Radically polymerizable polyether, method for producing said radically polymerizable polyether, polymerizable composition comprising said radically polymerizable polyether and radically polymerizable vinyl monomer, and copolymer, molded article and film each formed by radical polymerization of said polymerizable composition

Abstract

Provided is (1) a radically polymerizable polyether which imparts excellent mechanical properties including excellent transparency, a high degree of elongation at break and high bending strength to a copolymer produced by the radical polymerization of a radically polymerizable monomer, and a method for producing the radically polymerizable polyether; (2) a polymerizable composition comprising the radically polymerizable polyether and a radically polymerizable vinyl monomer, which enables the formation of a copolymer having excellent mechanical properties; and (3) a copolymer, a molded article and a film, each of which comprises the copolymer.

Claims

1. A radically polymerizable polyether (A) which has a mass average molecular weight of from 20,000 to 1,000,000 and a number average molecular weight of 20,000 to 100,000, comprising a polyalkylene ether backbone having a (meth)acryloyl group as a pendant group and a polytetramethylene ether backbone.

2. The radically polymerizable polyether (A) according to claim 1, which has a mass average molecular weight of from 20,000 to 1,000,000 and is represented by the following Formula (1): ##STR00006## wherein: m1 is from 1 to 7000, m2 is from 0 to 7000, n is from 1 to 14,000, R1 is a methyl group or hydrogen, and R2 and R3 are hydrogen or a hydrocarbon group having from 1 to 20 carbon atoms.

3. The radically polymerizable polyether (A) according to claim 2, wherein m1, m2, and n in Formula (1) are in a relation of 0.0005≦m1/(m1+m2+n)≦0.20.

4. The radically polymerizable polyether (A) according to claim 2, wherein m1, m2, and n in Formula (1) are in a relation of 0.001≦m1/(m1+m2+n)≦0.10.

5. A polymerizable composition (C) which comprises the radically polymerizable polyether (A) according to claim 1 and a radically polymerizable vinyl monomer (B), and wherein a composition ratio range of the component (A) to the component (B) is from 1 to 99% by mass of the component (A) and from 99 to 1% by mass of the component (B).

6. The polymerizable composition (C) according to claim 5, wherein the radically polymerizable vinyl monomer (B) is a (meth)acrylic monomer.

7. A copolymer formed by radical polymerization of the polymerizable composition (C) according to claim 5.

8. A molded article formed by radical polymerization of the polymerizable composition (C) according to claim 5 after being shaped into a desired shape.

9. A film formed by radical polymerization of the polymerizable composition (C) according to claim 5.

10. The film according to claim 9, which has a thickness of from 0.1 to 3000 μm.

11. The film according to claim 9, which has an elongation at break of 10% or more when a tension speed is 500 mm/min.

12. The film according to claim 9, which has a haze of 5% or less when a thickness thereof is 0.5 mm.

13. A method for producing a radically polymerizable polyether (A), wherein ring-opening polymerization of tetrahydrofuran is conducted by allowing from 1 to 20 parts by mass of a glycidyl ester (a) represented by the following Formula (2) to react with 100 parts by mass of tetrahydrofuran in the presence of a metal salt hydrate of trifluoromethanesulfonic acid (b) at from 0.1 to 5 parts by mass: ##STR00007## wherein: R is a straight-chain or branched chain hydrocarbon group having from 1 to 20 carbon atoms and substituted by a hydrocarbon group containing an unsaturated bond and having from 2 to 10 carbon atoms.

14. The method according to claim 13, wherein a mass ratio (a)/(b) of the glycidyl ester (a) to the metal salt hydrate of trifluoromethanesulfonic acid (b) is from 2 to 9.

15. The method according to claim 13, wherein the glycidyl ester (a) is glycidyl methacrylate.

16. The method according to claim 13, wherein the metal of the metal salt hydrate of trifluoromethanesulfonic acid (b) is one or more selected from the group consisting of scandium, yttrium, and lanthanoid.

17. The method according to claim 13, wherein the metal salt hydrate of trifluoromethanesulfonic acid (b) is ytterbium trifluoromethanesulfonate hydrate.

Description

EXAMPLES

(1) Hereinafter, the invention will be specifically described with reference to Examples.

(2) The evaluation of the radically polymerizable polyether (A) was carried out by the following methods.

(3) (1) .sup.1H-NMR Spectrum

(4) The structure of the compound was confirmed by .sup.1H-NMR spectrum.

(5) CDCl.sub.3 was used as the solvent for measurement and tetramethylsilane was used as the standard substance, and the measurement was conducted using a nuclear magnetic resonance apparatus (JNM EX-270 manufactured by JEOL Ltd.). The measurement temperature was room temperature, and the integration number for the measurement was 16 times.

(6) (2) Measurement of Molecular Weight

(7) The number average molecular weight (Mn), mass average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of the polymer were measured by GPC (HLC-8220 manufactured by Tosoh Corporation, column: TSK-GEL SUPER H-4000 and TSK-GEL SUPER H-2000 connected in series) using polystyrene as the standard substance.

(8) The measurement was conducted under the conditions of eluent: chloroform, measurement temperature: 40° C., and flow rate: 0.6 mL/min.

(9) The evaluation of the acrylic film obtained by copolymerizing the radically polymerizable polyether (A) and the radically polymerizable vinyl monomer (B) of the present Example was carried out by the following methods.

(10) (1) Total Luminous Transmittance

(11) The total luminous transmittance of the acrylic film cut into 5 cm.sup.2 was measured in conformity with JIS K7361-1 using a haze meter (trade name: NDH2000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).

(12) (2) Haze

(13) The value of haze of the acrylic film cut into 5 cm.sup.2 was measured in conformity with JIS K7105 using a haze meter (trade name: NDH2000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).

(14) (3) Glass Transition Temperature (Tg)

(15) A test piece of a dumbbell-shaped No. 1 type acrylic film was fabricated using Super Dumbbell Cutter (product name: SDK-100D manufactured by DUMBBELL CO., LTD.) and both ends thereof was cut. The test piece thus obtained was subjected to the measurement using a dynamic viscoelasticity measuring apparatus (trade name: EXSTARDMS6100 manufactured by Hitachi High-Tech Science Corporation) under the measurement conditions of a frequency of 1 Hz, a temperature of from 30 to 150° C., and a rate of temperature rise of 2° C./min, and the temperature at which the temperature-tan 8 curve thus obtained showed the maximum value was adopted as the glass transition temperature (Tg).

(16) (4) Elastic Modulus

(17) Five test pieces of a dumbbell-shaped No. 1 type acryl film were fabricated in conformity with JIS K6251 using Super Dumbbell Cutter (product name: SDK-100D manufactured by DUMBBELL CO., LTD.). The test piece thus obtained was subjected to the tensile test 5 times at room temperature of 23° C. and a tension speed of 500 mm/min using a tension testing machine (trade name: Strograph T manufactured by TOYO SEIKI SEISAKU-SHO, LTD.), and the average value of the tangential lines of the stress-strain curve at that time was determined and adopted as the elastic modulus.

(18) (5) Elongation at Break

(19) Five test pieces of a dumbbell-shaped No. 1 type acryl film were fabricated in conformity with JIS K6251 using Super Dumbbell Cutter (product name: SDK-100D manufactured by DUMBBELL CO., LTD.). The test piece thus obtained was subjected to the tensile test 5 times at room temperature of 23° C. and a tension speed of 500 mm/min using a tension testing machine (trade name: Strograph T manufactured by TOYO SEIKI SEISAKU-SHO, LTD.), and the elongation at break was determined as the average value.

(20) (6) Evaluation on Flexure

(21) The acrylic film cut into 5 cm.sup.2 was subjected to 90° flexure. Specifically, the layered article was cut into a size of 5 cm×5 cm and bent for 2 seconds so as to have a 90° curvature radius of 1 mm. The following two-stage evaluation was visually performed. (C): it is broken at the time of bending or in the middle of bending. (B): it is favorable without breaking or whitening.

Production Example 1

(22) To a 1000 ml three-necked flask equipped with a stirrer, a thermometer, and a cooling tube, 600 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and 2 g of ytterbium(III) trifluoromethanesulfonate hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at room temperature. After it was confirmed that ytterbium triflate hydrate was dissolved, 24 g of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. After the addition, the mixture was stirred for 11 hours at room temperature (25° C.). After stirring, 50 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto to stop the reaction. After the reaction was terminated, unreacted tetrahydrofuran or excess ethanol was distilled off using an evaporator, thereby obtaining 437 g of a white solid (yield: 70%).

(23) The mass average molecular weight of the white solid thus obtained by GPC measurement was 45,000. In addition, the result of .sup.1H-NMR measurement is presented below. The peaks of protons derived from the ring opening derivative of glycidyl methacrylate were observed at 5.55, 6.15, 4.15, 4.05, and 1.9, and the peaks of protons derived from the ring opening derivative of tetrahydrofuran were observed at from 3.1 to 3.9 and 1.6. It was confirmed that the white solid obtained from the above was a copolymer of poly(3-methacryloxypropene oxide) composed of a (meth)acryloyl backbone and polybutylene oxide. In addition, it was confirmed that the introduction rate, (m1/(m1+m2+n)), of poly(3-methacryloxypropene oxide) was 0.035 from the degree of polymerization, m, of poly(3-methacryloxypropene oxide) and the degree of polymerization, n, of polybutylene oxide in the radically polymerizable polyether.

(24) .sup.1H-NMR

(25) 0.95 (s′) 1.60 (m), 1.9 (s), 2.35 (s′) 3.1 to 3.9 (m), 4.05 (s), 4.25 (m), 5.55 (s), and 6.13 (s)

Production Example 2

(26) Production Example 2 was conducted in the same manner as in Production Example 1 except that the amounts of tetrahydrofuran, glycidyl methacrylate, ytterbium triflate hydrate, and ethanol used and the reaction time were changed to the amounts used and the reaction time presented in Table 1. The mass average molecular weight of the copolymer thus obtained by GPC measurement was 14500. In addition, the introduction rate, m1/(m1+m2+n), of the glycidyl methacrylate-derived backbone was 0.081 where the degree of polymerization of the glycidyl methacrylate-derived backbone was m and the degree of polymerization of tetrahydrofuran was n.

Production Example 1′

(27) To a separatory funnel, 60 g of the white solid obtained in Preparation Example 1 was transferred, 90 ml of ethyl acetate and 90 ml of pure water were added thereto, and the liquid separating operation was conducted. The organic layer after washing was dehydrated over anhydrous magnesium sulfate. This was filtered and ethyl acetate was then distilled off using an evaporator, thereby obtaining a white solid of radically polymerizable polyether. The results of GPC measurement and .sup.1H-NMR measurement were identical to those of Preparation Example 1.

(28) TABLE-US-00001 TABLE 1 Production Production Production Example 1 Example 1′ Example 2 Monomer A Glycidyl methacrylate/ 24 24 24 part by mass Monomer B Tetrahydrofuran/part by mass 600 600 600 Initiator Ytterbium 2 2 3 trifluoromethanesulfonate/ part by mass Terminator Ethanol/part by mass 50 50 50 Reaction temperature/° C. 25 25 25 Reaction time/hour 11 11 2 Yield/% 68 68 22 Number average molecular weight (Mn) 24900 24900 8400 Mass average molecular weight (Mw) 45000 45000 14500 Molecular weight distribution (Mw/Mn) 1.8 1.8 1.7 m1/(m1 + m2 + n) 0.035 0.035 0.081 Catalyst removing operation (aqueous cleaning) No Yes No

Example 1

(29) Preparation of Polymerizable Composition

(30) The polymerizable composition was obtained by adding the radically polymerizable polyether at 20% by mass produced in Preparation Example 1, methyl methacrylate at 80% by mass (trade name: ACRYESTER M manufactured by Mitsubishi Rayon Co., Ltd.), and 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184 manufactured by BASF Japan Ltd.) as the polymerization initiator at 0.3% by mass to 100% by mass of the monomer mixture of the radically polymerizable polyether and methyl methacrylate. Furthermore, dioctyl sodium sulfosuccinate (trade name: AEROSOL OT-100 manufactured by Nihon Cytec Industries Inc.) as the mold releasing agent was added thereto at 0.05% by mass and mixed, and the mixture was then subjected to the degassing treatment under reduced pressure.

(31) The glass plates of 300 mm long and 300 mm wide were faced each other at 0 5 mm intervals via a polyvinyl chloride gasket to form a mold, the polymerizable composition to which the mold releasing agent described above was added was injected into the mold thus formed. Subsequently, this mold was irradiated with light for 120 minutes at a peak illuminance of 2.1 mJ/cm.sup.2 using a chemical lamp to conduct the photopolymerization of the polymerizable composition having the mold releasing agent added, and the mold was subsequently heated for 30 minutes in an air oven at 130° C. to complete the polymerization. Thereafter, the mold was cooled to room temperature, the frame of the mold was removed, thereby obtaining an acrylic film having an average thickness of about 500 μm. The evaluation results are presented in Table 2.

Examples 2 to 4

(32) Examples 2 to 4 were conducted in the same manner as in Example 1 except that the amount of the radically polymerizable polyether produced in Production Example 1 used was changed to the amount presented in Table 2 to obtain acrylic films. The evaluation results are presented in Table 2.

Comparative Example 1

(33) Comparative Example 1 was conducted in the same manner as in Example 1 except that the radically polymerizable polyether produced in Preparation Example 1 was changed to the radically polymerizable polyether produced in Preparation Example 2 to obtain an acrylic film. The evaluation results are presented in Table 2.

(34) In Comparative Example 1, the mass average molecular weight of the radically polymerizable polyether was as low as less than 20000 and thus the transparency of the copolymer and the properties thereof with respect to flexure were poor.

(35) TABLE-US-00002 TABLE 2 Comparative Example 1 Example 1′ Example 2 Example 3 Example 4 Example 1 Radically polymerizable Production Example 1 20 — 30 40 50 — polyether (A)/ Production Example 1′ — 20 — — — — % by mass Production Example 2 — — — — — 20 (Meth)acrylic acid Methyl methacrylate 80 80 70 60 50 80 ester monomer (B)/ % by mass Initiator Irgacure 184/% by mass 0.3 0.3 0.3 0.3 0.3 0.3 Mold releasing agent AEROSOL AOT-100/% by mass 0.05 0.05 0.05 0.05 0.05 0.05 1st polymerization Illuminance/mW/cm.sup.2 2.1 2.1 2.1 2.1 2.1 2.1 condition Polymerization time/hour 2 2 2 2 2 2 2nd polymerization Polymerization temperature/° C. 130 130 130 130 130 130 condition Polymerization time/hour 0.5 0.5 0.5 0.5 0.5 0.5 Optical properties Total luminous transmittance/% 92.5 92.6 92.6 92.7 92.7 93.3 Haze/% 0.5 0.2 0.5 1.6 2.7 18.2 Mechanical properties Elongation at break/% 19.4 21.3 71.1 91.2 61.6 20.2 Elastic modulus/GPa 1.8 1.6 0.9 0.5 0.2 1.8 Flexural property B B B B B C Thermal properties Glass transition temperature/° C. 119 119 116 103 83 104

Example 1′

(36) Example 1′ was conducted in the same manner as in Example 1 except that the radically polymerizable polyether produced in Preparation Example 1 was changed to the radically polymerizable polyether produced in Preparation Example 1′ to obtain an acrylic film. The evaluation results are presented in Table 2.

(37) [Evaluation on Weather Resistance]

(38) In addition, the films obtained in Example 1 and Example 1′ were subjected to the weather resistance test. The weather resistance test of the acrylic films cut into 3 cm.sup.2 was conducted by DAIPLA METAL WEATHER KU-R4-W model (manufactured by DAIPLA WINTES CO., LTD.). The test cycle was as follows. Irradiation for 4 hours (humidity: 70% RH, black panel temperature: 63° C.)/condensation for 4 hours (humidity: 98% RH, black panel temperature: 30° C.)/shower for 10 seconds (70° C.)/darkness for 4 hours (humidity: 70% RH, black panel temperature: 65° C.)/shower for 10 seconds (30° C.). The optical properties of the film after a lapse of 96 hours under the conditions of a UV intensity of 140 mW/cm.sup.2 and the above test cycle were evaluated. The evaluation results are presented in Table 4.

(39) The film fabricated in Example 1′ maintained a high total luminous transmittance and a low haze value even after the weather resistance test. In Example 1′, the radically polymerizable polyether (A) was washed with water after the synthesis and thus the degradation in optical performance of the film fabricated after the weather resistance test was suppressed.

Example 5

(40) Preparation of Polymerizable Composition

(41) The polymerizable composition was obtained by adding the radically polymerizable polyether at 20% by mass produced in Preparation Example 1, methyl methacrylate at 80% by mass (trade name: ACRYESTER M manufactured by Mitsubishi Rayon Co., Ltd.), and t-hexyl peroxypivalate (trade name: Perhexyl PV) as the polymerization initiator at 0.3% by mass to 100% by mass of the monomer mixture of the radically polymerizable polyether and methyl methacrylate. Furthermore, dioctyl sodium sulfosuccinate (trade name: AEROSOL OT-100 manufactured by Nihon Cytec Industries Inc.) as the mold releasing agent was added thereto at 0.05% by mass and mixed, and the mixture was then subjected to the degassing treatment under reduced pressure.

(42) The glass plates of 300 mm long and 300 mm wide were faced each other at 3 mm intervals via a polyvinyl chloride gasket to form a mold, the polymerizable composition to which the mold releasing agent described above was added was injected into the mold thus formed. Subsequently, this mold was subjected to thermal polymerization for 120 minutes in a warm bath at 80° C. and subsequently heated for 30 minutes in an air oven at 130° C. to complete the polymerization. Thereafter, the mold was cooled to room temperature, the frame of the mold was removed, thereby obtaining an acrylic film having an average thickness of about 3000 μm. The evaluation results are presented in Table 3.

(43) [Evaluation on Impact Resistance]

(44) The impact resistance of the copolymer obtained in Example 5 was evaluated.

(45) Charpy Impact Test

(46) The Charpy impact strength of the copolymer obtained in Example 5 was measured in conformity with JIS-K7111. A test piece having a length of 8 cm×a width of 1 cm×and a thickness of 3 mm was cut out and the measurement was conducted under the condition of being flatwise and unnotched. The evaluation results are presented in Table 3.

(47) Falling Weight Impact Test

(48) The impact resistance of the copolymer obtained in Example 5 was evaluated using DuPont impact testing machine. A resin plate cut into a square of 50 mm for each side was used as the sample, and the 50% breaking energy was evaluated in conformity with the standard of JIS-K7211 at a punch radius of 7.9 mm and a mortar radius of 15 2 mm using a weight of 500 g. The evaluation results are presented in Table 3.

(49) TABLE-US-00003 TABLE 3 Example 5 Radically polymerizable Production Example 1 20 polyether (A)/ % by mass (Meth)acrylic acid Methyl methacrylate 80 ester monomer (B)/ % by mass Initiator Perhexyl PV/% by mass 0.3 Mold releasing agent AEROSOL AOT-100/% by mass 0.05 1st polymerization Polymerization temperature/° C. 80 condition Polymerization time/hour 2 2nd polymerization Polymerization temperature/° C. 130 condition Polymerization time/hour 0.5 Optical properties Total luminous transmittance/% 92.4 Haze/% 0.65 Impact resistance DuPont impact value/J 1.6 Charpy impact value/kJ/m.sup.2 65.9 Thermal properties Glass transition temperature/° C. 105.7

(50) TABLE-US-00004 TABLE 4 Example 1 Example 1′ Radically polymerizable Production Example 1 20 — polyether (A)/ Production Example 1′ — 20 % by mass Production Example 2 — — (Meth)acrylic acid Methyl methacrylate 80 80 ester monomer (B)/ % by mass Initiator Irgacure 184/% by mass 0.3 0.3 Mold releasing agent AEROSOL AOT-100/% by mass 0.05 0.05 1st polymerization Illuminance/mW/cm.sup.2 2.1 2.1 condition Polymerization time/hour 2 2 2nd polymerization Polymerization temperature/° C. 130 130 condition Polymerization time/hour 0.5 0.5 Optical properties Total luminous transmittance/% 92.5 92.6 Haze/% 0.5 0.2 Optical properties after Total luminous transmittance/% 84.2 91.8 weather resistance test Haze/% 25.1 3.5

(51) Reagents Used Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Ytterbium(III) trifluoromethanesulfonate hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) Ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) Methyl methacrylate (trade name: ACRYESTER M manufactured by Mitsubishi Rayon Co., Ltd.) 1-Hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184 manufactured by BASF Japan Ltd.) Dioctyl sodium sulfosuccinate (trade name: AEROSOL OT-100 manufactured by Nihon Cytec Industries Inc.) Ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and t-Hexyl peroxypivalate (trade name: Perhexyl PV manufactured by NOF CORPORATION)

Production Method Examples

(52) Hereinafter, the invention will be specifically described with reference to Examples.

(53) The evaluation of the polyether-based copolymer was carried out by the following methods.

(54) (1) .sup.1H-NMR Spectrum

(55) The structure of the compound was confirmed by .sup.1H-NMR spectrum.

(56) CDCl.sub.3 was used as the solvent for measurement and tetramethylsilane was used as the standard substance, and the measurement was conducted using a nuclear magnetic resonance apparatus (JNM EX-270 manufactured by JEOL Ltd.). The measurement temperature was room temperature, and the integration number for the measurement was 16 times.

(57) (2) Measurement of Molecular Weight

(58) The number average molecular weight (Mn), mass average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of the polymer were measured by GPC (HLC-8220 manufactured by Tosoh Corporation, column: TSK-GEL SUPER H-4000 and TSK-GEL SUPER H-2000 connected in series) using polystyrene as the standard substance.

(59) The measurement was conducted under the conditions of eluent: chloroform, measurement temperature: 40° C., and flow rate: 0.6 mL/min.

(60) (3) Yield

(61) The yield was calculated from the sum of the masses of tetrahydrofuran and glycidyl methacrylate introduced at the time of polymerization and the mass of the solid recovered after evaporation.

(62) (4) Evaluation on Polymerizability

(63) The polymerizability was judged according to the following criteria based on the results of (2) and (3). (A): number average molecular weight of 15,000 or more and yield of 40% or more (B): number average molecular weight of 15,000 or more or yield of 40% or more (C): number average molecular weight of less than 15,000 or/and yield of less than 40%

Production Method Example 1

(64) To a 1000 ml three-necked flask equipped with a stirrer, a thermometer, and a cooling tube, 100 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.67 g of ytterbium(III) trifluoromethanesulfonate hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at room temperature. After it was confirmed that ytterbium(III) trifluoromethanesulfonate hydrate was dissolved, 4 g of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. After the addition, the mixture was stirred for 7 hours at room temperature (25° C.). After stirring, 8.3 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto to stop the reaction. After the reaction was terminated, unreacted tetrahydrofuran or excess ethanol was distilled off using an evaporator, thereby obtaining 52 g of a white solid (yield: 50%).

(65) The mass average molecular weight of the white solid thus obtained by GPC measurement was 33,800. In addition, the result of .sup.1H-NMR measurement is presented below. The peaks of protons derived from the ring opening derivative of glycidyl methacrylate were observed at 5.55, 6.15, 4.15, 4.05, and 1.9, and the peaks of protons derived from the ring opening derivative of tetrahydrofuran were observed at from 3.1 to 3.9 and 1.6. It was confirmed that the white solid obtained from the above was a copolymer of poly(3-methacryloxypropene oxide) composed of a (meth)acryloyl backbone and polybutylene oxide. In addition, it was confirmed that the introduction rate, (m1/(m1+m2+n)), of poly(3-methacryloxypropene oxide) was 0.035 from the degree of polymerization, m, of poly(3-methacryloxypropene oxide) and the degree of polymerization, n, of polybutylene oxide in the radically polymerizable polyether.

(66) .sup.1H-NMR

(67) 0.95 (s′) 1.60 (m), 1.9 (s), 2.35 (s′) 3.1 to 3.9 (m), 4.05 (s), 4.25 (m), 5.55 (s), and 6.13 (s)

Production Method Example 2

(68) Production Method Example 2 was conducted in the same manner as in Production Method Example 1 except that the amounts of tetrahydrofuran, glycidyl methacrylate, ytterbium(III) trifluoromethanesulfonate hydrate, and ethanol used and the reaction time were changed to the amounts used and the reaction time presented in Table 5. The yield was 57% and the mass average molecular weight of the copolymer thus obtained by GPC measurement was 40900.

Production Method Example 3

(69) Production Method Example 3 was conducted in the same manner as in Production Method Example 1 except that glycidyl methacrylate was changed to R-glycidyl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and the amounts of tetrahydrofuran, ytterbium(III) trifluoromethanesulfonate hydrate, and ethanol used and the reaction time were changed to the amounts used and the reaction time presented in Table 5. The yield was 55% and the mass average molecular weight of the copolymer thus obtained by GPC measurement was 30400.

Production Method Example 4

(70) Production Method Example 4 was conducted in the same manner as in Production Method Example 1 except that the amounts of tetrahydrofuran, glycidyl methacrylate, ytterbium(III) trifluoromethanesulfonate hydrate, and ethanol used and the reaction time were changed to the amounts used and the reaction time presented in Table 5. The yield was 39% and the mass average molecular weight of the copolymer thus obtained by GPC measurement was 23400.

Production Method Comparative Example 1

(71) Production Method Comparative Example 1 was conducted in the same manner as in Production Method Example 1 except that glycidyl methacrylate was changed to 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Chemical Co., Ltd.) and the amounts of tetrahydrofuran, ytterbium(III) trifluoromethanesulfonate hydrate, and ethanol used and the reaction time were changed to the amounts used and the reaction time presented in Table 5. The yield was 27% and the mass average molecular weight of the copolymer thus obtained by GPC measurement was 16700. The carbonyl group was not adjacent to the glycidyl group as the glycidyl ester was changed to a glycidyl ether, thus the polymerization activity was not improved, and the molecular weight and the yield were lower as compared with those in Production Method Example 1 as a result.

(72) TABLE-US-00005 TABLE 5 Production Production Production Production Production Method Method Method Method Method Comparative Example 1 Example 2 Example 3 Example 4 Example 1 Monomer 1 Kind of monomer Tetrahydrofuran Tetrahydrofuran Tetrahydrofuran Tetrahydrofuran Tetrahydrofuran Part by mass 100 100 100 100 100 Monomer 2 Glycidyl ester (a) Glycidyl Glycidyl Glycidyl Glycidyl methacrylate methacrylate butyrate methacrylate Part by mass 4 4.5 4 2 0 Glycidyl ether 4-hydroxybutyl acrylate glycidyl ether Part by mass 0 0 0 0 4 Catalyst Kind of catalyst Ytterbium Ytterbium Ytterbium Ytterbium Ytterbium trifluorometh- trifluorometh- trifluorometh- trifluorometh- trifluorometh- anesulfonate anesulfonate anesulfonate anesulfonate anesulfonate hydrate hydrate hydrate hydrate hydrate Part by mass 0.67 1 0.67 0.67 0.67 Monomer 2/Catalyst 6 4.5 6 3 6 Polymerization Polymerization temperature/° C. 25 25 25 25 25 condition Polymerization time/hour 7 7 7 7 7 Polymerization Yield/% 50 57 55 39 27 result Number average molecular 21600 25700 16400 16300 11000 weight (Mn) Mass average molecular weight (Mw) 33800 40900 30400 23400 16700 Mw/Mn 1.6 1.6 1.9 1.4 1.5 Polymerizability A A A B C A • • • number average molecular weight of 15,000 or more and yield of 40% or more B • • • number average molecular weight of 15,000 or more or yield of 40% or more C • • • number average molecular weight of less than 15,000 and yield of less than 40%

INDUSTRIAL APPLICABILITY

(73) A (co)polymer produced from a radically polymerizable polyether and a radically polymerizable vinyl monomer exhibits excellent properties as described above, and thus it can be suitably used as a dense optical member of a flexible display front plate, a solar cell substrate, an organic EL substrate, a lighting cover, a liquid crystal display front plate, a light guide sheet, and the like.