Classifications

• • 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
  • C08G77/10—Equilibration 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
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used

Definitions

• the field of the invention is that of the development of silicone or polyorganosiloxane resins, hereinafter designated by POS resins.
• These functional MQ silicone resins can be liquid or solid at room temperature. They have been known for a very long time and are currently used in numerous applications such as, for example, in electrical insulating varnishes, heat-resistant coatings, encapsulation materials for semiconductor components, etc.
• the functional MQ POS resins (MM'Q) which are the subject of the present invention may also comprise siloxy units D and / or T, or even functionalized siloxy units D 'and / or T'.
• the main access routes to functional MQ resins are currently the condensation / hydrolysis processes using sodium silicate or allyl silicate.
• Patent US-B-4,774,310 describes the preparation of functionalized Si-H resins by redistribution of tetramethyledisiloxane (M ′ 2 ) in an MQ resin in solution in an organic solvent, in the presence of triflic acid or perfluoroalkanesulfonic acid (TFOH) .
• the reaction medium is heated to a temperature between 50 and 100 ° C., then the triflic acid catalyst is neutralized with NaHCO 3 .
• the MM'Q resins thus obtained can react with organic or organosiloxane substances carrying an olefinic unsaturation (column 2 line 66 to column 3 line 3).
• This patent makes also a vague and general allusion to the supported acid catalysts (column 2 line 18).
• US Pat. No. 5,494,979 discloses the preparation of MQ resins functionalized with acrylate radicals, by redistribution of polydiorganosiloxane oils carrying D units and D acrylic units : MD acrylate x D y M. This redistribution is carried out using a xylene solution of commercial MQ resin, using triflic acid as the preferred acid catalyst.
• the POS MD acrylate ⁇ ⁇ j y M used is as described in Example 2 of German patent n ° 3810140.
• This preparation of acrylate functionalized MQ resins also includes stages of neutralization, for example using sodium carbonate, then elimination of the solid residues by filtration.
• one of the essential objectives of the present invention is to provide an improved process for functionalizing silicone resins comprising M and Q siloxyl units, by redistribution using POSs carrying functional units or functionalization units ; this improved process should provide improvements in terms of ease of implementation, of significant increase in the functionalization rate of the redistributed resin as well as in the conversion rate of functional POS reagents, while keeping the cost of the process at the most low possible.
• Another essential objective of the invention is to provide a new acidic lyric system, based on triflic acid or derivative, useful or for the functionalization of silicone resins comprising M and Q units, by redistribution, by implementing a redistribution reagent consisting of a POS carrying functional or functionalization units, said catalytic system being endowed with properties such that it allows the improvement of the redistribution kinetics as well as of the yield and of the conversion rate of the reaction, and this without inducing complications on the methodological level nor prohibitive increase of the cost.
• Another essential objective of the invention is to significantly improve the catalysis, homogeneous or heterogeneous, of functionalization reactions of resins comprising M and Q siloxyl units by redistribution, by means of POS carrying functional or functionalization units.
• the improvement sought must be reflected in terms of the control, reliability and productivity of the corresponding industrial processes.
• Another objective targeted through the improvement of the catalytic system is to improve the quality of the functionalized MQ resins obtained, while optimizing safety and minimizing the ecotoxic impact of the industrial processes considered.
• Another essential objective of the invention is to provide a process for the functionalization of MQ silicone resins by redistribution, in which the inco ⁇ oration yield of the functionalization POS (M ′ 2 ) is significantly increased compared to those obtained by known processes. .
• Another essential objective of the invention is to provide a process for functionalizing MQ silicone resins by redistribution using POS for functionalization which process offers the possibility of controlling the rate of functionalities introduced as well as the location of these functions on the resin.
• Another essential objective of the invention is to propose a process for functionalizing MQ type silicone resins by redistribution, this process being capable of being applied to a wide variety of chemical functions, so as to be able to produce a wide variety of resins Functional MQs suitable for multiple applications, from a raw material constituted by a resin core at the periphery of which are chosen chemical functions.
• POS functionalized polyorganosiloxane
• non-basic is meant more precisely and for example within the meaning of the present invention, an inert charge incapable of reacting with the acid catalyst, to neutralize it and make it “catalytically” less active or even inactive.
• one of the essential constituent means of the invention relates to the catalytic system formed by a combination of triflic acid or one of its derivatives, with a non-basic charge (or inert support).
• the non-basic inert filler is chosen from the group of products comprising: carbon black, an acid or neutral oxide, and their mixtures.
• the acid or neutral oxide is selected from the group comprising: Al O 3 , Na O, TiO 2 , MgO, neutral or acid zeolites, silica and their mixtures.
• the catalytic system according to the invention is also remarkable in terms of kinetics.
• redistribution can be easily stopped by neutralization of the acid catalyst using a base (for example NaHCO 3 , Na 2 CO 3 , CaCO 3 ) and / or by deactivation by heat and / or by adsorption. (carbon black, diatomaceous earth ).
• a base for example NaHCO 3 , Na 2 CO 3 , CaCO 3
• deactivation by heat and / or by adsorption.
• carbon black, diatomaceous earth carbon black, diatomaceous earth .
• neutralization has the advantage that the final reaction medium is not aggressive with respect to functionalized MQ silicone resins. The stability of the latter at temperature and storage is only better.
• This process also makes it possible to control the functionalization rate of the MQ resin, or even the location of its functions on the resin.
• a core of MQ resin which constitutes a convenience
• the functions that may be inco ⁇ orated in the resin are, for example, of the Si-H, Si-Ni, Si-phenyl, Si-alkyl, Si-alkenyl, Si-alkyne, Si-alkyl halide, Si-alkyl- type. epoxide, Si-alkyl-polyether, Si-carbinol, Si-alkyl-ammonium, Si-alkyl-Carboxylic acid, Si-alkyl-thiol.
• Y is advantageously chosen from the group comprising: hydrogen an alkenyl an alkynyl an aryl (preferably a phenyl) an (alkyl) epoxy an ether or a polyether a carboxylic acid an amide an amine a halide an alcohol a thiol or any other sulfur derivative.
• the starting MQ resins can be either non-functionalized, or already functionalized.
• non-functionalized MQ resins these are commercial products, for example of formula (M X Q V ) Z with x between 0.5 and 1 and including between 0 and 1.
• the MQ resins already functionalized are in particular those obtained by the process in accordance with the present invention from non-functionalized starting MQ resins or by the process of synthesis from sodium silicate described in US Pat. No. 2,676,182.
• the starting MQ resin is in the form of a solution in an organic solvent such as for example xylene or toluene or in solution in the POSf oil for functionalization.
• non-basic inert filler it is a fine powder, that is to say whose particle size is such that the grains are between 0.001 and 300 ⁇ m.
• carbon black (the latter being preferred) which is in the form of powder, granule or any other molded shape.
• the carbon black powder is dispersed in the POSf functionalization oil.
• the POSf of formulas (IN.l), (IN.2), (IN.3) correspond respectively to disiloxanes, linear polyorganosiloxanes and cyclic ohgoorganosiloxanes. These POSf are for example M 2 , M 2 vi , MD X M, MD x D ' y M, M'D x D' y M ', MD x D vi y M, M vi D x D vi y M vi , M'D X M ', M Vi D x M vi .
• concentration of acid catalyst (I) is advantageously between 1 ppm and 2% relative to the starting resin.
• mass ratio of catalyst (I) / inert support is preferably between 0.1 and 10, preferably is of the order of 1.
• the non-basic inert filler is not linked to the acid catalyst (I) (triflic acid or derivatives). They coexist separately from each other in the reaction medium.
• the catalysis can be homogeneous or heterogeneous.
• the catalyst being in this case dissolved in the reaction medium.
• the non-basic inert charge can be an inert support on which the catalyst is, at least in part, absorbed or is intended to be, at least in part, absorbed.
• the catalyst is, at least in part, absorbed on an inert support different from the non-basic inert charge, the latter being moreover present in the reaction medium.
• the acid catalyst must be liquid under the conditions of use. But it can be solid at 25 ° C and be melted at the reaction temperature.
• the third variant of heterogeneous catalysis corresponds to a combination of the first and the second variant.
• the method according to the invention can be defined by other methodological characteristics, and in particular in that it comprises the following essential steps: 1- bringing together the starting POS resin, the POSf carrying functional units, the acid catalyst (I) and the non-basic inert filler (Al 2 O 3 , Na 2 O, TiO 2 , MgO, silica, earth diatom, zeolite, carbon black the latter being preferred), in an organic solvent; 2- reacting preferably at a temperature ⁇ r greater than or equal to room temperature and less than or equal to the boiling point of the solvent, and more preferably still between 50 ° C and 100 ° C; 3- optionally stopping the reaction by adding a neutralizing agent for the acid catalyst (I); 4- elimination of the inert charge (advantageously carbon black) from the reaction medium, preferably by filtration.
• 1- bringing together the starting POS resin, the POSf carrying functional units, the acid catalyst (I) and the non-basic inert filler (Al 2 O 3 , Na 2 O, TiO
• the organic solvent preferably xylene, toluene, white spirit
• MQ starting POS resin
• the non-basic inert filler preferably carbon black
• the non-basic inert filler is in the form of a powder dispersed in the POSf carrying functional units.
• the functionalization process by redistribution according to the invention makes it possible in particular to graft Si-H and / or Si-alkenyl (preferably vinyl) units, onto MQ resins. Since these H or alkenyl functions are reactive functions, among others, it is possible, in accordance with the invention, to carry out a second functionalization according to a hydrosilylation mechanism, so as to fix covalently on the MQ resin already functionalized, a second functional segment.
• reaction atmosphere be free of humidity.
• the reaction pressure is advantageously normal and the reaction temperature can range from room temperature (25 ° C for example) to a temperature of 150 ° C or more.
• the redistribution is stopped by deactivating the catalyst.
• a basic neutralizer such as for example sodium carbonate Na 2 CO 3 or sodium bicarbonate NaHCO 3 .
• Neutralization is all the more necessary when it is a homogeneous catalysis since in such a case, unlike heterogeneous catalysis, the catalyst is not removed at the end of the reaction.
• the redistributed and functionalized resin obtained is subjected to at least one other redistribution / functionalization, using POSs carrying functional patterns.
• the invention also relates to a catalytic system useful for the preparation of functionalized polyorganosiloxane (POS) resins and comprising units M: (R 3 SiO ⁇ / 2 ), Q: (SiO 4 2 ) and M ': (Y a R 3 .
• POS functionalized polyorganosiloxane
• a SiO ⁇ / 2 and possibly D: (R 2 SiO 2/2 ) and / or D ': (RYSiO 2 2 ) and / or T: (RSiO 3 2 ) and / or T': (YSiO 3 2 ) with , in these patterns: - the radicals R which are identical or different from each other and representing a Ci-Cio alkyl or a C 8 -C ⁇ aryl; the radicals Y being identical or different from each other and representing a functional group Y, preferably chosen from the group comprising: hydrogen • an alkenyl an alkynyl an aryl (preferably a phenyl) an (alkyl) epoxy an ether or a polyether "a carboxylic acid an amide an amino a halide an alcohol • a thiol or any other sulfur-containing derivative by redistribution of POS resins using POSs carrying functional units M 'and / or D' and / or T 'such as defined
• an acid or neutral oxide preferably selected from the group comprising: Al O 3 , Na 2 O, TiO , MgO, zeolite, silica, diatomaceous earth, carbon black and their mixtures

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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)
• Silicon Polymers (AREA)

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• 2002
  • 2002-03-26 FR FR0203769A patent/FR2837825B1/fr not_active Expired - Fee Related
• 2003
  • 2003-03-20 US US10/509,060 patent/US7411028B2/en not_active Expired - Fee Related
  • 2003-03-20 CN CNB03809231XA patent/CN100355812C/zh not_active Expired - Fee Related
  • 2003-03-20 AU AU2003233388A patent/AU2003233388A1/en not_active Abandoned
  • 2003-03-20 WO PCT/FR2003/000888 patent/WO2003080710A1/fr not_active Ceased
  • 2003-03-20 EP EP03727601A patent/EP1487902A1/de not_active Withdrawn
• 2008
  • 2008-06-19 US US12/142,318 patent/US20080255292A1/en not_active Abandoned

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