JPH026532A - Production of polyester ether copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer while preventing it from being degraded during its production and remarkably improving its productivity by melt-mixing a specified polyester with a specified polyether and polycondensing the mixture. CONSTITUTION:After or while a polyester of an intrinsic viscosity >=0.3 (dl/g) is melt-mixed with a hydroxyl group-terminated polyether of an MW>=200, they are subjected to polycondensation to obtain the purpose copolymer. Examples of the polyesters used include polymers synthesized from aromatic dicarboxylic acids or their alkyl esters and glycols (e.g., ethylene glycol). As said polyethers, at least either of polyethers of formula I (wherein R is a 2-5C alkyl) and formula II [wherein R<1> and R<2> are each a 2-5C alkylene; and X is formula III, -SO2-, -S-, -CH2-, -O- or -C(O)-] can be desirably used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a polyester ether copolymer, and more specifically, a polyester obtained by reducing an aromatic carboxylic acid or an alkyl ester thereof and a glycol;
When producing a copolymer with polyethers, a polycondensation reaction is performed under predetermined reaction conditions after or while melt-mixing polyester as one raw material and polyether as the other raw material. The present invention relates to a method for producing a copolymer.

[Prior Art and Problems] Polyester ether copolymers are attracting attention in the field of industrial plastics such as automobile parts and electrical and electronic parts because of their excellent moldability and physical properties. The manufacturing method is a method in which a polyether is allowed to coexist during transesterification of an aromatic dicarboxylic acid ester and a glycol, and a polycondensation reaction is carried out after the transesterification reaction, JP-A-58-1.
98527, a method in which an esterified product obtained by directly esterifying an aromatic dicarboxylic acid and a glycol is transferred to a polycondensation tank previously charged with polyether, and the polycondensation reaction is carried out, or JP-A-1988-1 A method such as No. 19696 in which an alkylene glycol is added to a polyester to form an oligoester, and then a polyether is added to carry out a polycondensation reaction has been reported.

However, these methods require complicated processes and associated equipment, and the long reaction time produces by-product polyethers such as diethylene glycol, which inevitably leads to a decline in quality and operability. Contains points.

c. Means for Solving the Problems] In view of the above circumstances, the present inventors have sought to solve the above problems (as a result of intensive research, they have come to provide the present invention).

That is, in the present invention, after melt-mixing a polyester with an intrinsic viscosity of 0.3 (di/g) or more and a polyether having a hydroxyl group at the end and a molecular weight of 200 or more,
Alternatively, the method for producing a polyester ether copolymer is characterized by carrying out a polycondensation reaction while melt-mixing.

The polyester used in the present invention includes aromatic dicarboxylic acids or alkyl esters thereof, such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
4.4'-dicarboxyldiphenyl, 4.4'-dicarboxylbenzophenone, bis(4-carboxylphenyl)ethane, etc., or their methyl, ethyl,
Alkyl esters such as propyl may be used alone or in combination, and glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexanedimethanol, etc. may be used alone or in combination.
Examples include homopolymers and/or copolymers synthesized from more than one species.

As the polyether used in the present invention, shell formula (I)
and (■) (I) lio+R・0+TH R: C, ~C2 alkylene group (in the formula, one R does not have to be the same) (II) H+O-R')-? 0-Q-X-Q-0
-(R”.

R', R2: CZ to C3 alkylene group [wherein (m+
n) R1 and R1 do not need to be the same. One of the following is preferably used: 〇10- or -C-.

Among these, those having an aromatic ring in the molecular chain, such as polyalkylene oxide adducts such as bisphenol A and bisphenol S, are particularly suitable because they can be melt-mixed at relatively high temperatures. The molecular weight of the polyether is 200 or more, preferably 200 to 1oooo. If it is less than 200, the melting point of the produced polymer will drop, which is undesirable. If it exceeds 10,000, the compatibility will be poor and it will be difficult to obtain a product of uniform quality.

The amount of polyether is 1 to 60 parts by weight, preferably 5 to 35 parts by weight.
Parts by weight. If the amount of polyether is less than 1 part by weight, the desired physical properties of the polymer cannot be obtained, which is not preferable. Also, 6
If it exceeds 0 parts by weight, the polyether will deteriorate significantly and its quality will deteriorate, which is not preferable. The intrinsic viscosity of polyester is 0°3 (di/g) or more, preferably 0.5 (dl
/g) or more. When the intrinsic viscosity is less than 0.3 (dl/g), the polycondensation reaction time becomes longer, which is not preferable.

How to melt and mix polyester and polyether in advance? A method of adding polyether to molten polyester. The polyether is heated in advance to 1507200°C in the presence of a stabilizer, and then the polyether is added all at once or continuously so that the polyester is uniformly blended with the polyether. Although the latter method is preferable because melting and mixing can be performed easily and quickly. As a stabilizer,
Phosphate esters, phosphite esters, amine compounds, thioethers, hindered phenols, etc. alone or in combination
More than one species can be used. Among these, combination use of triphenyl phosphate and hindered phenols is preferred. The amount of stabilizer is preferably o, oi to 5 parts by weight.

In the present invention, when producing the copolymer, catalysts commonly used to promote the reaction, such as metal oxides,
Carbonates, acetates, alcoholades, etc. can be used alone or in combination of two or more. Among them, preferred are tetra-n-butyl titanate, potassium titanyl oxalate, antimony dioxide, germanium oxide, and the like.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these. In addition, various values were determined by the following measurement method.

(I) Intrinsic viscosity (dl/g) 'phenol/tetrachloroethane-1/1 (weight ratio) Polymer concentration is 0.25 g/di and measurement temperature is 25°C
(2) Color By4, b value by negative color difference meter (3) Amount of diethylene glycol (D E C) [&4tχ]: Measured value by gas chromatography after decomposition with methanol/potassium hydroxide (4) Heating type! Reduction rate [%]: 280℃- by thermobalance
Measurement values by holding for 60 minutes Examples 1 to 4 In a reactor (about 41 mm) equipped with a stirrer and a gas outlet, the first
After adding raw materials other than polyester shown in the table, 200
℃, then under normal pressure and nitrogen atmosphere, pellet-shaped polyester cut into strands with a diameter of about 3φ was charged all at once, and heated to 260℃. Melting, 0.5~
The polycondensation reaction was carried out under vacuum in fin Hg-abs. Table 3 shows the measurement results of the obtained copolymer.

The numbers in Table 1 are parts by weight 1) Intrinsic viscosity 0.6 dl/g, 2) 3) Molecular weight 1500. 4) 5) Product name, manufactured by Ciba Geigy Intrinsic viscosity 0.8 dl/g Molecular weight 1000 Example 5 Pellet-shaped polyethylene terephthalate (
Intrinsic viscosity 0.6 dl/g) 100 parts (parts by weight, same hereinafter) were charged, heated and melted at 260°C, and then 43 parts of bisphenol A polyethylene oxide adduct (molecule 11000) was added so that the internal temperature did not fall below 240°C. Triphenyl phosphate 0.76 parts, Irganox-1010
After continuously adding 1,17 parts and 0.05 parts of antimony dioxide, the temperature was raised to 260°C and 0.5 to 1 mstlg-a
The polycondensation reaction was carried out under BS vacuum. Table 3 shows the measurement results of the obtained copolymer.

Comparative Example 1.4 Using the same apparatus as in Example, the raw materials shown in Table 2 were charged in bulk, and a predetermined amount of methanol was distilled out at about 200°C, and then heated to 260'C to produce 0.5ml/g -ab.
The polycondensation reaction was carried out under a vacuum of s. Table 4 shows the measurement results of the obtained copolymer.

Table *Molecular weight 100° Comparative Example 2 A device similar to that of Example with a rectification column added was used, and bishydroxyethyl terephthalate si was used as the first stage of the reaction.
A slurry of 36.4 parts of terephthalic acid and 16.4 parts of ethylene glycol was added continuously to 52.8 parts of i-former over about 3 hours while keeping the internal temperature at about 240°C, and a predetermined amount of water was added by rectification. I was able to leave. Next, 43 parts of bisphenol A polyethylene oxide (molecular weight 1000), 0.76 parts of triphenyl phosphate, Irganox-10101,17
1 part and 0.05 part of antimony trioxide were added, the temperature was raised to 260°C, and a polycondensation reaction was carried out under a vacuum of 0.5 mHg-abs.

Table 4 shows the measurement results of the obtained copolymer.

Comparative Example 3 100 parts of polyethylene terephthalate chips (intrinsic viscosity 0.6 dl/g), 135 parts of ethylene glycol, and 0.099 parts of zinc acetate were placed in the same apparatus as in Example 2.
After oligoesterifying ethylene glycol while refluxing it at 00°C for 1 hour, polyethylene glycol (molecules 11
500) 43 parts, triphenyl phosphate 0.76 parts, Irganox-10101, 17 parts, antimony dioxide 0
．． 0.5 parts of the copolymer was charged and heated to 260"C, and a polycondensation reaction was carried out under vacuum at 0.5 parts of g-abs. The measurement results of the obtained copolymer are shown in Table 4.

[Action/Effect]

According to Unegami, according to the present invention, (I) since polyester is used as a raw material, steps such as esterification reaction and transesterification reaction are not necessary; (2) special equipment is required for mixing polyester and polyether; (3) Since the reaction time is shortened, the amount of by-product polyether is reduced, and the thermal history of the polyether is also reduced, thus suppressing the deterioration of the polymer during production. (4) Production It has various advantages such as dramatically shortening time and speeding up the operating cycle, greatly improving productivity, and it will greatly contribute to the industrial world.

Patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. After melt-mixing a polyester with an intrinsic viscosity of 0.3 [dl/g] or more and a polyether having a hydroxyl group at the end and a molecular weight of 200 or more, or after melt-mixing A method for producing a polyester ether copolymer, comprising carrying out a polycondensation reaction. 2. The main chain has the following general formulas (I) and (II) (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R: C_2 to C_5 alkylene group (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ R^1, R^2: C_2 to C_5 alkylene group X: ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, -SO_2-, -S
-, -CH_2--O-, or ▲ Numerical formula, chemical formula, table, etc. ▼ The manufacturing method according to claim 1, wherein at least one polyether is used. 3. As the raw material polyester, terephthalic acid, isophthalic acid, 2,6 naphthalene dicarboxylic acid, 4,4'-dicarboxyldiphenyl, 4,4'dicarboxylbenzophenone, bis(4-carboxylphenyl)ethane or the methyl or ethyl thereof , alkyl esters such as propyl alone or two or more; glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, etc. alone or two or more;
2. The manufacturing method according to claim 1, wherein a homopolymer and/or copolymer synthesized from more than one species is used. 4. The manufacturing method according to claim 1 or 3, wherein the raw polyester is in the form of pellets or flakes or powder obtained by crushing or the like. 5. The manufacturing method according to claim 1, 3 or 4, wherein the polycondensation reaction is carried out after or while melt-mixing the polyester added to the pre-heated polyether. 6. The manufacturing method according to claim 1 or 2, wherein the polyether is a compound having a molecular weight of 200 to 10,000. 7. At least one stabilizer selected from phosphate esters, phosphite esters, amine compounds, thioethers, and hindered phenols when polyether is heated.
2. The method according to claim 1, wherein seeds are used.