CA2208251A1 - New silicon compounds with sterically hindered cyclic amine functions useful for the light and heat stabilization of polymers - Google Patents

Abstract

This invention concerns linear, cyclic or branched polyorganosiloxanes with at least three siloxyl units per molecule, including at least one (I) formula functional unit in which: R1 stands for an alkyl radical in C1 to C4 or phenyl; X is a monovalent group containing one (or several) amines, formula (II), where R is a hydrocarbonic group, U = -0 or -NR' - with R' being H or a hydrocarbonic group, Z is a tetra alkyl group -2,2,6,6 piperidinyl, x = 0 and 1; y = 0, 1 and 2; z = 1, 2 and 3; y + z = 3; and a is 0, 1 and 2. This invention also concerns the use of similar polyorganosiloxanes in polymers to improve their photostabilization.

Description

CA 022082 ~ 1 1997-06-09 NEW SILICONE COMPOUNDS
WITH STERICALLY HALF CYCLIC AMINE FUNCTIONS, The present invention relates, in its first object, to new compounds silicones comprising per molecule at least one sterically cyclic amine function congested linked to the silicon atom by a Sl-AC bond where A is a residue organosilicon with low carbon condensation; it also concerns, in its first object, silicone compounds comprising at least one function per molecule sterically hindered cyclic amine linked to the silicon atom by an Si-AC bond where A is an organosilicon residue of low carbon condensation, and at least one another function comp ~ ibilis ~ nte linked to silicon by an Si-C bond. It also concerns, in a second object, a process 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 ultraviolet (UV) radiation, oxygen from the air and heat Indeed, organic polymers, and more particularly polyolefins and polyalkadienes, undergo degradation when 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 stabilizers.
Among these UV stabilizers, cyclic hindered amines, in particular the 2,2,6,6 tetramethyl piperidines, are currently among the most effective.
However, in practice, one of the major problems relating to the use of these st ~ hilis ~ nts anti-UV is to obtain a good compromise between their effectiveness, which implies their mobility within the polymer, and the permanence of their action, which involves putting using high molecular weight molecules with excellent compatibility with the polymers to be stabilized It has been proposed in the prior art to use advantageously to polyorganosiloxanes carrying piperidinyl functions sterically crowded. As documents illustrating this previous state, one can by example cite 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 art previous describes polyorganosiloxanes which on the one hand have a structure in which each sterically hindered cyclic amine function is related to the silicon atom by a Si-AC bond where A is an organosilicon residue of weak CA 022082 ~ 1 1997-06-09 carbon condensation, and on the other hand have useful properties to improve the resistance of polymers against their degradation under the effect of UV radiation, the oxygen in the air and in the chalewr.
More specifically, the present invention relates in its first object, a 5 polyorganosiloxane comprising per molecule at least 3 siloxy units of which at least a functional siloxyl unit of formula:

(~) aXSi (O) 3 a (I) in which:
10 ~ The symbols R1 are identical or different and represent a radical monovalent hydrocarbon 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:

(IR) y --CH. CH ~ (CH2) x if ~
in which:
~ Ies symbols R, identical or different, are chosen from the radicals alkyl, linear or branched, having from 1 to 4 carbon atoms, phenyl, phenylalkyls where the linear or branched alkyl part has 1 to 3 atoms Carbon;
~ U represents -O- or -NR'-, R 'being a radical chosen from an atom of hydrogen or an alkyl radical, linear or branched, having from 1 to 6 atoms of carbon;
~ Ie symbol Z represents a monovalent group, whose free valence is carried by a carbon atom, comprising a secondary amine function or tertiary, included in a cyclic hydrocarbon chain comprising from 8 to 30 carbon atoms, in which the two cyclic carbon atoms located in positions a and a 'with respect to the cyclic nitrogen atom does have no hydrogen atom;
~ x is a number chosen from 0 and 1;
~ y is a number chosen from 0, 1 and 2;
~ z is a number chosen from 1, 2 and 3;
~ The sum y + z is always equal to 3;
~ a is a number chosen from 0, 1 and 2.
The polyorganosiloxane can also have at least one other functional unit of formula;

CA 022082 ~ 1 1997-06-09 (~) bWSi (O) 3 b (III) in which:
~ R1 symbols have the same meanings as those given above about of formula (I);
~ The symbol W represents a monovalent group with a compatibilizing function chosen among: an alkyl radical, linear or branched, having more than 4 carbon atoms; a radical of formula -R2-Coo-R3 in which R2 represents an alkylene radical, linear or branched, having 5 to 20 carbon atoms and R3 represents a radical alkyl, linear or branched, having from 1 to 12 carbon atoms; a radical of formula -R4-o- (R5-o) C-R6 in which R4 represents an alkylene radical, linear or branched, having 3 to 15 carbon atoms, R5 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 1 to 12 carbon atoms or an acyl radical -Co-R7 where R7 represents a radical linear or branched alkyl having 1 to 11 carbon atoms;
~ b is a number chosen from 0, 1 and 2.
The other possible siloxyl unit (s) of the polyorganosiloxane answers (s) to the formula:
(Rl) d (H) e Si (~) 4- (d + e) (IV) in which:
~ R1 symbols have the same meanings as those given above about of 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 30 identical or different between them; the same remark also applies to the siloxyl patterns of formulas (III) and (IV).
In this brief, it will be understood that we define by:
- "cyclic amine functions": monovalent Z groups not equipped with the ball joint divalent organosilicon [when, in formula (II), z = 1], trivalent (when z = 2) or CA 022082 ~ 1 1997-06-09 wo 96/18667 pcT ~ Rs5lol637 tetravalent (when z = 3) through which they are linked to the atoms of . . .
slllclum;
compatibilizing functions ": the possible monovalent groups W which are directly linked to the silicon atoms (in this case, Si-C bonds are formed);
norganopolysiloxanes (or polymers) mixed ": polymers which are both equipped with amine function (s) and compatibilizing function (s).
Given the values that the symbols a, b, d and e can take, we must further understand that the polyorganosiloxanes according to the invention can therefore present a linear, cyclic, branched structure (resin) or a mixture of these structures. In the case of linear polymers, these can optionally have up to 50 mol% of branching ["T" type patterns (BSiO3 / 2) eVou ~ Q ~
(SiO4 / 2), B being a monovalent organic residue].
When polyorganosiloxane resins are concerned, these consist of at least two different types of siloxyl units, namely units ~ M ~ (B3SiO1 / 2) eVou ~ T "and possibly motifs" D ~ (B2SiO2 / 2)]; the number of patterns ratio ~ M ~ /
number of patterns "Q" eVou "T" is generally between 4/1 and 0.5 / 1, and the ratio number of patterns "[)" / number of patterns ~ Q "eVou ~ T" is generally between 0 to 1 00/1.
Advantageously, the numbers of the units of formulas (I), and optionally (III) and (IV) are such that the polyorganosiloxanes according to the invention contain:
- at least 0.5 mol%, preferably from 8 to 90 mol%, of functions amines, and possibly - at least 0.5 mol%, preferably from 8 to 90 mol%, of functions compatibilizing. The molar% indicated express the number of moles of functions per 100 silicon atoms.
The preferred radicals R1 are: methyl, ethyl, n-propyl, isopropyl, n-butyl; more preferably, at least 80 mol% of the radicals R1 are methyls.
The X groups with cyclic amine function (s), which are preferred, are chosen among the groups X of formula (II) defined above in which the symbols R, U, x, y and z have the meanings given above and the symbol Z is a group of formula:
-CA 022082 ~ 1 1997-06-09 RP 'R8 ~ <N-- ~ 9 (V) ~ H,) f ~ R ~

OR:
~ The radicals R8, identical or different from each other, are chosen from the radicals alkyl, linear or branched, having from 1 to 3 carbon atoms, phenyl and 5 benzyl;
~ R9 is chosen from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 12 carbon atoms, the alkylcarbonyl radicals or the alkyl residue is a linear or branched residue having from 1 to 8 carbon atoms, the phenyl and benzyl radicals and an O- radical; and 10 ~ f is a number chosen from 0 and 1.
More preferably, the X groups with cyclic amine function (s) are chosen from the X groups of formula (II) defined above in which: ~ the radicals R are methyl eVou phenyl;
~ U represents -0- or -NR'-, R 'being a hydrogen atom or a methyl radical;
15 ~ Z is a cyclic amine function of formula (V) where the radicals R8 are methyls, the radical R9 represents a hydrogen atom or a methyl radical and ~ f is a number equal to 1;
~ x is zero, while y and z have the meanings given above about of the formula (II).
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 -R2-Coo-R3 in which R2 represents an alkylene radical, linear or branched, having 8 to 12 carbon atoms and R4 represents an alkyl radical, linear or branched, having from 1 to 6 carbon atoms; a radical of formula -R4-o- (R5-o) C-R6 in which R4 represents an alkylene radical, linear or branched, having from 3 to 6 carbon atoms, R5 represents a linear or branched alkylene radical having from 2 to 3 carbon atoms, c is a number from 0 to 6 and R6 represents a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or a radical acyl -Co-R7 where R7 represents an alkyl radical, linear or branched, having from 1 to 5 carbon atoms.
More preferably, the compatibilizing functions W are chosen among the n-octyl, n-undecyl, n-dodecyl, n-tridecyl, decamethylene radicals methyl or ethyl carboxylate CA 022082 ~ 1 1997-06-09 WO 96118667 PCT ~ R95 / 01637 The present invention, taken in its first object, aims more specifically again:
- optionally mixed, linear polydiorganosiloxane copolymers, statistics, sequenced or block, of average formula:

Y ~ O -i - O 'i O iO i - O' -i Y (Vl) ~ .1 X m W _n - --P - --q ~ 1 in which:
~ The symbols R1, X and W have the general meanings given above about formulas (I) and (Ill);
~ Ies symbols Y represents a monovalent radical chosen from R1, X, W and an atom hydrogen;
~ m is an integer or fractional number having 0 to i 80;
~ n is a whole or fractional number ranging from 0 to 180;
~ p is an integer or fraction ranging from 0 to 30;
~ q is an integer or fraction 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 2 û, 5; and the ratio 100 n / m + n + p + q + 2 2 0.5, this ratio being identical or different from the previous report;
- if m = 0 and possibly if n is different from 0: at least one of the substituents Y
represents the radical X; the sum n + p + q is in the range from 5 to 100; and the ratio 100n / n + p + q + 220.5;
- if m is different from 0 and n = 0: the sum m + p + q lies in the interval going from 5 to 100; the ratio 100 m / m + p + q + 2 2 0.5; and possibly at least one 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 substituents Y being the radical X; and possibly the other substituent Y being the radical W;
and those of medium formula:
Rl Rl Rl Rl Si - O, Si - O- Si-O, Si - O- tVII) _X _ r _ --s _ H _ t _R _ u CA 022082 ~ 1 1997-06-09 wo 96/18667 PCT / FRg5 / 0l637 in which:
~ The symbols R1, X and W have the general meanings given above about formulas (I) and (Ill);
~ r is a whole or fractional number ranging from 1 to 9;
5 ~ s is a whole or fractional number ranging from 0 to 9;
~ t is a whole or fractional number ranging from 0 to 1.5;
~ u is an integer or fraction ranging from 0 to 5;
~ The sum r + s + t + u is in the range from 3 to 10.
The polymers of formula (VI), which are preferred (so-called PL1 polymers) or very 10 preferred (so-called PL2 polymers) are those for which:
~ Ies symbols Y represent R1;
~ 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 an integer or fraction ranging from 0 to 15;
15 ~ q is a whole or fractional number ranging from 0 to 50;
~ Ia sum m + n + p + q is a whole or fractional number ranging from 10 to 100;
~ Ie ratio 100 m / m + n + p + q + 2 is in the range from 8 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 8 to 90, this ratio can be identical or 20 different from the previous report;
~ The radicals R1, X and W simultaneously have the preferred definitions (in PL1) or more preferential polymers (in the case of PL2 polymers) above for each of them.
The polymers of formula (Vll), which are preferred (so-called PC1 polymers) or very 25 preferred (so-called PC2 polymers) are those for which:
~ r is a whole or fractional number ranging from 1 to 4.5;
~ s is a whole or fractional number ranging from 0 to 4.5;
~ t is a whole or fractional number ranging from 0 to 0.75;
~ u is an integer or fraction ranging from 0 to 2.5;
30 ~ the sum r + s + t + u is a whole or fractional number ranging from 3 to 5;
~ The radicals R1, X and W simultaneously have the preferred definitions (in the case of PC1 polymers) or more preferential ones (in the case of PC2 polymers) above for each of them.
The polymers of formula (VI), 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.

CA 022082 ~ 1 1997-06-09 The polymers of formula (VII), which are especially suitable (so-called polymers PCS1) or more especially (so-called PCS2 polymers), are the PC1 polymers or PC2 defined above for which the symbol s is a number ranging from 1 to 4.5. Advantageously, the organopolysiloxanes optionally mixed with The invention can be obtained from, and this constitutes the second object of the invention:
~ corresponding organohydrogenpolysiloxanes (H), which are free of group (s) X with arnine function (s) Z and compatibilizing function (s) W, ~ ethylenically unsaturated organic compound (s) at the end of the chain (~) from which the group (s) X with amino function (s) is derived, 10 ~ and optionally (or) ethylenically unsaturated compound (s) at the end of string (_) from which the function (s) W are derived.
Thus, the optionally mixed polyorganosiloxanes of the invention can be obtained by using:
- in the case of polymers having an amine function (s) only: a reaction addition (hydrosilylation), or - in the case of mixed polymers with amine function (s) and function (s) compatibilizing (s): two simultaneous addition reactions (hydrosilylations) or successive, this from: corresponding organohydrogenpolysiloxanes (H) free of group (s) X with an amine function (s) Z and a function (s) W, of the ethylenically unsaturated organic compound (s) at the end of the chain (~) from which derives (nt) on (or the) group (s) X with amine function (s) Z and optionally of the compound (s) ethylenically unsaturated (s) at the end of the chain (-) from which the function (s) are (are) derived W ~
These hydrosilylation reactions can be carried out at a temperature of around 20 to 200 ~ C, preferably around 60 to 120 ~ C, in the presence of a catalyst based on a platinum group metal; we can cite in particular the platinum derivatives and complex described in US-A-3,715,334, US-A-3,814,730, US-A-3 159 601, US-A-3 159 662 The quantities of catalyst used are of the order of 1 to 300 parts per million, expressed as metal with respect to the reaction medium.
In the definition of the "mole of (~, we will consider as an elementary entity olefinic unsaturation capable of reacting with (H) by hydrosilylation. Likewise in the definition of the "mole of (_)", we will consider as an elementary entity Olefinic unsaturation capable of reacting with (H) by hydrosilylation.
The quantities of reagents that can be used correspond generally at a molar ratio [(~ Y) + possibly (_)] / SiH [of (H)] which is on the order of 1 to 5, preferably on the order of 1 to 2.

CA 022082 ~ 1 1997-06-09 WO ~ 6/18667 PCTIFR95 / 01637 Hydrosilylation reactions can take place in bulk or, preferably, at the within a volatile organic solvent such as toluene, xylene, methylcyclohexane, tetrahydrofuran, heptane, octane or isopropanol; the reaction medium can additionally contain a buffering agent consisting in particular of an alkaline salt of an acid 5 monocarboxylic such as for example sodium acetate.
At the end of the reactions, the crude optionally mixed polyorganosiloxanes which are obtained can be purified in particular by p ~ s ~ ge on a column filled with eer ion exchange eerou by simple devol ~ tilis ~ tion of the reagents introduced in excess and possibly of the solvent used, by heating between 100 and 10 1 80 ~ C under reduced pressure.
Organohydrogenopolysiloxanes (H) used for example in the preparation of linear mixed polydiorganosiloxanes of formula (Vl) are those of formula:
~ IR ~ R1 ~ R1 R
Y '- Si - O ISi - O lSi-O Si - Y' (VIII) R1 ~ 1 _ - H --v Rl q in which:
15 ~ the symbols R1 and q have the general or preferential meanings given below before about the formula (Vl);
~ Ies symbols Y 'represent R1 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 interval 20 ranging from 5 to 100 and then at least one of the radicals Y 'represents an atom hydrogen.
Organohydrogenopolysiloxanes (H) used for example in the preparation of cyclic mixed polydiorganosiloxanes of formula (Vll) are those of formula:

Rl Rl --Si-O, Si-O (IX) _ Rl _ _ H _ W
in which:
~ The symbols R1 and u have the general or preferential meanings given above before about the formula (Vll);
~ w is an integer or fractional number equal to r + s + t;
30 ~ the sum u + w is in the range from 3 to 10.

=
CA 022082 ~ 1 1997-06-09 WO 96/18667 PCT / ~ R95 / 01637 Such organohydrogenpolysiloxanes (H) of formulas (VIII) and (IX) are known in the literature and, for some, they are commercially available.
The unsaturated organic compounds (~), from which the X groups with cyclic amine function (s) are derived, are preferably those of formula:

CH. = CH ~ CH) - S, - U ~ N - R
(CH2) f ~ R8 (X) - Z

in which the symbols R, U, R8, R9, f, x, y and z have the general meanings or preferential given above with regard to formulas (II) and (V).
As compounds (~), there may be mentioned as specific examples the compounds formulas:
<9 CH3, If CH3 CH3 ~ IF O ~ -R
~ /

~ N ~ ~ N ~

~~~

in which R9 is a hydrogen atom or a methyl radical.
Unsaturated organic compounds (Y ~) with cyclic amine function (s) of formula (X) are compounds which, to the knowledge of the Applicant, are new products. Such compounds can be easily synthesized by making react:
~ an alcohol or an amino derivative of formula:

CA 022082 ~ 1 1997-06-09 ~ <R
H - U ~ N - R9 (XI) ~ H ~ ~ ~

in which U, R8, R9 and f have the general or preferential meanings given above with regard to the formulas (II) and (V) (in the case where U = -O-, we start an alcohol; in the case where U = -NR'-, we start from an amino derivative of the cyclic amine);
~ on a chlorosilane of formula:

(R) y CH7 = CH - (CH2) X Si - (Cl) (XII) in which x, y and z have the meanings given above with regard to the formula (II).
As specific examples of reagents of formula (Xl), mention may be made of: hydroxy-4 tetramethyl-2,2,6,6 piperidine and 4-hydroxy pentamethyl-1,2,2,6,6 piperidine.
As specific examples of reagents of formula (Xll), there may be mentioned:
CH2 = CH-Si (CH3) 2CI, CH2 = CH-Si (CH3) 2 (CI) 2 and CH2 = CH-Si- (CI) 3.
The reaction between an alcohol or an amino derivative of formula (Xl) and a chlorosilane 15 of formula (Xll) is generally carried out in the presence of an amine-type base tertiary aliphatic, such as for example triethylamine, operating within a inert polar solvent, for example tetrahydrofuran, and at a temperature ranging from room temperature (23 ~ C) to the reflux temperature of the reaction medium. The quantity of _Si-CI functions to be implemented is generally equivalent 20 to that of the alcohol or HNR 'functions. It is better to use excess base tertiary amine compared to the theoretical amount of releasable HCI. At the end of the reaction, the purification of the compounds (~) obtained is carried out according to conventional techniques such as distillation under reduced pressure eVou recrystallization in a suitable solvent The unsaturated compounds (_) from which the W functions are derived are compounds with ethylenic unsaturation, located at the end of the chain, liable to react in hydrosilylation in the presence of a catalyst based on a platinum group metal.
As compounds (_), Oll may cite by way of examples octene-1, undecene-1, dodecene-1, tridecene-1, methyl or ethyl undecenate.
The optionally mixed polyorganosiloxanes according to the invention can be used as stabilizers against oxidative and thermal light degradation of organic polymers, and this constitutes the third object of the invention.

CA 022082 ~ 1 1997-06-09 .

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 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 for variations in the relative numbers of different siloxyl units present in the siloxane chain of mixed compounds of the invention, these so-called compounds can be easily adapted to the various 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 polyorganosiloxane compound possibly mixed.
Usually these compositions contain from 0.04 to 20 milliequivalents in sterically hindered amine function (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 amine (s) sterically cluttered (s) per 100 9 of polymer.
By way of indication, generally the stabilized polymer 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 done during or after! a pr ~ iparztior; polymt re ~.
These compositions can also contain all the additives and stabilizers used usually with the polymers they contain. So we can implement the following stabilizers and additives: antioxidants such as alkylated monophenols, alkylated hydroquinones, hydroxylated diphenyl sulfides, alkylidene-bis-phenols, benzyl 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 metal deactivators; peroxide-destroying compounds; stabilizers polyamide; nucleating agents; fillers and reinforcing agents; others CA 022082 ~ 1 1997-06-09 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 objects, sheets, 5 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 Z amine functions, expressed in milliequivalents (meq) per 100 g of silicone oil, we mean the concentration that would have 10 silicone oil if all of the amine functions involved were grafted.

Example 1 Example of preparation of a mixed polyorganosiloxane with a silicon ball.

15 A - PreDaration of dimethyl. vinyl. (4-oxy-tetramethyl-7 ~ 6.6 piperidinyl) silane:
31.45 g are introduced into a 250 cm3 reactor, equipped with a central agitation system and the interior volume of which is maintained under an atmosphere of dry nitrogen.
(0.2 mole) 4-hydroxy-2,2,6,6 tetramethyl piperidine, 81 g (0.8 mole) triethylamine anhydrous (dried on potash) and 70% of anhydrous tetrahydrofuran. The middle is put 20 with stirring and brought to a temperature of 65 ~ C. We then color over a period of 50 minutes 24.13 9 (0.2 mole) of dimethyl, vinyl, chlorosilane and left for another 3 hours with stirring at the same temperature.
The triethylamine hydrochloride formed is filtered through a cellulosic filter and rinsed with 35 g of tetrahydrofuran. The filtrate is first distilled under atmospheric pressure 25 excess triethylamine and tetrahydrofuran, then distillation is carried out under reduced pressure (4,66,102 Pa) at 90 ~ C to isolate 28 9 (0.116 mole) of dimethyl, vinyl, (4-oxy-2,2,6,6 tetramethyl piperidinyl) pure silane at 99% by weight (purity determined by gas chromatography).

30 B - Preparation of mixed polyor ~ anosiloxane:
In a 100 cm3 reactor, equipped with a central agitation system and whose interior volume is maintained under an atmosphere of dry nitrogen, 26 g of toluene. The medium is stirred and brought to a temperature of 100 ~ C, then introduced 4.2 nm2 (4.2, ul) of a solution in the divinyltetramethyldisiloxane of a 35 platinum complex at 11.9% by weight of platinum ligated with divinyltetramethyl-disiloxane (Karstedt catalyst). 5 g are then poured simultaneously in 80 minutes a polymethylhydrogenosiloxane oil (i.e. 0.0792 mole of Si-H function), the features are:

CA 022082 ~ 1 1997-06-09 WO 96/18667 PCTll; R95 / 01637 .

~ Mn = 3160g;
~ 1580 meq H / 100 9, ~ medium structure:

(CH3) 3SiO - Si - O Si (CH3) 3 _50 and 11.48 9 (0.0475 mole) of dimethyl, vinyl, (4-oxy-2,2,6,6-tetramethyl piperidinyl) silane 99% pure by weight. 2 hours after the start of casting, the transformation rate of hydrogenosilane functions is 60% (in moles). We then sink in 20 minutes 10.08 9 (0.057 mole) of 95% by weight pure dodecene-1. 4 hours after the start of the first casting, the transformation rate of the hydrogen silane functions is 68%
mole; 2.1 nm3 (2.1 μl) of Karstedt catalyst are then added. 21 hours after start of the first pour, the transformation rate of the hydrogen silane functions is 82.3%; here again 4.2 nm3 (4.21 ~ 1) of Karstedt catalyst are added. 24 hours after the start of the first pour, the rate of transformation of the functions hydrogen silanes is 85.6%.
Is added again, by pouring into the reaction medium, 4.04 9 (0.023 mol) of dodecene-1 pure at 95% by weight. 29 hours after the start of the first pour, the transformation rate of the hydrogen silane functions is 88%.
The product obtained is then devolatilized for 2 hours at 110 ~ C under a reduced pressure of 1.33.102 Pa and 17 9 of a clear light brown oil are recovered, the characteristics are as follows:
~ Mn = 12774g;
~ 239.3 meq. of amine functions Z / 100 9 (this basicity index is measured by titration of the oil obtained using a 0.02 N perchloric acid solution);
~ average oil structure:

(CH ~) 3 SiO ~ O i-- ~ $ i ~) - Si (CH3) 3 _ (CH2) 2 -30 _ Cl2H2s -14 _H _ 6 '-i (CH3) 2 o CH ~ <CH3 NOT

CA 022082 ~ 1 1997-06-09 ~ proportion of Z functions: 57.7% (in moles of functions per 100 atoms of silicon);
~ proportion of function W: 26.9%.

FxemDle 2 Example of preparation of another mixed polyorganosiloxane with a silicon ball.

A - Preparation of methyl. vinyl. bis (4-oxy-2-tetramethyl ~ 6.6 ~ iDéridinyl) silane:
87.7 9 are introduced into a 500 cc reactor, equipped with a central agitation system and the interior volume of which is maintained under an atmosphere of dry nitrogen.
(0.558 mole) 4,2-hydroxy tetramethyl 2,2,6,6 piperidine, 210,7 g (2,086 moles) of anhydrous triethylamine (dried on potash) and 187.15 9 of anhydrous tetrahydrofuran.
The medium is stirred and brought to a temperature of 57 ~ C. We then sink on 55 minutes 42.4 g (0.3 mole) of methyl, vinyl, dichlorosilane. The medium temperature rises to 72 ~ C. After the end of the casting, we still leave with stirring for 8 hours at 60 ~ C.
The excess triethylamine and tetrahydrofuran are distilled, then the medium on cellulosic filter to remove the triethylamine hydrochloride and obtain 81 9 (0.19 mole) of methyl, vinyl, bis (4-oxy-tetramethyl-2,2,6,6 piperidinyl) 90% pure silane by weight (purity determined by gas chromatography) Then continue distillation under reduced pressure (7.98.102 Pa) at 157 ~ C to obtain 54.3 9 (0.135 mole) of the same product 95% pure by weight.

B- Preparation of mixed polyor ~ anosiloxane:
In a 100 cm3 reactor, equipped with a central agitation system and whose interior volume is maintained under an atmosphere of dry nitrogen, 44.8% of toluene. The medium is stirred and brought to a temperature of 100 ~ C, then introduced 4.2 nm2 (4.2, ul) of a solution in the divinyltetramethyldisiloxane of a platinum complex at 11.9% by weight of platinum bound by divinyltetramethyl-disiloxane (Karstedt catalyst) Then sinks simultaneously in 80 minutes 5.4 9 a polymethylhydrogenosiloxane oil (i.e. 0.085 mole of Si-H function), the features are:
~ Mn = 3160g;
~ 1580 meq H / 100 9, 35 ~ medium structure:

(CH3) 3SiO - ISi - o Si (CH3) 3 H ~ o CA 022082 ~ 1 1997-06-09 and 20.9 g (0.052 mole) of methyl, vinyl, bis (4-oxy-2,2,6,6-tetramethyl piperidinyl) silane 95% pure by weight. 3.5 hours after the start of casting, the transformation rate of hydrogen silane functions is 51.6% (in moles). 4 hours 10 minutes after start of the casting, 13.9 g (0.078 mole) of pure dodecene-1 are introduced over 15 minutes 5 95% by weight. 18 hours after the start of the first pour, the rate of transformation of the hydrogen silane functions is 92%. We then add 5.7 nm3 (5.7i ~ 1) of Karstedt catalyst. 42 hours after the start of the first pour, the transformation rate of the hydrogen silane functions is 97 ~ / O.
The product obtained is then devolatilized for 2 hours at 180 ~ C under a pressure reduced by 7.98.102 Pa and 25.8 9 of a clear light brown oil are recovered with the following characteristics:
~ Mn = 18050 g;
~ 352.6 meq. of amine functions Z / 100 9 (this basicity index is measured by titration of the oil obtained using a 0.02 N perchloric acid solution);
~ average oil structure:

(CH3) 3 SiO ~ o -i-- ~ $ io Si (CH3) 3 CH ~ H ~ _ (CH2) 2 _ 31 ~ 5 _ Cl2H2s -17 _H _ 1.5 H - N ~ --O-- ~ iCH3 > ~ O
CH3 CH3 ~
CH ~ ~ CH3 ~ proportion of Z functions: 60.6% (in moles of functions per 100 atoms of silicon);
20 ~ proportion of W function: 32.7%.

Example 3 Photostabilization of polypropylene (PP) Preparation of compositions:
- mixing for 3 minutes at 160 ~ C of 100 parts by weight of PP ELTEX (~) PHV001 P
(grade 10) + 0.2 part of a commercial antioxidant (see definition below) + 0.1 part calcium stearate + 0.2 part of st ~ hiiis ~ nt;

CA 022082 ~ 1 1997-06-09 Wo 96/18667 PCT ~ R95 / 01637 - compression under a plate press at 190 ~ C (1 minute of contacting + 1 minute of maintenance at 250.105 Pa + 1 minute of cooling at the same pressure).
We thus obtain quasi-circular plates of 200 micrometers of thickness ~ issuer where we cut test pieces.
* Control composition: stabilizer = CHIMASORB 944 (see formula below) containing 341 meq of piperidinyl functions per 100 9 of stabilizer.
* Compositions b and c: stabilizers = silicone oils respectively in the examples 1 (part B) and 2 (part B).
Definition of the commercial antioxidant used: 50/50 mixture by weight tetrakis (hydroxy-4'-ditertiobutyl-3 ', 5'-phenyl) -3 pentaerythrityl propionate (marketed under the name IRGANOX ~) 1010) and tris (ditertiobutyl-2,4-phenyl) phosphite (sold under the name IRGAFOS ~) 168).
CHIMASORB ~) 944 formula:

N --_ (CH,) 6 - N ~, N ~

I
HH C8Hl7 - n> l The three compositions are tested under UV A.
Under UV A degradation being much slower than under UV B, the stabilization is done by simply comparing the durations after which there is rupture of test pieces (D) For each composition, three test pieces are tested. ~, Conce "lr ~ lion in Duration of rupture of the test piece: amine function D / number of D (hour) (meq / 100 g meq / 100 g oil) Composition test 1 test 2 test 3 medium a 744 768 798 770 341 2.26 b 878 844 1079 897 239.3 3.75 c 1914 1938 1958 1937 342.6 5.65

Claims (17)

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

(I) in which:
~ the R1 symbols are the same or different and represent a radical monovalent hydrocarbon chosen from linear or branched alkyl radicals, having 1 to 4 carbon atoms and phenyl;
~ the symbol X represents a monovalent group of formula:

(II) in which:
~ the symbols R, identical or different, are chosen from the radicals alkyls, linear or branched, having from 1 to 4 carbon atoms, phenyl, phenylalkyls where the linear or branched alkyl part has 1 to 3 carbon atoms carbon;
~ U represents -O- or -NR'-, R' being a radical chosen from an atom of hydrogen or an alkyl radical, linear or branched, having from 1 to 6 atoms of carbon;
~ the symbols Z, identical or different, represent a monovalent group whose free valence is carried by a carbon atom and of formula (V) or:
~ the R8 radicals, which are identical or different from each other, are chosen from alkyl radicals. linear or branched, having 1 to 3 carbon atoms, phenyl and benzyl;
~ R9 is chosen from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 12 carbon atoms, the alkylcarbonyl radicals or the alkyl residue is a linear or branched residue having 1 to 8 carbon atoms, phenyl and benzyl radicals and an O radical;

~ x is a number selected from 0 and 1;
~ y is a number selected from 0, 1 and 2;
~ z is a number chosen from 1, 2 and 3;
~ the sum y + z is always equal to 3;
~ a is a number chosen from 0, 1 and 2.
~ f is a number chosen from 0 and 1. 2.- polyorganosiioxane according to claim 1, characterized in that the R1 radicals are: methyl, ethyl, n-propyl, isopropyl, n-butyl. 3.- Polyorganosiloxane according to any one of claims 1 to 2, characterized in that it further comprises at least one other functional unit of formula:

(III) in which:
~ the R1 symbols have the same meanings as those given above about of the formula (I);
~ the symbol W represents a chosen monovalent group with a compatibilizing function from: an alkyl radical, linear or branched, having more than 4 carbon atoms; a radical of formula -R2-COO-R3 in which R2 represents an alkylene radical, linear or branched, having from 5 to 20 carbon atoms and R3 represents a radical alkyl, linear or branched, having 1 to 12 carbon atoms; a radical of formula -R4-O-(R5-O)C-R6 in which R4 represents an alkylene radical, linear or branched, having from 3 to 15 carbon atoms, R5 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, a linear or branched alkyl radical having 1 to 12 carbon atoms or an acyl radical -CO-R7 where R7 represents a linear or branched alkyl radical having from 1 to 11 carbon atoms;
~ b is a number chosen from 0, 1 and 2. 4.- Polyorganosiloxanes according to claim 3 characterized in that the compatibilizing functions W are chosen: from an alkyl radical, linear or branched, having 5 to 18 carbon atoms; a radical of formula -R2-COO-R3 in which R2 represents an alkylene radical, linear or branched, having from 8 to 12 atoms of carbon and R4 represents an alkyl radical, linear or branched, having from 1 to 6 carbon atoms.

carbon; a radical of formula -R4-O-(R5-O)c-R6 in which R4 represents a alkylene radical, linear or branched, having from 3 to 6 carbon atoms, R5 represents a linear or branched alkylene radical having from 2 to 3 carbon atoms, c is a number from 0 to 6 and R6 represents a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or an acyl radical -CO-R7 where R7 represents an alkyl radical, linear or branched, having from 1 to 5 carbon atoms. 5.- Polyorganosiloxane according to any one of claims 1 to 4, characterized in that it further comprises other siloxyl unit(s) of formula:

(IV) in which:
~ the R1 symbols have the same meanings as those given above about of the formula (I);
~ d is a number chosen from 0, 1, 2 and 3;
~ e is a number selected from 0 and 1;
~ the sum d + e is at most equal to 3. 6.- Polyorganosiloxane according to any one of claims 1 to 5, characterized in that it is chosen from:
- optionally mixed, linear polydiorganosiloxane copolymers, statistics, sequenced or block, average formula:

<IMG) (VI) in which:
~ the symbols R1, X and W have the general meanings given above about formulas (I) and (III);
~ the symbols Y represent a monovalent radical chosen from R1, X, W and an atom hydrogen;
~ m is an integer or fractional number ranging from 0 to 180;
~ n is an integer or fractional number ranging from 0 to 180;
~ p is an integer or fractional number ranging from 0 to 30;
~ q is an integer or fractional number ranging from 0 to 100;
~ with the conditions that:
- if m is different from 0 and possibly if n is different from 0: the sum m + n + p + q is in the range of 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 the same or different from previous report;
- if m = 0 and possibly if n is different from 0: at least one of the substituents Y
represents the radical X; the sum n + p + q lies in the interval going from 5 to 100; and the ratio 100 n/n + p + q + 2 ~ 0.5;
- if m is different from 0 and n = 0: the sum m + p + q is located in the interval going from 5 to 100; the ratio 100 m / m + p + q + 2 ~ 0.5; and possibly at least one substituents Y represents the radical W;
- if m = 0 and n = 0: the sum p + q is in the range from 5 to 100; mon substituents Y being the radical X; and optionally the other substituent Y being the radical W;

and those of medium formula:

(VII) in which:
~ the symbols R1, X and W have the general meanings given above about formulas (I) and (III);
~ r is an integer or fractional number ranging from 1 to 9;
~ s is an integer or fractional number ranging from 0 to 9;
~ t is an integer or fractional number ranging from 0 to 1.5;

~ u is an integer or fractional number ranging from 0 to 5;
~ the sum r + s + t + u is in the range from 3 to 10. 7.- Mixed linear polyorganosiloxane PLS1 according to claim 6, characterized in that:
~ the symbols Y represent R1;
~ m is an integer or fractional number ranging from 1 to 90;
~ n is an integer or fractional number ranging from 1 to 90;
~ p is an integer or fractional number ranging from 0 to 15;
~ q is an integer or fractional number ranging 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;
~ the ratio 100 n / m + n + p + q + 2 is in the range from 8 to 90, this report may be the same or different from the previous report;
~ the radicals R1, X and W simultaneously have the definitions given above at about each of them in the aforementioned claims 2, 3 and 5. 8.- Mixed cyclic polyorganosiloxane PCS1 according to claim 6, characterized in that:
~ r is an integer or fractional number ranging from 1 to 4.5;
~ s is an integer or fractional number ranging from 1 to 4.5;
~ t is an integer or fractional number ranging from 0 to 0.75;
~ u is an integer or fractional number ranging from 0 to 2.5;
~ the sum r + s + t + u is an integer or fractional number ranging from 3 to 5;
~ the radicals R1, X and W simultaneously have the definitions given above at about each of them in the aforementioned claims 2, 3 and 5. 9.- Process for the preparation of a polyorganosiloxane, optionally mixed, according to any one of claims 1 to 8, characterized in that it consists in placing work:
- in the case of polymers with amine function(s) only: a reaction addition (hydrosilylation), or - in the case of mixed polymers with amine function(s) and with function(s) compatibilizer(s): two simultaneous addition reactions (hydrosilylations) or . successive, this from: corresponding organohydrogenpolysiloxanes (H) free of group(s) X with amine function(s) Z and function(s) W, of the ethylenically unsaturated organic compound(s) at the end of the chain (~) from which derives (nt) the (or the) group(s) X with amine function(s) Z and optionally the compound(s) ethylenically unsaturated at the end of the chain (~) from which the function(s) derive(s) W, and that the quantities of reactants involved correspond to a molar ratio [(~) +
optionally (~)]/SiH [of (H)] which is of the order of 1 to 5. 10.- Process according to claim 9, characterized in that the compounds unsaturated organic (~), from which the cyclic amine function(s) X groups are derived are those of formula:

(X) wherein the symbols R, U, R8, R9, f, x, y and z have the given meanings above with regard to formulas (II) and (V). 11.- Process according to claim 10, characterized in that the compounds unsaturated organic compounds (~) of formula (X) are prepared by reacting:
~ an alcohol or an amino derivative of formula:

(XI) in which U, R8, R9 and f have the meanings given above with regard to the formulas (II) and (V) (in the case where U = -O-, we start from an alcohol; in the case where U = - NR'-, starting from an amino derivative of the cyclic amine);
~ on a chlorosilane of formula:

(XI) in which x, y and z have the meanings given above with regard to formula (II). 12.- As a means for carrying out the method, according to claim 9, a new unsaturated organic compound (~) of formula:

(X) wherein the symbols R, U, R8, R9, f, x, y and z have the given meanings above with regard to formulas (II) and (V). 13.- Use of an effective amount of a polyorganosiloxane optionally mixture according to any one of Claims 1 to 8, as stabilizers against light, oxidative and thermal degradation of organic polymers. 14.- Use according to claim 13, 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 mixed. 15.- Organic polymer composition stabilized against the harmful effects of heat and UV, characterized in that it comprises an organic polymer with stabilize and an effective amount of at least one polyorganosiloxane compound optionally mixed according to any one of claims 1 to 8. 16.- Composition according to claim 15, characterized in that it comprises - for 100 g of organic polymer to stabilize, - an optionally mixed quantity of polyorganosiloxane according to any one of claims 1 to 8 which provides from 0.04 to 20 milliequivalents in amine function(s) sterically crowded. 17.- Composition according to claim 15 or 16, 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 mixtures thereof.