EP1487901A1 - Verfahren zur herstellung von funktionalisierten polyorganosiloxanharzen durch redistribution in anwesenheit mindestens eines derivates einer trifluormethansulfonsäure - Google Patents

Verfahren zur herstellung von funktionalisierten polyorganosiloxanharzen durch redistribution in anwesenheit mindestens eines derivates einer trifluormethansulfonsäure

Info

Publication number
EP1487901A1
EP1487901A1 EP03725309A EP03725309A EP1487901A1 EP 1487901 A1 EP1487901 A1 EP 1487901A1 EP 03725309 A EP03725309 A EP 03725309A EP 03725309 A EP03725309 A EP 03725309A EP 1487901 A1 EP1487901 A1 EP 1487901A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
redistribution
pos
units
resin
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Withdrawn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
EP03725309A
Other languages
English (en)
French (fr)
Inventor
Fernande Boisson
Gérard Mignani
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 EP1487901A1 publication Critical patent/EP1487901A1/de
Withdrawn legal-status Critical Current

Links

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

Definitions

  • POS resins 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 from sodium silicate or alkyl silicate. (US-B-2,676,182, US-B-2,814,601, US-B-2,857,356, US-B-4,707,531). These techniques are not without drawbacks, in particular in terms of ease of implementation, cost and production of ecotoxic and / or dangerous effluents. However, there is an alternative, a priori attractive, to these condensation / hydrolysis techniques, namely the redistribution of POS oils in a POS resin comprising MQ motifs.
  • 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 acr late x D y M. This redistribution is carried out using a xylene solution of commercial MQ resin, using triflic acid as preferred acid catalyst.
  • the POS MD acrylate x D 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 catalytic system useful or for the functionalization of silicone resins comprising M and Q units, by redistribution, by using a redistribution reagent constituted by 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 the transformation rate of the reaction, without inducing any complications on the methodological level or prohibitive increase in 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 efficiency of incorporation of the functionalization POS (M ′ 2 ) is significantly increased compared to those obtained by known methods.
  • 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.
  • Ci-Cio or a C 8 -C 12 aryl the radicals Y being identical or different from each other and representing a functional group Y, by redistribution of POS resins using POSf carrying functional units M 'and / or D' and / or T ', as defined above, in the presence of an acid catalyst, said process being characterized in that at least one catalyst of the following formula (I) is used:
  • ⁇ m is an integer greater than or equal to 1;
  • the acid catalyst must be liquid under the conditions of use.
  • acids whose acidity measured in the gas phase is greater than that of sulfuric acid, therefore in terms of ⁇ G ⁇ 302 Kcal / mole.
  • (CF 3 SO 2 ) 2 NH ⁇ G 292 Kcal / mole
  • (C 4 F 9 SO 2 ) 2 NH ⁇ G 284 Kcal / mole.
  • one of the essential constituent means of the invention relates to the catalytic system formed by three particular classes ( ⁇ ) (i), I (ii) and (I) (iii) of triflic acid derivatives.
  • the use of this catalytic system makes it possible to obtain incorporation yields in POS carrying functional units (for example M ′) greater than 50%, preferably 60% and more preferably still 70%, to be compared with yields obtained. in the processes according to the prior art capping at 30%.
  • 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.
  • a base for example NaHCO 3 , Na 2 CO 3 , CaCO 3 .
  • Neutralization is all the easier since the residual acidity is here clearly lower compared to that obtained after traditional redistribution catalysis.
  • neutralization has the advantage that the final reaction medium is not aggressive with respect to the functionalized MQ silicone resins. The stability of the latter at temperature and storage is all the 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
  • a mixture of catalysts comprising at least one catalyst of formula (I) as defined above and at least catalyst of the following formula (F):
  • Y is advantageously chosen from the group comprising:
  • the starting MQ resins can be either non-functionalized, or already functionalized.
  • MQ resins are commercial products, for example of formula (M x Q y ) 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.
  • the POSf of formulas (IN.l), (IN.2), (LV.3) correspond respectively to disiloxanes, linear polyorganosiloxanes and cyclic oligoorganosiloxanes.
  • POSf are for example M 2 , M 2 V V i 1 , MD X M, MD x D ' y M, M'D x D' y M ', MD x DV V i I y M, M Vi D x D Vi y M vi , M'D X M ', M Vi D x M vi , D x . Vi D y .
  • the acid catalyst of formula (I) (i) or (ii) or (iii) that the fluorinated chain C ra F 2n ⁇ + 1 can be lengthened so as to increase the acidity of the catalyst, and subsequently its efficiency.
  • the chosen catalyst has a melting point below the reaction temperature so that the catalyst is in the liquid state during the reaction.
  • the concentration of acid catalyst (I) is advantageously between 1 ppm and 2% relative to the starting resin.
  • the mass ratio catalyst (P / inert support (preferably carbon black) is preferably between 0.1 and 10, preferably is of the order of 1.
  • the catalysis can be homogeneous or heterogeneous.
  • the catalyst being in this case dissolved in the reaction medium.
  • the catalyst is, at least in part, absorbed on an inert support which may for example be carbon black or silica.
  • the method according to the invention can be defined by other methodological characteristics, and in particular in that it comprises the following essential steps:
  • the organic solvent preferably xylene and toluene
  • MQ starting POS resin solution
  • 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.
  • neutral gas for example argon or nitrogen.
  • 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.
  • an acid catalyst in this case triflic acid or its derivatives
  • deactivation can take place using 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 42 ) and M ': (Y a R 3.
  • ⁇ m is an integer greater than or equal to 1;
  • ⁇ n is an integer equal to 1 or 2 and A represents OH, NH2 or NH with:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
EP03725309A 2002-03-26 2003-03-20 Verfahren zur herstellung von funktionalisierten polyorganosiloxanharzen durch redistribution in anwesenheit mindestens eines derivates einer trifluormethansulfonsäure Withdrawn EP1487901A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0203771 2002-03-26
FR0203771A FR2837826B1 (fr) 2002-03-26 2002-03-26 Procede de preparation de resines polyorganosiloxane fonctionnalisees par redistribution en presence d'au moins un derive d'acide triflique
PCT/FR2003/000889 WO2003080711A1 (fr) 2002-03-26 2003-03-20 Procede de preparation de resines polyorganosiloxane fonctionnalisees par redistribution en presence d'au moins un derive d'acide triflique

Publications (1)

Publication Number Publication Date
EP1487901A1 true EP1487901A1 (de) 2004-12-22

Family

ID=27839205

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03725309A Withdrawn EP1487901A1 (de) 2002-03-26 2003-03-20 Verfahren zur herstellung von funktionalisierten polyorganosiloxanharzen durch redistribution in anwesenheit mindestens eines derivates einer trifluormethansulfonsäure

Country Status (6)

Country Link
US (2) US7402647B2 (de)
EP (1) EP1487901A1 (de)
CN (1) CN100339418C (de)
AU (1) AU2003227851A1 (de)
FR (1) FR2837826B1 (de)
WO (1) WO2003080711A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2837826B1 (fr) * 2002-03-26 2005-10-28 Rhodia Chimie Sa Procede de preparation de resines polyorganosiloxane fonctionnalisees par redistribution en presence d'au moins un derive d'acide triflique
FR2837825B1 (fr) * 2002-03-26 2005-02-25 Rhodia Chimie Sa Procede de preparation de resines polyorganosiloxane fonctionnalisees par redistribution en presence d'acide triflique et/ou d'au moins l'un de ses derives et de charge inerte non basique
JP7389061B2 (ja) 2018-08-24 2023-11-29 ダウ シリコーンズ コーポレーション ヒドロキシル末端ポリジオルガノシロキサンの縮合重合のため方法
CN112469769B (zh) 2018-08-24 2022-07-08 美国陶氏有机硅公司 用于羟基封端的聚二有机硅氧烷的缩合聚合的方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2676182A (en) 1950-09-13 1954-04-20 Dow Corning Copolymeric siloxanes and methods of preparing them
US2814601A (en) 1954-04-29 1957-11-26 Dow Corning Organopolysiloxane adhesive and pressure-sensitive adhesive tape containing same
DE1017883B (de) 1954-07-08 1957-10-17 Fellows Gear Shaper Co Schalt- und Vorschubeinrichtung fuer Zahnradherstellungsmaschinen
CA1091380A (en) * 1975-03-07 1980-12-09 Mark W. Siefken Polymerization of silanes
US4020043A (en) 1975-03-07 1977-04-26 Minnesota Mining And Manufacturing Company Vulcanizable alkoxysilyl capped polymer composition
US4222952A (en) * 1979-06-25 1980-09-16 Union Carbide Corporation Siloxane bond rearrangement effected by solid perfluorinated polymers containing pendant sulfonic acid groups
US4448927A (en) * 1983-03-14 1984-05-15 Dow Corning Corporation Method of polymerizing oligomers of polydiorganosiloxane in the presence of filler
JPS61195129A (ja) 1985-02-22 1986-08-29 Toray Silicone Co Ltd 有機けい素重合体の製造方法
GB8615862D0 (en) 1986-06-28 1986-08-06 Dow Corning Ltd Making siloxane resins
DE3810140C1 (de) 1988-03-25 1989-10-05 Th. Goldschmidt Ag, 4300 Essen, De
US4929691A (en) * 1989-03-28 1990-05-29 Dow Corning Corporation Liquid silicone resin compositions
DE4116014A1 (de) * 1991-05-16 1992-11-26 Wacker Chemie Gmbh Verfahren zur herstellung von organo(poly)siloxanen
US5494979A (en) 1993-03-26 1996-02-27 Th. Goldschmidt Ag Abhesive coating composition with an additive, which affects the degree of abhesiveness
JPH07228701A (ja) * 1994-02-18 1995-08-29 Toray Dow Corning Silicone Co Ltd ケイ素原子結合水素原子含有シリコーン樹脂の製造方法
EP0797612B1 (de) * 1994-12-12 1999-01-13 Hüls Silicone Gesellschaft mit beschränkter Haftung Verfahren zur herstellung von im wesentlichen cyclenfreien polyorgano-siloxanen und organofunktionellen siloxanen
US5510430A (en) 1995-03-31 1996-04-23 General Electric Company Method of functionalizing organosiloxane condensation products
FR2802540B1 (fr) * 1999-12-17 2002-05-24 Rhodia Chimie Sa Procede de preparation de polyorganosiloxanes par polymerisation catalysee par un systeme catalytique a base d'acide triflique ou de derives de l'acide triflique
JP4965033B2 (ja) * 2001-06-29 2012-07-04 東レ・ダウコーニング株式会社 液状アルコキシシリル官能性シリコーン樹脂、その製造方法および硬化性シリコーン樹脂組成物
FR2837826B1 (fr) * 2002-03-26 2005-10-28 Rhodia Chimie Sa Procede de preparation de resines polyorganosiloxane fonctionnalisees par redistribution en presence d'au moins un derive d'acide triflique
FR2837825B1 (fr) * 2002-03-26 2005-02-25 Rhodia Chimie Sa Procede de preparation de resines polyorganosiloxane fonctionnalisees par redistribution en presence d'acide triflique et/ou d'au moins l'un de ses derives et de charge inerte non basique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03080711A1 *

Also Published As

Publication number Publication date
AU2003227851A1 (en) 2003-10-08
CN1649939A (zh) 2005-08-03
FR2837826A1 (fr) 2003-10-03
US7402647B2 (en) 2008-07-22
US20050239987A1 (en) 2005-10-27
WO2003080711A1 (fr) 2003-10-02
US20080255322A1 (en) 2008-10-16
FR2837826B1 (fr) 2005-10-28
CN100339418C (zh) 2007-09-26

Similar Documents

Publication Publication Date Title
WO2005073279A1 (fr) Procede de preparation de polyorganosiloxanes (pos) par polymerisation par ouverture de cycle(s) et/ou redistribution de pos, en presence de carbene(s) et compositions de pos mises en oeuvre dans ce procede
EP0728793A1 (de) Verfahren zur Herstellung von Polyorganosiloxanharz, evtl. alkoxyliert, durch nicht-hydrolytische Kondensation
EP1856191B1 (de) Verfahren zur herstellung von organopolysiloxan durch polymerisation und umlagerung von cyclischen siloxanen
FR2802540A1 (fr) Procede de preparation de polyorganosiloxanes par polymerisation catalysee par un systeme catalytique a base d'acide triflique ou de derives de l'acide triflique
FR2707654A1 (fr) Procédé de préparation de fluides de polydiorganosiloxanes à terminaison triorganosiloxy à faible teneur en silanol.
EP2850122B1 (de) Material mit hohem brechungsindex
EP1487901A1 (de) Verfahren zur herstellung von funktionalisierten polyorganosiloxanharzen durch redistribution in anwesenheit mindestens eines derivates einer trifluormethansulfonsäure
EP1487902A1 (de) Verfahren zur herstellung von funktionalisierten polyorganosiloxanharzen durch redistribution in anwesenheit von trifluormethansulfonsäure und/oder derivaten davon und eines inerten nicht-basischen füllstoffes
WO2023180271A1 (fr) Dépolymérisation d'organopolysiloxane
CA2178996A1 (fr) Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
EP0023187B1 (de) Verfahren zum Kondensieren von Hydroxysilylgruppen enthaltenden Polysiloxanen in Gegenwart von Alkali- oder Erdalkalimetallen und polyheteromacropolycyclische Verbindung
EP1660563B1 (de) Funktionalisierung (epoxidierung) von silikonen und deren anwendung für antihaftbeschichtungen
WO2002064665A1 (fr) Materiau polymere hydrophile comprenant une matrice reticulee de polyorganosiloxanes et son procede de fabrication.
FR2663941A1 (fr) Procede de production d'organosiloxanes.
EP4724428A1 (de) Verfahren zur ringöffnungs- oder polykondensationspolymerisation
WO2024252074A1 (fr) Procede de polymerisation par ouverture de cycle
WO2025012532A1 (fr) Procede de polymerisation par ouverture de cycle ou par polycondensation
WO2004031200A1 (fr) Phosphates de silanoxyle, leur preparation et leur utilisation dans la synthese de polyorganosiloxanes lineaires
FR2751975A1 (fr) Procede pour preparer des copolymeres d'hydrogenosiloxane
EP0944668B1 (de) VERFAHREN ZUR HERSTELLUNG VON STABILEN SILIKONÖLEN DIE SiH-UND HYDROSILYLIERBARE GRUPPEN ENTHALTEN
WO2004092251A1 (fr) Procede de preparation de polyorganosiloxanes lineaires
FR2842204A1 (fr) Fonctionnalisation (epoxydation) de silicones et utilisation de ces silicones comme revetements anti-adherents

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040908

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20091110