JPS6239626A - Chlorine-containing aromatic polyester - Google Patents

Abstract

PURPOSE:The titled novel polyester, consisting of plural specific constituent units, melt moldable, having improved mechanical properties and capable of giving molded articles exhibiting optical anisotropy. CONSTITUTION:A polyester, obtained by polycondensing (A) an aromatic diol, e.g. chlorohydroquinone, with (B) a dicarboxylic acid, expressed by formula I and (C) an aromatic dicarboxylic acid, e.g. 4,4'-diphenyldicarboxylic acid, in the presence of a catalyst, e.g. stannous acetate, containing 10-100mol%, based on the total polyester, constituent units expressed by formula II (R is formula III, etc.) and 90-0mol%, based on the total polyester, constituent units expressed by formula IV (R' is biphenyl, etc.) and having >=0.35 inherent viscosity and 10-15,000 poises melt viscosity.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is a novel chlorine-containing aromatic compound that can be melt-molded at 400'C or less and can provide molded products having excellent mechanical properties and optical anisotropy. It relates to polyester resin.

<Conventional technology> In recent years, the demand for high performance plastics has increased, and many polymers with various new performances have been developed and put on the market. Liquid crystal polymers with characteristic optical anisotropy are attracting attention because of their excellent functional properties. (Tokuko Showa 55
Publication No. 482).

<Problems to be Solved by the Invention> However, although the aromatic polyester obtained by these methods has a relatively low melting point of 400'C or less, the elastic modulus of the spun yarn is still insufficient, and even more A high modulus of elasticity is desired.

Therefore, the present inventors conducted intensive studies with the aim of obtaining an aromatic polyester that can be melt-molded and has excellent mechanical properties such as high elastic modulus and an excellent balance of optical isomers.1.2-
Bis(2,6-dichlorophenoxy)ethane-4,4'
The inventors have discovered that a novel aromatic polyester that satisfactorily meets the above objectives can be obtained by reacting cicafrebonic acid with a specific aromatic diol to produce a chlorine-containing aromatic polyester.

Means for Solving the Problems〉 That is, the present invention provides the following structural units (I) and (II)
(1″?J?J simple) and (II)
A melt-moldable chlorine-containing material, characterized in that the structural unit (I) accounts for 10 to 100 mol% of the total, and the structural unit (IT) occupies 90 to 6 of the total.
1, Qo(c+'ri) 20-0-, and 1,2bis(2) used as a dicarboxylic acid component in the present invention.
, 6-dichlorophenoxy)ethane 4゜4' dicarboxylic acid and ethylene glycol or 1゜4-butanediol are known for example from Japanese Patent Publication No. 12914/1983. Although it has good self-extinguishing properties,
It is known that the elastic modulus is low, isotropic, and has no optical anisotropy. On the other hand, various diol components and 1゜2-
He discovered that polyester consisting of bis(2-chlorophenoxy)ethane-4゜4-dicarboxylic acid is self-extinguishing and can be made into a high elastic modulus fiber, and has filed an application (Japanese Unexamined Patent Publication No.
9-41331), we have developed a structure with the above-mentioned structure that not only exhibits self-extinguishing properties but also has optical anisotropy and performance as a liquid crystal polymer, can be melt-molded, and has an extremely excellent elastic modulus of the molded product. I discovered polyester.

In the chlorine-containing aromatic polyester of the present invention, the structural unit (
I) is composed of a diol component represented by HOROII and a bonic acid, and the structural unit (If> is composed of a diol component represented by HOROll and an aromatic dicarboxylic acid component represented by l+00cR'cOOtl).

The aromatic dicarboxylic acid constituting this @ structural unit (II) is at least one type of compound selected from the compounds represented by the following structural formula. Acidun 1102C-C;)0(C1h)20-C>-C02
tl ----1,2-his(phenoxy)ethane-4
,4-dicarboxylic acid 1,2-bis(2-chlorophenoxy)ethane-4,4
--Dicarboxylic acid or the aromatic diol constituting the structural units (I> and (II)) is at least one type selected from the compounds represented by the following structural units.

CI HD-9-OH...Methylhydroquinone C]13 (,-(:IC)-0112,6-sie1;' [1
=1-sibuphthalene1] The most preferred compounds of these are the aromatic diol of polyhydroquinone or methylhydroquinone and 1,2-bis(2,6-cyclooxylnoxy)ethane-
It is an aromatic dicarboxylic acid selected from 4,4'-dicalulfonic acid and 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid-phenyldicarboxylic acid.

The molar ratio of structural units (1) to (II) is 10/90/1
0010, preferably 15/85 to 10010.

That is, if the molar ratio is smaller than 10/90, the resulting aromatic polyester will have poor melt moldability, which is not preferable.

Water valve:゛:: ,,゛) Aromatic polyester can be manufactured according to the conventional polynisder combination method, and there are no particular restrictions on the manufacturing method, and typical manufacturing methods include the following (1) to ( :3) Law can be mentioned.

(1) Diesters of aromatic dihydroxy compounds such as chlorhydroni-1-nondiacetate and chlorhydroquinone-sib[]pine∆1~ and 1,2-bis(2,6-
Dichlorophenoxy> A method for producing dichlorophenoxy from an aromatic dicarboxylic acid mainly composed of ethane-4,4°-dicarboxylic acid by a de-E-nocarphonic acid polycondensation reaction.

(2) Aromatic hX dihydroxy compound such as chlorhydride quinone and 1-nyle ester of aromatic dicarboxylic acid mainly consisting of 1,2-bis(2,6-dichlorophenoxy)ethane-4,4'-dicarboxylic acid ) A method of producing by dephenol polycondensation.

<:J>L2-bis(2,6-dichlorophenoxy>ethane-4,4'-dicarboxylic acid-based aroma b
'A A method in which a desired amount of diphenyl carbonate is reacted with dicarphonic acid to form each diphenyl ester, and then an aromatic dihydroxy compound such as chlorohydroquinone is added and a dephenol polycondensation reaction is performed.

Typical catalysts used in the polycondensation reaction are metal compounds such as stannous acetate, tetrabutyl titanate-1, vinegar WXa, sodium acetate, potassium acetate, and antimony trioxide. It is effective when

Some of the aromatic polyesters of the invention can be measured for their logarithmic viscosity in pentafluorophenol, with a degree of closure of 0.1% (weight/container) of 60%.
'C value measured is preferably 0.35 or more, particularly 0.35 or more.
4 to 15.0 is preferred.

Further, the heat of melting of the aromatic polyester of the present invention is 10-
15. ○O○ poise is preferable, especially 20 to 5,000
Voice is more preferred.

d5, this melt viscosity is (liquid crystal starting temperature + 40 to 10
0'C) and shear rate 2.000 to 4.000 (1/sec)
This is a value measured using a Koka type flow tester under the following conditions.

In addition, when polycondensing the aromatic polyester of the present invention, 1.
! ,, In addition to the components constituting the structural units (I) and (II>), isophthalic acid, 3,3'-diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, 2.2--
Aromatic dicarboxylic acids such as diozoyl dicarboxylic acid, dicarboxylic acids such as henicarbonate hydroterenotalic acid, aromatic diol diols such as hydroquinone d3 and rTl-oxybenmonic acid, Other aromatic oxycarphonic acids such as 2,6-oxynano-1 and engineering acids can be further copolymerized within a range of a low v1 ratio which does not meet the purpose of the present invention.

The aromatic polyester of the present invention thus obtained has a low melting point of 400'C or less, and is suitable for extrusion molding, injection molding, and pressing.
It can be used for ordinary melt molding such as molding and blow molding, and can be used for textiles, films, three-dimensional molded products, containers, hoses, etc. 1. It is possible to do it.

During molding, glass fibers, carbon fibers, reinforcing agents such as asbestos, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, and mold release agents are added to the aromatic polynisdel of the present invention. and 5!1 [Additives such as refractories and other thermoplastic resins can be added to impart desired properties to the molded product.

Molded articles produced in this way can be heat treated to increase their strength and, in many cases, their modulus of elasticity.

This heat treatment can be carried out by heat treating the molded article in an inert atmosphere (eg, nitrogen, argon, helium, or water vapor) or in an oxygen-containing atmosphere (1911 air) at a temperature below the melting point of the polymer. This heat treatment may or may not be under tension and can be carried out for several minutes to the second sheet.

The molded article obtained from the novel aromatic polyester of the present invention has good optical anisotropy due to its parallel molecular arrangement and has extremely excellent mechanical properties.

<Example> The present invention will be briefly explained below with reference to Examples.

Example 1 Chlorhydroquinone diacetate 1-1 in a test tube
1.48C1 (5xlO-2E>, 4.4--Schiffl
', -Ll;L' dicarboxylic acid 8.47Q (3,
5xlO-2 mol), 3.3 g of 1,2-bis(2,6-dichlorophenoxy)ethane-4,4-dicarphonic acid
(0,75 x 10-2 mol), 2.27 g (0,
, 75 x 10-2 mol) and acetic acid removal was carried out under the following conditions. First, the reaction was carried out at 250 to 330°C for 3.0 hours in a nitrogen atmosphere, then the pressure was reduced to 0.6#HCI, and the mixture was further heated for 1.0 hours to complete the polycondensation and obtain a silver-black polymer. .

The theoretical structural formula of this polymer is as shown below, and the elemental analysis results of this polyester showed good agreement with the theoretical values shown in Table 1. In addition, when the thermal stability of this polymer was measured using a differential scanning calorimeter (PerkinElmer ■ model), the melting point was 3.
It was 00'C.

CI CI CI -eo602C-Q-0 (CHp) 20-Q-Co light n (Q/m/n molar ratio -70/15/15) Table 1 However, the oxygen content (%) is (100%- 0%-11%-0
1%). In addition, the melting point and optical anisotropy were confirmed by placing this polynisdel on a sample stage of a polarizing microscope and raising the temperature. As a result, the liquid crystal initiation temperature was 260'C, showing good optical anisotropy.

This polyester was subjected to a Koka-type flow tester and spun at a spinning temperature of 350'C1 spinneret hole diameter of 0.3 #φ to 0.0
A spun yarn of 7 trtmφ was obtained. The melt viscosity was 500 voices at 350°C and a shear rate of 3000 (1/sec).

The elastic modulus of this spun yarn was measured using a Leo Pylon DDV-II-EA manufactured by Toyo Baldwin Co., Ltd. at a frequency of 11 QIIZ, a heating temperature of 2°C/min, and a distance between ticks of 40 m. At 30'C, the elastic modulus was 72 GPa. This was inevitable due to the extremely high modulus of elasticity.

Example 2 Chlorhydroquinone diacetate 1-1 in a test tube for polymerization
1,48C] (5X10-2 mol), 4.4--diphenyldicarvone-2 mol), 1,2-bis(2,6-dichlorophenoxy)ethane-4,4-dicarbonate 126.60(1.
A small amount of condensation was carried out under the same conditions as in Example 1 to obtain a silver-black polymer.

The theoretical structural formula of this polymer is as follows, and the elemental analysis values of this polyester showed good agreement with the theoretical values as shown in Table 2. In addition, when the thermal stability of this polymer was measured using a differential scanning calorimeter (PerkinElmer model ■), the melting point was 30.
The temperature was 3°C.

Table 2 However, the oxygen content (%) is (100%-0%-H%-C1
%).

As a result of confirming the optical anisotropy by placing this polyester on a trial polarizing microscope and increasing the temperature, the liquid crystal start temperature was 2.
66°C, showing good optical anisotropy.

This polyester was spun under the same conditions as in Example 1 to obtain a spun yarn of 0.2 mmφ. Melt viscosity is 330'C1
The shear rate was 280 poise at a shear rate of 3,000 (1/sec).

The elastic modulus of this spun yarn was measured using Rheopybron DDV-1 [-EΔ manufactured by Toyo Baldwin Co., Ltd., and showed an extremely high elastic modulus of 49 GPa at 30'C.

Examples 3-8, Comparative Examples 3-7 Chlorhydroquinone diacetate-1-(
■), medyl hydroquinone diacetate-1~(II),
Diacetate (5x 10-2 mol) consisting of 2,6-diacedoxynaphthalene (I) and 1,2-bis(2,6
-dichlorophenoxy)ethane-4,4-dicarboxylic acid (IV), 4,4--diphenyldicarboxylic M(V
), 1.2-bis(phenoxy)ethane-4,4'-dicarboxylic acid (Vl), 1.2=bis(2-chlorophenoxy)ethane-4,/l-dicarboxylic acid (Vn)
, 2.6-naphthalene dicarboxylic acid (■) and terephthalic acid (IX) were charged and polymerized in the same manner as in Example 1.2. All of these polyesters had good fluidity and exhibited good optical anisotropy.

In contrast, chlorhydroquinone diacetate (I>
and 4,4-diphenyldicarboxylic acid (V) or 2,
Polyesters made of 6-naphthalene dicarboxylic acid (Vl) or terephthalic acid (IX) had poor fluidity and it was impossible to measure their melt viscosity.

<Effects of the present invention> The 'j'i aromatic polyester of the present invention can be melt-molded and is necessarily IN! ] Since it is possible to obtain a molded product with a modulus of elasticity,
It can be used for various purposes such as engineering plastics as metal substitute plastics.

Claims (1)

[Claims] The structural unit (I) is composed of structural units (I) and (II) shown in the following structural units (I) and (II), respectively.
) is 10 to 100 mol% of the total, the structural unit (II)
A melt-moldable chlorine-containing aromatic polyester, characterized in that it accounts for 90 to 0 mol% of the total amount. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (However, R in the formula is ▲There are mathematical formulas, chemical formulas, tables, etc.)
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R' is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
Indicates a group selected from ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼.