WO2009095344A1 - Matériau dégradable - Google Patents

Matériau dégradable Download PDF

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Publication number
WO2009095344A1
WO2009095344A1 PCT/EP2009/050644 EP2009050644W WO2009095344A1 WO 2009095344 A1 WO2009095344 A1 WO 2009095344A1 EP 2009050644 W EP2009050644 W EP 2009050644W WO 2009095344 A1 WO2009095344 A1 WO 2009095344A1
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Prior art keywords
alkyl
tert
component
substituted
butyl
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PCT/EP2009/050644
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English (en)
Inventor
Stefano Gardi
Massimiliano Sala
Claudia Pasti
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Basf Se
Ciba S.P.A.
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Publication of WO2009095344A1 publication Critical patent/WO2009095344A1/fr

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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2410/00—Agriculture-related articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2555/00—Personal care
    • 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
    • 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
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the present invention relates to a composition having accelerated degradability triggered by light and/or heat and/or humidity and containing an organic polymer, e.g. a natural and/or a synthetic polymer, and a particular degradation accelerator; to an article made of said composition; to the use of the degradation accelerator for controlling the weathering resistance and the degradation of a polymer article; as well as to several novel degradation accelarators.
  • an organic polymer e.g. a natural and/or a synthetic polymer, and a particular degradation accelerator
  • Plastic articles find widespread applications in everyday life because of their durability in use and cost effectiveness. With proper stabilization, most commercial plastics are made to last for years.
  • biodegradable materials of diverse origin and nature, which will maintain their function and integrity during service life, but disintegrate after use into carbon dioxide and water, either triggered by chemical means or by microorganisms.
  • One problem however is establishing a suitable equilibrium between biodegradability and integrity during service life.
  • the present invention relates to a composition containing (a) an organic polymer,
  • (b-l) one, two or more compounds of the formula (I) — (X) (Y) — (I) wherein m and n independently are an integer from 2 to 10 x 10 6 , preferably 40 to 5 x 10 6 ; the recurring units X can have the same definition or different definitions, the recurring units Y can have the same definition or different definitions and the recurring units X and Y can have a random distribution or a block distribution or are alternating; X is a group of the formula (ll-1-a) or (ll-1-b) and
  • Y is a group of the formula (II-2);
  • Xi, X 2 , X3, X 4 and X 5 independently of one another are hydrogen, d-C 4 alkyl or phenyl;
  • a 1 and A 2 independently of one another are -O 1/r M r , -O N (Ri) 4 , -0-R 2 or -N(R 3 ) 2 , or A 1 and A 2 together form the radical -O- or the group -N-O-A 0 ;
  • a 3 and A 4 independently of one another are -O 1/r M r , -O N (Ri) 41 -O-R 2 Or -N(Ra) 2 , or A 3 and A 4 together form the radical -O- or the group -N-O-A 0 ;
  • M is a metal cation of valency r with r being 1 , 2, 3 or 4;
  • Ri, R 2 and R 3 independently of one another are hydrogen, Ci-C 20 alkyl, C 3 -Ci 2 cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl; C 5 -Ci 2 cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms; phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl; or C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C 4 alkyl;
  • a 0 is hydrogen, Ci-C 30 alkyl, C 2 -C 3o alkenyl, C 3 -Ci 2 cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl; C 5 -Ci 2 cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms, Cr-Cgphenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C 4 alkyl; diphenylmethyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC 4 alkyl; triphenylmethyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 C r C 4 alkyl; C 2 -C 3o acyl, -COOE 0 , -
  • E 0 , E 1 and E 2 independently of one another are hydrogen, CrCi 8 alkyl, C 3 -Ci 8 alkenyl, C 3 -Ci 2 cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 CrC 4 alkyl; phenyl which is unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl; or C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C 4 alkyl; Yi, Y 2 , Y3 and Y 4 independently of one another are hydrogen, d-C 4 alkyl or phenyl; and (b-ll) optionally one, two or more inorganic or organic salts of a transition metal.
  • all recurring units X are indentical
  • all recurring units Y are identical and the recurring units X and Y can have a random distribution or a block distribution or are alternating.
  • composition preferably contains component (b-ll).
  • composition preferably contains the component (b-ll).
  • a further embodiment of the present invention is a degradation accelerator mixture containing the components (b-l) and (b-ll) as defined above.
  • the weight ratio of components (b-l)/(b-ll) is preferably 10 000/1 to 1/50 000, more preferably 2 000/1 to 1 /5 000 or 1 /100 to 100/1 or 1 /20 to 20/1.
  • the compounds of the formula (I) can be prepared according to known methods, for example in analogy to the methods described in the present examples. Several compounds of the formula (I) are commercially available.
  • end groups which terminate the polymeric compounds of the formula (I) depend on the preparation; e.g. on the chain termination agents (capping agents) used during the polymerization process. They can also be modified after polymerization.
  • a suitable example of the end groups is hydrogen. - A -
  • alkyl having up to 30 carbon atoms examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethyl- butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3- methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5
  • alkenyl having up to 30 carbon atoms examples include allyl, 2-methallyl, butenyl, pentenyl, hexenyl and oleyl.
  • the carbon atom in position 1 is preferably saturated.
  • C ⁇ -Cisalkenyl is particularly preferred.
  • C 3 -Ci 2 cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and 2-methylcyclohexyl.
  • C 5 -C 6 cycloalkyl unsubstituted or substituted by methyl are preferred.
  • Ci-C 4 alkyl examples of C 5 -Ci 2 cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C 4 alkyl are cyclohexenyl and methylcyclohexenyl.
  • phenyl substituted by 1 , 2 or 3 CrC 4 alkyl are 4-methylphenyl, 2-ethylphenyl, A- ethylphenyl, 4-isopropylphenyl, 4-tert-butyl phenyl, 4-sec-butylphenyl, 4-isobutylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,4-dimethylphenyl, 2,6-diethylphenyl, 2-ethyl- 6-methylphenyl and 2,6-diisopropylphenyl.
  • diphenylmethyl substituted on the phenyl by 1 , 2 or 3 CrC 4 alkyl is di[methylphenyl]methyl.
  • triphenylmethyl substituted on the phenyl by 1 , 2 or 3 Ci-C 4 alkyl is tris[methylphenyl]methyl.
  • Ci-C 4 alkyl are benzyl, 2-phenylethyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl and tert- butylbenzyl.
  • Examples of acyl having up to 30 carbon atoms are C 2 -C 3 oalkanoyl, C 3 -C 30 alkenoyl and unsubstituted or substituted benzoyl.
  • C 2 -C 2 oalkanoyl, C 3 -C 2 oalkenoyl and substituted benzoyl are preferred.
  • Acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, acryloyl and crotonoyl are more specific examples.
  • Ci-C 30 sulfonyl is the group s E wherein E 3 is Ci-C 30 alkyl, o
  • Examples of a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms are:
  • M is preferably a cation selected from the group consisting of alkali metal cations, earth alkali metal cations and transition metal cations, in particular from the group consisting of the cations of Li, Na, K, Ca, Mg, Mn, Fe, Co, Ni, Cu, V, Zn and Ce.
  • X is preferably one of the following groups
  • the groups (11-1 -a-2) and (ll-i-b-3) are particularly preferred.
  • the ratio m/n is preferably 1/5000 to 100/50, more preferably 1/2500 to 80/50, in particular 1/1000 to 1/5 or 60/50 to 40/50.
  • Component (b-ll) is preferably a metal salt of a fatty acid with a carbon number ranging from C 2 to C 3 6, in particular from Ci 2 to C 3 6- Particularly preferred examples are metal carboxylates of palmitic acid (Ci 6 ), stearic acid (Ci 8 ), oleic acid (Ci 8 ), linoleic acid (Ci 8 ), linolenic acid (Ci 8 ) and naphthenic acid. Further examples of component (b-ll) are aromatic acids, e.g. benzoic acid. Component (b-ll) as C 2 -C 36 carboxylate, in particular stearate, palmitate or naphthenate, of Fe, Ce, Co, Cu, V, Mn or Ni is of particular interest.
  • a further preferred embodiment of the present invention relates to component (b-ll) as a Ci 2 -C 20 alkanoate of Mn, or a Ci 2 -C 20 alkenoate of Mn.
  • component (b-ll) as a Ci 2 -C 20 alkanoate of Mn, or a Ci 2 -C 20 alkenoate of Mn.
  • Mn-stearate is particularly preferred.
  • component (b-ll) contains two different metal salts, in particular with different metal cations, e.g. in a molar ratio of 1 :9 to 9:1.
  • component (b-ll) containing two different metal salts are the following mixtures:
  • component (b-ll) are manganese titanate, manganese borate * ), manganese potassium sulfate * ), manganese pyrophosphate * ), manganese sulfamate * ), manganese ferrite, manganese(ll) tetraborate, containing calcium carbonate, manganese dioxide, manganese sulfate * ), manganese nitrate * ), manganese chloride * ), and manganese phosphate * ).
  • the composition may additionally contain one, two or more conventional additives which are either commercially available or can be prepared according to known methods. Examples of said conventional additives are listed below.
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylunde
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hvdroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Benzylphosphonat.es for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl- ⁇ -tert-butyl ⁇ -hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxy
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanedi- ol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha ⁇ j-trioxabi
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl
  • 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(3'
  • azol-2-ylphenyl 2-[2'-hydroxy-3'-( ⁇ , ⁇ -dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)-phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-( ⁇ , ⁇ -dimethylbenzyl)-phenyl]ben- zotriazole.
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, neopentyl tetra( ⁇ -cyano- ⁇ , ⁇ -di- phenylacrylate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g.
  • Sterically hindered amines for example carbonic acid bis(1-undecyloxy-2, 2,6,6- tetramethyl-4-piperidyl)ester, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2, 2,6,6- tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1- octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) n- butyl-3,5-di-tert-butyl-4-hydroxybenzylmalon
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphos
  • Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba Specialty Chemicals Inc.), tris(no- nylphenyl) phosphite,
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N
  • Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ - dodecyl
  • Polvamide stabilizers for example copper salts in combination with iodides and/or phos- phorus compounds and salts of divalent manganese.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • Other additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • the conventional additive is for example present in the composition in an amount of 0.001 to 10% by weight, preferably 0.001 to 5% by weight, relative to the weight of the organic polymer (component(a)).
  • composition which contains in addition one, two or more of the following components:
  • component (b-l) which is different from component (b-l), (b-XII) an acrylate polymer or copolymer or an acrylate derivative polymer or copolymer, is preferred.
  • component (b-l) an acrylate polymer or copolymer or an acrylate derivative polymer or copolymer, is preferred.
  • Component (b-lll) covers e.g. calcium carbonate, silicas, glass fibres, glass bulbs, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour, flours of other natural products, synthetic fibers and metal stearates used as fillers such as calcium stearate or zinc stearate; unsaturated organic polymers such as polybutadiene, polyisoprene, polyoctenamer, or unsaturated acids such as stearic acid, oleic acid, linoleic acid or linolenic acid; and further polymers such as polyethylene oxide or polypropylene oxide.
  • unsaturated organic polymers such as polybutadiene, polyisoprene, polyoctenamer, or unsaturated acids such as stearic acid, oleic acid, linoleic acid or linolenic acid
  • further polymers such as polyethylene oxide or
  • Component (b-IV) is for example carbon black, titanium dioxide (anatase or rutile which may range in particle size from e.g. 1000 ⁇ m to 10 nm and which may optionally be surface treated) or another organic or inorganic colour pigment frequently used in agricultural applications (for example carbon black, brown, silver, red, green).
  • Component (b-V) is preferably a hindered amine light stabilizer (HALS) or an UV absorber.
  • HALS hindered amine light stabilizer
  • UV absorber examples of preferred hindered amine light stabilizers are also those compounds which are disclosed for example as components (A), (B) and (C) in WO-A-01/92,392 which is incorporated by reference herein and which is equivalent to U.S. Patent Application No. 10/257,339.
  • Component (b-VI) is for example an antislip/antiblock additive, a plasticizer (e.g. polyglycol), an optical brightener, an antistatic agent, a blowing agent or a process stabilizer.
  • Component (b-VII) is for example a phenolic antioxidant.
  • Component (b-VIII) is for example a metal stearate, e.g. calcium stearate or zinc stearate; or zinc oxide (which may range in particle size from e.g. 1000 ⁇ m to 10 nm and which may optionally be surface treated).
  • the polyterpene resins used as component (b-IX) may be of natural or synthetic origin. They are either commercially available or can be prepared according to known methods.
  • the polyterpene resins are for example based on acyclic terpenes or cyclic terpenes, e.g. monocyclic terpenes or bicyclic terpenes. Polyterpenes based on terpene hydrocarbons are preferred.
  • acyclic terpenes are terpene hydrocarbons, e.g. myrcene, ocimene and beta-farnesene; terpene alcohols, e.g. dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), geraniol (3,7-dimethyl-trans-2,6-octadien-1-ol), nerol (3,7-dimethyl-cis-2,6-octadien-1-ol), linalool (3,7-dimethyl-1 ,6-octadien-3-ol), myrcenol (2-methyl-6-methylene-7-octen-2-ol), lavandulol, citronellol (3,7-dimethyl-6-octen-1-ol), trans- trans-farnesol (3,7,1 1-trimethyl-2,6,10-dodecatrien-1-ol) and trans-
  • terpene aldehydes and acetals e.g. citral (3,7-dimethyl-2,6-octadien-1-al), citral diethyl acetal (3,7-dimethyl-2,6-octadien-1- aldiethyl acetal), citronellal (3,7-dimethyl-6-octen-1-al), citronellyloxyacetaldehyde and
  • terpene ketones e.g. tagetone, solanone and geranylacetone (6,10-dimethyl-5,9-undecadien-2-one); terpene acids and esters, e.g.
  • cyclic terpenes are cyclic terpene hydrocarbons, e.g. limonene (1 ,8-p-methadiene), alpha-terpinene, gamma-terpinene (1 ,4-p-menthadiene), terpinolene, alpha-phellandrene (1 ,5-p-menthadiene), beta-phellandrene, alpha-pinene (2- pinene), beta-pinene (2(10)-pinene), camphene, 3-carene, caryophyllene, (+)-valencene, thujopsene, alpha-cedrene, beta-cedrene and longifolene; cyclic terpene alcohols and ethers, e.g.
  • carvone (1 ,8-p-mantadien-6-one), alpha-ionone (Ci 3 H 2 oO), beta-ionone (Ci 3 H 2 oO), gamma- ionone (Ci 3 H 2 oO), irone (alpha-, beta-, gamma-) (Ci 4 H 22 O), n-methylionone (alpha-, beta-, gamma-) (Ci 4 H 22 O), isomethylionone (alpha-, beta-, gamma-) (Ci 4 H 22 O), allylionone (Ci 6 H 24 O), pseudoionone, n-methylpseudoionone, isomethylpseudoionone, damascones (1- (2,6,6-trimethylcycohexenyl)-2-buten-1-ones; including beta-damascenone (1 -(2,6,6- trimethyl-1 ,3-cyclohadienyl)-2
  • alpha-terpinyl acetate (1-p-menthen-8-yl acetate), nopyl acetate ((-)-2-(6,6- dimethylbicyclo[3.1.1]hept-2-en-2-yl)ethyl acetate) and khusymil acetate.
  • terpenes which can serve as the basis for the polyterpenes are tricyclene, alpha-pinene, alpha-fenchene, camphene, beta-pinene, myrcene, cis-pinane, cis/trans-p-8-menthene, trans-2-p-menthene, p-3-menthene, trans-p-menthane, 3-carene, cis-p-menthane, 1 ,4-cineole, 1 ,8-cineole, alpha-terpinene, p-1-menthene, p-4(8)-menthene, limonene, p-cymene, gamma-terpinene, p-3,8-menthadiene, p-2,4(8)-menthadiene and terpinolene.
  • component (b-IX) are cycloaliphatic compounds structurally related to terpenes such as the following alcohols, e.g. 5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-3-methylpentan-2-ol; aldehydes, e.g.
  • ketones 2,4-dimethyl-3-cyclohexene carboxaldehyde, 4-(4-methyl-3-penten-1 -yl)-3-cyclohexene carboxaldehyde and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene carboxaldehyde; ketones, e.g.
  • the polyterpenes used in the present invention may also be derived from the copolymerisation of the aforementioned terpenes with other unsaturated organic compounds.
  • component (b-IX) are the unsaturated coal-tar by-product polymers such as cumarone-indene resins, rosin and the like.
  • Present component (b-IX) is preferably a polyterpene resin selected from the group consisting of poly-alpha-pinene, poly-beta-pinene, polylimonene or a copolymer of alpha- pinene, a copolymer of beta-pinene or a copolymer of limonene.
  • Poly-beta-pinene is particularly preferred.
  • Terpene-based hydrocarbon resins are typically based on products such as alpha-pinene, beta-pinene and d-limonene, which are obtained from the wood and citrus industry, respectively. Terpene-based resins have been available since the mid-1930s (Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons, 4. ed. (1994), Vol. 13, p. 717- 718). Polymerization of monoterpenes is most commonly accomplished by carbocationic polymerization utilizing Friedel-Crafts-type catalyst systems, such as aluminum chloride
  • the polyterpenes of the present invention have more than one terpene unit. They have preferably a molecular weight of about 400 g/mol to about 1400 g/mol.
  • Component (b-X) is in particular an inorganic peroxide or an inorganic superoxide, in particular of an alkali metal or an alkaline earth metal, or of a transition metal.
  • Suitable examples of component (b-X) as a peroxide are magnesium peroxide (MgO 2 ), calcium peroxide (CaO 2 ), strontium peroxide (SrO 2 ), barium peroxide (BaO 2 ), lithium peroxide (Li 2 O 2 ), sodium peroxide (Na 2 O 2 ), potassium peroxide (K 2 O 2 ), zinc peroxide (ZnO 2 ), silver peroxide (Ag 2 O 2 ), copper peroxide or iron peroxide.
  • MgO 2 magnesium peroxide
  • CaO 2 calcium peroxide
  • BaO 2 barium peroxide
  • Li 2 O 2 lithium peroxide
  • Na 2 O 2 sodium peroxide
  • K 2 O 2 potassium peroxide
  • component (b-X) as a superoxide are lithium superoxide (LiO 2 ), sodium superoxide (NaO 2 ), potassium superoxide (KO 2 ), rubidium superoxide (RbO 2 ) and cesium superoxide (CsO 2 ).
  • LiO 2 lithium superoxide
  • NaO 2 sodium superoxide
  • K 2 potassium superoxide
  • RbO 2 rubidium superoxide
  • CsO 2 cesium superoxide
  • LiO 2 lithium superoxide
  • sodium peroxide magnesium peroxide
  • calcium peroxide barium peroxide
  • zinc peroxide and potassium superoxide Particularly preferred are sodium peroxide, magnesium peroxide, calcium peroxide and zinc peroxide.
  • a comprehensive summary of inorganic peroxides or superoxides, which are useful for the present invention, is given in Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons, 4. ed. (1994), Vol. 18, pages 202-229, which is incorporated by
  • Component (b-X) is preferably an inorganic peroxide of an alkali metal, an alkaline earth metal or a transition metal, or an inorganic superoxide of an alkali metal, an alkaline earth metal or a transition metal.
  • component (b-X) are magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide, lithium peroxide, sodium peroxide, potassium peroxide, zinc peroxide, silver peroxide, copper peroxide, iron peroxide, lithium superoxide, sodium superoxide, potassium superoxide, rubidium superoxide and cesium superoxide; in particular sodium peroxide, magnesium peroxide, calcium peroxide and zinc peroxide; especially calcium peroxide.
  • Component (b-X) is conveniently a compound which - when in contact with humidity - reacts with water in order to liberate an active auxiliary prodegradant species, and which is thermoprocessable in a temperature range between 100° and 300° C.
  • Component (b-XI) is for example the degradation accelerator disclosed in WO-A-07/028,731 which is incorporated by reference herein.
  • N-trityloxyphthalimide N-stearoyloxyphthalimide, N-p-toluene-4-sulfonyloxyphthalimide, N-2-(4- dodecylbenzoyl)benzoyloxyphthalimide, N-N'-dihydroxypyromellitic diimide, N, N'-bis[stearoyloxy]pyromellitic diimide, N-stearoyloxy-1 ,8-naphthalimide, N-octyloxy-4- carboxylic acid octyl ester, N-octadecyloxyphthalimide, 1 ,12-bis[4-carboxy-N- hydroxyphthalimide] dodecyl diester, 1 ,12-bis(4-carboxy-N-stearoyloxyphthalimide) dodecyl diester, 1 ,12-bis[4-carboxy-N-tosyloxyphthalimide] dode
  • Component (X-Il) is for example an acrylate polymer or copolymer or an acrylate derivative polymer or copolymer.
  • Such polymers or copolymers are e.g. disclosed as compound of the formula (I) in WO Patent Application No. EP2007/05,446 which is incorporated by reference herein.
  • Preferred examples are the metal salts of a compound selected from the group consisting of polyacrylic acid, Ci-C 4 alkyl acrylate/acrylic acid copolymer, polymethacrylate, Ci-C 4 alkyl methacrylate/methacrylic acid copolymer, acrylic acid/methacrylic acid copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/CrC 4 alkyl acrylate/acrylic acid copolymer and ethylene/Ci-C 4 alkyl methacrylate/methacrylic acid copolymer.
  • composition according to the present invention which contains as component (b-ll) Mn-stearate or Co-stearate and as component component (b-VIII) Ca-stearate.
  • component (a) examples are:
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
  • ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LD
  • Hydrocarbon resins for example C 5 -Cg
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block copo
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotac- tic, hemi-isotactic or atactic; where atactic polymers are preferred.
  • Stereoblock polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpoly
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 1 1 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytet
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones or lactides for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoates as well as copolyether esters derived from hydroxyl- terminated polyethers, and also polyesters modified with polycarbonates or MBS.
  • Copolyesters may comprise, for example - but are not limited to - polybutylensuccinate/terephtalate, polybutyleneadipate/terephthalate, polytetramethyleneadipate/terephthalate, polybutylensuccinate/adipate, polybutylensuccinate/carbonate, poly-3-hydroxybutyrate/octanoate copolymer, poly-3- hydroxybutyrate/hexanoate/decanoate terpolymer.
  • aliphatic polyesters may comprise, for example - but are not limited to - the class of poly(hydroxyalkanoates), in particular, poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylenesuccinate, polypropylenesuccinate, polybutylenesuccinate, polyhexamethylenesuccinate, polyethyleneadipate, polypropyleneadipate, polybutyleneadipate, polyhexamethyleneadipate, polyethyleneoxalate, polypropyleneoxalate, polybutyleneoxalate, polyhexamethyleneoxalate, polyethylenesebacate, polypropylenesebacate, polybutylenesebacate and polylactic acid (PLA) as well as corresponding polyesters modified with polycarbonates or MBS.
  • polylactic acid designates a homo-polymer of preferably poly-L-lactide and any of its blends or alloys with other polymers; a co-polymer of lactic acid or lactide with other monomers, such as hydroxy-carboxylic acids, like for example, glycolic acid, 3-hydroxy- butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 6- hydroxy-caproic acid and cyclic forms thereof; the terms "lactic acid” or "lactide” include L- lactic acid, D-lactic acid, mixtures and dimers thereof, i.e. L-lactide, D-lactide, meso-lacide and any mixtures thereof.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
  • Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acry- lates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/
  • Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • Aqueous emulsions of natural or synthetic rubber e.g. natural latex or latices of carbo- xylated styrene/butadiene copolymers.
  • Component (a) is preferably a thermoplastic natural or synthetic polymer.
  • Preferred examples are a) Homo and copolymers of olefin monomers such as ethylene and propylene, but also higher 1 -olefins such as 1-butene, 1-pentene, 1-hexene or 1-octen. Preferred is polyethylene LDPE and LLDPE, HDPE and polypropylene.
  • Copolymers of one ore more 1 -olefins and /or diolefins with carbon monoxide and/or with other vinyl monomers including, but not limited to, acrylic acid and its corresponding acrylic esters, methacrylic acid and its corresponding esters, vinyl acetate, vinyl ketone, styrene, maleic acid anhydride and vinyl chloride.
  • Polyvinyl alcohol e) Other thermoplastics such as poly(meth)acrylate esters, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinylbutyral, ethylene-vinyl alcohol copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), liquid crystal polyesters (LCPs), polyacetals (e.g., POM), polyamides (PA), polycarbonates, polyurethane and polyphenylene sulfide (PPS); polymer blends or polymer alloys formed of two or more of these resins; and compounds obtained by adding fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulose fibers and glass beads, flame retardants, blowing agents, antimicrobial agents, crosslink
  • thermosetting resins can include thermosetting resins such as epoxy resins, melamine resins and unsaturated polyester resins; and compounds obtained by incorporating fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulose fibers and glass beads, flame retardants and the like either singly or in combination to these resins.
  • thermosetting resins such as epoxy resins, melamine resins and unsaturated polyester resins
  • fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulose fibers and glass beads, flame retardants and the like either singly or in combination to these resins.
  • component (a) are polyethylensuccinate, polybutylensuccinate, polybutylensuccinate/adipate, polybutylensuccinate/carbonate, polybutylensuccinate/terephtalate, polycaprolactone, poly(hydroxyalcanoates), poly 3-hydroxybutyrate, polylactic acid, polyester amides, or blends of these materials with natural or modified starch, polysaccarides, lignin, wood flour, cellulose and chitin.
  • component (a) is a polyolefin homo- or copolymer, a starch modified polyolefin or a starch based polymer composite.
  • component (a) is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.
  • the components can be added to the organic polymer in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25 % by weight.
  • the present invention is especially useful in all areas where degradation in humid environments is desired.
  • the use of the present additive mixture can be tailored according to the climatic conditions of the place where an article made of the above described composition will be finally stored for degradation.
  • a further embodiment of the present invention relates to an article made of a composition as defined above.
  • a brief description of some exemplary articles made in accordance with the invention follows.
  • the articles are required to have a relatively long service life followed by a relatively short period during which embrittlement and fragmentation occurs, either in situ or in a landfill.
  • the articles may be film products comprising polyolefins or other organic polymers.
  • suitable agricultural articles are mulch films, small tunnel films, banana bags, direct covers, nonwoven, twines, clips, nettings, pipes, tubes and pots.
  • Mulch films represent a particular preferred embodiment of the present invention.
  • Mulch films are used to protect crops in the early stages of their development. Mulch films, depending on the type of crop and on the purpose, can be laid after the seeding or at the same time as the seeding. They protect the crop until the crop has reached a certain development stage. When the harvest is finished, the field is prepared for another cultivation.
  • Standard plastic films have to be collected and disposed in order to allow the new cultivation.
  • the additive systems of the present invention (components (b-l) and optionally (b-ll) to (b-XII)), when added to the standard plastic mulch films, allow the film to keep its properties until the crop has reached the required development, then degradation starts and the film is completely embrittled when the new cultivation has to be started.
  • the length of the service period and of the time to degradation and time to complete disappearance depends on the type of crop and on the environmental conditions. Depending on the specific time requirements, the additive combinations are designed.
  • the required service periods and time to degradation and disappearance can be obtained.
  • Examples of typical life times of mulch films are 10 to 180 days, lifes up to 24 months can also be required and achieved.
  • a further preferred embodiment of the present invention is a mulch film containing the the components (b-l) and optionally (b-ll) to (b-XII) as defined above and having a life time of 10 to 720 days.
  • Mulch films can be mono or multilayer (preferably three layers), transparent or appropriately pigmented (white, black, silver, green, brown) on the base of the agronomic needs.
  • the thickness of the mulch films can range, for example, between 5 to 100 microns. Films from 10 to 60 microns are preferred. Blown films are particularly preferred. The films may be partly burried with soil.
  • a particularly preferred embodiment of the present invention is a mulch film made of a composition containing (a) a polyethylene
  • (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO 2
  • (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite
  • (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film (a) linear low density polyethylene,
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film (a) linear low density polyethylene,
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film (a) linear low density polyethylene,
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film (a) linear low density polyethylene, (b-l) 0.1 to 1 %, in particular 0.4 %, of a compound of the formula
  • RTM Tinuvin 783
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film (a) linear low density polyethylene, (b-l) 0.1 to 5%, in particular 1.6 %, of a compound of the formula '
  • RTM Tinuvin 783
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film (a) linear low density polyethylene,
  • (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film (a) linear low density polyethylene,
  • Non-transparent 10 to 25 micron monolayer or three-layer blown film
  • the carbon black is preferably added in the form of a masterbatch, e.g. PLASBLAK PE 2642 MB 40% LD (RTM)).
  • Examples of further suitable articles are a packaging material, preferably for consumer products such as food, beverage or cosmetics; a hygienic article and a medical article.
  • articles according to the present invention are geotextiles, landfill covers, industrial covers, waste covers, temporary scaffolding sheets, building films, silt fences, films for building temporary shelter constructions, disposable diapers, disposable garments, and the like.
  • the article is a packaging material such as a supermarket bag or a refuse sack.
  • the article according to the present invention when used for the construction area, it may be for example a geomembrane, a geotextile, a geogrid or a scaffolding film.
  • the article may be selected from the group consisting of films, fibers, profiles, bottles, tanks, containers, sheets, bags, styrofoam cups, plates, blister packages, boxes, package wrappings and tapes.
  • the article can be shaped, for example, by injection-molding, blow-molding, compression- molding, roto-molding, slush-molding, extrusion, film casting, film blowing, calendering, thermoforming, spinning or rotational casting.
  • the article, made in accordance with the invention will keep its properties during use and will degrade after its service life.
  • a further embodiment of the present invention relates to a method for controlling the weathering resistance and the degradation of an organic polymer, which method comprises incorporating into the organic polymer the components (b-l) and optionally (b-ll) to (b-XII) as defined herein.
  • n and n independently are an integer from 2 to 10 x 10 6 , and the recurring units have a random distribution or a block distribution or the two monomer units are alternating.
  • Example 1 Synthesis of ethylene-N-hydroxymaleimide copolymer with alternating monomer units.
  • Example 2 Synthesis of the disodium salt of ethylene-maleic acid with alternating monomer units.
  • a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 10.0 g of polyethylene-alt- maleic anhydride (available from Aldrich (RTM); 188050), 6.3 g of NaOH and 150 ml of a 1 :1 tetrahydrofuran/HOCH 3 solution. Then, the reaction mixture is maintained at reflux temperature for 6 hours. The reaction is cooled at room temperature and the insoluble product is recovered by filtering off the solution and exsiccated in oven under reduced pressure. The desired product is obtained as white solid with a melting point higher than 300 0 C.
  • Example 3 Synthesis of the manganese salt of polyethylene graft maleic acid. with random distribution of the repeating units.
  • a four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 10.0 g of polyethylene-graft- maleic anhydride 3% (Aldrich (RTM); 456632) and 150 ml of tetrahydrofuran. Then, the mixture is heated to reflux temperature and, when it is completely homogeneous, 0.19 g of NaOH in 2 ml of water is dropped to the solution letting to react for 15 minutes. 0.3 g of manganese dichloride in 3 ml of water is dropped to the reaction mixture maintained under stirring at reflux temperature. After 1 hour, 100 ml of water are charged to the reaction at 40 0 C. The insoluble product is then isolated filtering off the solution and exsiccated in oven under reduced pressure. The desired product is obtained as white solid.
  • RTM polyethylene-graft- maleic anhydride 3%
  • n/m molar ratio 441
  • the above shown compound can be prepared by reactive extrusion in analogy to the method described in KR-A-2000/006,774 and is also commercially available as FUSABOND E MB226D (RTM).
  • the above shown compound can be prepared by reactive extrusion in analogy to the method described in KR-A-2000/006,774 and is also commercially available from Aldrich (RTM) under No. 456,632.
  • the mixture is extruded at a maximum temperature of 200 0 C using an O. M. C. twin-screw extruder (model ebv 19/25) to granules, which are subsequently diluted with the same LLDPE and optionally with 2 weight % of FUSABOND E MB226D (RTM) in order to obtain the final composition which is converted to a film 12 ⁇ m thick, using a blow-extruder (Dolci (RTM)) working at a maximum temperature of 210°C.
  • Table 1 illustrates the final composition of the LLDPE films.
  • Tables 2 to 5 illustrate the results of carbonyl increment or time to cracking.
  • Table 6 illustrates the final composition of the LLDPE films.
  • Tables 7 and 8 illustrate the results of carbonyl increment or time to cracking.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne une composition contenant: (a) un polymère organique; (b-1) un, deux ou plusieurs composés de formule de formule (I) dans laquelle m et n sont indépendamment un nombre entier entre 2 et 10 x 106; les unités de répétition X peuvent avoir la même définition ou des définitions différentes; les unités de répétition Y peuvent avoir la même définition ou des définitions différentes et les unités de répétition X et Y peuvent avoir une distribution aléatoire ou un distribution en bloc; X est un groupe de formule (11-1-a) ou (11-1-b) et Y est un groupe de formule (II-2)dans laquelle : X1, X2, X3, X4 et X5 indépendamment les uns des autres sont hydrogène, alkyle ou phényle C1-C4 ; A1 et A2 sont indépendamment l'un de l'autre -O-1/r Mr+, -O- N+(R1)4, -O-R2 ou -N(R3)2, ou A1 et A2 forment ensemble le radical -O- ou le groupe -N-O-A0; A3 et A4 sont indépendamment l'un de l'autre -O-1/r Mr+, -O- N+(R1)4, -O-R2 ou -N(R3)2, ou A3 et A4 forment ensemble le radical -O- ou le groupe -N-O-A0; M est un cation métallique de valence 1, 2, 3 ou 4; R1, R2 et R3 sont indépendamment les uns des autres hydrogène, alkyle C1-C20, cycloalkyle C3-C12 substitué ou non substitué par 1, 2, ou 3 alkyle C1-C4 ; cycloalcényle C5-C12 substitué ou non substitué par 1, 2, ou 3 alkyle C1-C4 ; un hydrocarbyle bicyclique ou tricyclique ayant 6 à 10 atomes de carbone; phényle substitué ou non substitué par 1, 2, ou 3 alkyle C1-C4 ; ou phénylalkyle C7-C9 substitué ou non substitué sur le phényle
PCT/EP2009/050644 2008-01-31 2009-01-21 Matériau dégradable WO2009095344A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104031313A (zh) * 2014-06-27 2014-09-10 柳州市汉森机械制造有限公司 塑料地膜
WO2019053187A1 (fr) * 2017-09-18 2019-03-21 Basf Se Mélange d'additifs

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999014287A1 (fr) * 1997-09-16 1999-03-25 International Paper Company Melange de polymeres renfermant un desoxygenant pour applications d'emballage de produits alimentaires
US20030207056A1 (en) * 2002-05-03 2003-11-06 Will Wood Sealing element for vessel or container closures having improved barrier properties

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999014287A1 (fr) * 1997-09-16 1999-03-25 International Paper Company Melange de polymeres renfermant un desoxygenant pour applications d'emballage de produits alimentaires
US20030207056A1 (en) * 2002-05-03 2003-11-06 Will Wood Sealing element for vessel or container closures having improved barrier properties

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104031313A (zh) * 2014-06-27 2014-09-10 柳州市汉森机械制造有限公司 塑料地膜
WO2019053187A1 (fr) * 2017-09-18 2019-03-21 Basf Se Mélange d'additifs

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