THREE-DIMENSIONAL CONTROL CATALYST USED IN RADICAL POLYMERIZATION, POLYMER PRODUCTION METHOD, AND ACRYLIC POLYMER

Abstract

The present invention provides a stereocontrol catalyst for use in radical polymerization that is applicable to polymerization of a broad range of monomers and that enables polymerization with control of both molecular weight (molecular weight distribution) and stereoselectivity, a method for producing a polymer using the stereocontrol catalyst for use in radical polymerization, and an acrylic polymer. Provided is a stereocontrol catalyst for use in radical polymerization, containing: a rare-earth metal salt compound; and a hydroxy group-containing compound.

Claims

1. A stereocontrol catalyst for use in radical polymerization, comprising: a rare-earth metal salt compound; and a hydroxy group-containing compound.

2. The stereocontrol catalyst for use in radical polymerization according to claim 1, wherein the rare-earth metal salt compound is a rare-earth metal trifluoromethanesulfonate.

3. The stereocontrol catalyst for use in radical polymerization according to claim 1, wherein the rare-earth metal salt compound is a salt of a trivalent rare-earth metal.

4. The stereocontrol catalyst for use in radical polymerization according to claim 1, wherein the hydroxy group-containing compound is an alcoholic compound.

5. The stereocontrol catalyst for use in radical polymerization according to claim 1, wherein the hydroxy group-containing compound is a binaphthol derivative.

6. A method for producing a polymer, comprising: polymerizing a (meth)acrylic monomer under the presence of the stereocontrol catalyst for use in radical polymerization according to claim 1.

7. The method for producing a polymer according to claim 6, wherein the (meth)acrylic monomer is polymerized under the presence of the stereocontrol catalyst for use in radical polymerization in a solvent that contains a compound different from a hydroxy group-containing compound contained in the stereocontrol catalyst for use in radical polymerization.

8. The method for producing a polymer according to claim 6, which is performed by living radical polymerization.

9. An acrylic polymer comprising, in a molecule: a meso form; and a racemo form, the acrylic polymer having a percentage of a meso portion of 65% or more and a molecular weight distribution of 1.8 or less.

Description

DESCRIPTION OF EMBODIMENTS

[0083] In the following, the present invention is described in more detail with reference to examples. The present invention should not be limited to these examples.

Example 1

[Radical Polymerization]

[0084] In a nitrogen atmosphere, a glass reaction container was charged with 1.1 mL of dichloromethane as a solvent, 0.57 mmol of N,N-diethylacrylamide (DEAA) as a monomer, 0.23 mmol (0.20 equivalents) of ytterbium trifluoromethanesulfonate [Yb(OTf).sub.3] as a Lewis acid, 0.23 mmol (0.20 equivalents) of water as a ligand, and 0.017 mmol (0.03 equivalents) of azobisisobutyronitrile [AIBN] as an initiator. They were then uniformly mixed to prepare a polymerization reaction solution. The obtained polymerization reaction solution was polymerized at 0 C. for 14 hours while being irradiated with a 500-W mercury lamp, whereby a polymer was obtained.

Examples 2 to 15 and Comparative Examples 1 to 5

[0085] Polymers were obtained by polymerization as in Example 1, except that the polymerization conditions (temperature and time) were as shown in Table 1 and the types and amounts (equivalents) of monomer, Lewis acid, and ligand were as shown in Table 1.

[0086] DMAA represents N,N-dimethylacrylamide, Y(NTf.sub.2).sub.3 represents trifluoromethanesulfonimide yttrium, and Y(OTf).sub.3 represents yttrium trifluoromethanesulfonate. The conversion represents the percentage of polymerization of the monomer. The measurement device used was a .sup.1H-NMR device.

[0087] The binaphthol derivatives are compounds represented by the formula (2). The configuration [(R), (S), (rac)] and the number n of ethylene oxide units are shown in Table 1. In the table, la represents n=0, 1b represents n=1, and 1c represents n=2.

Example 16

[Living Radical Polymerization]

[0088] In a nitrogen atmosphere, a dry glass reaction container was charged with 1.1 mL of dichloromethane as a solvent, 0.57 mmol of N,N-diethylacrylamide (DEAA) as a monomer, 0.23 mmol (0.20 equivalents) of ytterbium trifluoromethanesulfonate [Yb(OTf).sub.3] as a Lewis acid, 0.23 mmol (0.20 equivalents) of water as a ligand, and 0.0057 mmol (0.20 equivalents) of an organotellurium compound represented by the formula (5) as a chain transfer agent. They were then stirred at room temperature for 30 minutes to prepare a polymerization reaction solution. The obtained polymerization reaction solution was polymerized at 0 C. for 10 hours while being irradiated with a 9.4-W LED lamp, whereby a polymer was obtained.

Examples 17 to 39 and Comparative Examples 6 to 10

[0089] Polymers were obtained by polymerization as in Example 16, except that the polymerization conditions (temperature and time) were as shown in Table 2 and the types and amounts (equivalents) of monomers, Lewis acids, and ligands were as shown in Table 2. Specifically, Examples 17 to 39 and Comparative Examples 6 to 10 used the organotellurium compound as a chain transfer agent. NIPAM represents N-isopropylacrylamide. The conversion in Table 2 represents the percentage of polymerization of the monomer. The binaphthol derivatives are compounds represented by the formula (2). The configuration [(R), (S), (rac)] and the number n of ethylene oxide units are shown in Table 2. In the table, la represents n=0, 1b represents n=1, and 1c represents n=2.

Evaluation Methods

[0090] The polymers obtained above were evaluated by the following methods. Tables 1 and 2 show the results. The results were verified taking the types of the monomers and the Lewis acids into consideration. The results of Comparative Examples 3 and 10 were shown as - (unmeasurable) because no polymer was formed.

[0091] (1) Molecular Weight Measurement (Mn and D)

[0092] The number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution D (Mw/Mn) of each polymer were measured by size exclusion chromatography (SEC). The measurement was performed using Shodex LF-604 (polystyrene gel column) produced by Showa Denko K.K.

[0093] (2) .sup.1H-NMR Measurement

[0094] The percentage of a meso form in each polymer was measured by .sup.1H-NMR measurement. The .sup.1H-NMR measurement was performed at 130 C. using a solution in DMSO-d.sub.6. The percentage of a meso form in a polymer chain serves as an index of stereoselectivity. A high percentage of a meso form is direct evidence of control of stereoselectivity.

TABLE-US-00001 TABLE 1 Evaluation Composition Polymerization conditions Meso form Monomer Lewis acid Ligand Temperature Time Conversion percentage type Type Equivalents Type Equivalents ( C.) (hr) (%) Mn D (%) Example 1 DEAA Yb(OTf).sub.3 0.20 H.sub.2O 0.20 0 14 97 41,700 3.9 94 Example 2 DEAA Yb(OTf).sub.3 0.20 CH.sub.3OH 0.20 0 14 89 25,000 4.1 94 Example 3 DEAA Yb(OTf).sub.3 0.20 (R)-1c 0.20 0 14 78 18,300 2.3 94 Example 4 DEAA Yb(OTf).sub.3 0.10 (R)-1c 0.10 0 14 96 2,700 3.2 88 Example 5 DEAA Yb(OTf).sub.3 0.30 (R)-1c 0.30 0 14 67 7,800 1.6 91 Example 6 DEAA Yb(OTf).sub.3 0.20 (S)-1c 0.20 0 14 79 17,200 1.9 94 Example 7 DEAA Yb(OTf).sub.3 0.20 (rac)-1c 0.20 0 14 96 15,000 2.0 94 Comparative DEAA None None 0 14 57 15,700 1.7 56 Example 1 Comparative DEAA Yb(OTf).sub.3 0.20 None 0 14 99 16,900 1.9 84 Example 2 Example 8 DEAA Y(NTf.sub.2).sub.3 0.20 (R)-1c 0.20 0 14 95 4,000 1.53 86 Example 9 DEAA Y(NTf.sub.2).sub.3 0.20 (rac)-1c 0.20 0 14 98 4,100 1.53 86 Comparative DEAA Y(NTf.sub.2).sub.3 0.20 None 0 14 9 Example 3 Example 10 DMAA Y(OTf).sub.3 0.20 (R)-1c 0.20 0 2 84 12,500 2 83 Example 11 DMAA Y(OTf).sub.3 0.50 H.sub.2O 0.50 0 2 45 14,700 1.8 72 Example 12 DMAA Y(OTf).sub.3 0.50 (R)-1a 0.50 0 2 48 8,200 1.6 68 Example 13 DMAA Y(OTf).sub.3 0.50 (R)-1b 0.50 0 2 95 9,800 2 78 Example 14 DMAA Y(OTf).sub.3 0.50 (R)-1c 0.50 0 2 89 10,000 1.6 82 Comparative DMAA Y(OTf).sub.3 0.20 None 0 2 55 5,400 1.6 62 Example 4 Example 15 DMAA Yb(OTf).sub.3 0.20 (R)-1c 0.20 0 2 45 29,000 2.7 84 Comparative DMAA None None 0 2 47 5,500 1.6 48 Example 5

TABLE-US-00002 TABLE 2 Composition Monomer Lewis acid Ligand Chain transfer type Type Equivalents Type Equivalents agent Example 16 DEAA Yb(OTf).sub.3 0.20 H.sub.2O 0.20 Organotellurium Example 17 DEAA Yb(OTf).sub.3 0.20 H.sub.2O 0.20 compound Example 18 DEAA Yb(OTf).sub.3 0.20 CH.sub.3OH 0.20 Example 19 DEAA Yb(OTf).sub.3 0.20 CH.sub.3OH 0.20 Example 20 DEAA Yb(OTf).sub.3 0.20 CH.sub.3OH 0.40 Example 21 DEAA Yb(OTf).sub.3 0.20 CH.sub.3OH 0.10 Example 22 DEAA Yb(OTf).sub.3 0.20 CH.sub.3OH 0.10 Example 23 DEAA Yb(OTf).sub.3 0.20 (CH.sub.3).sub.2CHOH 0.20 Example 24 DEAA Yb(OTf).sub.3 0.20 (CH.sub.3).sub.3COH 0.20 Example 25 DEAA Yb(OTf).sub.3 0.20 4-BrC.sub.6H.sub.4OH 0.20 Example 26 DEAA Yb(OTf).sub.3 0.20 CH.sub.3CH.sub.2OH 0.20 Example 27 DEAA Yb(OTf).sub.3 0.20 HO(CH.sub.2).sub.2OH 0.20 Example 28 DEAA Yb(OTf).sub.3 0.20 HO(CH.sub.2).sub.3OH 0.20 Example 29 DEAA Yb(OTf).sub.3 0.20 HO(CH.sub.2).sub.4OH 0.20 Example 30 DEAA Yb(OTf).sub.3 0.20 HOC(CH.sub.3).sub.2CH.sub.2CH(OH)CH.sub.3 0.20 Example 31 DEAA Yb(OTf).sub.3 0.20 HO(C.sub.2H.sub.4O).sub.3H 0.20 Example 32 DEAA Yb(OTf).sub.3 0.20 HO(C.sub.2H.sub.4O).sub.4H 0.20 Example 33 DEAA Yb(OTf).sub.3 0.20 CH.sub.3OC.sub.2H.sub.4OH 0.20 Example 34 DEAA Yb(OTf).sub.3 0.20 CH.sub.3O(C.sub.2H.sub.4O).sub.2H 0.20 Example 35 DEAA Yb(OTf).sub.3 0.20 (R)-1c 0.20 Example 36 NIPAM Yb(OTf).sub.3 0.20 H.sub.2O 0.20 Organotellurium Example 37 NIPAM Y(OTf).sub.3 0.10 H.sub.2O 0.10 compound Example 38 NIPAM Y(OTf).sub.3 0.10 CH.sub.3OH 0.10 Example 39 NIPAM Y(OTf).sub.3 0.10 CH.sub.3OH 1.00 Comparative DEAA None None Organotellurium Example 6 compound Comparative DEAA Yb(OTf).sub.3 0.20 None Example 7 Comparative DEAA Yb(OTf).sub.3 0.20 CH.sub.3O(C.sub.2H.sub.4O).sub.2CH.sub.3 0.20 Example 8 Comparative NIPAM Yb(OTf).sub.3 0.20 None Organotellurium Example 9 compound Comparative NIPAM Y(OTf).sub.3 0.10 None Example 10 Evaluation Polymerization conditions Meso form Temperature Time Conversion percentage ( C.) (hr) (%) Mn D (%) Example 16 0 10 99 19,500 1.09 94 Example 17 0 2 99 18,500 1.09 94 Example 18 0 14 99 22,800 1.09 94 Example 19 0 2 99 20,300 1.09 94 Example 20 0 14 99 22,800 1.09 94 Example 21 0 10 99 19,500 1.09 94 Example 22 0 2 99 19,100 1.1 94 Example 23 0 14 81 14,300 1.18 93 Example 24 0 14 98 17,400 1.12 88 Example 25 0 14 80 15,200 1.08 88 Example 26 0 14 99 21,200 1.1 94 Example 27 0 14 99 21,200 1.1 94 Example 28 0 14 99 21,200 1.12 94 Example 29 0 14 99 21,700 1.09 94 Example 30 0 14 59 13,000 1.15 94 Example 31 0 14 99 21,600 1.07 94 Example 32 0 14 24 6,800 1.16 94 Example 33 0 14 89 19,900 1.1 94 Example 34 0 14 70 16,100 1.14 94 Example 35 0 8 99 20,300 1.16 94 Example 36 0 10 47 21,700 1.5 67 Example 37 0 10 54 8,700 1.23 69 Example 38 0 12 52 11,700 1.13 75 Example 39 0 12 83 18,100 1.09 86 Comparative 25 70 90 11,000 1.04 56 Example 6 Comparative 0 10 99 15,400 1.08 84 Example 7 Comparative 0 14 90 20,400 1.11 84 Example 8 Comparative 0 10 35 10,200 1.31 64 Example 9 Comparative 0 10 4 Example 10

INDUSTRIAL APPLICABILITY

[0095] The present invention can provide a stereocontrol catalyst for use in radical polymerization that is applicable to polymerization of a broad range of monomers and that enables polymerization with control of both molecular weight (molecular weight distribution) and stereoselectivity, a method for producing a polymer using the stereocontrol catalyst for use in radical polymerization, and a polymer.