JPH023429A - Preparation of polyester ether copolymer - Google Patents

Abstract

PURPOSE:To prepare efficiently the subject copolymer having excellent quality by melt-mixing each specified polyester and polyether in a heating medium to thereby perform polycondensation thereof. CONSTITUTION:A polyester having an intrinsic viscosity of 0.3dl/g or larger, prepared from one or more arom. dicarboxylic acids or alkyl esters thereof, such as terephtalic acid or isophthalic acid, one or more glycols such as ethylene glycol and one of polyethers having OH groups and an MW of 200 or larger of pref. formula I (wherein R<3> is a 2-6C alkylene; r is 3-350) and formula II [wherein R<4-5> are each R<3>; X is -C(CH3)2-, -SO2-, -S-, -CH2-, -O-, -CO-; p and q are each 1-250] are melt-mixed in a heating medium, pref. a compd. selected from paraffines, polyolefins, silicone oils, compd. of formula III (wherein A<1-2> are each a phenyl group or a 5-20C cycloalkyl group; A<3> is a phenylene group or a 5-20C cycloakylene group; l is 0-3) and compd. of formula IV (wherein R<1-2> are each a 1-20C alkyl; m and n are each 0-5) to perform polycondensation thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a polyester ether copolymer. More specifically, the present invention relates to a method for producing a polyester ether copolymer by melt-mixing a specific polyester and a specific polyether in a heat medium and performing a polycondensation reaction.

[Prior Art/Problems to be Solved by the Invention] Polyester ether copolymers have excellent moldability and physical properties, and are therefore attracting attention in the field of industrial plastics such as automobile parts and electrical and electronic parts.

As a method for producing a polyester ether copolymer, ■ A method in which a polyether is allowed to coexist during transesterification of an aromatic dicarboxylic acid ester and a glycol, and the transesterification reaction and polycondensation reaction are carried out. ■ A method disclosed in JP-A-58-198527. As shown in JP-A-48-1999, a low molecular weight esterified product obtained by directly esterifying an aromatic dicarboxylic acid and a glycol is transferred to a polycondensation tank containing polyether in advance to carry out a polycondensation reaction. As disclosed in Japanese Patent No. 19696, a method has been reported in which alkylene glycol is added to polyester to form an oligoester, and then polyether is added to perform a polycondensation reaction.

However, all of these methods require complex processes and associated equipment.Since the reaction time is long, by-product polyethers such as diethylene glycol are produced, which inevitably leads to a decline in quality and operability. (2) In order to obtain a polymer with a high degree of polymerization, there are problems such as the need to further perform solid phase treatment on the resin after the reaction.

[Means for Solving the Problems] In view of the above circumstances, the present inventors have conducted extensive research to solve the above problems, and as a result, have arrived at the present invention.

That is, in the present invention, a polyester having an intrinsic viscosity of 0.3 [dN/g1 or more and a polyether having a hydroxyl group and a molecular weight of 200 or more are melt-mixed, and a polycondensation reaction is performed to obtain a polyester ether copolymer. The present invention relates to a method for producing a polyester ether copolymer, characterized in that the melt mixing and polycondensation reaction are carried out in a heating medium when producing the copolymer.

[Example] In the present invention, a polyester ether copolymer is produced by melt-mixing polyester and polyether and performing a polycondensation reaction.

The polyester has an intrinsic viscosity of 0.3 [dN/g] or more, preferably 0.5 [dN/g] or more, and more preferably 0.5 to 1.5 Cdl/g]. If the intrinsic viscosity is less than 0.5 ldn/g1, the polycondensation reaction time becomes long, which is not preferable.

On the other hand, polyesters exceeding 1.5 [dN /g] can be used, but such polyesters are generally of special grade and difficult to obtain.

Specific examples of the polyester include terephthalic acid, isophthalic acid, 2,8-naphthalene dicarboxylic acid, 4,4°-dicarboxyldiphenyl, 4,4"-dicarboxylbenzophenone, bis(4-carboxylphenyl)ethane, etc. aromatic dicarboxylic acids, IFJ or two or more of these alkyl esters such as methyl, ethyl, and propyl, and glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and cyclohexane dimetatool. Examples include polyesters synthesized from one or more of these.These may be used alone or in combination of two or more.

Further, the above-mentioned polyesters are usually preferably in the form of pellets, flakes obtained by crushing or the like, or powders because they are easy to handle and easily react with polyether.

The polyether used with the polyester is
having a hydroxyl group, preferably having a hydroxyl group at the end, and having a molecular weight of 200 or more, preferably 200 to 1
0000 polyether.

If the molecular weight of the polyether is less than 200, the melting point of the resulting polyester ether copolymer will be lowered, which is undesirable. If it exceeds 10,000, the compatibility between the polyether part and the polyester part will deteriorate during processing of the product. This tends to make it difficult to obtain products of uniform quality.

Typical examples of the polyether include the general formula (: % formula % (10 (wherein R'' is an alkylene group having 2 to 5 carbon atoms, r is an integer from 3 to 250, and one R3 is the same group). polyether represented by the general formula ([V); (wherein, R4R5 is an alkylene group having 2 to 5 carbon atoms,
X Bar C (CI 2- -9O2--S --C11
2--0- or -C0-1p1q Ha1~250]
Examples include polyethers represented by an integer, R4R5 (when two or more groups are present, they do not need to be the same group). Among these, bisphenol A
Products with aromatic rings in their molecular chains, such as (poly)alkylene oxide adducts such as 1-bisphenol S, are particularly useful because they have relatively good heat resistance and can undergo melt mixing and polycondensation reactions at high temperatures. preferable.

The polyethers may be used alone or in combination of two or more.

The usage ratio of the polyester and the polyether is
The amount of polyether is 1 to BO parts, preferably 5 to 35 parts, per 100 parts (by weight, hereinafter the same) of polyester.

If the proportion of polyether is less than 1 part, the desired physical properties (
If the amount exceeds 80 parts, the polyether tends to deteriorate.
Quality tends to deteriorate.

In the present invention, - Melt mixing and polycondensation reaction of the polyester and the polyether are performed in a heating medium.

The heating medium facilitates the mixing of polyester and polyether, allows the entire reaction system to be heated almost uniformly, facilitates the polycondensation reaction, and removes glycols such as ethylene glycol produced by the reaction. It is used to make it easier to remove.

The heat carrier is a thermally stable organic compound that can be handled as a fluid under melt mixing and polycondensation reaction temperatures;
Preferably, polyesters and compounds that are incompatible with the resulting polyester ether copolymer are used.

As used herein, the term "thermal medium and polyester etc. are not compatible" means that they do not substantially undergo a chemical reaction with polyester etc., causing swelling but not dissolution.

The heat medium may be, for example, paraffins, polyolefins, silicone oils, general formula (I): (wherein, At A2 is a phenyl group or a cycloalkyl group having 5 to 20 carbon atoms, and A'' is a phenylene group. or a cycloalkylene group having 5 to 20 carbon atoms, I is 0 to
(representing an integer of 3), general formula (I): (wherein, RI R2 is an alkyl group having 1 to 20 carbon atoms, ■ and n are integers of θ to 5, and each of RI R2 is 2 (When more than one group exists, they do not need to be the same group). These may be used alone or in combination of two or more.

Among the heat carriers, polyolefins are preferable from the viewpoint of thermal stability and boiling point, and triphenyls are preferable from the viewpoint of fluidity and cost.

Specific examples of the paraffins include paraffin and liquid paraffin; specific examples of the polyolefins include polymers of olefinic monomers such as ethylene, propylene, butadiene, and styrene; for example, polyethylene of about 70 to 110 ,polypropylene,
Specific examples of the compound represented by the general formula (1) include hydrogenated triphenyl; specific examples of the compound represented by the general formula (1) include triethyldiphenyl.

There is no particular limitation on the amount of heat medium used per 100 parts of the total amount of polyester and polyether, but it is usually 50 parts.
~500 copies are easy to use.

There are no particular limitations on the conditions during the melt mixing and polycondensation reaction of polyester and polyether, and the temperature is about 200 to 300°C, preferably 220 to 300°C, under normal pressure, reduced pressure, or increased pressure.
Examples of methods include heating and stirring at 280° C., adding a stabilizer if necessary, but the method is not limited to this method.

As the stabilizer, it is preferable to use, for example, phosphate esters, phosphite amine compounds, thioethers, hindered phenols, etc. alone or in combination with 2fi or more, but especially in combination with triphenyl phosphate and hindered phenols. is preferred. The amount of stabilizer used is preferably about 0.01 to 5 parts per 100 parts of the copolymer obtained.

Further, in the polycondensation reaction, a commonly used catalyst such as a metal oxide, carbonate, acetate, or alcoholade may be used alone or in an amount of 2 fi or more in order to accelerate the reaction. Preferred examples of the catalyst include tetra-n-butyl titanate, potassium titanyl oxalate, antimony dioxide, and germanium oxide.

According to the production method of the present invention, the use of a heating medium in the melt mixing and polycondensation reaction of polyester and polyether improves heat conduction, melts in a short time, and distills by-product glycol out of the reaction system. Since the reaction time is short, deterioration of the product polymer is suppressed, and a product polymer with a high degree of polymerization can be obtained.

Hereinafter, the manufacturing method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Reactor equipped with stirrer and gas outlet (capacity: 100 ml)
), add 30 ml of polyrethylene (Ml 75), and
After heating and melting at 30℃, bisphenol^ is added under stirring.
Polyethylene oxide adduct (MIflooG) 1.8
g, 0.033 g of triphenyl phosphate, 0.075 g of a hindered phenol stabilizer (manufactured by Ciba Geigy, trade name Irganox 1010), and 0.01 g of antimony dioxide were added. Next, polyethylene terephthalate (intrinsic viscosity 0.8 [dff/g) 2
8.2g was added and further heated to 280°C. After the contents have completely melted and mixed (this took about 15 minutes)
A polycondensation reaction was carried out for 40 minutes under a vacuum of lllllHg while maintaining the internal temperature at 280°C. Next, the produced copolymer was taken out, polyethylene was removed with para-xylene, and then dried.

Yield was 30g.

The physical properties of the obtained copolymer were measured by the method shown below.

The results are shown in Table 1.

(Intrinsic viscosity [d#/g]) Measured using phenol/tetrachloroethane-171 (weight ratio) at a copolymer concentration of 0.25 g/dR and 25°C.

(color tone) b value measured by colorimeter.

(Diethylene glycol (DEC) amount [wt%]) Value measured by gas chromatography after decomposition with methanol/potassium hydroxide.

(Heating weight loss rate [%]) Values measured using a thermobalance and held at 280°C for BO minutes.

Example 2 A copolymer was obtained in the same manner as in Example 1 except that the polycondensation reaction time was changed to 120 minutes. Yield was 30g.

The physical properties of the obtained copolymer were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 Dimethyl terephthalate 28 was added to the same apparatus as in Example 1.
．． 4 g and 10.9 g of ethylene glycol,
While stirring, the mixture was heated to 200° C., and a predetermined amount of methanol was distilled off (this time was 140 minutes). Next, bisphenol A polyethylene oxide adduct (Men 1000)
1.8g, triphenyl phosphate 0.83g, Irganox 10100. Add 075g of antimony dioxide and ot t and further heat to 260℃,
Polycondensation reaction was carried out under vacuum of 1111 g for 80 minutes.

Next, the produced copolymer was taken out and dried. Yield is 3
It was 0g-.

The physical properties of the obtained copolymer were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 Bisphenol A polyethylene oxide adduct (MWlooO) 1.1! g-, triphenyl phosphate 0°033g and Irganox 10
100.075F: was added and heated to 250°C, and then 211.2 g of polyethylene terephthalate and 0.01 g of antimony trioxide were gradually added to the polyether while stirring so that they were uniformly incorporated into the polyether. After the addition was completed, the mixture was heated to 2110° C. and melted and mixed (this time was approximately 110 minutes), followed by a polycondensation reaction for 40 minutes under a vacuum of 1 + a + sHg. Next, the produced copolymer was taken out and dried. Yield was 30g.

The physical properties of the obtained copolymer were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 30 ml of hydrogenated triphenyl was placed in the same apparatus as in Example 1 and heated to 250°C, and then, under stirring, bisphenol A polyethylene oxide adduct (MVlooO) 9
g, triphenyl phosphate O, 17 g.

Irganox 10100.28 g and polyethylene terephthalate (intrinsic viscosity 0.8 Cdl/g12
1 g was added. After further heating to 280°C and completely melting and mixing the contents (this took about 10 minutes), heat was heated for 200 minutes while blowing nitrogen gas at a rate of 0.1/min while keeping the internal temperature at 2θO°C. A condensation reaction was carried out (during which time triphenyl hydride (8 ml) was further added to keep the liquid level constant). Next, the produced copolymer was taken out, thoroughly washed with acetone, and then dried. Yield was 27g.

The physical properties of the obtained copolymer were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 30 ml of hydrogenated triphenyl was placed in the same apparatus as in Example 1, heated to 250°C, and then stirred, an oligomer obtained by direct esterification of terephthalic acid and ethylene glycol (direct esterification reaction time 200 minutes) 27.2 g, bisphenol A ethylene oxide adduct (MW 101000) triphenyl 9-phosphate 0.17 g, Irganox 10100.28 g
and 0.02 g of antimony dioxide were added. After further heating to 260°C to completely melt and mix the contents (this time was 10 minutes), polycondensation reaction took place for 450 minutes while blowing nitrogen gas at 0.5N/min while keeping the internal temperature at 260°C. (During this period, the liquid level was kept constant.
Further g ml of triphenyl hydride was added).

Next, the produced copolymer was taken out, thoroughly washed with acetone, and then dried. Yield was 2ftg.

The physical properties of the obtained copolymer were measured in the same manner as in Example 1. The results are shown in Table 1.

From the results shown in Table 1, according to the production method of the present invention,
It can be seen that a high molecular weight and high quality polyester ether copolymer can be produced in a short reaction time.

[Effects of the Invention] The production method of the present invention: (1) Uses polyester as a raw material, so an esterification reaction step is unnecessary, and can produce a high molecular weight copolymer; (2) Uses a heat medium. By doing so,
Mixing of polyester and polyether is done quickly and no special equipment is required. ■Since polyester is used as a raw material, the reaction time is shortened and the thermal history of the polyether is reduced in systems that use a heat medium. , As a result, the deterioration of the copolymer is suppressed. ■ A copolymer with a high degree of polymerization can be easily obtained by polycondensation in a solution state, and processes such as solid phase treatment are not required. ■ Total production time It has various advantages such as dramatically shortening the time required for the operation cycle and greatly improving productivity, and will greatly contribute to the industrial world.

Patent, patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. A polyester ether having an intrinsic viscosity of 0.3 [dl/g] or more and a polyether having a hydroxyl group and a molecular weight of 200 or more are melt-mixed and subjected to a polycondensation reaction. A method for producing a polyester ether copolymer, which comprises performing the melt mixing and polycondensation reaction in a heat medium when producing the copolymer. 2 The heat medium is paraffins, polyolefins, silicone oils, general formula (I): A^1-A^3_l-A^2 (I) (wherein A^1 and A^2 are phenyl groups or carbon A cycloalkyl group having 5 to 20 atoms, A^3 is a phenylene group or a cycloalkylene group having 5 to 20 carbon atoms, l is 0 to
(representing an integer of 3) and general formula (II)
: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 are alkyl groups having 1 to 20 carbon atoms, m and n are integers of 0 to 5, R^1 and R^2 2. The method according to claim 1, wherein the compound is a compound selected from the group consisting of compounds represented by (when two or more of each are present, they do not need to be the same group). 3 The polyethers have the general formula (III): ▲ Formula,
There are chemical formulas, tables, etc. ▼ (III) (In the formula, R^3 is an alkylene group with 2 to 5 carbon atoms, r is an integer from 3 to 250, and the r R^3s do not need to be the same group) and (or) general formula (IV): ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼
(IV) (In the formula, R^4 and R^5 are alkylene groups having 2 to 5 carbon atoms, and X is -C(CH_3)_2-, -SO_2-, -
S-, -CH_2-, -O- or -CO-, p and q are integers from 1 to 250, and when two or more of each of R^4 and R^5 exist, they do not need to be the same) The manufacturing method according to claim 1, which is a polyether represented by: 4 The molecular weight of the polyether is 200 to 10,000
The manufacturing method according to claim 1 or 3. 5 The polyester is terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxyldiphenyl, 4,4'-dicarboxylbenzophenone, bis(4-carboxylphenyl)ethane, and alkyl esters thereof and one or more selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and cyclohexanedimethanol. The method according to claim 1, wherein the polyester is synthesized from. 6. The manufacturing method according to claim 1 or 5, wherein the polyester is in the form of pellets, flakes, or powder.