EP1299452A1 - Derivate von maleinsäure und/oder fumarsäure enthaltende mutifunktionelle organopolysiloxane und verfahren zu deren herstellung - Google Patents

Derivate von maleinsäure und/oder fumarsäure enthaltende mutifunktionelle organopolysiloxane und verfahren zu deren herstellung

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Publication number
EP1299452A1
EP1299452A1 EP01945438A EP01945438A EP1299452A1 EP 1299452 A1 EP1299452 A1 EP 1299452A1 EP 01945438 A EP01945438 A EP 01945438A EP 01945438 A EP01945438 A EP 01945438A EP 1299452 A1 EP1299452 A1 EP 1299452A1
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Prior art keywords
symbols
pos
radical
linear
chosen
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English (en)
French (fr)
Inventor
Nathalie Guennouni
Gérard Mignani
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen

Definitions

  • the field of the present invention is that of new organosilicon compounds comprising a multifunctional polyorganosiloxane (abbreviated POS) comprising, per molecule, and attached to silicon atoms, on the one hand at least one hydroxyl radical and / or at least one radical alkoxyl and on the other hand at least one group containing an activated ethylenic double bond chosen from groups derived from maleic acid and groups derived from fumaric acid.
  • POS multifunctional polyorganosiloxane
  • the compounds comprising a multifunctional POS as referred to above are capable of exhibiting advantageous properties, for example, as a coupling agent (white filler-elastomer) in rubber compositions based on isoprene elastomer (s) ) including a white filler as a reinforcing filler.
  • groups derived from maleic acid the groups or functions consisting of the following residues: maleic acid itself; a maleic acid diester (or maleic ester); maleamic acid; an ester of maleamic acid (or maleic ester); a maleic acid diamide (or maleic amide or maleamide);
  • groups derived from fumaric acid the groups or functions consisting of the following residues: fumaric acid itself; a fumaric acid diester (or fumaric ester); fumaramic acid; a fumaramic acid ester (or fumaramic ester); a diamide of fumaric acid (or fumaric amide or fumaramide).
  • new multifunctional POSs carrying, in addition to at least one hydroxyl and / or alkoxyl radical, at least one group chosen from groups derived from maleic acid and groups derived from fumaric acid.
  • Another object of the present invention is therefore to provide methods for preparing POSs carrying functions derived from maleic acid and / or fumaric acid which are easy to implement and provide the undeniable advantage of being able to lead to POS functionalized with selectivities and yields at a level of excellence not yet achieved so far.
  • the present invention taken in its first object, relates to organosilicon compounds which comprise multifunctional POSs containing similar or different units of formula:
  • R 2 identical or different, each represent a monovalent hydrocarbon group chosen from an alkyl radical, linear or branched, having
  • the symbols R 2 are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, cyclohexyl and phenyl; more preferably, the symbols R 2 are methyl radicals; (2) the symbols Y, identical or different, each represent a hydroxyl or alkoxyl function R 1 O where R 1 represents an alkyl radical, linear or branched, having from 1 to 15 carbon atoms; preferably, the symbols Y are chosen from a hydroxyl radical and an alkoxyl radical, linear or branched, having from 1 to 6 carbon atoms; more preferably, the symbols Y are chosen from a hydroxyl radical and an alkoxyl radical, linear or branched having from 1 to 3 carbon atoms (that is to say methoxyl,
  • V represents a divalent radical -O- or -NR 6 -; preferably, the symbol V is a radical -O- or -NR 6 - where R 6 has the preferred definition indicated below; more preferably, the symbol V is a radical -O- or -NR 6 - where R 6 has the more preferred definition indicated below; + the symbol W represents a monovalent group COOR 7 or a monovalent group
  • R 3 is a divalent alkylene radical, linear or branched, comprising from 1 to 15 carbon atoms whose free valence is carried by a carbon atom and is linked to a silicon atom, said radical R 3 being able to be interrupted within of the alkylene chain by at least one heteroatom (such as oxygen and nitrogen) or at least one divalent group comprising at least one heteroatom (such as oxygen and nitrogen), and in particular by at least one divalent residue of general formula —rest- chosen from: -O-, -CO-, -CO-O-, -COO-cyclohexylene (optionally substituted by an OH radical) -, -O-alkylene (linear or branched C 2
  • R 3 also represents a divalent aromatic radical of general formula —radical— chosen from: -phenylene (ortho, meta or para) -alkylene (linear or branched in C 2 -C 6 ) -, -phenylene (ortho, meta or para) -O-alkylene (linear or branched C 2 -C 6 ) -, -alkylene (linear or branched C 2 -C 6 ) - phenylene (ortho, meta or para) -alkylene
  • R 3 represents an alkylene radical which corresponds to the following formulas: - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, -CH 2 -CH (CH 3 ) -, - (CH 2 ) 2 -CH (CH 3 ) -CH 2 -, - (CH 2 ) 3 -O- (CH 2 ) 3 -, - (CH 2 ) 3 -O-CH 2 -CH (CH 3 ) -CH 2 -, - (CH 2 ) 3 -O-CH 2 CH (OH) -CH 2 -; more preferably, R 3 is a radical - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 3 -O-CH 2 CH (OH) -CH 2 -; more preferably, R 3 is a radical - (CH 2 ) 2 -, - (CH 2 ) 3 -, -
  • R 4 and R 5 each represent a hydrogen atom, a halogen atom, a cyano radical or an alkyl radical, linear or branched, having from 1 to 6 carbon atoms
  • R 5 can also represent a monovalent group COOR 7 ; preferably, the symbols R 4 and R 5 are chosen from a hydrogen atom, a chlorine atom, and the methyl, ethyl, n-propyl, n-butyl radicals, R 5 can also represent a COOR 7 group where the radical R 7 has the preferred definition indicated below; more preferably, these symbols are chosen from a hydrogen atom and a methyl radical, R 5 possibly also representing a COOR 7 group where the radical R 7 has the more preferred definition indicated below;
  • the symbols R 6 , R 7 , R 8 and R 9 identical or different, each represent a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 atoms carbon or a phenyl radical, the symbols R 8 and R 9 being able, in addition, to form together and with the nitrogen atom, to which they are linked, a single saturated ring having from 3 to 8 carbon atoms in the ring; preferably, the symbols R 6 , R 7 , R 8 and R 9 are chosen from a hydrogen atom, and the methyl, ethyl, n-propyl, n-butyl radicals, the symbols R 8 and R 9 being able, in addition, forming together and with the nitrogen atom a pyrrolidinyl or piperidyl ring; more preferably, these symbols are chosen from a hydrogen atom and a methyl radical, the symbols R 8 and R 9 being able, in addition, to form together and with the nitrogen atom a piperidyl ring;
  • the rate of R 10 SiO 32 units (T" units) where R 10 is chosen from the radicals corresponding to the definitions of R 2 , Y and X, this rate being expressed by the number, per molecule, of these units per 100 silicon atoms, is 30% or less and preferably 20%; (6) the rate of Y functions, expressed by the number, per molecule, of Y functions per 100 silicon atoms, is at least 0.8% and, preferably, is in the range from 1 to 100 %; (7) the rate of X functions, expressed by the number, per molecule, of X functions per 100 silicon atoms, is at least 0.4% and, preferably, is in the range from 0.8 100 %.
  • each multifunctional POS of formula (I) can have either a linear structure or a cyclic structure, or a mixture of these structures, which structures may also have a certain molar amount of ramifications ("T" motifs).
  • each organosilicon compound forming part of the present invention may be in the form of a multifunctional POS in the pure state or in the form of a mixture of such POS with a variable quantity by weight (generally much lower 50% in the mixture) of another (or other) compound (s) which may (may) consist in: (i) one and / or the other of the starting reagents from which are prepared multifunctional POS, when the transformation rate of said reagents is not complete; and / or (ii) the product (s) resulting from a complete or incomplete modification of the silicone skeleton of the starting reagent (s); and / or (iii) the product (s) resulting from a modification of the silicone skeleton of the desired multifunctional POS, carried out by a condensation reaction, a hydrolysis and condensation reaction and / or a redistribution reaction.
  • the scope of the invention includes
  • n + p + q + r + s + t giving the total number of silicon atoms is in the range from 3 to 250
  • organosilicon compounds which are preferably used, mention may be made of those comprising oligomers and essentially linear POS / 1 polymers which correspond to formula (III) in which (we will then speak, abbreviated, in this case, POS / 1 polymers acid type):
  • R is in the range from 0 to 10
  • organosilicon compounds which are still preferably targeted, mention may be made of those comprising oligomers and essentially linear POS / 2 polymers which correspond to formula (III) in which (we will then speak, abbreviated, in this case, of POS / 2 of ester type): (1 "') the symbols T 1 are defined as indicated above in point (1');
  • n is in the range from 0 to 50
  • p is in the range from 0 to 20
  • n + p + q + r + s giving the total number of silicon atoms is in the range from more than 3 to 50,
  • organosilicon compounds which comprise multifunctional POSs chosen from the family of POSs in accordance with formula (I), which are cyclic and have the following average formula:
  • the second object of the present invention relates to the processes by which the organosilicon compounds according to the invention, comprising the multifunctional POSs in accordance with formulas (I), (III) and (III ') given above, can be prepared. These processes involve in particular:
  • organosilicon compounds comprising the multifunctional POSs in accordance with formulas (I), (III) and (III ′) are prepared by a process which consists, for example: (a) in hydrolyzing an aqueous organosilane of formula:
  • organosilicon compounds comprising POSs of formula (III) where the symbols T 1 and T 2 represent the motifs H0 1 2 and the symbol q is different from zero.
  • the organosilicon compounds which are preferably targeted in the context of the invention are those comprising POS / 1 polymers of acid type and those comprising POS / 2 polymers of ester type.
  • organosilicon compounds comprising POS / 1 polymers of the acid type corresponds to a process (d) consisting in carrying out a coupling reaction between:
  • an essentially linear amino POS having the same formula (III) as that given above with regard to the definition of the POS / 1 polymers, but in which the symbol X is now an amino function of formula - R 3 -NR 6 H where the symbols R 3 and R 6 are as defined above in point (3) concerning the formula (I); said amino POS is represented for short, in the following, by the simplified formula:
  • the amino POS of formula (X) can be prepared, in a manner known per se, by carrying out for example a redistribution and equilibration reaction between on the one hand a POS which results from a hydrolysis of an aikoxysilane carrying a function amine formula:
  • organosilicon compounds comprising the POS / 2 polymers of ester type, which constitute another category of organosilicon compounds which are also preferentially targeted within the framework of the present invention, can be prepared by applying the advantageous procedures defined below.
  • the organosilicon compounds comprising the POS / 2 polymers of the ester type can be prepared by esterification of an intermediate maleamic acid POS by carrying out the following steps: (e1) coupling reaction, as explained above concerning process (d), between the amino POS (X) and maleic anhydride (XI), then (e2) reaction of esterification of the medium comprising POS / 1 of the acid type formed, to lead to the compound comprising POS / 2 of desired ester type, applying the following synthesis scheme:
  • step (e2) With regard to the practical way of implementing step (e2), reference will be made for more details to the contents of the following documents which describe, possibly starting from other reagents, procedures applicable to carrying out this step. step:
  • the organosilicon compounds comprising the POS / 2 polymers of ester type can be prepared by formation of an amide function by adding the amino POS (X) to an ester derivative (XIV) obtained from a mono-ester of maleic acid (XIII), by carrying out the following stages: (f1) alcoholysis of maleic anhydride ( XI) with alcohol R 7 -OH, (f2) activation of the carboxylic acid function of the mono-ester of maleic acid (XIII) obtained, using the various activation methods described in the field of peptide synthesis , to lead to the activated ester derivative (XIV), then (f3) addition of the amino POS (X) to said activated ester derivative (XIV) to lead to the compound comprising POS / 2 of the desired ester type, by applying the synthesis scheme next :
  • step (f1) cf. in particular J. Med. Chem., 1983, 26, pages 174-181;
  • organosilanes are products which can be prepared by applying either of the methods (e1) and (e2) described above, in the conduct of which the amino POS (X) will be replaced by the amino alkoxysilane of formula (XII).
  • Carrying out methods (d), (e) and (f) leads to the production of an organosilicon compound which can be in the form of a multifunctional POS in the pure state or in the form of a mixture of a multifunctional POS with a variable quantity by weight (generally much less than 50% in the mixture) of another (or other) compound (s) which can (can) consist for example in a small quantity of the monofunctional POS cyclic of formula:
  • n is in the range from 1 to 9
  • n "+ q" is in the range from 3 to 10
  • said cyclic monofunctional POS being derived from a modification of the silicone skeleton of the desired multifunctional POS.
  • organosilicon compounds according to the invention comprising the multifunctional POSs in accordance with formulas (I), (III) and (III 1 ) given above, can be advantageously used as coupling agent for white filler-elastomer in elastomer compositions (s) of rubber type, natural (s) or synthetic (s), based on isoprene elastomer (s), comprising a white filler, in particular a siliceous material, as reinforcing filler, compositions which are intended the manufacture of articles or elastomer (s).
  • elastomeric article where the use of a coupling agent is most useful, are those subject in particular to the following constraints: variations in temperature and / or variations in high frequency stress in regime dynamic; and / or a significant static stress; and / or significant flexion fatigue in dynamic regime.
  • Types of articles are for example: conveyor belts, power transmission belts, flexible hoses, expansion joints, seals of household appliances, supports acting as engine vibration extractors either with metal fittings, either with a hydraulic fluid inside the elastomer, cables, cable sheaths, shoe soles and rollers for cable cars.
  • a coupling agent also called a binding agent, which has the function of ensuring the connection between the surface of the white filler particles and the elastomer, while facilitating the dispersion of this white charge within the elastomeric matrix.
  • the elastomer (s) compositions include:
  • compositions include (the parts are given by weight):
  • white filler preferably from 30 to 100 parts and more preferably from 30 to 80 parts, • an amount of coupling agent or organosilicon compound which provides 0.5 to 15 parts of multifunctional POS in the composition, preferably 0.8 to 10 parts and more preferably 1 to 8 parts.
  • the amount of coupling agent chosen from the aforementioned general and preferred areas, is determined so that it represents from 1% to 20%, preferably from 2 to 15%, more preferably from 3 at 8%, relative to the weight of the reinforcing white filler.
  • isoprene elastomers and of reinforcing white filler.
  • isoprene elastomers which are used for the rubber compositions, we mean more precisely:
  • - (2J) conjugated diene monomers other than isoprene, having from 4 to 22 carbon atoms, such as for example: 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, chloro- 2 1,3-butadiene (or chloroprene), 1-phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene; - (2.2) vinyl aromatic monomers having 8 to 20 carbon atoms, such as for example: styrene, ortho-, meta- or paramethylstyrene, the commercial "vinyl-toluene" mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinyl mesitylene, divinylbenzene, vinylnaphthalene;
  • vinyl nitrile monomers having from 3 to 12 carbon atoms, such as for example acrylonitrile, methacrylonitrile;
  • the acrylic ester monomers derived from acrylic acid or from methacrylic acid with alkanols having from 1 to 12 carbon atoms such as, for example, methyl acrylate, ethyl acrylate, sodium acrylate propyl, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate ;
  • copolymer polyisoprenes containing between 99% and 20% by weight of isoprenic units and between 1% and 80% by weight of diene units, aromatic vinyls, vinyl nitriles and / or acrylic esters, and consisting for example in poly (isoprene -butadiene), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene); (3) natural rubber;
  • (6) a mixture containing a majority quantity (ranging from 51% to 99.5% and preferably from 70% to 99% by weight) of the abovementioned elastomer (1) or (3) and a minority quantity (ranging from 49% to 0.5% and preferably from 30% to 1% by weight) of one or more diene elastomers other than isoprene.
  • diene elastomer other than isoprene is understood in a manner known per se: the homopolymers obtained by polymerization of one of the conjugated diene monomers defined above in point (2J), such as for example polybutadiene and polychloroprene; the copolymers obtained by copolymerization of at least two of the above-mentioned conjugated dienes (2.1) together or by copolymerization of one or more of the above-mentioned conjugated dienes (2J) with one or more of the above-mentioned unsaturated monomers (2.2), (2.3) and / or (2.4), such as for example poly (butadiene-styrene) and poly (butadiene-acrylonitrile).
  • isoprenic elastomers chosen from: (1) synthetic polyisoprenes homopolymers; (2) synthetic polyisoprenes copolymers consisting of poly (isoprene-butadiene), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene); (3) natural rubber; (4) butyl rubber; (5) a mixture of the above-mentioned elastomers (1) to (4) with one another; (6) a mixture containing a majority quantity of the abovementioned elastomer (1) or (3) and a minority quantity of diene elastomer other than isoprene consisting of polybutadiene, polychloroprene, poly (butadiene-styrene) and poly (butadiene-acrylonitrile).
  • isoprenic elastomers chosen from: (1) synthetic polyisoprenes homopolymers; (3) natural rubber; (5) a mixture of the above-mentioned elastomers (1) and (3); (6) a mixture containing a majority quantity of the abovementioned elastomer (1) or (3) and a minority quantity of diene elastomer other than isoprene consisting of polybutadiene and poly (butadiene-styrene).
  • reinforcing white charge is understood to define a “white” charge (that is to say inorganic or mineral), sometimes called “clear” charge, capable of reinforcing on its own, without other means than that of a coupling agent, an elastomer composition (s) of rubber type, natural (s) or synthetic (s).
  • the physical state under which the reinforcing white filler is present is immaterial, that is to say that said filler can be in the form of powder, micro pearls, granules or beads.
  • the reinforcing white filler consists of silica, alumina or a mixture of these two species.
  • the reinforcing white filler consists of silica, taken alone or as a mixture with alumina.
  • silica capable of being used all precipitated or pyrogenic silicas known to those skilled in the art having a BET specific surface area ⁇ 450 m 2 / g are suitable. Precipitation silicas are preferred, these can be conventional or highly dispersible.
  • highly dispersible silica any silica having an ability to disaggregate and to disperse in a very large polymer matrix observable by electron or optical microscopy, on fine sections.
  • highly dispersible silicas mention may be made of those having a specific CTAB surface of 450 m 2 / g or less and particularly those described in patent US-A-5,403,570 and patent applications WO-A-95 / 09127 and WO-A-95/09128 the content of which is incorporated here.
  • treated precipitated silicas such as for example silicas "doped" with aluminum described in patent application EP-A-0 735 088, the content of which is also incorporated here.
  • precipitation silicas having:
  • CTAB specific surface ranging from 100 to 240 m 2 / g, preferably from 100 to 180 m 2 / g,
  • BET specific surface area ranging from 100 to 250 m 2 / g, preferably from 100 to 190 m 2 / g,
  • DOP oil intake of less than 300 ml / 100 g, preferably ranging from 200 to 295 ml / 100 g,
  • silica also means blends of different silicas.
  • CTAB specific surface is determined according to the NFT 45007 method of November 1987.
  • BET specific surface is determined according to the method of BRUNAUER, EMMET, TELLER described in "The Journal of the American Chemical Society, vol. 80, page 309 (1938) "corresponding to standard NFT 45007 of November 1987.
  • the DOP oil intake is determined according to standard NFT 30-022 (March 1953) by using dioctylphthalate.
  • a highly dispersible alumina is advantageously used having:
  • BET specific surface area ranging from 30 to 400 m 2 / g, preferably from 80 to 250 m 2 / g,
  • an average particle size at most equal to 500 nm, preferably at most equal to 200 nm, and
  • aluminas A125, CR125, D65CR from the company BAIKOWSKI. It may be advantageous, if necessary, depending on the particular conditions of use of the coupling agents and the final destination of the rubber compositions, to add to the rubber composition at least one coupling activator.
  • the coupling activator when one is used, is preferably chosen from the group consisting of peroxides, hydroperoxides, azido compounds, bis (azo) compounds, peracids, peresters or a mixture of two or more more than two of these compounds.
  • the radical initiator when one is used, is chosen from peroxide of 1.1 bis (t-butyl) -3,3,5- trimethylcyclohexane, 1,1'-azobis (isobutyronitr ⁇ e ) and their mixture.
  • the radical initiator when one is used, is used in very small proportion in rubber compositions, namely at a rate ranging from 0.05 to 1 part, preferably from 0.05 to 0.5 parts, and more preferably still from 0.1 to 0.3 parts, per 100 parts of elastomer (s).
  • the rubber-type compositions also contain all or part of the other constituents and auxiliary additives usually used in the field of elastomer (s) and rubber (s) compositions.
  • vulcanization agents chosen from sulfur or sulfur-donor compounds, such as for example thiuram derivatives; vulcanization accelerators, such as, for example, guanidine derivatives, thiazole derivatives or sulfenamide derivatives; vulcanization activators such as, for example, zinc oxide, stearic acid and zinc stearate;
  • a conventional reinforcing filler such as carbon black (in this case, the reinforcing white filler used constitutes more than 50% of the weight of the whole reinforcing white filler + carbon black); a conventional white filler with little or no reinforcing, such as, for example, clays, bentonite, talc, chalk, kaolin, titanium dioxide or a mixture of these species; antioxidants; antiozonants, such as, for example, N-phenyl-N '- (1,3-dimethyl butyl) -p-phenylene diamine; - plasticizing agents and implementation aid agents.
  • a conventional reinforcing filler such as carbon black
  • a conventional white filler with little or no reinforcing such as, for example, clays, bentonite, talc, chalk, kaolin, titanium dioxide or a mixture of these species
  • antioxidants such as, for example, N-phenyl-N '- (1,3-dimethyl butyl) -p-pheny
  • the vulcanization (or baking) of the rubber-type compositions is carried out in a known manner at a temperature generally ranging from 130 ° C. to 200 ° C., for a sufficient time which can vary for example between 5 and 90 minutes depending in particular on the temperature. curing, the vulcanization system adopted and the vulcanization kinetics of the composition considered.
  • This example illustrates the preparation of an organosilicon compound according to the invention, comprising a POS / 1 polymer of acid type.
  • This compound is prepared by implementing method (d) which has been explained above in the present specification, consisting in reacting an amino POS of formula (X) with maleamic anhydride.
  • the reaction medium is left for 15 hours at room temperature (23 ° C.), then it is neutralized using 0.241 g of a mixture based on phosphoric acid and polydimethylsiloxane oligomers, operating at 90 ° C for 1 hour.
  • the reaction medium obtained is then devolatilized by operating at 180 ° C and under a reduced pressure of 3J0 2 Pa, for 30 minutes.
  • the amino POS was subjected to proton and silicon NMR analyzes. The results of these analyzes reveal a mixture of linear (85% molar) and cyclic (15% molar) structures having the following average formulas:
  • the amino POS thus obtained contains 0.5 mole of amino functions per 100 g of product.
  • a solution of maleic anhydride (30.67 g, or 0.3128 mole) in CH 2 CI is introduced into a 1 I glass reactor, fitted with a stirring system and a dropping funnel. 2 as solvent (400 cm 3 ), then the temperature of the reaction medium is lowered to 8 ° C., and the amine POS (62.11 g) is then poured gradually over a period of 1 hour 15 minutes while maintaining the temperature reaction medium at 8 ° C during casting. At the end of addition, the reaction medium is left for 15 hours at room temperature (23C C). The solvent is then removed under reduced pressure, operating at a temperature which does not exceed 30 ° C.
  • This example illustrates the preparation of an organosilicon compound according to the invention, comprising a POS / 2 polymer of ester type.
  • This compound is prepared by implementing method (f) [with activation method (2d)] which has been explained above in this memo.
  • maleic anhydride is introduced (698.1 g, or 7.12 moles), then it is melted by heating the reactor using '' an oil bath brought to 70 ° C. Once all of the anhydride has melted, methanol (221.4 g, or 6.92 moles) is introduced, with stirring, via a dropping funnel. The medium is then left under stirring for 20 hours at 23 ° C, then it is devolatilized by establishing a reduced pressure of 10.10 2 Pa for 1 hour, and finally it is filtered on filter paper. 786.9 g of monomethyl ester of maleic acid of formula (86% yield) are thus recovered:
  • N-hydroxysuccinimide 39.20 g, or 0.3406 mole
  • tetrahydrofuran as solvent
  • monomethyl ester of maleic acid 40.1 g, or 0.3085 mole
  • the reaction medium is stirred, and the dicyclohexylcarbodiimide (69.3 g, or 0.3363 mole) is poured in gradually, at room temperature (23 ° C.), over a period of 10 minutes.
  • the medium becomes heterogeneous due to the precipitation of dicyclohexylurea.
  • the reaction medium is filtered through
  • a polydimethylsiloxane oil ⁇ , ⁇ are introduced into another 1 liter reactor, also provided with mechanical stirring and with a condenser.
  • -dihydroxylated (230.92 g) having a viscosity of 50 mPa.s at 25 ° C and titrating 12% by weight of OH, as well as catalyst based on potassium siliconate (0.0416 g).
  • the reaction medium is heated at 90 ° C for 6 hours.
  • the reaction medium is left for 15 hours at room temperature (23 ° C), then it is neutralized using 0.0974 g of a mixture based on phosphoric acid and polydimethylsiloxane oligomers , operating at 90 ° C for 1 hour.
  • the reaction medium obtained is filtered through a microporous filter of 0.5 ⁇ m.
  • the POS thus obtained contains 0.51 amino function per 100 g of product.
  • the reaction medium is reacted at room temperature (23 ° C) for 15 hours. At the end of this time, the medium is transferred to a separating funnel, then it is washed 4 times in succession with water. The addition of a saturated aqueous NaCl solution is necessary to aid in the separation of the phases. The residual organic phase is recovered, dried over MgSO 4 , then filtered through filter paper and finally the solvent is removed under reduced pressure and at room temperature (23 ° C).
  • composition No. 2 control 2: coupling agent based on TESPT silane (4 pce);
  • Composition No. 3 Example 3): coupling agent or organosilicon compound, providing in the composition 4.66 phr of the POS / 1 polymer of the acid type, prepared in Example 1;
  • Example 4 coupling agent or organosilicon compound, providing in the composition 5.02 phr of the POS / 2 polymer of the ester type, prepared in Example 2.
  • the contents of the mixer are drained or dropped after 5 minutes.
  • the temperature reached is around 145 ° C.
  • the mixture obtained is then introduced on a roller mixer, maintained at 30 ° C, and TBBS, DPG and sulfur are introduced. After homogenization, the final mixture is calendered in the form of sheets 2.5 to 3 mm thick.
  • the composition to be tested is placed in the test chamber regulated at a temperature of 160 ° C., and the resistive torque, opposed by the composition, to a low amplitude oscillation of a biconical rotor included in the measurement is measured. test chamber, the composition completely filling the chamber in question.
  • the minimum torque which reflects the viscosity of the composition at the temperature considered the maximum torque and the delta-torque which reflect the rate of crosslinking caused by the action of the vulcanization system
  • the time T-90 necessary to obtain a vulcanization state corresponding to 90% of the complete vulcanization this time is taken as the optimum vulcanization
  • the TS-2 roasting time corresponding to the time necessary to have a rise of 2 points above the minimum torque at the temperature considered (160 ° C) and which reflects the time during which it is possible to use raw mixtures at this temperature without having initiation of vulcanization.
  • the measurements are carried out on the uniformly vulcanized compositions for 20 minutes at 160 ° C.
  • the tensile tests are carried out in accordance with the indications of standard NF T 46-002 with H2 type test pieces.
  • the modules 10%, 100%, 300%, and the breaking strength are expressed in MPa; the elongation at break is expressed in%.
  • the measurement is carried out according to the indications in standard ASTM D 3240. The given value is measured at 15 seconds.
  • (3) The measurement is carried out according to the indications in standard NF T 46-012 using method 2 with a rotating test tube holder. The measured value is the loss of substance (in mm 3 ) on abrasion; the lower it is, the better the abrasion resistance.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP01945438A 2000-06-16 2001-06-14 Derivate von maleinsäure und/oder fumarsäure enthaltende mutifunktionelle organopolysiloxane und verfahren zu deren herstellung Withdrawn EP1299452A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0007698 2000-06-16
FR0007698A FR2810327B1 (fr) 2000-06-16 2000-06-16 Nouveaux polyorganosiloxanes multifonctionnalises comprenant des groupes derives d'acide maleique et/ou d'acide fumarique et leurs procedes de preparation
PCT/FR2001/001857 WO2001096444A1 (fr) 2000-06-16 2001-06-14 Nouveaux polyorganosiloxanes multifonctionnalises comprenant des groupes derives d'acides maleique et/ou d'acide fumarique, et leurs procedes de preparation

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WO (1) WO2001096444A1 (de)

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CN100334135C (zh) 2000-06-16 2007-08-29 米其林技术公司 含有多官能聚有机硅氧烷作为偶联剂的轮胎橡胶组合物
DE102010002178A1 (de) * 2010-02-22 2011-08-25 Evonik Goldschmidt GmbH, 45127 Verfahren zur Herstellung von Amin-Amid-funktionellen Siloxanen
US11179312B2 (en) 2017-06-05 2021-11-23 Momentive Performance Materials Inc. Aqueous compositions for the treatment of hair
JP2019189803A (ja) * 2018-04-27 2019-10-31 ナガセケムテックス株式会社 アミック酸基含有ポリシロキサンの製造方法、オルガノポリシロキサン、アミック酸基含有樹脂組成物、硬化膜、半導体装置、及び電子部品の製造方法
US11090255B2 (en) 2018-12-04 2021-08-17 Momentive Performance Materials Inc. Use of polycarboxylic acid compounds for the treatment of fibrious amino acid based substrates, especially hair

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US3558741A (en) * 1969-05-05 1971-01-26 Gen Electric Imido-substituted organopolysiloxane compositions
US3576031A (en) * 1969-05-05 1971-04-20 Gen Electric Amide acid and imido-substituted organosilanes
JPS51125277A (en) * 1974-12-28 1976-11-01 Shin Etsu Chem Co Ltd Aprocess for preparing organosilane compounds
JPS51120804A (en) * 1975-04-14 1976-10-22 Dainippon Printing Co Ltd Plate for lithographic printing
CH649772A5 (de) * 1981-10-01 1985-06-14 Ciba Geigy Ag Lichtvernetzbare polysiloxane, verfahren zu deren herstellung und deren verwendung.

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AU2001267660A1 (en) 2001-12-24
FR2810327A1 (fr) 2001-12-21
FR2810327B1 (fr) 2002-12-06
WO2001096444A1 (fr) 2001-12-20
AR028955A1 (es) 2003-05-28

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