WO2010016801A1 - Polymère d'hydroxyacide stable à l'état fondu et résistant à l'hydrolyse - Google Patents

Polymère d'hydroxyacide stable à l'état fondu et résistant à l'hydrolyse Download PDF

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WO2010016801A1
WO2010016801A1 PCT/SG2009/000265 SG2009000265W WO2010016801A1 WO 2010016801 A1 WO2010016801 A1 WO 2010016801A1 SG 2009000265 W SG2009000265 W SG 2009000265W WO 2010016801 A1 WO2010016801 A1 WO 2010016801A1
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acid polymer
hydroxy acid
degree
stabilizing agent
stabilizing
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PCT/SG2009/000265
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English (en)
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Lianlong Hou
Shaofeng Wang
Bo JING
Siok Ling Sherlyn Yap
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Hydrochem (S) Pte Ltd
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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
    • C08G63/88—Post-polymerisation treatment
    • 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
    • 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

Definitions

  • the present invention generally relates to melt stable hydroxy acid polymer compositions having improved hydrolysis resistance properties.
  • hydroxy acid polymers such as lactic acid polymers
  • lactic acid polymers have gained increasing economic importance as a substitute for petroleum-based polymers.
  • the imminent depletion of oil resources worldwide has necessitated the development of alternative substitutes to these polymers.
  • landfill space and its associated hazardous incineration waste have led to an urgency to develop novel biodegradable polymers which can be converted to desired articles or devices.
  • a biodegradable polymer with similar strength properties of a petroleum-based polymer, yet based on renewable resources is highly favored. These strengthened polymers could be used in existing plastic molding equipment to manufacture a myriad of industrial and consumer goods, thereby easing the transition to biodegradable polymers and reducing the dependency for petroleum-based polymers .
  • hydroxy acid polymers mostly because of its ⁇ environmentally friendly" properties as these polymers are synthesized from lactic acid (derived from corn, a renewable plant feedstock) and biodegrades after use, if composted.
  • This renewable crop-based polymer represents an important substitute for petroleum-based polymers .
  • the manufacture of lactic acid polymers via the polymerization of lactic acids or lactide or its corresponding polymers thereof, is well known in the industry.
  • the presence of undesired chemical moieties in the polymer such as hydroxyl or carboxyl end groups, imparts instability to the polymer formed.
  • impurities such as residual activators, monomers and oligomers from polymerization reactions further accelerates the degradation of the polymer.
  • a positive aspect is the favorable biodegradation for composting the polymers at the end of its shelf life.
  • a negative aspect of such instability is the accelerated polymer degradation during processing at elevated temperatures. This instability has hampered the development of many lactic acid polymer resins suitable for commercial use.
  • Recent advancements have focused on improving the mechanical and physical properties of the polymers, such as strength, stiffness, moldability, dimensional stability and thermal stability.
  • One known process for producing lactic acid polymers with modified strength and dimensional stability comprises incorporating an elastomer into the polymer via melting both components together in an additional phase, wherein preferably, the elastomer has functional groups, which form covalent bonds with the polymer.
  • this method relies on the use of an additional compatibilizing agent, i.e. plasticizers, to improve the binding of the components together in the polymer, thus resulting in an increase in processing costs .
  • One known process to produce hydrolysis stable polymers comprises incorporating stabilizing agents such as carbodiimide compounds and phosphorus antioxidants into the polymer resin.
  • stabilizing agents such as carbodiimide compounds and phosphorus antioxidants
  • melt temperatures of 185°C that may further degrade the polymer since it is very sensitive to high temperatures.
  • stabilizing agents include hygroscopic polyhydroxy compounds, multifunctional carboxylic acids, and water scavengers such as anhydrides, acyl chlorides, isocyanates, alkoxy silanes, clay, alumina, silica, zeolites, calcium carbonate, sodium sulfate, bicarbonates and mixtures thereof.
  • melt-stable lactic acid polymer composition having increased melt-stability properties, and that exhibits sufficient compostability or degradability after its useful life to be manufactured into useful polymeric materials suitable as replacements for petroleum-based polymers that overcome, or at least ameliorate, one or more of the disadvantages described above .
  • a method for stabilizing hydroxy acid polymer comprising the steps of:
  • the hydroxyl acid polymer such as biodegradable polylactic acid
  • the catalyst is used to catalyze the polymerization of hydroxy acid polymer. However, upon completion of the polymerization reaction, the catalyst may undesirably promote the depolymerization of the hydroxy acid polymer.
  • the organic peroxide is added to the hydroxy acid polymer so that the catalyst is deactivated.
  • the organic peroxide may also act as a coupling agent, which aids in coupling the de-polymerized hydroxy acid polymer polymers together again.
  • the formed hydroxy acid polymer may decompose into smaller polymers due to instability.
  • the stabilizing agent acts as a coupling agent. More advantageously, the stabilizing agent is capable of neutralizing the acid by-products.
  • the stabilizing agent is capable of removing the water by-products. These acid and water by-products may further propagate degradation of the hydroxy acid polymer.
  • the stability of the hydroxy acid polymer can be improved and the degree of degradation of the hydroxy acid polymer can be greatly reduced.
  • a method for stabilizing hydroxy acid polymer such as polylactic acid (PLA) comprising the steps of: (a) adding about 0.01 wt% to about 1 wt% organic peroxide to a hydroxy acid polymer melt composition containing catalyst that catalyses the polymerization reaction to form the hydroxy acid polymer; and
  • the stabilizing agent comprising about 0.01 wt% to about 5 wt% anti-oxidant, about 0.01 wt% to about 5 wt% acid scavenger and about 0.1 wt% to about 10 wt% inorganic additive.
  • PVA polylactic acid
  • stabilizing agent added to the melt composition to at least partially reduce the rate of depolymerization of the hydroxy acid polymer within said melt composition
  • the stabilizing agent being selected from at least one, preferably at least two and more preferably at least three, of the following: (i) about 0.01 wt% to about 5 wt% anti-oxidant, (ii) about 0.01 wt% to about 5 wt% acid scavenger; (iii) about 0.1 wt% to about 10 wt% inorganic additive; and (iv) about 0.05 wt% to about 10 wt% water scavenger.
  • a hydroxy acid polymer composition comprising an organic peroxide and at least one stabilizing agent, wherein said stabilizing agent is selected to at least partially reduce the rate of depolymerization of the hydroxy acid polymer.
  • the hydroxy acid polymer composition as disclosed herein is melt-stable and hydrolysis resistant. More advantageously, the average molecular weight of the hydroxy acid polymer obtained is at least about 25,000, or at least about 50,000.
  • a hydroxy acid polymer composition comprising about 0.01 wt% to about 1 wt% organic peroxide and stabilizing agent selected to at least partially reduce the rate of depolymerization of the hydroxy acid polymer, the stabilizing agent being selected from the group consisting of about 0.01 wt% to about 5 wt% anti-oxidant , about 0.01 wt% to about 5 wt% acid scavenger and about 0.1 wt% to about 10 wt% inorganic additive.
  • a polylactic acid (PLA) ' composition comprising about 0.01 wt% to about 1 wt% organic peroxide and stabilizing agent selected to at least partially reduce the rate of depolymerization of the hydroxy acid polymer, the stabilizing agent comprising at least one, preferably at least two and more preferably at least three, of the following: (i) about 0.01 wt% to about 5 wt% anti-oxidant, (ii) about 0.01 wt% to about 5 wt% acid scavenger; (iii) about 0.1 wt% to about 10 wt% inorganic additive; and (iv) about 0.05 wt% to about 10 wt% water scavenger.
  • PHA polylactic acid
  • hydroxy acid as used herein means a carboxylic acid in which one or more hydrogen atom of the alkyl group has been replaced by a hydroxyl group.
  • hydroxy acid polymer as used herein means polymer of repeating hydroxy acid monomer units.
  • the "hydroxy acid polymer” refers to a hydroxy acid polymer having a molecular weight of more than 25,000, preferably more than 50,000. In some embodiments, the molecular weight of the hydroxy acid polymer is about 25,000 to about 350,000.
  • 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 hydroxy acid polymer, in a chemical reaction to form larger molecular weight polymer chains of hydroxy acid polymer.
  • the polymerization mechanism can be cationic, anionic, coordination or free radical polymerization.
  • the hydroxy 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 hydroxy acid polymer to thereby increase the molecular weight of said hydroxy acid polymer.
  • 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 hydroxy acid polymer, without being substantially consumed in the reaction.
  • the term "coupling agent” as used herein means a reagent that may be capable of joining or coupling one hydroxy acid or hydroxy acid polymer to another hydroxy acid or hydroxy acid polymer. When a hydroxy acid polymer decomposes, the coupling agent may also be capable of joining the depolymerized hydroxy acid polymer polymers together.
  • depolymerization refers to a reduction in the molecular weight of a hydroxy acid polymer by the breaking of bonds in the hydroxy acid polymer to produce shorter polymer chains of lower molecular weight.
  • rate of depolymerization refers to the degree of depolymerization of the hydroxy acid polymer over a particular time period.
  • 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 6 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.
  • Exemplary, non-limiting embodiments of a method for stabilizing hydroxy acid polymer comprising the steps of
  • the organic peroxide is added in an amount in the range of from about 0.01 wt% to about
  • the organic peroxide is selected from the group consisting of dilauroyl peroxide such as benzoyl peroxide, dialkanoyl peroxide such as lauroyl peroxide, alkylperoxy-alkylacetate such as tert- butylperoxy-diethylacetate, alkylperoxy-alkylhexanoate such as tert-butylperoxy-2-ethylhexanote, alkylperoxy- butyrate such as tert-butylperoxyisobutyrate, alkylperoxy acetate such as tert-butylperoxyacetate, alkylperoxy- benzoate such as tert-butylperoxybenzoate, dibenzoylperoxide, di-tert-butyl peroxide, and dicumyl peroxide.
  • dilauroyl peroxide such as benzoyl peroxide
  • dialkanoyl peroxide such as lauroyl peroxid
  • the stabilizing agent is selected to at least partially reduce the rate of depolymerization of the hydroxy acid polymer. Then stabilizing agent may be at least one of, preferably at least two of, more preferably at least three of an antioxidant, a water scavenger, an acid scavenger, an inorganic additive and mixtures thereof .
  • the acid scavenger is selected from the group consisting of epoxy, oxazoline, isocyanate and mixtures thereof.
  • the water scavenger is selected from the group consisting of isocyanate, carbodiimide, anhydride, acyl chloride, desiccant material and mixtures thereof .
  • the desiccant material may be selected from the group consisting of carbonate, bicarbonate, alumina, calcium oxide, sodium sulfate, silica gel, zeolite, clay, and mixtures thereof.
  • the epoxy matrix agent may be selected from the group consisting of an acrylic polymer epoxy resin, glycidyl methacrylate and epoxidized soybean oil.
  • the epoxy matrix agent may also be an oligomer or prepolymer with at least three epoxy groups, and the number average molecular weight is less than about 5,000.
  • the stabilizing agent may comprise carbodiimides such as N, N' -dicyclohexylcarbodiimide, N, N' -diisopropyl carbodiimide, bis (2, 6-diisopropylphenyl) carbodiimide, l-ethyl-3- (3-dimethylaminopropyl) -carbodiimide, stabaxol-P
  • carbodiimides such as N, N' -dicyclohexylcarbodiimide, N, N' -diisopropyl carbodiimide, bis (2, 6-diisopropylphenyl) carbodiimide, l-ethyl-3- (3-dimethylaminopropyl) -carbodiimide, stabaxol-P
  • the stabilizing agent may comprise a biodegradable polyester.
  • the biodegradable polyester may be selected from the group consisting of polybutylene succinate, polyhydroxyalkanoate, polycaprolactone, poly (vinyl alcohol) and mixtures thereof.
  • the stabilizing agent may also comprise inorganic additives such as clay, alumina, silica gel, calcium carbonate and calcium bicarbonates .
  • the inorganic additives are water scavengers that are capable of tying up water during storage .
  • the stabilizing agent may also comprise antioxidants such as phosphite antioxidants, hindered phenolic compounds such as trialkyl phosphites, mixed alkyl/aryl phosphites, alkylated aryl phosphites, sterically hindered aryl phosphites, aliphatic spirocyclic phosphites, sterically hindered phenyl spirocyclics, sterically hindered bisphosphonites, hydroxyphenyl propionates and mixtures thereof.
  • antioxidants such as phosphite antioxidants, hindered phenolic compounds such as trialkyl phosphites, mixed alkyl/aryl phosphites, alkylated
  • the stabilizing agent may comprise a weight percentage of peroxide, based on the weight of the hydroxy acid polymer, in the range of from about 0.01 wt% to about 1.0 wt%, from about 0.02 wt% to about 0.5 wt%, from about 0.05 wt% to about 0.2 wt%.
  • the stabilizing agent may comprise a weight percentage of epoxy matrix agent, based on the weight of the hydroxy acid polymer, in the range of from about 0.01 wt% to about 5.0 wt%, from about 0.05 wt% to about 2.5 wt%, from about 0.1 wt% to about 2.0 wt% .
  • the stabilizing agent may comprise a weight percentage of carbodiimide matrix agent, based on the weight of the hydroxy acid polymer, in the range of from about 0.05 wt% to about 10.0 wt%, from about 0.25 wt% to about 7.5 wt%, from about 0.5 wt% to about 5.0 wt% .
  • the stabilizing agent may comprise a weight percentage of antioxidant, based on the weight of the hydroxy acid polymer, in the range of from about 0.01 wt% to about 5.0 wt%, from about 0.05 wt% to about 2.5 wt%, from about 0.1 wt% to about 2.0 wt%.
  • the stabilizing agent may comprise a weight percentage of inorganic additive, based on the weight of the hydroxy acid polymer, in the range of from about 0.1 wt% to about 10.0 wt%, from about 0.5 wt% to about 7.5 wt%, from about 1.0 wt% to about 5.0 wt%.
  • the stabilizing agent may comprise at least one of an epoxy matrix agent, a carbodiimide matrix agent, an antioxidant and an inorganic additive.
  • the organic peroxide, epoxy matrix agent, carbodiimide matrix agent, antioxidant and inorganic additive may be added in the sequence as listed above.
  • the organic peroxide, epoxy matrix agent, carbodiimide matrix agent, antioxidant and inorganic additive are added in at least two separate steps during melt processing. Advantageously, this prevents the occurrence of undesirable side reactions between the different agents.
  • a mixture of the peroxide, antioxidant and epoxy matrix agent may first be added to the hydroxy acid polymer followed by a mixture of the epoxy matrix agent, carbodiimide matrix agent and inorganic additive.
  • the adding step (b) is undertaken in an extruder or a mixer.
  • the extruder may be a co- rotating twin screw extruder or a counter-rotating twin screw extruder.
  • the adding step (b) comprises the step of adding at least three stabilizing agents.
  • the at least three stabilizing agents may be mixed together prior to adding to said hydroxy acid polymer.
  • the at least three stabilizing agents may also be added directly to said hydroxy acid polymer without first mixing the said stabilizing agents together.
  • the at least three stabilizing agents may also be added sequentially to said hydroxy acid polymer.
  • the adding step (b) is undertaken at the same time as adding step (a) .
  • the adding step (b) is undertaken after adding step (a) .
  • a hydroxy acid polymer composition comprising an organic peroxide and at least one stabilizing agent, wherein said stabilizing agent is selected to reduce the rate of depolymerization of the hydroxy acid polymer.
  • the hydroxy acid polymer may have a weight average molecular weight of from about 25,000 to about 350,000, or from about 30,000 to about 300,000, or from about 40,000 to about 250,000, or from about 50,000 to about 200,000.
  • the hydroxy acid polymer is poly (lactic acid) (PLA) .
  • the pelletized lactic acid polymer-based resins and their corresponding stabilized polymers were dried in a rotational vacuum drier at a temperature of from 40 degree C to 85 degree C for a period of 12 hours to 76 hours.
  • the dried lactic acid polymer-based resins and stabilized polymers were then vacuum-packed in aluminum- plastic composite bags.
  • the dried lactic acid polymer-based resins and stabilized polymers were injected into different specimens for measuring of the mechanical and thermal properties according to the ASTM standards. Specifically, ASTM D638 was used for measuring tensile strength, ASTM D1238 was used for measuring melt flow rate, ASTM D256 was used for measuring Izod notched impact strength, and ASTM D790 was used for measuring flexural strength and modulus.
  • the weight-average molecular weight (Mw) of the lactic acid polymer was generally determined using GPC at a column temperature of 45 degree C, using chloroform as the solvent.
  • a refractive index detector was used with relative molecular weight calibrations using polystyrene standards .
  • DSC Differential Scanning Calorimeter
  • RV Reduced Viscosity
  • Acid Number (AN) AN was determined using Titrando 809 with Touch Control System (Metrohm AG, Switzerland) according to ASTM D664, using chloroform as a solvent for dissolving the samples.
  • the hydrolytic stability test was conducted under water conditions, according to the following process.
  • the hydrolytic stability test was also conducted under buffer solution conditions.
  • the process used was the same as that for the hydrolytic stability test conducted under water conditions as described above, except that sodium phosphate buffer solution having a pH value of 7.0 was used instead of water.
  • the stabilized lactic acid polymer was prepared according to the steps as described below.
  • the stabilized lactic acid polymer was prepared according to the steps as described below.
  • the moisture content of lactic acid polymer was below 500 parts-per-million by weight.
  • Example 3 Preparation of stabilized lactic acid polymers by adding peroxide, phosphite antioxidant, epoxy and carbodiimide matrix agent
  • step (vi) 4024 g of the treated and dried lactic acid polymer, followed by a mixture of 8 g (i.e. about 0.2 wt% of lactic acid polymer) ADR 4368C (epoxy matrix agent), 16 g (i.e. about 0.4 wt% of lactic acid polymer) octadecyl-3- (3, 5-di-tert-butyl-4- hydroxyphenyl) propionate ("1076”) and 40 g (i.e. about 1.0 wt% of lactic acid polymer) stabaxol P (carbodiimide matrix agent) were charged into the high speed mixer for mixing at a speed of 900 rpm, at 30 degree C for 3 min.
  • ADR 4368C epoxy matrix agent
  • 16 g i.e. about 0.4 wt% of lactic acid polymer
  • the lactic acid polymer was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • Example 2 above except that after step (v) , an additional step of surface treating of calcium carbonate as described above was conducted.
  • step (vi) 4024 g of the treated and dried lactic acid polymer, followed by a mixture of 4 g (i.e. 0.1 wt%) ADR 4385 (epoxy matrix agent), 82 g (i.e. 2.0 wt%) surface treated calcium carbonate and 16 g (i.e. 0.4 wt%) octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076) were charged into the high speed mixer for mixing at 900 rpm, at 30 degree C for 3 min.
  • ADR 4385 epoxy matrix agent
  • 82 g i.e. 2.0 wt% surface treated calcium carbonate
  • 16 g i.e. 0.4 wt%)
  • octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076) were charged into the high speed mixer for mixing at 900 rpm, at 30 degree C for 3 min.
  • step (ii) The steps for preparation of the stabilized lactic acid polymer in this Example were the same as those in Example 2 above except that in step (ii) , only 5 g (i.e. 0.1 wt%) tert-butyl peroxy benzonate and 20 g (i.e. 0.4 wt%) tris (nonylphenyl) phosphate (TNPP) antioxidant were charged into the high speed mixer.
  • step (ii) only 5 g (i.e. 0.1 wt%) tert-butyl peroxy benzonate and 20 g (i.e. 0.4 wt%) tris (nonylphenyl) phosphate (TNPP) antioxidant were charged into the high speed mixer.
  • step (v) an additional step of Master Batch (MB) preparation 1 as described above was conducted.
  • the lactic acid polymer was then extruded and pelletized similarly to steps (iii) to (v) as described above except that the corresponding temperatures within the extruder from zone 1 to zone 6 were 70 degree C,
  • the die temperature was set at 120 degree C and the melt temperature was set at 130 degree C.
  • the extruder was preheated and the motor speed was set at 15
  • the pellets were dried in a rotational vacuum drier at 45 degree C until the moisture content was below 500 ppm.
  • step (vi) 4020 g of the treated and dried lactic acid polymer, followed by 162 g MBl, 20 g (i.e. 05. wt%) ADR 4385 (epoxy matrix agent), 16 g (i.e. 0.4 wt%) octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 40 g (i.e. 1.0 wt%) stabaxol P (carbodiimide matrix agent) were charged into the high speed mixer for mixing at 900 rpm, 30 degree C for 3 min. The lactic acid polymers was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • step (ii) 10 g (0.2 wt%) ADR 4385 instead of only 5 g ADR 4385 was used, and after step (v) , an additional step of Master Batch (MB) preparation 2 as described above was conducted.
  • the lactic acid polymer was then extruded and pelletized similarly to steps (iii) to (v) as described above except that the corresponding temperatures of the extruder from zone 1 to zone 6 are 70 degree C, 120 degree C, 140 degree C, 130 degree C, 130 degree C, 120 degree C.
  • the die temperature was set at 120 degree C and the melt temperature was set at 130 degree C.
  • the extruder was preheated and the motor speed was set at 15 Hz and the feeding speed was set at 17 Hz.
  • the pellets were dried in a rotational vacuum drier at 45 degree C until the moisture content was below 500 ppm.
  • step (vi) 4028 g of the treated and dried lactic acid polymers, followed by 162 g MB2, 16 g (0.4 wt%) octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 40 g (1.0 wt%) stabaxol P (carbodiimide matrix agent) were charged into the high speed mixer for mixing at 900 rpm, 30 degree C for 3 min.
  • the lactic acid polymers was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • step (ii) The steps for preparation of the stabilized lactic acid polymer in this Example were the same as those in Example 4 above except that in step (ii) , 10 g (instead of only 5 g) ADR 4385 (epoxy matrix agent) was used, and after step (v) , an additional step of surface treating of calcium carbonate as describe above was conducted.
  • step (vi) 4028 g of the treated and dried lactic acid polymer, followed by a mixture of 82 g (2.0 wt%) surface treated calcium carbonate, 16 g (0.4 wt%) octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076) and 4O g (1.0 wt%) stabaxol P (carbodiimide matrix agent) were charged into the high speed mixer for mixing at 900 rpm, at 30 degree C for 3 min. The lactic acid polymer was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • step (vi) 4028 g of the treated and dried lactic acid • polymer, followed by a mixture of 82 g (2.0 wt%) surface treated calcium carbonate, 32 g (0.8 wt%) octadecyl-3-
  • the lactic acid polymer was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • step (ii) 10 g (0.2 wt%) octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate was also charged into the high speed mixer.
  • step (v) an additional step of Master Batch (MB) preparation 3 as described above was conducted.
  • the lactic acid polymer was then extruded and pelletized similarly to steps (iii) to (v) as described above except that the corresponding temperatures of the extruder from zone 1 to zone 6 are 70 degree C, 120 degree C, 140 degree C, 130 degree C, 130 degree C, 120 degree C.
  • the die temperature was set at 120 degree C and the melt temperature was set at 130 degree C.
  • the extruder was preheated and the motor speed was set at 15 Hz and the feeding speed was set at 17 Hz.
  • the pellets were dried in a rotational vacuum drier at 45 degree C until the moisture content was below 500 ppm.
  • step (vi) 4032 g of the treated and dried lactic acid polymer, followed by a mixture of 264 g MB3, 4 g (0.1 wt%) ADR 4385 (epoxy matrix agent) and 8 g (0.2 wt%) octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate were charged into the high speed mixer for mixing at 900 rpm, at 30 degree C for 3 min.
  • the lactic acid polymer was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • step (vi) The steps for preparation of the stabilized lactic acid polymer in this Example were the same as those in Example 7 above except that in step (vi) , 4028g of the treated and dried lactic acid polymer, followed by 80 g
  • Example 2 above except that after step (v) , an additional step of Master Batch (MB) preparation 4 as described above was conducted.
  • the lactic acid polymer was then extruded and pelletized similarly to steps (iii) to (v) as described above except that the corresponding temperatures within the extruder from zone 1 to zone 6 were 70 degree C, 120 degree C, 130 degree C, 130 degree C, 120 degree C, 110 degree C.
  • the die temperature was set at 120 degree C and the melt temperature was set at 130 degree C.
  • the extruder was preheated and the motor speed was set at 15 Hz and the feeding speed was set at 15 Hz.
  • the pellets were dried in a rotational vacuum drier at 45 degree C until the moisture content was below 500 ppm.
  • step (vi) 4024 g of the treated and dried lactic acid polymer, followed by a mixture of 176 g MB4, 16 g (0.4 wt%) ADR 4385 (epoxy matrix agent), 16 g (0.4 wt%) octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 80 g (2.0 wt%) N, N' -dicyclohexylcarbodiimide (DCC) were charged into the high speed mixer for mixing at 900 rpm, at 30 degree C for 3 min.
  • DCC N, N' -dicyclohexylcarbodiimide
  • the lactic acid polymer was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • Example 2 above except that after step (v) , an additional step of Master Batch (MB) preparation 5 as described above was conducted.
  • the lactic acid polymer was then extruded and pelletized similarly to steps (iii) to (v) as described above except that the corresponding temperatures within the extruder from zone 1 to zone 6 were 70 degree C r 120 degree C, 130 degree C, 130 degree C, 120 degree C, 110 degree C.
  • the die temperature was set at 120 degree C and the melt temperature was set at 130 degree C.
  • the extruder was preheated and the motor speed was set at 15 Hz and the feeding speed was set at 15 Hz.
  • the pellets were dried in a rotational vacuum drier at 45 degree C until the moisture content was below 500 ppm.
  • step (vi) 4020 g of the treated and dried lactic acid polymer, followed by a mixture of 352 g MB5 and 40 g
  • N, N' -dicyclohexylcarbodiimide (DCC) were charged into the high speed mixer for mixing at 900 rpm, at 30 degree C for 3 min.
  • the lactic acid polymer was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • Example 2 above except that after step (v) , an additional step of Master Batch (MB) preparation 6 as described above was conducted.
  • the lactic acid polymer was then extruded and pelletized similarly to steps (iii) to (v) as described above except that the corresponding temperatures within the extruder from zone 1 to zone 6 were 70 degree C, 120 degree C, 130 degree C, 130 degree C, 120 degree C, 110 degree; C.
  • the die temperature was set at 120 degree C and the melt temperature was set at 130 degree C.
  • the extruder was preheated and the motor speed was set at 15 Hz and the feeding speed was set at 15 Hz.
  • the pellets were dried in a rotational vacuum drier at 45 degree C until the moisture content was below 500 ppm.
  • step (vi) 4024 g of the treated and dried lactic acid polymer, followed by a mixture of 347 g MB ⁇ , 16 g
  • the lactic acid polymer was then extruded and pelletized in accordance with steps (iii) to (v) as described above.
  • step (iii) the corresponding temperatures within the extruder from zone 1 to zone 6 were 100 degree C, 180 degree C, 190 degree C,
  • the die temperature was set at 160 degree C and the melt temperature was set at 170 degree C.
  • the extruder was preheated and the motor speed was set at 20 Hz and the feeding speed was set at 15 Hz.
  • step (vi) 4024 g of the treated and dried lactic acid polymer, followed by a mixture of 800 g (20.0 wt%)
  • the stabilized lactic acid polymer was prepared according to the steps as described below. (A) 5 kg lactic acid polymer was charged into a high speed mixer.
  • RV refers to Reduced Viscosity (dL/g)
  • AN refers to Acid Number (mgKOH/g) .
  • RV refers to Reduced Viscosity (dL/g)
  • AN refers to Acid Number (mgKOH/g)
  • Example 1 the lactic acid polymer was stabilized by the addition of the organic peroxide only. Stabilizing agent was added. It is noted that the relative viscosity decreases by about 65% and the acid number increases by more than 400%.
  • Example 15 the lactic acid polymer was stabilized by the addition of two stabilizing agents, namely an antioxidant and an epoxy matrix agent. Organic peroxide was not added. It is noted that the relative viscosity decreases by about 70% and the acid number increases by more than 300%.
  • Example 5 the lactic acid polymer was stabilized by the addition of organic peroxide as well as stabilizing agents such as antioxidant, epoxy matrix agent, carbodiimide matrix agent, inorganic additive and other degradable polymer. It is noted that the relative viscosity decreases by only 6% and the acid number increases by only 110%.
  • hydroxy acid polymer such as poly (lactic acid)
  • organic peroxide is added to deactivate the catalyst that used for polymerization of the hydroxy acid polymer, as well as to act as a coupling agent for coupling the de-polymerized hydroxy acid polymers together again.
  • stabilizing agent not only acts as a coupling agent, but also is also capable of neutralizing acid by-products, and/or removing the water by-products.
  • the stability of the hydroxy acid polymer can be effectively improved and the degree of degradation of the hydroxy acid polymer can be greatly reduced.
  • the average molecular weight of the hydroxy acid polymer obtained is at least about 25,000, or at least about 50,000.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention porte sur un procédé de stabilisation de polymère d'hydroxyacide, comprenant les étapes consistant à (a) ajouter un peroxyde organique à une composition de masse fondue de polymère d'hydroxyacide contenant un catalyseur qui catalyse la réaction de polymérisation pour former le polymère d'hydroxyacide; et (b) ajouter au moins un agent de stabilisation à la composition de masse fondue de polymère d'hydroxyacide, ledit agent de stabilisation étant choisi pour réduire au moins partiellement la vitesse de dépolymérisation du polymère d'hydroxyacide à l'intérieur de ladite composition de masse fondue.
PCT/SG2009/000265 2008-08-07 2009-07-27 Polymère d'hydroxyacide stable à l'état fondu et résistant à l'hydrolyse WO2010016801A1 (fr)

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US61/086,842 2008-08-07

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KR101322600B1 (ko) 2012-03-28 2013-10-29 한국신발피혁연구원 생분해성 플라스틱 조성물
CN108676334A (zh) * 2018-05-16 2018-10-19 绍兴绿星新材料有限公司 一种硅胶改性聚乳酸材料及其制备方法

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KR101322600B1 (ko) 2012-03-28 2013-10-29 한국신발피혁연구원 생분해성 플라스틱 조성물
CN108676334A (zh) * 2018-05-16 2018-10-19 绍兴绿星新材料有限公司 一种硅胶改性聚乳酸材料及其制备方法
CN108676334B (zh) * 2018-05-16 2020-08-07 绍兴绿星新材料有限公司 一种硅胶改性聚乳酸材料及其制备方法

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