US3297584A - Liquid stabilizers for vinyl chloride resins comprising metal salts of epoxidized fatty acids - Google Patents

Liquid stabilizers for vinyl chloride resins comprising metal salts of epoxidized fatty acids Download PDF

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Publication number
US3297584A
US3297584A US157110A US15711061A US3297584A US 3297584 A US3297584 A US 3297584A US 157110 A US157110 A US 157110A US 15711061 A US15711061 A US 15711061A US 3297584 A US3297584 A US 3297584A
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acid
parts
vinyl chloride
fatty acids
cadmium
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US157110A
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Szczepanek Alfred
Koenen Gunter
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CHEM FAB HOESCH K G FA
Chemische Fabrik Hoesch K-G Firma
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CHEM FAB HOESCH K G FA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—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

Definitions

  • the present invention is concerned with liquid stabilizers for polyvinyl chloride and polyvinyl chloride mixed polymers and with a process for the production of said stabilizers.
  • Synthetic halogen-containing resins particularly polyvinyl chlorides and mixed polymerizates thereof, are stabilised with, inter alia, metal soap combinations based on cadmium, zinc and barium. These stabilizers are powders or plastics, according to the nature of the carboxylic acid used.
  • Powdery products which also good lubricants, general ly contain C to C straight chained fatty acids.
  • liquid polyvinyl chloride stabilizers i.e. solutions of metal soaps in solvents, are preferred which can be produced in a more pure form than powdery metal soaps.
  • the metal soap solutions must be as highly concentrated as possible.
  • metal soaps For the dissolving of the metal soaps, solvents must be used which are compatible with the synthetic resins. Generally, plasticizers are used for this purpose.
  • metal soaps of straight chained fatty acids only dissolve very slightly in organic solvents and solutions of this type solidity, even with a small percentage content of metal soap, to give solid gels.
  • barium and cadmium stearates are only soluble in dibutyl phthalate to about 0.5%. Therefore, they cannot be used for the production of liquid polyvinyl chloride stabilizer compositions with a high metal soap content.
  • liquid barium-cadmium stabilizers for polyvinyl chloride there are used as organic components, in place of the straight chained fatty acids with 820 carbon atoms, branched, short chained aliphatic carboxylic acids, such as ethyl-hexanoic acid, or phenols.
  • epoxidized unsaturated fatty acids their esters and glycerides.
  • fatty acid basis there may be used the naturally-occurring unsaturated oils which contain, in the main, oleic acid, linoleic acid, linolenic acid or ricinoleic" acid.
  • the metal soap solutions according to the present invention can contain single metal salts of the epoxidized unsaturated fatty acids or several such salts in combination with one another.
  • the preferred metal soaps of epoxy fatty acids are those of epoxy-stearic acid, diepoxy-stearic acid, hydroxyepoxy-stearic acid and mixtures thereof.
  • solvents for the metallic soaps of straight chained epoxidized fatty acids there are used those liquid organic compounds which are compatible with halogen-containing synthetic resins but which, however, preferably also act as plasticizers for the resins and increase the stabilizing effect of the barium-zinc-cadmium soaps.
  • the solubility of the metallic soaps is dependent upon the metallic component and on the epoxy fatty acid used. In general, the cadmium and zinc soaps are more easily soluble than the barium salts.
  • phosphite plasticizers such as phosphorous acid esters, especially triphenyl phosphite, phthalic acid esters with short chained alcohols, such as dibutyl phthalate, epoxy plasticizers, such as epoxy castor oil, and esters of ricinoleic acid with aliphatic long chained alcohols.
  • alkyl-phenols such as Z-isopropyl-phenol, 2-methyl-4-tertiary-butylphenol and 2,4-dimethyl-phenol, have a very strong solubilising action on the metallic salts of epoxidized straight chained fatty acids.
  • gelbreaking additives such as polar organic compounds, for example alkanolamines, especially triethanolamine, alcohols, phenols or aliphatic polyhydroxy compounds, can be used.
  • polar organic compounds for example alkanolamines, especially triethanolamine, alcohols, phenols or aliphatic polyhydroxy compounds.
  • the phosphite plasticizers also show gel-breaking properties.
  • one or two metallic soap components can consist of a known metallic soap which is soluble in organic solvents compatible with polyvinyl chloride.
  • the barium soap of epoxidized ricinoleic acid-cadmium octoate This possibility can be of significance when the metal content is to be increased Without an increase of the lubrication properties being necessary.
  • the barium soaps of epoxidized ricinoleic acid offer a particularly good combination possibility.
  • the barium-zinc-cadmium-epoxy metal soaps can be dissolved to give liquid stable solutions having a concenand 100 C. suffices.
  • the solutions are then freed by filtration, for example at an elevated temperature, from In general, a temperature between the undissolved components which are present as impurities in the starting materials, such as metallic hydroxides or metallic carbonates.
  • the ratio of the individual components to one another in the composition is determined by their synergistic effectiveness. Therefore, for the composition of a liquid composition of stabilizers the maximal effective ratio of the individual components to one another is determined and then, by the addition of a suitable solvent, particularly of a plasticizer, the desired viscosity adjusted.
  • a suitable solvent particularly of a plasticizer
  • the maximal ratio can be easily read ofl? from a graphic representation.
  • the evaluation takes place in the form of a phase diagram. In the case of more than three active stabilizers, it is recommended to keep constant one of the components for the graphic evaluation of the results.
  • FIGURE 2 of the accompanying drawings serves to show how particularly elfective mixtures of three active stabilizers can be ascertained.
  • the threecomponent combination cadmium-epoxy-hydroxy-stearate, p-tertiary-octyl-phenol and epoxidized castor oil is investigated.
  • the numbers 2 and 1 in the corners and in the middle of the diagram signify the amounts of the materials in question.
  • the static stability at 180 C. is deter mined in an oven for a mixture of 100 parts polyvinyl chloride, 50 parts dioctyl-phthalate and 2 parts of stabilizer.
  • the production and examination of the mixtures take place in the same manner as is described in the following examples.
  • test samples are taken from the oven and the time determined after which the original color of the mixture has changed to yellow-brown. These times are incorporated into the ternary diagram. Points of the same time are joined by broken lines. From FIGURE 2 of the accompanying drawings can be read off which ternary stabilizer mixture has the maximum effectiveness. The marginal conditions also show whether binary stabilizer mixtures can be used with advantage.
  • FIGURE 2 of the accompanying drawings has a double maximum at 1.6 parts cadmium soap of epoxidized castor oil and 0.4 part ptertiary-octyl phenol.
  • the maximum of the tertiary system lies at 0.25 part p-tertiary octyl phenol, 0.7 part cadmium soap of epoxidized ricinoleic acid and 1.05 parts epoxidized castor oil.
  • the metal soap solutions are produced in the following manner: The solid components are cold pasted with a little solvent and slowly heated with stirring. At about 80-90 C., the remaining amount of liquid is added portionwise and further heated until complete solution is obtained. In Example 1 the temperature must not exceed 140 C. and in Examples 2-4 must not exceed 90-100 C. since, otherwise, unnecessary colorations occurs. In all cases, the color of the solutions is yellow to yellow-brown. For the removal of non-dissolved components, such as metallic hydroxides, carbonates and the like, the solution is filtered at about 50 C. through a fine mesh sieve.
  • Example 1 9.9 parts p-tertiary-octyl-phenol, 27.4 parts cadmium soap from epoxidized castor oil, 42 parts epoxidized castor oil, 19.8 parts dibutyl phthalate and 0.9 part triethanolamine.
  • Example 2 6 parts cadmium epoxystearate, 4 parts barium epoxystearate, 10 parts 2,4-dimethylphenol and 2 parts triphenyl phosphite.
  • Example 3 8 parts cadmium epoxystearate, 10 parts 2,4-dimethylphenol and 2 parts triphenyl phosphite.
  • Example 4 (a) 6 parts cadmium soap of epoxidized castor oil, 4 parts barium soap of epoxidized castor oil, 10 parts of mixed 2,4- and 2,5-dimethylphenol and 2 parts of triphenyl phosphite.
  • Example 5 20 parts zinc epoxystearate, 20 parts 2,4- and 2,5-dimethylphenol and 5 parts triphenyl phosphite.
  • the same mixtures were subjected to a continuous rolling in a roller mill, the rollers rotating at the same speed, at 170 C. and by removal of test pieces at intervals of 10 minutes, the time was determined at which adhesion to the rollers or a coloration occurred.
  • the time until the adhesion to the rollers is regarded as a measure for the lubrication property of the mixture.
  • Liquid stabilizers for polymeric and copolymeric vinyl chloride comprising a solution containing 40 to 60 wt. percent of at least one member selected from the group consisting of barium, zinc, and cadmium soaps of epoxy stearic acid, diepoxy stearic acid, and hydroxy epoxy stearic acid in an organic solvent capable of simultaneously serving as a plasticizer and/or stabilizer for said polymeric vinyl chloride selected from the group consisting of alkyl monohydric phenols, esters of phthalic acid with short-chain aliphatic alcohols, substahtially neutral esters of phosphorous acid (H PO epoxidized castor oil, and esters of ricinoleic acid with aliphatic long chain alcohols prepared by heating a mixture of said soap group member and said organic solvent group mem' References Cited by the Examiner UNITED STATES PATENTS 1,932,889 19/1933 Groff 26045.9 2,564,646

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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)
US157110A 1960-12-09 1961-12-05 Liquid stabilizers for vinyl chloride resins comprising metal salts of epoxidized fatty acids Expired - Lifetime US3297584A (en)

Applications Claiming Priority (1)

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DEC22930A DE1262587B (de) 1960-12-09 1960-12-09 Stabilisieren von Polyvinylchlorid und Vinylchlorid-Mischpolymerisaten

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US3297584A true US3297584A (en) 1967-01-10

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JP (1) JPS4837574B1 (en))
BE (1) BE611161A (en))
CH (1) CH412319A (en))
DE (1) DE1262587B (en))
GB (1) GB926895A (en))
NL (1) NL272242A (en))

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3461081A (en) * 1964-07-17 1969-08-12 Mizusawa Industrial Chem Stabilizing agent for a halogen containing synthetic resin consisting of a basic inorganic acid salt of lead coated with a fatty acid soap of lead,cadmium or calcium

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764572A (en) * 1970-06-10 1973-10-09 Chem Werke Barlocher O Gmbh Process of granulating polymeric materials

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1932889A (en) * 1931-08-10 1933-10-31 Carbide & Carbon Chem Corp Record
US2564646A (en) * 1950-02-08 1951-08-14 Argus Chemical Lab Inc Haze resistant vinyl chloride polymers
US2684353A (en) * 1951-05-31 1954-07-20 Buffalo Electro Chem Co Method of stabilizing halogen containing polymeric substances against heat and lightwith salts of epoxy fatty acids
US2711401A (en) * 1951-11-23 1955-06-21 Ferro Corp Stabilized chlorine containing vinyl resins
US2820774A (en) * 1951-12-13 1958-01-21 Union Carbide Corp Vinyl chloride resin with lead salt and hindered phenol stabilizers
GB841890A (en) * 1956-05-15 1960-07-20 Argus Chem Polyvinyl chloride stabilizer
US2997454A (en) * 1959-05-18 1961-08-22 Argus Chem Polyvinyl chloride stabilizer combinations of phosphorus acid with triphosphites andheavy metal salts

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2510035A (en) * 1946-04-12 1950-05-30 Advance Solvents & Chemical Co Halogen-containing polymeric substances of improved heat and light stability and stabilizers therefor
BE539563A (en)) * 1954-07-28
GB752053A (en) * 1954-09-21 1956-07-04 Argus Chemical Lab Inc Substituted phenolated stabilizer composition
US2894923A (en) * 1955-06-17 1959-07-14 Monsanto Chemicals Light stable halogen-containing resins
GB828712A (en) * 1955-12-27 1960-02-24 Monsanto Chemicals Improvements in or relating to light stabilizer mixture

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1932889A (en) * 1931-08-10 1933-10-31 Carbide & Carbon Chem Corp Record
US2564646A (en) * 1950-02-08 1951-08-14 Argus Chemical Lab Inc Haze resistant vinyl chloride polymers
US2684353A (en) * 1951-05-31 1954-07-20 Buffalo Electro Chem Co Method of stabilizing halogen containing polymeric substances against heat and lightwith salts of epoxy fatty acids
US2711401A (en) * 1951-11-23 1955-06-21 Ferro Corp Stabilized chlorine containing vinyl resins
US2820774A (en) * 1951-12-13 1958-01-21 Union Carbide Corp Vinyl chloride resin with lead salt and hindered phenol stabilizers
GB841890A (en) * 1956-05-15 1960-07-20 Argus Chem Polyvinyl chloride stabilizer
US2997454A (en) * 1959-05-18 1961-08-22 Argus Chem Polyvinyl chloride stabilizer combinations of phosphorus acid with triphosphites andheavy metal salts

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3461081A (en) * 1964-07-17 1969-08-12 Mizusawa Industrial Chem Stabilizing agent for a halogen containing synthetic resin consisting of a basic inorganic acid salt of lead coated with a fatty acid soap of lead,cadmium or calcium

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GB926895A (en) 1963-05-22
CH412319A (de) 1966-04-30
DE1262587B (de) 1968-03-07
NL272242A (en))
BE611161A (en))

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