WO2010012688A1 - Increasing the hydrolysis resistance of biodegradable polyesters - Google Patents
Increasing the hydrolysis resistance of biodegradable polyesters Download PDFInfo
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- WO2010012688A1 WO2010012688A1 PCT/EP2009/059672 EP2009059672W WO2010012688A1 WO 2010012688 A1 WO2010012688 A1 WO 2010012688A1 EP 2009059672 W EP2009059672 W EP 2009059672W WO 2010012688 A1 WO2010012688 A1 WO 2010012688A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
- C08L23/0884—Epoxide-containing esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
Definitions
- the present invention relates to a method for increasing the hydrolysis resistance of biodegradable polyesters selected from the group consisting of polylactic acid and polyhydroxyalkanoate, characterized in that
- the biodegradable polyester are mixed 0.1 to 5 wt .-% of an epoxy group-containing copolymer based on styrene, acrylate and / or methacrylate in the extruder at 160 to 220 0 C.
- Biodegradable polyester mixtures selected from the group consisting of polylactic acid and polyhydroxyalkanoate have the great disadvantage that they degrade under processing conditions - for example in the extruder. The degradation is so rapid at temperatures above 150 0 C that the biopolymers are not suitable for many applications.
- the higher hydrolysis resistance is accompanied by an increased viscosity and improved shear stability of the biopolymer melts.
- the epoxide group-containing copolymers react under branching and chain extension with the resulting from the thermal or hydrolytic degradation fragments of the processed polyester. On the one hand, this leads to an increased molecular weight, but on the other hand also to a reduction in functional end groups, such as, for example, carboxyl end groups.
- polylactic acid As a biodegradable polyester, for example, polylactic acid is suitable.
- Polylactic acid having the following property profile is preferably used: a melt volume rate (MVR at 190 ° C and 2.16 kg according to ISO 1133 of 0.5 - preferably 2 - to 9 ml / 10 minutes a melting point below 175 ° C; a glass transition point (Tg) greater than 55 ° C a water content of less than 1000 ppm of a residual monomer content (L-lactide) of less than 0.3%. a molecular weight greater than 80,000 daltons.
- MVR melt volume rate
- Tg glass transition point
- Preferred polylactic acids are, for example, NatureWorks® 4020 or 4042D (polylactic acid from NatureWorks).
- Polyhydroxyalkanoates are understood as meaning primarily poly-4-hydroxybutyrates and poly-3-hydroxybutyrates, and furthermore copolyesters of the abovementioned hydroxybutyrates with 3-hydroxyvalerates.
- Poly-4-hydroxybutyrates are known in particular from the company Metabolix. They are sold under the trade name Mirel®.
- Poly-3-hydroxybutyrates are sold, for example, by PHB Industrial under the brand name Biocycle® and by Tianan under the name Enmat®.
- the polyhydroxyalkanoates generally have a molecular weight M w of from 100,000 to 1,000,000, and preferably from 300,000 to 600,000.
- epoxy group-containing copolymer based on styrene acrylic acid ester and / or methacrylic acid esters are particularly suitable.
- the epoxy groups bearing units are preferably glycidyl (meth) acrylates.
- Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight, of the copolymer have proven to be advantageous.
- the epoxy equivalent weight (EEW) in these polymers is preferably 150 to 3000, and more preferably 200 to 500 g / equivalent.
- the weight average molecular weight Mw of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000.
- the number-average molecular weight M n of the polymers is preferably from 400 to 6,000, in particular from 1,000 to 4,000.
- the polydispersity (Q) is copolymers of the above type are for example marketed by BASF Resins BV under the trademark Joncryl ® ADR generally between 1.5 and 5 containing epoxy groups.
- Epoxide group-containing copolymers of the abovementioned type are dissolved in 0.1 to 5
- Wt .-% preferably in 0.1 to 2 wt .-%, and particularly preferably in 0.2 to 1 wt .-%, based on the biopolymer used.
- the polymer melts may contain the usual additives.
- the effect found here of stabilizing the melts of biopolymers by adding epoxies xid tendency-containing copolymers is not affected.
- Usual additives are, for example
- Nucleating agents such as talc, chalk, carbon black, graphite, calcium or zinc stearate, poly-
- compatibilizers such as silanes, maleic anhydride, fumaric anhydride, isocyanates, diacid chlorides, antifog agents,
- Fillers such as glass fibers, starch, starch derivatives, cereals, cellulose derivatives, talc,
- the melting temperatures of the biopolymers were determined by DSC measurements with a device Exstet DSC 6200R from Seiko:
- the viscosity numbers were measured with a Miko Ubbelohde device type: M-II at 25 ° C, in phenol / o-dichlorobenzene 1: 1 according to DIN EN ISO 1628-1.
- melt viscosity of the samples over time was measured using a shear-tension controlled plate-plate rotation rheometer SR2 from Rheometric Scientific in
- the plate diameter was 25 mm, the plate spacing 1 mm.
- the set shear stress was 100 Pa, the measurement time was 30 min, it was preheated for 5 min.
- the measuring temperature is indicated in each case.
- Polylactic acid (PLA). Nature Works 4042D ® of the company Nature Works was 24 hours in vacuum at 5 mbar, the residual water content of 0.09 wt .-% epoxy groups-containing copolymer: Joncryl ® ADR 4368 from BASF Resins BV. Table: Melt viscosity of PLA with / without addition of Joncryl
- the copolymer of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) used consisted of 97% HB (3-hydroxybutyrate) and 3% HV (3-hydroxyvalerate) and was manufactured by Tianan.
- the melting point was 161 0 C
- the melt volume index was 11 ml / 10 min (2.16 kg at 170 0 C, according to ISO 1133).
- the present experiments clearly show that the melt viscosity of the pure PLA and PHB / V-C decreases rapidly melt already at 180 0, while the melt viscosity of 1 wt% with Joncryl ADR 4368 remains staggered melting constant and even increases slightly.
- these epoxies also show in relation to the hydrolysis resistance. While the viscosity (or molecular weight) of at 70 0 C in 95% humidity stored samples rapidly decreases, the viscosity numbers of the samples with 1% Joncryl ADR offset 4368 are significantly higher.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Erhöhung der Hydrolysebeständigkeit von biologisch abbaubaren Polyestern Increasing the hydrolysis resistance of biodegradable polyesters
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Erhöhung der Hydrolysebeständigkeit von biologisch abbaubaren Polyestern ausgewählt aus der Gruppe bestehend aus Polymilchsäure und Polyhydroxyalkanoat, dadurch gekennzeichnet, dassThe present invention relates to a method for increasing the hydrolysis resistance of biodegradable polyesters selected from the group consisting of polylactic acid and polyhydroxyalkanoate, characterized in that
dem biologisch abbaubaren Polyester 0,1 bis 5 Gew.-% eines Epoxidgruppen-haltigen Copolymers auf Basis Styrol, Acrylsäureester und/oder Methacrylsäureester im Extruder bei 160 bis 220 0C zugemischt werden.the biodegradable polyester are mixed 0.1 to 5 wt .-% of an epoxy group-containing copolymer based on styrene, acrylate and / or methacrylate in the extruder at 160 to 220 0 C.
Biologisch abbaubare Polyestermischungen ausgewählt aus der Gruppe bestehend aus Polymilchsäure und Polyhydroxyalkanoat haben den großen Nachteil, dass sie unter Verarbeitungsbedingungen - beispielsweise im Extruder - abbauen. Der Abbau ist bei Temperaturen über 150 0C so rasch, dass die Biopolymere für viele Anwendungen nicht in Frage kommen.Biodegradable polyester mixtures selected from the group consisting of polylactic acid and polyhydroxyalkanoate have the great disadvantage that they degrade under processing conditions - for example in the extruder. The degradation is so rapid at temperatures above 150 0 C that the biopolymers are not suitable for many applications.
Aus WO 2004/069912 ist bekannt, dass die Hydrolysebeständigkeit von Polyestern wie PBT durch Zugabe von epoxidierten natürlichen Ölen oder Fettsäureestern erhöht werden kann. Dieser Effekt reicht jedoch bei weitem nicht aus, die eingangs beschriebenen bei hohen Temperaturen labilen Biopolymere zu stabilisieren.From WO 2004/069912 it is known that the hydrolysis resistance of polyesters such as PBT can be increased by adding epoxidized natural oils or fatty acid esters. However, this effect is far from sufficient to stabilize the biopolymers labile at high temperatures described above.
Überraschenderweise wurde nun wie eingangs erwähnt gefunden, dass der Zusatz von 0,1 bis 5 Gew.-% eines Epoxidgruppen-haltigen Copolymers auf Basis Styrol, Acrylsäureester und/oder Methacrylsäureester im Extruder bei 160 bis 220 0C die Hydrolysestabilität der eingangs erwähnten Biopolymere entscheidend verbessert.Surprisingly, it has now been found, as mentioned above, that the addition of from 0.1 to 5% by weight of an epoxide group-containing copolymer based on styrene, acrylic ester and / or methacrylic acid ester in the extruder at 160 to 220 ° C. decisively determines the stability to hydrolysis of the biopolymers mentioned in the introduction improved.
Die höhere Hydrolysebeständigkeit geht mit einer erhöhten Viskosität und einer ver- besserten Scherstabilität der Biopolymerschmelzen einher. Die Epoxidgruppen- haltigen Copolymere reagieren dabei unter Verzweigung und Kettenverlängerung mit den durch den thermischen oder hydrolytischen Abbau entstandenen Bruchstücken der verarbeiteten Polyester. Dies führt, einerseits zu einem erhöhten Molekulargewicht, andererseits aber auch zu einer Verringerung von funktionellen Endgruppen, wie bei- spielsweise Carboxylendgruppen.The higher hydrolysis resistance is accompanied by an increased viscosity and improved shear stability of the biopolymer melts. The epoxide group-containing copolymers react under branching and chain extension with the resulting from the thermal or hydrolytic degradation fragments of the processed polyester. On the one hand, this leads to an increased molecular weight, but on the other hand also to a reduction in functional end groups, such as, for example, carboxyl end groups.
Als biologisch abbaubaren Polyester ist beispielsweise Polymilchsäure geeignet. Polymilchsäure mit dem folgenden Eigenschaftsprofil wird bevorzugt eingesetzt: einer Schmelzvolumenrate (MVR bei 190° C und 2.16 kg nach ISO 1133 von 0.5 - vorzugsweise 2 - bis 9 ml/10 Minuten einem Schmelzpunkt unter 175° C; einem Glaspunkt (Tg) größer 55°C einem Wassergehalt von kleiner 1000 ppm einem Monomeren-Restgehalt (L-Lactid) von kleiner 0.3%. einem Molekulargewicht von größer 80 000 Dalton.As a biodegradable polyester, for example, polylactic acid is suitable. Polylactic acid having the following property profile is preferably used: a melt volume rate (MVR at 190 ° C and 2.16 kg according to ISO 1133 of 0.5 - preferably 2 - to 9 ml / 10 minutes a melting point below 175 ° C; a glass transition point (Tg) greater than 55 ° C a water content of less than 1000 ppm of a residual monomer content (L-lactide) of less than 0.3%. a molecular weight greater than 80,000 daltons.
Bevorzugte Polymilchsäuren sind beispielsweise NatureWorks® 4020 oder 4042D (Polylmilchsäure der Fa. NatureWorks).Preferred polylactic acids are, for example, NatureWorks® 4020 or 4042D (polylactic acid from NatureWorks).
Unter Polyhydroxyalkanoaten werden in erster Linie Poly-4-hydroxybutyrate und PoIy- 3-hydroxybutyrate verstanden, weiterhin sind Copolyester der vorgenannten Hydroxy- butyrate mit 3-Hydroxyvaleraten umfasst. Poly-4-hydroxybutyrate sind insbesondere von der Fa. Metabolix bekannt. Sie werden unter dem Handelsnamen Mirel® vertrieben. Poly-3-hydroxybutyrate werden beispielsweise von der Fa. PHB Industrial unter dem Markennamen Biocycle® und von der Fa. Tianan unter dem Namen Enmat® vertrieben.Polyhydroxyalkanoates are understood as meaning primarily poly-4-hydroxybutyrates and poly-3-hydroxybutyrates, and furthermore copolyesters of the abovementioned hydroxybutyrates with 3-hydroxyvalerates. Poly-4-hydroxybutyrates are known in particular from the company Metabolix. They are sold under the trade name Mirel®. Poly-3-hydroxybutyrates are sold, for example, by PHB Industrial under the brand name Biocycle® and by Tianan under the name Enmat®.
Die Polyhydroxyalkanoate weisen in der Regel ein Molekulargewicht Mw von 100.000 bis 1.000.000 und vorzugsweise von 300.000 bis 600.000 auf.The polyhydroxyalkanoates generally have a molecular weight M w of from 100,000 to 1,000,000, and preferably from 300,000 to 600,000.
Als Epoxidgruppen-haltiges Copolymer auf Basis Styrol, Acrylsäureester und/oder Me- thacrylsäureester sind insbesondere geeignet. Die Epoxidgruppen tragenden Einheiten sind vorzugsweise Glycidyl(meth)acrylate. Als vorteilhaft haben sich Copolymere mit einem Glycidylmethacrylat-Anteil von größer 20, besonders bevorzugt von größer 30 und insbesondere bevorzugt von größer 50 Gew.-% des Copolymers erwiesen. Das Epoxid-Äquivalentgewicht (EEW) in diesen Polymeren beträgt vorzugsweise 150 bis 3000 und insbesondere bevorzugt 200 bis 500 g/Äquivalent. Das mittlere Molekulargewicht (Gewichtsmittel) Mw der Polymere beträgt vorzugsweise 2000 bis 25.000, insbesondere 3000 bis 8.000. Das mittlere Molekulargewicht (Zahlenmittel) Mn der PoIy- mere beträgt vorzugsweise 400 bis 6.000, insbesondere 1000 bis 4.000. Die PoIy- dispersität (Q) liegt im Allgemeinen zwischen 1.5 und 5. Epoxidgruppen-haltige Copolymere des obengenannten Typs werden beispielsweise von der BASF Resins B.V. unter der Marke Joncryl® ADR vertrieben.As an epoxy group-containing copolymer based on styrene, acrylic acid ester and / or methacrylic acid esters are particularly suitable. The epoxy groups bearing units are preferably glycidyl (meth) acrylates. Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight, of the copolymer have proven to be advantageous. The epoxy equivalent weight (EEW) in these polymers is preferably 150 to 3000, and more preferably 200 to 500 g / equivalent. The weight average molecular weight Mw of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000. The number-average molecular weight M n of the polymers is preferably from 400 to 6,000, in particular from 1,000 to 4,000. The polydispersity (Q) is copolymers of the above type are for example marketed by BASF Resins BV under the trademark Joncryl ® ADR generally between 1.5 and 5 containing epoxy groups.
Epoxidgruppen-haltige Copolymere des obengenannten Typs werden in 0,1 bis 5Epoxide group-containing copolymers of the abovementioned type are dissolved in 0.1 to 5
Gew.-%, bevorzugt in 0,1 bis 2 Gew.-%, und besonders bevorzugt in 0,2 bis 1 Gew.-%, bezogen auf das Biopolymer eingesetzt.Wt .-%, preferably in 0.1 to 2 wt .-%, and particularly preferably in 0.2 to 1 wt .-%, based on the biopolymer used.
Die Polymerschmelzen können die üblichen Additive enthalten. Der hier gefundene effekt der Stabilisierung der Schmelzen von Biopolymeren durch Zugabe von Epo- xidgruppen-haltigen Copolymeren wird dadurch nicht betroffen. Übliche Additiven sind beispielsweiseThe polymer melts may contain the usual additives. The effect found here of stabilizing the melts of biopolymers by adding epoxies xidgruppen-containing copolymers is not affected. Usual additives are, for example
Nukleierungsmittel wie Talkum, Kreide, Ruß, Graphit, Calcium- oder Zinkstearat, PoIy-Nucleating agents such as talc, chalk, carbon black, graphite, calcium or zinc stearate, poly-
D-Milchsäure, N,N'ethylen-bis-12-hydroxystearamid, Polyglykolsäure, Gleit- und Antiblockmittel,D-lactic acid, N, N'-ethylene-bis-12-hydroxystearamide, polyglycolic acid, lubricants and antiblocking agents,
Wachse,waxes,
Antistatika,antistatic agents,
Weitere Kompatibilizer wie Silane, Maleinsäureanhydrid, Fumarsäureanhydrid, Isocya- nate, Disäurechloride, Antifog-Mittel,Other compatibilizers such as silanes, maleic anhydride, fumaric anhydride, isocyanates, diacid chlorides, antifog agents,
UV-Stabilisatoren oderUV stabilizers or
Farbstoffe zu versehenTo provide dyes
Füllstoffe wie Glasfasern, Stärke, Stärkederivate, Cerealien, Cellulosederivate, Talkum,Fillers such as glass fibers, starch, starch derivatives, cereals, cellulose derivatives, talc,
Kreide, Ruß und Graphit.Chalk, soot and graphite.
BeispieleExamples
Die Schmelztemperaturen der Biopolymere wurden durch DSC Messungen mit einem Gerät Exstet DSC 6200R der Fa. Seiko bestimmt:The melting temperatures of the biopolymers were determined by DSC measurements with a device Exstet DSC 6200R from Seiko:
10 bis 15 mg der jeweiligen Proben wurden unter einer Stickstoffatmosphäre mit einer Aufheizrate von 20°C/min von -700C auf 2000C aufgeheizt. Als Schmelztemperaturen der Proben wurden die Peaktemperaturen des dabei beobachteten Schmelzpeaks angegeben. Als Referenz wurde jeweils ein leerer Probentiegel verwendet.10 to 15 mg of the respective samples were heated from -70 0 C to 200 0 C under a nitrogen atmosphere at a heating rate of 20 ° C / min. The melting temperatures of the samples were the peak temperatures of the observed melting peak indicated. For reference, an empty sample crucible was used in each case.
Die Viskositätszahlen wurden mit einem Miko-Ubbelohde Gerät Typ: M-Il bei 25°C, in Phenol/o-Dichlorbenzol 1 :1 gemäß DIN EN ISO 1628-1 gemessen.The viscosity numbers were measured with a Miko Ubbelohde device type: M-II at 25 ° C, in phenol / o-dichlorobenzene 1: 1 according to DIN EN ISO 1628-1.
Die Schmelzeviskosität der Proben über die Zeit wurde mit einem schubspannungsge- steuerten Platte-Platte Rotationsrheometer SR2 der Firma Rheometric Scientific inThe melt viscosity of the samples over time was measured using a shear-tension controlled plate-plate rotation rheometer SR2 from Rheometric Scientific in
Anlehnung an ISO 6721-10 bestimmt. Der Plattendurchmesser betrug 25 mm, der Plattenabstand 1 mm. Die eingestellte Schubspannung lag bei 100 Pa, die Messzeit betrug 30 min, es wurde 5 min vorgeheizt. Die Messtemperatur ist jeweils angegeben.Based on ISO 6721-10. The plate diameter was 25 mm, the plate spacing 1 mm. The set shear stress was 100 Pa, the measurement time was 30 min, it was preheated for 5 min. The measuring temperature is indicated in each case.
Eingesetzte Materialien:Materials used:
Polymilchsäure (PLA):NatureWorks® 4042D der Fa. NatureWorks wurde 24 Stunden im Vakuum bei 5 mbar getrocknet, Restwassergehalt 0,09 Gew.-% Epoxidgruppen-haltiges Copolymer: Joncryl® ADR 4368 der Fa. BASF Resins B.V. Tabelle: Schmelzviskosität von PLA bei/ohne Zugabe von JoncrylPolylactic acid (PLA). Nature Works 4042D ® of the company Nature Works was 24 hours in vacuum at 5 mbar, the residual water content of 0.09 wt .-% epoxy groups-containing copolymer: Joncryl ® ADR 4368 from BASF Resins BV. Table: Melt viscosity of PLA with / without addition of Joncryl
Versuche zum Einfluß der erfindungsgemässen Epoxide auf die Hydrolysebeständigkeit von PolyesternAttempts to influence the novel epoxides on the hydrolysis resistance of polyesters
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08161645 | 2008-08-01 | ||
| EP08161645.0 | 2008-08-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010012688A1 true WO2010012688A1 (en) | 2010-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2009/059672 Ceased WO2010012688A1 (en) | 2008-08-01 | 2009-07-27 | Increasing the hydrolysis resistance of biodegradable polyesters |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980160A (en) * | 2021-03-18 | 2021-06-18 | 合聚高分子材料科技(广东)有限公司 | Slow-degradation PBAT material and preparation method and application thereof |
| CN115895204A (en) * | 2022-11-16 | 2023-04-04 | 中国石油化工股份有限公司 | Polyglycolic acid enhanced anti-reflection polyester material, degradable mulching film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050154114A1 (en) * | 2003-12-22 | 2005-07-14 | Hale Wesley R. | Compatibilized blends of biodegradable polymers with improved rheology |
| WO2006002372A2 (en) * | 2004-06-23 | 2006-01-05 | Natureworks Llc | Branched polylactic acid polymers and method of preparing same |
| WO2006074815A1 (en) * | 2005-01-12 | 2006-07-20 | Basf Aktiengesellschaft | Biologically-degradable polyester mixture |
| WO2009089398A1 (en) * | 2008-01-09 | 2009-07-16 | E. I. Du Pont De Nemours And Company | Polyester composition resistant to hydrolysis |
-
2009
- 2009-07-27 WO PCT/EP2009/059672 patent/WO2010012688A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050154114A1 (en) * | 2003-12-22 | 2005-07-14 | Hale Wesley R. | Compatibilized blends of biodegradable polymers with improved rheology |
| WO2006002372A2 (en) * | 2004-06-23 | 2006-01-05 | Natureworks Llc | Branched polylactic acid polymers and method of preparing same |
| WO2006074815A1 (en) * | 2005-01-12 | 2006-07-20 | Basf Aktiengesellschaft | Biologically-degradable polyester mixture |
| WO2009089398A1 (en) * | 2008-01-09 | 2009-07-16 | E. I. Du Pont De Nemours And Company | Polyester composition resistant to hydrolysis |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980160A (en) * | 2021-03-18 | 2021-06-18 | 合聚高分子材料科技(广东)有限公司 | Slow-degradation PBAT material and preparation method and application thereof |
| CN115895204A (en) * | 2022-11-16 | 2023-04-04 | 中国石油化工股份有限公司 | Polyglycolic acid enhanced anti-reflection polyester material, degradable mulching film and preparation method thereof |
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