WO2008063988A2 - Translucent and opaque impact modifiers for polylactic acid - Google Patents
Translucent and opaque impact modifiers for polylactic acid Download PDFInfo
- Publication number
- WO2008063988A2 WO2008063988A2 PCT/US2007/084502 US2007084502W WO2008063988A2 WO 2008063988 A2 WO2008063988 A2 WO 2008063988A2 US 2007084502 W US2007084502 W US 2007084502W WO 2008063988 A2 WO2008063988 A2 WO 2008063988A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- biodegradable polymer
- composition
- polymer composition
- biodegradable
- impact
- Prior art date
Links
Classifications
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
Definitions
- the invention relates to a blend of one or more biodegradable polymers with one or more impact modifiers, for the purpose of improving the impact properties of the biodegradable polymer(s).
- the biodegradable polymer is preferably a polylactide or polyhydroxy butyrate.
- the composition comprises 30-99.9 weight percent of a degradable polymer and 0.1 to 15 weight percent of one or more impact modifiers. Haze levels can be controlled by the composition and percentage of impact modifier (or modifiers) selected, to produce a polymer composition having an appearance ranging from translucent to opaque.
- Biodegradable polymers based on polylactic acid (PLA) are one of the most attractive candidates as they can be readily produced from renewal agricultural sources such as corn. Recent developments in the manufacturing of the polymer economically from agricultural sources have accelerated the polymers emergence into the biodegradable plastic commodity market.
- Linear acrylic copolymers have been disclosed for use as process aids in a blend with a biopolymer, such as polylactide. (US Application 60/841,644). The disclosed linear acrylic copolymers do not provide satisfactory impact properties. Additives such as impact modifiers could be used in the polylactide composition.
- the invention relates to a biodegradable composition
- a biodegradable composition comprising: a) 30 to 99.9 weight percent of one or more biodegradable polymers; b) 0 - 69.9 weight percent of one or more biopolymer; and c) 0.1 to 15 weight percent of one or more impact modifiers.
- the invention also relates to a method for controlling the level of haze in an impact- modified biodegradable polymer composition by adjusting the composition and weight percentage of one or more impact modifiers.
- the invention relates to blends of one or more biodegradable polymer with impact modifiers to produce a composition having very good impact properties as well as a low to high haze.
- the biodegradable polymer of the invention can be a single biodegradable polymer, or a mixture of biodegradable polymers.
- Some examples of biodegradable polymers useful in the invention include, but are not limited to, polylactide and polyhydroxy butyrate.
- the biodegradable composition comprises 30 to 99.9 weight percent of the one or more biodegradable polymers.
- the preferred polylactide and polyhydroxy butyrate can be a normal or low molecular weight.
- other bio-polymers such as, but not limited to starch, cellulose, and polysaccharides may also be present. Additional biopolymers, such as but not limited to polycaprolactam, polyamide 11 and aliphatic or aromatic polyesters may also be present.
- the other bio-polymers may be present in the composition at from 0 - 69.9 weight percent.
- One or more impact modifiers is used at from 0.1 to 15 weight percent of the composition.
- the impact modifier can be a linear block copolymer, terpolymer, or tetramer; or a core/shell impact modifier.
- Useful linear block copolymers include, but are not limited to, acrylic block copolymers, and SBM-type (styrene, butadiene, methacrylate) block polymers.
- the block copolymers consists of at least one "hard” block, and at least one "soft” block.
- the hard blocks generally have a glass transition temperature (Tg) of greater than 2O 0 C, and more preferably greater than 5O 0 C.
- Tg glass transition temperature
- the hard block can be chosen from any thermopolymer meeting the Tg requirements.
- the hard block is composed primarily of methacrylate ester units, styrenic units, or a mixture thereof.
- the soft blocks generally have a Tg of less than 2O 0 C, and preferably less than O 0 C.
- Preferred soft blocks include polymers and copolymers of alkyl acrylates, dienes, styrenics, and mixtures thereof.
- the soft block is composed mainly of acrylate ester units or dienes.
- “Acrylic copolymers” as used herein, refers to copolymers having 60 percent or more of acrylic and/or methacrylic monomer units, "(meth) acrylate” is used herein to include both the acrylate, methacrylate or a mixture of both the acrylate and methacrylate.
- Useful acrylic monomers include, but are not limited to methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, cycloheyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentadecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phnoxyethyl (meth)acrylate, 2-hydroxyethy
- Preferred acrylic monomers include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethyl-hexyl-acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
- the block copolymers of the present invention are preferably formed by controlled radical polymerization (CRP).
- CRP controlled radical polymerization
- These processes generally combine a typical free-radical initiator with a compound to control the polymerization process and produce polymers of a specific composition, and having a controlled molecular weight and narrow molecular weight range.
- free-radical initiators used may be those known in the art, including, but not limited to peroxy compounds, peroxides, hydroperoxides and azo compounds which decompose thermally to provide free radicals.
- the initiator may also contain the control agent.
- controlled radical polymerization techniques include, but are not limited to, atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), boron-mediated polymerization, and catalytic chain transfer polymerization (CCT).
- ATRP atom transfer radical polymerization
- RAFT reversible addition fragmentation chain transfer polymerization
- NMP nitroxide-mediated polymerization
- boron-mediated polymerization boron-mediated polymerization
- CCT catalytic chain transfer polymerization
- nitroxide-mediated CRP One preferred method of controlled radical polymerization is nitroxide- mediated CRP.
- Nitroxide-mediated polymerization can occur in bulk, solvent, and aqueous polymerization, can be used in existing equipment at reaction times and temperature similar to other free radical polymerizations.
- One advantage of nitroxide- mediated CRP is that the nitroxide is generally innocuous and can remain in the reaction mix, while other CRP techniques require the removal of the control compounds from the final polymer.
- the core-shell (multi-layer) impact modifiers could have a soft (rubber or elastomer) core and a hard shell, a hard core covered with a soft elastomer-layer, and a hard shell, of other core-shell morphology known in the art.
- the rubber layers are composed of low glass transition (Tg) polymers, including, but not limited to, butyl acrylate (BA), ethylhexyl acrylate (EHA), butadiene (BD), butylacrylate/styrene, and many other combinations.
- the preferred glass transition temperature (Tg) of the elastomeric layer should be below 25 0 C.
- the elastomeric or rubber layer is normally crosslinked by a multifunctional monomer for improved energy absorption.
- Crosslinking monomers suitable for use as the crosslinker in the core/shell impact modifier are well known to those skilled in the art, and are generally monomers copolymerizable with the monounsaturated monomer present, and having ethylenically multifunctional groups that have approximately equal reactivity. Examples include, but are not limited to, divinylbenzene, glycol of di- and trimethacrylates and acrylates, triol triacrylates, methacrylates, and allyl methacrylates, etc.
- a grafting monomer is also used to enhance the interlayer grafting of impact modifiers and the matrix /modifier particle grafting.
- the grafting monomers can be any polyfunctional crosslinking monomers.
- the core ranges from 30 to 85 percent by weight of the impact modifier, and outer shells range from 15-70 weight percent.
- the crosslinker in the elastomeric layer ranges from 0 to 5.0%.
- the synthesis of core-shell impact modifiers is well known in the art, and there are many references, for example US 3,793,402, US 3,808,180, US3,971,835, and US3,671,610, incorporated herein by reference.
- the refractive index of the modifier particles, and/or matrix polymer can be matched against each other by using copolymerizable monomers with different refractive indices.
- Preferred monomers include, but are not limited to, styrene, alpha methylstyrene, and vinylidene fluoride monomers having unsaturated ethylenic group.
- non-core/shell impact modifiers are also possible for use in this invention, where super transparency and clarity may not be required.
- butadiene rubber can be incorporated into an acrylic matrix to achieve high ballistic resistance property.
- a preferred MBS type core/shell polymer is one having a 70-85% core of
- the acrylic copolymer impact modifier is an acrylate based copolymer with a core-shell polymer having a rubbery core, such as 1 ,3-dienes (also copolymers with vinyl aromatics) or alkyl acrylates with alkyl group containing 4 or more carbons and the shell is grafted onto the core and is comprised of monomers such as vinyl aromatics (e.g., styrene), alkyl methacrylates (alkyl group having 1-4 carbons), alkyl acrylates (alkyl group having 1-4 carbons), and acrylonitrile.
- a preferred acrylic type core/shell polymer is one having a 70-85% core of
- the bio degradradable polymer composition of the invention contains 30-99.9 weight percent of the biodegradable polymer, 0-69.9 weight percent of other biopolymers and from 0.1 - 15 weight percent of the acrylic copolymer(s).
- the ingredients may be admixed prior to processing, or may be combined during one or more processing steps, such as a melt-blending operation. This can be done, for instance by single-screw extrusion, twin-screw extrusion, Buss kneader, two-roll mill, impeller mixing. Any admixing operation resulting in a homogeneous distribution of acrylic-methacrylic copolymer in the biodegradable polymer is acceptable. Formation of the blend is not limited to a single-step formation.
- the carrier polymer may be, but is not limited to, polylactide, acrylic-methacrylic copolymers, and methacrylic homopolymers.
- the composition of the invention may additionally contain a variety of additives, including but not limited to, heat stabilizers, internal and external lubricants, other impact modifiers, process aids, melt strength additives, fillers, and pigments.
- additives including but not limited to, heat stabilizers, internal and external lubricants, other impact modifiers, process aids, melt strength additives, fillers, and pigments.
- the composition of the invention was found to have greatly improved the impact properties of the polylactide alone.
- the impact-modified biodegradable polymer composition can range from almost clear or translucent, to opaque, depending on the composition and level of impact modification.
- the acrylic polymers tend to produce a lower level of haze, leading to a more translucent character, while use of MBS-type impact modifiers produce a higher level of haze, and lead to a more opaque composition.
- composition of the invention can be processed using any known method, including but not limited to injection molding, extrusion, calendaring, blow molding, foaming and thermoforming.
- Useful articles that can be made using the biodegradable composition include but are not limited to packaging materials, films and bottles.
- Example 1 A blend of 90-99% polylactide containing 1-10% by weight of an MBS based modifier was formed by melt extrusion using a twin-screw extruder. The processing temperature and melt temperature during extrusion were maintained above the melting temperature of polylactide (>152°C) to ensure a homogeneous melt. The extrudate was pelletized and processed either via injection molded. Injection molding was performed with a nozzle temperature above polylactide melting temperature
- Control samples of PLA without any impact modifier had haze values below 4 and fell well below the lower limit of the test instrument, 8 in lbs.
- a blend of 90-99% polylactide containing 1-10% by weight of acrylic- methacrylic copolymer impact modifier was formed by melt extrusion using a twin- screw extruder.
- the processing temperature and melt temperature during extrusion were maintained above the melting temperature of polylactide (>152°C) to ensure a homogeneous melt.
- the extrudate was pelletized and processed either via injection molded. Injection molding was performed with a nozzle temperature above polylactide melting temperature (>152°C) and the mold temperature was maintained below polylactide glass transition temperature ( ⁇ 50°C).
- a single-cavity disc was used to make 41 mil thick disks. Haze measurements were performed on the disks using a Colormeter and dart drop impact measurements were performed with a Gardner Impact tester with a 8 Ib hemispherical impactor head. The following data was observed:
- Control samples of PLA without any impact modifier had haze values below 4 and fell well below the lower limit of the test instrument, 8 in lbs.
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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)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/515,640 US20120142823A1 (en) | 2006-11-21 | 2007-11-13 | Translucent and opaque impact modifiers for polylactic acid |
EP07864315A EP2084208A4 (en) | 2006-11-21 | 2007-11-13 | Translucent and opaque impact modifiers for polylactic acid |
CA2669554A CA2669554C (en) | 2006-11-21 | 2007-11-13 | Translucent and opaque impact modifiers for polylactic acid |
JP2009538448A JP5562644B2 (en) | 2006-11-21 | 2007-11-13 | Translucent and opaque impact modifier for polylactic acid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US86037506P | 2006-11-21 | 2006-11-21 | |
US60/860,375 | 2006-11-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2008063988A2 true WO2008063988A2 (en) | 2008-05-29 |
WO2008063988A3 WO2008063988A3 (en) | 2008-08-07 |
Family
ID=39430476
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/084502 WO2008063988A2 (en) | 2006-11-21 | 2007-11-13 | Translucent and opaque impact modifiers for polylactic acid |
Country Status (6)
Country | Link |
---|---|
US (1) | US20120142823A1 (en) |
EP (1) | EP2084208A4 (en) |
JP (1) | JP5562644B2 (en) |
CN (2) | CN101541853A (en) |
CA (1) | CA2669554C (en) |
WO (1) | WO2008063988A2 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009151977A1 (en) * | 2008-06-13 | 2009-12-17 | Arkema Inc. | Biodegradable impact-modified polymer compositions |
JP2010189472A (en) * | 2009-02-16 | 2010-09-02 | Unitika Ltd | Eco-friendly thermoplastic resin composition |
WO2012170215A1 (en) | 2011-06-08 | 2012-12-13 | Arkema Inc. | Foaming of thermoplastic materials with organic peroxides |
WO2014184057A1 (en) | 2013-05-14 | 2014-11-20 | Basf Se | Process for production of polymer powders |
WO2014184002A1 (en) * | 2013-05-14 | 2014-11-20 | Basf Se | Impact-resistance modifiers for polylactic acid |
US9267033B2 (en) | 2007-10-01 | 2016-02-23 | Arkema Inc. | Blends of biodegradable polymers and acrylic copolymers |
EP3039081A4 (en) * | 2013-08-29 | 2017-04-12 | Arkema, Inc. | Biodegradable impact-modified polymer compositions |
EP3632938B1 (en) * | 2018-10-05 | 2023-05-03 | Trinseo Europe GmbH | Vinylidene substituted aromatic monomer and cyclic (meth)acrylate ester polymers |
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US9987820B2 (en) | 2009-11-17 | 2018-06-05 | Arkema France | Multilayer structures containing biopolymers |
CN102906175B (en) | 2010-03-22 | 2016-03-16 | 科利来包装有限公司 | Make the additive of biopolymer article performance boost |
WO2014018817A1 (en) | 2012-07-27 | 2014-01-30 | Arkema France | Multilayer structures containing biopolymers |
CN103146164B (en) * | 2013-04-07 | 2016-03-30 | 苏州聚复高分子材料有限公司 | For the nanometer plasticizing polylactic acid material and preparation method thereof of rapid shaping |
CN104292824A (en) * | 2014-09-30 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Polymer nano-modified nylon 11 composite material and preparation method thereof |
US11230635B2 (en) * | 2016-11-11 | 2022-01-25 | Eastman Chemical Company | Cellulose ester and impact modifier compositions and articles made using these compositions |
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- 2007-11-13 JP JP2009538448A patent/JP5562644B2/en active Active
- 2007-11-13 WO PCT/US2007/084502 patent/WO2008063988A2/en active Application Filing
- 2007-11-13 CN CNA2007800429636A patent/CN101541853A/en active Pending
- 2007-11-13 CN CN201310306064XA patent/CN103319867A/en active Pending
- 2007-11-13 EP EP07864315A patent/EP2084208A4/en not_active Withdrawn
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9267033B2 (en) | 2007-10-01 | 2016-02-23 | Arkema Inc. | Blends of biodegradable polymers and acrylic copolymers |
WO2009151977A1 (en) * | 2008-06-13 | 2009-12-17 | Arkema Inc. | Biodegradable impact-modified polymer compositions |
CN102056595A (en) * | 2008-06-13 | 2011-05-11 | 阿科玛股份有限公司 | Biodegradable impact-modified polymer compositions |
US8524832B2 (en) | 2008-06-13 | 2013-09-03 | Arkema Inc. | Biodegradable impact-modified polymer compositions |
CN105062023B (en) * | 2008-06-13 | 2019-01-15 | 阿科玛股份有限公司 | The polymer composition of biodegradable impact modification |
JP2010189472A (en) * | 2009-02-16 | 2010-09-02 | Unitika Ltd | Eco-friendly thermoplastic resin composition |
WO2012170215A1 (en) | 2011-06-08 | 2012-12-13 | Arkema Inc. | Foaming of thermoplastic materials with organic peroxides |
WO2014184057A1 (en) | 2013-05-14 | 2014-11-20 | Basf Se | Process for production of polymer powders |
WO2014184002A1 (en) * | 2013-05-14 | 2014-11-20 | Basf Se | Impact-resistance modifiers for polylactic acid |
EP3039081A4 (en) * | 2013-08-29 | 2017-04-12 | Arkema, Inc. | Biodegradable impact-modified polymer compositions |
EP3632938B1 (en) * | 2018-10-05 | 2023-05-03 | Trinseo Europe GmbH | Vinylidene substituted aromatic monomer and cyclic (meth)acrylate ester polymers |
Also Published As
Publication number | Publication date |
---|---|
EP2084208A2 (en) | 2009-08-05 |
EP2084208A4 (en) | 2011-03-30 |
WO2008063988A3 (en) | 2008-08-07 |
US20120142823A1 (en) | 2012-06-07 |
CN101541853A (en) | 2009-09-23 |
JP5562644B2 (en) | 2014-07-30 |
JP2010510381A (en) | 2010-04-02 |
CN103319867A (en) | 2013-09-25 |
CA2669554C (en) | 2015-12-22 |
CA2669554A1 (en) | 2008-05-29 |
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