MXPA96002348A - New silicone compounds of aminasesterically underlying functions, useful for the stabilization of light and thermal polimes - Google Patents

Abstract

The present invention relates to linear, cyclic or branched polyorganosiloxanes having per molecule, at least three siloxyls of which at least one functional motif of the formula: (R1) aXSi (O) 3-a / 2 in the which R1 represents a C1 to C4 alkyl radical or phenyl, X contains a secondary or tertiary cyclic amine function, attached to the silica by an Si-AC bond wherein A is a moiety comprising a cyclic acetal group. X represents more precisely a monovalent group of formula (II): wherein R 2 is H or an alkyl radical, Z is a trivalent radical of aliphatic nature, such as for example the radical -CO-CH-CO-, of aromatic nature, as for example the radical. R3 to R6 are alkyl, phenyl and / or benzyl radicals: R7 is H or an alkyl, alkylcarbonyl, phenyl or benzyl radical, x = 0.1, 3, y = 0 or 1. The present invention also relates to the use of polyorganosiloxanes of this type, in polymers, to improve their photostabilization in particular

Description

NEW COMPOUNDS OF SILICONE FUNCTIONS AMINES ESTERICALLY UNDERLYING, USEFUL FOR THE STABILIZATION OF LIGHT AND THERMAL POLYMERS DESCRIPTION The present invention relates, in its first objective. with novel silicone compounds comprising, per molecule, at least one sterically underlying cyclic amine function linked to the silicon atom by a Si-A-C bond wherein A is a moiety comprising a cyclic acetal group; it is also related, in its first objective, to silicone compounds comprising, per molecule, at least one sterically underlying cyclic amine function linked to the silicon atom by a Si-AC bond and at least one other co-sensitizing function linked to silicon by a silicon atom. Si-C link. It is also related, in its second objective, to a process for preparing these silicone compounds. It is also related, in a third objective, with the use of the aforementioned compounds, in polymers to improve their resistance against degradation under the effect of ultra-violet (UV) radiation, oxygen from the air and heat.

Indeed, organic polymers, and more particularly polyolefins and polyalkadienes, are degraded when subjected to external agents and above all to the combined action of air and ultra-violet solar radiation. This degradation is generally limited by the introduction into the polymer of small amounts of stabilizing agents. Among these anti-UV stabilizers, the underlying steric cyclic amines, especially tetramethyl-2, 2, 6, 6-piperidines, are currently the most effective. However, in practice, one of the major problems related to the use of these anti-UV stabilizers is that of obtaining a good compromise between their effectiveness, which implies their mobility within the polymer, and the permanence of their action. , which involves the implementation of molecules of high molecular mass that have excellent compatibility with polymers that must be stabilized. It has been proposed in the prior art to resort advantageously to polyorganosiloxanes which carry sterically underlying piperidinoline functions. As documents illustrating this prior art, one can cite, for example, patent documents JP-A-01/096259, EP-AO 338 393, EP-AO 343 717, EP-AO 358 190, EP-A-0388 321 and EP-AO 491 659. However, according to the Applicant, no prior art document discloses polyorganosiloxanes which, on the one hand, have a structure in which each sterically underlying cyclic amine function, sterically linked to the silicon atom by a Si-AC bond where A is a moiety comprising a cyclic acetal group and, on the other hand, are endowed with useful properties to improve the resistance of the polymers against their degradation under the effect of UV radiation, oxygen of the air and of heat. More precisely, the present invention relates, in its first objective, to a polyorganosiloxane, characterized in that it comprises per molecule, at least 3 siloxyl motifs of which at least one siloxyl functional motif of formula (I): wherein: * the symbols R1 are identical or different and represent a monovalent hydrocarbon radical selected from alkyl radicals, linear or branched, having 1 to 4 carbon atoms and phenyl; * the symbol X represents a monovalent group of formula (II): wherein: - R 2 represents a hydrogen atom or an alkyl radical, linear or branched, having 1 to 3 carbon atoms; - the symbol z represents a trivalent group comprising at least 3 carbon atoms and is: a saturated or ethylenically unsaturated aliphatic radical, substituted or not, which may contain at least one carbonyl group linked by its free valencies, to two atoms constituting the cyclic acetal group: or an aromatic, onicyclic radical, substituted or not; or a condensed polycyclic aromatic radical, substituted or not; a polycyclic aromatic radical of various cyclic systems, condensed or not, whether or not substituted, linked together by valence bonds or by atoms or groups; the atoms or groups which can bind such cyclic aromatic systems can be, for example, the oxygen and sulfur atoms or the groups consisting of the linear or branched alkyl radicals having 1 to 3 carbon atoms and the groups - CO-, -S02- / -CONH-, -NH-, -COO-; - the links (1) and (2) starting from the symbol Z that concerns adjacent carbon atoms when Z represents an aromatic radical, and carbon atoms adjacent or in position ß one in relation to the other when Z represents an aliphatic radical; - the radicals R3, R4, R5 and R6, identical or different, are selected from radicals, alkyl, linear or branched, having from 1 to 3 carbon atoms, phenyl and benzyl; -R7 is selected from a hydrogen atom, linear or branched alkyl radicals having from 1 to 12 carbon atoms, alkylcarbonyl radicals wherein the alkyl moiety is a linear or branched moiety having from 1 to 8. carbon atoms, the phenyl and benzyl radicals and a radical 0-; - x is an integer selected from 0, 1, 2 and 3; - y is an integer selected between 0 and 1; * a is an integer selected from 0, 1 and 2. The polyorganosiloxane may also have another functional motif of formula (III): give) bwsi (?) 3 b ap) in which: * the symbols R1 have the same meanings as those given in the foregoing in relation to the formula (I); * the symbol W represents a monovalent group of conpatibilizing function selected from: an alkyl radical, linear or branched, having more than 4 carbon atoms; a radical of formula -R8-COO-R9 in which Ra represents a linear or branched alkylene radical, having from 5 to 20 carbon atoms and R9 represents an alkyl radical, linear or branched, having from 1 to 12 atoms of carbon; a radical of formula -R10-O- (R11-O) c-R12 in which R10 represents a straight or branched alkylene radical, having from 3 to 15 carbon atoms, R11 represents a straight or branched alkylene radical, having 1 to 3 carbon atoms, c is an integer from 0 to 10 and R12 represents a hydrogen atom, an alkyl radical, linear or branched having 1 to 12 carbon atoms or an acyl radical -CO- R13 wherein R13 represents an alkyl radical, linear or branched, having from 1 to 11 carbon atoms; * b is an integer selected from 0, 1 and 2. The other possible siloxyl reason (s) of the polyorganosiloxane, are of formula (IV): in which: * the symbols R1 have the same meanings as those given in the foregoing in relation to the formula (I); * d is an integer selected from 0, 1, 2 and 3; * e is an integer selected between 0 and 1; * the sum d + e is at most equal to 3. The siloxyl motifs of formula (I), when there are more than two, can be identical or different from each other; the same observation also applies to the siloxyls of formulas (III) and (IV). In the present specification, it will be understood that it is defined by: "cyclic amines functions": the monovalent groups X; "compatibilizing functions": the eventual monovalent groups which are directly linked to the silicon atoms (Si-C bonds are then formed in this case); - "mixed organopolysiloxanes (or polymers)": polymers that are equipped both with cyclic amine (s) and with compatibilizing function (s).

Taking into account the values that the symbols a, b, d & It should also be understood that the polyorganosiloxanes according to the invention can therefore have a linear, cyclic, branched structure (resin) or a mixture of these structures. In the case of linear polymers, these may optionally have up to 50% mol of branching ["T" type motifs (RSi03 / 2 and / or "Q" (Si04 2) J. When it comes to polyorganosiloxane resins, these are constituted by at least two different types of siloxyl motifs, namely: "M" motifs (R3Si? 1/2) and / or "t" and possibly "D" motifs (R2Si02 / 2), the ratio of the number of motives " M "/ number of reasons" Q "and / or" T ", is generally between 4/1 and 0.5 / 1, and the ratio of number of reasons" D "/ number of reasons" Q "and / or" T " "is generally comprised between 0 to 100/1 Advantageously, the number of reasons for formulas (I), and optionally (III) and (IV) are such that the polyorganosiloxanes according to the invention contain: - at least 0.5% , preferably from 8% to 90%, of cyclic amine functions, and optionally - at least 0.5 mol%, preferably from 8% to 90 mol%, of compatibilizing functions. s express the number of moles of functions per 100 silicon atoms. . Preferred R 1 radicals are: methyl, ethyl, n-propyl, isopropyl, n-butyl; more preferably, at least 80 mole% of radicals R1 are methyl. The cyclic amine functions that are represented by the X groups are preferably selected from the radicals of the formula (II) defined above, in which the symbols R2 'R3, R4, R5 and R6, R7, x & and, they have the meanings given in the foregoing with regard to formula (II) and the symbol Z represents a trivalent radical selected from: * an aliphatic radical; CO- wherein the right free valencies in coarse character are attached to the oxygen atoms of the cyclic acetal group, and R14 represents a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 3 carbon atoms or a radical of formula -C00R14_bls or -NHCOR14 ~ ° is wherein R -bis represents a linear or branched alkyl radical of 1 to 3 carbon atoms; and * an aromatic radical corresponding to the following formulas: wherein the free valencies in coarse character of each aromatic cyclic system are carried by two adjacent carbon atoms, and R15 represents -0-, -S-, a linear or branched alkylene group having from 1 to 3 carbon atoms, - CO-. -S02-, -CONH-, -NH- or -COO-. More preferably, the cyclic amine functional groups X are selected from the groups X of formula (II) which is defined in the foregoing, wherein: * R 2 represents a hydrogen atom or a methyl radical; * the symbol Z is a trivalent group of formula (II-1), wherein R 14 is a hydrogen atom, or of formula (II-2); * the radicals R3, R4, R5 and R6, identical, are methyl; * the radical R7 represents a hydrogen atom or a methyl radical; * x & and each represents an integer equal to 1. Preferred optional co-facilitating functions W are selected: from an alkyl radical, linear or branched, having more than 5 to 8 carbon atoms; a radical of formula -R8-COO-R9 in which R8 represents a linear or branched alkylene radical, having 8 to 12 carbon atoms and R9 represents an alkyl radical, linear or branched, having 1 to 6 atoms of carbon; a radical of formula -R10-O- (R1: 1-O) C-R12 in which R10 represents a branched linear alkylene radical, having from 3 to 6 carbon atoms, R11 represents an alkyl radical, linear or branched, having 2 to 3 carbon atoms, c is an integer from 0 to 6 and R12 represents a hydrogen atom, an alkyl radical, linear or branched having 1 to 6 carbon atoms or an acyl radical -CO -R13 wherein R13 represents an alkyl radical, linear or branched, having from 1 to 5 carbon atoms; The present invention, taken in its first objective, relates more precisely also to: polydiorganosiloxane copolymers optionally mixed, linear, static, sequenced or block, of average formula (V): in which: * the symbols R1, X and W have the general meanings given in the foregoing regarding the formulas (I) and (III); * the symbols Y represent a monovalent radical selected from R1, X, and a hydrogen atom; * m is a whole or fractional number that goes from 0 to 180; * n is a whole or fractional number that goes from 0 to 180; * p is a whole or fractional number that goes from 0 to 10; * q is a whole or fractional number that goes from 0 to 100; * with the conditions according to which: - if m is different from 0 and in the eventual case of mixed polymers if n is different from 0: the sum + n + p + q is in the range from 5 to 200; the ratio 100 m / (m + n + p + q + 2) is greater or equal to 0.5; and the ratio 100 n / (m + n + p + q + 2) is greater than or equal to 0.5; that relationship is identical or different from the relationship that precedes; if m = 0 and in the eventual case of the mixed polymers if n is different from 0: at least one of the substituents Y represents the radical X; the sum m + n + p + q is in the range from 5 to 100; and the ratio 100 n / (m + n + p + q + 2) is greater than or equal to 0.5; - if m is different from O and n = 0: the sum m + p + q is in the range from 5 to 100; the ratio 100 m / (m - • - p + q + 2) is greater or equal to 0.5; and in the eventual case of the mixed polymers, at least one of the substituents Y represents the radical W; if m = 0 and n = 0: the sum p + q is in the range from 5 to 100; one of the substituents Y represents the radical X; and in the eventual case of the mixed polymers, the other substituent Y represents the radical W; and those of average formula (VI) in which: * the symbols R1, X & W have the general meanings given in the foregoing in relation to formulas (I) and (III); * r is a whole or fractional number that goes from 1 to 9; * s is a whole or fractional number that goes from 0 to 9, • * t is an integer or fractional number that goes from 0 to 0.5; * u is a whole or fractional number that goes from 0 to 5; * the sum r + s + t + u is in the range from 3 to 10. The polymers of formula (V) that are preferred (polymers called PL1) or highly preferred (polymers called PL2), are those for which; * the symbols Y represent R1; * m is a whole or fractional number that goes from 1 to 90; * n is a whole or fractional number that goes from 0 to 90; * p is a whole or fractional number ranging from 0 to 5; * q is a whole or fractional number that goes from 0 to 50; * the sum m + n + p + q is an integer or fractional number ranging from 10 to 100; * the ratio 100 m / (m + n + p + q + 2) is in the range from 8 to 90; * with the condition according to which, if n is different from 0; the relation 100 n / (m + n + p + q + 2) is in the range from 8 to 90; that relationship may be identical or different from the relationship that precedes; * the radicals R1 and W simultaneously have the preferred definitions (in this case the polymers PL1) or more preferred (in the case of the polymers PL2) which are given in the foregoing purpose of each of them. The polymers of formula (VI), which are preferred (polymers called PCI) or highly preferred (polymers designated PC2), are those for which: * r is an integer or fractional ranging from 1 to 4.5; * s is a whole or fractional number that goes from 0 to 4.5; * t is a whole or fractional number that goes from 0 to 0.25; * u is a whole or fractional number that goes from 0 to 2.5; * the sum r + s + t + u is a whole or fractional number that goes from 3 to 5; * Radicals R1, X & w have simultaneously preferred definitions (in the case of PCI polymers) or more preferred (in the case of polymers PC2), which are given in the foregoing purpose of each of them. The polymers of formula (V) which are particularly suitable (polymers termed PLS1) or more especially well (polymers termed PLS2), are polymers PL1 or PL2 which are defined in the foregoing, for which the symbol n is an integer which ranges from 1 to 90. Polymers of formula (VI) which are particularly suitable (polymers known as PCS1) or more especially well (polymers known as PCS2) are the polymers PCI or PC2 defined above, for which the symbol s is an integer ranging from 1 to 4.5. Advantageously, the optionally mixed organopolysiloxanes of the invention can be obtained from this, and this constitutes the second object of the invention: * of the corresponding organohydrogenpolysiloxanes (H) which are free of cyclic amine (s) (s) ) X and of compatibilizing function (s) W; * of the ethylenically unsaturated organic compound (s) at the end of the chain (psi) from which the (or) function (s) X is derived; * and eventually of the ethylenically unsaturated compound (s) at the end of the chain (si) from which the (or) functions are derived. In this way, polyorganosiloxanes, optionally mixed , of the invention, can be obtained by putting into operation: - in the case of polymers with cyclic amine (s) only: an addition reaction (hydrosilylation), or - in the case of mixed polymers of function (is) cyclic amine (s) and of compatibilizing function (s): two addition reactions (hydrosilylations), simultaneous or successive; this starting from: corresponding organohydrogenpolysiloxanes (H) free of X and W functions, of the ethylenically unsaturated organic compound (s) at the end of the chain (psi) from which it derives (n) the (s) function (s) X and eventually the ethylenically unsaturated compound (s) at the end of the chain (ksi) from which the derivative (s) derive W. functions. Those hydrosilylation reactions can be carried out at a temperature of the order of 20 ° C to 200 ° C, preferably of the order of 60 ° C to 120 ° C, in the presence of a catalyst based on a metal of the platinum group; mention may be made in particular of the platinum derivatives and complexes described in: US-A-3 715 334, US-A-3 814 730, US-A-3 159 601, US-A-3 159 662. The amounts of catalyst that are put into work, are of the order of 1 to 300 parts per million, expressed in metal in relation to the reaction medium. In the definition of "mole of (psi)", the olefinic unsaturation that can react with (H) by hydrosilylation will be considered as an elementary entity. Likewise, in the definition of "mol de (ksi)", olefinic unsaturation that can react with (H) by means of hydrosilylation will be considered as an elementary entity. The quantities of reactants that can be put into work correspond to a molar ratio [(psi) + possibly (ksi)] / SiH- [of (H)] which is of the order of 1 to 5, preferably of the order of 1 to 2. The hydrosilylation reactions can take place in bulk or, preferably, in a volatile organic solvent such as toluene, xylene, methylcyclohexane, tetrahydrofuran, heptane, octane or isopropanol; The reaction medium can also contain a buffering agent consisting mainly of an alkaline salt of a monocarboxylic acid, such as, for example, sodium acetate. At the end of the reactions, the obtained raw mixed polyorganosiloxanes can be purified, in particular, by passing over a column filled with an ion exchange resin and / or by simple devolatilization of the reactants that were introduced in excess and, if necessary, of the Solvent placed on site, by heating operated between 100 ° C and 180 ° C under reduced pressure. The organohydrogenpolysiloxanes (H) which are used, for example, to prepare linear mixed polyorganosiloxanes of formula (V), are those of formula (VII): (VII) in which: * the symbols R1 and q have the general or preferred meanings given in the foregoing, with reference to the formula (V); * the symbols Y 'represent R1 or a hydrogen atom; * v is an integer or fractional number equal to m + n + p; * with the condition according to which, if v = 0, q is an integer lying in the range from 5 to 100 and then at least one of the radicals Y 'represents a hydrogen atom. The organohydrogenpolysiloxanes (H) which serve, for example, to prepare cyclic mixed polyorganosiloxanes of formula (VI), are those of formula (VIII): in which: * the symbols R1 and u have the general or preferred meanings given in the foregoing, with reference to the formula (VI); * w is a whole or fractional number equal to r + s + t; * the sum u + is in the range of 3 to 10. That type of organohydrogenpolysiloxanes (H) of formulas (VII) and (VIII) are known in the literature and, for some, are available commercially.

The unsaturated organic compounds (psi), from which the cyclic amine functional groups X are derived, are the compounds of formula (IX): wherein the symbols R2, Z, R3, R4, R5, R6, R7, x & and have the general or preferred meanings given in the foregoing in connection with formula (II). As compounds (psi), the compounds of formulas (IX-1) and (IX-2) may be mentioned by way of examples: (K-l) wherein R7 is a hydrogen atom or a methyl radical. The unsaturated organic compounds (psi) of formula (IX), from which the cyclic amine functional groups X are derived, are compounds which, according to the Applicant's knowledge, are new products.

The unsaturated compounds (psi) of formula (IX) in which the symbol Z represents an aliphatic moiety, can be prepared by reacting, in the presence of an acid catalyst: * an orthodiphenol or an acetal of formula (X): wherein the symbols R2, Z (aliphatic moiety) & x, have the general or preferred meanings given in the foregoing in connection with formula (II), and R16 represents a hydrogen atom or an alkyl radical, linear or branched, having from 1 to 3 carbon atoms, * with a ketone of formula (XI): wherein the symbols R3, R4, R5, R6, R7, & and have the general or preferred meanings given in the foregoing in connection with formula (II). As regards the practical way of putting the above procedure into practice, the content of the following document will be consulted for more details, which will describe, from other reagents, an operative mode applicable to carry out the procedure under consideration; see Heterocycles 32 (3), page 529 et seq. (1991). For the orthodiphenol or the acetal precursor of the formula (X), it can be obtained by reacting: * a chlorinated compound of the formula (XII): CHjSC- (c ^) - a (xp) * with an orthodiphenol or an acetal of formula : XIII): As regards the practical way of carrying out this synthesis of the orthodiphenol or acetal precursor of the formula (X), the content of the following document will be consulted for more details: see Text Book of Practical Organic Chemestry, 5a . edition (1989), page 682, VOGEL, Editor LONGMAN. In the case of the precursor ketone of the formula (XI), it corresponds to a product known and commercially available. The synthetic scheme, just described, of the different unsaturated compounds (psi) of formula (IX) wherein Z represents an aliphatic moiety, is particularly well applied when the symbol Z is the aliphatic radical of formula (II.1) which is mentioned in the preceding & x is an integer equal to, 2 or 3. The unsaturated compounds (psi) of formula (IX) in which the symbol Z represents an aromatic moiety, can be prepared by reacting, in the presence of an acid catalyst: * an orthodiphenol of formula (XIV): wherein the symbols R2, Z (aromatic moiety) & x, have the general or preferred meanings given in the foregoing with regard to formula (II), - either with an acetal of formula (transacetalization reaction) (XV): - either with a ketone of formula (XI) (acetalization reaction), formulas in which the symbols R3, R4, R5, R6, R7, & and have the general or preferred meanings given in the foregoing in connection with formula (II), and R17 represents an alkyl radical, linear or branched, having from 1 to 3 carbon atoms. As regards the practical way of putting the above procedure into practice, the content of the following documents will be consulted for more details, which will describe, from other reagents, operational modes applicable to the realization of the procedure under consideration: see transacetalization: Syn thesis (February 1986), pages 122 to 125; acetalization: FR-A-2 168 848 (from SANKYO). In the case of the orthodiphenol precursor of formula (XIV), it can be obtained by reacting: * a chlorinated compound of formula (XII), * with an orthodiphenol or an acetal of formula (XVI): and .OH H-Z. (XVI) OH As regards the practical way to put the aforementioned procedure into operation, the content of the following document will be consulted for more details: see JP-A-53/135943 (from UBE INDUSTRIE).

In the case of the acetal precursor of the formula (XV), this can be obtained by reacting, in a manner known per se, an aliphatic alcohol of the formula R 17 -OH, in which R 17 has the meaning given in the foregoing with regard to the formula (XV), with the ketone of formula (XI): see Synthesis (February 1986), pages 122 to 125. The synthetic scheme just described, of the different unsaturated compounds (psi) of formula (IX) in where Z represents an aromatic moiety, it is particularly well applied when the symbol Z is the aromatic radical of formula (II.2) mentioned in the preceding & and is an integer equal to 1 or 2. Whatever the definition of the aromatic symbol Z and the value of x, the crude product of the reaction of the reagent of formula (XVI) with the chlorinated compound of formula (XII) may contain small amounts of starting orthodiphenol (XVI) which has not reacted and / or di-unsaturated compounds of formula (XVII): In case of presence of these impurities, a purification of the crude product of the reaction under consideration will proceed. to eliminate the whole or, failing that, most of these impurities. The crude reaction product can contain, without problems, up to 2% by weight of these impurities. The unsaturated compounds (psi) of formula (IX) can also be constituted by applying another synthesis scheme in which, initially, an acetal of formula (XVIII) is prepared: and then, in a second time, the acetal of formula (XVIII) is reacted with the chlorinated compound of formula (XII). The preparation of the cyclic acetal of formula (XVIII) can be carried out starting from a reagent of formula (XIII) or (XVI): O-R16 H-Zs and ° H or H-ZN O-R16 OH ind Z = subtract aliphatique quand Z = subtract aromatique (xm) (XVI) applying the various operative modes described in what precedes the purpose of unsaturated synthesis pathways (psi), that is; reaction of the reagent (XIII) with the ketone (XI) or reaction of the reagent (XVI) with the acetal (XV) or the ketone (XI). The unsaturated compounds (ksi) from which the W functions derive are compounds which have an ethylenic unsaturation, located at the chain end, which can react in hydrosilylation in the presence of a catalyst based on a metal of the platinum group. As compounds (ksi), there may be mentioned, by way of example, octene-1, undecene-1, dodecene-1, tridecene-1, methyl or ethyl undecenoate. The optionally mixed polyorganosiloxanes according to the invention can be used as stabilizers against light degradation, oxidant and thermal of organic polymers, and this constitutes the third objective of the invention. By way of example of such organic polymers, mention may be made of polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulfonates, polyethers-sulfones, polyethers ketones, acrylic polymers, their copolymers and their mixtures Among these polymers, the compounds of the invention have a more particularly effective action with polyolefms and polyalkadienes such as polypropylene, high density polyethylene, linear low density polyethylene, low density polyurethane, polybutadiene, their copolymers and its mixtures. Taking into account the wide variations possibilities of the relative numbers of the different siloxyl motifs present in the siloxane chain of the mixed compounds of the invention, these compounds can be easily adapted to the different problems that have to be solved. Another objective also of the present invention, therefore, consists in the compositions of organic polymer stabilized against the harmful effects of heat and UV rays, by an effective amount of at least one polyorganosiloxane compound optionally mixed. Customarily, these compositions contain from 0.04 to 20 milliequivalents in sterically underlying cyclic amine (s) (s) per 100 grams of polymer to be stabilized. Preferably, the stabilized polymer compositions according to the invention contain from 0.20 to 4 milliequivalents in sterically substituting cyclic amine (s) (s) per 100 grams of polymer to be stabilized. The addition of optionally mixed polyorganosiloxane compounds can be carried out during or after the preparation of the polymers. These compositions may also contain the additives and stabilizers that are commonly used with the polymers they contain. In this way, the following stabilizers and additives can be put into operation; antioxidants such as alkylated monophenols, alkylated hydroquinones, hydroxylated diphenyl sulphides, alkylidene-bis-phenols, benzylic compounds, acylamino-phenols, esters or amides of (di-tert-butyl-3, 5-hydroxy-4-phenyl) -3-propionic acid , esters of (di-cyclohexyl-3, 5-hydroxy-4-phenyl) -3-propionic acid, light stabilizers such as esters of optionally substituted benzoic acids, acrylic esters, nickel compounds, oxalamides; phosphites and phosphonites; deactivators of metals; peroxide destroying compounds; polyamide stabilizers; nucleation agents; fillers and reinforcing agents; other additives, such as, for example, plasticizers, pigments, optical bluing agents, flame retardants. The polymer compositions stabilized in this manner can be applied in the most varied forms, for example in the form of molded objects, sheets, fibers, cellular materials (foam), profiles or coating products, or as suitable to form sheets or binders for paints, varnishes, glues or cements. The following examples illustrate the present invention: EXAMPLE 1 Preparation of the cyclic amine unsaturated compound (psi) of formula (IX-2), in which R7 is a hydrogen atom. 1) - Preparation of the precursor of formula (XIV) consisting of allyl-4-orthodiphenol: Into a glass flask equipped with a mechanical stirrer, with a cast ampoule, 109.1 g (2.73 moles) of NaOH and 1522 g of water are charged. After dissolving NaOH, 299.94 g (2.73 moles) of orthodiphenol are introduced; 26.23 g (0.19 mol) of CuCl2 and 33.93 g of an aqueous solution of ammonia at 28% by weight of NH4OH (either 0.27 mol of ammonia base). Then, a solution of 213 g (2.73 mol) of allyl chloride in isopropyl ether (270 g) is cast in 1 hour 15 minutes at a temperature between 36 ° C and 56 ° C. After the end of the casting, the reaction is continued for 35 minutes at 50 ° C. At the end of that time, the reaction medium is cooled to room temperature (23 ° C), and then the acid HCl (in the form of an aqueous solution at 36% by weight of pure HCl) is added to obtain a pH equal to 3. Separate the two phases that were formed operating hot (35 ° C). The aqueous phase is then extracted, 3 times with each time 200 cm3 of isopropyl ether. The organic phases are combined and the resulting solution is concentrated to the rotary evaporator operating between 25 ° C and 40 ° C under reduced pressure to 3,102 Pa, and then neutralized with 4.3 g of sodium carbonate. The product is then purified by fractional distillation under 4 Pa; 244.8 g (60% yield) of allyl-4-orthodiphenol are obtained (boiling point under a pressure of 4 Pa: 146 ° C, structure confirmed by nuclear magnetic resonance analysis of the proton). 2) - Preparation of the precursor of formula (XV) consisting of dimethyl acetal of tetramethyl-2,2,6,6-one-4-piperidine: In a glass flask, placed under a nitrogen atmosphere, equipped with an agitator mechanically, with a wash bulb, 30 g (0.19 mol) of triacetone amine and 51 g of methanol are charged. Then, a solution of 31.97 g (0.192 mol) of sulfonic acid in 77 g of methanol is slowly poured in, and then 40.6 g (0.38 mol) of methyl orthoformate are charged. Heat to reflux and distill the expected amount of methyl formate. Then, the methanol is distilled to precipitation. The crude product is filtered, and then washed twice with 100 cm 3 of toluene. 68 g (100% yield) of dimethyl acetal of the triacetone amine are obtained. The structure of the product is confirmed by nuclear magnetic resonance of the proton. 3) - Preparation of the unsaturated compound (psi) of formula (IX-2) wherein R7 = H: In a glass flask equipped with a mechanical stirrer, with a distillation column, introduce 41.99 g (0.12 mol) of dimethyl acetal of triacetone amine, 18 g (0.12 mol) of allyl-4-orthodiphenol, 1.05 g (0.006 mol) benzene sulfonic acid and 173 g of toluene.

The reaction mixture is brought to 61 ° C, at which temperature the boiling begins. Then, the mixture is distilled for 12 hours, continuously eliminating an azeotrope toluene-methanol that distills between 60 ° C and 70 ° C under atmospheric pressure. Then, the toluene is removed and after cooling to room temperature (23 ° C), 200 cpr of methylene chloride are added to the reaction mass. The organic phases obtained in this manner are then washed twice with 150 cm3 of an aqueous solution of NaHCO3 IN. The organic phase is dried over magnesium sulfate, and then the methylene chloride is evaporated at room temperature (25 ° C) under a reduced pressure to 1.33.102 Pa. Thus, 26.7 g (50% yield) are obtained. ) of the desired unsaturated product (psi), of formula (IX-2) in which R7 = H. The analysis by means of nuclear magnetic resonance of the proton, is in agreement with the following structure on which the chemical shifts of the protons are indicated (Indisolvent NMR: CDC13, 360 MHz): EXAMPLE 2 Preparation of a mixed organopolysiloxane: In a 1 liter reactor equipped with a mechanical agitation system, with two pouring ampoules and whose internal volume is maintained under a dry nitrogen atmosphere, 9.76 g (0.034 mol) of the unsaturated compound (psi) prepared at the end of example 1, and 10 cm3 of dry toluene. The reaction medium temperature is stirred at 90 ° C. Then, they are cast simultaneously, progressively, over a period of 5 hours. * 4.12 g (be 0.036 mol of function Si-H) of a polymethylhydrogensiloxane oil whose characteristics are the following: - Mn = 1630 g; - 868 milliequivalents of SiH / 100 g of oil; - medium structure: CH. I J (CH,) 3S¡0 '-Si- • S.-0- • HÍCHj), H I Oí, 14 8.5 * and 11 nm3 (or 11 μl) of a toluene solution of a platinum catalyst (catalyst called "KARSTEDT") containing 11 wt% Pt metal. After casting, the medium is allowed to react for 36 hours at 90 ° C. At the end of that time, the transformation rate of the Si-H functions is 92 mol%. Then, 10 g (0.089 mol) of octene-1 are added and left to react for 16 hours at 90 ° C. The transformation rate of the Si-H functions is 95 mol%. Then, the solvent is removed by a devolatilization which is operated for 3 hours at 100 ° C under reduced pressure of 6.65.102 Pa.

In this way, 12 g of a limpid oil are recovered whose characteristics are the following: - Mn = 5380 g; - 235 milliequivalents of cyclic amine functions / 100 g for a theory of 240 milliequivalents / 100 g (this low condition index is measured by determining the oil graduation obtained by means of 0.02 N perchloric acid solution); - average oil structure: * proportion of amine functions X: 52.6% (in moles of functions per 100 silica atoms): * function ratio: 1. 6% EXAMPLE 3: Photo stabilization of polypropylene: In a slow mixer, prepare the following 2 b compositions: Polypropylene ELTEX® P HV001P (grádolO 100 g? Oo g SI stabilizer according to example 2 that 0.2 g contains 235 meq amin functions pof: 100 stabilizer Stabilizer S2 commercial: CHIMASORB 944, (see formula below) containing 341 meq in piperidi- 0.2 g.

Formula of CHIMASORB 944 The above-mentioned compositions are converted, under identical operating conditions, to conduct films of 200 μm in thickness. The UV-stabilized polypropylene-based film originating from the composition (a) (example 3) and the polypropylene-based film stabilized with S2 originating from the composition (b) is subjected to the exposure of the same UV radiation. (test b). The aging of the films is followed by means of infrared spectrometry. In each test, the time of exposure T to the UV rays is measured, which is necessary so that the absorption in infrared spectrometry of the carbonyl band (1 1720 cm "1) resulting from the oxidation, is equal to the absorption of one band. infrared reference (CH band at 2722 c "1); in other words, the time T necessary to have in each case a degree of photo-oxidation is measured such that: absorption of the band C = 0 to 1720 cm "1 = 1 absorption of the CH2 band at 2722 cm" 1 It should be noted that, the longer the measured time is, the better is the protection conferred by the stabilizer (Groups C = 0 appear more slowly).

The results that were obtained are found in the following table: 0 5

Claims (19)

1. NOVELTY OF THE INVENTION Having described the invention, we consider it as a novelty and, therefore, claim as our property, what is contained in the following clauses. 1. Polyorganosiloxane, characterized in that it comprises per molecule, at least 3 siloxyl motifs of which at least one siloxyl functional motif of formula (I): (? axSiíO- > -a (I) wherein: * the symbols R1 are identical or different and represent a monovalent hydrocarbon radical selected from alkyl radicals, linear or branched, having 1 to 4 carbon atoms and phenyl; * the symbol X represents a monovalent group of formula (II): wherein: - R 2 represents a hydrogen atom or an alkyl radical, linear or branched, having 1 to 3 carbon atoms; - the symbol Z represents a trivalent group comprising at least 3 carbon atoms and is: a saturated or ethylenically unsaturated aliphatic radical, substituted or not, which may contain at least one carbonyl group linked by its free valencies, to two atoms constituting the cyclic acetal group: or a monicylic aromatic radical, substituted or not; or a condensed polycyclic aromatic radical, substituted or not; a polycyclic aromatic radical of various cyclic systems, condensed or not, whether or not substituted, linked together by valence bonds or by atoms or groups; - the links (1) and (2) starting from the symbol Z that concerns adjacent carbon atoms when Z represents an aromatic radical, and carbon atoms adjacent or in position ß one in relation to the other when Z represents an aliphatic radical; - the radicals R3, R4, R5 and R6, identical or different, are selected from radicals, alkyl, linear or branched, having from 1 to 3 carbon atoms, phenyl and benzyl; -R is selected from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 12 carbon atoms, alkylcarbonyl radicals wherein the alkyl radical is a linear or branched radical having from 1 to 8 carbon atoms. carbon atoms, the phenyl and benzyl radicals and a 0- radical; - x is an integer selected from 0, 1, 2 and 3; - y is an integer selected between 0 and 1; * a is an integer selected from 0, 1 and 2.
2. 2. Polyorganosiloxane according to clause 1, characterized in that the radicals R1 are: methyl, ethyl, n-propyl, isopropyl, n-butyl.
3. 3. Polyorganosiloxane according to clause 1 or 2, characterized in that the cyclic amine functions represented by the groups X are selected from the radicals of formula (II) defined below in which the symbols R2, R3, R4, R5, R6, R7, x & and they have the meanings given in the foregoing with regard to formula (II) and the symbol Z represents a trivalent radical between: * an aliphatic radical (II-1): wherein the right free valencies in coarse character are attached to the oxygen atoms of the cyclic acetal group, and R14 represents a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 3 carbon atoms or a radical of formula -C00R14"k * s or -NHC0R14" bis wherein R <4> -bis represents a linear or branched alkyl radical of 1 to 3 carbon atoms; and * an aromatic radical corresponding to the following formulas (II-2), (II-3), (II-4) and (II-5): m-2) wherein the free valencies in coarse character of each aromatic cyclic system are carried by two adjacent carbon atoms, and R15 represents -0-, -S-, a linear or branched alkylene group having from 1 to 3 carbon atoms, - CO-. -S02-, -CONH-, -NH- or -COO-.
4. 4. Polyorganosiloxane according to any of clauses 1 to 3, characterized in that it also comprises at least one other functional motif of formula (III): (^ bWSi (0) 3-b (m) in which: * the symbols R1 have the same meanings as those given in the foregoing in relation to the formula (I); * the symbol W represents a monovalent group of compatibilizing function selected from: an alkyl radical, linear or branched, having more than 4 carbon atoms; a radical of formula -R8-COO-R9 in which R8 represents a linear or branched alkylene radical, having from 5 to 20 carbon atoms and R9 represents an alkyl radical, linear or branched, having from 1 to 12 atoms of carbon; a radical of the formula -R- ^ -O-IRR-1) C-R12 in which R 10 represents a linear or branched alkylene radical, having from 3 to 15 carbon atoms, R 11 represents an alkylene radical, straight or branched , having 1 to 3 carbon atoms, c is an integer from 0 to 10 and R12 represents a hydrogen atom, an alkyl radical, linear or branched having 1 to 12 carbon atoms or an acyl radical -CO- R13 wherein R13 represents an alkyl radical, linear or branched, having from 1 to 11 carbon atoms; * b is a number selected from 0, 1 and 2.
5. 5. Polyorganosiloxane according to clause 4, characterized in that the optional compatibilizing functions are selected from: an alkyl radical, linear or branched, having from 5 to 18 carbon atoms; a radical of formula -R8-COO-R9 in which R8 represents a linear or branched alkylene radical, having 8 to 12 carbon atoms and R9 represents an alkyl radical, linear or branched, having 1 to 6 atoms of carbon; a radical of formula -R10-O- (R11-O) C-R12 in which R10 represents a linear or branched alkylene radical, having from 3 to 6 carbon atoms, R11 represents an alkylene radical, straight or branched has 2 to 3 carbon atoms, c is an integer from 0 to 6 and R12 represents a hydrogen atom, an alkyl radical, linear or branched having 1 to 6 carbon atoms or an acyl radical -CO-R13 in where R 13 represents an alkyl radical, linear or branched, having from 1 to 5 carbon atoms.
6. 6. Polyorganosiloxane according to any of clauses 1 to 5, characterized in that it also comprises another siloxy motif (s) of formula (IV): (i (H) S¡ (0) (IV) 4- (d + e) in which: * the symbols R1 have the same meanings as those given in the foregoing in relation to the formula (I); * d is an integer selected from 0, 1, 2 and 3; * e an integer selected between 0 and 1; * the sum d + e is at most equal to 3.
7. 7.- Polyorganosiloxane according to any of clauses 1 to 6, characterized in that it is selected from: - polydiorganosiloxane copolymers optionally mixed, linear, static, block or block, of formula average (V): in which: * the symbols R1, X and W have the general meanings given in the foregoing regarding the formulas (I) and (III); * the symbols Y represent a monovalent radical selected from R, X, and a hydrogen atom; * m is a whole or fractional number that goes from 0 to 180; * n is a whole or fractional number that goes from 0 to 180; * p is a whole or fractional number ranging from 0 to 10; * q is a whole or fractional number that goes from 0 to 100; * with the conditions according to which: - if m is different from O and in the eventual case of mixed polymers if n is different from 0: the sum m + n + p + q is in the range from 5 to 200; the ratio 100m / (m + n + p + q - + 2) is greater or equal to 0.5; and the ratio 100 n / (m + n + p + q + 2) is greater than or equal to 0.5; that relationship is identical or different from the relationship that precedes; if m = 0 and in the eventual case of the mixed polymers, if n is different from 0: at least one of the substituents Y represents the radical X; the sum m + n + p + q is in the range from 5 to 100; and the ratio 100 n / (m + n + p + q + 2) is greater than or equal to 0.5; - if m is different from 0 and n = 0: the sum m + p + q is in the range from 5 to 100; the ratio 100 m / (m + p + q + 2) is greater or equal to 0.5; and in the eventual case of the mixed polymers, at least one of the substituents Y represents the radical W; if m = 0 and n = 0: the sum p + q is in the range from 5 to 100; one of the substituents Y represents the radical X; and in the eventual case of the mixed polymers, the other substituent Y represents the radical W; and those of average formula (VI): (VI) in which: * the symbols R1, X and have the general meanings given in the foregoing regarding the formulas (I) and (III); * r is a whole or fractional number that goes from 1 to 9, • * s is a whole or fractional number that goes from 0 to 9; * t is a whole or fractional number that goes from 0 to 0.5; * u is a whole or fractional number that goes from 0 to 5; * the sum r + s + t + u is in the range from 3 to 10.
8. 8.- Mixed linear polyorganosiloxane PLSl, according to clause 7, characterized in that: * the symbols Y represent R1; * m is a whole or fractional number that goes from 1 to 90; * n is a whole or fractional number that goes from 1 to 90; * p is a whole or fractional number ranging from 0 to 5; * q is a whole or fractional number that goes from 0 to 50; * the sum m + n + p + q is an integer or fractional number ranging from 10 to 100; * the ratio 100 m / (m + n +? + q + 2) is in the range from 8 to 90; * with the condition according to which, if n is different from 0, the ratio 100 m / (m + n + p + q + 2) is in the range from 8 to 90; that relationship may be identical or different from the relationship that precedes; * Radicals R1 and W simultaneously have the definitions given in the foregoing for the purpose of each of them in clauses 2, 3 and 5 above.
9. 9. Mixed linear polyorganosiloxane PCS1, according to clause 7, characterized in that: * r is an integer or fractional number ranging from 1 to 4.5; * s is a whole or fractional number that goes from 1 to 4.5; * t is a whole or fractional number that goes from 0 to 0.25; * u is a whole or fractional number that goes from 0 to 2.5; * the sum r + s + t + u is a whole or fractional number that goes from 3 to 5; * Radicals R1 and W simultaneously have the definitions given in the foregoing for the purpose of each of them in clauses 2, 3 and 5 above.
10. 10. Process for preparing a polyorgano-siloxane, optionally mixed, according to any of clauses 1 to 9, characterized in that it consists of putting into operation: - in the case of polymers of cyclic amine (s) (s) ) only: an addition reaction (hydrosilylation), or - in the case of mixed polymers with cyclic amine function (s) only and comparative function (s): two addition reactions (hydrosilylations), simultaneous or successive; this starting from: corresponding organohydrogenpolysiloxanes (H) free of X and W functions, of the ethylenically unsaturated organic compound (s) at the end of the chain (psi) from which it derives (n) the (or) function (s) X and eventually of the ethylenically unsaturated compound (s) at the end of the chain (kei) from which it is deposited (or ) functions W, and q - the = quantities of reagents involved correspond to a molar relation [(psi) + eventually 'kei! ] SiH-lde (H)] which varies from 1 to 5. 11. Process according to clause 10, characterized in that the more saturated organic compounds, from which the cyclic amine functional groups X are derived are the compounds of the formula (IX ): in which the symbols R1-2, R3. R4, R, R °, R7, x & and have the meanings given in the foregoing to the purpose of the formula (
11. II.
12. 12.- Procedure according to clause 11, characterized in that the unsaturated organic compounds (psi) of formula (IX) in which the symbol Z represents an aliphatic moiety, is prepared by reacting, in the presence of an acid catalyst: * an orthodiphenol or an acetal of formula (X): wherein the symbols R2, Z (aliphatic moiety) & x, have the meanings given in the foregoing with regard to formula (II), and R16 represents a hydrogen atom or an alkyl radical, linear or branched, having from 1 to 3 carbon atoms, * with a Ketone of formula (XI): wherein the symbols R3, R4, R5, R6, R7, & and they have the meanings given in the foregoing in relation to formula (II).
13. 13. Process according to clause 11, characterized in that the unsaturated organic compounds (psi) of formula (IX) in which the symbol Z represents an aromatic residue, are prepared by reacting, in the presence of an acid catalyst: * an orthodiphenol of formula (XIV) wherein the symbols R, Z (aromatic moiety) and x, have the meanings given in the foregoing in relation to formula (II), - either with an acetal of formula (transacetalization reaction) (XV): - either with a ketone of formula (XI) (acetalization reaction), formulas in which the symbols R3, R4, R5, R6, R7, & and have the meanings given in the foregoing with regard to formula (II), and R17 represents an alkyl radical, linear or branched, having from 1 to 3 carbon atoms.
14. 14. - Process according to clause 11, characterized in that the unsaturated organic compounds (psi) of formula (IX) are prepared by reacting a cyclic acetal of formula (XVIII): with a chlorinated compound of formula (XII)
15. I CH2 = C- (CH.) Cl (XID formulas in which the symbols Z, R3, R4, R5, R6, R, and, R t x have the meanings given in what precedes the purpose of formula (II). 15. As a means to implement the process according to clause 10, a new unsaturated organic compound (psi) of formula (IX): wherein the symbols R2, Z, R3, R4, R, R6, R7, x & and they have the meanings given in the foregoing in relation to formula (II).
16. 16.- Use of an effective amount of a polyorganosiloxane optionally mixed "according to any of clauses 1 to 9, as stabilizers against the light, oxidant and thermal degradation of organic polymers
17. 17.- Use according to clause 16, characterized in that the organic polymers to be stabilized are selected from polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyethers-sulfones, polyether-ketones, acrylic polymers, their copolymers and their mixtures.
18. 18. - Composition of stabilized organic polymer against light, oxidant and thermal degradation, characterized in that it comprises: - per 100 g of organic polymer to be stabilized; - an amount of polyorganosiloxane optionally mixed according to any of clauses 1 to 9, which contributes 0.04 to 20 milliequivalents in sterically underlying cyclic function (s).
19. 19.- Composition according to clause 18, characterized in that the organic polymers to be stabilized, are selected among polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyethers-sulfones, polyethers-ketones, acrylic polymers, their copolymers and their mixtures. SUMMARY OF THE TECHNICAL CONTENT OF THE INVENTION The present invention relates to linear, cyclic or branched polyorganosiloxanes having per molecule, at least three siloxyl motifs of which at least one functional motif of the formula: (R1) XSi (O to ¿.2 wherein R1 represents an alkyl radical in Cl to C4 or phenyl, X contains a cyclic secondary or tertiary amine function, attached to the silica via a Si-A-C bond where A is a moiety comprising a cyclic acetal group. X represents more precisely a monovalent group of formula: wherein R2 is H or an alkyl radical; Z is a trivalent radical of aliphatic nature, such as for example the radical -CO-CH-CO-, or of an aromatic nature, such as for example the radical & R3 to Rd are alkyl, phenyl and / or benzyl radicals; R7 is H or an alkyl, alkylcarbonyl, phenyl or benzyl radical; x = 0, 1 or 3; y = 0 or 1. The present invention also relates to the use of polyorganosiloxanes of this type, in polymers, to improve their photostabilization in particular.