CA2548206C - Dyed polymethyl methacrylate bone cement and process for its production - Google Patents
Dyed polymethyl methacrylate bone cement and process for its production Download PDFInfo
- Publication number
- CA2548206C CA2548206C CA2548206A CA2548206A CA2548206C CA 2548206 C CA2548206 C CA 2548206C CA 2548206 A CA2548206 A CA 2548206A CA 2548206 A CA2548206 A CA 2548206A CA 2548206 C CA2548206 C CA 2548206C
- Authority
- CA
- Canada
- Prior art keywords
- polymethyl methacrylate
- bone cement
- methacrylate bone
- coupling agent
- dyed
- 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 - Fee Related
Links
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 51
- 239000002639 bone cement Substances 0.000 title claims abstract description 49
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 8
- 230000008569 process Effects 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000007822 coupling agent Substances 0.000 claims abstract description 39
- 239000000975 dye Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical class CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000002872 contrast media Substances 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 229930002875 chlorophyll Natural products 0.000 claims description 6
- 229940106705 chlorophyll Drugs 0.000 claims description 6
- 235000019804 chlorophyll Nutrition 0.000 claims description 6
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 5
- -1 aliphatic alcohols Chemical class 0.000 claims description 5
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical class CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 5
- 229940099898 chlorophyllin Drugs 0.000 claims description 5
- 235000019805 chlorophyllin Nutrition 0.000 claims description 5
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- UBEIMDKGOYBUKT-FLIQGJDUSA-N 1,2,3-trilinolenoylglycerol Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C\C=C/C\C=C/CC)COC(=O)CCCCCCC\C=C/C\C=C/C\C=C/CC UBEIMDKGOYBUKT-FLIQGJDUSA-N 0.000 claims description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 2
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 claims description 2
- FWCCXEACMBKDSC-HATLBPGASA-N OCCO.CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O.CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O.CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O Chemical compound OCCO.CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O.CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O.CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O FWCCXEACMBKDSC-HATLBPGASA-N 0.000 claims description 2
- NKSOSPOXQKNIKJ-CLFAGFIQSA-N Polyoxyethylene dioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOC(=O)CCCCCCC\C=C/CCCCCCCC NKSOSPOXQKNIKJ-CLFAGFIQSA-N 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 229930003779 Vitamin B12 Natural products 0.000 claims description 2
- 229960001506 brilliant green Drugs 0.000 claims description 2
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001746 carotenes Chemical class 0.000 claims description 2
- 235000005473 carotenes Nutrition 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 2
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 229940097275 indigo Drugs 0.000 claims description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N linoleic acid group Chemical class C(CCCCCCC\C=C/C\C=C/CCCCC)(=O)O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 229940107698 malachite green Drugs 0.000 claims description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011715 vitamin B12 Substances 0.000 claims description 2
- 235000019163 vitamin B12 Nutrition 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 150000003722 vitamin derivatives Chemical class 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 20
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004121 copper complexes of chlorophylls and chlorophyllins Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000006486 human diet Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229940063557 methacrylate Drugs 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
A dyed polymethyl methacrylate bone cement is described which is characterised by at least the surface of the polymer particles of the powder component being coated partially or completely with a mixture of one or several dyes and a hydrophobic, low molecular or oligomeric organic coupling agent, such a quantity of coupling agent being present that the polymer particles can be visually recognised as not having swollen.
Description
Patent application Heraeus Kulzer GmbH
Dyed polymethyl methacrylate bone cement and process for its production The subject matter of the invention is a dyed polymethyl methacrylate bone cement Polymethyl methacrylate bone cements (PMMA bone cements) have been widely used in the field of medicine for decades for anchoring endoprostheses in the bone (Klaus-Dieter Kuhn: Knochenzemente fur die Endoprothetik: ein aktueller Vergleich der physi-kalischen and chemischen Eigenschaften handelsublicher PMMA-Zemente (Bone cements for endoprosthetics: a current comparison of the physical and chemical prop-erties of commercial PMMA cements). Springer Verlag Berlin Heidelberg New York, 2001 ). Polymethyl methacrylate bone cements consist in general of a liquid monomer component and a powder component. The liquid monomer component consists of methyl methacrylate and an activator. N,N-Dimethyl-p-toluidine is preferably used as the activator. As a rule, the powder component consists of polymethyl methacrylate or po-lymethyl methacrylate co-methyl acrylate, an x-ray contrast agent and a radical initiator.
Zirconium dioxide and barium sulphate are commonly used as x-ray contrast agents.
Dibenzoyl peroxide is preferably used as radical initiator. After mixing the monomer component and the powder component, the bone cement is hardened by radical poly-merisation of the monomer within a few minutes.
After mixing, common polymethyl methacrylate bone cements are present as a white to slightly yellowish paste-like mass. As a result, an optical differentiation between the bone cement and the bone tissue causes problems from time to time when the mixed bone cement is introduced into the bone. However, it is desirable for the bone cement to be visually distinguishable without problems from the surrounding bone tissue.
For this reason, the polymethyl methacrylate bone cements which have been produced by Heraeus Kulzer GmbH for approximately 30 years have a green colour. This colour is achieved by way of a green monomer component and a green powder component.
Chlorophyllin is contained as dye in both components.
In the case of the polymethyl methacrylate bone cements from Heraeus Kulzer GmbH, the chlorophyllin is dissolved in the liquid monomer component by means of refined peanut oil (Biskin~) as solubiliser. Apart from the dyed monomer components, poly-methyl methacrylate bone cements can also contain a dyed powder component. A
method, known as such, for dyeing the powder component of the polymethyl methacry-late bone cements consists of using dyed polymethyl methacrylate particles or poly-methyl methacrylate co-methyl acrylate particles. These can be combined with a non-dyed second polymer in order to influence the characteristics of the polymethyl methacrylate bone cements. One of the problems occurring in this case involves accu-rately reproducing-the colour, the colour impression of the powder component even in the case of different mixing ratios of the dyed polymer to the non-dyed polymer.
The synthesis of dyed polymethyl methacrylate particles or polymethyl methacrylate co-methyl acrylate particles in the course of which the dye is enclosed, during bead polym-erisation, in the polymer beads being formed is highly complex and labour/time consum-ing under industrial conditions. A major reason for this is the occasionally low stability of dyes vis-a-vis the radical initiators used in bead polymerisation and vis-a-vis the radicals occurring during polymerisation. The initiators, in particular, can cause oxidation proc-esses and consequently decolourise the dye.
The consistent nature of the polymethyl methacrylate bone cements, in terms of colour, is an essential factor for the acceptance of the bone cements by the customer and con-sequently of economic importance.
The invention is consequently based on the object of developing a dyed polymethyl methacrylate bone cement which overcomes the known problems of the polymethyl methacrylate bone cements previously commonly used. The powder component of the polymethyl methacrylate bone cement should be such that the colour can be repro-duced reliably. It should be possible to use cheap undyed polymers such as polymethyl methacrylate or polymethyl methacrylate co-methyl acrylate or polymethyl methacrylate costyrene and copolymers or terpolymers of similar composition for the production of dyed polymethyl methacrylate bone cements. In this connection, it is important that the colour impression of the bone cement in the powder component is uniform. This means that the colour of the powder component must be recognisable visually as being homo-geneous. In addition, it is important that the powder component of the polymethyl methacrylate bone cement in terms of its flowability does not differ from the flowability and the swelling behaviour of undyed polymethyl methacrylate bone cements.
The object has been achieved according to the invention by a dyed polymethyl methacrylate bone cement in the case of which at least the surface of the polymer parti-cles of the powder component has been coated partially or completely with a mixture of one or several dyes and a hydrophobic, low molecular or oligomeric organic coupling agent, such a quantity of coupling agent being present that the polymer particles can be visually recognised as not having swollen. By using a hydrophobic coupling agent, it is possible to apply small quantities of dye evenly onto the polymer particles in such a way that these adhere firmly on the polymer particles. In this way, the dye or the dyes are fixed on the particle surface. It is important in this connection that only small quantities of coupling agent are present. Larger quantities of coupling agent might cause the polymer particles to partially swell or partially dissolve, thus caking them together. The flowability and consequently also the swellability of the powder component would thus change considerably compared with an undyed polymethyl methacrylate bone cement.
If necessary, the surface of the x-ray contrast agent barium sulphate and/or zirconium oxide or, if necessary, the surface of all the components of the powder component can be coated partially or completely with a mixture of one or several dyes and a hydropho-bic, low molecular or oligomeric organic coupling agent. Preferably, the dye or dyes are soluble or suspended in the hydrophobic, low molecular or oligomeric organic coupling agent. Thus, chlorophyllin (E141 ), for example, dissolves in Biskin or oleic acid ethyl ester. The term "suspended" should be understood to mean that the dye particles have a grain size of less than/equal to 1 Nm and are homogenously distributed in the coupling agent.
Moreover, oleic acid esters and/or elaidic acid esters and/or linoleic acid esters and/or linolenic acid esters of aliphatic alcohols with 1 to 22 carbon atoms or oligomers of these esters are preferred as coupling agents.
Moreover, methacrylic acid esters or acrylic acid esters of aliphatic alcohols with 4 to 16 carbon atoms or oligomers of these methacrylic acid esters or acrylic acid esters with a molecular weight of less than 3,000 g/mole are preferred as coupling agents.
It is also possible to use oligomers of this structure with molecular weights of more than 3,000 g/mole as coupling agents provided these are paste-like or viscous at room tempera-ture.
Oleic acid, elaidic acid, linolenic acid, glycerine trioleate, glycerine elaidinate, glycerine trilinolenate, ethylene glycol dioleinate, ethylene glycol dielaidinate, ethylene glycol trilinolenate and their oligomers are particularly preferred as coupling agents. These oligomers can be produced by the action of air at elevated temperatures, as so-called blown oils, or by heating in the absence of atmospheric oxygen as so-called stand oils.
It is also possible to use mixed esters of glycerine, of ethylene glycol, of sorbitol, of mannitol, of xylitol, of erythrols, of 1,1,1-trimethylol propane with the unsaturated fatty acids oleic acid, elaidic acid, linolenic acid and arachidonic acid and the oligomers derived therefrom as coupling agents.
Preferably, coupling agents are used in one embodiment which are produced syntheti-cally or partially synthetically and which contain no proteins or decomposition products of proteins. This characteristic is particularly important because the risk of allergies occurring is minimised when protein-free coupling agents are used.
However, refined peanut oil, hardened linseed oil, hardened rapeseed oil and sunflower oil can also be used as coupling agents. The use of further fats and vegetable oils commonly used in the human diet is also possible.
Appropriately, the coupling agent should contain free radical polymerisable double bonds. In this way, the coupling agent can take part in the polymerisation during curing of the bone cement and is firmly integrated into the bone cement.
Moreover, it is appropriate that mixtures of the coupling agent and the dye or the dyes in methyl methacrylate or mixtures of methyl methacrylate are soluble with other methacrylic acid esters such as methacrylic acid ethyl ester, methacrylic acid isobornyl ester and methacrylic acid 2-ethyl hexyl ester and acrylic acid esters such as acrylic acid methyl ester. On mixing of the powder components with the liquid monomer component, the mixture of the dye or the dyes and the coupling agent can dissolve in the liquid monomer component and dye this as well. This means that the coating is removed at least partially by the action of the monomer and forms a solution with the monomer. In this way, a uniform colour impression of the polymethyl methacrylate bone cement is achieved during curing because the free radical polymerising monomer con-tains the dye in the dissolved state and consequently polymerises during curing to form a polymer appearing coloured.
Particularly preferred dyes are chlorophyll, chlorophyllin (E141), indigo, malachite green, crystal violet, brilliant blue, brilliant green, copper phthalocyanin, cobalt phthalo-cyanin, carotene, vitamin B12 and derivates derived therefrom.
A process according to the invention for dyeing the powder component described above consists essentially of the polymer particles or mixtures of polymer particles and the x-ray contrast agent or mixtures of the polymer particles, the x-ray contrast agent and the initiator being coated with a liquid or paste-type mixture of the dye or the dyes and the coupling agent by mixing in a temperature range of 0 °C to 50 °C in the presence of air or inert gas in such a way that the layer thickness of the mixture on the coated particles is less than 2 pm and that the coated particles are not caked together. In this respect, it is particularly advantageous if the mixing process is carried out in such a way that the glass transition point of the polymer particles is not exceeded.
Exceeding the glass transition point leads to caking of the polymer particles and consequently the for-mation of agglomerates. The mixing process can advantageously be carried out in mixers commonly used in industry, such as mechanically agitated mixers or Rohn wheel mixers. Advantageously, the coating operation can be carried out at temperatures around 40 °C because the viscosity of the heated coupling agent is lower than the vis-cosity of the coupling agent at room temperature. Consequently, a uniform distribution of the coupling agent is more easily possible.
The invention will now be explained by the following examples without restricting the invention.
Example 1:
In a plastic bottle with a screw closure, 33.2 g of a polymethyl methacrylate co-methyl acrylate (molecular weight ~ 600,000 g/mole, particle size 4-50 Nm) are mixed with 4.0 mg of a mixture in the case of which 1.0 mg of chlorophyll are dissolved in 3.0 mg of oleic acid ethyl ester, in a Turbula tumble mixer for 24 hours at room temperature. After 24 hours, the previously colourless polymer has acquired a greenish coloration. The polymer particles have not swollen and not caked together. Subsequently, 6.3 g of zirconium dioxide and 0.84 g of dibenzoyl peroxide (desensitised with 25 %
water) are added to the dyed polymer and mixing is carried out for 10 minutes at room temperature by means of the Turbula tumble mixer. The free-flowing mixture formed which visually appears to be homogeneous is used as powder component of a polymethyl methacry-late bone cement.
Example 2:
In a plastic bottle with a screw closure, 33.2 g of a polymethyl methacrylate co-methyl acrylate (molecular weight ~ 600,000 g/mole, particle size 5-40 pm) and 6.3 g of zirco-nium dioxide are mixed with 3.0 mg of a mixture in the case of which 1.0 mg of chloro-phyll is dissolved in 2.0 mg of oleic acid ethyl ester, in a Turbula tumble mixer for 24 hours at room temperature. After 24 hours, the previously colourless polymer has cquired a greenish coloration. Subsequently, 0.84 g of dibenzoyl peroxide (desensitised with 25 % water) are added to the dyed mixture and mixed for 10 minutes at room temperature by means of the Turbula tumble mixer. The mixture formed which visually appears to be homogeneous is used as the powder component of a polymethyl methacrylate bone cement.
Example 3:
The powder component of a polymethyl methacrylate bone cement is produced in a manner analogous to example 1, although 4.0 mg of a mixture consisting of 1.0 mg of chlorophyll and 3.0 mg of glycerine trioleinate is used.
Example 4:
The powder component of a polymethyl methacrylate bone cement is produced in a manner analogous to example 1, although 4.0 mg of a mixture consisting of 1.0 mg of brilliant blue and 3.0 mg oleic acid are used Example 5:
A liquid monomer component is produced from 18.40 g of methyl methacrylate and 0.38 g of N,N-dimethyl-p-toluidine by mixing. This mixture represents the monomer component of the following cements.
39.00 g of the powder component of examples 1-4 are combined with 18.00 g of the monomer component respectively. On mixing of the powder component with the liquid monomer component, a green paste capable of plastic deformation is formed at room temperature after 1 minute. This remains processable for 3 minutes and then hardens.
A green solid is formed.
Example 6:
A liquid monomer component is produced by mixing 18.40 g of methyl methacrylate, 0.38 g of N,N-dimethyl-p-toluidine and 1.0 mg of chlorophyll which is dissolved in 2.0 mg oleic acid ethyl ester. This green mixture represents the monomer component of the following cements.
39.00 g of the powder component of examples 1-4 are combined with 18.00 g of the monomer component respectively. On mixing of the powder component with the liquid monomer component, a green paste capable of plastic deformation is formed at room temperature after 1 minute. This remains processable for 3 minutes and then hardens to form a green solid.
Dyed polymethyl methacrylate bone cement and process for its production The subject matter of the invention is a dyed polymethyl methacrylate bone cement Polymethyl methacrylate bone cements (PMMA bone cements) have been widely used in the field of medicine for decades for anchoring endoprostheses in the bone (Klaus-Dieter Kuhn: Knochenzemente fur die Endoprothetik: ein aktueller Vergleich der physi-kalischen and chemischen Eigenschaften handelsublicher PMMA-Zemente (Bone cements for endoprosthetics: a current comparison of the physical and chemical prop-erties of commercial PMMA cements). Springer Verlag Berlin Heidelberg New York, 2001 ). Polymethyl methacrylate bone cements consist in general of a liquid monomer component and a powder component. The liquid monomer component consists of methyl methacrylate and an activator. N,N-Dimethyl-p-toluidine is preferably used as the activator. As a rule, the powder component consists of polymethyl methacrylate or po-lymethyl methacrylate co-methyl acrylate, an x-ray contrast agent and a radical initiator.
Zirconium dioxide and barium sulphate are commonly used as x-ray contrast agents.
Dibenzoyl peroxide is preferably used as radical initiator. After mixing the monomer component and the powder component, the bone cement is hardened by radical poly-merisation of the monomer within a few minutes.
After mixing, common polymethyl methacrylate bone cements are present as a white to slightly yellowish paste-like mass. As a result, an optical differentiation between the bone cement and the bone tissue causes problems from time to time when the mixed bone cement is introduced into the bone. However, it is desirable for the bone cement to be visually distinguishable without problems from the surrounding bone tissue.
For this reason, the polymethyl methacrylate bone cements which have been produced by Heraeus Kulzer GmbH for approximately 30 years have a green colour. This colour is achieved by way of a green monomer component and a green powder component.
Chlorophyllin is contained as dye in both components.
In the case of the polymethyl methacrylate bone cements from Heraeus Kulzer GmbH, the chlorophyllin is dissolved in the liquid monomer component by means of refined peanut oil (Biskin~) as solubiliser. Apart from the dyed monomer components, poly-methyl methacrylate bone cements can also contain a dyed powder component. A
method, known as such, for dyeing the powder component of the polymethyl methacry-late bone cements consists of using dyed polymethyl methacrylate particles or poly-methyl methacrylate co-methyl acrylate particles. These can be combined with a non-dyed second polymer in order to influence the characteristics of the polymethyl methacrylate bone cements. One of the problems occurring in this case involves accu-rately reproducing-the colour, the colour impression of the powder component even in the case of different mixing ratios of the dyed polymer to the non-dyed polymer.
The synthesis of dyed polymethyl methacrylate particles or polymethyl methacrylate co-methyl acrylate particles in the course of which the dye is enclosed, during bead polym-erisation, in the polymer beads being formed is highly complex and labour/time consum-ing under industrial conditions. A major reason for this is the occasionally low stability of dyes vis-a-vis the radical initiators used in bead polymerisation and vis-a-vis the radicals occurring during polymerisation. The initiators, in particular, can cause oxidation proc-esses and consequently decolourise the dye.
The consistent nature of the polymethyl methacrylate bone cements, in terms of colour, is an essential factor for the acceptance of the bone cements by the customer and con-sequently of economic importance.
The invention is consequently based on the object of developing a dyed polymethyl methacrylate bone cement which overcomes the known problems of the polymethyl methacrylate bone cements previously commonly used. The powder component of the polymethyl methacrylate bone cement should be such that the colour can be repro-duced reliably. It should be possible to use cheap undyed polymers such as polymethyl methacrylate or polymethyl methacrylate co-methyl acrylate or polymethyl methacrylate costyrene and copolymers or terpolymers of similar composition for the production of dyed polymethyl methacrylate bone cements. In this connection, it is important that the colour impression of the bone cement in the powder component is uniform. This means that the colour of the powder component must be recognisable visually as being homo-geneous. In addition, it is important that the powder component of the polymethyl methacrylate bone cement in terms of its flowability does not differ from the flowability and the swelling behaviour of undyed polymethyl methacrylate bone cements.
The object has been achieved according to the invention by a dyed polymethyl methacrylate bone cement in the case of which at least the surface of the polymer parti-cles of the powder component has been coated partially or completely with a mixture of one or several dyes and a hydrophobic, low molecular or oligomeric organic coupling agent, such a quantity of coupling agent being present that the polymer particles can be visually recognised as not having swollen. By using a hydrophobic coupling agent, it is possible to apply small quantities of dye evenly onto the polymer particles in such a way that these adhere firmly on the polymer particles. In this way, the dye or the dyes are fixed on the particle surface. It is important in this connection that only small quantities of coupling agent are present. Larger quantities of coupling agent might cause the polymer particles to partially swell or partially dissolve, thus caking them together. The flowability and consequently also the swellability of the powder component would thus change considerably compared with an undyed polymethyl methacrylate bone cement.
If necessary, the surface of the x-ray contrast agent barium sulphate and/or zirconium oxide or, if necessary, the surface of all the components of the powder component can be coated partially or completely with a mixture of one or several dyes and a hydropho-bic, low molecular or oligomeric organic coupling agent. Preferably, the dye or dyes are soluble or suspended in the hydrophobic, low molecular or oligomeric organic coupling agent. Thus, chlorophyllin (E141 ), for example, dissolves in Biskin or oleic acid ethyl ester. The term "suspended" should be understood to mean that the dye particles have a grain size of less than/equal to 1 Nm and are homogenously distributed in the coupling agent.
Moreover, oleic acid esters and/or elaidic acid esters and/or linoleic acid esters and/or linolenic acid esters of aliphatic alcohols with 1 to 22 carbon atoms or oligomers of these esters are preferred as coupling agents.
Moreover, methacrylic acid esters or acrylic acid esters of aliphatic alcohols with 4 to 16 carbon atoms or oligomers of these methacrylic acid esters or acrylic acid esters with a molecular weight of less than 3,000 g/mole are preferred as coupling agents.
It is also possible to use oligomers of this structure with molecular weights of more than 3,000 g/mole as coupling agents provided these are paste-like or viscous at room tempera-ture.
Oleic acid, elaidic acid, linolenic acid, glycerine trioleate, glycerine elaidinate, glycerine trilinolenate, ethylene glycol dioleinate, ethylene glycol dielaidinate, ethylene glycol trilinolenate and their oligomers are particularly preferred as coupling agents. These oligomers can be produced by the action of air at elevated temperatures, as so-called blown oils, or by heating in the absence of atmospheric oxygen as so-called stand oils.
It is also possible to use mixed esters of glycerine, of ethylene glycol, of sorbitol, of mannitol, of xylitol, of erythrols, of 1,1,1-trimethylol propane with the unsaturated fatty acids oleic acid, elaidic acid, linolenic acid and arachidonic acid and the oligomers derived therefrom as coupling agents.
Preferably, coupling agents are used in one embodiment which are produced syntheti-cally or partially synthetically and which contain no proteins or decomposition products of proteins. This characteristic is particularly important because the risk of allergies occurring is minimised when protein-free coupling agents are used.
However, refined peanut oil, hardened linseed oil, hardened rapeseed oil and sunflower oil can also be used as coupling agents. The use of further fats and vegetable oils commonly used in the human diet is also possible.
Appropriately, the coupling agent should contain free radical polymerisable double bonds. In this way, the coupling agent can take part in the polymerisation during curing of the bone cement and is firmly integrated into the bone cement.
Moreover, it is appropriate that mixtures of the coupling agent and the dye or the dyes in methyl methacrylate or mixtures of methyl methacrylate are soluble with other methacrylic acid esters such as methacrylic acid ethyl ester, methacrylic acid isobornyl ester and methacrylic acid 2-ethyl hexyl ester and acrylic acid esters such as acrylic acid methyl ester. On mixing of the powder components with the liquid monomer component, the mixture of the dye or the dyes and the coupling agent can dissolve in the liquid monomer component and dye this as well. This means that the coating is removed at least partially by the action of the monomer and forms a solution with the monomer. In this way, a uniform colour impression of the polymethyl methacrylate bone cement is achieved during curing because the free radical polymerising monomer con-tains the dye in the dissolved state and consequently polymerises during curing to form a polymer appearing coloured.
Particularly preferred dyes are chlorophyll, chlorophyllin (E141), indigo, malachite green, crystal violet, brilliant blue, brilliant green, copper phthalocyanin, cobalt phthalo-cyanin, carotene, vitamin B12 and derivates derived therefrom.
A process according to the invention for dyeing the powder component described above consists essentially of the polymer particles or mixtures of polymer particles and the x-ray contrast agent or mixtures of the polymer particles, the x-ray contrast agent and the initiator being coated with a liquid or paste-type mixture of the dye or the dyes and the coupling agent by mixing in a temperature range of 0 °C to 50 °C in the presence of air or inert gas in such a way that the layer thickness of the mixture on the coated particles is less than 2 pm and that the coated particles are not caked together. In this respect, it is particularly advantageous if the mixing process is carried out in such a way that the glass transition point of the polymer particles is not exceeded.
Exceeding the glass transition point leads to caking of the polymer particles and consequently the for-mation of agglomerates. The mixing process can advantageously be carried out in mixers commonly used in industry, such as mechanically agitated mixers or Rohn wheel mixers. Advantageously, the coating operation can be carried out at temperatures around 40 °C because the viscosity of the heated coupling agent is lower than the vis-cosity of the coupling agent at room temperature. Consequently, a uniform distribution of the coupling agent is more easily possible.
The invention will now be explained by the following examples without restricting the invention.
Example 1:
In a plastic bottle with a screw closure, 33.2 g of a polymethyl methacrylate co-methyl acrylate (molecular weight ~ 600,000 g/mole, particle size 4-50 Nm) are mixed with 4.0 mg of a mixture in the case of which 1.0 mg of chlorophyll are dissolved in 3.0 mg of oleic acid ethyl ester, in a Turbula tumble mixer for 24 hours at room temperature. After 24 hours, the previously colourless polymer has acquired a greenish coloration. The polymer particles have not swollen and not caked together. Subsequently, 6.3 g of zirconium dioxide and 0.84 g of dibenzoyl peroxide (desensitised with 25 %
water) are added to the dyed polymer and mixing is carried out for 10 minutes at room temperature by means of the Turbula tumble mixer. The free-flowing mixture formed which visually appears to be homogeneous is used as powder component of a polymethyl methacry-late bone cement.
Example 2:
In a plastic bottle with a screw closure, 33.2 g of a polymethyl methacrylate co-methyl acrylate (molecular weight ~ 600,000 g/mole, particle size 5-40 pm) and 6.3 g of zirco-nium dioxide are mixed with 3.0 mg of a mixture in the case of which 1.0 mg of chloro-phyll is dissolved in 2.0 mg of oleic acid ethyl ester, in a Turbula tumble mixer for 24 hours at room temperature. After 24 hours, the previously colourless polymer has cquired a greenish coloration. Subsequently, 0.84 g of dibenzoyl peroxide (desensitised with 25 % water) are added to the dyed mixture and mixed for 10 minutes at room temperature by means of the Turbula tumble mixer. The mixture formed which visually appears to be homogeneous is used as the powder component of a polymethyl methacrylate bone cement.
Example 3:
The powder component of a polymethyl methacrylate bone cement is produced in a manner analogous to example 1, although 4.0 mg of a mixture consisting of 1.0 mg of chlorophyll and 3.0 mg of glycerine trioleinate is used.
Example 4:
The powder component of a polymethyl methacrylate bone cement is produced in a manner analogous to example 1, although 4.0 mg of a mixture consisting of 1.0 mg of brilliant blue and 3.0 mg oleic acid are used Example 5:
A liquid monomer component is produced from 18.40 g of methyl methacrylate and 0.38 g of N,N-dimethyl-p-toluidine by mixing. This mixture represents the monomer component of the following cements.
39.00 g of the powder component of examples 1-4 are combined with 18.00 g of the monomer component respectively. On mixing of the powder component with the liquid monomer component, a green paste capable of plastic deformation is formed at room temperature after 1 minute. This remains processable for 3 minutes and then hardens.
A green solid is formed.
Example 6:
A liquid monomer component is produced by mixing 18.40 g of methyl methacrylate, 0.38 g of N,N-dimethyl-p-toluidine and 1.0 mg of chlorophyll which is dissolved in 2.0 mg oleic acid ethyl ester. This green mixture represents the monomer component of the following cements.
39.00 g of the powder component of examples 1-4 are combined with 18.00 g of the monomer component respectively. On mixing of the powder component with the liquid monomer component, a green paste capable of plastic deformation is formed at room temperature after 1 minute. This remains processable for 3 minutes and then hardens to form a green solid.
Claims (13)
1. Dyed polymethyl methacrylate bone cement of a liquid and a powder component characterised in that at least the surface of the polymer particles of the powder component is partially or completely coated with a mixture of one or several dyes and a hydrophobic low molecular or oligomeric organic coupling agent, such a quantity of coupling agent being present that the polymer particles are visually recognisable as not having swollen.
2. Dyed polymethyl methacrylate bone cement according to claim 1 additionally containing in the powder component barium sulphate and/or zirconium oxide characterised in that the surface of the x-ray contrast agent barium sulphate and/or zirconium oxide or the surface of all the components of the powder component is also partially or completely coated with a mixture of one or several dyes and a hydrophobic low molecular or oligomeric organic coupling agent.
3. Dyed polymethyl methacrylate bone cement according to any one of claims 1 and 2, characterised in that the dye or dyes are dissolved or suspended in the hydro-phobic, low molecular or oligomeric organic coupling agent.
4. Dyed polymethyl methacrylate bone cement according to any one of claims 1-3, characterised in that the mass ratio of dye/dyes to hydrophobic, low molecular or oligomeric organic coupling agent is 1.0 to 0.1 to 1.0 to 10Ø
5. Dyed polymethyl methacrylate bone cement according to any one of claims 1-4, characterised in that the oleic esters and/or elaidic acid esters and/or linoleic acid esters and/or linolenic acid esters of the aliphatic alcohols with 1 to 22 carbon at-oms or oligomers of these esters are present as coupling agents.
6. Dyed polymethyl methacrylate bone cement according to any one of claims 1-5, characterised in that methacrylic acid esters or acrylic acid esters of the aliphatic alcohols with 4 to 16 carbon atoms or oligomers of these methacrylic acid esters or acrylic acid esters with a molecular weight of less than 3,000 g/mole are present as coupling agents.
7. Dyed polymethyl methacrylate bone cement according to any one of claims 1-6, characterised in that oleic acid, elaidic acid, linolenic acid, glycerine trioleat, glycerine elaidinate, glycerine trilinolenate, ethylene glycol dioleinate, ethylene glycol dielaidinate, ethylene glycol trilinolenate and their oligomers are present as coupling agents.
8. Dyed polymethyl methacrylate bone cement according to any one of claims 1-7, characterised in that coupling agents are present which are produced syntheti-cally or partially synthetically and do not contain proteins or decomposition prod-ucts of proteins.
9. Dyed polymethyl methacrylate bone cement according to any one of claims 1-7, characterised in that refined peanut oil, hardened linseed oil, hardened rapeseed oil and sunflower oil are present as coupling agents.
10. Dyed polymethyl methacrylate bone cement according to any one of claims 1-9, characterised in that the coupling agent contains free radical polymerisable dou-ble bonds.
11. Dyed polymethyl methacrylate bone cement according to any one of claims 1-10, characterised in that the mixtures of coupling agent and the dye or the dyes are soluble in methyl methacrylate.
12. Dyed polymethyl methacrylate bone cement according to any one of claims 1-11, characterised in that chlorophyll, chlorophyllin, indigo, malachite green, crystal violet, brilliant blue, brilliant green, copper phthalocyanin, cobalt phthalocyanin, carotene, vitamin B12 and derivatives derived therefrom are present as dyes.
13. Process for dyeing the polymer particles of the powder component of PMMA
bone cement characterised in that the polymer particles or mixtures of polymer particles and the x-ray contrast agent or mixtures of polymer particles, the x-ray contrast agent and the initiator are coated with a liquid or paste-type mixture of the dye or the dyes and the coupling agent by mixing in a temperature range of 0 °C to 50 °C in the presence of air or inert gas in such a way that the layer thickness of the mixture on the coated particles is less than 2 µm and that the coated particles are not caked together.
bone cement characterised in that the polymer particles or mixtures of polymer particles and the x-ray contrast agent or mixtures of polymer particles, the x-ray contrast agent and the initiator are coated with a liquid or paste-type mixture of the dye or the dyes and the coupling agent by mixing in a temperature range of 0 °C to 50 °C in the presence of air or inert gas in such a way that the layer thickness of the mixture on the coated particles is less than 2 µm and that the coated particles are not caked together.
Applications Claiming Priority (2)
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|---|---|---|---|
| DE102005032110A DE102005032110B3 (en) | 2005-07-07 | 2005-07-07 | Colored polymethyl-methacrylate cement to anchor endoprostheses in orthopoedic surgery incorporates a mixture of one or more dyes |
| DE102005032110.0 | 2005-07-07 |
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| CA2548206A1 CA2548206A1 (en) | 2007-01-07 |
| CA2548206C true CA2548206C (en) | 2010-07-06 |
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| CA2548206A Expired - Fee Related CA2548206C (en) | 2005-07-07 | 2006-05-25 | Dyed polymethyl methacrylate bone cement and process for its production |
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| US (1) | US7569621B2 (en) |
| EP (1) | EP1741455B1 (en) |
| JP (1) | JP4809144B2 (en) |
| CN (1) | CN100586488C (en) |
| AT (1) | ATE531399T1 (en) |
| AU (1) | AU2006202371B2 (en) |
| BR (1) | BRPI0602636B8 (en) |
| CA (1) | CA2548206C (en) |
| DE (1) | DE102005032110B3 (en) |
| DK (1) | DK1741455T3 (en) |
| ES (1) | ES2375725T3 (en) |
| PL (1) | PL1741455T3 (en) |
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| DE102005033210B4 (en) * | 2005-06-22 | 2008-04-30 | Heraeus Kulzer Gmbh | Polymethylmethacrylate bone cement |
| US8415406B2 (en) * | 2005-07-22 | 2013-04-09 | Howmedica Osteonics Corp. | Setting time indicator for acrylic bone cement |
| US20070021526A1 (en) * | 2005-07-22 | 2007-01-25 | Howmedica Osteonics Corp. | Setting time indicator for acrylic bone cement |
| US7754005B2 (en) * | 2006-05-02 | 2010-07-13 | Kyphon Sarl | Bone cement compositions comprising an indicator agent and related methods thereof |
| DE102007050762B3 (en) * | 2007-10-22 | 2009-05-07 | Heraeus Medical Gmbh | Paste polymethyl methacrylate bone cement and its use |
| KR101031864B1 (en) * | 2009-11-06 | 2011-05-02 | (주)인젝타 | Polymer -based bone cement using duality of paste-powder and loading apparatus thereof |
| DE102012022134A1 (en) * | 2012-11-13 | 2014-05-15 | Heraeus Medical Gmbh | Polymethylmethacrylate bone cement |
| CN105246517B (en) * | 2013-04-08 | 2018-06-12 | 伊诺西亚公司 | For the increased acrylic cement of sclerotin |
| CN105440921A (en) * | 2015-12-30 | 2016-03-30 | 曲少春 | Paint with good light transmission and preparation method of paint |
| DE102016209988A1 (en) * | 2016-06-07 | 2017-12-07 | Heraeus Medical Gmbh | Paste-like two-component polymethyl methacrylate bone cement |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2511122B2 (en) * | 1975-03-14 | 1977-06-08 | PRE-PRODUCT FOR THE PREPARATION OF BONE CEMENT | |
| DE2905878A1 (en) * | 1979-02-16 | 1980-08-28 | Merck Patent Gmbh | IMPLANTATION MATERIALS AND METHOD FOR THEIR PRODUCTION |
| DE3245956A1 (en) * | 1982-12-11 | 1984-06-14 | Beiersdorf Ag, 2000 Hamburg | SURGICAL MATERIAL |
| US4900546A (en) * | 1987-07-30 | 1990-02-13 | Pfizer Hospital Products Group, Inc. | Bone cement for sustained release of substances |
| US5258420A (en) * | 1987-07-30 | 1993-11-02 | Pfizer Hospital Products Group, Inc. | Bone cement for sustained release of substances |
| US6743438B2 (en) * | 1993-10-26 | 2004-06-01 | Pbh, Inc. | Colored contact lenses and method of making same |
| AU5973496A (en) * | 1995-06-06 | 1996-12-24 | Merck & Co., Inc. | Bisphosphonate cement composition to prevent aseptic loosening of orthopedic implant devices |
| DE19641775A1 (en) * | 1996-08-22 | 1998-02-26 | Merck Patent Gmbh | Process for the production of active ingredient-containing bone cements |
| AU747407B2 (en) * | 1998-04-14 | 2002-05-16 | Bioagency Ag | Use of organophosphoric compounds for the therapeutic and preventative treatment of infections |
| US6642285B1 (en) * | 1999-02-02 | 2003-11-04 | Robert Mathys Stiftung | Implant comprising calcium cement and hydrophobic liquid |
| WO2004071543A1 (en) * | 2003-02-13 | 2004-08-26 | Synthes Ag Chur | Injectable bone-replacement mixture |
| US20060062825A1 (en) * | 2004-04-19 | 2006-03-23 | Maria Maccecchini | Method of implanting a sterile, active agent-coated material and composition made according to same |
| DE102005033210B4 (en) * | 2005-06-22 | 2008-04-30 | Heraeus Kulzer Gmbh | Polymethylmethacrylate bone cement |
-
2005
- 2005-07-07 DE DE102005032110A patent/DE102005032110B3/en not_active Expired - Fee Related
-
2006
- 2006-05-20 DK DK06010459.3T patent/DK1741455T3/en active
- 2006-05-20 EP EP06010459A patent/EP1741455B1/en not_active Not-in-force
- 2006-05-20 ES ES06010459T patent/ES2375725T3/en active Active
- 2006-05-20 PL PL06010459T patent/PL1741455T3/en unknown
- 2006-05-20 PT PT06010459T patent/PT1741455E/en unknown
- 2006-05-20 AT AT06010459T patent/ATE531399T1/en active
- 2006-05-25 CA CA2548206A patent/CA2548206C/en not_active Expired - Fee Related
- 2006-06-02 AU AU2006202371A patent/AU2006202371B2/en not_active Ceased
- 2006-06-23 CN CN200610095919A patent/CN100586488C/en not_active Expired - Fee Related
- 2006-07-05 BR BRPI0602636A patent/BRPI0602636B8/en not_active IP Right Cessation
- 2006-07-06 JP JP2006186643A patent/JP4809144B2/en not_active Expired - Fee Related
- 2006-07-06 ZA ZA200605568A patent/ZA200605568B/en unknown
- 2006-07-07 US US11/483,339 patent/US7569621B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| DE102005032110B3 (en) | 2006-08-17 |
| JP4809144B2 (en) | 2011-11-09 |
| EP1741455A2 (en) | 2007-01-10 |
| BRPI0602636B8 (en) | 2021-06-22 |
| CA2548206A1 (en) | 2007-01-07 |
| CN1891306A (en) | 2007-01-10 |
| PL1741455T3 (en) | 2012-03-30 |
| JP2007014778A (en) | 2007-01-25 |
| EP1741455A3 (en) | 2010-01-13 |
| US20070031469A1 (en) | 2007-02-08 |
| BRPI0602636B1 (en) | 2018-05-22 |
| BRPI0602636A8 (en) | 2017-12-12 |
| AU2006202371A1 (en) | 2007-01-25 |
| ATE531399T1 (en) | 2011-11-15 |
| US7569621B2 (en) | 2009-08-04 |
| AU2006202371B2 (en) | 2008-08-21 |
| ZA200605568B (en) | 2007-09-26 |
| DK1741455T3 (en) | 2012-02-06 |
| CN100586488C (en) | 2010-02-03 |
| EP1741455B1 (en) | 2011-11-02 |
| ES2375725T3 (en) | 2012-03-05 |
| PT1741455E (en) | 2012-02-01 |
| BRPI0602636A (en) | 2007-03-06 |
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