JPS5941328A - Aromatic polyester - Google Patents

Abstract

PURPOSE:To prepare a novel aromatic polyester moldable by melt-molding, and giving a molded article having excellent mechanical properties and optical anisotropy, by using a specific aromatic dihydroxy compound and an aromatic dicarboxylic acid composed essentially of diphenyldicarboxylic acid. CONSTITUTION:(A) p-Hydroxybenzoic acid is made to react with (B) aromatic dihydroxy compounds composed of phenyl hydroquinone, 2,6-dihydroxynaphthalene and 2,6-dihydroxyanthraquinone and (C) aromatic dicarboxylic acid containing 4,4'-diphenyldicarboxylic acid as an essential component, to obtain the objective polymer composed of the structural units of formula I , formulaII (R is group of formula III, formula IV, etc.) and formula V(R<1> is group of formula IV, VI, VII, etc.), wherein the amounts of the unit I and the units II+V in the polymer are 10-85mol% and 90-15mol% respectively, and the molar ratio of the unit II/V is 100/0-30/70.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides molded products that can be melt-molded at temperatures below 400'C and have excellent mechanical properties and optical anisotropy! The present invention relates to a novel TC 7S aromatic polyester.

In recent years, the demand for higher performance plastics has been increasing, and many polymers with various new performances have been developed and are now on the market. It is noted [1] in that the liquid crystal polymer with a characteristic optical field of 15 has low mechanical properties.

Is this 6 completely aromatic as a crystalline polymer? A-popolysters are widely known, such as homopolymers and copolymers of p-hydroxyammon, mono-yuroic acid, which are commercially available under the trademark 'EKONOL'. However, since the melting point of the 4C-hydroquinobenzoic acid homopolymer is too high and cannot be melt-molded, a method of lowering the melting point by adding various components to 1)-hydroquinobenzoic acid has been investigated. :・]A method of copolymerizing phenylhydroquinone/, terephthalic acid and h/' or 2,6-naphthalenecarbonoic acid to hydroquinobenzoic acid (Published Patent Publication No. 1983) -500215"j')
, 1) --Polymerization of 2,6-dihydroquinonaphthalene and terephthalic acid to hydroquinobenzoic acid/j method (
1i) Jll/(Publication No. 54505941'j) and 1) -Hydroxyben, 2,6-; method for copolymerizing human quinoanoslaquinono and terephthalic acid (U.S. Pat. No. 4,224,433) Specifications) etc. have been proposed. However, although the aromatic polyester obtained by these methods has a relatively low melting point of less than 400), the elastic modulus of the spun yarn is still insufficient, and further improvement of the elastic modulus is required. desired.

Therefore, the present inventors conducted extensive research with the aim of obtaining an aromatic polyester that can be melt-molded and has a well-balanced mechanical property represented by a high modulus of elasticity and optical anisotropy.
- Part or all of the aromatic lenoJ rubonoic acid of an aromatic polyester consisting of a specific aromatic dihydroquine compound such as hydroquinobenzoic acid, phenylhydroquinono, and an aromatic dicarboxylic acid such as terephthalic acid is 4,4'-diphenyl It has been discovered that by substitution with dicarboxylic acid, a novel aromatic polyester that preferably meets the above objectives can be obtained, and the present invention has been achieved.

That is, the present invention consists of the following structural units (1) and (old or ([), (old and (ml), where the unit (1) is 10 to 85 mol% of the whole,
Occupies 0-15 mol%, unit (Ill / (Ill)
The object of the present invention is to provide a novel melt-moldable aromatic polyester characterized by a molar ratio of 10,010 to 30/70.

0 0 +01gQC-r<' -c+ ・・・
(Ill 11I 11
.

0 0 In the aromatic polyester of the present invention, the structure 1j
The position (]) is the structure Lli, l)γ of the polyester produced from 1)-hydroquinobenzoic acid, and the middle position (I
ll is the middle structure of a polyester produced from an aromatic dihydroquino compound such as phenylhydroquino 7 and 4,4'-lephenyl dihydroponoic acid, and the upper ifW structure +
4'' position (llll is aromatic 1h' such as phenylhydroquino, 4,4-position such as quinoquino compounds and terephthalic acid)
Each term refers to the structural center of a polyester produced from a aromatic dicarphonic acid other than '-diphenyldicarboxylic acid.

The Otoko polyester of the present invention has a melting point of 400'
It is possible to easily produce fibers, filtration, various molded products, etc., which are less than U and have low mechanical properties by ordinary melt molding. For example, the melting point of polyethylene terephthalate 1 is 256 Y, and the melting point of polyethylene 4,4'-diphenylcarboxylate is 355 T. Since the melting point of polyester is lower, it is expected that the polyester of the present invention containing 4,4'-lephenyldicarphonic acid as an essential component will have a very small %5M point. Contrary to expectations, the aromatic polyester of the present invention has a relatively low melting point of 400"C and excellent melt moldability.

In the aromatic polyester of the present invention, "- structure 11
'L(1''I(1) accounts for 10 to 85 mol% of the total, preferably 20 to 80 mol%, and 85 mol%
If it exceeds 10% by mole, the J aromatic polyester has a high (1A) resistance, making melt molding difficult. This is not desirable because it often happens.

"-Structure L) The i-position (11) and (III) account for 90 to 15 mol% of the total, particularly 80 to 20 mol%, and the molar ratio of units (Ill/(III+) is 10010 to 30 /70, especially 10010-50
/50 is preferred. Here, the unit (H) + (unit (11) in Illl is not preferable because the mechanical properties of the obtained aromatic polyester deteriorate if the proportion is less than 30 mol %).

In the aromatic polyester of the present invention, the aromatic dihydroquine component forming the -1- structural unit (Ill and (It)) is phenylhydroquinono, 2,6-recht D
A small amount of tC selected from quinopufucleno and 2.6-,,; human loki/anotraquinone is at least 1 (IF, and phenylhydroquinone is the most polite.
The acid components are terephthalic acid, 4,4'-leph-1-nyloquinodolenol sulfonate, 1,2-his(phenoxy)ethane-
At least one kind selected from 4,47-dicarboxylic acid, 1, and 2,6-naphucrelcarboxylic acid, and these can be used in combination of two or more, but especially 4, 1 of 4'-lefe-1-nyloquinodorecarboxylic acid
Historical use is most preferred.

The aromatic polyester of the present invention can be manufactured by applying the conventional polyester polymer bonding method, and there are no particular restrictions on the manufacturing method, but typical manufacturing methods include, for example, the following (1) to (
3) One example is the law.

+11 1)-acetoxybenzoic acid and diesters of aromatic rehydrogine compounds such as phenylhydroquinonodiacete-1-, phenylhy l'quinonodibropione-1, and 4,4'-diphenyllecarboxylic acid. A method for producing aromatic dicarboxylic acids by demonocarboxylic acid polycondensation reaction.

(211)-Phenyl ester of oxinobenzoic acid J:
A method produced by dephenol polycondensation from a lephenyl ester of an aromatic carboxylic acid containing an aromatic lehydroquino compound such as phenylhydroquino and 4,4'-lephenyldicarbonoic acid as one body θ; 0 ( 31r)-Oquinobenzoic acid and aromatic dicarboxylic acid mainly composed of 4,4'-diphenyldicarboxylic acid are reacted with the desired diphenylcarbonyl-1.
A method of producing a lephenyl ester, then adding an R' 117 lehydroquino compound such as phenylhydroquinono, and performing a phenol-depletion polycondensation reaction.

Typical catalysts used in the polybond reaction are metal compounds such as stannous acetate, tetrabutylnathane-1, lead acetate, and anotymone trioxide, which are particularly effective in dephenol polycondensation.

lfb The force of the present invention The gaps for the polyester group 6 polyester are
The components that make up ++ (isophthalic acid, 3.3'-
diphenyllecarvone M, 3,4'-diphenyllecar;1;) M, 2,2''-lephenylecarbonoic acid,
1.2-bis(2-ronrolfenoquino)ethane-4,4
'-Reno J Rubono acid li Dono'5 incense h! 1ltt Ei such as I Ellecarboxylic acid, hexahydroterephthalic acid, etc.
Other compounds such as the formula cycalho/M, hydroquinone, chlorohydroquinone, methylhydroquinone etc.
The aromatic group oquinocarbonoic acid and the like can be further polymerized within a small proportion that does not impair the first objective of the present invention.

The aromatic polyester of the present invention thus formed has a melting point of 40
It has a low temperature of less than 0%, and can be used for ordinary melt molding such as extrusion molding, injection molding, compression molding, and blow molding, and can be processed into fibers, filler molds, three-dimensional molded products, containers, hoses, etc. It is.

During fringing, the J'J polyester of the present invention is added with reinforcing agents such as glass fibers, carbon fibers, fibers, and asbestos, fillers, nucleating agents, pigments, oxidation inhibitors, stabilizers, plasticizers, Addition of lubricant, mold release agent, caustic material, etc. Δ1' and other heat 1 plastic resins are added to impart desired properties to the molded product (J
! You can do this.

The molded product of the present invention made from polyester has good optical anisotropy due to its parallel molecular alignment, and has good mechanical reliability. It's extremely sagging.

The present invention will be further explained below with reference to Examples.

Example 1 1]-acetoquinoam)trizoic acid 27y (
1,5x10 mol), phenylhytroquinoneleacetate-1-23.0 g (8,5x10 mol) and 206 g of 4,4'-diphenyldicarbonoic acid (8,
5 x 10' mol) was added thereto, and a deacidifying nail condensation reaction was carried out under the following conditions. First, under a nitrogen gas atmosphere at 200~
After reacting at 350°C for 2.5 hours, 350 c-c-
When the small condensation was completed under a pressure of 0.6 mHg and heated for 0.5 hours, the theoretical amount of 98% acetic acid was 11.8
1 was distilled out and a brown polymer was obtained.

The theoretical structure of this polymer, J2j formula, is as follows, and the phosphorus analysis of the polyester showed good agreement with the theoretical value as shown in Table 1.

m/n (mole ratio) = 15/85 Table 1 Also, when this polyester was placed on a sample polarizing microscope and the temperature was raised to confirm the melting point and optical anisotropy, the melting point was 316°C. It shows good optical anisotropy V1. This polyester was subjected to a Koka type flow tester and spun at a spinning temperature of 380'C111 with a gold hole diameter of 0.3 upφ tr L' 0. Q 9 #111φ spun yarn
It's II. This spun yarn was processed using a Toyo Poldwino ((1,) N1 manufactured by using a BIFRONO DDV-It-EA at a frequency of 0 ITz, a temperature increase rate of 2 days)/min, and a Nayanoku interval II.
IIi l#1440 MM dill P4.21
Total measurement L Tatoko') 30'(,' Te45 (+
It had an extremely high elastic modulus of Pa.

Example 2 1)-Acetoquinone, 1 (Froic acid (1), diacetyl quinophenyl hydride + I11.2, 6-,; acetyl quinophenyl hydride, 2, 6-acetyl quinophenyl hydride, 2, 6- (IV), 4,4'-phenyllecarbonoic acid f1'), terephthalic acid flli (among these, the beating component and the (Vl-il'l) component are prepared with the same number of moles) into the polymerization test t′1゛
(G) Polycondensation reaction was carried out in the same manner as in Example 1, Section C1.
Ta.

All of the obtained polymers exhibited optical anisotropy V1 as in No. 2.

Table 2

Claims (1)

[Claims] Position 11i of the following structure (1) and (11) or (1),
(11) and (Il++, 111ii f(1
) is 10 to 85 mol% of the total, position 711 (Ill
1+11 accounts for 90 to 15 mol% of the total, 11i b)
``f (If) / (Ill) molar ratio is 10010
~30. A melt-moldable aromatic polyester characterized by having a polyester of /70. -(-0ROC-R'-Csa...(Il+
1111 0 2- represents a t-co group. )