RADICAL POLYMERISATION ACTIVATOR FOR THE PRODUCTION OF COLOURED NON-TOXIC ORGANIC CEMENTS
(19)AUSTRALIAN PATENT OFFICE (54) TitleRADICAL POLYMERISATION ACTIVATOR FOR THE PRODUCTION OF COLOURED NON-TOXICORGANIC CEMENTS (51)6 International Patent Classification(s) A61K 006/083 (21) Application No: 2003262135(22) Application Date: 2003.04.16 (87) WIPONo: WO03/086327 (30) Priority Data (31) Number (32) Date 02/04710 2002.04.16(33) Country FR (43) Publication Date : 2003.10.27 (43) Publication Journal Date : 2003.12.04 (71) Applicant(s) POLYMEREXPERT SA (72) Inventor(s)MANGOU, Emmanuel; PAGNOUX,Marc; DEFFIEUX, AlainAnne; ROBIN, Sophie; DOLATKHANI, (H) Application NoAU2003262135 A1(19)AUSTRALIAN PATENT OFFICE (54) TitleRADICAL POLYMERISATION ACTIVATOR FOR THE PRODUCTION OF COLOURED NON-TOXICORGANIC CEMENTS (51)6 International Patent Classification(s) A61K 006/083 (21) Application No: 2003262135(22) Application Date: 2003.04.16 (87) WIPONo: WO03/086327 (30) Priority Data (31) Number (32) Date 02/04710 2002.04.16(33) Country FR (43) Publication Date : 2003.10.27 (43) Publication Journal Date : 2003.12.04 (71) Applicant(s) POLYMEREXPERT SA (72) Inventor(s)MANGOU, Emmanuel; PAGNOUX,Marc; DEFFIEUX, AlainAnne; ROBIN, Sophie; DOLATKHANI, Tertiary amines (I) are used as activators for the decomposition of radical initiators. Tertiary amines (I), namely aniline derivatives of formula (Ia) or polymers of formula (Ib) or (Ic), are used as activators for the decomposition of radical initiators. R3 = an electron donor group of molecular weight above 150 in the para or ortho position; x, y = 0.1-0.9; n = 5-1000 in (Ib) or 2-1000 in (Ic); R1, R2, R3' are not defined. Independent claims are also included for: (1) polymerizable composition comprising at least one monomer and (I); (2) kit for preparing a bone cement or dental cement comprising: (a) a powder and a radical initiator; and (b) a polymerizable composition as above. Claims 1. method of making a polymeric material, in particular a polymer cement, colored, based on an acrylic or methacrylic monomer, said method being carried out in the presence of a radical polymerization initiator such as peroxide and an activator of said radical polymerization initiator decomposition tertiary amine type, characterized in that said activator of decomposition of said radical polymerization initiator comprises a tertiary amine of the formula (I-): emi25.1 wherein: - the group r3 is an electron-donating group by resonance comprising at least one aromatic group which is capable of forming with the radical: [...] emi25.2 and in combination with said radical polymerization initiator, a conjugated system having an absorption in the visible range of the electromagnetic spectrum, for generating the coloration of said polymer or cement during the reaction of polymerization of said monomer, the moieties - ri r2 are respectively and independently: alkyl Cl to C16, preferably Cl to C5, linear or branched, <Desc/Clms Page number 26> * aryl groups or aryl alkyl c5 to C30, preferably C10 c5, ' alkylidene groups in c2 C15, preferably c2 to c5. 2. method according to claim 1, characterized in that said group comprises at least one amino r3 tertiary bonded to an aromatic group. 3. method according to one of claims 1 or 2, characterized in that the group r3 is a group of the form: emi26.1 wherein: X is selected from -: HC, the n, - and the R4, R6, and r6 r7 are selected from: alkyl c1 to C16, preferably Cl to C5, linear or branched, aryl or aryl alkyl c5 to C30, preferably C10 c5, of alkylidene in c2 C15, preferably c2 to c5. 4. method according to one of claims 1 to 3, characterized in that said activator has the formula: emi26.2 <Desc/Clms Page number 27> 5. method according to one of claims 1 or 2, characterized in that the grouping r3 is of the form: emi27.1 where: - the X 'is selected from: the CH2, 0.0 to-c6h4 above 0, n-H and, the n-R and the R8 -, r9 and R are respectively and independently:' alkyl groups c1 to C16, preferably c1 C5, linear or branched, an aryl or aryl alkyl c5 to C30, preferably C10 c5, ' alkylidene groups in c2 C15, preferably c2 to c5. 6. method according to one of claims 1 or 2, characterized in that said activator is n, n-, does, not tetramethylbenzidine. 7. method according to one of claims 1 or 2, characterized in that the grouping r3 is a group of the form: x2 emi27.2 - xi and being selected from: N and CH, - r10 to r15 being independently: ' alkyl groups c1 to C16, preferably c1 C5, linear or branched, <Desc/Clms Page number 28> 'aryl groups or aryl alkyl c5 to C30, preferably C10 c5, ' alkylidene groups in c2 C15, preferably c2 to c5. 8. method according to one of claims 1 to 7, characterized in that said radical polymerization initiator is benzoyl peroxide. 9. method according to one of claims 1 to 8, characterized in that it is carried out in the presence of at least one other activator decomposition of the free radical polymerization initiator, said additional promoter, belonging or not to the family of activators of formula (I-), said (or) activator (e) having the formula (I-) being in amount effective to impart the coloration of said polymeric material or said cement. 10. The method of claim 9, characterized in that it is carried out in the presence of at least one additional promoter selected from the group consisting of the [...], the [...] and mixtures thereof. 11. The method of any of claims 9 or 10, characterized in that it is carried out in the presence of an additional promoter corresponding to one of the two formulas (III) and (II) below: emi28.1 wherein: 0.1 - < x < 0.9 et 0.9 > > 0.1 therein, with x + y=1, 5 - n is between 1000 and, <Desc/Clms Page number 29> - R16 r17 and are independently: alkyl groups c1 to C16, preferably Cl to C5, linear or branched, an aryl or aryl alkyl c5 to C30, preferably C10 c5, alkylidene groups in c2 C15, preferably C5 or c2: [...] emi29.1 - wherein n is between 2 and 1000, - the R ' 3, and r19 r18 are respectively and independently :. alkyl groups Cl to C16, preferably Cl to C5, linear or branched, # aryl alkyl aryl groups or c5 to C30, preferably C10 c5, ' alkylidene groups in c2 C15, preferably c2 to c5. 12. polymerizable composition containing at least one acrylic or methacrylic monomer and at least one activator of decomposition of an initiator for free-radical polymerization, characterized in that it contains at least one activator of tertiary amine of the formula (I-): emi29.2 <Desc/Clms Page number 30> as defined in one of claims 1 to 7. 13. The polymerizable composition according to claim 12, characterized in that said grouping r3 comprises at least one tertiary amine linked to an aromatic group. 14. The polymerizable composition according to one of claims 12 or 13, characterized in that the group r3 is a group of the form: emi30.1 as defined in claim 3. 15. The polymerizable composition according to one of claims 12 to 14, characterized in that said activator has the formula: emi30.2 16. The polymerizable composition according to claim 12 or 13, characterized in that the grouping r3 is of the form: emi30.3 as defined in claim 5. <Desc/Clms Page number 31> 17. The polymerizable composition according to one of claims 12 or 13, characterized in that said activator is n, n-, does, not tetramethylbenzidine. 18. polymerizable composition according to one of claims 12 or 13, characterized in that the grouping r3 is a group of the form: emi31.1 as defined in claim 7. 19. The polymerizable composition according to one of claims 12 to 18, characterized in that it contains at least one other activator of decomposition of the radical polymerization initiator said additional promoter, belonging or not to the family of activators of formula (I-), said (or) activator (e) having the formula (I-) being in amount effective to impart the coloration of said polymeric material or said cement. 20. The polymerizable composition according to claim 19, characterized in that it contains at least one additional promoter selected from the group consisting of the [...], the [...] and mixtures thereof. 21. The polymerizable composition according to one of claims 18 to 20, characterized in that it contains at least one additional promoter responding one of formulae (III) or (III-) below, as defined in claim 10. <Desc/Clms Page number 32> EMI32.1 22. assembly for producing a cement colored acrylic or methacrylic, especially a bone cement, dental or cement for use in vertebroplasty or cement for use in building construction, comprising on the one hand a pulverulent product and a free-radical initiator, and a polymerizable composition as defined in any one of claims 12 to 21. 23. Assembly for producing a cement acrylic or methacrylic colored according to claim 22, characterized in that said powdery product is based on a polymer or a copolymer of methyl methacrylate. 24. Assembly for producing a cement acrylic or methacrylic colored according to one of claims 22 or 23, characterized in that said free radical initiator is benzoyl peroxide. 25. Acrylic or methacrylic coloured cement, such as bone cement, dental or cement for use in vertebroplasty or cement for use in building construction, characterized in that it is obtained by mixing a polymerizable composition according to <Desc/Clms Page number 33> of claims 12 to 21 with a radical polymerization initiator such as peroxide and a pulverulent product, particularly a powdery product based on a polymer or a copolymer of methyl methacrylate and/or a copolymer thereof.