EP1149123B1 - Peroxidierte polyorganosiloxane, verfahren zu deren herstellung und deren anwendung als bleichmittel in dentalmasse - Google Patents

Peroxidierte polyorganosiloxane, verfahren zu deren herstellung und deren anwendung als bleichmittel in dentalmasse Download PDF

Info

Publication number
EP1149123B1
EP1149123B1 EP99973300A EP99973300A EP1149123B1 EP 1149123 B1 EP1149123 B1 EP 1149123B1 EP 99973300 A EP99973300 A EP 99973300A EP 99973300 A EP99973300 A EP 99973300A EP 1149123 B1 EP1149123 B1 EP 1149123B1
Authority
EP
European Patent Office
Prior art keywords
fpo
functional groups
pos
polyorganosiloxanes
functional
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.)
Expired - Lifetime
Application number
EP99973300A
Other languages
English (en)
French (fr)
Other versions
EP1149123A1 (de
Inventor
Adrien Dromard
Gérard Mignani
Lucile Gambut
Frédéric DALLEMER
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
Rhodia Chimie SAS
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 Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1149123A1 publication Critical patent/EP1149123A1/de
Application granted granted Critical
Publication of EP1149123B1 publication Critical patent/EP1149123B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the field of the invention is that of applicable peroxidized systems especially in money laundering.
  • the oxidizing properties of these systems are more particularly appreciated in teeth whitening applications (e.g. toothpaste).
  • peroxidized systems referred to in the context of this presentation are functionalized polymers.
  • the present invention relates to perorganized polyorganosiloxanes (POS) thus as one of their preparation processes.
  • the invention also relates to silicone precursors of these POSs. peroxides.
  • the present invention includes an application aspect which comprises the use of peroxidized POSs according to the invention as active ingredient in laundering. More specifically, the invention relates to dental compositions, for example toothpastes, including peroxidized POS as a bleaching agent.
  • H 2 O 2 hydrogen peroxide
  • persalts percarbonates, perborates, calcium peroxides
  • H 2 O 2 will designate H 2 O 2 as such and its persalts.
  • the disadvantages of hydrogen peroxide are not negligible.
  • H 2 O 2 must be used in high concentration to be effective. This point is particularly troublesome given the aggressiveness of H 2 O 2 .
  • hydrogen peroxide has the disadvantage of being unstable.
  • European patent application No. 796 874 relates to a process for the preparation of polymers comprising peroxycarboxylic groups.
  • These peroxycarboxylic polymers are more specifically copolymers of N-vinylpyrolidone / maleic anhydride.
  • the hydrogen peroxide that we react with this copolymer allows the transformation of the carboxyls derived from the anhydride into peroxycarboxylic functions.
  • the performance of these copolymers peroxycarboxylates, in terms of bleaching, are not revealed by this request patent.
  • the peroxycarboxylated copolymers lack selectivity with respect to the teeth.
  • instability problems can be feared for teeth whitening applications of these copolymers.
  • PCT patent application WO 97/02 011 discloses dental oral compositions comprising conventional ingredients such as abrasives, binders, humectants, surfactants, sources of fluorine ions or other sweeteners, as well as two other essential ingredients for namely, on the one hand, an aminoalkylsilicone such as a polydimethylsiloxane comprising aminoalkyl units of the propylaminoethylamine type in the chains and at their ends and, on the other hand, a polydimethylsiloxane comprising pendant groups of polyoxyethylene and / or polyoxypropylene type and having a surfactant action.
  • an aminoalkylsilicone such as a polydimethylsiloxane comprising aminoalkyl units of the propylaminoethylamine type in the chains and at their ends and, on the other hand, a polydimethylsiloxane comprising pendant groups of polyoxyethylene and / or polyoxypropylene type and
  • This oral composition is presented as having improved anti-plaque and anti-bacterial properties, which complement excellent cleaning performance.
  • This oral composition can also comprise bleaching agents belonging to the family of inorganic peracid salts (persulfates, perborates, percarbonates and metal peroxides). These oral compositions are not satisfactory in terms of stability, toxicity, selectivity with respect to the teeth and efficacy of bleaching by oxidation.
  • Polyorganosiloxanes comprising ester groups of peracids carboxylic acids have been described in GB 897,973 and US 3,726,943; they can be useful as vulcanizing agents, as polymerization initiator, as coupling agents ...
  • Another essential objective of the invention is to provide a system for peroxidized bleaching especially for dental bleaching applications which allows to control the reactivity of the peroxide function, so as to limit as far as possible its transformation into aggressive free radicals.
  • Another essential objective of the invention is to provide a system for peroxidized bleaching usable in particular in dental bleaching and endowed with significantly improved storage stability.
  • Another essential objective of the invention is to provide a system for peroxide bleaching applied in dental bleaching (oral composition for treatment and maintenance of the teeth), having a better selectivity with respect to teeth to whiten.
  • Another essential objective of the invention is to provide an oxidizing system peroxidized, capable of being used as a controlled release system of oxidizing peroxide functions.
  • Another essential objective of the invention is to provide a process for obtaining of the aforementioned peroxidized oxidizing system, which is simple to implement and economic.
  • Another essential objective of the invention is to prescribe the use of the system peroxidized oxidant mentioned above, as a teeth whitening agent.
  • Another essential objective of the invention is to provide a composition dental with an effective, stable and selective bleaching agent.
  • these silicones functionalized with Fpo acyl peroxide are endowed with a specific affinity for the constituent materials of teeth (in hydroxyapatite) so these are selective vectors specific to route the chemical whitening functions to the teeth. It goes without saying that optimizes the efficiency of said functions. It follows that it is possible to reduce the doses, which is entirely in line with the decrease in the aggressiveness of the agent laundering.
  • these peroxide functional silicones are hydrophobic and have so the advantage of preserving the Fpo functions of water, which is an element major instability for them.
  • the new peroxidized polyorganosiloxanes with Fpo functions can be linear and / or branched and / or crosslinked polymers according to the percentage by weight of DTQ siloxyl patterns which they include.
  • Each Fpo acyl peroxide function belongs to a peroxycarboxylic acid, halide - chloride - or salt residue.
  • peroxycarboxylic residues are linked to the silicon of the POS chain by a hydrocarbon ball joint (that is to say comprising in particular carbon and hydrogen atoms), aliphatic and / or alicyclic and / or aromatic and / or heterocyclic optionally comprising one or more heteroatoms: N, O, S ..., possibly.
  • a hydrocarbon ball joint that is to say comprising in particular carbon and hydrogen atoms
  • aliphatic and / or alicyclic and / or aromatic and / or heterocyclic optionally comprising one or more heteroatoms: N, O, S ..., possibly.
  • the advantageous stabilizing action of Fstab on Fpo is a preferred characteristic of the functionalized POSs according to the invention.
  • the Fstabs are located on the functional substituents (pendant) E and / or G. Without this being limiting, it is preferable that the Fstabs are carried at least by the or the E, so as to be close to the Fpo to be stabilized. It is not forbidden to think that the stabilizing effect of Fstab is thus improved.
  • the optional functional substituents G each include, in addition to the one or more Fstab, a ball joint which ensures the connection with the silicone chain.
  • the ball joints of the substituents G are identical or different from each other, which meet the same definition as that given above for the ball joints of substituents E.
  • peroxidized POSs obtained by hydrosilylation of olefinic precursors of substituents E and G are preferred in accordance with the invention.
  • These hydrosilylation reactions can be carried out at a temperature of the order of 15 to 200 ° C, preferably of the order of 20 to 100 ° C, in the presence of a catalyst based on a metal from the group of platinum.
  • a catalyst based on a metal from the group of platinum Mention may in particular be made of the complex platinum derivatives described in US Pat. Nos. 3,715,334, 3,775,452, 3,814,730, 3,159,601, 3,159,662.
  • the quantities of platinum catalysts used are of the order of 1 to 300 parts per million, expressed as metal relative to the reaction medium.
  • the olefinic precursors used in these hydrosilylations do not comprise the acyl peroxide functions Fpo, but their non-peroxygenated forms F'po or any intermediate forms thereof. It is preferable in accordance with the invention to provide protection for the precursor functions F'po before hydrosilylation.
  • the POS grafted by hydrosilylation and carrying the F'po precursor functions are optionally purified and then subjected to an oxidation which allows the transformation of the F'po functions into Fpo functions.
  • the functional substituents E of Peroxidized POSs each include a ball joint comprising at least one pattern bicarboxylated and / or benzoxylated and / or imide.
  • the ball joint (s) of the functional substituent (s) E comprise at least one bicarboxylic motif
  • the Fpo function is obtained from an anhydride which is transformed, on the one hand, in an acyl peroxide function Fpo and, on the other hand, in an acid function Fstab carboxylic stabilization of neighboring Fpo.
  • the peroxidized POSs according to the invention are stable and have a high power whitening.
  • the present invention relates to a process for the preparation of POSs as defined above.
  • This process is characterized in that it essentially consists in oxidizing the polysiloxane precursors of the targeted peroxidized POSs.
  • This oxidation is carried out using at least one oxidant preferably chosen from the group comprising: H 2 O 2 , O 2 , O 3 and their mixtures,
  • These peroxidized POS precursors of POS are distinguished from the targeted peroxidized POS in that they comprise one or more F'po functions, Fpo precursors and consisting of: by carboxyl residues: with X 'corresponding to the same definition as that given for X above; and / or by acid anhydride residues
  • F'po functions can be final or included in a cycle.
  • the polysiloxane precursors with functional F'po can be obtained by cohydrolysis of chlorosilanes and non-alkoxysilanes functionalized and chlorosilanes or alkoxysilanes functionalized with substituents E and G.
  • the stage which follows the cohydrolysis can be a polycondensation and polymerization of hydrolysis products in the presence of diorganosiloxanes cyclic or a redistribution step in the presence of polydiorganosiloxanes.
  • the starting materials used can be hydrogenated polyorganosiloxanes which can be functionalized by reacting them according to a hydrosilylation reaction (addition with olefinic precursors of substituents E and G.). See above for more details on this hydrosilylation.
  • the polyorganosiloxane precursors carry functions F'po succinic anhydride linked to the silicon atoms by a ball joint - (CH 2 ) 3 -.
  • the precursors - POS present before the oxidation step to transform the F'po en Fpo, a molar purity ⁇ 90%, preferably ⁇ 95%.
  • this purification step is carried out by any known and appropriate method such as, for example, devolatilization or fractional precipitation in an organic solvent such as methanol.
  • the oxidizing agents could be hydrogen peroxide, oxygen, ozone and their mixtures.
  • the catalyst used can be a strong base, for example, a mineral base such as KOH or NaOH or even a strong acid, for example, a mineral acid such as H 2 SO 4 or organic such as MeSO 3 H.
  • the solvents used in these cases are, for example, ethyl acetate or Me SO 3 H.
  • the oxidizing agent is oxygen, it is possible to use a catalyst comprising Co 2+ .
  • this oxidation step can take place at temperature and pressure room.
  • the peroxidized POSs according to the invention are particularly suitable as bleaching agent and more particularly as a bleaching agent teeth, taking into account their properties of selectivity with respect to non-toxicity teeth, of controlled reactivity of the Fpo peroxide functions (limitation of the production of free radicals), non-toxicity and high efficiency at low doses.
  • the present invention also relates to a dental composition (for example an oral composition) - in particular toothpaste - characterized in that it comprises peroxygenated POSs as defined above at as a bleaching agent.
  • a dental composition for example an oral composition
  • toothpaste - characterized in that it comprises peroxygenated POSs as defined above at as a bleaching agent.
  • Example 1 preparation of a precursor - POS (B) of a peroxide POS according to the invention, this precursor being a polydimethylsiloxane with ends trimethylsilyles and carrying functional substituents of the -propyl-oxy-benzoic type
  • reaction medium After returning to ambient temperature, the reaction medium is neutralized by gradual addition over 1 h 30 min of 1 l of 36% hydrochloric acid (11 moles). The reaction medium becomes milky and it is filtered on a No. 4 frit under vacuum. A white filter cake is obtained which is washed with water (250 ml). To carry out the purification of the allyloxybenzoic acid present in the filter cake, one proceeds by recrystallization.
  • the filter cake 5 l of absolute ethanol and 750 ml of distilled water are charged into the 10 l reactor.
  • the reaction mass is brought to reflux (80 ° C.) and distilled water is gradually added until a single clear phase is obtained, namely 1.75 l of distilled water.
  • reaction mass is then transferred to a 10 l container which is cooled by ice.
  • the medium is left to recrystallize for 16 h and then filtered through a No. 4 frit under vacuum.
  • the cake is washed with distilled water (2 l used three times). Crystals are obtained which are dried under vacuum of 200 mmHg and at 70 ° C. The yield is 35%.
  • the protected product can be purified by vacuum distillation.
  • reaction medium After returning to ambient temperature, the reaction medium is filtered on a cardboard filter under pressure and then the reaction mass is returned to a single-color flask fitted with a magnetic bar.
  • the product is isolated by devolatilization at 120 ° C under vacuum of 1 mmHg.
  • the product thus isolated is deprotected by hydrolysis with distilled water (200 ml) which is poured onto the product to be deprotected in 1 hour 15 minutes and heating to 90 ° C. for 16 hours.
  • the medium becomes whitish.
  • the water is removed at 110 ° C. under a vacuum of 2 mmHg for 4 h 15 min. 58.40 g of hydrosilylated oil of structure B are then obtained.
  • the method used here is fractional precipitation. It is dissolve the grafted oil obtained in 1.3 in a hot alcohol. This alcohol can be more particularly methanol. Then the polymer is precipitated by addition water of basic pH. The operation is repeated another time. The third operation consists in hot solubilizing the silicone polymer in methanol and then adding water at acidic pH. The polymer thus purified is heated to 115 ° C. under a vacuum of 20 mmHg to remove residual water or alcohol. The product is finally placed in the oven at 100 ° C. under atmospheric pressure. A polymer of purity greater than 95% is obtained in weight.
  • Example 2 preparation of a precursor - POS (C) of a peroxide POS according to the invention, this precursor being a polydimethylsiloxane with ends trimethylsilyl and carrying functional substituents of the -propylanhydride type succinic
  • the polymer After placing the middle reaction in a single-color flask fitted with a magnetic bar, the polymer is isolated silicone grafted by devolatilizing the excess oligomer by heating to 180 ° C. under vacuum 2 mmHg. A silicone oil of structure C and of purity equal to 94% is obtained in weight.
  • Example 3 preparation of a precursor - POS (E) of a peroxide POS according to the invention, this precursor being a polydimethylsiloxane with ends trimethylsilyl and carrying functional substituents of the -propyl-succinimide type benzoic
  • EXAMPLE 5 OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS (-OO-) OF THE SUBSTITUTES E ARE INCLUDED IN PERACID CARBOXYL REMAINS FROM THE PRECURSOR POS AS EXAMPLE 2 (REMAINING ANHYDRIDES REMAINING)
  • EXAMPLE 6 OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS (-OO-) OF THE SUBSTITUTES ARE INCLUDED IN PERACID CARBOXYLIC RESIDUES FROM THE PRECURSOR POS AS EXAMPLE 2 (REMAINING ANHYDRIDES REMAINING)
  • EXAMPLE 8 OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS (-OO-) OF THE SUBSTITUTES ARE INCLUDED IN PERACID CARBOXYLIC RESIDUES FROM THE PRECURSOR POS AS EXAMPLE 2 (REMAINING ANHYDRIDES REMAINING)
  • Example 5 is reproduced with the difference that no KOH is used.
  • EXAMPLE 9 OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS (-OO-) OF THE SUBSTITUTES E ARE INCLUDED IN PERACID CARBOXYL REMAINS FROM THE PRECURSOR POS AS EXAMPLE 2 (REMAINING ANHYDRIDES REMAINING)
  • Example 6 is reproduced with the difference that the drop of KOH is replaced by a drop of H 3 PO 4 (85% in water).
  • EXAMPLE 10 OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS (-OO-) OF THE SUBSTITUTES E ARE INCLUDED IN PERACID CARBOXYLIC RESIDUES FROM THE POS PRECURSOR AS IN EXAMPLE 1 (PENDANT BENZOIC REMAINS)
  • EXAMPLE 11 EVALUATION OF THE WHITENING POWER OF THE POS PEROXIDE OF EXAMPLE 6

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Cosmetics (AREA)

Claims (12)

  1. Polyorganosiloxane (POS), enthaltend Siloxaneinheiten der folgenden Formel (I) RaEbGcSiO 4 - (a+b+c)2 wobei
    a+b+c=0 bis 3
    a, b, c = 0 bis 3
    R einem oder mehreren Resten, identisch oder verschieden, entspricht, wobei R ausgewählt ist aus einwertigen (monovalenten) Kohlenwasserstoffresten, vorzugsweise linearen, verzweigten und/oder ringförmigen Alkylen und/oder Arylen, besonders bevorzugt linearen oder verzweigten C1-C4-Alkylen und den Gruppen Phenyl, Xylyl und Tolyl;
    E einem oder mehreren einwertigen funktionellen Substituenten, identisch oder verschieden, ausgewählt aus (cyclo)aliphatischen und/oder aromatischen und/oder heterocyclischen Gruppen, die ein oder mehrere Acylperoxidfunktionen Fpo der Formel
    Figure 00350001
    tragen, wobei X H, einem Halogen, vorzugsweise Chlor, oder einem Kation entspricht, welches die Bildung eines Salzes mit einem Acylperoxidanion ermöglicht, vorzugsweise ausgewählt aus Elementen der Gruppen Ia und IIA des Periodensystems der Elemente und enthaltend gegebenenfalls jeweils ein oder mehrere Funktionen Fstab, identisch oder verschieden, welche in bezug auf Fpo stabilisierend sind und ausgewählt sind aus Funktionen, die sich über schwache Bindungen mit den Funktionen Fpo verbinden können;
    G einem oder mehreren funktionellen Substituenten, identisch oder verschieden, entspricht, die jeweils ein oder mehrere Funktionen Fstab, identisch oder verschieden, umfassen, die in bezug auf Fpo stabilisierend sind und ausgewählt sind aus Funktionen, die sich über schwache Bindungen mit den Funktionen Fpo verbinden können;
    mit der Maßgabe:
    (i) daß die Konzentration an Funktionen [Fpo], berechnet als Verhältnis Anzahl FpoGesamtanzahl an Siliciumatomen in den POS wie folgt definiert ist: Δ 0 < [Fpo] Δ vorzugsweise 0,01 ≤ [Fpo] ≤ 1,0 Δ besonders bevorzugt 0,1 ≤ [Fpo] ≤ 0,6
    (ii) daß die Konzentration in Mol-% an Siloxaneinheiten T (a+b+c = 1) und/oder Q (a+b+c = 0) wie folgt definiert ist: Δ 0 ≤ [T und/oder Q] ≤ 20 Δ vorzugsweise 0 ≤ [T und/oder Q] ≤ 10 Δ besonders bevorzugt 0 ≤ [T und/oder Q] ≤ 8.
  2. Polyorganosiloxane nach Anspruch 1, dadurch gekennzeichnet, daß in dem oder den Substituenten G der Formel (I) die Reste Fstab Funktionen entsprechen, die mit Fpo schwache Bindungen (Wasserstoffbindungen) ausbilden können und die ausgewählt sind aus der Gruppe von:
    funktionellen Einheiten mit Stickstoff und/oder Sauerstoff und/oder Fluor und/oder Schwefel und/oder Phosphor; Carboxyl-, Carboxylat-, Amid-, Imid-, Sulfonamid-, Hydroxyl-, Alkoxyl-, Amin- oder Organofluoreinheiten, die bevorzugt sind;
    kationischen Einheiten, vorzugsweise solchen, die ein oder mehrere quaternäre Amoniumgruppen umfassen,
    chelatbildenden bzw. chelatisierenden Einheiten mit einer oder mehreren Etherfunktionen und/oder einer oder mehreren Aminfunktionen und/oder chelatbildenden bzw. chelatisierenden Phosphonat- und/oder Sulfonateinheiten.
  3. Polyorganosiloxane nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß sie der folgenden Formel (II) entsprechen R1 3SiO―[SiR2 2O]m― [SiR2EO]n―[SiR2GO]o―SiR3 3 wobei:
    R1 und R3 unabhängig voneinander Wasserstoff, Hydroxyl oder einen einwertigen Rest darstellen, welcher derselben Definition entspricht, wie sie zuvor für R gegeben worden ist;
    R2 unabhängig Wasserstoff, Hydroxyl oder einen einwertigen Rest darstellt, welcher derselben Definition entspricht, wie sie zuvor für R gegeben worden ist;
    2 ≤m+n+o≤300
    vorzugsweise   3 ≤ m + n + o ≤ 50
    besonders bevorzugt   5 ≤ m + n + o ≤ 20
    0 ≤ m ≤ 200
    vorzugsweise   1 ≤ m ≤ 100
    besonders bevorzugt   1 ≤ m ≤ 10
    0 ≤ n ≤ 50
    vorzugsweise   1 ≤ n ≤ 10
    besonders bevorzugt   2 ≤ n ≤4
    0 ≤ o ≤ 50
    vorzugsweise   1 ≤ o ≤ 10
    besonders bevorzugt   2 ≤ o ≤ 4.
  4. Polyorganosiloxane nach Anspruch 3, dadurch gekennzeichnet, daß Δ R1, R3 = C1-C3-Alkyl, vorzugsweise -CH3 Δ R2 = C1-C3-Alkyl, vorzugsweise -CH3 Δ wobei der oder die funktionellen Substituenten E gleichzeitig Funktionen Fpo und Fstab enthalten.
  5. Polyorganosiloxane nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß E eine Carboxylpersäurefunktion Fpo und eine Carboxylsäurefunktion Fstab enthält.
  6. Verfahren zur Herstellung von POS nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Verfahren im wesentlichen darin besteht, Polysiloxanvorläufer dieser POS mit Hilfe mindestens eines Oxidationsmittels zu oxidieren, welches vorzugsweise ausgewählt ist aus der Gruppe von H2O2, O2, O3 und deren Mischungen,
    wobei sich die Polysiloxanvorläufer von den Polyorganosiloxanen (POS) dadurch unterscheiden, daß sie ein oder mehrere Funktionen F'po, die Vorläufer von Fpo sind, umfassen und aus Carbonsäureresten
    Figure 00380001
    wobei X' derselben Definition wie sie zuvor für X in Anspruch 1 gegeben worden ist, entspricht;
    und/oder aus Säureanhydridresten
    Figure 00380002
    bestehen.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Polyorganosiloxanvorläufer ausgewählt sind aus:
    ⇒ Trägem von Anhydridfunktionen F'po, wobei die Oxidation mit Hilfe von H2O2 in Gegenwart eines Katalysators vom Typ einer starken Base, vorzugsweise Kaliumhydroxid, durchgeführt wird;
    ⇒ und/oder Trägem von Carboxylfunktionen F'po, vorzugsweise Benzoylfunktionen, wobei die Oxidation mit Hilfe von H2O2 in Gegenwart eines Katalysators vom Typ einer starken Säure durchgeführt wird.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Polyorganosiloxanvorläufer Succinanhydridfunktionen F'po tragen, die über die Siliciumatome über eine Einheit -(CH2)3- verbunden sind.
  9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß man die POS-Vorläufer mit einer molaren Reinheit ≥ 90 %, vorzugsweise ≥ 95 %, einsetzt.
  10. Verwendung von Polyorganosiloxanen (POS) nach einem der Ansprüche 1 bis 5 oder erhältlich nach dem Verfahren nach einem der Ansprüche 6 bis 9 in einer Zahnpflegemittelzusammensetzung als Mittel zum Bleichen von Zähnen.
  11. Zahnpflegemittelzusammensetzung, insbesondere Zahnpasta bzw. Zahncreme, dadurch gekennzeichnet, daß sie mindestens ein Polyorganosiloxan (POS) nach einem der Ansprüche 1 bis 5 oder erhältlich nach dem Verfahren nach einem der Ansprüche 6 bis 9 als Bleichmittel enthält.
  12. Zahnpflegemittelzusammensetzung nach Anspruch 11, dadurch gekennzeichnet, daß sie enthält:
    0,1 bis 40 Gew.-% mindestens eines Polyorganosiloxans (POS)
    5 bis 40 Gew.-% mindestens eines Poliermittels und
    0,005 bis 2 Gew.-% mindestens einer fluorierten Verbindung.
EP99973300A 1998-12-09 1999-12-01 Peroxidierte polyorganosiloxane, verfahren zu deren herstellung und deren anwendung als bleichmittel in dentalmasse Expired - Lifetime EP1149123B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9815715A FR2787114B1 (fr) 1998-12-09 1998-12-09 Polyorganosiloxanes (pos) peroxydes, l'un de leurs procedes de preparation et leurs utilisations notamment a titre d'agent de blanchiment dans des compositions dentaires
FR9815715 1998-12-09
PCT/FR1999/002984 WO2000034360A1 (fr) 1998-12-09 1999-12-01 Polyorganosiloxanes (pos) peroxydes, l'un de leurs procedes de preparation et leurs utilisations notamment a titre d'agent de blanchiment dans des compositions dentaires

Publications (2)

Publication Number Publication Date
EP1149123A1 EP1149123A1 (de) 2001-10-31
EP1149123B1 true EP1149123B1 (de) 2004-06-09

Family

ID=9533907

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99973300A Expired - Lifetime EP1149123B1 (de) 1998-12-09 1999-12-01 Peroxidierte polyorganosiloxane, verfahren zu deren herstellung und deren anwendung als bleichmittel in dentalmasse

Country Status (8)

Country Link
US (2) US6841645B1 (de)
EP (1) EP1149123B1 (de)
AT (1) ATE268793T1 (de)
AU (1) AU1393300A (de)
DE (1) DE69917942T2 (de)
ES (1) ES2223196T3 (de)
FR (1) FR2787114B1 (de)
WO (1) WO2000034360A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2787114B1 (fr) * 1998-12-09 2001-02-16 Rhodia Chimie Sa Polyorganosiloxanes (pos) peroxydes, l'un de leurs procedes de preparation et leurs utilisations notamment a titre d'agent de blanchiment dans des compositions dentaires
DE19860364C2 (de) 1998-12-24 2001-12-13 3M Espe Ag Polymerisierbare Dentalmassen auf der Basis von zur Aushärtung befähigten Siloxanverbindungen, deren Verwendung und Herstellung
EP3502257B1 (de) * 2016-08-22 2023-02-15 Suzhou SJ Biomaterials, Ltd. Co. Festphasenträger zur verbesserung der detektionsempfindlichkeit und detektionskomponente

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2963501A (en) * 1959-04-06 1960-12-06 Dow Corning Organosilyl peroxides
US3726943A (en) * 1971-08-12 1973-04-10 Union Carbide Corp Ethylenically unsaturated monomer polymerization with silyl acyl peroxides and acyl peroxy polysiloxanes
JPH0617479B2 (ja) * 1986-08-28 1994-03-09 日本油脂株式会社 ジメチルシロキサン系ブロツク共重合体の製造方法
FR2787114B1 (fr) * 1998-12-09 2001-02-16 Rhodia Chimie Sa Polyorganosiloxanes (pos) peroxydes, l'un de leurs procedes de preparation et leurs utilisations notamment a titre d'agent de blanchiment dans des compositions dentaires

Also Published As

Publication number Publication date
FR2787114A1 (fr) 2000-06-16
DE69917942D1 (de) 2004-07-15
ES2223196T3 (es) 2005-02-16
AU1393300A (en) 2000-06-26
EP1149123A1 (de) 2001-10-31
DE69917942T2 (de) 2005-06-30
US6841645B1 (en) 2005-01-11
FR2787114B1 (fr) 2001-02-16
US20050003995A1 (en) 2005-01-06
WO2000034360A1 (fr) 2000-06-15
ATE268793T1 (de) 2004-06-15

Similar Documents

Publication Publication Date Title
EP0768997B1 (de) Polyalkoxylierte terpenderivate und sie enthaltende zusammensetzungen
WO1993001791A1 (fr) Melange azeotrope de thioglycolate d&#39;hydroxy-2 propyle et de thioglycolate d&#39;hydroxy-2 methyl-1 ethyle, son procede d&#39;obtention et son utilisation dans un procede de deformation permanente des cheveux
EP1302194B1 (de) Verwendung von einem Polyguanidinverbindung zur Behandlung oder Verformung des Haares, insbesondere zum Wellen und Glätten
FR2459043A1 (fr) Composition a base d&#39;un polycarboxylate complexe de magnesium pour combattre le tartre dentaire
CZ345097A3 (cs) Prostředky na čištění zubů
AU2018384632B2 (en) Oral care compositions comprising phosphonate and anionic group containing polymers
EP0396460B1 (de) Mit metallischen Kationen kompatible Kieselsäure für Zahnpflegemittelmischungen
FR2700118A1 (fr) Composition à usage buccal contre la plaque dentaire et son procédé d&#39;utilisation.
FR2515513A1 (fr) Dentifrice
EP1149123B1 (de) Peroxidierte polyorganosiloxane, verfahren zu deren herstellung und deren anwendung als bleichmittel in dentalmasse
CZ190997A3 (en) Preparations based on dimethicone derivatives providing aroma and acting as cooling or antimicrobial preparation
FR2497207A1 (fr) Composition antigingivite, son procede de preparation et son application
CA3186302C (fr) Complexe de gadolinium et d&#39;un ligand chelateur derive de pcta diastereoisomeriquement enrichi et procede de synthese
JPH10511093A (ja) シリコーン組成物
JP3956238B2 (ja) Ｎ―分枝鎖アルキル置換メルカプトアセトアミドに基づく毛髪のパーマネント加工剤及び加工法、並びに、その製造方法
CA2251640A1 (fr) Composition dentifrice comprenant un abrasif ou additif a base de silice et de carbonate de calcium, compatible avec le fluor
CA1155607A (fr) Compositions contenant un mono- ou polyalkylarylsulfonate de metal alcalin et l&#39;hydroperoxyde correspondant,procede pour leur preparation et compositions detergentes les contenant
FR2646601A1 (fr) Dentifrice et compositions orales utiles pour inhiber les calculs dentaires
FR2889447A1 (fr) Utilisation d&#39;un materiau mixte mineral/organique comme agent de protection contre les radiations ultraviolettes
JP5235050B2 (ja) 毛髪改質剤
EP0396459B1 (de) Kieselsäure für Zahnpflegemittelmischungen, welche mit organischen, aminierten Verbindungen vereinbar sind
BE893649A (fr) Dentifrice
CA2096909A1 (fr) Utilisation de silico-aluminate amorphe en tant que capteurs de precipites calciques
WO1995034532A1 (en) Alkyl sulfoacetate compositions and methods for preparing same
FR2540093A1 (fr) Procede de preparation d&#39;un silico-aluminate alcalin utilisable dans les compositions dentifrices

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: 20010516

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20011112

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: PEROXIDISED POLYORGANOSILOXANES (POS), ONE OF THE METHODS FOR PREPARING THEM AND THEIR USE AS BLEACHING AGENT IN DENTAL C

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040609

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040609

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040609

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040609

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69917942

Country of ref document: DE

Date of ref document: 20040715

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: FRENCH

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040909

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040909

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040909

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040915

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20040609

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2223196

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050310

BERE Be: lapsed

Owner name: *RHODIA CHIMIE

Effective date: 20041231

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

BERE Be: lapsed

Owner name: *RHODIA CHIMIE

Effective date: 20041231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041109

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20081218

Year of fee payment: 10

Ref country code: AT

Payment date: 20081211

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20081224

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20081212

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20081127

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20081126

Year of fee payment: 10

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20091201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091201

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091202