Poly (meth) acrylamide with a high stereoregularity and process for producing the same

Polymerization of an Optically Active Methacrylamide (1) Having an (R) Configuration

Under a nitrogen atmosphere, in an ampoule were charged 500 mg of methacrylamide (1) and 13.1 mg of AIBN, which was a polymerization initiator, and several kinds of a Lewis acid as a catalyst shown in Table 1 were charged, in predetermined amounts described there and 4.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polymethacrylamide. The triad tacticity (mm/mr/rr) as an index showing the stereoregularity was obtained by measurement by 13 C-NMR in a solvent of DMSO-d 6 at 80° C. The results are shown in Table 1.

Polymerization of an Optically Active Methacrylamide (2) Having an (S) Configuration

Under a nitrogen atmosphere, in an ampoule were charged 500 mg of methacrylamide (2) and 13.1 mg of AIBN, which was a polymerization initiator, and a Lewis acid as a catalyst shown in Table 1 was charged in predetermined amounts described there and 4.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polymethacrylamide. The triad tacticity (mm/mr/rr) as an index showing the stereoregularity was obtained by measurement by 13 C-NMR in a solvent of DMSO-d 6 at 80° C. The results are shown in Table 1.

Polymerization of a Methacrylamide (3) as a Racemic Form

Under a nitrogen atmosphere, in an ampoule were charged 500 mg of methacrylamide (3) and 13.1 mg of AIBN, which was a polymerization initiator, and a Lewis acid as the catalyst shown in Table 1 was charged in predetermined amounts described there and 4.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polymethacrylamide. The triad tacticity (mm/mr/rr) as an index showing the stereoregularity was obtained by measurement by 13 C-NMR in a solvent of DMSO-d 6 at 80° C. The results are shown in Table 1.

Comparative Example 1

Polymerization of an Optically Active Methacrylamide (1) Under the Condition that a Lewis Acid does not Exist

Under a nitrogen atmosphere, in an ampoule were charged 500 mg of methacrylamide (1) and 13.1 mg of AIBN, which was a polymerization initiator, and without a Lewis acid being added, 4.0 ml of chloroform was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polymethacrylamide. The triad tacticity (mm/mr/rr) as an index showing the stereoregularity was obtained by measurement by 13 C-NMR in a solvent of DMSO-d 6 at 80° C. The results are shown in Table 1.

Comparative Example 2

Polymerization of an Optically Active Methacrylamide (1) Using Dimethyl Dichlorosilane

Under a nitrogen atmosphere, in an ampoule were charged 500 mg of methacrylamide (1) and 13.1 mg of AIBN, which was a polymerization initiator, and 43.5 mg of dimethyl dichlorosilane as a catalyst was charged and 4.0 ml of chloroform was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polymethacrylamide. The triad tacticity (mm/mr/rr) as an index showing the stereoregularity was obtained by measurement by 13 C-NMR in a solvent of DMSO-d 6 at 80° C. The results are shown in Table 1.

Synthesis Example 4

Synthesis of an Optically Active Acrylamide (4) Having an (R) Configuration

In a nitrogen exchanged reaction vessel was charged (R)-(−)-phenylglycine methyl ester hydrochloride (16 g) and dry diethyl ether (250 ml) and triethylamine (22.2 ml) were added thereto. The mixture was stirred in an ice bath until dissolution. Thereafter, acrylic chloride (6.4 ml) diluted with dichloromethane (50 ml) was dripped therein in 2 hours. Then the temperature was returned to room temperature and stirring was performed for 24 hours.

After the reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and then with distilled water, the obtained organic layer was dehydrated and the solvent was distilled off under a reduced pressure to obtain a crude product. This was recrystallized from ethyl acetate to obtain the objective compound (4) (white needle-like crystal: 8.6 g, percent yield: 52%). The melting point of the obtained compound is within a range of 110.6 to 111.3° C.

Polymerization of an Optically Active Acrylamide (4) Having an (R) Configuration

Under a nitrogen atmosphere, in an ampoule were charged 2.0 g of acrylamide (4) and 20 mg of AIBN, which was a polymerization initiator, and a Lewis acid as a catalyst shown in Table 2 was charged in the predetermined amounts described there and 4.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polyacrylamide. The tacticity (m/r) as an index showing the stereoregularity was obtained by measurement by 1 H-NMR in a solvent of DMSO-d 6 at 170° C. The results are shown in Table 2.

Polymerization of an Optically Active Acrylamide (4) Having an (R) Configuration

Under a nitrogen atmosphere, in an ampoule were charged 500 mg of acrylamide (4) and 5 mg of AIBN, which was a polymerization initiator, and several kinds of a Lewis acid as a catalyst shown in Table 2 were charged, in predetermined amounts described there and 1.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polyacrylamide. The tacticity (m/r) as an index showing the stereoregularity was obtained by measurement by 1 H-NMR in a solvent of DMSO-d 6 at 170° C. The results are shown in Table 2.

Comparative Example 3

Polymerization of an Optically Active Acrylamide (4) Under the Condition That a Lewis Acid is Not Used

Under a nitrogen atmosphere, in an ampoule were charged 2.0 g of acrylamide (4) and 20 mg of AIBN, which was a polymerization initiator and, without a Lewis acid being added, 4.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polyacrylamide. The tacticity (m/r) as an index showing the stereoregularity was obtained by measurement by 1 H-NMR in a solvent of DMSO-d 6 at 170° C. The results are shown in Table 2.

Synthesis Example 5

Synthesis of an Acrylamide (5) as a Racemic Form

In a nitrogen exchanged reaction vessel was charged α-methylbenzylamine hydrochloride (26 g) as a racemic form and dry diethyl ether (250 ml) and triethylamine (22.2 ml) were added thereto. The mixture was stirred in an ice bath until dissolution. Thereafter, acryl chloride (18 ml) diluted with dichloromethane (50 ml) was dripped therein in 2 hours. Then the temperature was returned to room temperature and stirring was performed for 20 hours.

After the reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and then with distilled water, the obtained organic layer was dehydrated and the solvent was distilled off under a reduced pressure to obtain a crude product. This was recrystallized from ethyl acetate to obtain the objective compound (5) (white needle-like crystal: 29 g, percent yield: 82%). The melting point of the obtained compound is 63.2±0.2° C.

Polymerization of an Acrylamide (5) as a Racemic Form

Under a nitrogen atmosphere, in an ampoule were charged 400 mg of acrylamide (5) and 4 mg of AIBN, which was a polymerization initiator, and several kinds of a Lewis acid as a catalyst shown in Table 3 were charged, in predetermined amounts described there and 1.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoule was cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polyacrylamide. The tacticity (m/r) as an index showing the stereoregularity was obtained by measurement by 1 H-NMR in a solvent of DMSO-d 6 at 170° C. The results are shown in Table 3.

Comparative Example 4

Polymerization of an Acrylamide (5) Under the Condition That a Lewis Acid is Not Used

Under a nitrogen atmosphere, in an ampoule were charged 400 mg of an acrylamide (5) and 4 mg of AIBN, which was a polymerization initiator and without a Lewis acid being added, 1.0 ml of tetrahydrofuran was added. After the mixture was stirred, the temperature was elevated to 60° C. and polymerization was started.

After 24 hours from the start of the polymerization, the ampoules were cooled to −78° C. and the polymerization reaction mixture was dripped in methanol. The insoluble matter thus deposited was dried under a vacuum to obtain the objective polyacrylamide. The tacticity (m/r) as an index showing the stereoregularity was obtained by measurement by 1 H-NMR in a solvent of DMSO-d 6 at 170° C. The results are shown in Table 3.