EP0792324A1 - New silicon compounds with sterically hindered linear amine functions, useful for the heat and light stabilization of polymers - Google Patents

Abstract

The present invention relates to linear, cyclic or branched polyorganosiloxanes having, per molecule, at least three siloxyl patterns, of which at least one is a function pattern having the formula (I), wherein R1 is a phenyl C1-C4 alkyl radical, X contains a secondary or tertiary linear amine function linked to the silicon by a bond -Si-A-C, with A being a simple valence link or an oxygen atom. Said linear amine function may be, when A = valency link, a radical having the formula -R?8-CR9R10-NR11-R12¿, wherein R8 may be an alkylen or alkenylen rest; R?9 and R10¿ may represent alkyl rests; R11 may be H or alkyl; and R12 is a tertiary alkyl. The present invention also relates to the utilisation of said polyorganosiloxanes in polymers in order to improve particularly their photostabilization.

Description

 NOVEL SILICONE COMPOUNDS WITH STERICALLY HALFLED LINEAR AMINE FUNCTIONS, USEFUL FOR LIGHT AND THERMAL STABILIZATION OF POLYMERS

The present invention relates, in its first object, to novel silicone compounds comprising per molecule at least one sterically hindered linear amine function linked by a Si-O-C or Si-C bond to the silicon atom; it also relates, in its first subject, to silicone compounds comprising per molecule at least one sterically hindered linear amine function linked to the silicon atom by an Si-OC or Si-C bond, and at least one other compatibilizing function linked to the silicon through an Si-C bond. It also relates, in a second object, to processes for the preparation of said silicone compounds. It also relates, in a third object, to the use of such compounds in polymers to improve their resistance against degradation under the effect of ultra-violet (UV) radiation, oxygen in the air and heat. .

Indeed, organic polymers, and more particularly polyolefins and polyalkadienes, undergo degradation when they are subjected to external agents and in particular to the combined action of air and solar ultraviolet radiation.

This degradation is generally limited by the introduction into the polymer of small amounts of stabilizing agents.

Among these anti-UV stabilizers, sterically hindered amines, in particular tetramethyl-2,2,6,6 piperidines, are currently among the most effective.

However, in practice, one of the major problems relating to the use of these anti-UV stabilizers is to obtain a good compromise between their effectiveness, which implies their mobility within the polymer, and the permanence of their action, which involves the use of high molecular weight molecules having excellent compatibility with the polymers to be stabilized.

It has been proposed in the prior art to use advantageously polyorganosiloxanes carrying sterically hindered piperidinyl functions. As documents illustrating this prior state, mention may for example be made of patent documents JP-A-01/096259, EP-A-0 338 393, EP-A-0 343 717, EP-A-0 358 190, EP-A -0 388 321 and EP-A-0491 659.

However, to the knowledge of the Applicant, no document of the prior art describes polyorganosiloxanes which on the one hand have a structure in which each sterically hindered amino function has a linear structure, and on the other hand are endowed with useful properties to improve the resistance of polymers against their degradation under the effect of UV radiation, oxygen in the air and heat.

More precisely, the present invention relates, in its first object, to a polyorganosiloxane comprising per molecule at least 3 siloxy units, at least one of which is a functional siloxyl unit of formula:

(F? ⁾ XSi (O), ⁽ I ⁾

2 in which:

• the symbols R ^" ! Are identical or different and represent a monovalent hydrocarbon radical chosen from alkyl radicals, linear or branched, having from 1 to 4 carbon atoms and phenyl;

• the symbol X represents a monovalent group of formula -A-Z where:

• A is a simple valence bond or an oxygen atom;

• the symbol Z represents a monovalent group, the free valence of which is carried by a carbon atom, comprising a secondary or tertiary amine function, included in a linear hydrocarbon chain comprising from 9 to 40 carbon atoms, in which the two atoms carbon of the chain located in the α positions and with respect to the nitrogen atom do not contain a hydrogen atom; • a is a number chosen from 0, 1 and 2.

The polyorganosiloxane can also have at least one other functional unit of formula:

in which :

• the symbols R ^ have the same meanings as those given above with regard to formula (I);

• the symbol W represents a monovalent group with a compatibilizing function chosen from: an alkyl radical, linear or branched, having more than 4 carbon atoms; a radical of formula -R ^ -COO-R ^ in which R ^ represents an alkylene radical, linear or branched, having 5 to 20 carbon atoms and R3 represents an alkyl radical, linear or branched, having 1 to 12 atoms of carbon ; a radical of formula -R ⁴ -O- (R5-O) _C -RE> in which R ⁴ represents an alkylene radical, linear or branched, having 3 to 15 carbon atoms, R ^ represents an alkylene radical, linear or branched, having 1 to 3 carbon atoms, c is a number from 0 to 10 and R6 represents a hydrogen atom, an alkyl radical, linear or branched having from 1 to 12 carbon atoms or an acyl radical -CO-R ⁷ where R ⁷ represents a linear or branched alkyl radical having from 1 to 11 carbon atoms ;

• b is a number chosen from 0, 1 and 2.

The other possible siloxyl unit (s) of the polyorganosiloxane corresponds (s) to the formula:

⁽ R ¹⁾ , (H) If <0)

4- (d + e) (III)

in which :

• the symbols R ¹ have the same meanings as those given above with regard to formula (I);

• d is a number chosen from 0, 1, 2 and 3;

• e is a number chosen from 0 and 1; "The sum d + e is at most equal to 3.

The siloxy units of formula (I) when there are more than two, can be identical or different from one another; the same remark also applies to the siloxyl units of formulas (II) and (III).

In the present specification, it will be understood that we define by: - "linear amino functions": the monovalent groups Z not equipped with the ball joint A by means of which they are linked to the silicon atoms;

- "compatibilizing functions": the possible monovalent groups W which are directly linked to the silicon atoms (in this case, Si-C bonds are formed); - "mixed organopolysiloxanes (or polymers)": polymers which are equipped with both amine function (s) and compatibilizing function (s);

- "organopolysiloxanes without ball joint": the optionally mixed polymers according to the invention in the structure of which the linear amino functions are linked to the silicon atoms via the ball joint A = valential bond (in this case bonds were formed Si-C);

- "organopolysiloxanes with an oxygen ball joint": the optionally mixed polymers according to the invention in the structure of which the linear amino functions are linked to the silicon atoms via the ball joint A = -O- (in this case we formed Si-OC bonds); Given the values that the symbols a, b, d and e can take, 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. When linear polymers are involved, these can optionally have up to 50 mol% of branching ["T" type units (RSiθ3 / 2) and / or "Q (SiO _4/2 )].

When polyorganosiloxane resins are concerned, these consist of at least two different types of siloxy units, namely "M" (R3SiO- _| / 2) and / o "T" units and optionally units ^" D" (R2Siθ2 / 2). ; the ratio number of units "M" / number of units "Q" and / or "T" is generally between 4/1 and 0.5 / 1, and the ratio number of units "D" / number of units " Q "and / or" T "is generally between 0 to 100/1. Advantageously, the numbers of the units of formulas (I), and optionally (II) and (III) are such that the polyorganosiloxanes according to the invention contain:

- at least 0.5 mol%, preferably 10 to 90 mol%, of linear amino functions, and optionally | - at least 0.5 mol%, preferably from 10 to 90 mol%, of compatibilizing functions. The molar% indicated express the number of moles of functions per 100 silicon atoms.

The preferred radicals R ¹ are: methyl, ethyl, n-propyl, isopropyl, n-butyl; more preferably, at least 80 mol% of the radicals R ¹ are methyls.

The preferred Z amino functions are chosen:

(i) when A = valential bond: among the monovalent radicals of formula:

R9 - R ^ C-NR ¹¹ - ^ ² (IV)

in which :

• R8 represents a divalent organic radical of formula:

- B ¹ - (β2) _f - where: B ¹ is a divalent residue chosen from - CH2-CHR ^{1 3} - and - CH = CH-, with R ³ being a hydrogen atom or an alkyl radical, linear or branched , having 1 to 3 carbon atoms; B ^ is an alkylene residue, linear or branched, having from 1 to 10 carbon atoms, with f being a number equal to 0 or 1;

• the radicals R ⁹ and R ^{1 0} , identical or different, are chosen from alkyl radicals, linear or branched, having from 1 to 4 carbon atoms, phenyl and benzyl; • R ^{1 1} , which may be identical to R ⁹ and / or R ¹ 0, is chosen from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 3 carbon atoms and an O- radical;

• R ¹² represents a radical -CR ¹ R ⁵ R ¹⁶ where the residues R ¹⁴ <R ¹⁵ and R ¹⁶ , identical or different from each other, which may moreover be identical to R ⁹ and / or R ^" O, each represent the one of the radicals represented by R ⁹ and R10; (2i) when A = -O-: among the radicals of formula:

in which :

• R ^' ' ⁷ represents a divalent radical of formula:

where: R 2 is chosen from a hydrogen atom and the radicals represented by R ⁹ and

R ¹⁰ in formula (IV); B ³ is a divalent residue chosen from alkylene radicals, linear or branched, having from 1 to 10 carbon atoms and alkenylene radicals, linear or branched, having from 2 to 10 carbon atoms and comprising one or more unsaturation (s ) ethylenic (s) in the chain, with g being a number equal to 0 or 1;

• the radicals R ¹ ** and R- * ⁹ , identical or different, are chosen from the radicals represented by R ⁹ and R ^" O in formula (IV);

• R20, which may be identical to R ¹ 8 and / or R ¹⁹ , is chosen from a hydrogen atom and the radicals represented by R ^" ! ¹ in formula (IV); • R ²¹ represents a radical -CR ²⁴ R25R26 ₀ Ù | _es radicals R ^24, R ² 5 and R ^26, identical or different, which may further be identical to R ^22, R ¹ * and / or R ^19, each represent one of the radicals represented by R ⁹ and R ¹ 0 in formula (IV).

More preferably, the amino functions Z are chosen: (i) when A = valential link: among those of formula (IV) in which:

• R * is chosen from divalent radicals of formulas - CH2-CH2- (in this case R ¹³ = H and f = 0) and - CH2-CH2- (B ² ) f- (in this case R ¹³ = H) where B ² is a residue - (CH2J with h being a number from 1 to 6; • R ⁹ and R ¹⁴ , R ⁵ , R ^{1 6} (constitutive of R ¹² ) are methyl groups;

• R10 is chosen from linear alkyl radicals having from 1 to 3 carbon atoms; and

• R1 ï represents a hydrogen atom; (2i) when A = -O-: among those of formula (V) in which:

• R ¹⁷ is chosen from divalent radicals of formulas: - CCH3R ²² - (B ³ ) _g - where R ²² is a hydrogen atom and B ³ is a divalent residue of formula - (CH2) _j - with i being a number from 1 to 6;

R18, R19 _and R24 _] R25 _t R26 (constitutive of R ²¹ ) are methyl groups; and • R ² ^ represents a hydrogen atom.

In the definitions given above with regard to formulas (IV) and (V), the free valences appearing in bold are those which are linked to the silicon atoms either directly (when A = valential bond), or via of an oxygen atom (when A = -O-). The preferred optional compatibilizing functions W are chosen: from an alkyl radical, linear or branched, having 5 to 18 carbon atoms; a radical of formula -R ² -COO-R ³ in which R ² represents an alkylene radical, linear or branched, having from 8 to 12 carbon atoms and R ⁴ represents an alkyl radical, linear or branched, having from 1 to 6 carbon atoms; a radical of formula -R ⁴ -O- (R5-O) _c -R6 in which R ⁴ represents an alkylene radical, linear or branched, having 3 to 6 carbon atoms, R ^ represents a linear or branched alkylene radical having from 2 to 3 carbon atoms, c is a number from 0 to 6 and R ^ represents a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or an acyl radical -CO-R ⁷ where R ⁷ represents an alkyl radical, linear or branched, having from 1 to 5 carbon atoms.

More preferably, the compatibilizing functions W are chosen from the n-octyl, n-undecyl, n-dodecyl, n-tridecyl, methyl or ethyl decamethylene carboxylate radicals.

The present invention, taken in its first object, aims even more precisely:

- optionally mixed, linear, statistical, block or block polydiorganosiloxane copolymers, of average formula:

(V)

in which :

• the symbols R ¹ , X and W have the general meanings given above with regard to formulas (l) and (II);

• the symbols Y represent a monovalent radical chosen from R ¹ , X, W and a hydrogen atom;

• m is a whole or fractional number ranging from 0 to 180;

• n is a whole or fractional number ranging from 0 to 180;

• p is a whole or fractional number ranging from 0 to 10;

• q is a whole or fractional number ranging from 0 to 100; • with the conditions according to which:

- if m is different from 0 and possibly if n is different from 0: the sum m + n + p + q is in the range from 5 to 200; the ratio 100 m / m + n + p + q + 2;> 0.5; and the ratio 100 n / m + n + p + q + 2 ≥ 0.5, this ratio being identical to or different from the previous ratio; - if m = 0 and possibly 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 ≥ 0.5,

- if m is different from 0 and n = 0: the sum m + n + p + q is in the range from 5 to 100; the ratio 100 m / m + n + p + q + 2 ≥ 0.5; and optionally 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 being the radical X; and optionally the other substituent Y being the radical W;

and those of medium formula

in which: • the symbols R ¹ , X and W have the general meanings given above with regard to formulas (I) and (11);

• r is a whole or fractional number ranging from 1 to 9;

• s is a whole or fractional number ranging from 0 to 9;

• t is a whole or fractional number ranging from 0 to 0.5; • u is a whole or fractional number ranging from 0 to 5; • the sum r + s + t + u is in the range from 3 to 10.

The polymers of formula (V), which are preferred (so-called PL1 polymers) or very preferred (so-called PL2 polymers), are those for which:

• the symbols Y represent R ^; • m is a whole or fractional number ranging from 1 to 90;

• n is a whole or fractional number ranging from 0 to 90;

• p is a whole or fractional number ranging from 0 to 5;

• q is a whole or fractional number ranging from 0 to 50;

• the sum m + n + p + q is a whole or fractional number ranging from 10 to 100; ^“ The ratio 100 m / m + n + p + q + 2 is in the range from 10 to 90;

• with the condition that if n is different from 0, the ratio 100 n / m + n + p + q + 2 is in the range from 10 to 90, this ratio can be identical or different from the previous ratio;

• the radicals R ¹ , X and W simultaneously have the preferred definitions (in the case of PL1 polymers) or the more preferred definitions (in the case of PL2 polymers) given above with respect to each of them.

The polymers of formula (VI), which are preferred (so-called PC1 polymers) or very preferred (so-called PC2 polymers), are those for which: r is an integer or fractional number ranging from 1 to 4.5; • s is a whole or fractional number ranging from 0 to 4.5; t is an integer or fraction ranging from 0 to 0.25; u is a whole or fractional number ranging from 0 to 2.5; the sum r + s + t + u is a whole or fractional number ranging from 3 to 5; the radicals R ¹ , X and W simultaneously have the preferred definitions (in the case of PC1 polymers) or the more preferred definitions (in the case of PC2 polymers) given above with respect to each of them.

The polymers of formula (V), which are especially well suited (so-called PLS1 polymers) or especially well (so-called PLS2 polymers), are the polymers PL1 or PL2 defined above for which the symbol n is a number ranging from 1 to 90 . The polymers of formula (VI), which are especially suitable (so-called polymers

PCS1) or very specifically (so-called PCS2 polymers), are the PC1 or PC2 polymers defined above for which the symbol s is a number ranging from 1 to 4.5.

Advantageously, the optionally mixed organopolysiloxanes of the invention without a ball joint can be obtained from, and this constitutes a first modality of the second subject of the invention:

• corresponding organohydrogenpolysiloxanes (H), which are free of Z amino function (s) and W compatibilizing function (s), • ethylenically unsaturated organic compound (s) at the end of the chain (Ψ) from which the amine function (s) Z is derived,

• and optionally (or) ethylenically unsaturated compound (s) at the chain end (Ξ) from which the function (s) W are derived. Thus, the optionally mixed polyorganosiloxanes of the invention without ball joint can be obtained by using: in the case of polymers with amine function (s) only: an addition reaction (hydrosilylation), or in the case of mixed polymers with amine function (s) ) and with compatibilizing function (s): two simultaneous or successive addition reactions (hydrosilylations), starting from: corresponding organohydrogenopolysiloxanes (H) free of the Z and W functions, of the compound (s) ethylenically unsaturated organic (s) at the end of the chain (Ψ) from which the Z function (s) are derived and optionally from the ethylenically unsaturated compound (s) at the end chain (Ξ) from which the function (s) W are derived.

These hydrosilylation reactions can be carried out at a temperature of the order of 20 to 200 ° C, preferably of the order of 60 to 120 ° C. in the presence of a catalyst based on a platinum group metal; mention may in particular be made of the platinum derivatives and complexes described in US-A-3 715334. US-A-3 814730, US-A-3 159601, US-A-3 159662.

The amounts of catalyst used are from 1 to 300 parts per million, expressed as metal with respect to the reaction medium.

In the definition of the "mole of (Ψ)", we will consider as elementary entity the olefinic unsaturation capable of reacting with (H) by hydrosilylation. Similarly in the definition of the "mole of (Ξ)", we will consider as elementary entity the olefinic unsaturation capable of reacting with (H) by hydrosilylation.

The amounts of reagents that can be used generally correspond to a molar ratio [(Ψ) + optionally (Ξ)] / SiH [of (H)] which is of the order of 1 to 5, preferably of the order from 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 in particular of an alkaline salt of a monocarboxylic acid such as for example sodium acetate.

At the end of the reactions, the optionally crude mixed polyorganosiloxanes which are obtained can be purified in particular by passing over a column filled with an ion exchange resin and / or by simple devolatilization of the reactants introduced in excess and possibly of the solvent used, by heating operated between 100 and 180 ° C under reduced pressure.

The organohydrogenopolysiloxanes (H) used for example in the preparation of linear mixed polydiorganosiloxanes of formula (V) are those of formula:

in which :

• the symbols R ¹ and q have the general or preferential meanings given above with regard to the formula (V);

• the symbols Y 'represent R ^"1 or a hydrogen atom; • v is an integer or fractional number equal to m + n + p;

• with the condition that, if v = 0, q is a number in the range from 5 to 100 and then at least one of the radicals Y 'represents a hydrogen atom.

The organohydrogenopolysiloxanes (H) used for example in the preparation of the cyclic mixed polydiorganosiloxanes of formula (VI) are those of formula:

"wine.

in which: • the symbols R ^ and u have the general or preferential meanings given above with regard to the formula (VI);

• w is an integer or fractional number equal to r + s + 1;

• the sum u + w is in the range from 3 to 10.

Such organohydrogenpolysiloxanes (H) of formulas (VII) and (VIII) are known in the literature and, for some, they are commercially available.

The unsaturated organic compounds (Ψ), from which the Z functions are derived, are preferably those of formula:

R9

_R 2_i_ _Ν] Jl_ _R i2 (IX) in which :

• the symbol R26 is chosen from the radicals of formula: CH2 = CR ¹ - (B ² ) f- and CH = C- (B ² ) _f -;

• the symbols R ¹³ , B ² , f, R ⁹ , R ^{1 u} \ R ^{1 1} and R ¹² have the general or preferential meanings given above with regard to formula (IV).

As compounds (Ψ), there may be mentioned as examples: N-tertiobutyl (methyl-1, ethyl-1, butene-3 yl) amine, N-tertiobutyl (dimethyl-1, 1, propyne-2 yDamine , N-tertiobutyl (dimethyl-1 J, propene-2 yDamine.

The unsaturated amines (Ψ) are known compounds which are described, in particular in US-A-3,067,101. They can be prepared according to a first process, which is described in this prior art, consisting of the following:

First process:

It is carried out in 2 or 3 stages: (1) chlorination by HCI of the alcohol of formula

R26R9R10C-OH, then (2) condensation of the chlorine compound obtained with the amine R ^{1 2} -NHR ^{1 1} to yield the desired unsaturated amine, by applying the following synthesis scheme:

+ H ₂ O

l Action of ¹ - NHRU

In the case where R ²⁶ has the formula CH≡C- (B ² ) f- and where it is desired to obtain an amine equipped at the end of the chain with ethylenic unsaturation, it will then be possible to carry out a complementary step (3) consisting subjecting the amine (IX) formed above to acetylenic unsaturation, to a catalytic semi-hydrogenation to yield the amine of formula (IX) with R ²⁶ being the radical CH2≈CH- (B) _f -. Other methods which are advantageously usable, and to the knowledge of the Applicant are new methods, are the second and third methods defined below:

Second process:

Preparation of the compounds of formula (IX) in which R ^{1 1} = H, and R ²⁶ , R ⁹ , R 10 and R ¹² have the meanings indicated above.

This second process is carried out in 4 stages: (1) condensation of the hydroxylamine (in the form of hydrochloride) on the ketone R ¹² -CO-R ⁹ , then (2) addition of CH3SO2CI on the oxime obtained to lead to the mesylate 2 of the oxime, then (3) carrying out a Beckmann transposition of the mesylate 2 by action of the organomagnesium halide R ¹ θMgX, then (4) nucleophilic addition on the imine 4 obtained from the halide d 'organomagnesium R ² ^ MgX followed by acid hydrolysis, applying the following synthesis scheme:

NH— OH + R ¹ - CO-R ⁹ C = N-OH H, O

Action of CH, SO, Cl

MgX

(SO ₃ CH ₃ )

As regards the practical manner of carrying out steps (1) to (4), reference will be made to the contents of the following documents, which describe, starting from other reagents, procedures applicable to the conduct of the various stages of the process considered: cf. ME GARST et al., J. Org. Chem., 4Q_ (8), p. 1169 (1975) for step (1); cf. K. MARVOKA, S. NAKAI and H. YAMAMOTO, Organic Synthesis, £ & 185 (1988) for step (2); cf. K. HATTORI, K. MARVOKA and H. YAMAMOTO, Tetrahedron Letters, 22. (33), 3395-3396 (1982) for step (3) and cf. H. YAMAMOTO et al., J. Am. Chem. Soc. 1983, 105, 2831-2843 for step (4).

Third process:

Preparation of the compounds of formula IX in which R ^{1 1} ≈ H, and R ² ^, R9 _t R10 and R ¹² have the meanings indicated above.

This third process is carried out in 2 stages: (1) condensation of the amine R ¹² -NH2 and of the ketone R -CO-R ¹⁰ to lead to imine S, then (2) nucleophilic addition to imine 5 organomagnesium halide R ^ MgX followed by acid hydrolysis, applying the following synthetic scheme:

R9

R ^ -CO-R ¹⁰ + R ¹ - ² - NH, »C = N-Rl2 + H ₂ O

A Action de R ² 6j igX

! + acid hydrolysis

With regard to the practical way of carrying out steps (1) and (2), reference will be made to the contents of the following documents, which describe, starting from other reagents, procedures applicable to the conduct of the various stages of the process considered: cf. D.A. EVANS and LA. DOMEIER, Org.

Synth., 54, P- 93 (1974) for step (1) and cf. H. YAMAMOTO et al., J. Am. Chem. Soc.

1983, 105, 2831-2843 for step (2). The unsaturated compounds (Ξ) from which the W functions are derived are compounds having ethylenic unsaturation, located at the end of the chain, capable of reacting in hydrosilylation in the presence of a catalyst based on a platinum group metal. As compounds (Ξ), there may be mentioned, by way of example, octene-1, undecene-1, dodecene-1, tridecene-1, methyl or ethyl undecenoate. Advantageously, the optionally mixed organopolysiloxanes of the invention with an oxygen ball can be obtained from, and this contributes to a second method of the second object of the invention: • corresponding organohydrogenopolysilanes (H), which are free of Z amino function (s) equipped with the oxygen patella and of W compatibilizing function (s),

• hydroxylated organic compound (s) (Ψ ') from which the Z-amine function (s) equipped with the oxygen patella are derived,

• and possibly ethylenically unsaturated compound (s) at the end of the chain (Ξ) from which the W function (s) are derived.

Thus the optionally mixed polyorganosiloxanes of the invention with an oxygen ball joint can be obtained by using: - in the case of polymers having amine function (s) only: a dehydrogenocondensation reaction, or - in the case of mixed polymers with amine function (s) and compatibilizing function (s): simultaneous dehydrogenocondensation and addition (hydrosilylation) reactions or, preferably, successive dehydrogenocondensation and then addition (hydrosilylation) reactions, this from: corresponding organohydrogenopolysilanes (H) free of the Z functions equipped with the oxygen patella and W, of the organic compound (s) hydroxylated (Ψ ') from which derives (nt) ) the Z function (s) equipped with the oxygen patella, and the ethylenically unsaturated compound (s) at the end of the chain (Ξ) from which the (or) are derived the) W. function (s)

Said dehydrogenocondensation and hydrosilylation reactions can be carried out under the same operating conditions (in particular: nature and amount of catalyst; reaction temperatures; nature of optional solvents) as those described above in the context of addition reactions (hydrosilylations ) presiding over the preparation of polyorganosiloxanes without a ball joint.

In the definition of the "mole of (Ψ ')", we will consider here as elementary entity the OH function capable of reacting with (H) by dehydrogeno¬ condensation; the molar ratio [(Ψ ') + possibly (Ξ)] / SiH [of (H))] here also varies between 1 and 5 and, preferably between 1 and 2. The hydroxylated organic compounds (Ψ') from which the Z functions equipped with the oxygen patella (or: from which the monovalent X groups are derived), are preferably those of formula:

in which :

• the symbol R ²⁷ is a hydroxyl radical of formula: the symbols R ²² , B ³ , g, R ¹³ , R ¹⁹ , R ^ and R ²¹ have the general or preferential meanings given above with regard to the formula (V). As compounds (Ψ '), there may be mentioned as examples the species of formulas:

Hydroxylated amines (Ψ ') are compounds which, to the knowledge of the Applicant, are new products. Such hydroxylated amines (Ψ ') can be easily synthesized using the following methods:

Fourth process

Preparation of the compounds of formula (X) in which R ²⁷ is the radical

with g being a number different from zero, and R ²² , B ³ , R ¹⁸ , R ⁹ , R ²⁰ , R ²¹ have the meanings indicated above.

This fourth process is carried out in 3 stages: (1) chlorination by HCI of the alcohol of formula:

then (2) condensation of the chlorinated compound obtained β with the amine R ² ^ -NHR ² 0 to yield the ethylenically unsaturated amine 2. then (3) hydration in sulfuric medium of the double bond of amine 2. applying the following synthesis scheme:

With regard to the practical way of carrying out steps (1) to (3), reference will be made to the contents of the following documents which describe, where appropriate starting from other reagents, applicable procedures. the conduct of the various stages of the process under consideration: cf. US-A-3,067,101 for steps (1) and (2); cf. cf.J. MEINWALD, J. Am. Chem. Soc, 22, P 1617 (1955) for step (3).

Fifth process:

Preparation of the compounds of formula (X) in which R ²⁷ is the radical

CH ₃ HO-CH-

(in this case R ²² = H and g = 0), and R ¹ 8, R ¹⁹ , R ²⁰ , R ²¹ have the meanings indicated above.

This fifth process is carried out in 4 stages: (1) chlorination by HCI of the alcohol of formula: R18

CH≡CC-OH i _Λ R19 then (2) condensation of the chlorine compound obtained £ with the amine R ²¹ -NHR ² 0 to lead to the acetylenically unsaturated amine â, then (3) hydration in sulfuric medium of the triple bond of the amine â, then (4) reduction of the ketone formed u into alcohol in the presence of an appropriate reducing metal agent, by applying the following synthesis scheme:

Cl -h H ₂ O

(X)

With regard to the practical manner of carrying out steps (1) to (4), reference will be made for more details to the contents of the following documents which describe, where appropriate starting from other reagents, applicable procedures. the conduct of the various stages of the process under consideration: cf. US-A-3,067,101 for steps (1) and (2); cf. FR-A-2 476 104 for step (3); cf. RYLANDER "Catalytic hydrogenation over platinium metals" p. 238 to 290, Académie Press NY (1967) for step (4). The optionally mixed polyorganosiloxanes according to the invention can be used as stabilizers against the oxidative and thermal light degradation of organic polymers, and this constitutes the third subject of the invention.

By way of example of such organic polymers, mention may be made of polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyether sulfones, polyether ketones, acrylic polymers, their copolymers and their mixtures. .

Among these polymers, the compounds of the invention have a more particularly effective action with polyolefins and polyalkadienes such as polypropylene, high density polyethylene, linear low density polyethylene, low density polyethylene, polybutadiene, their copolymers and their mixtures.

Given the wide possibilities of variations in the relative numbers of the different siloxyl units present in the siloxane chain of the mixed compounds of the invention, these so-called compounds can be easily adapted to the different problems to be solved.

Yet another object of the present invention therefore consists in organic polymer compositions stabilized against the harmful effects of heat and UV by an effective amount of at least one optionally mixed polyorganosiloxane compound. Usually these compositions contain from 0.04 to 20 milliequivalents depending on the sterically hindered amine (s) per 100 g of polymer to be stabilized.

Preferably, the stabilized polymeric compositions according to the invention contain from 0.20 to 4 milliequivalents depending on the sterically hindered amine function (s) per 100 g of polymer. By way of indication, generally the stabilized polymeric compositions contain from 0.01% to 5% by weight of polyorganosiloxane compound optionally mixed with respect to the polymer.

The addition of optionally mixed polyorganosiloxane compounds can be carried out during or after the preparation of the polymers. These compositions can also contain all the additives and stabilizers usually used with the polymers they contain. Thus, the following stabilizers and additives can be used: antioxidants such as alkylated monophenols, alkylated hydroquinones, hydroxylated diphenyl sulfides, alkylidene-bisphenols, benzylic compounds, acylamino-phenols, esters or amides (3,5-di-tert-butyl-4-hydroxy-phenyl) -3 propionic acid, acid esters

(3,5-dicyclohexyl-4 hydroxy-phenyl) -3 propionic; light stabilizers such as optionally substituted benzoic acid esters, acrylic esters, nickel compounds, oxalamides; phosphites and phosphonites; of the metal deactivators; peroxide-destroying compounds; polyamide stabilizers; nucleating agents; fillers and reinforcing agents; other additives such as, for example, plasticizers, pigments, optical brighteners, flame retardants. The polymer compositions thus stabilized can be applied in the most varied forms, for example in the form of molded articles, sheets, fibers, cellular materials (foam), profiles or coating products, or as film-forming agents. (binders) for paints, varnishes, glues or cements. The following examples illustrate the present invention. In these examples, by theoretical concentration of amino functions Z, expressed in milliequivalents (meq) per 100 g of silicone oil, is meant the concentration that silicone oil would have if all of the amino functions involved were grafted.

Example 1

Example of preparation of a mixed organoDoIvsiloxane without ball joint

1) Preparation (by the technique in accordance with the first process) of N-tertiobutyl (1 methyl-1 ethyl-butene-3 yl) amine: In a 500 cm ³ reactor, 24 g (0.24 mole) of pinacolone CH3- are introduced

CO-C (CH3) 3.24 g (0.348 mole) of hydrochloride hydrochloride. 27.5 g (0.348 mole) of pyridine and 240 cm ³ of ethanol. The mixture is brought to its boiling temperature and thus maintained under reflux for 1 hour. At the end of this time, it is allowed to cool to room temperature (23 ° C) and, after the addition of 240 cm ³ of water. the pinacolone oxime which is dried at room temperature under reduced pressure of 1.33 × 10 ² Pa is isolated by filtration; 22 g (0J92 mole) of said oxime are thus recovered. The molar yield of recovered product is 80%.

22 g of the above oxime, 253 cm ³ of dichloromethane and 40 cm3 of triethylamine are charged into a second 1000 cm ³ reactor. The medium is cooled to -20 ° C and 29.7 g (0.20 mole) of methane sulfonic acid chloride CH3-SO2-CI are added gradually over a period of 30 minutes. After treatment of the reaction mass consisting of adding 250 cm ³ of ice water, then 150 cm ³ of sulfuric ether then decanting, then drying over Na2Sθ4 and concentrating the organic phase on a rotary evaporator, 29 are obtained, 7 g (0J 52 mole) of pinacolone oxime methanesulfonate. The molar yield of isolated product is 79%. 660 g of toluene and 29.7 g of methane sulfonate of pinacolone oxime are charged into a third 2000 cm ³ reactor, cooled to -70 ° C. Then, gradually poured over a period of 50 minutes, 126 cm ³ (0.456 mole) of a solution of ethylmagnesium bromide in sulfuric ether (solution containing 2 moles per liter of organomagnesium).

At the end of the pouring of the ethylmagnesium bromide solution, the temperature of the reaction mixture is allowed to rise to 0 ° C., then 89 cm ³ of a solution of solution are poured again gradually over a period of 60 minutes. allylmagnesium bromide in sulfuric ether (2 mole solution per liter). At the end of pouring, the reaction mixture is hydrolyzed by adding 700 cm ³ of water and 50 cm ³ of concentrated HCl. After decantation and separation, the organic phase is concentrated in a manner known per se in order to remove the toluene and the sulfuric ether. 14.6 g of the product of formula are thus recovered:

The analyzes made by infrared spectrometry, nuclear magnetic resonance of the proton and mass spectrometry, confirm the structure of this amine.

2) Preparation of the mixed organopolysiloxane

In a 250 cm ³ reactor, equipped with a stirring system and whose internal volume is maintained under an atmosphere of dry nitrogen. 13 cm ³ of dry toluene are introduced, 3.3 g (0.02 mole) of dodecene-1 at 95% by weight, 9.76 g (0.056 mole) of N-tertiobutyl (methyl-1, ethyl-1 butene -3 yl) amino and 0.016 g of sodium acetate. The mixture is stirred and the temperature of the reaction medium is brought to 110 ° C. 7 nm ³ (7 μl) of a solution are then introduced into the divinyltetramethyldisiloxane of a platinum complex containing 11.9% by weight of platinum bound by divinyltetramethyldisiloxane (Karstedt catalyst). Then poured, gradually over a period of 80 minutes, 3.78 g of a polymethylhydrogenosiloxane oil, the characteristics of which are as follows:

• Mn = 3160 g,

• 1580 meq H / 100 g,

• medium structure:

After pouring the oil with hydrogenosilyl functions, the reaction medium is left to react at 110 ° C. for 45 hours. At the end of this time, the transformation rate of the hydrogenosilyl functions is 93% (in moles).

The excess reagents and the solvent are then removed by devolatilization carried out for 2 hours at 140 ° C. under a reduced pressure of 1.33 × 10 ² Pa.

14.76 g of a clear oil are thus recovered, the characteristics of which are as follows:

• Mn = 10900 g;

• 245.9 meq of amino functions Z / 100 g, for a theory of 405 meq / 100 g (this basicity index is measured by titration of the oil obtained by means of a 0.02 N perchloric acid solution );

• average oil structure:

• proportion of Z functions: 51.2% (in moles of functions per 100 silicon atoms);

• proportion of W functions: 37.5%.

Example 2

Polypropylene photostabilization

In the slow mixer, the following 2 compositions a and b are prepared ab

Polypropylene ELTEX® P HV001P (grade 10) 100 q 100 q

Stabilizer S1 according to Example 1, part 2) 0.2 g containing 245.9 meq in amino functions for - 100 q of stabilizer

Commercial stabilizer S2: CHIMASORB 944, (see formula below), containing 341 meq in functions - 0.2 g piperidinyls per 100 q of stabilizer

The aforementioned compositions are transformed, under identical operating conditions, to yield films 200 μm thick.

The polypropylene-based film stabilized with S1 from the composition (Example 2) and the polypropylene-based film stabilized with S2 from the composition b (test b) are subjected to the same UV radiation exposure. The aging of the films is monitored by infrared spectrometry. The time of exposure T to UV rays which is necessary for the infrared spectrometry absorbance of the carbonyl band (at 1720 cm ⁻¹ ) resulting from the oxidation resulting from the oxidation to be equal to the absorbance of infrared reference band (CH2 band at 2722 cm ^{* 1} ); in other words, we measure the time T necessary to have in each case a degree of photooxidation such as:

band absorbance C = 0 to 1720 cm-1

= 1 absorbance of the CH2 strip at 2722cm " ¹

Note that the longer the measured time, the better the protection conferred by the stabilizer (groups C = 0 appear more slowly). The results obtained are collated in the following table

Film if damaged Film not stabilized

Example 2 Test b Control

Exposure time T to 75 70 20 UV in hours

T / number of meq / 100 g 0.31 0.21

Example 3

Preparation of an organopolvsiloxane without ball joint

262.4 g (1.786 mole) of N-tertiobutyl (dimethyl-1, 1) are introduced into a 1000 cm ³ tetracol reactor equipped with a central mechanical agitation, a thermometer and a ball cooler. propene-2 yl) 96% pure amine (mass).

The contents of the reactor are brought to 85 ° C. and the overhead of the reactor is inerted with nitrogen. We then run using two separate ampoules (the start of introduction is simultaneous): * firstly in 5 hours:

- 0.762 ml of the Karstedt catalyst solution described in Example 1 (part 2) and

- 30 g of dry toluene,

* and on the other hand in 30 minutes:

- 420 g (1.692 moles of Si-H functions) of a polymethylhydrogenosiloxane oil with a structure:

(CH, ⁾ , SiO

at 0.403 Si-H equivalent per 100 g of oil. Twice during the reaction (7 hours, then 22 hours after the start of the reaction) 0.275 ml of the Karstedt catalyst solution described in Example 1 (part 2) is added.

69 hours after the start of the reaction, the conversion rate of the hydrogenosilyl functions is 98.8% (in moles). The product obtained is then devolatilized for 4 hours at 80 ° C under a reduced pressure of 3.32.10 ² Pa. 588 g of a clear yellow oil are recovered, the characteristics of which are as follows:

• viscosity: 1000 mPas at 24 ° C;

• Mn = 6265 g;

• 244.6 meq of Z amino functions per 100 g of oil;

• medium structure:

more nuclear magnetic resonance reveals the presence of 0.8 mol% of T units; proportions of Z functions: 28J% (in moles of functions per 100 atoms of Si).

Example 4

Preparation of a mixed organopolvsiloxane without ball joint

70 g of dry toluene are introduced into a 1000 cm ³ tetracol reactor equipped with central mechanical stirring, a thermometer and a ball cooler.

The contents of the reactor are brought to 90 ° C., the reactor overhead is inerted with nitrogen and 0.042 ml of the Karstedt catalyst solution described in Example 1 (part 2) is introduced.

We then run simultaneously using two separate bulbs: * on the one hand:

- 201.78 g (1.78 mole) of octene-1 pure at 99% by mass, _* and on the other hand:

- 230 g (3.392 moles of Si-H functions) of a polymethylhydrogenosiloxane oil with a structure:

at 1.475 Si-H equivalents per 100 g of oil.

4 hours after the start of the reaction, the conversion rate of the hydrogenosilyl functions (into moles) is 50.8% (ie a conversion rate of the octene functions of 97%). We then sink using two separate bulbs (the start of the flows being simultaneous):

• on the one hand in 1 hour 15 minutes:

- 294.2 g (2.003 mole) of N tertiobutyl (dimethyl-1, 1 propene-2 y 96% pure amine by mass

• And on the other hand :

- 20 g of dry toluene and

- 627 mg of the Karstedt catalyst solution described in Example 1 (part 2).

18 hours after the start of these second injections, the transformation rate of the hydrogenosilyl functions is 98.3% (in moles).

The product obtained is then devolatilized for 4 hours at 90 ° C under a reduced pressure of 3.32.10 ² Pa. 623 g of a clear oil are recovered, the characteristics of which are as follows:

• viscosity: 1580 mPas at 24 ° C; • Mn = 4980 g;

• 241.3 meq of Z amino functions per 100 g of oil;

• medium structure:

(CH,), If

more nuclear magnetic resonance reveals the presence of 1.6 mol% of T units; proportions of Z functions: 42.9% (in moles of functions per 100 Si atoms); proportions of W functions: 49.9%.

Claims

1.- Polyorganosiloxane, characterized in that it comprises per molecule at least 3 siloxy units, at least one of which is a functional siloxyl unit of formula:

in which :

• the symbols R ¹ are identical or different and represent a monovalent hydrocarbon radical chosen from alkyl radicals, linear or branched, having from 1 to 4 carbon atoms and phenyl;

• the symbol X represents a monovalent group of formula -A-Z where:

• A is a simple valence bond or an oxygen atom;

• the symbol Z represents a monovalent group, the free valency of which is carried by a carbon atom, comprising a secondary or tertiary amine function, included in a linear hydrocarbon chain comprising from 9 to 40 carbon atoms, in which the two atoms carbon of the chain located in the α and α 'positions with respect to the nitrogen atom do not contain a hydrogen atom;

• a is a number chosen from 0, 1 and 2.

2. Polyorganosiloxane according to claim 1, characterized in that the radicals R ¹ are: methyl, ethyl, n-propyl, isopropyl, n-butyl.

3. Polyorganosiloxane according to claim 1 or 2, characterized in that the amino functions Z are chosen:

(i) when A = valential bond: among the monovalent radicals of formula:

in which: • R8 represents a divalent organic radical of formula:

- B ¹ - (B ² ) _f - where: B ¹ is a divalent residue chosen from - CH2-CHR ¹³ - and - CH≈CH-, with R ¹³ being a hydrogen atom or an alkyl radical, linear or branched , having from 1 to 3 carbon atoms; B ² is an alkylene residue, linear or branched, having from 1 to 10 carbon atoms, with f being a number equal to 0 or 1;

• the radicals R ⁹ and R ¹⁰ , identical or different, are chosen from alkyl radicals, linear or branched, having from 1 to 4 carbon atoms, phenyl and benzyl;

• R ^{1 1} , which may be identical to R ⁹ and / or R ^{1 υ} , is chosen from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 3 carbon atoms and an O- radical;

• R ¹² represents a radical -CR ¹⁴ R ¹⁵ R ¹⁶ where the residues R ¹⁴ 'R ¹⁵ and R ¹⁶ , identical or different from each other, which may moreover be identical to R ⁹ and / or R ^{1 υ} , each represent the one of the radicals represented by R ⁹ and R ^{1 ϋ} ; (2i) when A = -O-: among the radicals of formula:

in which :

• R ¹⁷ represents a divalent radical of formula:

where: R2 is chosen from a hydrogen atom and the radicals represented by R ⁹ and

R ^{1 υ} in formula (IV); B ³ is a divalent residue chosen from alkylene radicals, linear or branched, having from 1 to 10 carbon atoms and alkenylene radicals, linear or branched, having from 2 to 10 carbon atoms and comprising one or more unsaturation (s) ethylenic (s) in the chain, with g being a number equal to 0 or 1;

• the radicals R ¹³ and R ¹⁹ , identical or different, are chosen from the radicals represented by R ⁹ and R ¹⁰ in the formula (IV);

• R20, which may be identical to R ¹³ and / or R ¹⁹ , is chosen from a hydrogen atom and the radicals represented by R ^{1 1} in formula (IV); • R ²¹ represents a radical -CR ⁴ R ²⁵ R ²⁶ where the residues R ²⁴ , R ²⁵ and R ²⁶ , identical or different from each other, which can moreover be identical to R ²² , R ¹⁸ and / or R ¹⁹ . each represent one of the radicals represented by R ⁹ and R ¹⁰ in formula (IV).

4.- Polyorganosiloxane according to any one of claims 1 to 3, characterized in that it also comprises at least one other functional unit of formula:

in which :

• the symbols R ¹ have the same meanings as those given above with regard to formula (I);

• the symbol W represents a monovalent group with a compatibilizing function chosen from: an alkyl radical, linear or branched, having more than 4 carbon atoms; a radical of formula -R2-COO-R ³ in which R represents an alkylene radical, linear or branched, having 5 to 20 carbon atoms and R ³ represents an alkyl radical, linear or branched, having 1 to 12 atoms carbon; a radical of formula -R ⁴ -O- (R5-O) _C -R6 in which R ⁴ represents an alkylene radical, linear or branched, having 3 to 15 carbon atoms, R ⁵ represents an alkylene radical, linear or branched , having from 1 to 3 carbon atoms, c is a number from 0 to 10 and R6 represents a hydrogen atom, an alkyl radical, linear or branched having from 1 to 12 carbon atoms or an acyl radical -CO-R ⁷ where R ⁷ represents a linear or branched alkyl radical having from 1 to 11 carbon atoms; • b is a number chosen from 0, 1 and 2.

5. Polyorganosiloxane according to claim 4, characterized in that the compatibilizing functions W are chosen: from an alkyl radical, linear or branched, having from 5 to 18 carbon atoms; a radical of formula -R2-COO-R ³ in which R2 represents an alkylene radical, linear or branched, having from 8 to 12 carbon atoms and R ⁴ represents an alkyl radical, linear or branched, having from 1 to 6 atoms of carbon; a radical of formula -R ⁴ -O- (R ⁵ -O) _c -R6 in which R ⁴ represents an alkylene radical, linear or branched, having 3 to 6 carbon atoms, R ⁵ represents a linear or branched alkylene radical having from 2 to 3 carbon atoms, c is a number from 0 to 6 and R ^ represents a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or an acyl radical -CO- R ⁷ where R ⁷ represents an alkyl radical, linear or branched, having from 1 to 5 carbon atoms.

6.- Polyorganosiloxane according to any one of claims 1 to 5, characterized in that it further comprises other (s) unit (s) siloxyl (s) of formula

(R ¹ ), (H) If (O)

4- (d + e) (m)

in which :

• the symbols R ¹ have the same meanings as those given above with regard to formula (I);

• d is a number chosen from 0, 1, 2 and 3;

• e is a number chosen from 0 and 1;

• the sum d + e is at most equal to 3.

7. Polyorganosiloxane according to any one of Claims 1 to 6, characterized in that it is chosen from:

- optionally mixed, linear, statistical, block or block polydiorganosiloxane copolymers, of average formula:

in which :

• the symbols R ¹ , X and W have the general meanings given above with regard to formulas (I) and (II);

• the symbols Y represent a monovalent radical chosen from R ¹ , X, W and a hydrogen atom; • m is a whole or fractional number ranging from 0 to 180;

• n is a whole or fractional number ranging from 0 to 180;

• p is a whole or fractional number ranging from 0 to 10;

• q is a whole or fractional number ranging from 0 to 100;

• with the conditions according to which: - if m is different from 0 and possibly if n is different from 0: the sum m + n + p

+ q is in the range from 5 to 200; the ratio 100 m / m + n + p + q + 2 ≥ 0.5; and the ratio 100 n / m + n + p + q + 2> 0.5, this ratio being identical to or different from the previous ratio; - if m = 0 and possibly 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> 0.5,

- if m is different from 0 and n = 0: the sum m + n + p + q is in the range from 5 to 100; the ratio 100 m / m + n + p + q + 2 ≥ 0.5; and optionally 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 being the radical X; and optionally the other substituent Y being the radical W;

and those of medium formula:

in which :

• the symbols R ¹ , X and W have the general meanings given above with regard to formulas (I) and (II); r is a whole or fractional number ranging from 1 to 9; s is a whole or fractional number ranging from 0 to 9; t is an integer or fraction ranging from 0 to 0.5; u is a whole or fractional number ranging from 0 to 5; the sum r + s + t + u is in the range from 3 to 10.

8.- mixed linear polyorganosiloxane PLS1 according to claim 7, characterized in that:

• the symbols Y represent R ¹ ;

• m is a whole or fractional number ranging from 1 to 90;

• n is a whole or fractional number ranging from 1 to 90;

• p is a whole or fractional number ranging from 0 to 5; • q is a whole or fractional number ranging from 0 to 50;

• the sum m + n + p + q is a whole or fractional number ranging from 10 to 100;

• the ratio 100 m / m + n + p + q + 2 is in the range from 10 to 90;

• the ratio 100 n / m + n + p + q + 2 is in the range from 10 to 90, this ratio can be identical or different from the previous report; • the radicals R ¹ , X and W have simultaneously the definitions given above with respect to each of them in the aforementioned claims 2, 3 and 5.

9.- PCS1 mixed cyclic polyorganosiloxane according to claim 7, characterized in that: r is an integer or fractional number ranging from 1 to 4.5; s is a whole or fractional number ranging from 1 to 4.5; t is an integer or fraction ranging from 0 to 0.25; u is a whole or fractional number ranging from 0 to 2.5; “The sum r + s + 1 + u is a whole or fractional number ranging from 3 to 5; the radicals R, X and W simultaneously have the definitions given above with respect to each of them in the aforementioned claims 2, 3 and 5.

10.- Process for the preparation of a polyorganosiloxane, optionally mixed, without ball joint, according to any one of claims 1 to 9, characterized in that it consists in using: in the case of polymers with function (s) amine (s) only: an addition reaction (hydrosilylation), or in the case of mixed polymers with amine function (s) and with compatibilizing function (s): two addition reactions (hydrosilylation) simultaneous or successive, starting from: corresponding organohydrogenpolysiloxanes (H) free of the Z and W functions, of the ethylenically unsaturated organic compound (s) at the end of the chain (Ψ) from which derivative (nt) ) the Z function (s) and possibly the ethylenically unsaturated compound (s) at the end of the chain (Ξ) from which the W function (s) are derived, and that the quantities of reactants used correspond to a molar ratio [(Ψ) + possibly (Ξ)] / SiH [of (H)] which is of the order from 1 to 5.

11.- Method according to claim 10, characterized in that the unsaturated organic compounds (Ψ), from which the Z functions are derived, are preferably those of formula:

in which : • the symbol R ² ^ is chosen from the radicals of formula: CH2 = CR ¹ - (B ² ) f- and CH _≡ C- (B ² ) f-;

• the symbols R ^{1 3} , B ² , f, R ⁹ , R ^{1 υ} , R ^{1 1} and R ¹² have the meanings given above with regard to formula (IV).

12.- Method according to claim 11, characterized in that the unsaturated organic compounds (Ψ) of formula (IX) in which R ^{1 1} = H and R ² ^, R ⁹ , R10 and R ¹² have the meanings given, are prepared by linking the following 4 stages: (1) condensation of the hydroxylamine on the ketone R ¹² -CO-R ⁹ , then (2) addition of CH3SO2CI on the oxime obtained to lead to the oxime mesylate, then ( 3) realization of a Beckmann transposition of the mesylate by action of the organomagnesium halide R ÛMgX, then (4) nucleophilic addition on the imine obtained from the organomagnesium halide R ^ MgX followed by acid hydrolysis .

13.- Method according to claim 1 1, characterized in that the unsaturated organic compounds (Ψ) of formula (IX) in which R ^{1 1} = H and R ² * ", R ⁹ , R ¹ 0 and R ¹² have the given meanings, are prepared by linking the following 2 steps: (1) condensation of the amine R ^{1 2} -NH2 and of the ketone R ⁹ -CO-R ¹ 0 to lead to an imine, then (2) nucleophilic addition to imine obtained from the organomagnesium halide R ² ^ MgX followed by acid hydrolysis.

14.- Process for the preparation of a polyorganosiloxane, optionally mixed, with an oxygen ball joint, according to any one of claims 1 to 9, characterized in that it consists in using: - in the case of polymers having a function ( s) amine (s) only: a dehydrogenocondensation reaction, or - in the case of mixed polymers with amine function (s) and with compatibilizing function (s): dehydrogenocondensation and addition reactions ( hydrosilylation) or successive dehydrogenocondensation and addition (hydrosilylation) reactions, starting from: corresponding organohydrogenopolysilanes (H) free of the Z functions equipped with the patella oxygen and W, of the compound (s) ) hydroxylated organic (s) (Ψ ') from which derives the Z function (s) equipped with the oxygen patella, and the ethylenically unsaturated compound (s) ( s) at the end of the chain (Ξ) from which the function (s) W derive (s), and that the quantities of reagents used correspond to a molar ratio t (Ψ ') + possibly (Ξ)] / SiH [of (H)] which is of the order of 1 to 5.

15.- Method according to claim 14, characterized in that the hydroxylated organic compounds (Ψ ') from which the Z functions equipped with the oxygen ball joint are derived (or also: from which the monovalent groups X are derived), are those of formula:

in which :

• the symbol R ²⁷ is a hydroxyl radical of formula:

“The symbols R ²² , B ³ , g, R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ have the meanings given above with regard to the formula (V).

16.- Method according to claim 15, characterized in that the hydroxylated organic compounds (Ψ ') of formula (X) in which R ²⁷ is the radical

with g being a number different from zero, and R ²² , B ³ , R ¹⁸ , R ¹⁹ , R ^2u \ R ²¹ have the meanings indicated, are prepared by linking the following 3 steps: (1) chlorination by HCI of the formula alcohol:

then (2) condensation of the chlorinated compound obtained with the amine R ² -NHR ² ^ to yield an ethylenically unsaturated amine, then (3) hydration in sulfuric medium of the double bond of the amine obtained.

17.- Method according to claim 15, characterized in that the hydroxylated organic compounds (Ψ ') of formula (X) in which R ²⁷ is the radical

CH, i

HO-CH—

(in this case R ²² = H and g = 0), and R ^{1 8} , R ¹⁹ , R ²⁰ , R ²¹ have the meanings indicated, are prepared by chaining the 4 following steps: (1) chlorination by HCI of the formula alcohol:

R18

CH≡CC-OH i R19 then (2) condensation of the chlorine compound obtained with the amine R -NHR ^2ϋ to lead to an acetylenically unsaturated amine, then (3) hydration in sulfuric medium of the triple bond of the amine, then (4) reduction of the ketone formed into alcohol in the presence of an appropriate metallic reducing agent.

18. As a means for implementing the process according to claim 14, a new hydroxylated amine (Ψ ') of formula:

in which :

• the symbol R ²⁷ is a hydroxyl radical of formula:

• the symbols R ²² , B ³ , g, R ^{1 8} , R ^{1 9} , R ²⁰ and R ²¹ have the meanings given above with regard to the formula (V).

19.- Use of an effective amount of an optionally mixed polyorganosiloxane according to any one of claims 1 to 9, as stabilizers against the light, oxidative and thermal degradation of organic polymers.

20.- Use according to claim 19, characterized in that the organic polymers to be stabilized are chosen from polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyethersulfones, polyether ketones, acrylic polymers, their copolymers and their blends.

21. An organic polymer composition stabilized against light, oxidizing and thermal degradation, characterized in that it comprises: - per 100 g of organic polymers to be stabilized, - an amount of mixed polyorganosiloxane according to any one of claims 1 to 9 which provides 0.04 to 20 milliequivalents depending on the sterically hindered amine (s).

22. A composition according to claim 21, characterized in that the organic polymers to be stabilized are chosen from polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyether sulfones, polyether ketones, acrylic polymers, their copolymers and their blends.