WO2014104861A1

WO2014104861A1 - Environmentally friendly plasticizer, and resin composition using same

Info

Publication number: WO2014104861A1
Application number: PCT/KR2013/012413
Authority: WO
Inventors: 최진일; 안은숙
Original assignee: 한국화학연구원
Priority date: 2012-12-31
Filing date: 2013-12-31
Publication date: 2014-07-03

Abstract

The present invention provides a plasticizer for a biodegradable resin composition which can increase compatibility with a resin while maintaining the biodegradability of a resin and improving mechanical properties such as elongation, tensile strength, impact resistance and the like, has excellent thermal stability, flexibility, transparency, adhesion and cold resistance, particularly can be applied to a biodegradable resin of various fields due to a wide process temperature, generates no bleed-out, and has remarkable durability.

Description

Eco-friendly plasticizer and resin composition using same

The present invention relates to an environment-friendly plasticizer and a resin composition comprising the plasticizer.

In the field of polymers, biodegradable resins that decompose under the natural environment have been attracting attention with physical property requirements for compatibility and biodegradability in terms of environmental protection. Accordingly, studies are being actively conducted on polylactic acid, copolymers of lactic acid and other aliphatic hydroxycarboxylic acids, and polyesters derived from aliphatic polyhydric alcohols and aliphatic polyhydric carboxylic acids.

In particular, polylactic acid is mass-produced at low cost by using fermentation method of L-lactic acid as an eco-friendly resin using agricultural products that do not have a problem of resource depletion. However, such polylactic acid has a disadvantage in that it is hard, brittle, inflexible, and poor in workability because of its high crystallinity and rigid molecular structure. Therefore, it is not suitable for the use which requires flexibility, such as a film and a packaging material by itself.

As a method for softening polylactic acid, methods such as addition of a plasticizer, blending of soft polymers, copolymerization, and the like can be considered. However, when blending a soft polymer, it is limited to the blend of biodegradable resins, such as polybutylene succinate, from a biodegradable viewpoint. Therefore, in order to provide sufficient flexibility, a large amount of addition is required, and as a result, the properties of the polylactic acid may not be sufficiently expressed and may be damaged. In the case of copolymerization, physical properties such as melting point and heat resistance change according to the decrease in crystallinity and glass transition point.

On the other hand, when the plasticizer is added, a bleeding phenomenon may occur in which the plasticizer is soaked on the surface, which may contaminate the surface or adversely affect the transparency of the molded article. Therefore, plasticizer research and development that can prevent the deterioration of properties due to the addition of plasticizers is required.

Patent document 1 (Japanese Patent Laid-Open No. 1992-335060) relates to a composition in which a plasticizer is added to polylactic acid, and it is disclosed that adipic acid diisopropyl and dioctyl sebacate are preferred as the plasticizer, but the plasticizing effect is small and general. Low flexibility for film applications. In addition, although diethyl phthalate is described as a phthalic acid-based plasticizer, diethyl phthalate has a small plasticizing effect, is likely to bleed out, and there is a risk of harmfulness due to volatility.

As described above, plasticizers are added to improve the physical properties of environmentally friendly biodegradable resins, but there are various defects that are poor in processability and limited in mechanical properties. There is a need to develop a plasticizer having excellent mechanical properties and compatibility. In addition, eco-friendly biodegradable resins have room for improvement to be applicable to various ranges of industrial fields by applying such plasticizers.

The present invention has been made to solve the above problems, to ensure the durability, water resistance, and mechanical properties to meet the properties required as a plasticizer for eco-friendly biodegradable resins, having a wide processing temperature range and compatibility An object of the present invention is to provide a plasticizer for biodegradable resins having excellent bleeding and no bleeding phenomenon and a biodegradable resin containing the same.

In order to achieve the above technical object, the present invention provides a plasticizer for a biodegradable resin composition represented by the following formula (1).

[Formula 1]

In this case, in Chemical Formula 1, C _n H _2n is a linear or branched (C 2 -C 18) alkylene group, and m is an integer of 1 to 20.

In the plasticizer for a biodegradable resin composition according to an embodiment of the present invention, the plasticizer includes any one or more selected from compounds represented by the following Chemical Formulas 11 to 15.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In addition, the present invention provides a plasticizer for a biodegradable resin composition represented by the following formula (2).

[Formula 2]

In this Formula 2, R ₁ and R ₂ are independently a linear or branched (C 1 -C 18) alkyl group, C _n H _2n is a straight or branched (C 2 -C 18) alkylene group, and m is 1 to It is an integer of 20.

In the plasticizer for a biodegradable resin composition according to an embodiment of the present invention, the plasticizer includes any one or more selected from compounds represented by the following Chemical Formulas 21 to 23.

[Formula 21]

[Formula 22]

[Formula 23]

In addition, the present invention provides a plasticizer for a biodegradable resin composition represented by the following formula (3).

[Formula 3]

In this Formula 3, R ₃ and R ₄ are independently a linear or branched (C 1 -C 18) alkyl group, C _n H _2n is a straight or branched (C 2 -C 18) alkylene group, and m is 1 to 1 It is an integer of 20.

In the plasticizer for a biodegradable resin composition according to an embodiment of the present invention, the plasticizer includes any one or more selected from compounds represented by the following Chemical Formulas 31 to 34.

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

In the plasticizer for a biodegradable resin composition according to an embodiment of the present invention, the biodegradable resin is selected from the group consisting of polylactic acid, polycaprolactone, polyglycolic acid, polycarbonate, polysuccinate and polybutylene succinate It includes any one or more.

The present invention is a biodegradable resin comprising at least one resin selected from the group consisting of polylactic acid, polycaprolactone, polyglycolic acid, polycarbonate, polybutylene succinate and aliphatic polyester and a plasticizer represented by the following Chemical Formula 1 To provide a composition.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 to 3, C _n H _2n is a linear or branched (C2-C18) alkylene group, R ₁ to R ₄ is a linear or branched (C1-C18) alkyl group independently of each other, m is 1 Is an integer of 20 to.)

In the biodegradable resin composition according to an embodiment of the present invention, the composition includes 1 to 50 parts by weight of a plasticizer represented by Chemical Formula 1 based on 100 parts by weight of the resin.

In the biodegradable resin composition according to an embodiment of the present invention, the resin includes a weight average molecular weight of 50,000 to 300,000 g / mol.

The plasticizer according to the present invention can improve the compatibility with the resin while improving the mechanical properties such as elongation, tensile strength and impact resistance while maintaining the biodegradability of the resin, and has excellent thermal stability, flexibility, transparency, adhesion, and cold resistance. There is this. In addition, the processing temperature range is wide, excellent workability, can be applied to biodegradable resins of various fields, bleed out does not occur has excellent durability and environmentally friendly advantages.

In addition, the biodegradable resin composition comprising the plasticizer of the present invention is excellent in biodegradability, environmentally friendly, excellent in biocompatibility and bioabsorption, but also compatible with the resin, thermal stability, elongation, strength, flexibility, transparency, durability, etc. There is an advantage of excellent physical properties.

The present invention provides a plasticizer for a biodegradable resin composition and a biodegradable resin comprising the same, while maintaining biodegradability while improving compatibility and improving processability, and having excellent flexibility, durability, and mechanical properties. Provide the plasticizer displayed.

[Formula 1]

The plasticizer represented by Chemical Formula 1 according to the present invention may be obtained in one embodiment by a reaction mechanism shown in Scheme 1 below.

Scheme 1

In Scheme 1, the reaction solvent may be THF, but is not necessarily limited thereto.

More specifically, the plasticizer may be a specific compound represented by the following Chemical Formulas 11 to 15 (in the present invention, the Chemical Formulas 11 to 15 refer to Compounds 11 to 15, respectively), and the following compounds do not limit the present invention.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In Chemical Formulas 13 to 15 in the present invention

Is (C1-C20) alkyl, wherein the alkyl includes straight chain alkyl or branched alkyl.

[Formula 2]

The plasticizer represented by Chemical Formula 2 according to the present invention may be obtained in one embodiment by a reaction mechanism shown in Scheme 2 below. The plasticizer compound represented by Chemical Formula 2 may be obtained through a gas decomposition reaction and an esterification reaction, and specific compounds represented by the following Chemical Formulas 21 to 23 may be used to perform an oxa-Michael reaction using an alcohol as a Michael donor. It can be obtained through.

Scheme 2

In Scheme 2, the reaction solvent may be THF, but is not necessarily limited thereto.

More specifically, the plasticizer represented by Chemical Formula 2 may be a specific compound such as Chemical Formulas 21 to 23 (in the present invention, Chemical Formulas 21 to 23 may refer to Compounds 21 to 23, respectively), and the following compounds may limit the present invention. It is not.

The plasticizer represented by Chemical Formula 2 of the present invention includes any one or more selected from compounds represented by the following Chemical Formulas 21 to 23.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 3]

The plasticizer represented by Chemical Formula 3 according to the present invention may be obtained by, in one embodiment, a reaction mechanism shown in Scheme 3 below.

Scheme 3

In Scheme 3, the reaction solvent may be THF, but is not necessarily limited thereto.

More specifically, the plasticizer represented by Chemical Formula 3 may be a specific compound such as Chemical Formulas 31 to 34 (in the present invention, Chemical Formulas 31 to 34 may refer to Compounds 31 to 34, respectively), and the following compounds limit the present invention. It is not.

The plasticizer represented by Chemical Formula 3 of the present invention includes any one or more selected from compounds represented by the following Chemical Formulas 31 to 34.

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

In Chemical Formula 34 in the present invention

The plasticizer of the present invention may be used for a biodegradable resin, it is preferable to use polylactide (PLA) as the resin, more preferably using PLA or poly-L-lactic acid (PLLA) resin It is good.

The PLA has excellent biodegradability and is a circulating resource material, having intermediate properties between polyethylene terephthalate (PET) resin and polyamide (PA) resin, and directly condensing lactic acid or ring-opening lactide. It can be prepared by polymerization (ring opening polymerization) (ROP). The lactic acid and the lactide have the isomers of L-, D- and meso type, and the crystallinity, melting point, mechanical properties, etc., vary depending on the composition. In particular, the L-lactide polymer is crystalline compared to the amorphous D-form polymer and has excellent mechanical properties due to its crystallinity.

The PLA is applied to various fields as an environmentally friendly resin material, but has a disadvantage in that it is easy to decompose when heated at a high temperature for a long time, the workability is inferior, and after the processing is weak, it is easily broken due to its weak flexibility and impact resistance is required to overcome this, Thus, polyethylene glycol, citric acid ester, etc., which are compatible with PLA, may be used as a plasticizer, but due to the bleeding phenomenon, durability is limited, and thus its use is limited. In particular, in the case of polyethylene glycol, there is an alcohol group (-OH) at both ends, which may adversely affect the resin by transesterification with PLA, which is a polyester when heated to a high temperature. Therefore, glycols, which are structurally expected to have excellent compatibility with PLA resins, do not react with PLA when heated as a starting material, and by introducing ester groups having better affinity with PLA than alkyl groups at the ends of the glycol The compatibility and stability is higher than that of colloids, and in particular, by introducing a t-butyl group as a bulky group at both ends, the wedge action can be induced to reduce the bleeding phenomenon.

The present invention provides a biodegradable resin composition comprising at least one resin selected from the group consisting of polylactic acid, polycaprolactone, polybutylene succinate and aliphatic polyester and a plasticizer represented by the following formula (1).

[Formula 1]

[Formula 2]

[Formula 3]

The biodegradable resin composition comprising the plasticizer of the present invention may be prepared by a method well known in the art, for example, it is added to a resin having a sufficiently high molecular weight through crosslinking or curing or added to a precursor in oligomer form and then cured. It is known to proceed.

In the biodegradable resin composition according to an embodiment of the present invention, in order to express excellent compatibility of the plasticizer represented by Chemical Formula 1, PLA (poly lactic acid) or PLLA (poly L-lactic acid) is used as a phase separation resin. The polylactic acid may include Ingeo 4032D manufactured by NatureWorks, and the like, but is not necessarily limited to the biodegradable resin.

In the present invention, the weight average molecular weight of the biodegradable resin is preferably used 50,000 to 300,000 g / mol.

In addition, the composition comprises 1 to 50 parts by weight of the plasticizer represented by Formula 1 based on 100 parts by weight of the resin. The plasticizer preferably contains 5 to 30 parts by weight, more preferably 10 to 20 parts by weight.

The biodegradable resin composition according to the present invention is superior in physical properties of hardness, tensile strength, elongation, modulus of elasticity, bleeding and glass transition temperature as compared to the resin composition to which a plasticizer is added. Therefore, by producing a plastic using the biodegradable resin composition comprising the plasticizer of the present invention, excellent tensile strength and low glass transition temperature, excellent molding to the film, and also maintains flexibility at low temperatures, so that the film or artificial leather sheet and It is possible to process into the same flexible products, and excellent compatibility with the resins, bleeding does not occur, and the extractability by the organic solvent or water is lowered, the life of products such as films, sheets manufactured using the resin composition This can be extended.

Hereinafter, the specific examples and comparative examples will be described in more detail the configuration and effects of the present invention, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention. In Examples and Comparative Examples, physical properties were evaluated in the following manner.

(evaluation)

(1) Glass transition temperature (Tg) and melting point (Tm)

Tg was measured in the range of -30 ~ 240 ℃ using DSC. Tg is highly related to the compatibility of plasticizers.

(2) tensile strength and elongation

It measured according to ASTM D882-10 method. After pulling a film having a thickness of 40 μm, a width of 10 mm, and a length of 50 mm at a crosshead speed of 50 mm / min, the points at which the specimens were cut were measured.

(Example 1)

Acrylonitrile (145 ml, 2190) with ethylene glycol (60.0 ml, 957 mmol), KOH (2.00 g, 34 mmol), THF (300 ml) in water (3.0 ml), kept below 20 ^° C. mmol) was added dropwise for 4 hours and then stirred at room temperature for 16 hours. After confirming that the reaction was completed by GC, the solvent was concentrated under reduced pressure, and the residue was dissolved in 250 ml of dichloromethane (CH ₂ Cl ₂ ), washed with 50 ml of water and 30 ml of saturated salt, and 5.0 g of sodium sulfate (Na ₂ SO ₄ ). It was dried using, filtered and concentrated under reduced pressure to give a yellow liquid. The obtained Crude compound was purified by vacuum distillation to give a colorless transparent liquid ( Compound 11 , 82.7 g). (Yield 73%)

Boiling point: 181 ^o C / 1.2 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ3.73 (t, J = 6.3 Hz, 4H, 2 CH ₂ CH ₂ CN), 3.68 (s, 4H, 2CH ₂ O), 2.62 (t, J = 6.3 Hz , 4H, 2CH ₂ CN).

(Example 2)

Acrylonitrile (85 ml, 1284 mmol) was maintained in a THF (250 ml) solution of 1,4-butanediol (50.0 ml, 560 mmol), KOH (1.70 g, 29 mmol) at 20 ^o C or less. It was added dropwise for 2 hours and then stirred at room temperature for 16 hours. After confirming that the reaction was completed by GC, the solvent was concentrated under reduced pressure, and the residue was dissolved in 250 ml of dichloromethane (CH ₂ Cl ₂ ), washed with 50 ml of water and 30 ml of saturated salt, and 5.0 g of sodium sulfate (Na ₂ SO ₄ ). It was dried using, filtered and concentrated under reduced pressure to give a yellow liquid. The resulting Crude compound was purified by vacuum distillation to give a colorless transparent liquid ( Compound 12 , 76.5 g). (Yield 70%)

Boiling point: 167 ^o C / 0.1 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ 3.64 (t, J = 6.3 Hz, 4H, 2 CH ₂ CH ₂ CN), 3.52 (m, 4H, 2CH ₂ 0), 2.59 (t, J = 6.3 Hz , 4H, 2CH ₂ CN), 1.68 (m, 4H, 2 CH ₂ CH ₂ 0).

(Example 3)

Propylene glycol (50.0 ml, 663 mmol), KOH (4.00 g, 68 mmol), THF (200 ml) solution of water (6.0 ml) with acrylonitrile (95.0 ml, 1435) while maintaining 20 ^o C or less. mmol) was added dropwise for 4 hours and then stirred at room temperature for 24 hours. After confirming that the reaction was completed by GC, the solvent was concentrated under reduced pressure, and the residue was dissolved in 300 ml of dichloromethane (CH ₂ Cl ₂ ), washed with 50 ml of water and 50 ml of saturated salt, and 5.0 g of sodium sulfate (Na ₂ SO ₄ ). It was dried using, filtered and concentrated under reduced pressure to give a yellow liquid. The resulting Crude compound was purified by vacuum distillation to give a colorless transparent liquid ( Compound 13 , 82.7 g). (Yield 68%)

Boiling point: 184 ^o C / 0.5 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ 3.77 (t, J = 6.2 Hz, 4H, 2 CH ₂ CH ₂ CN), 3.71 (m, 1H, O CH HCH), 3.49 (m, 2H, O C H H CH and OCHH CH ), 2.62 (t, J = 6.2 Hz, 4H, 2CH ₂ CN), 1.17 (d, 3H, J = 6.4 Hz, CH ₃ ).

(Example 4)

Dipropylene glycol mixture (Mixture of isomers, 70.0 ml, 528 mmol), KOH (1.50 g, 25 mmol), THF (300 ml) solution of water (2.3 ml) while keeping the temperature below 20 ^o C Lyle (77.0 ml, 1162 mmol) was added dropwise for 4 hours and then stirred at room temperature for 24 hours. After confirming that the reaction was completed by GC, the solvent was concentrated under reduced pressure, and the residue was dissolved in 400 ml of dichloromethane (CH ₂ Cl ₂ ), washed with 50 ml of water and 50 ml of saturated salt, and 5.0 g of sodium sulfate (Na ₂ SO ₄ ). It was dried using, filtered and concentrated under reduced pressure to give a yellow liquid. The obtained Crude compound was purified by vacuum distillation to give a colorless transparent liquid ( Compound 14 , 62.9 g). (Yield 50%)

Boiling point: 191 ^o C / 1.6 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ 3.7 3.58 (m, 6H, 2 CH ₂ CH ₂ CN and 2OC H HCH), 3.49 3.33 (m, 4H, 2OCH H CH and 2OCHHC H ), 2.57 2.51 (m , 4H, 2CH ₂ CN), 1.10 1.07 (m, 6H, 2CH ₃ ).

(Example 5)

Tripropylene glycol mixture (Mixture of isomers, 100 ml, 505 mmol), KOH (1.00 g, 16.9 mmol), THF (150 ml) solution of water (1.5 ml) acrylonitrile while maintaining 20 ^° C. or less Lyle (77.0 ml, 1162 mmol) was added dropwise for 2 hours and then stirred at room temperature for 24 hours. After confirming that the reaction was completed by GC, the solvent was concentrated under reduced pressure, and the residue was dissolved in 200 ml of dichloromethane (CH ₂ Cl ₂ ), washed with 50 ml of water and 50 ml of saturated salt, and 5.0 g of sodium sulfate (Na ₂ SO ₄ ). It was dried using, filtered and concentrated under reduced pressure to give a yellow liquid. The obtained Crude compound was purified by vacuum distillation to give a colorless transparent liquid ( Compound 15 , 57.0 g). (Yield 38%)

Boiling point: 187 ^o C / 0.8 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ 3.78 3.60 (m, 7H, 2 CH ₂ CH ₂ CN and 3OC H HCH), 3.54 3.34 (m, 6H, 3OCH H CH and 3OCHHC H ), 2.62 2.56 (m , 4H, 2CH ₂ CN), 1.15 (m, 9H, 3CH ₃ ).

(Example 6)

To a mixture of ethylene glycol (20.0 g, 319 mmol) and KOH (3.800 g, 64 mmol) in THF (300 ml) was added dropwise tert-butyl acrylate (110 ml, 749 mmol) for 1 hour. And stirred at room temperature for 48 hours. The degree of reaction was analyzed by GC. The residue obtained by concentrating the reaction mixture was concentrated in 250 ml of dichloromethane (CH ₂ Cl ₂ ), washed with saturated brine (50 ml, twice), dried using 5.0 g of sodium sulfate (Na ₂ SO ₄ ), and then decompressed. Concentration gave a crude compound. The crude compound obtained was distilled under vacuum (1.7 mmHg, 158 占 폚) to obtain a colorless transparent liquid ( Compound 21 , 46.1 g). (Yield: 46%)

Boiling point: 158 ° C./1.7 mm Hg; ¹ H nmr (300 MHz, CDCl ₃ ) δ3.70 (t, J = 6.6 Hz, 4H, 2 CH ₂ CH ₂ CO), 3.58 (s, 4H, 2CH ₂ O), 2.49 (t, J = 6.6 Hz , 4H, 2CH ₂ CO), 1.44 (s, 18H, 2C (CH ₃ ) ₃ ).

(Example 7)

To a mixture of butanediol (18.0 ml, 202 mmol) and KOH (3.50 g, 59.3 mmol) in THF (200 ml) was added dropwise tert-butyl acrylate (70.0 ml, 476 mmol) for 1 hour. Stirred for 24 h. The degree of reaction was analyzed by GC. The reaction mixture was concentrated under reduced pressure, and the residue was dissolved in 200 ml of dichloromethane (CH ₂ Cl ₂ ), washed with saturated brine (50 ml, twice), dried using 5.0 g of sodium sulfate (Na ₂ SO ₄ ), and dried under reduced pressure. Concentration gave a crude compound. The crude compound obtained was distilled under vacuum (1.5 mmHg, 155 ° C) to obtain a colorless transparent liquid ( Compound 22 , 106.6 g). (Yield: 80%)

Boiling point: 155 ^o C / 1.5 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ 3.64 (t, J = 6.5 Hz, 4H, 2 CH ₂ CH ₂ CO), 3.43 (m, 4H, 2CH ₂ 0), 2.47 (t, J = 6.5 Hz , 4H, 2CH ₂ CO), 1.60 (m, 4H, 2 CH ₂ CH ₂ 0), 1.45 (s, 18H, 2C (CH ₃ ) ₃ ).

(Example 8)

To a mixture of diethylene glycol (20.0 ml, 209 mmol) and KOH (3.20 g, 54 mmol) in THF (200 ml) was added dropwise tert- butyl acrylate (75.0 ml, 505 mmol) for 1 hour. After that, the mixture was stirred at room temperature for 20 hours. The degree of reaction was analyzed by GC. The reaction mixture was concentrated under reduced pressure, and the residue was dissolved in 200 ml of dichloromethane (CH ₂ Cl ₂ ), washed with saturated brine (50 ml, twice), dried using 5.0 g of sodium sulfate (Na ₂ SO ₄ ), and dried under reduced pressure. Concentration gave a crude compound. The crude compound obtained was distilled under vacuum (0.8 mmHg, 173 ° C) to give a colorless transparent liquid ( Compound 23 , 41.2 g). (Yield: 54%)

Boiling point: 173 ° C./0.8 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ3.70 (t, J = 6.6 Hz, 4H, 2 CH ₂ CH ₂ CO), 3.61 (m, 8H, 4CH ₂ 0), 2.49 (t, J = 6.6 Hz , 4H, 2CH ₂ CO), 1.44 (s, 18H, 2C (CH ₃ ) ₃ ).

(Example 9)

To a THF (150 ml) mixture of Carbitol (55.0 ml, 402 mmol), KOH (1.00 g, 16.9 mmol) was added tert- butyl acrylate (50.0 ml, 337 mmol) for 30 minutes. After dropwise addition, the mixture was stirred at room temperature for 17 hours. The degree of reaction was analyzed by GC. The residue obtained by concentrating the reaction mixture was dissolved in 300 ml of dichloromethane (CH ₂ Cl ₂ ), washed with water (50 ml) and saturated brine (50 ml) and dried using 5.0 g of sodium sulfate (Na ₂ SO ₄ ). After concentration under reduced pressure to give a crude compound. The crude compound was purified by vacuum distillation to give a colorless transparent liquid ( Compound 31 , 52.2 g). (Yield 59%)

Boiling point: 155 ^o C / 1.4 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ3.71 (t, J = 6.6 Hz, 2H, CH ₂ CH ₂ CO), 3.66-3.57 (m, 8H, 4CH ₂ O), 3.53 (q, J = 7.0 Hz, 2H, CH ₂ CH ₃ ), 2.51 (t, J = 6.6 Hz, 2H, CH ₂ CO), 1.45 (s, 9H, C (CH ₃ ) ₃ ), 1.21 (t, J = 7.0 Hz, 3H , CH ₃ ).

(Example 10)

Tert- butyl acrylate (50.0) in THF (150 ml) mixture of diethylene glycol butyl ether (68.0 ml, 403 mmol), KOH (1.00 g, 16.9 mmol) ml, 337 mmol) was added dropwise for 30 minutes, followed by stirring at room temperature for 16 hours. The degree of reaction was analyzed by GC. The residue obtained by concentrating the reaction mixture was dissolved in 300 ml of dichloromethane (CH ₂ Cl ₂ ), washed with water (50 ml) and saturated brine (50 ml) and dried using 5.0 g of sodium sulfate (Na ₂ SO ₄ ). After concentration under reduced pressure to give a crude compound. The crude compound was purified by vacuum distillation to give a colorless transparent liquid ( Compound 32 , 64.0 g). (66% yield)

Boiling point: 137 ^o C / 1.2 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ3.71 (t, J = 6.6 Hz, 2H, CH ₂ CH ₂ CO), 3.65-3.57 (m, 8H, 4CH ₂ O), 3.46 (t, J = 6.7 Hz, 2H, O CH ₂ CH ₂ CH ₂ CH ₃ ), 2.51 (t, J = 6.6 Hz, 2H, CH ₂ CO), 1.56 (m, 2H, OCH ₂ CH ₂ CH ₂ CH ₃ ), 1.45 (s , 9H, C (CH ₃ ) ₃ ), 1.35 (m, 2H, OCH ₂ CH ₂ CH ₂ CH ₃ ), 0.91 (t, J = 7.4 Hz, 3H, CH ₃ ).

(Example 11)

Tert- butyl acrylate (di (propylene glycol) propyl ether, mixture of isomers} (90.0 ml, 465 mmol), THF (250 ml) mixture of KOH (3.00 g, 50.8 mmol) 80.0 ml, 539 mmol) was added dropwise for 1 hour and stirred at room temperature for 20 hours. The degree of reaction was analyzed by GC. The residue obtained by concentrating the reaction mixture under reduced pressure was dissolved in 500 ml of dichloromethane (CH ₂ Cl ₂ ), washed with water (50 ml) and saturated brine (50 ml) and dried using 5.0 g of sodium sulfate (Na ₂ SO ₄ ). After concentration under reduced pressure to give a crude compound. The crude compound obtained was purified by vacuum distillation to give a colorless transparent liquid ( Compound 33 , 77.8 g). (Yield 55%)

Boiling point: 168 ^o C / 2.1 mmHg; ¹ H nmr (300 MHz, CDCl ₃ ) δ 3.75 (t, J = 6.6 Hz, 2H, CH ₂ CH ₂ CO), 3.63-3.30 (m, 8H, 3CH ₂ O and 2CHO), 2.47 (t, J = 6.6 Hz, 2H, CH ₂ CO), 1.58 (m, 2H, CH ₂ CH ₃ ), 1.45 (s, 9H, C (CH ₃ ) ₃ ), 1.14 (br d, J = 6.2 Hz, 6H, 2CH ₃ ), 0.91 (t, J = 7.4 Hz, 3H, CH ₃ ).

(Comparative Example 1)

The plasticizer was not used as a control to compare the plasticizer and the plasticizer according to the embodiment of the present invention.

(Comparative Example 2)

In order to compare the plasticizer and the plasticizing performance according to the embodiment of the present invention, PEG 400 (poly (ethylene glycol), Mn = 400, Aldrich) was used as a control.

(Manufacture example 1)

Biodegradable Resin Composition

In order to evaluate the performance of the plasticizers prepared in Examples 1 to 11, a plasticizer was added to 3.60 g of polylactic acid (MW: 207,000 g / mol, Density: 1.25 g / cm ³ ) in the same composition as in Table 1 to dichloromethane (CH ₂ Cl ₂ ) was added to 100 ml to form a mixed solution, which was stirred for 16 hours at room temperature. 26 ml of the stirred solution was poured onto a glass plate having a size of 12 cm x 17 cm using a silicon wall and dried at 20 ° C. to 25 ° C. for one week to prepare a film having a thickness of 40 μm. 10 mm x 15 mm specimens were prepared using this film, and stored at 23 ° C. and 50% RH for 48 hours, followed by test measurements.

Table 1

division	Plasticizer content (% by weight)	Tensile Strength (MPa)	Elongation (%)	Tg (℃)	Tm (℃)
Example 1	10	-	-	31.4	149.0
Example 1	20	-	-	7.3	140.8
Example 2	10	28.0	303	13.2	148.7
Example 2	20	18.4	278	-	140.9
Example 3	10	-	-	29.6	148.6
Example 3	20	-	-	16.0	144.3
Example 4	10	26.3	237	28.1	149.0
Example 4	20	14.2	175	8.0	144.4
Example 5	10	31.5	248	28.9	150.5
Example 5	20	23.6	256	3.6	146.6
Example 6	10	28.5	202	36.6	151.1
Example 6	20	20.8	236	16.7	146.7
Example 7	10	35.3	206	31.4	150.3
Example 7	20	24.2	258	-	146.5
Example 8	10	32.4	225	33.0	151.4
Example 8	20	22.6	251	4.5	148.8
Example 9	10	27.4	250	27.9	150.7
Example 9	20	21.2	270	-	146.4
Example 10	10	28.5	254	27.5	150.2
Example 10	20	23.6	258	-	148.4
Example 11	10	30.4	221	32.8	151.4
Example 11	20	23.8	209	-	147.9
Comparative Example 1	0	64.2	5	52.3	155.8
Comparative Example 2	10	36.2	44	29.3	152.0
Comparative Example 2	20	26.2	206	-	147.1

When the plasticizer is added as shown in the example of Table 1, the Tg is lowered to increase flexibility, thereby remarkably improving the brittleness of PLA, and the Tm is lower than when the plasticizer is not used, thereby widening the processing temperature range. Decomposition did not occur at a lower temperature, and it was confirmed that the moldability could be stably improved, thereby significantly improving workability.

In the present invention as described above has been described by specific embodiments and limited embodiments and drawings, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, the present invention Those skilled in the art can make various modifications and variations from this description.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the claims as well as the following claims will belong to the scope of the present invention. .

Claims

Biodegradation comprising any one or more resins selected from the group consisting of polylactic acid, polycaprolactone, polyglycolic acid, polycarbonate, polybutylene succinate and aliphatic polyester and any plasticizer selected from the following Chemical Formulas 1 to 3 Resin composition.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 to 3, C n H 2n is a linear or branched (C2-C18) alkylene group, R 1 to R 4 is a linear or branched (C1-C18) alkyl group independently of each other, m is 1 Is an integer of 20 to.)
The method of claim 1,

The resin composition is a biodegradable resin composition comprising 1 to 50 parts by weight of any one of the plasticizers selected from Formulas 1 to 3 with respect to 100 parts by weight of the resin.
The method of claim 1,

The resin is a biodegradable resin composition comprising a weight average molecular weight of 50,000 to 300,000 g / mol.
Plasticizer for biodegradable resin composition represented by following formula (1).

[Formula 1]

(In Formula 1, C n H 2n is a straight or branched (C 2 -C 18) alkylene group, m is an integer of 1 to 20.)
The method of claim 4, wherein

The plasticizer is a plasticizer for a biodegradable resin composition comprising any one or more selected from compounds represented by the following formulas (11) to (15).

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]
Plasticizer for biodegradable resin composition represented by following formula (2).

[Formula 2]

In Formula 2, R 1 and R 2 are each independently a linear or branched (C 1 -C 18) alkyl group, C n H 2n is a straight or branched (C 2 -C 18) alkylene group, and m is 1 to 20 Is an integer of)
The method of claim 6,

The plasticizer is a plasticizer for a biodegradable resin composition comprising any one or more selected from compounds represented by the following formulas (21) to (23).

[Formula 21]

[Formula 22]

[Formula 23]
Plasticizer for biodegradable resin composition represented by following formula (3).

[Formula 3]

(In Formula 3, R 3 and R 4 are independently a linear or branched (C1-C18) alkyl group, C n H 2n is a straight or branched (C2-C18) alkylene group, m is 1 to 20 Is an integer of)
The method of claim 8,

The plasticizer is a plasticizer for a biodegradable resin composition comprising any one or more selected from compounds represented by the following formulas (31) to (34).

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]
The method according to any one of claims 4, 6 and 8,

The biodegradable resin is a plasticizer for biodegradable resin composition comprising any one or more selected from the group consisting of polylactic acid, polycaprolactone, polyglycolic acid, polycarbonate, polysuccinate and polybutylene succinate.