JPS60106832A - Fully aromatic polyester and its production - Google Patents

Abstract

PURPOSE:To obtain a fully aromatic polyester excellent in the heat resistance, etc., of a molding, by melt-polycondensing polyester materials such as an aromatic dicarboxylic acid and an aromatic dihydroxy compound at low temperature in the presence of a specified low-molecular compound. CONSTITUTION:Polyester materials such as an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and an aromatic hydroxycarboxylic acid are melt- polycondensed at a temperature <=330 deg.C in the presence of a low-molecular compound, MW<=1,000, unreactive with each of the materials and the formed polyester and difficultly distillable under the polycondensation conditions, e.g. N-methylphthalimide, so that the degree of blocking B represented by the equation may be 1.03 or above. In the above equation, x is a fraction of aromatic hydroxycarboxylic acid chains, y is a fraction of aromatic dicarboxylic acid/aromatic dihydroxy compound chains, and p is a molar fraction of an aromatic hydroxycarboxylic acid component.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention: 411 Field of the Invention The present invention relates to a wholly aromatic polyester and a method for producing the same. More specifically, the present invention provides excellent heat resistance for molded products such as fibers and films.

This invention relates to a wholly aromatic polyester that can exhibit dimensional stability 9 mechanical properties and a method for producing the same.

Prior art Fully aromatic polyesters derived from aromatic dicarboxylic acids, aromatic dihydroxy compounds, and aromatic oxycarboxylic acids have been studied and proposed for use in various applications because of their excellent mechanical properties. There is.

Such aromatic polyesters generally have a melt viscosity of 1.theta., and require very high temperatures of 3.30"C or higher for melting, '5' polymerization and/or melt molding.

In order to improve this polymerization and moldability, the present inventor conducted melt polymerization in the presence of a low-molecular compound that does not decompose itself under molding conditions, is substantially non-reactive with polyester, and does not volatilize. It has already been proposed to carry out melt polycondensation in 1987-277J7.

According to this melt polymerization, it is possible to lower the melt viscosity and melting point of the wholly aromatic polyester, and furthermore, when the wholly aromatic polyester is melt anisotropic, it is possible to lower its phase transition temperature. However, subsequent research into IC revealed that the heat resistance of the resulting molded products was not clear.

It became clear that the dimensional stability was less than that expected from the polymer's composition and was far from satisfactory.

Purpose of the Invention The present inventors formed a molded 41'I excellent in thermal one-dimensional female stability in a wholly aromatic polyester mainly composed of an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and an aromatic oxycarboxylic acid. Further studies were carried out in order to give the properties. ] Thermal 9 dimensional stability is clearly the same, and this chain pattern can be achieved in total by 1+ii using 13C NMR. The present inventors have discovered that this can be obtained, and have published the present invention.

The purpose of the present invention is to achieve one-plane thermal one-dimensional stability.
An object of the present invention is to provide a wholly aromatic polyester with excellent ik l]'J characteristics and a method for producing the same.

4171 inventions and effectiveness? The purpose of iAi is to use aromatic h1ζcycarphone, an aromatic dihydro axy compound, and mikakinocarpone as the main constituent, and to obtain a blocking rate (Ill) represented by the following formula (1).
is 1.03 or more, and is substantially non-reactive with the polyester and the raw material of the polyester and has a molecule of 1ti that is distilled off under polycondensation conditions.
This is achieved by the above-mentioned method for producing a wholly aromatic polyester by subjecting the polyester raw material to melt polycondensation at a temperature lower than 330° C. in the presence of a low-molecular compound having a molecular weight of less than 100°C.

B=-10- It is a sexual derivative.

As the aromatic dicarboxylic acid, for example, tele7 ta/+-
72,-r Phthalic acid, naphthalenedicarbone j'J1
．． Schiff J-nyldicarboxylic acid, diphenylsulfodicarbone T1? , diphenoxyethanecarphonic acid, diphenylneedledicarboxylic acid, methylterephthalic acid, and methylisophthalic acid'+'F'if. Especially terephthalic acid.

Isophthalyl'l M is preferred. Furthermore, an aromatic dihydro r+1-cy compound and 1. For example, hydro-coquinone, 1/zorcin, chlorhydroquinone.

Bu 181 Muhite 1 Guinone, Methyl Hyde A Quinone, Kocho-ru Hyde O Quinone, T-Buti! lehydroquinone,
t-'y milhide a-quinone, t-butylhide a-quinone, (α-phenylethyl)-hy J'ri quinone, (2
-phenylp-a-b-2-・r)hydroquinone, phenylhydroguinone, benzylhydroquinone, methoxyhydroquinone, 4,4'-dihydroxydiphenyl, 4,4-dihydroxydiphenyl ether, bis(4-hydroxyphenoxy)ethane, 2.2'-dimethyl-4,4'-dihydroxydiphenyl, 3.3'
-dimethoxy-4,4'-dihydroxydiphenyl ether, bis(2-chloro-4-hydroxyphenoxy)
Ethane.

2.2-bis(4'-hydroxyphenyl)propane,
Examples include 1,1-bis(4'-hydroxyphenyl)cyclohexane.

Among C), hydroquinone and two-substituted hydroquinones such as methyl isophthalic acid are particularly preferred.

Examples of aromatic oxycarboxylic acids include p-oxybenzoic acid, 4-oxydiphenyl-4'-carboxylic acid, and 3-oxybenzoic acid.
-chloro-4-oxybenzoic acid, 3-methoxy-4-
Oxybenzoic acid, 3-ethoxy-4-oxybenzoic acid.

2-methyl-4-oxybenzoic acid, 3-)thyl-4-oxybenzoic acid, 2-phenyl-4-oxybenzoic acid, 3-)
-Phenyl-4-oxybenzoin, 2-chloro-4-
Examples include 2-hydroxydiphenyl-47-carboxylic acid, 2-hydroxynaphthalene-6 and 2-hydroxynaphthalene-6.
). Among the stiff substances, p-oxybenzoic acid is preferred1. stomach.

y; ester-forming conductors of aromatic dicarboxylic acids, lower alkyl esters of aromatic dicarboxylic acids such as -Cl'l, -, I-,
7-esters, such as dimethyl ester, diethyl ester, dimethyl ester, ditolyl ester, dimethyl ester '4 &amp;
can. Among these, aryl esters are especially
Preferable for Yuleester h"#'j. For example, wo, 1:,
Examples include diphenyl are7thalate and isophthalic acid.

Ester-forming derivatives of aromatic dihydroxy compounds, such as lower fatty acid esters of aromatic dihydroxy compounds such as those mentioned above;
Propionate esters and the like can be cited. Examples include hydroquinone diacedate and hydroA'nondibuh(1onate).

Ester-forming derivatives of aromatic oxycarboxylic acids and 1-
Examples include lower alkyl esters, aryl esters, and lower fatty acid esters of aromatic oxycarboxylic acids as described above. Lower alkyl esters and aryl esters are esters about the carboxyl group of aromatic oxycarboxylic acids, and lower fatty acid esters are esters about the hydroxyl group of aromatic oxycarboxylic acids - for example, exemplified for p-oxybenzoic acid #. For example, methyl p-oxybenzoate.

Ethyl p-oxybenzoate, phenyl p-oxybenzoate, tolyl p-oxybenzoate.

Examples include p-7 setoxybenzoic acid and p-propionyloxybenzoic acid.

Ester-forming derivatives of aromatic oxycarboxylic acids include, in particular, allyl esters, especially phenyl esters, such as p
-oxybenzoic phenyl is preferred.

According to the method of the invention, the polyester raw material is
The full group or its ester-forming r-permeable group and the hydroxyl group or its ester-forming derivative group are used in a ratio of 5) 1 so that they are in substantially equal equivalent weight. In addition, in the case of carboxyl ester formation <<+:, in QJ using a polynyspool l1it old having a Jn-derived group, free hydroxyl groups should be present in the polyester raw material in the same proportion as the actual Jgt-1j17. Polyester J having Nisdell-forming hydroxyl-derived groups,
When using a member of the genus family, substantially equivalent amounts of free carboxyl groups should be present in the polyester raw material.

The polyester raw material 1) used in the present Kaburaaki method at 1.τ is as follows:
In addition to aromatic compounds as mentioned above, in the case of V, t,
”- may contain an ester-forming compound other than the aromatic compound J. Such other compounds can be used by substituting up to 307 groups of aromatic dicarboxylic acids with -C, such as adipic acid and cepacic acid.

Examples include aliphatic or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and ester-forming derivatives thereof such as alkyl esters and aryl esters.

Examples of aromatic dihydroxy compounds that can be used by substituting up to 307 groups include ethylene glycol, neopentylene glycol, and hexamethylene glycol.

Examples of aliphatic diols such as tetramethylene glycol and cyclohexaneconmethylol include alicyclic diols.

Further, examples of aromatic oxycarphonic acids that can be used by substituting up to 307 groups include p-hydroxyethoxybenzoic acid.

Examples include oxycarboxylic acids having an aliphatic hydroxyl group such as oxycaproic acid, or ester-forming derivatives thereof such as allyl esters, alkyl esters, and lower fatty acid esters. 1 J=, , ++ls 1 to 11 (1 and 11! 1 ester-forming compounds can be used in combination of 1 type or 2 or more, but 1 for U1), the total amount of C:L is the main It is preferable that the total amount of the aromatic compounds that are the constituent components does not exceed 307%.

There is no particular restriction on the ratio of aromatic oxycaproic acid used, but it is relative to aromatic dicarboxylic acid] o -! l o -
T: /L, %, preferably 20-80 mol, 'r
! rK7g':'F, L< is about 3o to 70 mol'Iy.

Also, what kind of fully aromatic polyester can be obtained by using a) leveling of each component or addition of aromatic oxycarboxylic acid to monomanic acid? '+1 The optical properties of 71Sr in the molten state change (2
, the case where the molten state shows no optical isotropy and the '11￥ direction I
There are cases where 11 is shown. The wholly aromatic polyester of the present invention may be one having isotropic melting or anisotropic melting, but it is more preferable to use one having anisotropic melting which forms a molded article with excellent mechanical properties. Yes.

The low-molecular compound used in the method of the present invention is substantially non-reactive with the polyester raw material and wholly aromatic polyester, and is at least difficult to distill off under the polycondensation reaction conditions, for example, has a boiling point at normal pressure of about Molecular weight 1 above 200℃
000 or less. As these low molecular weight compounds, those having a boiling point of about 250'C or higher, especially about 300C or higher, or those having a molecular weight of 800F or higher are preferably used.

The low-molecular-weight compound used in the method of the present invention may be any compound as long as it satisfies the above conditions, but for example, the following formula (n) 1 1 Here, AI is substituted. R1 is an n-valent aromatic residue or a chain or cyclic aliphatic residue, and these can be substituted to
or 2, provided that the imide ring in the formula is 5 or 6 members can be preferably mentioned.

In J-11', j formula (, U), the divalent aromatic residue representing A1 is, for example, 1,2-phenylene cram,
'+2, 2,3- or 1,8-naphthylene group.

5.6,7. R-detrahydro-1,2- or 2,3-
The naphthylene group can be mentioned f+'-. These groups are monovalent Ji groups which are non-reactive with fully aromatic polyesters.
It may be substituted with C. Such substituents include, for example, methyl, lower alkyl groups such as y-thyl, lower alkoxy groups such as methoxy and ethoxy, chlorine, bromine, etc., -[1/41
1. Phenyl group, phenokizino! 8. Examples of the link r1 which may be substituted with a mayyl group include hesyl and the like.

an 11-valent (n=1 or 2) aromatic residue representing 1. For example, phenyl group, naphthyl group, 5,6,7
．． 8-tetrahydro-1-12- or 3-naphthyl group,
Or the formula, <5z(J(ko,nteZ bar0-,-
8o, - again bar C1l, -te,! a monovalent aromatic residue such as a group of 718-Tetrahydro-i, z-, or 2,3-naphthylene group also has t, < 4i formula, 'Q-
zpe5 (Here -cz is -o-.

Mention may be made of divalent aromatic residues (in the case of n-2) such as -so, - or -CH, - groups, and monovalent (
Examples of aliphatic residues where n=1 or 2) include methyl,
A chain alkyl group having 1 to 18 carbon atoms such as ethyl, 7-tyl, hexyl, heptyl, ophyl, nonyl, tecyl, dodecyl ρ-myridityl, and stearyl, or a 5- or 6-membered negative cyclic alkyl group such as cyclohexyl or cyclopentyl. group (hereinafter, when n=1), or a chain alkylene group having 2 to 12 carbon atoms, such as ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, 1,3- or 1,4-
Cyclic alkylene group such as cyclohexylene group, /noilj °C·l·, 1. -guri'CH, - group (more than n-20
Yang r1) can be mentioned.

IN' may be replaced by Pf with the same It'lGP norm as described for A1.

” - As the imide compound represented by entry (11),
1; Compound c' when n = 1 in Suege formula (11): N-methylphthal 1'mide, N-ethyl-7thalimide, N-octylnotal, fmido, N-lauryl phthalimide Do, N-milisyl-1-[mido, N-setylphthalimide, N-stearyl phthalimide, N-niboru-1,11-phthalimide, N-lauryl-I,) l-linocoolimide , N-
Myristyl-1,8-nophthalubimide. N-cetyl-1,8-nafcoolimide, N-stearyl-1,
8-naphthalimide; in formula ('n) kl, n =
= 2, synthesis σ) Compounds include N,N'-ethylenebisphthalmide, N,N'-tetramethylenebisphthalimide, N,N-hexamethienebisphthalimide.
18 de,N,N'-octamethylenebisphthalimide, N,N'-decamethylenebisphthalimide, N,N
'-totecamethylene hisphthalimide, N,N'-neopentylene bisphthalimide, N,N'-tetramethylenebis(l,8-naphthalimide),'N,
N-hexamethylene his (1,8-naphthalimide).

N, N-octamethylene his (1,8-naphthalimide), N, N'-decamethylene his (1,8-naphthalimide), N, N'-dodecamethylene his (1,8
-phthalimide), N,N'-1,4-cyclohexylene hisphthalimide.

1-fullimido-3-phthalimitomethyl-3
, 5, 5-) II Methylcyc 'Cohexane.

N,N'-2,2,4-)limethylhexamethylenebisphthalimide, N,N'-2,4,4-trimethylhexamethylenebisphthalimide, 4,4'-bisphthalimide diphenyl ether.

3.4'-bisphthalimide diphenyl ether:
i, :+'-bisphthalimidodiphenyl sulfone, 4,4'-hisphthalimido diphenyl sulfone, 4,4'-bisphthalimido diphenylmethane, and the like.

The imide compound represented by the above formula (I) ζφ has the following properties: J, ni'', can be manufactured.

Honmei Aikaga-ga- uses the polyester raw material as described above in the presence of the low-molecular H1 compound as described above, in a state of melting and
．． This can be done by combining 14. The amount of the low molecular weight compound to be used is preferably 20 to 30 parts by weight, more preferably 30 to 250 parts by weight, particularly preferably 40 to 2 parts by weight, based on 100 parts by weight of the wholly aromatic polyester to be produced.
1+0 Il (do τ1 part.

As for the transaction method, a publicly known method can be used, but
In the present invention, the polymerization temperature is set to +4:io'' (
: It is necessary to lower the temperature. Pass'1: S,
In the polymerization of wholly aromatic polyesters, the polymerization temperature is generally raised sequentially from a low temperature, but the polymerization temperature in the present invention means the highest temperature at the final stage of polymerization.

The present inventor has clarified that even if the polymer composition is the same, the properties of the resulting polyester will differ if the polymerization temperature is different, and that the lower the polymerization temperature, the higher the melting rate and the higher the crystallization rate. Furthermore, the present inventors believe that this difference in properties is due to the chain pattern of each component constituting the polyester.
Specifically, this is due to the difference in the ratio of aromatic oxycarboxylic acid chains (blocking'' *), and the lower the combined temperature IW, the higher the blocking rate of aromatic oxycarboxylic acid components. I found it.

Although the exact reason why the blocking rate of the aromatic oxycarboxylic acid component increases when the polymerization temperature is low is not clear, the present inventor estimates that the carboxyl group of the aromatic oxycarboxylic acid or its ester forming property The reactivity of the derivative and the hydroxyl group or its ester-forming derivative is
carboxyl group of aromatic dicarboxylic acid, t
Unlike the reactivity of these ester-forming derivatives, the hydroxyl groups of aromatic dihydryl paroxy compounds, or their Nisdel-forming derivatives, the reactivity of the ester-forming derivatives is lower than that of the ester-forming derivatives, and therefore the polymerization temperature is lower. The lower the value, the more condensation reaction +1! The selection of +'1: is thought to increase the degree of reblocking.

In the J-L'>1i condensation reaction, a more preferable polymerization temperature is &1:'125'' CJ91, and a particularly preferable polymerization temperature is 320 UJ or less.

] 4. Blocking ratio B h of the aromatic reconstituted acid A/J sulfosic acid represented by the formula (1) in the fully aromatic poly-sprue l-1 of the present invention produced by the 1:t production method in Section 11. Since 03-1-, l:c It Jl is l(I.

13 = −−10−−−−1 ・・・・・・(I)p
1 g n-P Formula (1) Ic :t-i 1. Pa (, X is the fraction of aromatic oxycarboxylic acid chains in the fully aromatic polyester (
%), y is the fraction (ch) of aromatic dicarboxylic 1''-aromatic h-dihydro-oxy compound chains in the fully aromatic polyester.
, P represents the molar fraction (%) of the aromatic oxycarboxylic acid component in all the constituent components.

The method of calculating the above x, y, and P will be explained next.

Aromatic dicarboxylic acid component C), aromatic dihydroxy compound (component H) and aromatic oxycarboxylic acid (component 0)
In a wholly aromatic polyester composed of three components, the following four types of chain modes are considered.

Each chain of the acid component and glycol component is connected through an ester bond, and 1. There are different carbonyl carbons of the 4flR group corresponding to the chain pattern of the 4N group. [ru. As a result of a detailed study of 13C NMR of the above-mentioned fully aromatic polyester, the present inventor found that carbonyl carbon peaks were found to correspond to four types of chain modes.
It has been found that by quantifying this, it is possible to determine the fraction of four types of -chain types.

In formula (1), X is the fraction of O-0 chain, and y is c −L
It is expressed as a fraction of n chains. In addition, P can be calculated from the chain fraction determined by the above method, and “II
41 using other methods such as NMR and chromatographic analysis after depolymerization.
11 can also be determined. .

Using formula (1) from x, y, and P, a total of 11
As the name suggests, Bl is the valley component in a wholly aromatic polyester that is implanted from an aromatic carboxylic acid, an aromatic dihydro a-P compound, and an aromatic A=V dicarboxylic acid. represents the blocking IW of ] parameter, It = 2 in case of complete block III, B = 1 in case of complete random: ノ[; 11 = in case of complete reciprocity
It becomes O.

The wholly aromatic polyester of the present invention has a block size of 1.11
It is preferably 4 or more, particularly preferably 1.05 or more.

As mentioned above, the wholly aromatic polyester of the present invention has a structure with higher blockiness, and this is considered to be a factor in exhibiting excellent heat resistance, 2-dimensional stability, and 2-mechanical properties.

A wholly aromatic polyester composition obtained by a melt polymerization method in the presence of the above-mentioned low-molecular-weight compound is produced by a melt molding method.
For example, molded products such as films and fibers can be used.

These molded products may be further stretched if necessary.

A molded product with better mechanical resistance can be obtained.

Totally aromatic polyester composition +1; The low molecular weight compound in 71 is extracted and removed at any stage after melt polymerization by treatment with an organic additive that dissolves the low molecular weight compound but does not dissolve or decompose the aromatic polyester. be able to.

- Such organic solvents include, for example, aromatic puffed hydrogen having 6 to 9 carbon atoms, halogenated aliphatic hydrocarbons having 1 or 2 carbon atoms, aliphatic chthons or aliphatic esters having 3 to 6 carbon atoms, 5- or 6-membered ft% of cyclic polymer or t element ψJ
-3 aliphatic alcohols are preferably used.

JL Weight Fc GJ2, for example benzene, toluene.

Aromatic hydrocarbons having 6 to 9 carbon atoms such as ethylbenzene, quinolene, cumene, pseudocumene + 'tA ll-
'-G1.・), charcoal such as chloroporum, dichloroecune: ', halogenated aliphatic hydrocarbon of number 1 or 2;
111f carbon atoms having 3 to b carbon atoms, such as acetone, notyl ethyl ketone, and isobutyl ketone;
Methyl acetate, ethyl acet-l·, propyl acetate, methylbu 1.1 pis, i, -1·, ethylprobionate.

F I-1 Pirso sl; carbon number like --1-: U ~ 6
aliphatic groups; 5- or 6-membered cyclic ethers such as trahydrofuran, dioxane; or methyl, -
Examples include aliphatic alcohols having 1 to 3 carbon atoms such as J-tanol and propatool.

Among these, aromatic hydrocarbons having 6 to 9 carbon atoms, halogenated hydrocarbon scales having 1 or 2 carbon atoms, or 5- or 6-membered cyclic ethers are IF! It is preferably used for f.

If the molded product is a fiber or film, the extraction may be carried out under tension, and the extraction temperature may be between ambient temperature and the boiling point of the organic solvent used. . Extraction time depends on the type of low molecular compound used! 4H, 4+
Although it varies depending on the type of organic solvent, the extraction temperature, the form of the molded product, etc., it is usually about 1 second to 1 hour. By the above extraction process, 9o of low molecular weight compounds in the wholly aromatic polyesterol!
: 14 or more, preferably 95 times or more can be removed by removing 1 width or more.

It is preferable that the molded article made of the wholly aromatic polynisal thus obtained be heat treated as necessary.

During heat treatment, how to hold the molded product and keep it at a constant length.

Either under tension 1.'' or under restricted contraction conditions.

The heat treatment temperature may be any σ) temperature below the melting point of the fully aromatic polyester, but if the molded product is stretched, the temperature should be higher than the stretching temperature.4-1. stomach.

E: The molded product made of fully aromatic polyester obtained by Il'i Akira f) - is 11 times higher than the conventional one with the same composition.
- Bell:jJ, 1. 'J heat resistance 9 dimensional stability.

Mechanical (/IJfl) - Koori is extremely Ishikawa.

Examples Below, the present invention will be described in detail with reference to examples.
) at a heating rate of 2 o 'C/min. The melt viscosity was measured using a high temperature 0.5 m diameter and 7 m long shearing speed of 1 yen.
Measured at 100 sec 9 +, l; -, Shida specific gravity was measured by the floating method.

Also, part means At', :r (part.

Examples 1 to 3 and Comparative Example 1 128 parts of phenyl paraoxybenzoate, 127 parts of disoenyl inphthalate, 46 parts of hydroquinone, vinegar r1 sef
J1'-0.14 part of tin and 4,4' as a low molecular compound
- 112 parts of bisphthalimide diphenyl ether was placed in a three-necked reactor equipped with a stirrer, and 240 parts of bisphthalimide diphenyl ether was placed in a nitrogen stream at normal pressure.
The temperature was raised from °C to the polymerization temperature shown in Table 1 in about 120 minutes, and then the pressure was gradually reduced to an absolute pressure of 0.2+ after about 30 minutes.
xl1g and 12 were subjected to the time-consuming reaction shown in Table 1 under the same conditions to obtain a polymer containing a low molecular weight compound.

The polymer was then extracted in dioxane at 100° C. for about 1 hour and then extracted at 150° C. under vacuum at
After drying for about 2 hours, a polymer containing no low molecular weight compounds was obtained.

Table 1 shows the blocking rate (B) and melting point of the above polymers, and it can be seen that the blocking rate and melting point increase as the polymerization temperature becomes lower.

Table 1 Examples 4 to G and Comparative Example 2 Rose-like Kin'an 7S, Incense+';l! 214 parts of phenyl, 214 parts of isophthalic acid, 3 + 8 parts of 21% of phenyl, 116 i', 1 V of vinegar, 1'1'2 of vinegar
N30. : The polymerization temperature shown in Liemi 3 was raised at about 12 () hours, then the pressure was gradually reduced, and the pressure was gradually reduced to -A. 30 minutes 1 trip VR absolute use o, 2m
+mtl! +1!1)i shown in Table 2 under the same conditions as i/
Continuing the synthesis reaction of ll 11, a polymer containing a low molecular weight compound is produced.

The polymer was then treated in chloroform under reflux for about 1 hour to extract the 4,4'-bisphthalimido diphenyl ether and then dried at 150 DEG C. for 3 hours.

The blocking rate (Bl and melting point) of each polymer is shown in Table 2, and it can be seen that even if the composition is the same, the blocking rate and melting point increase as the polymerization temperature decreases.

Table 2 Reference Example (Blocking Ratio (Method of Bl)) Polymer σS3CNMR leaked in Actual hm Example 2 above
Spectrum (solvent CDC7, /CF, GOOD (1/
1) Figure 1K shows an enlarged view of the carbonyl carbon part in ).
Indicated.

The four peaks in Figure 1 are from the left: 5-isophthalic acid-Palau.
Yang-an, citric acid chain (C-0), isophthalic acid--itl quinono chain (C-'-H), paraoxyben-1+
1 acid-baraoxybenzoic acid chain (0-0, para A-・
)-zobenzoin Igarenbashi(0-,1(), corresponding to Tabi-ri゛(k J,...'<:,.The fraction (%) of these peak intensities is expressed as people n, y, Assuming that x and b, the mole fraction P of the paraphrase xy rest 1'f i'α component in all the constituent components can be expressed as y(: with Ht ;i,!?).

a-1-13-1-2x 1)-1----------11 roy in Figure 1 (1, L=22.4φ, b=23.3 coefficient, X=29 , 7 coefficients, y=:33.6 coefficients, and P =
43.6 daro and 1. C),.

Block f1. Yu+! , tl Liao) is represented by 1:witness, and the value of 13:2---1-,-,-,----m--P 1
017-1) By substitution, 13=1.07.

Example 7 and Comparative Example 3 The polymers polymerized in Example 2 and Comparative Example 1 were lθ~2
The chips were ground into 0 mesh chips and heated under high vacuum for 2 hours until the melt viscosity at 380°C was approximately 211,000 voids.
60~2! 1 (Solid phase polymerization was carried out at 1°C. The in-phase polymerization time was about 15 hours for the yN remer of Example 2 and about 4 hours for the polymer of Comparative Example 1.

These polymers were then heated to a polymer temperature of 36'0 to 37
0°C, Wl) Residence time of about 10 min. Horse chestnut 25 mm9
Using a 6-axis extruder [1] Extrude through a T-die with a diameter of 150 mm and a slit distance of 0.8 degrees, and the surface temperature was approximately 80.
It is drawn with a roller at ℃ at a draft of about 6, and the thickness is about 2.
A film of o()μ was obtained.

Next, the obtained film was treated in refluxing dioxane for about 30 minutes at a constant length to extract low-molecular compounds, and then ls
Dry for 90 minutes at o °C.

The extracted and dried film was stretched 2.2 times in the machine axis (MI) direction using a simultaneous biaxial stretching machine manufactured by Long.

3.1 times the horizontal axis (TI) direction and the same Hj at a temperature of 200℃
j Z +lil+ tt+ξ extension l5 then constant length lower 28
Heat treatment at 0℃ for 10 minutes J'+! , did.

The properties of the obtained film are shown in Table 3 (also.

Table 3 Table 3 shows 7+e L /, : ! +1+ <, The film obtained by the method of the present invention is mechanically superior to that of i;C/techniques. It can be seen that it has i l/l and 7 month stability.

Example 11118 and Comparison 1 Rari 4 The polymers polymerized in Example 114 and (') and Comparative Example 2 were subjected to solid phase polymerization in the same manner as described in Example 7.
One thing! 14 (Extraction and drying to obtain a film.

The film was stretched 2.5 times in the MD force direction at 200°C, and the change in specific gravity of this -axis stretched film was measured when it was heat treated at 230°C under a constant length.

The results are shown in Table 4, and it can be seen that the crystallization rate of the film obtained by the method of the present invention is significantly faster than that of the conventional film.

In addition, when the 4 (414) t1° strength of this -axis film was measured, the film of Example 8 had a strength of 38.4, an elongation of 3.s%, and a shear rate of 1090 kg/m.
A. The film of Comparative Example 4 has a strength of 33.0 kg/mr4
, elongation 3.5%, Young's modulus s 91) kg/y
+ and ivy.

[Brief explanation of drawings]

FIG. 1 is an enlarged view of the 13CNMR spectrum.

Claims (1)

[Scope of Claims] +]) A compound mainly composed of an aromatic dicarboxylic acid, an aromatic dihydroxy compound, and an aromatic oxycarboxylic acid 11!
, minutes, and the blocking rate ([$
) is a 3o3J:J-based polyester produced by melt polymerization. 1 (= −−−−1−−−−1～−−−=−1 ・・・
...(I)1)100-P (2) Aromatic-ζ is a dicarbonyl group 112. A polyester raw material mainly consisting of an aromatic dihydroxy compound, an aromatic oxycarboxylic acid, and/or an ester-forming derivative thereof is prepared under polycondensation conditions that are substantially non-reactive with respect to the above-mentioned raw materials and the wholly aromatic polyester to be produced. In the presence of low-molecular-weight compounds that are difficult to distill off under (-ft1000 or less,
The blocking rate (Bl is 1.0
A method for producing a fully aromatic polyester of 3 or more. B = −+ −−2−−− P 100−P ””’”(I) t3) 20 to 3.00 parts by weight of a low molecular weight compound is used per 100 parts by weight of the wholly aromatic polyester to be produced. The method for producing a wholly aromatic polyester as described in Item 2 above.