JPH03210328A - Nitrated cyclohexane polymer - Google Patents

Abstract

PURPOSE:To obtain the title polymer which is stable up to at least a specified temperature, can give a mixture of an elevated melting temperature when mixed with a well-known thermoplastic polymer, and has a structure containing specified nitrated aromatic rings. CONSTITUTION:A liquid crystal nitrated cyclohexane polymer of formula I (wherein X is H, Cl, CH3 or a group of formula II; l+m=x+y=1, and l >=0.1). This polymer is stable up to at least 300 deg.C and is either a polyester compound having a melting point of 175-300 deg.C, showing a liquid crystal phase and being moldable, or an infusible liquid crystal polyester compound. It can be mixed with a well-known polymer (mainly one with an m.p. of 250 deg.C or below) in any desired mixing ratio to give a mixture of an elevated melting temperature (therefore improved in the heat resistance of a molding) which can give a molding of improved mechanical strengths.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is a cyclohexane polymer having a liquid crystalline nitro group, and is a liquid crystalline polymer that is stable up to a decomposition temperature of 300° C. or higher.

[Prior Art] Polyesters containing cyclohexylene have been described in the literature in recent years. Here, the cyclohexylene unit is! ,
It is 4-cyclohexane dicarboxylic acid or 1,4-cyclohexane diol, and is a polyester made by combining this with other diols or dicarboxylic acids.

For example, U.S. Pat. No. 4,342,862 discloses that polyesters are treated with acidic mixtures of trans-1,4-cyclohexanedicarboxylic acid and other aromatic dicarboxylic acids and substituted hydroquinones such as methyl, phenyl or chloro-hydroquinone. It is described that it can be obtained by polycondensation of

The production of thermotropic liquid crystalline polyesters by polycondensation of only trans-cyclohexanedicarboxylic acid with some of the above-mentioned substituted hydroquinones is described in 07 Macromolecules" 19tI,
1824 (1986).

Polyesters of trans-1,4-cyclohexanediol and substituted aromatic dicarboxylic acids or mixtures of cis and trans forms of 1,4-cyclohexanediol and polyesters of aromatic or alicyclic dicarboxylic acids are also described in the above-mentioned documents. There is.

Other thermotropic liquid crystal polymers containing cyclohexane units include block copolyesters described in 0 Macromolecules, Vol. 2, p. 1626 (1981), such as polyoxy-trans-1,4
-cyclohexyleneoxycarbonyl-trans-1,
4-cyclohexylenecarbonyl-oxy-1,4-phenyleneoxyphthaloyl, or 1 Macrosoleculare hemiei
1874. 1145 pages, (19
There are copolymers described in J. H., which have a rigid structure, trans-! , obtained by polymerizing 4-cyclohexane dibenzoate with α,ω-alkanedicarboxylic acid.

In JP-A No. 64-40,519, a polyester is obtained by polymerizing 4.4°-bicyclohexanediol and an alkanedicarboxylic acid.

Also, JP-A-1-221,425, 1-221,427
, No. 1-225.831 discloses an engineering resin that is a polyarylether but has a cyano group introduced into its aromatic ring and has excellent heat resistance and mechanical strength.

[Problem II to be Solved by the Invention] In general, many liquid crystal polymers are known to be aromatic compounds. Recently, polymers containing a cyclohexane ring or a bicyclohexane ring have been discovered, but there are still few that meet physical requirements.

All cyclohexane polyester compounds have no melting point and decompose, making thermoplastic molding difficult. In order to improve this, an alkylene group is introduced 1
In order to solve this problem, the present inventor introduced an aromatic ring having a nitro group, which is stable up to 300°C or higher and has a melting point of 1.
A thermoformable polyester compound or an infusible liquid crystalline polyester compound exhibiting a liquid crystal phase at 75°C to 300°C was obtained.

The polymer of the present invention can be mixed with known polymers to adjust the melting temperature, and since it is a liquid crystal polymer, its mechanical strength can also be increased.

The known polymers include, for example, polyethylene, polypropylene, polyvinyl chloride, polystyrenes, polymethyl methacrylate, ABS, polyamides, polycarbonates, polyacrylates, polyesters such as polyethylene terephthalate or polybutylene terephthalate, or polyphenylene oxides. be.

In this way, the compounds of the present invention have the heat resistance of known polymers,
It is useful for improving chemical resistance and mechanical strength. or,
It has the potential to be used as an electronic material.

[Means for Solving the Problems] The present invention is a cyclohexane polymer having a liquid crystalline nitro group having the following formula:

The cyclohexane polymer having a nitro group of the present invention is
A typical production method that can be produced according to the conventional polycondensation method is as follows.

That is, 5-nitroisophthaloyl dichloride prepared from 5-nitroisophthalic acid and trans-hui prepared from trans-1,4-cyclohexanedicarboxylic acid;
4-cyclohexane dicarbonyl chloride and trans,
Trans-4,4°-bicyclohexanediol and substituted hydroquinone were reacted in 1,2,4-trichlorobenzene in the presence of pyridine to produce the desired liquid crystalline nitro group-containing cyclohexane polymer.

[Effect of the invention] According to the present invention, it is stable up to 300°C or higher and has a melting point of 17
A polyester compound that exhibits a liquid crystal phase at 5°C to 300°C and is moldable, or an infusible liquid crystalline polyester compound,
An aromatic ring-containing cyclohexane polyester that can be mixed with known thermoplastic polymers in any proportion is obtained.

Therefore, by mixing it with a known polymer (note: many have a melting point of 250°C or lower) in any proportion, it is possible to increase the melting temperature of the mixture (thus improving the heat resistance of the molded product). Moreover, the mechanical strength of molded articles made from the mixture can be improved. It also has the potential to be used as an electronic material.

This will be described in more detail in Examples below.

[Examples] The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples in any way.

The raw materials used in the examples were produced as follows.

(I) Production of trans,trans-4,4゛-bicyclohexanediol: Wiles et al., Journal of the American Chemical Society, 781, p. 1735 (19)
By the method described in 54), trans and cis mixed 4.4°-
Bicyclohexanediol was reacted with benzoyl chloride in dioxane in the presence of pyridine to give dibenzoate. Trans, trans-4,4°-bicyclohexane dibenzoate was produced by recrystallization. After hydrolysis with an aqueous potassium hydroxide solution, recrystallization was performed to produce the desired trans,trans-4,4'-bicyclohexanediol (melting point: 215.5-216.3°C).

(Ii) Production of trans-1,4-cyclohexane dicarbonyl chloride: Malachowski et al., Berichte, 71-%, 7B1
By the method described by Beige (1938), trans-! , 4-
Cyclohexanedicarboxylic acid was reacted with thionyl chloride using a pyridine catalyst. Thionyl chloride is distilled off,
After recrystallization with dry n-hexane, vacuum distillation (boiling point 120-1
The reactor was heated at 30° C. for 77.5 s (H8) and used for the reaction.

+1!1) Production of S-ditroisophthaloyl chloride 5-ditroisophthalic acid is reacted with thionyl chloride using a pyridine catalyst according to the method described in Jennings et al., Journal of the Chemical Society, 1173 pages (1957). Thionyl chloride was distilled off, and the product was recrystallized from dehydrated toluene and used for the reaction. (melting point 6
5.8 to 67.0℃) Thermal decomposition was performed using T manufactured by Seiko Electronics Co., Ltd.
Measurement was performed using a G/DT^-220 model at a heating rate of 10°C per minute. Also, the logarithmic viscosity is 5 when p-chlorophenol is used as a solvent.
Measurement was carried out at 0°C and at a concentration of 0.5 g/dj2.

Example 1 Poly(trans,trans-4,4'-bicyclohexylene-1,4-(3-phenyl)phenylene-trans-1,4-cyclohexylene dicarboxylate-1,
Production of 3-(5-nitro)phenylenedicarboxilade): 100 mJ with a stirrer, cooler, and nitrogen inlet tube! No. 3
In a double flask, add 0.19113 g of trans, trans-4,4'-bicyclohexanediol (1 mol)
), Phenylhydroki/N 1.6759g (!la
+ 5ol), trans-1,4-cyclohexane dicarbonyl chloride 0.1!27g (3m 5ol
), 5-nitroisophthaloyl dichloride 1.736g
(7 s mol) and pyridine 21λ and 1.2.4-
A reaction mixture of 15 sj2 of trichlorobenzene was added and the reaction was carried out at room temperature under a nitrogen atmosphere for 20 minutes, and then the mantle heater was heated to 220°C and the reaction mixture in the three-bottle flask was refluxed for 3 hours.

After cooling this reaction solution to 50°C, methanol 25
Pour the precipitate into Osj2 and add a small amount of methanol,
After washing with water, it was boiled with methanol and filtered (3 times) when ripe, yielding 3.39 g (yield 96.3%).

This polymer has a logarithmic viscosity of 0.31 and a melting point of lδ8~201.
°C, and the decomposition temperature was 328.1i °C.

Examples 2 to 12 As a diol component, trans, trans-4,4'-bicyclohexanediol, phenylhydroquinone, methylhydroquinone, chlorohydroquinone, hydroquinone,
Various polyesters were produced in the same manner as in Examples using trans-1,4-cyclohexane dicarbonyl chloride and 5-nitroisophthalyl dichloride in various proportions as the acid chloride component.

These results are shown in Table 1 together with the results of Example 1.

Procedural amendment (voluntary) 1. Indication of the case Patent Application No. 6.917 of 1990 2. Name of the invention Cyclohexane polymer having a nitro group 3. Person making the amendment Relationship to the case Patent applicant Kita, Osaka City, Osaka Prefecture 3-6-32 Nakanoshima-ku (530)
(207) Chisso Corporation Representative Sadao Nogi 4, Agent 4-4-15 Tsukiji, Chuo-ku, Tokyo (1005) Date of amendment order Voluntary amendment 6, No number of claims increased due to amendment 7, Amendment Detailed description of the invention in the subject specification.

8. Contents of amendment Correct the statement as follows.

(1) Change "Possible." in the second to first lines from the bottom of page 5 to "
there is a possibility. ” is corrected.

(2) Correct "(3-phenyl)" in the third line of page 10 to "(phenyl)".

(3) The following on the Genin side of “r acid loride component” in the table on page 12. Up

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) (In the above formula, x represents -H, -Cl, -CH_3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼.) So l+m=x+y=1
A cyclohexane polymer having a liquid crystalline nitro group, where l is 0.1 or more.