WO2001068890A2 - Prevention de la gelification de solutions de polyhydroxyalkanoate par le cisaillement - Google Patents

Prevention de la gelification de solutions de polyhydroxyalkanoate par le cisaillement Download PDF

Info

Publication number
WO2001068890A2
WO2001068890A2 PCT/US2001/007017 US0107017W WO0168890A2 WO 2001068890 A2 WO2001068890 A2 WO 2001068890A2 US 0107017 W US0107017 W US 0107017W WO 0168890 A2 WO0168890 A2 WO 0168890A2
Authority
WO
WIPO (PCT)
Prior art keywords
pha
solution
temperature
solvent
cooling
Prior art date
Application number
PCT/US2001/007017
Other languages
English (en)
Other versions
WO2001068890A3 (fr
Inventor
Devdatt L. Kurdikar
Mark D. Paster
Jianwei Zhang
Original Assignee
Metabolix, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Metabolix, Inc. filed Critical Metabolix, Inc.
Priority to AU2001250800A priority Critical patent/AU2001250800A1/en
Publication of WO2001068890A2 publication Critical patent/WO2001068890A2/fr
Publication of WO2001068890A3 publication Critical patent/WO2001068890A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • 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
    • C08G63/88—Post-polymerisation treatment
    • C08G63/89—Recovery of the polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • This invention relates to a process for the extraction and recovery of polyhydroxy- alkanoate (PHA) from biomass.
  • PHA polyhydroxy- alkanoate
  • biodegradable polymers There has been considerable interest in recent years in the use of biodegradable polymers to address concerns over plastic waste accumulation.
  • the potential worldwide market for biodegradable polymers is enormous.
  • Some of the markets and applications most amenable to the use of such biopolymers involve those having single, short use applications, including packaging, personal hygiene, garbage bags, and others. These applications, although poorly suited for recycling, are ideally suited for biodegradation through composting.
  • PHA biopolymers are thermoplastic polyesters produced by numerous microorganisms in response to nutrient limitation.
  • the commercial potential for PHA spans many industries, and is derived primarily from certain advantageous properties which distinguish PHA polymers from petrochemical-derived polymers, namely excellent biodegradability and natural renewability.
  • the success of PHA as a viable alternative to petrochemical-derived polymers, however, will depend upon the design and implementation of efficient and selective means of PHA production and recovery.
  • the present invention relates to a method of extracting PHA from a solution.
  • the method involves cooling the solution under shear.
  • One feature of the method is that the cooling PHA solution does not undergo gelation, but instead forms a flowable slurry of small
  • the present invention relates to a method of extracting polyhydroxyalkanoate (PHA) from a solution comprising a solvent and the PHA.
  • the method involves: providing the solution at a first temperature; cooling the solution to a second temperature, wherein the second temperature is effective to precipitate PHA, and concurrently shearing the solution, to yield a precipitated PHA substantially free of gelation; and recovering the precipitated PHA.
  • PHA polyhydroxyalkanoate
  • the present invention relates to a method of extracting PHA from a solution of PHA and biomass, involving: providing biomass having intracellular PHA; dissolving the PHA using a solvent and a first temperature effective for dissolving the PHA, the resulting solution of PHA having conditions of PHA concentration, solvent, and temperature effective upon cooling to produce a gel; cooling the solution to a second temperature effective for precipitation of the PHA and concurrently shearing the solution, to yield a precipitated PHA substantially free of gelation; and recovering the precipitated PHA.
  • the embodiments disclosed herein relate to novel methods for the recovery of PHA polymer from a solution comprising a solvent and the PHA.
  • the solution comprises a solvent and a PHA extracted from biomass materials, wherein the biomass materials are derived from PHA-producing plants or PHA-producing microorganisms
  • the present invention is directed to a method of extracting polyhydroxyalkanoate (PHA) from a solution comprising a solvent and the PHA, comprising: providing the solution at a first temperature; cooling the solution to a second temperature, wherein the second temperature is effective to precipitate PHA, and concurrently shearing the solution, to yield a precipitated PHA substantially free of gelation; and recovering the precipitated PHA.
  • PHA polyhydroxyalkanoate
  • the PHA can be any PHA known in the art or subsequently produced.
  • the methods of the present invention are applicable to the recovery of all types of PHA polymer.
  • PHA is a polymer made from repeating units having the following general structure:
  • R is preferably an H, alkyl, or alkenyl; p is 0, 1, 2, or 3; and n is an integer.
  • PHA can consist entirely of a single monomeric repeating unit, in which case it is referred to as a homopolymer.
  • Copolymers in contrast, contain two different types of monomeric units.
  • the polymer is referred to as a terpolymer.
  • the methods disclosed herein may also be applicable to the recovery of PHA which has been modified to provide improved or beneficial properties, for example by modification to contain hydroxy-terminated end groups.
  • the polymers described above, whether homo-, co-, or terpolymers, can be of any desirable molecular weight Mw.
  • Mw molecular weight
  • the Mw is greater than about 20 kD. More preferably, the Mw is in the range of from about 60 kD to about 500 kD. Most preferably, the Mw is in the range of from about 100 kD to about 400 kDa.
  • the solvent can be any solvent in which the PHA dissolves.
  • the solvent selected is one in which the PHA is highly soluble.
  • PHA composition and morphology are determinants of polymer solubility characteristics. Therefore, composition and morphology of the specific PHA being recovered are important considerations when selecting suitable solvents for use in the present invention.
  • PHBH (C4/C6) copolymer is typically more soluble than PHBV (C4/C5) copolymer, which is typically more soluble than PHB (C4) homopolymer.
  • a C4 alcohol for example, may be a suitable solvent for a particular PHA, but may not be a suitable solvent for a different PHA, depending upon polymer composition.
  • Ci -Cg and R ⁇ Ci -Cg, and cyclic and acyclic R ⁇ -CO-R ⁇ ketones where R ⁇ Cj-Cg and
  • Preferred solvents for use in the methods of the present invention include dimethyl formamide, dimethyl acetamide, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, butyl acetate, ethyl butyrate, propyl butyrate, butyl butyrate, methyl propionate, propyl propionate, butyl propionate, pentyl propionate, methyl valerate, ethyl valerate, 2-butanol, 2- methyl-1-propanol, 1-pentanol, 3-pentanol, 2-methyl-l-butanol, 3-methyl-l-butanol, 1-hexanol, 1-heptanol, cyclohexanol, 2-ethyl hexanol, 2-methoxy ethyl acetate and tetrahydrofurfuryl acetate.
  • Other preferred solvents include
  • a group of solvents that is generally preferred for many PHAs includes amyl alcohol, hexyl alcohol, ethylene glycol diacetate, 2-heptanone, butyl butyrate, 2-methyl 1-butanol, other alcohols, esters, and dioxanes.
  • Amyl alcohol is especially preferred.
  • the PHA concentration in the PHA-enriched solvent is typically between about 1 % and about 40% w/v.
  • the temperature of the solution before cooling (herein the "first temperature") can be any temperature in which the PHA is substantially soluble that is below the boiling point of the solvent and the melting point of the PHA.
  • the solvents will have boiling points above
  • boiling points will be in the range of 100- 180°C. Melting points of PHAs are typically in the range of 130-180°C.
  • the pressure of the solution before cooling can be any pressure useful in PHA processing, and most readily will be 1 atm. It is desirable that the rate and extent of shear during cooling be such to prevent gelation, i.e. to produce PHA in the form of discrete particles of small size (about 1 mm in diameter or less).
  • the Examples below describe the use of magnetic stirrers or impellers to provide stirring of at least about 100 rpm, preferably about 150 rpm to about 1000 rpm, for benchtop work (flask volume 500 mL).
  • Factors that will determine the rpm required for a stirrer or impeller to generate sufficient shear in an industrial-scale embodiment include: the volume of the vessel, the concentration of PHA in the solution, the size of the paddle or paddles of the stirrer or impeller, and the temperature to which the solution is to be cooled.
  • shear can be generated by sonication or other known methods. The process conditions required to generate sufficient shear will be readily determined, without undue experimentation, by one of ordinary skill in the art.
  • Cooling the solution can be performed by any known method. Preferably, cooling is performed by circulating air or water partially or completely around the vessel in which the solution is to be cooled.
  • the rate of cooling can be any rate possible using air- or water-cooling.
  • the temperature to which the solution is cooled (the "second temperature") can be from about 30°C to about 90°C, preferably from about 50°C to about 80°C, and in any event will be below the first temperature.
  • the lowest temperature to which the solution can be cooled without gelation will depend, as one of skill in the art will recognize, on the PHA used, the solvent used, and the rate of shear.
  • amyl alcohol as the solvent may result in gelation below about 50°C, whereas use of ethylene glycol diacetate may allow cooling to about 30°C.
  • the minimum temperature to which the solution can be cooled will be readily determined, without undue experimentation, by one of ordinary skill in the art.
  • the second temperature can be any temperature which is acceptable for further processing, as described below.
  • PHA will be present as a slurry of discrete particles in the solution.
  • PHA can be separated from the solvent by any method know in the art, for example, by filtration or centrifugation. The separated PHA can then undergo any other processing or manufacturing steps as known to one of ordinary skill in the art.
  • the solvent may be reused, either directly, by dilution into fresh solvent, or by distillation to separate the used solvent from any impurities therein. Other uses for the solvent may be apparent to one of ordinary skill in the art.
  • One advantage of this approach relates to the ease with which PHA can be recovered.
  • a precipitate forms which is easily removed from the solvent.
  • other solvent systems used for PHA extraction which involve subsequent recovery of PHA by temperature reduction typically result in a PHA-enriched solvent which forms a stable gel upon cooling. Additional steps are then required in order to separate PHA polymer from the gel. For example, the gel can be compressed into flakes, and remaining solvent present in the flakes can be removed by heat evaporation.
  • a "precipitating agent” refers to a second solvent or second solution in which the PHA is substantially (at least 50% w/v) less soluble than it is in the solvent recited in the above method.
  • the present invention advantageously provides methods for the recovery of PHA polymer without undesirable gel formation and without the requirement for precipitating agents by cooling the PHA-enriched solvent under shear.
  • the present invention relates to a method of extracting PHA from a solution of PHA and biomass, comprising: providing biomass having intracellular PHA; dissolving the PHA using a solvent and a first temperature effective for dissolving the PHA, the resulting solution of PHA having conditions of PHA concentration, solvent, and temperature effective upon cooling to produce a gel; cooling the solution to a second temperature effective for precipitation of the PHA and concurrently shearing the solution, to yield a precipitated PHA substantially free of gelation; and recovering the precipitated PHA.
  • the biomass can be any biomass containing intracellular PHA.
  • the biomass is microbiological or plant material.
  • Microbiological biomass can be derived from any unicellular organism that produces PHA, such as bacteria or yeast.
  • the production of PHA by the unicellular organism can be a characteristic of the organism as found in nature, a characteristic engineered in the organism by genetic engineering techniques, or both.
  • An exemplary unicellular organism that produces PHA is Alcaligenes eutrophus. Others are known to one of ordinary skill in the art.
  • the methods are applicable, for example, to PHA recovery from plants belonging to taxa having chlorophyll a and optionally one or more other chlorophylls in their photosynthetic apparatus.
  • the plants can be monocots or dicots.
  • Suitable plant source materials from which PHA can be recovered include roots, stems, leaves, flowers, fruits, or seeds.
  • the embodiments of the present invention are particularly useful for PHA recovery from oil-bearing seeds.
  • Oilseed crops such as canola, rapeseed, soybean, safflower, and sunflower, can be genetically engineered with the result of PHA being biosynthetically produced in the seeds of the crops.
  • PHA polymer In order to recover PHA polymer from the seeds, it is necessary to separate the polymer from the vegetable oil and oilseed meal also present.
  • the seeds are typically processed by conventional methods. For example, they can be crushed, dehulled, oil-extracted, or protein extracted, in any order, prior to PHA extraction.
  • the oilseed meal which is separated from the PHA-enriched solvent may be further processed and used as animal feed or an additive in animal feed.
  • the biomass Prior to the dissolving step, the biomass can be pretreated.
  • Pretreatment herein means removal or degradation of non-PHA cellular material, such as proteins, glycoproteins, oligosaccharides, other carbohydrates, and nucleic acids, in order to facilitate dissolving of PHA (by which is meant increasing the yield, the purity, or both of the PHA) in the solvent.
  • Techniques of pretreatment that are known to be effective include grinding, chemical digestion (e.g. by surfactants or peroxide), or enzymatic digestion (e.g. by proteinases or lysozyme).
  • Example 1 4.0 g of polyhydroxybutyrate-co-valerate (PHBV (8% HV)) was added to 100 cc of amyl alcohol in a 140 ml beaker containing a magnetic stirrer. The mixture was heated to 112°C on a hot plate while being stirred to obtain a clear solution of PHA in amyl alcohol. At that point, the heater was turned off and the solution was allowed to air-cool while being stirred by the magnetic stirrer (and occasionally manually with a spatula). Upon cooling to 57°C, the solution had not gelled and the entire slurry was fluid and could be filtered easily.
  • PHBV polyhydroxybutyrate-co-valerate
  • Example 2 6.03 g of PHBV (8% HV) was added to 150 ml amyl alcohol, which was preheated to 108°C in a 500 ml reaction flask equipped with a Lightnin R500® (Lightnin Mixing Equipment; Rochester, NY) impeller. The mixture was heated to 125°C in a hot oil bath while being stirred at 250 rpm to obtain a clear solution. At that point, the hot oil bath was removed and the solution was allowed to air-cool while being stirred at 250 rpm. Upon cooling to 61°C, the solution did not gel and the entire slurry of very fine polymer particles was fluid and could be filtered very easily.
  • PHBV 8% HV
  • Example 3 9.0283 g of PHBV (8% HV) was added to 150 ml amyl alcohol, preheated to 112°C, in a 500 ml reaction flask equipped with a Lightnin R500 impeller. The mixture was heated to 126°C in a hot oil bath while being stirred at 200 m to obtain a clear solution. At that point, the hot oil bath was removed and the solution was allowed to air-cool while being stirred at 250 ⁇ m. Significant polymer precipitation was observed around 84°C. Upon cooling to 58°C, the solution did not gel and the entire slurry of very fine and discrete polymer particles in amyl alcohol was fluid and could be filtered very easily.
  • Comparative Example 3a The solution produced in Example 3 was reheated to 123°C in the hot oil bath to obtain a clear solution and the same cooling procedure repeated, except that the solution was stirred at 100 ⁇ m. Upon cooling to 55°C, the solution gelled and some chunks of broken polymer gel were observed.
  • Example 4 12.02 g of PHBV (8% HV) was added to 150 ml amyl alcohol, preheated to
  • Comparative Example 5a The solution prepared in Example 5 was reheated to 1 15°C in the hot oil bath to obtain a clear solution and the same cooling procedure repeated, except that the solution was stirred at 80 ⁇ m. Upon cooling to room temperature, the solution gelled and some chunks of broken polymer gel were observed.
  • Example 6 0.9328 g of poly-hydroxyl-terminated-hydroxybutyrate (PHB-OH, (90% hydroxyl-terminated)) was added to 30 cc of amyl alcohol in a 100 ml round bottle containing a magnetic stirrer. The mixture was heated to 123°C in a hot oil bath while being stirred to obtain a clear solution. At that point, the hot oil bath was removed and the solution was allowed to air- cool while being stirred by the magnetic stirrer. The polymer solution remained flowable until it geled. Upon cooling to room temperature (e.g. ⁇ 22°C), the solution gelled.
  • room temperature e.g. ⁇ 22°C
  • Example 7 8.0048 g of PHBV (8% HV) was added to 200 ml hexyl alcohol preheated to 125°C in a 500 ml reaction flask equipped with a Lightnin R500 impeller. The polymer was completely dissolved at this temperature and a clear solution of PHBV (8% HV) in hexyl alcohol was obtained. At that point, the hot oil bath was removed and the solution was allowed to air- cool while being stirred at 300 ⁇ m. Upon cooling to 59°C, the solution did not gel and the entire slurry of fine and discrete polymer particles was fluid and could be filtered very easily. Comparative Example 7a: The solution produced in Example 7 was reheated to 119°C in the hot oil bath to obtain a clear solution and the same cooling procedure repeated, except that the solution was not stirred. Upon cooling to room temperature, the solution gelled.
  • Example 8 6.0014 g of PHBV (8% HV) was added to 150 ml ethylene glycol diacetate, preheated to 108°C in a 500 ml reaction flask equipped with a Lightnin R500 impeller. The mixture was heated to 124°C in a hot oil bath while being stirred at 300 rpm to obtain a clear solution. At that point, the hot oil bath was removed and the solution was allowed to air-cool while being stirred at 300 ⁇ m. Upon cooling to 32°C, the polymer solution did not gel, but discrete polymer precipitate particles were not visually observed.
  • Example 9 4.5001 g of PHBV (8% HV) was added to 150 ml 2-heptanone preheated to
  • Comparative Example 10 0.2995 g of PHBV (8% HV) was added to 10 ml 2-heptanone in a test tube. The mixture was heated in a hot oil bath to 128°C while being stirred by a magnetic stirring bar to obtain a clear solution. At that point, the hot oil bath was removed and the solution was allowed to air-cool without agitation. The solution was then cooled until it gelled. There was negligible amount of clear solvent observed in this polymer gel after being centrifuged.
  • Example 11 3.0059 g of PHBV (8% HV) was added to 150 ml butyl butyrate preheated to 115°C in a 500 ml reaction flask equipped with a Lightnin R500 impeller. The mixture was heated in a hot oil bath to 132°C while being stirred at 200 ⁇ m to obtain a clear solution. At that point, the hot oil bath was removed and the solution was allowed to air-cool while being stirred at 300 ⁇ m. Significant polymer precipitation was observed at 80°C. Upon cooling to 42°C, the polymer solution did not gel and polymer could be easily recovered by filtration, although discrete polymer precipitate particles were not visually observed. A portion of the solution was centrifuged and some clear solution on top of polymer precipitate was observed.
  • Comparative Example 12 0.3000 g of PHBV (8% HV) was added to 15 ml butyl butyrate in a test tube. The mixture was heated in a hot oil bath to 132°C while being stirred by a magnetic stirring bar to obtain a clear solution. At that point, the hot oil bath was removed and the solution was allowed to air-cool without agitation. Upon cooling, the polymer solution gelled. There was negligible amount of clear solvent observed in this polymer gel after being centrifuged.
  • Example 13 A mixture of corn stover / PHBV (8% HV) was prepared by blending 30.0 g dry ground corn stover with 5.3 g PHBV.
  • This pre-blended biomass was contacted with 178 ml amyl alcohol at 127°C for 90 minutes in a 500 ml reaction flask equipped with a Teflon single-blade impeller.
  • the biomass-PHA solution slurry was filtered using a pressure filter (D porosity, 10 - 20 mm). The pressure filter was maintained at 122°C to avoid polymer precipitation and loss in the biomass residue. The filtration was easy to perform with 2 - 3 psi N pressure differential.
  • a dark brown colored polymer solution was collected in a 250 ml three-neck round bottle which was maintained at 122°C in a hot oil bath.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

L'invention concerne un procédé pour extraire le polyhydroxyalkanoate (PHA) d'une solution qui comporte un solvant et le PHA, ce procédé comprenant les opérations suivantes: (i) porter la solution à une première température; (ii) refroidir la solution pour la porter à une deuxième température, propice à la précipitation du PHA, et procéder simultanément au cisaillement de la solution, afin d'obtenir un PHA précipité, sensiblement exempt de gélification; et (iii) recueillir le PHA précipité. Selon un mode de réalisation apparenté du procédé, on peut obtenir la solution comme suit: (a) constituer une biomasse dotée d'un PHA intracellulaire; et (b) dissoudre le PHA en utilisant un solvant et en appliquant une première température propice à la dissolution du PHA.
PCT/US2001/007017 2000-03-10 2001-03-05 Prevention de la gelification de solutions de polyhydroxyalkanoate par le cisaillement WO2001068890A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001250800A AU2001250800A1 (en) 2000-03-10 2001-03-05 Prevention of gelation of polyhydroxyalkanoate solutions using shear

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US18844000P 2000-03-10 2000-03-10
US60/188,440 2000-03-10

Publications (2)

Publication Number Publication Date
WO2001068890A2 true WO2001068890A2 (fr) 2001-09-20
WO2001068890A3 WO2001068890A3 (fr) 2002-04-18

Family

ID=22693156

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/007017 WO2001068890A2 (fr) 2000-03-10 2001-03-05 Prevention de la gelification de solutions de polyhydroxyalkanoate par le cisaillement

Country Status (2)

Country Link
AU (1) AU2001250800A1 (fr)
WO (1) WO2001068890A2 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1408065A1 (fr) * 2002-10-09 2004-04-14 Messo-Chemietechnik Gmbh Purification des biopolymères formant un gel
WO2004076582A1 (fr) 2003-02-21 2004-09-10 Metabolix Inc. Melanges de pha
WO2005052175A2 (fr) * 2003-11-28 2005-06-09 Phb Industrial S.A. Procede de recuperation de polyhydroxialcanoates ('phas') dans une biomasse cellulaire
WO2006004814A1 (fr) * 2004-06-29 2006-01-12 The Procter & Gamble Company Extraction au solvant de polyhydroxyalkanoates (pha) provenant d'une biomasse
EP1688450A1 (fr) † 2003-11-21 2006-08-09 Kaneka Corporation Procede de production de cristal polyhydroxyalcanoate
EP1802681A1 (fr) * 2004-09-13 2007-07-04 Metabolix, Inc. Procedes d'extraction de polymeres par solvant unique
US7252980B2 (en) 2002-08-06 2007-08-07 Metabolix Inc. Polymer extraction methods
WO2017063352A1 (fr) * 2015-10-13 2017-04-20 中国石油化工股份有限公司 Poudre de polyester aliphatique applicable au frittage laser sélectif, et son procédé de préparation
US10030135B2 (en) 2012-08-17 2018-07-24 Cj Cheiljedang Corporation Biobased rubber modifiers for polymer blends
US10611903B2 (en) 2014-03-27 2020-04-07 Cj Cheiljedang Corporation Highly filled polymer systems
US10669417B2 (en) 2013-05-30 2020-06-02 Cj Cheiljedang Corporation Recyclate blends
CN114479042A (zh) * 2020-10-26 2022-05-13 中国石油化工股份有限公司 一种封端改性的聚羟基脂肪酸酯及其制备方法和其薄膜

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998046783A1 (fr) * 1997-04-15 1998-10-22 Monsanto Company Extraction de pha a haute temperature au moyen de solvants pauvres en pha
WO1998046782A1 (fr) * 1997-04-15 1998-10-22 Monsanto Company Procedes d'extraction et de recuperation de pha a l'aide de solvants non halogenes
US5894062A (en) * 1994-08-18 1999-04-13 Monsanto Company Process for the recovery of polyhydroxyalkanoic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5894062A (en) * 1994-08-18 1999-04-13 Monsanto Company Process for the recovery of polyhydroxyalkanoic acid
WO1998046783A1 (fr) * 1997-04-15 1998-10-22 Monsanto Company Extraction de pha a haute temperature au moyen de solvants pauvres en pha
WO1998046782A1 (fr) * 1997-04-15 1998-10-22 Monsanto Company Procedes d'extraction et de recuperation de pha a l'aide de solvants non halogenes

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8003355B2 (en) 2002-08-06 2011-08-23 Metabolix, Inc. Polymer extraction methods
US7713720B2 (en) 2002-08-06 2010-05-11 Metabolix Inc. Polymer extraction methods
US7981642B2 (en) 2002-08-06 2011-07-19 Metabolix, Inc. Polymer extraction methods
US7252980B2 (en) 2002-08-06 2007-08-07 Metabolix Inc. Polymer extraction methods
EP1408065A1 (fr) * 2002-10-09 2004-04-14 Messo-Chemietechnik Gmbh Purification des biopolymères formant un gel
EP1935945A1 (fr) 2003-02-21 2008-06-25 Metabolix, Inc. Mélanges de PHA
EP2241605A2 (fr) 2003-02-21 2010-10-20 Metabolix, Inc. Mélanges de polyhydroxyalcanoates
WO2004076582A1 (fr) 2003-02-21 2004-09-10 Metabolix Inc. Melanges de pha
EP1688450A1 (fr) † 2003-11-21 2006-08-09 Kaneka Corporation Procede de production de cristal polyhydroxyalcanoate
EP1688450B2 (fr) † 2003-11-21 2012-08-01 Kaneka Corporation Procede de production de cristal polyhydroxyalcanoate
US9045595B2 (en) 2003-11-28 2015-06-02 Phb Industrial S.A. Process for recovering polyhydroxialkanoates (“PHAs”) from cellular biomass
WO2005052175A3 (fr) * 2003-11-28 2005-06-30 Phb Ind Sa Procede de recuperation de polyhydroxialcanoates ('phas') dans une biomasse cellulaire
WO2005052175A2 (fr) * 2003-11-28 2005-06-09 Phb Industrial S.A. Procede de recuperation de polyhydroxialcanoates ('phas') dans une biomasse cellulaire
US7226765B2 (en) 2004-06-29 2007-06-05 The Procter & Gamble Company Solvent extraction of polyhydroxyalkanoates from biomass
WO2006004814A1 (fr) * 2004-06-29 2006-01-12 The Procter & Gamble Company Extraction au solvant de polyhydroxyalkanoates (pha) provenant d'une biomasse
US7893194B2 (en) 2004-09-13 2011-02-22 Metabolix Inc. Single solvent polymer extraction methods
EP2256143A1 (fr) * 2004-09-13 2010-12-01 Metabolix, Inc. Procédés d'extraction de polyméres par solvent unique
EP1802681B1 (fr) * 2004-09-13 2011-11-02 Metabolix, Inc. Procedes d'extraction de polymeres par solvant unique
EP1802681A1 (fr) * 2004-09-13 2007-07-04 Metabolix, Inc. Procedes d'extraction de polymeres par solvant unique
US10030135B2 (en) 2012-08-17 2018-07-24 Cj Cheiljedang Corporation Biobased rubber modifiers for polymer blends
US10669417B2 (en) 2013-05-30 2020-06-02 Cj Cheiljedang Corporation Recyclate blends
US10611903B2 (en) 2014-03-27 2020-04-07 Cj Cheiljedang Corporation Highly filled polymer systems
WO2017063352A1 (fr) * 2015-10-13 2017-04-20 中国石油化工股份有限公司 Poudre de polyester aliphatique applicable au frittage laser sélectif, et son procédé de préparation
US10787546B2 (en) 2015-10-13 2020-09-29 China Petroleum & Chemical Corporation Aliphatic polyester resin powder suitable for selective laser sintering and its preparation method
DE112016004673B4 (de) 2015-10-13 2023-02-23 Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation Aliphatisches Polyesterharzpulver, dessen Herstellungsverfahren und Verwendung, sowie selektives Lasersinterverfahren
CN114479042A (zh) * 2020-10-26 2022-05-13 中国石油化工股份有限公司 一种封端改性的聚羟基脂肪酸酯及其制备方法和其薄膜

Also Published As

Publication number Publication date
WO2001068890A3 (fr) 2002-04-18
AU2001250800A1 (en) 2001-09-24

Similar Documents

Publication Publication Date Title
EP0973930B1 (fr) Extraction de pha a haute temperature a l' aide de faibles solvants a pha
US6043063A (en) Methods of PHA extraction and recovery using non-halogenated solvents
ES2403881T3 (es) Métodos de extracción de polímeros
US9045595B2 (en) Process for recovering polyhydroxialkanoates (“PHAs”) from cellular biomass
EP0776372B1 (fr) Procede de recuperation d'un acide hydroxyalcanoique
US7226765B2 (en) Solvent extraction of polyhydroxyalkanoates from biomass
EP1853713B1 (fr) Procédé d'isolement de polyhydroxyalkanoates (PHAs) à partir de cellules bactériennes par l'extraction par solvant
CA2373131C (fr) Purification de polyhydoxyalcanoates
EP0036699A1 (fr) Extraction de l'acide poly-bêta-hydroxybutyrique
WO2001068890A2 (fr) Prevention de la gelification de solutions de polyhydroxyalkanoate par le cisaillement
CA2579721C (fr) Procedes d'extraction de polymeres par solvant unique
US7514525B2 (en) Recovery and purification of polyhydroxyalkanoates
MXPA00009754A (es) Metodos para la separacion y purificacion de biopolimeros.
KR20230151744A (ko) 폴리 하이드록시 알카노에이트의 생산 방법
KR0145945B1 (ko) 고순도의 폴리-베타-하이드록시부틸산의 제조방법
LU et al. VERFAHREN ZUR GEWINNUNG VON POLYHYDROXYALKANOLATEN (PHAS) AUS ZELLBIOMASSE PROCEDE DE RECUPERATION DE POLYHYDROXIALCANOATES (" PHAS") DANS UNE BIOMASSE CELLULAIRE
MXPA06006073A (en) Process for recovering polyhydroxialkanoates ("phas") from cellular biomass

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: JP