WO2023182688A1 - 결정화도가 우수한 폴리락타이드 수지 조성물, 및 이의 제조 방법 - Google Patents
결정화도가 우수한 폴리락타이드 수지 조성물, 및 이의 제조 방법 Download PDFInfo
- Publication number
- WO2023182688A1 WO2023182688A1 PCT/KR2023/002705 KR2023002705W WO2023182688A1 WO 2023182688 A1 WO2023182688 A1 WO 2023182688A1 KR 2023002705 W KR2023002705 W KR 2023002705W WO 2023182688 A1 WO2023182688 A1 WO 2023182688A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- nucleating agent
- polaractide
- paragraph
- polylactide
- Prior art date
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 48
- 239000011342 resin composition Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title description 3
- 239000002667 nucleating agent Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical group O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 22
- PXQPEWDEAKTCGB-UHFFFAOYSA-N orotic acid Chemical compound OC(=O)C1=CC(=O)NC(=O)N1 PXQPEWDEAKTCGB-UHFFFAOYSA-N 0.000 claims description 20
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 16
- 229940035893 uracil Drugs 0.000 claims description 11
- 229960005010 orotic acid Drugs 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 26
- 239000004626 polylactic acid Substances 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229960002920 sorbitol Drugs 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- FBPFZTCFMRRESA-NQAPHZHOSA-N Sorbitol Chemical compound OCC(O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-NQAPHZHOSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- KGLPWQKSKUVKMJ-UHFFFAOYSA-N 2,3-dihydrophthalazine-1,4-dione Chemical compound C1=CC=C2C(=O)NNC(=O)C2=C1 KGLPWQKSKUVKMJ-UHFFFAOYSA-N 0.000 description 1
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 description 1
- KSILMCDYDAKOJD-UHFFFAOYSA-N 2-aminoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(N)C(=O)C2=C1 KSILMCDYDAKOJD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 cadmium phenylmalonate Chemical compound 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001434 poly(D-lactide) Polymers 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Definitions
- the present invention relates to a polylactide resin composition with excellent crystallinity and a method for producing the same.
- Polylactide (or polylactic acid; PLA) resin is manufactured based on bio-based materials, and is an eco-friendly material that emits less carbon dioxide, a global warming gas, during the manufacturing process and has the characteristic of being decomposed at a specific temperature and in composting facilities. am. In addition, it has recently been attracting attention as one of the materials that can replace existing crude oil-based resins as a response to waste plastic use and carbon emission regulations.
- polylactide resin has the advantage of being cheaper than other biodegradable polymers and having high tensile strength and modulus characteristics.
- polylactide resin has a rigid polymer main chain repeated in short units, has a slow crystallization rate due to slow chain mobility, has a long molding cycle, and thus has a problem of low productivity. Therefore, in order to improve these problems, much research is being conducted to improve productivity and heat resistance by introducing substances such as nucleating agents.
- the materials used as the nucleating agent are mainly inorganic nucleating agents, and materials such as talc, mica, and nanoclay are used, and some of them can be added during PLA molding to improve heat resistance and strength. It has been reported that it can be done. However, if these nucleating agents are added in excessive amounts, there is a problem of increased resin specific gravity and decreased transparency. Meanwhile, organic nucleating agents such as LAK 301 (aromatic sulfonate drivate), sodium benzoate, N-aminophthalimide, phthalhydrazide, and cadmium phenylmalonate are used as substances to improve crystallinity and transparency. However, these materials are not bio-based and have dispersion issues with PLA resin.
- LAK 301 aromatic sulfonate drivate
- sodium benzoate sodium benzoate
- N-aminophthalimide N-aminophthalimide
- phthalhydrazide phthalhydrazide
- the present invention is intended to provide a polylactide resin composition with excellent crystallinity by using a combination of specific nucleating agents.
- the present invention relates to a method for producing the polylactide resin composition.
- the present invention provides the following polylactide resin composition:
- polylactide resin polylactide resin; first nucleating agent; and a polaractide resin composition comprising a second nucleating agent, heat-treated at 25 to 120° C. for 1 to 30 minutes,
- the first nucleating agent is uracil or orotic acid
- the second nucleating agent is a compound containing a lactide oligomer structure
- polylactide resin used in the present invention is defined to encompass a homopolymer or copolymer containing the following repeating units.
- the polylactide resin may be manufactured by including the step of forming the repeating unit by ring-opening polymerization of a lactide monomer, and the polymer after the ring-opening polymerization and the forming process of the repeating unit are completed is called the “polylactide resin.” It can be referred to as ".
- lactide monomer can be defined as follows. Typically, lactide can be divided into L-lactide made of L-lactic acid, D-lactide made of D-lactic acid, and mesolactide made of one L-form and one D-form. Additionally, a 50:50 mixture of L-lactide and D-lactide is called D,L-lactide or rac-lactide. Among these lactides, it is known that if polymerization is performed using only L-lactide or D-lactide with high optical purity, L- or D-polylactide (PLLA or PDLA) with very high stereoregularity can be obtained.
- L- or D-polylactide PLLA or PDLA
- Lactide is known to have a faster crystallization rate and higher crystallization rate than polylactide, which has low optical purity.
- lactide monomer is defined to include all forms of lactide, regardless of differences in the characteristics of each form of lactide and the characteristics of the polylactide resin formed therefrom.
- the polylactide resin according to the present invention has, for example, a weight average molecular weight of 70,000 to 400,000.
- the present invention is characterized by improving the crystallinity of the polylactide resin by using the first and second nucleating agents together and heat-treating the composition at a specific temperature and for a specific time.
- the heat treatment temperature is 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, or 90°C or higher; It is 115°C or lower, or 110°C or lower. Most preferably, the heat treatment temperature is 90 to 110°C.
- the heat treatment time is 2 minutes or more, or 3 minutes or more; 25 minutes or less, 20 minutes or less, 15 minutes or less, 10 minutes or less, or 5 minutes or less. Most preferably, the heat treatment time is 3 to 5 minutes.
- the first nucleating agent is uracil or orotic acid.
- the first nucleating agent is a bio-based organic material that can be added to polylactide resin to act as a nucleation site and increase the crystallization rate by causing crystal nucleation at a high temperature.
- the first nucleating agent is included in an amount of 0.1 to 5% by weight based on the total weight of the polylactide resin composition. If the content is less than 0.1% by weight, the effect of using the first nucleating agent is insignificant, and if the content exceeds 5% by weight, there is a risk of impairing the inherent physical properties of the polylactide resin. More preferably, the first nucleating agent is 0.2% by weight or more, 0.3% by weight, 0.4% by weight, or 0.5% by weight or more relative to the total weight of the polylactide resin composition; 4.5 weight percent or less, 4.0 weight percent or less, or 3.5 weight percent or less.
- the second nucleating agent is a nucleating agent containing an oligomeric structure of lactide monomer. Due to the oligomeric structure of the lactide monomer, it has high compatibility with polylactide resin and is added to polylactide resin to play a role similar to a plasticizer. Accordingly, the degree of crystallinity can be increased by forming a free volume within the polylactide resin and improving the chain mobility of the polylactide resin.
- the second nucleating agent is a compound represented by the following formula (1):
- L is any one selected from the group consisting of:
- n1 is an integer from 1 to 4,
- n2 is an integer from 1 to 30,
- R is a substituent represented by the following formula (2),
- n the number of repeat units
- R' is hydrogen or acetyl
- the weight average molecular weight of the second nucleating agent can be adjusted depending on the number of each lactide repeating unit.
- the weight average molecular weight of the second nucleating agent is 1,000 to 50,000. More preferably, the weight average molecular weight of the second nucleating agent is 1,100 or more, 1,200 or more, 1,300 or more, 1,400 or more, or 1,500 or more; It is 40,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 9,000 or less, or 8,000 or less.
- the second nucleating agent is included in an amount of 3 to 25% by weight based on the total weight of the polylactide resin composition. If the content is less than 3% by weight, the effect of using the second nucleating agent is insignificant, and if the content exceeds 25% by weight, there is a risk of impairing the inherent physical properties of the polylactide resin. More preferably, the second nucleating agent is 3.5 wt% or more, 4.0 wt% or more, or 4.5 wt% or more based on the total weight of the polylactide resin composition; 24% by weight or less, 23% or less, 22% or less, or 21% or less by weight.
- the method for producing the polaractide resin composition according to the present invention described above includes the step of producing the above-described polaractide resin composition (step 1), and the polaractide resin composition prepared in step 1 at a temperature of 25 to 120. It includes heat treatment at °C for 1 to 30 minutes (step 2). At this time, the heat treatment temperature and time of step 2 are the same as described above.
- the polaractide resin composition according to the present invention described above has excellent crystallinity and thus has excellent processability while maintaining the inherent properties of polaractide resin.
- An oligomer was prepared using PEG-1000 (P10) as an initiator. Specifically, add Lactide:P10 to a 20 mL vial for a total of 4.5 g at a molar ratio of 16:1 (molar ratio), add Sn(Oct) 2 catalyst at 0.1 to 0.2 wt%, and add 4.5 g at 130°C. It was reacted for some time. After adjusting the temperature to 120°C, acetic anhydride (4 equivalents compared to the terminal OH group) was added, and the reaction proceeded for an additional 12 hours.
- An oligomer was prepared using sorbitol (SB) as an initiator. Specifically, add Lactide:SB to a 20 mL vial for a total of 4.5 g at a molar ratio of 24:1, add Sn(Oct) 2 catalyst at 0.1 to 0.2 wt%, and then react 4 times at 130°C. It was reacted for some time. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named SB-O-002, and the weight average molecular weight is shown in Tables 1 to 3 below.
- the mixture was placed in a vacuum oven and dried at 85°C for 4 hours. This was placed in a convection oven and heat treated for the temperature and time shown in Tables 1 to 3 below to prepare a polylactide resin composition.
- the physical properties of the first nucleating agent, the second nucleating agent, and the polylactide resin composition prepared above were measured by the following method.
- Mn number average molecular weight
- Mw weight average molecular weight
- Mw/Mn oligomer molecular weight distribution
- crystallinity analysis is performed during the first temperature increase. DSC was measured by heating to 250°C, which is above the melting temperature of PLA, at a heating rate of 10°C/min. When the temperature was raised, the melting peak, ⁇ Hm, was confirmed, and the crystallinity
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
항목 | 핵제 | 열처리 온도(℃) | 열처리 시간(분) | DSC, 1차 승온 | ||||
제1 핵제 (wt%) | 제2 핵제 (wt%) | Tcc (℃) | Tm (℃) | Xc (%) | ||||
종류 | Mw | |||||||
비교예 1 | - | - | - | 25 | 30 | 111.8 | 169.4 | 5.0 |
비교예 2 | 90 | 30 | 113.3 | 169.7 | 4.2 | |||
비교예 3 | 110 | 30 | - | 168.9 | 33.6 | |||
비교예 4 | D-sorbitol (1w%) | - | - | 25 | 30 | 108.3 | 169.4 | 4.3 |
비교예 5 | 90 | 30 | 94.6 | 167.7 | 25.0 | |||
비교예 6 | 110 | 30 | - | 168.2 | 34.2 | |||
비교예 7 | Uracil (1w%) | - | - | 25 | 30 | 108.8 | 169.8 | 4.7 |
비교예 8 | 90 | 30 | 98.3 | 168.1 | 32.7 | |||
비교예 9 | 110 | 30 | - | 168.4 | 33.9 | |||
비교예 10 | Orotic acid (1w%) | - | - | 25 | 30 | 107.5 | 169.0 | 4.6 |
비교예 11 | 90 | 30 | 104.0 | 167.4 | 35.3 | |||
비교예 12 | 110 | 30 | - | 167.9 | 33.7 | |||
실시예 1 | Uracil (1w%) | SB-O-002 (3w%) | 5,700 | 25 | 30 | 111.8 | 169.5 | 3.7 |
실시예 2 | 90 | 30 | 97.4 | 167.9 | 21.9 | |||
실시예 3 | 110 | 30 | - | 169.1 | 35.4 |
항목 | 핵제 | 열처리 온도(℃) | 열처리 시간(분) | DSC, 1차 승온 | ||||
제1 핵제 (wt%) | 제2 핵제 (wt%) | Tcc (℃) | Tm (℃) | Xc (%) | ||||
종류 | Mw | |||||||
비교예 13 | D-sorbitol (3w%) | - | - | 25 | 30 | 106.1 | 168.4 | 9.8 |
비교예 14 | 90 | 30 | 96.5 | 168.0 | 32.5 | |||
비교예 15 | 110 | 30 | - | 167.9 | 35.2 | |||
비교예 16 | Uracil (3w%) | - | - | 25 | 30 | 111.1 | 169.9 | 3.1 |
비교예 17 | 90 | 30 | 98.9 | 168.6 | 24.4 | |||
비교예 18 | 110 | 30 | - | 169.2 | 33 | |||
비교예 19 | Orotic acid (3w%) | - | - | 25 | 30 | - | 169.9 | 35 |
비교예 20 | 90 | 30 | 96.0 | 168.3 | 32.4 | |||
비교예 21 | 110 | 30 | - | 168.3 | 34.5 | |||
실시예 4 | Uracil (3w%) | P10-A-002 (5w%) | 6,000 | 25 | 30 | 101.1 | 167.9 | 11.7 |
실시예 5 | 90 | 30 | - | 168.0 | 37.5 | |||
실시예 6 | 110 | 30 | - | 167.8 | 36.6 | |||
실시예 7 | Uracil (3w%) | P10-A-002 (10w%) | 6,000 | 25 | 30 | 90.8 | 167.6 | 37.1 |
실시예 8 | 90 | 30 | - | 163.7 168.5 | 42.2 | |||
실시예 9 | 110 | 30 | - | 167.7 | 39.1 | |||
실시예 10 | Orotic acid (3w%) | P10-A-002 (5w%) | 6,000 | 25 | 30 | - | 169.1 | 38.5 |
실시예 11 | 90 | 30 | - | 169.0 | 37.4 | |||
실시예 12 | 110 | 30 | - | 167.3 | 34.8 | |||
실시예 13 | Orotic acid (3w%) | P10-A-002 (10w%) | 6,000 | 25 | 30 | - | 168.6 | 40.4 |
실시예 14 | 90 | 30 | - | 163.6 | 39.8 | |||
실시예 15 | 110 | 30 | - | 167.8 | 39 |
항목 | 핵제 | 열처리 온도(℃) | 열처리 시간(분) | DSC, 1차 승온 | ||||
제1 핵제 (wt%) | 제2 핵제 (wt%) | Tcc (℃) | Tm (℃) | Xc (%) | ||||
종류 | Mw | |||||||
비교예 22 | - | - | - | 110 | 30 | - | 168.9 | 33.6 |
비교예 23 | 1 | 119.1 | 167.2 | 1.9 | ||||
비교예 24 | 3 | 113.5 | 169.3 | 4.2 | ||||
비교예 25 | 5 | 102.8 | 169.1 | 31.1 | ||||
실시예 16 | Uracil (3w%) | P10-A-002 (5w%) | 6,000 | 110 | 30 | - | 167.8 | 36.6 |
실시예 17 | 1 | 96.6 | 167.3 | 18.4 | ||||
실시예 18 | 3 | - | 167.5 | 34 | ||||
실시예 19 | 5 | - | 167.4 | 36.7 | ||||
실시예 20 | Uracil (3w%) | P10-A-002 (10w%) | 6,000 | 110 | 30 | - | 167.7 | 39.1 |
실시예 21 | 1 | - | 168.5 | 38.9 | ||||
실시예 22 | 3 | - | 164.2 | 43 | ||||
실시예 23 | 5 | - | 165.1 | 42.3 | ||||
실시예 24 | Orotic acid (3w%) | P10-A-002 (5w%) | 6,000 | 110 | 30 | - | 167.3 | 34.8 |
실시예 25 | 1 | - | 167.3 | 33.6 | ||||
실시예 26 | 3 | - | 169.2 | 39.7 | ||||
실시예 27 | 5 | - | 168.6 | 39.2 | ||||
실시예 28 | Orotic acid (3w%) | P10-A-002 (10w%) | 6,000 | 110 | 30 | - | 167.8 | 39 |
실시예 29 | 1 | - | 164.4 | 44 | ||||
실시예 30 | 3 | - | 168.5 | 41.5 | ||||
실시예 31 | 5 | - | 163.7 | 43.7 |
Claims (12)
- 폴리락타이드 수지; 제1 핵제; 및 제2 핵제를 포함하는 폴라락타이드 수지 조성물을, 25 내지 120℃에서 1분 내지 30분 동안 열처리한 폴라락타이드 수지 조성물에 있어서,상기 제1 핵제는 유라실(uracil) 또는 오르트산(orotic acid)이고,상기 제2 핵제는 락타이드 올리고머 구조를 포함하는 화합물인,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 열처리 온도가 90 내지 110℃인,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 열처리 시간이 3분 내지 5분인,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 폴라락타이드 수지 조성물의 결정화도가 30% 이상인,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 폴리락타이드 수지의 중량평균분자량이 70,000 내지 400,000인,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 제1 핵제는 상기 폴리락타이드 수지 조성물 총 중량 대비 0.1 내지 5 중량%로 포함하는,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 제1 핵제는 상기 폴리락타이드 수지 조성물 총 중량 대비 0.5 내지 3.5 중량%로 포함하는,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 제2 핵제의 중량평균분자량은 1,000 내지 50,000인,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 제2 핵제는 상기 폴리락타이드 수지 조성물 총 중량 대비 3 내지 25 중량%로 포함하는,폴라락타이드 수지 조성물.
- 제1항에 있어서,상기 제2 핵제는 상기 폴리락타이드 수지 조성물 총 중량 대비 4.5 내지 21 중량%로 포함하는,폴라락타이드 수지 조성물.
- 1) 폴리락타이드 수지; 제1 핵제; 및 제2 핵제를 혼합하여 폴라락타이드 수지 조성물을 제조하는 단계(단계 1), 및2) 상기 단계 1에서 제조된 폴라락타이드 수지 조성물을 80 내지 120℃에서 1분 내지 10분 동안 열처리하는 단계(단계 2)를 포함하는,폴라락타이드 수지 조성물의 제조 방법에 있어서,상기 제1 핵제는 유라실(uracil) 또는 오르트산(orotic acid)이고,상기 제2 핵제는 락타이드 올리고머 구조를 포함하는 화합물인,제1항 내지 제11항 중 어느 한 항의 폴라락타이드 수지 조성물의 제조 방법.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP23775186.2A EP4332160A1 (en) | 2022-03-22 | 2023-02-27 | Polylactide resin composition having excellent crystallinity, and method for preparing same |
CN202380012038.8A CN117460771A (zh) | 2022-03-22 | 2023-02-27 | 结晶度优异的聚丙交酯树脂组合物及其制备方法 |
CA3220818A CA3220818A1 (en) | 2022-03-22 | 2023-02-27 | Polylactide resin composition excellent in crystallinity degree, and method for preparing the same |
AU2023240753A AU2023240753A1 (en) | 2022-03-22 | 2023-02-27 | Polylactide resin composition excellent in crystallinity degree, and method for preparing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2022-0035554 | 2022-03-22 | ||
KR1020220035554A KR20230137739A (ko) | 2022-03-22 | 2022-03-22 | 결정화도가 우수한 폴리락타이드 수지 조성물, 및 이의 제조 방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023182688A1 true WO2023182688A1 (ko) | 2023-09-28 |
Family
ID=88101354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2023/002705 WO2023182688A1 (ko) | 2022-03-22 | 2023-02-27 | 결정화도가 우수한 폴리락타이드 수지 조성물, 및 이의 제조 방법 |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP4332160A1 (ko) |
KR (1) | KR20230137739A (ko) |
CN (1) | CN117460771A (ko) |
AU (1) | AU2023240753A1 (ko) |
CA (1) | CA3220818A1 (ko) |
WO (1) | WO2023182688A1 (ko) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008115372A (ja) * | 2006-10-11 | 2008-05-22 | Kao Corp | 生分解性樹脂組成物 |
JP2010031203A (ja) * | 2008-07-31 | 2010-02-12 | Kao Corp | ポリ乳酸樹脂組成物の製造方法 |
JP2011080048A (ja) * | 2009-09-10 | 2011-04-21 | National Institute Of Advanced Industrial Science & Technology | ポリ乳酸樹脂組成物 |
JP2016011388A (ja) * | 2014-06-30 | 2016-01-21 | 株式会社リコー | ポリ乳酸樹脂組成物、及び成形体 |
-
2022
- 2022-03-22 KR KR1020220035554A patent/KR20230137739A/ko active Search and Examination
-
2023
- 2023-02-27 CN CN202380012038.8A patent/CN117460771A/zh active Pending
- 2023-02-27 AU AU2023240753A patent/AU2023240753A1/en active Pending
- 2023-02-27 CA CA3220818A patent/CA3220818A1/en active Pending
- 2023-02-27 WO PCT/KR2023/002705 patent/WO2023182688A1/ko active Application Filing
- 2023-02-27 EP EP23775186.2A patent/EP4332160A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008115372A (ja) * | 2006-10-11 | 2008-05-22 | Kao Corp | 生分解性樹脂組成物 |
JP2010031203A (ja) * | 2008-07-31 | 2010-02-12 | Kao Corp | ポリ乳酸樹脂組成物の製造方法 |
JP2011080048A (ja) * | 2009-09-10 | 2011-04-21 | National Institute Of Advanced Industrial Science & Technology | ポリ乳酸樹脂組成物 |
JP2016011388A (ja) * | 2014-06-30 | 2016-01-21 | 株式会社リコー | ポリ乳酸樹脂組成物、及び成形体 |
Non-Patent Citations (2)
Title |
---|
BIAN, X ET AL.: "Synthesis of multi-arm poly (L-lactide) and its modification on linear polylactide", POLYMER BULLETIN, vol. 74, 2017, pages 245 - 262, XP036126097, DOI: 10.1007/s00289-016-1713-4 * |
QIU ZHAOBIN, LI ZHISHENG: "Effect of orotic acid on the crystallization kinetics and morphology of biodegradable poly (L-lactide) as an efficient nucleating agent", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, AMERICAN CHEMICAL SOCIETY, vol. 50, no. 21, 2 November 2011 (2011-11-02), pages 12299 - 12303, XP093095504, ISSN: 0888-5885, DOI: 10.1021/ie2019596 * |
Also Published As
Publication number | Publication date |
---|---|
CA3220818A1 (en) | 2023-09-28 |
EP4332160A1 (en) | 2024-03-06 |
CN117460771A (zh) | 2024-01-26 |
AU2023240753A1 (en) | 2023-12-14 |
KR20230137739A (ko) | 2023-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2013073807A1 (ko) | 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품 | |
WO2019203542A1 (ko) | 무수당 알코올 유도체를 포함하는 친환경 열가소성 폴리에테르 에스테르 엘라스토머 및 이의 제조 방법 | |
WO2020197147A1 (ko) | 블록 공중합체 제조 방법 | |
WO2023033562A1 (ko) | 투명성과 충격강도가 우수한 생분해성 폴리에스테르 중합체 및 이를 포함하는 생분해성 고분자 조성물 | |
WO2023182688A1 (ko) | 결정화도가 우수한 폴리락타이드 수지 조성물, 및 이의 제조 방법 | |
WO2023182687A1 (ko) | 결정화 반감기가 우수한 폴리락타이드 수지 조성물, 및 이의 제조 방법 | |
WO2023182723A1 (ko) | 폴리락타이드 수지 조성물, 및 이의 제조 방법 | |
WO2016186470A1 (ko) | 신축성이 현저히 개선된 폴리락트산 공중합체 및 그 제조방법 | |
WO2013100288A1 (ko) | 분지상 폴리카보네이트-폴리실록산 공중합체 및 그 제조방법 | |
WO2023182686A1 (ko) | 결정화도가 우수한 폴리락타이드 수지 조성물, 및 이의 제조 방법 | |
WO2020197148A1 (ko) | 트리블록 공중합체 및 이의 제조 방법 | |
WO2017150750A1 (ko) | 공중합 폴리에스테르 수지 제조용 화합물 및 이를 이용한 공중합 폴리에스테르 수지의 제조방법 | |
WO2016093395A1 (ko) | 생분해성 폴리에스테르 수지 및 그로부터 얻어진 발포체 | |
WO2023239090A1 (ko) | 고도로 분지화된 폴리락타이드 수지, 및 이의 제조 방법 | |
WO2022075684A1 (ko) | 공중합체 및 이의 제조 방법 | |
JP2024521435A (ja) | 結晶化度に優れたポリラクチド樹脂組成物、及びその製造方法 | |
WO2023211078A1 (ko) | 고도로 분지화된 폴리락타이드 수지, 및 이의 제조 방법 | |
WO2022050815A1 (ko) | 폴리락테이트 입체이성질 복합체 및 이의 제조방법 | |
EP3880733A1 (en) | Functional resin composition comprising biomass-derived component | |
WO2023172085A1 (ko) | 생분해성 필름 | |
WO2022182160A1 (ko) | 인장강도가 우수한 폴리(락트산-b-3-하이드록시프로피온산) 블록 공중합체 및 이를 포함하는 물품 | |
WO2023027512A1 (ko) | 폴리(락트산-b-3-하이드록시프로피온산) 블록 공중합체 및 이의 제조 방법 | |
WO2022182154A1 (ko) | 투명성 특성이 우수한 폴리(락트산-b-3-하이드록시프로피온산) 블록 공중합체 및 이를 포함하는 물품 | |
WO2022255615A1 (ko) | 향상된 기계적 물성을 갖는 생분해성 퓨란계 복합체 및 이의 제조방법 | |
WO2024047618A2 (ko) | 열가소성 수지 조성물 및 이로부터 제조된 성형품 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23775186 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023775186 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 3220818 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202380012038.8 Country of ref document: CN Ref document number: 18565864 Country of ref document: US Ref document number: 2023240753 Country of ref document: AU Ref document number: AU2023240753 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2023775186 Country of ref document: EP Effective date: 20231127 |
|
ENP | Entry into the national phase |
Ref document number: 2023575947 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2023240753 Country of ref document: AU Date of ref document: 20230227 Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112023027145 Country of ref document: BR |