Radical polymerization initiator and method for producing polymers

Abstract

The present invention involves a radical polymerization initiator comprising an organotellurium compound represented by a formula (1), wherein R.sup.1 represents an alkyl group or the like, each of R.sup.2 and R.sup.3 independently represents a hydrogen atom or the like, and each of R.sup.4, R.sup.5, and R.sup.6 independently represents a hydrogen atom or the like. The present invention provides: a radical polymerization initiator that is useful for producing a polymer that includes a double bond at the molecular terminal; and a method for producing a polymer that utilizes the radical polymerization initiator. ##STR00001##

Claims

1. A method for producing a polymer comprising subjecting a radically polymerizable monomer to radical polymerization in a state in which a radical polymerization initiator is present in a polymerization system, wherein the radical polymerization initiator is an organotellurium compound represented by the following formula (1), ##STR00007## wherein R.sup.1 represents a group selected from: an alkyl group having 1 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); an aryl group having 6 to 20 carbon atoms which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); and an aromatic heterocyclic group which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms), each of R.sup.2 and R.sup.3 independently represents a group selected from: a hydrogen atom; an aliphatic hydrocarbon group having 1 to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); an aromatic heterocyclic group which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or a haloalkyl group having 1 to 8 carbon atoms); a halogen atom; a carboxyl group; a hydrocarbyl oxycarbonyl group having 2 to 10 carbon atoms; a cyano group; and an amide group, and each of R.sup.4, R.sup.5 and R.sup.6 independently represents a group selected from: a hydrogen atom; an aliphatic hydrocarbon group having 1 to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); an aromatic heterocyclic group which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); a halogen atom; a carboxyl group; a hydrocarbyl oxycarbonyl group having 2 to 10 carbon atoms; a cyano group; and an amide group, and a group represented by the following formula (2), wherein 2 groups selected from R.sup.2 to R.sup.6 may bond together to form a ring other than an aromatic ring, ##STR00008## wherein R.sup.7 represents a group selected from: an alkyl group having 1 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); an aryl group having 6 to 20 carbon atoms which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); and an aromatic heterocyclic group which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms), and each of R.sup.8 and R.sup.9 independently represents a group selected from: a hydrogen atom; an aliphatic hydrocarbon group having 1 to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); an aromatic heterocyclic group which is unsubstituted, or substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a nitro group, a cyano group, and CORa (wherein Ra represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a haloalkyl group having 1 to 8 carbon atoms); a halogen atom; a carboxyl group; a hydrocarbyl oxycarbonyl group having 2 to 10 carbon atoms; a cyano group; and an amide group, wherein the wavy line represents a bond with the carbon atoms constituting the double bond in formula (1), wherein one of the terminal of the polymer produced is a group represented by (R.sup.5)(R.sup.6)CC(R.sup.4)C(R.sup.2)(R.sup.3) that is derived from the organotellurium compound.

2. The method for producing a polymer according to claim 1, wherein the radically polymerizable monomer is subjected to radical polymerization in a state in which an azo-based radical generator is further present in the polymerization system.

3. The method for producing a polymer according to claim 1, wherein the radically polymerizable monomer is subjected to radical polymerization in a state in which light having a wavelength of 200 to 380 nm is applied to the polymerization system.

4. The method for producing a polymer according to claim 1, wherein the radically polymerizable monomer is subjected to radical polymerization in a state in which a ditelluride compound represented by a formula (3) is further present in the polymerization system,
R.sup.10TeTeR.sup.11(3) wherein each of R.sup.10 and R.sup.11 independently represents a group selected from an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaromatic ring group.

5. The method for producing a polymer according to claim 1, wherein the molecular weight distribution of the polymer produced is 1.01 to 2.50.

Description

EXAMPLES

(1) The invention is further described below by way of examples and the like.

(2) Note that the invention is not limited to the following examples and the like. Note that the units parts and % respectively refer to parts by weight and wt % unless otherwise indicated.

(3) The measurement methods used in connection with the examples are described below.

(4) .sup.1H-NMR measurement

(5) The .sup.1H-NMR measurement was performed using an NMR spectrometer BRUKER-500 (manufactured by BRUKER) (solvent: CDCl.sub.3 or d-DMSO).

(6) Gas Chromatography Measurement

(7) The gas chromatography measurement was performed using a gas chromatograph GC2010 (manufactured by Shimadzu Corporation) and a column ZB-5 (manufactured by Phenomenex). The quantitative determination was performed based on an internal standard method using mesitylene.

(8) Gel Permeation Chromatography (GPC) Measurement

(9) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the polymer were determined as polystyrene-equivalent values by gel permeation chromatography (GPC) measurement using a GPC system HLC-8220 (manufactured by Tosoh Corporation) (column: TSK-GEL G6000HHR, G5000HHR, G4000HHR, and G2500HHR (manufactured by Tosoh Corporation) (that were sequentially connected), eluent: tetrahydrofuran (THF)).

Synthesis Example 1

(10) A 300 mL three-necked flask was charged with 5.23 g (41 mmol) of metallic tellurium (manufactured by Aldrich (hereinafter the same)) and 45 mL of THF in a nitrogen atmosphere to prepare a suspension. The suspension was cooled to 0 C. with stirring. 45.0 mL (43.0 mmol) of methyllithium (1.10 M diethyl ether solution, manufactured by Kanto Chemical Co., Inc. (hereinafter the same)) was added dropwise to the suspension over 10 minutes while cooling the suspension with stirring. After the dropwise addition, the mixture contained in the three-necked flask was stirred at room temperature (25 C.) for 20 minutes to obtain a reaction solution in which the metallic tellurium had completely disappeared.

(11) 30 mL of a saturated NH.sub.4Cl aqueous solution was added to the reaction solution with stirring, and the mixture was stirred for 1 hour in air. The organic layer was separated, and sequentially washed with water and a saturated NaCl aqueous solution. The organic layer (i.e., the reaction solution subjected to washing) was dried over anhydrous magnesium sulfate, and filtered through Celite. The filtrate was concentrated under reduced pressure, and the concentrate was subjected to vacuum distillation (0.6 mmHg, 43 C.) to obtain 2.48 g (yield: 42%) of dimethyl ditelluride as a brown oily product.

(12) The .sup.1H-NMR data of the resulting dimethyl ditelluride is shown below. .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, ppm) 2.67 (s, 6H)

Synthesis Example 2

(13) A 300 mL three-necked flask was charged with 8.75 g (68.6 mmol) of metallic tellurium and 90 mL of THF in a nitrogen atmosphere to prepare a suspension. The suspension was cooled to 0 C. with stirring. 45.0 mL (72.0 mmol) of n-butyllithium (1.6 M hexane solution, manufactured by Kanto Chemical Co., Inc. (hereinafter the same)) was added dropwise to the suspension over 10 minutes while cooling the suspension with stirring. After the dropwise addition, the mixture contained in the three-necked flask was stirred at room temperature (25 C.) for 20 minutes to obtain a reaction solution in which the metallic tellurium had completely disappeared.

(14) 50 mL of a saturated NH.sub.4Cl aqueous solution was added to the reaction solution with stirring, and the mixture was stirred for 1 hour in air. The organic layer was separated, and sequentially washed with water and a saturated NaCl aqueous solution.

(15) The organic layer (i.e., the reaction solution subjected to washing) was dried over anhydrous magnesium sulfate, and filtered through Celite. The filtrate was concentrated under reduced pressure, and the concentrate was subjected to vacuum distillation (0.2 mmHg, 84 C.) to obtain 4.98 g (yield: 39%) of dibutyl ditelluride as a brown oily product.

(16) The .sup.1H-NMR data of the resulting dibutyl ditelluride is shown below. .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, ppm) 0.93 (t, J=7.4 Hz, 3H), 1.35-1.43 (m, 4H), 1.67-1.74 (m, 4H), 3.11 (t, J=7.4 Hz, 4H)

Example 1

(17) A 300 mL three-necked flask was charged with 11.48 g (90 mmol) of metallic tellurium and 86 mL of THF in a nitrogen atmosphere to prepare a suspension. The suspension was cooled to 0 C. with stirring. 86.0 mL (94.5 mmol) of methyllithium (1.10 M diethyl ether solution) was added dropwise to the suspension over 10 minutes while cooling the suspension with stirring. After the dropwise addition, the mixture contained in the three-necked flask was stirred at room temperature (25 C.) for 20 minutes to obtain a reaction solution in which the metallic tellurium had completely disappeared.

(18) The reaction solution was cooled to 0 C. with stirring. 11.4 g (94.5 mmol) of allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd. (hereinafter the same)) was added to the reaction solution while cooling the reaction solution with stirring. After reacting the mixture contained in the three-necked flask for 2 hours with stirring, the reaction solution was returned to room temperature.

(19) The resulting reaction solution was sequentially washed with deaerated water, a deaerated saturated NH.sub.4Cl aqueous solution, and a deaerated saturated NaCl aqueous solution. The organic layer (i.e., the reaction solution subjected to washing) was dried over anhydrous magnesium sulfate, and filtered through Celite in a nitrogen atmosphere.

(20) The filtrate was concentrated under reduced pressure, and the concentrate was subjected to vacuum distillation (33 mmHg, 55 C.) to obtain 6.55 g (yield: 40%) of 3-methyltellanyl-1-propene as a yellow oily product.

(21) The .sup.1H-NMR data of the resulting 3-methyltellanyl-1-propene is shown below. .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, ppm) 1.85 (s, 3H), 3.31 (d, J=8.5 Hz, 2H), 4.80 (d, J=9.0 Hz, 1H), 4.85 (d, J=17.0 Hz, 1H), 5.90-5.99 (m, 1H)

Example 2

(22) A 300 mL three-necked flask was charged with 6.38 g (50 mmol) of metallic tellurium and 50 mL of THF in a nitrogen atmosphere to prepare a suspension. The suspension was cooled to 0 C. with stirring. 48.6 mL (52.5 mmol) of phenyllithium (1.08 M cyclohexane-diethyl ether solution, manufactured by Kanto Chemical Co., Inc.) was added dropwise to the suspension over 10 minutes while cooling the suspension with stirring. After the dropwise addition, the mixture contained in the three-necked flask was stirred at room temperature (25 C.) for 20 minutes to obtain a reaction solution in which the metallic tellurium had completely disappeared.

(23) The reaction solution was cooled to 0 C. with stirring. 6.35 g (52.5 mmol) of allyl bromide was added to the reaction solution while cooling the reaction solution with stirring. After reacting the mixture contained in the three-necked flask for 2 hours with stirring, the reaction solution was returned to room temperature.

(24) The resulting reaction solution was sequentially washed with deaerated water, a deaerated saturated NH.sub.4Cl aqueous solution, and a deaerated saturated NaCl aqueous solution. The organic layer (i.e., the reaction solution subjected to washing) was dried over anhydrous magnesium sulfate, and filtered through Celite in a nitrogen atmosphere. The filtrate was concentrated under reduced pressure, and the concentrate was subjected to vacuum distillation (2.0 mmHg, 70 C.) to obtain 5.6 g (yield: 46%) of 3-phenyltellanyl-1-propene as a yellow oily product.

(25) The .sup.1H-NMR data of the resulting 3-phenyltellanyl-1-propene is shown below. .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, ppm) 3.63 (dd, 2H), 4.77 (d, J=10.0 Hz, 1H), 4.83 (dd, J=16.8 Hz, 1H), 6.03-6.12 (m, 1H), 7.18-7.78 (m, 5H)

Example 3

(26) A 300 mL three-necked flask was charged with 3.76 g (29.5 mmol) of metallic tellurium and 38 mL of THF in a nitrogen atmosphere to prepare a suspension. The suspension was cooled to 0 C. with stirring. 19.4 mL (31.0 mmol) of n-butyllithium (1.6 M hexane solution) was added dropwise to the suspension over 10 minutes while cooling the suspension with stirring. After the dropwise addition, the mixture contained in the three-necked flask was stirred at room temperature (25 C.) for 20 minutes to obtain a reaction solution in which the metallic tellurium had completely disappeared.

(27) The reaction solution was cooled to 0 C. with stirring. 5.0 g (31.0 mmol) of 3-bromocyclohexene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution while cooling the reaction solution with stirring. After reacting the mixture contained in the three-necked flask for 2 hours with stirring, the reaction solution was returned to room temperature.

(28) The resulting reaction solution was sequentially washed with deaerated water, a deaerated saturated NH.sub.4Cl aqueous solution, and a deaerated saturated NaCl aqueous solution. The organic layer (i.e., the reaction solution subjected to washing) was dried over anhydrous magnesium sulfate, and filtered through Celite in a nitrogen atmosphere.

(29) The filtrate was concentrated under reduced pressure, and the concentrate was subjected to vacuum distillation (1.0 mmHg, 82 C.) to obtain 4.47 g (yield: 57%) of 3-[(n-butyl)tellanyl]-1-cyclohexene as a yellow oily product.

(30) The .sup.1H-NMR data of the resulting 3-[(n-butyl)tellanyl]-1-cyclohexene is shown below.

(31) .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, ppm) 0.92 (t, J=7.5 Hz, 3H), 1.38 (dt, J=7.5 Hz, 14.8 Hz, 2H), 1.64-1.89 (m, 4H), 2.01-2.22 (m, 4H), 2.62-2.78 (m, 2H), 3.96-4.00 (m, 1H), 5.56-5.60 (m, 1H), 5.85-5.89 (m, 1H)

Example 4

(32) A 300 mL three-necked flask was charged with 3.39 g (26.6 mmol) of metallic tellurium and 25 mL of THF in a nitrogen atmosphere to prepare a suspension. The suspension was cooled to 0 C. with stirring. 25.1 mL (27.9 mmol) of methyllithium (1.11 M diethyl ether solution) was added dropwise to the suspension over 10 minutes while cooling the suspension with stirring. After the dropwise addition, the mixture contained in the three-necked flask was stirred at room temperature (25 C.) for 20 minutes to obtain a reaction solution in which the metallic tellurium had completely disappeared.

(33) The reaction solution was cooled to 0 C. with stirring. 5.0 g (27.9 mmol) of methyl 2-(bromomethyl)acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

(34) was added to the reaction solution while cooling the reaction solution with stirring. After reacting the mixture contained in the three-necked flask for 2 hours with stirring, the reaction solution was returned to room temperature.

(35) The resulting reaction solution was sequentially washed with deaerated water, a deaerated saturated NH.sub.4Cl aqueous solution, and a deaerated saturated NaCl aqueous solution. The organic layer (i.e., the reaction solution subjected to washing) was dried over anhydrous magnesium sulfate, and filtered through Celite in a nitrogen atmosphere. The filtrate was concentrated under reduced pressure, and the concentrate was subjected to vacuum distillation (1.0 mmHg, 52 C.) to obtain 2.3 g (yield: 36%) of methyl 2-(methyltellanylmethyl)acrylate as a yellow oily product.

(36) The .sup.1H-NMR data of the resulting methyl 2-(methyltellanylmethyl)acrylate is shown below.

(37) .sup.1H-NMR (500 MHz, CDCl.sub.3, TMS, ppm) 1.91 (s, 3H), 3.74 (s, 2H), 3.76 (s, 3H), 5.54 (s, 1H), 6.18 (s, 1H)

Example 5

(38) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL glass reaction vessel was charged with 0.68 g (10 mmol) of isoprene (manufactured by Tokyo Chemical Industry Co., Ltd. (hereinafter the same)), 0.53 g (10 mmol) of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter the same)), 36.7 mg (0.20 mmol) of 3-methyltellanyl-1-propene obtained in Example 1, 5.7 mg (0.02 mmol) of dimethyl ditelluride obtained in Synthesis Example 1, 24.4 mg (0.10 mmol) of 1,1-azobis(cyclohexane-1-carbonitrile) (manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter the same)), and 0.24 g of mesitylene (manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter the same)) (gas chromatography internal standard (hereinafter referred to as internal standard)), and the mixture was stirred at 80 C. for 16 hours to effect a polymerization reaction.

(39) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried to obtain an isoprene-acrylonitrile random copolymer.

(40) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 93% and 84%, respectively.

(41) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 7,060, 6,130, and 1.15, respectively.

(42) It was found by .sup.1H-NMR analysis that the isoprene-acrylonitrile random copolymer included a terminal double bond in a ratio of 98%.

Example 6

(43) A polymerization reaction was effected in the same manner as in Example 5, except that 1,1-azobis(cyclohexane-1-carbonitrile) was not added, and light was applied to the polymerization system during the polymerization reaction using an LED lamp (output: 6 W, 5% ND filter was used), to obtain an isoprene-acrylonitrile random copolymer.

(44) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 88% and 81%, respectively.

(45) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 6,730, 6,100, and 1.09, respectively.

(46) It was found by .sup.1H-NMR analysis that the isoprene-acrylonitrile random copolymer included a terminal double bond in a ratio of 96%.

Example 7

(47) A polymerization reaction was effected in the same manner as in Example 5, except that dimethyl ditelluride was not added, to obtain an isoprene-acrylonitrile random copolymer.

(48) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 92% and 82%, respectively.

(49) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 8,690, 6,980, and 1.25, respectively.

(50) It was found by .sup.1H-NMR analysis that the isoprene-acrylonitrile random copolymer included a terminal double bond in a ratio of 98%.

Example 8

(51) A polymerization reaction was effected in the same manner as in Example 5, except that dimethyl ditelluride and 1,1-azobis(cyclohexane-1-carbonitrile) were not added, and the polymerization reaction time was changed to 72 hours, to obtain an isoprene-acrylonitrile random copolymer.

(52) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 75% and 63%, respectively.

(53) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 4,160, 3,080, and 1.35, respectively.

(54) It was found by .sup.1H-NMR analysis that the isoprene-acrylonitrile random copolymer included a terminal double bond in a ratio of 97%.

Example 9

(55) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL glass reaction vessel was charged with 2.56 g (20 mmol) of n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter the same)), 36.7 mg (0.20 mmol) of 3-methyltellanyl-1-propene obtained in Example 1, 16.4 mg (0.10 mmol) of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter the same)), and 0.24 g of mesitylene (internal standard), and the mixture was stirred at 60 C. for 1 hour to effect a polymerization reaction.

(56) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried to obtain an n-butyl acrylate polymer.

(57) The conversion ratio of n-butyl acrylate determined by gas chromatography was 91%.

(58) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the n-butyl acrylate polymer determined by GPC (with respect to a polystyrene standard sample) were 18,970, 15,240, and 1.25, respectively.

(59) It was found by .sup.1H-NMR analysis that the n-butyl acrylate polymer included a terminal double bond in a ratio of 90%.

Example 10

(60) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL glass reaction vessel was charged with 2.56 g (20 mmol) of n-butyl acrylate, 36.7 mg (0.20 mmol) of 3-methyltellanyl-1-propene obtained in Example 1, 16.4 mg (0.10 mmol) of azobisisobutyronitrile, and 0.24 g of mesitylene (internal standard), and the mixture was stirred at 60 C. for 1 hour to effect a polymerization reaction. After the addition of 1.00 g (10 mmol) of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter the same)) and 28.5 mg (0.1 mmol) of dimethyl ditelluride obtained in Synthesis Example 1 to the reaction vessel, the mixture was stirred at 80 C. for 15 hours to effect a polymerization reaction.

(61) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried to obtain an n-butyl acrylate-methyl methacrylate block copolymer.

(62) The conversion ratio of methyl methacrylate determined by gas chromatography was 100%.

(63) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the n-butyl acrylate-methyl methacrylate block copolymer determined by GPC (with respect to a polystyrene standard sample) were 50,900, 29,600, and 1.71, respectively.

(64) It was found by .sup.1H-NMR analysis that the n-butyl acrylate-methyl methacrylate block copolymer included a terminal double bond in a ratio of 88%.

Example 11

(65) A polymerization reaction was effected in the same manner as in Example 9, except that 2.08 g (20 mmol) of styrene (manufactured by Tokyo Chemical Industry Co., Ltd. (hereinafter the same)) was used instead of n-butyl acrylate, to obtain a styrene polymer.

(66) The conversion ratio of styrene determined by gas chromatography was 91%.

(67) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the styrene polymer determined by GPC (with respect to a polystyrene standard sample) were 10,860, 8,150, and 1.33, respectively.

(68) It was found by .sup.1H-NMR analysis that the styrene polymer included a terminal double bond in a ratio of 97%.

Example 12

(69) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL glass reaction vessel was charged with 2.08 g (20 mmol) of styrene, 36.7 mg (0.20 mmol) of 3-methyltellanyl-1-propene obtained in Example 1, 16.4 mg (0.10 mmol) of azobisisobutyronitrile, and 0.24 g of mesitylene (internal standard), and the mixture was stirred at 60 C. for 1 hour to effect a polymerization reaction. After the addition of 1.00 g (10 mmol) of methyl methacrylate and 28.5 mg (0.1 mmol) of dimethyl ditelluride obtained in Synthesis Example 1 to the reaction vessel, the mixture was stirred at 80 C. for 15 hours to effect a polymerization reaction.

(70) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried to obtain a styrene-methyl methacrylate block copolymer.

(71) The conversion ratio of methyl methacrylate determined by gas chromatography was 100%.

(72) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the styrene-methyl methacrylate block copolymer determined by GPC (with respect to a polystyrene standard sample) were 26,600, 18,800, and 1.41, respectively.

(73) It was found by .sup.1H-NMR analysis that the styrene-methyl methacrylate block copolymer included a terminal double bond in a ratio of 92%.

Example 13

(74) A polymerization reaction was effected in the same manner as in Example 5, except that 1.00 g (10 mmol) of methyl methacrylate was used instead of acrylonitrile, to obtain an isoprene-methyl methacrylate random copolymer.

(75) The conversion ratio of isoprene and the conversion ratio of methyl methacrylate determined by gas chromatography were 97% and 90%, respectively.

(76) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-methyl methacrylate random copolymer determined by GPC (with respect to a polystyrene standard sample) were 9,110, 7,530, and 1.21, respectively.

(77) It was found by .sup.1H-NMR analysis that the isoprene-methyl methacrylate random copolymer included a terminal double bond in a ratio of 96%.

Example 14

(78) A polymerization reaction was effected in the same manner as in Example 5, except that 1.28 g (10 mmol) of n-butyl acrylate was used instead of acrylonitrile, to obtain an isoprene-n-butyl acrylate random copolymer.

(79) The conversion ratio of isoprene and the conversion ratio of n-butyl acrylate determined by gas chromatography were 99% and 87%, respectively.

(80) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-n-butyl acrylate random copolymer determined by GPC (with respect to a polystyrene standard sample) were 5,800, 4,700, and 1.23, respectively.

(81) It was found by .sup.1H-NMR analysis that the isoprene-n-butyl acrylate random copolymer included a terminal double bond in a ratio of 95%.

Example 15

(82) A polymerization reaction was effected in the same manner as in Example 5, except that 1.04 g (10 mmol) of styrene was used instead of acrylonitrile, to obtain an isoprene-styrene random copolymer.

(83) The conversion ratio of isoprene and the conversion ratio of styrene determined by gas chromatography were 93% and 73%, respectively.

(84) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-styrene random copolymer determined by GPC (with respect to a polystyrene standard sample) were 8,070, 6,580, and 1.19, respectively.

(85) It was found by .sup.1H-NMR analysis that the isoprene-styrene random copolymer included a terminal double bond in a ratio of 98%.

Example 16

(86) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL stainless steel autoclave was charged with 1.62 g (30 mmol) of 1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.59 g (30 mmol) of acrylonitrile, 0.6 mg (0.003 mmol) of 3-methyltellanyl-1-propene obtained in Example 1, 0.1 mg (0.0006 mmol) of dimethyl ditelluride, 1.5 mg (0.009 mmol) of 1,1-azobis(cyclohexane-1-carbonitrile), and 0.24 g of mesitylene (internal standard), and the mixture was stirred at 80 C. for 21 hours to effect a polymerization reaction.

(87) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried to obtain a butadiene-acrylonitrile random copolymer.

(88) The conversion ratio of 1,3-butadiene and the conversion ratio of acrylonitrile determined by gas chromatography were 81% and 58%, respectively.

(89) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the butadiene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 332,300, 223,000, and 1.49, respectively.

(90) It was found by .sup.1H-NMR analysis that the butadiene-acrylonitrile random copolymer included a terminal double bond in a ratio of 96%.

Example 17

(91) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL glass reaction vessel was charged with 0.68 g (10 mmol) of cis-1,3-pentadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.53 g (10 mmol) of acrylonitrile, 1.2 mg (0.0067 mmol) of 3-methyltellanyl-1-propene obtained in Example 1, 0.4 mg (0.0013 mmol) of dimethyl ditelluride, 0.8 mg (0.003 mmol) of 1,1-azobis(cyclohexane-1-carbonitrile), and 0.24 g of mesitylene (internal standard), and the mixture was stirred at 80 C. for 38 hours to effect a polymerization reaction.

(92) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried to obtain a cis-1,3-pentadiene-acrylonitrile random copolymer.

(93) The conversion ratio of cis-1,3-pentadiene and the conversion ratio of acrylonitrile determined by gas chromatography were 76% and 36%, respectively.

(94) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the cis-1,3-pentadiene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 89,400, 60,400, and 1.48, respectively.

(95) It was found by .sup.1H-NMR analysis that the cis-1,3-pentadiene-acrylonitrile random copolymer included a terminal double bond in a ratio of 92%.

Example 18

(96) A polymerization reaction was effected in the same manner as in Example 5, except that 49.1 mg (0.2 mmol) of 3-phenyltellanyl-1-propene obtained in Example 2 was used instead of 3-methyltellanyl-1-propene, and 8.2 mg (0.02 mmol) of diphenyl ditelluride (manufactured by Aldrich) was used instead of dimethyl ditelluride, to obtain an isoprene-acrylonitrile random copolymer.

(97) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 91% and 82%, respectively.

(98) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 5,740, 5,010, and 1.15, respectively.

(99) It was found by .sup.1H-NMR analysis that the isoprene-acrylonitrile random copolymer included a terminal double bond in a ratio of 94%.

Example 19

(100) A polymerization reaction was effected in the same manner as in Example 5, except that 52.9 mg (0.2 mmol) of 3-[(n-butyl)tellanyl]-1-cyclohexene obtained in Example 3 was used instead of 3-methyltellanyl-1-propene, and 7.5 mg (0.02 mmol) of dibutyl ditelluride obtained in Synthesis Example 2 was used instead of dimethyl ditelluride, to obtain an isoprene-acrylonitrile random copolymer.

(101) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 91% and 84%, respectively.

(102) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 7,770, 6,150, and 1.26, respectively.

(103) It was found by .sup.1H-NMR analysis that the isoprene-acrylonitrile random copolymer included a terminal double bond in a ratio of 99%.

Example 20

(104) A polymerization reaction was effected in the same manner as in Example 10, except that 48.3 mg (0.2 mmol) of methyl 2-(methyltellanylmethyl)acrylate obtained in Example 4 was used instead of 3-methyltellanyl-1-propene, to obtain an isoprene-acrylonitrile random copolymer.

(105) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 86% and 76%, respectively.

(106) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the isoprene-acrylonitrile random copolymer determined by GPC (with respect to a polystyrene standard sample) were 8,190, 5,570, and 1.47, respectively.

(107) It was found by .sup.1H-NMR analysis that the isoprene-acrylonitrile random copolymer included a terminal double bond in a ratio of 85%.

Example 21

(108) A polymerization reaction was effected in the same manner as in Example 9, except that 3.14 g (20 mmol) of 2-(dimethylamino)ethyl methacrylate was used instead of n-butyl acrylate, to obtain a 2-(dimethylamino)ethyl methacrylate polymer.

(109) The conversion ratio of 2-(dimethylamino)ethyl methacrylate determined by gas chromatography was 83%. The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the 2-(dimethylamino)ethyl methacrylate polymer determined by GPC (with respect to a polystyrene standard sample) were 25,900, 19,300, and 1.34, respectively.

(110) It was found by .sup.1H-NMR analysis that the 2-(dimethylamino)ethyl methacrylate polymer included a terminal double bond in a ratio of 87%.

Comparative Example 1

(111) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL glass reaction vessel was charged with 28.7 mg (0.2 mmol) of copper(I) bromide (manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter the same)), 34.7 mg (0.2 mmol) of N,N,N,N,N-pentamethyldiethylenetriamine (manufactured by Wako Pure Chemical Industries, Ltd.), 0.68 g (10 mmol) of isoprene, 0.53 g (10 mmol) of acrylonitrile, 24.2 mg (0.20 mmol) of allyl bromide, and 0.24 g of mesitylene (internal standard), and the mixture was stirred at 80 C. for 15 hours to effect a polymerization reaction.

(112) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried.

(113) The conversion ratio of isoprene and the conversion ratio of acrylonitrile determined by gas chromatography were 21% and 27%, respectively.

(114) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the resulting product determined by GPC (with respect to a polystyrene standard sample) were 370, 360, and 1.04, respectively. It was thus found that an oligomer was obtained by the polymerization reaction.

Comparative Example 2

(115) In a glovebox in which the internal atmosphere had been replaced by nitrogen, a 30 mL glass reaction vessel was charged with 28.7 mg (0.2 mmol) of copper(I) bromide, 34.7 mg (0.2 mmol) of N,N,N,N,N-pentamethyldiethylenetriamine, 2 mL of toluene, 3.14 g (20 mmol) of 2-(dimethylamino)ethyl methacrylate, 24.2 mg (0.20 mmol) of allyl bromide, and 0.24 g of mesitylene (internal standard), and the mixture was stirred at 80 C. for 15 hours to effect a polymerization reaction.

(116) The resulting polymerization reaction product was purified by evaporating a volatile component under reduced pressure, and the purified product was dried to obtain a 2-(dimethylamino)ethyl methacrylate polymer.

(117) The conversion ratio of 2-(dimethylamino)ethyl methacrylate determined by gas chromatography was 42%.

(118) The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) of the 2-(dimethylamino)ethyl methacrylate polymer determined by GPC (with respect to a polystyrene standard sample) were 36,000, 13,300, and 2.71, respectively. Specifically, the 2-(dimethylamino)ethyl methacrylate polymer had a relatively wide molecular weight distribution.