KR102325589B1 - Diol type polyester using lactone and method of preparing the same - Google Patents

Abstract

Disclosed are a diol-based polyester using lactone and a method for producing the same. The diol-based polyester is represented by Structural Formula 1, and the diol-based polyester has excellent weather resistance and stain resistance by utilizing a valerolactone-based compound derived from biomass. In addition, the diol-based polyester of the present invention is applied to powder coating and has better workability and chipping resistance compared to liquid coatings, and can reduce price and storage costs, so it can be used for home appliances, piping, automotive coatings, etc. .
[Structural Formula 1]

Description

Diol-based polyester using lactone and its manufacturing method

The present invention relates to a diol-based polyester using lactone and a method for preparing the same, and more particularly, to a biomass-derived valerolactone, which is ring-opened using a catalyst, and then reacted with a child sorbide derivative. It relates to a diol-based polyester and a method for producing the same.

Paints, which are widely used in various industries and homes to improve aesthetic effects and product finishes, are liquid and contain various solvents and diluents. However, recently, interest in environmental pollution caused by the above solvents and diluents is increasing domestically and internationally, and regulations on toxic volatile organic compounds have been legislated, thereby increasing the demand for eco-friendly products.

Powder coatings do not contain solvents such as organic solvents, reactive monomers, and water used in general coatings. If necessary, appropriate pigments and hardeners are blended to uniformly melt and mix the sprayed material, then cool the particles to a particle size within a certain range. It refers to a powdery coating composed of only the particle size within the specified range by grinding.

Powder paint, which is an eco-friendly paint that does not use any organic solvents, is widely used in various industries such as construction, home appliances and automobile industries. In particular, the demand for powder coatings using bio-resin is increasing mainly in overseas markets, but domestic technology development is in its infancy and the bio-resin used is entirely dependent on imports.

DSM and Roquette established a joint research system and secured a manufacturing process from starch to sorbitol through sorbitol and to succinic acid and butanediol through glucose, so that Polybutylene succinate (PBS) and Polyisosorbide succinate (PIS) ) reported that they have secured production technology (Biovision, Lyon, 8 March 2009, DSM), and in particular, reported that PIS has a high potential to be applied to powder coatings.

Since the development of raw materials and applied research is being conducted mainly in advanced countries, Korea must also reduce its dependence on technology through technology development and early commercialization.

An object of the present invention is to provide a diol-based polyester having excellent weather resistance and stain resistance by reacting a valerolactone-based compound that can be derived from biomass with a child sorbide derivative in consideration of the domestic situation where raw material development is insufficient.

According to one aspect of the present invention, there is provided a diol-based polyester represented by the structural formula (1).

[Structural Formula 1]

In Structural Formula 1,

이고,X is each independently a valence bond, a C1 to C5 alkylene group, or

ego,

R ³ is a C1 to C5 alkyl group,

R ⁴ is a valence bond or a C1 to C5 alkylene group,

Y is a carbon atom or a C2 to C5 alkenylene group,

R ¹ is each independently a hydrogen atom or a C1 to C9 alkyl group,

R ² is each independently a hydrogen atom or a C1 to C9 alkyl group,

p is each independently any one of an integer from 1 to 6,

m ₁ and m ₂ are each the number of repeats of the repeating unit,

The weight average molecular weight of the diol-based polyester is 3,000 to 1,000,000.

이고,In addition, according to another embodiment, each X is independently a valence bond, a C1 to C3 alkylene group, or

ego,

R ³ is a C1 to C3 alkyl group,

R ⁴ is a valence bond or a C1 to C3 alkylene group,

Y is a carbon atom or a C2 to C4 alkenylene group,

R ¹ is each independently a hydrogen atom or a C1 to C3 alkyl group,

R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

p may each independently be any one of an integer of 2 to 4.

In addition, according to another embodiment, each X is independently a valence bond, a methylene group or an ethylene group,

Y is a carbon atom,

R ¹ is each independently a hydrogen atom or a methyl group,

R ² are each a hydrogen atom,

p may each be 3.

In addition, the number average molecular weight of the diol-based polyester may be 1,500 to 200,000.

In addition, the diol-based polyester may be prepared from lactone derived from biomass.

,

,

,

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,

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,

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,

, 또는

로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다.In addition, the lactone

,

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,

,

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,

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, or

It may include one or more selected from the group consisting of.

According to another aspect of the present invention, there is provided a powder coating comprising the diol-based polyester.

According to another aspect of the present invention, a diol-based polyester comprising the step of preparing a diol-based polyester represented by Structural Formula 1 by reacting a lactone represented by Structural Formula 2 with a diol represented by Structural Formula 3 in Scheme 1 below A manufacturing method is provided.

[Scheme 1]

In Scheme 1,

이고,X is each independently a valence bond, a C1 to C5 alkylene group, or

ego,

R ³ is a C1 to C5 alkyl group,

R ⁴ is a valence bond or a C1 to C5 alkylene group,

Y is a carbon atom or a C2 to C5 alkenylene group,

R ¹ is each independently a hydrogen atom or a C1 to C9 alkyl group,

R ² is each independently a hydrogen atom or a C1 to C9 alkyl group,

p is each independently any one of an integer from 1 to 6,

m ₁ and m ₂ are each the number of repeats of the repeating unit,

The weight average molecular weight of the diol-based polyester is 3,000 to 1,000,000.

이고,In addition, according to another embodiment, each X is independently a valence bond, a C1 to C3 alkylene group, or

ego,

R ³ is a C1 to C3 alkyl group,

R ⁴ is a valence bond or a C1 to C3 alkylene group,

Y is a carbon atom or a C2 to C4 alkenylene group,

R ¹ is each independently a hydrogen atom or a C1 to C3 alkyl group,

R ² are each independently a hydrogen atom or a C1 to C3 alkyl group,

p may each independently be any one of an integer of 2 to 4.

In addition, according to another embodiment, each X is independently a valence bond, a methylene group or an ethylene group,

Y is a carbon atom,

R ¹ is each independently a hydrogen atom or a methyl group,

R ² are each a hydrogen atom,

p may each be 3.

In addition, the number average molecular weight of the diol-based polyester may be 1,500 to 200,000.

Also, the lactone may be derived from biomass.

The present invention can provide a diol-based polyester having excellent weather resistance and stain resistance by utilizing a valerolactone-based compound derived from biomass.

In addition, the diol-based polyester of the present invention is applied to powder coating and has better workability and chipping resistance than liquid coatings, and can reduce price and storage costs, so it can be used for home appliances, piping, automobile coatings, etc. .

1a is an NMR result of isosorbide diallyl ether, which is the first reaction product of Preparation Example 1. FIG.
FIG. 1b is an NMR result of propanediol isosorbide of Preparation Example 1. FIG.
2a is an NMR result of 2-(3-bromopropoxy)tetrahydro-2H-pyran (2-(3-bromopropoxy)tetrahydro-2H-pyran), which is the first reaction product of Preparation Example 2. FIG.
Figure 2b is a NMR result of the second reaction product of Preparation Example 2, tetrahydropyranyl propyl isosorbide.
3 is a graph showing the thermal behavior of the diol-based polyester prepared according to Examples 1 and 2 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of a related known technology may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is only used to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, but is one or more other features or It should be understood that the existence or addition of numbers, steps, acts, elements, or combinations thereof, is not precluded in advance.

As used herein, the term “alkyl group” refers to an aliphatic hydrocarbon group unless otherwise defined.

The alkyl group may be a “saturated alkyl group” that does not contain any double or triple bonds.

The alkyl group may be an "unsaturated alkyl group" containing at least one double or triple bond.

Alkyl groups, whether saturated or unsaturated, can be branched, straight-chain or cyclic.

The alkyl group may be a C1 to C30 alkyl group. More specifically, it may be a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C6 alkyl group.

For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. It indicates that it is selected from the group consisting of.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, a cyclo It means a butyl group, a cyclopentyl group, a cyclohexyl group, etc.

Hereinafter, the diol-based polyester of the present invention will be described.

The present invention provides a diol-based polyester represented by Structural Formula 1.

[Structural Formula 1]

In Structural Formula 1,

, 바람직하게는 원자가 결합, C1 내지 C3의 알킬렌기 또는

, 보다 바람직하게는 원자가 결합, 메틸렌기 또는 에틸렌기이고,X is each independently a valence bond, a C1 to C5 alkylene group, or

, preferably a valence bond, a C1 to C3 alkylene group, or

, more preferably a valence bond, a methylene group or an ethylene group,

R ³ is a C1 to C5 alkyl group, preferably a C1 to C3 alkyl group,

R ⁴ is a valence bond or a C1 to C5 alkylene group, preferably a valence bond or a C1 to C3 alkylene group,

R ¹ is each independently a hydrogen atom or a C1 to C9 alkyl group, preferably a hydrogen atom or a C1 to C3 alkyl group, more preferably a hydrogen atom or a methyl group,

R ² is each independently a hydrogen atom or a C1 to C9 alkyl group, preferably a hydrogen atom or a C1 to C3 alkyl group, more preferably a hydrogen atom,

p is each independently any one of the integers of 1 to 6, preferably any one of the integers of 2 to 4, more preferably 3,

m ₁ and m ₂ are each the number of repeats of the repeating unit,

The weight average molecular weight of the diol-based polyester may be 3,000 to 1,000,000.

The number average molecular weight of the diol-based polyester may be 1,500 to 200,000.

The diol-based polyester may be prepared from lactone derived from biomass.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, 또는

로 이루어진 군에서 선택된 1종 이상을 포함할 수 있으며, 바람직하게는

를 포함할 수 있다.The lactone is

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, or

It may include one or more selected from the group consisting of, preferably

may include.

In addition, the present invention provides a powder coating comprising the diol-based polyester.

Hereinafter, a method for producing the diol-based polyester of the present invention will be described.

The method for producing a diol-based polyester of the present invention may include preparing a diol-based polyester represented by Structural Formula 1 by reacting a lactone represented by Structural Formula 2 with a diol represented by Structural Formula 3 in Scheme 1 below.

[Scheme 1]

In Scheme 1,

Since the diol-based polyester represented by Structural Formula 1 is the same as the description of the above-described diol-based polyester of the present invention, the specific details thereof will be referred to.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes only, and the scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of propanediol isosorbide

[Scheme 1]

With reference to Scheme 1, a method for producing propanediol isosorbide will be described.

In a 50 mL round bottom flask, 1.46 g (10 mmol) of isosorbide and 3.366 g (60 mmol) of a 50% aqueous solution of potassium hydroxide (KOH) were stirred together for 15 minutes. Then, 0.032 g (0.06 mmol) of tetrabutylammonium bromide (TBAB) and 7.26 g (60 mmol) of allyl bromide were added dropwise, followed by stirring at 75° C. for 3 hours to react. Thereafter, unreacted allyl bromide was removed under vacuum. The reaction was cooled at room temperature, and filtered using 200 ml of methylene chloride. After extraction 2-3 times using distilled water (200ml), the organic layer is collected by washing 2-3 times using a saturated aqueous sodium chloride solution. Next, water in the organic layer was removed with 10 g of magnesium sulfate. After concentration, it was separated using column chromatography (Hex:EA=4:1) to obtain 78% isosorbide diallyl ether. The NMR result of the child carbide diallyl ether is shown in FIG. 1 .

0.226 g (1 mmol) of the child carbide diallyl ether was put into a 50 mL dried round bottom flask filled with argon (Ar), and the temperature was equilibrated at 0°C. Then, 4.4ml (4.4mmol) of 0.5M 9-borabicyclo[3.3.1]nonane (9-BBN) dissolved in tetrahydrofuran (THF) was added at 0°C. After dropwise addition very slowly, the mixture was stirred at room temperature for 2 hours. Then, 0.74ml (2.2mmol) of 3M sodium hydroxide (NaOH) and _{0.23ml (2.2mmol) of 30% hydrogen peroxide (H 2} O ₂ ) were slowly added dropwise at 0° C. sequentially. After stirring at room temperature for 2-3 hours and removing only THF with a concentrator, a large amount of methanol (MeOH) was added to precipitate the additional product as much as possible, followed by filtering using celite. After concentration to water, chloroform (CHCl ₃ ) was added, and _{water was removed with anhydrous magnesium sulfate (MgSO 4} ), filtered through celite, and concentrated once more. It was separated using column chromatography (Methanol:Ethyl acetate = 1:10) to prepare propanediol child carbide. The NMR result of the propanediol child carbide is shown in FIG. 2 .

Preparation Example 2: Preparation of propanediol isosorbide

[Scheme 2]

With reference to Scheme 2, a method for producing propanediol isosorbide will be described.

5.56 g (40 mmol) of 3-bromo-1-propanol and 3,4-dihydro-2H-pyran (3,4-Dihydro) in tetrahydrofuran (THF) as a solvent -2H-pyran, DHP) 3.95 g (47 mmol) was added and temperature equilibrated at 0 °C. Thereafter, 0.12 g (0.68 mmol) of p-toluenesulfonic acid (p-TSA) was added as a catalyst, followed by stirring for an additional 30 minutes. Then, the temperature was raised to room temperature and stirred for 12 hours. After the reaction was completed, the residue was further removed using sodium bicarbonate and water after washing with brine. Thereafter, water was removed with sodium sulfate, followed by column chromatography (Ethyl acetate:n-hexane = 1:3), and 2-(3-bromopropoxy)tetrahydro-2H-pyran (2-(3-bromopropoxy) ) tetrahydro-2H-pyran) was obtained.

After dissolving 2.63 g (18 mmol) of child carbide in 60 ml of dimethylformamide (N,N-Dimethylformamide, DMF), nitrogen was blown in. Then, 0.91 g (38 mmol) of sodium hydride contained in the oil was added dropwise, followed by stirring at 50° C. for 2 hours. 30ml of DMF in which the 2-(3-bromopropoxy)tetrahydro-2H-pyran was dissolved was slowly added dropwise, followed by stirring at room temperature for 24 hours. After removing the solvent, the _{residue was washed with water and CHCl 3} and then water was removed with sodium sulfate. Finally, it was separated by column chromatography (Petroleum ether:n-hexane = 1:1) to synthesize tetrahydropyranyl propyl isosorbide.

Finally, 5.17 g (12 mmol) of tetrahydropyranyl propyl isosorbide was dissolved in 50 ml of methanol, and a solution of 0.4 ml of 37% hydrochloric acid (HCl) in 5 ml of methanol was added, followed by reaction for 6 hours. The solvent was then removed in vacuo and neutralized with potassium carbonate. After washing the residue with water and CHCl ₃ , water was removed with sodium sulfate. Finally, it was separated by column chromatography (Ethyl acetate:Methanol = 10:1) to synthesize propanediol carbide.

Example One: propanediol Isosorbide used dior of polyester (ISO-PDO_1) Produce

[Scheme 3]

A method for producing a diol-based polyester will be described with reference to Scheme 3 above.

In a 2-neck 250ml round flask, delta-valerolactone (δ-Valerolactone) (2) 2.32 g (25 mmol) and propanediol isosorbide (3) 52.4 mg (0.2 mmol) prepared according to Preparation Example 1 A _{solution dissolved in 1ml of CHCl 3} solvent was added, a nitrogen (N ₂ ) balloon was connected, and the delta-valirolactone material was subjected to a ring-opening reaction while stirring for 10 minutes. After CHCl ₃ 26.6mg (0.1875mmol) of TBD catalyst (cat 1) dissolved in 1ml was put, and the nitrogen balloon was removed. Sequentially, while holding a vacuum, the CHCl ₃ solvent was removed to promote polymerization. Then, as the polymerization proceeded, the viscosity increased and the stirring speed was gradually decreased while stirring was continued until solid. Finally, a diol-based polyester (1) (ISO-PDO_1) was prepared by terminating the reaction when stirring was stopped. The number average molecular weight of the diol-based polyester (1) (ISO-PDO_1) was 17.7 k, and the molecular weight distribution was 1.51.

Example 2: propanediol Isosorbide used dior of polyester (ISO-PDO_2) Produce

Diol-based polyester (1) (ISO-PDO_2) in the same manner as in Example 1, except that 104.8 mg (0.4 mmol) was used instead of 52.4 mg (0.2 mmol) of propanediol carbide in Example 1 ) was prepared. The number average molecular weight of the diol-based polyester (1) (ISO-PDO_2) was 12.2 k, and the molecular weight distribution was 1.49.

comparative example One: propanediol Isosorbide unused dior polyester Produce

[Scheme 4]

A method for producing the diol-based polyester (1') without using propanediol child carbide will be described with reference to Scheme 4 above. In Scheme 4, n is the number of repeats of the repeating unit.

2.32g (25mmol) of Delta-Valerolactone (2) and CHCl _{3 in a 2-neck 250ml round flask} 26.6mg (0.1875mmol) of TBD catalyst (cat 1) dissolved in 1ml was added, and the CHCl ₃ solvent was removed while holding vacuum sequentially to prepare a diol-based polyester (1') (VL_ref). The number average molecular weight of the diol-based polyester (1') (VL_ref) was 28.1 k, and the molecular weight distribution was 1.62.

[Test Example]

Test Example 1: Analysis of thermal properties

3 is a graph showing the thermal behavior of the diol-based polyester prepared according to Examples 1 and 2 and Comparative Example 1. Referring to FIG. 3 , the difference in polymerization degree can be confirmed through the change in thermal properties according to the content of propanediol isosorbide, and as the content of propanediol isosorbide increases, T _m decreases, so that it can be applied after liquefaction even at a lower temperature. It has been confirmed that the possibility of

Although preferred embodiments of the present invention have been described above, those of ordinary skill in the art can add, change, delete or It will be possible to variously modify and change the present invention by addition, etc., which will also be included within the scope of the present invention. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form. The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (12)

For use in powder coatings, represented by the structural formula 1,
In Structural Formula 1 below

is derived from delta-valerolactone (δ-Valerolactone), a diol-based polyester:
[Structural Formula 1]

In Structural Formula 1,
X is an ethylene group,
Y is a carbon atom,
R ¹ is each a hydrogen atom,
R ² are each a hydrogen atom,
p is each 3,
m ₁ and m ₂ are each the number of repeats of the repeating unit,
The weight average molecular weight of the diol-based polyester is 3,000 to 1,000,000. delete delete According to claim 1,
The diol-based polyester, characterized in that the number average molecular weight of the diol-based polyester is 1,500 to 200,000. delete According to claim 1,
wherein the delta-valirolactone is derived from biomass,
The structural formula of the delta-valirolactone

Diol-based polyester, characterized in that A powder coating comprising the diol-based polyester of claim 1. A step of reacting a lactone represented by Structural Formula 2 with a diol represented by Structural Formula 3 in Reaction Scheme 1 below to prepare a diol-based polyester represented by Structural Formula 1,
The diol-based polyester is for use in powder coatings,
In Structural Formula 1 below

is derived from delta-valerolactone (δ-Valerolactone), a method for producing a diol-based polyester:
[Scheme 1]

In Scheme 1,
each X is an ethylene group,
Y is a carbon atom,
R ¹ is each a hydrogen atom,
R ² are each a hydrogen atom,
p is each 3,
m ₁ and m ₂ are each the number of repeats of the repeating unit,
The weight average molecular weight of the diol-based polyester is 3,000 to 1,000,000. delete delete 9. The method of claim 8,
The method for producing a diol-based polyester, characterized in that the number average molecular weight of the diol-based polyester is 1,500 to 200,000. 9. The method of claim 8,
A method for producing a diol-based polyester, wherein the lactone is derived from biomass.

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