EP0792321A1 - Silikonzusammensetzungen mit sterisch gehinderten cyclischen aminogruppe und deren anwendungen zur stabilisierung von polymeren gegen licht und hitze - Google Patents

Silikonzusammensetzungen mit sterisch gehinderten cyclischen aminogruppe und deren anwendungen zur stabilisierung von polymeren gegen licht und hitze

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Publication number
EP0792321A1
EP0792321A1 EP95940316A EP95940316A EP0792321A1 EP 0792321 A1 EP0792321 A1 EP 0792321A1 EP 95940316 A EP95940316 A EP 95940316A EP 95940316 A EP95940316 A EP 95940316A EP 0792321 A1 EP0792321 A1 EP 0792321A1
Authority
EP
European Patent Office
Prior art keywords
radical
carbon atoms
linear
branched
chosen
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.)
Ceased
Application number
EP95940316A
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English (en)
French (fr)
Inventor
Philippe Karrer
Jean-Manuel Mas
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 EP0792321A1 publication Critical patent/EP0792321A1/de
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/38Polysiloxanes modified by chemical after-treatment
    • C08G77/382Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/544Silicon-containing compounds containing nitrogen
    • C08K5/5477Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates, in its first object, to novel 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 a purely hydrocarbon 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 a purely hydrocarbon residue of low carbon condensation, and 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.
  • 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 secondary or tertiary amine function included in a cyclic hydrocarbon chain comprising from 8 to 30 carbon atoms, in which the two cyclic carbon atoms located in the positions ⁇ and a with respect to the cyclic nitrogen atom do not have no hydrogen atom;
  • a is a number chosen from 0, 1 and 2.
  • the poiyorganosiloxane can also have at least one other motif unit of formula:
  • R 1 have the same meanings as those given above in connection with the formula (I); • the symbol W represents a monovalent group with a compatibilizing function chosen from: an alkyl radical, linear or branched, having more than 4 carbon atoms; a radical of formula -R2-COO-R3 in which R2 represents an alkylene radical, linear or branched, having 5 to 20 carbon atoms and R3 represents an alkyl radical, linear or branched, having 1 to 12 carbon atoms; a radical of formula
  • R 4 represents an alkylene radical, linear or branched, having from 3 to 15 carbon atoms
  • R5 represents an alkylene radical, linear or branched, having from 1 to 3 carbon atoms
  • c is a number from 0 to 10
  • R6 represents a hydrogen atom, a linear or branched alkyl radical having from 1 to 12 carbon atoms or an acyl radical -CO-R 7 where R 7 represents a linear or branched alkyl radical having from 1 to 11 carbon atoms;
  • b is a number chosen from 0, 1 and 2.
  • siloxyl unit (s) of the poiyorganosiloxane 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 (II) and (III).
  • polyorganosiloxane resins consist of at least two different types of siloxy units, namely "M” (R3SiO ⁇ 2) and “T” units and possibly “D” units (R2Si ⁇ 2 / 2) l; e ratio number of units “M” / number of units “Q” and / or “T” is generally between 4/1 and 0.5 / 1, and the ratio number of units “D” / number of units “Q” and / or “T” is generally between 0 100/1.
  • the numbers of the units of formulas (I), and optionally (II) and (III) 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 radicals R 1 are: methyl, ethyl, n-propyl, isopropyl, n-butyl; more preferably, at least 80 mol% of the radicals R * l are methyls.
  • amino functions Z equipped with the ball joint A (that is to say the monovalent groups X), which are preferred, are chosen from the groups of formula:
  • A represents a divalent residue, having from 1 to 10 carbon atoms, chosen from the residues:
  • R 1 1 and R 1 ⁇ are chosen from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 3 carbon atoms, phenyl and benzyl; • to and A2 representing an alkylene radical, linear or branched, having from 2 to 10 carbon atoms where the 2 free valences are not carried by the same carbon atom, or a radical of formula:
  • R 1 3 which may be identical to the symbol R 14 , represents an alkylene radical, linear or branched, having 2 to 4 carbon atoms, the symbol R 14 represents an alkylene radical, linear or branched, having 1 to 2 atoms carbon, and g is a number 0 or 1; • R ⁇ is chosen from a hydrogen atom and a hydroxyl group;
  • radicals R ⁇ 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 1 0 is chosen from a hydrogen atom, alkyl radicals, linear or branched, having from 1 to 12 carbon atoms, alkyl carbonyl radicals or the alkyl radical is a linear or branched residue having from 1 to 8 atoms carbon, phenyl and benzyl radicals and an O- radical; and
  • f is a number chosen from 0 and 1;
  • the symbol R ⁇ is a hydroxyl group. More preferably, the monovalent groups -A-Z are chosen from those of formula (IV) in which:
  • A represents a divalent residue, having from 1 to 8 carbon atoms, chosen from the residues:
  • AA 1 or the symbols R 1 1 and R 12 t which are identical or different, are chosen from a hydrogen atom, a methyl and a phenyl;
  • radicals R ⁇ are methyl, the radical R 1 ⁇ is a hydrogen atom or a methyl radical;
  • 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 carbon atoms ; a radical of formula -R 4 -O- (R5- ⁇ ) c -R in which R 4 represents an alkylene radical, linear or branched, having 3 to 6 carbon atoms, represents a linear or branched alkylene radical having 2 with carbon atoms, c is a number from 0 to 6 and R *> represents a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or an acyl radical -CO-R 7 where R 7 represents an alkyl radical, linear or branched, having from 1 to 5 carbon atoms.
  • 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 represent a monovalent radical chosen from R ⁇ , X, W and a hydrogen atom; • m is a whole or fractional number ranging from 0 to 180;
  • n is a whole or fractional number ranging from 0 to 180;
  • the sum m + n + p + q is in the range from 5 to 100; the ratio 100 m / m + n + p + q + 2 ⁇ 0.5; and optionally at least one of the substituents Y represents the radical W;
  • r is a whole or fractional number ranging from 1 to 9;
  • t is a whole or fractional number ranging from 0 to 0.5;
  • u is a whole or fractional number ranging from 0 to 5;
  • the polymers of formula (V), which are preferred (so-called PL1 polymers) or very preferred (so-called PL2 polymers), are those for which: the symbols Y represent R 1 ; m is an integer or fraction 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 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 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 different from the previous ratio; • the radicals R 1 , X and W simultaneously have the preferred definitions (in the case of polymers PL1) or the more preferred
  • polymers of formula (VI), which are preferred (so-called PC1 polymers) or very preferred (so-called PC2 polymers), are those for which:
  • r is a whole or fractional number ranging from 1 to 4.5;
  • t is a whole or fractional number 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 polymers of formula (V), which are especially suitable (so-called PLS1 polymers) or very well (so-called PLS2 polymers), are the polymers PL1 or PL defined above for which the symbol n is a number ranging from 1 to 90 .
  • the polymers of formula (VI), which are especially suitable (so-called PCS1 polymers) or very well (so-called PCS2 polymers), are the PC1 or PC2 polymers defined above for which the symbol s is a number ranging from 1 to 4 , 5.
  • 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 the Z functions equipped (s) ) of the ball joint A and W, of the ethylenically unsaturated organic compound (s) at the end of the chain ( ⁇ ) from which the function (s) are (are) derived Z fitted with ball joint A and optionally with ethylenically unsaturated compound (s) at the end of the chain ( ⁇ ) from which the W function (s) derive (s).
  • organohydrogenpolysiloxanes (H) free of the Z functions equipped (s) ) of the ball joint A and W of the ethylenically unsaturated organic
  • hydrosilylation reactions can be carried out at a temperature of the order of 20 to 200 ° C, preferably of the order of 60 to 120 ° C, in the presence of a catalyst based on a metal from the group of platinum; mention may be made in particular of the platinum derivatives and complexes described in US-A-3715334, US-A-3814730, US-A-3 159601, US-A-3 159662.
  • 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 olefinic unsaturation capable of reacting with (H) by hydrosilylation we will consider as elementary entity the olefinic unsaturation capable of reacting with (H) by hydrosilylation.
  • the olefinic unsaturation capable of reacting with (H) by hydrosilylation we will consider as elementary entity the olefinic unsaturation capable of reacting with (H) by hydrosilylation.
  • the amounts of reagents that can be used generally correspond to a molar ratio [( ⁇ ) + 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.
  • 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 (V) are those of formula:
  • organohydrogenopolysiloxanes (H) used for example in the preparation of the cyclic mixed polydiorganosiloxanes of formula (VI) are those of formula:
  • organohydrogenpolysiloxanes (H) of formulas (VII) and (VIII) are known in the literature and, for some, they are commercially available.
  • R 15 represents the radical, from which the A2 residue is derived, which has 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; and the symbols R ⁇ , R 1 ⁇ and f have the general or preferential meanings given above with regard to formula (IV).
  • R 1 ⁇ is a hydrogen atom or a methyl radical.
  • the compounds of formula 1 are known in the literature and they can be prepared, according to the procedure described by D. COLLUM et al., J. Am. Chem. Soc. 113 (1991) pages 9575 and following, by carrying out a WITTIG-type reaction between tetramethyl-2,2,6,6 or pentamethyl-1, 2,2,6,6 piperidinone and the reagent
  • 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, 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 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. .
  • 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.
  • 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 poiyorganosiloxane 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 polymeric compositions according to the invention contain from 0.20 to 4 milliequivalents depending on the sterically hindered amine function (s) per 100 g of polymer.
  • the stabilized polymer compositions contain from 0.01% to 5% by weight of poiyorganosiloxane 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 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.
  • the mixture is left to return to ambient temperature and is left for another 1 hour 30 minutes with stirring.
  • 50 g of distilled water and then 110 g of a 10% hydrochloric acid solutio (0.3 mol) are introduced into the dropping funnel.
  • Two extractions of the reaction medium are carried out with 2 x 400 cm 3 of distilled water and all of the aqueous phases are combined.
  • aqueous phase On this aqueous phase four extractions are made with 4 x 250 cm 3 of diethyl ether.
  • the aqueous phase is transferred to a 2000 cm 3 reactor and 35 g of an aqueous sodium hydroxide solution at 40% by weight (0.35 mol) are added with vigorous stirring; an organic phase separates from the medium.
  • the two phases are separated and 3 extractions of the aqueous phase are carried out with 3 x 250 cm 3 of diethyl ether. All of the organic phases are dried over sodium sulfate. It is filtered and then most of the diethyl ether is removed on a rotary evaporator. This highly concentrated medium is then distilled under vacuum using a vigorous column 8 cm high (the product distills at 29 ° C under 5.32.1 O ⁇ Pa).
  • the medium After having poured the oil with hydrogenosilyl functions, the medium is left to react for 23 hours at 90 ° C. During this period, two more introductions of 5.4 nm 3 of Karstedt catalyst are carried out. At the end of this time, the transformation rate of the Si-H functions is 80% by mole.
  • 35.08 g (0.191 mole) of 98% pure triacetone amine are introduced into the dropping funnel and dissolved with 380 cm 3 of anhydrous ether.
  • a bowl of water at room temperature (23 ° C) is placed under the pentacol and the casting is carried out over a period of 1 hour 30 minutes.
  • the mixture is then left stirring for 1 hour, then the reaction medium is poured slowly over 600 cm 3 (0 mole) of an aqueous solution of hydrochloric acid at 1 mole per liter.
  • the organic phase is then separated from the aqueous phase; the aqueous phase is extracted twice with 200 cm 3 of ethyl acetate, then 85 g of potassium hydroxide are loaded into the aqueous phase. A gelation of the magnesium salts is observed.
  • the aqueous pha is then extracted 5 times with 1200 cm 3 of ethyl acetate, then the organic phases are combined and made alkaline with potassium hydroxide pellets in 50 cm of water until basicity persists.
  • the organic phase is then separated and dried over anhydrous sodium sulfate, then it is concentrated on a rotary evaporator.
  • Polypropylene ELTEX® P HV001P (grade 10) 100 g 100 q
  • Stabilizer S1 according to Example 1, part 2) 0.2 g containing 141.6 meq in amino functions for - 100 q of stabilizer
  • CHIMASORB 944 (see formula below), containing 341 meq in functions - 0.2 g piperidinyls per 100 g of stabilizer
  • compositions are transformed, under identical operating conditions, to yield films 200 ⁇ m thick.
  • the film based on polypropylene stabilized with S1 from the composition (example 3) and the film based on polypropylene stabilized with S2 from the composition b (test b) are subjected to the same UV radiation exposure.
  • the aging of the films is monitored by infrared spectrometry.
  • the time of exposure T to UV rays is measured which is necessary for the absorbance in infrared spectrometry of the carbonyl band (at 1720 cm -1 ) resulting from the oxidation to be equal to the absorbance of a infrared reference band (CH2 band at 2722 cm ' 1 ); in other words, the time T necessary to have in each case a degree of photooxidation is measured such that:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)
EP95940316A 1994-11-18 1995-11-15 Silikonzusammensetzungen mit sterisch gehinderten cyclischen aminogruppe und deren anwendungen zur stabilisierung von polymeren gegen licht und hitze Ceased EP0792321A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9414055A FR2727122B1 (fr) 1994-11-18 1994-11-18 Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
FR9414055 1994-11-18
PCT/FR1995/001503 WO1996016124A1 (fr) 1994-11-18 1995-11-15 Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres

Publications (1)

Publication Number Publication Date
EP0792321A1 true EP0792321A1 (de) 1997-09-03

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EP95940316A Ceased EP0792321A1 (de) 1994-11-18 1995-11-15 Silikonzusammensetzungen mit sterisch gehinderten cyclischen aminogruppe und deren anwendungen zur stabilisierung von polymeren gegen licht und hitze

Country Status (11)

Country Link
EP (1) EP0792321A1 (de)
JP (1) JPH10509758A (de)
AR (1) AR000254A1 (de)
AU (1) AU4180496A (de)
BR (1) BR9510398A (de)
CA (1) CA2207110A1 (de)
FR (1) FR2727122B1 (de)
IL (1) IL116029A0 (de)
TR (1) TR199501439A2 (de)
WO (1) WO1996016124A1 (de)
ZA (1) ZA959790B (de)

Families Citing this family (2)

* 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
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE68928836T2 (de) * 1988-04-14 1999-03-11 Kimberly-Clark Corp., Neenah, Wis. Oberflächen-modifizierte, schmelz-extrusionsfähige thermoplastische Zusammensetzung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9616124A1 *

Also Published As

Publication number Publication date
IL116029A0 (en) 1996-01-31
WO1996016124A1 (fr) 1996-05-30
FR2727122B1 (fr) 1997-01-03
JPH10509758A (ja) 1998-09-22
BR9510398A (pt) 1997-12-23
TR199501439A2 (tr) 1996-06-21
AU4180496A (en) 1996-06-17
CA2207110A1 (fr) 1996-05-30
ZA959790B (en) 1996-05-29
AR000254A1 (es) 1997-06-18
FR2727122A1 (fr) 1996-05-24

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