WO2002042368A2 - Procede pour stabiliser des polyolefines - Google Patents

Procede pour stabiliser des polyolefines Download PDF

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Publication number
WO2002042368A2
WO2002042368A2 PCT/EP2001/013596 EP0113596W WO0242368A2 WO 2002042368 A2 WO2002042368 A2 WO 2002042368A2 EP 0113596 W EP0113596 W EP 0113596W WO 0242368 A2 WO0242368 A2 WO 0242368A2
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tert
compounds
butyl
cιo
polyolefins
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PCT/EP2001/013596
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German (de)
English (en)
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WO2002042368A3 (fr
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Sylke Haremza
Manfred Appel
Hubert Trauth
Erik Hofmann
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Basf Aktiengesellschaft
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Priority to AU2002219136A priority Critical patent/AU2002219136A1/en
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Publication of WO2002042368A3 publication Critical patent/WO2002042368A3/fr

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    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds

Definitions

  • the invention relates to a process for the preparation of polyolefins which are exposed to the action of water and which are stabilized against visible and ultraviolet light, in which light stabilizers are added to the polyolefin.
  • the invention further relates to methods for reducing the yellowing of polyolefins stabilized against visible and ultraviolet light, which are exposed to the action of water.
  • the invention when exposed to water, relates to yellowing-resistant polyolefins which are stabilized against visible and ultraviolet light, and to moldings, foils and foams made from these polyolefins.
  • the invention relates to the use of light stabilizers in polyolefins which are exposed to the action of water.
  • Polyolefins especially the homo- and copolymers of ethylene and propylene, are usually used against visible and
  • UV traviolette
  • Polyolefins that contain light stabilizers and are exposed to water usually show increasing yellowing over time: initially opaque, white or
  • Polyolefins are exposed to water in numerous applications, e.g. for pipes for drinking water and waste water, fittings for drinking and waste water
  • packaging and foils in particular packaging for cosmetics (e.g. shampoo, creams, other water-containing cosmetic products) and packaging and foils for food (e.g. fruit, vegetables, meat and other water-containing foods), for drinking water bottles, in the entire outdoor area, e.g. Kleinmö-
  • cosmetics e.g. shampoo, creams, other water-containing cosmetic products
  • food e.g. fruit, vegetables, meat and other water-containing foods
  • the task was to remedy the disadvantages described.
  • the object was to provide a process with which light-stabilized polyolefins can be obtained which, under the action of water, yellow considerably less than the light-stabilized polyolefins of the prior art.
  • the process defined at the outset for the production of polyolefins was found. It is characterized in that the light stabilizers are selected from the following compounds a) to d)
  • R 1 and R ⁇ 1 are hydrogen, -CC o-alkyl, C -Coo "alkenyl, C 3 -C ⁇ o-cycloalkenyl, C ⁇ -C ⁇ alkoxy, aryl, hetero-aryl, optionally substituted,
  • X is ethyl, 2-ethylhexyl, pentaerythrityl, propane-1,2,3-triyl, polyalkylene glycol radical, n is an integer from 0 to 3, m is an integer from 1 to 4,
  • R 1 and R 2 are hydrogen, -CC o ⁇ alkyl, C -C -o alkenyl, C 3 -C ⁇ 0 - cycloalkyl, C 3 -C ⁇ o _ cycloalkenyl, C ⁇ ⁇ C ⁇ -alkoxy, C ⁇ -C o-alkoxycarbonyl, C ⁇ - C ⁇ alkylamino,
  • R 3 is hydrogen, COOR 5 , COR 5 , CONR 5 R 6 , CN,
  • R 5 to R 8 are hydrogen, -CC 20 alkyl, C 2 -C 10 alkenyl,
  • Y is hydrogen, COOR 1 or OH
  • A is hydrogen or S0 3 H
  • R 1 , R 11 and n have the meaning given in a).
  • the process defined at the outset for reducing yellowing was also found. It is characterized in that the light stabilizers used are selected from the compounds as defined above under a) to d).
  • the invention relates to the polyolefins defined at the outset, containing as light stabilizers at least one of the compounds a) to d) as defined above, and to moldings, films and foams made from these polyolefins.
  • the invention relates to the use of light stabilizers mentioned at the outset, these being selected from the compounds a) to d) as defined above.
  • Water includes all types of water, especially drinking water, domestic and commercial waste water, distilled, deionized and demineralized water, rainwater, groundwater, Surface water (rivers, lakes), sea water, spring water as well as mineral and medicinal water.
  • All polymers of olefins are suitable as polyolefins, in particular polymers of ethylene, propylene, but-l-ene, isobutylene and 4-methylpentene.
  • Polymers are understood to mean both homopolymers and copolymers of one of the monomers mentioned as the main monomer and other monomers as comonomers.
  • Preferred polyolefins are the homopolymers and copolymers of ethylene and the homopolymers and copolymers of propylene.
  • Suitable polyethylene (PE) homopolymers include:
  • PE-LD low density
  • LD low density
  • oxygen or peroxides as catalysts in autoclaves or tubular reactors.
  • PE-LLD linear low density
  • metal complex catalysts in the low pressure process from the gas phase, from a solution (e.g. petrol), in a suspension or with a modified high pressure process.
  • a solution e.g. petrol
  • PE-HD high density
  • HD medium pressure
  • Ziegler low pressure
  • Phillips 85 to 180 ° C
  • chromium oxide as a catalyst
  • molar masses about 50,000 g / mol.
  • Ziegler at 1 to 50 bar, 20 to 150 ° C
  • titanium halides, titanium esters or aluminum alkyls as catalysts, molar mass about 200,000 to 400,000 g / mol. Carried out in suspension, solution, gas phase or mass. Very weakly branched, crystallinity 60 to 80%, density 0.942 to 0.965 g / cm 3 .
  • PE-HD-HMW high molecular weight
  • HMW high molecular weight
  • Phillips or gas phase method High density and high molecular weight
  • PE-HD-UHMW ultra high molecular weight
  • Polyethylene which is produced in a gas phase fluidized bed process using (usually supported) catalysts, e.g. Lupolen® (Elenac).
  • Polyethylene which is produced using metallocene catalysts, is particularly preferred.
  • polyethylene is e.g. commercially available as Luflexen (Elenac).
  • Luflexen Elenac
  • the metal ozone catalyst system is described in more detail below.
  • R 8 to R 12 are hydrogen, Ci- to Cio-alkyl, 5- to 7-membered
  • Cycloalkyl which in turn can carry a C 1 -C 10 -alkyl as a substituent, C 6 - to cis-aryl or aryl-alkyl, where optionally two adjacent radicals together can represent cyclic groups having 4 to 15 C atoms or Si ( R 13 ) 3 with
  • R 13 is Ci- to Cio-alkyl, C 3 - to -CC 0 cycloalkyl or C 6 - to cis-aryl,
  • R 14 to R 18 hydrogen, C ⁇ ⁇ to Cio-alkyl, 5- to 7-membered
  • Cycloalkyl which in turn can carry a C 1 -C 10 -alkyl group as a substituent, is C 6 - to Cis-aryl or arylalkyl, and where appropriate two adjacent radicals together can also represent cyclic groups having 4 to 15 C atoms , or Si (R 19 ) 3 with
  • R 19 Ci to Cio alkyl, C 6 to C 5 aryl or C 3 to Cio cycloalkyl,
  • R 21 , R 22 and R 23 are the same or different and a hydrogen atom, a halogen atom, a C ⁇ -C ⁇ o-alkyl group, a C ⁇ -C ⁇ o-fluoroalkyl group, a C 6 -C ⁇ o-fluoroaryl group, a C ß -Cio aryl group, a C ⁇ -C ⁇ o ⁇ alkoxy group, a
  • a 0, - S, .NR 24 or PR 24 mean with
  • R 24 Ci- to Cio-alkyl, C 6 - to C 15 -aryl, C 3 - to C ⁇ 0 -cycloalkyl, alkylaryl or Si (R 25) 3,
  • R 25 is hydrogen, -C ⁇ to Cio-alkyl, C 6 - to cis-aryl, which in turn can be substituted with Ci- to C 4 -alkyl groups or C 3 - to Cio-cycloalkyl
  • metallocene complexes are, for example, in the
  • Such complex compounds can be synthesized according to methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred.
  • the metallocene complexes are activated by an
  • Suitable activators are in particular
  • Suitable metallocenium ion-forming compounds are in particular complex compounds selected from the group consisting of strong, neutral Lewis acids, the ionic compounds with Lewis acid cations and the ionic compounds with Bronsted acids as the cation.
  • M 4 is an element of III.
  • Main group of the periodic table means, in particular B, Al or Ga,
  • Ci- to Cio-alkyl for hydrogen, Ci- to Cio-alkyl, CQ- to Cis-aryl, alkyl-aryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms are in the aryl radical or fluorine, chlorine, bromine or iodine, in particular for haloaryls, preferably for pentafluorophenyl.
  • a stands for integers from 1 to 6
  • z stands for integers from 0 to 5 d corresponds to the difference a-z, whereby d is greater than or equal to 1.
  • Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable.
  • the triphenylmethyl cation, the silver cation and the 1, 1 '-dimethylferrocenyl cation should be mentioned in particular. They preferably have non-coordinating counterions, in particular boron compounds, as also mentioned in WO-A 91/09882, preferably tetrakis (pentafluorophenyl) borate. Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO-A 91/09882, the preferred cation is N, N-dimethylanilinium.
  • ethylene copolymers are suitable as ethylene copolymers, for example Luflexen® types (Elenac), Nordel® and Engage® (Dow, DuPont).
  • Suitable comonomers are all -olefins having 3 to 10 carbon atoms, in particular propylene, but-1-ene, hex-1-ene and oct-1-ene, and also alkyl acrylates and methacrylates with 1 to 20 carbon atoms in the alkyl radical , especially butyl acrylate.
  • Other suitable comonomers are dienes such as Butadiene, isoprene and octadiene and dicyclopentadiene.
  • They are usually statistical copolymers or block or impact copolymers.
  • Block or impact copolymers of ethylene and comonomers are polymers in which, in the first stage, a homopolymer of the comonomer or a random copolymer of the comonomer is prepared with up to 15% by weight, preferably up to 6% by weight, of ethylene and then in in the second stage, a comonomer-ethylene copolymer with ethylene contents of 15 to 80% by weight was polymerized.
  • so much of the comonomer-ethylene copolymer is polymerized in that the copolymer produced in the second stage has a proportion of 3 to 60% by weight in the end product.
  • the polymerization for producing the ethylene-comonomer copolymers can be carried out using a Ziegler-Natta catalyst system.
  • catalyst systems are used which, in addition to a titanium-containing solid component, also have cocatalysts in the form of organic aluminum compounds and electron donor compounds.
  • catalyst systems based on metal ocene compounds or based on polymerization-active metal complexes can also be used.
  • Copolymers of propylene also contain minor amounts
  • Propylene copolymerizable monomers for example C 2 -C 8 alk-1-enes such as, inter alia, ethylene, but-1-ene, pent-1-ene or
  • Suitable polypropylenes include homopolymers of propylene or copolymers of propylene with up to 50% by weight of other alk-1-enes polymerized in with up to 8 carbon atoms.
  • the copolymers of propylene are statistical copolymers or block or impact copolymers. If the copolymers of propylene have a random structure, they generally contain up to 15% by weight, preferably up to 6% by weight, other alk-1-enes with up to 8 C atoms, in particular ethylene, but-1 -en or a mixture of ethylene and but-l-ene.
  • Block or impact copolymers of propylene are polymers in which, in the first stage, a propylene homopolymer or a random copolymer of propylene with up to 15% by weight, preferably up to 6% by weight, of other alk-1-enes with up to produces to 8 carbon atoms and then in the second stage a propylene-ethylene copolymer with ethylene contents of 15 to 80 wt .-%, the propylene-ethylene copolymer additionally other C 4 -C 8 -alk-1-ene may contain, polymerized. As a rule, so much of the propylene-ethylene copolymer is polymerized in that the copolymer produced in the second stage has a proportion of 3 to 60% by weight in the end product.
  • the polymerization for the production of polypropylene can be carried out using a Ziegler-Natta catalyst system.
  • catalyst systems are used which, in addition to a titanium-containing solid component a), also have cocatalysts in the form of organic aluminum compounds b) and electron donor compounds c).
  • catalyst systems based on metal ocene compounds or based on polymerization-active metal complexes can also be used.
  • conventional Ziegler-Natta catalyst systems contain a titanium-containing solid component a), i.a. Halides or alcohols of trivalent or tetravalent titanium, also a halogen-containing magnesium compound, inorganic oxides such as silica gel as a carrier and electron donor compounds c).
  • a titanium-containing solid component a i.a. Halides or alcohols of trivalent or tetravalent titanium, also a halogen-containing magnesium compound, inorganic oxides such as silica gel as a carrier and electron donor compounds c).
  • carboxylic acid derivatives and ketones, ethers, alcohols or organosilicon compounds are suitable as such.
  • the titanium-containing solid component can be prepared by methods known per se. Examples include EP-A 45 975, EP-A 45 977, EP-A 86 473, EP-A 171 200, GB-A 2 111 066, US-A 4 857 613 and US Pat US-A 5 288 824 described. The method known from DE-A 195 29 240 is preferably used.
  • suitable aluminum compounds b) are also those compounds in which an alkyl group has been replaced by an alkoxy group or by a halogen atom, for example by chlorine or bromine.
  • the alkyl groups can be the same or different. Linear or branched alkyl groups are possible.
  • Trialkylaluminum compounds are preferably used, the alkyl groups of which each have 1 to 8 carbon atoms, for example trimethylaluminum, triethylaluminium, tri-isobutylaluminum, trioctylaluminum or methyldiethylaluminum or mixtures thereof.
  • electron donor compounds c) such as mono- or polyfunctional carboxylic acids, carboxylic anhydrides or carboxylic acid esters, furthermore ketones, ethers, alcohols, lactones, and organophosphorus and organosilicon compounds are generally used as further cocatalyst, the electron donor compounds c) being identical or can be different from the electron donor compounds used to produce the titanium-containing solid component a).
  • metallocene compounds or polymerization-active metal complexes can also be used for the production of polypropylene.
  • Metallocenes are to be understood here as meaning complex compounds of metals from subgroups of the periodic table with organic ligands, which together with compounds forming metallocenium ions result in effective catalyst systems.
  • the metallocene complexes are generally supported in the catalyst system for use in the production of polypropylene.
  • Inorganic oxides are frequently used as carriers, but organic carriers in the form of polymers, for example polyolefins, can also be used. Preference is given to the inorganic oxides described above, which are also used to prepare the titanium-containing solid component a).
  • metallocenes typically contain titanium, zirconium or hafnium as central atoms, zirconium being preferred.
  • the central atom is bonded via a ⁇ bond to at least one, usually substituted, cyclopentadienyl group and to further substituents.
  • the further substituents can be halogens, hydrogen or organic radicals, where fluorine,
  • Chlorine, bromine, or iodine or a -CC-alkyl group are preferred.
  • the cyclopentadienyl group can also be part of a corresponding heteroaromatic system.
  • Preferred metallocenes contain central atoms which are bonded to two substituted cyclopentadienyl groups via two identical or different ⁇ bonds, those which are particularly preferred in which substituents of the cyclopentadienyl groups are bonded to both cyclopentadienyl groups.
  • complexes are preferred whose substituted or unsubstituted cyclopentadienyl groups are additionally substituted by cyclic groups on two adjacent C atoms, it being possible for the cyclic groups to also be integrated in a heteroaromatic system.
  • Preferred metallocenes are also those which contain only one substituted or unsubstituted cyclopentadienyl group, but which is substituted by at least one radical which is also bonded to the central atom.
  • Suitable metallocene compounds are, for example, ethylene bis (indenyl) zirconium dichloride, ethylene bis (tetrahydroindenyl) zirconium dichloride, diphenylmethylene-9-fluorenylcyclopentadienylzirconium dichloride, dimethylsilane diylbis (-3-tert. Butyl-5-methylcyclopentirienium)
  • the metallocene compounds are either known or can be obtained by methods known per se. Mixtures of such metallocene compounds can also be used for catalysis, furthermore the metallocene complexes described in EP-A 416 815.
  • the metallocene catalyst systems also contain compounds which form metal ocenium ions. Strong, neutral Lewis acids, ionic compounds with Lewis acid cations or ionic compounds with Bronsted acids as the cation are suitable. Examples include tris (pentafluorophenyl) borane, tetrakis (pentafluorophenyl) borate or salts of N, N-dimethylanilinium. Open-chain or cyclic alumoxane compounds are also suitable as metallocenium ion-forming compounds. These are usually produced by reacting trialkyl aluminum with water and are generally in the form of mixtures of different lengths, both linear and cyclic chain molecules.
  • metallocene catalyst systems can organometallic compounds of the metals of I., II. Or III.
  • Main groups of the periodic table contain such as n-butyl lithium, n-butyl-n-octyl magnesium or tri-iso-butyl aluminum, triethyl aluminum or trimethyl aluminum.
  • the polypropylenes are prepared by polymerization in at least one, often also in two or more reaction zones connected in series (reactor cascade), in the gas phase, in a suspension or in a liquid phase (bulk phase).
  • reactor cascade The usual reactors used for the polymerization of C 2 -C 8 -alk-1-enes can be used. Suitable reactors include continuously operated stirred tanks, loop reactors or fluidized bed reactors. The size of the reactors is not essential. It depends on the output that is to be achieved in or in the individual reaction zones.
  • reaction bed generally consists of the polymer of C 2 -C 8 -alk-1-enes, which is poly erized in the respective reactor.
  • the polymerization for the preparation of the polypropylenes used is carried out under customary reaction conditions at temperatures from 40 to 120 ° C., in particular from 50 to 100 ° C. and pressures from 10 to 100 bar, in particular from 20 to 50 bar.
  • Suitable polypropylenes generally have a melt flow rate (MFR), according to ISO 1133, of 0.1 to 200 g / 10 min., In particular 0.2 to 100 g / 10 min., At 230 ° C. and under a weight of 2.16 kg.
  • MFR melt flow rate
  • Particularly preferred polyolefins are low density polyethylene homopolymer (PE-LD) and polypropylene homopolymer.
  • connection should be understood as a connection class, ie as a class of individual connections.
  • the compounds a) are cyanoacrylic acid esters of the formula I.
  • R 1 and R 11 are hydrogen, -CC 20 alkyl, C 2 -C 0 -alkenyl, C 3 -C 0 -cyclo- alkenyl, -C- 2 alkoxy, aryl, heteroaryl, optionally substituted, X ethyl, 2nd Ethylhexyl, pentaerythrityl,
  • Propane-1,2,3-triyl, polyalkylene glycol residue n integer from 0 to 3, m integer from 1 to 4.
  • n 0, i.e. the aromatic systems are unsubstituted.
  • M is preferably 1 or 4.
  • Univul®3035 commercially available e.g. as Univul®3035 from BASF.
  • X is preferably pentaerythrityl, which is derived from pentaerythritol
  • Univul® 3039 commercially available e.g. as Univul® 3039 from BASF.
  • X is preferably propane-1, 2, 3-triyl, which is derived from glycerol
  • Preferred polyalkylene glycol radicals X are derived from the formula
  • the 2-cyanoacrylic acid esters a) of the formula I are preferably obtained by reacting cyanoacetic acid esters of the general formula Ia
  • reaction can be carried out, for example, in aromatic solvents such as toluene or xylene (see, for example, Organikum, 19th edition, Verlag Barth für 1993, p. 476).
  • aromatic solvents such as toluene or xylene (see, for example, Organikum, 19th edition, Verlag Barth für 1993, p. 476).
  • polar organic solvents such as
  • Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, trialkyl orthoformate or alcohols such as n-propanol, n-butanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, cyclohexanol or similar compounds are used. If the starting compounds used already form a liquid mixture, an additional solvent can be dispensed with.
  • the reaction temperatures are preferably between 20 and 180 ° C, particularly preferably between 40 and 150 ° C.
  • the pressure is preferably normal atmospheric pressure.
  • a catalyst or a catalyst mixture is advantageous. Suitable catalysts are e.g. Ammonium aceta, piperidine and ß-alanine and their acetates.
  • Lewis acids such as A1C1 3 , ZrCl 4 , TiCl 4 or especially ZnCl 2 can also be used as catalysts for the reaction in the amounts customary for this.
  • the cyanoacetic esters Ia can, for example, by reacting cyanoacetic acid or its esters with the corresponding polyols X (0H) n in the presence of a catalyst such as boric acid, p-toluenesulfonic acid, Na 2 CO 3 or K 2 CO 3 or tetrabutyl orthotitanate, preferably in toluene or xylene getting produced.
  • a catalyst such as boric acid, p-toluenesulfonic acid, Na 2 CO 3 or K 2 CO 3 or tetrabutyl orthotitanate, preferably in toluene or xylene getting produced.
  • the compounds b) are 4,4-diarylbutadienes of the formula II
  • R 1 and R 2 are hydrogen, C 20 alkyl, C 2 -C ⁇ 0 alkenyl, C 3 -C ⁇ 0 -cycloalkyl, C 3 -C ⁇ 0 cycloalkenyl, C ⁇ -C ⁇ 2 -alkoxy, C 2 o-alkoxycarbonyl, -CC 2 -alkylamino, C 1 -C 12 -Dialkyla1rd.no, aryl, heteroaryl, optionally substituted, water-solubilizing substituents selected from the group consisting of carboxylate, sulfonate or ammonium residues;
  • Ci-Cao-Al yl C 2 -C ⁇ o alkenyl, C 3 -C ⁇ 0 cycloalkyl, C 7 -C ⁇ o bicycloalkyl, C 3 -C ⁇ o cycloalkenyl, C -C ⁇ o bicyclo alkenyl, aryl, heteroaryl, optionally substituted ;
  • R 5 to R 8 are hydrogen, C 2 -alkyl, C 2 -C ⁇ 0 alkenyl, C 3 -C ⁇ 0 -cycloalkyl, C 7 -C ⁇ o bicycloalkyl, C 3 -C ⁇ o cycloalkenyl, C -C ⁇ o Bicycloalkenyl, aryl, heteroaryl, optionally substituted;
  • Preferred compounds of the formula II are those in which
  • R 1 and R 2 independently of one another hydrogen, -CC 2 alkyl
  • R 3 is hydrogen, COOR 5 , COR 5 , CONR 5 R 6 , CN,
  • R 1 to R 6 are particularly preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, Called 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dirnethylpropyl, 2-ethylhexyl.
  • Branched or unbranched cyclopentyl and cyclohexyl are particularly preferred as cycloalkyl radicals for R 3 to R 6 .
  • Suitable mono- or dialkylamino radicals for R 1 and R 2 are particularly preferably methyl, ethyl, n-propyl, n-butyl, 2-methylpropyl, 1, 1-dirnethylpropyl, 2-ethylhexylamino.
  • Camphor derivatives are particularly preferred as bicycloalkyl radicals for R 3 to R 6 .
  • R 1 and R 2 can each be bound in the ortho, meta and / or para position on the aromatic.
  • R 1 and R 2 can be in the ortho / para or meta / para position.
  • Compounds of the formula II with n - 1 in which R 1 is equal to R 2 and both radicals are in the para position are preferred.
  • R 3 or R 4 is not H, CN, C 20 -C 20 alkyl, C 2 -C 0 alkenyl, aryl, heteroaryl, which may be substituted if R 4 or R 3 means COOR 5 or COOR 6 .
  • condensation above may also be catalyzed both base- be acid- 3 ⁇ .
  • Suitable catalysts are:
  • tertiary amines e.g. Pyridine, morpholine, triethylamine, triethanolamine
  • secondary amines e.g. Piperidine, dimethylamine, diethylamine
  • the amount of the catalysts is generally 0.1 to 50 mol%, preferably 0.5 to 20 mol%, of the amount of the ⁇ 5 aldehyde used. Is preferably carried out at temperatures from 20 to 150 ° C, particularly 30 to 100 ° C, particularly preferably 40 to 80 ° C. Special printing conditions are not required. lent; in general, the implementation is carried out at Atmospnaren ⁇ ruc. Alcohols, such as methanol, ethanol or isopropanol; Aromatics such as toluene or xylene; Hydrocarbons, for example heptane or hexane; chlorinated hydrocarbons, such as chloroform or dichloromethane; Migol, tetrahydrofuran can be used. The reaction can also be carried out without a solvent.
  • basic alkali and alkaline earth salts preferably those which are neither soluble in the starting materials nor in the products and can be easily separated off after the end of the reaction, particularly preferably: sodium, potassium or calcium carbonate or sodium hydrogen carbonate;
  • Alkaline earth oxides preferably calcium or magnesium oxide and basic zeolites.
  • the amount of the catalysts is generally 1 to 80 mol%, preferably 5 to 50 mol%, of the amount of the ester used.
  • the amount of alcohol used must be at least equimolar to the amount of starting ester used. Amounts of 200 to 500 mol% of the alcohol are preferably used.
  • the methanol or ethanol formed is removed by distillation. Is preferably carried out at temperatures from 50 to 250 ° C, particularly 60 to 150 ° C. Special printing conditions are not required; in general, the reaction is carried out at atmospheric pressure.
  • higher-boiling compounds such as xylenes, but also toluene or mixtures of the alcohols used with liquid, short-chain alkanes such as hexane and heptane can be used as solvents. It is preferred to work solvent-free in the alcohol used.
  • the transesterification can be carried out batchwise or continuously. In the continuous mode of operation, the reactants are preferably passed over a fixed bed of an insoluble base.
  • R 3 ⁇ R 4 the compounds of formula I can in principle in their various geometric isomers, ie with a Z, Z; Z, E; E, Z and / or E, E-configured service system.
  • the all-E and / or all-Z isomers are preferred as light stabilizers, and the all-E isomers are very particularly preferred.
  • the C C double bond between C-3 and C-4 (in the adjacent position to the diaryl system) in the E and / or Z configuration, preferably in the Z configuration.
  • Y is hydrogen, COOR 1 or OH
  • R 1 Z OR 1 or NR H A hydrogen or S0 3 H,
  • R 1 C -C 2 o-alkyl
  • R 11 -C-C 20 alkyl
  • R 1 and R 11 are both the same -C-C n-alkyl.
  • the compounds c) are prepared, for example, as described in DE-A 214 25 93.
  • Compounds d) are cinnamic acid esters of the formula IV
  • R 1 , R 11 and n have the meaning given in a).
  • R 11 C 1 -C 2 o-alkyl is likewise preferred.
  • R 11 C 6 -Co-alkyl, in particular Cs-alkyl, very particularly preferably 2-ethylhexyl, is particularly preferred.
  • the compounds d) are prepared in a conventional manner by esterification of the corresponding cinnamic acid
  • the compounds d) can also be prepared by the process described in EP-A 490 198: in a first reaction step, a dialkyl ketal of an aromatic aldehyde of the formula is used 0R a
  • connection classes a) to d more than one individual connection can be selected from each of the connection classes a) to d), and that light stabilizers from two or more of the connection classes a) to d) can also be used together. Accordingly, mixtures of different light stabilizers can also be used.
  • the light stabilizers are preferably added to the polyolefin in an amount of 0.005 to 10, in particular 0.01 to 5, and particularly preferably 0.05 to 2% by weight.
  • the amount is very particularly preferably 0.1 to 1% by weight.
  • further stabilizers can be added to the polyolefin, selected from groups a ') to x'):
  • V sterically hindered amines, w ') oxamides and x') 2- (2-hydroxyphenyl) -1,3, 5-triazines.
  • Group a ') of the alkylated monophenols includes, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6, dimethylphenol, 2,6-di-tert-butyl-4- ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl ) -4, 6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol, nonylphenols, which have a linear or branched side chain, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1 '-
  • Group b ') of the alkylthiomethylphenols include, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-di-dodecy1thiomethyl-1-4 - onylpheno1.
  • Group c ') of the hydroquinones and alkylated hydroquinones include, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6- diphenyl 4-octadecyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert- butyl-4-hydroxyphenyl stearate and bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
  • Group d ') of the tocopherols includes, for example, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylene succinate (" Tocofersolan ").
  • Group e ') of the hydroxylated diphenylthioethers includes, for example, 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert -butyl-3-methylphenol), 4, '-Thiobis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis- (3, 6-di-sec-amylphenol) and 4, 4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
  • Group f) of the alkylidene bisphenols includes, 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-ethylidene bis (4,6-di-tert-butylphenol), 2,2 'ethylidebis (6-tert-butyl-4 -isobutylphenol), 2,2 'methylenebis [6- ( ⁇ -methylbenzyl) -4-nonylphenol], 2,2' methylenebis [6- ( ⁇ , ⁇ -dimethylbenzyl) -4
  • Group g ') of the 0-, N- and S-benzyl compounds include, for example, 3, 5, 3', 5 'tetra-tert-butyl-4, 4' -dihydroxydibenzyl ether, octadecyl-4-hydroxy-3 , 5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3- hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide and isooctyl-3,5-di-tert-butyl-hydroxybenzyl mercaptoacetate.
  • Group h ') of the aromatic hydroxybenzyl compounds includes, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,4 5-di-tert-butyl-4-hydroxy-benzyl) -2, 3, 5, 6-tetramethylbenzene and 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) phenol.
  • Group i ') of the triazine compounds includes, for example, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-0ctylmercapto-4, 6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-0ctylmercapto-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 (3rd , 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) is
  • Group j ') of the benzylphosphonates include, for example, dimethyl-2, 5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3, 5-di-tert -butyl-4-hydroxybenzylphosphonate and dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate.
  • Group k ') of the acylaminophenols includes, for example, 4-hydroxylauroylanilide, 4-hydroxystearoylanilide and octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
  • esters of the propionic and acetic acid derivatives mentioned in group 1 ') are based on monohydric or polyhydric alcohols, for example methanol, ethanol, n-octanol, i-octanol, octa-decanol, 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) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropanediol and 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2]
  • the amides of the propionic acid derivative mentioned in group m ') are based on amine derivatives, for example N, N' - bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, '- Bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine and N, N 'bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
  • amine derivatives for example N, N' - bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, '- Bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine and N, N 'bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
  • group n ' also includes ascorbic acid derivatives such as, for example, ascorbyl palmitate, laurate and stearate, and ascorbyl sulfate and phosphate.
  • the group o ') of the antioxidants based on amine compounds include, for example, N, N' -di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) - p-phenylenediamine, N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N 'bis (1-methylheptyl) -p-phenylenediamine, N, N '-Dicyclo-hexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N' -phenyl-p-phenylene diamine, N- (1,
  • the group p ') of the phosphites and phosphonites include, for example, triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, triocadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di- tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythri
  • Group q ') of the 2- (2' -hydroxyphenyl) benzotriazoles includes, for example, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (3 ', 5' -di-tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2' -hydroxyphenyl) 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' -methylphenyl) -5-chloro -benzotriazole, 2- (3 '-sec-butyl- 5'-tert-butyl-2'-hydroxyphenyl) -
  • the group r ') of the sulfur-containing peroxide scavengers or sulfur-containing antioxidants include, for example, esters of 3, 3' thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis (ß-dodecylmercapto) propionate.
  • esters of 3, 3' thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide dioc
  • the group s') of the 2-hydroxybenzophenones include, for example, the 4-hydroxy, 4-methoxy, 4-0ctyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,, 2 ', 4' -Trihydroxy- and 2 '-Hydroxy-4, 4' -dimethoxy derivatives.
  • the group t ') of the esters of unsubstituted and substituted benzoic acid includes, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl benzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-but-butyl 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4, 6-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate.
  • the group u ') of the acrylates include, for example, ethyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, isooctyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, methyl ⁇ -methoxycarbonylcinnamate, methyl ⁇ -cyano- ⁇ -methyl-p -methoxy-cinnamate, butyl- ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate and methyl- ⁇ -methoxycarbonyl-p-methoxycinnamate.
  • Group v ') of the sterically hindered amines includes, for example, bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate, bis (2, 2,6, 6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) sebacate, bis (l-octyloxy-2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate, bis (1,2 , 2,6, 6-pentamethylpiperidin-4-yl) -n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product from 1- (2-hydroxyethyl) -2,2,6 , 6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2
  • the group w ') of the oxamides include, for example, 4,4'-dioctyl-oxyoxanilide, 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) oxa id, 2-ethoxy-5-tert-butyl-2' -ethoxanilide and its Mix with
  • the group x ') of 2- (2-hydroxyphenyl) -1, 3, 5-triazines includes, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, 2- (2-Hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine , 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6- bis (2,
  • the further stabilizers mentioned from groups a ') to x') are used in customary amounts, in particular in quantities of 0.001 to 1% by weight, based on that with the light stabilizers a) to d) and the further stabilizers a ') to x ') stabilized polyolefin.
  • the light stabilizers and, if present, the further stabilizers are added to the polyolefin.
  • the addition takes place in the usual way. So you can add the light stabilizers and possibly the other stabilizers to the starting monomer (olefin monomers) and polymerize the mixture of monomers and stabilizers.
  • the stabilizers can also be added during the polymerization of the olefin monomers.
  • a prerequisite for addition before or during the polymerization is that the stabilizers are stable under the polymerization conditions, that is to say they do not decompose, or decompose only slightly.
  • the light stabilizers a) to d) and, if present, the further stabilizers a ') to x'), are preferably added to the finished polyolefin. This is done in the usual way according to mixing methods known per se, for example with melting at temperatures of 150 to 300 ° C. However, the components can also be mixed "cold" without melting and the powdery or granular mixture is only melted and homogenized during processing.
  • the stabilizer (s) can be added together or separately from one another, all at once, in portions or continuously, over time or along a gradient.
  • part of the stabilizer can be added during the polymerization of the olefin monomers and the rest can only be added to the finished polyolefin.
  • Mixing devices for carrying out the process according to the invention are, for example, discontinuously operating, heated internal kneaders with or without a ram, continuously operating kneaders such as, for example, continuous internal kneaders, screw kneaders with axially oscillating screws, Banbury kneaders, furthermore extruders and roller mills, mixing roll mills with heated rollers and Calender.
  • Mixing is preferably carried out in a conventional extruder, it being possible for the components to be mixed or introduced individually, for example completely into the extruder via a funnel, or else in portions at a later point in the extruder to give the melted or solid product in the extruder.
  • Single or twin-screw extruders for example, are particularly suitable for melt extrusion.
  • a twin screw extruder is preferred.
  • the mixtures obtained can be pelletized or granulated, for example, or processed by generally known methods, for example by extrusion, injection molding, foaming with blowing agents, deep-drawing, blow molding or calendaring.
  • Moldings including semi-finished products, foils, films and foams
  • molding compounds for example pipes for drinking water and waste water, fittings for drinking and waste water pipes, packaging and foils, in particular packaging for cosmetics (eg shampoo, creams, other water-containing cosmetic products) and packaging and films for food (eg fruit, vegetables, meat and other water-containing food), drinking water bottles, molded articles in the entire outdoor area such as Garden furniture, windows and fittings, lamp housings, automotive exterior parts.
  • the molded articles are the subject of the invention. They are characterized by a significantly lower yellowing when exposed to water.
  • polyolefins which are stabilized against visible and ultraviolet light and which contain at least one of the compounds a) to d) as light stabilizers as defined at the outset are very resistant to yellowing when exposed to water. These polyolefins are also the subject of the invention. In particular, these stabilized polyolefins are more resistant to yellowing in the presence of water than the stabilized polyolefins of the prior art.
  • yellowing-resistant stabilized polyolefins contain at least one of the compounds al), a2), a3), cl) and dl) as light stabilizers. These polyolefins are also the subject of the invention.
  • Another object of the invention is a method for reducing the yellowing of polyolefins stabilized against visible and ultraviolet light, which are exposed to the action of water, characterized in that the used Light stabilizers are selected from the described compounds a) to d), in particular selected from the described compounds a1), a2), a3), cl) and dl).
  • the invention finally relates to the use of light stabilizers, selected from the compounds a) to d) as described above, in particular selected from the compounds al), a2), a3), cl) and dl) as described above, in polyolefins which are exposed to water.
  • PE Low density polyethylene homopolymer (PE-LD), density 0.919 g / cm 3 , melt flow rate MFR (melt flow rate) 0.25 g / 10 min determined according to ISO 1133 at 190 ° C and 2.16 kg load.
  • the product Lupolen® 1840 D from Basell was used.
  • PP polypropylene homopolymer, melt flow rate MFR 23 g / 10 min determined according to ISO 1133 at 230 ° C and 2.16 kg load.
  • Tinuvin® 234 product from Ciba was used.
  • V2 Benzotriazole of the formula
  • the Tinuvin 326 product from Ciba was used.
  • the polyolefin was cold premixed with the light stabilizer.
  • the type and amount of stabilizer in the polyolefin can be found in Tables 1 and 2.
  • This mixture was then melted and homogenized in a twin-screw extruder bursting peat ZE 25.
  • the melt temperature was 200 ° C for polyethylene and 220 ° C for polypropylene.
  • the melt was discharged and granulated.
  • Test specimens of 60 x 45 x 2 mm were produced from the granules in an Aarburg 220 M injection molding machine at a melt temperature of 200 ° C and a mold surface temperature of 220 ° C.
  • the extent of the yellowing was determined on the basis of the yellowness index (Yellowness Index Yl).
  • the Yl of all test specimens was first determined before being stored in water. The test specimens were then stored for 100 hours at 25 ° C. in daylight in deionized water or in drinking water. The Yl after storage in water was determined.
  • the Yl was determined according to DIN 6167 and DIN 5033 with standard light D65 and 10 ° normal observer.
  • a zero Yl means that the specimen is pure white.
  • Negative Yl values mean that the test specimen is bluish (the more negative Yl, the bluer), which is perceived by the human eye as particularly intense white.
  • Positive YI values mean that the test specimen is yellowish (the more positive Yl, the more yellow). The more negative the Yl, the whiter the specimen appears to the viewer, the more positive the Yl, the more yellow it appears to him.
  • Tables 1 and 2 summarize the composition of the molding compositions and the measured values.
  • the concentration data refer to the stabilized polyolefin (polyolefin + light stabilizer).
  • Demineralized water means fully demineralized water
  • V means for comparison
  • nb means not determined.
  • the intrinsic color of the polyolefins according to the invention before storage in water is significantly less than the intrinsic color of the polyolefins of the prior art: at 0.25% by weight stabilizer concentration in polyethylene, the Yl before water storage (demineralized water) is in the range for the polymer according to the invention from 0 to -3 (Examples 2 to 6), in the polymer not according to the invention in the range from +3.5 to +5 (7V and 8V). At 0.5% by weight stabilizer concentration in polyethylene, the Yl in the polymer according to the invention is in the range from 0 to -3 (9 to 13), in the non-inventive polymer in the range +3.6 to +7 (14V and 15V).
  • the Yl before water storage in the polymer according to the invention is in the range from +1 to +8.5 (17 to 21), in the polymer not according to the invention in the range from +13.8 to +15 ( 22V and 23V).
  • the Yl in the polymer according to the invention is in the range from +1 to +8 (24 to 27), in the polymer not according to the invention in the range from +12 to +14 (28V and 29V).
  • the inherent color of the molding compositions according to the invention is accordingly whiter than the inherent color of the molding compositions not according to the invention. Secondly, yellowing when exposed to water is not detectable or only weakly in the polyolefins according to the invention: after 100 hours of storage in water, the Yl of the molding compositions according to the invention changes
  • the molding compositions according to the invention accordingly do not yellow or only yellow slightly under the action of water, whereas the molding compositions not according to the invention yellow strongly.
  • the superiority of the polyolefins stabilized according to the invention is evident both in deionized water (demineralized water) and in ion-containing water (drinking water), and is therefore independent of the type of water.

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Abstract

La présente invention concerne un procédé de production de polyoléfines qui sont soumises à l'influence d'eau et qui sont stabilisées par rapport à une lumière visible et ultraviolette. Selon ce procédé, des photostabilisants sont ajoutés à la polyoléfine. Cette invention est caractérisée en ce que les photostabilisants sont choisis parmi les composés a) à d) : a) esters d'acide cyanoacrylique de formule (I) b) 4,4-diarylbutadiènes de formule (II) c) benzophénones de formule (III) d) esters d'acide cinnamique de formule (IV), les variables ayant les significations énoncées dans la description.
PCT/EP2001/013596 2000-11-23 2001-11-22 Procede pour stabiliser des polyolefines WO2002042368A2 (fr)

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