KR101276100B1 - Biodegradable Copolyester Resin made from Biomass Resources - Google Patents

Abstract

The biodegradable copolyester resin according to the present invention comprises (a) an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, (b) an aliphatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, And dicarboxylic acid components selected from the group consisting of mixtures thereof; And a glycol selected from the group consisting of (c) petroleum ethylene glycol, biomass-derived ethylene glycol or mixtures thereof, (d) isosorbide, neopentyl glycol or mixtures thereof, and mixtures thereof as second copolymerization component. It is produced by condensation polymerization of a component, comprises glutaric acid as the aliphatic dicarboxylic acid, contains isosorbide as the glycol component, and is excellent in heat resistance, spinning processability and biodegradability.

Description

Biodegradable Copolyester Resin made from Biomass Resources

The present invention relates to biodegradable copolyester resins made from biomass feedstocks. More specifically, the present invention relates to a copolyester resin having excellent heat resistance and biodegradability by using at least one copolymerization component of isosorbide and neopentyl glycol derived from biomass which can enhance biodegradability.

Polyesters such as polyethylene terephthalate (PET) produced by the condensation polymerization reaction of terephthalic acid and ethylene glycol are used in various applications such as fibers, molded articles, and films.

However, high molecular weight aromatic polyester resins such as polyethylene terephthalate having an Intrinsic Viscosity of 0.64 to 0.80 are not easily decomposed in the natural ecosystem after disposal, causing serious environmental pollution problems.

The general polyester resin has a rigid molecular structure because it has a hydrophilic structure in the main chain or side chains and consists only of aromatics, and thus exhibits excellent physical properties, but is not easily biodegradable. In order to solve this problem, there is increasing interest in the study of biodegradable polymers, and it is already known that such aliphatic polyesters are biodegradable. (Journal of Macromol. SCI-Chem A-23 (3). 1986, pp 393-409)

Representative biodegradable aliphatic polyesters include polyglycolide, polycaprolactone, polylactide, and the like, and are used in a wide range of fields such as fibers, films, and plastics in large quantities, but raw material costs are excessively expensive. Biodegradation during soil reclamation by copolymerizing aliphatic dicarboxylic acid and sulfonic acid group in polyester polymerization process such as Korean Patent Publication Nos. 94-14497 and 95-758 and US Pat. Nos. 5,348,348,5097004,5171308 Biodegradable polyester production techniques have been introduced to enable this.

However, aliphatic polyester such as polylactide has a problem in that it cannot be used as a universal polyester resin because of poor heat resistance.

In addition, the conventional aliphatic polyester has a low melting point due to the flexible structure of the main chain and low crystallinity, low thermal stability during melting, and is easy to thermally decompose. There is a problem that the use is extremely limited due to the lack of physical properties such as thermal strength.

On the other hand, Korean Patent Publication No. 195-000758 discloses a method for synthesizing a high molecular weight aliphatic polyester resin having a number average molecular weight of 30,000 or more by appropriately adjusting the reaction temperature, vacuum degree and catalyst conditions. However, the aliphatic polyester resin produced by this method has a problem that the weight average molecular weight is low, it is extremely sensitive to heat, and moldability is greatly reduced.

Accordingly, the development of biodegradable aliphatic polyester having sufficiently high heat resistance and molecular weight is required.

An object of the present invention is to provide a biodegradable copolyester resin having excellent heat resistance and excellent spinning processability.

Another object of the present invention is to provide a fiber made from a biodegradable copolyester resin.

The above and other objects of the present invention can be achieved by the present invention described below.

The biodegradable copolyester resin according to the present invention comprises (a) an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, (b) an aliphatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, And dicarboxylic acid components selected from the group consisting of mixtures thereof; And a glycol selected from the group consisting of (c) petroleum ethylene glycol, biomass-derived ethylene glycol or mixtures thereof, (d) isosorbide, neopentyl glycol or mixtures thereof, and mixtures thereof as second copolymerization component. It is prepared by condensation polymerization of a component, and comprises glutaric acid as the aliphatic dicarboxylic acid, and the isosorbide as the glycol component.

In one embodiment of the invention, the dicarboxylic acid component comprises (a) 60 to 95 mole% of an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, and (b) an aliphatic dicarboxylic acid, an acid anhydride thereof. Or 5 to 40 mol% of mixtures thereof.

In one embodiment of the invention, the glycol component (c) comprises 50 to 100 mol% of the biomass-derived ethylene glycol.

In one embodiment of the invention, the aliphatic dicarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimeric acid, subberic acid, azelaic acid, and sebacic acid.

In one embodiment of the present invention, the glycol component is a mixture of the petroleum ethylene glycol and the biomass-derived ethylene glycol 80 to 99.8 mol%, the isosorbide 0.1 to 10 mol% and the neopentyl glycol 0.1 to 10 mol Contains%

In one embodiment of the invention, the biodegradable copolyester resin is prepared using a catalyst selected from the group consisting of germanium, manganese acetate, titanium and mixtures thereof as a catalyst other than heavy metals.

The copolyester resin according to the present invention is very useful for producing high-quality polyester garment knitted fabrics, nonwoven fabrics and industrial textile products which are excellent in heat resistance, spinning and biodegradability.

Hereinafter, the present invention will be described in more detail.

Biodegradable Copolyester  Suzy

The biodegradable copolyester resin according to the present invention comprises (a) an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, (b) an aliphatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, And dicarboxylic acid components selected from the group consisting of mixtures thereof; And a glycol selected from the group consisting of (c) petroleum ethylene glycol, biomass-derived ethylene glycol or mixtures thereof, (d) isosorbide, neopentyl glycol or mixtures thereof, and mixtures thereof as second copolymerization component. It is prepared by condensation polymerization of a component, and comprises glutaric acid as the aliphatic dicarboxylic acid, and the isosorbide as the glycol component.

In one embodiment of the present invention, the dicarboxylic acid component which is the first copolymerization component is (a) 60 to 95 mol% of aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof; And (b) 5 to 40 mol% of an aliphatic dicarboxylic acid, an acid anhydride thereof, or a mixture thereof, and terephthalic acid, dimethyl terephthalic acid, and the like may be used as the aromatic dicarboxylic acid, and as the aliphatic dicarboxylic acid. Succinic acid, glutaric acid, adipic acid, pimeric acid, subberic acid, azelaic acid, sebacic acid, cyclic aliphatic dicarboxylic acid and the like may be used, and glutaric acid is preferably used.

In one embodiment of the present invention, the aromatic dicarboxylic acid, an acid anhydride thereof, or a mixture thereof may be included in an amount of 60 to 95 mol%, based on 100 mol% of the total dicarboxylic acid component. When the aromatic dicarboxylic acid, an acid anhydride thereof, or a mixture thereof is included in less than 60 mol%, color, heat resistance, and spinning processability may be lowered, and the strength of the fiber prepared therefrom may be lowered. If it is included in excess of mole%, the rate of biodegradation is significantly lowered, so that the effect of improving biodegradability may be insufficient.

In one embodiment of the present invention, the aliphatic dicarboxylic acid, an acid anhydride thereof, or a mixture thereof may be included in an amount of 5 to 40 mol%, based on 100 mol% of the total dicarboxylic acid component, and may be 30 mol% or less. It is preferred to be included. When the aliphatic dicarboxylic acid is included in less than 5 mol% biodegradation improvement effect may be insufficient, when included in more than 40 mol% color, heat resistance and radiation processability may be lowered and prepared from The strength of the fibers can also be lowered.

In one embodiment of the present invention, the second copolymer component glycol component is (c) petroleum ethylene glycol, biomass-derived ethylene glycol or a mixture thereof 80 ~ 99 mol%; And (d) 1 to 20 mol% of isosorbide, neopentyl glycol or mixtures thereof, and the glycol component is ethylene glycol, 1,3 propanediol, 1,4-butanediol, neopentyl glycol, polyethylene glycol , Isosorbide and the like can be used, and ethylene glycol is preferably used.

In one embodiment of the present invention, petroleum-based ethylene glycol, biomass-derived ethylene glycol, isosorbide, neopentyl glycol and mixtures thereof may be used as the glycol component, and cyclic aliphatic glycol may be used. Also, biomass-derived ethylene glycol is included within the range of no change in physical properties, and the use of non-petroleum-based biomass-derived ethylene glycol can reduce greenhouse gas emissions and reduce energy consumption in raw material manufacturing process. There is an advantage in terms of environment.

In one embodiment of the present invention, the mixture of the petroleum-based ethylene glycol and biomass-derived ethylene glycol may be included in 80 to 99 mol% with respect to 100 mol% of the total glycol component. When the mixture of the petroleum-based ethylene glycol and biomass-derived ethylene glycol is included in less than 80 mol%, color and spinning processability may be lowered, the strength of the fiber produced therefrom may be lowered, and 99 mol% When included in excess, the effect of improving biodegradability may be insufficient.

The isosorbide refers to 1,4: 3,6-dianhydro-D-sorbitol as a glycol derived from biomass and can be easily prepared from a renewable source such as sugars and starches, and the isosorbide Increases the glass transition temperature (Tg) and disturbs the structural regularity of the molecular chains of the copolymerized polyester, thereby improving biodegradability. Therefore, when a certain amount of isosorbide is used, the biodegradable copolyester resin in the present invention can increase the glass transition temperature and further improve the biodegradability.

In one embodiment of the present invention, the isosorbide may be included in 0.1 to 10 mol% with respect to 100 mol% of the total glycol component, preferably 1 mol% or more. When the isosorbide is included in less than 0.1 mol% biodegradation improvement effect may be insufficient, when it is included in more than 10 mol%, color, heat resistance and spinning processability may be reduced.

The neopentyl glycol is a petroleum glycol, in one embodiment of the present invention, the neopentyl glycol may be included in 0.1 to 10 mol% with respect to 100 mol% of the total glycol component, it is included in more than 3 mol% desirable. When the neopentyl glycol is included in excess of 10 mol%, color and spinning processability may be lowered, and the strength of the fiber produced therefrom may be lowered.

Biodegradable Copolyester  Method of producing resin

(1) Step 1: Melting of dicarboxylic acid component and glycol component

One step of the method for producing a biodegradable copolyester resin includes (a) an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, (b) an aliphatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, and a Dicarboxylic acid components selected from the group consisting of mixtures, and (c) petroleum ethylene glycol, biomass-derived ethylene glycol or mixtures thereof, (d) isosorbide, neopentyl glycol or mixtures thereof, and mixtures thereof After mixing a glycol component selected from the group consisting of a mixture, the mixture is melted at a temperature of 220 ° C or higher.

As the dicarboxylic acid component and the glycol component used in the first step, the dicarboxylic acid component and the glycol component of the biodegradable copolyester resin mentioned above may be used. The same may be applied to the method for preparing the resin.

(2) Step 2: Preparation of oligomers having a degree of polymerization of 3 or more

The second step of the biodegradable copolyester resin manufacturing method is to add a catalyst to the mixture of the molten dicarboxylic acid component and glycol component in order to increase the activity of the aromatic component and esterified for 1 hour at a temperature of 220 to 250 ℃ Reaction or transesterification is carried out to prepare an oligomer having a degree of polymerization of 3 or more, and by-product water and methanol or water are distilled out.

In one embodiment of the present invention, the catalyst is zinc (Zn), cobalt (Co), antimony trioxide (Sb ₂ O ₃ ), titanium (Ti), germanium (Ge), manganese (Mn), sodium (Na) and the like The included metal compound or a mixture thereof may be used, and it is preferable to use a metal compound containing sodium, germanium, manganese or titanium or a mixture thereof to reduce environmental pollution.

In one embodiment of the present invention, the catalyst may be included from 0.02 to 4.0% by weight relative to 100% by weight of the total biodegradable copolyester resin. If the catalyst is included in less than 0.02% by weight of water, methanol or glycol may not be released by the theoretical content, when included in more than 4.0% by weight may reduce the color of the biodegradable copolyester resin have.

(3) step 3: preparation of high molecular weight copolyester resin

 It is a step of preparing a high molecular weight copolyester resin by further condensation polymerization reaction of the oligomer having a degree of polymerization of 3 or more by the second step for 60 to 240 minutes at a temperature of 260 to 290 ℃ and a vacuum degree of 1.0 Torr or less.

In one embodiment of the present invention, the biodegradable copolyester resin prepared by the method for producing a biodegradable copolyester resin consisting of three steps has a glass transition temperature (Tg) of 50 ℃ or more, melting point 190 ℃ or more The intrinsic viscosity is 0.655 to 0.97 dL / g, and the content of diethylene glycol is 4 mol% or less.

In one embodiment of the present invention, the catalyst used in the second step may be used in 0.05 to 1.0% by weight based on 100% by weight of the total biodegradable copolyester resin at the beginning or end of the first or third step.

In one embodiment of the present invention, in order to minimize the content of diethylene glycol generated from the aromatic dicarboxylic acid (terephthalic acid), a base may be appropriately added during the preparation of the biodegradable copolyester resin.

In one embodiment of the present invention, a thermal stabilizer may be added at the beginning or end of the first, second or third stages, and one or more phosphorus thermal stabilizers such as trimethylphosphate, triethylphosphate, triphenylphosphate, etc. may be used. .

The features and other advantages of the present invention as described above will become more apparent from the following embodiments. However, the present invention is not limited to the following examples.

Example

Measurement of the evaluation items shown in the following Examples and Comparative Examples was as follows.

Melting point: Measured using a differential scanning calorimeter (Perkin Elmer, DSC).

* Intrinsic Viscosity (IV): The copolyester was dissolved in phenol / tetrachloroethane (50/50 by weight) to make a 0.5 wt% solution, and then measured at 35 ° C. with a Uberod viscometer.

* Color was measured by Color-b value using the Minolta CR-100 colorimeter.

* Spinning processability of spinning at 290 ℃ for more than 24 hours to evaluate the number of cuts and single yarns for 24 hours based on the following criteria.

?: 0 times,?: 1 to 2 times,?: 3 times to 5 times, X: 6 times or more

* Strength was measured using an INSTRON company's elongation measuring device.

* Biodegradability: After freezing and grinding the obtained copolyester chip, it is buried in compost which is maintained under constant conditions (30 ~ 40 ℃, humidity 55 ~ 60%) for biodegradation under composting conditions, Measured. Standard soil and landfill conditions used here were in accordance with ASTM D 5338-92.

Example  One

The ratio of 80 mole% of terephthalic acid and 20 mole% of glutaric acid to the dicarboxylic acid as the first copolymerization component in an ester reaction tank containing polyethylene terephthalate oligomer obtained by direct esterification of terephthalic acid and ethylene glycol After the addition, 50 mol% of biomass-derived ethylene glycol and 1 mol% of isosorbide were added to the second copolymerization component relative to the entire dicarboxylic acid component, and then in the presence of manganese acetate, which is a conventional transesterification catalyst. The transesterification reaction was completed at 245 ° C. for 1 hour. After adding antimony trioxide which is a condensation polymerization catalyst, it heated up to 285 degreeC under reduced pressure so that a final vacuum might be 1 mmHg or less, and the condensation polymerization reaction was performed.

The physical properties and fibrosis properties of the polycondensation-copolymerized biodegradable polyester resins were evaluated.

Example  2 to 4 and Comparative Example  1 to 5

As described in Table 1, terephthalic acid, glutaric acid, petroleum-based ethylene glycol, biomass-derived ethylene glycol, isosorbide, and neopentylglycol except for varying the copolymerization composition of the same procedure as in Example 1 was repeated.

Example Comparative Example One 2 3 4 5 One 2 3 4 Dicarboxylic acid component (mol%) Terephthalic acid 80 70 85 60 95 100 50 50 90 Glutaric acid 20 30 15 40 5 0 10 50 10 Glycol components
(mole%) Petroleum
Ethylene glycol 49 45 33 24 0 100 85 80 70 Derived from biomass
Ethylene glycol 50 50 60 70 80 0 0 5 0 Isosorbide One 5 7 3 5 0 15 10 15 Neopentyl glycol 0 0 0 3 10 0 0 5 15 Copolyester
characteristic Intrinsic viscosity 0.73 0.86 0.68 0.97 0.65 0.64 0.66 0.82 0.59 Color (b) 2.0 5.7 6.5 4.7 5.3 -2 12.1 14.5 15.3 Melting point (캜) 214 201 229 192 239 255 221 - 223 Glass transition temperature (캜) 63 67 69 53 75 80 80.3 10 79.1 Radiation characteristics Fairness ◎ ◎ ○ ○ ○ ◎ △ X X Strength (g / d) 3.1 2.9 2.8 2.8 2.5 4.0 2.4 1.7 1.8 Weight loss due to biodegradation
(%) 1 month later 0.5 2.1 1.5 3.2 0.5 0 1.2 6.9 1.2 2 months later 4.6 8.9 5.3 9.7 3.1 0 4.5 18.1 4.4 3 months later 8.7 20.8 10.5 23.5 5.3 0 6.1 31.7 7.1

Looking at Table 1, Example 1-5 is a copolyol using a specific amount of aromatic dicarboxylic acid, aliphatic dicarboxylic acid, petroleum ethylene glycol, biomass-derived ethylene glycol, isosorbide and neopentyl glycol Excellent color of ester resin, high melting point and high glass transition temperature. In addition, when the fiber is produced using the copolyester resin prepared in Example 1-5, the spinning processability is excellent, and the strength and biodegradability of the fiber produced is also excellent.

Comparative Example 1 uses only aromatic dicarboxylic acid and petroleum ethylene glycol, and does not use isosorbide or neopentyl glycol, so it has excellent color and raw material properties, but there is no aliphatic dicarboxylic acid that causes biodegradability. No weight loss due to In Comparative Example 2, too much isosorbide was used to reduce color and spinning processability. In Comparative Example 3, too much aliphatic dicarboxylic acid was used to decrease color and spinning processability, lower the melting point and the glass transition temperature, and lower the strength of the fabric. In addition, in Comparative Example 4, an excess of isosorbide and neopentyl glycol was used to decrease color and spinning processability, and the strength of the manufactured fiber was lowered.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

Dicarboxyl which consists of (a) aromatic dicarboxylic acid, its acid anhydride, or mixture thereof, and (b) aliphatic dicarboxylic acid containing glutaric acid, its acid anhydride, or mixture thereof as a 1st copolymerization component. Acid component; And
A glycol component composed of biomass-derived ethylene glycol, isosorbide and neopentyl glycol as the second copolymer component;
Lt; / RTI >
The dicarboxylic acid component is an aromatic dicarboxylic acid, an acid anhydride thereof, or a mixture thereof (a) of 60 to 95 mol%, an aliphatic dicarboxylic acid containing the glutaric acid, an acid anhydride thereof or these The mixture (b) is 5 to 40 mol%, the glycol component is 80 to 99.8 mol% of the biomass-derived ethylene glycol, 0.1 to 10 mol% of the isosorbide and 0.1 to 10 mol of the neopentyl glycol Biodegradable copolyester resin, characterized in that%.
delete delete The biodegradable copoly according to claim 1, wherein the aliphatic dicarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimeric acid, subberic acid, azelaic acid, and sebacic acid. Ester resin.
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