WO1992011298A1 - Photodegradable plastic composition - Google Patents

Photodegradable plastic composition Download PDF

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Publication number
WO1992011298A1
WO1992011298A1 PCT/US1991/009731 US9109731W WO9211298A1 WO 1992011298 A1 WO1992011298 A1 WO 1992011298A1 US 9109731 W US9109731 W US 9109731W WO 9211298 A1 WO9211298 A1 WO 9211298A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
transition metal
thermoplastic
metal compound
present
Prior art date
Application number
PCT/US1991/009731
Other languages
English (en)
French (fr)
Inventor
Graham M. Chapman
Robert H. Downie
Original Assignee
Ecostar International L.P.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecostar International L.P. filed Critical Ecostar International L.P.
Priority to KR1019930701906A priority Critical patent/KR930703370A/ko
Priority to JP50375992A priority patent/JP3184886B2/ja
Publication of WO1992011298A1 publication Critical patent/WO1992011298A1/en

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • 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
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • 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
    • C08K5/07—Aldehydes; Ketones

Definitions

  • This invention relates generally to plastic compositions, and more particularly, to a ther o- plastic composition which comprises a thermoplastic polymer such as polyetheylene or ethylene copolymers, polypropylene, polystyrene or polyurethane which is photodegradable when exposed to sunlight and/or ultraviolet light.
  • a thermoplastic polymer such as polyetheylene or ethylene copolymers, polypropylene, polystyrene or polyurethane which is photodegradable when exposed to sunlight and/or ultraviolet light.
  • Plastic waste is normally disposed of by recycling, incineration or burying in a landfill.
  • Some materials are improperly dis ⁇ posed of and become litter.
  • This litter is both esthetically objectionable and poses a threat to wildlife through possible entrapment and/or inges- tion. Therefore, there is a need for a material which will degrade harmlessly when exposed to sun ⁇ light, ultraviolet light or heat.
  • additive compositions which may be incorporated into thermoplastic materials to enhance degradation of the plastic. For example, U.S.
  • patent 4,931,488 discloses a thermoplastic polymer composition to which has been added a bio- logically degradable substance such as starch, an iron compound, an oxidizable substance selected from fatty acids and/or fatty acid esters and a transi ⁇ tion metal.
  • a bio- logically degradable substance such as starch, an iron compound, an oxidizable substance selected from fatty acids and/or fatty acid esters and a transi ⁇ tion metal.
  • This composition demonstrates biodegradation and photodegradation capability when exposed to heat, ultraviolet light, sunlight, or under compositing conditions. But, many states today require only that a plastic composition only be photodegradable. In this connection, the use of a composition such as that disclosed in patent 4,931,488 may not be advantageous.
  • the starch com- ponent in the composition becomes unnecessary when biodegradation is not required, and the starch may cause the product to become sensitive to moisture pickup during the production process and does little to enhance photodegradation. Therefore, a plastic composition which possesses the desired properties of thermoplastic materials, yet readily degrades when exposed to sun ⁇ light and/or ultraviolet light, is highly desirable.
  • thermoplastic materials it is the primary object of the present invention to provide a plastic composition which readily degrades when exposed to sunlight and/or ultraviolet light and to provide such a plas ⁇ tic composition for films, sheets or other moldings, which possesses the desired properties of known thermoplastic materials.
  • thermoplastic composition which is degradable under the action of sunlight and/or ultraviolet light and heat.
  • the thermoplastic com ⁇ position comprises a thermoplastic polymer, a first transition metal compound which may be a complex, a second transition metal compound and an aromatic ketone.
  • the thermoplastic polymer preferably comprises an olefin such as polyethylene, ethylene copolymers, polypropylene, polystyrene or polyurethane.
  • the first transition metal comprises an iron compound such as ferric hydroxy stearate, which is soluble in the composition and acts as an initiator which promotes further degradation.
  • the second transition metal comprises a copper compound which acts as a catalyst with the iron compound to enhance degradation.
  • the aromatic ketone includes benzophenone. It has been found that by using the composition of the present invention in a thermo ⁇ plastic material that a significant synergistic deg ⁇ radation effect occurs on the plastic when exposed to sunlight and/or ultraviolet light.
  • Fig. 1 is a graph illustrating loss of elonga ⁇ tion at break as a function of time in a plastic film product including the composition of the pre ⁇ - ent invention.
  • thermoplastic composition in accordance with the present invention facilitates biodegradation of thermoplastic materials under the action of sunlight and/or ultraviolet light and heat. That is, the chemicals in the composition in the presence of the sunlight or ultraviolet light and heat react to form free radicals which break the bonds cf the thermoplastic polymer resulting in a reduction of molecular weight and loss of physical properties. Thereafter, the thermoplastic material becomes weak and brittle which results in a material that is easily disintegrated by exposure to the ele ⁇ ments.
  • thermoplastic composition of the present invention comprises as one component thereof a ther ⁇ moplastic base of any known thermoplastic polymer and preferably polymers of olefins such as polyethylene, ethylene copolymers, polypoypylene, polystyrene or polyurethane.
  • Polyethylene as used herein, comprises any type of polyethylene, such as LDPE, LLDPE, LMDPE, MDPE, HDPE, ULDPE, etc.
  • Exam- pies of suitable ethylene copolymers include EVA,
  • composition of the present invention may be formed in any of the following manners.
  • the compo ⁇ sition may be added directly at the final production stage by the manufacturer, formed in a concentrate and supplied to the manufacturer to be added to the base resin or formed with the base resin and supplied to the manufacturer ready for use.
  • the first transition metal component preferably comprises an iron compound generally having the for ⁇ mula X-Fe, where X represents one or more ligands.
  • the compound may additionally be coupled to a fur ⁇ ther ligand Y.
  • Fe may designate iron in any known valancy.
  • the ligand X may be an inorganic or organic acid radical or likewise another ligand bonded in a complex.
  • suitable ligands X include OH-, C1-, Br-, I-, oxalate-, H-citrate-, NO- , N-.- EDTA or a carbonyl, nitrosyl or porphyrin radical.
  • Suitable ligands Y include carboxylic acid ions of aromatic or aliphatic monocarboxylic acid or of dicarboxylic acids, the aliphatic carboxylic acid preferably having 10 to 20 carbon atoms.
  • Ligand Y serves in general to increase the solubility of the compound X-Fe in the polymer.
  • the iron compound more preferably is comprised of iron stearate pres ⁇ ent in the final concentration of the present inven ⁇ tion in an amount from about 0.01 weight percent to about 0.5 weight percent, and more preferably in an amount from about 0.1 weight percent to about 0.3 weight percent. It is understood that the ranges listed herein are for purposes of illustration.
  • the amount listed for the upper limits is based on eco ⁇ nomics, and therefore, the components may be present in the concentration in amounts greater than those listed. Although, a saturation limit is reached at which further addition does not provide greater effectiveness. The minimum value listed provides minimum measurable improvements in photodegradation.
  • the second transition metal compound of the thermoplastic composition of the present invention acts as a catalyst with the first transition com ⁇ pound to enhance degradation of the thermoplastic material.
  • the compound may comprise a complex having the general formula Z'-Me, wherein Me desig ⁇ nates a transition metal other than iron if iron is the first transition metal and Z ' designates one or more ligands.
  • examples of ligands include OH-, C1-, Br-, I-, oxalate-, H-citrate-, NO ⁇ 2 , N,-, EDTA, as well as carboxylic acid ions of aromatic or aliphatic monocarboxylic or dicarboxylic acids, the aliphatic carboxylic acid preferably having 10 to 20 carbon atoms.
  • the preferred transition metals comprising Me are the transition metals of the first transition metal row in the periodic table, and more preferably copper and vanadium.
  • the most preferred second transition metal compound is copper stearate present in the final concentrate of the present invention in an amount from about 0.005 weight per ⁇ cent to about 0.1 weight percent, and more pre ⁇ ferably cupric stearate in an amount from about 0.01 weight percent to about 0.06 weight percent.
  • aromatic ketone component of the composi- tion of the present invention has been found to have a synergistic effect that speeds up the photodegradation of the thermoplastic. This is an unobvious finding since aromatic ketones generally are ultraviolet stabilizers.
  • aromatic ketones generally are ultraviolet stabilizers.
  • aro ⁇ matic ketones include benzophenone, anthraquinone, anthrone or derivatives such as acetylbenzophenone or 4-octyl benzophenone.
  • the more preferred aromatic ketone is benzophenone which is present in the concentration in an amount of from about 0.01 weight percent to about 0.7 weight percent and more preferably in an amount from about about 0.02 weight percent to about 0.15 weight percent.
  • Utilizing the composition of the present inven ⁇ tion is further advantageous in that the degradation can be controlled depending on the field of applica ⁇ tion by varying the concentration of the individual components, without the plastic material suffering a deterioration in its properties under normal use conditions.
  • Particular fields of application of the composition of the present invention include packaging materials, films for garbage bags for co - postable wastes, agricultural films, and in particu- lar those materials which may become litter such as disposable packaging.
  • the present invention makes it possible to manufacture products which do not pollute the environment and which can be degraded without additional energy consumption and without releasing harmful substances.
  • thermoplastic composition in a concentrate form in accordance with the present invention and its processing to give sheets, films, plates or other shapes is carried out by any conven- tional method.
  • the polyethylene may be combined with the appropriate amounts of iron stearate, copper stearate and benxophenone in a twin screw compounding extruder or equivalent and extruded and pelletized into a concentrate or mas- terbatch.
  • Extruded film, blow molded parts or injection moulded parts are made by combining this concentrate with polyethylene or other base resins in a film extruder or injection molding extruder, which is normally of the single screw type.
  • the chemicals could be added directly at the final production stage in the single screw extruder, this however is not very practical.
  • thermoplastic base i.e., polyethylene
  • the half life of biological degradation of polyethylene was extrapolated to be at least 100 years.
  • sun ⁇ light or heat free radicals such as, for example OH* are formed due to the presence of iron ions, and these can react with the polymers forming other free radicals.
  • These free polymer radicals are extremely reactive and can, inter alia, react further with oxygen, other chains, iron ions, and the like. Polymer chains are thus split and small chains with or without oxygen-containing groups, such as alco- hols, ketones, etc. are formed.
  • iron ions act both as an initiator and as a reaction promoter since iron-(in) hydroxide com ⁇ plexes are highly reactive. This can be illustrated the by the following equation:
  • Cu+ ions are reoxidized very fast to Cu 2+ ions by free radicals as follows:
  • this phase takes in general from about 10 to 60 days.
  • thermoplastic composition of the present invention formed in a concentrate wherein the compositional ranges of the various components are by weight percent of the total concentrate.
  • thermoplastic composition of the present invention formed in a concentrate wherein the compositional ranges of the various components are by weight percent of the total concentrate.
  • a From about 0.1 percent to about 0.3 per ⁇ cent iron stearate; b. From about 0.01 percent to about 0.06 per ⁇ cent copper stearate; c. From about .02 percent to about 0.15 per ⁇ cent benxophenone; d. Balance thermoplastic polymer.
  • thermoplastic composition of the present invention formed in a concentrate wherein the compositional ranges of the various components are by weight percent of the total concentrate.

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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)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/US1991/009731 1990-12-21 1991-12-20 Photodegradable plastic composition WO1992011298A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019930701906A KR930703370A (ko) 1990-12-21 1991-12-20 광분해성 플라스틱 조성물
JP50375992A JP3184886B2 (ja) 1990-12-21 1991-12-20 光劣化可能なプラスチック組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US63236290A 1990-12-21 1990-12-21
US632,362 1990-12-21

Publications (1)

Publication Number Publication Date
WO1992011298A1 true WO1992011298A1 (en) 1992-07-09

Family

ID=24535226

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/009731 WO1992011298A1 (en) 1990-12-21 1991-12-20 Photodegradable plastic composition

Country Status (5)

Country Link
EP (1) EP0563291A1 (enrdf_load_stackoverflow)
JP (1) JP3184886B2 (enrdf_load_stackoverflow)
KR (1) KR930703370A (enrdf_load_stackoverflow)
CA (1) CA2098911A1 (enrdf_load_stackoverflow)
WO (1) WO1992011298A1 (enrdf_load_stackoverflow)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5783425A (en) * 1993-10-27 1998-07-21 Ribozyme Pharmaceuticals, Inc. Amino and peptido modified enzymatic nucleic acid
US5814404A (en) * 1994-06-03 1998-09-29 Minnesota Mining And Manufacturing Company Degradable multilayer melt blown microfibers
US6410224B1 (en) 1992-12-07 2002-06-25 Ribozyme Pharmaceuticals, Inc. Ribozyme treatment of diseases or conditions related to levels of NF-κB
US6482872B2 (en) 1999-04-01 2002-11-19 Programmable Materials, Inc. Process for manufacturing a biodegradable polymeric composition
WO2004013216A1 (en) * 2002-07-31 2004-02-12 Polimeri Europa S.P.A. Beads of expandable vinylaromatic polymers and process for their preparation
WO2004094516A1 (en) * 2003-04-23 2004-11-04 Nor-X Industry As Additive for thermoplastics, use of and method for its manufacture, method for the manufacture of a thermoplastic containing such additive and thermoplastic so manufactured
WO2007028731A1 (en) * 2005-09-07 2007-03-15 Ciba Specialty Chemicals Holding Inc. A degradable polymer article
WO2007027163A3 (en) * 2005-09-01 2008-11-13 Super Film Ambalaj Sanayi Ve T Degradable biodegradable polypropylene film
WO2009016083A1 (en) * 2007-08-02 2009-02-05 Basf Se Degradation accelerator for polymers and polymer article comprising it
FR2943219A1 (fr) * 2009-03-20 2010-09-24 Polytek Innovations Produit a usage agricole et son procede de fabrication
CN103172981A (zh) * 2011-12-21 2013-06-26 香港生产力促进局 一种可降解聚合物组合物及其制备方法
CN106032422A (zh) * 2015-03-13 2016-10-19 香港纺织及成衣研发中心有限公司 一种可降解合成纤维组合物及其制备方法和制品
US9668913B2 (en) 2010-03-31 2017-06-06 Kobayashi Pharmaceutical Co., Ltd. Biodegradable disposable hand warmer
CN107001998A (zh) * 2014-11-18 2017-08-01 日油株式会社 铁皂、其制备方法及含有该铁皂的热塑性树脂组合物
US11155702B2 (en) 2016-11-22 2021-10-26 Polymateria Limited Degradable polymer and method of production

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6214915B1 (en) * 1998-12-10 2001-04-10 General Electric Company Stabilized thermoplastic compositions
CN111393738B (zh) * 2020-05-06 2022-12-02 江苏祎唯诺新材料科技有限公司 一种光降解型pe缠绕膜及其制备方法

Citations (3)

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US3941759A (en) * 1972-03-01 1976-03-02 Owens-Illinois, Inc. Degradable plastics containing dual-function additive system
US3981856A (en) * 1974-03-07 1976-09-21 Princeton Polymer Laboratories, Incorporated Degradable hydrocarbon polymers containing a metal compound and a benzotriazole
US4495315A (en) * 1970-09-18 1985-01-22 Sekisui Kagaku Kogyo Kabushiki Kaisha Photo-degradable styrene resin compositions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2200299B1 (enrdf_load_stackoverflow) * 1972-09-20 1978-10-20 Huels Chemische Werke Ag

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4495315A (en) * 1970-09-18 1985-01-22 Sekisui Kagaku Kogyo Kabushiki Kaisha Photo-degradable styrene resin compositions
US4517318A (en) * 1970-09-18 1985-05-14 Sekisu Kagaku Kogyo Kabushiki Kaisha Photo-degradable styrene resin compositions
US3941759A (en) * 1972-03-01 1976-03-02 Owens-Illinois, Inc. Degradable plastics containing dual-function additive system
US3981856A (en) * 1974-03-07 1976-09-21 Princeton Polymer Laboratories, Incorporated Degradable hydrocarbon polymers containing a metal compound and a benzotriazole

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0563291A4 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6410224B1 (en) 1992-12-07 2002-06-25 Ribozyme Pharmaceuticals, Inc. Ribozyme treatment of diseases or conditions related to levels of NF-κB
US5783425A (en) * 1993-10-27 1998-07-21 Ribozyme Pharmaceuticals, Inc. Amino and peptido modified enzymatic nucleic acid
US5814404A (en) * 1994-06-03 1998-09-29 Minnesota Mining And Manufacturing Company Degradable multilayer melt blown microfibers
US6482872B2 (en) 1999-04-01 2002-11-19 Programmable Materials, Inc. Process for manufacturing a biodegradable polymeric composition
WO2004013216A1 (en) * 2002-07-31 2004-02-12 Polimeri Europa S.P.A. Beads of expandable vinylaromatic polymers and process for their preparation
RU2307845C2 (ru) * 2002-07-31 2007-10-10 Полимери Эуропа С.П.А. Гранулы вспениваемых винилароматических полимеров и способ их получения
WO2004094516A1 (en) * 2003-04-23 2004-11-04 Nor-X Industry As Additive for thermoplastics, use of and method for its manufacture, method for the manufacture of a thermoplastic containing such additive and thermoplastic so manufactured
CN100436520C (zh) * 2003-04-23 2008-11-26 Nor-X工业公司 用于热塑性塑料的添加剂、其用途和制造方法,制造含这种添加剂的热塑性塑料的方法和如此制造的热塑性塑料
WO2007027163A3 (en) * 2005-09-01 2008-11-13 Super Film Ambalaj Sanayi Ve T Degradable biodegradable polypropylene film
WO2007028731A1 (en) * 2005-09-07 2007-03-15 Ciba Specialty Chemicals Holding Inc. A degradable polymer article
WO2009016083A1 (en) * 2007-08-02 2009-02-05 Basf Se Degradation accelerator for polymers and polymer article comprising it
FR2943219A1 (fr) * 2009-03-20 2010-09-24 Polytek Innovations Produit a usage agricole et son procede de fabrication
US9668913B2 (en) 2010-03-31 2017-06-06 Kobayashi Pharmaceutical Co., Ltd. Biodegradable disposable hand warmer
CN103172981A (zh) * 2011-12-21 2013-06-26 香港生产力促进局 一种可降解聚合物组合物及其制备方法
CN107001998A (zh) * 2014-11-18 2017-08-01 日油株式会社 铁皂、其制备方法及含有该铁皂的热塑性树脂组合物
CN107001998B (zh) * 2014-11-18 2020-07-24 日油株式会社 铁皂、其制备方法及含有该铁皂的热塑性树脂组合物
CN106032422A (zh) * 2015-03-13 2016-10-19 香港纺织及成衣研发中心有限公司 一种可降解合成纤维组合物及其制备方法和制品
US11155702B2 (en) 2016-11-22 2021-10-26 Polymateria Limited Degradable polymer and method of production

Also Published As

Publication number Publication date
EP0563291A1 (en) 1993-10-06
KR930703370A (ko) 1993-11-29
EP0563291A4 (enrdf_load_stackoverflow) 1994-04-13
JPH06504079A (ja) 1994-05-12
JP3184886B2 (ja) 2001-07-09
CA2098911A1 (en) 1992-06-22

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