KR101622546B1 - Pentablock copolymer and preparation method thereof - Google Patents
Pentablock copolymer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a pentablock copolymer and a process for producing the same. More specifically, the present invention relates to a pentablock copolymer which is composed of poly (propylene oxide), poly (ethylene oxide), poly (lactic acid) Pentablock copolymer:
[Chemical Formula 1]
(Where m and n are integers from 1 to 100).
Description
The present invention relates to pentablock copolymers and processes for their preparation.
Amphiphilic block copolymers have been extensively studied for application of environmental, electronic and medical techniques based on self-assembled nanostructures and aggregates formed in both solid and liquid states. Structural specifications and morphologies of AB and ABA type die blocks and triblock copolymers have been studied not only in solid phase but also in liquid phase. In the hydrophilic solvent, the hydrophobic block (B) of the AB and ABA block copolymer is located in the center portion and the hydrophilic block (A) appears in the outer portion of the colloid micelle.
The poly (ethylene oxide) -b-poly (ethylene oxide) (PEO-PPO-PEO) triblock copolymer is a well-known surfactant and is a compatibilizer of polymer blends. And is used as a nanocarrier for biomedical applications. Particularly, micelle particles made of pluronic polymers are one of candidates for various biomedical fields such as drug delivery and biosensors due to their biocompatibility, temperature sensitivity and good solubility in aqueous solution. Recently, some types of PEO-PPO-PEO block copolymers have been used as templates for inorganic / organic-inorganic nanostructured (mesoporous) mixed materials. PEO blocks are very useful because they bind to other polar materials because of oxygen atoms with dipole moments in the chain. However, pluronic triblock copolymers are used in a variety of biomedical applications because of their high solubility without degradation in vivo. In addition, the relatively low hydrophobicity of the PPO block creates a wide interface between the PPO and the PEO block, which limits its application as a suitable platform for organic-inorganic conjugates using precursors containing bulky hydrophobic groups.
Biodegradable poly (lactic acid) (PLA) and poly (glycolic acid) (PGA) are widely used in surgical seals, drug delivery systems and tissue engineering skeletons. In another sensor application, biodegradable polymers are one of the potential solutions to solve the problems of medical waste.
It is thus possible to combine the poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, poly (lactic acid) and poly (glycolic acid) The research on the substances that can be expressed is going on.
Prior art documents relating thereto include a method for producing a biocompatible particle having a multi-core structure disclosed in Korean Patent Laid-Open Publication No. 10-2012-0046595 (published on May 10, 2012), and a multi- ≪ / RTI >
Accordingly, the present invention relates to pentablock copolymers wherein a poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, poly (lactic acid) and poly (glycolic acid) .
The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.
In order to solve the above problems, the present invention relates to a pentablock copolymer comprising a poly (propylene oxide), a poly (ethylene oxide), a poly (lactic acid), and a poly (glycolic acid)
[Chemical Formula 1]
(Where m and n are integers from 1 to 100).
Here, the pentablock copolymer has a weight average molecular weight of 12,700 to 29,700, and the pentablock copolymer has a polydispersity index of 1.3 to 1.9.
The weight ratio of poly (lactic acid) to poly (glycolic acid) to poly (propylene oxide) and poly (ethylene oxide) is 2.5 to 4.0.
The present invention also relates to a process for preparing a poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, which comprises mixing and stirring the poly (ethylene oxide) -poly (propylene oxide) -poly And
Adding the D, L-lactide, glycolide and tin organic metal catalyst to the triblock copolymer, stirring the mixture, and cooling the mixture to room temperature.
The organic solvent may be selected from the group consisting of toluene, methylene chloride, and chloroform.
The organic solvent is mixed and stirred at 100-120 < 0 > C.
The poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer is added in an amount of 27.3 to 63.2% by weight of the total weight of the triblock copolymer, D, L-lactide and glycolide, The D, L-lactide is added in an amount of 29.4 to 60.5 wt% of the total weight of the triblock copolymer, D, L-lactide and glycolide, and the glycolide is the triblock copolymer, D, L- Tide and glycolide in an amount of 7.4 to 13.5% by weight based on the total weight of the composition.
The tin-based organometallic catalyst may be one selected from the group consisting of SnO (stannous oxide), SnCl 2 (stannous chloride) and Sn (Oct) 2 (stannous octoate) , L-lactide and glycolide in an amount of 0.5 to 1.5% by weight based on the total weight of the composition.
And stirring after addition of the tin-based organic metal catalyst is performed at 100 to 160 ° C.
According to the present invention, the biocompatibility, temperature responsiveness and excellent solubility of poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) (PEO-PPO-PEO) triblock copolymers are utilized, (Lactic acid) and poly (glycolic acid), which are used in drug delivery systems and skeletons for tissue engineering, are bonded to poly (ethylene oxide) chains to be made into multi-block copolymers and can be usefully used for biomaterials such as drug delivery .
In addition, when the pentablock copolymer according to the present invention is used as a carrier for drug delivery, PEO is contained in the form of a ring around the PLGA, so that the drug can be supplied to a desired point without leakage.
1 is a schematic view showing a method for producing a pentablock copolymer according to the present invention.
Figure 2 shows the 1 H NMR spectra of Example 2 and Example 4 in CDCl 3 .
Figure 3 shows 13 C NMR spectra of the 2 and 4 pentablock copolymers in CDCl 3 .
4 is a graph showing GPC chromatograms of the weight average molecular weights of the pentablock copolymers of Examples 1 to 5;
Fig. 5 shows changes in weight of the pentablock copolymers of Examples 1 to 5 as a result of elevating the temperature to 500 DEG C under a nitrogen atmosphere.
Figure 6 shows the DTG results for the pentablock copolymers of Examples 1 to 5.
7 is a transmission electron micrograph of the pentablock copolymer according to the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.
The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.
The present invention relates to a pentablock copolymer comprising a poly (propylene oxide), a poly (ethylene oxide), a poly (lactic acid) and a poly (glycolic acid)
[Chemical Formula 1]
(Where m and n are integers from 1 to 100).
The pentablock copolymer according to the present invention utilizes the biocompatibility, temperature responsiveness and good solubility of poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) (PEO-PPO-PEO) triblock copolymer At the same time, poly (lactic acid) and poly (glycolic acid) used in surgical sutures, drug delivery systems, and tissue engineering skeletons are combined with poly (ethylene oxide) chains to form multi-block copolymers and are useful for biomaterials such as drug delivery Can be used. In addition, when the pentablock copolymer according to the present invention is used as a carrier for drug delivery, PEO is contained in the form of a ring around the PLGA, so that the drug can be supplied to a desired point without leakage.
The pentablock copolymer according to the present invention has a weight average molecular weight of 12,700 to 29,700 and a polydispersity index of 1.3 to 1.9.
The weight ratio of poly (lactic acid) to poly (glycolic acid) to poly (propylene oxide) and poly (ethylene oxide) is 2.5 to 4.0.
The present invention also relates to a process for preparing a poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, which comprises mixing and stirring the poly (ethylene oxide) -poly (propylene oxide) -poly And
Adding the D, L-lactide, glycolide and tin organic metal catalyst to the triblock copolymer, stirring the mixture, and cooling the mixture to room temperature.
Hereinafter, the present invention will be described in detail.
The pentablock copolymer according to the present invention comprises the steps of mixing poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer into an organic solvent and stirring.
The poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) is specifically Pluronic F68 having a weight average molecular weight of 8,500 and the poly (ethylene oxide) -b-poly (propylene oxide) b-poly (ethylene oxide) triblock copolymer consisting of 30 units of hydrophobic PO (propylene oxide) block and 75 units of hydrophilic EO (ethylene oxide) block at both ends.
The organic solvent may be selected from the group consisting of toluene, methylene chloride, acetone, chloroform, ethanol, and methanol.
The stirring of the organic solvent is preferably performed at 100 to 120 ° C under an argon atmosphere. (Ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer can not be removed when the stirring is carried out at a temperature lower than 100 ° C, There is a problem that the chain of the triblock copolymer is damaged.
Next, the process for preparing a pentablock copolymer according to the present invention comprises the steps of adding D, L-lactide, glycolide and tin-based organometallic catalyst to the moisture-removed triblock copolymer, stirring the mixture, .
The poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer is added in an amount of 27.3 to 63.2 wt% of the total weight of the triblock copolymer, D, L-lactide and glycolide And the D, L-lactide is added in an amount of 29.4 to 60.5 wt% of the total weight of the triblock copolymer, D, L-lactide and glycolide, and the glycolide is the triblock copolymer, D, L - < / RTI > lactide and glycolide in a total amount of 7.4 to 13.5% by weight. The stability, solubility and size of micelles can be controlled by mixing the above-mentioned triblock copolymer, D, L-lactide and glycolide to the above-mentioned defined range, and based on the embodiment of the present invention, The length can be adjusted from 1 to 100 times the length of the entire chain.
The tin-based organometallic catalyst may be one selected from the group consisting of SnO (stannous oxide), SnCl 2 (stannous chloride), and Sn (Oct) 2 (Stannous octoate).
The tin-based organometallic catalyst is preferably added in an amount of 0.5 to 1.5% by weight based on the total weight of D, L-lactide and glycolide. When the tin-based organometallic catalyst is less than 0.5% by weight, the degree of chemical bonding between D, L-lactide and glycolide is so low that the monomers introduced at the initial stage of the reaction can not bond together and a multiblock copolymer having a desired length can not be formed If the amount exceeds 1.5% by weight, there is a problem that the reaction rate becomes too fast and the molecular weight distribution becomes large or the tin-based organic metal is present as an impurity in the final polymer.
The stirring after addition of the tin-based organic metal catalyst is preferably performed at 100 to 160 ° C. The D, L-lactide and glycolide monomers are ring opened with a tin-based organometallic catalyst and a poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer having terminal hydroxyl groups At the same time, hydrophilic glycolide monomers combine with poly (lactic acid) to form poly (lactic acid-co-glycolic acid) (PLGA) blocks.
The pentablock copolymer precipitated in powder form in the cooling process may be further filtered using a vacuum flask and dried under vacuum.
Example: Preparation of pentablock copolymer
D, L-lactide (DLLA) and glycolide (GA) were purchased from Aldrich and recrystallized with ethyl acetate and stored at -2 ° C prior to use of purified DLLA and GA. Pluronic F68 was purchased from Aldrich, dried under vacuum, and Sn (Oct) 2 was also purchased from Aldrich.
A 1 L round bottomed flask with a stopcock was treated under an argon atmosphere for 3 hours to remove water in the flask. 750 ml of toluene was added to the floronic F68, placed in a flask, and stirred at 120 캜 for 3 hours under an argon atmosphere to remove a small amount of water vapor in the F68 triblock copolymer. After cooling to room temperature, 1% by weight of D, L-lactide, 1% by weight of glycolide and Sn (Oct) 2 were added to the flask under an argon atmosphere, and the mixture was stirred at 120 ° C for 24 hours under an argon atmosphere. Lt; / RTI > The precipitated powder was put into 5000 mL of diethyl ether, filtered using a vacuum flask, and dried under vacuum for 30 days to prepare a pentablock copolymer powder (see FIGS. 1 and 7).
Table 1 below shows the contents of D, L-lactide, glycolide and F68 triblock copolymer in the process for preparing the pentablock copolymer according to the present invention based on the examples.
The PLGA-F68-PLGA of Examples 1 to 5 prepared by ring opening polymerization of cyclic D, L-lactide and glycolide monomers using octanoic acid tin (Sn (Oct) 2 ) The block copolymers have different compositions. The ring opening monomer is bonded to both ends of the pluronic F68 (EO 75 PO 30 EO 75 ) with terminal hydroxyl groups, and the reaction mechanism is judged to be a kind of coordination polymerization by the Sn (Oct) 2 catalyst . The molecular weight and the block composition were controlled by the amount of D, L-lactide and glycolide monomer added.
Experimental Example 1: Analysis of structure and composition of pentablock copolymer
The structure and composition of the pentablock copolymer according to the present invention were analyzed by 1 H and 13 C NMR Fourier Transform Analyzer, and the results are shown in FIG. 2 and FIG. 3.
Chemical shifts in ppm of the pentablock copolymer sample were obtained using tetramethylsilane (TMS) as a standard sample.
1 H NMR (500 MHz, CDCl 3, TMS), δ (ppm): 1.05-1.25 (m, -OCH 2 -CH (CH 3) -), 1.45-1.79 (m, -O-CH (CH 3) -CO- and HO-CH (CH 3 ) -CO-), 3.35-3.75 (m, -OCH 2 -CH 2 - and -OCH 2 -CH (CH 3 ) -), 4.20-4.40 -OCH 2 -CH 2 -O-), 4.55-5.00 (m, -OCH 2 -CO-), 5.05-5.45 (m, -O-CH (CH 3 ) -CO-) (see FIG.
13 C NMR (500 MHz, CDCl 3, TMS), δ (ppm): 16.66 (-O-CH (CH 3) -CO), 17.45 (-OCH 2 -CH (CH 3) -), 60.75 (-OCO -CH 2 -), 68.99 (-O -CH (CH 3) -CO-), 70.56 (-OCH 2 -CH 2 - and -OCH 2 -CH (CH 3) - ), 166.43 (-OCO-CH 2 -), 169.35 (-O-CH (CH 3) -CO -) ( See Figure 3).
Figure 2 shows the 1 H NMR spectra of Example 2 and Example 4 in CDCl 3 . {Poly (lactic acid), m -co- (glycolic acid) n} -b- poly (ethylene oxide) 75 -b- poly (propylene oxide) 30 -b- poly (ethylene oxide) -b- poly {75 (lactic acid) the number of - m -co- (glycolic acid)} n the degree of polymerization (m, n) within a PLGA block copolymer PPO in F68 triblock copolymer (, δ = 1.05-1.25 -OCH 2 -CH (CH 3)) methyl of PLA and PGA section on the basis of the (-O-CH (CH 3) -CO-, δ = 1.45-1.79) or methylene (-OCH 2 -CO-, δ = 4.55-5.00 ) are calculated from the peak intensity ratio of . 4.20-4.40 ppm the small peak in Fig. 2 (a) As shown in D, L- lactide or a PEO block in the associated ester group and glycolide in methylene protons (-CO-O-CH 2 -CH 2 -O appearing in -), indicating that a chemical bond has been successfully formed between the F68 copolymer and the cyclic LA and GA monomers. As shown in Figs. 2 (b) and 2 (c), the ratio of the peak intensities (f / a) showing the repeating unit ratio of PLA / PPO in Example 4 was larger than that in Example 2 . This means that the amount of PLA block in Example 4 is larger than that in Example 2. [ Similarly, the d / a ratios in Example 2 and Example 4 are different, which is due to the unit ratio of the PGA / PPO block.
Figure 3 shows 13 C NMR spectra of the 2 and 4 pentablock copolymers in CDCl 3 . Peaks at 17.45 ppm and 70.56 ppm are due to PPO and PEO blocks in the F68 polymer. The peaks at 16.66 ppm, 68.99 ppm and 169.45 ppm are for PLA and the peaks at 60.75 ppm and 166.43 ppm are for PGA. The degree of polymerization (m, n) of the PLGA block can be obtained from the respective peak intensity ratios and appears to be approximately the same as the peak intensity ratios obtained from 1 H NMR analysis.
From the NMR results of Examples 1 to 5, the number average molecular weight and weight ratio of each block were calculated and are shown in Table 2 below.
Raw material
product
The repeating units of EO in Examples 1 to 5 were calculated as 150 based on 30 units of PO block. b represents the weight ratio of (DLLA + GA) / (F68 + DLLA + GA) added to the raw material, and c represents the weight ratio of PLGA / (F68 + PLGA) calculated in the products (pentablock copolymer of Examples 1 to 5) .
Experimental Example 2: Analysis of number average molecular weight and weight average molecular weight and molecular weight distribution of pentablock copolymer
The number average molecular weight, weight average molecular weight and molecular weight distribution of the pentablock copolymer according to the present invention were analyzed by gel permeation chromatography (GPC), and the results are shown in FIG.
Gel permeation chromatography was performed on EcoSEC HLC 8320 GPC (Tosoh Co.) equipped with a differential refractometer as a detector. The pentablock copolymer was completely dissolved in the same concentration of 3 mg / mL tetrahydrofuran (THF) and filtered through a 0.45 [mu] m PTFE syringe filter. 10 μL of the block copolymer solution was injected into the GPC at a flow rate of 0.35 mL / min at 40 ° C. The molecular weight was obtained by calibrating with a calibration curve of polystyrene as a standard sample.
4 is a graph showing GPC chromatograms of the weight average molecular weights of the pentablock copolymers of Examples 1 to 5; P1, P2, P3, P4 and P5 in Fig. 4 represent Examples 1, 2, 3, 4 and 5, respectively. The molecular weight dispersion index (PDI) was obtained in the range of 1.32 to 1.91 as shown in Table 2 above. The dispersion index catalyst amount and the reaction temperature. The low dispersion index is due to the reaction temperature of 120 DEG C even though a large amount of catalyst (e.g., 1 wt% of the monomer) is used.
Experimental Example 3: Thermal Characterization of Pentablock Copolymer
The thermal characteristics of the pentablock copolymer according to the present invention were analyzed by thermogravimetric analysis (TGA) and differential thermal analysis (DTGA). The results are shown in FIG. 5 and FIG.
Thermogravimetric analysis (TGA) and differential thermogravimetric analysis (DTGA) were analyzed in a TA Q50 TGA system. The thermogravimetric and differential thermogravimetric profiles were recorded under a nitrogen atmosphere (100 mL / min) to 500 DEG C at a heating rate of 5 DEG C / min.
5 shows the weight change of the pentablock copolymers of Examples 1 to 5 by raising the temperature to 500 DEG C in a nitrogen atmosphere. P1, P2, P3, P4 and P5 in Fig. 5 indicate Examples 1, 2, 3, 4 and 5, respectively. Thermal degradation represents a two step change consisting of a first stage (Step I) at 160 to 260 ° C and a second stage (Step II) at 320 to 400 ° C. No degradation was observed at 100-160 ° C, indicating that there is no PLGA chain polymerized independently of the F68 polymer chain. The weight percentages at the ends of step I (e.g., 260 占 폚) were measured as 67.7, 53.9, 45.9, 36.5, and 30.4, which correspond to Example 1, Example 2, Example 3, This corresponds to Example 5. The reduced weight is approximately equal to the weight percent of PLGA, indicating that most PLGA blocks have been degraded to 260 占 폚. Figure 6 is the DTG results for the pentablock copolymers of Examples 1 to 5 and shows the degradation pattern with two steps. P1, P2, P3, P4 and P5 in Fig. 6 represent Examples 1, 2, 3, 4 and 5, respectively. The TGA results show that the PLGA block can be selectively removed and the weight ratio of PLGA block in the block copolymer can be estimated.
Although the specific examples of the pentablock copolymer according to the present invention and the production method thereof have been described so far, it is apparent that various modifications can be made without departing from the scope of the present invention.
Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.
It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.
Claims (13)
The poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer is added in an amount of 27.3 to 63.2 wt% of the total weight of the triblock copolymer, D, L-lactide and glycolide, The D, L-lactide is added in an amount of 29.4 to 60.5 wt% of the total weight of the triblock copolymer, D, L-lactide and glycolide, and the glycolide is the triblock copolymer, D, L- Tide and glycolide in an amount of 7.4 to 13.5% by weight based on the total weight of the PLGA block to adjust the length of the PLGA block to 1 to 100 relative to the total chain length,
The tin-based organometallic catalyst can not bind all the monomers added at the beginning of the reaction and can not form a multiblock copolymer having a desired length. The tin-based organometallic catalyst prevents the tin-based organic metal from being present as impurities in the final polymer, To 0.5 to 1.5% by weight of the total weight of D, L-lactide and glycolide,
Poly (ethylene oxide), poly (ethylene oxide), poly (lactic acid), and poly (lactic acid) obtained by stirring at 100 to 120 ° C for 24 hours under the argon site geometry after the addition of the tin-based organometallic catalyst and cooling to room temperature. (Pluronic F68 + PLGA) having a weight ratio of from 0.345 to 0.720, a weight average molecular weight of from 12,700 to 29,700 and a polydispersity index of from 1.3 to 20,000, 1.9, and exhibiting thermal degradation at 160 to 260 占 폚 and 320 to 400 占 폚, and having thermal properties without weight loss due to thermal degradation at 261 to 319 占 폚.
[Chemical Formula 1]
Here, m and n are integers of 1 to 100.
[Chemical Formula 1]
Here, m and n are integers of 1 to 100.
The poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer is added in an amount of 27.3 to 63.2 wt% of the total weight of the triblock copolymer, D, L-lactide and glycolide, The D, L-lactide is added in an amount of 29.4 to 60.5 wt% of the total weight of the triblock copolymer, D, L-lactide and glycolide, and the glycolide is the triblock copolymer, D, L- Tide and glycolide in an amount of 7.4 to 13.5% by weight based on the total weight of the PLGA block to adjust the length of the PLGA block to 1 to 100 relative to the total chain length,
The tin-based organometallic catalyst can not bind all the monomers added at the beginning of the reaction and can not form a multiblock copolymer having a desired length. The tin-based organometallic catalyst prevents the tin-based organic metal from being present as impurities in the final polymer, To 0.5 to 1.5% by weight of the total weight of D, L-lactide and glycolide,
The pentablock copolymer has a weight average molecular weight of 12,700 to 29,700, a polydispersity index of 1.3 to 1.9,
Characterized in that the pentablock copolymer exhibits thermal degradation at 160 to 260 DEG C and 320 to 400 DEG C and thermal properties without weight loss due to thermal degradation at 261 to 319 DEG C, ≪ / RTI >
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