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 peroxide systems applicable in particular in bleaching, disinfection, cleaning, initiation of polymerizations (for example radical) or epoxidation reactions.
• the oxidizing properties of these systems are more particularly appreciated in bleaching applications, in particular dental (e.g. toothpaste) or detergent.
• the peroxide systems referred to in the context of this presentation are functionalized polymers.
• the present invention relates to polyorganosiloxanes (POS) peroxides as well as one of their methods of preparation.
• the invention also relates to silicone precursors of these peroxide POSs.
• the present invention includes an application aspect which includes the use of the peroxide POSs according to the invention as active ingredient in bleaching, disinfection, cleaning and initiation of chemical reactions. More specifically, the invention relates to dental compositions, for example toothpastes, or detergents comprising POS peroxides 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.
• peracid compounds constituted by a support have been proposed in US patent No. 5,698,326 inorganic formed by silica and carrying peracid functionalities. These compounds can be obtained by reacting silica substituted with a siloxylalkylamine residue with a trimellitic anhydride, the carboxylic function of the benzyl ring of which is then oxidized to transform it into a peracid function. This corresponds to the following formula:
• the grafting of the peracid function on the inorganic silica support is supposed to allow stabilization of the peracid function.
• this stability could be further improved.
• these peroxidized silicas are difficult to disperse in relatively viscous compositions such as toothpaste.
• European patent application No. 796 874 relates to a process for the preparation of polymers comprising peroxycarboxylic groups.
• These peroxycarboxylic polymers are more precisely copolymers of N-vinylpyrolidone / maleic anhydride.
• the hydrogen peroxide which is reacted with this copolymer allows the conversion of the carboxyls obtained from the anhydride into peroxycarboxylic functions.
• the performance of these peroxycarboxylated copolymers, in terms of bleaching, is not revealed by this patent application.
• instability problems can be feared for dental bleaching applications of these copolymers.
• PCT patent application WO 97/02 01 1 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 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 type and / or polyoxypropylene 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 type and / or polyoxypropylene and having
• This oral composition is presented as having improved anti-plaque and anti-bacterial properties, which complement excellent cleaning performance.
• This oral composition can also include 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.
• Another essential objective of the invention is to provide a peroxide whitening system in particular for dental whitening applications which makes it possible 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 peroxide whitening system usable in particular in dental whitening and endowed with significantly improved storage stability.
• Another essential objective of the invention is to provide a peroxide whitening system applied in dental whitening (oral composition for the treatment and maintenance of teeth), having better selectivity with respect to the teeth to be whitened.
• Another essential objective of the invention is to provide an oxidizing peroxide system, capable of being used as a system for controlled release of oxidizing peroxide functions, or even of free radicals initiating chemical reactions.
• Another essential objective of the invention is to provide a process for obtaining the above-mentioned peroxide oxidizing system, which is simple to implement and economical.
• Another essential objective of the invention is to prescribe the use of the above-mentioned peroxide oxidizing system, as a bleaching agent, a disinfecting agent, a cleaning agent or an agent for initiating reactions. chemicals.
• Another essential objective of the invention is to provide a dental composition provided with an effective, stable and selective whitening agent.
• Another essential objective of the invention is to provide a washing composition comprising an efficient, stable and economical bleaching agent.
• D a + b + c 0 to 3
• D a, b, c - 0 to 3 DR corresponds to one or more identical or different radicals, R being chosen from hydro-carbon monovalent groups, preferably from linear, branched alkyls and / or cyclic and / or aryls, and more preferably still among linear or branched C1-C4 alkyls and phenyl, xylyl and tolyl groups;
• DE corresponds to one or more identical or different functional substituents between them monovalent, carrying one or more peroxo (-OO-) Fpo functions and optionally each comprising one or more Fstab stabilizing Fpo functions, identical or different between themselves and chosen from functions capable of binding via weak links with Fpo functions;
• D G corresponds to one or more identical or different functional substituents with one another and each comprising one or more Fstab stabilizing functions of Fpo, identical or different from one another and chosen from the functions capable of binding via weak bonds with the Fpo functions; - ”with the conditions under which:
• these silicones functionalized with Fpo peroxo are endowed with a specific affinity with respect to the constituent materials of the teeth (in particular hydroxyapatite) so that they are selective vectors capable of carrying the bleaching functions. chemical on the teeth. It goes without saying that this optimizes the efficiency of said functions. It follows that it is possible to reduce the doses, which is entirely in the direction of reducing the aggressiveness of the bleaching agent.
• these peroxide functional silicones are hydrophobic and therefore have the advantage of preserving the Fpo functions of water, which is a major element of instability for these.
• the new peroxidic polyorganosiloxanes with Fpo functions can be linear and / or branched and / or crosslinked polymers according to the percentage by weight of DTQ siloxyl units which they comprise.
• the substituents E of the siloxane units (I) are identical, or different from one another and are chosen from hydrocarbon, (cyclo) aliphatic and / or aromatic and / or heterocyclic groups optionally comprising one or more heteroatoms - preferably O, N, S, Si-, these groups possibly being substituted,
• R x representing a monovalent hydrocarbon radical, that is to say comprising, inter alia, hydrogen and carbon atoms, aliphatic and / or alicyclic and / or aromatic and / or heterocyclic optionally comprising one or more heteroatoms (N, O, S 3), this radical possibly being substituted, R x possibly being able to answer the same definition as that given above for R in the formula (I), to a halogen preferably chlorine or to a cation allowing to form a salt with the peroxo anion and preferably chosen from among the elements of columns la and
• each peroxo Fpo function belongs to a peroxycarboxylic residue (acids - esters - halides - chlorides - or salts) or even a peroxide residue derived from compounds comprising sulfur, phosphorus, boron or silicon.
• X alkyl groups
• peroxycarboxylic and non-carboxylic residues are connected to the silicon of the POS chain by a hydrocarbon ball (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 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 set including:
• the ball joint forms the functional substituent E.
• the ball joint is, for example, of the -alkyl-O-aryl (benzyl), -alkyl anhydride, -alkylimide-aryl (benzyl) type, among others.
• 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 (pendant) substituents 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 possible stabilization functions Fstab of the substituents E and / or G of formula (I) correspond to functions which can generate weak bonds (hydrogen bonds, eg) with Fpo, and selected in the group including:
• the functional units comprising nitrogen and / or oxygen and / or fluorine, and / or sulfur and / or phosphorus; the carboxylic, carboxylate, amide, imide, sulfonamide, hydroxyl, alkoxyl, amino or organofluoric units being preferred;
• - cationic units preferably those comprising one or more quaternary ammoniums; - »chelating units comprising one or more ether functions and / or one or more amino functions, and / or phosphonate and / or sulfonate chelating units.
• the optional functional substituents G each comprise, in addition to the Fstab (s), 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 correspond to the same definition as that given above for the ball joints of the substituents E.
• the peroxide POSs which are the subject of the invention can be obtained: either from chlorosilanes or alkoxysilanes carrying the substituents E, chlorosilanes or alkoxysilanes carrying the substituents G and chlorosilanes or alkoxysilanes carrying the substituents R and / or hydrogen, by cohydrolysis, polycondensation and polymerization of the hydrolysed products in the presence of cyclic diorganosiloxanes or redistribution in the presence of polydiorganosiloxanes ... or from polydiorganosiloxanes functionalized by hydrosilylation of hydrogenated polydiorganosiloxanes using integral or partial olefinic precursors of the functional substituents
• the peroxides POS obtained by hydrosilylation of olefinic precursors of substituents E and G are preferred.
• 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 Mention may in particular be made of the complex derivatives of platinum 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 include the peroxo Fpo functions, 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
• 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 peroxide POSs correspond to the formula (H) given below in which
• R 1 , R 3 independently representing a hydrogen, a hydroxyl or a monovalent residue corresponding to the same definition as that given for R above,
• R 2 independently represent hydrogen, a hydroxyl or a monovalent residue corresponding to the same definition as that given for R above,
• 0 ⁇ n ⁇ 50 preferably 1 ⁇ n ⁇ 10 and more preferably still 2 ⁇ n ⁇ 4
• 0 ⁇ o ⁇ 50 preferably 1 ⁇ o ⁇ 10 and more preferably still 2 ⁇ o ⁇ 4.
• the polyorganosiloxanes are characterized in that:
• the functional substituent (s) E comprise both Fpo and Fstab functions.
• the functional substituents E of the peroxide POSs each comprise a ball joint comprising at least one bicarboxylated and / or benzoxylated and / or imide unit.
• the ball joint (s) of the functional substituent (s) E comprise at least one bicarboxylic unit
• the Fpo function is obtained from an anhydride which is transformed, on the one hand , in Fpo and, on the other hand, in a carboxylic Fstab function for stabilizing the neighboring Fpo.
• the peroxide POSs according to the invention are stable and have a strong whitening power.
• 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 peroxide POSs.
• This oxidation is carried out using at least one oxidant preferably chosen from the group comprising:
• the polysiloxane precursors with F'po functions can be obtained by cohydroiysis of chlorosilanes and non-functionalized alkoxysilanes and chlorosilanes or alkoxysilanes functionalized with substituents E and G.
• the step which follows the cohydroiysis can be a polycondensation and a polymerization of the hydrolysis products, in the presence of cyclic diorganosiloxanes 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 the substituents E and G). See above for more details on this hydrosilylation.
• the precursors - POS which are subjected to an oxidation to obtain POS peroxides targeted are selected from the POSs carrying functional substituents E;
• the -POS precursors selected are:
• 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, an inorganic base such as
• KOH or NaOH or else a strong acid for example, a mineral acid such as H 2 SO 4 or an organic acid such as MeSO 3 H.
• a strong acid for example, a mineral acid such as H 2 SO 4 or an organic acid such as MeSO 3 H.
• the solvents used in these cases are, for example, acetate ethyl 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 ambient temperature and pressure.
• the present invention also relates to POS precursors with F'po precursor function as defined above. These new POS precursors as such constitute intermediate products of the process according to the invention.
• the present invention relates to the use of peroxide POSs as defined above by way of:
• the peroxide POSs according to the invention are particularly suitable as a bleaching agent and more particularly still as a bleaching agent for teeth, taking into account their properties of selectivity with respect to the teeth of non-toxicity, of controlled reactivity of the peroxide functions Fpo (limitation of the production of free radicals), of non-toxicity and of high efficiency at low dose.
• 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 by way of bleaching agent.
• a dental composition for example an oral composition
• toothpaste - characterized in that it comprises peroxygenated POSs as defined above by way of bleaching agent.
• the dental composition according to the invention contains: peroxygenated POS in an amount of 0.1 to 40% by weight, preferably of 0.1 to 10% by weight, and more preferably still on the order of 1 to 5% by weight; - polishing abrasives at a rate of 5 to 40% by weight, preferably from 5 to 35% by weight, these abrasives can be in particular silica, precipitated calcium carbonate, magnesium carbonate, calcium phosphates, oxides of zinc or tin titanium, talc, kaolin, abrasive particles comprising a core of calcium material, preferably calcium carbonate and a shell of an idrophobic product, preferably a fatty acid salt and more preferably still Na stearate; one or more fluorinated compounds corresponding to a concentration of the order of 0.005 to 2%, preferably from 0.1 to 1% by weight of fluorine in said composition, these fluorinated compounds
• anionic surfactants such as sodium, magnesium, ammonium, ethanolamine salts, Cg-Cis alkyl sulphates which may optionally contain up to 10 oxyethylene and or oxypropylene units (especially sodium lauryl sulphate) alkyl sulphoacetates C 8 -C ⁇ g (including sodium lauryl sulfoacetate) alkyl sulphoacetates C 8 -C ⁇ 8 (particularly sodium dioctylsulfosuccinate) alkyl sarcosinates, C 8 -C ⁇ 8 (sodium lauryl sarcosinate particular) alkyl phosphates, C 8 8 may -C ⁇ optionally contain up to 10 oxyethylene and or oxypropylene alkyl ether C 8 -C ⁇ 8 carboxylate units containing up to 10 oxyethylene and or oxypropylene units sulfated monoglycerides
• nonionic surfactants such as fatty sorbitan esters optional
• the peroxidized or peroxygenated POSs according to the invention are not only suitable for whitening and cleaning the teeth. In fact, they have been found to be quite effective as bleaching agents in detergent compositions.
• the present invention therefore also relates to detergent compositions comprising peroxygenated POSs or peroxides according to the invention as defined above, as bleaching agents.
• Example 1 preparation of a precursor - POS (B) of a peroxide POS according to the invention, this precursor being a polydimethylsiloxane with trimethylsilyl ends and carrying functional substituents of the -propyl-oxy-benzoic type
• the reaction medium After returning to ambient temperature, the reaction medium is neutralized by gradual addition over 1 hour 30 minutes of 1 liter of 36% hydrochloric acid (11 moles). The reaction medium becomes milky and it is filtered on frit No. 4 under vacuum. A white filter cake is obtained which is washed with water (250 ml). In order to purify the allyloxybenzoic acid present in the filter cake, the process is carried out by recrystallization. In the 10 l reactor, the cake is loaded. filtration, 5 1 of absolute ethanol and 750 ml of distilled water. The reaction mass is brought to reflux (80 ° C.) and distilled water is gradually added until a single clear phase is obtained, ie 1.75 1 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 then filtered on a No. 4 frit under vacuum The cake is washed with distilled water (2 I used in three times) Crystals are obtained which are dried under vacuum of 200 mmHg and at 70 ° C. The yield is 35%
• Example 2 Preparation of a precursor - POS (C) of a peroxide POS according to the invention, this precursor being a polydimethylsiloxane with trimethylsilyl ends and carrying functional substituents of the -propyl- succinic anhydride type
• the reaction medium After returning to ambient temperature, the reaction medium is filtered on cardboard under nitrogen pressure. After placing the reaction medium in a single-necked flask fitted with a magnetic bar, the grafted silicone polymer is isolated by devolatilizing the excess oligomer by heating to 180 ° C. under a vacuum of 2 mmHg. A silicone oil of structure C and of purity equal to 94% by weight is obtained.
• Example 3 is reproduced with the difference that the aminopropyldimethoxymethylsilane used in point 3.1 is replaced. for aminoethylaminopropyldimethoxymethylsilane and a precursor - POS or silicone oil F is obtained in fine:
• EXAMPLE 5 OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS
• the POS used is prepared according to the methodology given in Example 6
• the product is stored dried at 5 ° C and 25 ° C
• EXAMPLE 8 OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS
• 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). Results ''
• a - Contamination of the PAH powder a - Measurement of the initial whiteness of the powder
• a measurement of the initial whiteness of the PAH powder is carried out. It is performed on the Minolta CR-241 device. Three measurements are made to obtain an average value of Lo, ao, bo.
• the powder is washed with three times 20 ml of hot deionized water until the filtrate is colorless.
• the powder recovered in the form of agglomerates is ground using a mortar and pestle.
• 6.5 g of oxidizing solution (containing the equivalent of 0.3% of H 2 O 2 ) and 50 mg of dirty PAH powder are transferred to a crystal polystyrene bottle with a capacity of ⁇ 40 ml.
• the whole is placed on the PROMAX 2020 back-and-forth agitator for the desired time (15 min, 30 min, 1h, 2h, ...) at the rate of 250 round trips.
• the medium is then diluted by adding 20 ml of ethanol before being filtered.
• the powder is washed with three times 30 ml of ethanol.
• the whole filter + bleached powder is dried in the open air in a hood.
• the new whiteness of the bleached powder can be measured (Le), and the whitening power of the oxidizing solution can be calculated.
• the bleaching power of the oxidizing compound is calculated from the value
• L * represents the clarity of the sample, its values range between 0 and 100.
• the whitening power is calculated as follows: ⁇ Whitening power:

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• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Silicon Polymers (AREA)
• Cosmetics (AREA)

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• 1998
  • 1998-12-09 FR FR9815715A patent/FR2787114B1/fr not_active Expired - Fee Related
• 1999
  • 1999-12-01 AU AU13933/00A patent/AU1393300A/en not_active Abandoned
  • 1999-12-01 ES ES99973300T patent/ES2223196T3/es not_active Expired - Lifetime
  • 1999-12-01 WO PCT/FR1999/002984 patent/WO2000034360A1/fr active IP Right Grant
  • 1999-12-01 EP EP99973300A patent/EP1149123B1/de not_active Expired - Lifetime
  • 1999-12-01 AT AT99973300T patent/ATE268793T1/de not_active IP Right Cessation
  • 1999-12-01 US US09/857,578 patent/US6841645B1/en not_active Expired - Fee Related
  • 1999-12-01 DE DE69917942T patent/DE69917942T2/de not_active Expired - Fee Related
• 2004
  • 2004-07-23 US US10/898,055 patent/US20050003995A1/en not_active Abandoned

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