WO2008071534A1 - Combinaisons stabilisantes pour polymères contenant des halogènes - Google Patents

Combinaisons stabilisantes pour polymères contenant des halogènes Download PDF

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WO2008071534A1
WO2008071534A1 PCT/EP2007/062786 EP2007062786W WO2008071534A1 WO 2008071534 A1 WO2008071534 A1 WO 2008071534A1 EP 2007062786 W EP2007062786 W EP 2007062786W WO 2008071534 A1 WO2008071534 A1 WO 2008071534A1
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Prior art keywords
stabilizer
acid
lead
stabilizer system
halogen
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PCT/EP2007/062786
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German (de)
English (en)
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Trupti Dave
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Ika Innovative Kunststoffaufbereitung Gmbh & Co.Kg
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Priority to EP07822856A priority Critical patent/EP2113007A1/fr
Publication of WO2008071534A1 publication Critical patent/WO2008071534A1/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
    • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

  • the present invention relates to stabilizer systems for halogen-containing polymers and to compositions and articles containing the stabilizer systems and the use of the systems and compositions.
  • halogen-containing plastics tend to undergo undesired decomposition and degradation reactions during thermal stress during processing or in long-term use.
  • This problem can be solved by the use of stabilizers added to the halogen-containing polymer before or during processing.
  • the known stabilizers include, for example, the lead, organotin, calcium-zinc and barium-zinc stabilizers and organic stabilizers.
  • stabilizers have been added for a long time in the processing of halogen-containing polymers, which should prevent degradation of the halogen-containing polymer during processing. It is known to improve the performance of lead stabilizers with perchlorate salts.
  • JP-A 58173159 describes the combination of tribasic lead sulfate and potassium perchlorate.
  • the latter compound is used only in very small quantities and can be due to their poor dissolving power in water or organic solvents in PVC only poorly incorporated and distributed homogeneously.
  • WO-A 2005/059027 also describes stabilizer compositions containing lead compounds and perchlorates. Furthermore, JP-A 02182741 describes only the use in PVC copolymers.
  • the stabilizer combinations known from the prior art are usually combinations containing heavy metal-containing stabilizers. In principle, good stabilization results can be achieved with these stabilizers. However, the amount used is high in relation to the performance.
  • a stabilizer system for halogen-containing polymers containing at least one inner complex selected from the group consisting of co-ordination polymeric catena ⁇ -2,2 ', 2 "nitrilotrisethanol perchlorato metal inner complex and coordination polymer catena ⁇ 2,2', 2" nitrilotrisethanol trifluoromethanesulfonato metal inner complex ; and
  • At least one heavy metal-containing stabilizer which is different from the at least one inner complex and is a lead-containing or an organotin stabilizer.
  • a stabilizer system according to the invention has at least two different components which can develop a stabilizing effect.
  • One component is a lead or organotin stabilizer. Preference is given to a lead stabilizer.
  • the inventive stabilizer system may contain a lead or organotin stabilizer or more lead or organotin stabilizers.
  • the stabilizer system according to the invention preferably contains one lead stabilizer or several lead stabilizers.
  • metal-containing stabilizers may be contained in the stabilizer system according to the invention.
  • This is preferably at least one calcium-zinc or barium-zinc stabilizer, these preferably containing the corresponding metal carboxylates, in particular fatty metal carboxylates.
  • lead-containing stabilizers are in the context of the present invention, in principle, all organic or inorganic lead compounds. Particularly suitable are, for example, basic lead salts of inorganic acids such as tribasic lead sulphate, tetrabasic lead sulphate, dibasic lead phosphide or dibasic lead phosphite sulphite or lead carbonate (lead white), lead salts of linear or branched, saturated or unsaturated, aliphatic or araliphatic or aromatic organic monocarboxylic acids such as acetic acid, Propionic, butyric, valeric, hexanoic, enanthic, octanoic, neodecanoic, 2-ethylhexanoic, pelargonic, decanoic, undecanoic, dodecanoic (lauric), tridecanoic, myristic, palmitic, 3,6-dioxahept
  • Citric acid or dimerized or trimerized linoleic acid.
  • cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid, tetrahydrophthalic acid, A-methyltetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • Particularly suitable are neutral or basic lead stearate, lead white, 3- or 4-basic lead sulfate, 2-basic lead phosphite, 2- basic lead phthalate or 4-basic lead fumarate. Very particular preference is given to 2-basic lead phosphite and 3-basic lead sulphate.
  • lead compounds for stabilization are products such as those obtained by reacting lead oxide with hydroxy carboxylic acids, for example
  • Dimethylolpropionic acid are available. Such compounds and their preparation are described in EP 0 313 113.
  • lead phosphite or sulphate or their mixtures with at least one organic lead compound, in particular with a lead carboxylate
  • Lead stearate or lead oleate Very particular preference is given to 2-basic lead phosphite and 3-basic lead sulfate and their mixtures with lead or calcium stearate or their combination with calcium-zinc-fatty acid carboxylates.
  • the content of a stabilizer system according to the invention of lead stabilizers is at least 5% by weight, preferably from 10 to 95% by weight, particularly preferably from 20 to 90% by weight, and very particularly preferably from 30 to 75% by weight.
  • the base content preferably varies from 1: 1 to 10: 1.
  • Suitable calcium-zinc or barium-zinc stabilizers in the context of the present invention are certain inorganic calcium, barium and zinc compounds and in principle all calcium, barium and zinc carboxylates and the phenolates of these metals.
  • zinc oxide, calcium, barium or zinc hydroxide or sulfate, zinc or barium carbonate, barium nonylphenolate, zinc sulfide, barium or zinc oxide or hydroxide addition compounds, such as overbased ones, are particularly suitable
  • the carboxylates are derived from carboxylic acids as exemplified above for lead stabilizers. Preferred are combinations of calcium-zinc stabilizers with lead stabilizers.
  • An alternative heavy metal component is an organotin stabilizer.
  • the stabilizer system according to the invention may contain one or more organotin stabilizers. Preference is given to mixtures of mono- and diorganotin stabilizers.
  • Examples include compounds of the composition:
  • Suitable calcium-zinc or barium-zinc stabilizers in the context of the present invention are certain inorganic calcium, barium and zinc compounds and in principle all calcium, barium and zinc carboxylates and the phenolates of these metals.
  • zinc oxide, calcium, barium or zinc hydroxide, zinc or barium carbonate or sulfate, barium nonylphenolate, zinc sulfide, addition compounds such as overbased calcium, barium or zinc carbonates or carboxylates are particularly suitable.
  • the carboxylates are derived from carboxylic acids as mentioned above Lead stabilizers are described by way of example. Preferred are combinations of barium-zinc with organotin stabilizers.
  • the stabilizer system according to the invention contains at least one inner complex selected from the group consisting of coordination-polymer catena ⁇ -2,2 ', 2 "-nitrilotrisethanol-perchlorato-metal inner complex and coordination polymer catena ⁇ -2,2'. , 2 "-nitrilotrisethanol- trifluoromethanesulfonato (triflato) -metal-inner complex.
  • the stabilizer system according to the invention can thus contain such a perchlorato inner complex, a plurality of such perchlorato inner complexes and no triflate inner complex, such a triflato inner complex, a plurality of such triflate inner complexes and no perchlorato inner complex or both perchlorato and triflato complexes.
  • the stabilizer system according to the invention may contain further stabilizers.
  • the stabilizer system according to the invention preferably additionally contains only the abovementioned metal-containing stabilizers which are not lead or organotin stabilizers and none of the abovementioned internal complexes. Further preferably, the stabilizer system according to the invention contains only the abovementioned combination of lead or organotin stabilizer and inner complex.
  • the at least one coordination-polymer catena- ⁇ -2,2 ', 2 "-nitrilotrisethanol perchlorato (triflato) -metal inner complex is preferably an inner complex with the monomer unit of the formula (I)
  • Mt Li, Na, K, Mg, Ca, Sr, Ba and Zn;
  • An OClO 3 or OS (O 2 ) CF 3 ;
  • q 1 or 2.
  • a preferred embodiment is therefore a stabilizer system according to the invention in which the at least one inner complex is a coordination-polymer catena- ⁇ -2,2 ', 2 "-nitrilotrisethanol perchlorato-metal inner complex.
  • Mt Na.
  • a preferred embodiment is therefore a stabilizer system according to the invention in which the metal of the inner complex is sodium.
  • Very particularly preferred is the use of the coordination polymer catena ⁇ -2,2 ', 2 "nitrilotrisethanol perchlorato sodium inner complex.
  • the proportion of the at least one coordination-polymer catena- ⁇ -2,2 ', 2 "-nitilotrisethanol perchlorato (triflato) -metal-inner complex is in the context of the present invention preferably 0.001-1.0% by weight, preferably 0.01%. 0.5 wt .-% and particularly preferably 0.05 to 0.1 wt .-% based on the total amount of the stabilizer system.
  • a stabilizer system according to the invention contain further additives, such as:
  • HALS sterically hindered amines
  • the stabilizer system according to the invention additionally contains at least one antioxidant and / or an alcohol selected from polyols and sugar alcohols or heterocyclic aminoalcohols.
  • Suitable additives are inorganic bases such as oxides or hydroxides of magnesium, calcium, barium, aluminum and zinc or organic bases such as melamine, cyanoguanidine and guanamines such as aceto and benzoguanamine, triethanolamine, triisopropanolamine, tripropanolamine, triisobutanolamine, tributanolamine and reaction products of ⁇ -olefmoxides with primary and secondary amines.
  • the amount used of these bases is 0.1 to 20 wt .-%.
  • epoxy compounds are epoxidized soybean oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, and epoxidized cottonseed oil.
  • glycidyl compounds are compounds with the glycidyl group:
  • glycidyl and .beta.-methylglycidyl esters obtainable by reacting a compound having at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or .beta.-methyl-epichlorohydrin. The reaction is conveniently carried out in the presence of bases.
  • aliphatic carboxylic acids can be used as compounds having at least one carboxyl group in the molecule.
  • carboxylic acids are glutaric acid,
  • cycloaliphatic carboxylic acids for example cyclohexane carboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • aromatic carboxylic acids for example benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.
  • carboxyl-terminated adducts eg. Trimellitic acid and polyols such as glycerine or 2,2-bis (4-hydroxycyclohexyl) propane.
  • polyols such as glycerine or 2,2-bis (4-hydroxycyclohexyl) propane.
  • epoxide compounds which can be used in the context of this invention can be found in EP 0 506 617. II) glycidyl or (.beta.-methyl glycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxyl group and / or phenolic hydroxy group and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.
  • Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-l, 2-diol, or poly (oxypropylene) glycols, propane-l, 3 -diol, butane-1,4-diol, poly (oxytetramethylene) glycols, pentane-l, 5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1 , 1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, as well as polyepichlorohydrins, butanol, amyl alcohol, pentanol, and monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol and CyCcrA
  • cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) -propane or 1, L-bis- (hydroxymethyl) -cyclohex-3-ene or they have aromatic nuclei such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.
  • cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) -propane or 1, L-bis- (hydroxymethyl) -cyclohex-3-ene or they have aromatic nuclei such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamin
  • the epoxy compounds may also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone; or they are based on polynuclear phenols, for example bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-) hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone or condensation products of phenols with formaldehyde such as phenol novolacs obtained under acidic conditions.
  • mononuclear phenols such as phenol, resorcinol or hydroquinone
  • polynuclear phenols for example bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-) hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone or condensation products of
  • terminal epoxides are, for example: glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-biphenyl glycidyl ether, N- (2,3-epoxypropyl) phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether.
  • amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane, but also N, N , O-triglyzidyl-m-aminophenol or N 5 N 5 O-triglycidyl-p-aminopheno 1.
  • the (N-glycidyl) compounds also include N, N'-di-, N, N ', N "-Tri- and N 5 N', N", N "'-Tetraglyzidylderivate of cycloalkylene, such as ethyleneurea or 1,3-propyleneurea, and N, N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.
  • S-glycidyl compounds such as di-S-glycidyl derivatives derived from dithiols such as ethane-l, 2-dithiol or bis (4-mercaptomethylphenyl) ether.
  • Epoxide compounds having a radical of the above formula in which R 1 and R 3 together are --CH 2 --CH 2 - and n is 0 are bis (2,3-epoxycyclopentyl) ethers, 2,3-epoxycyclopentyl glycidyl ethers or 1,2 bis (2,3-epoxyzyklopentyloxy) ethane.
  • An epoxy resin having a radical of the above formula in which R 1 and R 3 together are -CH 2 -CH 2 - and n is 1 is, for example, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3 ', 4'-epoxy-6' methylcyclohexyl) -methyl ester.
  • Suitable terminal epoxides include: a) liquid bisphenol A diglycidyl ethers such as Araldit® GY 240, Araldit® GY 250, Araldit® GY 260, Araldit® GY 266, Araldit® GY 2600, Araldit® MY 790 and Epicote® 828 (BADGE ); b) solid bisphenol 1-A diglycidyl ethers such as Araldit® GT 6071, Araldit® GT 7071, Araldit® GT 7072, Araldit® GT 6063, Araldit® GT 7203, Araldit® GT 6064, Araldit® GS 7304, Araldit® GS 7004, Araldit® GT 6084, Araldit® GT 1999, Araldit® GT 7077, Araldit® GT 6097, Araldit® GT 7097, Araldit® GS 7008, Araldit® GT 6099, Arald
  • Tetraglycidyl 4-4'-methylenebenzamine or N, N, N ', N'-tetraglycidyldiaminophenylmethane such as Araldit® MY 720, Araldit® MY 721.
  • Epoxy compounds having two functional groups are preferably used. However, it is also possible in principle to use epoxide compounds having one, three or more functional groups. Primarily epoxy compounds, especially diglycidyl compounds, are used with aromatic groups.
  • a mixture of different epoxy compounds can be used.
  • Useful 1,3-dicarbonyl compounds are linear or cyclic dicarbonyl compounds.
  • R'iCO of formula CHR 2 are preferably dicarbonyl - COR ⁇ used 3 wherein R'i Ci-C 22 alkyl, C 5 -C 10 hydroxyalkyl, C 2 -C 18 alkenyl, phenyl, substituted by OH, C 1 -C 4 -alkyl, Ci-C 4 -alkoxy or halogen substituted phenyl, C 7 -C 10 - phenylalkyl, C 5 -C 12 -Zykloalkyl, by Ci-C4-alkyl-substituted Cs-Ci 2 -Zykloalkyl or a group -RYS -R ⁇ 6 or -RYO-R ⁇ 6 ; R ⁇ 2 is hydrogen, C 1 -C 8 -alkyl, C 2 -C 2 - alkenyl, phenyl
  • R'i and as alkyl may in particular be C 1 -C 18 -alkyl, for.
  • R 'i and R " 3 as hydroxyalkyl are in particular a group - (CH 2 ) n -OH, where n is 5, 6 or 7.
  • R'i and R "2 as alkenyl may be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.
  • R'i and R " 3 as phenyl substituted by OH, alkyl, alkoxy or halogen can be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.
  • R'i and R "3 as phenylalkyl are in particular benzyl
  • R" 2 and R "3 as cycloalkyl or alkylcycloalkyl are in particular cyclohexyl or methylcyclohexyl.
  • R "2 as alkyl may in particular be C 1 -C 4 -alkyl, and R" 2 as C 2 -C 12 -alkenyl may in particular be allyl.
  • R "2 as alkylphenyl may in particular be tolyl.
  • R" 2 as phenylalkyl may in particular be benzyl.
  • R 1 is hydrogen.
  • R 3 as the alkoxy may be e.g. Methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodezyloxy, tridezyloxy, tetradezyloxy or octadezyloxy.
  • R as Ci-Cio-alkylene is in particular C2-C4-alkylene.
  • R "6 as alkyl is in particular C 4 -C 12 -alkyl, for example butyl, hexyl, octyl, decyl or dodezyl.
  • R e as alkylphenyl is in particular tolyl.
  • R e as phenylalkyl is in particular benzyl.
  • 1,3-dicarbonyl compounds of the above general formula and their alkali, alkaline earth and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptanedione-2,4, benzoylacetone, dibenzoylmethane, Lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-
  • Hydroxycapronylbenzoylmethane tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetylphenylmethane, Stearoyl-4-methoxybenzoylmethane, bis (4-tert-butyl) butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, biscyclohexanoylmethane, di-pivaloylmethane, 2-acetyl-cyclopentanone, 2-benzoylcyclopentanone, diacetylacetic acid, methyl, e
  • 1,3-diketo compounds of the above formula in which K is C 1 -C 18 -alkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy, C 1 -C 10 -phenylalkyl or cyclohexyl, R 2 is hydrogen and R 3 has one of the meanings given for R ⁇ .
  • heterocyclic 2,4-diones such as N-phenyl-3-acetylpyrrolidine-2,4-dione. Further representatives of this category are described in PS EP 0,734,414 A1.
  • the 1,3-diketo compounds may be used in an amount of, for example, 0.01 to 10, preferably 0.01 to 3 and especially 0.01 to 2 parts by weight, based on 100 parts by weight of PVC.
  • Examples of compounds of this type are: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinit, Tetramethylcyclohexanol, tetramethylolcyclopentanol, tetramethylolpyranol, glycerin, diglycerin, polyglycerol, thiodiglycerine or 1-O-o-C-D-glycopyranosyl-D-mannitol dihydrate.
  • polyol syrups such as sorbitol, mannitol and maltitol syrups.
  • the polyols may be in an amount of, for example, 0.01 to 20, suitably from 0.1 to 20 and in particular from 0.1 to 10 parts by weight, based on 100 parts by weight of PVC applied.
  • HALS Sterically hindered amines
  • heterocyclic amino alcohols The sterically hindered amines are generally compounds containing the group
  • a and V independently of one another are C 8 alkyl, C 3-8 alkenyl, C 5-8 -Zykloalkyl-, or C7-9 phenylalkyl or, together optionally replaced by O, NH or CH 3 -N interrupted Form C2-5 -alkylene, or a cyclic sterically hindered amine, in particular a compound from the series of alkyl or polyalkylpiperidines, especially the tetramethylpiperidines containing the group
  • polyalkylpiperidine compounds are the following (in the case of the oligomeric or polymeric compounds, n and r are in the range from 2 to 200, preferably in the range from 2 to 10, in particular from 3 to 7).
  • n and r are in the range from 2 to 200, preferably in the range from 2 to 10, in particular from 3 to 7).
  • An extensive list of such compounds can be found in EP 0 796 888 B1.
  • heterocyclic compounds are used as the amino alcohols. Examples of these are: EO, PO and BO reaction products of ethylene and propylene ureas, parabanic acid, hydantoins, barbituric acids, glycolurils and isocyanuric acids.
  • Particularly preferred in the context of the present invention is the use of tris (hydroxyethyl) isocyanate (THEIC) or tris (hydroxypropyl) isocyanate as a constituent of the stabilizer system according to the invention.
  • the content of a stabilizer system of the invention to THEIC for example, about 0.01 to about 10 wt .-%.
  • Hydrotalcites Hydrotalcites, zeolites, alkali metal aluminosilicates and dawsonites
  • hydrotalcites zeolites and alkali metal alkoxides (Dawsonite).
  • the hydrotalcites may be based on Al / Mg / carbonate, Al / Mg / Ti / carbonate, Li / Mg / carbonate or Li / Al / Mg / carbonate, compounds of the hydrotalcite series may be represented by the following general formula:
  • M 2+ cation of one or more metals of the group Mg, Ca, Sr,
  • a n represents an anion of valence n
  • b n is a number of 1-2, 0 ⁇ x ⁇ 0.5
  • d is one Number is 0-20.
  • Preference is given to compounds with A n OH “ , ClO 4 " , HCO 3 “ , CH 3 COO “ , C 6 H 5 COO “ , CO 3 2” , (CHOHCOO) 2 2 “ , (CH 2 COO) 2 2” , CH 3 CHOHCOO “ , HPO 3 " or HPO 4 2 " .
  • hydrotalcites are Al 2 O 3 6MgO * * CO * 12 H 2 O, Mg4, 5 Al2 (OH) i3 * CO 3 * 3.5 H 2 O, 4MgO Al 2 O 3 * * * CO 2 9H 2 O, 4MgO * Al 2 O 3 * CO 2 * 6H 2 O, ZnO * 3MgO * Al 2 O 3 * CO 2 * 8-9 H 2 O and ZnO * 3MgO * Al 2 O 3 * CO 2 * 5-6 H 2 O
  • Zeolites can be described by the formula M x / n [(A10 2 ) x (Si0 2 ) y ] * w H 2 O, where n is the charge of the cation M; M is an element of the first or second main group, such as Li, Na, K or NH 4, and Mg, Ca, Sr or Ba; y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.
  • zeolites sodium aluminosilicates of the formulas
  • NaI 2 Al 2 SiI 2 O 48 * 27 H 2 O [zeolite A], Na 6 Al 6 Si 6 O 24 * 2 NaX * 7.5 H 2 O, X OH, halogen, ClO 4 [sodalite]; Na 6 Al 6 Si 30 O 72 * 24 H 2 O; Na 8 Al 8 Si 40 O 96 * 24 H 2 O; NaI 6 Ali 6 Si 24 O 80 * 16 H 2 O; NaI 6 Ali 6 Si 32 O 96 * 16 H 2 O; Na 56 Al 56 SiI 36 O 384 * 250 H 2 O [zeolite Y], Na 86 Al 86 SiI 06 O 384 * 264 H 2 O [zeolite X]; Na 2 O, Al 2 O 3 , (2-5) SiO 2 , (3,5-1O) H 2 O [zeolite P]; Na 2 O, Al 2 O 3 , 2SiO 2 , * (3,5-10) H 2 O (zeolite MAP); or the zeolites which can be prepared by partial or complete exchange of the Na 6
  • Na zeolite A and Na zeolite MAP see also PS - US Pat. No. 6,531,533
  • zeolites with extremely small particle size in particular of the Na-A and Na-P type, as described in PS - US 6,096,820.
  • hydrotalcites, zeolites and alkali metal alkoxides which are suitable as additives may be present in a stabilizer system according to the invention in an amount of up to about 50% by weight, for example up to about 30% by weight.
  • additives may be used in amounts of, for example, 0.1 to 20, suitably 0.1 to 10 and especially 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.
  • trioctyl tridecyl, tridodezyl, tritridezyl, tripentadezyl, trioleyl, tristearyl, triphenyl, trilauryl, tricresyl, tris-nonylphenyl, tris-2,4-t-butylphenyl or Trizyklohexylphosphit.
  • phosphites are differently mixed aryl-dialkyl- or alkyl-diaryl phosphites, such as phenyldioctyl, phenyldidezyl, phenyldidodezyl, phenylditridezyl, phenylditetradezyl, phenyldipentadezyl, octyldiphenyl, decyldi-phenyl, undecyldiphenyl, dodecyldiphenyl, tridecyldiphenyl , Tetradecyldiphenyl, pentadezyldiphenyl, oleyldiphenyl, stearyldiphenyl and dodecylbis-2,4-di-t-butyl-phenylphosphite.
  • phosphites of various diols or polyols for example tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, tetraisodicyl dipropylene glycol diphosphite, tris-dipropylene glycol 1-phosphite, tetramethyloxyclohexanol-decyldiphosphite, tetramethyloxycyclohexanol-butoxy-ethoxy ethyldiphosphite, tetramethyloxyclohexanol nonylphenyl diphosphite, bis-nonylphenyl-di-trimethylolpropane diphosphite, bis-2-butoxyethyldimethylolpropane diphosphite, trishydroxyethylisocyanurate hexadecyltriphos
  • the organic phosphites may be used in an amount of, for example, 0.01 to 10, preferably 0.05 to 5, and especially 0.1 to 3, parts by weight, based on 100 parts by weight of PVC.
  • a stabilizer system according to the invention may contain the described phosphite compounds in an amount of up to about 30% by weight, in particular up to about 10% by weight.
  • sterically hindered phenols such as alkylated monophenols, e.g. For example, 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, eg, 2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, e.g. As 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, eg. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), alkylidene-bisphenol Ie, z .B.
  • alkylated monophenols e.g.
  • 2,6-di-tert-butyl-4-methylphenol alkylthiomethylphenols
  • 2,4-dioctylthiomethyl-6-tert-butylphenol alkylated hydroquinones
  • antioxidants may be used in an amount of, for example, 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of PVC become.
  • Examples are 2- (2'-hydroxyphenyl) -benzotriazoles, e.g. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-hydroxybenzophenones, esters of optionally substituted benzoic acids, e.g. 4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds, oxalic acid diamides, e.g. 4,4'-di-octyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl-oxanilide, 2- (2-hydroxyphenyl) -l, 3,5-triazine, e.g.
  • 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethyl) phenyl) -l, 3,5-triazine, sterically hindered amines based on tetramethylpiperidine or tetramethylpiperazinone or tetramethylmorpholinone, eg Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate and benzoxazinones such as 1,4-bis benzoxazinonyl-benzene.
  • Examples of these are bis-benzene (1,4) -oxazoles, phenylcoumarins and bis-styrylbiphenyls such as 4-methyl-7-diethylaminocoumarin, 3-phenyl-7- (4-methyl-6-butoxybenzoxazo-1) -coumarin , 4,4'-Bis (benzoxazol-2-yl) stilbene and 1,4-bis (-benzoxazol-2-yl) -naphthalene.
  • Preference is given to solutions of optical brighteners in a plasticizer, for example DOP.
  • pigments are also suitable as part of the stabilizer system according to the invention.
  • Suitable substances are known to the person skilled in the art.
  • inorganic pigments are TiO 2 , zirconia-based pigments, BaSO 4 , zinc oxide (zinc white) and lithopone (zinc sulfide / barium sulfate), carbon black, carbon black-titanium dioxide mixtures, iron oxide pigments, Sb 2 O 3 , (Ti, Ba, Sb) O 2 , Cr 2 O 3 , spinels such as cobalt blue and cobalt green, Cd (S 5 Se), ultramarine blue.
  • Organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments.
  • TiO 2 is also in micronized form. A definition and other descriptions can be found in the Handbook of PVC Formulating, EJWickson, John Wiley & Sons, New York, 1993. propellant
  • Propellants are e.g. organic azo and hydrazo compounds, tetrazoles, oxazines, isatric anhydride, N-methylisatinic anhydride, as well as soda and sodium bicarbonate. Preference is given to azodicarbonamide and sodium bicarbonate and mixtures thereof. Very particular preference is given to isatric anhydride or N-methylisatinic anhydride, especially in soft PVC or semi-hard PVC.
  • Antistatic antistatic agents are classified into nonionic (a), anionic (b), cationic (c) and amphoteric (d) classes.
  • To (a) include fatty acid ethoxylates, fatty acid esters, ethoxylated fatty alkylamines, fatty acid diethanolamides and ethoxylated phenols and alcohols, and polyglycol monofatty acid esters.
  • To (b) include alkali fatty bisulfonates and phosphoric acid bis-fatty alcohol ester alkali salts.
  • To (c) include quaternary fatty alkyl ammonium salts and to (d) include fatty alkyl betaines and fatty alkyl imidazoline betaines. Individual preferred compounds are lauric diethanolamide, myristyl diethanolamine, Na octadecyl sulfonate and Na bis-octadecyl phosphate.
  • Lubricant A stabilizer system of the invention may further contain lubricants.
  • Suitable lubricants are, for example: montan waxes, fatty acid esters, PE and PP waxes, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps, furthermore fatty ketones, and combinations thereof, as listed in PS EP 0259.783 A1.
  • a stabilizer system according to the invention may contain the lubricants described in an amount of up to about 70% by weight, in particular up to about 40% by weight.
  • organic plasticizers are, for example, those from the following groups:
  • phthalic acid esters such as preferably di-2-ethylhexyl, di-isononyl and diisodecyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate ), DIDP (diisodiacyl phthalate) are known
  • esters of aliphatic dicarboxylic acids in particular esters of adipic, azelaic and sebacic acid, preferably di-2-ethylhexyl adipate and diisoctyl adipate
  • trimellitic acid esters for example tri-2-ethylhexyl trimellitate, triisodecyltrimellitate ( mixture), tri-iso-tridezyltrimellitat, tri-iso-oktyltrimellitat (mixture) and tri-Ce-Cg-alkyl, tri-alkyl C 6 -C 0, tri-C 7 -C 9 alkyl and Tn C 9 -Ci i -alkyl trimellitates; common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (tri-benzyl trimellitate), and TITDTM (tri-iso
  • (v) polymer plasticizer The most common starting materials for their preparation are dicarboxylic acids such as adipic, phthalic, azelaic and sebacic acids; Diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol, (s. AdmEx ® grades of Velsicol Corp. and PX-811 of Asahi Denka)
  • Phosphoric acid esters A definition of these esters can be found in the above-mentioned "TASCHENBUCH der Kunststoffadditive” chapter 5.9.5, SS. 408 - 412.
  • Examples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-di-phenyl phosphate, cresyl diphenyl phosphate, resorcin-bis-diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate; preferred are tri-2-ethylhexyl phosphate and Reofos ® 50 and 95 (Ciba Specialty Chemicals)
  • glycol esters e.g. Diglykolbenzoate
  • citric acid ester e.g. Tributyl citrate and acetyltributyl citrate as described in PS - WO 02/05206
  • plasticizers may contain in an amount of, for example, up to about 99.5% by weight, more preferably up to about 30% by weight, up to about 20% by weight or up to about 10% by weight.
  • the lower limit for the described plasticizers as part of the inventive stabilizer systems is about 0.1 wt .-% or more, for example about 0.5 wt .-%, 1 wt .-%, 2 wt. -% or 5 wt .-%.
  • Another object of the present invention is a composition comprising a halogen-containing polymer and a stabilizer system according to the invention.
  • the amount of the stabilizer system according to the invention based on the halogen-containing polymer is 0.1 to 20 wt .-%.
  • the halogen-containing polymer is preferably a chlorine-containing polymer, such as polyvinyl chloride (PVC). Further preferably, the halogen-containing polymer is a hard, soft or paste PVC. Also preferably, the halogen-containing polymer is a recycled polymer.
  • PVC polyvinyl chloride
  • Another object of the present invention is the use of the stabilizer system according to the invention for stabilizing a halogen-containing, in particular chlorine-containing, polymer.
  • chlorine-containing polymers to be stabilized are polymers of vinyl chloride, vinylidene chloride, vinyl resins containing vinyl chloride units, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; Vinylidene chloride polymers and copolymers thereof with
  • graft polymers of PVC with EVA, ABS and MBS as well as graft polymers of PVC with PMMA.
  • Preferred substrates are also mixtures of the abovementioned homopolymers and copolymers, in particular
  • Vinyl chloride homopolymers with other thermoplastic or / and elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones, in particular from the group ABS, NBR, NAR, SAN and EVA.
  • the related abbreviations for the copolymers are familiar to the person skilled in the art and mean the following: ABS acrylonitrile-butadiene-styrene; SAN styrene-acrylonitrile; NBR acrylonitrile-butadiene; NAR acrylonitrile acrylate; EVA ethylene vinyl acetate.
  • ASA acrylate-based styrene-acrylonitrile copolymers
  • Preferred as a component in this context are polymer compositions containing as components (i) and (ii) a mixture of 25-75 wt .-% PVC and 75-25 wt .-% of said copolymers. From Of particular importance as a component are compositions of (i) 100 parts by weight of PVC and (ii) 0-300 parts by weight of ABS and / or SAN-modified ABS and 0-80 parts by weight of the copolymers NBR, NAR and / or EVA, but especially EVA.
  • PVC recyclate is also suitable for stabilization in the context of this invention.
  • PVC recyclate is particularly preferred.
  • Another use of the stabilizer system according to the invention is that antistatic properties can be imparted to the finished article made of hard or soft PVC. In this way it is possible to reduce the use of expensive antistatic agents.
  • Preferred for this application is soft PVC or semi-rigid PVC.
  • the present invention relates to articles containing a composition of the invention.
  • These are preferably commodities.
  • wood composite plastics WPC Wood Plastic Composites
  • foils foils
  • profiles floor coverings
  • automotive parts wall-mounted wallpaper
  • hoses injection molded parts or wire sheathing.
  • the present invention relates to the use of a composition according to the invention for producing an article according to the invention.
  • Another object of the invention are utility (utensils), which in particular contain PVC and stabilizer systems according to the invention.
  • compositions according to the invention are particularly suitable, in the form of hard formulations, for hollow bodies (bottles), packaging films (thermoforming films), blown films, "crash pad” films (automobiles), pipes, foams, heavy profiles (window frames), Lichtwandpro file, Baupro foils, blister packs (also produced by the Luvitherm method), profiles, sidings, fittings, office films, margarine mugs, praline packaging and apparatus housings, insulators, computer housings and components of household appliances as well as for electronic applications, in particular in the semiconductor field, which are particularly suitable for the production of window profiles with high whiteness and surface gloss.
  • compositions in the form of semi-hard and soft formulations are for wire sheathing, cable insulation, decorative films, roofing foils, foams, agricultural films, hoses, sealing profiles, flooring, wallpaper, automotive parts, soft films, injection molded parts (blow molding), office films and Foils suitable for inflatable halls.
  • Examples of the use of the compositions according to the invention as plastisols are toys (rotational molding), artificial leather, flooring, textile coatings, wallpaper, coil coatings and underbody protection for motor vehicles.
  • sintered PVC applications of the compositions according to the invention are slush, slush mold and coil coatings and in E-PVC for films produced by the Luvitherm compiler. For further information, see “Kunststoffhandbuch PVC", Volume 2/2, W. Becker / H. Braun, 2nd ed., 1985, Carl Hanser Verlag, pp. 1236-1277.
  • Application Testing Examples 1 to 13
  • composition of the formulations is shown in Table 1 below (all data in phr):
  • the DHC is a measure of the HCl elimination of PVC, which takes place under thermal stress.
  • the split-off hydrochloric acid is charged with nitrogen gas into a receiver with dist. Rinsed water and there measured the increase in conductivity in microsiemens per centimeter ( ⁇ S / cm). The corresponding minute values [Min] are used as key figures. The longer the time interval to reach a certain conductivity, the more thermostable is the PVC sample.
  • TEAP addition to the lead stabilizer at reduced dosage shows a similar improvement to that of 1 (3 vs 2 and 1).
  • TEAP or NaP gives a clear improvement in the values at transition to TEAP (5 vs. 7, 6 vs. 8, 10 vs. 12 and 11 vs. 13). 5. Equivalent addition of TEAP or NaP shows comparable or still improved values (6 vs. 7 and 11 vs. 12).
  • Figure 1 shows the yellowness index (YI) as a function of time (t) in minutes, with the graph at 70 min. the upper measuring point of the curve for example 1, the mean measuring point of the curve for example 3 and the lower measuring point of the curve for example 2 are to be assigned.
  • Results can be interpreted as follows:

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Abstract

La présente invention concerne un système stabilisant destiné à des polymères contenant des halogènes, ledit système contenant au moins un complexe interne choisi dans le groupe qui comprend un complexe interne polymère de coordination catena-μ-2,2',2'-nitrilotriséthanol-perchlorato-métal et un complexe interne polymère de coordination catena-μ-2,2',2'-nitrilotriséthanol-trifluorométhane sulfonato-métal; et au moins un stabilisant qui contient des métaux lourds, est différent dudit/desdits complexe(s) interne(s) et est un stabilisant contenant du plomb ou un stabilisant organostannique. L'invention concerne également des compositions et des objets contenant le système stabilisant, ainsi que leur utilisation.
PCT/EP2007/062786 2006-12-13 2007-11-26 Combinaisons stabilisantes pour polymères contenant des halogènes WO2008071534A1 (fr)

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DE102009020813A1 (de) 2009-05-11 2010-11-18 Osram Gesellschaft mit beschränkter Haftung Hochdruckentladungslampe für Kraftfahrzeugscheinwerfer

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EP1466941A2 (fr) * 2003-04-11 2004-10-13 Rohm And Haas Company Composition de stabilisateur thermique pour polymères vinyliques halogénés
WO2006136191A1 (fr) * 2005-06-23 2006-12-28 Catena Additives Gmbh & Co. Kg Complexes internes de triethanolaminoperchlorato(triflato)-metal polymeres de coordination utilises en tant qu'additifs pour des polymeres de synthese

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EP1466941A2 (fr) * 2003-04-11 2004-10-13 Rohm And Haas Company Composition de stabilisateur thermique pour polymères vinyliques halogénés
WO2006136191A1 (fr) * 2005-06-23 2006-12-28 Catena Additives Gmbh & Co. Kg Complexes internes de triethanolaminoperchlorato(triflato)-metal polymeres de coordination utilises en tant qu'additifs pour des polymeres de synthese

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Publication number Priority date Publication date Assignee Title
DE102009020813A1 (de) 2009-05-11 2010-11-18 Osram Gesellschaft mit beschränkter Haftung Hochdruckentladungslampe für Kraftfahrzeugscheinwerfer

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