CA2726602A1 - Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging - Google Patents
Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging Download PDFInfo
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- CA2726602A1 CA2726602A1 CA2726602A CA2726602A CA2726602A1 CA 2726602 A1 CA2726602 A1 CA 2726602A1 CA 2726602 A CA2726602 A CA 2726602A CA 2726602 A CA2726602 A CA 2726602A CA 2726602 A1 CA2726602 A1 CA 2726602A1
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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
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- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K5/13—Phenols; Phenolates
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The disclosed technology pertains to pro-oxidant additives, composed of several compounds, which when added to plastic polymers (such as polyethylene or polypropylene), imparts to them a property whereby they fragment and bio-assimilate after a programmed in-use life cycle. The compounds used with such polyolefin polymers consist of Ferric Stearate as a photo-oxidation inducer, Manganese Stearate and/or Cobalt stearate as a thermo-oxidation inducer along with/without calcium carbonate balanced with a phenolic anti-oxidant to ensure six months to twelve months of service life without mechanical loss in strength.
Description
B&P File No. 20416-3 BERESKIN & PARR LLP/S.E.N.C.R.L., s.r.I. CANADA
Title: OXO-BIODEGRADABLE ADDITIVES FOR
USE IN FOSSIL FUEL POLYMER FILMS
AND ONCE-USED PACKAGING
Inventor(s): Aman ur Rahman TITLE
Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging.
FIELD
The invention broadly falls in the technical field of Chemistry. More particularly the present invention is in the technical field of oxo-biodegradability of fossil fuel polymers. More specifically the invention relates to chemical elements used in defined percentage composition to achieve oxo-biodegradability of polyolefin namely polyethylene and polypropylene, as proven by a unique, accelerated, `pass-fail' criteria established by France's leading Research Institute on the subject..
The final product material containing one or more of the chemical components as described above is subjected to test protocols developed by Centre National d' Evaluation de Photo protection (CNEP) and SEESIB ( Synthese et Etude des sysmemes a Interet Biologique, to oxo-biodegrade in a 3-5 years span after exposure to the environment. The CNEP's testing protocol based on macro-molecular considerations is currently the only accelerated pass/fail protocol with results reflective of actual environmental conditions and bio-assimilation time frame.
BACKGROUND
It was in the early 1930s that scientists discovered polyethylene, the first of the series in plastic polymer substances. Polyethylene was synthesized by polymerizing gaseous hydrocarbon ethylene. The resultant product of such polymerization resulted in a material which has a high strength to weight ratio. It was found that this solid material offered many commercially interesting properties: it was cheap, durable, flexible and chemically resistant.
Almost immediately after its discovery, the use of plastics have given rise to a variety of packaging products such as polyethylene and polypropylene plastic films, bottles, cups, disposable snack food containers and such.
Besides the fact that available landfill space is becoming scarce, plastic poses much problem even after disposal as, they tend to remain in the environment without degradation. Some countries have promoted incineration of used plastic instead of disposal;
however such incineration processes contribute directly to air pollution. It has been estimated that more than half of the manufactured synthetic polymers are used in packaging materials and 90%
ultimately end up as garbage. The rate of accumulation of non-degradable plastic components is estimated to be 25 million tons per year. Most plastics available in the market are non bio-degradable. However, those available biodegradable plastic vary considerably in their actual performance in the environment when compared to test methods. This is attributed mainly due to the composition of the chemical substances used in the polymer and largely because of the testing protocols.
Oxo-biodegradable plastics are thus called because of their property to degrade in both aerobic and anaerobic environments. Extensive research over the last two decades has led to the discovery that polymers in presence of certain organic salts of transition metals can accelerate the process of photo and thermo oxidation. The resultant residue, invisible to the human eye, are highly fragmented parts of the polymer molecule which have been oxidized into short-chain oligomers with acidic chain ends and into non-polymeric carbonyl group compounds such as alcohols, ketones, esters, lactones, fatty acids which support metabolic activities in microbes leading to further biotic-mediated polymer degradation.
The new compounds, hydrophilic in nature, form part of the food chain for soil microbes, bacteria and fungi and are consumed by them, yielding carbon dioxide, water and biomass.
Due to the slow rate of carbon dioxide liberation it is taken up by nature's photo-synthesis process by which plant life is created and supported.
There is no dissent amongst the world-wide scientific community on the theory and results of photo and thermo oxidation on fossil fuel polymers (general chemical reaction for polyethylene degradation is as shown in Annexure 1) containing organic salts of transition metals and their eventual bio-assimilation. The issue is for establishing an accelerated testing protocol to certify that a given recipe of the photo and thermo oxidation inducers would perform as required/claimed. Until recently there was only one known guideline to determine Oxo-biodegradability of plastic polymers - known as the ASTM 6954. However, ASTM
6954 itself states that it addresses test methods and is only a guideline recommended for comparative study for polymer performance and is therefore not a pass/fail criterion for oxo-biodegradability of products.
Currently the most logical and scientific approach to establishing an accelerated test protocol for the abiotic and biotic degradation of fossil fuel polymers has been put forward by the Centre Nationale d'Evaluation de photoprotection (CNEP) and SEESIB ( Synthese et Etude des sysmemes a Interet Biologique) (M. Koutny et. al.: Acquired biodegradability of polyethylene containing pro-oxidant additives. Polymer Degradation and Stability Journal.
91(2006) 1495-1507; and S. Fontanella et.al.: Comparison of the biodegradability of various polyethylene films containing pro-oxidant additives. Polymer Degradation and Stability Journal. 95 (2010) 1011-1021). These protocols are consistent with actual field behavior which was verified independently by American and Italian Researchers (Andrea Corti et. al.:
Oxidation and biodegradation of polyethylene films containing pro-oxidant additives:
.Synergistic effects of sunlight exposure, thermal aging and.fungal biodegradation. Polymer Degradation and Stability Journal. 95 (2010) 1106-1114)).
SUMMARY
The present invention discloses information relating to a balanced recipe of pro and anti oxidant additives for used in polyolefin films and packaging material that permit the final product to qualify as oxo-biodegradable under scientifically based `Pass-Fail' test protocols in an effort to solve the issue of certifiable oxo-biodegradability when compared to self-claimed oxo-biodegradable products in the markets. The invention describes chemical compounds which when added in defined percentage to conventional fossil fuel based polyolefins accelerate their degradation process after a pre-established `in-use' life.
The first aspect of the invention is a recipe for an oxo-biodegradable (OBD) master batch, consisting of 1% - 25% of Ferric Stearate acting as a photo-oxidation inducer 1% - 30%
Manganese Stearate and/or 1% - 15% Cobalt Stearate acting as thermo-oxidation inducers along with 0.1 - 2% phenolic antioxidant for in-use mechanical integrity of 6 months to 1 year. This recipe is made in a fossil fuel derived polyolefin base with Calcium Carbonate acting as inert filler.
The second and the most critical aspect is to prepare and submit articles, such as films/
disposable food trays etc., identical to those in actual everyday use by consumers, for testing under the CNEP/SEESIB protocols, in a shape and form as near to the actual article used by consumers in the market place (which ensures that the final product will behave as predicted in the accelerated lab tests under the protocols.). This involves diluting the OBD master batch into the same polyolefin polymers that are in actual use by convertors and preparing samples that replicate the end-use shape, thickness and weight.
Title: OXO-BIODEGRADABLE ADDITIVES FOR
USE IN FOSSIL FUEL POLYMER FILMS
AND ONCE-USED PACKAGING
Inventor(s): Aman ur Rahman TITLE
Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging.
FIELD
The invention broadly falls in the technical field of Chemistry. More particularly the present invention is in the technical field of oxo-biodegradability of fossil fuel polymers. More specifically the invention relates to chemical elements used in defined percentage composition to achieve oxo-biodegradability of polyolefin namely polyethylene and polypropylene, as proven by a unique, accelerated, `pass-fail' criteria established by France's leading Research Institute on the subject..
The final product material containing one or more of the chemical components as described above is subjected to test protocols developed by Centre National d' Evaluation de Photo protection (CNEP) and SEESIB ( Synthese et Etude des sysmemes a Interet Biologique, to oxo-biodegrade in a 3-5 years span after exposure to the environment. The CNEP's testing protocol based on macro-molecular considerations is currently the only accelerated pass/fail protocol with results reflective of actual environmental conditions and bio-assimilation time frame.
BACKGROUND
It was in the early 1930s that scientists discovered polyethylene, the first of the series in plastic polymer substances. Polyethylene was synthesized by polymerizing gaseous hydrocarbon ethylene. The resultant product of such polymerization resulted in a material which has a high strength to weight ratio. It was found that this solid material offered many commercially interesting properties: it was cheap, durable, flexible and chemically resistant.
Almost immediately after its discovery, the use of plastics have given rise to a variety of packaging products such as polyethylene and polypropylene plastic films, bottles, cups, disposable snack food containers and such.
Besides the fact that available landfill space is becoming scarce, plastic poses much problem even after disposal as, they tend to remain in the environment without degradation. Some countries have promoted incineration of used plastic instead of disposal;
however such incineration processes contribute directly to air pollution. It has been estimated that more than half of the manufactured synthetic polymers are used in packaging materials and 90%
ultimately end up as garbage. The rate of accumulation of non-degradable plastic components is estimated to be 25 million tons per year. Most plastics available in the market are non bio-degradable. However, those available biodegradable plastic vary considerably in their actual performance in the environment when compared to test methods. This is attributed mainly due to the composition of the chemical substances used in the polymer and largely because of the testing protocols.
Oxo-biodegradable plastics are thus called because of their property to degrade in both aerobic and anaerobic environments. Extensive research over the last two decades has led to the discovery that polymers in presence of certain organic salts of transition metals can accelerate the process of photo and thermo oxidation. The resultant residue, invisible to the human eye, are highly fragmented parts of the polymer molecule which have been oxidized into short-chain oligomers with acidic chain ends and into non-polymeric carbonyl group compounds such as alcohols, ketones, esters, lactones, fatty acids which support metabolic activities in microbes leading to further biotic-mediated polymer degradation.
The new compounds, hydrophilic in nature, form part of the food chain for soil microbes, bacteria and fungi and are consumed by them, yielding carbon dioxide, water and biomass.
Due to the slow rate of carbon dioxide liberation it is taken up by nature's photo-synthesis process by which plant life is created and supported.
There is no dissent amongst the world-wide scientific community on the theory and results of photo and thermo oxidation on fossil fuel polymers (general chemical reaction for polyethylene degradation is as shown in Annexure 1) containing organic salts of transition metals and their eventual bio-assimilation. The issue is for establishing an accelerated testing protocol to certify that a given recipe of the photo and thermo oxidation inducers would perform as required/claimed. Until recently there was only one known guideline to determine Oxo-biodegradability of plastic polymers - known as the ASTM 6954. However, ASTM
6954 itself states that it addresses test methods and is only a guideline recommended for comparative study for polymer performance and is therefore not a pass/fail criterion for oxo-biodegradability of products.
Currently the most logical and scientific approach to establishing an accelerated test protocol for the abiotic and biotic degradation of fossil fuel polymers has been put forward by the Centre Nationale d'Evaluation de photoprotection (CNEP) and SEESIB ( Synthese et Etude des sysmemes a Interet Biologique) (M. Koutny et. al.: Acquired biodegradability of polyethylene containing pro-oxidant additives. Polymer Degradation and Stability Journal.
91(2006) 1495-1507; and S. Fontanella et.al.: Comparison of the biodegradability of various polyethylene films containing pro-oxidant additives. Polymer Degradation and Stability Journal. 95 (2010) 1011-1021). These protocols are consistent with actual field behavior which was verified independently by American and Italian Researchers (Andrea Corti et. al.:
Oxidation and biodegradation of polyethylene films containing pro-oxidant additives:
.Synergistic effects of sunlight exposure, thermal aging and.fungal biodegradation. Polymer Degradation and Stability Journal. 95 (2010) 1106-1114)).
SUMMARY
The present invention discloses information relating to a balanced recipe of pro and anti oxidant additives for used in polyolefin films and packaging material that permit the final product to qualify as oxo-biodegradable under scientifically based `Pass-Fail' test protocols in an effort to solve the issue of certifiable oxo-biodegradability when compared to self-claimed oxo-biodegradable products in the markets. The invention describes chemical compounds which when added in defined percentage to conventional fossil fuel based polyolefins accelerate their degradation process after a pre-established `in-use' life.
The first aspect of the invention is a recipe for an oxo-biodegradable (OBD) master batch, consisting of 1% - 25% of Ferric Stearate acting as a photo-oxidation inducer 1% - 30%
Manganese Stearate and/or 1% - 15% Cobalt Stearate acting as thermo-oxidation inducers along with 0.1 - 2% phenolic antioxidant for in-use mechanical integrity of 6 months to 1 year. This recipe is made in a fossil fuel derived polyolefin base with Calcium Carbonate acting as inert filler.
The second and the most critical aspect is to prepare and submit articles, such as films/
disposable food trays etc., identical to those in actual everyday use by consumers, for testing under the CNEP/SEESIB protocols, in a shape and form as near to the actual article used by consumers in the market place (which ensures that the final product will behave as predicted in the accelerated lab tests under the protocols.). This involves diluting the OBD master batch into the same polyolefin polymers that are in actual use by convertors and preparing samples that replicate the end-use shape, thickness and weight.
The thermo-oxidative process continues even if the article is buried, such as in landfills, though at a slower rate. Thus the additive promotes conversion of the plastic films into particle size invisible to the human eye and of a chemical nature that forms part of the food chain of soil microbes, fungi and bacteria. The product also contains stabilizers that ensure mechanical strength and durability to the film to ensure highest integrity in service during an initial 12 month period. After this initial phase of actual use, the oxidative fragmentation process commences, leading to eventual bio-assimilation in a period of 3 to 5 years. The film also undergoes similar fragmentation and bio-assimilation when accidentally blown into marine environment. The graphical representation for the gradual abiotic degradation of polymers is shown in Annexure 2.
There is currently only one testing protocol (Annexure 3), based on macro-molecular considerations which is developed by the French National Centre for Photo-Chemistry (CNEP) and SEESIB ( Synthese et Etude des sysmemes a lnteret Biologique) that can confirm oxo-biodegradability of plastic polymers based on accelerated laboratory degradation studies conducted by pre-aging (in special ovens, SEPAP 12-24) under defined temperature and radiation parameters followed by FR Infra Red Spectroscopic examination of residue ( as shown in Annexure 5) to establish if pre-set minimum levels of specific degradation products are achieved. The extent and type of molecular degradation that takes place under the laid down abiotic tests and established by the FTIR results, indirectly testifies to the biodegradability of the material after photo and thermal oxidation in the normal environment.
However for ensuring certification that such biotic degradation occurs, the residue of the material that qualifies the three criteria under Abiotic Testing (as described in Annexure 4) is subjected to the biotic tests laid down in the test protocols.
The final product is certified as being oxo-biodegradable under the above stated CNEP &
SEESIB protocol requirements. Certification and supporting laboratory test result data for Abiotic degradation of our recipe are attached (Annexure 4 and Annexure 5 respectively).
ANNEXUREI
General chemical reaction involved in photo and thermo oxidation of polyethylene Representation of design of an oxo-biodegradable packaging film along with the gradual abiotic degradation of polymers Design of an oxobiodegradabte packaging film lniti1! b ncl; p 1yrner maft -atabiitza(3) phototrxiucer -them nducer *fitlerstdywIp"ntstproces3 agents MB as Me At, tt C.,. trd by' Matnx Corxfrd C tfd pho(6nduoat matrix +UtFimarto mahVstabdtzers/,N" nduex f tttermanducer 1 1 ;Phase 2 j I t Aar ss ra 41u~ n ;¾ and first lit,mot, C)xtd.rtlurt ! i 11-b 4 ResuIttc.~aa cu, ~,mu.,- , vrzxtt;r at(, 0 Ir~r,t J.,.i.t ruxcr txSsr icf ~ Ct~t2:'6Y _ runs ,?y rate[' ~~qe .;:ni.. -frr Er,A"S+~t a N'x7 c~at;i9 a C NEP
Centre Nao:,nil d E vai,,at,,.t i de Ptcst 3. utectk)n ROT(}( ()L. F(R 111 Y F\ I 1 A FIO
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There is currently only one testing protocol (Annexure 3), based on macro-molecular considerations which is developed by the French National Centre for Photo-Chemistry (CNEP) and SEESIB ( Synthese et Etude des sysmemes a lnteret Biologique) that can confirm oxo-biodegradability of plastic polymers based on accelerated laboratory degradation studies conducted by pre-aging (in special ovens, SEPAP 12-24) under defined temperature and radiation parameters followed by FR Infra Red Spectroscopic examination of residue ( as shown in Annexure 5) to establish if pre-set minimum levels of specific degradation products are achieved. The extent and type of molecular degradation that takes place under the laid down abiotic tests and established by the FTIR results, indirectly testifies to the biodegradability of the material after photo and thermal oxidation in the normal environment.
However for ensuring certification that such biotic degradation occurs, the residue of the material that qualifies the three criteria under Abiotic Testing (as described in Annexure 4) is subjected to the biotic tests laid down in the test protocols.
The final product is certified as being oxo-biodegradable under the above stated CNEP &
SEESIB protocol requirements. Certification and supporting laboratory test result data for Abiotic degradation of our recipe are attached (Annexure 4 and Annexure 5 respectively).
ANNEXUREI
General chemical reaction involved in photo and thermo oxidation of polyethylene Representation of design of an oxo-biodegradable packaging film along with the gradual abiotic degradation of polymers Design of an oxobiodegradabte packaging film lniti1! b ncl; p 1yrner maft -atabiitza(3) phototrxiucer -them nducer *fitlerstdywIp"ntstproces3 agents MB as Me At, tt C.,. trd by' Matnx Corxfrd C tfd pho(6nduoat matrix +UtFimarto mahVstabdtzers/,N" nduex f tttermanducer 1 1 ;Phase 2 j I t Aar ss ra 41u~ n ;¾ and first lit,mot, C)xtd.rtlurt ! i 11-b 4 ResuIttc.~aa cu, ~,mu.,- , vrzxtt;r at(, 0 Ir~r,t J.,.i.t ruxcr txSsr icf ~ Ct~t2:'6Y _ runs ,?y rate[' ~~qe .;:ni.. -frr Er,A"S+~t a N'x7 c~at;i9 a C NEP
Centre Nao:,nil d E vai,,at,,.t i de Ptcst 3. utectk)n ROT(}( ()L. F(R 111 Y F\ I 1 A FIO
OF iIIF. tC CHIRi II Any n 1MRII ITY
0IAfI)II IV'%I I'I) POI.9r'F`THI1 EM FH Ms' F= .'kA1,I 11(3`^. 4I'71,1 HI(IIt"O'ti1041011VIES
-. ~irtlPtÃi:~ fry UAW.
is `i. tt E... r 4. Vi t a wo +ciuh up Iõ :4tt alwnrhxn., A
c rtr 177 :. ~õ L 7 i"M
~_ . .. t r43 414 a< ..... _ ., a -- .'K ,. .. ~ . sr.
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~wmwc Itic Note {'._ plc' i rtl~'d .( t,!, .,,I t i<< 1 ~ Ii1 4 ! tsf IIr,Itc;,ilt) Contra National d'Evaluation do Photo protection t ¾ '1,'iJlf RE Cc r, ~., CERTIFICATION
itc t.Cilt{t' Pt 111 : 0 ` . l t t i l r,tt t}c l i f i J( %I P! 1Cllftlcti Itftt 1111 lilln ~ft ,ai sltppltcJ bV f ncri,;'<;tit, I I C.. f )t,ha4 'v I Ind I::crcrte~,1 !~~ .tnzta,nm;' Ovr lilu lrrnli?a;)I~ ? ddintvt ;:I' to") w.)tuiictl 1)I' rrylrttrttrUFf)4 a,1 liar ~:~ta~ltllc ,If ~artS~ttui~, lai3.1 ah1AVn i ICf the 1'r,itn),til 14 th_- I'.AalUiititi'1 (It 1k AIItnttk {
)\id,111110A It i u,.1<I!iff ttf)c tiilnv iktit~ 3: ti ,it fIT t l4l lllrtlt-I'CiMit,l i1!iSti;'t,,t4 aritl Psilu=,.! At di, j;luril,)I i'cJ}nrr (lchuu' and SL? 91, i.l'V, +'rh4) aIn1I cr.nluitrl;l zr SIv. 5amc tlftt'.id1 Ii I,1 ti i111I,1)t1it,, 1 [1r cr Lni i(,ult',I '.iil)CH,l rc ca!- ,.C'i', .. ni tt4A9n:"S, It ;t.ri 1'.i,Y. ClI
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t.ft, .'?III 'u (t i t 1:0 A X1.,,1 -1 I;Int titiv:> ullltrcd ,it !h cA1cl1 AM in AL PV OW, WWI 0C=1 vfdatiOJi I1f ~7` and in fP 0, hi< tr, o-utõ-,stn1 Ittort at'Iil + tf1:a1 ~iaitafact3 11,;)'. th,, flit)) õilv Iitt i iL:J .IN: m itfn cvItifllid 4, 1;ulli01 a1RI a yrir In ,,,{, as ,.,yttncd It bt,- ctp,hhihtlit', titilis~}t,,1ul,l t',c a"u td 1^~tn~ the l="F, 11141 II1 S'1It ,'>vr.?ltcat~ altd ill `+iafur~ tioit't LJnI.cl ;ItF ai t'ici i cc-t-Fc:i.cid..aul 1'+tilslull: i iii a juatt adcu:r;ctc 'idJ t1v.iicJ i'r dint 1 fduhtlik -'\ , --,>ni; n' i'rti ~tacnl` lrprd. ( 1! 1 t'1 ~(, itcr rr, I
if lt.`Iibt,'ll' tta 14 ai"lur: i l.1+i A,1t1 ~ ':u~ ! )r Ia%,lu. 4 '(t tj IN V.
t'CYt tl,i 4}M1 t,! i. 'd? l' lli LifcU!'d II) Zi.4t`arill dli õA, i.a /)I '1 /1 i11n ~. .._.. ,~ ;, 1,II GI
+,,
Claims
1. Any one of the group consisting of a method, apparatus, product, and chemical composition as described herein.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2726602A CA2726602A1 (en) | 2010-12-30 | 2010-12-30 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
| PCT/CA2011/001385 WO2012088585A1 (en) | 2010-12-30 | 2011-12-20 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
| CA2821357A CA2821357C (en) | 2010-12-30 | 2011-12-20 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
| TW100149338A TW201237087A (en) | 2010-12-30 | 2011-12-28 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2726602A CA2726602A1 (en) | 2010-12-30 | 2010-12-30 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2726602A1 true CA2726602A1 (en) | 2012-06-30 |
Family
ID=46382122
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2726602A Abandoned CA2726602A1 (en) | 2010-12-30 | 2010-12-30 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
| CA2821357A Active CA2821357C (en) | 2010-12-30 | 2011-12-20 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2821357A Active CA2821357C (en) | 2010-12-30 | 2011-12-20 | Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging |
Country Status (3)
| Country | Link |
|---|---|
| CA (2) | CA2726602A1 (en) |
| TW (1) | TW201237087A (en) |
| WO (1) | WO2012088585A1 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112014004921B1 (en) | 2011-09-07 | 2020-12-08 | Concentrx Pharmaceuticals, Inc. | dry powder inhalation device |
| CZ2012881A3 (en) * | 2012-12-07 | 2014-02-26 | Polymer Institute Brno, Spol. S R.O. | Oxo-degradable polyolefin material |
| US20150013611A1 (en) * | 2013-07-12 | 2015-01-15 | Wanda Weder & William Straeter, not individually but solely as Trustees of The Family Trust U/T/A - | Compositions and kits comprising at least two organisms and methods for causing, enhancing, and/or expediting biodegradation of articles using same |
| US10752759B2 (en) | 2015-06-30 | 2020-08-25 | BiologiQ, Inc. | Methods for forming blended films including renewable carbohydrate-based polymeric materials with high blow up ratios and/or narrow die gaps for increased strength |
| US11674014B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Blending of small particle starch powder with synthetic polymers for increased strength and other properties |
| US11046840B2 (en) | 2015-06-30 | 2021-06-29 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable plastic materials |
| US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
| US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
| US10995201B2 (en) | 2015-06-30 | 2021-05-04 | BiologiQ, Inc. | Articles formed with biodegradable materials and strength characteristics of the same |
| US11111363B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability |
| US11111355B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Addition of biodegradability lending additives to plastic materials |
| US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
| US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
| US10920044B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Carbohydrate-based plastic materials with reduced odor |
| US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
| US11149144B2 (en) | 2015-06-30 | 2021-10-19 | BiologiQ, Inc. | Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material |
| US10919203B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Articles formed with biodegradable materials and biodegradability characteristics thereof |
| US11414608B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor used with opportunity feedstocks |
| US11414607B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor with increased production rate of converted products |
| FR3043323B1 (en) * | 2015-11-05 | 2017-12-08 | Cleanis | OXO-BIODEGRADABLE ANTI-MICROBIAL CONTAINER |
| US11421164B2 (en) | 2016-06-08 | 2022-08-23 | Hydrocarbon Technology & Innovation, Llc | Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product |
| US11732203B2 (en) | 2017-03-02 | 2023-08-22 | Hydrocarbon Technology & Innovation, Llc | Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling |
| EP3600504B1 (en) | 2017-03-28 | 2023-07-12 | Concentrx Pharmaceuticals, Inc. | Device for delivering dry powder medicaments |
| WO2018227166A1 (en) * | 2017-06-09 | 2018-12-13 | Hedgehog Group LLC | Oxo-degradable rigid and flexible packaging |
| RU2683831C1 (en) * | 2017-12-11 | 2019-04-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет инженерных технологий" (ФГБОУ ВО "ВГУИТ") | Method of producing polyfunctional additive, means for oxo and biocorbing polyolefins |
| BR112020021530A2 (en) * | 2018-04-23 | 2021-01-19 | Biologiq, Inc | ADDITION OF ADDITIVES THAT CONFER BIODEGRADABILITY TO PLASTIC MATERIALS |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3921333A (en) * | 1972-07-28 | 1975-11-25 | Union Carbide Corp | Transplanter containers made from biodegradable-environmentally degradable blends |
| US5258422A (en) * | 1992-05-05 | 1993-11-02 | Tredegar Industries, Inc. | Compostable thermoplastic compositions |
| NO324368B1 (en) * | 2003-04-23 | 2007-10-01 | Normors As | Process for preparing additive for thermoplastics and such prepared additive as well as thermoplastics containing such additive. |
| KR20090015904A (en) * | 2006-05-11 | 2009-02-12 | 시바 홀딩 인코포레이티드 | Polymer article modified with a metal cation containing compound |
-
2010
- 2010-12-30 CA CA2726602A patent/CA2726602A1/en not_active Abandoned
-
2011
- 2011-12-20 CA CA2821357A patent/CA2821357C/en active Active
- 2011-12-20 WO PCT/CA2011/001385 patent/WO2012088585A1/en active Application Filing
- 2011-12-28 TW TW100149338A patent/TW201237087A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2821357C (en) | 2017-03-07 |
| WO2012088585A1 (en) | 2012-07-05 |
| CA2821357A1 (en) | 2012-07-05 |
| TW201237087A (en) | 2012-09-16 |
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