KR860000975B1 - Method of producing for polyester-polyether bock copolymer compositions - Google Patents

Abstract

A thermal oxidn. stabilizer consisting of the phenothiazine or quinolines compds. of formula(I), sulphurous compd. having a formula of R3-S-R4, and phenolic compd. of formula(II) was mixed with polyester-polyether copolymers to produce polyesterpolyether block copolymers. The said block copolymers have a thermal oxidn. resistivity. Where R1 is 0 - 15C alkyl or aryl; R' is the same as R1 or 1 - 18C hydrocarbon contg. a radical of -COO-, -CO-, or -CONH-; m is 1 - 3 integer; R3 is 2 - 25C hydrocarbons; R4 is H or R3 ; R2 is 1 - 11C hydrocarbon which is cycloalkyl or contains -S- or -CONH- ; n is 1 - 3 integer.

Description

Process for preparing polyester-polyether block copolymer composition

The present invention relates to a method for producing a polyester-polyether block copolymer composition which is stable against heat and oxygen in the air and has excellent thermal oxidation resistance.

A polyester-polyether block copolymer having a polyester portion and a polyether portion alternately in a molecular chain is a thermoplastic having high elasticity in rubber, in which the polyester portion is bonded as a hard segment and the polyether portions as a soft segment. Known as a resin.

Polyesters that give rigid properties to plastics by forming hard segments are short-chain polyesters composed of dibasic acids and glycols, and polyethers that give the flexible properties of rubber by forming soft segments are also dibasic acids and aliphatic. It is a long chain polyether composed of a polyglycol component. Here, as the dibasic acid component, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, etc. are used, and as the glycol component, a low molecular weight (molecular weight of 250 or less) diol having 2 to 15 carbon atoms, that is, ethylene glycol and propylene. Glycol butanediol, pentamethylene glycol, decamethylene glycol and the like are used, and as the aliphatic polyglycol component, polyethylene glycol, polyisopropylene glycol, polytetramethylene glycol and the like are used.

These polyester-polyether block copolymers are applied to hoses, belts, tires, and sporting goods by utilizing their high elasticity, but are degraded, colored, or cracked on the surface due to the action of oxygen, heat, and ozone in the air. Along with this, mechanical properties such as lowering degree of polymerization and lowering elongation are also significantly reduced. This phenomenon is particularly accelerated when exposed to hot air, and thus the copolymer alone cannot be used. Therefore, various stabilizers are added to the copolymer for the purpose of preventing such degradation.

Various stabilizer effects for preventing deterioration of conventional polyester-polyether copolymers are disclosed in Japanese Patent Application Laid-Open No. 46-38,911 and U.S. Patent No. 3,763,189. In addition, it exposes various problems such as excessive input or contamination due to discoloration of the stabilizer.

The present inventors have made a careful observation in view of the fact that the polyester-polyether copolymer has a thermal oxidation decomposition mechanism separate from polyamide or polyester, and particularly has an ether (-0-) moiety that is sensitive to oxidation. The present invention has been completed by knowing that a polyester-polyether block copolymer having a specific amount of a specific three component as a stabilizer exhibits particularly excellent deterioration resistance.

In other words, the object of the present invention is a polyester-polyether block air stabilizer comprising a phenoliazine compound or a quinoline compound as the first component and a sulfur compound and a phenol compound as the second and third components, respectively. The present invention provides a method for producing a polyester-polyether block copolymer composition having excellent heat oxidation resistance and excellent contamination by copolymerizing the composition.

The present invention is described in detail as follows.

The present invention uses a phenoliazine compound or a quinoline compound represented by formula (I) as a first component, and a sulfur compound represented by formula (II) as a second component, and is represented by formula (III) It is a method of manufacturing the polyester-polyether block copolymer composition which is excellent in thermal oxidation prevention by making the polyester-polyether copolymer the stabilizer which consists of this three-component system using a phenol type compound as a 3rd component.

In the above formula, R ₁ is an alkyl or aryl group having 0-15 carbon atoms, R ₁ 'is a hydrocarbon having 1-18 carbon atoms, and may include -COO-, -CO-, -CONH- groups in the molecular chain or may be the same as R _1. , m is an integer of 1-3.

R ₃ -5-R ₃ ‥‥‥‥‥‥‥‥‥‥ (II)

Above formula R ₃ is good may include -COO-, -CONH- in the molecular chain of a hydrocarbon as a carbon number of 2-25, R ₄ is the same as the hydrocarbon group may or R _3, such as a hydrogen atom, or R _3.

을 포함해도 좋으며, n은 1-3의 정수이다.R ₁ is an alkyl or aryl group having 0-15 carbon atoms, R ₂ is a hydrocarbon having 1-11 carbon atoms, cycloalkyl having 4 or more carbon atoms, or -S-,

It may contain, n is an integer of 1-3.

In the present invention, the amount of the stabilizer added is 100 parts by weight of the phenolic or quinoline compound in the range of 0.01-0.5 parts, sulfur compounds 0.05-1.5 parts, phenolic compounds 0.05-2.0 parts to form a three-component system However, if it is added below this range, the effect is insignificant. If it is added above, the effect does not increase very much and only the pollution degree is not good.

On the other hand, the addition time of the stabilizer may be added at any time before, during, or after the copolymerization, but it is preferable to add the stabilizer after the polymerization in consideration of some influences on which the stabilizer may be modified or the stabilizer may affect the polymerization reaction.

An example of the phenoliazine compound used in the present invention is 3,7-dioctylphenorazine, and the quinoline compound is represented by the general formula (I) as 6-ethoxy-1,2-dihydro-2. Examples include polymers of 2,4-trimethylquinoline, 6-dodecyl-1,2-dihydro-2,2,4-trimethylquinoline and 1,2-dihydro-2,2,4-trimethylquinoline. Can be. In addition, sulfur compounds are compounds represented by the general formula (II), and examples thereof include disperarylthiodipropionate or dilaurylthiodipropionate, and phenolic compounds are compounds represented by general formula (III). For example, 1,3,5-pris (4-tertarybutyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H , 5H) trione and 1,1,3-tris (2-methyl-4-hydroxy-5-tertiarybutyl-phenyl) butane.

In the present invention, by forming a stabilizer in a three-component system, it is possible to produce a copolymer composition having excellent heat oxidation resistance and extremely low contamination. The functions of the added three-component stabilizer are as follows.

That is, phenoliazine and the quinoline-based compound (first component) represented by the general formula (I) serve to inhibit radical reaction by binding to radicals generated in the polymer and promoting oxidation. When the metal catalyst introduced at the time is left, the metal catalyst serves to activate the oxidation and thus deactivates the metal catalyst.

The photo compound represented by the general formula (II) (the second component) acts as a peroxide decomposer that decomposes the peroxide, which is another factor of the oxidation reaction, into a stable compound, and plays a synergistic effect to further increase the stabilization effect. Do it.

In addition, the phenolic compound (third component) represented by the general formula (III) plays a role of suppressing radical reaction as in the case of the first component, and generates a structural steric hindrance to suppress the atmosphere composition of the oxidation reaction. And it acts to increase the stabilization effect as in the case of the second component.

The excellent thermal oxidation resistance which is represented by the composition of the three-component stabilizer as described above in the polyester-polyether block copolymer is described in detail with the preparation process in the following examples and compared with a known composition as follows.

Example 1

A mixture of 351 g (1.81 mole) of dimethylene terephthalate, 219 g (2.43 mole) of 1,4-butanediol and 468.5 g (1.33% by weight of DMT) of polytetramethylene glycol (average molecular weight 950-1,100) was placed in a polymerization vessel and nitrogen was added. Blowing off to remove contact with air, 0.67 g (0.02 mol) of titanium tetrabutoxide was added as a catalyst, and then the temperature was gradually raised from atmospheric pressure to 205 DEG C while stirring to distill methanol. As soon as the methanol effluent was almost stopped, the polyester-polyether block copolymer having the required degree of kendo was continuously raised until the temperature was raised to 255 ° C while the pressure was gradually reduced and the reaction continued until a constant load was reached at a pressure of 0.1 mmHg. Synthesized.

The synthesized solution phase copolymer is cooled in cold water and cut into chips to form a chip. The copolymer thus obtained had a melting point of 167 DEG C measured by DSC as a white good elastic material.

15 g of the prepared copolymer was taken and placed in a round flask equipped with heat and melted at 185 ° C. under a pressure of 6.0 mmHg or less, and nitrogen was put into a container to bring the interior to an atmospheric condition. Various stabilizer addition compositions were prepared by adding a certain amount of various stabilizers thereto, followed by good stirring for about 10 minutes. Each composition in the molten state was molded into a film of 1 mm thickness under nitrogen atmosphere, naturally cooled to room temperature, and then cut to a weight of 0.15 mg as a sample, and the weight loss was measured at 250 ° C. using isothermal TGA method. The thermal oxidation resistance was observed, and the composition conditions and results are shown in Table 1.

TABLE 1

Comparison of Three-Component Composition Conditions, Heat Oxidation Resistance and Color

(※ Addition composition amount is a unit of weight part with respect to 100 parts of copolymers)

Example 2

In the same manner as in Example 1 was prepared a copolymer of chip state having a good elasticity of white melting point of 168 ℃ DSC and dried to a moisture content of 0.1% by weight or less, and then added a certain amount of various stabilizers for 1 hour After mixing, a specimen according to ASTM D1708 specifications was fabricated with a molding injection molding machine.

The prepared specimens were placed in a hot air oven controlled at 140 ° C. and aged for 100 hours, and then the tensile strength was measured to measure the tensile strength reduction rate according to aging. Indicated.

TABLE 2

Comparison of Three-Component Composition Conditions and Thermal Oxidation Resistance

(※ Addition amount is in parts by weight based on 100 parts of copolymer)

The present invention is not limited to only those exemplified in the above examples, and in the examples, (a) in the known heat-resistant composition is N, N'-dinaphthyl-para, which is a known stabilizer in the copolymer prepared in the present invention. 0.4 parts by weight of phenylenediamine is added, and (b) 0.1 parts by weight of 2,2'-methylenebis (4-methyl-6-tertiarybutylphenol) and dilauryl thiodipropionate. It refers to a three-component heat-resistant composition added at the same time 0.2 parts by weight and 0.2 parts by weight of trephenyl phosphate, the weight reduction rate and tensile strength reduction rate of the present invention shows a significantly smaller value compared with the known three-component composition of the present invention It can be seen that it has excellent thermal oxidation resistance.

Claims (2)

Phenothiazine compound or quinoline compound represented by general formula (I) as a first component, sulfur compound represented by general formula (II) as a second component, and a phenolic compound represented by general formula (III) A method for producing a polyester-polyether block copolymer composition having excellent thermal oxidation resistance by forming a thermal oxidation stabilizer composed of this three-component system into a polyester-polyether copolymer using as a third component.

Wherein R ₁ is an alkyl or aryl group having 0-15 carbon atoms, and R 'is a hydrocarbon having 1-18 carbon atoms that may contain -COO-, -CO-, -CONH- groups in the molecular chain, or may be the same as R ₁ Is an integer of 1-3. R ₃ -SR ₄ ‥‥‥‥‥‥ (II) R ₃ is good above formula may contain a -COO-, -CONH- in the molecular chain of a hydrocarbon as a carbon number of 2-25, R ₅ may the same as the hydrocarbon group or R _3, such as a hydrogen atom, or R _3.

R ₁ is an alkyl or aryl group having 0-15 carbon atoms, R ₂ is a hydrocarbon having 1-11 carbon atoms, cycloalkyl having 4 or more carbon atoms, or -S-,

-NH- may be included and n is an integer of 1-3. The amount of the stabilizer to be added is 0.01-0.5 parts of a phenoliazine compound or a quinoline compound, 0.05-1.5 parts of a sulfur compound, and 0.05-1.5 of a phenol compound based on 100 parts by weight of the polyester-polyether copolymer. The method is added so as to be in a range of 2 parts.