JPS58198527A - Production of polyester/polyether copolymer - Google Patents

Abstract

PURPOSE:To produce the titled copolymer stably without encountering any trouble of foaming at the start of polycondensation, by esterifying a dicarboxylic acid with a low-MW glycol, then transferring the product to a polycondensation tank in which a polyalkylene glycol is present, and effecting the polycondensation of the product. CONSTITUTION:In the production of a polyester/polyether copolymer by a direct polycondensation process from a dicarboxylic acid component based on an aromatic dicarboxylic acid, a low-MW glycol component based on 1,4-butanediol and a polyalkylene glycol, MW of 400-6,000, the dicarboxylic acid is esterified with the low-MW glycol in an esterification tank, and then the esterified product is transferred to a polycondensation tank previously charged with a polyalkylene glycol, or transferred to the polycondensation tank simultaneously with the charge of the tank with the polyalkylene glycol, and then polycondensed. It is possible to produce the titled copolymer stably without encountering any trouble of foaming at the start of polycondensation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a dicarboxylic acid containing an aromatic dicarboxylic acid as a main component, a low molecular weight fil glycol containing 1,4-butanediol as a -1 component, and a molecular %i of 400 to 6,000.
Polyester-polyether 3'[r!
II. In particular, the present invention relates to a method for solving the problem of foaming at the start of polycondensation, which occurs when producing a polyester-polyether copolymer A'i by a direct batch polymerization method.

Polyester-polyether composites in which aromatic polyester is used as a hard segment and polyalkylene glycol is used as a soft segment have been attracting attention in recent years as a new thermo-tzf plastic elastomer that can replace conventional natural rubber and synthetic rubber.

Such polyester-polyether copolymers soften at relatively low temperatures and have good fluidity, so they can be economically molded using conventional thermoplastic plastic molding methods (e.g., injection molding or extrusion molding). At the same time, it has many features such as excellent rubber elasticity, easy adhesion, thermal decomposition resistance, oxidative decomposition resistance, and chemical resistance. Therefore, it is expected to be used in a wide range of applications such as tubes, hoses, belts, tires, films, and elastic threads.

As methods for producing polyester-polyether copolymers, the so-called direct polymerization method using dicarboxylic acid as a starting material and the so-called transesterification polymerization method using dicarboxylic diester as a starting material are known, but these methods have disadvantages in terms of raw material cost and The former direct polymerization method is economically advantageous because the by-product tetrahydrofuran can be easily recovered and reused. Furthermore, there is a direct batch polymerization method in which polymolecular weight glyfur and polyalkylene glycol are subjected to an esterification reaction in an esterification tank, and then the esterified product is transferred to a polycondensation tank for polycondensation reaction; A method is known in which dicarboxylic acid is esterified with low molecular weight glycole, then polyalkylene glycol is added to the esterified product, and the polycondensation reaction is carried out in a polycondensation tank. It is more preferable because it has the following advantages: the thermal history of alkylene glycol is small, there is no concern that the esterification tank will be contaminated with thermal decomposition products of polyalkylene glycol, and it is easy to clean when changing types. .

However, in the method described in Section 2, the esterification product foams violently immediately after being transferred to the polycondensation tank, and the liquid level rises, causing frequent troubles in which the esterification product flows out into the vacuum circuit, etc. - It is difficult to stably produce polyether copolymers. This bubbling trouble is particularly noticeable when the polyester-polyether copolymer, which is the residual polymer from the previous batch, is attached to the polycondensation tank.

The present inventors have solved the foaming problem when transferring such esterified products, and have solved the problem of foaming when transferring such esterified products.
As a result of extensive research into methods for stably producing polyether copolymers, the present invention was completed. That is, dicarboxylic acids whose main component is aromatic dicarboxylic acids, low molecular weight glycols whose main component is 1,4-butanediol, and polyolefins having a molecular weight of 400 to 6,000.

When producing a polyester-polyether copolymer by direct polymerization with realkylene glycol, first, dicarboxylic acid is esterified with low molecular weight glycol in an esterification tank, and then the esterified product is converted into polyalkylene glycol. Transfer to the existing polycondensation tank,
It has been found that by subsequently carrying out a polycondensation reaction, it is possible to eliminate the bubbles that occur immediately after the esterification product is transferred to a polycondensation tank, and it is possible to stably produce a polyester-polyether copolymer. It is.

What is important here is to have polyalkylene glycol present in the polycondensation tank when transferring the esterified product to the polycondensation tank. Examples include transferring the esterification product to a polycondensation tank to which polyalkylene glycol has been charged in advance, or transferring the esterified product to the polycondensation tank simultaneously with charging polyalkylene glycol to the polycondensation tank. If the esterified product is transferred to the polycondensation tank before the polyalkylene gellicol is charged, the esterified product will foam violently immediately after the transfer, causing problems such as clogging of the vacuum circuit, and the polyester-polyether coexistence will be stable. It is not possible to produce polymers.

The dicarboxylic acid in the present invention is a dicarboxylic acid containing 50 mol% or more of aromatic dicarboxylic acid, and aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2+6-naphthalene dicarboxylic acid, l, 5- Naphthalene dicarboxylic acid, 1,2-bis(phenoxy)ethane T'+1''-dicarboxylic acid, diphenyl p, p'-dicarboxylic acid, etc. are used, and terephthalic acid and isophthalic acid are particularly preferably used.Furthermore, cono-phosphoric acid is used. , adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexanedicarboxylic acid, etc., or aliphatic dicarboxylic acids or alicyclic dicarboxylic acids can also be used in an amount of less than 50 mol %.

The low molecular weight glycol in the present invention is a glycol containing at least 70 mol% of 1,4-butanediol, including ethylene glycol, 1,3-propanediol, 1,6-hexanediol, diethylene glycol, triethyleneglyfur and A primary diol compound having a molecular weight of less than 250, such as 1,4-cyclohexane dimetatool, may be used in combination with less than 30 mol%.

Furthermore, polyalkylene gelylcols having a molecular weight of 400 to 6,00o refer to polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof, particularly polyalkylenes whose main components are polytetramethylene glycol and tetramethylene oxide units. Glyfur copolymers are preferably used. If the molecular weight of the polyalkylene glycol is less than 400, the pro-roughness of the polyester-polyether copolymer will decrease, resulting in unfavorable effects such as a decrease in polymer melting and -1z.

If the molecular weight of the polyalkylene glycol is 6,000 or more, the resulting polymer tends to become opaque, which is not preferable.

Furthermore, p-(β-hydroxyethoxy)an 51! aromatic acid,
Small amounts of oxycarboxylic acids such as p-oxymethylbenzoic acid, trifunctional or higher functional polycarboxylic acids such as trimelide, trimesic acid, and pyromellitic acid can also be used.

Polyalkylene gelylcol in the polymer in the present invention/
The weight percent of the dicarboxylic acid repeating unit (i.e., soft segment unit) can be appropriately selected depending on the required properties of the polymer, especially the required elasticity, required hardness, etc., but it is usually 10 to 80 tonne weight %, particularly 10 to 80 weight percent. The technique of the present invention is preferably applicable to 80% by weight polymer.

Next, the present invention will be explained in more detail based on embodiments. First, dicarboxylic acid, low molecular weight glycol, and esterification catalyst are charged into an esterification tank, and the temperature is increased from around 150°C.
The temperature is gradually raised to 20 to 240°C, and the esterification reaction is carried out while the water and tetrahydrofuran produced are distilled out of the system through a rectification column. The molar ratio of low molecular weight glyfur to dicarboxylic acid is preferably 12 to 3.0, particularly preferably 14 to 2.2.

If the molar ratio of low molecular weight glyfur is too low, the esterification reaction rate will decrease and the esterification reaction will be difficult to complete, which is not preferable. Moreover, if the molar ratio of this charge is too high, the amount of by-product of tetrahydrofuran will increase, which is not preferable.

As the esterification catalyst, conventionally known titanium compounds and/or tin compounds can be used. Specific examples of titanium compounds include tetraalkyl titanates, reaction products of tetraalkyl titanates and alkylene glycols, and titanyl compounds. Further, specific examples of tin compounds include monoalkyltin compounds such as mono n-butyl-monohuman oxytin oxide, mono n-butyltin triacetate, mono n-butyltin monooctylate, mono n-butyltin monoacetate, diphenyltin oxide, Moro-butyltin diacetate.

Examples include dialkyl (or diaryl) tin compounds such as diphenyltin oxide, diphenyltin diacetate, and di-n-butyltin dioctylate.

The amount of esterification catalyst added is from 001 to the produced polymer.
0.5@sunny% is preferred, and 003-02 free time% is particularly preferred.

The esterification reaction time is influenced by the catalyst species, catalyst amount, anti-1+j, temperature, molar ratio of low molecular weight glycol charged, etc., but is generally about 2 to 7 hours.

The esterification reaction product is then transferred to a polycondensation tank previously charged with polyalkylene glycol. Alternatively, the esterification reaction product is transferred to the polycondensation tank at the same time as the polyalkylene glycol is charged into the polycondensation tank.

After the transfer is completed, the pressure is gradually reduced to a high vacuum of 1 ml (g or less) and polycondensation is carried out at 230 to 250°C for several hours to produce the desired polyester-polyether copolymer for synthetic leather. Polycondensation catalysts, stabilizers, pigments, other modifiers, etc. can also be added as necessary at the start of the reaction.

As such a polycondensation catalyst, titanium compounds exemplified as esterification catalysts are generally used. Further, as the stabilizer, conventionally known hindered phenol antioxidants, amine antioxidants 1, phosphorus coloring inhibitors, benzophenone light stabilizers, benzotriazole light stabilizers, and the like can be used. The following compounds are exemplified as hindered phenolic antioxidants preferably used in the present invention.

-Bu j, -Bu (IRGANOX 1098 from Ciba Geigy Japan)
-Bu -Bu t-Bu Cs Hs t-ButBuOO
gHll According to the present invention, troubles caused by foaming when transferring an esterified product to a polycondensation tank, that is, troubles in which the esterified product flows out into a vacuum circuit, etc., can be solved, and
The polycondensation reaction can be carried out smoothly, and a polyester-polyether copolymer can be stably produced.

The present invention will be described in more detail below based on Examples, but it is obvious that the present invention is not limited to these Examples.

Example 1 524 parts of terephthalic acid, 52 parts of l,4-butanediol.
9 parts, tetrabutyl titanium) 0.028 parts (a small amount of 1
, 4-butanediol) and mo/n-butyl-
0.02 parts of monohydroxytin oxide (a small amount of 1
．． (suspended in 4-butanediol) is charged into an esterification tank equipped with a rectification column and a stirrer, and the esterification reaction is carried out while gradually increasing the temperature from 160°C to 230°C, and the resulting water and detrahydrofuran are It was distilled off through a rectification tower.

After the esterification reaction was completed, 0510 parts of tetrabutyl titanate was dissolved in a small amount of 1,4-butanediol as a polycondensation catalyst, and 0.510 parts of tetrabutyl titanate was added as a stabilizer.
X //1010 (E-book made by Ciba-Geigy) 01
0 part was suspended in a small amount of 1,4-butanediol and added. Next, a polycondensation tank containing a small amount of the remaining polymer from the previous batch (polymer composition is the same as the polymer produced in Example 1) with a number average molecular weight of 1. After charging 31.0 parts of OOO polytetrabutylene glycol, the esterified product was transferred from the esterification tank to the polycondensation tank. Then, the pressure was gradually reduced from normal pressure to 1 mHg or less over 1 hour, and at the same time the temperature was raised to 245°C and polycondensation was carried out at 245°C + 1 mHg or less for 3 hours to form a strong and elastic highly polymerized polyester-polyether copolymer. A polymer was obtained.

There was only slight foaming when the esterified product was transferred to the polycondensation tank, and no trouble was observed in which the esterified product leaked into the vacuum circuit or the like.

Example 2 An esterified product obtained by esterifying in the same manner as in Example 1 and then adding a polycondensation catalyst and a stabilizer was treated with a small amount of can residue polymer from the previous batch (polymer composition is the same as the polymer produced in Example 1) attached. A polycondensation tank with a number average molecular weight of 1,000
The mixture was transferred simultaneously with the addition of 310 parts of polytetramethylene glycol. Next, the pressure was gradually reduced from normal pressure to below leaHg over 1 hour, and at the same time the temperature was raised to 245°C.
Polycondensation was carried out at 45 DEG C. and below 1 mHg for 3 hours to obtain a strong and elastic highly polymerized polyester-polyether copolymer.

There was only slight foaming when the esterified product was transferred to the polycondensation tank, and no trouble was observed in which the esterified product leaked into the vacuum circuit or the like.

Comparative Example 1 An esterified product obtained by esterifying in the same manner as in Example 1 and then adding a polycondensation catalyst and a stabilizer was prepared by adding a small amount of the remaining polymer from the previous batch (polymer composition is the same as the polymer produced in Example 1). Transferred to the attached polycondensation tank. Immediately after the transfer, the esterified product foamed vigorously, the liquid level rose, and some of the esterified product leaked into the vacuum circuit. Next, polyalkylene gellicol 31. has a number average molecular weight of 1,000.
0 part was charged into a polycondensation tank and polycondensed in the same manner as in Example 1, but because the vacuum circuit was clogged with the esterification product, the polycondensation tank could not be brought to a high degree of vacuum, resulting in a high degree of polymerization. No polyester-polyether copolymer was obtained.

Example 3 Terephthalic acid 358 parts, isophthalic acid 153m, 114 parts
-499 parts of butanediol, 0 parts of tetrabutyl titanate
．． Part 034 -.

m- The residue (dissolved in a small amount of 1,4-butanediol) was charged into an esterification tank equipped with a rectification column and a stirrer, and 160
The esterification reaction was carried out while gradually increasing the temperature from .degree. C. to 230.degree. C., and the resulting water and tetrahydrofuran were distilled off through a rectification column.

After the esterification reaction was completed, 012 parts of tetrabutyl titanate and 0.01 g of magnesium acetate were dissolved in a small amount of 1,4-butanediol as a polymerization catalyst and added, and further 0.010 parts of RGANOX//1010 as a stabilizer were added. was suspended in a small amount of 1,4-butanediol and added.

Next, polytetramethylene glycol 3 with a number average molecular weight of 1,000 is placed in a polycondensation tank to which a small amount of the remaining polymer from the previous batch (polymer composition is the same as the polymer produced in Example 3) is attached.
After charging 5.4 parts, the esterified product was transferred from the esterification tank to the polycondensation tank. Then l m from normal pressure
Gradually reduce the pressure to below Hg over 1 hour, and at the same time
The temperature was raised to 5°C, and polycondensation was carried out at 245°C for 3 hours at 1-Hg or less to obtain a strong and elastic highly polymerized polyester-polyether copolymer.

When the esterified product was transferred to the polycondensation tank, there was very little foaming, and no problems were observed with the esterified product leaking into the vacuum circuit, etc.

Patent applicant: Toshi Co., Ltd.

Claims (1)

[Claims] Dicarboxylic acid m containing aromatic dicarboxylic acid as a main component, 1.
When producing a polyester-polyether copolymer by a direct polymerization method using a low molecular weight glycol containing 4-butanediol as a main component and a polyalkylene glycol having a molecular weight of 400 to 6,000, first, a low molecular weight dicarboxylic acid is processed in an esterification tank. After the esterification reaction with glycol, the esterification product is clarified and transferred to a polycondensation tank containing polyalkylene glycol.
A method for producing a polyester-polyether copolymer, which comprises charging the polyester-polyether copolymer to the polycondensation tank at the same time as transferring the polycondensation tank to the polycondensation tank, and then subjecting it to a polycondensation reaction.