JPH01103614A - Vinylidene cyanide copolymer - Google Patents

Abstract

PURPOSE:To make it possible to produce a vinylidene cyanide copolymer which is transparent and has a high dielectric constant, by copolymerizing vinylidene cyanide with a specific vinyl compound. CONSTITUTION:The title copolymer is produced by copolymerizing vinylidene cyanide (A) of formula I with a vinyl compound (B) of formula II. In formula II, Z is a hydrogen atom. or a 1-7C saturated hydrocarbon group, R is a group CnH2n+1COO- when Z is a hydrogen atom., and R is a group CH3COO- or a group having a benzene ring when Z is a 1-6C saturated hydrocarbon group. The amount of the component (B) to be used is on the order of 0.8-20 molar equivalents per molar equivalent of the component (A). It is preferred that the amount is 1-8 molar equivalents in the synthesis of an alternating copolymer and 8-20 molar equivalents in the synthesis of a random copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a copolymer of vinylidene cyanide and a vinyl compound. More specifically, the present invention relates to a copolymer of vinylidene cyanide and a vinyl compound that provides a transparent molded product with a high dielectric constant.

[Prior art]

Copolymers of vinylidene cyanide and various vinyl compounds (H, Qilbert et aA, *J, Ant
Chem.

5oc-* 78, 1669 (1956), etc.), but there are no examples of the above copolymers.

[Summary of the invention]

The present invention is basically a compound obtained by copolymerizing vinylidene cyanide represented by the following structural formula Q and a vinyl compound represented by the following structural formula (B) (2 is H or CHs''). (Here, 2 is a hydrogen atom or a saturated hydrocarbon having 1 to 6 carbon atoms, and 6 is a saturated hydrocarbon having 1 to 6 carbon atoms, and when 2 is a hydrogen atom, 2 is a saturated hydrocarbon having 1 to 6 carbon atoms. (When R is hydrogen, R is a CLCoO- group or a group having a benzene ring.) The copolymer of the present invention has excellent transparency, and when converted into an electret, it has excellent pyroelectricity,
Gives piezoelectricity.

[Description of specific configuration of the invention]

The vinylidene cyanide copolymer of the present invention has the following structural formula (
It is obtained by copolymerizing the vinylidene cyanide monomer represented by A) and the vinyl compound monomer represented by the following structural formula (B).

Here, 2 is a hydrogen atom (hereinafter sometimes referred to as an H atom) or a saturated hydrocarbon having 1 to 6 carbon atoms.
When is a H atom, R is a CnHzn+ICO〇- group (n is 0 or an odd or even number of 4 to 9), and when 2 is a saturated hydrocarbon having 1 to 6 carbon atoms, R has a CH3COO- group or a benzene ring. It's basic.

Vinylidene cyanide and vinyl compounds form dindam or alternating copolymers.

The ratio of the component derived from vinylidene cyanide and the component derived from the vinyl compound in the random copolymer is the molar ratio of vinyl compound (6)/vinylidene cyanide (4).
/A is in the range of 0.8 to 2G, preferably 0.9 to 15.

The copolymer of the present invention, both the alternating copolymer and the random copolymer, is a resin with low crystallinity, and has a gas transition point of 100 to 100.
The temperature is 250°C, preferably in the range of 140 to 200°C.

The molecular weight is 200,000 to 10,000, preferably 500,000 to 10,000.
It is in the range of 00,000.

When 2 of the vinyl compound is a hydrogen atom, R is C
In the nHzH+t coo- group, n is 0 or an odd number from 4 to 9 or an even number -1■. Therefore, R is H! It is a carboxyl group having an Ic element or a linear or branched saturated hydrocarbon. Examples of such egg-bearing hydrocarbon groups include nonyl group, naphthyl group, heptyl group, hexyl group, pendel group, and butyl group. Among these groups, preferred examples of groups having branched hydrocarbons include secondary hydrocarbons and tertiary carbon groups.

When 2 of the vinyl compound is a saturated hydrocarbon having 1 to 6 carbon atoms, =R is a CHs COO- group or a group having a benzene ring.

Preferred examples of the group having a benzene ring are phenyl group,
It is a naphthyl group. Further, the saturated hydrocarbon having 1 to 6 carbon atoms constituting 2 may be a branched hydrocarbon having four linear secondary carbons or a tertiary carbon. Preferred hydrocarbons include methyl and ethyl groups.

As a method for producing the copolymer of the present invention, vinylidene cyanide and a vinyl compound can be polymerized in a solvent or in the absence of a solvent using a radical initiator.

It can also be produced by slurry polymerization or polymerization in an angle.

The amount of fecal vinyl compound used is 0.8 to 20 molar equivalents per 1 molar equivalent of vinylidene cyanide, and when synthesizing alternating copolymers, 1 to 8 molar equivalents and random copolymers are used. In the case of polymers, it is desirable to use 8 to 20 molar equivalents.

When using a solvent, it is preferable to use one or more solvents selected from aprotic solvents such as evaporate, benzene, toluene, xylene, etc., and aliphatic hydrocarbons such as pentane, hexane, heptane, etc. good.

In the case of slurry polymerization, the polymerization temperature is 0 to 150°C, preferably 50 to 80°C.

In the case of polymerization in an ampoule, there are no particular restrictions, but from 0 to
It can be carried out at 100°C.

The catalyst used in producing the copolymer of the present invention is a known radical generating initiator. Specifically, oxygen, dialkyl(-oxides and derivatives such as ditarjarypdel peroxide, tertiary-butylcumyl peroxide, dicumyl peroxide), diacyl/(-oxides such as dicumyl peroxide, dioctanoyl peroxide, etc.) Cooxides, peroxydicarbonates such as diisoprobyl(-oxydicarbonate, di-2-ethylhexyl-oxydicarbonate), tert-butyl peroxyin butyrate, tert-butyl peroxy pivalate, tert- Oxyesters such as butyl peroxylaurate, methyl ethyl ketone <-yc-+ side, ketone peroxides such as fuchlorhexanone peroxide L2=
2-bistarchybutylperoxyoctane, 1.
<-oxyketals such as l-bis(tert-butylperoxy)cyclohexane, hydroperoxides such as tertiarypterno idrono(-oxide), cumene I idrono(-oxide), 292'-azobisisoprodenitrile Azo compounds such as are useful.

After the polymerization is completed, an aprotic solvent is poured into the reaction mixture to separate the resulting polymer. Subsequently, the desired copolymer is obtained by washing and drying the produced polymer.

[Usefulness of the copolymer of the present invention]

The copolymer of the present invention is a polymer having highly polar cyano groups and ester groups, and can be molded by general molding methods such as casting, pressing, and injection molding. It can be used as an insulating layer for KL elements. The polarized material can be applied as a highly functional material such as piezoelectric or pyroelectric material.

Further, since the molded article made of the copolymer of the present invention has excellent transparency, it is useful as optical materials such as fibers and lenses, and as optical elements utilizing high dielectric constant.

Next, the present invention will be illustrated in more detail with examples.

However, the invention is not limited to these examples in any way.

〔Example〕

Vinylidene cyanide 102 (0.13 mOj), vinyl formate 45 F (0.13 mOj), synthesized by a conventional method, was placed in a 950 Od four flask equipped with a stirrer, a Dimroth, and a temperature needle.
To 0.63 mon%, add 25 d1 of toluene, 25 d1 of heptane, 25 d1 of diisopropyl/(-oxydicarbonate (several 10 capes), and under an argon gas flow, 50 ml of
The mixture was heated and stirred at ℃ for 3 hours.

The precipitated polymer was separated by F, washed with toluene and ethanol in that order, and then dried under reduced pressure at 80° C. overnight. The product yield was 10.1 f, and the yield was 53%. This product was subjected to "H-NMR.

Analysis by 13C-8MR1 infrared absorption (IR) and elemental analysis confirmed that it was a 1:1 alternating copolymer. The IR absorption spectrum was as shown in FIG. The main physical property data (powder) is shown below.

O glass transition temperature (Tg) 152°C O intrinsic viscosity [da] 0.5 0 Elemental analysis results Vinylidene cyanide (VDCN) content 53 mol% Measurement was performed at room temperature (25°C), and the results shown in Table 1 were obtained.

Lesson 1 [Example 2] In a 300d4 black flask equipped with a stirrer, a Dimroth, and a thermometer, vinylidene cyanide 6F (0.08 moj), vinyl piperate 50
(0.4 mon, manufactured by Wako Pure Chemical Industries), heptane 1211j
, lauroyl peroxide 61q were added thereto, and the mixture was heated and stirred at 70° C. for 4 hours under an argon gas flow. The precipitated polymer was separated from P, washed with toluene and ethanol in that order, and then dried under reduced pressure at 80° C. overnight. The yield of the product was 7.4 tons, and the yield was 47%. When this product was analyzed by 1H-NMR, C-NMR, IR, and elemental analysis, it was confirmed that it was a 1:1 alternating copolymer. The main physical property data (powder) is shown below.

0 Glass transition temperature (Tg) 171°C O Intrinsic viscosity [η] 2.2 0 Elemental analysis results VDCN content 55 mol% Example 1
After forming a film using the same method as above, the dielectric constant was adjusted to room temperature (
25° C.), and the results shown in Table 2 were obtained.

Table 2 also shows the polarized cast film.
Table 3 shows the results of measuring the piezoelectric constant d31.

Table 3 [Example 3] Vinylidene cyanide 1 Of (0.13 moi) synthesized by a conventional method and impropenyl acetate 68 F (0.64 mon (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), 20 d of toluene, and several grains of diimpropyl peroxydicarbonate (several 1011 F) were added, and the mixture was heated and stirred at 70° C. for 1 hour under a gas stream.

The viscous reaction solution was poured into toluene, and the precipitated polymer was washed separately with toluene and ethanol, and then dried under reduced pressure at 80° C. overnight. The yield of product was 121F, with a yield of 53%. When this product was analyzed by H-NMR, C-NMRX IR, and elemental analysis, it was confirmed that it was a 1:1 alternating copolymer. The IR absorption spectrum was as shown in Figure 2. The main physical property data (powder) is shown below.

O Glass transition temperature (Tg) 1 i 2°C 0 Intrinsic viscosity (7) 0.5 0 Elemental analysis results VDCN content 50 molsi The obtained powder was dissolved in a DMA solvent and a film was made by solvent casting method, and dielectric The rate was measured at room temperature (25°C). The results are shown in Section 4.

Table 4 [Example 4] Vinylidene cyanide 20F (0.26 mof) and α-methylstyrene 30 synthesized by a conventional method were placed in a 300 d four-loaf flask equipped with a stirrer, a Dimroth, and a thermometer.
f (0.26 mon, Wako Tsumugi Co., Ltd.), toluene 50
-, 20η of lauroyl peroxide was added, and the mixture was stirred at room temperature under an argon gas stream.

When the heat generation subsided, the mixture was heated and stirred at 70° C. for 1.5 hours. The precipitated polymer was separated from each other, dissolved in acetone, and reprecipitated in toluene. It was washed with ethanol and then dried under reduced pressure at 80° C. overnight.

The yield of product was 7.12% and the yield was 14% wax. This product was subjected to H-NMR and C-NMR.

Analysis by IR and elemental analysis confirmed that it was a 1:1 alternating copolymer. The main physical property data (
powder).

O glass transition temperature (Tg) 1 s 1℃O
Intrinsic viscosity [η] 0.4 0 Elemental analysis results V'DCN content 52.6 mol% A film was prepared in the same manner as in Example 1, and the dielectric constant was measured at room temperature (25° C.). The results are shown in Table 5.

Table 5 [Example 5] Vinylidene cyanide 5 f (0.06 mon) and vinyl butyrate 4 synthesized by a conventional method were placed in a 300 m four-loaf flask equipped with a stirrer, a Dimroth, and a thermometer.
0f (0.35m0A, Tokyo Kasei #R, LaFloyl Peroxide 51q was added, under argon gas flow, 70
The mixture was heated and stirred at ℃ for 2 hours.

The precipitated polymer was separated and washed with toluene and ethanol in that order, and then dried under reduced pressure at 80° C. overnight. The yield of the product was 10.5f and 85%. This product was subjected to "H-NMR.

When analyzed by C-NMR% IR% elemental analysis, it was confirmed that it was a 1:1 alternating copolymer.The IH absorption spectrum was 9 as shown in Figure 3.

The main physical property data (powder) is shown below.

O glass transition temperature (Tg) i ta 2℃O
Intrinsic viscosity (v) e, sO elemental analysis results VDCN content 50 mol% In addition, the obtained powder was dissolved in DMA solvent to create a paper film by solvent casting method, and the dielectric constant was measured at room @ (25 ° C) K” tl:
(It was determined. The results are shown in Table 6.

Table 6 Furthermore, Table 7 shows the results of measuring the dielectric constant at a frequency of 100 Hz and a predetermined temperature.

(Left below) 7th floor! In addition, the piezoelectric constant tlss and Kt of the cast film were measured by stretching the cast film about 3 times in the uniaxial direction in a silicone oil path adjusted to 190° C. and subjecting it to polarization treatment.

The results are shown in Table 8.

Table 8 [Example 6] Vinylidene cyanide 5f (0.06m0JI), vinylhexano
50 f (0.35 mob, manufactured by Tokyo Kasei) and LaFloyl peroxide 5q were added, and under an argon gas flow,
The mixture was stirred at 70°C for 3 hours. Separate the precipitated polymer t-F, wash with toluene and ethanol in this order, and then
It was dried under reduced pressure at 80°C overnight. Product yield is 9.6t
The reaction time was 6 seconds, and the yield was 68%. This product is called “H-
NMR% "C-NMR%" When analyzed by IR and elemental analysis, it was confirmed that it was a l:l alternating copolymer.

The main physical property data (powder) is shown below.

O glass transition temperature (Tg) z 14℃ O intrinsic viscosity [ma] 2.5 0 Elemental analysis requested VDCN content 51 mol% After making a paper film in the same manner as in Example 1, the dielectric constant was adjusted to 1 m (25C). The results are shown in Table 9.

Table 9 Table 10 shows the results of measuring the electrical dissipation rate at a frequency of 100 Hz and a predetermined temperature.

Table 10 also shows piezoelectric constants dat and Kt as in Example 5.
was measured. The results are shown in Table 11.

Table 11

[Brief explanation of the drawing]

FIGS. 1, 2, and 3 show the infrared absorption spectra of the copolymerization products of Example 11, Example 3, and Example 5, respectively. Patent applicant: Mitsubishi Yuka Co., Ltd. Agent: Masahisa Hase Patent attorney: Patent attorney Takaya Yamamoto

Claims (1)

[Claims] (1) A vinylidene cyanide copolymer obtained by copolymerizing vinylidene cyanide represented by the following structural formula (A) and a vinyl compound represented by the following structural formula (B). [In the ceremony, Z
is a hydrogen atom or a saturated hydrocarbon having 1 to 6 carbon atoms, and when Z is a hydrogen atom, R is CnH_2_n_+_1C
OO- group (n=0 or an integer of 4 to 9), Z has 1 to 1 carbon atoms
When R is a saturated hydrocarbon of 6, R is a CH_3COO- group or a group having a benzene ring. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B)