KR102306907B1 - Toughened PLA compositions containing polyamide 11 based thermoplastic elastomer and preparation method thereof - Google Patents

Abstract

The present invention relates to a method for preparing a toughened PLA composition containing an elastomer based on polyamide 11. More specifically, a polyamide 11-based elastomer prepared by condensation reaction of a diamine terminal group-containing polyamide 11 prepared from a vegetable oil-derived 11-aminoundecanoic acid derivative with a dimer acid derivative prepared from a vegetable oil-derived fatty acid methyl ester was prepared. And it relates to a toughened PLA composition prepared by blending it with PLA. The polyamide elastomer alternating copolymer according to the present invention has improved impact strength depending on the heating temperature, so it can be used in various ways as automobile materials, electrical and electronic materials, hot melt adhesives, etc. In particular, the polyamide 11-based copolymer according to the present invention Elastomer alternating copolymer resin is a very effective thermoplastic elastomer to solve the brittle problem of PLA and improve toughness through blending with PLA.

Description

Toughened PLA compositions containing polyamide 11 based thermoplastic elastomer and preparation method thereof

The present invention relates to a toughened PLA composition containing an elastomer based on polyamide 11 and a method for preparing the same. More specifically, a polyamide 11-based elastomer prepared by condensation reaction of a diamine terminal group-containing polyamide 11 prepared from a vegetable oil-derived 11-aminoundecanoic acid derivative with a dimer acid derivative prepared from a vegetable oil-derived fatty acid methyl ester was prepared. And it relates to a toughened PLA composition prepared by blending it with PLA, and a manufacturing method thereof.

Recently, in order to solve problems such as global warming and secure sustainable growth, many studies are being actively conducted to reduce greenhouse gas and replace petrochemical raw materials. As a solution to this problem, biomass-derived monomer polymerization type bioplastics have similar physical properties and application fields to existing plastics, so they have ease of market entry when developed, so that the commercialization potential is higher than any other bioplastics.

Among these bioplastics, PLA (Poly(lactic acid)) material is a bioplastic that Cargill of the United States succeeded in commercializing jointly with Dow Chemical in 2001, and is currently recognized as the most successful bioplastic. It is a bioplastic produced from 100% biomass as a material produced by producing lactic acid through a chemical process, converting lactic acid to lactide through a chemical process, and then polymerization.

Characteristics of this PLA material are excellent rigidity, good transparency, but low impact strength due to a rigid chain structure and low heat resistance due to low crystallization rate. By controlling the relative proportions, it is possible to prepare PLA with a glass transition temperature (Tg) of about 50 °C to 80 °C and a melting point of 130 °C to 180 °C, or PLA with about 40% or less crystalline, but poly-L- Because the elongation at break of lactic acid (PLLA) is only a few percent, and the glass transition temperature of PLLA polymers is much higher than room temperature, PLLA moldings tend to be brittle and glassy at room temperature.

Various studies have been published to solve the brittle problem of PLA and improve toughness. For example, as a traditional blending method that improves the low impact strength and heat resistance of PLA by mixing PLA with other PLA or other copolymers, there have been many studies on blending PLA with petroleum-based resins such as polyester or polycarbonate. The polycarbonate/PLA blend has high impact strength and heat resistance, and Samsung Electronics has already applied the PLA/PC blend commercially to mobile phone housings in 2008.

In addition, studies have been conducted on PLA/polyolefin blends that prevent hydrolysis by preventing the moisture absorption of PLA due to the moisture absorption resistance of polyolefins. After that, Sharp in Japan conducted a study to improve the compatibility of PLA and polyolefin. However, in general, there was a limit to improving the mechanical properties of the PLA/polyolefin blend due to the low compatibility between the two components. -Hydroxy valerate (PHBV), poly-R-3-hydroxy butyrate (PHB), poly-R,S-3-hydroxy butyrate, poly-3-hydroxy octanoate, poly(hexamethylene succinate) ), poly(butylene succinate), poly(ethylene/butylene succinate), poly(ethylene oxide), poly(phosphazene), poly(sebacic anhydride), poly(vinyl alcohol) and poly(vinyl acetate) ) have been reported. A mixture of PLA containing several components has also been reported. For example, U.S. Patent No. 5,939,467 describes a molded article made of a mixture of PLA, polyhydroxy alkanoate and polyurethane (or polycaprolactone), In addition, although the above-listed molded article possesses many properties, the polymer does not mix properly during blending, and undesirable phase separation occurs, which also exhibits poor mechanical properties.

In general, elastomers added to impart toughness to PLA or other polymers must meet several criteria. First, the elastomer should be well distributed in a small area (typically 0.1-1.0 μm) in the polymer matrix, have good interfacial adhesion with PLA, and the glass transition temperature should be at least ^{20 °C lower than the test/use temperature.} The added elastomer must not have a low molecular weight, the elastomer must not be miscible with the matrix polymer, and it must be thermally stable to the PLA processing temperature. It is known that when these factors are met, PLA molded bodies with improved toughness can be manufactured, and generally more toughness is obtained as the amount of added elastomer increases, but usually contains more than a critical level for toughness to be improved. Should be. That is, in blends containing PLA, excellent toughness can be achieved with 15-25% impact modifier, but there is little improvement in toughness until 3-5% is added. In blending these polymers, compounding is generally the most practical way for end users to mix impact modifiers with PLA, and their success depends on proper material selection and optimization of mechanical operation.

The addition of impact modifiers or elastomers here does not always give positive results. When rubber, one of the elastomers, is included in a hard polymer, the modulus always decreases in proportion to the amount added. For example, rubber-modified polystyrene (HIPS) has a lower modulus than polystyrene (3000 psi vs. 6000 psi), and is caused by additives or polymer interactions. There is a potential for chemical interactions and decomposition due to color formation or loss of molecular weight, as most reinforced materials are two-phase mixed, so opaque and generally not easily colored in dark colors such as blue or black. do. At this time, using very small rubber particles and matching the refractive index of rubber with that of PLA can help maintain transparency, but the addition of impact modifiers generally increases the viscosity of the system, which will affect processing. It is possible and entails the problem that higher pressure or processing temperature is required.

On the other hand, natural rubber may be a desirable impact modifier for PLA because it is a renewable resource, but it is known to have the disadvantage of not showing the desired toughness improvement, and olefin elastomers such as polybutadiene, ethylene-propylene and EPDM elastomers are not compatible with PLA. However, it is known that functionalized elastomers of these structures can be mixed with PLA to improve toughness, but most of these are petroleum-based materials, and due to future petroleum resource depletion and environmental issues, sustainable resource-based thermoplastic elastomers (Thermoplastics) It is necessary to replace it with an elastomer: TPE) material. However, since the mechanical properties and economic feasibility of TPE materials based on sustainable resources developed so far are inferior to those of petroleum based TPE materials, the entry of TPE materials based on sustainable resources into the market is inevitably limited. The development of a new sustainable resource-based TPE material that can solve these weaknesses is urgently needed.

Meanwhile, among various thermoplastic TPEs, polyamide TPE is an engineering material in the form of a multi-block copolymer in which crystalline polyamide forms a hard segment and rubbery polyether or polyester with a low glass transition temperature forms a soft segment. Therefore, polyamide TPE is capable of strong intermolecular hydrogen bonding, so it has superior formability and physical properties than TPE. The possibility of substituting the material used is increasing.

In particular, among sustainable resource-based polyamides, commercially available nylon 11 derived from biomass is called "Rilsan", developed by Arkema in France and commercialized by Fujitsu in Japan, and used in computers, etc. Polyamide 11 uses castor oil as a raw material and is used in various fields such as automobiles, electronic devices, and sporting goods. forming a market. Polyamide 11 (PA11) is an aliphatic polyamide that can be obtained by condensation polymerization of 11-aminoundecide acid obtained from castor oil. Because it has a low melting point of 185°C compared to other polyamides, it has superior temperature-dependent impact resistance compared to other polyamide resins, excellent hydrolysis resistance, and resistance to many chemicals. As a prior art for a method for producing a polyamide 11 resin prepared from a dimer acid derivative derived from Korean Patent Laid-Open Publication No. 10-2018-0030531, etc., but in this prior art, Regarding the production, there is a disadvantage in that a method for producing an elastomer based on polyamide 11 cannot be provided.

Therefore, an object of the present invention is to prepare a polyamide 11-based elastomer by copolymerizing a polyamide 11 unit having a diamine functional group and a flexible dimer acid derivative based on waste vegetable oil, and blending it with PLA to provide a PLA toughening composition. have.

US Patent No. 5,939,467 Republic of Korea Patent Publication No. 10-2018-0030531

An object of the present invention is to improve the physical properties such as impact strength according to the temperature of the existing vegetable oil-derived polyamide 11 by copolymerizing a polyamide 11 unit having a diamine functional group and a flexible dimer acid derivative based on waste vegetable oil, thereby providing excellent formability and modulus of elasticity. and to prepare an elastomeric alternating copolymer resin based on polyamide 11 having impact resistance.

In addition, in the present invention, it is an object of the present invention to provide a material for automobiles, a material for electrical and electronic devices, and a hot melt adhesive comprising a polyamide 11-based elastomer alternating copolymer resin.

In addition, the present invention intends to provide a PLA toughening composition including an alternating elastomer copolymer based on polyamide 11 and various molded articles using the same.

For the purpose of the present invention described above, the present inventors first prepared polyamide 11 having a diamine end group by copolymerizing an 11-amino undecanoic acid derivative derived from vegetable oil in the presence of a small amount of diamine, and a dimer acid derivative derived from animal or vegetable oil or waste oil and A polyamide 11-based alternating elastomer copolymer was prepared by performing a condensation reaction of It was confirmed that it was very effective and used in the manufacture of a toughened PLA composition.

According to the present invention, a polyamide elastomer alternating copolymer prepared by the condensation reaction of polyamide 11 having a diamine end group prepared from an 11-amino undecanoic acid derivative, which is a metathesis product of vegetable oil, and a dimer acid derivative prepared from a fatty acid methyl ester derived from waste vegetable oil. It can be used in various ways as automobile materials, electrical and electronic materials, hot melt adhesives, etc.

In particular, the polyamide 11-based elastomeric alternating copolymer resin according to the present invention is a thermoplastic elastomer that is very effective in solving the brittle problem of PLA and improving toughness through blending with PLA.

1 shows the tensile strength analysis results of the alternating polyamide 11-based elastomer copolymer prepared according to an embodiment of the present invention.
Figure 2 shows the impact strength analysis results of the polyamide 11-based elastomer alternating copolymer prepared according to an embodiment of the present invention.
3 shows the tensile test results of the toughened polylactic acid composition containing the polyamide 11-based elastomer prepared according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In order to solve the above problems, the present invention provides a method for preparing an alternating polyamide 11-based elastomer copolymer.

The alternating elastomeric copolymer based on polyamide 11 according to an embodiment of the present invention comprises the steps of preparing an 11-amino undecanoic acid derivative; preparing polyamide 11 having a diamine end group by copolymerizing the 11-amino undecanoic acid derivative; and condensing the polyamide 11 having the diamine end group with a dimer acid derivative.

According to one embodiment of the present invention, the 11-amino undecanoic acid derivative may have a chemical structure of the following Chemical Formula 1 derived from vegetable oil.

<Formula 1>

In Formula 1, R ₁ is either H or a C ₁ -C ₁₀ linear, branched or cyclic alkyl group, or a C ₆ -C ₁₀ aryl group or C ₇ -C ₁₀ aralkyl group.

According to one embodiment of the present invention, the step of preparing the polyamide 11 may be a copolymerization reaction of an 11-amino undecanoic acid derivative and a diamine having the chemical structure of Formula 2 below.

<Formula 2>

또는

중 하나이다.In Formula 2, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

one of them

According to an embodiment of the present invention, the dimer acid derivative may have a chemical structure of the following Chemical Formula 3 derived from animal oil, vegetable oil or waste oil.

<Formula 3>

In Formula 3, R ₃ is one of acyclic, monocyclic, bicyclic, aromatic, or C ₁ -C ₆ alkylene group, and R ₄ is H or C ₁ -C ₁₀ straight chain , a branched or cyclic alkyl group.

More specifically, the chemical structure of Formula 3 is selected from the group consisting of lauric fatty acid, myristic fatty acid, palmitic fatty acid, stearic fatty acid, oleic fatty acid, linoleic fatty acid, linoleic fatty acid, vegetable oil, animal oil and waste oil. It may be obtained from one or more fatty acids.

The dimer acid derivative according to an embodiment of the present invention is unsaturated such as _{oleic acid (C 18} H ₃₄ O ₂ ), linoleic acid (C ₁₈ H ₃₂ O ₂ ), and linolenic acid (C ₁₈ H ₃₀ O _{2 ).} Polymerized fatty acids obtained by dimerizing fatty acids by condensation with a catalyst are preferred.

In general, commercially available dimer acids prepared from fatty acids containing oleic acid such as tall oil fatty acid and linoleic acid as main components are C18 monomeric acid (monomer) 5 to 15% by weight, C36 dimer acid (dimer) 60 to 80% by weight, and C54 It has a composition of 10 to 35% by weight of the above higher polymeric acid (trimer).

The dimer acid derivative according to an embodiment of the present invention is more preferably a dicarboxylic acid having 36 carbon atoms obtained from an unsaturated fatty acid having 18 carbon parts (eg, oleic fatty acid, linoleic fatty acid) such as tall oil fatty acid, and the following formula It may be an acyclic, monocyclic, polycyclic or aromatic cyclic type having any one of the chemical structures of 3-1, Formula 3-2, Formula 3-3, and Formula 3-4.

<Formula 3-1>

<Formula 3-2>

<Formula 3-3>

<Formula 3-4>

According to an embodiment of the present invention, the polyamide 11 having a diamine end group may have a chemical structure of the following Chemical Formula 4;

<Formula 4>

또는

중 하나이고, x는 반복단위의 수로 1 내지 100의 정수이다.In Formula 4, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

and x is an integer of 1 to 100 as the number of repeating units.

According to an exemplary embodiment of the present invention, the polyamide 11-based alternating elastomer copolymer may have a chemical structure of Formula 5 below.

<Formula 5>

또는

중 하나이고, R₃는 비환식(acyclic), 단환식(monocyclic), 이환식(bicyclic), 방향족, 또는 C₁-C₆ 알킬렌기 중 하나이며, x는 반복단위의 수로 1 내지 100의 정수이고, n은 반복단위의 수로 2 내지 70의 정수이다.In Formula 5, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

one of, and R ₃ is one of acyclic, monocyclic, bicyclic, aromatic, or C ₁ -C ₆ alkylene group, x is an integer from 1 to 100 as the number of repeating units, n is the number of repeating units It is an integer from 2 to 70.

In addition, the present invention provides an alternating elastomer copolymer based on polyamide 11, characterized in that it has the chemical structure of Chemical Formula 5 below.

<Formula 5>

또는

중 하나이고, R₃는 비환식(acyclic), 단환식(monocyclic), 이환식(bicyclic), 방향족, 또는 C₁-C₆ 알킬렌기 중 하나이며, x는 반복단위의 수로 1 내지 100의 정수이고, n은 반복단위의 수로 2 내지 70의 정수이다.In Formula 5, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

one of, and R ₃ is one of acyclic, monocyclic, bicyclic, aromatic, or C ₁ -C ₆ alkylene group, x is an integer from 1 to 100 as the number of repeating units, n is the number of repeating units It is an integer from 2 to 70.

The polyamide 11-based alternating elastomer copolymer according to an embodiment of the present invention has physical properties such as high heat resistance, dimensional stability, mechanical properties, chemical resistance, and molding processability required in the fields of electric/electronic parts and automobile parts. Since it can be satisfied, it can be used as a material for automobiles, as a material for electrical and electronic use, and as a hot melt adhesive.

Second, the present invention provides a toughening polylactic acid composition containing an elastomer based on polyamide 11 and a method for preparing the same.

According to one embodiment of the present invention, the toughening polylactic acid composition comprises 50 to 90 wt% of poly(lactic acid) (PLA); and 10 to 50 wt% of an alternating polyamide 11-based copolymer prepared by condensation reaction of polyamide 11 having a diamine end group with a dimer acid derivative.

According to an embodiment of the present invention, in the toughening polylactic acid composition, the polylactic acid may be poly-L-lactic acid (PLLA).

According to one embodiment of the present invention, in the toughened polylactic acid composition, the dimer acid derivative is lauric fatty acid, myristic fatty acid, palmitic fatty acid, stearic fatty acid, oleic fatty acid, linoleic fatty acid, linoleic fatty acid, vegetable oil , may be at least one fatty acid derivative selected from the group consisting of animal oil and waste oil, and the content of the dimer acid derivative in the polyamide 11-based alternating elastomer copolymer is more preferably 10 to 40 wt%.

According to one embodiment of the present invention, when the content of the dimer acid derivative of the polyamide 11-based alternating elastomer copolymer is in the range of 10 to 40 wt%, the impact strength of the polyamide 11-based alternating elastomer copolymer is 11-amino undecanoic acid. It has an effect of improving more than twice as much as polyamide 11, which is a homopolymer of the derivative, so it is more preferable for the preparation of a toughened PLA composition.

According to one embodiment of the present invention, the polyamide 11 having a diamine end group is a polyamide 11 prepared through a copolymerization reaction of an 11-amino undecanoic acid derivative having a chemical structure of Formula 1 and a diamine having a chemical structure of Formula 2 below. It may be a toughening polylactic acid composition containing an amide 11 based elastomer.

<Formula 1>

In Formula 1, R ₁ is one of H or a C ₁ -C ₁₀ linear, branched or cyclic alkyl group, or a C ₆ -C ₁₀ aryl group or C ₇ -C ₁₀ aralkyl group,

<Formula 2>

또는

중 하나이다.In Formula 2, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

one of them

According to one embodiment of the present invention, the dimer acid derivative is a toughening polylactic acid composition containing an elastomer based on polyamide 11, characterized in that it has the chemical structure of the following formula 3 derived from animal oil, vegetable oil or waste oil can

<Formula 3>

In Formula 3, R ₃ is one of acyclic, monocyclic, bicyclic, aromatic, or C ₁ -C ₆ alkylene group, and R ₄ is H or a C ₁ -C ₁₀ linear, branched or cyclic alkyl group one of them

More specifically, the chemical structure of Formula 3 is selected from the group consisting of lauric fatty acid, myristic fatty acid, palmitic fatty acid, stearic fatty acid, oleic fatty acid, linoleic fatty acid, linoleic fatty acid, vegetable oil, animal oil and waste oil. It may be obtained from one or more fatty acids.

More specifically, the dimer acid derivative according to an embodiment of the present invention may be a dicarboxylic acid having 36 carbon atoms obtained from an unsaturated fatty acid having 18 carbon atoms (eg, oleic fatty acid, linoleic fatty acid) such as tall oil fatty acid, Any one of the chemical structures of Chemical Formulas 3-1, 3-2, 3-3, and 3-4 may be acyclic, monocyclic, polycyclic, and aromatic cyclic types.

<Formula 3-1>

<Formula 3-2>

<Formula 3-3>

<Formula 3-4>

According to one embodiment of the present invention, the polyamide 11 having a diamine end group may be a toughening polylactic acid composition containing a polyamide 11-based elastomer, characterized in that it has the chemical structure of Chemical Formula 4 below.

<Formula 4>

또는

중 하나이고, x는 반복단위의 수로 1 내지 100의 정수이다.In Formula 4, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

and x is an integer of 1 to 100 as the number of repeating units.

According to one embodiment of the present invention, the polyamide 11-based elastomer alternating copolymer may be a toughening polylactic acid composition containing a polyamide 11-based elastomer, characterized in that it has the chemical structure of Formula 5 below.

<Formula 5>

또는

중 하나이고, R₃는 비환식(acyclic), 단환식(monocyclic), 이환식(bicyclic), 방향족, 또는 C₁-C₆ 알킬렌기 중 하나이며, x는 반복단위의 수로 1 내지 100의 정수이고, n은 반복단위의 수로 2 내지 70의 정수이다.In Formula 5, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

one of, and R ₃ is one of acyclic, monocyclic, bicyclic, aromatic, or C ₁ -C ₆ alkylene group, x is an integer from 1 to 100 as the number of repeating units, n is the number of repeating units It is an integer from 2 to 70.

According to one embodiment of the present invention, the polyamide 11-based elastomer alternating copolymer has an impact strength of at least twice that of polyamide 11, which is a homopolymer of an 11-amino undecanoic acid derivative, containing a polyamide 11-based elastomer. It is effective in toughening polylactic acid compositions.

According to one embodiment of the present invention, the polylactic acid composition may be manufactured into a molded article using various known molding methods, for example, extrusion, injection, press, and the like, and the specific shape of the molded article to be manufactured is not limited.

Hereinafter, embodiments and examples of the present invention will be described in detail so that a person with general knowledge in the technical field to which the present application pertains can easily carry out the preferred embodiment of the present invention as shown in the accompanying drawings. In particular, the technical spirit of the present invention and its core configuration and operation are not limited by this. In addition, the content of the present invention may be implemented in various other types of equipment, and is not limited to the implementation examples and embodiments described herein.

<Example 1> Preparation of thermoplastic polyamide elastomer alternating copolymer

20 g (0.1 mol) of 11-amino undecanoic acid and 0.8 g (0.007 mol) of 1,6-hexamethylenediamine were placed in a 3-neck 100 ml reactor equipped with a mechanical stirrer, and stirred at 190 ^o C under nitrogen atmosphere. ^{After reacting at 230 o} C for 2 hours for 1 hour, polyamide was synthesized at both ends of the amine. After the reaction, it ^{was dissolved in 40 ml of 160 o} C NMP, slowly added to distilled water to remove unreacted substances, and then an amine having a molecular weight of 5,000 g/mol. A polyamide resin at both ends was obtained (yield 95%). In a three-neck 100ml reactor equipped with another mechanical stirrer, 15 g (0.003 mol) of the amine-terminated polyamide synthesized above and 1.71 g (Mw 565 g/mol, 0.003 mol) of dimer acid (Aldrich, 68783-41-5) ^{was added and reacted at 260 o} C for 2 hours while stirring under a nitrogen atmosphere to synthesize a polyamide elastomer alternating copolymer in which the dimer acid derivative content was 10.0 wt% of the total amount (yield 95%).

<Example 2> Preparation of thermoplastic polyamide elastomer alternating copolymer

In Example 1, 20 g (0.1 mol) of 11-amino undecanoic acid was used in the same manner, and 3.4 g (0.03 mol) of 1,6-hexamethylenediamine was used to prepare a polyamide resin with a molecular weight of 1300 g/mol. synthesized. Example using 14.1 g (0.01 mol) of the synthesized amine both terminal polyamide resin and 1.71 g (Mw 565 g/mol, 0.003 mol) of dimer acid (Aldrich, 68783-41-5) 6.2 g (0.01 mol) A polyamide elastomer alternating copolymer having a dimer acid derivative content of 30.0 wt % of the total amount was synthesized in a yield of 95% by reaction in the same manner as in 1 .

<Example 3> Preparation of thermoplastic polyamide elastomer alternating copolymer

In Example 1, 20 g (0.1 mol) of 11-amino undecanoic acid was used in the same manner, and 5.8 g (0.05 mol) of 1,6-hexamethylenediamine was used to prepare an amine-terminated polyamide resin having a molecular weight of 800 g/mol. synthesized. Example using 13.6 g (0.017 mol) of the synthesized amine both terminal polyamide resin and 1.71 g (Mw 565 g/mol, 0.003 mol) of dimer acid (Aldrich, 68783-41-5) 9.7 g (0.017 mol) A polyamide elastomer alternating copolymer having a dimer acid derivative content of 40.0 wt % of the total amount was synthesized in a yield of 96% by reaction in the same manner as in 1 .

<Comparative Example 1> Preparation of polyamide 11 resin

In Example 1, without using 1,6-hexamethylenediamine and dimer acid, 20 g (0.1 mol) of 11-amino undecanoic acid alone was used to prepare polyamide 11 resin in the same manner as in Example 1.

<Comparative Example 2> Preparation of thermoplastic polyamide elastomer random copolymer

11-amino undecanoic acid 40.3 g (0.2 mol), dimer acid (Aldrich, 68783-41-5) 1.71 g (Mw 565 g/mol; 0.003 mol) was added to 4 g (10wt% of amino acid, Mw 565g/mol, 0.007mol) 0.8 g (0.007 mol) of 1,6-hexamethylenediamine, and the temperature was raised while stirring under a nitrogen atmosphere to react at 120° C. for 1 hour. . After the reaction, a polyamide elastomer copolymer was synthesized by further reaction at 230 ° C. for 2 hours. After the reaction, the reaction temperature was cooled to 190 ° C., dissolved in 60 mL of NMP, and slowly added to distilled water to remove unreacted reactants. A polyamide resin was obtained (yield 90%).

<Comparative Example 3> Preparation of thermoplastic polyamide elastomer random copolymer

A desired polyamide resin was obtained in the same manner as in Comparative Example 2, except that the dimer acid derivative content was modified to be 30.0 wt% of the amino acid.

<Comparative Example 4> Preparation of thermoplastic polyamide elastomer random copolymer

A desired polyamide resin was obtained in the same manner as in Comparative Example 2, except that the dimer acid derivative content was modified to be 50.0 wt% of the amino acid.

<Experimental Example 1> Thermal property evaluation

Thermal properties were evaluated using the polyamide resins prepared in Examples 1-3 and Comparative Examples 1-4. Specifically, the thermal properties of the polyamide resin were evaluated using DSC (TA Q-1000 DSC instrument) and TGA (TA Q-500 TGA instrument), and the results are shown in Table 1 below.

polyamide
elastomer dimer acid
derivative
content(%) TGA Results DSC Results Td,,5% (℃) Residency
(%) Tg Tm ΔHf
(J/g) XPA Example 1 10 446.2 0.7 46.6 173.4 30.34 16 Example 2 30 446.6 0.3 41.25 152.9 28.49 15 Example 3 40 443.5 <0.1 40.72 128.4 28.15 15 Comparative Example 1 0 420 <0.1 52.0 183 47.5 25 Comparative Example 2 10 422 0.2 45.7 182 31.9 17 Comparative Example 3 30 427 0.3 19.7 169 28.0 15 Comparative Example 4 50 427 0.3 19.4 169 27.8 15

Looking at the TGA results in Table 1, the temperature (Td, 5%) when 5% of the polyamide resin Example 1-3 synthesized as an alternating copolymer was decomposed was improved compared to Comparative Example 1-4. Looking at the DSC results, in particular, the Tg of Comparative Example 2-4 is similar or higher than that of Comparative Example 2-4, so it is thermally stable even at room temperature. It can be seen that the moldability is excellent by showing similar or lower values compared to 1-4.

<Experimental Example 2> Mechanical property evaluation

Mechanical properties were evaluated using the polyamide resins prepared in Examples 1-3 and Comparative Examples 1-4. Specifically, the polyamide resins of Examples 1-3 and Comparative Examples 1-4 were molded into a film at 200° C., and their mechanical properties (Young's modulus, tensile strength, and stretch rate) were measured, and the results are shown in FIG. 1 and Table 2 below.

polyamide elastomer Young's modulus
(MPa) Tensile strength at break
(MPa) stretch rate at break
(%) Example 1 326 ±60 50.7 ±2.5 495 ±21 Example 2 197 ±70 51.5 ±2.4 793 ±41 Example 3 165 ±40 46.7 ±4.2 732 ±65 Comparative Example 1 308 ±4 41.4 ±1.1 231 ±49 Comparative Example 2 255 ±9 45.7 ±3.0 538 ±74 Comparative Example 3 241 ±10 40.1 ±11.1 560 ±16 Comparative Example 4 97 ±14 27.9 ±2.5 631 ±20

1 and Table 2, it can be seen that the polyamide resin of Example 1-3 exhibits improved mechanical properties compared to Comparative Example 1-4. It can be seen that the polyamide resin has excellent mechanical properties.

<Experimental Example 3> Mechanical property evaluation

Using the polyamide resins prepared in Examples 1-3 and Comparative Example 1, mechanical properties were evaluated. Specifically, the polyamide resins of Examples 1-3 and Comparative Example 1 were used to make impact strength specimens at 200° C. through an injection machine, and their mechanical properties (impact strength) were measured, and the results are shown in FIG. 2 and Table 3 below. shown in

polyamide elastomer Dimer acid derivative content, % Impact strength, KJ/m ² Example 1 10 12.4 ±4.1 Example 2 30 15.4 ±7.0 Example 3 40 >25 Comparative Example 1 0 6.1 ±0.5 Comparative Example 2 10 4.2 ±1.7 Comparative Example 3 30 6.7 ±4.0 Comparative Example 4 50 6.9 ±3.8

Accordingly, the polyamide resin of the present invention has excellent properties compared to the prior art and exhibits easy melt molding properties, so it is useful in the fields of clothing materials, industrial materials, engineering plastics, electric/electronic parts, automobile parts, etc. It can be seen that it can be used

<Preparation Example> Preparation of toughened PLA composition

The polyamide 11-based alternating elastomeric copolymer prepared according to Examples 1 to 3 of the present invention was mixed with PLLA (Nature works 2003D, Mw=158KDa, PDI=2.3) so that the total amount was 18 g, but the polyamide 11-based copolymer was mixed. The mixing amount of the alternating elastomer copolymer was 5, 10, 20, 30 and 50 wt%, and it was put into an extruder (HAAKE MiniLab3 Microcompounder, Thermo Scientific) and maintained at 200 ℃ for 8 minutes at 100 rpm, and then the mixture was discharged. . A toughened PLA composition was prepared.

<Experimental Example 4> Evaluation of mechanical properties of toughened PLA composition

Using the toughened PLA composition prepared in Preparation Example, put into an extruder and inject the mixture into a mold at 200 ° C (mold temperature 50 ° C, 10 psi) to obtain a dog bone-shaped specimen (ASTM D1708 microtensile bar) and impact strength A specimen (ISO180) was made, and its mechanical properties, tensile strength and (25°C, 50mm/min, QRS-S11H, Quro) and impact strength (IT504, Tinius Olsen) were measured, and the results are shown in FIG. 3 and Table 4 below. summarized and shown.

Psalter
(Polyamide 11 content) Yield Stress
(MPa) Stress at break
(MPa) strain at break
(%) Toughness
(MJ/m ³ ) neat PLA 65.57±1.21 65.57±1.21 0.64±1.21 4.33 5 wt% PA-11 64.57±1.44 62.30±4.62 17.98±11.98 4.36 10 wt% PA-11 58.22±3.42 36.39±2.07 183.37±10.52 88.27 20 wt% PA-11 53.20±2.75 41.30±3.12 319.0±28.14 115.20 30 wt% PA-11 42.91±1.95 39.06±4.0 358.20±40.07 122.10 50 wt% PA-11 33.95±3.56 45.37±5.85 483.27±58.22 169.60

Claims (10)

50 to 90 wt % of poly(lactic acid) (PLA); and
10 to 50 wt% of an alternating elastomeric copolymer based on polyamide 11 prepared by condensation reaction of polyamide 11 having diamine end groups with a dimer acid derivative,
The polyamide 11-based elastomer alternating copolymer is
The impact strength is more than twice that of polyamide 11, a homopolymer of 11-amino undecanoic acid derivative,
A toughened polylactic acid composition containing an elastomer based on polyamide 11, characterized in that the melting temperature is lower than that of an elastomer random copolymer based on polyamide 11 containing the same amount of dimer acid derivative. The method according to claim 1,
Wherein the polylactic acid is poly-L-lactic acid (PLLA). The method according to claim 1,
The dimer acid derivative is at least one fatty acid derivative selected from the group consisting of lauric fatty acid, myristic fatty acid, palmitic fatty acid, stearic fatty acid, oleic fatty acid, linoleic fatty acid, linolenic fatty acid, vegetable oil, animal oil and waste oil. A toughening polylactic acid composition containing an elastomer based on polyamide 11, characterized in that The method according to claim 1,
The toughened polylactic acid composition containing the polyamide 11-based elastomer, characterized in that the polyamide 11-based elastomer alternating copolymer has a dimer acid derivative content of 10 to 40 wt%. The method according to claim 1,
The polyamide 11 having a diamine end group is a polyamide 11-based, characterized in that it is prepared through a copolymerization reaction of an 11-amino undecanoic acid derivative having a chemical structure of Formula 1 below and a diamine having a chemical structure of Formula 2 below. Toughened polylactic acid composition containing elastomer:
<Formula 1>

In Formula 1, R ₁ is one of H or a C ₁ -C ₁₀ linear, branched or cyclic alkyl group, or a C ₆ -C ₁₀ aryl group or C ₇ -C ₁₀ aralkyl group,
<Formula 2>

In Formula 2, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

one of them The method according to claim 1,
The dimer acid derivative is a toughened polylactic acid composition containing an elastomer based on polyamide 11, characterized in that it has the chemical structure of the following formula 3 derived from animal oil, vegetable oil or waste oil:
<Formula 3>

In Formula 3, R ₃ is one of acyclic, monocyclic, bicyclic, aromatic, or C ₁ -C ₆ alkylene group, and R ₄ is H or a C ₁ -C ₁₀ linear, branched or cyclic alkyl group one of them The method according to claim 1,
A toughening polylactic acid composition containing an elastomer based on polyamide 11, characterized in that the polyamide 11 having diamine end groups has a chemical structure of the following Chemical Formula 4:
<Formula 4>

In Formula 4, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

and x is an integer of 1 to 100 as the number of repeating units. The method according to claim 1,
A toughened polylactic acid composition containing an elastomer based on polyamide 11, characterized in that the polyamide 11-based elastomer alternating copolymer has the chemical structure of the following formula (5):
<Formula 5>

In Formula 5, R ₂ is C ₁ -C ₂₀ straight or branched chain alkylene, C ₃ -C ₂₀ cycloalkylene, C ₆ -C ₂₀ arylene,

or

one of, and R ₃ is one of acyclic, monocyclic, bicyclic, aromatic, or C ₁ -C ₆ alkylene group, x is an integer from 1 to 100 as the number of repeating units, n is the number of repeating units It is an integer from 2 to 70. delete A molded article comprising the polylactic acid composition according to any one of claims 1 to 8.

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