EP1771507A2 - Systeme de stabilisateur destine a des polymeres halogenes - Google Patents

Systeme de stabilisateur destine a des polymeres halogenes

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Publication number
EP1771507A2
EP1771507A2 EP05772430A EP05772430A EP1771507A2 EP 1771507 A2 EP1771507 A2 EP 1771507A2 EP 05772430 A EP05772430 A EP 05772430A EP 05772430 A EP05772430 A EP 05772430A EP 1771507 A2 EP1771507 A2 EP 1771507A2
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EP
European Patent Office
Prior art keywords
acid
pvc
stabilizer system
chlorine
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05772430A
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German (de)
English (en)
Inventor
Wolfgang Wehner
Thomas Wannemacher
Trupti Dave
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Catena Additives GmbH and Co KG
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Artemis Research GmbH and Co KG
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Filing date
Publication date
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Publication of EP1771507A2 publication Critical patent/EP1771507A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • 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 stabilizer system for halogen-containing polymers and a method for stabilizing halogen-containing polymers.
  • the polymer is especially PVC.
  • halogen-containing plastics or molding compositions prepared therefrom are prone to degradation or decomposition reactions when exposed to thermal stress or coming into contact with high-energy radiation, for example ultraviolet light.
  • urea derivatives such as N, N'-diphenylthiourea and monophenylurea were described for the stabilization of PVC (cf. "Plastics Additives Handbook" H.
  • Stabilizers SS 1071-1091.
  • these additives have only a limited field of application, for example for the stabilization of emulsion PVC (Luvitherm process).
  • Ureide are described in the form of the linear representatives as cyanacetylureas (cyanacetylcarbamides) or in the form of (hetero) cycles as 6-aminouracils. Cyclourides with 6-iminobarbituric acid (barbituric acid imide) structure have not been mentioned so far.
  • EP 0,962,491 B1 cites cyanacetylureas as stabilizers for halogen-containing polymers.
  • Kostabilisatoren mainly based on metal.
  • Combinations of 6-aminouracils with costabilizers have also been reported, but these are also mainly metal compounds (synthetic minerals).
  • EP 1,327,661 A1 describes 6-aminouracil combinations with dawsonites.
  • EP 1,327,658 A1 mentions 6-aminouracil combinations with organotin compounds.
  • EP 1,327,662 A1 discloses 6-aminouracil combinations with alkali and alkaline earth hydroxides.
  • EP 1,325,941 A1 discloses 6-aminouracil combinations with zeolites.
  • EP 1,046,668 B1 mentions 6-aminouracil combinations with hydrotalcites.
  • EP 0 930 332 B1 claims 6-aminouracil combinations with further CaJM and Li / Al / Ti compounds.
  • EP 0.625.546 Bl protects the combination of fatty acid Zn salts with glycidyl compounds for semi-hard and soft PVC.
  • EP 0.677.550 Bl names combinations of glycidyl compounds, antioxidant and Na perchlorate.
  • EP 0 677 551 A2 claims compositions of glycidyl compounds and perchlorate salts for the stabilization of plasticized PVC. All three publications work in the field in the presence of zinc soaps and glycidylphenol ethers or N-glycidyl compounds. The application is also limited to semi-hard and soft PVC at most. Heavy metal-free blends (ie total waiver of Zn salts) are not described here.
  • EP 1,327,659 A1 names 6-aminouracil combinations with glycidyl compounds, virtually omitting zinc compounds.
  • diglycidylphenol ethers for example BADGE
  • WO 02/072684 A1 mentions aminocrotonic acid ester combinations with perchlorate salts.
  • metal-containing costabilizers are additionally named. In a large number of applications, however, attention must be paid to a reduced metal content, for example in the manufacture of cables and insulators.
  • EP 0174.412 Al describes combinations of dicyandiamide with substituted benzamides and works in the absence of zinc salts. In practice, however, this approach is limited to the use of E-PVC, wherein the light stability proves to be insufficient.
  • a solution to this problem is a stabilizer system for halogen-containing polymers containing a linear or / and cyclic ureide of the formula (A-I) or / and a polyminocinate of the formula (A-2):
  • R 1 , R 2 independently of one another H 5 C 1 -C 22 -alkyl, cyclohexyl, (meth) allyl, oleyl, phenyl, benzyl, phenethyl, (tetrahydro) naphthyl, meth (eth) oxy (ethyl) propyl, CH 2 -
  • R la is H, Ci- 22 alkyl, cyclohexyl, (meth) allyl, oleyl, phenyl, benzyl, phenethyl,
  • R 3 unbranched or branched C 2 -C 20 -alkylene, which may be interrupted by 1 to 4 O or S atoms and / or substituted by 1 to 4 OH groups, or
  • R 5 H or (! C 3 - C o-alkylidene) i / 2; wherein said alkylidene may be interrupted by up to 2 O atoms or may have up to 2 substituents independently selected from the group consisting of OH, phenyl and hydroxyphenyl.
  • R 6 H, hydroxy-C 2 - C ⁇ alkyl, 3-Q - Cio-alkoxy-2-hydroxypropyl or mono- to
  • radicals in brackets are further alternative radicals, so polyethylene (propylene) glycol means polyethylene glycol or polypropylene glycol. This also applies below.
  • the substituents R 1 and R 2 may be Q-O 22 -alkyl, namely methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadezyl, hexadecyl, Heptadecyl, octadecyl, nonadezyl, eicosyl, heneicosyl and docosyl, where these radicals may be branched or unbranched.
  • R 1 and R 2 may be cyclohexyl, (meth) allyl, oleyl, phenyl, benzyl, phenethyl, methoxyethyl, ethoxyethyl, methoxypropyl and ethoxypropyl.
  • Preferred are allyl and phenethyl, cyclohexyl, benzyl, methoxypropyl and ethoxypropyl, particularly preferred are cyclohexyl, benzyl, methoxypropyl and ethoxypropyl.
  • C 1 -C 10 -alkyl contains, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl , Neodecyl.
  • R 5 is hydrogen or (C 3 - C O alkylidene) i / 2 - ladex Vz says that this is is bis-products, so to alkylidene-bis-6-aminouracils.
  • Alkylidene groups which may be mentioned are ethylidene, propylidene, butylidene, pentylidene, hexylidene, heptylidene, octylidene, nonylidene and decylidene, as well as salicylidene and cynnamylidene.
  • the term applies to linear and branched representatives. Preference is given to propylidene, hexylidene, meptylidene and octylidene. particularly preferred are hexylidene and heptylidene.
  • the substituent R 6 designates hydrogen and hydroxy-C 2 -C 4 -alkyl.
  • the latter group contains 2-hydroxyethyl, 2- and 3-hydroxypropyl as well as 2-, 3- and 4-hydroxybutyl. Preference is given to 2-hydroxyethyl and also 2- and 3-hydroxypropyl. Particularly preferred is hydrogen.
  • R 6 allyl or 3-C 1 -C 10 -alkoxy-2-hydroxypropyl. These include 3-methoxy, 3-ethoxy, 3-propoxy, 3-butoxy, 3-pentoxy, 3-hexoxy, 3-heptoxy, 3-octoxy, 3-nonoxy and 3-decoxy -2-hydroxypropyl. Preferred are allyl, 3-butoxy, 3-octoxy and 3-decoxy-2-hydroxypropyl.
  • the substituent R 6 is mono- to trisubstituted phenyl, where the substituents hydroxy, and / or Ci - C 4 alkyl and / or Ci - C 4 alkoxy and the combination of hydroxy with methyl, ethyl, propyl and butyl and hydroxy with methoxy, ethoxy, propoxy and butoxy.
  • the hydroxy, methyl, butyl, methoxy and ethoxy radical are substituents.
  • Particularly preferred is the hydroxy and methoxy group.
  • Preference is given to mono- and disubstitution. But especially preferred is the mono-substitution.
  • Also particularly preferred in the multiple substitution are the combinations of hydroxy with meth (eth) oxy or hydroxy with monomethyl or dimethyl and the combinations of methyl, ethyl, propyl and butyl with methoxy, ethoxy, propoxy and butoxy.
  • Specific examples are: 2-, 3- and 4-hydroxyphenyl; 2-hydroxy-4-methylphenyl; 2-hydroxy-5-methylphenyl; 2-hydroxy-5-t-butylphenyl; and 2-, 3- and 4-meth (eth) oxyphenyl.
  • the hydrates may be present as hemi, sesqui- or dihydrate, for example.
  • Tetrite is preferably erythritol, arabinitol and xylitol, hexitol is preferably mannitol and sorbitol.
  • R 4 represents as R 1 CO preferably formyl, acetyl, propionyl, butyroyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridekanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, octadecanoyl, oleoyl, acryloyl, crotonoyl, phenylacetyl, Phenylpropionyl and carbamoyl.
  • azyl cyanamides in particular C 8 - cis fatty acid azyl cyanamides, as well as magnesium and calcium cyanamide.
  • Particularly preferred is dicyandiamide or an alkali or alkaline earth metal salt of a Azylzyanamides.
  • Melamine may also be present as a salt in the form of the phosphate or isocyanurate salt.
  • (AI) - Linear acylureas (linear crayes, acyl carbamides, acyl ureas) such as [1] N, N'-dimethyl-, [2] N, N'-diethyl-, [3] N, N'-dipropyl-, [ 4] N, N'-diallyl, [5] N, N'-dibutyl, [6] N, N'-dioctyl, [7] N, N'-didodezyl, and [8] N, N'- Dibenzylzyanazetureid.
  • N- or N'-monomethyl- [10] N- or N'-monoethyl-, [11] N- or N'-monopropyl-, [12] N- or N'-monoallyl-, [13 ] N- or N'-monobutyl, [14] N or N'-monopentyl, [15] N or N'-monohexyl, [16] N or N'-monoheptyl and [17] N - or N'-monooctyl, [18] N, N'-monocyclohexyl [19] N, N'-monobenzyl and [20]
  • N N'-Mono ⁇ henylzyanazetureid. Preference is given to [1], [2], [3], [4], [5], [8], [9], [10], [11], [12], [13], [18], [19] and [20]. Particularly preferred are [1], [4], [8], [12], [18], [19] and [20]. Very particular preference is [I].
  • N- or N'-monomethyl- [30] N- or N'-monoethyl-, [31] N- or N'- Monopropyl, [32] N or N'-monoallyl, [33] N or N'-monobutyl, [34] N or N'-monopentyl, [35] N or N'-monohexyl , [36] N- or N'-monoheptyl- [37] N- or N'-monooctyl-, [38] N or N'-monocyclohexyl- or [39] N or N'-monophenyl- and [40] N , N'-monobenzyl-6-iminobarbituric acid.
  • Particularly preferred are [21], [24], [28], [32], [37], [38], [39] and [40].
  • Very particularly preferred is [21].
  • Further preferred is a cycloureide, in particular an N- or N'-substituted or (N, N) -di-substituted 6 (4) -imidobarbituric acid.
  • (AI) - cycloacylureas (6-aminouracils or 6 (4) -aminopyrimidinediones-2,4) such as [41] N, N'-dimethyl, [42] N, N'-diethyl, [43] N , N'-dipropyl, [44] N, N'-diallyl, [45] N,
  • N-dibutyl [46] N, N'-dioctyl and [47] N, N'-didodezyl, [48] N, N'-dibenzyl-6-aminourazil. [49] N- or N'-monomethyl-, [50] N- or N'-monoethyl-, [51] N- or
  • N'-mono-propyl [52] N- or N'-monoallyl, [53] N or N'-monobutyl, [54] N- or
  • N'-monopentyl [55] N or N'-monohexyl, [56] N or N'-monoheptyl, [57] N or N'-monooctyl, [58] N or N ' - monocyclohexyl,
  • Preferred hydrates are the hemi- and monohydrates of [42], [43], [44] and [45].
  • exocyclic N atom-substituted 6-amino acids such as hydroxyethylamino and hydroxypropylamino derivatives or hydroxyanilino, methoxyanilino and ethoxyanilinouracils.
  • 6-amino acids are available in the chemicals trade: [1], [9] and [41] are “commodities” and are used as “bulk” chemicals in the technical caffeine or theobromine synthesis.
  • Relevant literature syntheses are available for 6-iminobarbituric acids.
  • Particularly preferred are [104], [105], [116] and [117].
  • Very particularly preferred are [116] and [117]. Both compounds are produced on an industrial scale.
  • (B-2) monomers [140] cyanamide and its salts, in particular [141] calcium cyanamide, [142] monomethyl, [143] monoethyl, [144] monopropyl, [145] monobutyl, [146] monopentyl , [147] monohexyl, [148] monoheptyl, [149] monooctyl, [150] monophenyl and [151] monobenzyl cyanamide, and [152] monoallyl cyanamide.
  • melamine (s) e such as [188] melamine, [189] melamine perchlorate, [190] oxalate, [191] sulfate, [192] nitrate, [193] phosphate, and [194 ] -isocyanurate.
  • N-substituted melamines such as [195] N-monobutyl, [196] N-monooctyl, [197] N-monodezyl, [198] N-monododezyl, [199] N-monotetradezyl, [200] N-monohexadezyl, [201] N-monooctadecyl, [202] N-monophenylmelamine.
  • N-monoacetyl [204] N-monopropionyl, [205] N-monobutyroylmelamine, [206] N-monophenyl, [207] N-monoallyl, and [208] N-monobenzylmelamine, [209] o Hydroxyphenylmelamine and [210,211] 2-hydroxyethyl (propyl) -melamine.
  • N-N'-substituted melamines such as [212] N, N'-dibutyl, [213] N, N'-dioctyl, [214] N 5 N'-didezyl, [215] N, N'- Dihexadecyl- and [216] N, N'-dioctadezylmelamine and [217,218] N, N'-bis-2-hydroxyethyl (propyl) melamine.
  • N, N ', N "-substituted melamines such as [219] N, N', N" -tributyl, [220] N, N ', N "-trioctyl-, [221] N, N', N" Tridecyl, [222] N, N ', N "-tetradecyl, [223] N, N', N" -trihexadezyl and [224] N, N ', N "-trioctadezylmelamine and [225] N, N ', N'-phenyl-bis-hydroxyethyl and [226] N, N', N "-tris-hydroxyethylmelamine, [227] N, N ', N" -triazetyl, [228] N, N', N "- Tripropionyl-, [229] N, N ', N" -Tribenzoylmelamin and [230] N,
  • [187] as well as its calcium and magnesium salt, and [188] or [194] are "commodities.”
  • the Ca and Mg salts can also be synthesized "in situ" during PVC processing or previously during compounding Magnesium or potassium hydroxide are produced.
  • eutectics with substituted ureas, or aniline derivatives or with aminobenzenesulfonamides are particularly preferred.
  • R 1 or R 2 methyl, ethyl, cyclohexyl, allyl, benzyl or hydrogen; and (BI) bisepoxypropyl ether of a C 2 -Cg alkanediol, a polyethylene (propylene) glycol or glycerol or a polyglycerol or a trisepoxypropyl ether of Glyzerins or the trimethylolethane (propane) s or pentaerythritol tetraglycidyl ether.
  • R 1 or R 2 methyl, ethyl, cyclohexyl or benzyl and (BI) bisepoxypropyl ethers of ethylene, propylene, butylene, neopentyl glycol or hexanediol or of glycerol or a trisepoxypropyl ether of glycerol, trimethylolethane (propane) s or pentaerythritol tetraglycidyl ether.
  • R 1 or R 2 methyl, ethyl, cyclohexyl or benzyl and (B-2) cyanamide, acetylcyanamide or their sodium or calcium salts, dicyandiamide (cyanoguanidine) or triaminotriazine-1,3,5 (melamine).
  • A-2) Bisaminocrotonic acid ester of 1,4-butanediol and / or thiodiglycol and (BI) bisepoxypropyl ether of ethylene, propylene, butylene and neopentyl glycol or hexanediol or glycerol or trisepoxypropyl ether of glycerol, trimethylolethane or -propane or pentaerythritol tetraglycidyl ether.
  • the compounds from groups (A) and (B) are suitably used in the halogen-containing polymer from 0.01 to 10 phr, preferably from 0.05 to 5 and in particular from 0.1 to 3 phr.
  • this salt being a perchlorate salt (CI) Perfluoralkansulfonat salt (C-2) or a Ci - Cig-Alkylschwefelklar salt (C-3).
  • these salts are present as alkali or alkaline earth salts.
  • Perchlorate salt (C-I) is preferably alkali metal, alkaline earth metal, aluminum, hydrotalcite, katoite, hydrocalumite and lithium hydrotalcite perchlorate as described in EP 0,549,340 A1. [236] Ni, [237] Na, [238] K, [239] Mg, and [240] Ca perchlorate are mentioned.
  • Perfluoroalkanesulfonate salt (C-2) preferably means salt of the "Triflic”, “Pentaflic”, “Heptaflic” and “Nonaflic” acids; Very particular preference is given to Na and K triflate or Mg or Ca and Al triflate, as well as NEU triflate.
  • Sulfate ester salt (C-3) is preferably Li, Na, K, Mg, Ca, Sr, Ba, Ln, Ce, Al, Zn and NtU sulfate esters.
  • Sulfate ester means sulfuric acid half ester; preferred are methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and octadecylsulfuric acid monoesters; Very particular preference is given to Na-methyl, -octyl, -dezyl and -dodecyl sulfate esters as well as the analogous K or Mg, Ca and Al salts.
  • Na-butyl [247] Na-dodecyl, [248] Na-hexadecyl, [249] Na-octadecyl, and [250] Na-octyl sulfate are examples.
  • Component (C-2) is mostly available in the chemicals trade.
  • the salts, such as the underlying acids, are described in Kirk Othmer, Encyclopedia of Chemical Technology, 4th Ed., John Wiley & Sons., NY, Vol. 11, SS 558-564 (1994) and Chem. Rev. 77, SS 69 -90 (1977).
  • the components (CI), (C-2) and (C-3) can be used depending on the water solubility or water solubility in various common dosage forms (Formu ⁇ lierungen), for example as a salt or as a solution in water or in an organic solvent or Mounted on a support material such as PVC, Ca-silicate, zeolites or hydrotalcites.
  • a support material such as PVC, Ca-silicate, zeolites or hydrotalcites.
  • examples of such formulations are also corresponding salts with alcohols (polyols, cyclodextrins) or ether alcohols, amino alcohols or Ester alcohols or crown ethers are complexed or dissolved therein.
  • Preferred are complexes or solutions in glycol mono- and diglycol monobutyl ether.
  • amine complexes e.g. Complexes of Na or K perchlorate or triflate with triethanol or triisopropanolamine or ethylene or propylene urea or ethylene thiourea, imidazolidinone or imidazolidinedione.
  • ethylene or propylene carbonate can be used as a solvent for these salts or complexes.
  • the compounds of category (C) are advantageously used in the halogen-containing polymer from 0.001 to 5 phr, preferably from 0.01 to 3 phr and very particularly from 0.01 to 2 phr.
  • component (C) the perchlorates (C-I) and the triflates of (C-2) are particularly preferred.
  • A-2 a bisaminocrotonic acid ester of 1,4-butanediol and / or thiodiglycol and
  • BI a bisepoxypropyl ether of ethylene, propylene, butylene and neopentyl glycol or hexanediol or glycerol or a trisepoxypropyl ether of glycerol, trimethylolethane or propane or pentaerythritol tetraglycidyl ether and a perchlorate salt (CI).
  • A-2 a bisaminocrotonic acid ester of butanediol-1,4 or / and thiodiglycol and (B-2) cyanamide, acetylcyanamide, dicyandiamide (cyanoguanidine) or triaminotriazine-1,3,5 (melamine), and a perchlorate salt (CI ).
  • Cycloacylic acids [21] with [118], [119], [120], [121], [135], [136], [137], [138], [139], and [ 237] or [238] Cycloacylureas (6-aminouracils):
  • Cycloacylic acids (6-iminobarbituric acids): [21] with [187] and [237] or [238]
  • the two or three combinations (A + B) or (A + B + C) according to the invention may contain one or more sterically hindered amines (D) as further components (D).
  • the hindered amine is generally a compound containing the group
  • a and W are independently Ci-s-alkyl, C3- 8 alkenyl, C5-8 -Zykloalkyl-, or C 7 -9 -phenylalkyl-, or together optionally interrupted by O, NH or CH 3 -N interrupted C 2 - 5 form alkylene, or a cyclic sterically hindered amine, in particular a compound from the series of the alkyl or polyalkylpiperidines, in particular of 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):
  • Et ethyl
  • Pr propyl
  • Bu butyl
  • the compounds of component (D) are advantageously used for stabilization in the chlorine-containing polymer at from 0.01 to 10, preferably from 0.05 to 5, in particular from 0.1 to 3, parts per 100 parts of polymer.
  • a single sterically hindered amine a mixture of various sterically hindered amines can also be used in the context of the present invention.
  • the amines mentioned are frequently known compounds; many of them are commercially available.
  • the compounds may be present in the polymer at 0.005 to 5, preferably at 0.01 to 2 and especially at 0.01 to 1%.
  • Q is a 4-8 membered ring system which may be interrupted by 1 or 2 X atoms or NR 1 groupings and wherein X, R 1 and R 2 are independently as defined above.
  • TEA triethanolamine
  • TIPA triisopropanolamine
  • TIBA triisobutanolamine
  • DEA isoproporolanol, iso
  • TEA TEA
  • TIPA TEBA
  • TEBA TEBA
  • DEA DEA
  • DEPA and DEBA or MEA MEPA and MEBA adducts to alkene oxides are particularly preferred as the ⁇ component.
  • the substances of category (E) are to be used in the chlorine-containing polymer expediently from 0.01 to 10 phr, preferably from 0.05 to 5 phr and in particular from 0.1 or 2.0 phr.
  • These new stabilizer systems are particularly well suited for the stabilization of chlorine-containing polymers , in particular of PVC.
  • Pre-stabilization makes it possible for the polymer to have to add heat stabilizers in a reduced amount during processing since it is less prone to damage, be it in the form of conventional stabilizers, such as organotin compounds or Ba / Zn or Ca / Zn fatty acid carboxylates or generally metal soaps, or even in the form of completely novel and completely heavy metal-free stabilizer types on an organic basis. This procedure can mean a saving in capital resources and conserves resources, so it can be classified as particularly advantageous under economic and environmental aspects.
  • Stabilizer systems are preferably suitable for hard or soft PVC, suspension or emulsion PVC, especially if they are premixed in the presence of PVC.
  • Stabilizers or additives may furthermore be added to the combinations according to the invention.
  • a further preferred subject of the invention are therefore in particular mixtures of at least one stabilizer component (AI) or (A-2) with at least one further co-component (BI) or (B-2) or (AI) with (BI) or ( B-2) and (A-2) with (BI) and (C) or (A-2) with (B-2) and (C) optionally containing an additional co-component (C) and / or (D) or / and (E) is added, with at least one further customary stabilizer or additive.
  • Preferred as a further component group are phosphites, polyols and disaccharide alcohols, ⁇ -diketones, thiophosphites and thiophosphates, mercaptocarboxylic esters,
  • Dihydropyridines hydrotalcites, zeolites (alkali or alkaline earth metal aluminosilicates), metal soaps, zinc compounds, alkali and alkaline earth compounds, epoxidized
  • Fillers lubricants, plasticisers, pigments, antioxidants, UV absorbers,
  • Light stabilizers optical brighteners, propellants, antistatic agents, biocides (antimicrobials),
  • Antifogging agents impact modifiers, processing aids, gelling agents, flame retardants, metal deactivators and compatibilizers.
  • Epoxidized fatty acid esters and other epoxide compounds as well as polyols, alkaline earth and aluminum soaps and also Mg, Ca and Al hydroxides, zeolites, hydrotalcites and phosphites are particularly preferred as a further component type.
  • Very particularly preferred are phosphites, disaccharide alcohols, dehydrated hydrotalcites and zeolites and calcium or magnesium hydroxide or calcium stearate or basic Mg, Ca or Al salts or "overbased" compounds of magnesium and calcium.
  • Organic phosphites are known co-stabilizers for chlorine-containing polymers. Examples are trioctyl, tridecyl, tridodezyl, tritridezyl, tripentadezyl, trioleyl, tristearyl, triphenyl, trilauryl, tricresyl, tris-nonylphenyl, tris-2,4-t-butyl-phenyl or tricyclohexyl phosphite , Further suitable phosphites are differently mixed aryldialkyl- or alkyldiarylphosphites, such as phenyldioctyl, phenyldidezyl, phenyldidodezyl, phenylditridezyl, phenylditetradezyl, phenyldipentadezyl, octyldiphenyl, decyldiphenyl, undecyldiphenyl, dodecyldiphen
  • phosphites of different diols or polyols for example tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, tetraisodecyl dipropylene glycol diphosphite, tris-dipropylene glycol phosphite, tetramethylolcyclohexanol-decyldiphosphite, tetramethylolcyclohexanolbutoxy- ethoxy-ethyldiphosphite, tetramethylolcyclohexanol-nonylphenyl-diphosphite, bis-nonyl-phenyl-di-trimethylolpropane-diphosphite, bis-2-butoxy-ethyl-di-trimethylol-propane-diphosphite, trishydroxyeth
  • 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.
  • 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, Tetra- methylcyclohexanol, tetramethylolcyclopentanol, tetramethylolpyranol, glycerin, diglycerin, polyglycerol, thiodiglycerine or 10- ⁇ -D-glycopyranosyl-D-mannitol dihydrate.
  • disaccharide alcohols Preference is given to disaccharide alcohols.
  • polyol syrups such as sorbitol, mannitol and maltitol syrups.
  • the polyols may be used in an amount of, for example, from 0.01 to 20, suitably from 0.1 to 20, and especially from 0.1 to 10 parts by weight, based on 100 parts by weight of PVC.
  • Useful 1,3-dicarbonyl compounds are linear or cyclic dicarbonyl compounds.
  • Dicarbonyl compounds are preferably of the formula IT 1 CHR 2 CO - COR V related 3 wherein R ⁇ C 1 -C 22 -alkyl, C 5 -C 0 hydroxyalkyl, C 2 -C 18 alkenyl, phenyl, substituted by OH, C 1 -C 4 -AlkVl, C 1 -C 4 -alkoxy or halogen-substituted phenyl, C 7 -C 10 - phenylalkyl, C 5 -C 12 -cycloalkyl, by C r C 4 alkyl-substituted C 5 -C 12 -cycloalkyl or a Group -RYS-R ⁇ 6 or -RYO-R ⁇ 6 ;
  • R "2 is hydrogen, C r C 8 alkyl, C 2 -C 12 - alkenyl,
  • R ⁇ and R V 3 as alkyl may be in particular Ci-Qs-alkyl, z.
  • R'i and R ⁇ 3 as hydroxyalkyl in particular represent a group - (CH 2 ) n -OH, where n is 5,
  • R ⁇ and R s 2 as alkenyl may be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.
  • R "i and R V 3 as phenyl substituted by OH, alkyl, alkoxy or halogen may be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl
  • R 1 and R 3 V 3 as phenylalkyl in particular, benzyl, R v 2 and R V 3 as the cycloalkyl or alkylcycloalkyl are in particular cyclohexyl or methylcyclohexyl.
  • R v 2 as alkyl can be in particular CrC 4 -AlkVl.
  • R 2 as C 2 -Q 2 -alkenyl may in particular be allyl
  • R v 2 as alkylphenyl may in particular be tolyl
  • R N 2 as phenylalkyl may in particular be benzyl
  • R 2 is preferably hydrogen.
  • R V 3 as the alkoxy may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodezyloxy, tridezyloxy, tetradezyloxy or octadezyloxy.
  • R v 5 as Ci-Ci O alkylene is in particular C 2 -C 4 alkylene.
  • R N 6 as alkyl is in particular C 4 -C 12 alkyl, z. Butyl, hexyl, octyl, decyl or dodecyl.
  • R V 6 as alkylphenyl is in particular tolyl.
  • R v 6 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, A-
  • Methoxybenzoylbenzoylmethane bis (4-methoxybenzoyl) ethane, 1-benzoyl-1-azetylnonane, benzoyl-acetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, biscyclohexanoylmethane, Di-pivaloyl-methane, 2-acetyl-cyclopentanone, 2-benzoyl-cyclopentanone, methyl, ethyl and di-acetylacetate, benzoyl, Methyl and ethyl propionyl- and butyryl-acetoacetate, triazetylmethane, methyl, ethyl, hexane, octyl, do
  • 1,3-diketo compounds of the above formula in which IT 1 is C 1 -C 6 -alkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy, C 7 -C 10 -phenylalkyl or cyclohexyl, IT 2 is hydrogen and R v 3 has one of the meanings given to R'i. Also included are heterocyclic 2,4-diones such as N-phenyl-3-acetylpyrrolidine
  • Diketo compounds can 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.
  • Tri-thiophosphoric acid tris (karbo-trimethylcyclohexyloxy) methyl ester, trithiophosphoric acid S, S, S-tris- (carboxy-o-octyloxy) -methyl ester, trithiophosphoric acid S, S, S-tris- (karbo-2 ethylhexyloxy) methyl ester, trithiophosphoric acid S, S, S-tris-l- (carboxy-hexyloxy) -ethyl ester, trithiophosphoric acid S, S, S-tris-1- (carbo-2-ethylhexyloxy) -ethyl ester, trithiophosphoric acid S, S, S-tris-2- (carbo-2-ethylhexyloxy) ethyl ester.
  • esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, the mercaptobenzoic acids or thiolactic acid, mercaptoethyl stearate and oleate are esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, the mercaptobenzoic acids or thiolactic acid, mercaptoethyl stearate and oleate, as described in the publications FR-A 2,459,816, EP 0,090,748 A1, FR-A 2,552,440, EP 0 365 483 A1.
  • the mercapto carboxylic acid esters also include polyol esters or their partial esters. dihydropyridines
  • Suitable monomeric dihydropyridines are compounds as described in FR-A 2,039,496, EP 0 002 007 A1, EP 0 362 012 A1 and EP 0,240,754 A1. Preferred are those of the formula '
  • Z is CO 2 CH 3 , CO 2 C 2 H 5 , CO 2 11 C 12 H 25 or CO 2 C 2 H 4 -S- 11 Ci 2 H 2 S stands.
  • T is unsubstituted Q ⁇ alkyl
  • L has the same meanings as T
  • m and n represent numbers from 0 to 20
  • k is 0 or 1
  • R and R "independently of one another are ethylene, propylene, butylene or an alkylene or Cycloalkylene bismethylene group of the type - (CpH 2p -X-) t C p H 2p -, p is 2 to 8, t is 0 to 10 and X is oxygen or sulfur.
  • the (poly) - dihydropyridines can be used in the chlorine-containing polymer expediently to 0.001 to 5 and especially 0.005 to 1 parts by weight, based on the polymer. Particular preference is given to thio ⁇ -ethylenebis (5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate).
  • a n represents an anion with the valence -n
  • b n is a number of 1-2, 0 ⁇ x ⁇ 0.5
  • d is a number from 0-20.
  • Preference is given to compounds having A ⁇ OH “ , ClO 4 " , HCO 3 " , CH 3 COO " , C 6 H 5 COO " , CO 3 2" ,
  • hydrotalcites examples are
  • Alkamizer 1 and 2 5 are particularly preferred.
  • Alkamizer P 93-2 manufactured by Kyowa Chemical Ind. Co., JP
  • Very particular preference is given to using dehydrated hydrotalcites.
  • Zeolites alkali or alkaline earth metal aluminosilicates
  • M can be described by the formula M ⁇ / n [(A10 2 ) x (Si0 2 ) y ] -wH 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.
  • Na zeolite A and Na zeolite MAP see also 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 US 6,096,820.
  • the hydrotalcites and / or zeolites can be used in amounts of, for example, 0.1 to 20, advantageously 0.1 to 10 and in particular 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.
  • Epoxidized fatty acid esters and other epoxide compounds Epoxidized fatty acid esters and other epoxide compounds
  • the inventive stabilizer combination may preferably contain at least one epoxidized fatty acid ester.
  • esters of fatty acids from natural sources such as soybean oil or rapeseed oil
  • it can also be synthetic products such as epoxidized butyl oleate used.
  • epoxidized polybutadiene and polyisoprene if appropriate also in partially hydroxylated form, or glycidyl acrylate and glycidyl methacrylate as homopolymer or copolymer.
  • These epoxy compounds may also be applied to an alumino salt compound; see also DE 4.031.818 A1.
  • Metal soaps are mainly metal carboxylates, preferably longer chain carboxylic acids. Common examples are stearates and laurates, including oleates and salts of short-chain aliphatic or aromatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, sorbic acid; Oxalic, malonic, succinic, glutaric, adipic, fumaric, citric, benzoic, salicylic, phthalic, hemimellitic, trimellitic, pyromellitic.
  • metals may be mentioned: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce and rare earth metals. Often one uses so-called synergistic mixtures such as barium / zinc,
  • Magnesium / zinc, calcium / zinc or calcium / magnesium / zinc stabilizers can be used individually or in mixtures. An overview of common metal soaps can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5 th Ed., Vol. A16 (1985), p. 361 ff.). Preferred are magnesium, potassium and zinc soaps.
  • the zinc-containing organic compounds having a Zn-O bond are zinc enolates, zinc phenolates and / or zinc carboxylates.
  • the latter are compounds from the series of the aliphatic saturated and unsaturated Ci 22 -Karboxylate, aliphatic saturated or unsaturated C 2-22 -Karboxylate which are substituted with at least one OH group or the chain interrupted by one or more O atoms, is (oxa acids), the cyclic and bicyclic carboxylates having 5-22 carbon atoms, the unsubstituted, substituted with at least one OH group and / or
  • Ci - ⁇ - alkyl substituted Phenylkarboxylate the phenyl-C i ö -alkylkarboxylate, or optionally alkyl substituted with Ci- 12 phenates, or abietic acid.
  • Zn-S compounds are, for example, Zn-mercaptides, Zn-mercaptocarboxylates and Zn-mercapto carboxylic acid esters.
  • the zinc salts of monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid , Lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, ricinoleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid,
  • monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid,
  • Zinc salts of divalent carboxylic acids or their monoesters such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-l, 5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, octane-1, 8-dicarboxylic acid, 3,6,9-trioxadekane-l, 10-dicarboxylic acid, lactic acid, malonic acid, maleic acid,
  • the zinc olates are preferably enolates of acetylacetazetone, of benzoylacetazetone, of dibenzoylmethane and of enolates of acetoacetic and benzoylacetic esters and of dehydroacetic acid.
  • inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate or zinc sulfide can be used.
  • the metal soaps or mixtures thereof may be used in an amount of, for example, 0.001 to 10 parts by weight, advantageously 0.01 to 8 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight PVC, are applied.
  • hydroxy carboxylate metal salts may be present, where the metal may be an alkali or alkaline earth metal or aluminum. Preference is given to sodium, potassium, magnesium or calcium.
  • the hydroxy carboxylic acid may be glycolic, lactic, malic, tartaric or citric acid or salicylic or 4-hydroxybenzoic acid or else glycerol, gluconic and succinic acid (see for example GB 1,694,873 and EP .303,564 A1).
  • These layer lattice compounds are in hydrated form.
  • other layer lattice compounds such as Al (OH) 3 and Ii-hydrotalzite can be used. Further details can be found in EP 0.930.332 Al. The synthesis of L-CAM perchlorate is described, for example, in EP 0,761,756 A1.
  • fillers are calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, china clay, talc, glass fibers, glass beads, wood flour, mica, metal oxides or metal hydroxides, carbon black, graphite, rock flour, barite, glass fibers, talc, kaolin and chalk related. Preference is given to chalk '(also Coated form) (HANDBOOK OF PVC Formulating EJ Wickson, John Wiley & Sons, 1993, pp. 393-449) and reinforcing agents (Handbook of KUNSTSTOFFADDnTVE, R. Gumbleter & H. Müller, Carl Hanser, 1990, S 549-615).
  • the fillers may be used in an amount of preferably at least 1 part, for example 5 to 200, advantageously 5 to 150 and in particular 5 to 100 parts by weight, based on 100 parts by weight of PVC.
  • 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 EP 0,259,783 A1.
  • Preferred is calcium stearate. softener
  • Suitable organic plasticizers are, for example, those from the following groups:
  • phthalic acid esters such as preferably di-2-ethylhexyl, di-isononyl and di-iso-decyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DEMP (diisononyl phthalate ), DIDP (diisodecyl phthalate) are known
  • esters of aliphatic dicarboxylic acids in particular esters of adipic, azelaic and sebacic, preferably di-2-ethylhexyladi ⁇ at and di-iso-oktyladipat
  • trimellitic acid esters for example tri-2-ethylhexyl trimellitate, Tri-iso-dezyltri- mellitate (mixture), tri-iso-tridezyltrimellitat, tri-iso-oktyl
  • polymer plasticizer The most common starting materials for their preparation are dicarboxylic acids such as adipic, phthalic, azelaic and sebacic acid; 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) ( vi) Phosphoric Acid Esters: A definition of these esters can be found in the "TASCHENBUCH DER PLASTICS ADDEDIVE" chapter 5.9.5, pp. 408-412.
  • phosphoric acid esters examples include tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphite, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate; preferred are tri-2-ethylhexyl phosphate and Reofos® 50 and 95 (Ciba Spezi Rundenchemie) (vii) chlorinated hydrocarbons (paraffins) (viii) hydrocarbons (ix) monoesters, eg butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkyl sulfonic acid esters (x) glycol esters, eg Diglykolbenzoate
  • citric acid esters for example tributyl citrate and acetyltributyl citrate, as described in WO 02/05206
  • perhydrophthalic, isophthalic and terephthalic esters and perhydroglycol and diglycol zoate esters Preference is given to perhydro-diisononyl phthalate (Hexamoll® DINCH - BASF) as described in DE 197.56.913 Al, DE 199.27.977 Al, DE 199.27.978 Al and DE 199.27.979 Al.
  • plasticizers A definition of these plasticizers and examples of such are in "TASCHENBUCH DER KUNSTSTOFFADD ⁇ IVE", R. Gumbleter / H. Müller, Carl Hanser Verlag, 3rd ed.,
  • plasticizers can be used in one
  • Hard or semi-hard PVC preferably contains up to 20%, more preferably up to 5% or no plasticizer.
  • inorganic pigments are TiO 2 , zirconia-based pigments, BaSO 4 , zinc oxide (zinc white) and lithopone
  • Organic pigments are e.g. Azo pigments, phthalocyanine pigments,
  • Quinacridone pigments perylene pigments, diketo-pyrrolopyrrole pigments and anthraquinone pigments.
  • TiO 2 is also in micronized form.
  • Antioxidants include hindered phenol, 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.
  • 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'-di-octyloxy-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-butoxybenzoxazoi) -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.
  • Propellants are e.g. organic azo and hydrazo compounds, tetrazoles, oxazines,
  • 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 Alkalifettalkansulfonate and phosphoric acid bis-fatty alcohol ester alkali metal salts.
  • C) includes fatty alkyl quaternary ammonium salts and (d) includes fatty alkyl betaines and fatty alkyl imidazoline betaines.
  • component (A) is lauric diethanolamide, myristyl diethanolamine, Na octadecyl sulfonate and Na bis-octadecyl phosphate.
  • component (A) allows in many cases due to the inherent properties of a reduction in the amount of expensive antistatic agents.
  • Further stabilizers may be phenylurea, 2-p-tolylmdol, 3-hydroxyaniline and its N-phenyl derivative, 2-pyrrolecarboxylic acid (see EP 1,299,466 A1), 2,4-diphenylpyrrole and 2-alkyl-4-phenylpyrrole. 3-carboxylic acid esters, 3-amino-4-alkyl / phenylpyrrole-3-carbonates and Ca-hydroxyaluminum hydrogenphosphites (CHAP compounds see EP 0 506 831 A1).
  • stabilizer systems which additionally contain azetazetein-substituted indole or a urea or an aniline derivative.
  • azetazetein-substituted indole or a urea or an aniline derivative examples of suitable
  • a particular preference lies in the combination of the blends (AI, A-2) / (Bl, B-2) with phosphite esters, wherein the additional phosphite distearylpentaerythritol diphosphite, triphenyl phosphite, tris-nonylphenyl phosphite, phenyldidezyl phosphite,
  • compositions containing a chlorine-containing polymer and a stabilizer system according to the invention are compositions containing a chlorine-containing polymer and a stabilizer system according to the invention.
  • the compounds of the general formulas (Al / A-2) and (Bl / B-2) are advantageously from 0.01 to 10, preferably from 0.05 to 5, in order to achieve stabilization in the chlorine-containing polymer to 100 parts by weight of polymer.
  • the salts (CI), (C-2) and (C-3) may be used in an amount of, for example, 0.001 to 10, preferably 0.01 to 5, particularly preferably 0.01 to 3 parts by weight, based on 100 wt . -Parts polymer.
  • Preferred are compositions wherein the ratio of the compound of general formulas (A) and (B) to salt (CI), (C-2) and (C-3) by weight is in the range of 2: 8 : 1 to 5: 20: 1.
  • compositions contain, based on 100 parts by weight of chlorine-containing polymer, 0.01-10 parts by weight of compound (AI) or / and (A-2) and 0.01-10 parts by weight of compound (BI) or / and (B-2).
  • compositions according to the invention preferably additionally contain 0.01-10 parts by weight of compound (E1) or (E2).
  • compositions according to the invention preferably contain, based on 100 parts by weight of chlorine-containing polymer, additionally 0.001-5 parts by weight of a perchlorate salt (C-I).
  • Examples of the chlorine-containing polymers to be stabilized are polymers of vinyl chloride, vinylidene chloride, vinyl resins containing vinyl chloride units in their structure, 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 the Vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of the 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
  • graft polymers of PVC with EVA, ABS and MBS are also suitable.
  • 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.
  • 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.
  • acrylate-based styrene-acrylonitrile copolymers are also suitable.
  • 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.
  • compositions of 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.
  • recyclates of chlorine-containing polymers which are the above-described polymers which have suffered damage as a result of processing, use or storage.
  • PVC recyclate is particularly preferred.
  • Another use of the stabilizer combinations 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.
  • Another object of the invention are utility (utensils) containing PVC and inventive systems.
  • TEA, TIPA tertiary alkanolamines
  • the co-usable compounds as well as the chlorine-containing polymers are generally known to the person skilled in the art and are described in detail in "HANDBUCH DER KUNSTOFFADD ⁇ TVE", R. Gumbleter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989 and 4th ed. 2001, in DE 197.41.778 A1 and EP 0.967.245 A1, to which express reference is hereby made.
  • the stabilization according to the invention is suitable both for chlorine-containing polymer compositions which are not plasticized or plasticizer-free or substantially plasticizer-free compositions, and for plasticized compositions. Particular preference is given to applications in rigid PVC or PVC semi-hard.
  • compositions of 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), light-wall profiles, building profiles, Films (also manufactured by the Luvitherm method), profiles, sidings, fittings, office films and equipment housings, insulators, computers and components of household appliances as well as for electronic applications, in particular in the semiconductor field, especially for the production of window profiles with high whiteness and surface gloss
  • Compositions in the form of semi-hard and soft formulations are suitable for wire sheathings, cable insulation, decorative films, roofing foils, foams, agricultural films, hoses, sealing profiles, flooring, wallpaper, automotive parts, flexible films, injection molded parts, office films and films for inflatable halls for d
  • the use of the compositions according to the invention as plastisols is: synthetic leather, floor coverings, textile coatings, wallpaper, coil coatings and underbody protection for motor vehicles.
  • Examples of 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 method.
  • KUNSTSTOFFHAM BUCH PVC
  • the components (Al) / (A-2) and (Bl) / (B-2) may be premixed together with other stabilizers or additives or PVC substrate, preferably as further stabilizers alkaline earth hydroxides, zeolites, hydrotalcites, hydrokalumites or Katoite can be present.
  • So-called hot mixer operating in a temperature range from 80 0 C to 120 0 C are very special preference is given here.
  • an optimal homogenization is achieved.
  • stabilizers and other additives diffuse into the PVC grain. Presence of smaller amounts of water does not interfere, but may even have a positive influence.
  • a variant consists in that the mixing process in a lubricant melt, which may contain Ca-stearate or Mg-laurate or stearate or (hydroxy) stearic acid, in the presence of a Ca or Mg hydroxide, a Mg, Ca or Al salt or "overbased" compounds of magnesium and calcium or a polyol or a zeolite, wherein maltitol, lactitol, palatinite or zeolite A, Ca hydroxide, a basic Ca or Mg -SaiIz or an "overbased" compound of magnesium or calcium is preferred.
  • the components (AI) or / and (A-2) and the components (BI) or / and (B-2) are added, wherein the components (D) and (E ) may be included in the premix.
  • the stabilizers may suitably be incorporated in another variant by the following methods: as emulsion or dispersion (one possibility is, for example, the form of a pasty mixture, an advantage of the system according to the invention in this dosage form is the stability of the paste); as a dry mix during the premixing of additional components or polymer blends; by adding directly to the processing equipment (e.g., calenders, mixers, kneaders, extruders and the like) or as a solution or melt or as flakes or pellets in dust-free form as a one-pack.
  • processing equipment e.g., calenders, mixers, kneaders, extruders and the like
  • binders which preferably consist of cellulose ethers or esters (mainly hydroxyethyl, hydroxypropyl and hydroxypropylmethylcellulose or carboxymethylcellulose).
  • binders which preferably consist of cellulose ethers or esters (mainly hydroxyethyl, hydroxypropyl and hydroxypropylmethylcellulose or carboxymethylcellulose).
  • binders which preferably consist of cellulose ethers or esters (mainly hydroxyethyl, hydroxypropyl and hydroxypropylmethylcellulose or carboxymethylcellulose).
  • polyvinyl alcohol or polyvinylpyrrolidone may also be added.
  • the polymer stabilized according to the invention can be prepared in a manner known per se, for which purpose the stabilizer mixture according to the invention and optionally further additives are mixed with the polymer using devices known per se, such as the abovementioned processing apparatuses.
  • the stabilizers can be added individually or in mixture or in the form of so-called masterbatches.
  • the stabilized polymer of the present invention can be brought into the desired shape in known manners. Such methods are, for example, grinding, Calendering, extruding, injection molding or spinning, furthermore extrusion blowing.
  • the stabilized polymer can also be made into foams.
  • the invention thus also provides a process for stabilizing chlorine-containing polymers by adding the stabilizer mixture according to the invention to a chlorine-containing polymer, as well as articles which contain PVC which is stabilized by the stabilizer mixtures according to the invention.
  • Another component of the invention is to use the combinations of (A-1) / (A-2) and (B-1) / (B-2) for the pre-stabilization of, in particular, PVC.
  • the polymerization of PVC is known to be carried out in an aqueous medium, which is why it is necessary to dry the polymer to a powder before further processing into a finished article, which is associated with a thermal stress which leads to damage of the "virgin" polymer It has now been found that an addition of the systems according to the invention during the polymerization process leads to a reduction in the described damage.This effect makes it possible to reduce the amount of heat stabilizers, even conventional ones, during the subsequent stabilization (actual thermostabilization), resulting in a saving of money.
  • Another object of the invention is a process for the stabilization of chlorine-containing polymers by adding a stabilizer mixture according to the invention to a chlorine-containing polymer, in particular soft PVC oer paste PVC.
  • the soft PVC may be suitable for the production of floors, automotive parts, wall cladding, flexible films, hoses, injection molded parts or preferably for wire sheathing (cable).
  • the chlorine-containing polymer may be a rigid PVC.
  • the chlorine-containing polymer can also be used for the production of films (also Luvitherm), PVC pipes or profiles, preferably of window profiles.
  • Another object of the invention is the use of stabilizer mixtures according to the invention for the pre-stabilization of chlorine-containing polymers, such as PVC.
  • PVC K value 60 of the type NORVINYL ® -S6045
  • Table 1 the additives BI, AK, MS, HT, ZA and BO are in accordance.
  • the powders thus obtained are dried at 60 ° C. in a drying oven to constant weight.
  • the DHC is a measure of the HCl elimination of PVC that occurs 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 (uS / cm). The key figures are minute values (min). The longer the time interval to reach a certain conductivity, the more thermostable is the PVC sample.
  • the powder samples of the invention are more thermally stable than SdT powder samples (Nos. 1-3) and have higher minute values.
  • Example 2 DHC roller skins 8) A) Production of the rolled skins: 100 tees. the dry blends prepared in accordance with IA 10) each plasticized with the addition of 0.5-0.8 parts 9) of a paraffin-based lubricant on a Collin Labormeßwalzwerk 5 minutes at 180 0 C. The resulting films (thickness 0.3 mm) are fed to further measurements.
  • Test strips (16 mm ⁇ 300 mm) are cut out from the rolled skins prepared according to Example 2A. These are in a Mathis Thermotester (Type LTE-T; Feed: 5mm basic time 5 or 45 minutes cycle time 5min) loaded at 180 0 C to the dark discoloration (burning). Subsequently, the YI value (yellowness index) according to ASTM-1925-70 is determined 12) and compared with the YI value of the unloaded rolling coat (zero minute value). The results are summarized in Tab. 4a and 4b.
  • Tab. 4a Stat. Heat test of unboosted samples (min.)
  • Tab. 4b Stat. Heat test of boosted samples (min.)
  • Tab. 4a shows an improvement of the initial color (AF) -5 min. Value as well as the color retention (FH) and long-term stability (LZ) -10 to 70 min. Value of the erfindugsuccen
  • Tab. 4b shows a serious improvement in the AF (zero minute and five minute value) and the FH and LZ -45 to 80 min. Value of the invention Sample (No. 6) i.Vgl. to the SdT (Nr.2).
  • BE bisphenol A diglycidyl ether (BADGE company ALDRICH)
  • the preparation of the powder samples is carried out as described in Example 1, with the modification that 100 TIe. PVC of the type VINNOLIT S3160 (K value 60) are used and according to Tab. 5 the additives BI, AU, BE, PE and BO are added.
  • Example 5 The following parts are used in Example 5 (see Table 7)
  • PE glycerol bis-epoxypropyl ether
  • Example 5 DHC values / powder samples

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un système de stabilisateur destiné à des polymères chlorés, notamment à du PVC, contenant au moins un azylureïde linéaire ou cyclique (A-1) et/ou un polyaminocrotonester (A-2) et un polyépoxypropylalcooléther (B-1) et/ou un dérivé cyanamide (B-2). Ledit système de stabilisateur peut également contenir une amine à encombrement stérique (D) ou une éthanolamine tertiaire (E) et/ou un perchlorate (C-1), perfluoroalcane-sulfonate (C-2) et/ou un sel de sulfatester (C-3). Ledit système de stabilisateur peut notamment se présenter sous la forme d'une combinaison d'acide N,N'-diméthyl-6-barbiturique en tant que composant (A-1), de trisépoxypropylglycérine en tant que composant (B-1) ou de dicyanodiamide en tant que composant (B-2). Ladite combinaison contient également du perchlorate de sodium ou de potassium en tant que composant (C-1). L'invention concerne également la fabrication dudit système de stabilisateur, des compositions de polymères contenant ledit système de stabilisateur et des articles d'usage courant réalisés à partir de ces compositions, tels que des profilés de fenêtres ou des gaines de câbles.
EP05772430A 2004-07-30 2005-07-26 Systeme de stabilisateur destine a des polymeres halogenes Withdrawn EP1771507A2 (fr)

Applications Claiming Priority (2)

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DE102004037369A DE102004037369A1 (de) 2004-07-30 2004-07-30 Stabilisatorsystem für halogenhaltige Polymere
PCT/EP2005/008106 WO2006013040A2 (fr) 2004-07-30 2005-07-26 Systeme de stabilisateur destine a des polymeres halogenes

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WO (1) WO2006013040A2 (fr)

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US20090306257A1 (en) 2009-12-10
WO2006013040A3 (fr) 2006-09-21
DE102004037369A1 (de) 2006-03-23
WO2006013040A2 (fr) 2006-02-09
AU2005268973A1 (en) 2006-02-09

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