JPH05239194A - New cold-resistant elastomer - Google Patents

Abstract

PURPOSE:To obtain the subject elastomer consisting of a specific structural formula, having intrinsic viscosity of a prescribed value or above, exhibiting rubber elasticity and self-reinforcing type property at low temperature, excellent in thermotropic liquid crystal property and useful for coating, etc., at low temperatures. CONSTITUTION:The objective elastomer consists of a structural formula expressed by formula I {R1 is formula II (X is O, S, CH2, etc.; (1) is positive integer); R2 is formula III ((k) is positive integer), or (CH2CH2O)n [(n) is positive integer]; (m) is positive integer} and has >=0.30dl/g intrinsic viscosity. Furthermore, the elastomer is obtained by reacting, e.g. an equimoler mixture of a compound of formula IV and a compound of formula V with an alkylenediphenyl carbamate of formula VI.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cold-resistant elastomer, which has rubber elasticity and self-reinforced properties particularly at low temperatures (around -30 ° C) and is suitable for low-temperature flexible films and paints. Providing a flexible elastomer.

[0002]

2. Description of the Related Art In recent years, attention has been paid to a thermoplastic elastomer which exhibits rubber elasticity similar to vulcanized rubber at room temperature and exhibits thermoplastic behavior at high temperature. Unlike the vulcanized rubber, which requires a long vulcanization step, this thermoplastic elastomer can be easily processed by injection molding, and has already been put into practical use in automobile parts and the like. Recently, polyamide,
Various thermochromic (hereinafter referred to as thermotropic) liquid crystalline polymers such as polyimide, polyurethane and polycarbonate have been found. We have already conducted research on liquid crystalline polymers having a low glass transition point, and have succeeded in developing a polycarbonate having a glass transition point (Tg) below room temperature. It is considered possible to develop a thermoplastic thermotropic liquid crystalline elastomer composed of a hard segment and a soft segment by chemically bonding the polycarbonate segment and the polyurethane segment.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of extensive studies in order to solve these unresearched problems, and as a result, it was made to provide a new cold-resistant elastomer. A novel cold-resistant elastomer having the following structural formula [V], having an intrinsic viscosity of at least 0.30 dl / g or more and having thermotropic liquid crystallinity.

[Chemical 2]

[0004]

EXAMPLES Examples of the novel cold-resistant elastomer of the present invention will be described in detail below with reference to the accompanying drawings.

[Chemical 3] And a bishydroxyalkyleneoxy derivative (I) of diphenyl represented by

[Chemical 4] Polyethylene glycol (II) and / or

[Chemical 5] And an equimolar mixture of bishydroxyalkylenedimethylsiloxane (III)

[Chemical 6] Alkylenediphenylcarbamate (IV) represented by
By reacting with, a novel cold-resistant elastomer having the following structural formula (V) can be produced.

[Chemical 7] Here, l, n, m, and k are positive integers, respectively, but in the case of the present invention, l = 2 to 6, n = 9, 13, 68,
Particularly good results were shown at 193, m = 2 to 6,8,10, and k = 2 to 4. Examples of (I) used for producing the elastomer of the present invention include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone,
4,4'-biphenol, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenylmethane, bishydroxyalkyleneoxy derivative (I) of 4,4'-dihydroxydiphenyl sulfide and the like are used.

Next, examples of specific production of the novel cold-resistant elastomer of the present invention will be shown below.

EXAMPLE 1 0.096 g (0.25 mmol) of 4,4'-bis (6-hydroxyhexamethyleneoxy) biphenyl, polyethylene glycol (molecular weight 400)
0.100 g (0.25 mmol) and 0.178 g (0.50 mmol) of 1,6-carbamoylhexane were heated with stirring at 140 ° C. under a nitrogen atmosphere. Then, the reaction temperature was gradually raised to 180 ° C. over 1 hour. Next, 180 to 19 for 30 minutes under a reduced pressure of 12 Torr.
After reacting by heating at 0 ° C., the degree of reduced pressure was further raised to 1 Torr and the reaction was carried out at 190 to 200 ° C. for 30 minutes. afterwards,
The product was dissolved in 5 ml of chloroform and poured into methanol for reprecipitation for purification. 40 ° C
The product was dried under reduced pressure for 24 hours to obtain the novel cold-resistant elastomer of the present invention.

The yield and viscosity test, elemental analysis test, and solubility test results of the novel cold-resistant elastomer (V) of the present invention are shown in FIG. As is clear from FIG. 1, as a result of carrying out with four kinds of polyethylene glycol n of 9, 13, 68, 193, the yield of the novel cold-resistant elastomer (V) of the present invention is 86 to 96% and at least 0. A high molecular weight polymer having an intrinsic viscosity of 0.3 dl / g or more was obtained, and the reproducibility was also good. Next, as a result of a solubility test, good solubility was shown in a solvent such as chloroform. (See Figure 1.)
Therefore, a flexible film was prepared from a chloroform solution and the cold-resistant elastomer (V) of the present invention was characterized by elemental analysis, FTIR, NMR, polarizing microscope, DSC and viscoelasticity. An example of elemental analysis results is shown for a polyurethane obtained from polyethylene glycol with n = 193. (See FIG. 1.) As is apparent from FIG. 1, the calculated value and the actually measured value are substantially the same. Urethane carbonyl 1686cm ^-1 in the IR spectrum of the cold elastomers (V) of the present invention, C-O-C in 1262 and 1246cm ^-1,
NH urethane to 3322cm ^-1, 2938cm ^-1 and 2
There was CH stretching vibration at 865 cm ^-1 , confirming the synthesis of the polymer. (See FIG. 2.) Next, as a result of observation by a polarization microscope, a clear liquid crystal phase was shown in the case of the polymers from polyethylene glycol of n = 9 and 13, but n = 1.
In the case of No. 93, it was difficult to determine the presence or absence of liquid crystallinity. n =
In the cases of 9 and 13, smectic A phase and smectic C phase were confirmed. This finding was also confirmed by DSC, and the corresponding endothermic peak was observed. (See FIG. 3.) Next, FIG. 4 shows the viscoelasticity measurement results. As is apparent from the figure, the glass transition temperatures at n = 9, 13, and 193 were -32 ° C, -35 ° C, and -38 ° C, respectively. (N = 1
Not shown in the case of 3,193. )

Up to now, taking a typical elastomer as an example,
Although it has been described, it goes without saying that various modifications are included within the scope of the present invention in designing various derivatives of monomers and production of cold-resistant elastomers from various derivatives.

[0008]

As described above, according to the cold-resistant elastomer of the present invention, since it has rubber elasticity and self-strengthening property at low temperature (around -30 ° C), it can be used for insulating low temperature flexible films and electric wires. Not only is it most suitable for materials and low-temperature paints, but it has a great effect that it can be applied in a wide range, so its industrial value is very large.

[Brief description of drawings]

[FIG. 1] (a), yield and viscosity test (b), elemental analysis test (c), solubility test

FIG. 2 FTIR test

FIG. 3 DSC test

[Fig. 4] Viscoelasticity test

Claims (1)

[Claims] 1. A novel cold-resistant elastomer having the following structural formula [V], having an intrinsic viscosity of at least 0.30 dl / g or more and having thermotropic (thermochromic) liquid crystallinity. [Chemical 1]