KR0120828B1 - Aliphatic copolyester and method for making the-same - Google Patents

Abstract

Prodn. of aliphatic polyesters by T-die melt extrusion is effected using a polyester obtd. by(1) esterifying or ester-interchanging at below 220 deg.c,a reaction mixt. of (a)succinic acid or anhydride or ester, (b)1,4-butanediol, (c)1-30 mol.% 1,4-cyclohexanedimethanol and (d)0.01-1 mol. % multifunctional cpd. contg. at least 3 OH and/or carboxy qps. , (2)catalytically polycondensing the oligomer at 240-260 deg.C under a reduced pressure of not more than 1mm Hg. The aliphatic copolyesters have sufficiently high melt viscosity and melt strength to allow film extrusion.

Description

Aliphatic Copolyester and Method for Making the Same

The present invention relates to a novel aliphatic copolyester and a method for preparing the same, and more specifically, a crystallization behavior based on one component and 1,4-butanediol selected from succinic acid, succinic anhydride or succinic acid ester compound 1,4-cyclohexane dimethanol as a monomer for the control of 1 to 30 mol%, a compound having a trifunctional or more than trifunctional with respect to one component selected from succinic acid, succinic anhydride or succinic acid ester compound, A method for producing an aliphatic copolyester characterized in that the addition of a succinic anhydride or succinic acid ester compound in an amount of 0.01 to 1 mol% to esterification or transesterification, followed by a polycondensation reaction, and It relates to a novel aliphatic copolyester prepared therefrom.

Aromatic polyesters, especially polyethylene terephthalate, have excellent physical and chemical properties and are widely used in films, molded articles, glass fiber reinforced plastics, adhesives, paints, and the like, but aliphatic polyesters can be used as paints and adhesives. However, not only the film formability and molding processability are sufficient, but also the desired melt viscosity or melt strength is difficult to be obtained, and even when molded, the mechanical properties are poor.

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 is 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 the 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 generally poly and determined by the elasticity of the melt, and the factors affecting the elasticity include molecular weight distribution, branching degree, and type and amount of additives. 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 melt strength. In addition, there are other factors that greatly influence the molding process, and the crystallization rate and crystallization of the polymer can be controlled according to the molding process, which is also important.

On the other hand, Japanese Patent Application Laid-Open No. 4-189822, 4-189823, etc., undergoes a condensation polymerization reaction through esterification of aliphatic dicarboxylic acids and aliphatic divalent glycols, and then adds and reacts an isocyanate compound to increase the molecular weight. 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, an object of the present invention is to provide an aliphatic copolymer polyester which 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.

It is another object of the present invention to provide a method for producing an aliphatic copolyester 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 It has a high molecular weight and has high melt viscosity and melt strength by carrying out polycondensation reaction after the esterification or transesterification reaction of the compound having a multifunctional or more than trifunctional polyfunctional as a main component and the monomer for controlling the crystal behavior. The aliphatic copolyester which can obtain a molded product was economically easy to obtain.

The present invention will be described in more detail as follows.

1,4-cyclohexanedimethanol as succinic acid, succinic anhydride as a monomer for controlling the crystallization behavior as a main component and 1,4-butanediol selected from succinic acid, succinic anhydride or succinic acid ester compound Or from 1 to 30 mol% of a component selected from the succinic acid ester compound, and a compound having a trifunctional or higher polyfunctionality, from 0.01 to 1 mol% of a component selected from the group consisting of succinic acid, succinic anhydride or After the addition and the esterification or transesterification reaction at a temperature of 220 ℃ or less, the esterification or transesterification product is added to the reactor with the condenser and the stirrer, and the thermal stabilizer, catalyst and other aids are added to Polycondensation reaction was carried out at a temperature of 240 ~ 260 ℃ under high vacuum to prepare the 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, 1,4-cyclohexane dimethanol has a structure having a bulky property as a non-planar structure is effective to lower the crystallization rate, the amount of 1,4-cyclohexane dimethanol is used as succinic acid or succinic acid It is preferable to use it in the ratio of 1-30 mol% with respect to an anhydride or succinate ester compound, More preferably, it is 1-25 mol%. When the amount of 1,4-cyclohexanedimethanol is used exceeds 30 mol%, the formed copolymer becomes very strong, such as elastomer, making it unsuitable for extrusion blow molding or blown film production. In case of addition, there was no addition 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, benzetetracarboxylic 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 thus greatly improve the melt viscosity and melt strength. 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 the succinic succinic anhydride or succinic acid ester compound, the reaction proceeds in a very short time to obtain a high molecular weight polymer. As the degree of crosslinking increases rapidly, 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, halogenated tin salts such as tin oxide, tin chloride, and tin sulfide, 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 condensation polymerization reaction of this invention, 1.0 * 10 <^-4> -1 * 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, for example, 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 derivative, phenylphosphonic acid can be used, and among these, phosphoric acid, trimethyl phosphoric acid, triphenyl phosphoric acid, etc. were excellent in the effect. Moreover, the brand name Iganox 1010, Iganox 1222, Igaforce 168 etc. which are the products of Ciba-Geigy Co., can also be used. The amount of phosphorus compound used as a heat stabilizer is 1.0 × 10 ⁻⁶ −1 × 10 ⁻³ mol / gram oligomer with respect to the oligomer obtained by esterification or transesterification.

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.

On the other hand, the melt strength of the aliphatic copolyester of the present invention is measured by a capillary rheometer based on ASTM D-3835, the value is obtained by the following formula.

only, Is the diameter of the rheometer die (= 0.1 inch)

Is shear rate The diameter of the polymer melt is now 6 inches long when extruded through a die that is now 0.1 inches long and 0.25 inches long.

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

CHDM: 1,4-cyclohexanedimethanol TME: trimethylolethane

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

Mw: weight average molecular weight MS: melt strength

UTS: Tensile Strength Elon: Cutting Elongation

L: Color whiteness b: Color whiteness

Example 1

BD 136g (1.5108mol), CHDM 16.8g (0.1150mol), SA 137g (1.1601mol), TME 0.7g (0.0058mol) and 90% by weight of 1,4-butanediol and tetrabutyltita 10 wt% of Nate was mixed, and 1.02 g (0.0003 mol) of CAT prepared by stirring at a temperature of 50 ° C. for 3 hours was added, and the temperature in the reactor was raised from room temperature to 120 ° C. over 40 minutes, and stirred at 120 minutes. After the reaction was heated up to 210 ° C., the resulting side reaction product was completely discharged through the condenser, and then the pressure in the reactor was gradually reduced to 0.5 mmHg over 45 minutes while the temperature was raised to 245 ° C. for 120 minutes. After proceeding with the stirring reaction, the stirring was stopped and nitrogen was introduced into the reactor to pressurize and discharge the polymer to obtain a desired aliphatic polyester copolymer. 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 differential calorimetry (℃)

Melt Viscosity: Temperature of 190 ℃ using Rheometer of RDS-7700 The viscosity at is measured.

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

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

[Examples 2 to 10 and Comparative Examples 1 to 3]

An aliphatic polyester copolymer was obtained in the same manner as in Example 1 except that the amount of 1,4-cyclohexanedimethanol, the kind and amount of the compound having polyfunctionality were changed as shown in Table 1, Table 1 shows the physical properties measured in the same manner as in Example 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, Methanol, a side reaction, is allowed to flow 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. The desired aliphatic polyester copolymer was obtained. 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. The desired aliphatic polyester copolymer was obtained. 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 reactant propanol was flowed through the condenser completely. 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. The desired aliphatic polyester copolymer was obtained. 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, Butaneol, a side reactant, is allowed to flow out completely through the condenser. Then, 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. The desired aliphatic polyester copolymer was obtained. The physical properties of the prepared resin were measured, and the results are shown in Table 2.

Claims (3)

In aliphatic copolymerized polyesters having one compound selected from succinic acid, succinic anhydride, or succinic acid ester compounds as acid components and 1,4-butanediol as diol components, 1,4-cyclohexanedimethanol is acidic. An aliphatic copolymer polyester obtained by copolymerizing 1-30 mol% and trifunctional or more than trifunctional polyfunctional compound with respect to an acid component at 0.01-1 mol% with respect to an acid component. The aliphatic copolymer according to claim 1, wherein the polyfunctional compound is one compound selected from trimellitic acid, trimellitic anhydride, triethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol or glycerin. polyester. 1,4-cyclohexanedimethanol in the preparation of aliphatic copolyester with 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 1 to 30 mol% of the acid component, trifunctional or more than trifunctional polyfunctional compound in an amount of 0.01 to 1 mol% relative to the acid component and esterification or transesterification at a temperature of 220 ℃ or less to obtain a reaction product, A polycondensation reaction is carried out at a temperature of 240 to 260 ° C. under high vacuum of 1 mmHg or less.