JPH01297425A - High-elastic modulus copolyester - Google Patents

Abstract

PURPOSE:To obtain the subject polyester with a specified melt viscosity, excellent in mechanical properties and capable of melt molding by carrying out copolymerization between a hydroquinone having a cyclohexyl group, an aromatic dihydroxy compound, a dicarboxylic acid, etc. CONSTITUTION:(A) A substituted hydroquinone to be the structural unit of formula I (X is cyclohexyl, etc.), (B) an aromatic dihydroxy compound to be the structural unit of formula II (R1 is aromatic residue), (C) 4,4'- diphenyldicarboxylic acid to be the structural unit of formula III, (D) an aromatic dicarboxylic acid to be the structural unit of formula IV (R2 is formula V, etc.) and (E) an aromatic hydroxycarboxylic acid to be the structural unit of formula VI (R3 is formula V, etc.) are subjected to, e.g., deacetylation polymerization to provide the objective polyester with 10-15000 poise melt viscosity and respective mol ratios of the components (A)/(B)=2/8-8/2 and the components (C)/(D)=10/0-3/7.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel high modulus copolymerized polyester that can be melt-molded at 450°C or lower and can provide excellent mechanical properties and optical anisotropy. It is.

In recent years, the demand for higher performance plastics has increased, and many polymers with novel performance properties have been developed and are now available on the market. Optically anisotropic liquid crystal polymers are attracting attention because of their excellent mechanical properties.

This liquid crystal polymer is P-hydroxy 7 benzoit 4
, 4'~polyester copolymerized with binenol and terephthalic acid, polyester copolymerized with P-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, P-hydroxybenzoic acid, and dtc polyethylene terephthalate)
Polyesters copolymerized with (PET) are widely known.

In addition, dihydroxy compounds such as phenylnohydroquinone and 4,4'-diphenyl are used to obtain polyesters that are melt moldable and have well-balanced mechanical properties such as high elastic modulus and optical anisotropy. Polyesters made of dicarboxylic acids are disclosed in JP-A-58-194949, JP-A-59-41329, and JP-A-60-19272.
4@, disclosed in JP-A-60-192725 and JP-A-62-39620, and consists of P-hydroxybenzoic acid, a dihydroxy compound such as phenylhydrobutylene, and 4,4'-diphenylcarboxylic acid. Polyester is disclosed in JP-A-59-41328 and JP-A-6.
1-106621, JP-A-62-20523, JP-A-62-39623, and JP-A-62-
It is disclosed in Japanese Patent No. 48722.

≦Problems to be Solved by the Invention> However, in P-hydroxybenzoic acid listed in Item σ, 4.
Polyester copolymerized with 4'-biphenol and terephthalic acid, 2,6-hydroxynaphthoic acid, or polyethylene terephthalate has a relatively low liquid crystal temperature of 450°C or less, but the elastic modulus of its spun yarn and injection molded products is still low. Not enough.

Furthermore, the polyester consisting of the dihydroxy compound e and 4,4'-dimino acid, or the polyester copolymerized with P-hydroxybenzoic acid, is also sufficiently satisfactory although its elastic modulus is somewhat high. It wasn't.

Therefore, an object of the present invention is to obtain a copolyester having an even higher modulus of elasticity.

<Means for solving the problem> That is, the present invention consists of the following +:A structural units to (V), and the molar ratio of structural units (I)/(I) is 2/8 to 8/
2. The molar ratio of A4 structural unit (2)/■ is IO10~3/
7, and ((I) + (I) ) and [(I1 10 faces) are in a substantially equimolar ratio, and the structural unit (V)/C core I)] is 00 to 80 mol% Melt viscosity lO ~ 15,0
00 voids (liquid crystal start temperature +40℃, shear rate 1.00
It is a composite polyester with a d elastic modulus (measured at 01/sec).

・・・・・・・・・ (I) +0-, R, -09 (QCpe) (Σco) ・・・・・・・・・ (■
・・・・・・・・・ qv) +OCRz CO+d ・・・・・・・・・ (v) +OR, co+.

(However, 1) In the formula, X is ω and/or -an(cut
)-C>, R1 is b)0-, b)-CI
Cf(,C(C1(,).

(showing the group above).

In the high modulus copolymerized polyester e of the present invention, the structural unit (I) is a structural unit obtained by removing hydrogen from the hydroxyl group of cyclohexylhydroquino/and/or α-methylbenzylhydroquinone, p is 4
, 4'-dihydroxybiphenyl, hydroquinone, 4
．． one or more aromatic dihydroxy compounds selected from 4'-dihydroxydiphenyl ether, chlorohydroquinone, methylhydroΦone, tart-butylhydroquinone, phenylhydroquinone, 2゜6-cyhydroxyna7talene, 2,7-hydroxynaphthane; Indicates a structural unit with hydrogen removed from the hydroxyl group. In addition, structural unit a) indicates a structural unit obtained by removing the hydroxyl group of 4,47-diphenyldicarboxylic acid, and the structural unit surface is terephthalic acid, 2,6-naphthalenedicarboxylic acid, l
, 2-bis(phenoxy)ethane-4゜4'-dicarboxylic acid, 1, 2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-dicarboxydiphenyl ether, isophthalic acid It represents a structural unit obtained by removing the hydroxyl group of one or more aromatic dicarboxylic acids selected from The structural units of each compound are shown below.

Furthermore, the structural unit (V) is P-hydroxybenzoic acid, 3
- Chloro-4-hydroxybenzoic acid, P-hydroxybiphenylcarboxylic acid and 6-hydroxy-2-naphthoic acid are also the structural units of polyesters formed from one or more selected aromatic hydroxycarboxylic acids.

The polyester copolymerized with a modulus of elasticity of the present invention usually has a melting point of 450°C or lower, and can be easily molded into fibers, films, various molded products, etc. with excellent mechanical properties by ordinary melt molding. It is possible.

In the tin modulus copolymerized polyester of the present invention, the molar ratio of the structural units (I)/(I) is from 2/8 to 8/2, preferably from 25/75 to 75/25. In addition, the structural unit (the molar ratio of ID/@ is 1O10 to 3/7, preferably IO10 to 515. Structural unit α)
/((I) + (I)) is 0 to 80 mol%,
If it exceeds 80 mol%, melt fluidity and mechanical properties will deteriorate, which is not preferable.

The high elastic modulus conjugated polyester of the present invention can be manufactured according to the conventional direct bonding method of polyester, and the manufacturing method is specially described.
Although there is no limit to this, typical manufacturing methods include the following (I) to (4).
) law.

(I) a diester of aromatic dihydroxy compound 12 such as cyclohexylhydroquinone diacetate; and 4.
A method for producing from monoesters of aromatic dicarboxylic acids such as 4'-diphenyldicarboxylic acid and aromatic hydroxycarboxylic acids such as P-acetoxybenzoic acid by demonocarbo/Arashi condensation.

(2) Reacting an aromatic dihydrogen compound such as cyclohexylhydroquinone with an aromatic dicarboxylic acid such as 4,4'-diphenyldicarboxylic acid or an aromatic hydroxylboxylic acid such as P-hydroxybenzoic acid with acetic anhydride to remove acetic acid. A method of manufacturing by polymerization 4.

(3) From diphenyl esters of aromatic dicarbo/acids such as 4.4'-diphenyl dicarboxylic acid and phenyl esters of aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and aromatic dihydroxy compounds such as hexylhydroquinone. A method of producing by dephenol polycondensation.

(4) Aromatic dicarboxylic acids such as 4.4'-diphenyldicarboxylic acid and hydroxycarboxylic acids such as P-hydroxybenzoic acid are reacted with a desired diphenyl carbonate to convert the carboxyl group into phenyl ester, and then cyclohexylhydroquinone, etc. A method of manufacturing by adding an aromatic dihydroxy compound and performing a phenol-free polycondensation reaction.

Typical catalysts used in this polycondensation reaction are metal compounds such as stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate and potassium acetate, and antimony trioxide, which are particularly effective in dephenol polycondensation. It is.

Some of the high modulus copolymerized polyesters of the present invention have an intrinsic viscosity that can be measured in pentafluorophenol, with a value of 0.1% (ffl/filtration).
The value measured at 60° C. is preferably 0.35 or more, particularly preferably 0.4 to 15.0.

Further, the melt viscosity of the high elastic modulus copolyester of the present invention is preferably 10 to 15,000 voids, particularly 50 to 1
0,000 voids is more preferred.

The melt viscosity is a value measured using a Koka type flow tester at a shear rate of 1,000 (I/sec) at ([crystal initiation temperature + 40° C.)].

In addition, when polycondensing the high elastic modulus copolyester of the present invention, in addition to the components constituting ~(V) in the above structural units, 3,3'-diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, Aromatic dicarboxylic acids such as 2,2'-diphenyldicarboxylic acid, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid, P-aminobenzoic acid, P-phenyl diamine, etc., which impair the purpose of the present invention Further copolymerization can be carried out to a certain extent.

The high elastic modulus copolyester of the present invention thus obtained is 4
Melt molding is possible at temperatures below 50°C, extrusion molding,
It can be subjected to ordinary melt molding such as injection molding, compression molding, and blow molding, and can be used to mold fibers, films, three-dimensional molded products,
It can be processed into containers, hoses, etc.

During molding, reinforcing agents such as glass fiber, carbon Aeam, and asbestos, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, and mold release agents are added to the high elastic modulus copolyester of the present invention during molding. And molded products by adding additives such as flame retardants and other thermoplastic resins? This allows desired properties to be imparted.

The molded article made from the novel polyester having a low modulus and elastic modulus of the present invention exhibits good optical anisotropy due to its parallel molecular arrangement, and has extremely excellent mechanical properties.

Note that the strength of the thus obtained molded article can be increased by heat treatment, and the elastic modulus can also be increased in many cases.

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 (eg 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 a period of several minutes to several days.

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

Example 1 54% of P-acetoxybenzoic acid was added to a test tube. Of (
0,3-1:Jl/), cyclohexylhydroquinone diacetate) 27.6 F (0,1 mol), phenylnohydroquinone diacetate) 27.01 (
48.41 (0.1 mol) of 4,4'-diphenyldicarboxylic acid (0.2 mol) was charged, 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 gas atmosphere, and then the temperature was raised to 350°C. After that, the pressure inside the system was gradually reduced, and the LO time circle reaction was further carried out under a reduced pressure of 1 mHI.
When the condensation reaction was completed, acetic acid was distilled out and an ivory-colored polymer was obtained.

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

17m/n = 6/2/2 (molar ratio) Table 1 However, the oxygen content (5) was calculated from (I00%-0%-H%).

This polyester was placed on the sample stage of a polarizing microscope Wl mirror, and the optical anisotropy was confirmed by increasing the temperature and applying shearing force.Results23
It exhibited good optical anisotropy at temperatures above 2°C. In addition, the thermal properties of this polymer were measured using a differential scanning hot air meter (PerkinElmer type I).
As a result of measurement, no melting point peak was detected at a glass transition temperature of 181'C.

This polyester was subjected to a flow tester at 272°C.
As a result of melt spinning with a spindle hole diameter of 0.3 mm and a spindle length of 10 mm, a spun yarn with a fiber diameter of 0.0511 mm was obtained. The melt viscosity was 1.800 voids at a shear rate of 1,000 (If seconds).

This spun yarn is used as Leo Vipron D manufactured by Toyo Boldfin ■.
Using DV-1-EA type, frequency 110, heating rate 2℃
When the dynamic elastic modulus was measured at a chuck distance of M 40 m/min, it was found to be an extremely high elastic modulus of 90 GPa at 30°C.

Example 2 P-acetoxybenzoic acid 54.0f (0,
3 mol), α-methylbenzylhydroquinone diacetate 29.8 y (0.1 mol), phenylhydroquinone diacetate 27. Of (U, 1 mol) and 4,4'-diphenyldicarvone@48.4y (0,2
The TL condensation reaction was carried out under the same conditions as (mol).

The theoretical structural formula of this polyester is as follows, and the elemental analysis results of this polyester showed good agreement with the theoretical values as shown in Table 2.

1fm/n = 6/2/2 (molar ratio) 2nd
In the table, the oxygen content (oxygen content) was calculated from (I00%-0%-H96).

This polyester was placed on the sample stage of a polarizing microscope, and the temperature was raised to 240℃ by applying shearing force and confirming the optical anisotropy.
The above results showed good optical anisotropy. In addition, as in Example 1, the glass transition temperature was measured using a differential scanning thermometer.
No melting point peak was detected at 58°C.

This polymer was subjected to a 70-tester and melt-spun at 280°C, with a nozzle hole diameter of 0.3 and a nozzle length of LOW.
A spun yarn with a magnetic fiber diameter of 0.05 m was obtained.

The melt viscosity is 1.9 at a shear rate of 1,000 (If seconds).
It was 00 boys. The dynamic elastic modulus of this spun yarn was measured using a LeoVipron DDV-1-EAq manufactured by Toyo Boldfin■ at a frequency of 110H, a temperature increase rate of 2℃/min, and a distance between chucks of 40 degrees.It was found to be 85 at 30℃. GPa
The elastic modulus was extremely high.

Examples 3 to 20, Comparative Examples 1 to 5 In a polymerization test tube, α-methylbenzylhydroquinone diacetate (I), 4,4′-diacetoxybiphenyl (4),
Hydroquinone diacetate, 4.4'-diacetoxydiphenyl ether (D1 Chlorhydroquinone diacetate (2), Methylhydroginone diacetate 0
1% t-butylnohydroquinone diacetate) (vl
), phenyleno-1-hydroquinone diacetate) (IX
), 2.6-diacedoxynaphthalene (X), 2.7-
A diacetate component consisting of diacetoxynaphthalene(s), 4,4'-diphenyl dicarboxylic acid (XI), terephthalic acid (XI), and 2,6-sypvy dicarboxylic acid:
y acid (Iff), 1,2-bis(phenoxy)ethane-
4,4'-dicarboxylic acid (XY), l, 2-bis(
2-chlorophenoxy)ethane-4,4'-dicarboxylic acid (X), 4,4'-ditzenyl ether dicarboxylic acid (XVII), isophthalic acid (XVill)
, a dicarboxylic acid component consisting of hegisahydrotere7talic acid (MIX) and P-acetoxybenzoic acid (IN),
3-chloro-4-acetoxybenzoic acid (XXI), 4
-acetoxybiphenyl-4'-carboxylic acid (IXIl
) and an acetoquine carboxylic acid component consisting of 6-hydroxy-2-su7toic acid (XXi[), respectively, are combined as shown in Table 3 to obtain [diacetate component] = [dicarboxylic acid component] (number of moles). A single polycondensation reaction was carried out in the same manner as in Example 1 by charging the mixture into a polymerization test tube. The liquid crystal onset temperature and melt viscosity of the obtained polymer were measured.

Furthermore, these polymers were melt-spun with a spinneret hole diameter Q of 3 mφ to obtain spun yarns.

The composition of the present invention has good fluidity and the resulting spun yarn has a high elastic modulus, but compositions other than the present invention have poor fluidity and may solidify during polymerization or be impossible to spin. Even when spun yarn was obtained, its elastic modulus was low.

<Effects of the Invention> The high elastic modulus congenerated polyester of the present invention can be melt-molded at temperatures below 450°C, and the resulting molded product has high mechanical properties, making it suitable for use in the field of engineering/engineering plastics. It is useful as a metal substitute material.

Director of Patent Application Institute of Artificial Technology

Claims (1)

[Claims] Structural unit (I) consisting of the following structural units (I) to (V)
)/(II) molar ratio is 2/8 to 8/2, the structural unit (II
The molar ratio of I)/(IV) is 10/0 to 3/7, and [(
I) + (II)] and [(III) + (IV)] are in substantially equimolar proportions, and the structural unit (V)/[(I) + (II
)] is 0 to 80 mol%, and the melt viscosity is 10 to 15,000.
Poise (liquid crystal start temperature +40℃, shear rate 1,0001
/sec). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
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(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
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