Zwitterionic compound, method for producing the same, and vinyl ether compound

Abstract

To provide a novel zwitterionic compound having a vinyl ether skeleton and exhibiting high solubility in organic solvents.SOLUTION: The zwitterionic compound is represented by general formula (1) in the figure. In general formula (1), R1 and R2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms; L1 represents a divalent hydrocarbon group; L2 represents a divalent aliphatic hydrocarbon group; X represents SO3- or CO2-; and the total number of carbon atoms in L1, R1 and R2 is 8 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to zwitterionic compounds, a method for producing the same, and vinyl ether compounds. More specifically, the present invention relates to zwitterionic compounds having a vinyl ether skeleton, a method for producing the same, and vinyl ether compounds.

Background Art

[0002] A zwitterionic compound refers to a salt-type compound having an anionic group and a cationic group within one molecule. Zwitterionic compounds having a (meth)acrylic skeleton or a styrene skeleton are used as monomers, and their polymers are used in various fields such as inks, coating agents, adhesives, and medical materials.

[0003] For example, Patent Documents 1 and 2 disclose the use of a polymer produced from a zwitterionic compound having a (meth)acrylic skeleton as a coating agent. Patent Document 3 also discloses the use of a polymer obtained from a zwitterionic compound having a (meth)acrylic skeleton as a medical material (a non-bioadhesive material).

[0004] By the way, since the (meth)acrylic skeleton has a highly hydrolyzable ester bond or amide bond in the molecule, it is known to have a problem of low stability during long-term use, and zwitterionic compounds having a styrene skeleton have been proposed (see, for example, Patent Document 4). The present applicant has synthesized a zwitterionic compound having a vinyl ether skeleton in consideration of the long-term use stability of the polymer and proposed its use in fields such as inks, coating agents, adhesives, and medical materials (see, for example, Patent Document 5).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] The zwitterionic compound having a vinyl ether skeleton described in Patent Document 5 has high solubility in polar solvents such as water. However, the zwitterionic compound hardly dissolves in organic solvents such as acetonitrile at room temperature.

[0007] When producing a polymer from a zwitterionic compound, it is copolymerized with other polymerizable monomers to control physical properties such as hydrophobicity. Although other polymerizable monomers usually dissolve in organic solvents, they do not dissolve in water. Therefore, considering the production of a polymer, a zwitterionic compound having a vinyl ether skeleton with high solubility in an organic solvent is desirable.

[0008] Therefore, the problem to be solved by the present invention is to provide a novel zwitterionic compound having a vinyl ether skeleton with high solubility in an organic solvent. [Means for Solving the Problems]

[0009] The present applicant has found that, in the zwitterionic compound having a vinyl ether skeleton described in Patent Document 5, when the oxyalkylene chain is changed to a hydrocarbon chain, the solubility in an organic solvent increases, and the present invention has been completed.

[0010] According to the present invention, there are provided a zwitterionic compound and a method for producing the same, as shown below, and a vinyl ether compound used as a raw material for producing the zwitterionic compound.

[0011] [1] The zwitterionic compound represented by the following general formula (1).

[0012] [Chemical formula] (In general formula (1), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L 1 represents a divalent hydrocarbon group, L 2 represents a divalent aliphatic hydrocarbon group, X represents SO 3 - or CO 2 - , and the total number of carbon atoms of L 1 , R 1 and R 2 is 8 or more.)

[0013] [2] The zwitterionic compound according to [1], wherein R 1 and R 2 in the general formula (1) are each independently a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 8 carbon atoms.

[0014] [3] The zwitterionic compound according to [2], wherein R 1 and R 2 in the general formula (1) are each independently a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms.

[0015] [4] The zwitterionic compound according to [3], wherein R 1 and R 2 in the general formula (1) are each independently a linear alkyl group having 1 to 4 carbon atoms.

[0016] [5] The zwitterionic compound according to [1], wherein L 1 in the general formula (1) is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms.

[0017] [6] L in the general formula (1) 1 and L 2 are each independently a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, the zwitterionic compound according to [5] above.

[0018] [7] L in the general formula (1) 1 is an alkylene group having 2 to 6 carbon atoms, and L 2 is an alkylene group having 1 to 4 carbon atoms, the zwitterionic compound according to [6] above.

[0019] [8] A step of reacting an amino alcohol compound represented by the following general formula (2) with acetylene under basic conditions to obtain a vinyl ether compound represented by the following general formula (3); A step of reacting the vinyl ether compound with a sultone compound or a lactone compound to obtain a compound represented by the following general formula (1-1), a method for producing a zwitterionic compound.

[0020] [Chemical formula] (In the general formula (2), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, and L 1 represents a divalent hydrocarbon group, and the total number of carbon atoms of L 1 , R 1 and R 2 is 8 or more.)

[0021] [Chemical formula] (In the general formula (3), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, and L 1 represents a divalent hydrocarbon group, and the total number of carbon atoms of L 1 , R 1 and R 2 is 8 or more.)

[0022] [Chemical formula] (In general formula (1-1), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L 1 represents a divalent hydrocarbon group, L 2 represents a divalent aliphatic hydrocarbon group, and X represents SO 3 - or CO 2 - and the sum of the carbon numbers of L 1 , R 1 and R 2 is 8 or more.)

[0023] [9] The method for producing the zwitterion compound according to [8], wherein the sultone compound is a compound represented by the following general formula (4).

[0024] [Chemical formula] (In general formula (4), m1 represents an integer of 2 to 4.)

[0025]

[10] The method for producing the zwitterion compound according to [8], wherein the lactone compound is a compound represented by the following general formula (5).

[0026] [Chemical formula] (In general formula (5), m2 represents an integer of 1 to 6.)

[0027]

[11] A vinyl ether compound represented by the following general formula (3).

[0028] [Chemical formula] (In general formula (3), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L 1 represents a divalent hydrocarbon group, L 1 , R1 and R 2 The total number of carbon atoms of is 8 or more.)

Advantages of the Invention

[0029] The zwitterionic compound of the present invention is excellent in solubility in organic solvents. Further, the method for producing a zwitterionic compound of the present invention can easily produce a zwitterionic compound having excellent solubility in organic solvents. Furthermore, the vinyl ether compound of the present invention can be suitably used as a raw material for producing the zwitterionic compound of the present invention.

Brief Description of the Drawings

[0030]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Mode for Carrying Out the Invention

[0031] Hereinafter, the present invention will be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and exemplifications, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0032] In this specification, the numerical range indicated by "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stepwise descriptions. Also, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0033] In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, the term "step" includes not only an independent step but also this term even when it cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved.

[0034] Also, in this specification, the "aliphatic hydrocarbon group" includes any of those that can be linear, branched, and / or cyclic, unless otherwise specified. The "alicyclic hydrocarbon group" includes any of monocyclic, polycyclic, and spiro ring types. The "aromatic hydrocarbon group" includes a group in which a hydrocarbon group is bonded to an aromatic ring. In addition, when stereoisomers exist, all stereoisomers are included.

[0035] (1) Zwitterionic compound: An embodiment of the zwitterionic compound of the present invention is a zwitterionic compound represented by the following general formula (1).

[0036] [Chemical formula] (In general formula (1), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L 1 represents a divalent hydrocarbon group, L 2 represents a divalent aliphatic hydrocarbon group, X represents SO 3 - or CO 2 - and the total number of carbon atoms of L 1 , R 1 and R 2 is 8 or more.)

[0037] The zwitterionic compound represented by general formula (1) is a novel zwitterionic compound having a vinyl ether skeleton and having high solubility in organic solvents. Therefore, when the zwitterionic compound of this embodiment is copolymerized with other polymerizable monomers to produce a polymer with controlled physical properties such as hydrophobicity, it has high solubility in organic solvents, and it is easy to produce a zwitterionic polymer derived from the zwitterionic compound by a radical polymerization reaction.

[0038] In general formula (1), R 1 and R 2 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms. R 1 and R 2 are each independently preferably a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably each independently a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and particularly preferably each independently a linear alkyl group having 1 to 4 carbon atoms.

[0039] In general formula (1), L 1The divalent hydrocarbon group represented by is not particularly limited, but for example, it is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms, more preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 2 to 6 carbon atoms. L 1 By using the above-mentioned divalent hydrocarbon group as , the solubility of the zwitterionic compound in an organic solvent can be increased.

[0040] Also, in the general formula (1), L 2 The divalent aliphatic hydrocarbon group represented by is not particularly limited, but for example, it is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.

[0041] In the zwitterionic compound represented by the general formula (1), L 1 and L 2 are preferably divalent aliphatic hydrocarbon groups having 1 to 8 carbon atoms independently of each other, L 1 is an alkylene group having 2 to 6 carbon atoms, and L 2 is particularly preferably an alkylene group having 1 to 4 carbon atoms.

[0042] In the zwitterionic compound represented by the general formula (1), the total number of carbon atoms of L 1 , R 1 and R 2 in the general formula (1) is 8 or more. By configuring in this way, the solubility in an organic solvent can be effectively increased.

[0043] In the general formula (1), X represents SO 3 - or CO 2 - .

[0044] The zwitterionic compound represented by the general formula (1) is a polymerizable compound and can be used as a monomer. The polymer is not particularly limited and can be used in various fields such as inks, coating agents, adhesives, and medical materials, for example.

[0045] (2) Method for producing a zwitterionic compound: Next, an embodiment of the method for producing the zwitterionic compound of the present invention will be described. The method for producing the zwitterionic compound of this embodiment includes a step A of reacting an amino alcohol compound represented by the following general formula (2) with acetylene under basic conditions to obtain a vinyl ether compound represented by the following general formula (3), and a step B of reacting the obtained vinyl ether compound with a sultone compound or a lactone compound to obtain a compound represented by the following general formula (1-1).

[0046]

Chemical formula

[0047]

Chemical formula

[0048]

Chemical formula

[0049] According to the method for producing the zwitterionic compound of the present embodiment, the zwitterionic compound represented by the general formula (1) described above can be easily produced. Hereinafter, steps A and B in the method for producing the zwitterionic compound of the present embodiment will be described in more detail.

[0050] Step A is a step of reacting an amino alcohol compound represented by the above general formula (2) (hereinafter also referred to as "amino alcohol compound A") with acetylene under basic conditions to obtain a vinyl ether compound represented by the above general formula (3) (hereinafter also referred to as "vinyl ether compound B"). That is, step A is a step of vinylating amino alcohol compound A with acetylene to obtain vinyl ether compound B.

[0051] In the general formula (2) representing amino alcohol compound A, R 1 and R 2 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and L 1 represents a divalent hydrocarbon group. Further, in the general formula (3) representing vinyl ether compound B, R 1 and R 2 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and L 1 represents a divalent hydrocarbon group. R 1 , R 2 and L 1 in these general formulas (2) and (3) are the R 1 , R 2 and L in the general formula (1) described above1 It is the same as

[0052] In Step A, the reaction proceeds under basic conditions, that is, by maintaining the reaction system basic. The basicity in the reaction system can be achieved, for example, by adding a base to the reaction system. The base is not particularly limited, and examples include alkali metal compounds. Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and alcoholates obtained by reacting these hydroxides with alcohol. Particularly preferred bases include potassium hydroxide and potassium t-butoxide. There is no particular limitation on the amount of the base used. For example, it is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and particularly preferably 5 to 20 mol% based on the amino alcohol compound A.

[0053] The reaction temperature in Step A is not particularly limited, but is usually 50 to 200°C, preferably 90 to 200°C. From the viewpoint of the reaction rate, it is 100°C or higher, and from the viewpoints of economy and suppression of side reactions, it is more preferably 150°C or lower. When the reaction temperature exceeds 200°C, the partial pressure of the amino alcohol compound A increases, resulting in a decrease in the reaction efficiency, which is not preferable. On the other hand, when the reaction temperature is less than 50°C, the reaction efficiency between the amino alcohol compound A and acetylene decreases, which is not preferable.

[0054] Process A can be carried out in any reaction mode, i.e., continuous process, semi - continuous process or batch process, as long as the amino alcohol compound A can react with acetylene. In the continuous process, for example, the amino alcohol compound A, the basic compound and acetylene can be continuously supplied, and the reaction mixture can be continuously discharged. In the semi - continuous process, a part of the amino alcohol compound A, the basic compound and acetylene can be continuously supplied, and the reaction mixture can be continuously discharged. In the batch process, a part of the amino alcohol compound A, the basic compound and acetylene can be charged into the reactor in advance in the total amount, and the reaction mixture can be discharged after the reaction is completed. In each of the above - mentioned processes, for example, a specific solvent may be further added. Examples of the solvent include dimethyl sulfoxide, dimethylimidazolidinone, N - methylpyrrolidone, and glyme - based solvents.

[0055] The supply pressure of acetylene is not particularly limited, but it is preferably 0.01 MPa (gauge pressure) or more, and more preferably 0.15 MPa (gauge pressure) or more and 1.0 MPa or less from the viewpoints of productivity, suppression of side reactions and safety.

[0056] Next, as Process B, the vinyl ether compound B obtained in Process A is reacted with a sultone compound or a lactone compound to obtain the compound represented by the above general formula (1 - 1). The compound represented by the general formula (1 - 1) thus obtained is the zwitterionic compound represented by the general formula (1) described above. R in the general formula (1 - 1) 1 , R 2 , L 1 and L 2 are the same as R 1 , R 2 , L 1 and L 2 in the general formula (1) described above.

[0057] In step B, first, it is preferable to dissolve the obtained vinyl ether compound B in a solvent. The type of the solvent can be appropriately selected according to the type of the obtained vinyl ether compound B (i.e., the vinyl ether compound represented by the general formula (3)), and is not particularly limited, but it is preferably an anhydrous solvent. For example, as the anhydrous solvent, super dehydrated acetone and super dehydrated methyl ethyl ketone (MEK) can be mentioned. Further, the reaction in step B is preferably carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.

[0058] Next, a sultone compound or a lactone compound is added to the solution in which the vinyl ether compound B is dissolved. There is no particular limitation on the addition amount of the sultone compound or the lactone compound. For example, it is preferably 0.95 to 1.10 equivalents, more preferably 1.00 to 1.05 equivalents, and particularly preferably 1.01 to 1.03 equivalents with respect to the amino alcohol compound A.

[0059] After adding the sultone compound or the lactone compound, the solution in which the vinyl ether compound B is dissolved may be heated. For example, after adding the sultone compound or the lactone compound at 10°C over 30 to 60 minutes, it may be heated to room temperature over about 1 hour, and further heated from room temperature to the reflux state over 30 to 90 minutes to carry out the reaction.

[0060] As described above, the vinyl ether compound B is reacted with the sultone compound or the lactone compound to obtain the compound represented by the above general formula (1-1).

[0061] There is no particular limitation on the sultone compound and the lactone compound used in step B, but the sultone compound is preferably a compound represented by the following general formula (4), and the lactone compound is preferably a compound represented by the following general formula (5).

[0062]

Chemical formula

[0063] [Chemical Formula] (In General Formula (5), m2 represents an integer from 1 to 6.)

[0064] For example, examples of the sultone compound represented by General Formula (4) include 1,2 - ethanesultone, 1,3 - propanesultone, and 1,4 - butanesultone. Examples of the lactone compound represented by General Formula (5) include α - acetolactone, β - propiolactone, γ - butyrolactone, δ - valerolactone, ε - caprolactone, and the like.

[0065] The compound represented by General Formula (1 - 1) produced by the method for producing an amphoteric ion compound of the present embodiment is less likely to hydrolyze, has excellent stability, is less likely to self - polymerize, and also has excellent stability compared to conventional amphoteric ion monomers. In addition, the compound represented by General Formula (1 - 1) has high solubility in organic solvents, and it is easy to produce an amphoteric ion polymer derived from the amphoteric ion compound by a radical polymerization reaction.

[0066] (3) Vinyl ether compound: Next, an embodiment of the vinyl ether compound of the present invention will be described. The vinyl ether compound of the present embodiment is a vinyl ether compound represented by the above General Formula (3). That is, the vinyl ether compound of the present embodiment is the vinyl ether compound B obtained in Step A of the method for producing an amphoteric ion compound described above. Such a vinyl ether compound represented by General Formula (3) can be suitably used as a raw material for producing an amphoteric ion compound represented by General Formula (1). Specifically, an amphoteric ion compound represented by General Formula (1) can be produced by reacting the vinyl ether compound represented by General Formula (3) with a sultone compound or a lactone compound.

Examples

[0067] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited in any way by these examples. In the examples, “%” is based on mass unless otherwise specified.

[0068] The types of analytical instruments used for measurement are shown below. [NMR]: “JNM-ECZ400R / S1 (trade name)”, manufactured by JEOL Ltd. Heavy solvent: DMSO-d 6 Or D 2 O

[0069] [Gas chromatography (GC)]: “GC-2030 (trade name)”, manufactured by Shimadzu Corporation

[0070] (Production Example 1: Synthesis of vinyl ether compound) Into a 300 ml SUS pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, a gas inlet tube, and a gas purge line, 150 g (1.04 mol) of N,N-dimethylaminohexanol with a purity of ≧99% and 7.90 g (0.14 mol) of potassium hydroxide with a purity of 95.0% were charged. Nitrogen gas was passed through for about 10 minutes under stirring, and the inside of the vessel was replaced with nitrogen. After switching the nitrogen gas to acetylene gas and similarly replacing the inside of the vessel with acetylene gas, the reaction vessel was sealed, and acetylene gas was pressured into the vessel at a pressure of 0.180 MPa. Then, while maintaining the gauge pressure at 0.180 MPa, the temperature was gradually increased and controlled to maintain the temperature inside the reaction vessel at 140 °C, and the reaction was carried out for about 9 hours and 30 minutes. During this period, acetylene gas was sequentially replenished to keep the pressure inside the reaction vessel constantly at 0.180 MPa. After the reaction was completed, the remaining acetylene gas was purged to obtain 181 g of a reaction solution. As a result of gas chromatography analysis, the conversion of N,N-dimethylaminohexanol proceeded quantitatively, and the selectivity for 6-(dimethylamino)hexyl vinyl ether was 98%.

[0071] Next, this reaction solution was distilled under reduced pressure (22 mmHg), and 137 g of the fraction distilled at a column top temperature of 106 °C was collected. As a result of analysis by NMR, it was 6-(dimethylamino)hexyl vinyl ether represented by the following formula (6). The distillation started at a column top temperature of 103 °C and the column top temperature became constant at 106 °C, so the flask was changed to the main distillation flask. The main distillation was carried out at a column top temperature of 106 °C, and the reduced pressure was released when the column top temperature reached 75 °C or lower, and the distillation was completed. The main distillation was almost only the target product, and the yield was 137 g (yield: 78%, GC purity: 99.6%). Using a 400 MHz NMR apparatus, the NMR (DMSO-d 6 ) of 6-(dimethylamino)hexyl vinyl ether was measured. 1 The 1H-NMR chart is shown in Figure 1, 13 and the 13C-NMR chart is shown in Figure 2.

[0072]

Chemical formula

[0073] (Production Example 2: Synthesis of vinyl ether compound) Into a 300 ml SUS pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, a gas inlet tube, and a gas purge line, 100 g (0.58 mol) of N,N-dibutylaminoethanol with a purity of ≧99% and 5.35 g (0.10 mol) of potassium hydroxide with a purity of 95.0% were charged, and nitrogen gas was passed through for about 10 minutes under stirring to replace the inside of the vessel with nitrogen. The nitrogen gas was switched to acetylene gas, and after similarly replacing the inside of the vessel with acetylene gas, the reaction vessel was sealed, and acetylene gas was pressured into the vessel at a pressure of 0.180 MPa. Next, while maintaining the gauge pressure at 0.180 MPa, the temperature was gradually increased and controlled to maintain the internal temperature of the reaction vessel at 140 °C, and the reaction was carried out for about 5 hours and 20 minutes. During this time, acetylene gas was sequentially replenished to always maintain the pressure inside the reaction vessel at 0.180 MPa. After the reaction was completed, the remaining acetylene gas was purged to obtain 118 g of a reaction solution. As a result of gas chromatography analysis, the conversion of N,N-dibutylaminoethanol proceeded quantitatively, and the selectivity of 2-(dibutylamino)ethyl vinyl ether was 99%.

[0074] Next, the reaction solution was distilled under reduced pressure (14 mmHg), and 137 g of the fraction distilled at a top temperature of 102 °C was collected. As a result of analysis by NMR, it was 2-(dibutylamino)ethyl vinyl ether represented by the following formula (7). The distillation started at a top temperature of 99 °C, and since the top temperature became constant at 102 °C, it was changed to the flask for the main distillate. The main distillate was distilled at a top temperature of 102 °C, and when the distillation ended, the reduced pressure was released to complete the distillation. The main distillate was almost only the target product, and the yield was 79 g (yield: 67%, GC purity: 99.6%). Using a 400 MHz NMR apparatus, the NMR (DMSO-d 6 ) of 2-(dibutylamino)ethyl vinyl ether was measured. 1 The 1H-NMR chart is shown in Figure 3, 13 and the 13C-NMR chart is shown in Figure 4.

[0075]

Chemical formula

[0076] (Example 1: Synthesis of zwitterionic compound (1)) Into a reaction vessel equipped with a stirrer, 8.6 g (50 mmol) of 6-(dimethylamino)hexyl vinyl ether obtained in Production Example 1 and 30 ml of super-dehydrated acetone were charged and cooled to 10 °C. Then, a solution prepared by dissolving 6.4 g (52.5 mmol) of propane sultone in 20 ml of super-dehydrated acetone was added dropwise. The temperature was gradually raised to room temperature and reacted for 72 hours. Approximately 50 ml of super-dehydrated acetone was added, and the white solid precipitated under a nitrogen atmosphere was separated by filtration and washed twice with 20 ml of super-dehydrated acetone. Then, by drying under reduced pressure at 50 °C, 14.2 g of the zwitterionic compound (1) represented by the following formula (8) was obtained. The yield was 97%. Using a 400 MHz NMR apparatus, the NMR (DMSO-d 6 ) of the zwitterionic compound (1) was measured. 1 The 1H-NMR chart is shown in Figure 5, 13 and the 13C-NMR chart is shown in Figure 6.

[0077]

Chemical formula

[0078] (Example 2: Synthesis of Zwitterionic Compound (2)) Into a reaction vessel equipped with a stirrer, 8.6 g (50 mmol) of 6-(dimethylamino)hexyl vinyl ether obtained in Production Example 1 and 30 ml of ultra-dehydrated methyl ethyl ketone (hereinafter referred to as "MEK") were charged and cooled to 10°C. Then, a solution prepared by dissolving 7.1 g (52.5 mmol) of butanesultone in 20 ml of ultra-dehydrated MEK was added dropwise. The temperature was gradually raised to the temperature for heating under reflux (about 80°C) and the reaction was carried out for 24 hours. Approximately 50 ml of ultra-dehydrated MEK was added and the mixture was gradually cooled to room temperature. The white solid precipitated under a nitrogen atmosphere was separated by filtration and washed twice with 20 ml of ultra-dehydrated MEK. Then, by drying under reduced pressure at 50°C, 11.4 g of the zwitterionic compound (2) represented by the following formula (9) was obtained. The yield was 78%. Using a 400 MHz NMR apparatus, the NMR (DMSO-d 6 ) of the zwitterionic compound (2) was measured. 1 The 1H-NMR chart is shown in Fig. 7, 13 and the 13C-NMR chart is shown in Fig. 8.

[0079] [Chemical formula]

[0080] (Example 3: Synthesis of Zwitterionic Compound (3)) 8.5 g (50 mmol) of 6-(dimethylamino)hexyl vinyl ether obtained in Production Example 1 and 30 ml of super-dehydrated acetone were charged into a reaction vessel equipped with a stirring device, and the mixture was cooled to 10°C. Then, 3.8 g (52.5 mmol) of β-propiolactone was added dropwise over 30 to 60 minutes. The temperature was gradually raised to room temperature, and the mixture was reacted for 24 hours. Approximately 50 ml of super-dehydrated acetone was added, and the white solid precipitated under a nitrogen atmosphere was separated by filtration and washed twice with 20 ml of super-dehydrated acetone. Then, by drying under reduced pressure at 50°C, 6.5 g of the zwitterionic compound (3) represented by the following formula (10) was obtained. The yield was 88%. Using a 400 MHz NMR apparatus, the NMR (D 2 O) of the zwitterionic compound (3) was measured. 1 The 1H-NMR chart is shown in Fig. 9, 13 and the 13C-NMR chart is shown in Fig. 10.

[0081]

Chemical formula

[0082] (Example 4: Synthesis of zwitterionic compound (4)) 10.0 g (50 mmol) of 2-(dibutylamino)ethyl vinyl ether obtained in Production Example 2 and 30 ml of super-dehydrated acetone were charged into a reaction vessel equipped with a stirring device, and the mixture was cooled to 10°C. Then, a solution prepared by dissolving 6.4 g (52.5 mmol) of propane sultone in 20 ml of super-dehydrated MEK was added dropwise. The temperature was gradually raised to heating under reflux, and the mixture was reacted for 24 hours. Approximately 50 ml of super-dehydrated acetone was added and gradually cooled to room temperature. The white solid precipitated under a nitrogen atmosphere was separated by filtration and washed twice with 20 ml of super-dehydrated acetone. Then, by drying under reduced pressure at 50°C, 12.1 g of the zwitterionic compound (4) represented by the following formula (11) was obtained. The yield was 75%. Using a 400 MHz NMR apparatus, the NMR (D 2 O) of the zwitterionic compound (4) was measured. 1 The 1H-NMR chart is shown in Fig. 11, 13 and the 13C-NMR chart is shown in Fig. 12.

[0083]

Chemical formula

[0084] (Measurement of Solubility) For 1 g each of the zwitterionic compounds (1) synthesized in Example 1, the zwitterionic compound (2) synthesized in Example 2, and the zwitterionic compound (4) synthesized in Example 4, various solvents at 20 °C were added, and the solubility was evaluated according to the following criteria. Further, as a comparative example, a zwitterionic compound (5) of the following formula (12) was synthesized in the same manner as in Example 3 of the above Patent Document 5 (Japanese Patent Application Laid-Open No. 2021-155409), and various solvents at 20 °C were added to 1 g of the synthesized zwitterionic compound (5) of the following formula (12), and the solubility was similarly evaluated according to the following criteria. The evaluation results are shown in Table 1. A: Dissolves more than 25% by mass. B: Dissolves more than 9% by mass and 25% by mass or less. C: Dissolves more than 2.5% by mass and 9% by mass or less. D: Dissolves more than 0.5% by mass and 2.5% by mass or less. E: Dissolves 0.5% by mass or less or does not dissolve.

[0085]

Chemical Formula

[0086]

Table 1

[0087] As can be seen from Table 1, the zwitterionic compounds (1), (2) and (4) corresponding to the zwitterionic compound represented by the general formula (1) above were highly soluble not only in polar solvents but also in acetonitrile. In particular, the zwitterionic compound (4) was highly soluble in acetonitrile. On the other hand, the zwitterionic compound (5) represented by the above formula (12) synthesized by the conventional method was highly soluble in polar solvents but had low solubility in acetonitrile. The applicant of the present application has confirmed that a polymer can be produced by performing a radical polymerization reaction with a maleimide compound in acetonitrile using the zwitterionic compound (1), (2) or (4) corresponding to the present invention.

Industrial Applicability

[0088] The zwitterionic compound of the present invention can be used as a monomer, and the polymer thereof can be used in various fields such as inks, coating agents, adhesives, and medical materials.

Claims

1. A zwitterionic compound represented by the following general formula (1). 【Chemical 1】 (In general formula (1), R １ and R ２ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L １ represents a divalent hydrocarbon group, L ２ represents a divalent aliphatic hydrocarbon group, X represents SO ３ － or CO ２ － and the total number of carbon atoms of L １ , R １ and R ２ is 8 or more.)

2. R in the general formula (1) above １ and R ２ are each independently a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 8 carbon atoms. The zwitterionic compound according to claim 1.

3. R in the general formula (1) above １ and R ２ are, independently of each other, a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms. The zwitterionic compound according to claim 2.

4. R in the general formula (1) above １ and R ２ are each independently a linear alkyl group having 1 to 4 carbon atoms, the zwitterionic compound according to claim 3.

5. L in the general formula (1) １ The zwitterionic compound according to claim 1, wherein L is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms.

6. L in the general formula (1) above １ and L ２ are each independently a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, the zwitterionic compound according to claim 5.

7. L in the general formula (1) above １ is an alkylene group having 2 to 6 carbon atoms, and L ２ is an alkylene group having 1 to 4 carbon atoms. The zwitterionic compound according to claim 6

8. A step of reacting an amino alcohol compound represented by the following general formula (2) with acetylene under basic conditions to obtain a vinyl ether compound represented by the following general formula (3); A method for producing a zwitterionic compound, comprising: reacting the vinyl ether compound with a sultone compound or a lactone compound to obtain a compound represented by the following general formula (1-1). 【Chemical 2】 (In general formula (2), R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, L １ represents a divalent hydrocarbon group, and the total number of carbon atoms in L １ , R １ and R ２ is 8 or more.) 【Chemical Formula 3】 (In general formula (3), R １ and R ２ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L １ represents a divalent hydrocarbon group, L １ , R １ and R ２ have a total carbon number of 8 or more.) 【Chemical Formula 4】 (In general formula (1-1), R １ and R ２ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L １ represents a divalent hydrocarbon group, L ２ represents a divalent aliphatic hydrocarbon group, X represents SO ３ － or CO ２ － and the total number of carbon atoms of L １ , R １ and R ２ is 8 or more.)

9. The method for producing a zwitterionic compound according to claim 8, wherein the sultone compound is a compound represented by the following general formula (4). 【Chemical Formula 5】 (In general formula (4), m1 represents an integer of 2 to 4.)

10. The method for producing a zwitterionic compound according to claim 8, wherein the lactone compound is a compound represented by the following general formula (5). 【Chemical Formula 6】 (In general formula (5), m2 represents an integer of 1 to 6.)

11. A vinyl ether compound represented by the following general formula (3). [Chemical Formula 7] (In general formula (3), R １ and R ２ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, L １ represents a divalent hydrocarbon group, and the total number of carbon atoms in L １ , R １ and R ２ is 8 or more.)

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