EP0000746B1 - Composés d'organoétain, leur préparation et leur application - Google Patents

Composés d'organoétain, leur préparation et leur application Download PDF

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Publication number
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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EP
European Patent Office
Prior art keywords
alkyl
radicals
radical
organotin
organotin compounds
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Expired
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EP78100532A
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German (de)
English (en)
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EP0000746A1 (fr
Inventor
Helmut Dr. Korbanka
Franz Dr. Scheidl
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Hoechst AG
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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 Table
    • 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 Table
    • 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.

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

Claims (6)

1. Mélange de composés organostanniques caractérisé en ce que ceux-ci répondent aux formules:
Figure imgb0031
dans lesquelles:
R1 représente -OH, -NH2, un radical alkylamino, un radical arylamino, un radical alcoxy ou un radical aryloxy, ces deux derniers radicaux pouvant également porter un substituant respectivement arylique ou alkylique et portant éventuellement comme substituants supplémentaires, qu'ils soient ou non porteurs respectivement d'un substituant arylique ou alkylique, un halogène ou un radical hydroxy, thioéther, éther et/ou carboxy,
R2 à R4 représentent des substituants identiques ou différents, plus précisément:
a) de 0 à 2 atomes d'hydrogène ainsi que
b) des radicaux alkyles contenant de 1 à 30 atomes de carbone avec la condition qu'au moins l'un de ces radicaux soit un groupe
Figure imgb0032
dans lequel R1 a la signification indiquée ci-dessus et n désigne un nombre de 1 à 15,
R5 représente un radical ―S―(CH2)m―CO2-alkyl, -S-alkyl, -02C-alkyl ou -02C-CH=CH-CO2- alkyl, l'indice m désignant le nombre 1 ou le nombre 2 et le radical alkyle pouvant en outre contenir des radicaux -0-, -S- ou ―CO2― et des substituents -OH, et les radicaux R1 à R5 qui se correspondent dans les deux composants I et II du mélange sont toujours identiques.
2. Mélange de composés organostanniques selon la revendication 1, caractérisé en ce que, dans les deux composantes, R1 représente un radical alcoxy contenant de 1 à 30 atomes de carbone, R2 représente un radical
Figure imgb0033
 dans lequel R1 a la signification indiquée ci-dessus pour ce symbole, R3 et R4 représentent chacun un atome d'hydrogène et R5 a la signification donnée à la revendication 1.
3. Mélange de composés organostanniques selon l'une des revendications 1 et 2, caractérisé en ce que le rapport pondéral de la composante I à la composante Il est compris entre environ 1 : 0,01 et 1 : 4.
4. Procédé de préparation des mélanges de composés organostanniques selon l'une quelconque des revendications 1 à 3, par réaction d'halogénures d'organo-étains avec des mercaptans, des esters d'acides mercapto-alcanoïques, des acides alcanoïques ou des esters partiels d'acides carboxyliques, en présence d'accepteurs d'halogénures d'hydrogène et éventuellement de solvants inertes, effectuée de façon connue, procédé caractérisé en ce qu'on utilise des mélanges d'halogénures d'organo-étains répondant aux formules générales:
Figure imgb0034
dans lesquelles R1 à R4 ont les significations données à la revendication 1 et Hal représente le chlore, le brome ou l'iode.
5. Application des composés organostanniques selon l'une quelconque des revendications 1 à 3 comme stabilisants pour des polymères contenant des halogènes, en des quantités comprises entre 0,1 et 10 parties en poids pour 100 parties en poids de polymère.
6. Matières à mouler synthétiques à base de polymères contenant du chlore, qui renferment, comme stabilisants, des composés organostanniques selon l'une quelconque des revendications 1 à 3.
EP78100532A 1977-08-09 1978-07-28 Composés d'organoétain, leur préparation et leur application Expired EP0000746B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2735810 1977-08-09
DE2735810A DE2735810B2 (de) 1977-08-09 1977-08-09 Gemische aus Organozinnverbindungen und ihre Verwendung als Stabilisatoren für chlorhaltige Polymere

Publications (2)

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EP0000746A1 EP0000746A1 (fr) 1979-02-21
EP0000746B1 true EP0000746B1 (fr) 1981-01-28

Family

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Family Applications (1)

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EP78100532A Expired EP0000746B1 (fr) 1977-08-09 1978-07-28 Composés d'organoétain, leur préparation et leur application

Country Status (6)

Country Link
US (1) US4237043A (fr)
EP (1) EP0000746B1 (fr)
JP (1) JPS5430119A (fr)
CA (1) CA1116625A (fr)
DE (2) DE2735810B2 (fr)
IT (1) IT1098005B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2457298A1 (fr) * 1979-05-23 1980-12-19 Elf Aquitaine Compositions de stabilisants organostanniques pour resines halogeno-vinyliques
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 (fr) * 1997-01-09 1999-02-26 Atochem North America Elf Composition a base de maleates d'organoetain de poids moleculaire eleve utilisable pour stabiliser des polymeres thermoplastiques. procede d'obtention de ladite composition
FR2758142B1 (fr) * 1997-01-09 1999-02-26 Atochem North America Elf Composition a base de maleates d'organoetain utilisable pour stabiliser et lubrifier des polymeres thermoplastiques. procede d'obtention de ladite composition
EP2123659A1 (fr) * 2008-05-15 2009-11-25 Arkema France Composés de monoalkyltine à pureté élevée et utilisations associées

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3440255A (en) * 1967-09-28 1969-04-22 Sumio Matsuda Process for preparing organotin halides
NL7412230A (nl) * 1974-09-16 1976-03-18 Akzo Nv Werkwijze voor de bereiding van organotintri- halogeniden.
US4105684A (en) * 1974-09-16 1978-08-08 Akzo N.V. Process for the preparation of organotin trihalides
NL7503116A (nl) * 1975-03-17 1976-09-21 Akzo Nv Werkwijze voor het bereiden van organotindihaloge- niden, alsmede daarvan afgeleide organotinstabi- lisatoren.
US4080363A (en) * 1975-03-17 1978-03-21 Akzo N.V. Process for making organotin dihalides and trihalides and stabilizers prepared therefrom

Also Published As

Publication number Publication date
DE2735810B2 (de) 1981-01-29
IT7826560A0 (it) 1978-08-07
EP0000746A1 (fr) 1979-02-21
US4237043A (en) 1980-12-02
JPS5430119A (en) 1979-03-06
IT1098005B (it) 1985-08-31
CA1116625A (fr) 1982-01-19
DE2735810A1 (de) 1979-02-15
DE2860371D1 (en) 1981-03-19

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