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WO2003050178A1 - Composition a base d'additifs facilitant la degradation de polymeres - Google Patents

Composition a base d'additifs facilitant la degradation de polymeres Download PDF

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Publication number
WO2003050178A1
WO2003050178A1 PCT/KR2002/002042 KR0202042W WO03050178A1 WO 2003050178 A1 WO2003050178 A1 WO 2003050178A1 KR 0202042 W KR0202042 W KR 0202042W WO 03050178 A1 WO03050178 A1 WO 03050178A1
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WO
WIPO (PCT)
Prior art keywords
weight
polymer
additive composition
acid
parts
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/KR2002/002042
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English (en)
Inventor
Yong-Il Roe
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.)
EL TECHNOLOGY Co Ltd
Original Assignee
EL TECHNOLOGY Co Ltd
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 EL TECHNOLOGY Co Ltd filed Critical EL TECHNOLOGY Co Ltd
Priority to AU2002366622A priority Critical patent/AU2002366622A1/en
Publication of WO2003050178A1 publication Critical patent/WO2003050178A1/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
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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

Definitions

  • the present invention relates to an additive composition, and more particularly, to an additive composition capable of promoting polymer degradation.
  • Plastic articles manufactured from stable or stabilized polymer such as polyethylene (PE), polypropylene (PP), and polystyrene (PS), are durable goods.
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • Degradable plastic articles can be manufactured mainly in two ways - by using biodegradable polymer or by adding degradation promoter into conventional thermoplastic polymer.
  • biodegradable polymer including starch modified for thermal plasticity as disclosed in U.S. Patent Nos. 5,462,982 and 5,314,934, is easily affected by water, so that their functionality is poor in contrast to conventional plastic polymers.
  • pro-oxidant is used as polymer degradation promoter(U.S. Patent Nos. 5,854,982 and 5,314,934).
  • the polymer degradation rate depends on oxygen content and the rate of oxygen permeating into the plastic polymer. Disclosure of the Invention
  • the preset invention provides an additive composition capable of accelerating polymer degradation when added to a polymer, while retaining the shelf-life and functionality of the polymer.
  • the present invention also provides a polymer composition containing the above additive composition, which makes polymer products manufactured therefrom degradable to be environmentally favorable while retaining the shelf-life and functionality of the polymers.
  • An additive composition for promoting polymer degradation comprises: 0.001-2.0 parts by weight of a transition metal salt containing an anionic component derived from C- 1 -C 9 organic acid, or C ⁇ 0 -C 30 substituted or unsubstituted saturated or unsaturated fatty acid; 0.1-3.0 parts by weight of at least one unsaturated organic compound selected from the group consisting of C 4 -C 22 unsaturated fatty acid, C 4 -C 22 unsaturated fatty acid ester, unsaturated natural polymer having a weight-average molecular weight of 10, 000-3, 000, 000D, and unsaturated synthetic polymer having a weight-average molecular weight of 2,500-2,000,000D; and 40-98 parts by weight of at least one polymer component selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylenepropylene, polyethylenestyrene, polypropylenestyrene, and polyethylenepropylenestyrene.
  • Suitable polymer components for an additive composition according to the present invention may comprise 20-49 parts by weight of a homopolymer and 20-49 parts by weight of a copolymer.
  • a suitable transition metal for a transition metal salt is derived from, but is not limited to, cobalt, manganese, copper, vanadium, and iron.
  • Suitable C 1 -C 9 organic acid for the anionic component of such a transition metal salt includes, but is not limited to, acetic acid, citric acid, and tartaric acid.
  • 0 -C 3 o substituted or unsubstituted saturated or unsaturated fatty acid for the anionic component of such a transition metal salt includes, but is not limited to, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, and 12-hydroxystearic acid.
  • the transition metal salt in the additive composition according to the present invention promotes oxidation and photolysis of polymers.
  • a Fe-based salt known for its powerful photodegradation promoting effect is preferred for non-recyclable polymer products, whereas a Mg-based salt capable of effectively accelerating thermo-oxidation under non-solar irradiation conditions is preferred for plastic products that are recyclable, for example, as barnyard manure.
  • the unsaturated organic compound in the additive composition according to the present invention mainly acts to accelerate thermal decomposition of polymer.
  • unsaturated natural polymer such as unsaturated fatty acid, unsaturated fatty acid ester, and isoprene polymer
  • unsaturated synthetic polymer which are used in the present invention contains highly available unsaturated sites.
  • Optimal unsaturated organic compound for the additive composition according to the present invention is selected in consideration of various factors, for example, cost, functionality, and odor.
  • Suitable unsaturated natural polymer for the unsaturated organic compound of the additive composition has a weight-average molecular weight of, preferably, 10,000-1 , 000, 000D, and more preferably, 10,000-500,0000.
  • Suitable unsaturated synthetic polymer for the unsaturated organic compound of the additive composition has a weight-average molecular weight of, preferably, 2,500-1 ,000,000D, and more preferably, of 2,500-500, 000D.
  • the additive composition according to the present invention may further comprise 50 parts or less by weight of a biodegradable polymer. Examples of such a biodegradable polymer include natural polymers and synthetic polymers.
  • natural polymers include animal origin proteins, such as casein and its salts, and gelatin, plant origin proteins, such as soy proteins, starch and its derivatives, cellulose and its derivatives, lignocellulose, chitosan, and the like.
  • starch examples include any processed, chemically modified, or natural starch, including wheat starch, corn starch, potato starch, rice starch, and plant origin starches, for example, derived from cassaba, tapioca, and pea.
  • Examples of chemically or cross-linked modified starches include esterified starches with 1-3 organic acid substitutes for hydroxy groups and etherified starches with 1-3 organic alcohol substitutes for hydroxy groups.
  • Examples of cellulose and derivatives thereof include wood flours, wood fiber derived from plants, such as grasses and grains, and chemically modified cellulose, such as esterified cellulose with 1-3 organic acid substitutes for hydroxy groups and etherified cellulose with 1-3 organic alcohol substitutes for hydroxy groups.
  • Examples of synthetic biodegradable polymer for the additive composition according to the present invention include: an aliphatic polyester produced by condensation and polymerization of a compound of formula HO-A-OH and a compound of formula HOOC-B-COOH; an aliphatic polyester produced by ring opening and polymerization of C 2 -C 20 caprolactons; an aliphatic polyester produced by self condensation and polymerization of compounds of formula HOOC-D-OH; and an aliphatic/aromatic polyester produced by condensation and polymerization of a compound of formula HO-E-OH and a compound of formula HOOC-G-COOH, wherein A, B, D, and E in the above formulae are C 2 -C 20 alkylene, and G is C 6 -C 2 o arylene or alkylarylene.
  • biodegradable polymer into the additive composition according to the present invention helps oxygen delivery to polymers to be degraded and accelerates oxidation of the polymer.
  • the amount of biodegradable polymer is determined so as not to adversely affect the functionality of the letdown polymers of products.
  • the additive composition according to the present invention may further comprise a desiccant in an amount of 5 parts or less by weight.
  • a desiccant examples include calcium oxide, magnesium perchlorate, phosphorous pentoxide, and the like.
  • the additive composition according to the present invention may further comprise a filler in an amount of no greater than 5 parts by weight.
  • the addition of fillers accelerates oxygen delivery to polymers to be degraded and thus oxidation of the polymer. Suitable fillers include any material that is inert and does not melt at the processing temperature of polymers, for example, calcium carbonate, mica, silica, alumina, and the like.
  • a polymer composition according to the present invention comprises: 3-50 parts by weight of an additive composition according to the present invention; and 50-97 parts by weight of a letdown polymer, wherein the letdown polymer is at least one selected from the group consisting of polyethyelenes, polypropylenes, polystyrenes, polyethylenepropylenes, polyethylenestyrenes, polypropylenestyrenes, and polyethylenepropylenestyrenes.
  • composition of the polymer composition according to the present invention may be appropriately varied according to the kind of the final plastic product and the thickness thereof.
  • the amount of inert and insoluble filler is limited.
  • relatively thick plastic products for example, of a thickness of 30 microns or greater, produced by injection molding, it is preferable to appropriately adjust the ratio of the filler particles and the letdown polymer.
  • a polymer composition according to the present invention may further comprise an antioxidant for needed shelf-life and biodegradability.
  • Suitable examples of such an antioxidant include ketone-amine antioxidant, aldehyde-amine antioxidant, phenylnaphthylamine antioxidant, phenylnaphthylamine antioxidants, substituted diphenylamine antioxidant, paraphenylene-diamine derivative antioxidant, substituted phenol antioxidant, phenylalkane antioxidant, phenylsulfide antioxidant, phosphite antioxidant, and the like. These antioxidants may be mixed with the letdown polymer.
  • the polymer compositions according to the present invention can be used for degradable plastic products with the original functionality and performance of the conventional polymer products.
  • Example 1 Preparation of an additive composition(l) as a degradation promoter 0.04 parts by weight of magnesium stearate, 1.2 parts by weight of polyisoprene, 2.0 parts by weight of starch, 0.4 parts by weight of calcium oxide, and 96.36 parts by weight of straight-chain low density polyethylene containing 200 ppm of Irganox 1010 ® and 600 ppm of Irgafos 168 ® were mixed at 160°C to provide an additive composition.
  • an additive composition(l) as a degradation promoter 0.04 parts by weight of magnesium stearate, 1.2 parts by weight of polyisoprene, 2.0 parts by weight of starch, 0.4 parts by weight of calcium oxide, and 96.36 parts by weight of straight-chain low density polyethylene containing 200 ppm of Irganox 1010 ® and 600 ppm of Irgafos 168 ® were mixed at 160°C to provide an additive composition.
  • Example 2 Preparation of an additive composition ⁇ ) as a degradation promoter
  • an additive composition for use as a degradation promoter was prepared with the following composition:
  • degradable polymer compositions containing the degradation promoting additive compositions of Examples 1 were prepared, and a degradation test was conducted using these degradable polymer compositions.
  • Example 1 The additive composition of Example 1 was added into low density polyethylene (LDPE) in an amount of 10% by weight and 20% by weight, and two sheets of transparent films were manufactured from the mixtures. The thickness of each transparent film was about 30 m. The resulting transparent polymer films were sent to the SP Swedish National Testing and Research Institute for degradation testing.
  • LDPE low density polyethylene
  • thermo-oxidative degradations were evaluated for the polymer films.
  • the degradation rate of polymers may vary depending on the kinds and amounts of polymer and additives, processing temperature, and amount of oxygen.
  • the main object of this degradation testing was to find out the relationship between processing (degradation) temperature and time and amount of oxygen, which is considered to be important to produce degradable low-molecular weight oxides.
  • Thermo-oxidative degradations were carried out at 50°C, 60°C, and 70°C, which belong to a general range of polymer decomposition temperatures.
  • amount of oxygen supplied during the test was varied using air and an oxygen/nitrogen mixture(air, 10w% oxygen, 20% oxygen) were optionally added.
  • the effect of thermo-oxidative degradation was verified by measuring changes in molecular weight by means of size exclusive chromatography (SEC).
  • Tables 3 and 4 show changes in weight-average molecular weight and number-average molecular weight, respectively, for polymer compositions containing 20% by weight of the additive composition of Example 1.
  • amount of degradation promoting additive composition is found to be another influential factor on polymer degradation.
  • the molecular weights after degradation were about 30-50% smaller than when 10% by weight of the degradation promoting additive composition was used.
  • Oxygen content seems to be less influential on polymer degradation. There was no significant difference in the molecular weight after degradation with different amounts of oxygen, between the film containing 10% by weight of the additive composition and the film containing 20 % by weight of the same.
  • the degradation promoting additive composition of Example 1 was added into LDPE in an amount of 10% by weight and 20% by weight, and two sheets of biodegradable polymer foils of a weight of about 25g each were manufactured from the two polymer compositions. These biodegradable polymer foils were left in an oven at 70°C for 4 weeks for pre-aging. The resulting pre-aged polymer foils were mixed with microbial activated soil, which contained very low amounts of easily degradable carbon sources. Each of the mixtures was filled in a glass column and incubated at 60°C. Soil microorganisms produced new biomass by degrading the organic compounds (polymer samples). During the incubation, the soil columns were continuously aerated with oxygen.
  • the amount of carbon dioxide produced during the incubation was measured to investigate the degree of polymer degradation (into inorganic materials) in soil samples.
  • Carbon dioxide produced by the soil microorganisms and release from the glass column was trapped in sodium hydroxide solutions to convert it into sodium carbonate.
  • An aliquot of the sodium hydroxide solution was collected at regular intervals and analyzed by titration to measure carbonic acid content.
  • the initial carbon content of the test composition (polymer foil) was measured before the mineralization test, and a theoretical content of carbon dioxide that can be produced from the carbon source of the test composition was calculated based on the initial carbon content measured before the mineralization test.
  • a degree of mineralization (degradation into inorganic materials) of the test composition was measured as the ratio of carbon dioxide content between the experimental and theoretical values.
  • the mineralization test for measuring the degradability of test samples was conducted for 9 weeks. The results are shown in Tables 5 and 6 below.
  • *2 %CO 2 production corrected values under the assumption that glucose is completely degraded to CO 2 and biomass.
  • Polymer compositions according to the present invention were prepared in the same manner as in Examples 3 and 4, with the exception that polyethylene, polypropylene, polystyrene, polyethylenepropylene, polyethylenestyrene, polypropylenestyrene, and polyethylenepropylenestyrene, instead of LDPE, were used as the letdown polymer of the polymer compositions. The results were similar to those from Examples 3 and 4.
  • additive compositions capable of promoting polymer degradation and polymer compositions containing the same according to the present invention in manufacturing polymer products makes the polymer products degradable to be environmentally favorable while appropriately retaining the shelf-life and functionality of the constituent polymers.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

Cette invention, qui a trait à une composition à base d'additifs facilitant la dégradation de polymères, concerne également une composition polymère contenant cette composition à base d'additifs. Cette composition contient, de 0,001 à 2,0 parties en poids d'un sel de métal de transition renfermant un composant anionique dérivé d'un acide organique porteur de 1 à 9 atomes de carbone, ou d'un acide gras saturé ou insaturé, substitué ou non, porteur de 10 à 30 atomes de carbone, de 0,1 à 3,0 parties en poids d'au moins un composé organique insaturé choisi dans le groupe constitué par un acide gras insaturé porteur de 4 à 22 atomes de carbone, un ester d'acide gras insaturé porteur de 4à 22 atomes de carbone, un polymère naturel insaturé dont le poids moléculaire moyen en poids est compris entre 10,000 et 3,000 000 D et par un polymère synthétique insaturé dont le poids moléculaire moyen en poids est compris entre 2,500 et 2,000 000 D, ainsi que de 40 à 98 parties en poids d'au moins un composant polymère, choisi dans le groupe constitué par un polyéthylène, un polypropylène, un polystyrène, un polyéthylènepropylène, un polyéthylènestyrène, un polypropylènestyrène ainsi que par un polyéthylènepropylènestyrène.
PCT/KR2002/002042 2001-11-03 2002-11-02 Composition a base d'additifs facilitant la degradation de polymeres Ceased WO2003050178A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002366622A AU2002366622A1 (en) 2001-11-03 2002-11-02 Additive composition for promoting polymer degradation

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KR2001/68377 2001-11-03
KR1020010068377A KR100346998B1 (ko) 2001-11-03 2001-11-03 폴리머의 분해를 촉진시키기 위한 첨가제 조성물

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006009502A1 (fr) * 2004-07-19 2006-01-26 Add-X Biotech Ab Conditionnements
WO2007027163A3 (fr) * 2005-09-01 2008-11-13 Super Film Ambalaj Sanayi Ve T Film en polypropylène biorienté dégradable et/ou biodégradable
WO2012125101A1 (fr) * 2011-03-14 2012-09-20 Esp Solutions Ltd. Emballage constitué d'un polymère comprenant une matière de remplissage pro-oxydante
US20130067637A1 (en) * 2011-09-15 2013-03-21 Inteplast Group, Ltd. Disposable gloves and glove material compositions including a coloring agent
CN110234699A (zh) * 2016-11-22 2019-09-13 聚合材料有限公司 可降解聚合物组合物及其生产方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100939544B1 (ko) * 2009-06-30 2010-02-03 유종철 보온성과 분해성이 뛰어난 일회용품용 합성수지 조성물
KR101039877B1 (ko) * 2011-02-17 2011-06-09 동아화학 주식회사 오산화인을 이용한 폴리우레탄 생분해성 플라스틱

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935141A (en) * 1971-09-27 1976-01-27 Union Carbide Corporation Environmentally degradable ethylene polymeric compositions
US5212219A (en) * 1987-05-21 1993-05-18 Epron Industries Limited Degradable plastics
US5308897A (en) * 1993-01-14 1994-05-03 Industrial Technology Research Institute Degradable plastics

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935141A (en) * 1971-09-27 1976-01-27 Union Carbide Corporation Environmentally degradable ethylene polymeric compositions
US5212219A (en) * 1987-05-21 1993-05-18 Epron Industries Limited Degradable plastics
US5308897A (en) * 1993-01-14 1994-05-03 Industrial Technology Research Institute Degradable plastics

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006009502A1 (fr) * 2004-07-19 2006-01-26 Add-X Biotech Ab Conditionnements
US7767283B2 (en) 2004-07-19 2010-08-03 Add-X Biotech Ab Packages
WO2007027163A3 (fr) * 2005-09-01 2008-11-13 Super Film Ambalaj Sanayi Ve T Film en polypropylène biorienté dégradable et/ou biodégradable
WO2012125101A1 (fr) * 2011-03-14 2012-09-20 Esp Solutions Ltd. Emballage constitué d'un polymère comprenant une matière de remplissage pro-oxydante
US20130067637A1 (en) * 2011-09-15 2013-03-21 Inteplast Group, Ltd. Disposable gloves and glove material compositions including a coloring agent
US9131737B2 (en) * 2011-09-15 2015-09-15 Inteplast Group, Ltd. Disposable gloves and glove material compositions including a coloring agent
CN110234699A (zh) * 2016-11-22 2019-09-13 聚合材料有限公司 可降解聚合物组合物及其生产方法
US11155702B2 (en) * 2016-11-22 2021-10-26 Polymateria Limited Degradable polymer and method of production

Also Published As

Publication number Publication date
KR20010113577A (ko) 2001-12-28
AU2002366622A1 (en) 2003-06-23
KR100346998B1 (ko) 2002-07-31

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