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WO1989010381A1 - Composition biologiquement decomposable - Google Patents

Composition biologiquement decomposable Download PDF

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Publication number
WO1989010381A1
WO1989010381A1 PCT/FI1989/000075 FI8900075W WO8910381A1 WO 1989010381 A1 WO1989010381 A1 WO 1989010381A1 FI 8900075 W FI8900075 W FI 8900075W WO 8910381 A1 WO8910381 A1 WO 8910381A1
Authority
WO
WIPO (PCT)
Prior art keywords
biopolymer
composition
synthetic polymer
starch
film
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/FI1989/000075
Other languages
English (en)
Inventor
Hannu L. Suominen
Juhani Melartin
Kalervo Karimo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Amerplast Oy
Original Assignee
Amerplast Oy
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 Amerplast Oy filed Critical Amerplast Oy
Publication of WO1989010381A1 publication Critical patent/WO1989010381A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a biologically decomposable composition, comprising a composition consisting of a biopolymer and at least one synthetic polymer, the composition further including a material causing in certain conditions disintegration of the chains of the synthetic polymer and/or the synthetic polymer of the composition having been treated in a manner that the chains of the synthetic polymer disintegrate in certain conditions.
  • EP-230143 discloses a synthetic polymer decomposing agent which is sensitive to light.
  • the additive disintegrates polyethene chains as the composition is exposed to light.
  • polyethylene will be decomposed as it is exposed to the effect of light for a lengthy period of time.
  • the above deals particularly with mechanisms for chopping the synthetic polymer in a biologically decompos able composition.
  • this can be effected either by means of an additive incorporated in a composition for cutting off in certain conditions the chains of a synthetic polymer or by treating the synthetic polymer itself in a manner that the polymer chains break in certain conditions. It is natural that a combination of the above factors can be utilized.
  • the most important reason for these treatments is that certain synthetic polymers, such as polyethylene polymer, do not decompose microbiologically.
  • the synthetic polymer surrounds starch particles (biopolymer).
  • biopolymer contained therein consists of starch particles which have a relatively large, size and a relatively small reactive surface.
  • the large biopolymer particles considerably impair the strength characteristics of a film.
  • decomposition of such compounds is very slow because of small active surface area.
  • An object of this invention is to provide a biologically decomposable composition which to the maximum extent overcomes the weaknesses of prior known compositions.
  • a biologically decomposable composition of the invention is mainly characterized in that the biopolymer is ezymatically modified.
  • the advantage gained by the invention can be clearly seen e.g. when the biopolymer used is starch.
  • Starch can be enzymatically modified so that the surface of starch particles is only partially hydrolyzed.
  • partial hydrolysis on the surface of a particle around he diminishing core develops a dextrine chain layer which has the effect that, in theory, the particle "dissolves" without any boundary surface in a synthetic polymer, such as polyethylene.
  • a synthetic polymer such as polyethylene
  • the particle size of a biopolymer can be adjusted as desired. In principle, this means that the actual core of a particle diminishes especially when starch is used and around the core there is grown a dextrine chain layer. Thus, the amount of biopolymer in relation to synthetic polymer can be increased without impairing the mechanical properties of a composition. This is due to the fact that the enzymatically modified biopolymer sort of dissolves in synthetic polymer.
  • the biopolymer treating enzyme remains as stable on the surface of biopolymer particles in partial hydrolysis. The enzyme is activated by the action of water, whereby the starch dissolves and it is a microbiologically readily available source of energy.
  • the enzymatic ally modified biopolymer can be dried so it can be readily mixed within synthetic polymer granulate and extruded into a plastic film.
  • one preferred biopolymer is starch.
  • An enzymatic modification on starch according to the invention can be preferably effected with alfa-amylase, e.g. ⁇ -1,4 glucan-4 clucan-hydrolase: (E.C. 3.2.1.1.) particularly with heat-resistant alfaamylase.
  • alfa-amylase e.g. ⁇ -1,4 glucan-4 clucan-hydrolase: (E.C. 3.2.1.1.) particularly with heat-resistant alfaamylase.
  • a characteristic feature of heat-resistant alfa-mylase is that its action activates as temperature is rising and the thermal denaturation of an enzyme protein is very slow as it is bound to substrate (starch).
  • the alfa-amylase enzyme remains bound to its substrate as high as at 180oC, i.e. for example at polyethylene film production temperature, for a sufficiently long period of time so as not to be destroyed in the production of film.
  • Another preferred biopolymer is cellulose.
  • the enzyme used for its enzymatic modification is cellulase, e.g. 1,4- ⁇ -D-glucan cellobiohydrolase: (E.C. 3.2.1.91.), especially a cellulase that form cellodextrines.
  • the invention is further illustrated in the accompanying drawing showing diagrammatically the effect of the enzymatic modification of biopolymer particle on the structure of such particle.
  • the top of fig. 1 (2) shows biopolymer particles prior to modification and as they would be incorporated e.g. in a film-making process in the prior art solutions.
  • the bottom (b) of fig. 1 shows biopolymer particles obtained by enzymatic modification. Both groups of particles are provided with vertical lines on either side thereof for describing the boundary surfaces of e.g. a produced plastic film.
  • the biopolymer particle forms in the resulting film a cavity which significantly decreases the overall strength of a film at this point.
  • a modified biopolymer particle whose core is relatively small and which consists of members, such as dextrine chains (in the case of starch), branching off the core, does not produce a similar cavity effect on a plastic film and, thus, the strength impairing effect of a biopolymer composition is substantially lesser.
  • fig. 1 shows one advantage of the invention, namely the fact, especially when starch is used, the dextrine chains extend at least in certain places all the way to the surface of a film providing for water a kind of capillary duct system directly inside the composition.
  • Enzymatically modified rice starch and polyethylene were mixed with each other at a ratio of 1:1.
  • This mixture was melt stirred by means of a co-kneeter type of extruder from Buss AG (model MDK/E46 11D; screw length 506 mm; diameter 46 mm; screw temperature from forward end 140°C, 140°C, 140°C, 140°C).
  • the melt mix ture of melt polyethylene and modified starch was finally compressed through the orifices (7 orifices, diameter 3 mm) at the end of the extruder and sliced by means of a cutter into a water basin by means of a cutter operating immediately downstream of the orifices and dried to form a master batch granulate.
  • biopolymers rice starch, cellulose and modified cellulose
  • master batches containing 50 % of biopolymer were used to prepare master batches containing 50 % of biopolymer.
  • Film-blowing was effected by means of a Luigi Bandera ⁇ niblock type of 1 -screw film-blowing extruder (screw length 1125 mm; diameter 45 mm; compression ratios 2,57:1 and 2.24:1; nozzle diameter 150 mm; nozzle slit 1 mm).
  • the film-blowing conditions were as follows: temperatures from forward end of screw (set values) 130°C, 140°C, 140°C, 140°C, 140°C and 140°C; temperature of melt appr. 160°C; speed of rotation of screw 79 rpm; running speed 8-10 min and,blowing ratio 1.8.
  • the above-described film-blowing extruder was used with varying biopolymer additions (1.5 - 6.0 % as dry) to preparepolyethylene films by employing a polyethylene grade whose melt index was 1.2 and density 0.922.
  • the thicknesses of such manufactured films varied within the range of 70-90 ⁇ m (tables 1 and 2).
  • Table 1 indicates how the enzymatic modification of a biopolymer improves the mechanical strength properties of a film compared with polyethylene having enzymatically unmodified biopolymer added therein.
  • a 3 % addition provides a 30 % improvement in tensile strength, 20 % in elongation and appr. 22 % in drop value.
  • a film of modified rice starch is 5 um thinner than a film of rice starch (RT).
  • the change of particle size due to modification is also clearly seen in table 1 as the mean particle size of starch diminishes to about one fifth of the original.
  • the enzymatic modification provides similar improvements.
  • the improvement in tensile strength by virtue of modification is appr. 24 %, in elongation nearly 20 % and in drop value more than 20 %.
  • the particle size diminishes by virtue of modification to about half from the original.
  • EMRT enzymatically modified rice starch
  • EMS enzymatically modified cellulose
  • the mean particle size of biopolymer is determined with Malvern 2600 device in aqueous phase.
  • Table 2 indicates the effect of an increase in the amount of biopolymer on the mechanical strength properties of a polyethylene film.
  • modified rice starch provides for mechanically stronger film properties compared to original rice starch (RT).
  • the difference between EMRT and RT increases dramatically as the amount of biopolymer in a polyethylene film increases.
  • the difference between EMRT and RT varies within the range of 6-12 % in favour of EMRT while a 6 % addition of biopolymer increases the difference in mechanical strength properties to the range of 30-96 % in favour of EMRT.
  • modified rice starch When modified rice starch was added in a polyethylene film (1.5 - 6.0 %), its mechanical strength properties were impaired only by 20 % while the similar additions of rice starch impaired the values considerably more, i.e. 60 %.
  • KS/PS 300/550 330/610 240/520 350/610 200/370 260/500
  • Tests were effected according to ASTM standard, STM G 21-70 1980. The test was effected with 100 ⁇ 80 mm sized test specimens which were incubated in glass Petri dishes (150 ⁇ 150 ⁇ 25 mm) for 4 weeks at 28°C. Sufficient relative air humidity in the incubation space was secured by placing a vessel containing saturated KNO 3 -solution (Rh 92 %) on the incubator floor. The controls used were test specimens that were not sterilized and not treated with mould suspension. The organic nature of mould suspension was checked with standardized test dishes. The mould-formation of plastics was observed at one-week intervals. The test fungi were as follows
  • test specimens The mould-formation of test specimens was rated visually and microscopically as follows:
  • the enclosed table 3 shows that the mould-formation in a compsition having enzymatically modified rice starch was more vigorous than with a polyethylene film having unmodified rice starch added therein. TABLE 3 The average mould-formation of test specimens
  • EMRT enzymatically modified rice starch
  • UV photosensitive component
  • a biologically decomposable composition of the invention can also be processed into a product by the application of other processes prior known in plastics manufacturing, such as injection moulding, blowing technique, extrusion moulding, vacuum moulding, rotational casting or various foaming techniques.
  • plastics manufacturing such as injection moulding, blowing technique, extrusion moulding, vacuum moulding, rotational casting or various foaming techniques.
  • the examples deal with blown films for the reason that the manufacturing of a thin-walled film is in technical sense most demanding, particularly in view of the workability of a biologically decomposablw composition.
  • plastics manufacturing techniques can be applied which facilitate the manufacturing of an end product at such temperatures that an enzymatically modified biopolymer maintains its characteristics promoting the decomposition of a composition in certain conditions.
  • the upper limit temperature range can be considered to be 220-250°C.
  • the synthetic polymer comprises polyethylene.
  • polyoleophines overall are included in those synthetic polymers that can be employed in a composition of the invention.
  • the agents belonging in the group of polyoleophines include e.g. HD-polyethylene, LD-polyethylene and polypropylene.
  • polystyrene is a synthetic polymer suitable for a biologically decomposable composition of the invention.
  • rice starch provides for the besz comparative results in unmodified form.
  • corn starch etc. can be used as a biopolymer of the invention.
  • Enzymatic modification makes it possible to reduce their particle size as desired.
  • starch it can be said that enzymatic modification provides for such a particle size distribution in which the mean particle size is smaller than 10 ⁇ m.
  • cellulose it can be said that enzymatic modification provides for such a particle size distribution in which the mean particle size is smaller than 20 ⁇ m (fig. 1).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

La composition biologiquement décomposable décrite comprend une composition constituée par un biopolymère et par par un polymère synthétique. La composition contient en outre une substance entraînant dans certaines conditions la désintégration des chaînes du polymère synthétique et/ou le polymère synthétique de la compositoin est traité pour que les chaînes du polymère synthétique se désintègrent dans certaines conditions. Le biopolymère est modifié par voie enzymatique.
PCT/FI1989/000075 1988-04-27 1989-04-24 Composition biologiquement decomposable Ceased WO1989010381A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI881965A FI881965A7 (fi) 1988-04-27 1988-04-27 Biologisesti hajoava yhdistelmä
FI881965 1988-04-27

Publications (1)

Publication Number Publication Date
WO1989010381A1 true WO1989010381A1 (fr) 1989-11-02

Family

ID=8526363

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1989/000075 Ceased WO1989010381A1 (fr) 1988-04-27 1989-04-24 Composition biologiquement decomposable

Country Status (2)

Country Link
FI (1) FI881965A7 (fr)
WO (1) WO1989010381A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0421415A1 (fr) * 1989-10-05 1991-04-10 Biodata Oy Film de couverture biologiquement dégradable et méthode de fabrication
EP0421413A1 (fr) * 1989-10-05 1991-04-10 Biodata Oy Film biologiquement dégradable et méthode de fabrication
US5095054A (en) * 1988-02-03 1992-03-10 Warner-Lambert Company Polymer compositions containing destructurized starch
DE4202414A1 (de) * 1992-01-16 1993-08-05 Nien Made Enterprise Co Jalousielamelle und verfahren zur herstellung derselben
WO1998002046A1 (fr) * 1996-07-15 1998-01-22 Kalle Nalo Gmbh & Co. Kg Articles moules en hydrate de cellulose a surface modifiee par voie enzymatique
WO2016198650A1 (fr) * 2015-06-12 2016-12-15 Carbios Composition de mélange-maître comprenant une concentration élevée d'entités biologiques
US10287561B2 (en) 2014-10-21 2019-05-14 Carbios Polypeptide having a polyester degrading activity and uses thereof
US10385183B2 (en) 2014-05-16 2019-08-20 Carbios Process of recycling mixed PET plastic articles
US10508269B2 (en) 2015-03-13 2019-12-17 Carbios Polypeptide having a polyester degrading activity and uses thereof
US10626242B2 (en) 2014-12-19 2020-04-21 Carbios Plastic compound and preparation process
US10717996B2 (en) 2015-12-21 2020-07-21 Carbios Recombinant yeast cells producing polylactic acid and uses thereof
US10767026B2 (en) 2016-05-19 2020-09-08 Carbios Process for degrading plastic products

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032802A1 (fr) * 1980-01-17 1981-07-29 THE GOVERNMENT OF THE UNITED STATES OF AMERICA as represented by the Secretary Department of Commerce Feuilles flexibles biodégradables sans support et leur fabrication
SE454444B (sv) * 1981-06-23 1988-05-02 Roquette Freres Forfarande for framstellning av en temporer skyddande beleggning pa ett foremal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0032802A1 (fr) * 1980-01-17 1981-07-29 THE GOVERNMENT OF THE UNITED STATES OF AMERICA as represented by the Secretary Department of Commerce Feuilles flexibles biodégradables sans support et leur fabrication
SE454444B (sv) * 1981-06-23 1988-05-02 Roquette Freres Forfarande for framstellning av en temporer skyddande beleggning pa ett foremal

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095054A (en) * 1988-02-03 1992-03-10 Warner-Lambert Company Polymer compositions containing destructurized starch
EP0421415A1 (fr) * 1989-10-05 1991-04-10 Biodata Oy Film de couverture biologiquement dégradable et méthode de fabrication
EP0421413A1 (fr) * 1989-10-05 1991-04-10 Biodata Oy Film biologiquement dégradable et méthode de fabrication
US5316847A (en) * 1989-10-05 1994-05-31 Biodata Oy Biologically degradable films comprising enzyme-coated bio-degradable polymer particles
DE4202414A1 (de) * 1992-01-16 1993-08-05 Nien Made Enterprise Co Jalousielamelle und verfahren zur herstellung derselben
WO1998002046A1 (fr) * 1996-07-15 1998-01-22 Kalle Nalo Gmbh & Co. Kg Articles moules en hydrate de cellulose a surface modifiee par voie enzymatique
US6761944B1 (en) 1996-07-15 2004-07-13 Kalle Nalo Gmbh & Co. Kg Moulded articles of cellulose hydrate with enzymatically modified surface
US10385183B2 (en) 2014-05-16 2019-08-20 Carbios Process of recycling mixed PET plastic articles
US10287561B2 (en) 2014-10-21 2019-05-14 Carbios Polypeptide having a polyester degrading activity and uses thereof
US10626242B2 (en) 2014-12-19 2020-04-21 Carbios Plastic compound and preparation process
US10508269B2 (en) 2015-03-13 2019-12-17 Carbios Polypeptide having a polyester degrading activity and uses thereof
WO2016198650A1 (fr) * 2015-06-12 2016-12-15 Carbios Composition de mélange-maître comprenant une concentration élevée d'entités biologiques
US10723848B2 (en) 2015-06-12 2020-07-28 Carbios Masterbatch composition comprising a high concentration of biological entities
US11198767B2 (en) 2015-06-12 2021-12-14 Carbios Process for preparing a biodegradable plastic composition
US11802185B2 (en) 2015-06-12 2023-10-31 Carbios Masterbatch composition comprising a high concentration of biological entities
US10717996B2 (en) 2015-12-21 2020-07-21 Carbios Recombinant yeast cells producing polylactic acid and uses thereof
US10767026B2 (en) 2016-05-19 2020-09-08 Carbios Process for degrading plastic products
US11377533B2 (en) 2016-05-19 2022-07-05 Carbios Process for degrading plastic products

Also Published As

Publication number Publication date
FI881965A0 (fi) 1988-04-27
FI881965L (fi) 1989-10-28
FI881965A7 (fi) 1989-10-28

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