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WO2008036049A1 - Procédé de fabrication d'un polyhydroxy acide de masse moléculaire élevée - Google Patents

Procédé de fabrication d'un polyhydroxy acide de masse moléculaire élevée Download PDF

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Publication number
WO2008036049A1
WO2008036049A1 PCT/SG2007/000238 SG2007000238W WO2008036049A1 WO 2008036049 A1 WO2008036049 A1 WO 2008036049A1 SG 2007000238 W SG2007000238 W SG 2007000238W WO 2008036049 A1 WO2008036049 A1 WO 2008036049A1
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WIPO (PCT)
Prior art keywords
acid
molecular weight
degree
prepolymer
hydroxy
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Application number
PCT/SG2007/000238
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English (en)
Inventor
Wang Shaofeng
Huang Yuqiang
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Hyflux Ltd
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Publication of WO2008036049A1 publication Critical patent/WO2008036049A1/fr

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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
    • 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
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/14—Peroxides

Definitions

  • the present invention generally relates to a process for producing a high molecular weight polyhydroxy acid.
  • the present invention also relates to a system for performing the process.
  • Polyhydroxy acids are highly useful materials due to their chemical, mechanical and physical properties. In recent years, polyhydroxy acids have gained increasing economic importance due to their biodegradability as they can be degraded, under natural conditions, to carbon dioxide and water by microorganisms.
  • Polyhydroxy acids such as polylactic acid
  • polylactic acid have been woven into fibers using conventional melt-spinning processes. Spunbound and meltblown non-wovens fibers are also easily produced from polylactic acid. These materials may be used in various applications such as household and industrial wipes, diapers, feminine hygiene products, disposable garments, and UV resistant fabrics.
  • polylactic acid is bioasborable and can be assimilated by a biological system, it can be readily used for implants in bone or soft tissue and for resorbable sutures .
  • the polyhydroxy acids must have a high molecular weight in the order of at least 50,000 to exhibit mechanical strength beyond a certain level .
  • One known processes for producing a polyhydroxycarboxylic acid comprises dehydrating via a condensation reaction, an aliphatic mono-hydroxycarboxylic acid in a reaction mixture containing an organic solvent and in the substantial absence of water to obtain polyhydroxycarboxylic acid having a weight average molecular weight of at least about 50,000.
  • this process relies on the use of an organic solvent which may be harmful to the environment.
  • the organic solvent must be removed from the final polymer, which increases processing costs.
  • One known process for producing high molecular weight polylactic acid involves ring-opening polymerization of a lactide using a stannous octoate catalyst.
  • the process involves the formation of the lactide from a oligocondensate of lactic acid.
  • the lactide must be isolated and purifyied ' before making the high molecular weight polylactic acid, which increases the costs of production.
  • a problem with these known methods is that the purification step is complex and therefore expensive, as it requires the use of multiple unit operations (i.e. distillation columns, evaporators, heat exchangers, pumps, etc) to separate the water and other impurities such as lactic acid and oligomers thereof from the cyclic dimers.
  • the synthesis of high molecular weight polyhydroxy acids involves the production of water as a by-product in the polycondensation dehydration reaction.
  • the production of water acts as an inhibitor of the polymerization reaction and it is difficult to efficiently and to substantially remove from the reactant polymer.
  • Known synthetic methods have suggested complex water removal steps, such as successive distillation of water and the cyclic dimers .
  • the equipment designs employed in these processes have been inefficient and have resulted in loss of both the feed product and the cyclic dimers.
  • a process for producing a high molecular weight polyhydroxy acid comprising the steps of: (a) condensating a hydroxy acid with a functionalizing agent, said functionalizing agent being selected to form a polyhydroxy acid prepolymer having at least three terminal hydroxyl groups thereon after said condensating; and (b) polymerizing said pre-polymer in the presence of a coupling agent under conditions to form said high molecular weight polyhydroxy acid.
  • the coupling agent is an isocyanate coupling agent.
  • the polyhydroxy acid prepolymer having at least three terminal hydroxyl groups thereon allows the formation of high molecular weight polyhydroxy acid in the polymerizing step.
  • the polyhydroxy acid prepolymer having at least three terminal hydroxyl groups thereon utilizes less isocyanate coupling agent relative to a prepolymer having less than three terminal hydroxyl groups.
  • the polyhydroxy acid prepolymer having at least three terminal hydroxyl groups thereon allows the formation of high molecular weight polyhydroxy acid in the polymerizing step.
  • a polyhydroxy acid prepolymer having at least three terminal hydroxyl groups for producing high molecular weight polyhydroxy acid comprising the step of:
  • a high molecular weight polyhydroxy acid made in a process comprising the steps of:
  • a reactor having a reaction zone containing a polymerizing monomeric mixture of polyhydroxy acid prepolymer having at least three terminal hydroxyl groups and a coupling agent, wherein said reaction zone is operated under conditions to form said high molecular weight polyhydroxy acid from said polymerizing monomeric mixture.
  • high molecular weight polyhydroxy acid means a polyhydroxy acid having a molecular weight of more than 100,000, preferably more than 150,000. In some embodiments, the high molecular weight of the polyhydroxy acid is about 100,000 to about 450,000.
  • hydroxy acid as used herein means a carboxylic acid in which one or more hydrogen atom of the aliphatic or aromatic group has been replaced by a hydroxyl group .
  • polyhydroxy acid as used herein means polymer of repeating hydroxy acid monomer units.
  • aliphatic hydroxycarboxylic acid refers generally to acids having alcoholic hydroxyl and carboxyl in the molecule, such as lactic acid, glycolic acid, malic acid, tartaric acid, citric acid, hydroacrylic acid, ⁇ - hydroxybutyric acid, glyceric acid, tartronic acid and like aliphatic hydroxycarboxylic acids.
  • the term "functionalizing agent” in the context of this specification is to be interpreted broadly to include any compound capable of a condensation reaction with a hydroxy acid to form a prepolymer having at least three terminal hydroxyl groups.
  • the functionalizing agent may include at least one polyalcohol and optionally at least one of a polycarboxylic and a diol or a polycarboxylic acid in combination with a diol.
  • polyalcohol means alcohols having at least three hydroxyl groups and optionally encompasses other subsistent functional groups.
  • polyalcohols include (carbon chains may be straight chains, breached chains, aromatic, or alicyclic) , pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, open and cyclic condensation products of glycerol (and/or other polyalcohols) such as diglycerols, triglycerols, tetraglycerols, pentaglycerols, and hexaglycerols; diglycidyl ether, diglycidyl-di-ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether, butanediol-diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolmethane triglycidyl ether, glycerol, 1, 5, 6, 9-decanetetrol, 1,1,4,4
  • polycarboxylic acids comprises all acids having more than one carboxyl group.
  • exemplary non- limitive examples of polycarboxylic acids include citric acid (i.e., 2-hydroxy-l, 2, 3-propane tricarboxylic acid), 1, 2, 3-propane tricarboxylic acid, 1, 2, 3, 4-butane tetracarboxylic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid (i.e., 2,2'- oxybis (butanedioic acid) ) , thiodisuccinic acid, trans-1- propene-1, 2, 3-tricarboxylic acid, all cis-1, 2,3,4- cyclopentanetetracarboxylic acid, benzenehexacarboxylic acid, alkyl-cycloalkyltricarboxylic acid, trimethyl- cyclohexanetricarboxylic acid, 1, 3, 5-trimethyl-l, 3, 5-
  • diol refers to all molecules which have at least two alcohol functionalities thereon.
  • exemplary, non-limiting diols include saturated and unsaturated alkyl diols such as ethanediol (ethylene glycol) , ethenediol, diethylene glycol, neopentyl glycol, 1, 2-propanediol (propylene glycol), 1, 3-propanediol, 2,3- propanediol, 1, 2-propenediol, 1, 3-propenediol, 2,3- propenediol, 1, 4-butanediol, 1, 3-butanediol, 1,2- butanediol, 2, 4-butanediol, 2, 3-butanediol, 3,4- butanediol, 1, 4-butenediol, 1, 3-butenediol, 1,2- butenediol, 2, 4-butenediol, 2, 3-butenediol, 3,4- butanedio
  • catalyst is to be interpreted broadly to include any substance that increases the rate of reaction of the aliphatic hydroxycarboxylic acid, or polymerization of said polyhydroxy acid, without being substantially consumed in the reaction.
  • polymerize means not only “homopolymerization” but also “copolymerization” .
  • the terms are to be interpreted broadly to include any process whereby monomer molecules react with each other, or with a polymer chain of polyhydroxy acid, in a chemical reaction to form larger molecular weight polymer chains of polyhydroxy acid.
  • the polymerization mechanism can be cationic, anionic, coordination or free radical polymerization.
  • the polyhydroxy acid polymer chains may be linear chains or a three-dimensional network of polymer chains.
  • the terms may include ring-opening reaction of cyclic dimers with polyhydroxy acid to thereby increase the molecular weight of said polyhydroxy acid.
  • polymer includes not only “homopolymers” but also “copolymers”.
  • prepolymer denotes a low molecular weight polymer comprising monomers of hydroxycarboxylic acid monomer units that are further polymerizable. Typically, the molecular weight of said prepolymers is less than about 100,000, more typically between about 15,000 to about 60,000.
  • ⁇ polylactic acid prepolymer would refer to a polylactic acid having a molecular weight less than 100,000 and which can be further polymerized to a higher molecular weight.
  • n hydroxyl groups describes the functional group -OH when it is a substituent in an organic compound.
  • Coupled agent refers to any reagent capable of facilitating coupling between two or more prepolymers in a polymerization reaction.
  • isocyanate coupling agent includes mono isocyanates, diisocyanates and polyisocyanates .
  • Exemplary diisocyanate and polyisocyanate compounds include aromatic polyisocyanates such as 2,4- tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, 2, 4 ' -diphenylmethane diisocyanate, p-phenylene diisocyanate, and polymethylene polyphenylene polyisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate (HMDI) , and tetramethylxylylene diisocyanate (TMXDI) ; alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) ; arylaliphatic polyisocyanates such as xylylene diisocyanate; and the polyisocyanate as mentioned above modified with carbodiimide or isocyanurate; which may be used either alone or in combination of two or more.
  • polymerization conditions and grammatical variations thereof is defined herein to mean conditions, such as temperature and pressure, which are sufficient to promote polymerization of the polyhydroxy acid.
  • reaction zone is to be interpreted broadly to include any region or space in which the dehydration condensation reaction of a polyhydroxy acid prepolymer occurs to form high molecular weight polyhydroxy acid.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to ⁇ should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • a process for producing a high molecular weight polyhydroxy acid in particular a polyhydroxy carboxylic acid, more particularly a polylactic acid, will now be disclosed.
  • a high molecular weight polyhydroxy acid can be produced directly from aliphatic hydroxy acid.
  • the process can be used to produce a high molecular weight polylactic acid directly from lactic acid.
  • the process comprises the steps of:
  • Exemplary aliphatic hydroxy acids include, for example, lactic acid, glycolic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2- hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxy- 2-methylpropanoic acid, 2-hydroxy-2-methylbutanoic acid, 2-hydroxy-2-ethylbutanoic acid, 2-hydroxy-2- methylpentanoic acid, 2-hydroxy-2-ethylpentanoic acid, 2- hydroxy-2-propylpentanoic acid, 2-hydroxy-2-butylpentanoic acid, 2-hydroxy-2-methylhexanoic acid, 2-hydroxy-2- ethylhexanoic acid, 2-hydroxy-2-propylhexanoic acid, 2- hydroxy-2-butylhexanoic acid, 2-hydroxy-2-pentylhexanoic acid, 2-hydroxy-2-methylheptanoic acid, 2-hydroxy-2- ethyl
  • aliphatic hydroxy acid and the polymer of the same have optically active carbon in the molecule and are distinguished in the form of a D-isomer, L-isomer and D/L- isomer, respectively. Any of these isomers can be used in the disclosed process.
  • the aliphatic hydroxy acid may be lactic acid which may be either optically active (e.g., D- or L-lactide) or inactive (i.e., D, L- lactide) or a mixture of optical active and inactive forms .
  • the condensating step (a) may comprise the step of:
  • the heating step (al) may be undertaken in an inert atmosphere such as with nitrogen gas being injected through the hydroxy acid.
  • the condensating step (a) may comprise the step of: (a2) applying a vacuum to said hydroxy acid as it reacts with said functionalizing agent.
  • the vacuum may be applied in the range of about 0.1 mmHg to about 600 mmHg. In one embodiment, the vacuum may be applied in the range of about 5 mmHg to about 200 mmHg.
  • application of the vacuum ensures that the volatile phase is removed from the liquid phase during its formation.
  • the vacuum can also be used to increase the passage of said water across the membrane and thereby facilitate formation of said permeate vapor stream.
  • the condensating step (a) may comprise the step of: (a3) agitating said mixture of hydroxy acid and functionalizing agent.
  • the agitating may be undertaken at a speed of about 200 rpm.
  • the condensating step (a) may comprise the step of: (a4) removing condensed water formed during polycondensation by vacuum and/or nitrogen.
  • the condensating step (a) may comprise the step of: (a5) providing a catalyst to said hydroxy acid as it undergoes polymerization.
  • the catalyst may be suitable for dehydration.
  • Exemplary catalysts which can be used in the invention are metals, metal salts, hydroxides and oxides in the group I, II, III, IV and V of the periodic table and include, for example, zinc, tin, aluminum, magnesium, antimony, titanium, zirconium and other metals such as tin oxide, antimony oxide, lead oxide, aluminum oxide, magnesium oxide, titanium oxide and other metal oxides; zinc chloride, stannous chloride, stannic chloride, stannous bromide, stannic bromide, antimony fluoride, magnesium chloride, aluminum chloride and other metal halogenides; sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, zinc hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, cesium hydroxide, strontium hydroxide, barium hydroxide, lithium hydroxide, zirconium hydroxide and other metal hydroxides; tin
  • the amount of these catalysts are in the range of 0.0001-10% by weight in said liquid phase.
  • the catalyst is selected from the group consisting of tin octoate (tin [II] 2-ethylhexanoate) , tin chloride (tin [II] 2- chloride) , toluene-4-sulfonic acid monohydrate (TSA) , zinc octoate and zinc chloride.
  • the condensating step (a) may comprise the step of: (a ⁇ ) adding of ⁇ -caprolactone.
  • the functionalizing agent should be carefully chosen to ensure that at least three, preferably four, hydroxyl groups are formed on the terminal ends of the prepolymer on reaction of the functionalizing agent with said hydroxy acid.
  • the functionalizing agent should comprise one or more of the following: (i) a polyalcohol;
  • composition of the functionalizing agent may be any one of:
  • a prepolymer with at least three terminal hydroxyl groups is formed from said aliphatic hydroxy acid, or oligomer thereof.
  • the said prepolymer may be in a molten state, and may have a weight average molecular mass of 15,000 to 60,000.
  • the said prepolymer is formed by hydroxy acid, and 25 to 0.001% of said prepolymer is formed by functionalizing agent containing at least three functional end groups, and/or 50 to 0.001% of diol monomers and/or 50 to 0.001% of diacid, wherein the number of moles of hydroxyl groups are more than the acid groups
  • the process comprises adding a isocyanate coupling agent to said formed polyhydroxy acid to further polymerize said prepolymers by coupling.
  • the polymerizing step (b) may comprise the step of: (bl) heating said polyhydroxy acid from about 140 degree C to about 250 degree C, or from about 140 degree C to about 200 degree C, more preferably from about 160 degree C to about 180 degree C.
  • the polymerizing step (b) may comprise the step of: (b2) agitating said polyhydroxy acid at a rotational speed of about 30 rpm.
  • the polymerizing step (b) may comprise the step of adding a stabilizer to the prepolymers or the formed polyhydroxy acid.
  • the stabilizer may be one or more peroxide. Suitable peroxides are taught in the published European Patent No. EP 0 737 219, and are incorporated herein.
  • the addition of peroxide slows down the decrease in molar mass. This effectively stabilizes the said formed polyhydroxy acid by reducing the scission of chains.
  • the peroxides acting as stabilizers may have a short half-life. In one embodiment, the half-life of the peroxide is below 10 seconds or below 5 seconds.
  • Exemplary peroxides which can be used are organic peroxy compounds and include, for example, dilauroyl peroxide, tert-butlyperoxy-diethylacetate, t-butylperoxy- 2-ethylhexanoate, tert-butylperoxyisobutyrate, tert- butylperoxyacetate, tert-butylperoxybenzoate and dibenzoylperoxide .
  • a process for producing a polylactic acid from crude lactic acid comprising the steps of: (a) polymerizing said crude lactic acid with said functionalizing agent by heating at a temperature from 50 degree C to 210 degree C, or from 100 degree C to 200 degree C with agitation to form polylactic acid prepolymer having a molecular weight in the range of about 10,000 to about 100,000;
  • the introduction of at least three terminal hydroxyl groups into the prepolymer allows the prepolymer to be highly reactive even with longer chain prepolymers.
  • a polyhydroxy acid prepolymer having at least three terminal hydroxyl groups facilitates the polymerization of larger weight polyhydroxy acid polymers within a shorter time frame relative to polyhydroxy acid polymers produced from short chain prepolymers.
  • a more reactive polyhydroxy acid prepolymer may also result in less coupling agent having to be used to produce the high molecular weight polyhydroxy acid polymer.
  • the system comprising a reactor having a reaction zone containing a polymerizing monomeric mixture of polyhydroxy acid prepolymer having at least three terminal hydroxyl groups and an isocyanate coupling agent, wherein said reaction zone is operated under conditions to form said high molecular weight polyhydroxy acid from said polymerizing monomeric mixture.
  • the reactor may comprises a fluid jacket surrounding at least a portion of the outer surface of said enclosed chamber for receiving heated fluid therein in use.
  • said reaction zone is in fluid communication with a vacuum
  • said reactor comprises an agitator disposed within said enclosed chamber to agitate said liquid phase therein in use.
  • the reactor may be a screw extruder. Different screws may be selected to obtain different desired compression ratios.
  • the extruder has an acid-resistant barrel and screw, and the extruder screw has a compression ratio of between approximately 1.5:1 and 3:1.
  • different screw configurations provide different types of mixing. Some examples of screw designs include those with no mixing sections, one mixing section, and two mixing sections.
  • the extruder is a twin screw extruder.
  • a twin screw mixer may provide advantages of a more stable flow, easier feeding, and better control over the process relative to a single screw extruder although a single screw extruder could still be used. This is attributed to the positive pumping effect and lack of compression caused by the twin screw mixer.
  • An exemplary twin screw extruder is disclosed in International PCT Published Application No. WO/2003/035349.
  • Non-limiting examples of the invention will be further described in greater detail by reference to specific embodiments and experimental examples, which should not be construed as in any way limiting the scope of the invention.
  • the particular embodiments and experimental examples that will be described relate to formation of polylactic acids, it should be realized that the process and apparatus disclosed herein may be applied to produce other polyhydroxycarboxylic acids.
  • the polymerization was carried out as in Example 2 with the exception that the amount of hexamethylene diisocyanate (99%, Merck) used was 84.3 g.
  • the product polymer obtained was transparent with Mw 187,397 and polydispersity 2.86. DSC-analysis indicated that the glass transition temperature of the polymer was 49 degree C.
  • the reactor with 12 L of capacity was loaded with 9 kg of 88 wt% commercial L-lactic acid (ADM, USA) , 50 g 1, 4-butanediol (99%, Lancaster), and 12 g glycerin (98%, Sigma-Aldrich) , and 8 g stannous octoate (95%, Sigma- Aldrich) was added as a catalyst.
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling.
  • the vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg.
  • the total polymerization was around 20 to 40 hours.
  • the condensed water formed during polycondensation was removed by vacuum and/or nitrogen.
  • the prepolymer was obtained with Mw 20,508 and polydispersity 1.39. DSC- analysis indicated that the glass transition temperature of the prepolymer was 50.5 degree C with melting peaks at 141.7 degree C.
  • the product polymer obtained was transparent with Mw
  • Example 7 The reactor with 12 L of capacity was loaded with 9 kg of 88 wt% commercial L-lactic acid (ADM, USA) , 720 g ⁇ - caprolactone (99%, Lancaster), 62 g 1, 4-butanediol ⁇ 99%, Lancaster), and 9.5 g glycerin (98%, Sigma-Aldrich) , and 9 g stannous octoate (95%, Sigma-Aldrich) was added as a catalyst.
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling.
  • the vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg.
  • the total polymerization was around 20 to 40 hours.
  • the condensed water formed during polycondensation was removed by vacuum and/or nitrogen.
  • the prepolymer was obtained with Mw 19,258 and polydispersity 1.5. DSC-analysis indicated that the glass transition temperature of the prepolymer was 35.9 degree C.
  • Example 9 80 g of the prepolymer prepared from Example 7 was fed into a Banbury mixer (Changzhou, China) at temperature 160 degree C and agitation speed 20 rpm. 1.9 g of hexamethylene diisocyanate (99%, Merck) was added into the homogeneously mixed prepolymer when the melting was completed. The temperature was then raised to 180 degree C and polymerization was further carried out for 10 minutes. The product polymer was obtained with Mw 213,599 and polydispersity 4.07. DSC-analysis indicated that the glass transition temperature of the polymer was 41 degree C.
  • Example 9 80 g of the prepolymer prepared from Example 7 was fed into a Banbury mixer (Changzhou, China) at temperature 160 degree C and agitation speed 20 rpm. 1.9 g of hexamethylene diisocyanate (99%, Merck) was added into the homogeneously mixed prepolymer when the melting was completed. The temperature was then raised to 180 degree C and polymerization was further carried out for 10 minutes. The
  • the polymerization was carried out as in Example 7 with the exception that the amount of hexamethylene diisocyanate (99%, Merck) used was 2.1 g.
  • the product polymer obtained was transparent with Mw 254,492 and polydispersity 4.49. DSC-analysis indicated that the glass transition temperature of the polymer was 41 degree C.
  • the reactor with 12 L of capacity was loaded with 9 kg of 88 wt% commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illinois, USA), 60.5 g 1, 4-butanediol (99%, Lancaster), and 5 g pentaerythritol (98%, Sigma- Aldrich) , and 9 g stannous octoate (95%, Sigma-Aldrich) was added as a catalyst.
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling.
  • the vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg.
  • the total polymerization was around 20 to 40 hours.
  • the condensed water formed during polycondensation was removed by vacuum and/or nitrogen.
  • the prepolymer was obtained with Mw 21,916 and polydispersity 1.4. DSC- analysis indicated that the glass transition temperature of the prepolymer was 51.6 degree C with melting peaks at 141.3 degree C.
  • the reactor with 500 ml of capacity was loaded with 400 g of 88 wt% commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illinois, USA), 0.8 g succinic acid (99%, Lancaster), 3.4 g 1, 4-butanediol (99%, Lancaster), and 0.2 g pentaerythritol (98%, Sigma-Aldrich) , and 0.4 g stannous octoate (95%, Sigma-Aldrich) was added as a catalyst.
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling.
  • the vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg.
  • the total polymerization was around 20 to 40 hours.
  • the condensed water formed during polycondensation was removed by vacuum and/or nitrogen.
  • the prepolymer was obtained with Mw 20,266 and polydispersity 1.34. DSC-analysis indicated that the glass transition temperature of the prepolymer was 47 degree C with melting peaks at 147.4 degree C.
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling. The vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg. The total polymerization was around 20 to 40 hours. The condensed water formed during polycondensation was removed by vacuum and/or nitrogen. The prepolymer was obtained with Mw 20,392 and polydispersity 1.42. DSC-analysis indicated that the glass transition temperature of the prepolymer was 49.5 degree C with melting peaks at 151.2 degree C.
  • Example 16 The reactor with 12 L of capacity was loaded with 400 g of 88 wt% commercial L-lactic acid (Archer Daniels).
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling.
  • the vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg.
  • the total polymerization was around 20 to 40 hours.
  • the condensed water formed during polycondensation was removed by vacuum and/or nitrogen.
  • the prepolymer was obtained with Mw 21,370 and polydispersity 1.39. DSC-analysis indicated that the glass transition temperature of the prepolymer was 50.2 degree C with melting peaks at 150.5 degree C.
  • the reactor with 500 ml of capacity was loaded with 500 g of 88 wt% commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illinois, USA), and 6.65 g pentaerythritol (98%, Sigma-Aldrich), and 0.4 g stannous octoate (95%, Sigma-Aldrich) was added as a catalyst.
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling.
  • the vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg.
  • the total polymerization was around 20 to 40 hours.
  • the condensed water formed during polycondensation was removed by vacuum and/or nitrogen.
  • the prepolymer was obtained with Mw 14,754 and polydispersity 1.30. DSC-analysis indicated that the glass transition temperature of the prepolymer was 49.5 degree C with melting peaks at 151.2 degree C.
  • the reactor with 12 L of capacity was loaded with 9 kg of 88 wt% commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illinois, USA), 19.5 g 1, 4-butanediol (99%, Lancaster), and 9.0 g pentaerythritol (98%, Sigma- Aldrich) , and 8 g stannous octoate (95%, Sigma-Aldrich) was added as a catalyst.
  • the reaction mixture was heated at 100 degree C with an agitation speed of 200 rpm. The temperature was increased steadily from 100 degree C to 190 degree C with nitrogen bubbling.
  • the vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h, and then steadily increased from 100 mmHg to 5 mmHg.
  • the total polymerization was around 20 to 40 hours.
  • the condensed water formed during polycondensation was removed by vacuum and/or nitrogen.
  • the prepolymer was obtained with Mw 43,923 and polydispersity 1.72. DSC- analysis indicated that the glass transition temperature of the prepolymer was 53.1 degree C with melting peaks at 148 degree C.
  • Example 21 1.9 kg of the prepolymer prepared from Example 20 was mixed with 36.5 g of hexamethylene diisocyanate (99%,
  • Example 23 80 g of the prepolymer prepared from Example 22 was fed into a Banbury mixer (Changzhou, China) at temperature 160 degree C and agitation speed 20 rpm. 1.0 g of hexamethylene diisocyanate (99%, Merck) was added into the homogeneously mixed prepolymer when the melting was completed. The temperature was then raised to 180 degree C and polymerization was further carried out for 5 minutes. The product polymer was obtained with Mw 252,322 and polydispersity 4.78. DSC-analysis indicated that the glass transition temperature of the polymer was 50.5 degree C.
  • the disclosed process produced a polylactic acid that has a high molecular weight.
  • the produced high molecular weight polylactic acids exhibit sufficient mechanical strength such that they can be used in applications, such as in medical implants .
  • the disclosed process efficiently produces high molecular weight polyhydroxy acids with minimal prepolymer and lactic acid loss from the system.
  • the disclosed process allows high molecular weight polygydroxy acid to be formed without complex and expensive purification steps (i.e. as for formation of HMW polylactic acid from lactides) .
  • the disclosed process does not require the use of multiple unit operations (i.e. distillation columns, evaporators, heat exchangers, etc) to separate the water from the cyclic . . dimmers (i.e. lactides) .
  • the disclosed process is not as capital-intensive as other known HMW polylactic acid processes .
  • the disclosed system and process are relatively simple to operate and maintain.
  • the disclosed system and process do not produce any environmentally harmful by-products.

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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

L'invention concerne un procédé de fabrication d'un polyhydroxy acide de masse moléculaire élevée, comprenant les étapes consistant à condenser un hydroxy acide avec un agent fonctionnalisant, ledit agent fonctionnalisant étant choisi pour former un prépolymère de polyhydroxy acide comportant au moins trois groupes hydroxyle terminaux après ladite condensation ; et polymériser ledit prépolymère en présence d'un agent de couplage dans des conditions permettant de former ledit polyhydroxy acide de masse moléculaire élevée.
PCT/SG2007/000238 2006-09-21 2007-08-07 Procédé de fabrication d'un polyhydroxy acide de masse moléculaire élevée WO2008036049A1 (fr)

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CN111454553A (zh) * 2020-05-18 2020-07-28 长沙乐远化工科技有限公司 一种改性聚乳酸材料及制备方法
CN113045736A (zh) * 2019-12-27 2021-06-29 美国达克有限责任公司 用于具有降低的气体渗透性的容器和薄膜的聚(乙醇酸)
US20220380525A1 (en) * 2019-12-18 2022-12-01 Solvay Specialty Polymers Usa, Llc Glycolic acid polymer
CN116355327B (zh) * 2023-04-10 2023-08-29 舒氏集团有限公司 一种可降解pvc薄膜及胶带的制备方法

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WO2020087223A1 (fr) * 2018-10-29 2020-05-07 Pujing Chemical Industry Co., Ltd Nouvel acide polyglycolique et son procédé de préparation par polycondensation
AU2018448114B2 (en) 2018-10-29 2024-03-28 Pujing Chemical Industry Co., Ltd Polyglycolic acid resin and production process thereof

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WO1994019384A1 (fr) * 1993-02-16 1994-09-01 E.I. Du Pont De Nemours And Company COPOLYMERES POLYLACTIDIQUES CONSTITUES PAR UNE SUCCESSION DE BLOCS (ABA)¿n?
WO2006055049A1 (fr) * 2004-07-30 2006-05-26 Advanced Cardiovascular Systems, Inc. Revetements pour dispositifs implantables contenant des poly(hydroxy-alcanoates) et des liaisons diacides

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EP0295055A2 (fr) * 1987-06-09 1988-12-14 Biomedical Polymers International, Ltd. Matériaux polymériques biodégradables à base de polyétherglycols, procédé pour leur préparation et articles chirurgicaux
WO1994019384A1 (fr) * 1993-02-16 1994-09-01 E.I. Du Pont De Nemours And Company COPOLYMERES POLYLACTIDIQUES CONSTITUES PAR UNE SUCCESSION DE BLOCS (ABA)¿n?
WO2006055049A1 (fr) * 2004-07-30 2006-05-26 Advanced Cardiovascular Systems, Inc. Revetements pour dispositifs implantables contenant des poly(hydroxy-alcanoates) et des liaisons diacides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220380525A1 (en) * 2019-12-18 2022-12-01 Solvay Specialty Polymers Usa, Llc Glycolic acid polymer
CN113045736A (zh) * 2019-12-27 2021-06-29 美国达克有限责任公司 用于具有降低的气体渗透性的容器和薄膜的聚(乙醇酸)
CN113045736B (zh) * 2019-12-27 2024-08-02 美国达克有限责任公司 用于具有降低的气体渗透性的容器和薄膜的聚(乙醇酸)
CN111454553A (zh) * 2020-05-18 2020-07-28 长沙乐远化工科技有限公司 一种改性聚乳酸材料及制备方法
CN116355327B (zh) * 2023-04-10 2023-08-29 舒氏集团有限公司 一种可降解pvc薄膜及胶带的制备方法

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