KR101644962B1 - Biodegradable polylactide-based aliphatic/aromatic copolyester resin composition and method for preparing the same - Google Patents
Biodegradable polylactide-based aliphatic/aromatic copolyester resin composition and method for preparing the same Download PDFInfo
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- KR101644962B1 KR101644962B1 KR1020160013179A KR20160013179A KR101644962B1 KR 101644962 B1 KR101644962 B1 KR 101644962B1 KR 1020160013179 A KR1020160013179 A KR 1020160013179A KR 20160013179 A KR20160013179 A KR 20160013179A KR 101644962 B1 KR101644962 B1 KR 101644962B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
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Abstract
Description
The present invention relates to biodegradable polylactide based aliphatic copolyester polymers and processes for their preparation.
Plastic is an indispensable product in the modern industrial society, and its usage is gradually increasing. However, recent environmental pollution caused by plastic products discarded after use has become a big issue in the world, and the reuse of plastic products, incineration, and development of biodegradable plastics are emerging as measures to reduce these inconveniences. Of these, biodegradable plastics are attracting attention as eco-friendly products that fundamentally solve environmental pollution. In the present invention, the biodegradable plastics are synthesized with polylactides for coating with raw materials and aliphatic copolyesters, The aim is to prevent contamination.
The biodegradable resin for coating has been tried to dissolve in chloroform, which is strong in toxicity. However, since biodegradation characteristics, molecular weight and various physical properties are different from each other, application of the product is limited, Solvents have limited their use.
A method for synthesizing a high molecular weight aliphatic polyester resin by appropriately controlling the reaction temperature, the vacuum temperature, the degree of vacuum, and the catalyst condition as one method for practical use of the biodegradable aliphatic copolyester dissolved in chloroform having such toxicity Is disclosed in Korean Patent Application No. 2000-0042622. However, the aliphatic copolyester resin prepared by this method is dissolved in chloroform which is strong in toxicity, so that the tensile strength is lower than that of general-purpose polyethylene in use, the esterification reaction step is one step, the molecular structure repeating unit is considerably random, Is very slow and the workability during processing is low.
Accordingly, unlike conventional biodegradable aliphatic polyesters, the present invention solves the problems of the conventional biodegradable copolyesters, and has a biodegradability sufficient for practical use as a compound having a new structure and properties, Which is comparable to a general-purpose resin, to obtain a biodegradable polylactide-based soluble copolyester resin having excellent mechanical properties and processability.
The present invention relates to an acidic mixture of an aliphatic dicarboxylic acid or an anhydride thereof and an aromatic carboxylic acid or anhydride thereof; A compound of the polylactide of the formula (1); And an aliphatic glycol, wherein the acidic mixture mixture and the aliphatic glycol in the mixture are subjected to a first ester exchange reaction, and then the second acidic component The mixture is fed to a second esterification reaction, and the second-order aliphatic / aromatic oligomer is subjected to a polycondensation reaction to remove excess glycol under high vacuum to carry out a condensation polymerization, thereby obtaining a highly soluble polylactide- Thereby providing an aliphatic / aromatic copolyester resin composition.
According to the present invention, in the synthesis of a polylactide-based aliphatic / aromatic copolyester, an aliphatic / aromatic oligomer having a long chain as a kind of chain extender is synthesized and added to the reaction product to obtain a product using a conventional multifunctional monomer And the problem of gelation is solved. Further, by obtaining an aliphatic / aromatic copolyester containing a polylactide having a higher molecular weight than that of a conventional aliphatic / aromatic copolyester, the working temperature range It is possible to obtain a resin which is wide and easy to manufacture and which makes it easy to produce a product. The resulting polylactide-based aliphatic / aromatic copolyesters are superior in mechanical properties to aliphatic / aromatic copolyesters of the prior art, and are generally dissolved in toluene, methyl ethyl ketone and the like, which are widely used solvents, Not only can it be widely used, but also biodegradability is similar to that of conventional biodegradable polylactide-containing aliphatic polyesters, which can lead to increased use of biodegradable polylactide-containing aliphatic / aromatic copolyesters Which can lead to reduction of environmental pollution caused by waste plastics.
The present inventors have found that a carbodiimide compound and a polylactide having a weight average molecular weight of 200 to 200,000 are used for the purpose of improving molecular structure, solubility and reactivity in order to achieve the above object. In the aliphatic copolyester reaction step And a multistage reaction was introduced. The unsaturated compound used in the present invention can be obtained by reacting a unsaturated compound having a double bond such as malic acid or fumaric acid with a dicarboxylic acid to obtain an aliphatic / aromatic copolyester resin composition containing a biodegradable polylactide having excellent solubility.
In one aspect, the present invention provides a process for producing an aliphatic / aromatic copolyester resin composition comprising a biodegradable polylactide having excellent solubility,
(i) obtaining a first ester exchange reaction product of an aromatic dicarboxylic acid (or acid anhydride thereof) and an aliphatic (or cyclic aliphatic) glycol;
(or an anhydride thereof) and an aliphatic (or cyclic aliphatic) aliphatic dicarboxylic acid (or anhydride thereof) in the presence of a first reaction product of step (i) and a polylactide having a molecular weight of 200 to 200,000, ) Glycol to obtain a secondary esterification reaction product; And
(Iii) polycondensation of the reaction product of step (ii). The present invention also provides a process for producing an aliphatic / aromatic copolyester resin composition comprising the biodegradable polylactide having excellent solubility.
Preferably, the present invention relates to an acidic mixture of 20 to 80 mol% of an aliphatic dicarboxylic acid or anhydride thereof and 80 to 20 mol% of an aromatic carboxylic acid or anhydride thereof; 50 to 99 parts by weight of a polylactide compound represented by the following formula (1) based on 100 parts by weight of the total of the acidic component mixture and the following aliphatic glycol; And an aliphatic glycol having a molar ratio of 1.15 to 1.5 based on 1 mole of the acidic mixture, wherein the acidic mixture and the aliphatic glycol in the mixture After the first transesterification reaction, a second esterification reaction is carried out by introducing an acidic mixture to the second reaction product. In the reaction product, the second-reacted aliphatic / aromatic oligomer is subjected to a tertiary polycondensation reaction, The present invention provides a polylactide-based aliphatic / aromatic copolyester resin composition having excellent solubility, prepared by condensation polymerization while removing glycol:
(1) - [OCH 3 CHOC] n -
In this formula,
and n is an integer of 2 to 2,000.
Preferably, in the polylactide-based aliphatic / aromatic copolyester resin composition of the present invention having excellent solubility, at most 5 parts by weight, based on 100 parts by weight of the total weight of the acid mixture and the aliphatic glycol, ) Carbodiimide or a mixture thereof may further be added during the primary transesterification reaction:
(2) R One -N = C = N-R < 2
In this formula,
R 1 and R 2 are the same or different and each is an alkyl group having 4 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms.
As a preferable specific example of this embodiment, the aliphatic polydiol may be selected from a single component or a mixed component among ethylene glycol and 1,4-butanediol.
In another preferred embodiment, when producing an aliphatic / aromatic polydiol, the reaction temperature is in the range of 160 to 180 DEG C and a tin-based metal catalyst may be used.
As another example, the molar ratio of the aromatic dicarboxylic acid (or its acid anhydride) and the aliphatic (including cyclic aliphatic) glycol used in the primary esterification reaction and transesterification reaction is in the range of 1: 1.15 to 1: 2.0 do.
As another example, specific examples of the use of aromatic dicarboxylic acid (or an acid anhydride thereof) include terephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, 4-methylphthalic acid, 4-methylphthalic anhydride, dimethylterephthalate and dimethyl phthalate , But is not limited thereto. These aromatic dicarboxylic acids (or acid anhydrides thereof) may be used alone or in a mixture of two or more.
As another example, aliphatic (including cyclic aliphatic) glycols used in the esterification reaction and the transesterification reaction include ethylene glycol, diethyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, Diol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, But are not limited to, octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol and decamethylglycol. These aliphatic (including cyclic aliphatic) glycols can be used alone or as a mixture of two or more.
In another preferred specific example, the temperature range in which the primary esterification reaction and the esterification exchange reaction are carried out is preferably maintained at 180 to 220 캜, which is the activation temperature of the aromatic component.
As another example, aliphatic (including cyclic group) dicarboxylic acids (or acid anhydrides) include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, 1,9-nonanedicarboxylic acid, , 10-decanedicarboxylic acid, and acid anhydrides thereof. These aliphatic (including cyclic aliphatic) dicarboxylic acids (or acid anhydrides thereof) may be used alone or as a mixture of two or more.
As another preferable example, the execution temperature of the secondary esterification reaction and transesterification reaction is suitably in the range of 150 to 180 캜.
As another specific example, the aromatic dicarboxylic acid (or an acid anhydride thereof) and the aliphatic dicarboxylic acid (or an acid anhydride thereof) used in the production process of the aliphatic / aromatic copolyester polymer of the present invention have a molar ratio of 0.3: 0.7 to 0.7 : 0.3 molar ratio is suitable.
As another specific example, the content of aliphatic / aromatic polydiol present in the secondary esterification reaction and the esterification exchange reaction is in the range of 5 to 30% by weight of the theoretical amount of the aliphatic / aromatic copolyester polymer as the final product.
After the transesterification reaction, the polyolefin having a weight average molecular weight of 200 to 200,000 is added to the aliphatic / aromatic copolyester resin in an amount of 50 to 99% based on the total weight, It is preferable to carry out the treatment for 180 to 240 minutes under a degree of vacuum of 0.005 to 2.0 torr at 260 占 폚.
The carbodiimide compound represented by the formula (2) used in the present invention is 1,3-dicyclohexylcarbodiimide, HMV8CA sold by Nisshinbo, HMV-15CA, etc. The amount of the carbodiimide compound added to the mixture of the acidic components and the aliphatic glycol is 100 Is at most 5 parts by weight based on parts by weight.
As another preferred example, the catalyst may be added at the initial stage or the end stage of the polycondensation reaction in the stage 2 after the first stage transesterification reaction and in the stage 3 after the second esterification reaction. Such a catalyst may be used in the range of 0.02 to 2.0 wt% based on the total weight of reactants. Specific examples of such catalysts include any one or two or more mixed catalysts selected from among metal compounds including Ti, Ge, Zn, Fe, Mn, Co, Zr and the like, preferably titanate, tin oxide, antimonate And is preferably an organometallic compound, and in particular, one or a mixture of two or more selected from the group consisting of tetrabutyl titanate, calcium acetate, antimony trioxide, monobutylene oxide, zinc acetate and tetrapropyl titanate is preferable.
As another specific example, stabilizers may be further added at the beginning or end of the esterification reaction, the esterification exchange reaction and the polycondensation reaction. These stabilizers are suitably used in the range of 0.02 to 2.0 wt% based on the weight of the total reactants. Such stabilizers include, but are not limited to, trimethyl phosphate, phosphoric acid, and triphenyl phosphate. These stabilizers may be used alone or as a mixture of two or more.
In another aspect, the present invention relates to a process for preparing a polymer chain having a number average molecular weight of from 40,000 to 80,000, wherein the number of aromatic dicarboxylic acid components is 10 or less in the dicarboxylic acid position of the polymer chain, Range, a weight average molecular weight of 100,000 to 250,000, a melting point of 70 to 160 캜, a melt flow index of 0.1 to 50 (190 캜, 2,160 g), and a processability and biodegradability do.
Preferably, in the polylactide-based aliphatic / aromatic copolyester resin composition of the present invention having excellent solubility, the weight average molecular weight of the polylactide compound of formula (1) is 200 to 200,000.
Preferably, in the polylactide-based aliphatic / aromatic copolyester resin composition of the present invention having excellent solubility, the carbodiimide compound of formula (2) is 1,3-dicyclohexylcarbodiimide, HMV-8CA, HMV-10B, bis- (2,6-diisopropyl-phenylyne-2,4-carbodiimide), poly- (1,3,5-triisopropyl-phenylyne-2,4-carbodiimide ), And mixtures of two or more thereof.
Preferably, in the polylactide-based aliphatic / aromatic copolyester resin composition of the present invention having excellent solubility, the aliphatic dicarboxylic acid is succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, , 4-cyclohexanedicarboxylic acid, and compounds of two or more thereof.
Preferably, in the polylactide-based aliphatic / aromatic copolyester resin composition of the present invention having excellent solubility, the aromatic dicarboxylic acid is terephthalic acid, isophthalic acid, 2,6-naphthoic acid and ester-forming derivatives thereof, ≪ / RTI >
Preferably, in the polylactide-based aliphatic / aromatic copolyester resin composition of the present invention having excellent solubility, the aliphatic glycol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,4-butanediol, , 1,2-cyclohexanedimethanol, and two or more of these groups.
Preferably, in the polylactide-based aliphatic / aromatic copolyester resin composition of the present invention having excellent solubility, the polylactide-based aliphatic / aromatic copolyester resin composition is a mixture of toluene, methyl ethyl ketone , Or dissolved in ethyl acetate and used for coating.
Hereinafter, the present invention will be described in detail.
In the present invention, an aliphatic / aromatic copolyester resin composition containing a polylactide is a biodegradable resin composition. First, an aliphatic / aromatic oligomer for raising an aliphatic / aromatic copolyester containing a polylactide in a high molecular weight In the process, glycol and dicarboxylic acid are added thereto, and water generated as a by-product of the reaction is distilled off while stirring the reactants under a 160-180 ° C tin-based metal catalyst condition to produce an aliphatic / aromatic oligomer.
The molecular weight of the aliphatic / aromatic oligomer used in the production of the aliphatic / aromatic oligomer is in the range of 200 to 1,000. When the molecular weight is 200 or less, the solubility may be reduced due to a short distance between the aromatic components in the molecular structure of the aliphatic / aromatic oligomer. When the molecular weight is 1,000 or more, the reaction rate is lowered and the color becomes poor. Later, when producing aliphatic / aromatic copolyesters containing polylactides, the reaction rate may be slowed down and the cooling rate may slow the molding.
The thus synthesized aliphatic / aromatic oligomers can be synthesized by the addition of the following carbodiimide (formula (2)) and optional polylactide (formula (1)) to produce a polylactide-containing aliphatic / aromatic copolyester in multi- It is added to the 2 step process and used as diol component. When added in Step 1, the block of the aromatic component is elongated and affects the decomposability and solubility.
Specifically, in the first stage of the synthesis of an aliphatic / aromatic copolyester including a polylactide system, an aromatic dicarboxylic acid (or an acid anhydride) containing an aromatic group and an aromatic dicarboxylic acid (or anhydride) in a molecular structure such as dimethyl terephthalate and terephthalic acid, Is reacted with an aliphatic (including cyclic aliphatic) glycol containing at least one selected from butanediol and ethylene glycol. The possible combinations of reactants at this stage are described in detail below.
(1) a component comprising dimethyl terephthalate (including terephthalic acid) alone, and (2) a carbodiimide compound and (1) a polylactide compound: ethylene glycol alone or in combination with ethylene glycol and other glycols A glycol having an alkylene group (including a cyclic alkylene group)),
(2) a component comprising dimethyl terephthalate (including terephthalic acid) alone, and (2) a carbodiimide compound and (1) a polylactide-based compound: 1,4-butanediol alone or in combination with 1,4- A glycol having an alkylene group (including a cyclic alkylene group) having 2 to 3, 5 to 10 carbon atoms)
(3) a mixed component of dimethyl terephthalate (including terephthalic acid) alone or a mixture of thymethyl terephthalate (including terephthalic acid) and other aromatic dicarboxylic acids (or acid anhydrides thereof) and (2) a carbodiimide compound and Ingredients containing a lactide-based compound: ethylene glycol alone,
(4) a mixed component of dimethyl terephthalate (including terephthalic acid) alone or a mixture of dimethyl terephthalate (including terephthalic acid) and other aromatic dicarboxylic acid (or acid anhydride thereof) and (2) a carbodiimide compound and Ingredients Containing Tyride-Based Compounds: 1,4-butanediol alone,
(5) a mixed component of dimethyl phthalate (including terephthalic acid) alone or a mixture of dimethyl phthalate (including terephthalic acid) and other aromatic dicarboxylic acid (or acid anhydride thereof) and (2) a carbodiimide compound and a polylactide Component: a mixed component of ethylene glycol alone or an ethylene glycol and other glycol (a glycol having an alkylene group having 3 to 10 carbon atoms (including a cyclic alkylene group)),
(6) a mixed component of dimethyl terephthalate (including terephthalic acid) alone or a mixture of thymethyl terephthalate (including terephthalic acid) and other aromatic dicarboxylic acids (or acid anhydrides thereof) and (2) a carbodiimide compound and Component comprising a lactide-based compound: 1,4-butanediol alone or a mixture of 1,4-butanediol and other glycols (glycols having an alkylene group having 2 to 3, 5 to 10 carbon atoms (including a cyclic alkylene group)) Mixed ingredients.
Any one reaction combination selected from these reaction components is fed into the reactor and the water or methanol is completely drained through the esterification reaction and the esterification exchange reaction while maintaining the temperature of the aromatic component at 180 to 220 캜. The molar ratio of the aromatic dicarboxylic acid (or acid anhydride) and the aliphatic (including cyclic aliphatic) glycol introduced in the first step reaction is preferably 1: 1.15 to 1: 2.0, more preferably 1: 1.13 to 1: 1.15 .
In the second step reaction, in the presence of the first-step reaction product, the aliphatic / aromatic oligomer synthesized in the above manner is added in an amount of 1 to 50% by weight based on 100 parts by weight of the aliphatic / aromatic copolyester theoretically produced, After addition of a carbodiimide compound with a molecular weight of 200 to 200,000, an aliphatic (including cyclic aliphatic) glycol is added to carry out an esterification reaction and an esterification exchange reaction to completely drain the water to obtain a reaction product. When the polylactide having a weight average molecular weight of 200 to 200,000 charged is less than 1% by weight based on 100 parts by weight of the theoretical amount of the aromatic / aromatic copolyester, the effect is not expected to be expected. The increase in aromatic components may result in poor processability, solubility, and degradability. The aliphatic (including cyclic aliphatic) glycol introduced in this step is added in a molar ratio of 1: 1.35 to 1: 1.45 to the dicarboxylic acid (or acid anhydride thereof), more specifically 1: 1.38 to 1: 1.42, The reaction is carried out at a temperature of 150 to 180 DEG C to lower the activity of the aromatic dicarboxylic acid (or acid anhydride thereof). When the reaction temperature is lower than 150 ° C., water is difficult to be spilled out. When the reaction temperature is higher than 180 ° C., the aromatic dicarboxylic acid (or an acid anhydride) component which has not reacted in the first step is activated and reacted, give. In particular, the aliphatic / aromatic polydiols contain an aromatic component, and the effect may be further detrimental to biodegradability.
Finally, in the third step reaction, the polymer resin obtained in the above two-step reaction is polymerized at a temperature of 220-260 DEG C and a vacuum degree of 0.005-2.0 torr for 180-240 minutes to obtain a polymerized polylactide copolyester To produce a resin. The copolyester produced here has a number average molecular weight of 40,000 to 80,000 and a weight average molecular weight of 100,000 to 250,000.
In the present invention, the catalyst may be added at the initial stage or the late stage of the esterification reaction, the ester exchange reaction or the polycondensation reaction of the first to third stages, and the added amount thereof is 0.02 to 2.0% by weight based on the total weight of the composition. If the amount of the catalyst is less than 0.02% by weight, the theoretical amount of water, methanol and unreacted glycol can not be discharged theoretically or takes considerable time. On the other hand, when the amount of the catalyst exceeds 2.0% by weight, the theoretical amounts of methanol, The outflow of unreacted glycol is easy, but it can affect color and its properties. The catalyst used herein may be any one or a mixture of two or more selected from metal compounds including Ti, Ge, Zn, Fe, Mn, Co, Zr and the like, preferably titanate, tin oxide, The organic metal compound containing nate is used, and more preferably one or more mixed catalysts selected from tetrabutylate, calcium acetate, antimony trioxide, monobutyltinoxine, zinc acetate, antimony acetate and tetrapropyl titanate Is used.
In addition, a stabilizer may be added at the early stage or the late stage of the esterification reaction, ester exchange reaction or polycondensation reaction of the first stage to the third stage, and the amount of the stabilizer added is 0.02 to 2.0% by weight based on the total weight of the composition. If it is less than 0.02% by weight, the effect as a stabilizer can not be obtained and the color becomes poor. On the other hand, when the amount of the stabilizer added exceeds 2.0% by weight, the reaction rate becomes long and it becomes difficult to obtain a polyester having a high molecular weight. Therefore, the amount of the stabilizer to be added is 0.22% by weight. As the stabilizer, any one or two or more mixed stabilizers selected from phosphate-based stabilizers such as trimethyl phosphate, phosphoric acid, triphenyl phosphate and the like may be used.
That is, the aliphatic / aromatic copolyester resin containing the polylactide having excellent biodegradability of the present invention is obtained by synthesizing an aliphatic / aromatic oligomer and adding it to the two-step reaction, Molecular weight polymer and is a copolyester having a number average molecular weight of 100,000 to 250,000. The melting point is 70 to 160 DEG C and the melt flow index is 0.1 to 50 (190 DEG C, 2160 g). The melting point was measured using a Perkin Elmer differential scanning calorimeter at a heating rate of 10 ° C / min. The melt flow index was measured at 190 ° C under a load of 2,160 g according to ASTM D1238. The molecular weight was measured by gel chromatography, and the tensile strength and elongation were measured by ASTM D882 method after hot pressing each resin to a thickness of 50 탆.
The polylactide copolyester resin thus produced is easily dissolved in toluene, MEK, EA, IPA, etc., and can be utilized as various kinds of ink, coating agent and the like.
Example One
The reactor was replaced with nitrogen, and 106.2 g of succinic acid, 19.4 g of dimethyl terephthalate and 117 g of 1,4-butanediol were charged. Then, 0.03 g of antimony trioxide and 0.02 g of zinc acetate were added and esterification exchange reaction was carried out at 200 ° C. for two hours After the theoretical amount of methanol was distilled out, 106.2 g of succinic acid, 0.1 g of HMV-8CA, 0.4 g of trimethyl phosphate and 300 g of polylactide having a molecular weight of 10,000 were added to the obtained esterified product, After the elution, condensation polymerization was carried out under high vacuum of 1 torr for 2 hours and 30 minutes to obtain an aliphatic / aromatic copolyester.
The number average molecular weight of the obtained sample was 18,000, the weight average molecular weight was 62,000, and the melting point was 119 占 폚. After 3 months, the weight loss was 16% and dissolved in toluene solvent.
Example 2
After replacing the 100 liter reactor with nitrogen, 117 g of 1,4-butanediol, 19.4 g of dimethyl terephthalate and 0.02 g of tin dioctoate were added and the esterification exchange reaction was carried out at 230 to 240 ° C to completely remove the theoretical methanol flow rate Respectively. Next, 131.4 g of adipic acid was added, and the mixture was heated to 180 ° C with slow stirring to carry out the esterification reaction to remove the generated water. In this process, 0.03 g of tetrabutyl orthotitanate, 0.1 g of HMV-8CA, 300 g of polylactide having a molecular weight of 200, and 0.002 g of a 50% aqueous solution of phosphorous acid were added and subjected to polycondensation reaction at a temperature of 230 to 240 ° C and a high vacuum of less than 1 torr Was allowed to proceed for about 2 hours to obtain a polylactide copolyester.
The resin thus obtained had a melting point of 84 占 폚, a number average molecular weight of 14,320 and a weight average molecular weight of 98,350. Degradability After 3 months, the weight loss was 32% and dissolved in methyl ethyl ketone and toluene solvent.
Example 3
After replacing the 100 liter reactor with nitrogen, 117 g of 1,4-butanediol, 97 g of dimethyl terephthalate and 50 g of tin dioctoate were added, followed by transesterification at 230 to 240 ° C to completely remove the theoretical methanol flow rate. Subsequently, adipic acid (73 g) was added, and the mixture was heated to 180 DEG C while being stirred slowly to carry out an esterification reaction to remove water generated. In this process, 400 g of a polylactide having a weight average molecular weight of 100,000, 0.01 g of tetrabutyl orthotitanate, 0.1 g of HMV-8CA and 0.02 g of a 50% aqueous solution of phosphorous acid were added and stirred at a temperature of 230 to 240 ° C and a high- After about 2 hours of polymerization, the melt was cooled to 200 DEG C and 0.4 g of hexamethylene diisocyanate was added over 15 minutes, then the mixture was stirred. The polyester was granulated and processed into a film.
The resin thus obtained had a melting point of 108.3 g, a number average molecular weight of 17,589, and a weight average molecular weight of 113,550. Degradation test After 3 months, the weight loss was 28% and dissolved in methyl ethyl ketone and toluene solvent.
Claims (9)
A first ester exchange reaction of the acidic mixture in the mixture with an aliphatic glycol, followed by a second esterification reaction with a polylactide compound of formula (1) In the reaction product, the aliphatic / aromatic oligomer subjected to the second reaction through the tertiary polycondensation reaction is subjected to condensation polymerization while removing excess glycol under high vacuum,
Up to 5 parts by weight of a carbodiimide of the following formula (2), or a mixture thereof, based on 100 parts by weight of the total weight of the acidic mixture and the aliphatic glycol, is further added during the first transesterification reaction. An excellent polylactide-based aliphatic / aromatic copolyester resin composition:
(1) - [OCH 3 CHOC] n -
(2) R 1 -N = C = NR 2
In this formula,
n is an integer of 2 to 2000,
R 1 and R 2 are the same or different and each is an alkyl group having 4 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109721976A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | Poly (lactic acid) composition and preparation method thereof and biaxially stretched polylactic acid film and preparation method thereof |
| CN109721699A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | Polylactic acid copolyesters and preparation method thereof and biaxially stretched polylactic acid copolyester film and preparation method thereof |
| KR102276291B1 (en) * | 2020-07-24 | 2021-07-12 | 남경보 | Biodegradable polycyclohexadimethyleneterephthalate resin and the manufacturing method thereof |
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| KR20110082702A (en) * | 2010-01-12 | 2011-07-20 | 주식회사 그린케미칼 | Biodegradable resin composition, method for production thereof and biodegradable film therefrom |
| KR101068030B1 (en) * | 2011-06-03 | 2011-09-28 | 주식회사 지오솔테크 | Hydrolysis resistant and biodegradable aliphatic/aromatic copolyester resin composition |
| KR20120113883A (en) * | 2011-04-06 | 2012-10-16 | 에스케이케미칼주식회사 | Polyester binder resin for coating application and coating composition including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20110082702A (en) * | 2010-01-12 | 2011-07-20 | 주식회사 그린케미칼 | Biodegradable resin composition, method for production thereof and biodegradable film therefrom |
| KR20120113883A (en) * | 2011-04-06 | 2012-10-16 | 에스케이케미칼주식회사 | Polyester binder resin for coating application and coating composition including the same |
| KR101068030B1 (en) * | 2011-06-03 | 2011-09-28 | 주식회사 지오솔테크 | Hydrolysis resistant and biodegradable aliphatic/aromatic copolyester resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109721976A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | Poly (lactic acid) composition and preparation method thereof and biaxially stretched polylactic acid film and preparation method thereof |
| CN109721699A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | Polylactic acid copolyesters and preparation method thereof and biaxially stretched polylactic acid copolyester film and preparation method thereof |
| CN109721699B (en) * | 2017-10-31 | 2022-03-29 | 中国石油化工股份有限公司 | Polylactic acid copolyester and preparation method thereof, and biaxially stretched polylactic acid copolyester film and preparation method thereof |
| KR102276291B1 (en) * | 2020-07-24 | 2021-07-12 | 남경보 | Biodegradable polycyclohexadimethyleneterephthalate resin and the manufacturing method thereof |
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