkoxyalkyl) acrylate after the purification step of obtaining the purified α- (unsaturated alkoxyalkyl) acrylate from the crude α- (unsaturated alkoxyalkyl) acrylate. A process for producing an α- (unsaturated alkoxyalkyl) acrylate composition. The production method includes α- (hydroxymethyl) acrylate and the following general formula (III):

(Wherein, R ^2, R ³ and R ⁴ are the the same as the symbols in formula (I).) Claims, characterized in that it comprises the step of reacting an unsaturated alcohol represented by The manufacturing method of the alpha- (unsaturated alkoxyalkyl) acrylate composition of 9. The said unsaturated alcohol contains allyl alcohol, The manufacturing method of the alpha- (unsaturated alkoxyalkyl) acrylate composition of Claim 7, 8 or 10 characterized by the above-mentioned. The said manufacturing method includes the process made to react in presence of an amine catalyst, The manufacturing method of the alpha- (unsaturated alkoxyalkyl) acrylate composition in any one of Claims 7-11 characterized by the above-mentioned.