Vinylidene cyanide copolymer

Abstract: Disclosed is a vinylidene cyanide copolymer obtained by copolymerization of vinylidene cyanide and two kinds of vinyl compounds. By formation of a ternary copolymer, a monomer difficultly copolymerizable with vinylidene cyanide can be incorporated into the polymer, and high piezoelectric performance can be obtained when polarized.

Description: BACKGROUND OF THE INVENTION This invention relates to a ternary copolymer of vinylidene cyanide with two different kinds of vinyl compounds which gives a molded product with transparent and high dielectric constant. A large number of copolymers of vinylidene cyanide with various vinyl compounds have been known (e.g, H, Gilbert et al., J. Am. Chem. Soc., 78, 1669 (1956)), but there is no example of a ternary copolymer with two different kinds of vinyl compounds. US-2716106 relates to an interpolymer comprising vinylidene cyanide copolymerized with two other monoolefinic monomers. These two other monoolefinic monomers can be selected from nonhalogenated or halogenated monoolefinic hydrocarbons, monoolefinically unsaturated esters such as vinyl acetate or vinyl butyrate, alkyl acrylates, isopropenyl esters, vinyl α-haloesters, allyl derivatives, alkyl α-haloacrylates or maleate or fumarate derivatives. This document does not mention pyroelectric or piezoelectric characteristics of the above terpolymers. EP-A-0 264 240 reveals a vinylidene cyanide copolymer that includes yinylidene cyanide units and units of a further vinyl monomer. In a preferred embodiment, this copolymer comprises the units of the vinyl compound and the vinylidene cyanide in a molar ratio of 0.8 : 20. The above copolymers preferably show a molecular weight of from 200,000 to 1,500,000. This document relates to binary resin compositions, e.g. copolymers containing vinylidene cyanide and vinyl formate or vinylidene cyanide and vinyl butyrate. SUMMARY OF THE INVENTION An object of the present invention is to provide a ternary copolymer obtained by copolymerization of vinylidene cyanide with two different kinds of vinyl compounds. The ternary copolymer of the present invention has excellent transparency and can be formed into an electret to give excellent pyroelectric and piezoelectric characteristics. The present invention is a random or alternate vinylidene cyanide ternary copolymer comprising the structural units represented by (I), (II) and (III) shown below, with the total molar ratio of (II) and (III) to (I) being 0.8 to 20, having a weight average molecular weight (Mw) of 200,000 to 1,500,000, low crystallinity and a glass transition temperature of 100 to 250°C: wherein R 1 and R 2 are different, and R 1 represents a hydrogen atom or a methyl group and R 2 represents a hydrogen atom or a propyl group. DESCRIPTION OF THE PREFERRED EMBODIMENTS Of the ternary copolymers of the present invention, vinylidene cyanide-vinyl acetate-vinyl formate ternary copolymer, vinylidene cyanide-vinyl acetate-vinyl butyrate ternary copolymer or vinylidene cyanide-vinyl formate-vinyl butyrate ternary copolymer are the embodiments Vinylidene cyanide units (I), and the vinyl units (II) and (III) can form a random copolymer. The ratio of vinylidene cyanide units (I) to the vinyl units (II) and (III) in the random copolymer is, in a molar ratio of {(II) + (III)}/(I), within the range of from 0.8 to 20, preferably from 0.9 to 15. The ratio of the vinyl units (II) to (III) may be preferably within the range of from 0.2/1 to 5/1, more preferably 0.3/1 to 3/1, particularly preferably 0.5/1 to 2.0/1. The copolymer of the present invention is a resin having low crystallinity, with a glass transition point being within the range of from 100 to 250 °C, preferably from 140 to 200 °C. When the present polymer is molded into a film or a disc, for imparting strength which can stand use, its molecular weight (Mw: weight average molecular weight) should be within the range of from 200,000 to 1,500,000, preferably from 500,000 to 1,000,000. As the method for preparing the copolymer of the present invention, it can be prepared by polymerizing vinylidene cyanide together with vinyl compounds CH 2 =CHOCOR 1 and CH 2 =CHOCOR 2 in a solvent, in a slurry or in absence of a solvent by use of a radical polymerization initiator. The total amount of the two kinds of vinyl compounds (II) and (III) used may be 0.8 to 20 mole equivalents based on one mole of vinylidene cyanide (I), and desirably 8 to 20 mole equivalents. When an alternate copolymer is synthesized, 1 to 8 mole equivalents of (II) and (III) based on one mole (I) are preferred. Here, the alternate copolymer means a copolymer comprising the above three structural units represented by (I) to (III) wherein the structural unit represented by (I) and either one of the structural units represented by (II) and (III) are alternately polymerized. The molar ratio of the two kinds of vinyl compounds (IT) and (III) can be varied as desired corresponding to the desired polymer species. When a solvent is employed, it is preferred to carry out the reaction in a solvent system selected from among aprotic solvents such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane and heptane. The polymerization temperature may be 0 to 150 °C, but desirably 50 to 80 °C, in the case of slurry polymerization. In the case of polymerization in an ampoule or an autoclave, the temperature is not particularly limited, but the reaction can be carried out at 0 to 100 °C. As the radical polymerization initiator, there can be employed, for example, organic peroxides such as lauroyl peroxide, benzoyl peroxide, acetyl peroxide and diisopropyl peroxycarbonate, or azo compounds such as 2,2'-azobisisobutyronitrile. After completion of the polymerization, an aprotic solvent is poured into the reaction mixture, and the polymer formed is separated by filtration. Subsequently, the polymer formed is washed and dried to give the desired copolymer. The polymer obtained can be molded into a desired shape such as film, fiber and others by casting, spin coating, dipping, pressing, extrusion, injection, etc. By way of stretching, cyano groups can be readily oriented in one direction. Stretching may be practiced at a temperature range of from Tg + 10 °C to Tg - 10 °C relative to the glass transition temperature (Tg) of the polymer, and stretching may be effected to 1.5 to 6-fold, preferably 3 to 6-fold relative to the length before stretching. Also, by applying a high potential on the product obtained to effect polarization, the dipoles such as cyano groups can be oriented in the vertical direction relative to the film surface. Polarization may be effected at a temperature of the glass transition temperature (Tg) + 10 °C to Tg - 10 °C for 0.5 to 5 hours, preferably 0.5 to 2 hours. The copolymer of the present invention is a polymer having cyano groups and ester groups with great polarity, can be molded according to molding methods in general, namely casting, pressing and injection molding, and the molded product has high dielectric characteristic and can be used as the insulating layer for condensors and EL devices. Also, a molded product with good transparency can be obtained, and it is also useful as the optical material such as fiber and lens. And, those subjected to polarization treatment can be used not only as high functional materials such as piezoelectric and pyroelectric materials, but are also useful as the optical materials such as light wavelength converting device, optical shutter, optical deflecting device, optical strength·phase modulating device and high speed optical switching device, thus being of practical value in application for optical communication, optical information processing and optical working. EXAMPLES The present invention is described specifically by referring to Examples. However, the present invention is not limited by these Examples at all. Example 1 A 200 ml autoclave equipped with a stirring device was charged with 20 g (0.26 mole) of vinylidene cyanide, 46.8 g (0.65 mole) of vinyl formate, 55.9 g (0.65 mole, available from Wako Junyaku K.K.) of vinyl acetate and 20 mg of lauroyl peroxide, and the mixture was stirred under heating at 80 °C for 2 hours. After returned to atmospheric pressure, toluene was added, the polymer was separated by filtration, washed successively with toluene and methanol, in this order, and dried under reduced pressure at 80 °C overnight. The yield of the product was found to be 15.5 g. When the product was subjected to elemental analysis by 1 H-NMR, 13 C-NMR and IR (infrared absorption spectrum), the molar ratio of vinylidene cyanide units to the two kinds of vinyl units was confirmed to be approximately 1 : 1, and that of vinyl formate units to vinyl acetate units 1 : 1.47. In IR-absorption spectrum, respective absorptions ν CO = 1740 cm -1 and ν CN = 2250 cm -1 of CO and CN were recognized. In the following, main physical properties data (powder) of the product are shown: Glass transition temperature (Tg): 167 °C Intrinsic viscosity [η]: 3.5 dl/g Elemental analysis results: vinylidene cyanide content 50 mole %. The powder obtained was dissolved in dimethylacetamide (DMA) solvent, and a film was prepared according to the solvent cast method and the dielectric constant was measured at room temperature (25 °C). The results are shown in Table 1. Frequency Dielectric constant 100 Hz 4.72 1 kHz 4.47 100 kHz 4.02 Also, the relationship between temperature and dielectric constant was determined at a frequency of 100 Hz, and the results are shown in Table 2. Measurement temperature (°C) Dielectric constant 130 6.8 140 7.6 150 9.2 160 31 170 118 Also, the cast film stretched to about 3-fold in monoaxial direction in a silicone oil bath controlled to 162 °C followed by polarization treatment was subjected to measurement of piezoelectric constant d 31 and K t . The value of d 31 showing a transverse piezoelectric effect was obtained by measuring a charged amount generated on the surface of a sample at 110 Hz and a stress at the sectional surface of the sample by use of Vibron-II (trade name, manufactured by Toyo Boldwin Co.). The electromechanical bonding constant K t showing a longitudinal piezoelectric effect was obtained by applying a high frequency voltage (1 to 100 MHz) to a sample and analyzing an electric impedance at a resonance point. The results are shown in Table 3. Polarization temperature (°C) Electrical field strength (kV/cm) Polarization time (hr) d 31 (CGSesu) K t (%) 156 450 1 8.0 x 10 -8 12.7 156 600 1 12.1 x 10 -8 15.1 156 700 1 13.3 x 10 -8 14.8 The intrinsic viscosity [η] was measured by preparing DMF solutions of known concentrations with the use of an Ostwald type viscometer. The molecular weight of the polymer was measured by GPC (gel permeation chromatography) (DMF) and determined as calculated from PS (polystyrene). Example 2 Example 1 was repeated except for using 18.7 g (0.26 mole) of vinyl formate and 89.4 g (1.04 mole, available from Wako Junyaku K.K.) of vinyl acetate to obtain 15.9 g of the product. When the product was analyzed similarly as in Example 1, the molar ratio of vinylidene cyanide units to the two kinds of vinyl units was confirmed to be approximately 1 : 1, and the molar ratio of vinyl formate units to vinyl acetate units of 1 : 6. In the following, main physical properties data (powder) of the product are shown: Glass transition temperature (Tg): 178 °C Intrinsic viscosity [η]: 4.7 dl/g Elemental analysis results: vinylidene cyanide content 50 mole %. The powder obtained was dissolved in dimethylacetamide (DMA) solvent, and a film was prepared according to the solvent cast method and the dielectric constant was measured at room temperature (25 °C). The results are shown in Table 4. Frequency Dielectric constant 100 Hz 3.97 1 kHz 3.81 100 kHz 3.51 Also, the relationship between temperature and dielectric constant was determined at a frequency of 100 Hz, and the results are shown in Table 5. Measurement temperature (°C) Dielectric constant 140 5.8 150 6.4 160 7.6 170 43 180 117 Also, the cast film stretched to about 3-fold in monoaxial direction in a silicone oil bath controlled to 178 °C followed by polarization treatment was subjected to measurement of piezoelectric constant d 31 and K t . The results are shown in Table 6. Polarization temperature (°C) Electrical field strength (kV/cm) Polarization time (hr) d 31 (CGSesu) K t (%) 168 450 1 11.0 x 10 -8 12.5 168 600 1 11.6 x 10 -8 14.2 168 700 1 13.0 x 10 -8 16.9

Claims: A random or alternate vinylidene cyanide ternary copolymer comprising the structural units represented by (I), (II) and (III) shown below, with the total molar ratio of (II) and (III) to (I) being 0.8 to 20, having a weight average molecular weight (Mw) of 200,000 to 1,500,000, low crystallinity and a glass transition temperature of 100 to 250°C: wherein R 1 and R 2 are different, and R 1 represents a hydrogen atom or a methyl group and R 2 represents a hydrogen atom or a propyl group, and wherein in the alternate ternary copolymer the structural units represental by (I) and either one of the structural units represented by (II) and (III) are alternately polymerized. The random or alternate vinylidene cyanide ternary copolymer according to claim 1, wherein the molar ratio of the vinyl unit (II) and the vinyl unit (III) is 0.2/1 to 5/1. The random or alternate vinylidene cyanide ternary copolymer according to claim 1, wherein said copolymer has a glass transition temperature of 140 to 200°C.

Inventors: FUJIMOTO YUKIKO, KISHIMOTO MANABU, SEO IWAO, FUJIMOTO, YUKIKO, KISHIMOTO, MANABU, SEO, IWAO, FUJIMOTO, YUKIKO, C/O TSUKUBA RESEARCH CENT., KISHIMOTO, MANABU, C/O TSUKUBA RESEARCH CENT., SEO, IWAO, C/O TSUKUBA RESEARCH CENT.
Applicants: MITSUBISHI CHEM CORP, MITSUBISHI CHEMICAL CORPORATION
Application year: 1990
Main classification: C08F222
IPC codes: C08F20, C08F218, C08F222