CA2171429A1 - Surgical cements - Google Patents
Surgical cementsInfo
- Publication number
- CA2171429A1 CA2171429A1 CA 2171429 CA2171429A CA2171429A1 CA 2171429 A1 CA2171429 A1 CA 2171429A1 CA 2171429 CA2171429 CA 2171429 CA 2171429 A CA2171429 A CA 2171429A CA 2171429 A1 CA2171429 A1 CA 2171429A1
- Authority
- CA
- Canada
- Prior art keywords
- surgical cement
- cement according
- formula
- surgical
- compound
- 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.)
- Abandoned
Links
- 239000004568 cement Substances 0.000 title claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 9
- 239000004067 bulking agent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 125000005389 trialkylsiloxy group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000007943 implant Substances 0.000 claims description 4
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- JELMRODZPIMJOP-UHFFFAOYSA-N [3-silyl-1,3,3-tris(trimethylsilyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O[Si](C)(C)C)CC([SiH3])(O[Si](C)(C)C)O[Si](C)(C)C JELMRODZPIMJOP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 12
- 239000003999 initiator Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002639 bone cement Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 haloalkyl methacrylates Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000012966 redox initiator Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 230000002028 premature Effects 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 150000004992 toluidines Chemical class 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003479 dental cement Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- 101100456896 Drosophila melanogaster metl gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- YFONKFDEZLYQDH-OPQQBVKSSA-N N-[(1R,2S)-2,6-dimethyindan-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine Chemical compound C[C@@H](F)C1=NC(N)=NC(N[C@H]2C3=CC(C)=CC=C3C[C@@H]2C)=N1 YFONKFDEZLYQDH-OPQQBVKSSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- A61L24/04—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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Materials For Medical Uses (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
There is described a surgical cement comprising a bulking agent, a polymerisable monomer and an activator characterised in that the polymerisable monomer is an acrylate; methods for its preparation and its use.
Description
- 2 1 7 1~ 9 ~ c ~r ~r c ~ r ~
r CEMENTS
The present invention re!ates to cements and, in particular surgical cements such as bone cements and dental cements Bone cements are frequently used in the fixation of prostheses to living bone. Such cements are typically polymeric materials. It is known to use acrylic monomers in the preparation of such polymeric cements, however, they suffer from the disadvantage that residual low molecular weight acrylates may be present in the cements and the cements may suffer from fatigue fractures. In addition, excessive heat may be generated on curing known cPments.
Improved bone cements are known from European Patent Application No.218471. Bone cements described therein comprise a solid powder phase, eg. a bulking agent, comprising n-butyl methacrylate.
It is also known to use polyacrylates as, eg. film coatings in the area of woundcare, for example, British Patent No.G81278572 describes the use of monomers such as methoxyethyl methacrylate in the preparation of woundcare films.
Orthopaedic cements are also known from US Patent No.4404327 which describes cements prepared from a mixture of methacrylate monomers and a polymer in powder form, formed from an ester or esters of acrylic or methacrylic acid. However, there is no discfosure in US Patent No.4404327 of the use haloalkyl methacrylates or (trialkylsiloxy)silyl methacrylates.
JP-A-49057054 describes dental adhesives comprising (meth) acryloxyalkylenetris(dialkyl-siloxy)silane however there is no disclosure of the use of trialkyl siloxy silyl moieties.
We have now surprisingly found that certain monomeric acrylates are useful as polymerisable monomers in the preparation of surgical cements.
A~lENo~o SHEE7 .
According to the invention we provide a surgical cement comprising a bulking agent, a polymerisable monomer and an activator characterised in that the polymerisable monomer is a 5 compound of formula 1, CH
Il 2 CH3CC02(CH 2) nX
in which n is an integer from 1 to 6, and X is halogen or (trialkylsiloxy)silyl.
~- When X is halogen it may be bromo, fluoro, iodo but preferably chloro. When X is (trialkylsiloxy)silyl, the alkyl group defined therein 15 may be alkyl C1 to 6, preferably alkyl C1 to 4 and especially methyl.
It is not essential, but preferable, that the three alkyl groups in the trialkylsiloxy moiety are the same.
The integer n is preferably from 1 to 4. When X is halogen, n 20 is preferably 1 to 3 and especially 2. When X is (trialkylsiloxy)silyl, n is preferably 2 to 4 and especially 3.
Thus, the most preferred silyl methacrylate is tris (trimethylsiloxy)-3-silylpropyl methacrylate (TRIS) which is available 25 from Fluorochem in the UK. The most preferred haloalkyl methacrylate is 2-chloroethyl methacrylate (CEMA) which is available from Lancaster Synthesis in the UK.
The surgical cement according to the invention may comprise 30 a solid and a liquid component system. The solid component may comprise a bulking agent whilst the liquid component comprises a polymerisable monomer as hereinbefore defined and an activator.
The bulking agent usually comprises a powdered methacrylate 35 polymer, eg. a methacrylate such as polymethyl methacrylate ..
~ ~,.
.
2a (PMMA). Alternatively, the bulking agent may contain a compound or a mixture of compounds of formula I in polymerised form.
Any conventionally known activators may be used, but preferred activators are toluidines and especially N-alkyl C1 to 6 toluidines, eg. N,N-dialkyl toluidines such as N,N-dimethyl toluidine.
A polymerisation initiator will be required for the cement to cure. The initiator may be included in the solid component. Such initiators include radical initiators, such as peroxides, eg. benzoyl ., WO 95/07107 ~ 1 7 1 ~ ~ 9 PCT/GBg4/01970 peroxide, thus polymerisation of the monomer, leading to cement setting or curing may start SpG nld~leously when the solid and liquid components are mixed.
..
Allen~ali~/ely, redox initiators may be used. A redox initiator may be included in the solid or liquid component. Curing can be initiated in the presence of a redox initiator by the addition of water.
Preferred oxidising or reducing agents of redox catalysts are those described in European Patent No.94222. One such prere initiator may be sodium metabisulphite/Cu (Il).
The solid and liquid con~ponents may be supplied as a premixed cen~ei ll. Polymerisation of the premixed cen,ent may be inilialed either by the addition of a radical initiator, or aller"ali./ely a redox initiator may be included in the premixed cement such that the illilidliull may be co"""el1ced by the addition of water.
In order to avoid premature setting it is essential that the initiator and the activator be in separate components of the system.
In the case of radical activated cemer"s the activator, is preferaL ly in the liquid co",po"ent and thus the initiator is preferably in the solid component, or alternatively the initiator may be added separately, eg. to the premixed cement. It is a particular advantage of the redox catalysed system that the initiation reaction is catalysed by the addition of water which may be added separately.
The cement accGrdil)g to the invention may optionally coi"~,ise a radio-opaque material. Such radio-opaque materials are preferably incorporated into the solid component phase. Any conventional radio-opaque materials may be used, but prerer, ed materials include salts, such as zirconium and/or barium salts, eg.
zirconium dioxide and/or barium sulphate.
By the inclusion of monomers such as compounds of formula I
in either the polymerised form or as monomeric components, an improved surgical cement can be formulated which benefits from having one or more of the following properties:
2~ 71~29 4 (i) a lower glass transition temperature material such as TRIS which has a crack blunting function and as such improves the fatigue properties of the surgical cement, (ii) red~ ~ced odour; and (iii) radio-opacity.
In addition, if incorporating a compound of formula I in the 10 polymerised form in the liquid component or a premixed cement this red(lces the conce, Ill aLion of polymerisable double bonds prior to set and hence reduces the amount of heat generated for a specific quantity of cement.
A readily activatable cement can be prod~ ~ced which, eg. on ~xposl ~re to a water-activated polymerisation catalyst, produces a cement of good strength.
The present invention in a still further aspect provides the use of a co""~ound of formula I in the manufacture of a surgical cement or a col"ponent of a surgical cement as hereinbefore described.
Generally the compound of formula I accounts for 0.5 to 50%
w/w of the solid and liquid component system or of the premixed cement.
The present invention is a still further aspect provides the use of a compound of formula I in the manufacture of a surgical cement or a component of a surgical cement as hereinbefore described.
A water curable composition accordi, lg to the invention may include those water-activatable vinyl polymerisation catalysts described in European Patent No.94222.
Suitable vinyl polymerisation catalysts of this type are well known in the literature.
~ = =
WO 9S/07107 2 17 1 ~ 2 9 PCT/GB94/01970 Where the catalyst is a redox catalyst the premixed cer"ei1l may be in association with the oxidising agent or reducing agent or preferably both.
The amount of catalyst used in the polymerisation process eg.
in ~ssoci-lion with the premixed ce",e"t is suitably 0.1 to 10% by weight and prererably 0.2 a~.p, oxi,Y~ately 3% eg. 0.2 to 2% by weight of the prepolymer.
Desirably in surgical cei"ents of the present invention those compollel 11~ containing polymerisable material may be in ~.ssoci~tion with a polymerisation inhibitor to prevent premature poiymerisation during its p,epa,dlion and storage.
Suitable poly",e,isalion inhibitors include polymerisation inhibitors of the art. A favoured inhibitor for preventing premature polymerisation of such polymerisable materials during storage is p-methoxyphenol.
In use curing of the cements may be brought about by either mixing of the solid and liquid co",ponents or adding a suitable initiator or water to the premixed cement.
By the term surgical cement we mean bone cements and/or dental cel"el,ls although bone cements are preferred.
Accor.ling to the invention we also provide a method of fixing a prosthesis into a patient which comprises the application of a surgical cement accordi"g to the invention to an implantable prosthesis prior or during implant.
By the term prosthesis we include surgical ie. orthopaedic or dental ie. orthodontic prostheses.
The invention will now be illustrated but in no way limited by the following Examples.
Example 1 The liquid component for a 4 bone cement formulations are shown in Table 1. Formulation 1 was the control. For each 5 formulation each of the ingredients was measured into a small beaker and mixed thoroughly.
~, TABLE I
Forrnulation No. 1 2 3 4 Methyl r"ell ,aa ylate Oml 1 9ml 1 8ml 1 6ml NN dimethyl toluidine .4ml .4ml .4ml .4ml TRIS - 1 ml 2ml 4ml For each of the above formulations 33.69 medium MW
polymethylmethacrylate powder was mixed with 5.99 zirconium dioxide and 0.49 benzoyl peroxide. To this the required liquid c~,l"~o"ent was added and stirred in for 1 minute ev~Gu~ted for 1.5 15 minutes and then poured into dumbell moulds. After 30 minutes curing was complete and the dumbells were removed from their moulds.
The dumbells were tested for ulli",ate tensile strength.
The results are illustrated in Table ll.
TABLE ll Forrnulation No. Mean Tensile Strength (M/Pa) 23.3 2 24.5 3 25.5 4 16.5 2~7~29 ExamPle 2 The liquid cor",vo"ent for 3 bone ce",enl formulations are shown in Table 1. Formulation 2 was the negative control and 3 the 5 positive control. For each formulation each of the ingredients was measured into a small beaker and mixed thoroughly.
TABLE I
Formulation No. 1 2 3 Methyl metl,ac,~late - 20ml 20ml Chloroethyl ~ Lha~ylate 20ml NN dimethyltoluidine 0.4ml 0.4ml 0.4ml TABLE ll Formulation No. 1 2 3 Medium MW poly methyl 36.3g 36.39 36.39 Illell ,ac, ylate Zirconium dioxide - - 5.99 Benzoyl peroxide 0.4g 0.49 0.49 Each of the powder components were made up by mixing the 15 dry ingredients in a 4OZ bottle. To each the required liquid component was added and stirred in for 1 minute evAc~ ted for 1.5 minutes and then poured into dumbell moulds. After 30 minutes curing was complete and the dumbells were removed from their moulds.
The dumbells were x-rayed to det~r",ine relative film exposures.
r CEMENTS
The present invention re!ates to cements and, in particular surgical cements such as bone cements and dental cements Bone cements are frequently used in the fixation of prostheses to living bone. Such cements are typically polymeric materials. It is known to use acrylic monomers in the preparation of such polymeric cements, however, they suffer from the disadvantage that residual low molecular weight acrylates may be present in the cements and the cements may suffer from fatigue fractures. In addition, excessive heat may be generated on curing known cPments.
Improved bone cements are known from European Patent Application No.218471. Bone cements described therein comprise a solid powder phase, eg. a bulking agent, comprising n-butyl methacrylate.
It is also known to use polyacrylates as, eg. film coatings in the area of woundcare, for example, British Patent No.G81278572 describes the use of monomers such as methoxyethyl methacrylate in the preparation of woundcare films.
Orthopaedic cements are also known from US Patent No.4404327 which describes cements prepared from a mixture of methacrylate monomers and a polymer in powder form, formed from an ester or esters of acrylic or methacrylic acid. However, there is no discfosure in US Patent No.4404327 of the use haloalkyl methacrylates or (trialkylsiloxy)silyl methacrylates.
JP-A-49057054 describes dental adhesives comprising (meth) acryloxyalkylenetris(dialkyl-siloxy)silane however there is no disclosure of the use of trialkyl siloxy silyl moieties.
We have now surprisingly found that certain monomeric acrylates are useful as polymerisable monomers in the preparation of surgical cements.
A~lENo~o SHEE7 .
According to the invention we provide a surgical cement comprising a bulking agent, a polymerisable monomer and an activator characterised in that the polymerisable monomer is a 5 compound of formula 1, CH
Il 2 CH3CC02(CH 2) nX
in which n is an integer from 1 to 6, and X is halogen or (trialkylsiloxy)silyl.
~- When X is halogen it may be bromo, fluoro, iodo but preferably chloro. When X is (trialkylsiloxy)silyl, the alkyl group defined therein 15 may be alkyl C1 to 6, preferably alkyl C1 to 4 and especially methyl.
It is not essential, but preferable, that the three alkyl groups in the trialkylsiloxy moiety are the same.
The integer n is preferably from 1 to 4. When X is halogen, n 20 is preferably 1 to 3 and especially 2. When X is (trialkylsiloxy)silyl, n is preferably 2 to 4 and especially 3.
Thus, the most preferred silyl methacrylate is tris (trimethylsiloxy)-3-silylpropyl methacrylate (TRIS) which is available 25 from Fluorochem in the UK. The most preferred haloalkyl methacrylate is 2-chloroethyl methacrylate (CEMA) which is available from Lancaster Synthesis in the UK.
The surgical cement according to the invention may comprise 30 a solid and a liquid component system. The solid component may comprise a bulking agent whilst the liquid component comprises a polymerisable monomer as hereinbefore defined and an activator.
The bulking agent usually comprises a powdered methacrylate 35 polymer, eg. a methacrylate such as polymethyl methacrylate ..
~ ~,.
.
2a (PMMA). Alternatively, the bulking agent may contain a compound or a mixture of compounds of formula I in polymerised form.
Any conventionally known activators may be used, but preferred activators are toluidines and especially N-alkyl C1 to 6 toluidines, eg. N,N-dialkyl toluidines such as N,N-dimethyl toluidine.
A polymerisation initiator will be required for the cement to cure. The initiator may be included in the solid component. Such initiators include radical initiators, such as peroxides, eg. benzoyl ., WO 95/07107 ~ 1 7 1 ~ ~ 9 PCT/GBg4/01970 peroxide, thus polymerisation of the monomer, leading to cement setting or curing may start SpG nld~leously when the solid and liquid components are mixed.
..
Allen~ali~/ely, redox initiators may be used. A redox initiator may be included in the solid or liquid component. Curing can be initiated in the presence of a redox initiator by the addition of water.
Preferred oxidising or reducing agents of redox catalysts are those described in European Patent No.94222. One such prere initiator may be sodium metabisulphite/Cu (Il).
The solid and liquid con~ponents may be supplied as a premixed cen~ei ll. Polymerisation of the premixed cen,ent may be inilialed either by the addition of a radical initiator, or aller"ali./ely a redox initiator may be included in the premixed cement such that the illilidliull may be co"""el1ced by the addition of water.
In order to avoid premature setting it is essential that the initiator and the activator be in separate components of the system.
In the case of radical activated cemer"s the activator, is preferaL ly in the liquid co",po"ent and thus the initiator is preferably in the solid component, or alternatively the initiator may be added separately, eg. to the premixed cement. It is a particular advantage of the redox catalysed system that the initiation reaction is catalysed by the addition of water which may be added separately.
The cement accGrdil)g to the invention may optionally coi"~,ise a radio-opaque material. Such radio-opaque materials are preferably incorporated into the solid component phase. Any conventional radio-opaque materials may be used, but prerer, ed materials include salts, such as zirconium and/or barium salts, eg.
zirconium dioxide and/or barium sulphate.
By the inclusion of monomers such as compounds of formula I
in either the polymerised form or as monomeric components, an improved surgical cement can be formulated which benefits from having one or more of the following properties:
2~ 71~29 4 (i) a lower glass transition temperature material such as TRIS which has a crack blunting function and as such improves the fatigue properties of the surgical cement, (ii) red~ ~ced odour; and (iii) radio-opacity.
In addition, if incorporating a compound of formula I in the 10 polymerised form in the liquid component or a premixed cement this red(lces the conce, Ill aLion of polymerisable double bonds prior to set and hence reduces the amount of heat generated for a specific quantity of cement.
A readily activatable cement can be prod~ ~ced which, eg. on ~xposl ~re to a water-activated polymerisation catalyst, produces a cement of good strength.
The present invention in a still further aspect provides the use of a co""~ound of formula I in the manufacture of a surgical cement or a col"ponent of a surgical cement as hereinbefore described.
Generally the compound of formula I accounts for 0.5 to 50%
w/w of the solid and liquid component system or of the premixed cement.
The present invention is a still further aspect provides the use of a compound of formula I in the manufacture of a surgical cement or a component of a surgical cement as hereinbefore described.
A water curable composition accordi, lg to the invention may include those water-activatable vinyl polymerisation catalysts described in European Patent No.94222.
Suitable vinyl polymerisation catalysts of this type are well known in the literature.
~ = =
WO 9S/07107 2 17 1 ~ 2 9 PCT/GB94/01970 Where the catalyst is a redox catalyst the premixed cer"ei1l may be in association with the oxidising agent or reducing agent or preferably both.
The amount of catalyst used in the polymerisation process eg.
in ~ssoci-lion with the premixed ce",e"t is suitably 0.1 to 10% by weight and prererably 0.2 a~.p, oxi,Y~ately 3% eg. 0.2 to 2% by weight of the prepolymer.
Desirably in surgical cei"ents of the present invention those compollel 11~ containing polymerisable material may be in ~.ssoci~tion with a polymerisation inhibitor to prevent premature poiymerisation during its p,epa,dlion and storage.
Suitable poly",e,isalion inhibitors include polymerisation inhibitors of the art. A favoured inhibitor for preventing premature polymerisation of such polymerisable materials during storage is p-methoxyphenol.
In use curing of the cements may be brought about by either mixing of the solid and liquid co",ponents or adding a suitable initiator or water to the premixed cement.
By the term surgical cement we mean bone cements and/or dental cel"el,ls although bone cements are preferred.
Accor.ling to the invention we also provide a method of fixing a prosthesis into a patient which comprises the application of a surgical cement accordi"g to the invention to an implantable prosthesis prior or during implant.
By the term prosthesis we include surgical ie. orthopaedic or dental ie. orthodontic prostheses.
The invention will now be illustrated but in no way limited by the following Examples.
Example 1 The liquid component for a 4 bone cement formulations are shown in Table 1. Formulation 1 was the control. For each 5 formulation each of the ingredients was measured into a small beaker and mixed thoroughly.
~, TABLE I
Forrnulation No. 1 2 3 4 Methyl r"ell ,aa ylate Oml 1 9ml 1 8ml 1 6ml NN dimethyl toluidine .4ml .4ml .4ml .4ml TRIS - 1 ml 2ml 4ml For each of the above formulations 33.69 medium MW
polymethylmethacrylate powder was mixed with 5.99 zirconium dioxide and 0.49 benzoyl peroxide. To this the required liquid c~,l"~o"ent was added and stirred in for 1 minute ev~Gu~ted for 1.5 15 minutes and then poured into dumbell moulds. After 30 minutes curing was complete and the dumbells were removed from their moulds.
The dumbells were tested for ulli",ate tensile strength.
The results are illustrated in Table ll.
TABLE ll Forrnulation No. Mean Tensile Strength (M/Pa) 23.3 2 24.5 3 25.5 4 16.5 2~7~29 ExamPle 2 The liquid cor",vo"ent for 3 bone ce",enl formulations are shown in Table 1. Formulation 2 was the negative control and 3 the 5 positive control. For each formulation each of the ingredients was measured into a small beaker and mixed thoroughly.
TABLE I
Formulation No. 1 2 3 Methyl metl,ac,~late - 20ml 20ml Chloroethyl ~ Lha~ylate 20ml NN dimethyltoluidine 0.4ml 0.4ml 0.4ml TABLE ll Formulation No. 1 2 3 Medium MW poly methyl 36.3g 36.39 36.39 Illell ,ac, ylate Zirconium dioxide - - 5.99 Benzoyl peroxide 0.4g 0.49 0.49 Each of the powder components were made up by mixing the 15 dry ingredients in a 4OZ bottle. To each the required liquid component was added and stirred in for 1 minute evAc~ ted for 1.5 minutes and then poured into dumbell moulds. After 30 minutes curing was complete and the dumbells were removed from their moulds.
The dumbells were x-rayed to det~r",ine relative film exposures.
Claims (13)
1. A surgical cement comprising a bulking agent, a polymerisable monomer and an activator characterised in that the polymerisable monomer is a compound of formula I, I
in which n is an integer from 1 to 6, and X is halogen, or (trialkylsiloxy) silyl.
in which n is an integer from 1 to 6, and X is halogen, or (trialkylsiloxy) silyl.
2. A surgical cement according to claim 1 wherein X is chloro.
3. A surgical cement according to claim 1 wherein the compound of formula I is 2-chloroethyl methacrylate.
4. A surgical cement according to claim 1 wherein the compound of formula I is tris(trimethylsiloxy)-3-silylpropyl methacrylate.
5. A surgical cement according to any one of the previous claims comprising a solid and a liquid component system.
6. A surgical cement according to claim 5 wherein the solid component comprises a bulking agent.
7. A surgical cement according to claim 5 wherein the bulking agent contains a compound of formula I in polymerised form.
8. A surgical cement according to claim 5 wherein the liquid component comprises a polymerisable monomer and an activator.
9. A surgical cement according to claim 1 which is radio-opaque.
10. A surgical cement according to claim 1 comprising from 0.5 to 50% w/w of a compound of formula I.
11. The use of a compound of formula I, I
in which n is an integer from 1 to 6, and X is halogen, or (trialkylsiloxy) silyl, in the manufacture of a surgical cement.
in which n is an integer from 1 to 6, and X is halogen, or (trialkylsiloxy) silyl, in the manufacture of a surgical cement.
12. A method of fixing a prosthesis into a patient which comprises the application of a surgical cement according to claim 1 to an implantable prosthesis prior or during implant.
13. A method according to claim 12 wherein the implant is an orthopaedic implant.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9318826.6 | 1993-09-10 | ||
| GB9318827.4 | 1993-09-10 | ||
| GB939318827A GB9318827D0 (en) | 1993-09-10 | 1993-09-10 | Cements |
| GB939318826A GB9318826D0 (en) | 1993-09-10 | 1993-09-10 | Cements |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2171429A1 true CA2171429A1 (en) | 1995-03-16 |
Family
ID=26303503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2171429 Abandoned CA2171429A1 (en) | 1993-09-10 | 1994-09-09 | Surgical cements |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0722346A1 (en) |
| JP (1) | JPH09502117A (en) |
| AU (1) | AU7618594A (en) |
| CA (1) | CA2171429A1 (en) |
| WO (1) | WO1995007107A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512073B2 (en) * | 1972-10-03 | 1980-03-29 | ||
| US4404327A (en) * | 1979-10-31 | 1983-09-13 | Crugnola Aldo M | Orthopaedic cement from acrylate polymers |
| JPS57501430A (en) * | 1980-09-24 | 1982-08-12 | ||
| JPH0611683B2 (en) * | 1990-07-09 | 1994-02-16 | 富士システムズ株式会社 | Dental adhesive |
-
1994
- 1994-09-09 CA CA 2171429 patent/CA2171429A1/en not_active Abandoned
- 1994-09-09 WO PCT/GB1994/001970 patent/WO1995007107A1/en not_active Application Discontinuation
- 1994-09-09 JP JP7508557A patent/JPH09502117A/en active Pending
- 1994-09-09 AU AU76185/94A patent/AU7618594A/en not_active Abandoned
- 1994-09-09 EP EP94926290A patent/EP0722346A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09502117A (en) | 1997-03-04 |
| AU7618594A (en) | 1995-03-27 |
| EP0722346A1 (en) | 1996-07-24 |
| WO1995007107A1 (en) | 1995-03-16 |
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