EP0792315A1 - Composes silicones a fonctions amines cycliques steriquement encombrees et a fonctions compatibilisantes et leur utilisation dans la stabilisation lumiere et thermique des polymeres - Google Patents

Composes silicones a fonctions amines cycliques steriquement encombrees et a fonctions compatibilisantes et leur utilisation dans la stabilisation lumiere et thermique des polymeres

Info

Publication number
EP0792315A1
EP0792315A1 EP95939339A EP95939339A EP0792315A1 EP 0792315 A1 EP0792315 A1 EP 0792315A1 EP 95939339 A EP95939339 A EP 95939339A EP 95939339 A EP95939339 A EP 95939339A EP 0792315 A1 EP0792315 A1 EP 0792315A1
Authority
EP
European Patent Office
Prior art keywords
radical
linear
branched
carbon atoms
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95939339A
Other languages
German (de)
English (en)
French (fr)
Inventor
Philippe Karrer
Gérard Mignani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0792315A1 publication Critical patent/EP0792315A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen

Definitions

  • the present invention relates, in its first object, to new mixed silicone compounds comprising in their structure sterically hindered cyclic amine functions linked to silicon atoms by Si-OC or Si-alkylenecarbonyloxy-C bonds, and other functions linked to silicon by compatibilizing Si-C bonds. 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.
  • UV ultra-violet
  • This degradation is generally limited by the introduction into the polymer of small amounts of stabilizing agents.
  • stabilizing agents include sterically hindered amines, in particular tetramethyl-2,2,6,6 piperidines, are currently among the most effective.
  • organopolysiloxanes which carry sterically hindered piperidinyl functions of which the piperidinyl group can be linked to the silicon atom by a Si-OC bond (cf. in particular EP-A-0-343 717 and EP-A-0 358 190) or a Si-alkylene carbonyloxy-C bond (cf. in particular EP -A-0 358 190, EP-A-0 388 321 and EP-A-0 491 659).
  • the Applicant has found new mixed polyorganosiloxanes carrying a share of sterically hindered amine function (s) linked to silicon by a single Si-OC bond or Si-alkylene carboxy-C, and on the other hand of particular function (s) with compatibilizing action linked to silicon by an Si-C bond, which are endowed with useful properties for improving the resistance of polymers against their degradation under the effect of UV radiation, oxygen in the air and heat.
  • the present invention relates in its first object to a polyorganosiloxane comprising per molecule at least 3 siloxy units, of which: - at least one 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;
  • A is a divalent radical chosen from an oxygen atom and a radical of formula -CH2-CHR2-COO- with R ⁇ being a hydrogen atom or an alkyl radical, linear or branched having from 1 to 3 carbon atoms , the free valence carried by the carbon atom being linked to the silicon 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 cyclic hydrocarbon chain comprising from 8 to 30 carbon atoms, in which the two atoms cyclic carbon located in the ⁇ and ⁇ positions with respect to the cyclic nitrogen atom do not contain a hydrogen atom;
  • a is a number chosen from 0, 1 and 2;
  • 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 10 carbon atoms; a radical of formula -R ⁇ -COO-R ⁇ in which R3 represents an alkylene radical, linear or branched, having 5 to 20 carbon atoms and R 4 represents an alkyl radical, linear or branched, having 1 to 12 atoms of carbon ; a radical of formula
  • R 5 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
  • R 7 represents a hydrogen atom, a linear or branched alkyl radical having from 1 to 12 carbon atoms or an acyl radical -CO-R ⁇
  • 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 polyorganosiloxane comprises, optionally in addition, at least one other siloxyl unit of 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 (II) and (III).
  • amino functions the monovalent Z groups not equipped with the ball joint A by means of which they are linked to the silicon atoms
  • - "compatibilizing functions” the monovalent groups W which are directly linked to the silicon atoms (in this case, Si-C bonds are formed);
  • the mixed polyorganosiloxanes according to the invention can therefore have a linear, cyclic, branched structure (resin) or a mixture of these structures.
  • these may optionally have up to 50 mol% of branching ["T" (RSi ⁇ 3 / 2) and / or "Q" type units
  • 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 1 are methyls.
  • the preferred carboxylate patella is chosen from the divalent radicals -CH2-CH2- COO- and -CH 2 -CH (CH 3 ) -COO-.
  • the preferred amino functions Z are chosen from amino, secondary or tertiary functions, included in a cyclic hydrocarbon chain, of formula:
  • radicals R 9 identical or different from one another, are chosen from alkyl radicals, linear or branched, having from 1 to 3 carbon atoms, phenyl and benzyl,
  • R 10 is chosen from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 12 carbon atoms, alkylcarbonyl radicals in which the alkyl residue is a linear or branched residue having from 1 to 8 carbon atoms, phenyl and benzyl radicals and an O- radical;
  • the amino functions Z are chosen from those of formula (IV) in which the radicals R 9 are methyl, the radical R 1 0 represents a hydrogen atom or a methyl radical and h is a number equal to 1.
  • the preferred compatibilizing functions W are chosen: from an alkyl radical, linear or branched, having 11 to 30 carbon atoms; a radical of formula -R3-COO-R 4 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 5 -O- (R6-O) c -R 7 in which R 5 represents an alkylene radical, linear or branched, having 9 to 12 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
  • the compatibilizing functions W are chosen from the radicals n-undecyl, n-dodecyl, n-tridecyl, methyl or ethyl decamethylene carboxylate.
  • the present invention taken in its first object, aims even more precisely:
  • R 1 , X and W have the general meanings given above with regard to the formulas (I) and (II); the symbols Y represents a monovalent radical chosen from R 1 , X, W and a hydrogen atom; m is an integer or fractional number ranging from 0 to 180; n is an integer or fraction ranging from 0 to 180; p is an integer or fraction ranging from 0 to 10; q is an integer or fraction ranging from 0 to 100; with the conditions under which:
  • 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;
  • 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;
  • At least one of the substituents Y represents the radical W; the sum m + n + p + q is in the range from 5 to 100; and the ratio 100 m / m + n + p + q + 2 ⁇ 0.5; and
  • r is a whole or fractional number ranging from 1 to 9;
  • u is a whole or fractional number ranging from 0 to 5;
  • the polymers of formula (V) which are preferred (so-called PL1 polymers) or very preferred (so-called PL2 polymers), are those for which: * according to a first method: the symbols Y represent R ⁇ ; m is an integer or fraction 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 an integer or fraction 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 being identical or different from the previous ratio; “The radicals R 1 , X and W simultaneously have the preferred definitions (in the case of polymers PL1) or more preferred definitions (in the
  • 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 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 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 mixed organopolysiloxanes of the invention with an oxygen ball can be obtained from, and this constitutes a first modality of the second subject of the invention: • of the corresponding organohydrogenopolysiloxanes (H), which are free of function (s) Z amine (s) equipped with the oxygen patella and function (s)
  • the mixed polyorganosiloxanes of the invention with an oxygen ball joint can be obtained by simultaneous dehydrogenocondensation and addition (hydrosilylation) reaction or, preferably, by successive dehydrogenocondensation and addition (hydrosilylation) reactions, this from: corresponding organohydrogenopolysiloxanes (H) free of the Z functions equipped with the oxygen patella and W, of the organic compound (s) hydroxylated (s) ( ⁇ ) from which derive (s) the Z function (s) equipped with the oxygen patella, and ethylenically unsaturated compound (s) at the end of the chain ( ⁇ ) from which the W function (s) are derived.
  • dehydrogenocondensation and 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 metal-based catalyst.
  • platinum group mention may be made in particular of the platinum derivatives and complexes described in US-A-3,715,334, US-A-3,814,730, US-A-3,159,601, US-A-3,159,662.
  • the amounts of catalyst used are of the order of 1 to 300 parts per million, expressed as metal relative to the reaction medium.
  • mole of ( ⁇ ) ' we will consider as elementary entity the OH function capable of reacting with (H) by dehydrogenocondensation.
  • mole of ( ⁇ ) we will consider as entity elementary olefinic unsaturation capable of reacting with (H) by hydrosilylation.
  • the quantities of reagents which can be used generally correspond to a molar ratio [( ⁇ ) + ( ⁇ )] / SiH [of (H)] which is on the order of 1 to 5, preferably on the order of 1 to 2.
  • the dehydrogenocondensation and hydrosilylation reactions can take place in bulk or, preferably, within a volatile organic solvent such as toluene, xylene, methylcyclohexane, tetrahydrofuran, heptane, octane or the 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.
  • a volatile organic solvent such as toluene, xylene, methylcyclohexane, tetrahydrofuran, heptane, octane or the 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 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 optionally 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:
  • 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 (VI) are those of formula:
  • w is an integer or fractional number equal to r + s + t;
  • organohydrogenpolysiloxanes (H) of formulas (VII) and (VIII) are known in the literature and, for some, they are commercially available.
  • hydroxylated organic compounds ( ⁇ ), from which the Z functions equipped with the oxygen ball joint are derived (or also: from which the monovalent groups X are derived), are preferably those of formula:
  • the unsaturated compounds ( ⁇ ), 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.
  • compounds ( ⁇ ) there may be mentioned as examples: undecene-1, dodecene-1, tridecene-1, methyl or ethyl undeceneate.
  • the mixed organopolysiloxanes of the invention with a carboxylate patella can be obtained from, and this contributes to a second modality of the second object of the invention,:
  • the mixed polyorganosiloxanes of the invention with a carboxylate ball joint can be obtained by reaction of simultaneous or successive additions (hydrosilylations), this from: corresponding organohydrogenpolysilanes (H) free from the Z functions equipped with the ball joint carboxylate and W , of the ethylenically unsaturated organic compound (s) at the end of the chain ( ⁇ ") from which the Z function (s) equipped with the carboxylate patella are derived , and (or) ethylenically unsaturated compound (s) at the end of the chain ( ⁇ ) from which the W function (s) are derived.
  • hydrosilylations this from: corresponding organohydrogenpolysilanes (H) free from the Z functions equipped with the ball joint carboxylate and W , of the ethylenically unsaturated organic compound (s) at the end of the chain ( ⁇ ") from which the Z function (s) equipped with the carboxylate patella are derived , and (
  • Said simultaneous or successive 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 the dehydrogenocondensation and additions to the preparation of mixed polyorganosiloxanes with oxygen ball joints.
  • said simultaneous or successive hydrosilylation reactions are carried out in the presence of an agent for inhibiting radical polymerization chosen in particular from: alkylated or aikoxylated monophenols [such as, for example, para-methoxyphenol, bis (ditertiobutyl-3, 5 4-hydroxyphenyDmethane and their mixtures].
  • the amount by weight of such an agent is generally between 0.001% and 0J%.
  • the molar ratio [( ⁇ ') + ( ⁇ )] / SiH [of (H))] also varies between 1 and 5 and, preferably between 1 and 2.
  • the unsaturated organic compounds ( ⁇ ') from which the Z functions equipped with the carboxylate ball joint are derived are preferably those of formula:
  • ⁇ ′ examples: tetramethyl-2,2,6,6 piperidinyl-4 (meth) acrylate, 1,2-pentamethyl-1,2,6,6 (meth) acrylate , 6 piperidinyl-4.
  • These compounds are known in the literature (cf. in particular W. LAU et al., J. Polym. Sci. Part A: Polym. Chem., 30 (1992) pages 983 et seq.) And they can be prepared by reaction of piperidinol compounds on methyl (meth) acrylate in the presence of a catalyst based on a metal alcoholate.
  • the 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.
  • these said compounds can be easily adaptable 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 mixed polyorganosiloxane compound.
  • compositions contain from 0.04 to 20 milliequivalents depending on the sterically hindered amine (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 mixed polyorganosiloxane compound relative to the polymer.
  • the addition of the 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 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; 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.
  • binder for paints, varnishes, glues or cements.
  • Example of preparation of a mixed or ⁇ anooolvsiloxan ⁇ with an oxygen ball joint In a 250 cm 3 reactor, equipped with a central stirring system and the internal volume of which is maintained under an atmosphere of dry nitrogen, 25 g (0J59 mole) are introduced. ) of 4,2-hydroxy-2,2,6,6 tetramethyl piperidine, 100 cm 3 of dry toluene, 0.01 g of sodium acetate and 22 nm 3 (or ⁇ l) of a solution in divinyltetramethyldisiloxane a platinum complex at 12% by weight of platinum ligated with divinyltetramethyldisiloxane (Karstedt catalyst).
  • reaction medium is brought to 100 ° C., then 20 g of a polymethylhydrogenosiloxane oil (ie 0.316 mole of Si-H functions) are poured over a period of 3 hours, the characteristics of which are as follows:
  • the reaction medium After pouring the oil with hydrogenosilyl functions in 3 hours, the reaction medium is left to react at 100 ° C. for 24 hours. At the end of this time, the transformation rate of the hydrogenosilyl functions is 34% (in moles).
  • proportion of Z functions 38.5% (in moles of functions per 100 silicon atoms); proportion of W functions: 57.5%.
  • Example 2 In a reactor of 250 cm 3, equipped as in Example 1 was charged with 27.3 g (0J 59 mol) of hydroxy-4-pentamethyl-1, 2,2,6,6 and 100 cm 3 of toluene containing 0.012 g of sodium acetate. 60 nm 3 (or ⁇ l) of the Karstedt catalyst solution described in Example 1 are added in two batches.
  • the reaction medium is brought to 90 ° C., then 20 g of the polymethylhydrogenosiloxane oil used in Example 1 are poured in gradually over a period of 3 hours (ie 0.316 mol of Si-H functions).
  • 0.6 g (0.024 mole) of magnesium is introduced into a 250 cm 3 reactor, fitted with a central mechanical stirrer, a thermometer and a thermally insulated distillation column 45 cm in height, and the nitrogen reactor sky; then 10 cm 3 of dry methanol and 0.5 g of dibromo-1, 2 ethane are introduced.
  • the reaction medium is brought to 45 ° C., there is formation of hydrogen and magnesium dimethoxylate.
  • 40 g (0.25 mole) of 4-hydroxy-2,2,6,6 piperidine-hydroxy then 142 g (1.42 mole) of methyl methacrylate (title mass: 99.8%), and the reaction medium is brought to its reflux temperature.
  • the methanol formed distills.
  • the reaction medium is allowed to cool to room temperature (23 ° C.), then it is poured into 660 cm 3 of water.
  • the mixture obtained is filtered through “kieselguhr” type earth available commercially under the trademark Clarcel DIT 2R.
  • the two phases are separated and the aqueous phase is extracted with 3 times 200 cm 3 of methyl methacrylate.
  • the organic medium is concentrated using a rotary evaporator; 55.3 g of a light yellow solid are thus recovered (yield of isolated product: 88.6% by weight relative to the quantity of piperidinol used).
  • the solid product obtained is recrystallized using a mixture of 20 cm 3 of acetone with 10 cm 3 of water. After drying at room temperature (23 ° C.) at 1.33 ⁇ 10 2 Pa, 49J g of white solid are recovered, the melting point of which is 60 ° C. (measured by DSC analysis). The yield of recrystallized product is 80%. NMR and infrared analyzes confirm the structure of the expected product.
  • a precipitate is formed which is fittrated, then the organic phase is dried over anhydrous sodium sulfate. Filtered again, then the medium is concentrated by evaporation of methyl methacrylate on a rotary evaporator (80 ° C under 7.98.10 Pa). From this concentrated medium, 56.7 g (0.233 mole) of 1,2-pentamethyl methacrylate are extracted by distillation under reduced pressure (75 ° C. under 0J J 0 2 Pa) in a vigorous column 45 cm high, 2,6,6 piperidinyl-4 98% pure (mass).
  • the contents of the reactor are brought to 108 ° C. and the overhead of the reactor is inerted with nitrogen. It is then poured simultaneously in 80 minutes and using two separate syringes:
  • the degree of transformation of the hydrogenosilyl functions is 71% (ie a degree of transformation of the pentamethyl piperidinyl methacrylate functions of 93%); 8 g (0.0474 mole) of 95% by weight dodecene-1 are then injected in 20 minutes while maintaining the temperature at 108 ° O 4 hours after the end of the injection of dodecene, the rate of transformation of the hydrogenosilyl functions is 98.2%.
  • the contents of the reactor are brought to 110 ° C. and the sky is inerted with nitrogen.
  • compositions b and c are tested under UV B, the compositions d and e under UV A.
  • the control composition a is tested under UV A and UV B to serve as comparison.
  • degradation is monitored by Infra-Red spectrometry. We measure every two days, until the film breaks, the increase in absorbance (in abbreviation A2) of the carbonyl band at 1720 cm -1 resulting from the degradation of the PP and we reduce this absorbance absorbance (abbreviation A1) of a band of an inert group (methylene at 2722 cm'1).
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)
  • Lock And Its Accessories (AREA)
EP95939339A 1994-11-18 1995-11-15 Composes silicones a fonctions amines cycliques steriquement encombrees et a fonctions compatibilisantes et leur utilisation dans la stabilisation lumiere et thermique des polymeres Withdrawn EP0792315A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9414053A FR2727120B1 (fr) 1994-11-18 1994-11-18 Nouveaux composes silicones mixtes a fonctions amines cycliques steriquement encombrees et a fonctions compatibilisantes et leur utilisation dans la stabilisation lumiere et thermique des polymeres
FR9414053 1994-11-18
PCT/FR1995/001501 WO1996016110A1 (fr) 1994-11-18 1995-11-15 Composes silicones a fonctions amines cycliques steriquement encombrees et a fonctions compatibilisantes et leur utilisation dans la stabilisation lumiere et thermique des polymeres

Publications (1)

Publication Number Publication Date
EP0792315A1 true EP0792315A1 (fr) 1997-09-03

Family

ID=9469085

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95939339A Withdrawn EP0792315A1 (fr) 1994-11-18 1995-11-15 Composes silicones a fonctions amines cycliques steriquement encombrees et a fonctions compatibilisantes et leur utilisation dans la stabilisation lumiere et thermique des polymeres

Country Status (14)

Country Link
EP (1) EP0792315A1 (ja)
JP (1) JPH10509756A (ja)
AR (1) AR000252A1 (ja)
AT (1) ATE184070T1 (ja)
AU (1) AU4120396A (ja)
BR (1) BR9510401A (ja)
CA (1) CA2207112A1 (ja)
ES (1) ES2137547T3 (ja)
FR (1) FR2727120B1 (ja)
IL (1) IL116027A0 (ja)
TR (1) TR199501440A2 (ja)
TW (1) TW340857B (ja)
WO (1) WO1996016110A1 (ja)
ZA (1) ZA959788B (ja)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2735481B1 (fr) * 1995-06-16 1997-08-22 Rhone Poulenc Chimie Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
US7651642B2 (en) 2001-07-23 2010-01-26 Momentive Performance Materials Inc. Stabilized polyorganosiloxane composition
FR2921663A1 (fr) * 2007-10-02 2009-04-03 Bluestar Silicones France Soc Polyorganosiloxanes a fonction piperidine depourvus de toxicite par contact cutane et utilisation de ces derniers dans des compositions cosmetiques
CN114854023A (zh) * 2022-05-07 2022-08-05 宿迁联宏新材料有限公司 一种聚烯烃树脂用光稳定剂及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4177186A (en) * 1975-05-28 1979-12-04 Ciba-Geigy Corporation Stabilization of light-sensitive polymers
US4927898A (en) * 1988-09-06 1990-05-22 Union Carbide Chemicals And Plastics Company Inc. Polysiloxanes with sterically hindered heterocyclic moiety
FR2642764B1 (fr) * 1989-02-03 1993-05-28 Rhone Poulenc Chimie Nouveaux composes a fonction piperidinyle et leur application dans la photostabilisation des polymeres
JPH0649350A (ja) * 1992-07-28 1994-02-22 Nippon G Ii Plast Kk 耐光性の改善されたポリフェニレンエーテル系樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9616110A1 *

Also Published As

Publication number Publication date
ATE184070T1 (de) 1999-09-15
TW340857B (en) 1998-09-21
BR9510401A (pt) 1997-12-23
WO1996016110A1 (fr) 1996-05-30
JPH10509756A (ja) 1998-09-22
IL116027A0 (en) 1996-01-31
FR2727120B1 (fr) 1997-01-03
FR2727120A1 (fr) 1996-05-24
CA2207112A1 (fr) 1996-05-30
AR000252A1 (es) 1997-06-18
ZA959788B (en) 1996-05-29
AU4120396A (en) 1996-06-17
ES2137547T3 (es) 1999-12-16
TR199501440A2 (tr) 1996-06-21

Similar Documents

Publication Publication Date Title
CA2007931C (fr) Nouveaux composes a fonction piperidinyle et leur application dans la photostabilisation des polymeres
EP0792322B1 (fr) Polyorganosiloxanes fonctionnalises et l'un de leurs procedes de preparation
BE1012526A5 (fr) Melange stabilisant, composition le contenant et procede l'utilisant pour stabiliser une matiere organique.
BE1011937A3 (fr) Compose stabilisant, composition le contenant et procede l'utilisant.
FR2727119A1 (fr) Polyorganosiloxanes fonctionnalises et l'un de leurs procedes de preparation
FR2727420A1 (fr) Composes de piperidine contenant des groupes silicies, composition les contenant et procede les utlisant pour stabiliser des matieres organiques
FR2702479A1 (fr) Nouveaux composés de type polyméthyl-pipéridine contenant des groupes silane et appropriés en tant que stabilisants de matières organiques.
EP0797613A2 (fr) Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
EP0748849A1 (fr) Composés silicones à fonctions amines cycliques stériquement encombrées, utiles pour stabilisation lumière et thermique des polymères
EP0792315A1 (fr) Composes silicones a fonctions amines cycliques steriquement encombrees et a fonctions compatibilisantes et leur utilisation dans la stabilisation lumiere et thermique des polymeres
BE1009032A3 (fr) Nouveaux derives de 2,2,6,6-tetramethylpiperidine utilisables comme agents stabilisants a la lumiere, a la chaleur et a l'oxydation pour des materiaux organiques.
FR2476104A1 (fr) Compositions de polyolefine stabilisees contre la radiation ultraviolette avec des amines a chaine ouverte, comportant un encombrement sterique
FR2727122A1 (fr) Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
WO1996016127A1 (fr) Nouveaux composes silicones a fonctions amines lineaires steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
FR2549483A1 (fr) Composes polymeres contenant des radicaux de piperidine et compositions de polymeres les contenant
FR2727419A1 (fr) Composes de piperidine et de triazine contenant des groupes silicies, composition les contenant et procede les utilisant pour stabiliser des matieres organiques
BE1011936A3 (fr) Produits et melanges stabilisants, composition les contenant et procede les utilisant.
EP0325881A2 (fr) Diorganopolysiloxane à fonction benzylidène-3 camphre
FR2611960A1 (fr) Procede de preparation de diamines aromatiques a groupement diorganopolysiloxane
FR2653768A1 (fr) Nouveaux composes a motif tetramethylpiperidinyle.
FR2620715A1 (fr) Compositions de resines synthetiques ayant un comportement au feu ameliore renfermant une polyolefine, un additif ignifugeant phosphore associe a des composes bromes et oxyde d'antimoine ou bien associe ou combine avec un compose azote et eventuellement d'autres additifs et/ou charges et objets conformes produits a partir de ces compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970517

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT DE DK ES FR GB IE IT NL

17Q First examination report despatched

Effective date: 19970910

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHODIA CHIMIE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19990120