WO1995034524A1 - Basic zinc carboxylates - Google Patents
Basic zinc carboxylates Download PDFInfo
- Publication number
- WO1995034524A1 WO1995034524A1 PCT/EP1995/002247 EP9502247W WO9534524A1 WO 1995034524 A1 WO1995034524 A1 WO 1995034524A1 EP 9502247 W EP9502247 W EP 9502247W WO 9534524 A1 WO9534524 A1 WO 9534524A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acids
- weight
- content
- carbon
- zinc
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
- C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
Definitions
- the present invention relates to new basic zinc carboxylate, both liquid and solid compositions, a method for their preparation and their use as lubricant additives, as polymer stabilisers, as promoters or emuisifiers for rubber and fungicides.
- the invention provides an effective stabiliser for use in polyvinyl chloride which, may replace the more toxic Cadmin, Lead and Barium stabilisers currently used.
- the present invention therefore provides solid zinc superbase soaps in the form of zinc carboxylates, the carboxylic acids consisting of a mixture or otherwise of saturated organic carboxylic acids containing from 7 to 13 carbon atoms, having the following characteristics, optionally the products may also contain zinc carbonate. a linear acid content of between 0 and 40% by weight,
- the zinc superbase soaps are preferably prepared from saturated C ⁇ , Cg and C10 organic carboxylic acids which consist of isomeric mixtures and which are generally known as oxo acids. These oxo acids are characterized by a low linear acid content, generally less than or equal to 10% by weight, a low content of acids which are branched on carbon 2, generally less than or equal to 10% by weight, and a high content of acids which are mono- or polysubstituted on carbon 3 and/or carbons of higher rank, which is generally greater than 80% by weight.
- the oxo acids are obtained by hydroformylation of C7, C ⁇ and Cg olefins, followed by an oxidation.
- the zinc soaps according to the invention are prepared from the C ⁇ saturated carboxylic acid (that is containing 8 carbon atoms) marketed under the trademark Cekanoic, this acid consisting of an isomeric mixture of octanoic acids containing at most 10% by weight of n-octanoic acid, at most 10% by weight of C ⁇ acids which are branched on carbon 2 and at least 80% by weight of C ⁇ acids which are branched on carbon 3 and/or the carbons of higher rank.
- Cekanoic this acid consisting of an isomeric mixture of octanoic acids containing at most 10% by weight of n-octanoic acid, at most 10% by weight of C ⁇ acids which are branched on carbon 2 and at least 80% by weight of C ⁇ acids which are branched on carbon 3 and/or the carbons of higher rank.
- Cekanoic C 10 ac 'd
- organic carboxylic acids which are also suitable for the present invention there may also be added the derivatives which are mono- or polysubstituted in the 3-position and/or of higher rank of the acids corresponding to heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undeca ⁇ oic acid and dodeca ⁇ oic acid.
- these include, for example, 3-methylhexanoic acid, isooctanoic acid, 4,5-dimethylhexanoic acid, isononanoic acid,
- the present invention also relates to a process for the preparation of the zinc superbase soaps described above, according to which a zinc oxide and/or hydroxide is reacted with the appropriate acid, with stirring.
- the reaction may include the addition of carbon dioxide (CO2) which is bubbled through the reaction mixture and at least one organic carboxylic acid, in the presence of at least one promoter which make CO2 fixation easier and at least one catalyst, and in that the water formed during the reaction is removed.
- CO2 carbon dioxide
- the process is characterized in that the reaction is performed in at least one organic solvent at a temperature of between 80 and 120°C, and in that the said acid is a saturated organic carboxylic acid containing from 7 to 13 carbon atoms, in which the content of linear acids is less than or equal to 40% by weight, in which the content of acids branched on carbon 2 is less than or equal to 20% by weight, and in which the content of acids branched on carbon 3 and/or the carbons of higher rank is equal to or higher than 40% by weight.
- the organic solvent may be removed preferably by evaporation.
- the organic solvent is allowed to evaporate during the reaction and is recycled into the reaction mixture so as to produce therein a bubbling action which promotes the reaction.
- a plasticiser ester such as a phthalate or adipate may be used as the solvent which is particularly useful when the zinc carboxylate is to be used as a stabiliser for polyvinyl chloride.
- At least one nonpolar organic solvent chosen from naphtha, hexane, kerosene, benzene, toluene or xylene is used among the organic solvents which can be used in the process according to the invention. It is also possible to use a mixture of paraffinic hydrocarbons of mineral or synthetic origin, preferably containing a low proportion of aromatic and/or naphthenic hydrocarbons, such as white spirit.
- polar organic solvents such as alcohols, for example 1-butanol, 2-butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol and its ethers, mixtures of alcohols derived from paraffin, or methyl ethyl ketone.
- the molar ratio of zinc to the organic carboxylic acid employed in the reaction is generally between 0.55 and 2, which corresponds to a basicity of between 1.1 and 4.
- an hourly flow rate of carbon dioxide is imposed such that the hourly mass ratio of carbon dioxide to zinc is between 0.5 and 2, and preferably between 0.7 and 1.5.
- metal oxides for example, aluminium oxide AI2O3, silver oxide Ag2 ⁇ , magnesium oxide MgO, and zinc carboxylates such as zinc octanoate.
- labile hydrogen compounds such as alcohols, for example methanol, 2-propanol, octyl alcohol, ethylene glycol, triethylene glycol, strearyl alcohol, cyclohexylene glycol alcohol, cyclohexyl alcohol, aromatic alcohols such as phenol; amines, for example aniline, phenylenediamine, or dodecylamine; or, yet again, a mixture of alcohols and/or amines, for example of methanol and aqueous ammonia.
- alcohols for example methanol, 2-propanol, octyl alcohol, ethylene glycol, triethylene glycol, strearyl alcohol, cyclohexylene glycol alcohol, cyclohexyl alcohol, aromatic alcohols such as phenol; amines, for example aniline, phenylenediamine, or dodecylamine; or, yet again, a mixture of alcohols and/or amines, for example of methanol and a
- the material used in methanol which gives the highest basicities and the shortest filtration times during the preparation of the calcium soap according to the invention.
- the promoters are used in a proportion of 1 to 25% by weight of final zinc salt, and preferably in a proportion of 5 to 15%.
- the solution was slowly heated to 165°C to remove the water from the reactor 15 and maintained at 165°C until no more water comes over.
- the solution was slowly heated to 110°C and then put vacuum on it to remove the water from the reactor. Filtration was carried out at 110°C to yield the end 25 product as a viscous light yellow liquid.
- the end product is a clear product. 35
- the Toluene is evaporated and a white solid paste is formed.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95923295A EP0804404A1 (en) | 1994-06-10 | 1995-06-08 | Basic zinc carboxylates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9411698.5 | 1994-06-10 | ||
GB9411698A GB9411698D0 (en) | 1994-06-10 | 1994-06-10 | Improved basic zinc carboxylates |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995034524A1 true WO1995034524A1 (en) | 1995-12-21 |
Family
ID=10756558
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1995/002247 WO1995034524A1 (en) | 1994-06-10 | 1995-06-08 | Basic zinc carboxylates |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0804404A1 (en) |
CA (1) | CA2200777A1 (en) |
GB (1) | GB9411698D0 (en) |
WO (1) | WO1995034524A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000046173A1 (en) * | 1999-02-03 | 2000-08-10 | Cognis Deutschland Gmbh | Method for producing overbased zinc soaps |
JP2006515331A (en) * | 2003-03-18 | 2006-05-25 | ザ プロクター アンド ギャンブル カンパニー | Composition comprising zinc-containing layered material having high relative zinc reaction activity |
US8119168B2 (en) | 2002-04-22 | 2012-02-21 | The Procter & Gamble Company | Personal care compositions comprising a zinc containing material in an aqueous surfactant composition |
US8796252B2 (en) | 1999-06-25 | 2014-08-05 | Arch Chemicals, Inc. | Pyrithione biocides enhanced by zinc metal ions and organic amines |
US20150025258A1 (en) * | 2013-07-19 | 2015-01-22 | Baker Hughes Incorporation | Oil soluble hydrogen sulfide scavenger |
US9381382B2 (en) | 2002-06-04 | 2016-07-05 | The Procter & Gamble Company | Composition comprising a particulate zinc material, a pyrithione or a polyvalent metal salt of a pyrithione and a gel network |
US9381148B2 (en) | 2003-03-18 | 2016-07-05 | The Procter & Gamble Company | Composition comprising particulate zinc material with a high relative zinc lability |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3730943A (en) * | 1965-09-03 | 1973-05-01 | Cincinnati Milacron Chem | Stabilized vinyl chloride polymers |
EP0010807A1 (en) * | 1978-10-26 | 1980-05-14 | Akzo N.V. | Derivatives of branched-chain monocarboxylic acids, engine lubricating oils, lubricant compositions for polymers, wax compositions in which these derivatives are incorporated and a process for preparing said branched-chain monocarboxylic acids |
WO1993008246A1 (en) * | 1991-10-14 | 1993-04-29 | Exxon Chemical Patents Inc. | Improved overbased carboxylates |
-
1994
- 1994-06-10 GB GB9411698A patent/GB9411698D0/en active Pending
-
1995
- 1995-06-08 CA CA 2200777 patent/CA2200777A1/en not_active Abandoned
- 1995-06-08 EP EP95923295A patent/EP0804404A1/en not_active Withdrawn
- 1995-06-08 WO PCT/EP1995/002247 patent/WO1995034524A1/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3730943A (en) * | 1965-09-03 | 1973-05-01 | Cincinnati Milacron Chem | Stabilized vinyl chloride polymers |
EP0010807A1 (en) * | 1978-10-26 | 1980-05-14 | Akzo N.V. | Derivatives of branched-chain monocarboxylic acids, engine lubricating oils, lubricant compositions for polymers, wax compositions in which these derivatives are incorporated and a process for preparing said branched-chain monocarboxylic acids |
WO1993008246A1 (en) * | 1991-10-14 | 1993-04-29 | Exxon Chemical Patents Inc. | Improved overbased carboxylates |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000046173A1 (en) * | 1999-02-03 | 2000-08-10 | Cognis Deutschland Gmbh | Method for producing overbased zinc soaps |
US6649585B1 (en) | 1999-02-03 | 2003-11-18 | Cognis Deutschland Gmbh & Co. Kg | Processes for preparing superbasic zinc soaps and methods of using said soaps |
US8796252B2 (en) | 1999-06-25 | 2014-08-05 | Arch Chemicals, Inc. | Pyrithione biocides enhanced by zinc metal ions and organic amines |
US8119168B2 (en) | 2002-04-22 | 2012-02-21 | The Procter & Gamble Company | Personal care compositions comprising a zinc containing material in an aqueous surfactant composition |
US9381382B2 (en) | 2002-06-04 | 2016-07-05 | The Procter & Gamble Company | Composition comprising a particulate zinc material, a pyrithione or a polyvalent metal salt of a pyrithione and a gel network |
JP2006515331A (en) * | 2003-03-18 | 2006-05-25 | ザ プロクター アンド ギャンブル カンパニー | Composition comprising zinc-containing layered material having high relative zinc reaction activity |
US9381148B2 (en) | 2003-03-18 | 2016-07-05 | The Procter & Gamble Company | Composition comprising particulate zinc material with a high relative zinc lability |
US20150025258A1 (en) * | 2013-07-19 | 2015-01-22 | Baker Hughes Incorporation | Oil soluble hydrogen sulfide scavenger |
US9353026B2 (en) * | 2013-07-19 | 2016-05-31 | Baker Hughes Incorporated | Oil soluble hydrogen sulfide scavenger |
Also Published As
Publication number | Publication date |
---|---|
EP0804404A1 (en) | 1997-11-05 |
CA2200777A1 (en) | 1995-12-21 |
GB9411698D0 (en) | 1994-08-03 |
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