WO2010022683A1 - 一种利用双螺杆挤出机制备聚乳酸及其制品的方法 - Google Patents
一种利用双螺杆挤出机制备聚乳酸及其制品的方法 Download PDFInfo
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- WO2010022683A1 WO2010022683A1 PCT/CN2009/073674 CN2009073674W WO2010022683A1 WO 2010022683 A1 WO2010022683 A1 WO 2010022683A1 CN 2009073674 W CN2009073674 W CN 2009073674W WO 2010022683 A1 WO2010022683 A1 WO 2010022683A1
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 56
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 62
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 57
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 56
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 43
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 43
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000005843 halogen group Chemical group 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 15
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 125000004429 atom Chemical group 0.000 claims description 38
- 238000001125 extrusion Methods 0.000 claims description 23
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 21
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical group C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 16
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 10
- -1 alcohol compound Chemical class 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 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 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 229940067107 phenylethyl alcohol Drugs 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 10
- 229960004217 benzyl alcohol Drugs 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 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 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
-
- 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
- C08G63/785—Preparation processes characterised by the apparatus used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/68—Barrels or cylinders
- B29C48/682—Barrels or cylinders for twin screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
- B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
- B29K2067/046—PLA, i.e. polylactic acid or polylactide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0059—Degradable
- B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
Definitions
- the invention belongs to the technical field of polymer materials, and particularly relates to a method for controllably preparing polylactic acid and its products by using twin-screw extrusion technology. Background technique
- polylactic acid As a kind of polymer material, polylactic acid has good biocompatibility and degradability, has no pollution to the environment, and has broad application prospects in the fields of medicine, textile and packaging.
- the catalysts used in the ring opening polymerization process are generally organotin salts, organic salts and organoaluminum salts such as JP0124651, CN1544504 and CN1814644.
- the organometallic catalyst remaining in the product limits the application of the resulting polylactic acid and cannot be applied to fields such as biomedicine and microelectronics.
- Eric F. Conner et al. (Eric F. Conner et al. Journal of the American Chemical Society, 2002, 124, 914) first applied a class of high-efficiency organic catalysts, N-heterocyclic carbene, to lactide in 2001. Ring opening polymerization.
- N-heterocyclic carbene is sensitive to air and water, and its preparation and application are greatly hindered. Therefore, the catalytic lactide ring-opening polymerization can only be limited to the laboratory scale, and it is difficult to scale production.
- N-heterocyclic carbene To overcome the limitation of N-heterocyclic carbene to air and water, chemists have conducted more research on the storage form of N-heterocyclic carbene.
- Hung A. Duong et al. Hung A. Duong et al. Chemical Communications, 2004, 112 found that: N-heterocyclic carbenes and CO 2 react to form carbene carbon dioxide adducts. At a certain temperature, the carbene carbon dioxide adduct can remove C0 2 and release the carbene.
- Adriana T et al. (Adriana T et al. Journal of Organometallic Chemistry, 2006, 691, 5356) suggest that carbene carbon dioxide adducts can be used as a storage form for N-heterocyclic carbene.
- the application of reactive extrusion technology is also limited: the reaction needs to be completed in one step, there can be no intermediate operation steps; the reaction should be controlled within the time limit of the reaction extrusion technology, generally 5 ⁇ 30 minutes; The reaction is carried out in a molten state at a high temperature.
- the application of reactive extrusion technology in polylactic acid is mainly focused on the modification of polylactic acid. Due to the limitation of polymerization time, reactive extrusion technology is applied to the polymerization process of polylactic acid, which is mainly prepared from lactic acid, lactide or their derivatives, and then mixed with one or more monomers.
- the addition or polycondensation reaction is carried out on a screw extruder, such as: JP940215520, JP94009602
- a screw extruder such as: JP940215520, JP94009602
- Jacobsen S. The equivalent molecular weight of stannous octoate and triphenylphosphine was used as a catalyst.
- the molecular weight of the lactide was determined by twin-screw reaction extrusion ring-opening polymerization.
- polylactic acid is prepared by one-step extrusion of lactide.
- the obtained polylactic acid contains a metal residue; the terminal structure of the polylactic acid is not clear; the molecular weight of the polylactic acid target cannot be controlled, and these factors limit the application field of the polylactic acid. Summary of the invention
- the technical problem to be solved by the present invention is to provide a method for preparing a polylactic acid and a product thereof by using a twin-screw extruder.
- the polylactic acid obtained by the method has no metal residue, has a controllable molecular weight and terminal structure, and has a narrow molecular weight distribution.
- N-heterocyclic carbene is extremely sensitive to water and oxygen, the environment for its preparation, transfer and catalytic reaction requires anhydrous and oxygen-free. This requirement allows the transfer of N-heterocyclic carbene, that is, the addition of N-heterocyclic carbene to the reaction extrusion.
- the system is inoperable.
- the present invention employs a carbene carbon dioxide adduct which is stable to water and oxygen and which can form an N-heterocyclic card after removing co 2 at a certain temperature (decarboxylation temperature). Guest.
- the decarboxylation temperature is determined by the ring-substituting group of the carbene carbon dioxide adduct.
- the present invention finds a carbene carbon dioxide adduct having a suitable decarboxylation temperature by adjusting a substituent group on the carbene carbon dioxide adduct ring, and is applied to the reaction extrusion of the lactide ring-opening polymerization, that is, the carbene carbon dioxide adduct obtained by screening.
- the decarboxylation temperature is suitable for both the lactide ring opening polymerization and the reaction extrusion process.
- the invention adopts the carbene carbon dioxide adduct as a precursor of the organic small molecule catalyst, and is applied to the ring-opening polymerization of lactide to have high catalytic activity, and also solves the problem of metal residue in the obtained polylactic acid.
- the present invention also considers the reaction time requirement of the reaction extrusion technique in the screening of the carbene carbon dioxide adduct catalyst precursor; the present invention Screening of N-heterocyclic carbene yields a class of carbene carbon dioxide adduct catalyst precursors with higher catalytic activity, which accelerates the reaction rate.
- the appropriate temperature, the aspect ratio and the rotational speed of the screw can be further selected during the reaction extrusion process, so that the reaction system obtains better dispersibility and further accelerates the reaction, thereby shortening the reaction time.
- the controllability of the polylactic acid terminal structure and molecular weight, such as the narrow molecular weight distribution, can be solved by adding an active hydrogen-containing compound (R-0-H) as a starter in the ring-opening polymerization reaction, and the polylactic acid end structures are respectively R-0- and -OH.
- the ratio of the lactide monomer to the starter determines the target molecular weight of the resulting polylactic acid.
- the N-heterocyclic carbene-catalyzed ring-opening polymerization of lactide is a living polymerization, and the reaction extrusion system has good dispersibility, which allows the obtained polylactic acid to achieve a narrow molecular weight distribution. .
- the carbene carbon dioxide adduct of the present invention is used as a catalyst precursor mixed with lactide, and the N-heterocyclic carbene is released during the reaction extrusion process by a reaction extrusion technique to catalyze the ring-opening polymerization of lactide.
- a narrow molecular weight distribution polylactic acid and an article thereof having a controllable molecular weight and terminal structure, and no metal residue can be synthesized in one step.
- RR 2 is selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and substituted by one or more of an atom, a hydroxyl group, a phenyl group and a cyano group, a cycloalkyl group of 3 to 6 carbon atoms, an atom, an adamantyl group, a phenyl group and the same or different groups in a phenyl group substituted by one or more of an atom, a hydroxyl group, an alkyl group and a cyano group; 3 , R 4 is selected from the group consisting of hydrogen, halogen atom, cyano group, hydroxyl group, alkyl group having 1 to 4 carbon atoms, having 1 to 4 carbon atoms and being one of a halogen atom, a hydroxyl group, a phenyl group and a cyano group.
- RR 2 is selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and substituted by one or more of an atom, a hydroxyl group, a phenyl group and a cyano group, a cycloalkyl group of 3 to 6 carbon atoms, an atom, an adamantyl group, a phenyl group and the same or different groups in a phenyl group substituted by one or more of an atom, a hydroxyl group, an alkyl group and a cyano group; 3 , R 4 is selected from the group consisting of hydrogen, halogen atom, cyano group, hydroxyl group, alkyl group having 1 to 4 carbon atoms, having 1 to 4 carbon atoms and being one of a halogen atom, a hydroxyl group, a phenyl group and a cyano group.
- RR 2 is selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and substituted by one or more of an atom, a hydroxyl group, a phenyl group and a cyano group, a cycloalkyl group of 3 to 6 carbon atoms, an atom, an adamantyl group, a phenyl group and the same or different groups in a phenyl group substituted by one or more of an atom, a hydroxyl group, an alkyl group and a cyano group; 3 is selected from the group consisting of hydrogen, a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, having 1 to 4 carbon atoms and being one or more of a halogen atom, a hydroxyl group, a phenyl group and a cyano group.
- R 2 and R 3 are bonded to form an unsubstituted five or six Element N-heterocyclic.
- the carbene carbon dioxide adduct and the lactide may be mixed in a molar ratio of 1:5 to 2000, preferably 1 :100 to 1000.
- the lactide may be L-lactide, D-lactide, meso-lactide or racemic lactide, or L-lactide, D-lactide and Meso-propion. A mixture of esters in any ratio.
- the twin-screw extruder in the above method is specifically a twin-screw co-injection type extruder, wherein the barrel is heated by a plurality of heating units, and the temperature of each section is independently controlled by circulating cooling water;
- the temperature can be 50. C ⁇ 300. Any of the same or different temperatures in C, preferably any of the same or different temperatures from 100 ° C to 200 ° C; the gas pressure in the barrel may be 0.5 kPa to 1 kPa; the length to diameter ratio of the screw may be 30 to 70; It can be from 5 rpm to 200 rpm; the feeding speed can be from 0.5 kg/hr to 5 kg/hr.
- the head of the twin-screw extruder can also be connected to the molding equipment, and the polylactic acid and its products are directly extruded.
- Figure 1 is a schematic diagram of the barrel section of a twin-screw extruder. Wherein, 1 is the feed section; 2 is the I zone; 3 is the II zone; 4 is the crotch zone; 5 is the IV zone; 6 is the feed hopper; 7 is the vacuum valve.
- 1 is the feed section; 2 is the I zone; 3 is the II zone; 4 is the crotch zone; 5 is the IV zone; 6 is the feed hopper; 7 is the vacuum valve.
- the twin-screw extruder was first flushed with argon gas, and the lactide, the initiator (or no) and the carbene carbon dioxide adduct were uniformly mixed and uniformly fed into the extruder.
- the structural formula and numbering of the carbene carbon dioxide adduct used in the following examples are shown in Table 1.
- Table 1 List of carbene carbon dioxide adducts used in the examples
- Figure 1 is a schematic view of the barrel section of the twin-screw extruder.
- the barrel of the twin-screw extruder in the following examples is divided into 4 zones, and the temperature of each section is independently controlled by circulating cooling water.
- the method of operation of the twin-screw extruder is prior art in the art, and those skilled in the art can perform the operations in accordance with the parameters of the twin-screw extruder below.
- the molecular weight and molecular weight distribution of the polylactic acid in the examples were measured by gel permeation chromatography (chloroform was a mobile phase, 35 C, with reference to polystyrene standards).
- chloroform was a mobile phase, 35 C, with reference to polystyrene standards.
- the temperature settings of each zone of the barrel are as follows:
- Zone I 140 °C Zone II: 185 °C Zone III: 200 °C Zone IV: 185 °C L-lactide (672g, 4.67mol) and carbene carbon dioxide adduct a (0.36g,
- the parameters of the twin-screw extruder are as follows:
- Zone I 120 °C Zone II: 175 °C Zone III: 180 °C Zone IV: 175 °C D-lactide (2016g, 14mol) and carbene carbon dioxide adduct b (1210.38g,
- Screw speed 80rpm
- Vacuum 0.5kPa Length to diameter ratio: 48
- Screw speed 50rpm
- Vacuum 0.8kPa Length to diameter ratio: 40
- the temperature settings of each zone of the barrel are as follows:
- Zone I 120 °C Zone II: 175 °C Zone III: 180 °C Zone IV: 175 °C racemic lactide (2016g, 14mol), carbene carbon dioxide adduct d ( 15.83g,
- the parameters of the twin-screw extruder are as follows:
- Screw speed 80rpm
- Vacuum 0.5kPa Length to diameter ratio: 40
- the parameters of the twin-screw extruder are as follows:
- Zone I 50 °C Zone II: 145 °C Zone III: 200 °CW zone: 185 °C will be meso-lactide (2016g, 14mol), carbene carbon dioxide adduct f ( 4.87g, 0.014 mol) and phenylethyl alcohol (1.71 g, 0.014 mol) were uniformly mixed and uniformly fed into a twin-screw extruder.
- the extrusion was carried out according to the above operating parameters, and the extruder head was connected to a molding apparatus and directly molded to obtain 1966 g of polylactic acid having a molecular weight of 104,000 and a molecular weight distribution of 1.6.
- Example 7 Example 7
- the parameters of the twin-screw extruder are as follows:
- Zone I 145 °C Zone II: 150 °C Zone III: 170 °C Zone IV: 135 °C L-lactide (2016g, 14mol), carbene carbon dioxide adduct g (1293.49g, 2.8mol) and methanol (224.21 g, 7 mol) was uniformly mixed and fed into the twin-screw extruder at a constant rate.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1905 g of polylactic acid having a molecular weight of 288, and the molecular weight distribution was 1.5.
- Example 8 Example 8
- the parameters of the twin-screw extruder are as follows:
- Screw speed 200rpm
- Vacuum 0.5kPa Length to diameter ratio: 48
- the temperature settings of each zone of the barrel are as follows:
- Zone I 170 °C Zone II: 185 °C Zone III: 200 °C Zone IV: 140 °C D-lactide (2016g, 14mol), carbene carbon dioxide adduct h (119.75g, 0.35mol) and Methanol (5.61 g, 0.175 mol) was uniformly mixed and fed into a twin-screw extruder at a constant rate.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1924 g of polylactic acid having a molecular weight of 11,000, and a molecular weight distribution of 1.7.
- Example 9 Example 9
- the parameters of the twin-screw extruder are as follows:
- the parameters of the twin-screw extruder are as follows:
- Zone I 145 °C Zone II: 185 °C Zone III: 300 °C Zone IV: 185 °C L-lactide (2016g, 14mol), carbene carbon dioxide adduct j ( 7.22g,
- the parameters of the twin-screw extruder are as follows:
- Screw speed lOOrpm
- Vacuum 0.5kPa Length to diameter ratio: 48
- Feeding speed 5kg/h
- the temperature settings of each zone of the barrel are as follows:
- Zone I 165 °C Zone II: 200 °C Zone III: 300 °C Zone IV: 185 °C L-lactide (2016g, 14mol), carbene carbon dioxide adduct k (5.63g, 0.028mol) and benzene Methanol (3.03 g, 0.028 mol) was uniformly mixed and fed into the twin-screw extruder at a constant rate.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1906 g of a polylactic acid having a molecular weight of 78,000 and a molecular weight distribution of 1.7.
- Example 12 Example 12:
- the parameters of the twin-screw extruder are as follows:
- Screw speed 150rpm
- Vacuum lkPa Length to diameter ratio: 48
- Feeding speed 1.0kg/h
- the temperature settings of each barrel are as follows:
- Zone I 145 °C Zone II: 185 °C Zone III: 200 °C Zone IV: 165 °C L-lactide (2016g, 14mol), Carbene Carbonate Adduct 1 ( 7.87g, 0.028 mol) and benzyl alcohol (6.05 g, 0.056 mol) were uniformly mixed and uniformly fed into a twin-screw extruder.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1983 g of polylactic acid having a molecular weight of 31,000, and a molecular weight distribution of 1.4.
- Screw speed 125rpm Vacuum: 0..8kPa Aspect ratio: 48 Feeding speed: 1.5kg/h
- the temperature settings of each zone of the barrel are as follows:
- Screw speed 150rpm
- Vacuum lkPa Length to diameter ratio: 40
- Feeding speed 1.5kg/h
- the temperature settings of each barrel are as follows:
- Zone I 180 °C Zone II: 225 °C Zone III: 300 °C Zone IV: 185 °C L-lactide (2016g, 14mol), carbene carbon dioxide adduct n (5.04g, 0.023mol) and methanol (0.74 g, 0.023 mol) was uniformly mixed and fed into a twin-screw extruder at a constant rate.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1921 g of polylactic acid having a molecular weight of 92,000, and a molecular weight distribution of 1.8.
- Example 15 Example 15
- the parameters of the twin-screw extruder are as follows:
- Screw speed 150 rpm Vacuum: 0.7 kPa Aspect ratio: 48 Feeding speed: 2.5 kg/h
- the temperature settings of each zone of the barrel are as follows:
- Screw speed 150rpm
- Vacuum lkPa Length to diameter ratio: 48
- Feeding speed 1.5kg/h
- the temperature settings of each barrel are as follows:
- Zone I 165 °C Zone II: 185 °C Zone III: 250 °C Zone IV: 185 °C L-lactide (2016g, 14mol), carbene carbon dioxide adduct p (6.56g, 0.023mol) and benzene
- decyl alcohol 3.78 g, 0.035 mol
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1994 g of polylactic acid having a molecular weight of 58,000 and a molecular weight distribution of 1.5.
- Screw speed 125rpm
- Vacuum lkPa Length to diameter ratio: 40
- Feeding speed 1.5kg/h
- the temperature settings of each barrel are as follows:
- Zone I 185 °C Zone II: 225 °C Zone III: 300 °C Zone IV: 165 °C L-lactide (2016g, 14mol), carbene carbon dioxide adduct q ( 4.37g, 0.018mol) and benzene Ethanol ( 2.20 g, 0.018 mol) was uniformly mixed and fed into the twin-screw extruder at a constant rate.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1903 g of polylactic acid having a molecular weight of 109,000, and a molecular weight distribution of 2.0.
- the parameters of the twin-screw extruder are as follows:
- Screw speed 150 rpm
- Vacuum 0.8 kPa
- Aspect ratio 48
- the temperature settings of each zone of the barrel are as follows:
- Zone I 200°C Zone II: 225°C Zone III: 280°C Zone IV: 165°C L-lactide (2016g, 14mol), carbene carbon dioxide adduct r ( 8.14g, 0.023mol) and benzyl alcohol (3.78g, 0.035mol) were uniformly mixed and fed into the twin-screw extruder at a constant rate.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1963 g of polylactic acid having a molecular weight of 56,000 and a molecular weight distribution of 1.8.
- Example 19 Example 19
- the parameters of the twin-screw extruder are as follows:
- Screw speed 125rpm
- Vacuum 0.5kPa Length to diameter ratio: 48
- Feeding speed 1.5kg/h
- the temperature settings of each zone of the barrel are as follows:
- Zone I 145 °C Zone II: 165 °C Zone III: 250 °C Zone IV: 185 °C L-lactide (2016g, 14mol), carbene carbon dioxide adduct s ( 5.36g, 0.035mol ) and benzene Methanol (7.56 g, 0.07 mol) was uniformly mixed and fed into the twin-screw extruder at a constant rate.
- the reaction was extruded according to the above operating parameters, and air-cooled to obtain 1935 g of polylactic acid having a molecular weight of 35,000 and a molecular weight distribution of 1.4.
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JP2011524171A JP5452598B2 (ja) | 2008-09-01 | 2009-09-01 | 二軸スクリュ式押出機によるポリ乳酸及びその製品の製造方法 |
EP09809268.7A EP2327735B1 (en) | 2008-09-01 | 2009-09-01 | Method for preparing polylactic acid and products thereof using a twin-screw extruder |
US13/034,030 US8241545B2 (en) | 2008-09-01 | 2011-02-24 | Method of making polylactic acid and its products |
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US20110218301A1 (en) * | 2010-03-08 | 2011-09-08 | Nemoto Taichi | Polymer and method for producing the same |
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JP2013224398A (ja) * | 2011-08-12 | 2013-10-31 | Ricoh Co Ltd | ポリマー生成物、成形体、医療用成形体、トナー、及びポリマー組成物 |
CN105694017A (zh) * | 2014-11-28 | 2016-06-22 | 黑龙江鑫达企业集团有限公司 | 一种双螺杆反应挤出法开环聚合聚乳酸制备方法 |
CN105218793A (zh) * | 2015-11-17 | 2016-01-06 | 南京工业大学 | 一种用卡宾衍生物催化制备聚酯多元醇的方法 |
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CN101665566A (zh) | 2010-03-10 |
US20110140307A1 (en) | 2011-06-16 |
CN101665566B (zh) | 2012-01-04 |
EP2327735A1 (en) | 2011-06-01 |
EP2327735B1 (en) | 2016-12-21 |
JP5452598B2 (ja) | 2014-03-26 |
EP2327735A4 (en) | 2013-11-20 |
JP2012501358A (ja) | 2012-01-19 |
US8241545B2 (en) | 2012-08-14 |
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