Composition containing acrylic acid derivative, and method for stabilizing acrylic acid derivative

Abstract

An object of the present invention is to provide a method for stabilizing an acrylic acid derivative, and a composition containing an acrylic acid derivative in which the acrylic acid derivative is stabilized. The present invention provides a composition comprising: (A) an acrylic acid derivative represented by Formula (I): ##STR00001##
(wherein, R.sup.1 and R.sup.2 are the same or different, and each represents alkyl, fluoroalkyl, aryl that may have one or more substituents, halogen, or hydrogen; R.sup.c represents a group: OR.sup.3 (wherein R.sup.3 represents alkyl, fluoroalkyl, aryl that may have one or more substituents, or hydrogen) or halogen; and X represents fluoroalkyl, alkyl, hydrogen, or halogen); and (B) amide, wherein the content of acrylic acid derivative (A) is 30% (w/w) or more.

Claims

1. A composition comprising (A) an acrylic acid derivative corresponding to Formula (I): ##STR00006## wherein R.sup.1 and R.sup.2 are hydrogen; R.sup.c is a group: OR.sup.3 (wherein R.sup.3 is C.sub.1-4 alkyl or hydrogen) or fluorine; and X is fluorine; and (B) amide of the formula: R.sup.10R.sup.11NCOR.sup.12, wherein R.sup.10 and R.sup.11 are independently C.sub.1-3 alkyl; and R.sup.12 is hydrogen or C.sub.1-3 alkyl, wherein the content of the acrylic acid derivative corresponding to Formula (I) is 30% (w/w) or more.

2. The composition according to claim 1, wherein amide (B) is C.sub.1-6 amide.

3. The composition according to claim 2, wherein amide (B) is N,N-dimethylformamide or N,N-dimethylacetamide.

4. A method for stabilizing an acrylic acid derivative corresponding to Formula (I): ##STR00007## wherein R.sup.1 and R.sup.2 are hydrogen; R.sup.c is a group: OR.sup.3 (wherein R.sup.3 is C.sub.1-4 alkyl or hydrogen) or fluorine; and X is fluorine, the method comprising making the acrylic acid derivative corresponding to Formula (I) coexist with amide of the formula: R.sup.10R.sup.11NCOR.sup.12, wherein R.sup.10 and R.sup.11 are independently C.sub.1-3 alkyl; and R.sup.12 is hydrogen or C.sub.1-3 alkyl, with the proviso that the method excludes making the acrylic acid derivative corresponding to Formula (I) coexist with a polymerization inhibitor.

Description

DESCRIPTION OF EMBODIMENTS

Terms

(1) The symbols and the abbreviations in this specification are to be interpreted as having the general meanings in the related technical field to which the present invention pertains, according to the context of this specification, unless otherwise specified.

(2) In this specification, room temperature means a temperature in a range of 10 to 40 C.

(3) In this specification, the term comprise/contain is intended to mean both consist essentially of and consist of.

(4) In this specification, stabilization of an acrylic acid derivative refers to preventing an acrylic acid derivative from changing into a different substance, such as a polymer.

(5) In this specification, alkyl (the term alkyl encompasses the alkyl moiety in fluoroalkyl or the like) may be a cyclic, linear, or branched alkyl.

(6) In this specification, alkyl may be, for example, a C.sub.1-20, C.sub.1-12, C.sub.1-6, C.sub.1-4, or C.sub.1-3 alkyl.

(7) In this specification, specific examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, and like linear or branched alkyl.

(8) In this specification, specific examples of alkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and like C.sub.3-6 cyclic alkyl (cycloalkyl).

(9) In this specification, fluoroalkyl refers to an alkyl in which at least one hydrogen is replaced by fluorine.

(10) In this specification, the number of fluorines in the fluoroalkyl may be one or more (the maximum replaceable number from 1; e.g., 1 to 3, 1 to 6, or 1 to 12).

(11) The fluoroalkyl encompasses perfluoroalkyl. The perfluoroalkyl refers to an alkyl in which all of the hydrogens are replaced by fluorines.

(12) In this specification, examples of fluoroalkyl include C.sub.1-20, C.sub.1-12, C.sub.1-6, C.sub.1-4, and C.sub.1-3 fluoroalkyls.

(13) In this specification, the fluoroalkyl may be a linear or branched fluoroalkyl.

(14) In this specification, specific examples of fluoroalkyl include fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, tetrafluoropropyl (e.g., HCF.sub.2CF.sub.2CH.sub.2), hexafluoropropyl (e.g., (CF.sub.3).sub.2CH), nonafluorobutyl, octafluoropentyl (e.g., HCF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2), and tridecafluorohexyl.

(15) In this specification, examples of aryl include phenyl and naphthyl.

(16) In this specification, examples of halogen include fluorine, chlorine, bromine, and iodine.

(17) In this specification, the alkoxy is an alkyl-O-group.

(18) In this specification, examples of acyl include alkanoyl (i.e., alkyl-CO-group).

(19) In this specification, examples of ester include alkylcarbonyloxy (i.e., alkyl-COO-group), and alkoxycarbonyl (i.e., alkyl-OCO-group).

(20) Composition

(21) The composition of the present invention comprises:

(22) (A) an acrylic acid derivative represented by Formula (I):

(23) ##STR00005##

(24) (wherein, R.sup.1 and R.sup.2 are the same or different, and each represents alkyl, fluoroalkyl, aryl that may have one or more substituents, halogen, or hydrogen; R.sup.c represents a group: OR.sup.3 (wherein R.sup.3 represents alkyl, fluoroalkyl, aryl that may have one or more substituents, or hydrogen) or halogen; and X represents fluoroalkyl, alkyl, hydrogen, or halogen).

(25) (in this specification, this derivative may also be referred to as acrylic acid derivative (A)); and

(26) (B) amide,

(27) wherein the content of acrylic acid derivative (A) is 30% (w/w) or more.

(28) Acrylic Acid Derivative (A)

(29) Each symbol in Formula (1) representing acrylic acid derivative (A) is explained below.

(30) Preferable examples of the substituents of the aryl that may have one or more substituents represented by R.sup.1, R.sup.2, and R.sup.3 include fluorine, alkyl, alkoxy, acyl, ester, cyano, nitro, and fluoroalkyl. More preferable examples include fluorine.

(31) The number of the substituents is preferably 0 (i.e., unsubstituted), 1, 2, or 3.

(32) R.sup.1 is preferably hydrogen, C.sub.1-20 (preferably C.sub.1-12, more preferably C.sub.1-6, further preferably C.sub.1-4, further more preferably C.sub.1-3, particularly preferably C.sub.1 or C.sub.2) alkyl, or C.sub.1-20 fluoroalkyl, and more preferably hydrogen.

(33) R.sup.2 is preferably hydrogen, C.sub.1-20 (preferably C.sub.1-12, more preferably C.sub.1-6, further preferably C.sub.1-4, further more preferably C.sub.1-3, particularly preferably C.sub.1 or C.sub.2) alkyl, or C.sub.1-20 (preferably C.sub.1-12, more preferably C.sub.1-6, further preferably C.sub.1-4, further more preferably C.sub.1-3, particularly preferably C.sub.1 or C.sub.2) fluoroalkyl, and more preferably hydrogen.

(34) The halogen represented by R.sup.c is preferably fluorine or chlorine, more preferably fluorine.

(35) R.sup.c is preferably represented by a formula: OR.sup.3.

(36) R.sup.3 is preferably C.sub.1-20 (preferably C.sub.1-12, more preferably C.sub.1-6, further preferably C.sub.1-4, further more preferably C.sub.1-3, particularly preferably C.sub.1 or C.sub.2) linear alkyl.

(37) X is C.sub.1-20 (preferably C.sub.1-12, more preferably C.sub.1-6, further preferably C.sub.1-4, further more preferably C.sub.1-3, particularly preferably C.sub.1 or C.sub.2) fluoroalkyl, fluorine, or chlorine, and more preferably fluorine.

(38) In Formula (I), preferably,

(39) R.sup.1 is hydrogen;

(40) R.sup.2 is hydrogen;

(41) R.sup.c is a group: OR.sup.3,

(42) R.sup.3 is methyl or ethyl (more preferably methyl), and

(43) X is fluorine or chlorine (more preferably fluorine).

(44) The composition of the present invention may comprise one or more kinds of acrylic acid derivative (A); however, the composition of the present invention preferably comprises only one kind of acrylic acid derivative (A).

(45) Acrylic acid derivative (A) used in the present invention may be produced by a known method or a similar method thereof, or may be obtained from commercial suppliers.

(46) When R.sup.c in Formula (I) is a group: OR.sup.3, acrylic acid derivative (A) used in the present invention may be produced, for example, through the production methods disclosed in International Publication No. 2014/034906, JP2014-24755A, U.S. Pat. No. 3,262,968, and the like, or similar methods thereof.

(47) When R.sup.c in Formula (I) is halogen, acrylic acid derivative (A) used in the present invention may be produced, for example, through the production methods disclosed in JPS60-078940A, JPS61-085345A, and the like, or similar methods thereof.

(48) The content of acrylic acid derivative (A) in the composition of the present invention is 30% (w/w) or more.

(49) Generally, when the concentration of acrylic acid derivative (A) is high, unintended polymerization reaction or the like more easily occurs. However, in the composition of the present invention, even when the content of acrylic acid derivative (A) is high, acrylic acid derivative (A) is stable.

(50) Further, the content of acrylic acid derivative (A) in the composition of the present invention is preferably 40% (w/w) or more, 50% (w/w) or more, 60% (w/w) or more, 70% (w/w) or more, 80% (w/w) or more, or 90% (w/w) or more.

(51) The upper limit of the content of acrylic acid derivative (A) in the composition of the present invention is, for example, but not particularly limited to, 98% (w/w), 95% (w/w), or 90% (w/w). However, as it would be obvious to a person skilled in the art, the upper limit of the content of acrylic acid derivative (A) in the composition of the present invention may be limited depending on the amount of amide (B) contained in the composition of the present invention.

(52) Amide (B)

(53) Examples of amide (B) contained in the composition of the present invention include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, and N,N-diethylacetamide.

(54) Amide (B) contained in the composition of the present invention is preferably represented by a formula: R.sup.10R.sup.11NCOR.sup.12 (wherein R.sup.10 and R.sup.11 represent C.sub.1-3 alkyl, and R.sup.12 represents hydrogen or C.sub.1-3 alkyl).

(55) Amide (B) contained in the composition of the present invention is preferably C.sub.3-8 amide.

(56) Amide (B) contained in the composition of the present invention is particularly preferably N,N-dimethylformamide or N,N-dimethylacetamide.

(57) In the present invention, amide (B) may be a single kind of amide (B) or a combination of two or more kinds.

(58) The lower limit of the content of amide (B) in the composition of the present invention is preferably 0.01% (w/w), 0.05% (w/w), 0.1% (w/w), 0.5% (w/w), 1.0% (w/w), more preferably 3.0% (w/w), and further preferably 5.0% (w/w).

(59) In accomplishing the stabilization of acrylic acid derivative (A), the upper limit of the content of amide (B) in the composition of the present invention is not particularly limited; however, using amide (B) in an amount more than the amount ensuring the desired stabilization of acrylic acid derivative (A) is a disadvantage in terms of cost. Therefore, the upper limit of the content of amide (B) in the composition of the present invention is generally, for example, 50% (w/w), 40% (w/w), 30% (w/w), 20% (w/w), or 10% (w/w).

(60) The content of amide (B) in the composition of the present invention is preferably in a range of 0.01 to 50% (w/w), more preferably in a range of 1.0 to 40% (w/w), further preferably 5.0 to 30% (w/w), further more preferably in a range of 1 to 3% (w/w).

(61) In the composition of the present invention, the lower limit of the ratio of amide (B) to acrylic acid derivative (A) [amide (B)/acrylic acid derivative (A)] is preferably 0.01% (w/w), 0.05% (w/w), more preferably 0.1% (w/w), further preferably 0.5% (w/w), further more preferably 1.0% (w/w), particularly preferably 3.0%, more particularly preferably 5.0% (w/w).

(62) In accomplishing the stabilization of acrylic acid derivative (A), the upper limit of the ratio of amide (B) to acrylic acid derivative (A) [amide (B)/acrylic acid derivative (A)] is not particularly limited; however, using amide (B) in an amount more than the amount ensuring the desired stabilization of acrylic acid derivative (A) is a disadvantage in terms of cost. Therefore, the upper limit of the ratio of amide (B) to acrylic acid derivative (A) [amide (B)/acrylic acid derivative (A)] is generally, for example, 200% (w/w), 190% (w/w), 170% (w/w), 150% (w/w), 100% (w/w), 70% (w/w), 50% (w/w), 40% (w/w), or 30% (w/w).

(63) In the composition of the present invention, the ratio of amide (B) to acrylic acid derivative (A) is preferably in a range of 0.01 to 200% (w/w), more preferably in a range of 0.1 to 190% (w/w), further preferably 1 to 170% (w/w), further more preferably 3 to 50% (w/w), and particularly preferably in a range of 5 to 50% (w/w).

(64) Optional Components

(65) The composition of the present invention may contain optional components in addition to acrylic acid derivative (A) and amide (B). The optional components may be impurities that coexist with acrylic acid derivative (A) or amide (B) prepared for the production of the composition of the present invention.

(66) Examples of the optional components include water and organic solvents.

(67) In the composition of the present invention, since acrylic acid derivative (A) is stabilized by amide (B), the significance in using a polymerization inhibitor for the purpose of stabilizing acrylic acid derivative (A) is small; however, the composition of the present invention may contain a polymerization inhibitor as an optional component.

(68) As a method for preventing unintended polymerization reaction or the like, a method of using a polymerization inhibitor, such as the polymerization inhibitor disclosed in Patent Document 2, has been known. However, acrylic acid derivative (A) may be exposed to various conditions, for example, upon storage or at the time of use. Since the boiling points of versatile polymerization inhibitors greatly differ from that of an acrylic acid derivative, it is often difficult to make them coexist with an acrylic acid derivative. In this case, the polymerization inhibitors cannot fully exhibit the function.

(69) Stability of the Composition of the Present Invention

(70) In the composition of the present invention, acrylic acid derivative (A) is stabilized. More specifically, acrylic acid derivative (A) contained in the composition of the present invention has high stability.

(71) Specifically, for example, acrylic acid derivative (A) in the composition of the present invention is prevented from changing into a polymer or the like, compared with a case in which acrylic acid derivative (A) does not coexist with amide (B).

(72) In the present invention, the change of acrylic acid derivative (A) into a different substance may be analyzed, for example, using NMR analysis or the like. Further, for example, the change of acrylic acid derivative into a polymer may be easily detected by observation of a change of a colorless transparent solution of acrylic acid derivative into a solid, or the like.

(73) In the composition of the present invention, acrylic acid derivative (A) is stabilized by the coexistence with amide (B).

(74) A method for making the acrylic acid derivative coexist with a polymerization inhibitor has been known as a means for stabilizing an acrylic acid derivative.

(75) However, since acrylic acid derivative (A) may be exposed to various conditions, for example, upon storage or at the time of use, the coexistence of a polymerization inhibitor with an acrylic acid derivative may be difficult in some cases. In this case, the polymerization inhibitor cannot fully exhibit its function.

(76) In contrast, since amide (B) may have a boiling point similar to that of acrylic acid derivative (A), it is easy to make amide (B) coexist with acrylic acid derivative (A). Therefore, acrylic acid derivative (A) in the composition of the present invention is stable under various conditions.

(77) Production Method

(78) The composition of the present invention may be produced by mixing acrylic acid derivative (A), amide (B), and optional components using, for example, a usual method such as stirring. Some or all of amide (B) may be contained as an impurity or an additive in acrylic acid derivative (A) prepared for the production of the composition of the present invention.

(79) Method for Stabilizing Acrylic Acid Derivative (A)

(80) The method for stabilizing the acrylic acid derivative (acrylic acid derivative (A)) represented by Formula (I) of the present invention comprises making acrylic acid derivative (A) coexist with amide (amide (B)).

(81) The method for making acrylic acid derivative (A) coexist with amide (B) is not particularly limited. Examples of the method include:

(82) [1] a method of mixing acrylic acid derivative (A) and amide (B);

(83) [2] a method of producing amide (B) in a system containing acrylic acid derivative (A);

(84) [3] a method of producing acrylic acid derivative (A) in a system containing amide (B); and

(85) [4] a method of individually producing acrylic acid derivative (A) and amide (B) in a single system.

(86) The same explanation of acrylic acid derivative (A) as that regarding the composition of the present invention can be applied to acrylic acid derivative (A) used in the method for stabilizing acrylic acid derivative (A) of the present invention.

(87) The same explanation of amide (B) as that regarding the composition of the present invention can be applied to amide (B) used in the method for stabilizing acrylic acid derivative (A) of the present invention.

(88) In the method for stabilizing acrylic acid derivative (A) of the present invention, preferably, amide (B) is used at a predetermined ratio relative to acrylic acid derivative (A). The ratio is as described above regarding the composition of the present invention.

(89) The details of the method for stabilizing acrylic acid derivative (A) including the above matters can be understood from the above explanation regarding the composition of the present invention.

EXAMPLES

(90) The present invention is described below in more detail with reference to Examples. However, the present invention is not limited to these Examples.

Example 1

(91) 2-fluoroacryloyl fluoride purified by distillation was prepared.

(92) 0.23 g of N,N-dimethylacetamide and 9.92 g of 2-fluoroacryloyl fluoride were mixed, thereby preparing a sample composition. 9.9 g of 2-fluoroacryloyl fluoride purified by distillation was used as a control. They were both transparent liquids when prepared.

(93) The sample composition, and 2-fluoroacryloyl fluoride as a control were each placed individual sample bottles. Each bottle was closed with a cap and allowed to stand for a day at room temperature. Thereafter, the characteristics of the two samples were observed. The results revealed that a solid was observed in the control, whereas the sample composition containing N,N-dimethylacetamide and 2-fluoroacryloyl fluoride was a transparent liquid and no change in the characteristics was observed.

(94) This confirmed that N,N-dimethylacetamide stabilizes 2-fluoroacryloyl fluoride.

Example 2

(95) Each sample was prepared by adding N,N-dimethylformamide in an amount specified in Table 1 per 100 mass % of 2-fluoroacrylic acid methyl ester.

(96) The samples were placed in individual sample bottles. Each bottle was closed with a cap and allowed to stand for 5 hours at 60 C. Thereafter, the characteristics of each sample were observed. The results revealed that no change in characteristics was observed in any sample until after 3 hours. However, thereafter, the viscosity increased in 2-fluoroacrylic acid methyl ester in which N,N-dimethylformamide was not added (sample 2-1) (control), and this sample was completely solidified after 5 hours. In contrast, the characteristics of the sample compositions containing N,N-dimethylformamide and 2-fluoroacrylic acid methyl ester (sample 2-2 and sample 2-3) were not changed even after 5 hours.

(97) This confirmed that N,N-dimethylacetamide stabilizes 2-fluoroacrylic acid methyl ester.

(98) TABLE-US-00001 TABLE 1 Sample N,N-dimethylformamide (mass %) 2-1 0.0 2-2 3.0 2-3 5.0