JPS6050821B2 - copolymerized polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel copolyester and a method for producing it.

More specifically, it is concerned with novel copolyester polyesters that are melt moldable and provide shaped articles such as fibers or films with high Young's modulus. Conventionally, polyester terephthalate has excellent mechanical strength, heat resistance, and chemical resistance, and is therefore widely used as a material for fibers, films, plastics, etc.

However, it cannot be said that polyethylene phthalate fibers are sufficient for industrial applications, such as tire cords, which require particularly high strength and Young Σ. On the other hand, aromatic polyamides such as poly p-phenylene terephthalamide and poly p-benzamide are known as fibers with extremely high strength and young cap, but these can be easily made into fibers by melt spinning such as polyethylene terephthalate. In contrast to spinning, fibers are generally produced by solution spinning (dry spinning or wet spinning), which has many industrial disadvantages such as solvent recovery and other disadvantages. , 5 In order to eliminate this drawback, fibers made of copolyester containing components such as p-oxybenzoic acid, hydroquinone, terephthalic acid, and isophthalic acid have been proposed (see JP-A-50-43223).

However, in this case Te10 is used as the dicarboxylic acid component.
When phthalic acid is used, the resulting polyester has an extremely high melting point, making it difficult to melt-spun such a copolyester to obtain relatively high strength, high Young's modulus fibers, and isophthalic acid as a dicarboxylic acid component. Although there is the advantage that the melting temperature of copolyester fibers can be greatly lowered by using 15% copolyester, it is said that fibers with a particularly high Young's modulus (for example, 9/1 or more for 250i) cannot be obtained by spinning alone. It has its drawbacks. The present inventors have arrived at the present invention as a result of extensive studies on copolyesters that can be melt-molded and provide fibers or films with a high Young's modulus of 20. .

1 That is, the present invention has 1 oxybenzoic acid residue^, dioxybenzene residue 5
A polyester consisting of a 25-group residue (B) and a dicarboxylic acid residue (C), in which the dicarboxylic acid residue
The acid residue (C) is a diphenyl ether dicarboxylic acid residue, and the ratio of residues (B) and (C) is as follows:
[In the formula, MA, MB, and MC represent the number of moles of the remaining portions (A), (B), and (C), respectively.

It is a C copolymerized polyester having an intrinsic viscosity of 0.3 or more, which satisfies the following. The copolyester referred to in the present invention is a novel copolyester containing the three components (A), (B), and (C) as main constituents.

The oxybenzoic acid residue (4) which is a constituent component of the copolymerized polyester is (here, R is a halogen atom, an alkyl and/or an alkoxy group, and n is O or a number from 1 to 4)
The compound providing the residue (4) is p-
Oxybenzoic acid, m-oxybenzoic acid and p- and m-
There are compounds in which the benzene nucleus of oxybenzoic acid is substituted with one or more types of chlorine atom, bromine atom, fluorine atom, methyl group, ethyl group, methoxy group, ethoxy group, etc. Examples of substituted substances include 3 -chloro-4-oxybenzoic acid, 3-bromo-4-oxybenzoic acid, 3-methyl-4-oxybenzoic acid, 3-methoxy-4-oxybenzoic acid, 3,5-dichloro-4-oxybenzoic acid, 4- Examples include chloro-3-oxybenzoic acid, 4-methyl-3-oxybenzoic acid, and 4-methoxy-3-oxybenzoic acid.

In this invention, this! It is preferable that 50 mol% or more, more preferably 70 mol% or more of the benzoic acids be p-oxybenzoic acid or a nuclear substituted derivative thereof, and particularly preferably p-oxybenzoic acid. Taking the case of a p-oxybenzoic acid residue as an example, in addition to p-oxybenzoic acid, lower aliphatic carboxylic acid esters such as p-acetoxybenzoic acid, and p-oxybenzoic acid can be used as compounds providing the residue. Examples include aryl esters or lower alkyl esters such as phenyl p-oxybenzoate, p-oxyphenyl p-oxybenzoate, and methyl p-oxybenzoate. Furthermore, the dioxybenzene residue (B) is represented by 5 (where R is the same as defined above), and the residue (
Compounds giving B) include hydroquinone, resorcinol, and the dioxybenzene nucleus containing a chlorine atom, a bromine atom,
There are compounds in which one or more of fluorine atoms, methyl groups, ethyl groups, methoxy groups, ethoxy groups, etc. are substituted. Examples of these substituted derivatives include hydroquinone chloride,
Hydroquinone bromide, methylhydroquinone, methoxyhydroquinone, 2,5-dimethoxyhydroquinone,
Examples include resorcinol chloride, methylresorcinol, and methoxyhydrodaquinone.

In the present invention, 5 of these dioxybenzenes
It is preferred that 0 mol%, more preferably 70 mol% or more, be substituted or unsubstituted hydroquinone. For example, when the dioxybenzene residue (B) is a hydroquinone residue, in addition to hydroquinone, lower aliphatic carbon atoms such as p-diacetoxyhydroquinone and p-dibenzoyloxybenzene can be used as compounds providing the residue. Preferred examples include acids and esters of aromatic carboxylic acids. Furthermore, the diphenyl ether dicarboxylic acid residue of the dicarboxylic acid residue (C) is
\JL~2ノ■ (Here, Rl and R2 are hydrogen atoms, alkyl groups, and alkoxy groups, and I and m are numbers from 1 to 4),
Compounds providing the residue (C) include diphenyl ether-3,4''-dicarboxylic acid, diphenyl ether-4
,4″-dicarboxylic acid, diphenyl ether-3,3″
-dicarboxylic acids and compounds in which the benzene nucleus of these diphenyl ether dicarboxylic acids is substituted with one or more chlorine atoms, bromine atoms, fluorine atoms, methyl groups, ethyl groups, methoxy groups, ethoxy groups, etc.;
Examples of substituted substances include diphenyl ether 2
-chloro-3,4'-dicarboxylic acid, diphenyl ether-2'-methyl-3,4''-dicarboxylic acid, diphenyl ether-4-ethoxy-3,4''-dicarboxylic acid, diphenyl ether-2,2''-dibromo 4,4″
-dicarboxylic acid, diphenyl ether-4,4''-dimethoxy-3,3''-dicarboxylic acid, and the like.

5 In the present invention, it is preferable that 50 mol % or more, especially 70 mol % or more of these diphenyl ether dicarboxylic acids are diphenyl ether dicarboxylic acids having no substituents. -dicarboxylic acid is most preferred. Taking the case where the diphenyl ether dicarboxylic acid residue is a diphenyl ether-3,4''-dicarboxylic acid residue as an example, the compound providing the residue is diphenyl ether-3,45- Other dicarboxylic acids include phenyl esters, aryl esters such as methyl esters, and lower alkyl esters of the dicarboxylic acids. By introducing such a diphenyl ether dicarboxylic acid residue into a copolyester, a new copolyester can be obtained that is easy to melt and mold and provides a molded article with high strength and high Young's modulus.

The copolymerized polyester of the present invention comprises its constituent components (A),
(B) and (C) are within the following ranges.

(However, in the formula, MA, MB, and MC are the same as above.) More preferable copolyesters are those within the following range.
(In the formula, MA, MB, and MC are the same as above.) Particularly preferred copolyesters are those within the following range.

The copolymerized polyester of the present invention is the above-mentioned CA), and (C)
Each constituent component is constituted in a proportion that satisfies the above formula, and has an intrinsic viscosity of 0.3 or more. If the intrinsic viscosity of the copolyester is too low, fibers or films with the desired high Young's modulus cannot be obtained. The copolymerized polyester of the present invention uses p-oxybenzoic acid as a compound providing oxybenzoic acid residues, and dioxybenzene residues (B
) can be produced by the following method, for example, hydroquinone can be produced by the following method. can.

That is, a method in which an aryl carbonate such as diphenyl carbonate is added to 1p-oxybenzoic acid and diphenyl ether-3,4''-dicarboxylic acid, heated to perform an esterification reaction, and then heated to polycondensate with hydroquinone; 2 Diphenyl ether 3,4''- instead of diphenyl ether 3,4!-dicarboxylic acid
Polycondensation method according to method 1 except for using an esterification product of dicarboxylic acid and phenol and/or hydroquinone; phenyl 3p-oxybenzoate, diphenyl ether-diphenyl 3,4'-dicarbozoate and Method for heating and polycondensing a mixture of hydroquinone; 4p
-acetoxybenzoic acid, diphenyl ether 3,4″
- It can be produced by heating a mixture of dicarboxylic acid and hydroquinone diacetate and subjecting it to polycondensation.

Here, the aryl carbonate includes monocarbonates such as diphenyl carbonate, ditolyl carbonate, diphenyl carbonate, bis p-hydroxyphenyl carbonate, phenyltriyl carbonate, phenyl p-hydroxyphenyl carbonate, etc. Examples include polycarbonates such as polyphenylene carbonate.

In the present invention, the aryl ester of diphenyl ether dicarboxylic acid can be produced by conventionally known methods, but it is advantageous to produce it by an esterification reaction between diphenyl ether dicarboxylic acid and a phenol such as phenol, cresol, p-butylphenol, etc. Can be used for

The use of such esterified products is highly effective when producing copolyesters by method 2. In the present invention, in the esterification reaction between diphenyl ether dicarboxylic acid and the above-mentioned phenols or diphenols such as hydroquinone, the hydroxyl group of the phenol or diphenol is 1 times or more in mole, preferably 1.1 to 4 times as much as the carboxyl group of the dicarboxylic acid. molar, particularly preferably 1.2 to 2 times the molar amount, 230 to 400°C, preferably 2
The reaction is carried out while heating to 40 to 360°C and distilling water produced as a result of the esterification reaction out of the reaction system.

The esterification reaction usually takes 1 to 12 hours, and can be carried out under pressure of 10'l'K9/Clt if necessary. At this time, the esterification rate is 50% or more, preferably 70% or more.
% or more, particularly preferably 85% or more. Here, the esterification rate is determined from the following formula. Although a catalyst is not necessarily required in the esterification reaction,
Preferably a catalyst is used.

Such catalysts include titanium tetrabutoxide,
Titanyl oxalate, stannous acetate, lead oxide, antimony trioxide, antimony pentoxide, bismuth trioxide, cerium acetate, lanthanum oxide, lithium oxide, sodium metal,
Titanium, tin, such as potassium benzoate, zinc carbonate, etc.
Examples include metals such as lead, antimony bismuth, cerium, lanthanum, lithium, sodium, potassium, and zinc, and compounds containing these metals. In addition, the amount of these catalysts used is 0.00% relative to the dicarboxylic acid.
5 to -0.5 mol%, preferably 0.01 to 0.1 mol%. Production methods 1 and 2 of copolyester of the present invention
In , oxybenzoic acid is reacted with an aryl carbonate. When diphenyl ether dicarboxylic acid or an esterified product of phenyl ether dicarboxylic acid containing a free carboxyl group is present during this reaction, the free carboxyl group reacts with the aryl carbonate.
Therefore, the amount of aryl carbonate to be added is 0.3 to 1.1 times the mole of carbonate bonds contained in the aryl carbonate per 3 amounts of total free carboxyl groups contained in the reaction system containing oxybenzoic acid. Preferably, the amount should be approximately 1 molar. The reaction of the aryl carbonate with oxybenzoic acid, a mixture of oxybenzoic acid and diphenyl ether dicarboxylic acid, or an ester thereof is carried out at a temperature of 200 to 300°C, preferably 220 to 250°C. The process is continued until the generation of carbon dioxide gas is substantially stopped.

This reaction is suitable for 1 to 6 hours and is preferably catalyzed. As for this catalyst 4, the same catalyst as in the above esterification reaction can be used in a range of 0.005 to 0.5 mol % with respect to the carboxylic acid component as in the case of the esterification reaction. Copolymerization of the present invention The polycondensation reaction of polyester is carried out at a temperature range of 200 to 400°C, preferably 250 to 380°C.The initial stage of polycondensation is preferably carried out in a molten state. It is produced in the polycondensation reaction. Phenols and/or diphenols are removed from the reaction system, and lower aliphatic carboxylic acids or aromatic carboxylic acids are removed from the reaction system in polyester production method 4. Therefore, the reaction pressure is lower than that of the polycondensation reaction. In the early stage of the reaction, the pressure may be around normal pressure, but in the final stage, for example, 100 WfLHg or less (50 to 0.01T0nHg)
It is preferable that When producing the copolymerized polyester of the present invention, if the above-mentioned production method is followed, oxybenzoic acid and (
or) its derivatives, diphenyl ether dicarboxylic acid and/or its derivatives are not significantly lost by decomposition. On the other hand, a portion of dioxybenzene and/or its derivatives are distilled out of the polycondensation reaction system during polycondensation.

Therefore, a preferable charging ratio of raw materials in the production of copolymerized polyester can be expressed by the following formula. [However, in the formula, NA, NB, and NC each represent the number of moles of oxybenzoic acid and (or) its derivative (4) dioxybenzene and (or) its derivative (B) diphenyl ether dicarboxylic acid and (or) its derivative C) show.

] The ratio of NB to NC that is particularly preferable here differs depending on the production method of the homopolymerized polyester, but in the case of pre-flooding production method 4: i1 In production methods 1 and 3, when phenols are used in the esterification reaction in the above production method 2 This is the case where diphenols were used in the esterification reaction in Production Method 2.

If the amount of NB used relative to NC is too small or too large, it will be difficult to obtain a high polymer.

It is preferable to follow the method 1, 2, or 3 for producing a copolyester of the present invention because no corrosive gas such as acetic acid is generated, and the resulting copolyester has good hydrolysis resistance.

The copolymerized polyester obtained in this way has a temperature of 300 to 400
A polyester molded article can be obtained by melting at 0° C. and extrusion molding.

For example, polyester fiber is made of copolymerized polyester with 24%
Melt and extrude at 0 to 400'C, draft rate 5 to 5001, winding speed 10 to 500rT1/TrIIL
It can be obtained by winding it up. At that time, polyester fibers do not necessarily require heat treatment, and can be melt-spun and wound to have a strength of 3 g/De or more and a Young's modulus of 250.
0k9/Tr! It can have a high strength of 1 t or more and a high Young's modulus. This fiber can be advantageously used for tire cords, rubber reinforcing materials, fillers, and other heat-resistant industrial materials.
In addition, the polyester film is made of copolymerized polyester with 24%
It can be obtained by melt extrusion at 0 to 400'C and winding on a drum. A conventionally known device can be used as the film forming machine. The draft during extrusion is 1~
W is preferably 1 to 5. The film extruded onto the drum may be left to cool at room temperature, or may be rapidly cooled in water. The polyester film thus obtained has sufficiently high Young's modulus (more than 700k9/d) and strength (30k9/Ml) compared to polyethylene terephthalate.
L or more). This film can be advantageously used as an industrial material. Molded products using the copolymerized polyester of the present invention have sufficient strength even without heat treatment as described in JP-A-50-43223, but the strength can be further increased by heat treatment. be able to.

Molded products using the copolyester of the present invention have a high Young's modulus and excellent hydrolytic stability, so they can be effectively used as industrial materials such as tire cords, rubber reinforcing agents, fillers, and films.

Examples will be explained below.

All "parts" in the examples mean "parts by weight."

In addition, in the present invention, the intrinsic viscosity of the copolymerized polyester is 0.
．． 05g was dissolved in 10ml (7) p-chlorophenol, the relative viscosity (ηr) was determined using an Ostwald viscometer at 50°C, and the relative viscosity (ηr) was calculated using the following formula.
[However, the formula indicates the concentration of polyester, which is 0.5g/
It is d1.

] Also, the flow start temperature is 0.5mm for the copolymerized polyester with a diameter of 0.
Place it in a high-performance flow tester equipped with a cap of 5Tf$L and length 4WrIIL, raise the temperature at about 5℃ per minute under a pressure of 100k9/d, and determine the temperature at which the copolyester starts to flow out from the cap. did.

Example 1 12.42 parts of p-oxybenzoic acid, 15.48 parts of diphenyl ether-3,4''-dicarboxylic acid, 44.94 parts of diphenyl carbonate and 0.010 parts of potassium carbonate were placed in an esterification kettle, and the After reacting at ~270°C for 3 hours (at normal pressure), 6.93 parts of hydroquinone and 0.013 parts of triphenyl phosphate were added, the temperature was raised to 300°C and the reaction was continued for 15 minutes, and then 0.93 parts of stannous acetate was added. 0
15 parts was added, the temperature was raised to 350°C, the polycondensation reaction was carried out at normal pressure for 1 hour, and the pressure of the reaction system was gradually reduced to 520Tf.
Polycondensation was carried out for 5 minutes under 0 nHg.

The intrinsic viscosity of the obtained copolyester was 0.988, MA/(MA+MB+MC) was 0.43, and the flow start temperature determined by a flow tester was 325°C.
It was hot. This copolyester melts at 360C,
It was extruded using a spinning machine with a spinneret having a diameter of θ0.3Tf0rL and wound at a speed of 50 n1/min. The fineness of the obtained fiber was 40 denier, the strength was 4.5 g/Del Young's modulus was 4000 kg/Mltl, and the elongation was 2%. Example 2 Same as Example 1 except that the amounts of diphenyl ether-3,4''-dicarboxylic acid diphenyl carbonate and hydroquinone were changed to 7.74 parts, 32.W parts, and 3.47 parts, respectively. Polycondensation reaction of copolyester was carried out in the same manner.

The intrinsic viscosity of the obtained copolyester was 1.02,
MA/(MA+MB+MC) was 0.60 and the flow onset temperature was 325°C. This copolyester is 35
It can be melt-spun at 0'C, and the fiber obtained by performing the same procedure as in Example 1 has a strength of 4 g/Del and a Young's modulus of 38.
00k9/d1 elongation was 2%.

Example 3 Example except that diphenyl ether-494''-dicarboxylic acid was used instead of diphenyl ether-3,4'-dicarboxylic acid, and the original polycondensation time for 2-Hg was changed to 1 minute. A polycondensation reaction of copolyester was carried out in the same manner as in Example 1.

The copolyester obtained had an intrinsic viscosity of 0.500, MA/(MA+MB+MC) of 0.43, and a -flow onset temperature of 340°C.

This copolyester was melted at 380°C and spun in the same manner as in Example 1. The strength of the obtained fiber is 2.5g
/Del Young's modulus is 3500kg/Tnltl elongation is 1
It was %.

Example 4 The amounts of p-oxybenzoic acid, diphenyl ether, 34'-dicarboxylic acid, diphenyl carbonate and hydroquinone in Example 1 were changed to 5.24 parts and 2 parts, respectively.
2. Ujibe, 47. Actual 3 except for 1 part and 9.93 parts.
A polycondensation reaction of copolyester was carried out in the same manner as in Example 1.

The intrinsic viscosity of the obtained copolyester was 1.05,
MA/(MA+DE+MC) was 0.18, and the flow onset temperature was 323°C. This copolyester is 350
The fiber obtained in the same manner as in Example 1 has a strength of 4.2 g/Del and a Young's modulus of 2.
700k9/m! t, and the elongation was 2%. Comparative Example 1 p-oxybenzoic acid and diphenyl ether in Example 1
The amounts of Teru-3,4''-dicarboxylic acid, diphenyl carbonate, and hydroquinone were 2.35 parts and 24 parts, respectively.
(Corporate) Department, 47. A polycondensation reaction of copolyester was carried out in the same manner as in Example 1 except that the amount used was 11.15 parts.

The intrinsic viscosity of the obtained copolyester was 1.12,
MA/(MA+■+MC) was 0.08, and the flow onset temperature was 298°C. This copolyester is 350
The fiber obtained in the same manner as in Example 1 has a strength of 4.4 g/Del and a Young's modulus of 3.
The 50k9/Wltl elongation was 65%. Comparative Example 2 27.6 parts of p-oxybenzoic acid, 1.2 parts of diphenyl ether-3,4''-dicarboxylic acid, 45.84 parts of diphenyl carbonate, and 0.012 ffV of potassium carbonate)
was placed in an esterification pot and reacted at 250 to 270°C for 3 hours at normal pressure, then 0.58 parts of hydroquinone and 0.013 parts of triphenyl phosphate were added, and the mixture was heated to 300°C and reacted with one powder. , followed by 0.015 stannous acetate
The mixture was heated to 350° C. and polycondensed at normal pressure for 1 hour.

Claims (1)

[Scope of Claims] 1. A polyester consisting essentially of an oxybenzoic acid residue (A), a dioxybenzene residue (B), and a carboxylic acid residue (C), wherein the dicarboxylic acid residue ( C) is a diphenyl ether dicarboxylic acid residue, and the residue (
The ratio of A), (B), and (C) satisfies the following formula: 0.1≦(M
A/MA+MB+MC)≦0.7 [However, in the formula, MA, M
B and MC indicate the number of moles of residues (A), (B), and (C), respectively. ] A copolymerized polyester having an intrinsic viscosity of 0.3 or more.