KR0120832B1 - Aliphatic copolyester and method of making the same - Google Patents

Abstract

Prodn. of aliphatic polyesters by T-die melt extrusion is effected using a polyester obtd. by (i) esterifying or ester-interchanging at below 220 deg.C, a reaction mixt. of (a) succinic acid or anhydride or ester, (b) 1:1.2-1.7 mol.% 1,4 -butanediol, (c) 1-25 mol. % alcohoxyfied bisphenol A(ii) and (d) 0.01-1.0 mol. % multifunctional cpd. such as trimethylolpropane, pentaeristritol contg. at least 30H and/or carboxy gps. , and (ii) catalytically polycondensing the olygomer at 240-260 deg.C under the reduced pressure of not more than 1mm Hg.

Description

Aliphatic Copolyester and Method for Making the Same

The present invention relates to an aliphatic copolyester having excellent melt strength and a method for preparing the same, and more particularly, to one component and 1,4-butanediol selected from succinic acid, succinic anhydride or succinic acid ester compound as acid components. 1-30 mol%, trifunctional or higher polyfunctionality of the alkoxylated bisphenol A compound represented by the following formula (I) with respect to one component selected from succinic acid, succinic anhydride or succinic acid ester compound Aliphatic copolymerization comprising adding a compound having succinic acid, succinic anhydride or succinic acid ester compound in an amount of 0.01 to 1 mol% based on one component selected from the group consisting of esterification or transesterification, followed by condensation polymerization. It relates to a process for preparing polyester and to novel aliphatic copolyesters prepared therefrom.

Where x and y are each an integer from 1 to 10, where x + y ≦ 10,

R = H or CH ₃

Aromatic polyesters, especially polyethylene terephthalate, have excellent physical and chemical properties, so they are widely used in films, molded products, glass fiber reinforced plastics, adhesives, paints, etc., but aliphatic polyesters have insufficient film formability and moldability. Its use has been limited to paints, adhesives and the like.

That is, in the case of using aliphatic compounds as dicarboxylic acid and glycol components in the production of polyester, even if the polycondensation reaction is carried out after esterification or transesterification, sufficient melt viscosity or melt strength to give excellent film formability and moldability Although it is difficult to obtain and the molding process, the process workability and mechanical properties of the molded product are poor.

In general, a method of increasing the molecular weight is mainly used as a method for improving the mechanical properties or the melt strength of aliphatic polyester. However, in the method of increasing the molecular weight, if the molecular weight is excessively increased, the melt viscosity becomes very high and it becomes very difficult to pass through an extruder during processing, so it is very important to properly control the degree of increase of the molecular weight. On the other hand, the melt strength of the polymer is usually determined by the elasticity of the polymer melt, and factors affecting elasticity include molecular weight distribution, branching degree, additive type and amount. However, in general, the higher the molecular weight, the higher the degree of branching, and the more entanglement of the polymer melt, the higher the elasticity. In the case of polyester, particles such as stearic acid or talc and silica have an effect of improving the melt strength. It is known. In addition, another factor that greatly affects the molding process is the crystallization rate, which is also important because the crystallization rate and crystallization of the polymer can be controlled according to the molding process.

On the other hand, Japanese Patent Laid-Open Nos. 4-189822, 4-189823 and the like undergo polycondensation reaction through esterification reaction of aliphatic dicarboxylic acids and aliphatic divalent glycols, and then further react the isocyanate compound to increase the molecular weight to increase the melting point. Although attempts were made to improve the degree and melt strength, it was not only economical by using a separate isocyanate compound but also had to be complicated and difficult in the process because a separate addition reaction had to be performed.

Accordingly, it is an object of the present invention to provide an aliphatic copolyester that can be used for extrusion molding and blown film production by increasing the molecular weight of aliphatic polyester to improve melt viscosity and melt strength.

Another object of the present invention is to provide a method for producing an aliphatic copolymer polyester of the above object.

In order to achieve the above object as well as another object that can be easily expressed in the present invention, one component and 1,4-butanediol selected from Succinic acid, Succinic anhyride or succinic acid ester compound The main component is a polyfunctional or more than trifunctional compound and the alkoxylated bisphenol A compound of formula (I) undergoes a polycondensation reaction after esterification or transesterification reaction to have a high molecular weight, high melt viscosity and mechanical properties The aliphatic copolyester from which this excellent molded product can be obtained was easily obtained economically.

The present invention is described in more detail as follows.

The alkoxylated bisphenol A compound represented by the formula (I) is mainly composed of one component selected from succinic acid, succinic anhydride or succinic acid ester compound and 1,4-butanediol, and succinic acid, succinic anhydride or succinate. 1-30 mol% of a compound selected from the acid ester compound and a compound having trifunctional or higher polyfunctionality are contained in a ratio of 0.01-1 mol% with respect to one component selected from succinic acid, succinic anhydride, or succinic acid ester compound. After addition and esterification or transesterification at a temperature of 220 ° C. or less, the esterification or transesterification product was introduced into a reactor equipped with a condenser and a stirrer, and a thermal stabilizer, a catalyst, and other assistants were added under a high vacuum of 1 mmHg or less. Polycondensation reaction at a temperature of 240-260 ℃ to prepare an aliphatic copolymer polyester of the present invention.

Succinic acid ester compounds that can be used in the present invention include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dioctyl succinate, and the like, and succinic acid and succinic anhydride. Alternatively, the reaction molar ratio of the succinic acid ester compound and 1,4-butanediol is 1: 1 to 1: 2, and more preferably 1: 1.2 to 1: 1.7. Do. In the present invention, since the alkoxylated bisphenol A compound of formula (I) has a structure having a bulky property such as -CH ₃ in the side chain, it is effective to lower the crystallization rate, and the amount of the compound of formula (I) is used as succinic acid or succinate. It is preferable to use it in the ratio of 1-30 mol%, More preferably, it is 1-25 mol% with respect to a citrate anhydride or a succinic acid ester compound. When the amount of the compound of Formula (I) is more than 30 mol%, the formed copolymer becomes very strong, such as an elastomer, making it unsuitable for extrusion blow molding or blown film production. There was no effect.

As a compound having a trifunctional or higher polyfunctionality, one having a hydroxy group or a carboxyl group as a functional group is preferable, and trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, and tris (2-hydroxyethyl) isocyanurate , Trimellitic acid, trimellitic anhydride, benzenetetracarboxylic acid, benzenetetracarboxylic acid anhydride and the like can be used, and the molecular weight of the polymer produced by the small amount copolymerization reaction of a trifunctional or higher polyfunctional compound is rapidly And the melt viscosity and melt strength are thus greatly improved. At this time, it is important to copolymerize the compound having a trifunctional or higher polyfunctionality in the range of 0.01 to 1 mol% with respect to the succinic acid, the succinic anhydride or the succinic acid ester compound. When a compound having a trifunctional or higher polyfunctionality is copolymerized in a range exceeding 1 mol% with respect to succinic acid, succinic anhydride or succinic acid ester compound, the reaction proceeds in a very short time to obtain a high molecular weight polymer. However, due to the rapid increase in the degree of crosslinking, a gel is formed, which is in an unsuitable polymer state for molding, and when used at 0.01 mol% or less, there is a problem in that an additive effect is not expressed.

When the esterification or transesterification reaction is carried out at 220 ℃ or less is suitable to minimize the by-product generation and pyrolysis. As the polycondensation catalyst used in the present invention, it was excellent to use a tin compound or a titanium compound. Examples of the tin compound include tin oxides such as tin oxide and tin oxide, halogen tin salts such as cuprous oxide, tin chloride, and tin sulfate, monobutyl tin oxide, dibutyl tin oxide, and monobutyl hydroxy tin oxide. And organic tin compounds such as dibutyltin dichloride, tetraphenyltin and tetrabutyltin, and titanium-based compounds include tetrabutyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetra (2-ethylhexyl) Titanate and the like can be used. As for the addition amount of the catalyst used in the polycondensation reaction of this invention, 1.0 * 10 <^-4> -1.0 * 10 <^-3> mol / gram oligomer is suitable with respect to the oligomer obtained by esterification or transesterification reaction. At this time, when the amount of the catalyst is used too much, the discoloration of the polymer occurs badly, and when too little, the reaction rate is slowed.

Thermal stabilizers in the present invention include phosphorus compounds, such as phosphoric acid, monomethyl phosphoric acid, trimethyl phosphoric acid, tributyl phosphoric acid, trioctyl phosphoric acid, monophenyl phosphoric acid, triphenyl phosphoric acid and derivatives thereof, phosphorous acid triphenyl phosphoric acid, trimethyl phosphoric acid and the like Derivatives, phenylphosphonic acid, and the like can be used, among which phosphoric acid, trimethyl phosphoric acid, triphenyl phosphoric acid, and the like have excellent effects. Moreover, the brand name Iganox 1010, Iganox 1222, Igaforce 168 etc. which are the products of Ciba-Geigy Co., Ltd. can also be used. The amount of the phosphorus compound as a heat stabilizer is 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁶ mol / gram oligomer, more preferably 0.5 × 10 ^{−6 to} 1.5 × 10 ⁻⁶ , based on the oligomer obtained by esterification or transesterification reaction. Mole / gram oligomer.

As other preparations used in the present invention, titanium dioxide, talc, sodium sulfide, silicon dioxide and the like can be used as the nucleating agent. In the present invention, in order to obtain a high molecular weight aliphatic copolymer polyester having a high melt viscosity and a high melt strength, it is important to polycondense under high vacuum conditions, and the reaction temperature is 240 to 260 ° C. If the reaction temperature is less than 240 ℃ the polycondensation reaction rate is very slow to obtain a polymer of the desired high molecular weight, it is difficult to obtain a polymer of the desired high molecular weight, and if it exceeds 260 ℃ rather than the thermal decomposition is worse the physical properties and color tone of the obtained polymer.

The melt strength value is closely related to extrusion blow molding and is known to be suitable for molding when the measured value according to ASTM D-3835 at the process temperature has a value of at least 10 (US Pat. No. 4,983,711), The melt strength (hereinafter, referred to as MS) of the aliphatic copolyester of the present invention was excellent at 10 or more.

The following examples and comparative examples to explain in more detail the aliphatic copolymer polyester of the present invention and a method for producing the same, but does not limit the scope of the present invention, the abbreviations described in the examples and comparative examples are as follows.

SA: Succinic acid DMS: Dimethyl succinate

DES: diethyl succinate DPS: dipropyl succinate

DBS: dibutyl succinate BD: 1,4-butanediol

EBPA ^* : Dimethyl-bis- [4- (2-hydroxyethoxy) phenyl] methane

TME: trimethylol ethane TMP: trimethylolpropane

TMA: trimellitic acid TMAN: trimellitic anhydride

PNT: pentaerythritol DPNT: dipentaerythritol

GLY: Glycerin CAT: Catalytic Slurry

IV: Intrinsic Viscosity MP: Crystal Melting Point

MV: Melt Viscosity MS: Melt Strength

UTS: Tensile Strength Elon: Cutting Elongation

L: whiteness in color b: zodiacal color

* When x = 1, y = 1, R = H in the compound of formula (I)

Example 1

BD 136g (1.5108mol), EBPA 36.5g (0.1153mol), SA 137g (1.1601mol), TME 0.7g (0.0058mol) and CAT 1.02g (0.0003mol) were added to the reactor equipped with the stirrer and condenser. The temperature was raised to 120 ° C. over 40 minutes from room temperature, the reaction was heated to 210 ° C. over 120 minutes while stirring, and the resulting side reactant water was completely discharged through a condenser, followed by pressure in the reactor for 45 minutes. The pressure was slowly reduced to 0.5mmHg and the stirring reaction was continued for 120 minutes while the temperature was raised to 245 ° C. Then, the stirring was stopped and nitrogen was introduced into the reactor to pressurize and discharge the polymer to produce the desired aliphatic polyester copolymer. Got. The physical properties of the prepared resin were measured by the following method, and the results are shown in Table 1.

Intrinsic viscosity: The polymer is dissolved in orthochlorophenol at a temperature of 30 ° C. and the intrinsic viscosity (dl / g) is measured using a capillary viscometer.

Crystal melting point: Measured using a differential calorimeter. (℃)

Melt Viscosity: Rheometers of RDS-7700, manufactured by Rheometrics, were used to measure the viscosity at a temperature of 190 ° C and 10 ³ sec ^-1 .

Melt strength: Measured by capillary rheometer according to ASTM D-3835. The value is obtained by the following formula.

only, Is the diameter of the rheometer die (= 0.1 inch), Is the diameter of the polymer melt with a length of 6 inches when extruded through a die of 0.1 inch diameter and 0.25 inch length with a shear rate of 20 sec ⁻¹ .

Tensile strength: measured according to ASTM D-412 (Kg / ㎠)

Elongation at break: measured according to ASTM D-412 (%)

[Comparative Examples 1-2 and Examples 2-10]

An aliphatic polyester copolymer was obtained in the same manner as in Example 1, except that the amount of EBPA, the kind and amount of the compound having polyfunctionality were changed as shown in Table 1, and then, in the same manner as in Example 1 Physical properties were measured and listed in Table 1.

[Examples 11 to 12 and Comparative Example 4]

Into a reactor equipped with a stirrer and a condenser, the ingredients were introduced as shown in Table 2, and the temperature in the reactor was raised to 120 ° C. over 40 minutes from room temperature, and then heated up to 210 ° C. over 120 minutes with stirring. The side reactant methanol was flowed out completely through the condenser. Subsequently, the pressure in the reactor was gradually reduced to 0.5 mmHg over 45 minutes and the stirring reaction was performed for 120 minutes while the temperature was raised to 248 ° C. Then, the stirring was stopped and nitrogen was introduced into the reactor to pressurize and discharge the polymer. To obtain the desired aliphatic polyester copolymer. The physical properties of the prepared resin were measured, and the results are shown in Table 2.

[Examples 13 to 14 and Comparative Example 5]

Into a reactor equipped with a stirrer and a condenser, the ingredients were introduced as shown in Table 2, and the temperature in the reactor was raised to 120 ° C. over 40 minutes from room temperature, and then heated up to 210 ° C. over 120 minutes with stirring. Ethanol, a side reaction, was completely discharged through the condenser. Subsequently, the pressure in the reactor was gradually reduced to 0.5 mmHg over 45 minutes, and the stirring reaction was performed for 120 minutes while the temperature was raised to 252 ° C. Then, the stirring was stopped and nitrogen was introduced into the reactor to pressurize and discharge the polymer. To obtain the desired aliphatic polyester copolymer. The physical properties of the prepared resin were measured, and the results are shown in Table 2.

[Examples 15 to 16]

Into a reactor equipped with a stirrer and a condenser, the ingredients were introduced as shown in Table 2, and the temperature in the reactor was raised to 120 ° C. over 40 minutes from room temperature, and then heated up to 210 ° C. over 120 minutes with stirring. The side reaction of propanol was completely flowed through the condenser. Subsequently, the pressure in the reactor was gradually reduced to 0.5 mmHg over 45 minutes and the stirring reaction was performed for 120 minutes while the temperature was raised to 251 ° C. Then, the stirring was stopped and nitrogen was introduced into the reactor to pressurize and discharge the polymer. To obtain the desired aliphatic polyester copolymer. The physical properties of the prepared resin were measured, and the results are shown in Table 2.

Example 17

Into a reactor equipped with a stirrer and a condenser, the ingredients were introduced as shown in Table 2, and the temperature in the reactor was raised to 120 ° C. over 40 minutes from room temperature, and then heated up to 210 ° C. over 120 minutes with stirring. The side reactant butanol was flowed out completely through the condenser. Subsequently, the pressure in the reactor was gradually reduced to 0.5 mmHg over 45 minutes and the stirring reaction was performed for 120 minutes while the temperature was raised to 246 ° C. Then, the stirring was stopped and nitrogen was introduced into the reactor to pressurize and discharge the polymer. To obtain the desired aliphatic polyester copolymer. The physical properties of the prepared resin were measured, and the results are shown in Table 2.

Claims (4)

In preparing a polyester using one compound selected from succinic acid, succinic anhydride, or succinic acid ester compound as an acid component and 1,4-butanediol as a diol component, the alkoxylation represented by the following formula (I) An aliphatic copolymer polyester produced by copolymerizing a bisphenol A compound in an amount of 1-30 mol% with respect to an acid component and 0.01-1 mol% with respect to an acid component. Where x and y are each an integer of 1-10, where x + y≤10, R = H or CH ₃ The polyfunctional compound of claim 1, wherein the polyfunctional compound is trimellitic acid, trimellitic anhydride, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, glycerin, tris (2-hydroxyethyl) isocyanurate, An aliphatic copolymer polyester, characterized in that it is one compound selected from benzenetetracarboxylic acid and benzenetetracarboxylic acid anhydride. The aliphatic copolymer polyester according to claim 1, wherein the succinic acid ester compound is dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dioctyl succinate. In preparing a polyester using one compound selected from succinic acid, succinic anhydride or succinic acid ester compound as an acid component and 1,4-butanediol as a diol component, the alkoxylation represented by the formula (I) One bisphenol A compound is added in an amount of 1-30 mol% based on the acid component and at least trifunctional polyfunctional compound at 0.01-1 mol% with respect to the acid component, followed by esterification or transesterification at a temperature of 220 ° C. or lower. A method for producing an aliphatic copolymer polyester, characterized in that a product is obtained and subjected to a polycondensation reaction at a temperature of 240-260 ° C. under a high vacuum of 1 mmHg or less.