JPS6295318A - Production of polyester - Google Patents

Abstract

PURPOSE:To produce a polyester containing double bond in molecule and having high melting point using melt-polymerization process, by using fumaric acid (or its ester-forming derivative) as a part of dicarboxylic acid component and carrying out the polycondensation reaction at a specific temperature. CONSTITUTION:The objective polyester can be produced by (1) reacting (A) a dicarboxylic acid and/or its ester-forming derivative composed mainly of terephthalic acid and containing 1-20mol% fumaric acid and/or its ester-forming derivative with (B) a 2-6C alkylene glycol, (2) reacting the reaction product at 230-260 deg.C under normal temperature using a titanium- or tin-based catalyst preferably in the presence of (C) 0.1-2wt% hindered phenol stabilizer based on the polyester to remove excess glycol from the reaction system and (3) continuing the reaction for >=5hr while gradually reducing the pressure of the system.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing polyester containing unsaturated bonds and having fiber-forming ability. More specifically, it relates to a method for producing polyalkylene terephthalate copolymerized with fumaric acid, and the resulting polyester can be molded into fibers, films, etc., can be made three-dimensional using double bonds, or can have other functionalities. Possible to add functional groups A (provides polyester).

<Prior Art> It is well known that unsaturated polyesters are used as thermosetting resins, for example by styrene melting and subsequent curing.

However, these unsaturated polyesters are generally of low molecular weight, and saturated carboxylic acids such as ortho-7 tal and inphthal are amorphous and have high solubility in styrene, etc. It's just M-made.

No attempt has been made to obtain unsaturated polyesters of high molecular weight.

When trying to combine a 21-bonded gold compound such as maleic acid or fumaric acid with 1, for example, polyethylene terephthalate, due to the reaction of the double bond.

Since it is a crosslinked polymer, it is said that it cannot undergo a melt polymerization reaction like ordinary polyethylene terephthalate, which is thought to be the reason why there are no polyesters in this field so far.

<Object of the Invention> An object of the present invention is to provide a polyalkylene fugrate containing a knee bond and copolymerized with filtrate fumaric acid by a melting process.

<Structure of the Invention> The inventors of the present invention have discovered that if fumaric acid is selected as the double bond-containing monomer and the lambda reaction temperature is set to 230 to 260°C, polymerization is possible without gelation. 1. The present invention This is what led to this.

That is, 1 the present invention is a dicarboxylic acid mainly composed of terephthalic acid, and its ester-forming isomer is reacted with at least one alkylene glycol to produce a glycol ester of the dicarboxylic acid and/or a low polymer thereof. let me,
In producing a polyester by subjecting the product to a condensation reaction in the absence of (. This is a polyester manufacturing method that is characterized by being carried out at a temperature of 260°C.

In the present invention, the ester-forming visiting conductor refers to a compound that can react with glyfur to form an ester group and become a polyester, such as a lower alcohol ester having 1 to 4 carbon atoms.

Also, in the present invention, a terephthalic acid component.

In addition to the fumaric acid component, other dicarboxylic acid components may be combined with less than 20 mol%, and a portion of the alkylene glycol used (usually 20 mol% or less) may be mixed with other diol components. good.

Examples of such co-acid components include phthalate.

Isofucle, naphthalene dicarboxylic acids, diphenyl dicarboxylic acids, diphenoxyethane dicarboxylic oxides,
Cyclohexanedicarboxylic acids, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, alkylene glycols other than the glycol used as a base,
Aliphatic diols such as diethylene glycol, triethylene glycol, poly(oxyethylene) glycol, and d-ring diols such as cyclohexane dimetatool;
- Aromatic diols such as itoquinone and hisphenols, and oxycarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acids, and hydroxynaphthoic acids.

These copolymerization components have particularly low copolymerization of fumaric acid (i.e., when producing a polyester with a melting point of 255°C or higher, copolymerization is required to lower the melting point due to the relationship between polycondensation temperature and melting point). You can also.

The N condensation reaction of the polyester of the present invention is carried out in the same manner as ordinary melt polymerization. That is, the first step is to react a dicarboxylic acid or its ester-forming conductor with a glycol in the presence or absence of a catalyst, and the resulting dicarboxylic acid σ-glyfur ester or its low polymer is reacted under reduced pressure. Generally, a method is adopted in which the second stage reaction is carried out. In this first stage esterification or transesterification reaction, the internal σ is 24% at a humidity temperature of 260°C or less and 1%.
It is preferable to keep the temperature below θ°C. Other conditions, catalysts, etc. are the same as those for producing polyethylene terephthalate and polyethylene terephthalate. 1. The second stage reaction is carried out at a temperature of 230 to 260°C.
There is mourning. The rest is similar to normal bath melting 1 and 161, that is, after removing excess glyfur by reacting at normal pressure,
This is a method in which the pressure is gradually reduced and the reaction is finally carried out in a high vacuum of 200 Pa or less. If the reaction temperature is lower than 230°C, the reaction will not proceed sufficiently, and if it is higher than 260°C, gelation will occur, making it impossible to obtain a polyester having the desired fiber-forming ability. If this reaction takes a long time, gelation may occur, so it is desirable to follow the catalyst 9 reaction conditions 1 reaction apparatus so that the desired polyester can be obtained in a 5 hour step reaction.

Particularly from this point of view, titanium-based or soot thread catalysts are preferred as catalysts, titanium quasi esters, carbon Y titanium salts,
Preferable catalysts include organic tin compounds (such as sialgyl tin peroxide) and carboxylic acid tin salts.
Preferably, 0 mmol is used.

Since gelation may occur in the above reaction or may occur during molding, etc., it is a preferable method to add a stabilizer at σ. As stabilizers, hindered phenol stabilizers, sulfur stabilizers, amine thread stabilizers, etc. are used.
Examples of specific examples include triethylene glyph-ruhis [3-[3-t-phthyl-5-methyl-4-hydroxyphenol ν)propionate], ], 6-hexanethiol-rubis (3-( 3,5-di-t-butyl-4-
hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,
5-di-t-butylanilino)-L3.5-) riazine, pentaerythrityl-tetrakis (3-(3,5-di-t-butyls-4-hydrodoxyphenylene/shinfuhiohonito)), 2.2- Thio-diethylenebis(3-(:
L5-di-t-phthyl-4-hydroxyphenyl)
propionate], ophtateryl-3-(3,5-)-
t-7'Tyl-4-hydroxyphenyl) fropione
), 2,2-thiobis(4-methyl-6-t-butylphenol), N,N'-hexamethylenebis(3,5-
di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-7thi-4-human pquin-benzyl 7-ospho-un-todiethyl ester, l, :(,5
-) ') Methyl-2,4,6-tris(3,5-di-
t-butyl-4-human 11-xybenzyl)benzene, bis(3,5-di-t-/'ethyl-4-hytroquine benzylphosphonic acid) calcium, N,N'-bis[
3-(3,5-di-t-glythyl-4-hydroxyphenyl)bup-pionyl]hydrazine, tetrakis(2,4-
Hindered phenolic stabilizers such as di-t-butylphenyl)-4,4'-biphenylene phosphonite and tris(2,4-di-t-butylphenyl) phosphite can be mentioned. Hindered phenol stabilizers are particularly preferred, and hindered phenol is used in combination with a compound containing an -8- group such as late ester of thiodipropion, or a compound containing -N- is used in combination with hindered phenol. It is also preferable. Among the hindered phenol stabilizers, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-monobutylanilino) 11315-triazine, 2,2-thio-diethylenebis [3-(3,5-di-t-butyl-4
-Hydroxyphenyl)flopione) ), 2.
2-thiobis(4-methyl-6-t-butylphenol) is preferred. The saturation ratio of these stabilizers is preferably in the range of 0.01 to 2 times the amount of polyester obtained.
・. The cooling period may be either at the beginning or during the reaction σ), but it is preferable to cool it from the beginning because it is easy and does not cause gelation even if the temperature rises too much during the reaction.

<Effects of the Invention> According to the present invention, a double bond is formed in the molecule and the melting point is 2.
Polyesters having a high melting point such as 00°C or higher [σ] can be produced by a bath melting method.1 Polyesters having such double bonds can be melt-molded and then subjected to, for example, crosslinking. It is possible to make an infusible molded product or to impart functions by reacting with other functional compounds.

<Example> Dimethyl terephthalate 194 fAB, ethylene glycol 130 parts, and calcium acetate monohydrate 0.12 f
Li was charged into a reactor equipped with a stirrer and a distillation column, and after heating, almost all of the methanol produced was distilled off, and then 65 parts of phosphorous acid was added.

On the other hand, transfer the material to a pressure-receivable reaction vessel equipped with a stirrer,
12 parts of fumaric acid and 0.19 parts of No. C Auger were cooled and reacted under pressure at 250°C for 45 minutes to eject water and ethylene glycol.
I reacted for a minute.

Finally, the obtained reaction product, which had an accuracy of 50 PaO in the reactor, was discharged into water and made into a chimney. Orthofururphenol was measured at 25°C and 5°C, and the accuracy was 0.63. In addition, as a result of tljl determination using NM and R, it was confirmed that the double bond was calculated in comparison with the benzene nucleus and was approximately 10% relative to terephthalic acid.

Comparative Example 1 As a result, the viscosity rapidly increased 30 minutes after the start of depressurization, and the product became rubbery.

Comparative Example 2 Fumaric acid U) used in Example J
When the reaction was carried out in the same manner as in Example 1 except that the amount was changed to 36 parts, the mixture became rubbery 80 minutes after the start of decompression.

Comparative Example J In Example 1, the second stage reaction was carried out at 285° C. with the ordinary polymerization reaction of polyethylene terephthalate, and the product became rubbery after 45 minutes.

Marishio 1[2 194 parts of dimethyl terephthalate, 180 parts of tetramethylene glycol, and 0.0 parts of titanium ketorabdoxide.
After carrying out transesterification reaction of 19 parts under normal pressure at a temperature below 230°C, 6 parts of 12 parts of fumaric acid were added, and the reaction was carried out at 240°C under nitrogen atmosphere at normal pressure for 30 minutes, and the pressure was gradually reduced for 2 hours. The reaction was allowed to take place for 15 minutes. The obtained polymer has a hard southern viscosity of 0.8
It was 4.

Example 3 The procedure was repeated in the same manner as in Example 2 except that 230 parts of hexamethylene glycol was added instead of 180 parts of tetramethylene glycol used in JM Example 2. After the pressure was gradually reduced, the reaction temperature was reduced to 250 parts after 1 hour. ℃ for another 2 hours
2 (obtained polymer α) intrinsic viscosity is 0.79
Met.

Claims (1)

[Claims] 1. A dicarboxylic acid mainly consisting of terephthalic acid and/or its ester-forming derivative and at least one alkylene glycol are reacted to produce a dicarboxylic acid glycol ester and/or its low polymer. Then, in producing a polyester by subjecting the product to a polycondensation reaction, fumaric acid and/or its ester-forming derivative is used in an amount of 1 to 20 mol% of the total dicarboxylic acid components, and the polycondensation reaction is carried out at 230 to 260°C. A method for producing polyester characterized by carrying out the process at a temperature of . 2. The method for producing polyester according to claim 1, wherein the polycondensation reaction is carried out in the presence of a hindered phenol stabilizer in an amount of 0.1 to 2% by weight based on the polyester. 3. The method for producing polyester according to claim 1 or 2, wherein the alkylene glycol is an alkylene glycol having 2 to 6 carbon atoms.