WO2022270869A1 - 폴리락트산 중합체의 제조 방법 - Google Patents
폴리락트산 중합체의 제조 방법 Download PDFInfo
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- WO2022270869A1 WO2022270869A1 PCT/KR2022/008774 KR2022008774W WO2022270869A1 WO 2022270869 A1 WO2022270869 A1 WO 2022270869A1 KR 2022008774 W KR2022008774 W KR 2022008774W WO 2022270869 A1 WO2022270869 A1 WO 2022270869A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polylactic acid
- acid polymer
- molecular weight
- mol
- phosphinite
- Prior art date
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 20
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 125000005538 phosphinite group Chemical group 0.000 claims description 15
- -1 biphenylyl Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 28
- 239000004310 lactic acid Substances 0.000 abstract description 14
- 235000014655 lactic acid Nutrition 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000004626 polylactic acid Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 6
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DEUBQKHJAWPZIU-UHFFFAOYSA-N (4-methoxyphenyl)-phenyl-propan-2-yloxyphosphane Chemical compound C1=CC(OC)=CC=C1P(OC(C)C)C1=CC=CC=C1 DEUBQKHJAWPZIU-UHFFFAOYSA-N 0.000 description 1
- LXFQSRIDYRFTJW-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=CC(C)=C(S(O)(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-N 0.000 description 1
- IRLYGRLEBKCYPY-UHFFFAOYSA-N 2,5-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(C)C(S(O)(=O)=O)=C1 IRLYGRLEBKCYPY-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
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000012888 cubic function Methods 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WRDZMZGYHVUYRU-UHFFFAOYSA-N n-[(4-methoxyphenyl)methyl]aniline Chemical compound C1=CC(OC)=CC=C1CNC1=CC=CC=C1 WRDZMZGYHVUYRU-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Definitions
- the present invention relates to a method for producing a polylactic acid polymer, and relates to a method for preparing a polylactic acid polymer having a high molecular weight and good color characteristics by using a specific catalyst combination in a ring-opening polymerization reaction of a lactic acid oligomer.
- Polylactic acid is a plant-derived resin obtained from plants such as corn, and has attracted attention as an eco-friendly material having biodegradable properties.
- polylactic acid is produced by polymerizing lactic acid produced by microbial fermentation, but only a low molecular weight polymer is produced by direct polymerization of lactic acid.
- a method of polymerizing low molecular weight polylactic acid obtained by direct polymerization of lactic acid to polylactic acid having a higher molecular weight using a chain coupling agent but the process is complicated and couple Since the ringing agent and the organic solvent are used together, there is a disadvantage in that it is not easy to remove them.
- the present invention provides a method for producing a polylactic acid polymer having a high molecular weight, good color characteristics, and a sufficiently fast polymerization rate by using a specific catalyst combination in the ring-opening polymerization of lactic acid oligomers.
- the present invention provides a method for preparing a polylactic acid polymer, comprising preparing a polylactic acid polymer by ring-opening polymerization of lactide in the presence of a tin-based catalyst and a phosphinite-based cocatalyst.
- the present inventors have confirmed that a polylactic acid polymer having a high molecular weight, good color characteristics, and an improved polymerization rate can be easily prepared by using a specific catalyst combination in a ring-opening polymerization reaction of lactic acid oligomers, and the present invention has been completed.
- a step of preparing a polylactic acid polymer by ring-opening polymerization (ROP) of lactide is included.
- the ring-opening polymerization is performed in the presence of a combination catalyst of a tin-based catalyst and a phosphinite-based cocatalyst, so that the polymerization rate is sufficiently fast and the reaction conversion rate is significantly improved compared to the case of using a conventional tin-based catalyst alone. It is easy to achieve high molecular weight. In addition, it is economical because it is possible to reduce the amount of tin-based catalyst used during the reaction, and the polylactic acid polymer finally produced has no color change problem while maintaining eco-friendliness and biodegradability, so it is easy to apply to various fields. In particular, by using the combination catalyst, a polylactic acid polymer having a very high molecular weight having a weight average molecular weight of about 400,000 or more can be easily prepared through the ring-opening polymerization.
- the tin-based catalyst may be Sn(Oct) 2 .
- the phosphinite-based cocatalyst may be one or more selected from compounds represented by Formula 1 below:
- R 1 is substituted or unsubstituted C 1-30 alkyl or substituted or unsubstituted C 6-30 aryl;
- R 2 and R 3 are each independently a substituted or unsubstituted C 1-30 alkyl or a substituted or unsubstituted C 6-30 aryl.
- said R 1 is methyl, ethyl, propyl, isopropyl, phenyl, biphenylyl or naphthyl, more preferably ethyl, propyl, isopropyl or phenyl.
- R 2 and R 3 are each independently methyl, ethyl, propyl, isopropyl, phenyl, biphenylyl or naphthyl, which are substituted or unsubstituted with methoxy, ethoxy, propoxy or isopropoxy can be redeemed More preferably, it is ethyl, propyl, isopropyl or phenyl, which phenyl may be unsubstituted or substituted with methoxy, ethoxy, propoxy or isopropoxy.
- the phosphinite-based cocatalyst may be one or more selected from compounds represented by Formulas 1-1 to 1-3 below:
- the tin-based catalyst and the phosphinite-based cocatalyst may be included in a molar ratio of 1:0.1 to 1:5, and the reaction conversion rate is significantly improved in the molar ratio range, and high molecular weight is easily achieved. More preferably, the tin-based catalyst and the phosphinite-based cocatalyst may be used in a molar ratio of 1:0.5 to 1:3, 1:0.8 to 1:2, or 1:0.9 to 1:1.5.
- the tin-based catalyst may be included in an amount of 0.001 mol% to 0.05 mol% relative to the lactide content, can promote ring-opening polymerization with high reactivity within the above range, is used in a relatively small amount and is economical, and has a color in the final polymer. It is desirable that it does not cause change. More preferably, the tin-based catalyst may be included in an amount of 0.0015 mol% to 0.03 mol%, 0.0015 mol% to 0.01 mol%, or 0.002 mol% to 0.01 mol% based on the lactide content. In addition, excellent catalytic activity can be realized by satisfying the above content range and simultaneously satisfying the above molar ratio range with the phosphinite-based cocatalyst.
- the phosphinite-based cocatalyst may be included in an amount of 0.001 mol% to 0.05 mol% relative to the lactide content, and it is preferable to promote condensation polymerization with high reactivity within the above range. More preferably, the phosphinite-based cocatalyst may be included in an amount of 0.0015 mol% to 0.03 mol%, 0.0015 mol% to 0.01 mol%, or 0.002 mol% to 0.01 mol% based on the lactide content. In addition, the content range may be satisfied and the molar ratio range with the above-described tin-based catalyst may be satisfied.
- the ring-opening polymerization reaction may proceed as a bulk polymerization that does not substantially use a solvent.
- substantially not using a solvent may encompass the case of using a small amount of solvent for dissolving the catalyst, for example, a maximum of less than 10 ml of solvent per 1 Kg of lactide used.
- a process for solvent removal after polymerization it is possible to omit a process for solvent removal after polymerization, and decomposition or loss of the resin in the solvent removal process can be suppressed.
- the polylactic acid polymer can be obtained with high conversion and yield by the bulk polymerization.
- the ring-opening polymerization may be carried out at 150 ° C to 200 ° C and 0.5 bar to 2 bar for 30 minutes to 6 hours, preferably, at 170 ° C to 190 ° C and 0.7 bar to 1.5 bar for 1 hour to 3 hours.
- the reaction can be carried out while When polymerization is performed under the above conditions, the conversion rate per hour is high, and the desired high molecular weight polylactic acid polymer can be efficiently prepared, and the resulting polymer has little discoloration.
- the lactide may be prepared according to a method commonly used in sugar, or a commercially available product may be used.
- L-lactide from FORUSORB L-lactide from TCI
- L-lactide from Sigma-aldrich L-lactide from Acros organics, but are not limited thereto.
- lactide prepared through the following steps may be used.
- step 1-1 of preparing a lactic acid prepolymer by condensation polymerization of lactic acid and depolymerization of the low molecular weight lactic acid prepolymer prepared through the condensation polymerization reaction Lactide can be produced by including 1-2 steps.
- the 'lactic acid' refers to L-lactic acid, D-lactic acid, or a mixture thereof.
- Reaction conditions of each step are not particularly limited, and for example, step 1-1 may be performed in the presence of a sulfonic acid-based catalyst and a tin-based catalyst.
- the sulfonic acid-based catalyst is p-toluenesulfonic acid, m -xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid.
- the tin-based catalyst is SnCl 2 .
- step 1-1 may be performed at 150 ° C. to 200 ° C. for 110 minutes to 130 minutes, followed by reaction at 150 ° C. to 200 ° C. and 10 mbar to 30 mbar for 1 hour to 5 hours.
- Steps 1-2 may be performed in the presence of a tin-based catalyst, and preferably, the tin-based catalyst is Sn(Oct) 2 .
- the step 1-2 may be performed at 200 ° C. to 250 ° C. and 8 mbar to 12 mbar for 1 hour to 5 hours, preferably, at 200 ° C. to 230 ° C. and 9 mbar to 11 mbar for 2 hours to 4 hours.
- the reaction can be carried out over time.
- the preparation method has an excellent conversion rate by using two types of combination catalysts.
- a polylactic acid polymer having a high molecular weight can be prepared with a relatively short reaction time and/or excellent conversion even when a small amount of catalyst is used.
- the preparation method exhibits a conversion rate of 75% or more, preferably a high conversion rate of 75% to 99%, 75% to 97%, 80% or more, 90% or more or 95% or more.
- the conversion rate means the percentage of the amount of reaction (number of moles) relative to the amount of lactide supplied (number of moles), and a specific method for measuring the conversion rate will be described in detail in experimental examples to be described later.
- a polylactic acid polymer prepared according to the above-described manufacturing method is provided.
- the weight average molecular weight (Mw) of the polylactic acid polymer may be 50,000 to 600,000, preferably 100,000 to 500,000. By satisfying the above range, it is suitable to realize physical properties required by commercial applications such as packaging materials, films, fibers, and durable materials.
- the number average molecular weight (Mn) of the polylactic acid polymer may be 25,000 to 300,000, preferably 50,000 to 250,000.
- the polylactic acid polymer may have a polydispersity index (PDI) of 1.0 to 3.0, preferably 1.5 to 2.5.
- PDI polydispersity index
- the polylactic acid polymer exhibits excellent color characteristics and has a Y.I. (yellow index) value of 2.4 or less, preferably 2.35 or less, 2.15 or less, 2.0 or less, 1.7 or 1.5 or less, 1.0 to 2.4, or 1.0 to 2.35, 1.0 to 2.15, 1.0 to 2.0, 1.0 to 1.7, or 1.0 to 1.5.
- Y.I. yellow index
- an article including the polylactic acid polymer is provided.
- the article may include packaging materials, films, non-woven fabrics, fibers, coffee capsules, durable materials, cigarette filters, and the like, and may be applied to the article to produce eco-friendly products that have excellent biodegradation characteristics and reduce CO 2 generation.
- the polylactic acid polymer according to the present invention provides a method for producing a polylactic acid polymer having a high conversion rate per hour and a high molecular weight by using a specific combination catalyst in the ring-opening polymerization of lactic acid oligomers.
- the polylactic acid polymer has excellent color characteristics while maintaining eco-friendliness and biodegradability.
- the inside of the flask was vacuumed and maintained in a 60 ° C oil bath for 1 hour to remove solvent and impurities.
- a ring-opening polymerization reaction was performed by raising the temperature to 180° C. under an Ar atmosphere at normal pressure (1 bar) for 1 hour to prepare a polylactic acid polymer.
- EDP ethylenediphenylphosphinate
- EDP cocatalyst ethylenediphenylphosphinate
- Example 1 a polylactic acid polymer was prepared in the same manner as in Example 1, except that the reaction time was increased from 1 hour to 2 hours.
- Example 1 a polylactic acid polymer was prepared in the same manner as in Example 1, except that the reaction time was increased from 1 hour to 3 hours.
- Example 1 a polylactic acid polymer was prepared in the same manner as in Example 1, except that the cocatalyst EDP was not used.
- Example 1 a polylactic acid polymer was prepared in the same manner as in Example 1, except that the cocatalyst EDP was not used and the reaction time was increased to 3 hours.
- Example 1 except that the cocatalyst EDP was not used, the content of Sn(Oct) 2 was increased to 100 ppm mol, and the reaction time was maintained as long as 3 hours, poly A lactic acid polymer was prepared.
- Example 1 a polylactic acid polymer was prepared in the same manner as in Example 1, except that triphenylphosphine was used in the same amount instead of the cocatalyst ethylenediphenylphosphinate (EDP).
- EDP cocatalyst ethylenediphenylphosphinate
- the conversion rate defined as the percentage of the reaction amount (moles) to the supply amount (moles) of lactide was measured.
- NMR nuclear magnetic resonance, Bruker 500 MHz solution NMR
- CDCl 3 was used as a solvent
- 1 H NMR was measured
- peaks of PLA and lactide appearing between 4.9 ppm and 5.2 ppm were measured.
- the conversion rate was measured by comparing area integration.
- the polymers prepared in Examples and Comparative Examples were dried in a vacuum oven at 135° C. for 24 hours to remove residual lactide and moisture and evaluate color change characteristics.
- 2 g of the polymer sample was dissolved in 40 ml of CHCl 3 and the YI (yellow index) of the resin was measured using Ultrascan VIS (HunterLab Co.) equipment transmission mode.
- Comparative Examples 1 to 3 using only the conventional Sn(Oct) 2 instead of the two types of combination catalysts, it was confirmed that it was difficult to prepare a polymer having a weight average molecular weight of 400,000 or more.
- Comparative Example 1 although there is no problem in color characteristics using the same content of Sn(Oct) 2 as in Example 1, it was confirmed that the conversion rate and molecular weight characteristics were significantly lowered compared to Examples.
- the conversion rate could be implemented at the same level as the Example by increasing the reaction time or increasing the amount of catalyst used, but in this case, it was confirmed that the degree of increase in molecular weight was low.
- the amount of Sn(Oct) 2 catalyst was increased, YI was significantly increased, and it was confirmed that color characteristics were deteriorated.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
구분 | 전환율(%) | 분자량 | 색변화 평가 | ||
Mn | Mw | PDI | Y.I. | ||
실시예 1 | 79.51 | 204,000 | 432,300 | 2.12 | 1.12 |
실시예 2 | 78.28 | 143,000 | 403,900 | 2.76 | 1.23 |
실시예 3 | 76.60 | 141,700 | 402,600 | 2.77 | 1.06 |
실시예 4 | 94.76 | 198,400 | 441,400 | 2.22 | 1.69 |
실시예 5 | 95.11 | 178,900 | 421,800 | 2.35 | 2.14 |
비교예 1 | 73.07 | 145,300 | 352,800 | 2.43 | 1.22 |
비교예 2 | 86.34 | 162,900 | 388,500 | 2.39 | 2.43 |
비교예 3 | 95.36 | 158,500 | 396,900 | 2.50 | 6.48 |
비교예 4 | 73.84 | 180,600 | 366,800 | 2.03 | 1.19 |
Claims (11)
- 주석계 촉매 및 포스피나이트계 조촉매의 존재 하에 락타이드를 개환 중합하여 폴리락트산 중합체를 제조하는 단계를 포함하는,폴리락트산 중합체의 제조 방법.
- 제1항에 있어서,상기 주석계 촉매는 Sn(Oct)2인,폴리락트산 중합체의 제조 방법.
- 제1항에 있어서,상기 포스피나이트계 조촉매는 하기 화학식 1로 표시되는 화합물 중에서 선택되는 1종 이상인,폴리락트산 중합체의 제조 방법:[화학식 1]P(OR1)(R2)(R3)식 중에서,R1은 치환 또는 비치환된 C1-30 알킬, 또는 치환 또는 비치환된 C6-30 아릴이고,R2 및 R3는 각각 독립적으로, 치환 또는 비치환된 C1-30 알킬, 또는 치환 또는 비치환된 C6-30 아릴이다.
- 제3항에 있어서,상기 R1는 메틸, 에틸, 프로필, 이소프로필, 페닐, 비페닐릴 또는 나프틸인,폴리락트산 중합체의 제조 방법:
- 제3항에 있어서,상기 R2 및 R3는 각각 독립적으로 메틸, 에틸, 프로필, 이소프로필, 페닐, 비페닐릴 또는 나프틸이고, 이들은 메톡시, 에톡시, 프로폭시 또는 이소프로폭시로 치환 또는 비치환되는,폴리락트산 중합체의 제조 방법:
- 제1항에 있어서,상기 주석계 촉매 및 포스피나이트계 조촉매는 1:0.1 내지 1:5의 몰비로 포함되는,폴리락트산 중합체의 제조 방법.
- 제1항에 있어서,상기 주석계 촉매는 락타이드 함량 대비 0.001mol% 내지 0.05mol%로 포함되는,폴리락트산 중합체의 제조 방법.
- 제1항에 있어서,상기 포스피나이트계 조촉매는 락타이드 함량 대비 0.001mol% 내지 0.05mol%로 포함되는,폴리락트산 중합체의 제조 방법.
- 제1항에 있어서,상기 개환 중합은 150℃ 내지 200℃ 및 0.5bar 내지 2bar 에서 30분 내지 6시간 동안 반응을 수행하는,폴리락트산 중합체의 제조 방법.
- 제1항에 있어서,상기 폴리락트산 중합체의 중량평균분자량은 50,000 내지 600,000인,폴리락트산 중합체의 제조 방법.
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