PRECURSOR OF (METH)ACRYLAMIDE COMPOUND

FIELD OF THE INVENTION

The present invention relates to a compound which is a precursor of a (meth)acrylamide compound.

BACKGROUND OF THE INVENTION

(Meth)acrylamides are polymerizable compounds showing high reactivity. These compounds are widely utilized as a raw material or a crosslinking agent of various kinds of synthetic resins in an industrial application such as a coating material, paint, printing ink, an adhesive, and a resist material. For example, an ink composition containing the (meth)acrylamides as a radical polymerizable compound is described in JP-A-2005-307198 ("JP-A" means unexamined published Japanese patent application). The (meth)acrylamides are generally obtained by reacting an amine compound with a (meth)acrylate. However, the method results in low yield because an alkylamine compound further reacts with a (meth)acrylic group of an amidated compound thus obtained, or this is further amidated.

Further, methods for producing (meth)acrylamides by reacting an alkylamine with an alkyl acid alkyl to convert them into an aminoamide (amide adduct), and thermally decomposing the resultant or adjusting a concentration of a monoalkylamine are known (for example, JP-A-4-208258 and U.S. Patent No. 2,683,741). However, these methods still have a problem of suppressing by-products when a plurality of (meth)acrylamide groups are included in one molecule. Under the circumstances, a novel precursor (synthetic intermediate) for efficiently producing a compound that has a plurality of (meth)acrylamide groups and that is useful for the raw material or the crosslinking agent for various kinds of synthetic resins, particularly the ink composition, has been desired.

SUMMARY OF THE INVENTION

The present invention resides in a compound represented by formula (1): wherein in formula (1), Z represents a residue obtained by removing n hydrogen atoms from hydroxyl groups of a polyol; n represents an integer of 3 to 6; R1 represents a hydrogen atom or a methyl group; R2 represents an alkylene group having 1 to 8 carbon atom(s); X1 represents a halogen atom; and a plurality of R's, R2S, and X's may be the same or different from each other. Other and further objects, features and advantages of the invention will appear more fully from the following description, appropriately referring to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWING

Fig. 1 is a !H-NMR spectrum chart of the exemplified compound (1) synthesized in Example 1 as described later.

Fig. 2 is a 13C-NMR spectrum chart of the exemplified compound (1) synthesized in Example 1.

Fig. 3 is an IR spectrum chart of the exemplified compound (1) synthesized in Example 1.

Fig. 4 is a MS spectrum chart of the exemplified compound (1) synthesized in Example 1.

Fig. 5 is a 'H-NMR spectrum chart of the exemplified compound (2) synthesized in Example 2 as described later.

Fig. 6 is a l3C-NMR spectrum chart of the exemplified compound (2) synthesized in Example 2.

Fig. 7 is a IR spectrum chart of the exemplified compound (2) synthesized in Example 2.

Fig. 8 is a MS spectrum chart of the exemplified compound (2) synthesized in Example 2.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have found that a compound can be used as a synthetic precursor of a (meth)acrylamide compound, and that a higher yield can be achieved according to a synthetic method through the precursor, as compared with the conventional method. The present invention has been completed based on the finding. According to the present invention, there is provided the following means:

< 1 > A compound represented by formula (1): wherein in formula (1), Z represents a residue obtained by removing n hydrogen atoms from hydroxyl groups of a polyol; n represents an integer of 3 to 6; R1 represents a hydrogen atom or a methyl group; R2 represents an alkylene group having 1 to 8 carbon atom(s); X1 represents a halogen atom; and a plurality of R's, R2s, and X's may be the same or different from each other.

<2> The compound according to the above item <1>, wherein the compound is a synthetic intermediate of a (meth)acrylamide compound represented by formula (A):wherein in formula (A), Z represents a residue obtained by removing n hydrogen atoms from hydroxyl groups of a polyol; n represents an integer of 3 to 6; R1 represents a hydrogen atom or a methyl group; R2 represents an alkylene group having 1 to 8 carbon atom(s); and a plurality of R!s and R2s may be the same or different from each other.

In the present specification, the term "(meth)acrylamide" means acrylamide and/or methacrylamide. Further, in the present specification, "to" denotes a range including numerical values described before and after it as a minimum value and a maximum value. [Precursor compound] The compound of the present invention is represented by the following formula (1), and can be used as the precursor (synthetic intermediate) for synthesizing the polymerizable compound such as the (meth)acryl amide compound. In formula (1), Z represents a residue obtained by removing n hydrogen atoms from hydroxyl groups of a polyol. The polyol is preferably a polyhydric alcohol having 3 to 6 hydroxyl groups, more preferably a polyhydric alcohol having 3 to 5 hydroxyl groups, and still more preferably a polyhydric alcohol having 3 to 4 hydroxyl groups. The polyol preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 6 carbon atoms. Moreover, the polyol may be a polyhydric alcohol condensate compound formed by intermolecular condensation (dehydration) of two or more molecules of polyhydric alcohol compounds.

Specific examples of the polyol include glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, xylitol, sorbitol, erythritol, pentaerythritol, dipentaerythritol, mannitol, and tris(2-hydroxyethyl)isocyanurate. Among the polyols, glycerin, erythritol, or pentaerythritol is preferable. In formula (1), n represents an integer of 3 to 6. n is preferably an integer of 3 to 5, and more preferably an integer of 3 to 4. In formula (1), R1 represents a hydrogen atom or a methyl group. R! is preferably a hydrogen atom. A plurality of R*s may be the same or different from each other, and preferably the same. In formula (1), R2 represents an alkylene group having 1 to 8 carbon atom(s). The alkylene group may be a straight or branched chain. R2 is preferably an alkylene group having 2 to 5 carbon atom(s), and more preferably an alkylene group having 3 to 4 carbon atom(s). A plurality of R2s may be the same or different from each other, and preferably the same.

In formula (1), X1 represents a halogen atom. X1 is preferably a iodine atom, a bromine atom or a chlorine atom, and particularly preferably a chlorine atom. A plurality of X's may be the same or different from each other, and preferably the same. The compound represented by formula (1) is particularly preferably a compound represented the following formula (2) or formula (3). In formula (2) and formula (3), R1 and X1 each have the same meanings as those of R1 and X1 in formula (1) and preferable range of R1 and X1 are also the same as those of R1 and X1 in formula (1). A plurality of RJs and X's may be the same or different from each other. Hereinafter, specific examples of the compound represented by formula (1) in the present invention are shown, but the present invention is not limited thereto.

[Synthetic method of the precursor compound]

Specific examples of the method for synthesizing the compound represented by formula (I) include the following general synthetic methods using an amine compound as a starting material.

• Synthetic method 1 A method in which an amine compound is allowed to react with an acid halide compound in the presence of a base.

• Synthetic method 2 A method in which an amine compound is allowed to react with a carboxylic acid compound and a condensing agent in the presence of a base.

• Synthetic method 3 A method for synthesizing the precursor compound according to an ester-amide exchange reaction by heating an amine compound and an ester compound.

These reactions can be performed according to a method described in Shin Jikken Kagaku Koza (New Experimental Chemistry Course) 14, Synthesis and Reaction of Organic Compounds (V), 11.6: Protection of Amino Groups, pp. 2555 to 2569. Examples of an amine compound used in the above-described synthetic method include the following compounds. These amine compound may be used from a commercial product, or may be synthesized according to the generally known reaction (for example, the substitution reaction of amine; the reduction reaction of nitro, azide, or nitrile; the hydrolysis reaction of amide, imine, or isocyanate) by using the compound that can be the synthetic precursor of the amine compound.

In particular, a commercially available polyol can be synthesized by converting -OH as a hydroxyl group of the polyol into -OCH2(CR')CN with (meth)acrylonitrile, and then reducing the obtained nitrile group to form -OQ^CR1) CH2NH2. Herein, R1 represents a hydrogen atom or a methyl group. Specific examples are shown hereinafter. [Method for synthesizing a (meth)acrylamide compound using a precursor compound] The compound represented by formula (I) according to the present invention can be used as a precursor for synthesizing a (meth)acrylamide compound represented by formula (A). In formula (A), Z represents a residue obtained by removing n hydrogen atoms from hydroxyl groups of a polyol; n represents an integer of 3 to 6; R1 represents a hydrogen atom or a methyl group; R2 represents an alkylene group having 1 to 8 carbon atom(s); and a plurality of R's and R2s may be the same or different from each other.

In synthesis of the (meth)acrylamide compound using the compound represented by the formula (1) of the present invention (hereinafter, the compound is referred to as the precursor compound of the present invention), for example, the (meth)acrylamide compound can be obtained by allowing a base (an organic base and/or an inorganic base) to act on the precursor compound of the present invention, and forming a carbon-to-carbon double bond at a terminal according to an elimination reaction between X1 of the precursor and a hydrogen atom bound to the carbon atom to which R1 is bonded. In the following synthetic scheme 1, a specific example of a method is shown for synthesizing a precursor compound of the present invention [a compound represented by formula (2) in the following scheme] from an amine compound, and further synthesizing a (meth)acrylamide compound 1 from the precursor. In addition, R1 and X1 in the following synthetic scheme have the same meanings as those of R1 and X1 in formula (2) as described above.

Synthetic scheme 1

According to the above synthetic scheme, first, glycerin is used as a starting material (A) to allow a hydroxyl group of glycerin to react with acrylonitrile or methacrylonitrile, and thus a (meth)acrylonitrile adduct is obtained as an intermediate (B). Next, the intermediate (B) obtained is allowed to react with hydrogen in the presence of a catalyst, and thus an amine form as an intermediate (C) is obtained according to a hydrogenation reaction. The intermediate (C) obtained is further allowed to react with 3-chloropropionic acid chloride or 3-chloro-2-methylpropionic acid chloride to perform amidation, and thus a compound represented by formula (2) as a precursor compound of the present invention can be obtained. As an amidating agent, di 3-chloropropionic anhydride or di 3-chloro-2-methylpropionic acid anhydride may be used in place of the above acid chloride.

When both 3-chloropropionic acid chloride and 3-chloro-2-methylpropionic acid chloride are used in the above amidation process, a compound represented by formula (2) having both a 3-chloropropionic acid amide group and a 3-chloro-2-methylpropionic acid amide group in the same molecule can be obtained as a final product. Finally, the (meth)acrylamide compound 1 can be derived from the compound represented by formula (2) by allowing a base to act on the compound. In the above synthetic scheme 1, the process from (A) to (B) is preferably performed at 0 to 60°C for 30 minutes to 8 hours, the process from (B) to (C) is preferably performed at 20 to 45°C for 2 hours to 16 hours, the process from (C) to the compound represented by formula (2) is preferably performed at 0 to 30°C for 30 minutes to 6 hours, and a process for synthesizing the (meth)acrylamide compound 1 from the compound represented by formula (2) is preferably performed at 0°C to 60°C for 1 hour to 12 hours. The precursor compound of the present invention and the (meth)acrylamide compound as the final compound can be isolated and collected from a reaction production mixture according to an ordinary method. The compounds can be isolated, for example, by extraction with an organic solvent, crystallization using a poor solvent, column chromatography using silica gel.

A compound represented by formula (3) and a (meth)acrylamide compound derived from the compound can also be synthesized in a manner similar to the case of the compound represented by formula (2) except that a starting material is changed from glycerin to pentaerythritol in the above-described scheme 1. The precursor compound of the present invention can be easily converted into the (meth)acrylamide compound. According to a synthetic reaction of the (meth)acrylamide compound through the precursor compound of the present invention as the synthetic intermediate as shown in the above-described synthetic scheme, the (meth)acrylamide compound as the final product can be obtained with a high yield. The synthetic reaction through the precursor compound of the present invention as the intermediate can produce the (meth)acrylamide compound with a high yield, as compared with a general synthetic method in which the (meth)acrylamide compound is synthesized by allowing (meth)acrylic acid chloride or (meth)acrylic anhydride to react with an amine compound under basic conditions.

The (meth)acrylamide compound as obtained by the precursor compound of the present invention polymerizes by light or heat to show hardening properties. Therefore, the (meth)acrylamide compound can be used in various applications as a radical polymerizable compound. In particular, the compound represented by formula (A) as obtained by the compound represented by formula (I) of the present invention is useful as a crosslinking agent or a curing agent for a photosensitive resin composition or inkjet ink. For example, when the compound is used in Examples as described in JP-A-2011-214001, JP-A-2011-248354, or JP-A-2012-32556, an effect as described in these documents is exhibited. According to the present invention, it is possible to provide a compound useful as a precursor for synthesizing a (meth)acrylamide compound. The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. In the following Examples, the terms "part" and "%" with respect to the composition are values by mass, unless they are indicated differently in particular.

EXAMPLES A compound in which R1 is H, and X1 is CI (chlorine atom) in the formula (2) was synthesized as follows. Hereinafter, the compound is referred to as an exemplified compound (1).

Exemplified compound (1) Synthesis of exemplified compound (1) In a 1 L volume autoclave, 40 g of 1,2,3-tris (2-cyano-ethoxy) propane (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 wt % of Co catalyst (Raney Cobalt 2700, made by W. R. Grace & Co.), and 600 mL of solution (25% aqueous ammonia: methanol = 1:1) were put, the resultant mixture was suspended, and a reaction vessel was sealed. Hydrogen at 10 MPa was introduced into the reaction vessel, and a reaction was allowed at a reaction temperature of 25°C for 16 hours. Disappearance of the raw materials was confirmed by means of !H NMR, the reaction mixture was subjected to Celite filtration, and the Celite filter was washed with methanol several times. A solvent was distilled off from the filtrate under reduced pressure, and thus an intermediate (C) was obtained. The intermediate (C) obtained was used for the next reaction without further purification. To a 2 L volume three-necked flask equipped with a stirrer, 26.3 g of intermediate (C), 35.35 g (3.5 equivalents) of triethylamine, and 1 L of acetonitrile were added, and 41.57 g (3.3 equivalents) of 3-chloropropionic acid chloride was added dropwise over 2 hours in an ice bath, and then the resultant mixture was stirred at room temperature for 1 hour.

Disappearance of the raw materials was confirmed by means of 'H-NMR, a solvent was distilled off from the reaction mixture under reduced pressure, and the resultant product was subjected to Celite filtration, and the solvent was again distilled off under reduced pressure. Finally, the resultant product was purified by means of column chromatography (ethyl acetate : methanol = 4 : 1), and thus a white solid at normal temperature was obtained (yield: 60%). The white solid obtained was identified by means of 'H-NMR, 13C-NMR, IR, and MS under the following measuring conditions. Identified data are shown in Figs. lto4. [H-NMR Solvent: deuterochloroform, Internal standard: TMS 13C-NMR Solvent: deuterochloroform, Internal standard: TMS IR A spectrum was measured according to a potassium bromide (KBr) tablet method, and converted into absorbance. MS Solvent: MeOH/H20 = 9/1, 10 mM CH3COONH4 As a result of the above identification, the white solid was confirmed to have a structure of the exemplified compound (1).

Example 2

A compound in which R1 is H, and X1 is CI (chlorine atom) in the formula (3) was synthesized as follows. Hereinafter, the compound is referred to as an exemplified compound (2). Synthesis of exemplified compound (2) The following intermediate (C) was synthesized according to the method as described in WO 2009/154747, or a method equivalent thereto. To a 2 L volume three-necked flask equipped with a stirrer, 36.4 g of intermediate (C), 48.48 g (4.8 equivalents) of triethylamine, and 1 L of acetonitrile were added, and 55.42 g (4.4 equivalents) of 3-chloropropionic acid chloride was added dropwise over 2 hours in an ice bath, and then the resultant mixture was stirred at room temperature for 1 hour. Disappearance of the raw materials was confirmed by means of ^-NMR, a solvent was distilled off from the reaction mixture under reduced pressure, and the resultant product was subjected to Celite filtration, and the solvent was again distilled off under reduced pressure. Finally, the resultant product was purified by means of column chromatography (ethyl acetate : methanol = 4.5 : 1), and thus a white solid at normal temperature was obtained (yield: 53%).

The white solid obtained was identified by means of 'H-NMR, I3C-NMR, IR, and MS under the following measuring conditions. Identified data are shown in Figs. 5 to 8. !H-NMR

Solvent: deuterochloroform, Internal standard: TMS 13C-NMR

Solvent: deuterochloroform, Internal standard: TMS IR

A spectrum was measured according to a potassium bromide (KBr) tablet method, and converted into absorbance. MS

Solvent: MeOH/H20 = 9/1, 10 mM CH3COONH4

As a result of the above identification, the white solid was confirmed to have a structure of the exemplified compound (2). Reference example: Derivation of Acrylamide Compound from exemplified Compound (1) or exemplified compound (2), and Evaluation of Hardening Properties of the Acrylamide Compound

1. Synthesis of acrylamide compound from exemplified compound (1) or exemplified compound (2) An acrylamide compound (Al) and an acrylamide compound (Al) were obtained by allowing a base to act on the exemplified compound (1) obtained in Example 1 and the exemplified compound (2) obtained in Example 2 according to the method as described in Russian Journal of General Chemistry, 2005, Vol. 75, No. 6, pp. 915-922, and U. S. Patent No. 4,914,225, or according to amethod equivalent thereto.

2. Evaluation of hardening properties of acrylamide compound (Al) and acrylamide compound (A2) The hardening properties (thermosetting properties) of the acrylamide compound (Al) and acrylamide compound (A2) obtained were evaluated according to the following procedures.

[Evaluation of hardening properties] A sample solution containing the acrylamide compound (Al) or acrylamide compound (A2), a radical polymerization initiator, and an organic solvent was prepared and applied onto a copper plate, and then this was heated, and progress of radical polymerization and a sense of touch before and after heating were evaluated. In addition, the progress of radical polymerization was confirmed by a thermal decrease of ! a peak at 806 cm"1 arising from an acrylic group by using FT-IR (VARIAN 3100 FT-IR (trade name), made by Varian, Inc.). The details are shown below. A sample liquid 1A for evaluation was prepared by dissolving 250 mg of acrylamide compound (Al) and 25 mg of azobisisobutyronitril (AIBN) as the radical polymerization initiator in 1 mL of methanol. Then, 10 uL of this sample liquid 1A j for evaluation was measured, and applied onto the copper plate. The copper plate onto which the sample liquid was applied was measured by means of FT-IR, and the peak at 806 cm"1 arising from the acrylic group was confirmed. Then, the copper plate was heated in an oven at 100°C for 1 hour under a nitrogen atmosphere. When the copper plate after heating was again measured by means of FT-IR, the peak at 806 cm"1 arising from the acrylic group decreased. From this result, the progress of radical polymerization of acrylamide compound (Al) was confirmed.

Furthermore, when the sense of touch before and after heating was evaluated, no stickiness was felt on the sample plate after heating when the sample plate was touched, and no change was felt when the sample plate was rubbed with a ball of a finger, as compared with the sense before rubbing. These results show a fact that the sample liquid applied onto the copper plate was hardened by heating. Then, hardening properties of the acrylamide compound (A2) were evaluated in a manner similar to the acrylamide compound (Al). As a result, the acrylamide compound (A2) was also confirmed to have hardening properties in a degree similar to the acrylamide compound (Al). Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims. This application claims priority on Patent Application No. 2012-065145 filed in Japan on March 22, 2012, which is entirely herein incorporated by reference.

WHAT IS CLAIMED IS:

1. A compound represented by formula (1): wherein in formula (1), Z represents a residue obtained by removing n hydrogen atoms from hydroxyl groups of a polyol; n represents an integer of 3 to 6; R1 represents a hydrogen atom or a methyl group; R2 represents an alkylene group having 1 to 8 carbon atom(s); X1 represents a halogen atom; and a plurality of RJs, R2s, and x's may be the same or different from each other.

2. The compound according to Claim 1, wherein the compound is a synthetic intermediate of a (meth)acrylamide compound represented by formula (A): wherein in formula (A), Z represents a residue obtained by removing n hydrogen atoms from hydroxyl groups of a polyol; n represents an integer of 3 to 6; R1 represents a hydrogen atom or a methyl group; R2 represents an alkylene group having 1 to 8 carbon atom(s); and a plurality of R's and R2s may be the same or different from each other.