JPS5941331A - Halogen-containing aromatic polyester - Google Patents

Abstract

PURPOSE:To provide the titled novel polymer derived from bis(2-chlorophenoxy) ethane-dicarboxylic acid and a specific aromatic diol, moldable by melt-molding, and giving a molded article having excellent optical anisotropy, mechanical properties and self-extinguishing property. CONSTITUTION:The objective polyester composed of the recurring unit of formula I (R is group of formula II-VI; X is Cl or Br bonded to the o-position based on the adjacent O atom of the benzene ring) is prepared by reacting (A) a dicarboxylic acid component comprising 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid and/or 1,2-bis(2-bromophenoxy)ethane-4,4'-dicarboxylic acid with (B) an aromatic diol component composed of 4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, methylhydroquinone, chlorohydroquinone, and phenylhydroquinone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel halogen-containing aromatic compound that can be melt-molded at temperatures below 400°C and can be used to produce molded products having excellent optical anisotropy, mechanical V1 quality, and self-extinguishing properties. It concerns polyester.

In recent years, there has been an increasing demand for higher performance plastics, and many polymers with various new properties have been developed and put on the market. Among them, polymers with optical anisotropy, which is characterized by parallel arrangement of molecular chains, are particularly popular. This liquid crystal polymer is attracting attention for its thin properties, but these liquid crystal polymers include aromatic polyesters, aromatic recarbono acids such as terephthalic acid, aromatic carbonols such as phenylhydroquino7, In addition to these, aromatic polyesters such as 1]-hydroquine benzoic acid are known, but while these polyesters have low optical anisotropy, their melting points are too high and melt molding is impossible. Furthermore, it has the disadvantage of insufficient mechanical properties, typified by elastic modulus, and the reality is that even higher performance is desired.

Therefore, the present inventors have developed optical properties, melt moldability, and
``A unique and mechanical 1/1 quality that is in equilibrium''
Steal's take j (as a result of careful consideration of 1 as [1]
．． 2-bis(2-chlorophenoquino)ethane-4,4'
-Lev J) Lepono acid wa 4 earth bi/Majko wa 1,2-His(
A halogen-containing aromatic compound is prepared by using 2-bromophenoquine)ethane-4゜4'-1:J rubonoic acid as a dicarboxylic acid component and reacting it with a specific aromatic group. The present invention was achieved based on the discovery that polyester can be melt-molded at temperatures below 400°C and can provide molded articles having excellent optical anisotropy, mechanical properties, and even self-extinguishing properties.

In other words, the present invention provides a halogen-containing aromatic polyester whose main constituent is a repeating unit represented by the following general formula (1).

X is a chlorine or bromine atom, and is bonded at the ortho position to the adjacent oxygen Jiff r- of the benzeno nucleus. ) 1゜2-His used as a dicarboxylic acid component in the present invention
(2-chlorophenoquino)efno-4,4'-recarphonoic acid or 1,2-his (2-bromophenoquino)ethane-4,4'-dicarboxylic acid and a fat such as ethylene glycol or 1,4-butanediol Polyesters prepared by reacting group diols are described, for example, in Japanese Patent Publication No. 1795-1982 and Japanese Patent Application Laid-open No. 49-1989. 52292
Although this polyester has good self-extinguishing properties, it has poor elastic modulus, is isotropy, and has no optical anisotropy. On the other hand, the halogen-containing aromatic polyester of the present invention, which uses a specific aromatic diol as the diol component, not only exhibits the same self-extinguishing property as the polyester, but also exhibits the ability to be used as a liquid crystal polymer at an optical angle of 5°+S ji f'l. -C's 111ri1. : I own
It can be melt-molded, and the bullet III rate of the manufactured product is extremely low.

In this research, in the 9-halokeno9'r' N group polyester, the j'l+'h b'r and nocal small acids constituting the repeating position 111 of the general formula (1) have the structural formula Selected from 11 combinations 1/I! It is at least one type.

(However, X represents a chlorine or bromine atom, and is bonded at the ortho position to the adjacent oxygen atom of the heno-7) nucleus. ) Further, the repeating position 111 of general formula (1) (1) is at least one selected from the 11 compounds represented by the above structural units.

Among these aromatic long ols, 4,4'-rehydroquinobiphenyl is most preferred.

Note that the halogen-containing aromatic polyester of the present invention has
1.2-His(2-chlorophenoquino)efno4,
4'-recarphonoic acid and/or 1,2-his (2
-Zol: ] 50 mol% or more of l-phenoquino)ethane-4,4'-dicarboxylic acid is other aromatic dicarboxylic acid,
For example, terephthalic acid, 1,2-his (phenoquino)
Ethano-4,4'-dicarboxylic acid, 2,6-naphthalenodicarboxylic acid, 4,4''; phenyl dicarboxylic acid and 4,4'-; phenyl oxide dicarboxylic acid. dicalho, acid component 50
If it is more than 111% by mole, the melt moldability and optical anisotropy of the polyester 111 will be low.
F. In addition, if there is a small proportion of Jl, inophthalic acid and hexahydroterephthalic acid IL, the Recarbeau acid component of any song,
Hydroquinone
-Oquinoamine, 1: It is also possible to further polymerize 9-carboxylic acid, 1:J acid, etc.

The halogen-containing aromatic polyester of the present invention can be produced according to the conventional polycondensation method for polyesters, and there are no particular restrictions on the production method. 2) One example is the law.

(1) A method for producing a diester compound of an aromatic diol and a carphonic acid of the following fi N group by demonocarboxylic acid polycondensation reaction.

(2) A method of producing by dephenol polycondensation reaction from a lephenyl ester compound of a carbonic acid and the following aromatic diol.

Particularly, method (1) is preferable because the polycondensation reaction proceeds without a catalyst, and in method (2), the polycondensation reaction MW includes stannous acetate, dibutyl titanate, lead acetate, anotimony oxide, etc. metal compounds can be used.

The halogen-containing aromatic polyester of the present invention thus obtained has a low melting point of 400°C or less, and can be subjected to ordinary melt molding such as extrusion molding, injection molding, compression molding, and blow molding, and can be used to produce fibers, films, and three-dimensional molded products. , spring molds, hoses, etc., and can be easily blended with other thermoplastic polymers.

During molding, the halogen-containing aromatic polyester of the present invention is mixed with glass fiber, carbon [L] reinforcing agents such as asbestos, fillers, nucleating agents, antioxidants, stabilizers, n
Adding additives such as J plastics, lubricants, mold release agents, etc. gives desired properties to molded products! can be used.

The molded article obtained from the novel aromatic polyester of the present invention has good optical anisotropy at 400°C or lower due to its parallel molecular arrangement, and has a self-extinguishing 1'l wamabi formation (in Japanese). 1
The quality is 1f4i and scooping 1.

The present invention will be further explained below using Examples.

Practical biIIi Example 1 1 mouth Aikawa test 'j'-'+ 4,4'-rease I, quinohephenyl 2F0 da (10 to 10-' mol), 1.2
-His(2-Julohuenoquino)ethane-4,4'-
Retunorbonoic acid 26.0 da (7xlO'mol) and 1
．． 2-His(phenoquino)ethane-4,4'-lecarponoic acid 9.1g (3xlO'mol) was added to 1μ of 11゜Next step (carry out the de-I'll acid polycondensation reaction with 'l -)
f:.

After reacting for 1.8 hours at 230 to 360 degrees Celsius under a nitrogen gas atmosphere, the pressure was reduced to 0.5 #MITg, and the mixture was further heated for 0.5 hours to complete the polycondensation.
11^1 acid 12. o y is distilled brown polymer is I
I was jealous.

The theoretical structural formula of this polymer is as follows: The elemental analysis results of this polyester were in good agreement with the theoretical values as shown in Table 1.

1)/1η=7'/3 (molar ratio)
%-C1%). Also, place this polyester on the sample stage of a polarizing microscope, and use sil'riii! When the melting point and optical anisotropy were confirmed, the melting point was 3.
The temperature was 22° C. and good optical anisotropy was exhibited. This polymer was subjected to a high-speed flow tester and spun at 6111 degrees at 370 degrees Celsius.
, spinneret hole diameter Q, 3 Spinning with scrap φ 0.17
A spun yarn of mmφ was obtained. This spun yarn was made into Toyo Bold Dry J (m)n1 and produced into Obayburono DDV-II-EA.
When the elastic modulus was measured at a frequency of 110I (z, heating rate of 2'C/min, and a gap between two parts s40 arp), it was 41 GPa at 300, which is extremely high.

For comparison, a polyester made from phenylhydroquinone and terephthalic acid was prepared using JP-A-53-654211.
1'l of polymer spun yarn bullets polymerized according to ffl publication
rate? When measured, it was 20GPa at 300℃.

Example 2: Test Yji: Rareacetoquinochlorhydroquinone, Rareacetoquinomethylhydroquinone or 414
'-Reacetoquinohyphenyl (both 10・, 10-
2 mol) and 1,2-His(2-chlorophenoxy)ethane-4,4'-*carboxylic acid (IOXIO' mol) and carried out a polycondensation reaction under the same procedure as in Example 1. Ta.

Confirm the melting point and optical anisotropy of the obtained polymer.Polyesters from diacetoquine chlorohydroquinone, rarecetoquine methylhydroquinone, and 4.4'-;ace1-quinohyphenyl have optical anisotropy. Show your gender,
It was found that the polyester made from diacetoquinomethylhydroquino exhibits a unique behavior in that it becomes isotropic from 375C (Table 2).

The polymer of Experiment N2 was spun as in Example 1 at a spinning temperature of 340'C to obtain a spun yarn of 0.15 thread Mφ. This spun yarn was made into Rheovibro:/DDV-11-E A
When the elastic modulus was measured using
J) with high elastic modulus.

Example 3 Diace I/quinochlorhydroquinono 4.6y (5X1
0 mole) and 230 da (5y,
10'mol) for polymerization test? Example 2 of 7 including 11 in S.
Polycondensation was carried out under the same conditions as above to obtain a polymer having the above structural formula.

1 This polymer showed good optical anisotropy at 122'C and had excellent self-extinguishing properties.

Claims (1)

[Claims] 1. The repetition represented by the general formula (1) + 1, 7 is 1
a) Rokeno yj aromatic polyester as an essential component. , X is a salt atom or a bromine atom, and for the adjacent acid atom of the benzeno nucleus, or!・Conjunct to position)