EP0000746B1 - Organo tin compounds, their preparation and their application - Google Patents

Organo tin compounds, their preparation and their application Download PDF

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EP0000746B1
EP0000746B1 EP78100532A EP78100532A EP0000746B1 EP 0000746 B1 EP0000746 B1 EP 0000746B1 EP 78100532 A EP78100532 A EP 78100532A EP 78100532 A EP78100532 A EP 78100532A EP 0000746 B1 EP0000746 B1 EP 0000746B1
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Prior art keywords
alkyl
radicals
radical
organotin
organotin compounds
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EP0000746A1 (en
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Helmut Dr. Korbanka
Franz Dr. Scheidl
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/22—Tin compounds
    • C07F7/2224—Compounds having one or more tin-oxygen linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/22—Tin compounds
    • C07F7/226—Compounds with one or more Sn-S linkages
    • 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds

Definitions

  • the invention relates to new organotin compounds, a process for their preparation and their use as stabilizers for halogen-containing polymers.
  • Lead salts of organic and / or inorganic acids barium, cadmium, calcium, strontium, zinc and other metal salts of organic acids or other H-acidic compounds, such as e.g. Phenols and acid esters, as well as organotin compounds are used.
  • the most effective heat stabilizers include organotin compounds such as organotin mercaptides, thioglycolates and carboxylates.
  • R 1 are OH. NH 3 , alkyl and arylamino such as 0-alkyl radicals such as -OCH 3 , ⁇ OC 2 H5, ⁇ OC 8 H 17 , ⁇ 0 ⁇ CH 2 ⁇ CH 2 ⁇ 0 ⁇ C 2 H 9 , and 0-aryl residues such as Examples of R 2 to R 4 are at least one radical: with R 1 as mentioned above, besides: H, methyl, ethyl, propyl, hexyl, dodecyl, octadecyl, etc.
  • R 5 examples of R 5 are known residues which are always used in tin stabilizer chemistry.
  • Examples include the mercaptide series ⁇ S ⁇ C 8 H 17 , -SC 12 H 25 , ⁇ S ⁇ C 18 H 25 , and the alkylthiocarboxylate series, for example
  • Alkyl heptyl, undecyl, heptadecyl, etc.
  • Alkyl methyl, butyl, octyl, dodecyl, etc.
  • radicals R 5 are in DT-OSS 1 418 001, 1 418 017, 1 418 019, 1 494 332, 1 544 729, 1 569 070, 1 569 136, 1 569 170, 1 694 936, 1 801 274 and 2 006 711, GB-PS 1 439 752 and US-PS 3 925 309.
  • Organotin halide mixtures of the formulas are used SnHal 3 off - the meaning of the symbols R 1 to R 4 is given above;
  • Hal is Cl, Br, J - which, according to the German patent application P 27 357 57, are accessible by reacting certain substituted olefins with metallic tin and hydrogen chloride and sets them at temperatures between about 0 and 150, preferably 15 to 80 ° C.
  • Organotin halides which are preferably used are those according to the above formula in which R 1 0-alkyl having 1 to 30, preferably 1 to 20 and in particular 1 to 10 carbon atoms, R 3 and R 4 are hydrogen and with the preferred meanings given for R 1 .
  • Preferred reaction components which represent the radical R 5 in the process products are esters of thioglycolic acid, esters of thiopropionic acid, alkyl mercaptans with preferably 8 to 18 C atoms, such as octyl, dodecyl or stearyl mercaptan, fatty acids with 8 to 34 C atoms, for example Lauric acid, 2-ethylhexanoic acid, stearic acid, montanic acid and maleic acid monoester.
  • organotin halides used are mixtures of tri and dihalides (ratio of organotin dichloride / organotin trichloride depending on the production process between 1: 0.01 to 1: 4), the organotin compounds according to the invention are also mixtures, which is not disadvantageous for the claimed use, because it is known from the practice of organotin stabilizers that mixtures of diaalkyl and monoalkyltin stabilizers in chlorine-containing polymers such as polyvinyl chloride have a synergistic stabilizing effect.
  • organotin stabilizers according to the invention show a very good stabilizing effect in halogen-containing polymers, for example chlorinated polyethylene, hard and soft polyvinyl chloride, polyvinylidene chloride, polyvinyl chloroacetate and vinyl chloride-a-olefin copolymers, which is comparable to that of be known compounds, for example from dibutyltin stabilizers.
  • halogen-containing polymers for example chlorinated polyethylene, hard and soft polyvinyl chloride, polyvinylidene chloride, polyvinyl chloroacetate and vinyl chloride-a-olefin copolymers, which is comparable to that of be known compounds, for example from dibutyltin stabilizers.
  • thermoplastic compositions stabilized with the new compounds have improved transparency.
  • the new stabilizers are generally used together with other known stabilizers, such as calcium stearate or other stabilizing metal salts, stabilizing aids (epoxies, organophosphites), antioxidants such as phenols, UV-stabilizing compounds, lubricants, plasticizers, pigments, fillers and auxiliaries and the like. used. They are used in amounts of 0.1 to 10, preferably 0.2 to 5 and in particular 0.5 to 3 parts by weight, based on 100 parts by weight of polymer.
  • Examples 1 to 10 described the preparation of the new organotin compounds
  • Examples 11 to 32 show the polyvinyl chloride stabilizing effect compared to known organotin compounds.
  • Example 1 a number of further organotin stabilizers were prepared using the reactants listed in Table 1 below. 0.2 equivalent of the organotin halide, 0.2 mol of the reaction component, 0.2 mol of triethylamine as hydrogen chloride acceptor and a total of 350 ml of toluene were used. In all cases, approximately 27.5 g of triethylamine hydrochloride were isolated as a precipitate. As in Example 1, the organotin compounds obtained contained practically no chlorine. Table 2 shows the results in detail, Table 1 lists the starting materials and their amounts.
  • the mixtures are applied to a laboratory two-roll mill heated to 180 ° C. and, at a speed of 20 rpm, rolled into a skin within one minute. Samples are taken from this at intervals of 5 minutes, the colors of which are compared with those of an internal color scale. The individual tests run until the rolled skin takes on a dark brown to black color.
  • a rolled skin is first produced from the mixtures, as described above, and this is then rolled on the rolling mill at 180 ° C. for 10 minutes. About 0.5 mm thick platelets with a diameter of 30 mm are then punched from the fur drawn by the roller. The platelets are wrapped with an aluminum foil and annealed at 180 ° C in a heated cabinet with air circulation. A plate is then removed every 10 minutes and its color compared with the color scale.
  • the new stabilizers have a comparable PVC-stabilizing effect compared to the known dibutyltin stabilizers (examples 21 to 24 and 32) with the same amounts of tin in the formulation and corresponding residues, but have less influence on the transparency of the test specimens.

Description

Die Erfindung betrifft neue Organozinnverbindungen, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Stabilisatoren für halogenhaltige Polymere.The invention relates to new organotin compounds, a process for their preparation and their use as stabilizers for halogen-containing polymers.

Bei der Verarbeitung halogenhaltiger Polymerer, insbesondere Polymerer und Copolymerer des Vinylchlorids und Vinyldenchlorids müssen diesen Wärmestabilisatoren zugesetzt werden, um Zersetzungen, die zu Verfärbungen, zu Versprödungen und zur Verschlechterung der mechanischen Eigenschaften führen, zu verhindern oder weitgehend zu verzögern.When processing halogen-containing polymers, in particular polymers and copolymers of vinyl chloride and vinyldenchloride, these heat stabilizers must be added in order to prevent or largely delay decomposition, which leads to discoloration, embrittlement and deterioration in the mechanical properties.

Als Wärniestabilisatoren werden im allgemeinen Bleisalze von organischen und/oder anorganischen Säuren, Barium-, Cadmium-, Calcium-, Strontium-, Zink- und andere Metallsalze organischer Säuren oder anderer H-acider Verbindungen, wie z.B. Phenole und saure Ester, sowie Organozinnverbindungen verwendet. Zu den wirksamsten Wärmestabilisatoren zählen Organozinnverbindungen wie Organozinnmercaptide, -thioglykolate und -carboxylate.Lead salts of organic and / or inorganic acids, barium, cadmium, calcium, strontium, zinc and other metal salts of organic acids or other H-acidic compounds, such as e.g. Phenols and acid esters, as well as organotin compounds are used. The most effective heat stabilizers include organotin compounds such as organotin mercaptides, thioglycolates and carboxylates.

Es wurde gefunden, daß sich Gemischebisher nicht bekannter Organozinnverbindungen der allgemeinen Formeln

Figure imgb0001
wobei die verwendeten Symbole die nachstehende Bedeutung haben, hervorragend als Wärmestabilisatoren für halogenhaltige Polymere eignen. In den Formel bedeutet:

  • R1 OH, -NH2, einen Alkylaminorest, einen Arylaminorest, einen 0-Alkylrest oder einen O-Arylrest, wobei die beiden letztgenannten Reste auch aryl- bzw. alkylsubstituiert sein können und sowohl als solche als auch in der aryl- bzw. alkylsubstituierten Form als Substituenten gegebenenfalls noch Halogen oder eine Hydroxyl-, Thioäther-, Äther- und/oder Carboxylgruppe tragen,
  • R2 bis R4 gleiche oder verschiedene Substituenten, und zwar
    • a) 0 bis zwei Wasserstoffatome sowie
    • b) Alkylreste mit ein bis 30 C-Atomen sind mit der Bedingung, daß mindestens einer dieser Reste eine Gruppe
      Figure imgb0002
      ist, wobei R1 die oben angegebene Bedeutung hat und n für eine Zahl von 1 bis 15 steht,
  • R5 ―S―(CH2]m-CO2-Alkyl, -S-Alkyl-, -02C-Alkyl und -02C-CH=CH-CO2-Alkyl, wobei m die Zahl 1 oder 2 ist und der Alkylrest gegebenenfalls noch -0-, -S- oder ―CO2-Gruppen und OH-Substituenten enthalten kann.
It has been found that mixtures of previously unknown organotin compounds of the general formulas
Figure imgb0001
 the symbols used have the following meanings, are outstandingly suitable as heat stabilizers for halogen-containing polymers. In the formula:
  • R 1 OH, -NH 2 , an alkylamino radical, an arylamino radical, a 0-alkyl radical or an O-aryl radical, where the latter two radicals can also be aryl- or alkyl-substituted and both as such and in the aryl- or alkyl-substituted Halogen or a hydroxyl, thioether, ether and / or carboxyl group may also be in the form of substituents,
  • R 2 to R 4 are the same or different substituents
    • a) 0 to two hydrogen atoms as well
    • b) Alkyl radicals with one to 30 carbon atoms are on the condition that at least one of these radicals is a group
      Figure imgb0002
       where R 1 has the meaning given above and n stands for a number from 1 to 15,
  • R 5 ―S― (CH 2 ] m -CO 2 alkyl, -S-alkyl-, -0 2 C-alkyl and -0 2 C-CH = CH-CO 2 alkyl, where m is the number 1 or 2 is and the alkyl radical may optionally also contain -0-, -S- or ―CO 2 groups and OH substituents.

Die sich in den beiden Gemischkomponenten I und II entsprechenden Reste R1 bis R5 sind stets gleich.The radicals R 1 to R 5 corresponding to the two mixture components I and II are always the same.

Beispiele für R1 sind OH. NH3, Alkyl- und Arylaminorest wie

Figure imgb0003
0-Alkylreste wie -OCH3, ―OC2H5, ―OC8H17,
Figure imgb0004
―0―CH2―CH2―0―C2H9,
Figure imgb0005
und 0-Arylreste wie
Figure imgb0006
Beispiele für R2 bis R4 sind mindestens ein Rest:
Figure imgb0007
mit R 1 wie vorstehend genannt, daneben: H, Methyl, Äthyl, Propyl, Hexyl, Dodecyl, Octadecyl usf.Examples of R 1 are OH. NH 3 , alkyl and arylamino such as
Figure imgb0003
 0-alkyl radicals such as -OCH 3 , ―OC 2 H5, ―OC 8 H 17 ,
Figure imgb0004
 ―0 ― CH 2 ―CH 2 ―0 ― C 2 H 9 ,
Figure imgb0005
 and 0-aryl residues such as
Figure imgb0006
 Examples of R 2 to R 4 are at least one radical:
Figure imgb0007
 with R 1 as mentioned above, besides: H, methyl, ethyl, propyl, hexyl, dodecyl, octadecyl, etc.

Beispiele für R5 sind an sich bekannte, in der Zinnstabilisatoreri-Chemie stets verwendete Reste.Examples of R 5 are known residues which are always used in tin stabilizer chemistry.

Genannt seien z.B. aus der Mercaptid-Reihe ―S―C8H17, -S-C12H25, ―S―C18H25, aus der Alkylthiocarboxylat-Reihe z.B.Examples include the mercaptide series ―S ― C 8 H 17 , -SC 12 H 25 , ―S ― C 18 H 25 , and the alkylthiocarboxylate series, for example

―S―(CH2)n―CO2-Alky (n = 1 und 2; Alkyl = Octyl, Lauryl, Octadecyl, 2-Hydroxy-octadecyl usf.), aus der Carboxylatreihe z.B.

Figure imgb0008
―S― (CH 2 ) n ― CO 2 -alky (n = 1 and 2; alkyl = octyl, lauryl, octadecyl, 2-hydroxy-octadecyl, etc.), from the carboxylate series, for example
Figure imgb0008

Alkyl (Alkyl = Heptyl, Undecyl, Heptadecyl usf.) und aus der Partialesterreihe z.B.

Figure imgb0009
.Alkyl (Alkyl = Methyl, Butyl, Octyl, Dodecyl usf.)Alkyl (alkyl = heptyl, undecyl, heptadecyl, etc.) and from the partial ester series, for example
Figure imgb0009
 .Alkyl (alkyl = methyl, butyl, octyl, dodecyl, etc.)

Weitere bekannte Beispiele für Reste R5 sind in den DT-OSS 1 418 001, 1 418 017, 1 418 019, 1 494 332, 1 544 729, 1 569 070, 1 569 136, 1 569 170, 1 694 936, 1 801 274 und 2 006 711, der GB-PS 1 439 752 sowie der US-PS 3 925 309 beschrieben.Further known examples of radicals R 5 are in DT-OSS 1 418 001, 1 418 017, 1 418 019, 1 494 332, 1 544 729, 1 569 070, 1 569 136, 1 569 170, 1 694 936, 1 801 274 and 2 006 711, GB-PS 1 439 752 and US-PS 3 925 309.

Die neuen Organozinnverbindungen werden nach aus der Organo-Zinnchemie bekannten Verfahren erhalten. Man geht von Organozinnhalogenidgemischen der Formeln

Figure imgb0010
SnHal3 aus - die Bedeutung der Symbole R1 bis R4 ist oben angegeben; Hal ist Cl, Br, J - die nach den Angaben der deutschen Patentanmeldung P 27 357 57 durch Umsetzen von bestimmten, substituierten Olefinen mit metallischem Zinn und Chlorwasserstoff zugänglich sind und setzt diese bei Temperaturen zwischen etwa 0 und 150, vorzugsweise 15 bis 80°C mit Mercaptanen, Thiocarbonsäuren, Carbonsäuren und Partialestern wie Maleinsäuremonoestern in Gegenwart von Halogenwasserstoffakzeptoren wie NaOH, NaHC03, KHCO3 oder Aminen, wie Triäthylamin, Pyridin usf. und gegebenenfalls in inerten Lösungsmitteln, wie Athern, Ketonen, Estern, aliphatischen oder aromatischen Kohlenwasserstoffen um. Eine weitere Möglichkeit besteht darin, daß man die Organozinnhalogenide zu Organozinnoxiden hydrolysiert und letztere mit den -SH- oder ―CO2H-Verbindungen unter Abspaltung von Wasser zur Reaktion bringt.The new organotin compounds are obtained by methods known from organotin chemistry. Organotin halide mixtures of the formulas are used
Figure imgb0010
 SnHal 3 off - the meaning of the symbols R 1 to R 4 is given above; Hal is Cl, Br, J - which, according to the German patent application P 27 357 57, are accessible by reacting certain substituted olefins with metallic tin and hydrogen chloride and sets them at temperatures between about 0 and 150, preferably 15 to 80 ° C. with mercaptans, thiocarboxylic acids, carboxylic acids and partial esters such as maleic acid monoesters in the presence of hydrogen halide acceptors such as NaOH, NaHC0 3 , KHCO 3 or amines such as triethylamine, pyridine etc. and, if appropriate, in inert solvents such as ethers, ketones, esters, aliphatic or aromatic hydrocarbons. Another possibility is to hydrolyze the organotin halides to organotin oxides and to react the latter with the -SH or ―CO 2 H compounds with elimination of water.

Bevorzugt eingesetzte Organozinnhalogenide sind solche gemäß vorstehender Formel, bei denen R1 0-Alkyl mit 1 bis 30, vorzugsweise 1 bis 20 und insbesondere 1 bis 10 Kohlenstoffatomen, R3 und R4 Wasserstoff und

Figure imgb0011
mit den für R1 angegebenen, bevorzugten Bedeutungen ist. Bevorzugte Reaktionskomponenten, die in den Verfahrensprodukten den Rest R5 darstellen, sind Ester der Thioglykolsäure, Ester der Thiopropionsäure, Alkylmercaptane mit bevorzugt 8 bis 18 C-Atomen wie Octyl-, Dodecyl- oder Stearylmercaptan, Fettsäuren mit 8 bis 34 C-Atomen, beispielsweise Laurinsäure, 2-Athylhexansäure, Stearinsäure, Montansäure sowie Maleinsäuremonoester.Organotin halides which are preferably used are those according to the above formula in which R 1 0-alkyl having 1 to 30, preferably 1 to 20 and in particular 1 to 10 carbon atoms, R 3 and R 4 are hydrogen and
Figure imgb0011
 with the preferred meanings given for R 1 . Preferred reaction components which represent the radical R 5 in the process products are esters of thioglycolic acid, esters of thiopropionic acid, alkyl mercaptans with preferably 8 to 18 C atoms, such as octyl, dodecyl or stearyl mercaptan, fatty acids with 8 to 34 C atoms, for example Lauric acid, 2-ethylhexanoic acid, stearic acid, montanic acid and maleic acid monoester.

Da die eingesetzten Organozinnhalogenide Gemische aus Tri- und Dihalogenidendarstellen (Verhältnis Organozinndichlorid/Organozinntrichlorid je nach Herstellverfahren zwischen 1 : 0,01 bis 1 : 4), sind die Organozinnverbindungen gemäß der Erfindung ebenfalls Gemische, was für den beanspruchten Verwendungszweck jedoch nicht von Nachteil ist, denn aus der Organozinnstabilisatoren-Praxis ist bekannt, daß Gemische aus Diaalkyl- und Monoalkylzinnstabilisatoren in chlorhaltigen Polymeren wie Polyvinylchlorid einen synergistischen stabilisierenden Effekt aufweisen. Falls gewünscht, kann man selbstverständlich auch die reinen Di- und Monoorganozinnstabilisatoren der allgemeinen Formeln I und II herstellen, muß jedoch dann von reinen Di- bzw. Trihalogeniden, die aus den Mischungen nach bekannten Methoden (z.B. fraktionierte Kristallisation) isolierbar sind, ausgehen.Since the organotin halides used are mixtures of tri and dihalides (ratio of organotin dichloride / organotin trichloride depending on the production process between 1: 0.01 to 1: 4), the organotin compounds according to the invention are also mixtures, which is not disadvantageous for the claimed use, because it is known from the practice of organotin stabilizers that mixtures of diaalkyl and monoalkyltin stabilizers in chlorine-containing polymers such as polyvinyl chloride have a synergistic stabilizing effect. If desired, it is of course also possible to prepare the pure di- and monoorganotin stabilizers of the general formulas I and II, but must then be based on pure di- or trihalides which can be isolated from the mixtures by known methods (e.g. fractional crystallization).

Einige typische Vertreter der erfindungsgemäßen Organozinn-Verbindungen seien im folgenden aufgezählt; die Erfindung soll jedoch nicht auf die genannten Substanzen beschränkt werden.Some typical representatives of the organotin compounds according to the invention are listed below; however, the invention is not intended to be limited to the substances mentioned.

Gemische aus Di- und Mono-(bis-2,3-carbomethoxy-)-propyl-zinn-di- und -trioctylthioglykolat

Figure imgb0012
und
Figure imgb0013
Gemisch aus Di- und Mono-(bis-2,4-carbobutoxy-)butyl-zinn-di- und tri-n-dodecylmercaptid
Figure imgb0014
und
Figure imgb0015
Gemisch aus Di- und Mono-(bis-2,3-carbophenoxy-)propyl-zinn-di- und -trilaurat
Figure imgb0016
und
Figure imgb0017
Gemisch aus Di- und Mono - (bis - 2,3 - carbo - 2 - hydroxy - tetradecoxy-)propyl - zinn - di- und -trimonobutylmaleinat
Figure imgb0018
und
Figure imgb0019
Gemisch aus Di- und Mono-(bis-2,3-anilino-carbonyl-)propyl-zinn-di- und -tributylthiopropionat
Figure imgb0020
und
Figure imgb0021
 Mixtures of di- and mono- (bis-2,3-carbomethoxy -) - propyl-tin-di- and trioctylthioglycolate
Figure imgb0012
 and
Figure imgb0013
 Mixture of di- and mono- (bis-2,4-carbobutoxy-) butyl-tin-di- and tri-n-dodecyl mercaptide
Figure imgb0014
 and
Figure imgb0015
 Mixture of di and mono (bis-2,3-carbophenoxy) propyl tin di and trilaurate
Figure imgb0016
 and
Figure imgb0017
 Mixture of di- and mono - (bis - 2,3 - carbo - 2 - hydroxy - tetradecoxy-) propyl - tin - di- and trimonobutyl maleate
Figure imgb0018
 and
Figure imgb0019
 Mixture of di- and mono- (bis-2,3-anilino-carbonyl) propyl-tin-di- and -tributylthiopropionat
Figure imgb0020
 and
Figure imgb0021

Die erfindungsgemäßen Organozinnstabilisatoren zeigen in halogenhaltigen Polymerisaten, beispeilsweise Chlorpolyäthylen, Hart- und Weich-Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylchloracetat und Vinylchlorid-a-Olefin-Copolymerisaten eine sehr gute stabilisierende Wirkung, die der von bekannten Verbindungen, beispielsweise von Dibutylzinnstabilisatoren entspricht. Darüber hinaus wird beobachtet, daß mit den neuen Verbindungen stabilisierte thermoplastische Massen eine verbesserte Transparenz aufweisen.The organotin stabilizers according to the invention show a very good stabilizing effect in halogen-containing polymers, for example chlorinated polyethylene, hard and soft polyvinyl chloride, polyvinylidene chloride, polyvinyl chloroacetate and vinyl chloride-a-olefin copolymers, which is comparable to that of be known compounds, for example from dibutyltin stabilizers. In addition, it is observed that thermoplastic compositions stabilized with the new compounds have improved transparency.

Die neuen Stabilisatoren werden im allgemeinen zusammen mit anderen bekannten Stabilisatoren, wie Calcium-stearat oder anderen stabilisierenden Metallsalzen, stabilisierenden Hilfsmitteln (Epoxide, Organophosphite), Antioxidanten wie Phenole, UV-stabilisierenden Verbindungen, Gleitmitteln, Weichmachern, Pigmenten, Füll- und Hilfsstoffen u.ä.verwendet. Man setzt sie in Mengen von 0,1 bis 10, vorzugsweise 0,2 bis 5 und insbesondere 0,5 bis 3 Gewichtsteilen, bezogen auf 100 Gewichtsteile Polymeres, ein.The new stabilizers are generally used together with other known stabilizers, such as calcium stearate or other stabilizing metal salts, stabilizing aids (epoxies, organophosphites), antioxidants such as phenols, UV-stabilizing compounds, lubricants, plasticizers, pigments, fillers and auxiliaries and the like. used. They are used in amounts of 0.1 to 10, preferably 0.2 to 5 and in particular 0.5 to 3 parts by weight, based on 100 parts by weight of polymer.

Die folgenden Beispiele sollen die Erfindung weiter erläutern. Die Beispiele 1 bis 10 beschrieben die Herstellung der neuen Organozinnverbindungen, die Beispiele 11 bis 32 zeigen die Polyvinylchloridstabilisierende Wirkung im Vergleich zu bekannten Organozinnverbindungen.The following examples are intended to explain the invention further. Examples 1 to 10 described the preparation of the new organotin compounds, Examples 11 to 32 show the polyvinyl chloride stabilizing effect compared to known organotin compounds.

Beispiel 1example 1

In einem mit Rühreinrichtung, Innenthermometer und Tropftrichter ausgestatteten 500-ml-Dreihalskolben wurden 40,8 g (0,2 Mol) Thioglykolsäure-2-äthyl-hexylester, 36,0 g (0,2 Äquivalent Chlor) eines Gemisches aus ca. 59 Gew.-% Di-(bis-2,3-carbomethoxy-)propyl-zinndichlorid und ca. 41 Gew.-% Mono-(bis-2,3-carbomethoxy-)propyl-zinntrichlorid (Chlorgehalt des Gemisches: 19,7%, Zinngehalt: 21,8%) und 300 ml Toluol vorgelegt. Bei 20°C wurde eine Lösung von 20,2 g (0,2 Mol) Triäthylamin in 50 ml Toluol zugetropft. Sodann wurde 2 Stunden bei Raumtemperatur weitergerührt. Anschließend wurde der entstandene Niederschlag (27,5 g Triäthylammoniumchlorid) abgesaugt. Aus dem Filtrat wurde nach Abdestillieren des Toluols der Organozinnstabilisator in Form einer gelblichen Flüssigkeit als Rückstand isoliert.In a 500 ml three-necked flask equipped with a stirring device, internal thermometer and dropping funnel, 40.8 g (0.2 mol) of 2-ethylhexyl thioglycolic acid, 36.0 g (0.2 equivalent of chlorine) of a mixture of approx. 59 % By weight di- (bis-2,3-carbomethoxy-) propyltin dichloride and approx. 41% by weight mono- (bis-2,3-carbomethoxy-) propyltin trichloride (chlorine content of the mixture: 19.7 %, Tin content: 21.8%) and 300 ml of toluene. A solution of 20.2 g (0.2 mol) of triethylamine in 50 ml of toluene was added dropwise at 20 ° C. Then stirring was continued for 2 hours at room temperature. The precipitate formed (27.5 g of triethylammonium chloride) was then filtered off with suction. After the toluene had been distilled off, the organotin stabilizer was isolated as a residue from the filtrate in the form of a yellowish liquid.

Ausbeute: 69,5 g Organozinn-2-äthylhexylthioglykolat;Yield: 69.5 g of organotin-2-ethylhexylthioglycolate; Analyse: 11,3% SnAnalysis: 11.3% Sn 0,1% CI0.1% CI Beispiele 2 bis 10Examples 2 to 10

Nach der im Beispiel 1 beschriebenen Verfahrensweise wurde unter Einsatz der in der nachstehenden Tabelle 1 zusammengestellten Reaktionspartner eine Anzahl weiterer Organozinnstabilisatoren hergestellt. Es wurden stets 0,2 Äquivalent des Organozinnhalogenids, 0,2 Mol der Reaktionskomponente, 0,2 Mol Triäthylamin als Chlorwasserstoff-Akzeptor und als Lösungsmittel insgesamt 350 ml Toluol eingesetzt. In allen Fällen wurden ca. 27,5 g Triäthylamin-Hydrochlorid als Niederschlag isoliert. Die erhaltenen Organozinnverbindungen enthielten wie in Beispiel 1 praktisch kein Chlor. In Tabelle 2 sind die Ergebnisse im einzelnen aufgeführt, Tabelle 1 nennt die Ausgangsmaterialien und ihre Einsatzmengen.

Figure imgb0022
Figure imgb0023
Figure imgb0024
 According to the procedure described in Example 1, a number of further organotin stabilizers were prepared using the reactants listed in Table 1 below. 0.2 equivalent of the organotin halide, 0.2 mol of the reaction component, 0.2 mol of triethylamine as hydrogen chloride acceptor and a total of 350 ml of toluene were used. In all cases, approximately 27.5 g of triethylamine hydrochloride were isolated as a precipitate. As in Example 1, the organotin compounds obtained contained practically no chlorine. Table 2 shows the results in detail, Table 1 lists the starting materials and their amounts.
Figure imgb0022
Figure imgb0023
Figure imgb0024

Beispiele 11 bis 32Examples 11 to 32

Diese Beispiel zeigen die stabilisierende Wirkung der neuen Organozinnstabilisatoren bei der Verarbeitung von PVC. Die angegebenen Teile sind stets Gewichtsteile.These examples show the stabilizing effect of the new organotin stabilizers in the processing of PVC. The parts specified are always parts by weight.

Jeweils 100 Teile eines Suspensions-Polyvinylchlorids vom K-Wert 68 wurden mit 0,4 Teilen Calciumstearat, 0,4 Teilen Kohlenwasserstoffwachs vom Tropfpunkt ca. 90°C und dem zu prüfenden Organozinnstabilisator in einer solchen Menge, daß stets in etwa der gleiche Zinngehalt im Ansatz vorhanden war, vermischt. Zu Vergleichszwecken wurden bekannte Zinnstabilisatoren in die Prüfungen einbezogen.In each case 100 parts of a suspension polyvinyl chloride with a K value of 68 were mixed with 0.4 parts of calcium stearate, 0.4 parts of hydrocarbon wax from the dropping point at about 90 ° C. and the organotin stabilizer to be tested in such an amount that the tin content in the mixture was always approximately the same Approach was present, mixed. Known tin stabilizers were included in the tests for comparison purposes.

Zur Bestimmung der dynamischen Wärmestabilität werden die Mischungen auf ein 180°C beheiztes Labor-Zweiwalzwerk aufgetragen und bei einer Tourenzahl von 20 UpM innerhalb von einer Minute zu einem Fell verwalzt. Von diesem werden in Abständen von 5 Minuten Proben entnommen, deren Farben mit denen einer internen Farbskala verglichen werden. Die einzelnen Versuche laufen jeweils so lange, bis das Walzfell eine dunkelbraune bis schwarze Farbe annimmt.To determine the dynamic thermal stability, the mixtures are applied to a laboratory two-roll mill heated to 180 ° C. and, at a speed of 20 rpm, rolled into a skin within one minute. Samples are taken from this at intervals of 5 minutes, the colors of which are compared with those of an internal color scale. The individual tests run until the rolled skin takes on a dark brown to black color.

Um die statische Wärmestabilität zu ermitteln, wird - wie oben beschrieben - zunächst aus den Mischungen ein Walzfell hergestellt und dieses noch 10 Minuten bei 180°C auf dem Walzwerk gewalzt. Aus dem von der Walze gezogenen Fell werden sodann ca. 0,5 mm starke Plättchen mit einem Durchmesser von 30 mm gestanzt. Die Plättchen werden mit einer Aluminiumfolie umwickelt und bei 180°C in einem Wärmeschrank mit Luftumwälzung getempert. Im Abstand von 10 Minuten wird dann jeweils ein Plättchen entnommen und dessen Farbe mit der Farbskala verglichen.In order to determine the static heat stability, a rolled skin is first produced from the mixtures, as described above, and this is then rolled on the rolling mill at 180 ° C. for 10 minutes. About 0.5 mm thick platelets with a diameter of 30 mm are then punched from the fur drawn by the roller. The platelets are wrapped with an aluminum foil and annealed at 180 ° C in a heated cabinet with air circulation. A plate is then removed every 10 minutes and its color compared with the color scale.

In der verwendeten Farbskala bedeuten die Wertzahlen

  • 1 = wasserhell
  • 2 = geringer Gelbstich
  • 3 = starke Gelbfärbung
  • 4 = tiefe, gelbbraune Farbe
  • 5 = dunkelbraun bis schwarz.
In the color scale used, the value numbers mean
  • 1 = water-clear
  • 2 = slight yellow tinge
  • 3 = strong yellowing
  • 4 = deep yellow-brown color
  • 5 = dark brown to black.

Die Versuchsbedingungen sowie die Ergebnisse sind in den Tabellen 3 und 4 zusammengestellt. Wie ersichtlich, besitzen die neuen Stabilisatoren im Vergleich zu den bekannten Dibutylzinnstabilisatoren (Beispiele 21 bis 24 und 32) bei gleichen Mengen Zinn in der Rezeptur und entsprechenden Resten eine vergleichbare PVC-stabilisierende Wirkung, beeinflussen jedoch die Transparenz der Prüfkörper weniger.

Figure imgb0025
Figure imgb0026
 The test conditions and the results are summarized in Tables 3 and 4. As can be seen, the new stabilizers have a comparable PVC-stabilizing effect compared to the known dibutyltin stabilizers (examples 21 to 24 and 32) with the same amounts of tin in the formulation and corresponding residues, but have less influence on the transparency of the test specimens.
Figure imgb0025
Figure imgb0026

Claims (6)

1. Mixture of organotin compounds having the formulae
Figure imgb0035
in which
R1 is OH, -NH2, an alkylamino or arylamino radical, an O-alkyl or O-aryl radical, both the latter radicals being optionally substituted by aryl or alkyl and both the latter substituted or unsubstituted radicals carrying optionally as additional substituents halogen or a hydroxy, thioether, ether and/or carboxyl group;
R2 to R4, being identical or different, each are
a) 0 to 2 hydrogen atoms, or
b) alkyl radicals having from 1 to 30 carbon atoms, with the proviso that at least one of these radicals is a
Figure imgb0036
group, where R1 is as defined above and

n an integer of from 1 to 15;
RS is ―S―(CH2)m―CO2-alkyl, -S-alkyl, -02C-alkyl or ―O2C―CH=H―CO2-alkyl). m being 1 or 2 and the alkyl radical optionally containing -0-, -S- or -C02 groups and OH substituents;

and the radicals R' to R5 corresponding to one another in the components and II of the mixture always being identical.
2. Mixture of organotin compounds as claimed in claim 1, wherein in both components the radical R' is O-alkyl having from 1 to 30 carbon atoms, the radical R2 is
Figure imgb0037
(R' being as defined in this claim), the radicals R3 and R4 each are hydrogen and the radical R5 is as defined in claim 1.
3. Mixture of organotin compounds as claimed in claims 1 and 2, wherein the weight ratio of component I to component II is from about 1:0.01 to 1:4.
4. Process for the manufacture of mixtures of organotin compounds as claimed in claims 1 to 3 by reaction of organotin halides with mercaptans, thiocarboxylic acid esters, carboxylic acids or carboxylic acid partial esters in the presence of hydrogen halide acceptors and optionally inert solvents, according to known methods, which comprises using mixtures of organotin halides of the formulae
Figure imgb0038
in which the radicals R1 to R4 are defined as in claim 1 and Hal is chlorine, bromine or iodine.
5. Use of the organotin compounds as claimed in claims 1 to 3 as stabilizers for halogen- containing polymers in amounts of from 0.1 to 10 parts by weight per 100 parts by weight of polymer.
6. Plastics molding compositions on the basis of chlorine-containing polymers which contain organotin compounds as claimed in claims 1 to 3 as stabilizers.
EP78100532A 1977-08-09 1978-07-28 Organo tin compounds, their preparation and their application Expired EP0000746B1 (en)

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FR2457298A1 (en) * 1979-05-23 1980-12-19 Elf Aquitaine ORGANOSTANNIC STABILIZER COMPOSITIONS FOR HALOGENO-VINYL RESINS
US4360619A (en) * 1981-02-26 1982-11-23 Carstab Corporation Stabilizer compositions and polymers containing same
US4314934A (en) * 1981-02-26 1982-02-09 Carstab Corporation Organohalide polymers stabilized with an organotin compound and an ortho mercapto phenol compound
US4988750A (en) * 1981-07-17 1991-01-29 Schering Ag Non-toxic stabilizer for halogenated polymer
PL147517B1 (en) * 1985-09-25 1989-06-30 Politechnika Warszawska Method of obtaining cyanoorganic compounds
GB8724049D0 (en) * 1987-10-14 1987-11-18 Kodak Ltd Organotin compounds as anionic ionophores
US5470995A (en) * 1993-06-29 1995-11-28 Morton International, Inc. Continuous process for making a dialkyltin thiocarboxylic acid ester
FR2758141B1 (en) * 1997-01-09 1999-02-26 Atochem North America Elf COMPOSITION BASED ON HIGH MOLECULAR WEIGHT ORGANOETAN MALEATES USEFUL FOR STABILIZING THERMOPLASTIC POLYMERS. PROCESS FOR OBTAINING THE SAME
FR2758142B1 (en) * 1997-01-09 1999-02-26 Atochem North America Elf COMPOSITION BASED ON ORGANO-TIN MALEATES THAT CAN BE USED FOR STABILIZING AND LUBRICATING THERMOPLASTIC POLYMERS. PROCEDURE FOR OBTAINING THE SAID COMPOSITION
EP2123659A1 (en) * 2008-05-15 2009-11-25 Arkema France High purity monoalkyltin compounds and uses thereof

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US3440255A (en) * 1967-09-28 1969-04-22 Sumio Matsuda Process for preparing organotin halides
US4105684A (en) * 1974-09-16 1978-08-08 Akzo N.V. Process for the preparation of organotin trihalides
NL7412230A (en) * 1974-09-16 1976-03-18 Akzo Nv PROCESS FOR THE PREPARATION OF ORGANOTINTRI HALOGENIDES.
NL7503116A (en) * 1975-03-17 1976-09-21 Akzo Nv PROCEDURE FOR PREPARING ORGANOTIN DIHALOGENIDES AND ORGANOTIN STABILIZERS DERIVED FROM THEREOF.
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