EP1401992A1 - Verfahren zur herstellung einer schmiermittelzusammensetzung auf basis von polysiloxanen, die keinen wasserstoff entwickelt - Google Patents

Verfahren zur herstellung einer schmiermittelzusammensetzung auf basis von polysiloxanen, die keinen wasserstoff entwickelt

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Publication number
EP1401992A1
EP1401992A1 EP02745465A EP02745465A EP1401992A1 EP 1401992 A1 EP1401992 A1 EP 1401992A1 EP 02745465 A EP02745465 A EP 02745465A EP 02745465 A EP02745465 A EP 02745465A EP 1401992 A1 EP1401992 A1 EP 1401992A1
Authority
EP
European Patent Office
Prior art keywords
emulsion
radicals
water
constituent
weight
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Withdrawn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
EP02745465A
Other languages
English (en)
French (fr)
Inventor
Gérald GUICHARD
Ian Hawkins
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.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1401992A1 publication Critical patent/EP1401992A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M2229/04—Siloxanes with specific structure
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/042—Siloxanes with specific structure containing aromatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/043—Siloxanes with specific structure containing carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/044—Siloxanes with specific structure containing silicon-to-hydrogen bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/045—Siloxanes with specific structure containing silicon-to-hydroxyl bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/047—Siloxanes with specific structure containing alkylene oxide groups
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/048—Siloxanes with specific structure containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/051—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/052—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/053—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M2229/04—Siloxanes with specific structure
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    • C10M2229/054—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing phosphorus
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/32—Wires, ropes or cables lubricants
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/34—Lubricating-sealants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/38—Conveyors or chain belts
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/40—Generators or electric motors in oil or gas winning field
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/42—Flashing oils or marking oils
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/44—Super vacuum or supercritical use
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/50—Medical uses
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the invention relates to an improved process for the preparation of a lubricating composition, suitable in particular for the lubrication of vulcanization bladders used during the shaping and vulcanization of pneumatic or semi-pneumatic tires.
  • the invention also relates to the lubricant compositions thus obtained. It also relates to their use for the lubrication of various articles, in particular vulcanization bladders as well as pneumatic or semi-pneumatic tires. It also relates to various articles, in particular vulcanization bladders as well as pneumatic or semi-pneumatic tires, coated with said lubricating composition.
  • Rubber tires for vehicles are usually manufactured by molding and vulcanizing a raw (or unvulcanized) and unshaped casing, in a molding press in which the raw casing is pressed outward against the surface of a mold. by means of an internal fluid expandable bladder.
  • the raw envelope is shaped against the external surface of the mold which defines the design of the tread of the envelope and the configuration of the sides.
  • the envelope is vulcanized.
  • the bladder is expanded by the internal pressure supplied by a fluid such as hot gas, hot water and / or steam, which also participates in the transfer of heat for vulcanization.
  • the envelope is then allowed to cool a little in the mold, this cooling being sometimes favored by the introduction of cold or cooler water into the bladder.
  • the mold is opened, the bladder is deflated by releasing the pressure of the internal fluid and the envelope is removed from the envelope mold.
  • This use of shell vulcanization bladders is well known in the art.
  • the bladder If adequate lubrication is not provided between the bladder and the inner surface of the envelope, the bladder generally tends to curl, which results in deformation of the envelope in the mold and also excessive wear and etching. from the surface of the bladder itself.
  • the surface of the bladder also tends to stick on the inner surface of the envelope after the vulcanization of the envelope and during the part of the vulcanization cycle of the envelope during which the bladder is deflated.
  • air bubbles can be trapped between the surfaces of the bladder and the envelope, and favor the appearance of vulcanization defects in the envelopes resulting from an inadequate heat transfer.
  • the external surface of the bladder or the internal surface of the raw or unvulcanized casing is coated with an appropriate lubricant, sometimes referred to as "jacketing cement", so as to facilitate sliding, and thus minimizing the risks of sticking, between the external surface of the bladder and the internal surface of the raw envelope.
  • an appropriate lubricant sometimes referred to as "jacketing cement”
  • the various qualities which one should expect from a good lubricating composition are to have excellent durability properties (the durability of a lubricating composition corresponds to the number of tires produced without degradation of the external surface of the bladder) and excellent elasticity properties (marked by a tensile elongation at break of the film of crosslinked lubricating composition, at least equal to 200%, measured according to standard AFNOR-T 46002).
  • lubricant compositions described in FR-A-2 494 294 are known in particular, which contain, as main constituents, a reactive polydimethylsiloxane preferably having hydroxyl end groups, a crosslinking agent preferably comprising Si-H functions and optionally a polycondensation catalyst.
  • crosslinking agent with Si-H function (s) examples are methyltrihydrogénosiiane and diméthyldihydrogénosilane.
  • the disadvantage of lubricating compositions of this type is their instability on storage. There is indeed a creaming of the emulsion following the evolution of hydrogen during transport and storage of the lubricant composition. The evolution of hydrogen responsible for the instability of the compositions of the prior art results essentially from the decomposition of the constituents with Si-H function (s).
  • compositions which are the subject of EP ⁇ A-0 635 559 are lubricating compositions based on polysiloxanes which partly meet these requirements. These compositions are in particular more stable in that they do not give off hydrogen during storage.
  • These compositions, which are in the form of emulsions comprise, as essential constituents, a non-reactive polydimethylsiloxane, a reactive polydimethylsiloxane, preferably with hydroxy or alkoxy termination and a crosslinking agent based on a hydrolysable organosilane. Their durability is however insufficient for practical use in the production of pneumatic or semi-pneumatic tires.
  • the present invention provides an improved process for the preparation of an improved lubricating composition which does not release hydrogen and which, moreover, has excellent sliding, durability and elasticity properties, which makes them perfectly suitable in particular for the lubrication of vulcanization bladders used during shaping and vulcanization of pneumatic and semi-pneumatic tires.
  • the present invention relates to a process for the preparation of a lubricating composition in the form of an oil-in-water emulsion, characterized in that it comprises the direct mixing of two oil-in-water emulsions (A) and (B) made beforehand, said prior emulsions (A) and (B) meeting the following characteristics of constitution (i) to (4i): (i) the prior emulsion (A) comprises:
  • the monovalent organic substituents identical or different from one another, bonded to silicon atoms are chosen from alkyl, cycoalkyl, alkenyl, aryl, alkylarylene and arylalkylene radicals,
  • component (d) a condensation catalyst capable of catalyzing the reaction of component (b) with component (c);
  • each of the previous emulsions (A) and (B) has the following composition by weight, the composition by weight of (A) possibly being identical or different from that of (B):
  • component (b) - from 0.5 to 50 parts by weight of component (b); - from 0.1 to 20 parts by weight of the constituent (c);
  • the emulsion (A) / emulsion (B) weight ratio, at the time of mixing the pre-emulsions, is in the range from 1.5 to 4, preferably from 1.8 to 3, and so more preferred from 2.1 to 2.6.
  • constituents (a), (a 1 ), (b), (c), (d) and (e) of the emulsions are defined with reference to their initial chemical structure, that is to say that which characterizes them before emulsification.
  • dynamic viscosity in the context of the invention the Newtonian type viscosity, that is to say the dynamic viscosity, measured in a manner known per se at a given temperature, at a sufficiently low shear rate gradient so that the viscosity measured is independent of the speed gradient.
  • Each of the non-reactive polydiorganosiloxane oils of component (a) has a dynamic viscosity generally between 5.10 "2 and 30.10 2 Pa.s at 25 ° C.
  • the dynamic viscosity varies between 5.10 " 2 and 30 Pa.s, better still between 0.1 and 5 Pa.s.
  • non-reactive means an oil which, under the conditions of emulsification, preparation of the lubricating composition and use, does not react chemically with any of the constituents of the composition.
  • radicals R 2 and R 3 monovalent organic substituents of the various siloxyl units mentioned above, have the following definitions: • the radicals R 2 , identical or different from each other, are chosen from: linear or branched alkyl radicals in C ⁇ C 6 (such as for example methyl, ethyl, propyl, isopropyl, butyie, isobutyl, t-butyl, n-pentyl, n-hexyl), C 3 -C 8 cycloalkyl radicals (such as for example cyclopentyl, cyclohexyl), and linear or branched C 2 -C 8 alkenyl radicals (such as for example vinyl, allyl),
  • radicals R 3 are chosen from: aryl radicals C 6 -C 10 (such as for example phenyl, naphthyl), alkylarylene radicals C 6 -C ⁇ 5 (such as for example tolyls , xylyl), C 6 -C 5 arylalkylene radicals (such as for example benzyl); and - where 5 to 50%, and better still 8 to 35%, in number of the substituents R 2 , R 3 and R 4 are aromatic radicals R 3 .
  • aryl radicals C 6 -C 10 such as for example phenyl, naphthyl
  • alkylarylene radicals C 6 -C ⁇ 5 such as for example tolyls , xylyl
  • C 6 -C 5 arylalkylene radicals such as for example benzyl
  • component (a) consists of at least one linear polyorganosiloxane:
  • radicals R 2 identical or different between them, are chosen from the methyl, ethyl, propyl and isopropyl radicals
  • radicals R 3 identical or different from each other, are chosen from the phenyl, tolyl and benzyl radicals
  • R 2 and R 3 are phenyl, tolyl and / or benzyl radicals.
  • At least one linear polyorganosiloxane is used as constituent (a) having, per molecule, a ratio (in number) of aromatic substituents R 3 / Si at least equal to 0.04, preferably ranging from 0.09 to 1 and better going from 0.16 to 0.7.
  • Component (a) is generally introduced into the prior emulsion (A) at a rate of 5 to 95 parts by weight per 100 parts by weight of the mixture of constituents (a) + (b) + (c) + (d), preferably 50 to 95, more preferably 75 to 95.
  • Each of the reactive linear polydiorganosiloxane oils of component (a 1 ) having at least two OH groups per molecule has a dynamic viscosity at 25 ° C generally between 5.10 "2 and 30.10 2 Pa.s. Preferably, the viscosity varies between 5.10 2 and 30 Pa.s, better still between 0.1 and 5 Pa.s.
  • the term "reactive" designates the reactivity of the constituent
  • the constituent (a 1 ) reacts with the crosslinking agent under the conditions for preparing the emulsion.
  • the monovalent organic substituents of the oil (a ') are: linear or branched alkyl radicals; linear or branched alkenyl radicals; cycloalkyl or cycloalkenyl radicals; cycloalkylalkylene or cycloalkenylalkylene radicals; these radicals are optionally substituted by -OH and / or amino (optionally substituted) and / or halogen and / or cyano groups.
  • the substituent of the amino group can be an alkyl radical, a cycloaikyl radical or a cycloalkyialkylene radical. Mention may be made, as halogen, of chlorine, fluorine, bromine or iodine, fluorine being more specifically suitable.
  • the organic substituents of (or) oil (s) (a ′) are: CC 6 alkyl radicals; C 3 -C 8 cycloalkyls; C 2 -C 8 alkenyls; or C 5 -C 8 cycloalkenyl; said radicals optionally substituted with hydroxyl and / or amino (optionally substituted), and / or halo, and / or cyano.
  • the substituents of the amino group are for example: (d-CeJalkyle; (C 2 -C 8 ) alkenyl; (C 3 -C 8 ) cycloalkyle.
  • R 5 and R 6 identical or different, represent: (CC 6 ) alkyl; (C 3 -C 8 ) cycloalkyl; (C 2 -C 8 ) alkenyl; (C 5 -C 8 ) cycloalkenyl; each of the aforementioned radicals being optionally substituted with a halogen atom (and preferably fluorine) or a cyano residue.
  • oil (s) (a ') to ⁇ , ⁇ -dihydroxypolydimethylsiloxanes, and in particular oils of this type prepared by the anionic polymerization process described in the aforementioned American patents: US 2 891,920 and especially US 3,294,725 (cited as reference).
  • the constituent (a ') is introduced into the prior emulsion (B) at a rate of 5 to
  • Component (b) is formed of at least one polyorganosiloxane resin, carrier before emulsification of condensed hydroxyl groups.
  • each substituent R 1 represents a monovalent organic group.
  • R 1 is a C ⁇ -C 20 hydrocarbon radical optionally carrying one or more substituents.
  • hydrocarbon radicals are: an alkyl radical, linear or branched, having from 1 to 6 carbon atoms; an alkenyl radical, linear or branched, having from 2 to 8 carbon atoms; a cycloaikyl radical having from 3 to 8 carbon atoms; or a cycloalkenyl radical having 5 to 8 carbon atoms.
  • the substituents of the hydrocarbon radical may be groups -OR 'or -O-CO-R' in which R 'is a hydrocarbon radical as defined above for R 1 , unsubstituted.
  • Other substituents of the hydrocarbon radical can be amino, amidated, epoxidized or ureido functions.
  • R a represents a valential bond or represents a divalent alkylene radical, linear or branched, in C C-io; and R 7 and R 8 independently represent: H; a (C -, - C 6 ) alkyl radical; a (C 3 -C 8 ) cycloalkyl radical; or an (C 6 -C ⁇ 0 ) aryl radical;
  • R 9 and R 11 identical or different, represent:
  • R 10 represents: a hydrogen atom; (C ⁇ -C 6 ) alkyl, for example methyl; (C 2 -C 7 ) alkylcarbonyl; (C 6 -C ⁇ 0 ) aryl and for example phenyl; (C 6 -C 10 ) aryl- (C CeJalkylène and for example benzyl; or alternatively R 10 represents O; and • the function of formula:
  • R 9 and R 10 are as defined above. It is however preferable that the concentration of -OR ′, -O-CO-R ′, amino, amidated, epoxidized or ureido functions, when they are present in the resin, is limited, so as not to exceed the tolerance threshold beyond which the stability of the emulsion would be compromised.
  • the silicone resins (b) are well-known branched organopolysiloxane polymers whose methods of preparation are described in numerous patents. As concrete examples of resins which can be used, mention may be made of MQ, MDQ,
  • each OH group is carried by a silicon atom belonging to an M, D or T motif.
  • hydroxylated organopolysiloxane resins not comprising, in their structure, a Q motif. More preferably, mention may be made of hydroxylated DT and MDT resins comprising - at least 20% by weight of T units and having a weight content of hydroxyl group ranging from 0.1 to 10% and better still from 0.2 to 5%.
  • hydroxylated DT and MDT resins comprising - at least 20% by weight of T units and having a weight content of hydroxyl group ranging from 0.1 to 10% and better still from 0.2 to 5%.
  • the resin (b) is liquid at room temperature.
  • the resin has a dynamic viscosity at 25 ° C of between 0.2 and 200 Pa.s.
  • the resin is incorporated in the preliminary emulsions (A) and (B) in an amount of 0.5 to 50 parts by weight per hundred parts by weight of the sum of the constituents (a), (b), (c) and (d ) or (a 1 ), (b), (c) and (d), preferably at a rate of 3 to 30, better still from 5 to 15 parts by weight.
  • Component (c) consisting of at least one crosslinker soluble in the silicone phase comprises at least two functions capable of reacting with the resin (s) (b) so as to cause crosslinking of the resin (s) (s).
  • said reactive functions of the crosslinker react with the resin under the conditions for preparing the emulsion.
  • a represents 0 or 1, so that the crosslinker has the formula: Si (Zi) 4 or YSi (Zi) 3 .
  • the groups Zi are identical to each other.
  • a more preferred group of crosslinkers is formed in particular by all of the organotrialcoxysilanes, organotriacyloxysilanes, organotrioximosilanes and tetraaikylsilicates.
  • the radicals are chosen more particularly: (C CeJalkyle; (C 2 -C 8 ) alkenyl; (C 3 -C 8 ) cycloalkyle; (C 6 -C ⁇ 0 ) aryl; (C 6 -C 15 ) alkylarylene; or (C 6 -C 15 ) arylalkylene.
  • groups Y By way of example of groups Y, mention may be made of methyl, ethyl, vinyl or phenyl radicals.
  • Zi represents methoxy, ethoxy, propoxy, methoxyethoxy, acetoxy or an oxime group.
  • methyltrimethoxysilane methyltriethoxysilane, ethyltriethoxysilane and / or vinyltrimethoxysilane.
  • Each prior emulsion (A) and (B) comprises from 0.1 to 20 parts by weight, per hundred parts by weight of the sum of the constituents (a) + (b) + (c) + (d) or (a 1 ) + (b) + (c) + (d), of the constituent (c), preferably from 0.2 to 10 parts by weight, better still from 0.5 to 5.
  • the condensation catalyst (d) is chosen from those conventionally used in the art for catalyzing the crosslinking of resins of type (b) using crosslinking agents of type (c) defined above.
  • organometallic salt there may be mentioned zirconium naphthenate and zirconium octylate.
  • Said catalyst is preferably a tin catalytic compound, generally an organotin salt.
  • organotin salts which can be used are described in particular in the work by
  • catalytic compound with tin either distannoxanes, or polyorganostannoxanes, or the reaction product of a tin salt, in particular of a tin dicarboxylate on ethyl polysilicate, as described in US-A-3,862,919.
  • reaction product of an alkyl silicate or an alkyltrialkoxysilane on (dibutyltin diacetate as described in Belgian patent BE-A-842,305 may also be suitable.
  • tin II salt such as SnCI 2 or stannous octoate, is used.
  • the catalyst is the tin salt of an organic acid, such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, zinc naphthenate, cobalt naphthenate, zinc octylate, cobalt octylate and dioctyltin di (isomercaptoacetate).
  • the preferred tin salts are the tin bischelates (EP-A-147 323 and
  • EP-A-235 049 diorgano-tin dicarboxylates and, in particular, dibutyl- or dioctyltin diversatates (British patent GB-A-1 289 900, dibutyl- or dioctyltin diacetate, dibutyl dilaurate) or dioctyltin or the hydrolysis products of the precipitated species (for example diorgano and polystannoxanes).
  • the catalyst (d) is generally introduced into each of the prior emulsions (A) and (B) in an amount of 0.05 to 10 parts by weight, per hundred parts by weight of the sum of the constituents (a) + (b) + (c) + (d) or (a ') + (b) + (c) + (d), preferably correctly from 0.08 to 5 parts by weight, and better still from 0.1 to 2 parts by weight.
  • Dioctyltin dilaurate is most particularly preferred.
  • the nature of the surfactant (e) will be easily determined by a person skilled in the art, the objective being to prepare a stable emulsion.
  • the anionic, cationic, nonionic and zwitterionic surfactants can be used alone or as a mixture.
  • anionic surfactant there may be mentioned the alkali metal salts of aromatic sulfonic hydrocarbon acids or the alkali metal salts of alkylsulfuric acids.
  • Non-ionic surfactants are more particularly preferred in the context of the invention.
  • alkyl or aryl ethers of poly (alkylene oxide) polyoxyethylenated sorbitan hexastearate, polyoxyethylenated sorbitan oleate having a saponification number from 102 to 108 and a hydroxyl number from 25 to 35 and the ethers of cetylstearyl and poly (ethylene oxide).
  • poly (alkylene oxide) aryl ether polyoxyethylenated alkylphenols may be mentioned.
  • alkyl ether of poly (alkylene oxide) there may be mentioned isodecyl ether of polyethylene glycol and trimethylnonyl ether of polyethylene glycol containing 3 to 15 units of ethylene oxide per molecule.
  • the amount of surfactant (e) depends on the type of each of the constituents present as well as on the very nature of the surfactant used. As a general rule, each prior emulsion comprises from 0.5 to 10% by weight of surfactant (better still from 0.5 to 5% by weight) and from 40 to 95% by weight of water (better still from 45 to 90 % in weight).
  • each prior emulsion (A) and (B) or only one of the two prior emulsions (A) or (B) may further comprise a constituent (g) consisting of at least one water-soluble crosslinking agent chosen from silanes and / or hydroxylated polydiorganosiloxanes, said crosslinking agent carrying, per molecule, in addition to at least one OH group, at least one organic group with function Fr, Fr representing a.
  • a constituent (g) consisting of at least one water-soluble crosslinking agent chosen from silanes and / or hydroxylated polydiorganosiloxanes, said crosslinking agent carrying, per molecule, in addition to at least one OH group, at least one organic group with function Fr, Fr representing a.
  • water-solubility should be understood to mean the ability of a product to dissolve in water at a temperature of 25 ° C, at least 5% by weight.
  • the optional organic substituents of the crosslinking agent other than the OH group (s) and the Fr function organic group (s) are: alkyl radicals, linear or branched, having from 1 to 6 carbon atoms; cycloalkyl radicals having from 3 to 8 carbon atoms; alkenyl radicals, linear or branched, having from 2 to 8 carbon atoms; aryl radicals having 6 to 10 carbon atoms; alkylarylene radicals having 6 to 15 carbon atoms; or arylalkylene radicals having 6 to 15 carbon atoms.
  • Fr is an optionally substituted amino function.
  • an organic group with a preferred Fr function is a group of formula: -R a -NR 7 R 8
  • R a , R b , R G , R 7 , R 8 , R 9 , R 10 and R 11 are as defined above with regard to the definition of constituent (b).
  • the water-soluble crosslinking agent has the formula:
  • R 8 R 7 NR a -Si (OH) 3 in which R a , R 7 and R 8 are as defined above. Even more preferably, R a represents (CrC 10 ) alkylene, and R 7 and R 8 independently represent a hydrogen atom or a (CC 6 ) alkyl group.
  • the water-soluble crosslinking agent can also be a linear and / or cyclic hydroxylated polydiorganosiloxane, with MD (if linear) and / or D (if cyclic) siloxy units, and / or a hydroxylated polydiorganosiloxane resin having, in its structure, units siloxyls T optionally associated with units M and or D and / or T, or alternatively siloxyl units Q associated with units M and / or D.
  • This linear, cyclic or network polydiorganosiloxane is not substituted by organic hydrolyzable functions such as alkoxy functions.
  • G being an organic substituent which meets the definition given above for the “optional organic substituents” either represents a hydroxyl group or else is a function Fr, it being understood that in each molecular structure, at least one of the symbols G represents a group hydroxyl and at least one other of the symbols G represents a function Fr.
  • G is: (Ci-CeJalkyle (for example methyl, ethyl, isopropyl, tert-butyl and n-hexyl); hydroxyl; (C 2 -C 8 ) alkenyl (for example vinyl or allyl); or even a function Fr, the preferred functions Fr being as defined above.
  • linear hydroxyl polydiorganosiloxanes which can be used as crosslinking agent (g)
  • This constituent (g) when it is present in the prior emulsion (A) or (B) or in the two emulsions, is used in an amount of 0.5 to 15 parts by weight per hundred parts by weight of the sum of constituents (a) + (b) + (c) + (d) + (g) or (a ') + (b) + (c)
  • component (g) notably improves the durability of the lubricating composition.
  • Each prior emulsion (A) and (B) or only one of the two prior emulsions (A) or (B) may also contain one or more additional ingredients such as, for example, film-forming polymers, complementary lubricants, anti-friction agents, coalescing agents, wetting or dispersing agents, mineral fillers, air release agents, anti-foaming agents, thickeners, stabilizers, preservatives such as biocides and antifungals, in amounts which can vary considerably, for example, between 0.2 and 50% by weight of the prior emulsion.
  • additional ingredients such as, for example, film-forming polymers, complementary lubricants, anti-friction agents, coalescing agents, wetting or dispersing agents, mineral fillers, air release agents, anti-foaming agents, thickeners, stabilizers, preservatives such as biocides and antifungals, in amounts which can vary considerably, for example, between 0.2 and 50% by weight of the prior emulsion.
  • thickeners are cellulosic (carboxymethylcellulose), acrylic, polyurethane thickeners, hydrocolloid gums (xanthan gum) and mixtures thereof.
  • coalescing agent glycols and / or aliphatic petroleum fractions (petroleum distillation fractions) may be used.
  • Wetting or dispersible agents which can be used in the context of the invention are, for example, phosphates and / or polyacrylics, such as for example sodium hexametaphosphate and sodium polyacrylates.
  • the prior emulsions (A) and (B) can be prepared in a conventional manner by using conventional methods of the prior art.
  • a first method consists in emulsifying, in an aqueous phase comprising all of the water-soluble constituents, a mixture of the lipophilic constituents (a) or (a '), (b), (c), (d), in the presence of the surfactant (e).
  • An oil-in-water preemulsion can first be prepared from only a few of the constituents forming the final emulsion. Then the missing constituents can be added, either directly to the emulsion (case of water-soluble constituents), or subsequently in the form of emulsion (case of constituents soluble in the silicone phase).
  • the catalyst (d) and the film-forming polymer can be added, either directly to the silicone phase before emulsification, or after formation of the emulsion, in the form of an additional emulsion.
  • the emulsification can be direct or proceed by inversion.
  • a preferred variant consists in particular in preparing an oil-in-water preemulsion comprising all of the constituents (a) or (a '), (b) and (c) and optionally (g), in the presence of the surfactant (e) before add the missing constituents to this preemulsion in the form of additional emulsion (s).
  • the invention relates to a process for the preparation of a lubricating composition in the form of an oil-in-water emulsion, characterized in that it comprises the steps (1) and ( 2) following: - step (1) where the prior emulsions (A) and (B) are prepared, at room temperature (23 ° C) using the same operating mode comprising the sequences ⁇ , ⁇ and ⁇ consisting:
  • a water-soluble crosslinking agent (g) When incorporated into the prior emulsion (s), it is preferably incorporated, in the form of an aqueous solution, at the same time as the catalyst ( d), to an oil-in-water emulsion containing all of the constituents (a) or (a), (b), (c) and (e).
  • the additional catalyst emulsion (d) as well as any emulsion added to the emulsion resulting from the sequence ⁇ is preferably prepared in the presence of the same surfactant as with the sequence ⁇ .
  • any other type of surfactant such as for example a poly (vinyl alcohol).
  • the latter surfactant is particularly useful in the case where it is desired to prepare an additional emulsion of a tin catalyst.
  • the additional ingredient (s) mentioned above, when one or more is used, can advantageously be incorporated, in whole or in part, in the prior emulsion (s) ( s) at the level of the sequence ⁇ and / or at the level of the sequence ⁇ and / or at the level of the possible sequence ⁇ .
  • the method of the invention may further comprise an additional step of heating the resulting lubricating composition, for example at a temperature ranging from 30 to 40 ° C. This step accelerates the crosslinking processes. It can be replaced by a step of storing the lubricating composition at room temperature (23 ° C.) until complete crosslinking.
  • the oils and resins (a), (a 1 ) and (b) as well as the crosslinkers (c) and (g) are commercially available or easily accessible to those skilled in the art by implementing the conventional methods described in the prior art.
  • the functionalization is easily carried out by substitution or appropriate addition reaction.
  • hydrolysable organofunctional substituents (Sofh) capable of generating volatile organic compounds (VOCs) in situ during crosslinking by condensation are, for example, alkoxy, acetoxy, ketiminoxy, enoxy.
  • the heterocondensation mechanisms involved are of the OH / OH and OH / OR d type , these OH or OR d being carried by the hydroiysates derived from silanes Si and S 2 .
  • Hydroiysates derived from Sofh are alcohols, in this case.
  • the silane Si is advantageously a trialcoxysilane, preferably a trimethoxysilane, a triethoxysilane, a methyldimethoxysilane or a methyidiethoxysilane, carrying an amino function Fr of the type:
  • the Sofhs which it comprises are preferably C 1 -C 6 alkoxy radicals, for example: methoxy, ethoxy or propoxy.
  • This silane S 2 preferably an alkoxysilane, can also contain at least one CC 6 alkyl substituent, for example: methyl, ethyl, propyl.
  • the optional crosslinker (g) is a resin obtained:
  • the silane S 3 is preferably a substituted alkoxysilane Fr. It may be, for example, a trialcoxysilane making it possible to obtain a hydroxylated resin with T units, also called T (OH) resin.
  • This silane S 3 can be of the same type as the silane S T as defined above.
  • the functions Fr substituting S 3 correspond to the same definition as that given above.
  • a crosslinking agent (g) of the polydiorganosiloxane resin type mention may be made of that obtained from ⁇ -aminopropyltriethoxysilane hydrolyzed and subjected to a "stripping" of the ethanol formed by the hydrolysis.
  • the lubricant compositions which can be obtained by implementing the process which has just been described, comprising the direct mixing of the two emulsions (A) and (B) made beforehand.
  • Another subject of the invention is the use of the lubricant composition thus obtained for the lubrication of various articles. More particularly, the invention relates to the use of the lubricating composition for the lubrication of the vulcanization bladder, made of rubber and expandable, during the shaping and vulcanization of pneumatic or semi-pneumatic tires.
  • the lubricant composition of the invention can be applied in any way, and for example by spraying, brushing or even using a sponge or a brush. I! it is preferable to operate so as to cover the article to be coated with an even layer of coating.
  • the lubrication of the vulcanization bladder used during the shaping and vulcanization of pneumatic or semi-pneumatic tires can be carried out in two different ways.
  • a raw tire is placed in a tire mold, an expandable bladder is placed in the mold, the mold is closed and the bladder is expanded by applying internal fluid pressure. hot, so that the bandage is pressed against the mold, shaped and vulcanized.
  • the mold is then opened, the bladder is deflated and the bandage is recovered, shaped and vulcanized.
  • the same bladder is used for the manufacture of approximately a few hundred bandages.
  • the expandable rubber bladder used during the manufacture of the tires is initially coated with a lubricating composition according to the invention. Initially, the lubrication of the bladder is direct. Then there is a phenomenon of exhaustion of the lubricating effect of this bladder.
  • bladder lubrication takes place in this case by transfer.
  • the present invention therefore also relates to the use of the lubricating composition for the lubrication of raw pneumatic or semi-pneumatic tires, comprising or not comprising on their external surface elements which will constitute the external tread intended to come into contact with the ground.
  • the lubricant composition of the invention does not comprise any Si-H bonding component so that the risk of evolution of hydrogen during storage or transport is zero.
  • the lubricant composition of the invention also exhibits excellent sliding properties, durability and elasticity.
  • the expandable rubber bladder before being coated on its external surface (that which comes into contact with the tire) with a lubricating composition prepared according to the process of the present invention, can undergo a pretreatment consisting in applying in any way (for example by spraying, brushing, or using a sponge or a brush) a regular layer of a primary composition in the form of an oil-in-water emulsion, said emulsion being obtained by the process comprising the direct mixing of the two oil-in-water emulsions (A) and (B) made in the prelims, which are defined above, but this time using proportions of the two previous emulsions (A) and ( B) which are such that the weight ratio emulsion (A) / emulsion (B), at the time of direct mixing, is now in the range from 0.1 to 0.7, preferably from 0.3 to 0 , 5, and more preferably from 0.35 to 0.45.
  • the present invention also relates to articles lubricated using the lubricant composition capable of
  • the invention relates to: - an expandable rubber bladder coated on its external surface with a composition according to the invention, for the shaping and vulcanization of pneumatic or semi-pneumatic tires;
  • an expandable rubber bladder obtainable by heating the expandable bladder defined above, in particular at 80-180 ° C (preferably 130-170 ° C), so as to ensure total crosslinking of the crosslinkable constituents of the emulsion;
  • lubricating composition 1 prepared according to the process of the present invention comprising a water-soluble crosslinking agent (component (g)
  • Step 1)
  • Ph C 6 H 5 (2) MDT resin having a hydroxylation rate of 0.5% by weight, an average number per molecule of organic radicals for a silicon atom of 1.5, a dynamic viscosity at 25 ° C of 0.1 Pa. s and the following proportions of siloxy units:
  • dioctyltin dilaurate emulsion in water prepared using polyvinyl alcohol as a surfactant.
  • MDT resin having a hydroxylation rate of 0.5% by weight, an average number per molecule of organic radicals for a silicon atom of 1.5, a dynamic viscosity at 25 ° C of 0.1 Pa. s and the following proportions of siloxy units: M: 17% by mole
  • the preliminary emulsons (A) and (B) are prepared using the same procedure, comprising the following sequences ⁇ and ⁇ :
  • a mixture of non-reactive phenylated siloxane oil (case of emulsion (A)) or reactive hydroxylated polydimethylsiloxane oil (case of emulsion (B)), MDT-OH resin, methyltriethoxysilane, surfactant and a part of distilled water (according to a water / surfactant ratio of 1, 2, or 2.35% by weight of water) is homogenized beforehand with moderate stirring (50 revolutions / minute) for 15 minutes at temperature ambient (23 ° C).
  • the mixture thus obtained is treated by grinding until phase inversion using a Moritz ® mill, to pass a fluid phase water / oil to a thick oil phase / water.
  • the dilution of the thick phase obtained is carried out with average stirring in 40 minutes, using a quantity of distilled water determined to obtain an emulsion whose dry matter is 50% (i.e. 45.59% by weight d 'water).
  • the bactericidal agent and the antioxidant agent are added during dilution.
  • the silane (g) and the catalyst (d) are added to the previously produced emulsion, then homogenization with moderate stirring is carried out for 10 minutes, followed by filtration.
  • the biocide and the antifoam are then added to the emulsion, and the mixture is stirred for another 10 minutes.
  • the emulsion thus obtained is characterized by an average particle size of 0.4 ⁇ m.
  • the xanthan gum and the wetting agent are loaded into another container, mixed for 10 minutes with vigorous stirring, then added to the emulsion previously produced. Stirred further, at moderate speed, for 30 minutes.
  • the final emulsion is characterized by a proportion of dry matter (60 min, 120 ° C) of 48.8% by weight.
  • the prior emulsions (A) and (B), prepared as indicated above, are mixed at ambient temperature (23 ° C.), operating with moderate stirring (50 revolutions / minute) for 15 minutes, the prior emulsions (A ) and (B) being entered in the following respective proportions:
  • the lubricating composition 1 obtained is characterized by an average particle size (measured before the addition of xanthan gum and the wetting agent) of 0.4 ⁇ m and a proportion of dry matter (60 min, 120 ° C.) of 48, 8% by weight.
  • Example 2 this is a comparative example which illustrates a lubricating composition (lubricating composition 2) prepared, not by direct mixing of two prior emulsions (A) and (B), but by directly producing a single emulsion from of the mixture of constituents (a) and (a ') with the other constituents and additional ingredients.
  • a single emulsion is therefore prepared, the nature and proportions of the constituents of which are given in Table 4 below:
  • the process used to prepare the lubricating composition 2 is identical to the process, comprising the sequences ⁇ and ⁇ , described in step (1) of Example 1.
  • the emulsion obtained is characterized by an average particle size (measured before the addition of xanthan gum and the wetting agent) of 0.402 ⁇ m and a proportion of dry matter (60 min, 120 ° C.) of 48.5% in weight.
  • Example 3 this is another comparative example which illustrates a lubricating composition (lubricating composition 3) prepared by directly producing, there too, a single emulsion from the constituents and additional ingredients, the nature and proportions of which are given in the following table 5:
  • the process used to prepare the lubricating composition 3 is identical to the process, comprising the sequences ⁇ and ⁇ , described in step (1) of Example 1.
  • the emulsion obtained is characterized by an average particle size (measured before the addition of xanthan gum and the wetting agent) of 0.402 ⁇ m and a proportion of dry matter (60 min, 120 ° C.) of 48.5% in weight.
  • a low coefficient of friction reflects good sliding properties.
  • the tests for measuring the coefficients of friction and of the durability were adapted to the application of the lubricating composition on an expandable rubber bladder.
  • the objective of this test is to assess the sliding power of a lubricating composition placed at the interface between the inflatable bladder and the internal surface of the tire envelope.
  • This test is carried out by sliding on a rubber surface, the composition of which is that of the inflatable bladder, a metal pad of determined weight, under which is fixed a tire casing film (50 ⁇ 70 mm).
  • the surface of the inflatable bladder is previously treated with the lubricating composition according to a procedure close to that used in production.
  • the coefficient of friction is measured using a dynamometer (at the speed of 100 mm / min). Five successive passages are carried out on the same inflatable bladder sample, each time changing the tire envelope sample.
  • the five passages give information on the exhaustion of the lubricating composition during successive moldings.
  • This slip test is representative of the performance to be achieved on the industrial tool, it is a first selection criterion.
  • the durability of a lubricating composition corresponds to the number of tires produced without degrading the surface of the inflatable bladder.
  • An inflatable bladder film previously treated with the lubricating composition to be evaluated, is pressed in contact with an unvulcanized tire casing film, according to a series of pressure and temperature cycles simulating the stages of manufacturing a pneumatic on the industrial tool.
  • the tire cover film is replaced with each mold.
  • the test is finished when the two surfaces in contact remain bonded.
  • the lubricating composition on the surface of the inflatable bladder film is exhausted and no longer plays the role of lubricating interface.
  • Table 6 below reports the coefficients of friction obtained on each pass for each of the lubricant compositions 1, 2 and 3 of Examples 1, 2 and 3. The results were obtained after one week of storage of the lubricant compositions 1, 2 and 3.
EP02745465A 2001-05-23 2002-05-22 Verfahren zur herstellung einer schmiermittelzusammensetzung auf basis von polysiloxanen, die keinen wasserstoff entwickelt Withdrawn EP1401992A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0106816A FR2825099B1 (fr) 2001-05-23 2001-05-23 Procede de preparation d'une composition lubrifiante a base de polysiloxanes ne degageant pas d'hydrogene
FR0106816 2001-05-23
PCT/FR2002/001723 WO2002094971A1 (fr) 2001-05-23 2002-05-22 Procede de preparation d'une composition lubrifiante a base de polysiloxanes ne degageant pas d'hydrogene

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US (1) US7439211B2 (de)
EP (1) EP1401992A1 (de)
JP (1) JP4313047B2 (de)
CA (1) CA2446627A1 (de)
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WO (1) WO2002094971A1 (de)

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FR2858777B1 (fr) * 2003-08-12 2007-02-09 B Rossow Et Cie Ets Procede de formulation d'emulsions huile-dans-eau complexes et stables, formulations ainsi obtenues et procede de formulation de produits contenant les dites emulsions
FR2884170B1 (fr) * 2005-04-08 2007-10-12 Rhodia Chimie Sa Utilisation d'une composition a base de siloxane destinee au moulage-demoulage de pneumatiques
FR2902438A1 (fr) * 2006-06-20 2007-12-21 Rhodia Recherches & Tech Composition lubrifiante a base de siloxane, ne degageant pas d'hydrogene, son procede de preparation et son utilisation
US9896640B2 (en) * 2012-11-28 2018-02-20 Dow Corning Corporation Method of reducing friction and wear between surfaces under a high load condition
US10113084B2 (en) * 2014-05-22 2018-10-30 Illinois Tool Works, Inc. Mold release agent
JP6476980B2 (ja) * 2015-02-20 2019-03-06 信越化学工業株式会社 タイヤブラダー用離型剤、タイヤブラダー及び空気タイヤ
CN105199109B (zh) * 2015-09-29 2017-10-10 广州有色金属研究院 一种化妆品用mdt型苯甲基硅油的制备方法
US20220396094A1 (en) * 2019-11-27 2022-12-15 The Yokohama Rubber Co., Ltd. Pneumatic tire

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Publication number Publication date
FR2825099B1 (fr) 2003-07-18
US7439211B2 (en) 2008-10-21
WO2002094971A1 (fr) 2002-11-28
US20040209785A1 (en) 2004-10-21
JP4313047B2 (ja) 2009-08-12
FR2825099A1 (fr) 2002-11-29
CA2446627A1 (fr) 2002-11-28
JP2004531413A (ja) 2004-10-14

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