KR102353368B1 - Lignin and vegetable oil based thermoplastic elastomers and the method of manufacturing the same, molded article made of lignin and vegetable oil based thermoplastic elastomers - Google Patents

Abstract

It is an object of the present invention to provide a lignin and vegetable oil-based thermoplastic elastomer manufactured as a sustainable material that can replace petroleum-based materials. Another object of the present invention is to provide a method for producing a thermoplastic elastomer based on lignin and vegetable oil that can implement desired properties by controlling the ratio of soft and hard without using a metal catalyst in the manufacturing process.
The present invention comprises the steps of (a) esterifying Guaiacol and Acrylic Anhydride to synthesize Guaiacol Acrylate represented by Chemical Formula 1; (b) polymerizing a chain transfer agent (CTA) on lauryl acrylate to synthesize CTA-poly(lauryl acrylate) represented by Formula 2; And (c) Poly(Guaiacol Acrylate) and CTA-poly(lauryl acrylate) are polymerized to poly(Guaiacol acrylate)-poly(lauryl acrylate)-poly represented by Chemical Formula 3 (Guirecol acrylate) provides a method for producing a lignin and vegetable oil-based thermoplastic elastomer comprising the step of synthesizing a triblock copolymer.

Description

LIGNIN AND VEGETABLE OIL BASED THERMOPLASTIC ELASTOMERS AND THE METHOD OF MANUFACTURING THE SAME, MOLDED ARTICLE MADE OF LIGNIN AND VEGETABLE OIL BASED THERMOPLASTIC ELASTOMERS

The present invention relates to a lignin and vegetable oil-based thermoplastic elastomer, a method for producing the same, and a molded article prepared from a lignin and vegetable oil-based thermoplastic elastomer, and more particularly, to a sustainable material, and to control physical properties so that it can be applied in various fields It relates to an easy lignin and vegetable oil-based thermoplastic elastomer, a method for producing the same, and a molded article prepared from a lignin and vegetable oil-based thermoplastic elastomer.

Thermoplastic elastomer (TPE) refers to a polymer that can be molded and regenerated in the same way as general thermoplastics while maintaining excellent elasticity. Such thermoplastic elastomers are widely used in automobile parts, medical products, adhesive/coated products, electric wires and cables, sports products, and the like.

Among thermoplastic elastomers, the styrene series occupies the largest market. Among them, polystyrene-polybutadiene-polystyrene (poly(styrene)-poly(butadiene)-poly(styrene), SBS) and polystyrene produced by living anionic polymerization Styrene-based linear ABA triblock copolymers such as -polyisoprene-polystyrene (poly(styrene)-poly(isoprene)-poly(styrene), SIS) are widely used.

ABA triblock copolymer has a micro-phase structure in which one medium-chain soft segment (B) imparting elasticity and two end-chain hard segments (A) imparting rigidity do not mix with each other. separated structure) to have two phase structures. The synthesis of triblock copolymers as thermoplastic elastomers requires precise control over nanoscale structures. By closely understanding the phase behavior of the triblock copolymer, the desired mechanical properties can be reached by tuning the molecular architecture and composition.

However, the styrene-based linear ABA triblock copolymer has two major limitations. First, the carbon unsaturated double bond of the medium chain soft polybutadiene (poly(butadiene), PB) or polyisoprene (PI) may be easily oxidized or decomposed by ultraviolet rays. Second, the upper service temperature (upper service temperature) is limited to the glass transition temperature (glass transition temperature, T _g ) of polystyrene 100 ℃. In addition to this, while it has sufficient price competitiveness, its application range is quite limited because it falls short of vulcanized rubber in oil resistance, heat resistance, and ozone resistance, or it has the disadvantage that it has the lowest resistance to hydrocarbon-based oils or solvents among TPEs.

On the other hand, most commercially available thermoplastic elastomers are synthesized from petroleum-based materials. However, since petroleum-based materials cause problems of global warming and resource depletion, sustainable materials that can replace them are attracting attention. However, a polymer synthesized from a sustainable material has a problem in that it has weaker thermal and mechanical properties than a polymer synthesized from a petroleum-based material.

Republic of Korea Patent Publication No. 10-0580790 (announced on May 16, 2006)

It is an object of the present invention to provide a lignin and vegetable oil-based thermoplastic elastomer manufactured as a sustainable material that can replace petroleum-based materials.

In addition, an object of the present invention is to provide a method for producing a thermoplastic elastomer based on lignin and vegetable oil, which is eco-friendly because it does not use a metal catalyst in the manufacturing process, and can implement desired properties by controlling the ratio of soft and hard.

In order to achieve the above object, the present invention synthesizes Guaiacol Acrylate represented by the following Chemical Formula 1 by esterification reaction of (a) Guaiacol and Acrylic Anhydride. to do;

(b) polymerizing a chain transfer agent (CTA) in lauryl acrylate to synthesize CTA-poly(lauryl acrylate) represented by the following Chemical Formula 2; and

(c) Poly(Guaiacol acrylate)-poly(lauryl acrylate)-poly represented by the following Chemical Formula 3 by polymerizing the Guaiacol Acrylate and CTA-poly(lauryl acrylate) (Guirecol acrylate) synthesizing a triblock copolymer;

It provides a method for producing a lignin and vegetable oil-based thermoplastic elastomer comprising a.

[Formula 1]

[Formula 2]

[Formula 3]

The acrylic anhydride of step (a) can be obtained by reacting acrylic acid with di-tert-butyl dicarbonate.

The polymerization of steps (b) and (c) may be reversible addition-fragmentation chain transfer (RAFT).

The polymerization of steps (b) and (c) may be carried out at 60 to 80° C. for 2 to 4 hours, and then rapidly cooled and dried at 60 to 80° C. for 70 to 75 hours.

The poly(wirechol acrylate) may be added in an amount of 30 to 60 wt% based on the triblock copolymer.

The step (b) further comprises acrylate urethane (Acrylate Urethane) and polymerization to synthesize CTA-poly(lauryl acrylate-acrylate urethane) represented by the following Chemical Formula 4, and the step (c) is wire Poly(Guaiacol Acrylate)-poly(lauryl acrylate-acrylate urethane) represented by the following Chemical Formula 5 by polymerizing CTA-poly(lauryl acrylate-acrylate urethane) with Guaiacol Acrylate -Provides a method for producing a lignin and vegetable oil-based thermoplastic elastomer, characterized by synthesizing a poly(Guirecol acrylate) triblock copolymer.

[Formula 4]

[Formula 5]

The present invention also provides a lignin and vegetable oil-based thermoplastic elastomer, which is represented by the following Chemical Formula 3, and is a (Guirecol acrylate)-poly(lauryl acrylate)-poly(Guirecol acrylate) triblock copolymer. provides

[Formula 3]

The poly(wire call acrylate) may be 30 to 65 wt% based on the triblock copolymer.

The triblock copolymer may have a thermal decomposition temperature of 335 to 355 °C.

The present invention also provides lignin represented by the following formula (5), which is a poly(Guirechol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Guirecol acrylate) triblock copolymer. and vegetable oil-based thermoplastic elastomers.

[Formula 5]

The triblock copolymer may have excellent mechanical properties by further including hydrogen bonds.

The present invention also provides a molded article made of a lignin and vegetable oil-based thermoplastic elastomer represented by the following formula (3).

[Formula 3]

The present invention also provides a molded article made of a lignin and vegetable oil-based thermoplastic elastomer represented by the following formula (5).

[Formula 5]

According to the method for producing a lignin and vegetable oil-based thermoplastic elastomer according to the present invention, a thermoplastic elastomer that can be applied to various fields can be manufactured by adjusting the ratio of soft and hard to control physical properties.

In addition, the present invention has the advantage of using an organic catalyst instead of a metal catalyst, and using lauryl acrylate obtained from coconut oil and wirecol obtained from lignin as monomers to produce an eco-friendly and sustainable thermoplastic elastomer There is this.

1 is a process flow diagram of a method for manufacturing a lignin and vegetable oil-based thermoplastic elastomer according to an embodiment of the present invention.
^{FIG. 2A is a 1} H-NMR spectrum of poly(lauryl acrylate) according to an embodiment of the present invention, and FIG. 2B is poly(Gwirechol acrylate)-poly(lauryl) according to an embodiment of the present invention. ^{It is a graph showing the 1} H-NMR spectrum of the acrylate)-poly(Guirechol acrylate) triblock copolymer.
3 is a poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer according to an embodiment of the present invention showing size exclusion chromatography (SEC) It is a graph.
Figure 4 (a) monomers and followed by a call acrylate synthesis step, (b) ¹ H-NMR of not acrylic anhydride synthesis step spectrum, (c) and followed by a graph showing the ¹ H-NMR spectrum of the call acrylate synthetic steps to be.
Figure 5 is (a) poly (lauryl acrylate) - poly (lauryl acrylate) - poly (Guirecol acrylate) differential scanning calorimetry (DSC) data of the triblock copolymer, (b) poly (and It is a graph showing thermogravimetric analysis (TGA) data of earcol acrylate)-poly(lauryl acrylate)-poly(Guirecol acrylate) triblock copolymer.
6 shows the incineration X of poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer according to the volume ratio of the wirechol acrylate measured at 25 ° C. It is a graph showing SAXS data.
Figure 7 is a stress-strain diagram of a poly(Guirecol acrylate)-poly(lauryl acrylate)-poly(Guirecol acrylate) triblock copolymer according to the mass ratio of the wirechol acrylate. It is a graph comparing curves).
^{8 is a graph showing a 1} H-NMR spectrum of a poly (lauryl acrylate-acrylate urethane) mid block.
9 is a view ^{showing the synthesis and 1} H-NMR spectrum of urethane acrylate.
^{10 is a 1} H-NMR spectrum and size exclusion chromatography (SEC) of a poly(Guirecol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Guirecol acrylate) triblock copolymer. is a graph representing
11 is a poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer and poly(Gwirechol acrylate)-poly(lauryl acrylate-acrylate It is a graph comparing the tensile strength of urethane)-poly(wirechol acrylate) triblock copolymers.

It should be noted that, in the following description, only the parts necessary for understanding the embodiments of the present invention will be described, and descriptions of other parts will be omitted in the scope not disturbing the gist of the present invention.

The terms or words used in the present specification and claims described below should not be construed as being limited to their ordinary or dictionary meanings, and the inventors have appropriate concepts of terms to describe their invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined in Accordingly, the embodiments described in this specification and the configurations shown in the drawings are only preferred embodiments of the present invention, and do not represent all of the technical spirit of the present invention, so various equivalents that can be substituted for them at the time of the present application It should be understood that there may be variations and variations.

Hereinafter, the present invention will be described in detail.

Manufacturing method of lignin and vegetable oil-based thermoplastic elastomer

1 is a process flow diagram of a method for manufacturing a lignin and vegetable oil-based thermoplastic elastomer according to an embodiment of the present invention.

1, the lignin and vegetable oil-based thermoplastic elastomer according to an embodiment of the present invention is (a) represented by the following formula (1) by esterification reaction of Guaiacol and Acrylic Anhydride synthesizing Guaiacol Acrylate; (b) polymerizing a chain transfer agent (CTA) in lauryl acrylate to synthesize CTA-poly(lauryl acrylate) represented by the following Chemical Formula 2; and (c) Poly(Guaiacol Acrylate)-poly(lauryl acrylate)- represented by the following Chemical Formula 3 by polymerizing the Guaiacol Acrylate and CTA-poly(lauryl acrylate) prepared by synthesizing a poly(Guirecol acrylate) triblock copolymer.

[Formula 1]

[Formula 2]

[Formula 3]

First, (a) Guaiacol and acrylic anhydride are esterified to synthesize Guaiacol Acrylate represented by the following Chemical Formula 1 (S10).

[Formula 1]

The guaiacol can be obtained by decomposing lignin. Lignin is a phenolic polymer present in the woody part of trees, and has many advantages for replacing petroleum-based substances because it is inexpensive, abundant, and reusable.

Softwoods have a higher lignin content than hardwoods containing 22% lignin because about 30% of the woody part is made of lignin. Therefore, conifers are more aromatic than hardwoods.

By decomposing such lignin, various phenolic monomers such as vanillin, guaiacol, and cresol can be obtained. The phenolic monomer can be polymerized through methacrylation, and since it has a glass transition temperature of 100 °C or higher, it can be used as a sustainable hard phase. Therefore, the use temperature range can be wider than that of the styrene-based thermoplastic elastomer.

Among them, wirechol is the most abundant phenolic monomer in lignin, and when polymerized into a polymer, it may have a higher glass transition temperature than other lignin-based polymers.

Scheme 1 below is a reaction scheme for preparing acrylic anhydride by reacting acrylic acid with di-tert-butyl dicarbonate.

[Scheme 1]

The acrylic anhydride may be prepared by stirring acrylic acid and di-tert-butyl dicarbonate at room temperature for 10 to 14 hours.

The following Reaction Scheme 2 is a reaction scheme for preparing Guirecol acrylate by reacting lignin-derived Guirecol with acrylic anhydride.

[Scheme 2]

The guaiacol acrylate (Guaiacol Acrylate) can be prepared by introducing a vinyl group to the guaiacol by esterification reaction of guaiacol and acrylic anhydride, and Guaiacol and acrylic anhydride at 35 to 55 ° C. It can be prepared by stirring for 22 to 26 hours. The reaction may proceed under a catalyst, and it is preferable to use dimethylaminopyridine (DMAP).

Next, (b) polymerizing a chain transfer agent (CTA) in lauryl acrylate to synthesize CTA-poly(lauryl acrylate) represented by the following Chemical Formula 2 (S20).

[Formula 2]

The lauryl acrylate (Lauryl Acrylate) monomer may be obtained by decomposing vegetable oil and may serve as a soft phase.

Both the soft phase and the hard phase may use sustainable and abundant monomers.

Scheme 3 below is a reaction scheme showing the process of synthesizing Macro CTA-poly(lauryl acrylate) represented by Chemical Formula 2 by polymerizing a chain transfer agent (CTA) in lauryl acrylate obtained by decomposing coconut oil.

[Scheme 3]

In the above step, reversible addition-fragmentation chain transfer (RAFT) is performed with a polymerization solution containing lauryl acrylate, a radical initiator, a chain transfer agent and a solvent to perform Macro CTA-poly(lauryl acrylate) is manufactured

The radical initiator is not particularly limited and may be appropriately selected in consideration of polymerization efficiency. For example, an azo compound such as azobisisobutyronitrile (AIBN) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2'-azobis-(2,4-dimethylvaleronitrile)), or benzoyl (BPO) peroxide) or DTBP (di-t-butyl peroxide) can be used, and 2,2`-azobis(2-methylpropionitrile) (2,2`-Azobis(2-methylpropionitrile); AIBN )) is preferred.

The chain transfer agent is poly(Guirecol acrylate)-poly(delta-hexalactone)-poly(Guirecol acrylate) reversible addition-fragmentation chain transfer polymerization for preparing triblock copolymer , RAFT) may be added to perform a transfer reaction in the reaction, and various chain transfer agents known in the art may be used.

The chain transfer agent includes cyanomethyl dodecyl trithiocarbonate (CDTC), 2-dodecylthiocarbonothioylthio-2-methylpropanoic acid (2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid; DDMAT). ), 2-cyano-2-propyl dodecyl trithiocarbonate (2-cyano-2-propyl dodecyl trithiocarbonate; CPDT) or 4-cyano-4-dodecyl sulfanylthiocarbonylsulfanyl pentanoic acid (4 -cyano-4-[(dodecyl sulfanyl thiocarbonyl)sulfanyl]pentanoic acid; CDSPA), etc. can be used, and 3,5-bis-2-dodecylthiocarbonothioylthio-1-oxopropoxy-benzoic acid (3 ,5-bis(2-dodecylthiocarbonothioylthio-1-oxopropoxy)benzoic acid; BTCBA) is preferably used. By using a chain transfer agent that can develop in both directions, it is possible to obtain a polymer with a controlled high molecular weight, symmetric structure.

As the solvent, water, toluene, benzene, acetonitrile, dimethylformamide, tetrahydrofuran, etc. may be used, and 1,4-dioxane may be preferably used.

The reversible addition-segmentation chain transfer polymerization reaction may be performed at 60 to 80° C. for 2 to 4 hours, and then rapidly cooled and dried at 60 to 80° C. for 70 to 75 hours.

Finally, (c) polymerizing Guaiacol Acrylate and CTA-poly(lauryl acrylate) to obtain poly(guaiacol acrylate)-poly(lauryl acrylate) represented by the following Chemical Formula 3 -A poly (Gwirechol acrylate) triblock copolymer is synthesized (S30).

[Formula 3]

The following Reaction Scheme 4 is a poly(wirechol acrylate)-poly(lauryl acrylate)-poly(wire Chole acrylate) shows the process of synthesizing the triblock copolymer.

[Scheme 4]

In the above step, reversible addition-fragmentation chain transfer (RAFT) is performed with a polymerization solution containing wirecol acrylate, Macro CTA-poly(lauryl acrylate), a radical initiator and a solvent to obtain poly (Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymers are prepared.

The radical initiator is not particularly limited and may be appropriately selected in consideration of polymerization efficiency. For example, an azo compound such as azobisisobutyronitrile (AIBN) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2'-azobis-(2,4-dimethylvaleronitrile)), or benzoyl (BPO) peroxide) or DTBP (di-t-butyl peroxide) can be used, and 2,2`-azobis(2-methylpropionitrile) (2,2`-Azobis(2-methylpropionitrile); AIBN )) is preferred.

As the solvent, 1,4-dioxane, water, benzene, acetonitrile, dimethylformamide, tetrahydrofuran, etc. may be used, and toluene may be preferably used .

The reversible addition-segmentation chain transfer polymerization reaction may be performed at 60 to 80° C. for 2 to 4 hours, and then dried at 60 to 80° C. for 70 to 75 hours after quenching.

The poly(wire call acrylate) may be prepared by adding 30 to 60 wt% based on the triblock copolymer. When poly(wirecol acrylate) is added in an amount of less than 30% with respect to the triblock copolymer, the hard phase does not achieve sufficient physical crosslinking to have elasticity, and when it is added in excess of 60%, the hard phase becomes too strong and has sufficient elongation not be able to have

The step (b) further comprises acrylate urethane (Acrylate Urethane) and polymerization to synthesize CTA-poly(lauryl acrylate-acrylate urethane) represented by the following Chemical Formula 4,

In step (c), poly(Guaiacol Acrylate) and CTA-poly(lauryl acrylate-acrylate urethane) are polymerized and poly(Guaiacol acrylate)-poly(La) represented by the following Chemical Formula 5 A triblock copolymer of uryl acrylate-acrylate urethane)-poly(Guirecol acrylate) can be synthesized.

[Formula 4]

[Formula 5]

Poly(Guirecol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Gwirechol acrylate) triblock copolymer by further comprising the acrylate urethane (Acrylate Urethane) and polymerization The step is to form a hydrogen bond network through the copolymerization of acrylate urethane having a low glass transition temperature on the soft phase to increase additional mechanical properties.

The acrylate urethane may be prepared by stirring ethyl acetate and ethyl isocyanate together with a catalyst. The reaction of ethyl acetate and ethyl isocyanate may be performed under a catalyst at room temperature for 10 to 14 hours.

The catalyst is triethylenediamine, dimethylcyclohexylamine, or dimethylethanolamine, and preferably dibutyltin dilaurate may be used.

Scheme 5 below shows a process for synthesizing poly(lauryl acrylate)-poly(acrylate urethane) by polymerizing the lauryl acrylate, acrylate urethane, and a chain transfer agent. The following reaction method and conditions may be performed in the same manner as in step (b).

[Scheme 5]

Reaction Scheme 6 below is poly(Gwirechol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly by polymerizing the wirechol acrylate and Macro CTA-poly(lauryl acrylate-acrylate urethane) (Guirecol acrylate) shows the process of synthesizing the triblock copolymer. The following reaction method and conditions may be performed in the same manner as in step (c).

[Scheme 6]

Thermoplastic elastomers based on lignin and vegetable oil

According to another aspect of the present invention, the present invention is characterized in that it is a triblock copolymer represented by the following Chemical Formula 3, and is poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate). lignin and vegetable oil-based thermoplastic elastomers.

[Formula 3]

The poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer is composed of wirechol acrylate (GA) and CTA-poly(lauryl acrylate). reversible addition-fragmentation chain transfer polymerization (RAFT).

The poly(wire call acrylate) may be 30 to 65 wt% based on the triblock copolymer.

The poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer may have a thermal decomposition temperature of 335 to 355°C.

Since the triblock copolymer contains a polymer of soft poly(lauryl acrylate) and hard poly(wirechol acrylate), phase separation occurs. The poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer according to an embodiment of the present invention exhibits excellent phase separation properties and, if necessary, It is possible to form a nanoscale structure by micro phase separation. The shape and size of the nanoscale structure may be controlled by the molecular weight of the soft poly(lauryl acrylate) and the hard poly(wirecol acrylate) or the ratio thereof. Therefore, according to the manufacturing method of the present invention, there is an advantage in that it is possible to make a thermoplastic elastomer that is applied to various fields by controlling the total molecular weight of the triblock copolymer or the fraction of hard poly(wirecol acrylate).

According to another aspect of the present invention, the present invention is represented by the following Chemical Formula 5, poly(Gwirechol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Gwirechol acrylate) triblock It provides a thermoplastic elastomer based on lignin and vegetable oil, characterized in that it is a copolymer.

[Formula 5]

The poly(Gwirechol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Gwirechol acrylate) triblock copolymer may further include a hydrogen bond to exhibit excellent mechanical properties.

Molded body made of lignin and vegetable oil-based thermoplastic elastomer

According to another aspect of the present invention, there is provided a molded article made of a thermoplastic elastomer based on lignin and vegetable oil represented by the following formula (3).

[Formula 3]

According to another aspect of the present invention, the present invention provides a molded article made of a thermoplastic elastomer based on lignin and vegetable oil represented by the following Chemical Formula 5.

[Formula 5]

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiment according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiment described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

<Material>

Materials used in Preparation Examples, Examples and Experimental Examples below, all reagents sensitive to oxygen and moisture were stored in a glove box filled with nitrogen gas and used. Lauryl acrylate was purchased from TCI as dodecyl acrylate and used, and Guaiacol was purchased from Sigma-Aldrich. A bidirectional chain transporter, 3.5-bis-2-dodecylthiocarbonothioylthio-1-oxopropoxyl-benzoic acid (3.5-bis(2-dodecylthiocarbonothioylthio-1-oxopropoxy)benzoic acid; BTCBA), is also available from Sigma-Aldrich. It was purchased and stored in a refrigerator in a glove box. Acrylic acid, di-tert-butyl dicarbonate, magnesium carbonate hydroxide, and DMAP were purchased from Sigma-Aldrich. Other solvents or reagents were used without further purification.

<Preparation Example 1> Synthesis of acrylic anhydride

In a flask, 126.105 g of acrylic acid (1.75 mol of vinyl functional group), 157.775 g of di-tert-butyl dicarbonate (0.7 mol of carbonate functional group), 2.361 g of magnesium carbonate hydroxide catalyst ( 28 mmol) was added, and the reaction was stirred at room temperature for 12 hours. It was removed with 400 ml of ultrapure water (DI water) × 3 times, and 400 mL of sodium bicarbonate. Thereafter, impurities were removed through distillation under reduced pressure at 35 °C of 32 mmHg to obtain acrylic anhydride in a yield of 68%.

<Preparation Example 2> Synthesis of wire call acrylate

49.465 g (OH functional group 39.8 mmol) and DMAP 2.434 g (19.95 mmol) were stirred in a flask to completely dissolve the catalyst. While slowly adding 60.3 g (47.8 mmol) of acrylic anhydride, the mixture was stirred at room temperature for 3 hours. After that, the reaction is carried out at 45°C for 24 hours. After the reaction is completed, dilute in 250 mL of MC, remove excess acrylic anhydride with 500 mL of sodium bicarbonate, and dry with _{MgSO 4 .} The dried compound was subjected to column chromatography under EA:HEX=1:7 mixed solvent conditions to obtain pure wirechol acrylate in a yield of 30%.

<Preparation Example 3> Synthesis of Acrylate Urethane

After putting 1 drop of dibutyltin dilaurate catalyst in the flask, the experiment was carried out in a glove box. Into the flask, 2.725 mL (2.81 M) of ethyl acetate from which oxygen was removed through a freeze-pump thaw was added, and 1.081 g (9.309 mmol) of 2-hydroxyethyl acrylate was added. Then block the entrance with septa. 0.724 mL (7.63 mmol) of ethyl isocyanate stored in the glove box was taken out by syringe, and ethyl isocyanate was slowly dropped dropwise while stirring a 50 mL round flask containing the reactant in an ice bath. react After that, it is stirred at room temperature for 12 hours. After the reaction is completed, the acrylate urethane is diluted in 10 mL of ethyl acetate and worked-up with 20 mL of ultrapure water. After drying with MgSO ₄ , the catalyst was removed using Celite, and urethane acrylate was obtained in a yield of 70%.

<Preparation Example 4> RAFT polymerization of poly (lauryl acrylate)

2,2`-Azobis(2-methylpropionitrile) (AIBN) was used without further purification, and dodecyl acrylate (lauryl acrylate) was used as a monomethyl ether hydroquinone inhibitor through Alumina column. ) was removed and used. Lauryl acrylate 30 g (0.125 mol), BTCBA 0.115 g (0.141 mmol), AIBN 0.00231 g (0.0141 mmol) and 1,4-dioxane 30 mL are added to the flask and stirred. After that, the freeze-pump-thaw is performed 3 times to remove oxygen, and a nitrogen environment is made through N2 purge. After reacting in an oil bath at 70 °C for 3 hours, the flask is immersed in ice water and quenched by creating an oxygen environment. PLAc was purified in methanol and dried in a vacuum oven at 70 °C for 3 days. The copolymerization of acrylate urethane was synthesized in the same manner as above by varying the ratio of lauryl acrylate and acrylate urethane monomer.

<Preparation Example 5> Poly(Guirecol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) Synthesis of triblock copolymers

A triple block copolymer was synthesized using the RAFT polymerization method. A copolymer having about 33 wt% of poly(Guirecol acrylate) was prepared in the following manner. 10 g (0.056 mol) of wirechol acrylate, 5 g of poly(lauryl acrylate) midblock (Macro CTA, 0.0325 mmol), 0.0107 g (0.065 mmol) of AIBN and 50 mL of toluene are placed in a 250 mL flask and stirred. . Freeze-pump-thaw is performed until oxygen does not come out, and a nitrogen environment is made through _{N 2 purge.} After reacting in an oil bath at 70 ° C, quenching is performed by making it in an oxygen environment with ice water. The poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triple block copolymer was purified in methanol and dried in a vacuum oven at 70° C. for 3 days. In case of using Macro-CTA copolymerized with lauryl acrylate and acrylate urethane, proceed in the same way.

<Analysis method>

In the experimental examples for the following examples, the following analysis method was used.

1) Nuclear magnetic resonance spectroscopy

¹ H-NMR spectrum was used to measure the molecular weight of the polymer. The concentration of the sample was analyzed by diluting _{CDCl 3 to 5 mg/ml.} As analysis equipment, Bruker Avance III HD-700 spectrometer (700 MHz) and Bruker DPX-500 spctrometer (500 MHz) were used. The internal standard of CDCl _{3 is} Tetramethylsilane (TMS) was used, and the chemical shift was 7.26 ppm.

2) Gel permeation chromatography

An Agilent 1260 Infinity LC system with a refractive index detector was used for the number-average molecular weight (Mn) and molecular weight distribution (the dispersity, Ð) of the synthesized polymer. Styragel HT4, HT3 and HT2 (10 μm, 7.8 Х 300 nm) were used for the column, and THF (Duksan, HPLC Grade) at 40°C was used for the mobile phase. Samples were measured in a volume of 100 μl while passing at a constant flow rate of 1 mL/min. The titration curve was made using a polystyrene standard sample (shedex).

3) Differential scanning calorimetry

To confirm the glass transition temperature ( T _g ) of the synthesized polymer, differential scanning calorimetry was performed _{in the N 2} gas state having a flow rate of 50 mL/min using TA Q-1000 DSC. After loading 5-8 mg of a polymer sample into a sealed aluminum DSC, heating from 25 °C to 200 °C eliminates the effect of thermal traces. Thereafter, after cooling to -80 °C, it is heated to 200 °C at a constant rate of 10 °C/min. obtained T _g The values are data obtained during the second heating.

4) Thermogravimetric analyzer

To check the thermal decomposition temperature ( T _d ) of the synthesized polymer, it is heated from 25 ℃ to 600 ℃ at a constant rate of 10 ℃/min in _{the N 2} gas state using TA Q-500 TGA equipment.

5) Small-angle X-ray scattering

Synchrotron SAXS equipment was used through the 9A U-SAXS beamline of the Pohang Accelerator Research Center to observe the microdomain structure according to the mass ratio of the glass phase of the synthesized triblock copolymer. The sample was analyzed in a film state, and the scattering vector (q) versus the scattering intensity was measured by integrating the two-dimensional image as the result of the analysis.

6) Tensile strength/mechanical strength

The tensile strength test of the synthesized polymer was conducted at room temperature using QRS-S11H (Quro) equipment. The film obtained by slowly blowing the solvent into the PFA dish was prepared as a dog-bone-shaped specimen and used for testing. For test conditions, a stress-strain curve was obtained by pulling a load cell of 100 N at room temperature at a speed of 130 mm/min.

<Example 1> Poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer synthesis 1

Poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer was synthesized through two-step RAFT polymerization.

A 130 K soft-phase mid block was synthesized using a chain carrier that can be developed in both directions, and the mass ratio of the hard phase side block was 30 wt%. For the initiation of AIBN, the reaction temperature was set at 70 ° C. The equivalent weight of the chain transporter and the monomer of the soft phase was BTCB: LAc = 1:887.5, and the equivalent weight of the hard phase was PLAc-MIX macro-CTA: GA = 1:1728.2. .

<Example 2> Poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer synthesis 2

It was synthesized in the same manner as in Example 1, except that the mass ratio of the hard phase side block was synthesized at 50 wt%.

<Example 3> Poly(Gwirechol acrylate)-poly(lauryl acrylate)-poly(Gwirechol acrylate) triblock copolymer synthesis 3

It was synthesized in the same manner as in Example 1, except that the mass ratio of the hard phase side block was synthesized at 60 wt%.

<Experimental Example 1> Confirmation of structure, molecular weight, and conversion rate for Examples 1-3

^{1 The} structure, molecular weight, and conversion rate were confirmed through H-NMR spectrum. For the soft phase, the conversion rate was calculated by comparing the integral values of the two proton peaks next to the vinyl group of lauryl acrylate monomer, which appeared at 6.4 ppm, 6.1 ppm, and 5.8 ppm, and the ester, a lauryl acrylate repeating unit, which appeared at 4.0 ppm. The average conversion was about 60%, and based on this conversion, the theoretical molecular weight M _n (Theo.) can be obtained. Unreacted monomers and AIBN can be removed through purification using methanol. Based on the 2, 4 proton peaks of 4.8 ppm and 3.3 ppm next to the trithiocarbonates of the bidirectional chain transporter used in the reaction, the integral value of the soft phase repeat unit peak was calculated, and the number average molecular weight M _n (NMR) was calculated. can decide (Table 1)

[Table 1] Poly(lauryl acrylate) soft phase molecular weight data

Sequential polymerization of hard phase side blocks was synthesized using a soft phase polymer as a macro-chain carrier. As before, the conversion rate was confirmed by comparing the integral value of the methoxy peak of the 3.8 ppm Guairchol acrylate monomer and the repeating unit peak of 3.6 ppm through ^{1 H-NMR.} The molecular weight of the hard phase was determined through the integral value of the 3.6 ppm methoxy (Methoxy) peak based on the integral value of the soft phase of 4.0 ppm. (Fig. 2) (Table 2)

[Table 2] Molecular weight data of triblock copolymer

As shown in Figure 3, the soft phase peak of a single peak was confirmed through size exclusion chromatography (SEC), and as the mass ratio of the sequentially synthesized hard phase increased, the peak shifted to the left, indicating that the hard phase was successfully developed. Confirmed. As a result, triblock copolymers having a soft phase of 130 K and a hard phase of 33.4, 49.3, and 62.9 wt%, respectively, were synthesized.

The Guirecol acrylate monomer was synthesized through esterification with Guairchol after synthesizing acrylic anhydride. Work-up was performed to remove t-butanol and acrylic acid, an excess reactant, generated by the reaction of di-tert-butyl dicarbonate, and 1.27 ppm each. and 6.46, 6.14, and 5.90 ppm peaks were confirmed to be removed. After that, distillation was performed to remove impurities present in the reactant acrylic acid, and it was confirmed that the peaks of 4.49 ppm and 2.93 ppm were removed. Then, after the reaction of pure acrylic anhydride with Guirecol, the NMR data confirmed that a symmetrical impurity peak appeared, and EA:　Hex = 1:7 was separated by column chromatography with a mixed solvent. (Fig. 4)

<Experimental Example 2> Thermal properties and shape analysis for Examples 1-3

In order to check whether the synthesized triple block copolymer forms microphase separation, differential scanning calorimetry was performed to observe the glass transition temperature of each phase. As a result of the analysis, it was confirmed that values corresponding to the glass transition temperature (T _g ) of the soft phase and the hard phase, poly(lauryl acrylate) and poly(wirechol acrylate) homopolymer, were clearly distinguished and observed. The soft phase poly(lauryl acrylate) has a melting temperature ( T _m ) of 2.3 °C, and the hard phase poly(Guirecol acrylate) has a glass transition temperature ( T _g ) of 83 °C and is a triple block copolymer It has been demonstrated that the transition temperature of is also similar to the microphase separation. In particular, it can be seen that the glass transition temperature ( T _g ) of the hard phase is 80° C. or higher, indicating that it has an excellent glass transition temperature value among the hard phases synthesized using the previously sustainable monomer.

Thermogravimetric analysis was performed to observe the pyrolysis temperature. As a result of the analysis, it could be seen that decomposition occurred in step 1, and as a result of observing the thermal decomposition temperature of the homopolymer of the soft phase and hard phase, respectively, the decomposition was observed only in step 1 because it had a similar value of about 340 °C. It can be seen that the pyrolysis temperature tends to decrease as the mass ratio of the hard phase increases. In addition, it was demonstrated that the triblock copolymer synthesized through a pyrolysis temperature of 340 °C has excellent thermal stability. (Fig. 5) (Table 3)

[Table 3] Thermal properties of triblock copolymer

SAXS measurement was performed to compare the distance between the microdomains and the shape of the microdomains according to the change in the ratio of the hard phase at room temperature. Samples annealed at room temperature for 24 hours were measured. It can be seen that the domain shape formed until the volume ratio of the hard phase is 32.5% is predicted to be spherical, and it can be seen that it changes to cylindrical and lamellar as the volume increases. In addition, it was verified that the center distance between the microdomains and the domains increased according to the relationship through the decrease in q as the volume ratio increased (Fig. 6).

<Experimental Example 3> Mechanical properties of Examples 1-3

The mechanical properties of the synthesized triblock copolymer were measured through a tensile test. It was confirmed what kind of tendency it had as the mass ratio of the hard phase was different for the same soft phase. As the hard phase increases, the strain decreases and the stress increases. The measured strain value can confirm the flexibility of the synthesized polymer, and the stress value can judge the mechanical strength. As the hard phase increased, the strain decreased because the fluidity and migration of the polymer chains decreased, but it can be judged that the strength increased as the degree of physical crosslinking increased. Therefore, it was confirmed that the desired physical properties could be controlled by adjusting the ratio of the soft phase and the hard phase.

<Example 4> Poly(Guirecol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Gwirechol acrylate) triblock copolymer

In order for general polymers to exhibit excellent mechanical properties, sufficient entanglement of polymer chains is required. Therefore, in order to further improve the entanglement of polymers using sustainable monomers, hydrogen bonds, which are non-covalent cross-linking bonds, were introduced.

The soft phase was synthesized by adjusting the mass ratio of lauryl acrylate and 20 wt% of acrylate urethane, and the hard phase was synthesized by adjusting the mass ratio of lauryl acrylate and 20 wt% of acrylate urethane, and mechanical properties were observed according to the difference in the mass ratio of acrylate urethane using 50 wt% of wirechol acrylate. .

<Experimental Example 4> Molecular weight and conversion for Example 4

¹ The molecular weight and conversion rate of the acrylate urethane were measured through H-NMR spectrum. The conversion rate of acrylate urethane was confirmed through the integral value of the monomer at 4.15 ppm and the polymer repeating unit at 4.22 ppm. The mass ratio was determined through the integral value of the acrylate urethane peak of 4.22 ppm and lauryl acrylate of 4.00 ppm (Fig. 8) (Table 4).

[Table 4] Poly (lauryl acrylate-acrylate urethane) copolymer soft phase molecular weight data

The acrylate urethane monomer used for copolymerization was synthesized by the reaction of 2-hydroxyethyl acrylate and an excess of ethyl isocyanate. Conversion was confirmed through a peak of 1.31 ppm, and removal of 2-hydroxyethyl acrylate appearing at a peak of 3.88 ppm was confirmed through work-up. (Fig. 9)

The light phase was synthesized by fixing at 50 wt%, and the peak was

It was confirmed that it moved to the left. (Fig. 10) (Table 5)

[Table 5] Molecular weight data of poly(Gwirechol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Gwirechol acrylate) triblock copolymer

<Experimental Example 5> Mechanical properties for Example 4

When 20 wt% of acrylate urethane was copolymerized, it can be observed that the overall stress of the triblock copolymer is increased. On the other hand, it can be seen that the elongation value decreased slightly. It can be seen that as the mass ratio of acrylate urethane increased, the crosslinking density increased according to the increase in the degree of hydrogen bonding. In addition, this result was shown because the fluidity of the entire polymer chain was reduced. (Fig. 11) (Table 6)

[Table 6] Tensile strength of poly(wirechol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(wirechol acrylate) triblock copolymer

In the Examples and Experimental Examples, vegetable oil and lignin-based thermoplastic elastomers having a linear structure of ABA were synthesized by varying the ratio of hard phases, and properties were compared. Through differential scanning calorimetry (DSC), it was confirmed that the intrinsic phase transition temperature of the soft phase and the hard phase, respectively, appeared, and that microphase separation was established. In addition, the phase separation behavior of the thermoplastic elastomer was also confirmed through small-incineration X-ray scattering (SAXS), and it was observed that as the volume ratio of the hard phase increased, the shape of the domain increased to a spherical-cylindrical-lamellar shape. In addition, in order to examine the mechanical properties of the synthesized triblock copolymer, a specimen was prepared and a tensile strength test was performed. As the ratio of hard phase increased, physical cross-linking in the polymer increased, so the elongation value decreased and the strength increased. Through this, it can be seen that desired physical properties can be realized by differently controlling the ratio of the soft phase and the hard phase. Finally, in order to further improve mechanical properties, a functional group capable of hydrogen bonding was introduced, and it can be seen that the mechanical properties can be adjusted according to the degree of improvement of the hydrogen bonding network.

Specific examples of the lignin and vegetable oil-based thermoplastic elastomer according to an embodiment of the present invention, a method for manufacturing the same, and a molded article made of a lignin and vegetable oil-based thermoplastic elastomer according to an embodiment have been described, but within the limits that do not depart from the scope of the present invention It is obvious that various implementation modifications are possible in .

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the following claims as well as the claims and equivalents.

That is, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims; All changes or modifications derived from the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (13)

(a) esterification reaction of Guaiacol and Acrylic Anhydride to synthesize Guaiacol Acrylate represented by the following Chemical Formula 1;
(b) polymerizing a chain transfer agent (CTA) to lauryl acrylate and acrylate urethane to synthesize CTA-poly (lauryl acrylate-acrylate urethane) represented by the following Chemical Formula 4 step; and
(c) Poly(Guaiacol Acrylate)-poly(lauryl acrylic) represented by the following Chemical Formula 5 by polymerizing the Guaiacol Acrylate and CTA-poly(lauryl acrylate-acrylate urethane) synthesizing a rate-acrylate urethane)-poly(Guirecol acrylate) triblock copolymer;
A method for producing a lignin and vegetable oil-based thermoplastic elastomer comprising a.
[Formula 1]

[Formula 4]

[Formula 5]

According to claim 1,
The acrylic anhydride of step (a) is lignin and vegetable oil-based thermoplastic, characterized in that it is obtained by reacting acrylic acid with di-tert-butyl dicarbonate A method for manufacturing an elastic body.
According to claim 1,
The polymerization of steps (b) and (c) is
A method for producing a thermoplastic elastomer based on lignin and vegetable oil, characterized in that reversible addition-fragmentation chain transfer (RAFT).
4. The method of claim 1 or 3,
The polymerization of steps (b) and (c) is
A method for producing a thermoplastic elastomer based on lignin and vegetable oil, characterized in that it is carried out at 60 to 80° C. for 2 to 4 hours, and then dried at 60 to 80° C. for 70 to 75 hours after quenching.
According to claim 1,
The poly(wire call acrylate) is
A method for producing a thermoplastic elastomer based on lignin and vegetable oil, characterized in that it is added in an amount of 30 to 60 wt% based on the triblock copolymer.
delete delete delete delete A thermoplastic elastomer based on lignin and vegetable oil, which is represented by the following Chemical Formula 5, and is a poly(Guirecol acrylate)-poly(lauryl acrylate-acrylate urethane)-poly(Guirecol acrylate) triblock copolymer .
[Formula 5]

[Claim 11] The lignin and vegetable oil-based thermoplastic elastomer according to claim 10, wherein the triblock copolymer further includes a hydrogen bond and has excellent mechanical properties.
delete A molded article prepared from a thermoplastic elastomer based on lignin and vegetable oil represented by the following Chemical Formula 5.
[Formula 5]

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