KR101235016B1 - Biodegradable Copolyester Resin with High Thermal Property and Process of Preparation thereof - Google Patents
Biodegradable Copolyester Resin with High Thermal Property and Process of Preparation thereof Download PDFInfo
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- KR101235016B1 KR101235016B1 KR1020100041251A KR20100041251A KR101235016B1 KR 101235016 B1 KR101235016 B1 KR 101235016B1 KR 1020100041251 A KR1020100041251 A KR 1020100041251A KR 20100041251 A KR20100041251 A KR 20100041251A KR 101235016 B1 KR101235016 B1 KR 101235016B1
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Abstract
The present invention provides a component selected from the group consisting of aromatic dicarboxylic acids or acid anhydrides thereof, petroleum or biomass-derived aliphatic dicarboxylic acids, hydroxy benzoic acids or mixtures thereof; And aliphatic glycols selected from the group consisting of petroleum or biomass-derived ethylene glycol, 1,2-propanediol, neopentylglycol, isosorbide; It provides a copolyester resin prepared by condensation polymerization of a polymerization reaction comprising a. The copolyester resin according to the present invention improves biodegradability while maintaining physical properties and thermal stability of the polyester, and is excellent in environmental friendliness, thermal stability, and heat resistance.
Description
The present invention relates to an aliphatic-containing copolyester resin and a method for producing the same, and more particularly, to a copolyester resin which is biodegradable and maintains physical properties of a polyester, which is environmentally friendly and excellent in thermal stability. And a method for producing the same.
Polyester resins, which are variously used for fibers, plastic molded articles, films, and the like, are high molecular weight aromatic polyester resins produced by a condensation polymerization reaction of terephthalic acid and ethylene glycol. The high molecular weight polyester here refers to a polymer having an intrinsic viscosity [?] Of 0.55 to 1.1 (dL / g). However, the aromatic polyester resin does not decompose in the natural ecosystem after disposal, causing a long time environmental pollution problem.
On the other hand, it is already known that aliphatic polyesters are biodegradable (Journal of Macromol. SCI-Chem A-23 (3). 1986, pp 393-409). Some applications include medical materials, agriculture, fishing materials and packaging materials, and other practical researches are being conducted.
However, due to the flexible structure and low crystallinity of the main chain, the existing aliphatic polyester is easy to be thermally decomposed due to its low melting point and low thermal stability during melting, and its high melt flow index makes the molding process difficult, as well as its tensile strength and tear strength. There is a problem that the use is limited due to poor physical properties. The practical use of such aliphatic polyester has to raise the number average molecular weight to 20,000 or more, but it is difficult to raise the number average molecular weight of the aliphatic polyester to 15,000 or more in a commonly known condensation polymerization system.
As a method for solving this problem, a method of 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 is disclosed in Korean Patent Publication No. 1995-758. However, the aliphatic polyester resin produced by this method has a low weight average molecular weight, is extremely sensitive to heat, and has very low thermal stability.
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.
On the other hand, aromatic polyester resins are stable in physical properties such as high molecular weight, thermal stability, tensile strength, but biodegradability has been a problem that does not rot when landfill. In other words, there is a problem that is not environmentally friendly, such as not be decomposed well when used and discarded after use. Therefore, unlike conventional materials, biodegradable materials that can be quickly decomposed into oxygen, carbon dioxide, water, etc., are easily made when soil is buried without imparting extra artificial temperature conditions. Related technology development patents include U.S. Pat.Nos. 5,505,348,509,044,5171308, etc., and the contents of the technology can be biodegraded during landfill by copolymerizing aliphatic dicarboxylic acid and sulfonic acid groups in the polyester polymerization process. Let it. However, while the physical properties and thermal stability are improved by the aromatic component, problems such as degrading biodegradability remain unsolved.
An object of the present invention is to provide a copolyester resin having excellent thermal properties and a method for producing the same.
Another object of the present invention is to provide a biodegradable environmentally friendly copolyester resin and a method of manufacturing the same.
In the present invention, in order to improve the biodegradability while maintaining the physical properties and thermal stability of the polyester, aliphatic dicarboxylic acid was introduced to develop a copolyester resin.
In one aspect of the invention, the one-step reaction comprises an aromatic dicarboxylic acid containing an aromatic such as terephthalic acid, dimethyl terephthalic acid (or an acid anhydride thereof) and an aliphatic (including cyclic aliphatic) derived from petroleum or biomass. At least one component selected from the group consisting of hydroxy benzoic acid and a component selected from the group consisting of petroleum or biomass-derived ethylene glycol, 1,2-propanediol, neopentylglycol and isosorbide, Melt the raw material completely.
In the two-step reaction, an ester reaction catalyst is added to increase the activity of the aromatic component, and an oligomer having a polymerization degree of 3 or more is prepared through esterification and transesterification at 220-250 ° C. for 1 hour, and water and methanol are completely discharged.
In the final three step reaction, the obtained resin is further condensation-polymerized to prepare a high molecular weight copolyester resin having excellent physical properties and biodegradation properties.
The copolyester resin according to the present invention improves biodegradability while maintaining physical properties and thermal stability of the polyester, and is excellent in environmental friendliness and heat resistance.
Hereinafter, the present invention will be described in more detail.
The present invention provides an aromatic dicarboxylic acid (or an acid anhydride thereof) containing an aromatic such as terephthalic acid and dimethyl terephthalic acid in a one-step reaction; And / or one or more components selected from the group consisting of petroleum or biomass derived aliphatic (including cycloaliphatic) dicarboxylic acids, hydroxy benzoic acid; And petroleum or biomass-derived ethylene glycol, 1,2-propanediol, neopentylglycol, isosorbide belonging to aliphatic glycol; And melt the raw material completely at a temperature of 220 ℃ or higher. The petroleum- or biomass-derived aliphatic dicarboxylic acid lowers the glass transition temperature of the polymer and improves biodegradability with deterioration of physical properties, and 1,2-propanediol, isosorbide, etc. belonging to the aliphatic glycol are copolymerized. It has the purpose and effect of disturbing the structural regularity of the polyester molecular chain to enhance biodegradability.
In the two-step reaction, an ester reaction catalyst is added to increase the activity of the aromatic component, and an oligomer having a polymerization degree of 3 or more is prepared through esterification and transesterification at 220-250 ° C. for 1 hour, and water and methanol are completely discharged.
In the final three step reaction, the obtained resin is further condensation-polymerized to prepare a high molecular weight copolyester resin having excellent physical properties and biodegradation properties.
In the one-step reaction, a copolymerization raw material may be added preferably in the following composition. ① a mixed component of certain components with ethylene glycol and other glycols in terephthalic acid (dimethyl terephthalic acid) and aliphatic dicarboxylic acid derived from petroleum or biomass, and ② in terephthalic acid (dimethyl terephthalic acid) and aliphatic dicarboxylic acid derived from petroleum or biomass. A certain component and 1,2-propanediol sole component derived from petroleum or biomass, or a mixed component of 1,2-propanediol and other glycols, ③ terephthalic acid (dimethyl terephthalic acid) and aliphatic dicarboxylic acid derived from petroleum or biomass (Including cyclic aliphatic), mixed components of other aromatic carboxylic acids and sole components of ethylene glycol, ④ terephthalic acid (dimethyl terephthalic acid) and aliphatic dicarboxylic acids derived from petroleum or biomass (including cyclic aliphatic), other aromatic carboxylic acids Mixed components of ethylene glycol and other glycols, ⑤ terephthal (Dimethyl terephthalic acid) and petroleum or biomass-derived aliphatic dicarboxylic acids (including cyclic aliphatic), mixed components of other aromatic carboxylic acids with petroleum or biomass-derived 1,2-propanediol and other glycols, (6) It is preferable to add as a polymerization reactant in the composition of a certain component and petroleum- or biomass-derived ethylene glycol among terephthalic acid (dimethyl terephthalic acid) and petroleum or biomass-derived aliphatic dicarboxylic acid.
In addition, according to the present invention, there is provided a method for producing the copolyester resin, the production method as described above is composed of a three-step reaction, will be described in more detail by dividing step by step below.
The molar ratio of the aliphatic (including cyclic aliphatic) dicarboxylic acid (or its acid anhydride) and the aliphatic (including cyclic aliphatic) glycol which is introduced in the first step reaction is 1: 1.05 ~ 1: 3.0 Is preferred, and is more preferably added in a ratio of 1: 1.1 to 1: 2.5. The content of the petroleum-based or biomass-derived aliphatic component in the total dicarboxylic acid added in the first step reaction is preferably 10 to 15 mol%. This is because if the content is 15 mol% or more, the melting point of the copolyester is low, spinning processability is low, and if it is less than 10 mol%, biodegradability is deteriorated by the aromatic component.
In the two-stage reaction, to increase the activity of the aromatic components, an ester reaction catalyst is added, and an oligomer having a polymerization degree of 3 or more is prepared by esterification and transesterification at a temperature of 220 to 250 ° C. for 1 hour. Obtain the resin.
Finally, in the three-step reaction, the resin obtained in the two-step reaction is condensation-polymerized at a temperature of 280 ° C. and a vacuum of 1.0 Torr or less for 60 to 240 minutes to produce a high molecular weight copolyester resin. At this time, the produced copolyester is characterized in that the intrinsic viscosity [η] is 0.55 ~ 1.1 dL / g.
Meanwhile, according to the present invention, a catalyst may be added at the beginning or end of the first to second stage esterification or transesterification and at the beginning or end of the three stage condensation polymerization reaction, the addition amount being 0.02 relative to the total composition weight. 4.0 wt%. If the addition amount is less than 0.02% by weight, it is difficult to flow out the theoretical amount of water, methanol or glycol. On the other hand, when the addition amount of the catalyst exceeds 4.0% by weight, the theoretical amount of water, methanol or glycol easily flows out, but may affect the color of the polymer. As the catalyst, any one or a mixed catalyst selected from metal compounds including Zn, Co, Sb 2 O 3, Ti, Ge, Mn, and the like may be used. Preferably, a metal compound containing Ti, Sb 2 O 3 may be used, and more preferably any one or two or more mixed catalysts selected from heavy metal-free Ge, Mn, Ti (titanium based) polymerization catalysts may be used.
In addition, a thermal stabilizer may be added at the beginning or end of the first to third stage esterification reaction or transesterification reaction and at the beginning of the third stage condensation polymerization reaction, the addition amount of which is 0.05 to 1.0 wt% based on the total weight of the composition. to be. If the added amount is less than 0.05% by weight, the effect as a stabilizer cannot be obtained and the color becomes worse. On the other hand, when the added amount of the stabilizer exceeds 1.0% by weight, the reaction time becomes long and it is difficult to obtain a high molecular weight copolyester. As the stabilizer, any one or two or more mixed stabilizers selected from phosphate (P) -based stabilizers such as trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP) and the like are used.
In the physical properties of the copolyester resin of the present invention prepared by the above step the ultimate viscosity is 0.55 ~ 1.1, the glass transition temperature is 55 ℃ or more, the melting point is 225 ℃ or more, the melt viscosity is 270 ℃ at 2700 Poise It is characterized by.
Example
Example 1
Glutaric acid in terephthalic acid and aliphatic dicarboxylic acid was added at a ratio of 90 mol%: 10 mol%, and then ethylene glycol 97 mol% and 1,2-propanediol 3 mol were used as a glycol component. After the addition of%, the transesterification reaction was completed at 245 ° C. for 1 hour in the presence of a conventional transesterification catalyst of manganese acetate or zinc acetate. The addition amount is 0.02 to 4.0 weight% with respect to the weight of the whole composition. Tetranormal butoxy titanate, which is a condensation polymerization reaction catalyst, is added thereto, and the amount thereof is 0.05 to 1.0% by weight based on the total weight of the composition. The condensation polymerization reaction was carried out by heating up to 280 ° C while reducing the final vacuum degree to 1.0 Torr or lower. The physical properties of the copolyester obtained at this time were measured. The measurement results are shown in Table 1.
After the obtained copolyester chip is fiberized through a common spinning process, it is buried in the compost maintained at a constant condition (30-40 ° C., humidity 55-60%) for biodegradation under composting conditions and biodegradation at regular time intervals. Was measured. Biodegradation landfill conditions were according to ASTM Standards D5338-92.
Examples 2-5 and Comparative Examples 1-4
As shown in Table 1, except that the copolymer composition ratio of terephthalic acid, glutaric acid, hydroxybenzoic acid, petroleum or biomass-derived ethylene glycol, 1,2-propanediol, isosorbide and the like is different from that of Example 1 The same procedure was repeated.
As can be seen from the results of Table 1, Examples 1 to 5 are 1,2-propane which is an aliphatic dicarboxylic acid and aliphatic glycol derived from petroleum or biomass for the purpose of improving biodegradability and glass transition temperature. It is a composition copolymerized with diol, isosorbide, etc., and it is stable in physical properties such as glass transition temperature and melting point of polymer resin due to the optimal composition of aliphatic dicarboxylic acid. Comparative Examples 2 to 3 have problems of poor processability and thermal stability due to an increase in copolymerization composition and a decrease in glass transition and melting point, and poor color of resins. Comparative Example 4 is an aliphatic derived from petroleum or biomass. The thermal stability and processability of the dicarboxylic acid is reduced, but the biodegradability is poor. The.
Claims (8)
The petroleum or biomass-derived aliphatic dicarboxylic acid is contained in 10 to 15 mol% based on 100 mol% of the total dicarboxylic acid,
The glass transition temperature of the copolyester resin is 55 ℃ or more, the melting point is 225 ℃ or more biodegradable copolyester resin, characterized in that.
Adding an ester reaction catalyst to increase the activity of the aromatic component, preparing an oligomer resin having a polymerization degree of 3 or higher through an esterification reaction or a transesterification reaction at a temperature of 220 to 250 ° C. for 1 hour, and distilling water and methanol; And
Condensation polymerization of the oligomer resin for 60 to 240 minutes at a reaction temperature of 260 to 280 ° C. and a vacuum of 1.0 Torr or less;
Lt; / RTI >
The petroleum or biomass-derived aliphatic dicarboxylic acid is added in 10 to 15 mol% based on 100 mol% of all dicarboxylic acids,
The catalyst is a method for producing a biodegradable copolyester resin, characterized in that using a catalyst selected from the group consisting of germanium, manganese acetate, titanium-based (Ti) polymerization catalysts and mixtures thereof free of heavy metals.
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| KR1020100041251A KR101235016B1 (en) | 2010-05-03 | 2010-05-03 | Biodegradable Copolyester Resin with High Thermal Property and Process of Preparation thereof |
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| KR101235016B1 true KR101235016B1 (en) | 2013-02-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101815945B1 (en) * | 2017-05-25 | 2018-02-22 | 주식회사 삼양사 | Polyester resin prepared by using carbonate diol derived from anhydrosugar alcohol and method for preparing the same, and powder coating composition comprising the resin |
| KR101891179B1 (en) | 2017-05-25 | 2018-08-24 | 주식회사 삼양사 | Polyester resin prepared by using polyhydric alcohol and method for preparing the same, and powder coating composition comprising the resin |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140018468A (en) | 2012-07-30 | 2014-02-13 | 삼성정밀화학 주식회사 | Method of preparation for biodegradable co-polyester with divided addition of aromatic dicarboxylic acid compound |
| KR102036809B1 (en) * | 2013-04-05 | 2019-10-25 | 도레이케미칼 주식회사 | Polymer for bio plastics, Composition of the same and Preparing method thereof |
| KR101502051B1 (en) * | 2013-08-07 | 2015-03-13 | 주식회사 휴비스 | Eco-friendly Copolyester Resin and Process of Preparing Same |
| KR101592845B1 (en) * | 2014-01-22 | 2016-02-19 | 주식회사 휴비스 | Eco-friendly Copolyester Resin, Foamed Article, and Method of Preparation thereof |
| KR101644068B1 (en) * | 2014-11-25 | 2016-08-01 | 주식회사 휴비스 | Polytrimethyleneterephthalate Composite Fibers Using materials from biomass and Method Preparing Same |
| KR102063626B1 (en) * | 2018-03-20 | 2020-01-08 | (주) 티엘씨 코리아 | Biodegradable copolyester resin manufactured by esterification and condensation polymerization of aliphatic/aromatic dicarboxylic acid and glycol |
| WO2020226200A1 (en) * | 2019-05-07 | 2020-11-12 | Tlc Korea Co., Ltd. | Biodegradable copolyester resin produced by esterification and polycondensation of biomass-derived aliphatic dicarboxylic acid and aromatic dicarboxylic acid with diol and production method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000042622A (en) * | 1998-12-26 | 2000-07-15 | 주덕영 | Process for producing polyester and its composition |
| US6485819B2 (en) * | 2000-12-19 | 2002-11-26 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic copolyesters |
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- 2010-05-03 KR KR1020100041251A patent/KR101235016B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000042622A (en) * | 1998-12-26 | 2000-07-15 | 주덕영 | Process for producing polyester and its composition |
| US6485819B2 (en) * | 2000-12-19 | 2002-11-26 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic copolyesters |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101815945B1 (en) * | 2017-05-25 | 2018-02-22 | 주식회사 삼양사 | Polyester resin prepared by using carbonate diol derived from anhydrosugar alcohol and method for preparing the same, and powder coating composition comprising the resin |
| KR101891179B1 (en) | 2017-05-25 | 2018-08-24 | 주식회사 삼양사 | Polyester resin prepared by using polyhydric alcohol and method for preparing the same, and powder coating composition comprising the resin |
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| KR20110121796A (en) | 2011-11-09 |
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