Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/54—Nitrogen-containing linkages

Definitions

• the present invention relates, in its first subject, to novel silicone compounds comprising per molecule at least one sterically hindered cyclic amine function linked to the silicon atom by an SI-A-C bond where A is an organosilicon residue of low carbon condensation; it also relates, in its first object, to silicone compounds comprising per molecule at least one sterically hindered cyclic amine function linked to the silicon atom by an Si-AC bond where A is an organosilicon residue of low carbon condensation, and to at least one other compatibilizing function linked to silicon by an Si-C bond. It also relates, in a second object, to 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 ultra-violet (UV) radiation, oxygen in the air and heat. .
• UV ultra-violet
• 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.
• cyclic hindered amines in particular 2,2,2,6,6-tetramethyl piperidines
• 2,2,2,6,6-tetramethyl piperidines are currently among the most effective.
• 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.
• 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:
• 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:
• R which are identical or different, are chosen from alkyl radicals, linear or branched, having from 1 to 4 carbon atoms, phenyl, phenylalkyls in which the linear or branched alkyl part has 1 to 3 carbon atoms;
• U represents -O- or -NR'-, R 'being a radical chosen from a hydrogen atom or an alkyl radical, linear or branched, having from 1 to 6 carbon atoms; 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 cyclic hydrocarbon chain comprising from 8 to
• the polyorganosiloxane can also have at least one other functional unit of formula: in which :
• 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 R ⁇ represents an alkyl radical, linear or branched, having 1 to 12 carbon atoms; a radical of formula
• 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
• R6 represents a hydrogen atom, an alkyl radical, linear or branched having from 1 to 12 carbon atoms or an acyl radical -CO-P7
• R ⁇ 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:
• d is a number chosen from 0, 1, 2 and 3;
• e is a number chosen from 0 and 1;
• 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 (III) and (IV).
• the polyorganosiloxanes according to the invention can therefore have a linear, cyclic, branched structure (resin) or a mixture of these structures.
• these can optionally have up to 50 mol% of branching ["T" (BSÎO3 / 2) and / or "Q" type units
• polyorganosiloxane resins these consist of at least two different types of siloxy units, namely "M" units (B3SiO-
• the numbers of the units of formulas (I), and optionally (III) and (IV) are such that the polyorganosiloxanes according to the invention contain:
• the molar% indicated express the number of moles of functions per 100 silicon atoms.
• the preferred R 1 radicals are: methyl, ethyl, n-propyl, isopropyl, n-butyl; more preferably, at least 80 mol% of the radicals R " ! are methyls.
• the groups X with cyclic amine function (s), which are preferred, are chosen from 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: or :
• radicals R are chosen from alkyl radicals, linear or branched, having from 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, alkylcarbonyl radicals or the alkyl radical is a linear or branched residue having from 1 to 8 carbon atoms, phenyl and benzyl radicals and an O- radical; and • f is a number chosen from 0 and 1.
• the X groups with cyclic amine function (s) are chosen from the X groups of formula (II) defined above in which:
• U represents -0- or -NR'-, R 'being a hydrogen atom or a methyl radical
• Z is a cyclic amine function of formula (V) where the radicals R ⁇ are methyl, the radical R ⁇ represents a hydrogen atom or a methyl radical and
• 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 ⁇ -COO-R ⁇ in which R ⁇ represents an alkylene radical, linear or branched, having 8 to 12 carbon atoms and R 4 represents an alkyl radical, linear or branched, having 1 to 6 atoms of 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 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 R6 represents a hydrogen atom, an alkyl radical, linear or branched, having 1 to 6 carbon atoms or an acyl radical
• 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:
• Y represents a monovalent radical chosen from R1, X, W and a hydrogen atom
• m is a whole or fractional number ranging from 0 to 180;
• 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;
• 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 in the range from 5 to 100; the ratio 100 m / m + p + q + 2 ⁇ 0.5; and optionally at least one of the substituents Y represents the radical W;
• t is a whole or fractional number ranging from 0 to 1.5;
• u is a whole or fractional number ranging from 0 to 5;
• polymers of formula (VI), which are preferred (so-called PL1 polymers) or very preferred (so-called PL2 polymers), are those for which:
• m is a whole or fractional number ranging from 1 to 90;
• n is a whole or fractional number ranging from 0 to 90
• the optionally mixed organopolysiloxanes of the invention can be obtained from, and this constitutes the second subject of the invention:
• the optionally mixed polyorganosiloxanes of the invention can be obtained by using: in the case of polymers containing amine function (s) only: an addition reaction (hydrosilylation), or in the case of mixed polymers with amine function (s) and compatibilizing function (s): two simultaneous or successive addition reactions (hydrosilylations), starting from: corresponding organohydrogenpolysiloxanes (H) free of group (s) X to amine function (s) Z and of function (S) W, of the ethylene unsaturated organic compound (s) at the end of the chain ( ⁇ ) from which derives (s) the (or the) group (s) X with amine function (s) Z and optionally of the ethylenically unsaturated compound (s) at the end of the chain ( ⁇ ) from which the derivative (s) are (are) derived function (s) W.
• 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 e 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-3715334. US-A-3814730, US-A-3 159601, US-A-3 159 662.
• the amounts of catalyst used are of the order of 1 to 300 parts per million, expressed as metal relative to the reaction medium.
• the amounts of reagents that can be used generally correspond to a molar ratio [( ⁇ ) + optionally ( ⁇ )] / 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.
• the crude optionally 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 reagents introduced in excess and optionally of the solvent used, by heating operated between 100 and 180 ° C under reduced pressure.
• organohydrogenopolysiloxanes (H) used for example in the preparation of linear mixed polydiorganosiloxanes of formula (VI) are those of formula:
• v is an integer or fractional number equal to m + n + p;
• organohydrogenopolysiloxanes (H) used for example in the preparation of the cyclic mixed polydiorganosiloxanes of formula (VII) are those of formula:
• w is an integer or fractional number equal to r + s + 1;
• 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:
• the reaction between an alcohol or an amino derivative of formula (XI) and a chlorosilane of formula (XII) is generally carried out in the presence of a base of tertiary aliphatic amine type, such as for example triethylamine, by 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.
• a base of tertiary aliphatic amine type such as for example triethylamine
• a inert polar solvent for example tetrahydrofuran
• the purification of the compounds ( ⁇ ) obtained is carried out according to conventional techniques such as, for example, distillation under reduced pressure and / or recrystallization from an appropriate solvent.
• the unsaturated compounds ( ⁇ ) from which the W functions are derived are compounds having ethylenic unsaturation, situated at the end of the chain, capable of reacting in hydrosilylation in the presence of a catalyst based on a platinum group metal.
• compounds ( ⁇ ) there may be mentioned, by way of example, octene-1, undecene-1, dodecene-1, tridecene-1, methyl or ethyl undecenoate.
• the optionally mixed polyorganosiloxanes according to the invention can be used as stabilizers against the oxidative and thermal light degradation of organic polymers, and this constitutes the third subject of the invention.
• organic polymers mention may be made of polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyether sulfones, polyether ketones, acrylic polymers, their copolymers and their mixtures. .
• 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.
• polyolefins and polyalkadienes such as polypropylene, high density polyethylene, linear low density polyethylene, low density polyethylene, polybutadiene, their copolymers and their mixtures.
• 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.
• compositions contain from 0.04 to 20 milliequivalents depending on the sterically hindered amine function (s) per 100 g of polymer to be stabilized.
• the stabilized polymer 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.
• 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.
• compositions can also contain all the additives and stabilizers usually used with the polymers they contain.
• stabilizers and additives can therefore be used: antioxidants such as alkylated monophenols, alkylated hydroquinones, hydroxylated diphenyl sulfides, alkylidene-bisphenols, benzylic compounds, acylamino-phenols, esters or amides (3,5-4-hydroxy-4-hydroxyphenyl) -3-propionic acid; esters of (3,5-dicyclohexyl-3,5-hydroxy-4-phenyl) -3-propionic acid; light stabilizers such as optionally substituted benzoic acid esters, acrylic esters, nickel compounds, oxalamides; phosphites and phosphonites; metal deactivators; peroxide-destroying compounds; polyamide stabilizers; nucleating agents; fillers and reinforcing agents; others 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.
• 31.45 g (0.2 mole) of 4-hydroxy-2-tetramethyl are introduced into a 250 c ⁇ reactor equipped with a central agitation system and the interior volume of which is maintained under an atmosphere of dry nitrogen.
• the medium is stirred and brought to a temperature of 65 ° C. 24.13 g (0.2 mole) of dimethyl, vinyl and chlorosilane are then poured over a period of 50 minutes and the mixture is left stirring for 3 hours at the same temperature.
• the triethylamine hydrochloride formed is filtered through a cellulosic filter and rinsed with 35 g of tetrahydrofuran. From the filtrate, the excess of triethylamine and tetrahydrofuran are firstly distilled under atmospheric pressure, then distillation is carried out under reduced pressure (4.66 ⁇ 10 2 Pa) at 90 ° C. to isolate 28 g (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).
• the product obtained is then devolatilized for 2 hours at 110 ° C under a reduced pressure of 1.33.10 2 Pa and 17 g of a clear light brown oil are recovered, the characteristics of which are as follows:
• 87.7 g are introduced into a 500 cnA reactor equipped with a central agitation system and the interior volume of which is maintained under an atmosphere of dry nitrogen.
• the medium is stirred and brought to a temperature of 57 ° C. 42.4 g (0.3 mole) of methyl, vinyl and dichlorosilane are then poured over a period of 55 minutes. The temperature of the medium goes up to 72 ° C. After the end of the casting, the mixture is left stirring for 8 hours at 60 ° C.
• the product obtained is then devolatilized for 2 hours at 180 ° C under a reduced pressure of 7.98.10 2 Pa and 25.8 g of a clear light brown oil are recovered, the characteristics of which are as follows:
• proportion of Z functions 60.6% (in moles of functions per 100 silicon atoms); proportion of function W: 32.7%.
• compositions are tested under UV A.
• the stabilization test is carried out by simply comparing the durations at the end of which there is rupture of the test specimens (D). For each composition, three test pieces are tested.

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