KR20220151567A - Branched poly(lactic acid-3-hydroxypropionic acid) polymer and method for preparation thereof - Google Patents

Abstract

The present invention is to provide a novel branched poly(lactic acid-3-hydroxypropionic acid) copolymer capable of realizing excellent production yield while maintaining the inherent physical properties of poly(3-hydroxypropionic acid) and a preparation method thereof.

Description

Branched poly(lactic acid-3-hydroxypropionic acid) copolymer and method for preparing the same {Branched poly(lactic acid-3-hydroxypropionic acid) polymer and method for preparation thereof}

The present invention relates to novel branched poly(lactic acid-3-hydroxypropionic acid) copolymers and methods for their preparation.

Polylactic acid (PLA) is a plant-derived resin obtained from plants such as corn, and has attracted attention as an eco-friendly material having excellent tensile strength and elastic modulus while having biodegradable properties.

Unlike petroleum-based resins such as polystyrene resin, polyvinyl chloride resin, and polyethylene, which are used in the past, it has effects such as preventing petroleum resource depletion and suppressing carbon dioxide emission, so it can reduce environmental pollution, which is a disadvantage of petroleum-based plastic products. have. Therefore, as the environmental pollution problem due to waste plastics has emerged as a social problem, efforts are being made to expand the scope of application to product fields where general plastics (petroleum-based resins) were used, such as food packaging materials and containers, and electronic product cases.

However, compared to conventional petroleum-based resins, polylactic acid has poor impact resistance and heat resistance, and its application range is limited. In addition, it has poor elongation to break characteristics and is easily broken (brittleness), so there is a limit as a general-purpose resin.

In order to improve the above disadvantages, research on copolymers containing other repeating units in polylactic acid is being conducted, and in particular, 3-hydroxypropionic acid (3HP) is used as a comonomer to improve elongation. is getting attention In particular, a lactic acid-3HP block copolymer is attracting attention, and the copolymer has an effect of improving elongation characteristics while maintaining the inherent characteristics of polylactic acid.

However, in terms of commercialization, it is required to prepare a high molecular weight lactic acid-3HP block copolymer. In the process of condensation polymerization of 3-hydroxypropionic acid, a low molecular weight cyclic structure is generated, and a high molecular weight poly(3HP) -Hydroxypropionate) cannot be produced, and the production yield of poly(3-hydroxypropionate) also decreases.

Therefore, in order to improve the structural limitations, research on preparing copolymers with other monomers is being conducted, but there is a problem in that it is difficult to prepare a resin that achieves excellent manufacturing yield while maintaining the inherent physical properties of poly(3-hydroxypropionic acid). .

The present invention is to provide a novel branched poly(lactic acid-3-hydroxypropionic acid) copolymer exhibiting excellent physical properties and a preparation method thereof.

First, in the present specification, the term “substituted or unsubstituted” means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy groups; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, but is not limited thereto.

In this specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

In the present specification, the heteroaryl group is a heterocyclic group containing at least one of O, N, Si, and S as a heterogeneous element and having an aromatic property, and the number of carbon atoms is not particularly limited, but those having 2 to 60 carbon atoms desirable. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group (phenanthroline), thiazolyl group, isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but not limited thereto.

In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

In order to solve the problems of the present invention, the present invention provides a branched poly(lactic acid-3-hydroxypropionic acid) copolymer represented by Formula 1 below:

[Formula 1]

R-[AB] _k

In Formula 1,

R is a trivalent or higher functional group derived from a polyfunctional monomer,

A is a direct bond or a linking group derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane;

B is a substituent represented by Formula 1-1 or Formula 1-2 below,

[Formula 1-1]

[Formula 1-2]

* is the part connected to A,

k is an integer greater than or equal to 3;

n is an integer from 1 to 700;

m is an integer from 10 to 5,000.

In addition, the present invention is a first step of preparing a branched poly (3-hydroxypropionic acid) polymer; and

The branched poly (3-hydroxypropionic acid) polymer and lactide are subjected to ring-opening polymerization to obtain a branched poly (lactic acid-3-hydroxypropionic acid) copolymer represented by Formula 1 below in a second step. (Lactic acid-3-hydroxypropionic acid) A method for preparing the copolymer is provided.

In order to prepare a poly(lactic acid-3-hydroxypropionic acid) copolymer, conventional P3HP (polyhydroxypropionic acid) is synthesized and lactide is added thereto to perform ring-opening polymerization, or PLA (polylactic acid) and P3HP, respectively, are synthesized. There was a problem in that process efficiency was lowered because a multi-step reaction of separately polymerizing and then annealing them was applied. In particular, during this multi-step reaction process, low-molecular-weight by-products, particularly cyclic oligomers, are generated, and since condensation polymerization does not proceed with cyclic oligomers, the production yield of the copolymer is reduced, and an additional process requiring separation of the by-products is required. There was a necessary problem.

Therefore, the present inventors form a novel branched poly(3-hydroxypropionic acid) polymer using a unique multifunctional monomer, and when copolymerized with PLA through a ring-opening reaction, it has excellent physical properties and yield of synthesis Furthermore, the outstanding thing was confirmed and this invention was completed.

In particular, with the introduction of the novel branched structure, it is confirmed that the processability of the resin can be improved because the viscosity is rapidly lowered at a high shear rate, and the brittleness can be compensated for by lowering the crystallinity by the structure, and the present invention completed.

Hereinafter, the novel polymer structure of the present invention and its manufacturing method will be described in detail.

(Branched poly(lactic acid-3-hydroxypropionic acid) copolymer)

In one embodiment of the invention, the branched poly(lactic acid-3-hydroxypropionic acid) copolymer is represented by Formula 1 below:

[Formula 1]

R-[AB] _k

In Formula 1,

R is a trivalent or higher functional group derived from a polyfunctional monomer,

A is a direct bond or a linking group derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane;

B is a substituent represented by Formula 1-1 or Formula 1-2 below,

[Formula 1-1]

[Formula 1-2]

k is an integer greater than or equal to 3;

n is an integer from 1 to 700;

m is an integer from 10 to 5,000.

Here, the branched type is a polymer of monomers having three or more functional groups, and the R part in Formula 1 is defined as a branched structure.

Preferably, k is an integer from 3 to 10 or from 3 to 8.

Preferably, R is substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _6-60 aryl, or one or more of N, O and S A trivalent or higher linking group derived from a substituted or unsubstituted C _2-60 heteroaryl containing, wherein at least one of the carbon atoms of the alkyl, cycloalkyl, aryl and heteroaryl is selected from the group consisting of N, O and S It is unsubstituted or substituted with at least one selected heteroatom or carbonyl.

The copolymer is prepared by condensation polymerization of 3-hydroxypropionic acid and a multifunctional monomer, or lactide is added to a branched poly(3-hydroxypropionic acid) polymer prepared by ring-opening polymerization of β-propiolactone and a multifunctional monomer. is ring-opening polymerization to form a poly(lactic acid-3-hydroxypropionic acid) copolymer.

The multifunctional monomer is preferably, glycerol, pentaerythritol, 3-arm-poly (ethylene glycol) _{n = 2 ~ 15} , 4-arm-poly (ethylene glycol) _{n = 2 ~ 10} , di (trimethylol propane) , tripentaerythritol, xylitol, sorbitol, inositol, cholic acid, β-cyclodextrin, tetrahydroxyperylene, 2,2'-bis(hydroxymethyl)butyric acid (BHB), pyridinetetraamine (PTA), di Ethyltriaminepentaacetic acid, melamine, propane-1,2,3-triamine, tetraacetylene pentaamine, benzene-1,3,5-triamine, toluene-2,4,6-triisocyanate, 2-isocyanate Anatoethyl-2,6-diisocyanato caproate, triphenylphetan-4,4,4-triisocyanate, trimethylolpropane, triethanolamine, triglycidyl and s-triazine-1,3,5- Triethanol ether etc. are mentioned.

The copolymer may have a weight average molecular weight (Mw) of 30,000 to 500,000, preferably 32,000 to 300,000, 35,000 to 280,000, or 38,000 to 270,000, or 32,000 or more, 35,000 or more, or 38,000 or more, or 38,000 or less. 280,000 or less, or 270,000 or less. When it has the corresponding weight average molecular weight value, it is suitable for realizing proper processability.

The copolymer may have a number average molecular weight (Mn) of 10,000 to 150,000, preferably 15,000 to 120,000, 20,000 to 100,000, or 23,000 to 80,000, or 15,000 or more, 20,000 or more, or 23,000 or less, or 120,000 or less. It may be 100,000 or less, or 8,000 or less.

The copolymer may have a polydispersity index (PDI) of 1.5 to 5.0, preferably 1.6 to 4.5 or 1.61 to 4.0, 1.6 or more, 1.61 or more, 4.5 or less, or 4.0 or less.

(Method for producing branched poly(lactic acid-3-hydroxypropionic acid) copolymer)

According to another embodiment of the present invention, a method for preparing the branched poly(lactic acid-3-hydroxypropionic acid) copolymer is provided.

Specifically, the first step of preparing a branched poly(3-hydroxypropionic acid) polymer; and

The branched poly(3-hydroxypropionic acid) polymer and lactide are subjected to ring-opening polymerization to obtain a branched poly(lactic acid-3-hydroxypropionic acid) copolymer represented by Formula 1 below in a second step:

[Formula 1]

R-[AB] _k

In Formula 1,

R is a trivalent or higher functional group derived from a polyfunctional monomer,

A is a direct bond or a linking group derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane;

B is a substituent represented by Formula 1-1 or Formula 1-2 below,

[Formula 1-1]

[Formula 1-2]

k is an integer greater than or equal to 3;

n is an integer from 1 to 700;

m is an integer from 10 to 5,000.

Here, the structure represented by Formula 1 applies the same content as the above-described branched poly(3-hydroxypropionic acid) polymer, and the specific type and content of the monomers forming the polymer are the same as those described above. Therefore, it will not be described in detail here.

Hereinafter, each step will be described in detail.

(First step)

In the first step, the branched poly(3-hydroxypropionic acid) polymer is prepared by condensation polymerization of 3-hydroxypropionic acid and a multifunctional monomer, or by ring-opening polymerization of β-propiolactone and a multifunctional monomer. manufacture

Here, the multifunctional monomer is glycerol, pentaerythritol, 3-arm-poly (ethylene glycol) _{n = 2 to 15} , 4-arm-poly (ethylene glycol) _{n = 2 to 10} , di (trimethylol propane), Tripentaerythritol, xylitol, sorbitol, inositol, cholic acid, β-cyclodextrin, tetrahydroxyperylene, 2,2'-bis(hydroxymethyl)butyric acid (BHB), pyridinetetraamine (PTA), diethyl Triaminepentaacetic acid, melamine, propane-1,2,3-triamine, tetraacetylene pentaamine, benzene-1,3,5-triamine, toluene-2,4,6-triisocyanate, 2-isocyanate Itoethyl-2,6-diisocyanato caproate, triphenylphetane-4,4,4-triisocyanate, trimethylolpropane, triethanolamine, triglycidyl and s-triazine-1,3,5-triethanol Ether etc. are mentioned.

The branched poly(3-hydroxypropionic acid) polymer polymerized in the above step may be represented by Formula 2 below:

[Formula 2]

R-[A-(B')n] _k

In Formula 2,

R is a trivalent or higher functional group derived from a polyfunctional monomer,

A is a direct bond or a linking group derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane;

B' is a substituent represented by the following formula 1'-1 or formula 1'-2,

[Formula 1'-1]

[Formula 1'-2]

* is the part connected to A,

k is an integer greater than or equal to 3;

n is an integer from 1 to 700;

In the first step, when the branched poly(3-hydroxypropionic acid) polymer is prepared by condensation polymerization of 3-hydroxypropionic acid and a polyfunctional monomer, with respect to the 3-hydroxypropionic acid content, the polyfunctional monomer 0.1 It may be polymerized by being included in mol% to 20 mol%. When polymerized in the above content range, it is suitable for forming a desired branched structure with an appropriate crosslinking structure in excellent yield. When the amount of the polyfunctional monomer is less than 0.1 mol%, it is difficult to form the desired cross-linked structure, and when it exceeds 20 mol%, it is difficult to obtain a high-molecular-weight polymer due to cross-linking in the form of a relatively low molecular weight oligomer, and the reaction time is long, resulting in process efficiency There is a problem with this degradation. Preferably, the polyfunctional monomer content is 0.1 mol% to 15 mol%, 0.5 mol% to 10 mol%, or 1 mol% to 8 mol%, or 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more, or 15 mol% Or less, 10 mol% or less or 8 mol% or less may be used. In this case, the polymer can be formed without the aforementioned problems.

In addition, in the first step, when the branched poly(3-hydroxypropionic acid) polymer is prepared by ring-opening polymerization of β-propiolactone and a multifunctional monomer, with respect to the β-propiolactone content, the polyfunctional monomer It may be polymerized by being included in 0.1 mol% to 20 mol%. When polymerized in the above content range, it is suitable for forming a desired branched structure with an appropriate crosslinking structure in excellent yield. When the amount of the polyfunctional monomer is less than 0.1 mol%, it is difficult to form the desired cross-linked structure, and when it exceeds 20 mol%, it is difficult to obtain a high-molecular-weight polymer due to cross-linking in the form of a relatively low molecular weight oligomer, and the reaction time is long, resulting in process efficiency There is a problem with this degradation. Preferably, the polyfunctional monomer content is 0.1 mol% to 15 mol%, 0.5 mol% to 10 mol%, or 1 mol% to 8 mol%, or 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more, or 15 mol% Or less, 10 mol% or less or 8 mol% or less may be used. In this case, the polymer can be formed without the aforementioned problems.

The branched poly(3-hydroxypropionic acid) polymer may have a weight average molecular weight (Mw) of 1,000 to 100,000, preferably 1,500 to 80,000, 1,900 to 50,000, 2,000 to 40,000, or 5,000 to 30,000, or 1,500 or more. , 1,900 or more, 2,000 or more, or 2,000 or more, or 80,000 or less, 50,000 or less, 40,000 or less, or 30,000 or less.

The first step may be performed in the presence of a sulfonic acid-based catalyst and a tin-based catalyst. The catalyst has an effect of promoting polymerization and suppressing the generation of cyclic oligomers during polymerization.

Preferably, the sulfonic acid-based catalyst is p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. Also preferably, the tin-based catalyst is SnCl ₂ or Sn(oct) ₂ .

Preferably, the sulfonic acid-based catalyst is used in an amount of 0.001 mol% to 1 mol%, respectively, relative to 3-hydroxypropionic acid or β-propiolactone. Polymerization may be promoted within the above range and generation of cyclic oligomers may be suppressed. Preferably, the content of the sulfonic acid-based catalyst is 0.01 mol% to 0.8 mol%, or 0.02 mol% to 0.5 mol%, or 0.01 mol% or more, or 0.02 mol% or more, 0.8 mol% or less, or 0.5 mol% may be below.

Preferably, the tin-based catalyst is used in an amount of 0.00025 mol% to 1 mol%, respectively, relative to 3-hydroxypropionic acid or β-propiolactone. Polymerization may be promoted within the above range and generation of cyclic oligomers may be suppressed. Preferably, the tin-based catalyst is 0.001 mol% to 0.8 mol%, 0.005 to 0.5 mol%, or 0.01 to 0.3 mol%, or 0.001 mol% or more, 0.005 mol% or more, or 0.01 mol% or more, or 0.8 mol% % or less, 0.5 mol% or less, or 0.3 mol% or less.

The polymerization may be performed at 80 °C to 100 °C and 8 mbar to 12 mbar for 110 minutes to 130 minutes, followed by a reaction for 4 hours to 26 hours under a vacuum condition of 10 ^-2 torr. When melt polymerization is performed under the above conditions, generation of products of side reactions can be suppressed.

More specifically, the oligomerization reaction is performed at 80 ° C. to 100 ° C. and 8 mbar to 12 mbar for 110 minutes to 130 minutes, and then the reaction proceeds for 4 hours to 26 hours under a vacuum condition of 10 ^-2 torr to form the polymer of Formula 1. can be formed.

The subsequent polymerization may be carried out at the same temperature as the oligomerization reaction, or may be carried out by raising the temperature to 100 ° C to 120 ° C.

Preferably, after performing the reaction at about 90 ± 3 ° C and about 10 ± 1 mbar for about 120 ± 5 minutes, the temperature is raised to the same temperature or about 110 ± 3 ° C and the reaction is performed under vacuum conditions of about 10 ^-2 torr. can do. For reference, the reaction after oligomerization can be appropriately adjusted according to the content range of the polyfunctional monomer used, and when an excessive amount of the polyfunctional monomer is used, chain transfer as a side reaction occurs as the reaction time increases. It may occur and gelation may occur, so it can be performed by appropriately adjusting within about 24 hours.

On the other hand, if necessary, the 3-hydroxypropionic acid (or β-propiolactone) and the polyfunctional monomer may be independently pretreated before polymerization at 30 ° C to 100 ° C and 30 mbar to 150 mbar before polymerization. Through the pretreatment step, moisture present in 3-hydroxypropionic acid and the multifunctional monomer may be removed.

(Step 2)

Next, a second step is performed to obtain the branched poly(lactic acid-3-hydroxypropionic acid) copolymer represented by Chemical Formula 1 by ring-opening polymerization of the branched poly(3-hydroxypropionic acid) polymer and lactide. .

'Lactide' used in the present invention is L-lactide, D-lactide, meso-lactide consisting of one L-form and one D-form, or L-lactide and D-lactide at 50: A mixture in a weight ratio of 50 refers to D,L-lactide or rac-lactide.

In the second step, 0.1 to 40 parts by weight of the branched poly(3-hydroxypropionic acid) polymer may be included, preferably 0.5 to 20 parts by weight or 1 to 15 parts by weight, based on 100 parts by weight of lactide. 0.5 parts by weight or more or 1 part by weight or more, 20 parts by weight or less, or 10 parts by weight or less may be used. It is preferably used in the above content range to form a polymer having a new target branched structure.

In the second step, the polymerization may be carried out in the presence of a catalyst represented by Formula 3:

[Formula 3]

MA ¹ _p A ² _2-p

In Formula 3,

M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr;

p is an integer from 0 to 2;

A ¹ and A ² are each independently an alkoxy or carboxyl group.

Preferably, in the second step, the polymerization may be performed under a tin(II) 2-ethylhexanoate (Sn(Oct) ₂ ) catalyst.

In the second step, the polymerization may be carried out for 60 minutes to 120 minutes under nitrogen conditions of 150 ° C to 250 ° C, and preferably, under nitrogen conditions of 170 ° C to 200 ° C, 80 The reaction can be carried out for minutes to 100 minutes. In the case of polymerization under the above conditions, generation of products of side reactions can be suppressed, which is preferable.

On the other hand, if necessary, before polymerization, the branched poly(3-hydroxypropionic acid) polymer and lactide prepared in step 1 may be each independently pretreated at room temperature for about 5 hours to 24 hours before polymerization. Through the pretreatment step, moisture present in the branched poly(3-hydroxypropionic acid) polymer and lactide may be removed.

(article)

In addition, according to another embodiment of the present invention, an article comprising the novel branched poly(lactic acid-3-hydroxypropionic acid) copolymer is provided.

The article may include a packaging material, a film, a nonwoven fabric, and the like, and when applied to the article, elongation characteristics may be excellent and brittleness may be supplemented at the same time.

As described above, the branched poly(lactic acid-3-hydroxypropionic acid) copolymer and method for preparing the same according to the present invention implements excellent production yield while maintaining the inherent physical properties of poly(3-hydroxypropionic acid). polymers can be produced effectively.

Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

<Examples and Comparative Examples>

Example 1

(Step 1) 3-hydroxypropionic acid (3HP) dissolved in water and glycerol were put in an RBF and dried at 90°C and 100 torr for 2 hours.

70 g of dried 3-hydroxypropionic acid (3HP) and 7.156 g of glycerol (10 mol% compared to 3HP) were added to the reactor, and 295.6 mg of p-TSA (0.2 mol% compared to 3HP) was used as a catalyst at 90 ° C and 10 mbar for 2 hours. during the oligomerization reaction. A branched copolymer (Mw 2,700) was prepared by adding 157.4 mg of SnCl ₂ (0.05 mol% compared to 3HP) as a cocatalyst at a vacuum of 0.1 torr (t = 5) and conducting an additional polymerization reaction for 8 hours.

(Step 2) 4 g of the prepared branched P3HP copolymer and 40 g of lactide were put in a reactor, and moisture was vacuum dried at room temperature for about 16 hours. 180 ul of a Sn(Oct) ₂ solution having a concentration of 0.01 M in toluene was injected into the reactor, and the toluene was vacuum dried for 30 minutes. Next, the reactor was filled with nitrogen, and the reaction was performed in an oil bath preheated to 180° C. for 90 minutes, and a product containing a novel branched P3HP-co-PLA copolymer was obtained. In order to remove residual lactide in the product, devolatilization was performed at 140° C. for 4 hours to prepare a branched P3HP-co-PLA copolymer.

Example 2

In step 1 of Example 1, a branched P3HP copolymer (Mw: 2,300) was prepared in the same manner, except that 5 mol% of glycerol was used relative to 3HP.

In addition, in step 2 of Example 1, a branched P3HP-co-PLA copolymer was prepared in the same manner, except that the reaction time was 60 minutes.

Example 3

In step 1 of Example 1, a branched P3HP copolymer (Mw: 16,000) was prepared in the same manner, except that 1 mol% of glycerol was used relative to 3HP.

In addition, in step 2 of Example 1, a branched P3HP-co-PLA copolymer was prepared in the same manner, except that the reaction time was 70 minutes.

Example 4

In step 1 of Example 1, a branched P3HP copolymer (Mw: 39,000) was prepared in the same manner, except that 0.5 mol% of glycerol was used relative to 3HP.

In addition, in step 2 of Example 1, a branched P3HP-co-PLA copolymer was prepared in the same manner, except that the reaction time was 90 minutes.

Comparative Example 1

4 g of Linear P3HP copolymer (Mw 9,600) and 40 g of lactide prepared by a single condensation reaction of 3-hydroxypropionic acid (3HP) were placed in a reactor, and moisture was vacuum dried at room temperature for about 16 hours. 180 ul of a Sn(Oct) ₂ solution having a concentration of 0.01 M in toluene was injected into the reactor, and the toluene was vacuum dried for 30 minutes. Next, the reactor was filled with nitrogen, and the reaction was performed in an oil bath preheated to 180° C. for 90 minutes, and a product containing a novel branched P3HP-co-PLA copolymer was obtained. In order to remove residual lactide in the product, devolatilization was performed at 140° C. for 4 hours to prepare a P3HP-co-PLA copolymer.

Comparative Example 2

In Comparative Example 1, the same method was performed except that the linear P3HP copolymer (Mw 28,500) prepared by a single condensation reaction of 3-hydroxypropionic acid (3HP) was used in the same amount and the reaction time was 60 minutes. To prepare a P3HP-co-PLA copolymer.

<Experimental example>

The properties of the copolymers prepared in Examples and Comparative Examples were evaluated as follows.

1) GPC (gel permeation chromatography) molecular weight evaluation

For each step of the copolymer prepared in the above Examples and Comparative Examples, molecular weight was evaluated using Water e2695 model equipment and Agilent Plgel mixed c and b colum. The sample was prepared with chloroform as a solvent at 4 mg/ml and injected in 20 ul. The weight average molecular weight, number average molecular weight, and polydispersity index were measured by gel permeation chromatography (GPC: Tosoh ECO SEC Elite), and the results are shown in Table 1 below.

Solvent: chloroform (eluent)

Flow rate: 1.0 ml/min

Column temperature: 40 ℃

Standard: Polystyrene (corrected by cubic function)

division Molecular weight characterization Mn Mw PDI Example 1 24,073 38,963 1.61 Example 2 66,306 264,804 3.99 Example 3 55,769 171,131 3.06 Example 4 66,667 168,322 2.52 Comparative Example 1 40,310 112,000 2.7 Comparative Example 2 60,189 164,201 2.7

DSC (differential scanning calorimetry) thermal property evaluation

Thermal properties (Tg, Tm, cold crystallization (2nd heating result), Tc (1st cooling result)) in a nitrogen gas flow state using a TA DSC250 model equipment for each step of the copolymer prepared in the above Examples and Comparative Examples was measured, and the results are shown in Table 2 below.

Heat up from 40℃ to 190℃ at 10℃/min (1st heating) / Maintain temperature at 190℃ for 10 minutes

Cooling at 10℃/min from 190℃ to -60℃ (1st cooling) / Maintaining temperature at -60℃ for 10 minutes

-60℃~190℃, heating at 10℃/min (2 ^nd heating)

division Evaluation of polymer thermal properties Tc Tg Cold crystallization Tm Temperature ( ^o C) ΔH (J/g) Temperature ( ^o C) Temperature ( ^o C) ΔH (J/g) Temperature ( ^o C) ΔH (J/g) Example 1 98.1 9.78 45 103.68 21.14 155.5 36.2 Example 2 91.17 5.62 49.1 105.4 24.17 159.7 33.7 Example 3 112.2 34.9 50.0 N.D. N.D. 167.6 38.2 Example 4 109.6 34.2 54.1 N.D. N.D. 168.9 38.0 Comparative Example 1 98.3 35.02 50.0 N.D. N.D. 169.1 40.4 Comparative Example 2 97.1 38.8 50.9 N.D. N.D. 174 41

In general, when the crystallization rate is high, the enthalpy of Tc is high and there is little or no cold crystallization, and the higher the crystallinity, the higher the enthalpy of Tm. In addition, when the crystallinity is high, the strength of the material is increased, but it is brittle and has no elasticity. However, in the case of the branch structure as in the present invention, it can be confirmed that the brittle property can be lowered by lowering the crystallinity.

More specifically, as can be seen in Tables 1 and 2 above, as the brancher content increases in the same molecular weight range, cold crystallization is observed, and it can be seen that the temperature and enthalpy value of Tc tend to decrease. Accordingly, it can be confirmed that the enthalpy value of Tm is lowered.

Claims (18)

Branched poly(lactic acid-3-hydroxypropionic acid) copolymer represented by Formula 1:
[Formula 1]
R-[AB] _k
In Formula 1,
R is a trivalent or higher functional group derived from a polyfunctional monomer,
A is a direct bond or a linking group derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane;
B is a substituent represented by Formula 1-1 or Formula 1-2 below,
[Formula 1-1]

[Formula 1-2]

k is an integer greater than or equal to 3;
n is an integer from 1 to 700;
m is an integer from 10 to 5,000.
According to claim 1,
R is a substituted or unsubstituted C _1-60 alkyl, a substituted or unsubstituted C _3-60 cycloalkyl, a substituted or unsubstituted C _6-60 aryl, or a substituted group containing at least one of N, O and S; It is a trivalent or higher linking group derived from an unsubstituted C _2-60 heteroaryl, and at least one of the carbon atoms of the alkyl, cycloalkyl, aryl, and heteroaryl is selected from the group consisting of N, O, and S. unsubstituted or substituted by an atom or carbonyl,
A branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 1,
The polymer is
3-hydroxypropionic acid is condensation polymerized with a multifunctional monomer, or β-propiolactone is ring-opened polymerized with a branched poly(3-hydroxypropionic acid) polymer obtained by ring-opening polymerization with a multifunctional monomer,
A branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 3,
The multifunctional monomer,
Glycerol, pentaerythritol, 3-arm-poly(ethylene glycol) _n=2~15 , 4-arm-poly(ethylene glycol) _n=2~10 , di(trimethylolpropane), tripentaerythritol, xylitol, sorbitol, Inositol, cholic acid, β-cyclodextrin, tetrahydroxyperylene, 2,2'-bis(hydroxymethyl)butyric acid (BHB), pyridinetetraamine (PTA), diethyltriaminepentaacetic acid, melamine, propane -1,2,3-triamine, tetraacetylene pentaamine, benzene-1,3,5-triamine, toluene-2,4,6-triisocyanate, 2-isocyanatoethyl-2,6-di selected from the group consisting of isocyanato caproate, triphenylphetane-4,4,4-triisocyanate, trimethylolpropane, triethanolamine, triglycidyl and s-triazine-1,3,5-triethanol ether;
A branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 1,
The weight average molecular weight (Mw) is 30,000 to 500,000,
A branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
A first step of preparing a branched poly(3-hydroxypropionic acid) polymer; and
The branched poly (3-hydroxypropionic acid) polymer and lactide are subjected to ring-opening polymerization to obtain a branched poly (lactic acid-3-hydroxypropionic acid) copolymer represented by Formula 1 below in a second step. Method for preparing (lactic acid-3-hydroxypropionic acid) copolymer:
[Formula 1]
R-[AB] _k
In Formula 1,
R is a trivalent or higher functional group derived from a polyfunctional monomer,
A is a direct bond or a linking group derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane;
B is a substituent represented by Formula 1-1 or Formula 1-2 below,
[Formula 1-1]

[Formula 1-2]

k is an integer greater than or equal to 3;
n is an integer from 1 to 700;
m is an integer from 10 to 5,000.
According to claim 6,
The branched poly(3-hydroxypropionic acid) polymer is represented by Formula 2 below,
Process for preparing the branched poly(lactic acid-3-hydroxypropionic acid) copolymer:
[Formula 2]
R-[A-(B')n] _k
In Formula 2,
R is a trivalent or higher functional group derived from a polyfunctional monomer,
A is a direct bond or a linking group derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane;
B' is a substituent represented by the following formula 1'-1 or formula 1'-2,
[Formula 1'-1]

[Formula 1'-2]

* is the part connected to A,
k is an integer greater than or equal to 3;
n is an integer from 1 to 700;
According to claim 6,
The weight average molecular weight of the branched poly(3-hydroxypropionic acid) polymer is 1,000 to 100,000,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 6,
In the first step, the branched poly(3-hydroxypropionic acid) polymer is prepared by condensation polymerization of 3-hydroxypropionic acid and a multifunctional monomer, or by ring-opening polymerization of β-propiolactone and a multifunctional monomer. manufacturing,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 9,
The multifunctional monomer,
Glycerol, pentaerythritol, 3-arm-poly(ethylene glycol) _n=2~15 , 4-arm-poly(ethylene glycol) _n=2~10 , di(trimethylolpropane), tripentaerythritol, xylitol, sorbitol, Inositol, cholic acid, β-cyclodextrin, tetrahydroxyperylene, 2,2'-bis(hydroxymethyl)butyric acid (BHB), pyridinetetraamine (PTA), diethyltriaminepentaacetic acid, melamine, propane -1,2,3-triamine, tetraacetylene pentaamine, benzene-1,3,5-triamine, toluene-2,4,6-triisocyanate, 2-isocyanatoethyl-2,6-di selected from the group consisting of isocyanato caproate, triphenylphetane-4,4,4-triisocyanate, trimethylolpropane, triethanolamine, triglycidyl and s-triazine-1,3,5-triethanol ether;
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 9,
In the first step,
When the branched poly(3-hydroxypropionic acid) polymer is prepared by condensation polymerization of 3-hydroxypropionic acid and a multifunctional monomer,
With respect to the 3-hydroxypropionic acid content, contained in 0.1 mol% to 20 mol% of the polyfunctional monomer,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 9,
In the first step,
When the branched poly(3-hydroxypropionic acid) polymer is prepared by ring-opening polymerization of β-propiolactone and a multifunctional monomer,
With respect to the β-propiolactone content, contained in 0.1 mol% to 20 mol% of the multifunctional monomer,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 6,
In the second step, 0.1 to 40 parts by weight of a branched poly(3-hydroxypropionic acid) polymer based on 100 parts by weight of lactide,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 6,
The first step is performed in the presence of a sulfonic acid-based catalyst and a tin-based catalyst,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 6,
In the first step, after performing the reaction at 80 ° C. to 100 ° C. and 8 mbar to 12 mbar for 110 minutes to 130 minutes,
Carrying out the reaction for 4 hours to 26 hours under vacuum conditions of 10 ^-2 torr,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 6,
In the second step, the polymerization is carried out under a catalyst represented by Formula 3 below,
Process for preparing the branched poly(lactic acid-3-hydroxypropionic acid) copolymer:
[Formula 3]
MA ¹ _p A ² _2-p
In Formula 3,
M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr;
p is an integer from 0 to 2;
A ¹ and A ² are each independently an alkoxy or carboxyl group.
According to claim 6,
In the second step, the polymerization is carried out under a tin (II) 2-ethylhexanoate (Sn(Oct) ₂ ) catalyst.
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.
According to claim 6,
In the second step, the polymerization is carried out for 60 minutes to 120 minutes under 150 ℃ to 250 ℃ nitrogen conditions,
A method for producing a branched poly(lactic acid-3-hydroxypropionic acid) copolymer.