JPS60235834A - Production of highly polymerized polyester - Google Patents

Abstract

PURPOSE:To obtain a highly polymerized, heat-resistant polyester reduced in the content of terminal carboxyl groups, by reacting an adduct between a bisoxazoline compound and a dicarboxylic acid compound with a linear saturated polyester in a molten state. CONSTITUTION:An addition reaction is effected between a bisoxazoline compound of the formula (wherein R is a bivalent organic group and n is 0 or 1), e.g., 2,2'-methylenebis(2-oxazoline), and a dicarboxylic acid compound (e.g., terephthalic or isophthalic acids) at a molar ratio of 1.5-3:1. 0.3-10wt% obtained adduct is reacted in a molten state with a linear saturated polyester in the presence of 0.001-0.1wt% quat. phosphonium salt compound (e.g., tetramethylphosphonium chloride) or tert. phosphine compound (e.g., trimethylphosphine) to obtain the purpose highly polymerized polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is referred to as a terminal carboxyl group (hereinafter referred to as (Coo) I). ) is related to a method for producing a heat-resistant polyester with a high degree of polymerization.

(Prior Art) Although various methods have been proposed for reducing the (COOI+) of polyester, a method of reacting polyester with a bisoxazoline compound has recently attracted attention.

For example, JP-A-50-59525 proposes a method of spinning polyester by adding a phenylenebisoxapurine compound. According to this method, the (COOH) of the polyester is reduced and the molecular weight is reduced. It is said that it has a reinforcing effect and can at least partially offset the degradation that occurs during spinning.

However, when the present inventors investigated this method, the decomposition of the polyester occurred due to remelting, and this was not sufficiently compensated for, resulting in a slight decrease in the molecular weight.
The effect of reducing (COOH) was also not sufficient.

(Object of the invention) The present invention provides a method for producing a polyester with a high degree of polymerization, excellent heat resistance, and good moldability (spinning) by effectively reducing the [C00 old] of polyester and increasing the degree of polymerization. The purpose is to

(Structure of the Invention) As a result of intensive research to achieve this object, the present inventors found that when a bisoxazoline compound is reacted with polyester in the form of a reaction adduct with a dicarboxylic acid compound, the melt viscosity increases, and the polyester The present inventors have discovered that more favorable results can be obtained when a specific compound is present as a catalyst during this reaction, and the present invention has been achieved. .

That is, the gist of the present invention is as follows.

fl) Molar ratio of substantially linear saturated polyester, bisoxazoline compound and dicarboxylic acid compound from 1.5 to
A method for producing a highly polymerized polyester, which comprises reacting a 3:l reaction adduct in a molten state with 0.3 to 10% by weight.

(2) The molar ratio of the substantially linear saturated polyester, the bisoxazoline compound, and the dicarboxylic acid compound is 1.5 to
3:1 reaction adduct 0.3-10%.

A method for producing a highly polymerized polyester characterized by reacting it in a molten state in the presence of 0.001 to 0.1% by weight of a quaternary phosphonium salt compound or a tertiary phosphine compound.

(3) The molar ratio of the substantially cotton-like saturated polyester, the bisoxazoline compound, and the dicarboxylic acid compound is 1.5 to 1.5.
3; and 0.3 to 10% by weight of the reaction adduct of 1.

Alkali metal halide 0.001-0.05% by weight
A method for producing a highly polymerized polyester, which comprises reacting in a molten state in the presence of.

Specific examples of the polyester in the present invention include terephthalic acid and isophthalic acid. naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid,
Acid components such as succinic acid, adipic acid, speric acid, sebacic acid, cyclohexanedicarboxylic acid, hydroxybenzoic acid, and ε-hydroxycaproic acid, and ethylene glycol, trimethylene glycol, and tetramethylene glycol.

Examples include polyesters with glycol components such as hexamethylene glycol and cyclohexane dimetatool, with polyethylene terephthalate being a typical example.

In addition to the above-mentioned bifunctional components, trifunctional or higher functional components such as trimellitic acid and pentaerythritol may be copolymerized within a range that does not impair the fiber-forming ability of the polyester.

The bisoxazoline compound in the present invention is represented by the following general formula.

(R is a divalent organic group, n is an integer of 0 or 1.

In the formula, the hydrogen atom may be substituted with an alkyl group or an alkyl group. ) Specific examples of the bisoxazoline compound represented by this general formula include 2.2'-methylenebis(2-oxazoline), 2.2'-ethylenebis(2-oxazoline), 2.2'-ethylenebis( 4-methyl-2-oxazoline), 2.2'-propylenebis(2-oxazoline), 2.2'-tetramethylenebis(2
-oxazoline), 2.2'-hexamethylenebis(2-oxazoline), 2,2''-octamethylenebis(2-oxazoline), 2.2''-p-phenylenebis(2-oxazoline), 2. 2'-p-phenylenebis(4-methyl-2-oxaprine), 2,2'-p-
Phenylenebis(4,4-dimethyl-2-oxazoline), 2,2°-p-phenylenebis(4-phenyl-2-oxazoline), 2.2''-m-phenylenebis(2-oxazoline), 2. 2'-m-phenylenebis(4-methyl-2-oxazoline).

2.2°-m-phenylenebis(4,4-dimethyl-2
-oxazoline), 2,2'-m-phenylenebis(4
-phenyl-2-oxazoline), 2.2”-0-
Phenylenebis(2-oxazoline), 2.2"-
〇-Phenicinbis(4-methyl-2-oxazoline)
, 2.2'-bis(2-oxazoline), 2.
2”-bis(4-methyl-2-oxazoline), 2.2
'-bis(4-ethyl-2-oxazoline), 2.2
”-bis(4-phenyl-2-oxazoline) and the like.

Examples of the dicarboxylic acid compound to be reacted with the bisoxazoline compound include dicarboxylic acids, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, and hexadecanedicarboxylic acid, which are exemplified as components constituting the polyester.

Octadecanedicarboxylic acid, eicosandicarboxylic acid,
Long chain dicarboxylic acids such as tocosandicarboxylic acid and tetracosandicarboxylic acid can be used.

A reaction adduct of a bisoxazoline compound and a dicarboxylic acid compound (referred to as a BO-DA reaction adduct) is.

The molar ratio of both is 1.5 to 3:1. Preferably 148-2.
Mix at a ratio of 2:1 and heat at 90°C or higher, preferably at 12°C.
It can be easily obtained by stirring the reaction under nitrogen gas flow at 0° C. or below.

What is the amount of the BO/D^ reaction adduct used in the present invention?

The amount is 0.3 to 10% by weight based on the polyester. If this amount is too small, the degree of blocking of (COOII) will be low, and if it is too large, the reaction will proceed satisfactorily.

Undesirable problems such as decomposition of unreacted BO-D^ reaction adducts and loss of the original properties of polyester occur.

What is the reaction between polyester and BO-D^ reaction adduct?

After the polyester reaches an intrinsic viscosity of 0.50, the 80·DA reaction adduct is added, and the reaction is carried out at a temperature higher than the melting temperature of the polyester for 3 minutes or more. Note that the intrinsic viscosity here is phenol/tetrachloroethane (
1/1 weight) using a mixed solvent.

Measured at 20°C. During the reaction, it is of course necessary that the atmosphere is filled with an inert gas such as nitrogen gas, or that active gases such as oxygen that promote the decomposition of polyester are blocked by other methods, and that the reaction is stirred. Should be done below.

The BO/DA reaction adduct may be added and mixed before the polycondensation of polyester is completed, but after the completion of one polymerization.

It can be added to molten polyester and mixed for melt spinning, or added to powdered solid polyester and mixed.

A method of melt spinning and reaction can also be adopted.

Further, specific examples of the quaternary phosphonium salt compound and the tertiary phosphine compound in the second invention include the following, and these may be used alone or in combination of two or more. .

Quaternary phosphonium salt compounds tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, methyltriphenylphosphonium chloride, ethyltriphenylphosphonium chloride.

Benzyltriphenylphosphonium chloride, (2-
Methyl)propenyltriphenylphosphonium chloride, benzylphenyl(p-methoxy)phenyl α-naphthylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide .

Ethyltriphenylphosphonium bromide, (diphenyl)methyltriphenylphosphonium bromide, vinyltriphenylphosphonium bromide.

(cyclopropyl)methyltriphenylphosphonium bromide, (phenoxy)ethyltriphenylphosphonium bromide, (hendiyl)methyltriphenylphosphonium bromide, (acetyl)methyltriphenylphosphonium bromide, (methoxycarbonyl)methyltriphenylphosphonium bromide Mido, (1-hendiyl)ethyltriphenylphosphonium bromide, methylphenylbenzylphosphonium bromide, butylphenyldibenzylphosphonium bromide, methylpropylphenylhensylphosphonium bromide, tetramethylphosphonium iodite, tetraethylphosphonium iodite, tetrabutyl Phosbonium iodide, tetraphenylphosphonium iodide, methyltrinoenylphosphonium iodide, ethyltrinoenylphosphonium iodide, methylphenyldihenylphosphonium iodide.

Tertiary phosphine compound trimethylsphine 5 Triethylphosphine, triisopropylphosphine, tributylphosphine, trioctylphosphine, trinonylphosphine, triphenylphosphine, trihensylphosphine, tritolylphosphine, tricyclohexylbosphine, ethyldimethylbosphine.

α-naphthyldiphenylphosphine, p-tolyldiphenylphosphine, vinyldiphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine,
Dimethylphenylphosphine.

Diethylphenylphosphine, dibenzylphenylphosphine, dimethylcyclohexylphosphine.

The amount of the quaternary phosphonium salt compound or tertiary phosphine compound added is 0.001 to 0.1% by weight based on the polyester. If this amount is too small, the catalytic effect will not be sufficient, whereas if it is too large, unfavorable results such as coloring and decomposition of the polymer will occur.

Further, the alkali metal halides in the third invention include lithium, sodium, and potassium.

A chloride, bromide, fluoride or iodide of cesium or rubidium is used, particularly preferred examples include potassium iodide and cesium fluoride.

Examples include sodium bromide.

The amount of the alkali metal halide added is 0.001 to 0.05% by weight based on the polyester. If this amount is too small, the catalytic effect will be insufficient, while if it is too large, the regeneration of (COOH) will be promoted.

It is desirable to add the catalyst at the same time as or before the addition of the BO・DA reaction adduct. Especially in the case of alkali metal halides, since they are difficult to dissolve in the 80・D＾ reaction adduct, they should be added in advance. It is desirable to contain it in polyester.

By using a catalyst, the reaction between the polyester and the BO-DA reaction adduct proceeds smoothly, and a polyester with a high degree of polymerization and good heat resistance can be easily obtained.

Note that in obtaining the polyester of the present invention, it is of course possible to add other additives to the polyester for other purposes.

The final form of polyester in the present invention is fiber.

It may be a film or other molded product.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Examples and Comparative Examples The intrinsic viscosity obtained from terephthalic acid and ethylene glycol by a conventional method was 0.73. The additives shown in Table 1 were blended with polyethylene terephthalate chips having an equivalent amount of (COOI+) of 24 g per 106 g of polymer, and the mixture was spun using a spinneret having a spinning hole with a diameter of 0.5 mm. The spinning conditions were a temperature of 300°C, a residence time of 3 to 12 minutes,
The discharge amount was 300 g/min and the winding speed was 317 IIlZ minutes, and the obtained yarn was 8520 d/192 f. The obtained undrawn yarn was stretched 3.8 times at 90° C. in the first stage, and then subjected to tension heat treatment at 220° C. to finally obtain a drawn yarn of 1500 d/192 f.

Regarding the obtained drawn yarn, the strength retention rate (^) when the drawn yarn was exposed to pure ammonia gas at 150°C for 3 hours and the strength retention when the drawn yarn was subjected to moist heat treatment at 120°C in an autoclave for 100 hours The ratio (-) was measured.

The results are shown in Table 1.

In Table 1, the BO・D^ reaction adducts are all reaction adducts in a ratio of 1 mol of dicarboxylic acid compound to 2 mol of bisoxazoline compound, and MBO is 2.2'
-m-phenylenebis(2-oxazoline), 5
IIA stands for succinic acid, ADA stands for adipic acid, TPA stands for terephthalic acid, and IP^ stands for isophthalic acid.

The BO/OA reaction adduct is prepared by heating a mixture of a bisoxapurine compound and a dicarboxylic acid compound at 170°C for 90°C with stirring.
It was obtained by reacting under nitrogen gas flow for 3 minutes.

In addition, the amount of the 80-DA reaction adduct added was 1.5% by weight based on the polyester, and Comparative Example 5 was an MI
This is an example in which 1.5% by weight of IO was added to the polyester.

Table 1 Table 1 (Continued) (Effects of the Invention) As described above, according to the method of the present invention, a polyester with a high degree of polymerization with reduced (COOH) can be easily obtained, and this polyester has a high thermal stability, In other words, it has extremely improved resistance to hydrolysis and amine decomposition at high temperatures, and its practical value includes performance enhancement in conventional applications, rationalization of processes, and new applications in fields where it could not be applied previously. The improvement is dramatic.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Scope of Claims] (11 Molar ratio of substantially linear saturated polyester, bisoxazoline compound, and dicarboxylic acid compound is 1.5 to
A method for producing a highly polymerized polyester, which comprises reacting a 3:1 reaction adduct in a molten state with 0.3 to 10% by weight. (2) The molar ratio of the substantially cotton-like saturated polyester, the bisoxazoline compound, and the dicarboxylic acid compound is 1.5 to 1.5.
3:1 reaction adduct 0.3-10% by weight, quaternary phosphonium salt compound or tertiary phosphine compound 0.0
1. A method for producing a highly polymerized polyester, which comprises reacting in a molten state in the presence of 0.01 to 0.1% by weight. (3) The molar ratio of the substantially cotton-like saturated polyester, the bisoxazoline compound, and the dicarboxylic acid compound is 1.5 to
Production of a highly polymerized polyester characterized by reacting 0.3 to 10% by weight of a 3:1 reaction adduct in the molten state in the presence of 0.001 to 0.05% by weight of an alkali metal halide. Law.