WO2006010233A1 - Films photodegradables derives du polyethylene - Google Patents

Films photodegradables derives du polyethylene Download PDF

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Publication number
WO2006010233A1
WO2006010233A1 PCT/BR2004/000137 BR2004000137W WO2006010233A1 WO 2006010233 A1 WO2006010233 A1 WO 2006010233A1 BR 2004000137 W BR2004000137 W BR 2004000137W WO 2006010233 A1 WO2006010233 A1 WO 2006010233A1
Authority
WO
WIPO (PCT)
Prior art keywords
ldpe
polyethylene
films
photo
pure
Prior art date
Application number
PCT/BR2004/000137
Other languages
English (en)
Inventor
Marco Aurélio DE PAOLI
Ralf Giesse
Original Assignee
Universidade Estadual De Campinas - Unicamp
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 Universidade Estadual De Campinas - Unicamp filed Critical Universidade Estadual De Campinas - Unicamp
Priority to PCT/BR2004/000137 priority Critical patent/WO2006010233A1/fr
Publication of WO2006010233A1 publication Critical patent/WO2006010233A1/fr

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Classifications

    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms

Definitions

  • the invention deals with the application of acrylic polyesters into low-density polyethylene (LDPE) films, which is a polymer commercially used in packaging materials.
  • LDPE low-density polyethylene
  • This invention serves to reduce LDPE lifetime under solar light (ultraviolet radiation) after its use, i.e., to turn it into a photodegradable LDPE, i.e., degradable under solar light or ultraviolet (UV) radiation.
  • Another invention describes a composition, which includes modified starch, photosensibilizer, degradation controlling agent and talcum powder, to produce biodegradable and photodegradable polyethylene (4). Evaluated technical problems were in the manipulation of aluminum-titanium coupling agents, to treat starch and talcum powder, the latter offering exposure risk.
  • Another process presents the formation of a basic material capable of suffering under light and biological degradation, which includes polyolefin resin, modified starch, photodegradation agent, oxidation accelerator, auto-oxidation agent, degradation controlling agent and calcium carbonate (5). It was not informed how much polyethylene useful lifetime was reduced.
  • Another variation shows the preparation of a degradable additive composed material for polyolefinic resins, which contains an polyhydroxi-carbonyl aliphatic acid (citric acid or monosodic citrate), a metal carboxilate (preferably cobalt stereate), and stabilizers compounds or oxidants (calcium oxide and iron oxide pigments), specially for the use in bin and agricultural application bags (6).
  • a degradable additive composed material for polyolefinic resins, which contains an polyhydroxi-carbonyl aliphatic acid (citric acid or monosodic citrate), a metal carboxilate (preferably cobalt stereate), and stabilizers compounds or oxidants (calcium oxide and iron oxide pigments), specially for the use in bin and agricultural application bags (6).
  • a metallic carboxilate a polyhydroxi-carboxylic acid
  • an iron oxide pigment (7).
  • This invent is used in polymers to make dustbin bags, shop bags, material for disposable napkins, packaging films, films for using in
  • the present invention presents less amount of ingredients for producing the photodegradable films derived from LDPE, by only sorbing the pure LDPE into the liquid monomer containing the dissolved photoinitiator, followed by its photopolimerization in the LDPE matrix.
  • this photodegradable material has no natural fibers nor starch in it, it does not suffer microorganisms attack during its use before being discarded. Furthermore at the half lifetime of pure LDPE under UV radiation, the derived film samples were already brittle.
  • UV radiation medium pressure mercury vapor lamps with main emission at 254 nm, with average intensity of 1.7 mW/cm 2 and average energy of 0,018 J/cm 2 , both measured 10 cm from radiation source
  • UV radiation medium pressure mercury vapor lamps with main emission at 254 nm, with average intensity of 1.7 mW/cm 2 and average energy of 0,018 J/cm 2 , both measured 10 cm from radiation source
  • ATR attenuated total reflectance
  • UV/visible spectrophotometry that: 1) a greater photo degradability of LDPE/PX in relation to pure LDPE, 2) the beginning of the photodegradation registered inside the films and not on the surface, and 3) the significant loss of mass of the LDPE/PX films during the photodegradation.
  • the carboxylic acid is the chemical species present in more proportion (circa 50 %) as a product of photodegradation compared to ketone, aldehide, etc.
  • the benzophenone, used as a photoinitiator in the process of photopolymerization of the monomer X is not responsible for the initiation of the photodegradation of the LDPE/PX films, because it is totally consumed in the preparation of the materials by photochemical polymerization.
  • the polyethylene plastics absorb the acrylic monomers, passing under UV radiation for 0 to 5 hours, for the photopolymerization of these monomers in the LDPE matrix.
  • These plastics, containing now the acrylic polyesters, are employed as packaging materials, always protected from solar or UV irradiation. When discarded, they must be exposed to the sun or to UV irradiation, to undergo the photodegradation process.
  • the photochemical degradation of pure LDPE occurred in a 500 to 1000 h period, while of LDPE/PX films occurred from 250 to 500 h.
  • the pure LDPE needs several decades to degrade in the environment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un procédé qui permet d'obtenir des dérivés de films de polyéthylène à faible densité ('Low Density Polyethylene' ou LDPE) par sorption par la matrice de polyéthylène de monomères d'acrylique et d'acétate de vinyle, suivie par la photopolymérisation du matériau imprégné. Le procédé de l'invention permet d'obtenir des films minces, dans lesquels un polymère d'acétate de vinyle ou d'acrylique est mélangé à la matrice de polyéthylène en très petites quantités (dans des concentrations comprises entre 1 et 2 %), sans dépôt de matière en surface. Les films précités ont démontré, par la spectrophotométrie UV-visible et les spectres de transmittance et de réflectance dans l'infrarouge (réflectance totale atténuée ou ATR - ' attenuated total reflectance'): 1) la meilleure photodégradabilité du LDPE/PX [PX représentant PAA pour l'acide poly(acrylique), PEA pour le poly(éthyl acrylate), PMA pour le poly(méthyl acrylate), PMNA pour le poly(méthyl métacrylate) et PVA pour le poly(vinyl acétate)] par comparaison avec le LDPE pur; 2) un début de photodégradation qui est enregistré dans la masse des films et non à leur surface; et 3) une perte massique significative au cours de la photodégradation. En ce qui concerne les propriétés mécaniques auxquelles fait référence la norme ASTM D 882, les films LDPE/PAA présentent des valeurs de contrainte à la rupture et d'allongement à la rupture similaires à celles du LDPE pur, tandis que les films obtenus à partir de LDPE/PX (X=EA, MA, MMA et VA) présentent des valeurs inférieures (d'environ 25 à 30 %). Des échantillons de LDPE/PX (X=EA, MA, MMA et VA) photodégradés donnent des valeurs de contrainte à la rupture et d'allongement à la rupture inférieures d'environ 50 % aux valeurs obtenues avec des films de LDPE pur photodégradés. Arrivés à la moitié de la durée de vie du LDPE pur sous rayonnement UV, les échantillons de films LDPE/PX sont déjà friables. Les résultats montrent que l'introduction du second composant dans la matrice étudiée permet d'obtenir des films polymères photodégradables dérivés du polyéthylène pur, pouvant contribuer à résoudre des problèmes tels que celui des résidus plastiques en interaction avec l'environnement, par exemple.
PCT/BR2004/000137 2004-07-29 2004-07-29 Films photodegradables derives du polyethylene WO2006010233A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/BR2004/000137 WO2006010233A1 (fr) 2004-07-29 2004-07-29 Films photodegradables derives du polyethylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/BR2004/000137 WO2006010233A1 (fr) 2004-07-29 2004-07-29 Films photodegradables derives du polyethylene

Publications (1)

Publication Number Publication Date
WO2006010233A1 true WO2006010233A1 (fr) 2006-02-02

Family

ID=34958164

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2004/000137 WO2006010233A1 (fr) 2004-07-29 2004-07-29 Films photodegradables derives du polyethylene

Country Status (1)

Country Link
WO (1) WO2006010233A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108084311A (zh) * 2017-12-28 2018-05-29 宁波俐辰新能源有限公司 一种生态种植用无公害透光薄膜及其制造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB876535A (en) * 1958-11-05 1961-09-06 Dow Chemical Co Graft copolymers and shaped articles consisting of or containing them
US3137674A (en) * 1960-12-09 1964-06-16 Grace W R & Co Polyethylene modified with a vinyl compound
US3226454A (en) * 1964-05-20 1965-12-28 Grace W R & Co Polyethylene composition containing cross-linked polyethylene graft copolymer and process therefor
EP0477736A1 (fr) * 1990-09-27 1992-04-01 Hoechst Aktiengesellschaft Polymère greffé à base d'un polyéthylène de masse moléculaire très élevée
EP0527688A1 (fr) * 1991-08-14 1993-02-17 Ecp Enichem Polymeres France Procédé pour le greffage dans la ligne d'acides et anhydrides d'acides carboxyliques à insaturation éthylénique sur des homopolymères ou copolymères de l'éthylène et installation pour la mise en oeuvre de ce procédé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB876535A (en) * 1958-11-05 1961-09-06 Dow Chemical Co Graft copolymers and shaped articles consisting of or containing them
US3137674A (en) * 1960-12-09 1964-06-16 Grace W R & Co Polyethylene modified with a vinyl compound
US3226454A (en) * 1964-05-20 1965-12-28 Grace W R & Co Polyethylene composition containing cross-linked polyethylene graft copolymer and process therefor
EP0477736A1 (fr) * 1990-09-27 1992-04-01 Hoechst Aktiengesellschaft Polymère greffé à base d'un polyéthylène de masse moléculaire très élevée
EP0527688A1 (fr) * 1991-08-14 1993-02-17 Ecp Enichem Polymeres France Procédé pour le greffage dans la ligne d'acides et anhydrides d'acides carboxyliques à insaturation éthylénique sur des homopolymères ou copolymères de l'éthylène et installation pour la mise en oeuvre de ce procédé

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108084311A (zh) * 2017-12-28 2018-05-29 宁波俐辰新能源有限公司 一种生态种植用无公害透光薄膜及其制造方法

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