WO2024090423A1

WO2024090423A1 - (meth)acrylate-containing composition

Info

Publication number: WO2024090423A1
Application number: PCT/JP2023/038309
Authority: WO
Inventors: 英明長野; 大谷　巌
Original assignee: 株式会社日本触媒
Priority date: 2022-10-24
Filing date: 2023-10-24
Publication date: 2024-05-02

Abstract

The purpose of the present invention is to provide: a composition which contains a novel compound that has excellent handling properties; and a production method, use or the like of this composition. The present invention provides a (meth)acrylate-containing composition which contains two or more isomers of a (meth)acrylate that is represented by general formula (1) (wherein R1 represents a hydrogen atom or a methyl group; R2 and R3 each represent an alkyl group; the total number of carbon atoms in R2 and R3 is 6 to 22; and n represents a number of 1 to 3). This (meth)acrylate-containing composition contains (A) the isomer wherein R2 is a methyl group and (B) the isomer wherein R2 is an alkyl group having 2 or more carbon atoms.

Description

(Meth)acrylate-containing composition

The present invention relates to a composition containing a novel (meth)acrylate, a method for producing the composition, and a water/oil repellent using the (meth)acrylate.

A fluorine-based water and oil repellent composition that combines a higher alkyl (meth)acrylate and a fluorine-based polyfluoroalkyl (meth)acrylate is introduced in the following Patent Document 1.

JP 2002-201463 A Japanese Patent Application Laid-Open No. 08-071429 JP 2002-326974 A Japanese Patent Application Laid-Open No. 6-33043 Japanese Patent Application Laid-Open No. 11-349987 Japanese Patent Application Laid-Open No. 10-167990 Japanese Patent No. 2703752 JP 2023-78348 A

It is well known that long-chain alkyl (meth)acrylates are used as components of water and oil repellent compositions. Long-chain alkyl acrylates have melting points that solidify in winter, with acrylates with 12 alkyl carbon atoms at about 4°C, acrylates with 14 carbon atoms at about 14°C, acrylates with 16 carbon atoms at about 17°C, and acrylates with 18 carbon atoms at about 28°C. Therefore, when removing products filled in drums in winter, they must be heated to a temperature above their melting point. However, if heated to a temperature higher than the melting point, this product contains polymerizable groups, and polymerization will begin when heated, causing heat to build up inside the drum, which may lead to an explosion. For this reason, they are difficult to handle, as they must be dissolved slowly over a period of time at a temperature 20°C to 30°C higher than the melting point.

After extensive research, the inventors have found that a novel (meth)acrylate compound represented by general formula (1) has a similar structure to long-chain alkyl (meth)acrylates, but has physical properties with a lower melting point and can be handled without heating, making it easy to handle. They have also found that the novel (meth)acrylate compound is effective as a water and oil repellent. Based on this knowledge, the inventors have completed the present invention.

We have provided a composition containing a novel compound that is easy to handle, as well as its manufacturing method and uses.

FIG. 1 is a chart obtained by carrying out H-NMR measurement on the reaction product ((2-[(1-methylundecyl)oxy]ethyl acrylate) isomer mixture) obtained in Example 1.

FIG. 2 is a chart obtained by carrying out H-NMR measurement on the reaction product ((2-[(1-methyltridecyl)oxy]ethyl acrylate) isomer mixture) obtained in Example 3.

FIG. 3 is a chart obtained by carrying out H-NMR measurement on the acrylate polymer obtained in Example 4.

(Definition)
"(Meth)acrylic" means "acrylic or methacrylic". "(Meth)acrylate" means "acrylate or methacrylate". In this specification, "structural unit derived from a monomer" means a structural unit formed by polymerization of a monomer, and more specifically, means a structure formed by cleavage of a carbon-carbon double bond of a monomer.

(Example of the present invention)
The preferred configurations of the present invention are described in the following items [1] to [12].
[1] A (meth)acrylate-containing composition comprising two or more isomers of a (meth)acrylate represented by the following general formula (1), the isomer (A) being an isomer in which ^R2 is a methyl group, and the isomer (B) being an isomer in which ^R2 is an alkyl group having two or more carbon atoms:

(In the formula, ^R1 represents a hydrogen atom or a methyl group. ^R2 and ^R3 represent alkyl groups, and the total number of carbon atoms of ^R2 and ^R3 is 6 to 22. n is a number from 1 to 3.)
[2] A method for producing the (meth)acrylate-containing composition according to the above [1], the method comprising the steps of: heat-treating a mixture containing an alcohol represented by the following general formula (2) and a polymerization inhibitor; and adding (meth)acrylic acid and an esterification catalyst to the composition containing the alcohol represented by the general formula (2) obtained by the heat treatment step, thereby carrying out an esterification reaction.

(In the formula, ^R2 and ^R3 are alkyl groups, the total number of carbon atoms of ^R2 and ^R3 is 6 to 22, and n is a number from 1 to 3.)
[3] A method for producing the (meth)acrylate-containing composition according to the above [1], the method comprising the steps of: heat-treating a mixture containing an alcohol represented by the following general formula (2) and a polymerization inhibitor; and adding a (meth)acrylic acid ester represented by the following general formula (3) and an ester exchange catalyst to the composition containing the alcohol represented by the general formula (2) obtained by the heat treatment step, thereby carrying out an ester exchange reaction.

(In the formula, ^R2 and ^R3 are alkyl groups, the total number of carbon atoms of ^R2 and ^R3 is 6 to 22, and n is a number from 1 to 3.)

(In the formula, ^R1 represents a hydrogen atom or a methyl group, and ^R4 represents an alkyl group having 1 to 8 carbon atoms.)
[4] The method according to [2] or [3] above, characterized in that the heat treatment uses at least one polymerization inhibitor selected from a quinone-based polymerization inhibitor, an alkylphenol-based polymerization inhibitor, an amine-based polymerization inhibitor, an N-oxyl-based polymerization inhibitor, and a phenothiazine.
[5] The method for producing a (meth)acrylate according to any one of [2] to [4] above, wherein the heat treatment is carried out at a temperature within the range of 25° C. to 100° C.
[6] The method for producing a (meth)acrylate according to any one of [2] to [5] above, wherein the heat treatment is carried out for 10 minutes to 120 hours.
[7] The production method according to any one of the above [2] to [6], characterized in that the amount of the polymerization inhibitor is within the range of 10 ppm by weight to 10% by weight based on 100% by weight of the alcohol represented by the above general formula (2).
[8] A polymer containing a structural unit derived from a (meth)acrylate represented by the following general formula (1):

(In the formula, ^R1 represents a hydrogen atom or a methyl group. ^R2 and ^R3 represent alkyl groups, and the total number of carbon atoms of ^R2 and ^R3 is 6 to 22. n is a number from 1 to 3.)
[9] The polymer according to [8] above, which has a structure in which the (meth)acrylate is added to a polymer having an active hydrogen-containing functional group.
[10] A water/oil repellent comprising the polymer according to [8] or [9] above.
[11] A method for imparting water and oil repellency to a substrate, comprising a step of adhering the polymer according to [8] or [9] above to the substrate.
[12] The method for imparting water and oil repellency to a substrate according to the above-mentioned [11], wherein the step of adhering the polymer is carried out by applying the polymer onto the substrate, and the method includes a step of introducing crosslinks between the polymers after the step of adhering the polymer to form a coating layer.

<Composition of the present invention>
The present invention relates to a composition (hereinafter also referred to as the "(meth)acrylate composition of the present invention") containing two or more isomers that are (meth)acrylate compounds (hereinafter also referred to as the "(meth)acrylate of the present invention"), and a production method thereof, and the compounds (isomers) are commonly represented by the following general formula (1).

(In the formula, ^R1 is a hydrogen atom or a methyl group, ^R2 and ^R3 are alkyl groups, the total number of carbon atoms of ^R2 and ^R3 is 6 to 22, and n is a number from 1 to 3.)

The (meth)acrylate composition of the present invention contains the above-mentioned isomer (A) in which ^R2 is a methyl group and the above-mentioned isomer (B) in which ^R2 is an alkyl group having 2 or more carbon atoms. ^R3 in the isomers (A) and (B) is not particularly limited as long as the total carbon number of ^R2 and ^R3 is the same in the isomers (A) and (B) and is in the range of 6 to 22.
The (meth)acrylate composition of the present invention contains two or more types of such isomers, and thus has lower crystallinity and a lower melting point than when only one type of isomer is contained, thereby sufficiently suppressing freezing in winter and providing excellent handleability.
In addition, the (meth)acrylate represented by the above general formula (1) has a branched alkyl group at the ethylene glycol terminal, and therefore tends to have a higher glass transition temperature than those having a linear alkyl group.

The (meth)acrylate composition of the present invention preferably contains 1 to 50 mol % of the isomer (A) in which R ² is a methyl group, and 50 to 99 mol % of the isomer (B) in which R ² is an alkyl group having 2 or more carbon atoms. More preferably, the (meth)acrylate composition contains 2 to 40 mol % of the isomer (A) in which R ² is a methyl group, and 60 to 98 mol % of the isomer (B) in which R ² is an alkyl group having 2 or more carbon atoms. Even more preferably, the (meth)acrylate composition contains 5 to 30 mol % of the isomer (A) in which R ² is a methyl group, and 70 to 95 mol % of the isomer (B) in which R ² is an alkyl group having ² or more carbon atoms.
Moreover, the above-mentioned isomer (B) may be one or more kinds of compounds, so long as it is a compound corresponding to an isomer of the above-mentioned isomer (A).
The composition preferably consists essentially of the (meth)acrylate compound of the present invention, and contains the (meth)acrylate compound in an amount of 90 mol % or more, desirably 95 mol % or more, and more preferably 98 mol % or more.
The proportion of the (meth)acrylate compound of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on 100% by mass of the composition.

The total number of carbon atoms in ^R2 and ^R3 in the above general formula (1) is preferably 7 to 21, more preferably 9 to 19, and even more preferably 11 to 17. If the total number of carbon atoms in ^R2 and ^R3 is less than 6, the water and oil repellency will be reduced, which is not preferable. Also, if the total number of carbon atoms in ^R2 and ^R3 exceeds 22, the availability of olefins with that number of carbon atoms will be reduced.

The above ^R2 and ^R3 are alkyl groups, and are not particularly limited as long as the total number of carbon atoms of ^R2 and ^R3 is 6 to 22. The alkyl group may be any of linear, branched, and cyclic, but it is preferable that ^R2 and ^R3 are each a linear alkyl group.
That is, the (meth)acrylate of the present invention preferably has a secondary alkyl group at the ethylene glycol terminal.

^R2 in the above isomer (B) is an alkyl group having 2 or more carbon atoms, and the total number of carbon atoms of ^R2 and ^R3 may be the same as that of isomer (A), but is preferably an alkyl group having 8 to 20 carbon atoms. More preferred examples of ^R2 in the above isomer (B) are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

In the above general formula (1), n is the repeating unit (number of moles added) of the ethylene glycol chain, and is a number from 1 to 3. However, a larger n is not preferred because it increases the affinity for water. For this reason, n is preferably 1 to 2, and more preferably 1 to 1.5.

The compositions of the present invention may include any compound.
The composition of the present invention may contain a compound represented by the following general formula (2).
The composition of the present invention is not particularly limited, but the content of the compound represented by the following general formula (2) is preferably 0 to 10 mass % relative to 100 mass % of the compound represented by the above general formula (1).

The composition of the present invention may contain a polymerization inhibitor. The composition of the present invention is not particularly limited, but it is preferable that the polymerization inhibitor is contained in a ratio of 0.00001% or more and 5% or less by mass based on 100% by mass of the compound represented by the above general formula (1). If it is within the above range, the storage stability of the composition of the present invention tends to be improved.
The polymerization inhibitor is not particularly limited, but examples thereof include the compounds described below.

The composition of the present invention may contain a polymerization initiator. Examples of polymerization initiators include compounds that generate radicals when exposed to heat or light. Specific examples include the polymerization initiators described below.

The content ratio of the polymerization initiator is not particularly limited, but the composition of the present invention preferably contains the polymerization initiator in a ratio of 0.01% by mass or more and 5% by mass or less relative to 100% by mass of the compound represented by the above general formula (1). If it is within the above range, there is a tendency that the polymerization of the composition of the present invention will be less delayed.

The composition of the present invention may contain a radical polymerizable compound other than the compound represented by the above general formula (1). Examples of the radical polymerizable compound include compounds that undergo radical polymerization by heat or light. Specific examples include the monomers described below.
The composition of the present invention is not particularly limited, but the ratio of the radical polymerizable compound other than the compound represented by the above general formula (1) to 100% by mass of the compound represented by the above general formula (1) is preferably 0% by mass or more and 99% by mass or less, more preferably 0 to 80% by mass, even more preferably 0 to 60% by mass, still more preferably 0 to 40% by mass, still more preferably 0 to 20% by mass, and particularly preferably 0 to 10% by mass.

The composition of the present invention may contain a polymer having a weight average molecular weight of 2000 or less, such as a polymer of (meth)acrylic acid or a polymer of alkyl (meth)acrylate, but the content of the polymer is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the compound represented by the above general formula (1).
The weight average molecular weight can be measured by gel permeation chromatography or a static light scattering method.

<Production Method>
The (meth)acrylate-containing composition of the present invention can be produced by esterification or transesterification as described below. The mixing ratio of the (meth)acrylate isomers in the (meth)acrylate composition of the present invention is derived from the mixing ratio of the isomers of the alcohols described below used as raw materials (and further the mixing ratio of the isomers of the olefins used as raw materials for the alcohols).
The present invention also relates to a method for producing a (meth)acrylate-containing composition, comprising: a step of heat-treating a mixture containing an alcohol represented by general formula (2) and a polymerization inhibitor; and a step of adding (meth)acrylic acid and an esterification catalyst to the composition containing the alcohol represented by general formula (2) obtained by the heat-treatment step, thereby carrying out an esterification reaction.
The present invention also relates to a method for producing a (meth)acrylate-containing composition, the method comprising: a step of heat-treating a mixture containing an alcohol represented by the above general formula (2) and a polymerization inhibitor; and a step of adding a (meth)acrylic acid ester represented by the following general formula (3) and an ester exchange catalyst to the composition containing the alcohol represented by the general formula (2) obtained by the heat treatment step, thereby carrying out an ester exchange reaction.

(In the formula, ^R1 represents a hydrogen atom or a methyl group, and ^R4 represents an alkyl group having 1 to 8 carbon atoms.)
The alkyl group having 1 to 8 carbon atoms may be straight-chain, branched or cyclic.

The alcohol used as a raw material for the (meth)acrylate represented by the general formula (1) in the present invention is the alcohol represented by the above general formula (2).
In the above formula (2), the total number of carbon atoms in R ² and R ³ is preferably 7 to 21, more preferably 9 to 19, and even more preferably 11 to 17.
Furthermore, n is preferably 1 to 2, and more preferably 1 to 1.5.

In general, alcohols encompassing the general formula (2) can be synthesized by various methods, such as a method of adding an alkylene oxide to a higher alcohol, a method of dehydrating and condensing a higher alcohol with a (poly)alkylene glycol, a method of condensing a chlorinated paraffin with a (poly)alkylene glycol, and a method of adding a (poly)alkylene glycol to a long-chain olefin.
However, the method of adding an alkylene oxide to a higher alcohol or the method of dehydrating and condensing a higher alcohol with a (poly)alkylene glycol generally results in a long polyethylene glycol chain length (n in general formula (2)) unlike the structure of general formula (2), which is undesirable because it increases the affinity for water.
In the method of obtaining the structure of the general formula (2) by condensing chlorinated paraffin with (poly)alkylene glycol, it is possible to synthesize the structure, but there is a concern that waste containing chlorine will be generated. For this reason, the method of adding (poly)alkylene glycol to long-chain olefin is preferable. As a publicly known method, the method described in JP-A-11-349987, JP-A-10-167990, and Japanese Patent No. 2703752 can be adopted.

As raw materials for synthesizing the alcohol represented by the general formula (2), an olefin having 7 to 23 carbon atoms and ethylene glycol can be used.
In the general formula (2), as the raw material for synthesizing the alcohol in which ^R2 is a methyl group, a 1-olefin having 7 to 23 carbon atoms and ethylene glycol can be used. Specific examples of the 1-olefin include 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and 1-docosene.
The alcohol represented by the above general formula (2) is preferably an addition product of the above 1-olefin and ethylene glycol. The 1-olefin may be one type, or two or more types may be appropriately mixed. The 1-olefin is preferably 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, or 1-docosene having 8 to 22 carbon atoms, more preferably 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or 1-eicosene having 10 to 20 carbon atoms in total, and even more preferably 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene having 12 to 18 carbon atoms.
In the general formula (2), as a raw material for synthesizing an alcohol in which ^R2 is an alkyl group having 2 or more carbon atoms, an internal olefin having 7 to 23 carbon atoms and in which the double bond is not located at the α-position and ethylene glycol can be used.

When ethylene glycol is added to an olefin by the methods described in JP-A-11-349987, JP-A-10-167990, and Japanese Patent No. 2703752, an isomerization reaction occurs during the reaction, and the reaction product becomes a mixture of 30 to 90 mol % of component (A) in which R ² is a methyl group and 70 to 10 mol % of component (B) in which R ² is an alkyl group having 2 or more carbon atoms, and n has a distribution of 1 to 3.
The repeating unit n of the ethylene glycol chain is the number of moles added, which is 1 to 3. However, a larger n is not preferred because it increases the affinity for water, and therefore n is preferably 1 to 2, and more preferably 1 to 1.5.

The alcohol represented by the above general formula (2) is not particularly limited, but specific examples include 2-[(1-methylpentyl)oxy]ethanol, 2-[(1-methylhexyl)oxy]ethanol, 2-[(1-methylheptyl)oxy]ethanol, 2-[(1-methyloctyl)oxy]ethanol, 2-[(1-methylnonyl)oxy]ethanol, 2-[(1-methyldecyl)oxy]ethanol, 2-[(1-methylundecyl)oxy]ethanol, 2-[(1-methyldodecyl)oxy]ethanol, )oxy]ethanol, 2-[(1-methyltridecyl)oxy]ethanol, 2-[(1-methyltetradecyl)oxy]ethanol, 2-[(1-methylpentadecyl)oxy]ethanol, 2-[(1-methylhexadecyl)oxy]ethanol, 2-[(1-methylheptadecyl)oxy]ethanol, 2-[(1-methyloctadecyl)oxy]ethanol, 2-[(1-methylnonadecyl)oxy]ethanol, 2-[(1-methyleicosadecyl)oxy]ethanol; 2-[(1- 2-[(1-ethylbutyl)oxy]ethanol, 2-[(1-ethylpentyl)oxy]ethanol, 2-[(1-ethylhexyl)oxy]ethanol, 2-[(1-ethylheptyl)oxy]ethanol, 2-[(1-ethyloctyl)oxy]ethanol, 2-[(1-ethylnonyl)oxy]ethanol, 2-[(1-ethyldecyl)oxy]ethanol, 2-[(1-ethylundecyl)oxy]ethanol, 2-[(1-ethyldodecyl)oxy]ethanol, 2-[(1-ethyltridecyl)oxy]ethanol, 2-[(1-ethyltetradecyl)oxy]ethanol, 2-[(1-ethylpentadecyl)oxy]ethanol, 2-[(1-ethylhexadecyl)oxy]ethanol, 2-[(1-ethylheptadecyl)oxy]ethanol, 2-[(1-ethyloctadecyl)oxy]ethanol, 2-[(1-ethylnonadecyl)oxy]ethanol, 2-[(1-ethyleicosadecyl)oxy]ethanol; 2-[(1-n-propyl n-propyl)oxy]ethanol, 2-[( 1-n-propylbutyl)oxy]ethanol, 2-[(1-n-propylpentyl)oxy]ethanol, 2-[(1-n-propylpentyl)oxy]ethanol, 2-[(1-n-propylheptyl)oxy]ethanol, 2-[(1-n-propyloctyl)oxy]ethanol, 2-[(1-n-propylnonyl)oxy]ethanol, 2-[(1-n-propylundecyl)oxy]ethanol, 2-[(1-n-propyltridecyl)oxy]ethanol, 2-[(1-n-propyl 2-[(1-n-butyl-n-butyl)oxy]ethanol, 2-[(1-n-butylpentyl)oxy]ethanol, 2-[(1-n-butylhexyl)oxy]ethanol, 2-[(1-n-butylheptyl)oxy]ethanol, 2-[(1-n-butyloctyl)oxy]ethanol, 2-[(1-n-butylnonyl)oxy]ethanol, 2-[(1-n-butyldecyl)oxy]ethanol, 2-[(1-n-butylundecyl)oxy]ethanol , 2-[(1-n-butyldodecyl)oxy]ethanol, 2-[(1-n-butyltetradecyl)oxy]ethanol; 2-[(1-n-pentyl n-pentyl)oxy]ethanol, 2-[(1-n-pentylheptyl)oxy]ethanol, 2-[(1-n-pentyloctyl)oxy]ethanol, 2-[(1-n-pentylnonyl)oxy]ethanol, 2-[(1-n-pentylundecyl)oxy]ethanol, 2-[(1-n-pentyltridecyl)oxy]ethanol, 2-[( 1-n-pentylpentadecyl)oxy]ethanol; 2-[(1-n-hexylhexyl)oxy]ethanol, 2-[(1-n-hexylheptyl)oxy]ethanol, 2-[(1-n-hexyloctyl)oxy]ethanol, 2-[(1-n-hexylnonyl)oxy]ethanol, 2-[(1-n-hexylundecyl)oxy]ethanol, 2-[(1-n-hexyltridecyl)oxy]ethanol, 2-[(1-n-hexylpentadecyl)oxy]ethanol, etc.

As the alcohol represented by the general formula (2), among the above compounds, 2-[(1-methylundecyl)oxy]ethanol, 2-[(1-methyltridecyl)oxy]ethanol, 2-[(1-methylpentadecyl)oxy]ethanol, 2-[(1-methylheptadecyl)oxy]ethanol; 2-[(1-ethylundecyl)oxy]ethanol, 2-[(1-ethyltridecyl)oxy]ethanol, 2-[(1-ethylpentadecyl)oxy]ethanol, 2-[(1-ethylheptadecyl)oxy]ethanol, etc. are preferred.

Synthesis by Esterification
The (meth)acrylate of the present invention can be obtained by esterifying an alcohol represented by the following general formula (2) (hereinafter the same) with (meth)acrylic acid.
At this time, it was found that if (meth)acrylic acid, a toluene solvent, an acid catalyst, and a polymerization inhibitor were charged as in the case of normal esterification in the synthesis of (meth)acrylate, and the reaction was carried out at 80° C. while refluxing the toluene solvent in the presence of an oxygen-containing gas, a runaway polymerization reaction occurred immediately after the start of the reaction.
As a result of extensive investigations, the inventors have found that the cause of this runaway polymerization reaction lies in the raw material alcohol of general formula (2), and have also found that the runaway polymerization can be suppressed by carrying out a pretreatment for the esterification, namely, a heat treatment in the presence of an alcohol and a polymerization inhibitor, and then adding (meth)acrylic acid and an acid catalyst to carry out the esterification.

<Heat treatment>
The heat treatment may be performed without a solvent, but can be performed in the presence of a solvent. The solvent is preferably selected from the solvents to be used in the subsequent esterification. In the case of esterification, a solvent that forms an azeotrope with water and forms two liquid phases with water is preferred, and benzene, toluene, xylene, hexane, heptane, octane, and cyclohexane are more preferred.

The heat treatment is preferably carried out at a temperature within a range of 25° C. to 100° C. The heat treatment is preferably carried out for 10 minutes to 120 hours.
In one preferred embodiment of the present invention, the heat treatment is carried out at a temperature in the range of 25° C. to 100° C. for 10 minutes to 120 hours. More preferably, the heat treatment is carried out at a temperature in the range of 40° C. to 90° C. for 30 minutes to 50 hours, and even more preferably, at a temperature in the range of 50° C. to 80° C. for 60 minutes to 20 hours.

Examples of the polymerization inhibitor include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroquinone, and the like. amine-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine; N-oxyl-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl. Among these, at least one selected from hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl is preferred, and hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl are more preferred.
In one preferred embodiment of the present invention, at least one polymerization inhibitor selected from the group consisting of quinone-based polymerization inhibitors, alkylphenol-based polymerization inhibitors, amine-based polymerization inhibitors, N-oxyl-based polymerization inhibitors, and phenothiazine is used as the polymerization inhibitor.

The amount of the polymerization inhibitor used is 10 ppm by weight to 10% by weight, preferably 100 ppm by weight to 5% by weight, more preferably 200 ppm by weight to 1% by weight, and even more preferably 500 ppm by weight to 0.5% by weight, based on 100% by weight of the alcohol represented by the above general formula (2).
An oxygen-containing gas may be bubbled in during the heat treatment.

<Esterification reaction>
After the heat treatment, (meth)acrylic acid and an esterification catalyst are added to carry out esterification. The amount of (meth)acrylic acid is 0.5 to 5 equivalents, preferably 0.8 to 2 equivalents, more preferably 1 to 1.5 equivalents, relative to the alcohol.
The esterification catalyst may be a known acid catalyst, and examples of the acid catalysts that are generally used include hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, strongly acidic ion exchange resins, heteropolyacids such as phosphotungstic acid, and metal oxides. Preferred are sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, and strongly acidic ion exchange resins.

The amount of the acid catalyst is 0.001 mol% to 50 mol% relative to the (meth)acrylic acid, preferably 0.01 mol% to 10 mol%, and more preferably 0.1 mol% to 5 mol%.

During the esterification reaction, a polymerization inhibitor may be added. Also, an oxygen-containing gas may be blown into the reaction liquid.

Since the esterification reaction is a dehydration reaction, it is preferable to carry out the reaction in the presence of a solvent that forms an azeotrope with water while removing water from the system. The reaction temperature is preferably 50°C to 120°C. If the temperature is lower than 50°C, the reaction time will be longer, and if the temperature exceeds 120°C, the possibility of runaway polymerization increases.
In order to achieve this reaction temperature, it is preferable to appropriately increase or decrease the pressure in the reaction system.

After the reaction is complete, the desired secondary (meth)acrylate compound can be obtained by purifying it using standard methods such as washing with alkaline water, washing with water, drying, and removing the solvent. Distillation may also be used as an alternative purification method.

Synthesis by Transesterification
The (meth)acrylate of the present invention can be obtained by transesterifying an alcohol represented by the general formula (2) with a (meth)acrylic acid ester (alkyl (meth)acrylate) represented by the above general formula (3). At this time, it was found that if a (meth)acrylate, a solvent, a transesterification catalyst, and a polymerization inhibitor are charged and the reaction is carried out at 80° C. while refluxing the solvent in the presence of an oxygen-containing gas, as in the transesterification reaction in the synthesis of a normal (meth)acrylate, a runaway polymerization reaction occurs immediately after the start of the reaction.
As a result of extensive investigations, the inventors have found that the cause of this runaway polymerization reaction lies in the raw material alcohol of general formula (2), and have also discovered that the runaway polymerization can be suppressed by carrying out a pretreatment for the transesterification reaction, namely, by carrying out a heat treatment in the presence of an alcohol and a polymerization inhibitor, and then adding an alkyl (meth)acrylate and an ester catalyst to carry out esterification.

<Heat treatment>
The heat treatment may be performed without a solvent, but can be performed in the presence of a solvent, and the solvent is preferably selected from the solvents used in the subsequent transesterification reaction. In addition, the transesterification reaction is preferably performed using a solvent that discharges the alkyl alcohol by-produced from the alkyl (meth)acrylate out of the system, and hexane, heptane, octane, cyclohexane, etc. are preferably used. In addition, since the alkyl (meth)acrylate forms an azeotropic composition with the by-produced alcohol, a method of discharging it out of the system using the alkyl (meth)acrylate as a solvent can also be adopted.

Examples of the alkyl (meth)acrylate include (meth)acrylates having a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms. Among these, (meth)acrylates having an alkyl group having 1 to 4 carbon atoms are preferably used.
Specific examples of alkyl (meth)acrylates include the following compounds: (meth)acrylic acid lower alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate. These can be used alone or in combination.

The heat treatment is preferably carried out for 10 minutes to 120 hours. The heat treatment is also preferably carried out at a temperature in the range of 25°C to 100°C. More preferably, the heat treatment is carried out at a temperature in the range of 25°C to 100°C for 10 minutes to 120 hours, even more preferably at a temperature in the range of 40°C to 90°C for 30 minutes to 50 hours, and even more preferably at a temperature in the range of 50°C to 80°C for 60 minutes to 20 hours.

The above-mentioned polymerization inhibitors include, for example, quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydro amine-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine; N-oxyl-based polymerization inhibitors such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl. Among these, at least one selected from hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl is preferred, with hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl being more preferred.

The amount of the polymerization inhibitor used is 10 ppm by weight to 10% by weight, preferably in the range of 100 ppm by weight to 5% by weight, more preferably in the range of 200 ppm by weight to 1% by weight, and even more preferably in the range of 500 ppm by weight to 0.5% by weight, based on 100% by weight of the polyethylene glycol mono-higher alkyl ether.
An oxygen-containing gas may be bubbled in during the heat treatment.

<Transesterification reaction>
After the heat treatment, an alkyl (meth)acrylate and an ester exchange catalyst are added to carry out an ester exchange reaction. The alkyl (meth)acrylate is the alkyl (meth)acrylate described above, and the amount is 0.5 to 5 equivalents, preferably 0.8 to 2 equivalents, more preferably 1 to 1.5 equivalents, relative to the alcohol. When the alkyl (meth)acrylate is used as an excluding solvent for the by-produced alcohol, it may be further added.

A known catalyst may be used for the ester exchange, and the catalyst is not particularly limited, but specific examples thereof include oxides such as calcium oxide, barium oxide, lead oxide, zinc oxide, and zirconium oxide; hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, thallium hydroxide, tin hydroxide, lead hydroxide, and nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, and nickel chloride; carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, zinc carbonate, and nickel carbonate; hydrogen carbonates such as potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate; phosphates such as sodium phosphate, potassium phosphate, rubidium phosphate, lead phosphate, zinc phosphate, and nickel phosphate; nitrates such as lithium nitrate, calcium nitrate, lead nitrate, zinc nitrate, and nickel nitrate; carboxylates such as lithium acetate, calcium acetate, lead acetate, zinc acetate, and nickel acetate; sodium methoxide, sodium ethoxide, potassium methoxide, potassium eth ... Examples of the alkoxy compounds include lithium t-butoxide, calcium methoxide, calcium ethoxide, barium methoxide, barium ethoxide, tetraethoxytitanium, tetrabutoxytitanium, tetraisopropoxytitanate, and tetra(2-ethylhexanoxy)titanium; acetylacetonate complexes such as lithium acetylacetonate, zirconia acetylacetonate, zinc acetylacetonate, dibutoxytin acetylacetonate, and dibutoxytitanium acetylacetonate; quaternary ammonium alkoxides such as tetramethylammonium methoxide, tetramethylammonium t-butoxide, and trimethylbenzylammonium ethoxide; dialkyltin compounds such as dimethyltin oxide, methylbutyltin oxide, dibutyltin oxide, and dioctyltin oxide; distannoxanes such as bis(dibutyltin acetate) oxide and bis(dibutyltin laurate) oxide; and dialkyltin dicarboxylates such as dibutyltin diacetate and dibutyltin dilaurate. These may be used alone or in combination of two or more. Among these transesterification catalysts, potassium carbonate, cesium carbonate, tetraethoxytitanium, tetrabutoxytitanium, tetraisopropoxytitanate, tetra(2-ethylhexanoxy)titanium, zirconia acetylacetonate, dibutyltin oxide, dioctyltin oxide, bis(dibutyltin acetate) oxide, bis(dibutyltin laurate) oxide, dibutyltin diacetate, and dibutyltin dilaurate are preferably used.

The amount of the transesterification catalyst used is not particularly limited, but specifically, relative to the alcohol represented by general formula (2), it is preferably 0.001 mol% or more, more preferably 0.005 mol% or more, even more preferably 0.01 mol% or more, particularly preferably 0.05 mol% or more, preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less. The above range of the transesterification catalyst amount is preferable in terms of yield and economy.

During the ester exchange reaction, a polymerization inhibitor may be added. Also, an oxygen-containing gas may be blown into the reaction liquid.

Since the transesterification reaction produces alcohol as a by-product, it is preferable to carry out the reaction while removing the by-product alcohol from the system. The reaction temperature is preferably 50°C to 120°C. If the temperature is lower than 50°C, the reaction time will be longer, and if the temperature exceeds 120°C, the possibility of runaway polymerization increases.
In order to achieve this reaction temperature, it is preferable to appropriately increase or decrease the pressure in the reaction system.
After the reaction is completed, the target secondary (meth)acrylate compound can be obtained by purifying the product by a conventional method such as acid washing, water washing, filtration, drying, and solvent removal. As another purification method, distillation may be used.

<Polymer>
The (meth)acrylate of the present invention is a (meth)acrylate represented by general formula (1) and has a carbon-carbon double bond, so that it can be used as a monomer to obtain a polymer.
The polymer may be composed of structural units derived from the (meth)acrylate of the present invention, but may also contain other structural units. For example, the polymer may contain 0.1 to 100 mol % of structural units derived from the (meth)acrylate of the present invention based on the total structural units.
The proportion of structural units derived from the (meth)acrylate of the present invention is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, even more preferably 20 to 100 mol%, still more preferably 25 to 100 mol%, still more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%, and particularly preferably 70 to 100 mol%.

Copolymerizable monomers include alkyl acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, and octadecyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, and methoxydiethylene glycol (meth)acrylate. acrylate, alkyl polyoxyalkyl (meth)acrylates such as methoxypropylene glycol (meth)acrylate, ethoxypropylene glycol (meth)acrylate, and methoxydipropylene glycol (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; glycidyl (meth)acrylate; acrylate and other glycidyl group-containing compounds, aminoacrylates such as 2-(dimethylamino)ethyl (meth)acrylate and 2-(diethylamino)ethyl (meth)acrylate, ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and isobornyl (meth)acrylate, styrene, α-methylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. Silicon-containing monomers such as 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane, vinyl chloride, (meth)acrylates having an Rf group (a group in which two or more hydrogen atoms of an alkyl group are replaced with fluorine atoms) (the Rf group may contain halogen atoms other than fluorine atoms. The other halogen atoms are preferably chlorine atoms. Furthermore, an ether-type oxygen atom or a thioether-type sulfur atom may be inserted between the carbon-carbon bonds in the Rf group.) can be used as one or more of the copolymerizable monomers. In addition to the above, polyether aliphatic urethane acrylate, polycarbonate urethane acrylate, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, isobornyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, and tricyclodecane dimethanol diacrylate can also be used as copolymerizable monomers.

The weight average molecular weight of the polymer in the present invention is preferably, for example, 1,000 to 10,000,000 as determined by the static light scattering method.

The glass transition temperature of the polymer in the present invention is desirably, for example, −40° C. or higher. The upper limit of the glass transition temperature of the polymer of the present disclosure is desirably, for example, 80° C. or lower.
The glass transition temperature is calculated by using the glass transition temperature of a homopolymer of the monomer used in the monomer component constituting the polymer.
Formula (I): 1/Tg = Σ(Wm/Tgm)/100 (I)
In the formula, Wm is the content (mass%) of monomer m in the monomer components constituting the polymer, and Tgm is the glass transition temperature (absolute temperature: K) of a homopolymer of monomer m.

<Polymerization method>
The polymerization to obtain the polymer of the present invention is expected to be carried out in the presence of a polymerization initiator.
Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane)hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as potassium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
The polymerization initiators may be used alone or in combination of two or more.

The amount of polymerization initiator used may be appropriately set depending on the type of polymerization initiator, etc., and is not particularly limited, but may be, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and may be, for example, 2 parts by mass or less, preferably 1 part by mass or less, relative to 100 parts by mass of the monomer component.

In the above polymerization reaction, additives such as a chain transfer agent may be included in the reaction system. Any appropriate additive may be used as the additive. For example, additives such as mercaptoethanol, thioglycolic acid, and sodium disulfite may be added during polymerization.

The polymerization reaction may be carried out in the presence of a reducing agent (e.g., sodium hydrogen sulfite), a decomposing agent for the polymerization initiator (e.g., a transition metal salt such as ferrous sulfate), a chain transfer agent [e.g., a compound having a thiol group (e.g., tert-dodecyl mercaptan)], a pH buffer, a chelating agent, etc., as necessary.

<Addition Polymer>
As an alternative method for obtaining the polymer of the present invention, a method can be employed in which a (meth)acrylate is added to a polymer having a functional group having an active hydrogen capable of being added to an olefin.
For example, a method of adding a (meth)acrylate to a polymer having a primary or secondary amino group in the molecule, a method of adding a (meth)acrylate to a polymer having a thiol group in the molecule, a reaction with a polymer having a hydroxyl group in the molecule, etc. can be used.
The polymers having active hydrogen may be used alone or in combination of two or more kinds.

The amount of (meth)acrylate used relative to the active hydrogen-containing polymer may be appropriately set depending on the number of active hydrogen groups contained, and is not particularly limited. However, the amount of (meth)acrylate relative to the active hydrogen group equivalent may be, for example, 0.1 to 100 equivalents, preferably 0.5 to 80 equivalents.

The addition of active hydrogen groups is a reaction known as Michael addition, and although a catalyst does not have to be used, it is acceptable to use one. Any known catalyst can be used.

<Application A>
The compound of the present invention can be used, for example, as a water/oil repellent for textile products.
The present invention also relates to a water/oil repellent comprising a polymer containing a structural unit derived from the (meth)acrylate of the present invention.
The water/oil repellent can be used by applying it to a substrate. In this case, a polymer can be synthesized in advance using the (meth)acrylate compound of the present invention as a monomer, and a water/oil repellent containing the polymer can be applied. In this case, a functional group that reacts with urethane resin, epoxy resin, etc., such as a hydroxyl group, a carboxyl group, or a silanol group, is provided to the polymer chain, and crosslinking is formed and cured to form a coating layer, which imparts water/oil repellency to the substrate.
The substrate is not particularly limited, but examples thereof include fibers and films.

The present invention is also a method for imparting water and oil repellency to a substrate, comprising the step of adhering a polymer to the substrate.
The step of attaching the polymer is preferably carried out by coating the polymer on the substrate.
The method for imparting water and oil repellency to a substrate preferably includes a step of forming a coating layer by introducing crosslinks between the polymers after the polymer adhesion step.
The present invention also relates to a method for producing a water- and oil-repellent substrate, the method comprising the steps of: applying a polymer containing a structural unit derived from the (meth)acrylate of the present invention onto a substrate; and, after the step of applying the polymer, introducing crosslinks between the polymers to form a coating layer.
In the step of applying the polymer onto the substrate, it is preferable to apply a solution of the polymer diluted with water or a solvent onto the substrate by spraying.

<Application B>
The compound of the present invention can be used, for example, as ink, paint, pressure sensitive adhesive, adhesive, UV curable resin diluent, water/oil repellent, etc., and is preferably used as a water/oil repellent.
The water/oil repellent can be used by applying it to a substrate. In this case, a polymer can be synthesized in advance using the compound of the present invention as a monomer, and a water/oil repellent containing the polymer can be applied. In this case, the polymer chain is provided with a functional group that reacts with urethane resin, epoxy resin, etc., such as a hydroxyl group, a carboxyl group, or a silanol group, and crosslinked to form a coating layer that is cured to impart water/oil repellency to the substrate.

<Application C>
From the viewpoint of specific products, the compound of the present invention is expected to be used as an adhesive or sealing material for electronic components or semiconductor elements, a raw material for a constituent material of a film or prepreg, an ink for 3D printing, a quantum dot ink, an adhesive such as a UV-curable lamination adhesive or a UV-curable hot melt adhesive, a sealant, or the like.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Note that, unless otherwise specified, parts and percentages in the examples are by weight.

[Synthesis Example 1]
Synthesis of higher secondary alcohol monoethoxylate precursor 5% by mass of BEA-type zeolite (product name: VALFOR CP811 BL-25) manufactured by PQ Corp. was added to 1-dodecene, and the mixture was reacted in a liquid phase at 150° C. for 10 hours to obtain a dodecene isomer mixture (consisting of 25 mol % of 1-dodecene and 75 mol % of inner dodecene). 810 g (4.82 mol), 900 g (14.52 mol) of monoethylene glycol (MEG), and 100 g of BEA-type zeolite (product name: VALFOR CP811 BL-25) manufactured by PQ Corp. as a catalyst were charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen, and then the mixture was maintained in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150°C while stirring at a rotation speed of 600 rpm, and the mixture was reacted at the same temperature for 3 hours. Thereafter, the reaction liquid was cooled to room temperature, the upper dodecene phase was separated, and unreacted dodecene was distilled off, and then 155 g of an isomer mixture of secondary dodecanol monoethoxylate (alcohol (1)) was obtained at a boiling point range of 129 to 131°C (temperature at the top of the distillation tower; the same applies below) at a reduced pressure of 2 mmHg. The secondary dodecanol monoethoxylate (1) contained 0.3% by mass of MEG and MEG polymers. 155 g of secondary dodecanol monoethoxylate (alcohol (1)) was added to a separable flask, and the mixture was washed by stirring with 25 g of water at 70°C for 30 minutes at 100 rpm using a stirring blade, and the operation of separating the aqueous layer was repeated three times, and further dehydration was performed to obtain purified secondary dodecanol monoethoxylate (alcohol (1)). The (poly)ethylene glycol content in the ethoxylate was 0.02% by mass.

[Synthesis Example 2]
810 g (4.13 mol) of a tetradecene isomer mixture (consisting of 1-tetradecene: 6 mol%, 2-tetradecene: 15 mol%, 3-tetradecene: 18 mol%, 4-tetradecene: 20 mol%, 5-tetradecene: 17 mol%, and 6,7-tetradecene: 24 mol%) obtained by adding 5 mass% of BEA-type zeolite (trade name: VALFOR CP811 BL-25) manufactured by PQ Corporation to 1-tetradecene and reacting in a liquid phase at 150° C. for 13 hours, 900 g (14.52 mol) of monoethylene glycol (MEG), and BEA-type zeolite (trade name: VALFOR CP811 BL-25) manufactured by PQ Corporation as a catalyst were added. BL-25) 100g was charged into a 3000ml glass reactor equipped with a stirring blade and a reflux condenser, the gas phase was replaced with nitrogen, and then the mixture was maintained in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150°C while stirring at a rotation speed of 600 rpm, and the mixture was reacted at the same temperature for 3 hours. Thereafter, the reaction liquid was cooled to room temperature, and the upper tetradecene phase was separated. This tetradecene phase contained 103g of secondary tetradecanol monoethoxylate (alcohol (2)), 0.4g of MEG and MEG polymers. 840g of this tetradecene phase was added to a separable flask as 200g of a water/MeOH=90/10 solution (mass ratio), and the mixture was stirred at 60°C for 30 minutes at 100 rpm using a stirring blade, and the operation of separating the aqueous layer was repeated three times. Then, the oil layer was distilled. After distilling off unreacted tetradecene, 102 g of a purified isomer mixture of secondary tetradecanol monoethoxylate (alcohol (2)) was obtained at a reduced pressure of 5 mmHg and a boiling point range of 170 to 174° C. The content of (poly)ethylene glycol in the ethoxylate was 0.03% by mass.

[Synthesis Example 3]
930 g (4.14 mol) of a hexadecene isomer mixture (consisting of 1-hexadecene: 6 mol%, 2-hexadecene: 15 mol%, 3-hexadecene: 18 mol%, 4-hexadecene: 20 mol%, 5-hexadecene: 17 mol%, and 6,7-hexadecene: 24 mol%) obtained by adding 5 mass% of BEA-type zeolite (product name: VALFOR CP811 BL-25) manufactured by PQ Corporation to 1-hexadecene and reacting in a liquid phase at 150° C. for 13 hours, 900 g (14.52 mol) of monoethylene glycol (MEG), and BEA-type zeolite (product name: VALFOR CP811 BL-25) manufactured by PQ Corporation as a catalyst were added. BL-25) 100g was charged into a 3000ml glass reactor equipped with a stirring blade and a reflux condenser, the gas phase was replaced with nitrogen, and then the mixture was maintained in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150°C while stirring at a rotation speed of 600 rpm, and the mixture was reacted at the same temperature for 3 hours. Thereafter, the reaction liquid was cooled to room temperature, and the upper hexadecene phase was separated. This hexadecene phase contained 109.8g of secondary hexadecanol monoethoxylate (alcohol (3)), 0.4g of MEG and MEG polymers. 840g of this hexadecene phase was added to a separable flask in 200g of water/MeOH = 90/10 solution (mass ratio), and the mixture was stirred at 60°C for 30 minutes at 100 rpm using a stirring blade, and the operation of separating the aqueous layer was repeated three times. Then, the oil layer was distilled. After distilling off unreacted tetradecene, 108 g of a purified secondary hexadecanol monoethoxylate (alcohol (3)) was obtained at a reduced pressure of 1 mmHg and a boiling point range of 165 to 169°C (temperature at the top of the distillation column; the same applies below). The content of (poly)ethylene glycol in the ethoxylate was 0.03% by mass.

[Example 1]
<Direct esterification with acrylic acid>
Into a four-neck flask equipped with a thermometer, a stirrer, a condenser, and a gas inlet tube, 139 g (0.60 mol) of the alcohol (1) synthesized in Synthesis Example 1, 100 g of toluene as an organic solvent, and 0.14 g of phenothiazine (1000 ppm by weight relative to the alcohol) as a polymerization inhibitor were heated at 80° C. for 4 hours.
To this liquid, 65.3 g (0.91 mol) of acrylic acid and 5.3 g of methanesulfonic acid as an acid catalyst were added, and esterification reaction was carried out by removing condensed water while refluxing toluene at 350 mmHg while blowing in 7% oxygen/nitrogen gas.
The amount of water of condensation generated was 10.8 g. The reaction solution was transferred to a separating funnel and washed twice with 100 g of a 4% aqueous sodium hydroxide solution, and further washed twice with 100 g of water. The upper organic layer was transferred to a four-necked flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, and heated under reduced pressure while blowing in 7% oxygen/nitrogen gas to distill off the toluene, obtaining 159 g of a product (2-[(1-methylundecyl)oxy]ethyl acrylate isomer mixture). The purity of this acrylate product was 98%, and it contained unreacted alcohol.
This product was stored in a refrigerator at -20°C for 70 hours, but no crystal precipitation was observed.
The H-NMR of the product was measured, and the NMR chart is shown in FIG.

[Comparative Example 1]
In the production method described in Example 1, the contents were charged into a flask all at once and the esterification reaction was carried out without the heat treatment at 80° C. for 4 hours. After about 1 hour, the formation of a polymer of acrylic acid was observed.

[Example 2]
<Transesterification reaction with methyl acrylate>
Into a flask equipped with a stirrer, a thermometer, and a fractionating column, 164 g (0.63 mol) of the alcohol (2) synthesized in Synthesis Example 2 and 0.16 g (1000 ppm by weight relative to the alcohol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor were charged, and the mixture was heated at 80° C. for 4 hours with stirring.
To this liquid, 273 g (3.17 mol) of methyl acrylate and 9.0 g of tetraisopropoxy titanate as a catalyst were charged and heated with stirring. After refluxing was started, a mixture of methanol and methyl acrylate was removed from the fractionating column while an equal amount of methyl acrylate was added to the removed liquid to carry out a reaction, thereby obtaining 189 g of a product (2-[(1-methyltridecyl)oxy]ethyl acrylate) isomer mixture. Analysis of the reaction liquid showed that the conversion rate of 2-[(1-methyltridecyl)oxy]ethanol to the product was 95 mol%.
This product was stored in a refrigerator at -20°C for 70 hours, but no crystal precipitation was observed.

[Comparative Example 2]
In the production method described in Example 2, the contents were charged into a flask all at once to carry out the transesterification reaction without the heat treatment at 80° C. for 4 hours. After about 1 hour, the reaction liquid was found to have thickened, and a polymer of methyl acrylate was formed.

[Example 3]
Into a four-neck flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, 164 g (0.57 mol) of the alcohol (3) synthesized in Synthesis Example 3, 100 g of toluene as an organic solvent, and 0.82 g of phenothiazine (5,000 ppm by weight relative to the alcohol) as a polymerization inhibitor were charged, and the mixture was heated at 40° C. for 80 hours with stirring.
To this liquid, 68.2 g (0.95 mol) of acrylic acid and 5.5 g of methanesulfonic acid as an acid catalyst were added, and esterification reaction was carried out by removing condensed water while refluxing toluene at 350 mmHg while blowing in 7% oxygen/nitrogen gas.
The amount of condensed water generated was 11 g. The reaction liquid was transferred to a separating funnel and washed twice with 100 g of a 4% aqueous sodium hydroxide solution, and further washed twice with 100 g of water. The upper organic layer was transferred to a four-necked flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, and heated under reduced pressure while blowing in 7% oxygen/nitrogen gas to distill off the toluene, obtaining 190 g of a product (2-[(1-methylpentadecyl)oxy]ethyl acrylate) isomer mixture. The purity of this acrylate product was 96%, and it contained unreacted alcohol.
When this product was stored in a refrigerator at -20°C for 10 hours, it crystallized, but no crystal precipitation was observed at -5°C.
It has been shown that it is possible to obtain the compounds of the present invention by the processes described in Examples 1 to 3 above.

[Example 4]
20 g of the (meth)acrylate synthesized in Example 3, 100 g of dioxane as an organic solvent, and 0.4 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were added to a four-neck flask equipped with a thermometer, a stirrer, a cooling tube, and a gas inlet tube, and polymerization was carried out at 70° C. After polymerization for 2 hours, the reaction solution had become viscous, and the production of a polymer was confirmed. The produced polymer was subjected to NMR measurement, and it was found to contain 2% of unpolymerized components.

[Example 5]
In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 20 parts of the acrylate synthesized in Example 4 was heated and melted, and 1 part of a nonionic surfactant (product name "Noigen ES-149D", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 63 parts of warm water (60°C) were mixed and emulsified using a high-pressure emulsifier to prepare an aqueous dispersion (emulsion) with a nonvolatile content of 25%.
20 parts of this aqueous dispersion was mixed with 5 parts of polyethyleneimine (product name "Epomin (registered trademark) HM-2000", manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 30,000) to prepare an aqueous dispersion (water repellent composition) having a non-volatile content of 25%.
The water repellent composition was diluted 25 times with water, and a polyester fabric (Polyester Tropical, manufactured by Teijin Co., Ltd.) was immersed in the diluted water repellent composition. The polyester fabric to which the water repellent composition was applied was dried in a dryer at 180°C for 5 minutes to obtain a water repellent fiber. The amount of the water repellent composition applied to the polyester fabric was 1.3 g/ ^m2 .
The obtained fiber was tested according to the spray method of JIS L 1092 (2009) at a shower water temperature of 20° C. The results were evaluated visually and showed that some adhesion and wetness was present on the surface, but other areas were not.

[Reference Example 1]
The same procedure as in Example 5 was carried out except that 20 parts of stearyl acrylate was used in place of 20 parts of the acrylate synthesized in Example 4, to obtain a reference polyester fiber.
The obtained fiber was tested according to the spray method of JIS L 1092 (2009) with shower water at a temperature of 20° C. The results were evaluated visually, and the surface was wetted, but no water droplets were observed.

The evaluation of Example 5 above demonstrated that the (meth)acrylate of the present invention has a water-repellent effect.

Claims

A (meth)acrylate-containing composition comprising two or more isomers of a (meth)acrylate represented by the following general formula (1), the composition comprising isomer (A) in which R2 is a methyl group and isomer (B) in which R2 is an alkyl group having two or more carbon atoms:

(In the formula, R1 represents a hydrogen atom or a methyl group. R2 and R3 represent alkyl groups, and the total number of carbon atoms of R2 and R3 is 6 to 22. n is a number from 1 to 3.)
10. A method for producing the (meth)acrylate-containing composition of claim 1, comprising:
The production method includes a step of heat-treating a mixture containing an alcohol represented by the following general formula (2) and a polymerization inhibitor,
and adding (meth)acrylic acid and an esterification catalyst to the composition containing the alcohol represented by general formula (2) obtained by the heat treatment step, thereby carrying out an esterification reaction.
A method for producing a (meth)acrylate-containing composition.

(In the formula, R2 and R3 are alkyl groups, the total number of carbon atoms of R2 and R3 is 6 to 22, and n is a number from 1 to 3.)
10. A method for producing the (meth)acrylate-containing composition of claim 1, comprising:
The production method includes a step of heat-treating a mixture containing an alcohol represented by the following general formula (2) and a polymerization inhibitor,
and adding a (meth)acrylic acid ester represented by the following general formula (3) and an ester exchange catalyst to the composition containing the alcohol represented by the general formula (2) obtained by the heat treatment step to carry out an ester exchange reaction.
A method for producing a (meth)acrylate-containing composition.

(In the formula, R2 and R3 are alkyl groups, the total number of carbon atoms of R2 and R3 is 6 to 22, and n is a number from 1 to 3.)

(In the formula, R1 represents a hydrogen atom or a methyl group, and R4 represents an alkyl group having 1 to 8 carbon atoms.)
The manufacturing method according to claim 2 or 3, characterized in that the heat treatment uses at least one polymerization inhibitor selected from the group consisting of quinone-based polymerization inhibitors, alkylphenol-based polymerization inhibitors, amine-based polymerization inhibitors, N-oxyl-based polymerization inhibitors, and phenothiazine.
The method for producing a (meth)acrylate according to any one of claims 2 to 4, characterized in that the heat treatment is carried out at a temperature within the range of 25°C to 100°C.
The method for producing a (meth)acrylate according to any one of claims 2 to 5, characterized in that the heat treatment is carried out for 10 minutes to 120 hours.
The method of any one of claims 2 to 6, characterized in that the amount of the polymerization inhibitor is in the range of 10 ppm by weight to 10% by weight relative to 100% by weight of the alcohol represented by the general formula (2).
A polymer containing a structural unit derived from a (meth)acrylate represented by the following general formula (1):

(In the formula, R1 represents a hydrogen atom or a methyl group. R2 and R3 represent alkyl groups, and the total number of carbon atoms of R2 and R3 is 6 to 22. n is a number from 1 to 3.)
A water/oil repellent containing the polymer described in claim 8.
A method for imparting water and oil repellency to a substrate, comprising a step of adhering the polymer described in claim 8 to the substrate.
The method for imparting water and oil repellency to a substrate according to claim 10, comprising: a step of forming a coating layer by introducing crosslinks between the polymers after the polymer adhering step, the step of adhering the polymer to the substrate by coating the polymer on the substrate.