GB2150938A - Hydrophilic polyurethane acrylate compositions - Google Patents
Hydrophilic polyurethane acrylate compositions Download PDFInfo
- Publication number
- GB2150938A GB2150938A GB08332382A GB8332382A GB2150938A GB 2150938 A GB2150938 A GB 2150938A GB 08332382 A GB08332382 A GB 08332382A GB 8332382 A GB8332382 A GB 8332382A GB 2150938 A GB2150938 A GB 2150938A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composition
- acrylate
- hydrophilic
- hydrophilic polyurethane
- polyurethane
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000004814 polyurethane Substances 0.000 title claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 239000003814 drug Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 239000007943 implant Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000003433 contraceptive agent Substances 0.000 claims abstract description 7
- 230000002254 contraceptive effect Effects 0.000 claims abstract description 7
- 238000000502 dialysis Methods 0.000 claims abstract description 5
- 239000000017 hydrogel Substances 0.000 claims abstract description 4
- 239000008280 blood Substances 0.000 claims abstract description 3
- 210000004369 blood Anatomy 0.000 claims abstract description 3
- 238000007654 immersion Methods 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229940124976 antitubercular drug Drugs 0.000 claims description 2
- 239000005556 hormone Substances 0.000 claims description 2
- 229940088597 hormone Drugs 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical group C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004306 sulfadiazine Drugs 0.000 claims description 2
- 239000011782 vitamin Substances 0.000 claims description 2
- 229940088594 vitamin Drugs 0.000 claims description 2
- 229930003231 vitamin Natural products 0.000 claims description 2
- 235000013343 vitamin Nutrition 0.000 claims description 2
- MIQWEMDDUPSLRW-UHFFFAOYSA-N [O].O=C=O Chemical group [O].O=C=O MIQWEMDDUPSLRW-UHFFFAOYSA-N 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 125000002345 steroid group Chemical group 0.000 claims 1
- 150000003722 vitamin derivatives Chemical class 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 27
- 238000000576 coating method Methods 0.000 abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000013270 controlled release Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 239000002250 absorbent Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000010612 desalination reaction Methods 0.000 abstract description 2
- 239000003456 ion exchange resin Substances 0.000 abstract description 2
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 230000002792 vascular Effects 0.000 abstract description 2
- 239000000206 moulding compound Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- -1 nitrile carbonates Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 150000002596 lactones Chemical class 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 5
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 239000011953 free-radical catalyst Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- OGLCQHRZUSEXNB-UAPNVWQMSA-N (2r,3r,3ar,6ar)-2,3,6-trihydroxy-3,3a,6,6a-tetrahydro-2h-furo[3,2-b]furan-5-one Chemical compound OC1C(=O)O[C@@H]2[C@@H](O)[C@H](O)O[C@@H]21 OGLCQHRZUSEXNB-UAPNVWQMSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- UYUXSRADSPPKRZ-UHFFFAOYSA-N D-glucuronic acid gamma-lactone Natural products O=CC(O)C1OC(=O)C(O)C1O UYUXSRADSPPKRZ-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CCFQKJBRMQOAFR-UHFFFAOYSA-N N=C=O.N=C=O.CCC1=CC=CC=C1CC Chemical compound N=C=O.N=C=O.CCC1=CC=CC=C1CC CCFQKJBRMQOAFR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 229940092738 beeswax Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- YGXPXNPJGDEFTN-UHFFFAOYSA-N carbonic acid;hexanedinitrile Chemical compound OC(O)=O.N#CCCCCC#N YGXPXNPJGDEFTN-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- LTLCGIKWGSDBMN-UHFFFAOYSA-L dimercury diacetate Chemical compound CC(=O)O[Hg][Hg]OC(C)=O LTLCGIKWGSDBMN-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 210000004905 finger nail Anatomy 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 229950002441 glucurolactone Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000829 suppository Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 239000000814 tuberculostatic agent Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2004—Excipients; Inactive ingredients
- A61K9/2022—Organic macromolecular compounds
- A61K9/2031—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyethylene oxide, poloxamers
-
- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0052—Mixtures of macromolecular compounds
-
- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/0066—Medicaments; Biocides
-
- 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
- A61L27/26—Mixtures of macromolecular compounds
-
- 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
- A61L27/52—Hydrogels or hydrocolloids
-
- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/22—Lipids, fatty acids, e.g. prostaglandins, oils, fats, waxes
- A61L2300/222—Steroids, e.g. corticosteroids
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/428—Vitamins, e.g. tocopherol, riboflavin
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/43—Hormones, e.g. dexamethasone
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Transplantation (AREA)
- Dermatology (AREA)
- Engineering & Computer Science (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Pharmacology & Pharmacy (AREA)
- Molecular Biology (AREA)
- Biomedical Technology (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Dispersion Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Hydrophilic polyurethane/acrylate compositions which form a hydrogel upon immersion in water and is permeable to gases, ions and nonionic materials of various molecular weights comprise 100 pbw of a hydrophilic polyurethane and 10 to 50 pbw of an acrylate which is a monoacrylic or monomethacrylic ester of an alcohol of less than 13 carbon atoms. The compositions may be moulded to form shaped products, and are useful as coatings, moulding compounds absorbents, controlled release agents, ion-exchange resins, in the manufacture of dialysis membranes, cannulae, contact lenses, packaging components, desalination membranes, burn dressings, contraceptive devices, sutures, surgical implants, blood oxygenators, i.u.d., vascular prosthesis, oral delivery systems, battery separate plates, eye bandages, corneal prosthesis, anti-fog coatings, surgical drapes, oxygen exchange membranes, gas-permeable membranes, and in protective and drag-resistant coatings. Medicaments may be distributed in the compositions.
Description
SPECIFICATION
Polyurethane acrylate compositions
This invention relates to hydrophilic polyurethane acrylate compositions. More particularly, the present invention relates to compositions obtained by the reaction of one or more acrylates in the presence of one or more hydrophilic polyurethanes that may be obtained by the reaction of a polyalkylene glycol with a diisocyanate.
In published British Patent Application No. 2086927A are described polyurethane/diacrylate compositions which are substantially insoluble in alcohol such as ethanol and methanol. The hydrophilic polyurethane acrylate compositions of the present invention will form a hydrogel upon immersion in water and are permeable to gases, ions and nonionic materials of various molecular weights. Unlike the hydrophilic polyurethane diacrylate compositions, however, they are soluble in alcohol.
The hydrophilic polyurethane acrylate compositions of the present invention may be prepared by reacting an acrylate in the presence of one or more hydrophilic polyurethanes. A free radical catalyst may be present to initiate the reaction of the acrylate.
The hydrophilic polyurethanes that are employed as one component of the present invention may be made by the reaction of:
(A) one or more diols having a number average molecular weight in the range of from 106 to 20,000, selected from the group consisting of:
(a) diethylene glycol,
(b) long-chain polyoxyalkylene diols, and
(c) dialkanol amines, with
(B) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates in the presence of an organic tin catalyst.If desired, a polyfunctional lactone having the formula:
wherein R1 is a monovalent radical selected from the group consisting of -H, -OH2 NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)#CH2OH; n being an integerfrom Oto 5; and R2 is a divalent radical -(-CH)H)rn-; m being an integer from 2 to 10; and ethers derived from said lactones; may be added in amounts of from 0.1% to 30% of the weight of the total reaction mixture. Polyurethane resins containing such polyfunctional lactones are described in British Patents No. 1605079 and 1605080.
The hydrophilic polyurethane component which is present with the diacrylate at the time of its reaction contains diethylene glycol and a long-chain diol. The long-chain diols should have a molecular weight of at least 106 and preferably 1450 to 7500. Suitable diols consist predominantly of oxyethylene or oxypropylene groups, though a minor proportion of other oxyalkylene groups may be included.
The polyisocyanate used to make the first component of the present invention may be represented by
R(NCO)n wherein n is greater than 1, preferably 2-4, and R is an aliphatic, alicyclic, aliphatic-alicyclic, aromatic, or aliphatic-ammatic hydrocarbon compound of from 4 to 26 carbon atoms, but more conventionally from 6to 20 generally from 6to 13 carbon atoms.Representative examples of the above isocyanates are: tetramethylene diisocyanate; hexamethylene diisocyanate; trimethylhexamethylene diisocyanate; dimer acid diisocyanate; isophorone diisocyanate; diethylbenzene diisocyanate; decamethylene 1 ,10-diisocyanate; cyclohexylene 1,2-diisocyanate and cyclohexylene 1,4-diisocyanate and the aromatic isocyanate such as 2,4-and 2,6-tolylene diisocyanate; 4,4-diphenylmethane diisocyanate; 1,5naphthalene diisocyanate; dianisidine diisocyanate; tolidine diisocyanate; a polymeric polyisocyanate such as neopentyl tetra isocyanate; m-xylylene diisocyanate; tetrahydronaphthalene-1,5 diisocyanate; and bis (4-isocyanatophenyl) methane.
The preferred isocyanate is methylene di (cyclohexyl isocyanate). Other but slightly less preferred diisocyanates are trimethyl hexamethylene diisocyanate and isophorone diisocyanate.
Other compounds which are useful are the isocyanate equivalents which produce the urethane linkages such as the nitrile carbonate, that is, the adiponitrile carbonate of the formula:
In the manufacture of the hydrophilic polyurethane resin component of this invention, low molecular weight glycols such as diethylene glycol and dipropylene glycol or an aromatic glycol may be added to the reaction mixture. The preferred low molecular weight aromatic polyols are bisphenol A and 4,4'sulfonyldiphenol.
The proportions in which the longchain polyglycol and the low molecular weight glycol, that is, diethylene glycol are present in the hydrophilic polyurethane component of this invention depends on the hydrophobic-hydrophilic balance present in each and desired in the final composition. Increasing the molecular weight of the long-chain polyoxyethylene glycol andior the amount of this polyol contributes strong hydrophilic properties to the final product. This effect may be counter-balanced by increasing the proportion of low molecular weight glycol, that is, diethylene glycol or dipropylene glycol.
Keeping the above in mind (that it is the number of polyethylene oxide groups in the polymer molecular that determines hydrophilic properties), it is a simple matter to choose mixtures of reactants such that the hydrophilic polyurethane to be present at the time of reacting the acrylate will have the desired properties.
By choosing the molecular weight of the polyethylene glycol or using two polyalkylene glycols of different molecular weight one may "tailor make" the hydrophilic polyurethane component to satisfy a wide range of properties. It will be understood that the term "hydrophilic polyurethanes" as used throughout the specification and claims is used to describe polyurethanes which form hydrogelsthrough hydrogen bonding and which take up at least 20 weight percent water when immersed in water. Moreover, the hydrophilic polyurethane acrylate compositions of the present invention, like the hydrophilic polyurethane component also form hydrogels when immersed in water that take up at least 20 weight percent water.
As mentioned above, the hydrophilic polyurethane component that is reacted with acrylate to form the compositions of the present invention may contain a polyfunctional lactone. Representative examples of the polyfunctional lactones are those derived from polysaccharides and monosaccharides such as mannolactone, delta gluconolactone, sorbolactone and D-glucuronolactone.
It is desirable that the lactones employed have at least 3 and preferably 4 or more hydroxyl groups in the molecule or at least 1 more than is required to form a linear polyurethane chain. The free (unreacted) hydroxyl groups remain in the polymer backbone and are available for crosslinking the polymer. The lactone ring is also reactive and may be opened, that is, by hydrolysis, to form carboxylate groups or carboxyl groups in the polymer backbone.
In making the first component of the present invention, the glycols are mixed with the lactone, if present, and the polyisocyanate is reacted with the mixture although other techniques may be used. The reaction is catalyzed by known catalyst for such reaction, suitable ones being tin salts and organic tin esters such as dibutyl tin dilaurate, tertiary amines e.g. triethylene diamine (DABCD), N,N,N',N '4etramethyl-1,3-butane diamine and other recognized catalyst for urethane reactions which are well known in the art. The reaction can be conducted in the absence or presence of diluent or solvent.
The second component of the composition of the present invention is an acrylate. When used throughout the specification and claims the term "acrylate" shall mean and be the monoacrylic or monomethacrylic ester of an alcohol having less than 13 carbon atoms which may be made by combining one mole of acrylic or methacrylic acid with one mole of an alcohol. The preferred acrylates are hydroxyethyl methacrylate, methyl methacrylate and methyl acrylate although other esters of acrylic and methacrylic acid may be used.
In preparing the hydrophilic polyurethane acrylate composition of the present invention, 100 parts by weight of one or more polyurethanes are preferably dissolved together with from about 10 to about 50 parts by weight of one or more acrylates in a solvent such as methanol or 95% ethanol and a free radical catalyst is added to initiate polymerization of the acrylate. The solution of the two components may be cast to form a film and heat cured at temperatures in the range of 110,0 to 1 350C or alternatively, the cast film may be cured by the action of ultraviolet light. If insolubilization of the two component composition is to be initiated by ultraviolet light, it is not necessary that the free radical catalyst be present.It may be desirable, however, to add an ultraviolet absorber such as Rhodamine B or an azo type catalyst such as azo bis-isobutyl nitrile to the mixture of the two components.
If it is desired to prepare shaped articles or tubing from the hydrophilic polyurethane acrylate compositions of the present invention, the solvent may be removed under reduced pressure and the residual mixture can be molded at temperatures of 11000 to 13500 for from about 20 to about 60 minutes to cure the hydrophilic polyurethane acrylate composition.
The hydrophilic polyurethane acrylate compositions of the present invention absorb water and the amount of water that is absorbed may be varied by the nature of the hydrophilic polyurethane present and bythe amounts and types of acrylate present in the composition.
The above described hydrophilic polyurethane acrylate resin compositions are also useful as coatings, molding compounds, absorbents, controlled release agents, ion exchange resins, in dentistry, and in the manufacture of dialysis membrane cannulae, contact lenses, packaging components, desalination membranes, burn dressings, contraceptive devices, sutures, surgical implants, blood oxygenators, intrauterine devices, vascular prostheses, oral delivery systems, battery separator plates, eye bandages, corneal prostheses, anti-fog coatings, surgical drapes, oxygen exchange membranes, artificial finger nails, finger stalls adhesives, gas permeable membranes, and in protective and drag resistant coatings.
The practice of the invention is further illustrated by the following examples without being restricted thereto, the parts being by weight, unless otherwise stated.
Example I
A polyurethane polymer is prepared by melting together in a container 822.3 parts of CARBOWAX 8,000 (a polyethylene glycol having a number average molecular weight of 8,000 manufactured by Union Carbide
Corporation, New York, New York 10017), 23.0 parts of diethylene glycol, 5.4 parts of water. The mixture becomes clear at about 800C and is cooled to 750C. When the temperature reaches 75"C, 149.7 parts of methylene bis-cyclohexyl-4,4'-isocyanate (a product identified as DESMODUR W by the Mo bay Chemical
Corporation, Penn Lincoln Parkway West, Pittsburgh, Pennsylvania 15205).The mixture is stirred at 750C for 15 minutes, cooled to 50 C and then there is added 2.0 parts by volume of an organic tin catalyst, dibutyl tin dilaurate (a product identified as T12 (manufactured by Metal and Thermite Company of Rahway, New
Jersey). The catalyst is added and the reaction mixture is allowed to exotherm from 500C to 750C. The molten product is poured atatemperatureof75'Cinto polypropylene pans and heated in an oven at 1 OOOC to complete the reaction and form a foamed hydrophilic polyurethane product. When immersed in water, 100 parts of this product will absorb 470 parts of water, (water uptake 470%).
The polyurethane product is cooled to room temperature, removed from the pans and dissolved in 95% ethanol to give a solution containing 9.82% by weight solids. To 305.5 parts of this polyurethane solution in ethanol is added with stirring 6.0 parts of hydroxyethyl methacrylate and 0.427 parts by volume of tert butyl peroctoate. The solvent is evaporated at room temperature under vacuum to give a product containing 100 parts of hydrophilic polyurethane and 20 parts of hydroxyethyl methacrylate, that is subsequently cured at a temperature of 121 'C for 20 minutes. This product, after curing, takes up 408%-428% water and exhibits 70%-75% elongation.
Example Il A contact lens may be prepared by spinning from solution. The mixture of 305.5 parts of polyurethane solution in ethanol, 6.0 parts of hydroxyethyl methacrylate and 0.427 parts by volume of tert butyl peroctoate described above in Example I, is evaporated under vacuum to increase the solids content until the solution viscosity reaches 12-15 poise (approximately 11 %-12% non-volatile).
A concave mold conforming to the desired shape of the convex side of a contact lens is mounted on a vertical shaft that can be rotated at a top speed of 200 rpm.
The concave portion of the mold is half filled with the 12-15 poise solution. The mold is slowly started and brought to top speed over 5 minutes. It is allowed to spin at top speed for an additional 5 minutes. The spinning mold is allowed to come to rest.
The mold is then placed in an oven with a nitrogen atmosphere. The temperature is allowed to raise slowly to 125 C and is maintained for 20 minutes. After cooling, the mold is placed in water and the polymer hydrates and becomes separated from the mold.
If desired, the polyurethane-hydroxyethyl methacrylate composition described above in Example I may be mixed with, or used to encapsulate drugs prior to the curing step. Drugs that may be dispersed in this manner are, for example, vitamins, hormones, steroids, drug protagonists and anti-tubercular drugs.
The cured polymer will slowly release the drug when placed in an aqueous or saline solution or in body fluids. The resin composition described in this Example, therefore, may be formed into any convenient shape, for example, tablets for oral ingestion, implants, intrauterine devices, diaphragms and suppositories to provide a controlled release of the drug. If desirable, a contraceptive such as lactic acid may be added to the diaphragm or contraceptive during manufacture.
Example Ill To 305.5 parts of the 9.82% ethanol solution containing 30 parts of a hydrophilic polyurethane resin described in Example I above is added 6.0 parts of methyl acrylate and 0.427 parts of tert butyl peroctoate.
The solvent is evaporated at room temperature under vacuum to give a product comprising 100 parts of hydrophilic polyurethane and 20 parts of methyl acrylate.
This product may be cured in various shapes by heating in an oven at 1210C for 30-60 minutes under nitrogen. The cured polyurethane methyl acrylate composition will take up from 716%-758% water and has about 112% elongation.
Alternatively, the polyurethane-methyl acrylate composition may be pressed into the form of a flat sheet or a contact lens by heating under pressure in a press at 1 00'C and increasing the temperature to 1 30'C for 2 minutes while maintaining the pressure. The sheet may be used as a membrane for water and vapor transmissions and has medicinal applications as a surgical drape (which may be coated on one side with an adhesive) as it is particularly advantageous as a burn dressing into which medicaments such as sulfadiazine may be incorporated. The polyurethane-acrylate composition (containing as little as 10 weight percent methyl acrylate is useful as a dialysis membrane and finds application in separation techniques.
Example IV A polyurethane methyl methacrylate composition is made by the method described in Example I above from the following mixture:
Hydrophilic polyurethane (9.8%
ethanol solution of Example 1) 305.5 parts
Methyl methacrylate 6.0 parts
Tert butyl peroctoate 0.432 parts
The solution may be evaporated to dryness at room temperature under vacuum to give a product which may be extruded under heat and pressure to produce a hydrophilic canula having desirable physical properties. If desired a medicament may be incorporation with the resin prior to extrusion. The polyurethane acrylate composition of the Example (in ethanol solution) may also be employed to coat a preformed canula and cured at a temperature of 120 C following evaporation of the solvent.
When the above composition is cured in an oven with an inert atmosphere at 201 C for 30 minutes, the resulting product will take up 726% water and has an elongation of 111%.
Cured cast or molded films that are useful as wound dressings and will slowly release iodine may be prepared from the resin composition of this Example by incorporating in the polyurethane-methyl methacrylate composition, after curing, iodine.
Example V
To the solution of 305.5 parts of hydrophilic polyurethane (9.82% solids), 6 parts of hydroxyethyl methacrylate, and 0.427 parts of tert butyl perotoate in ethanol described above in Example I, may be suspended 3% by weight of mercurous acetate and 1% by weight bee's wax (based on resin solids). This solution can be applied to the hull of a boat and will be cured by the actinic rays of the sun to form an insoluble coating which will decrease drug resistance and inhibit marine growth by the slow release of mercury.
Example Vl The solution of 305.5 parts of hydrophilic polyurethane (9.82% solids), 6 parts of hydroxyethyl methacrylate, and 0.427 parts of tert butyl peroctoate in ethanol described above in Example I is heated at room temperature under vacuum to remove the ethanol. The resulting white solid may be extruded at temperatures below the curing temperature under pressure to form tubing which is subsequently cured and is water and gas permeable. Such tubing is useful in kidney dialysis equipment.
Claims (37)
1. A hydrophilic polyurethanetacrylate composition which will form a hydrogel upon immersion in water and is permeable to gases, ions and nonionic materials of various molecular weights, said composition comprising substantially 100 parts of a hydrophilic polyurethane and from 10 to 50 parts by weight of an acrylate.
2. A hydrophilic polyurethanelacrylate composition as claimed in Claim 1 wherein said acrylate is hydroxyethyl methacrylate.
3. A hydrophilic polyurethanelacrylate composition as claimed in Claim 1 wherein said acrylate is methyl methacrylate.
4. A hydrophilic polyurethanelacrylate composition as claimed in Claim 1 wherein said acrylate is methyl acrylate.
5. A hydrophilic polyurethane/acrylate composition as claimed in any preceding Claim wherein said acrylate comprises substantially 17 weight percent of said composition.
6. A hydrophilic polyurethane/acrylate composition as claimed in any preceding Claim wherein said polyurethane is derived from a mixture of polyols and a diisocyanate.
7. A hydrophilic polyurethanelacrylate composition as claimed in Claim 6 wherein one of said polyols is a polyol having a molecular weight of 8,000.
8. A composition as claimed in Claim 1 and substantially as hereinbefore described with reference to any of the Examples.
9. A burn dressing which comprises a hydrophilic polyurethanelacrylate composition as claimed in any preceding Claim in the form of a film.
10. A burn dressing as claimed in Claim 9 having present in said hydrophilic polyurethane acrylate composition a medicament.
11. A burn dressing as claimed in Claim 10 wherein said medicament is sulfadiazine.
12. An implant which comprises a hydrophilic polyurethanelacrylate composition as claimed in any of
Claims 1 to 8 and containing a medicament.
13. An implant as claimed in Claim 12 wherein said medicament is an anti-tubercular drug.
14. An implant as claimed in Claim 12 wherein said medicament is a drug protagonist.
15. An implant as claimed in Claim 12 wherein said medicament is a hormone.
16. An implant as claimed in Claim 12 wherein said medicament is a steroid.
17. An implant as claimed in Claim 12 wherein said medicament is a vitamin.
18. An implant as claimed in Claim 12 in the form of a contraceptive device.
19. A contraceptive device as claimed in Claim 18 in the shape of a diaphragm.
20. A contraceptive device as claimed in Claim 18 in the form of an intrauterine device containing an active component.
21. An intrauterine device as claimed in Claim 20 wherein the active component is lactic acid.
22. A canula, the walls of which are formed of a hydrophilic polyurethaneiacrylate composition as claimed in any of Claims 1 to 8.
23. A canula as claimed in Claim 22 wherein said hydrophilic polyurethane/acrylate composition has distributed throughout its mass a medicament.
24. A canula as claimed in Claim 22 wherein said medicament is iodine.
25. A canula, at least one wall of which is coated with a hydrophilic polyurethane/acrylate composition as claimed in any of Claims 1 to 8.
26. An oral delivery system comprising a pharmacologically active agent and a hydrophilic polyurethane/acrylate composition as claimed in any of Claims 1 to 8 as a carrier vehicle therefor.
27. A gas permeable membrane formed of a hydrophilic polyurethaneiacrylate composition as claimed in any of Claims 1 to 8.
28. A corneal prosthesis comprising a hydrophilic polyurethaneiacrylate composition as claimed in any of Claims 1 to 8.
29. A method of imparting moisture to dry gas which comprises passing the gas through a tube formed of a hydrophilic polyurethane/acrylate composition as claimed in any of Claims 1 to 8.
30. A surgical drape comprising a film of a hydrophilic polyurethane/acrylate composition as claimed in any of Claims 1 to 8.
31. A dialysis membrane formed of the hydrophilic polyurethane/acrylate composition of Claim 1.
32. A blood oxygenator which comprises a carbon dioxide - oxygen exchange membrane wherein said membrane is formed of hydrophilic polyurethane/acrylate composition as claimed in any of Claims 1 to 8.
33. A contact lens which comprises molded hydrophilic polyurethaneiacrylate composition as claimed in any of Claims 1 to 8.
34. A shaped article which comprises a hydrophilic polyurethane/acrylate composition as claimed in any of Claims 1 to 8 which has been molded to form a predetermined shape.
35. A method of preparing a hydrophilic polyurethane acrylate composition which comprises reacting from 10 to 50 parts by weight of an acrylate in the presence of substantially 100 parts by weight of a hydrophilic polyurethane.
36. A transparent object that has been rendered fog resistant by the application thereto of a hydrophilic polyurethaneiacrylate composition as claimed in any of Claims 1 to 8.
37. A boat, the hull of which has been coated with a composition to provide drag resistant properties, wherein said composition is a hydrophilic polyurethane/acrylate composition as claimed in any of Claims 1 to8.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08332382A GB2150938B (en) | 1983-12-05 | 1983-12-05 | Hydrophilic polyurethane acrylate compositions |
| DE19833344001 DE3344001A1 (en) | 1983-12-05 | 1983-12-06 | HYDROPHILE POLYURETHANE ACRYLATE COMPOSITION AND THEIR USE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08332382A GB2150938B (en) | 1983-12-05 | 1983-12-05 | Hydrophilic polyurethane acrylate compositions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8332382D0 GB8332382D0 (en) | 1984-01-11 |
| GB2150938A true GB2150938A (en) | 1985-07-10 |
| GB2150938B GB2150938B (en) | 1987-04-23 |
Family
ID=10552827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08332382A Expired GB2150938B (en) | 1983-12-05 | 1983-12-05 | Hydrophilic polyurethane acrylate compositions |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE3344001A1 (en) |
| GB (1) | GB2150938B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2557576A1 (en) * | 1984-01-03 | 1985-07-05 | Gould Francis | Hydrophilic polyurethane acrylate composition, process for its preparation and its use as burn dressing, implant, contraceptive, intrauterine device, cannula, oral application system, gas-permeable membrane, corneal prosthesis, surgical dressing, dialysis membrane, contact lens and coating for boat hulls |
| GB2190037A (en) * | 1986-05-10 | 1987-11-11 | Victaulic Plc | Improvements in or relating to the moulding of plastics products |
| GB2199040A (en) * | 1986-12-06 | 1988-06-29 | Smith & Nephew Ass | Adhesives, their preparation and use |
| JPS63225679A (en) * | 1986-12-06 | 1988-09-20 | スミス アンド ネフュー ピーエルシー | Adhesive, and its production and use |
| WO1989003860A1 (en) * | 1987-10-14 | 1989-05-05 | Tyndale Plains-Hunter, Ltd. | Moisture sensitive elastomer compositions |
| GB2215207A (en) * | 1988-01-28 | 1989-09-20 | Fulmer Yarsley Ltd | Sustained release pharmaceutical dosage units |
| US4874373A (en) * | 1987-03-03 | 1989-10-17 | Luther Ronald B | Dip formed catheter and assembly |
| GB2235462A (en) * | 1989-08-15 | 1991-03-06 | Nat Res Dev | Polymeric materials |
| DE9200765U1 (en) * | 1991-01-23 | 1992-04-16 | British Technology Group plc, London | Composition for controlled drug release |
| US5261896A (en) * | 1990-01-10 | 1993-11-16 | Rochester Medical Corporation | Sustained release bactericidal cannula |
| WO1994004587A1 (en) * | 1992-08-19 | 1994-03-03 | Smith & Nephew Research Ltd | Polymer products |
| US5360402A (en) * | 1990-01-10 | 1994-11-01 | Rochester Medical Corporation | Hand-actuated retention catheter |
| US5725576A (en) * | 1995-06-01 | 1998-03-10 | Mezhotraslevoi Nauchno-Tekhnichesky Komplex "Mikrokhirurgia Glaza" | Polymer material for making an elastic intraocular lens and a lens based on said material |
| US6346121B1 (en) * | 1996-08-26 | 2002-02-12 | The Lions Eye Institute Of Western Australia Incorporated | Ocular socket prosthesis |
| WO2006120454A1 (en) * | 2005-05-12 | 2006-11-16 | Medtrade Products Limited | Film forming composition |
| DE102007002783A1 (en) | 2007-01-18 | 2008-08-07 | Bayer Materialscience Ag | Hydrogels of hydrophilic polyurethane (meth) acrylates |
| US8864730B2 (en) | 2005-04-12 | 2014-10-21 | Rochester Medical Corporation | Silicone rubber male external catheter with absorbent and adhesive |
| US9707375B2 (en) | 2011-03-14 | 2017-07-18 | Rochester Medical Corporation, a subsidiary of C. R. Bard, Inc. | Catheter grip and method |
| US9872969B2 (en) | 2012-11-20 | 2018-01-23 | Rochester Medical Corporation, a subsidiary of C.R. Bard, Inc. | Catheter in bag without additional packaging |
| US10092728B2 (en) | 2012-11-20 | 2018-10-09 | Rochester Medical Corporation, a subsidiary of C.R. Bard, Inc. | Sheath for securing urinary catheter |
| US10857324B2 (en) | 2014-08-26 | 2020-12-08 | C. R. Bard, Inc. | Urinary catheter |
| US11547599B2 (en) | 2017-09-19 | 2023-01-10 | C. R. Bard, Inc. | Urinary catheter bridging device, systems and methods thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6626888B1 (en) | 1990-01-10 | 2003-09-30 | Rochester Medical Corporation | Method of shaping structures with an overcoat layer including female urinary catheter |
| US5971954A (en) | 1990-01-10 | 1999-10-26 | Rochester Medical Corporation | Method of making catheter |
| US5670111A (en) | 1990-01-10 | 1997-09-23 | Rochester Medical Corporation | Method of shaping structures with an overcoat layer including female urinary catheter |
| US5269770A (en) | 1990-01-10 | 1993-12-14 | Rochester Medical Corporation | Microcidal agent releasing catheter with balloon |
| DE4111098A1 (en) * | 1991-04-05 | 1992-10-08 | Beiersdorf Ag | HYDROPHILIC SHEARS AND METHOD FOR THE PRODUCTION THEREOF |
| DE102008023798A1 (en) * | 2008-05-15 | 2009-11-19 | Hans Hermann Schulz | Hydrogel, which is formed by in situ radiation curing of at least one urethane acrylate-precursor, useful for treating wounds, where the precursor is obtained from polyalkylene oxide, diisocyanate and unsaturated alcohol |
| CN114984297A (en) * | 2022-06-13 | 2022-09-02 | 湖北唯美医疗用品有限公司 | Preparation method of ultraviolet-cured rapid hemostatic hydrogel material and hemostatic hydrogel material prepared by same |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1342278A (en) * | 1970-04-22 | 1974-01-03 | Rohm & Haas | Polyurethane-coated substrates |
| GB1441108A (en) * | 1973-01-23 | 1976-06-30 | Redfarn C A | Cross linked polymers |
| GB1450906A (en) * | 1972-12-04 | 1976-09-29 | Basf Ag | Manufacture of thin layers of polyurethane elastomers |
| US4116786A (en) * | 1976-06-08 | 1978-09-26 | Union Carbide Corporation | Radiation curable coating compositions containing an acrylate-capped, polyether urethane and a polysiloxane |
| GB2002009A (en) * | 1977-07-12 | 1979-02-14 | Union Carbide Corp | >Radiation curable coating composition |
| GB1545061A (en) * | 1975-03-12 | 1979-05-02 | Loctite Corp | Curable poly(alkylene)ether polyol-based resins having improved properties |
| GB2010880A (en) * | 1977-12-23 | 1979-07-04 | Armstrong Cork Co | Curable coating compositions and coatings obtained therefrom |
| GB2012290A (en) * | 1978-01-03 | 1979-07-25 | Lord Corp | Actinic radiation curable formulations |
| GB2018263A (en) * | 1978-03-30 | 1979-10-17 | Union Carbide Corp | Acrylyl capped urethane obligomers |
| GB1575898A (en) * | 1977-03-21 | 1980-10-01 | Witco Chemical Corp | Crosslinkable polyurethane resins |
| GB1590412A (en) * | 1976-08-02 | 1981-06-03 | Lord Corp | Radiation curable compositions |
| GB1590413A (en) * | 1976-07-23 | 1981-06-03 | Lord Corp | Radiation curable coating composition |
| GB1599203A (en) * | 1977-02-07 | 1981-09-30 | Goodyear Tire & Rubber | Polyetherurethane composition and polymer prepared by photopolymerization |
| EP0043073A2 (en) * | 1980-06-25 | 1982-01-06 | E.I. Du Pont De Nemours And Company | Photocurable polyurethane film coatings |
| GB2086927A (en) * | 1980-11-12 | 1982-05-19 | Johnston Christian William | Hydrophilic polyurethane/diacrylate compositions |
| GB2112794A (en) * | 1981-12-31 | 1983-07-27 | Ppg Industries Inc | Polyurea-polyurethane acrylate polymer dispersions |
-
1983
- 1983-12-05 GB GB08332382A patent/GB2150938B/en not_active Expired
- 1983-12-06 DE DE19833344001 patent/DE3344001A1/en not_active Withdrawn
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1342278A (en) * | 1970-04-22 | 1974-01-03 | Rohm & Haas | Polyurethane-coated substrates |
| GB1450906A (en) * | 1972-12-04 | 1976-09-29 | Basf Ag | Manufacture of thin layers of polyurethane elastomers |
| GB1441108A (en) * | 1973-01-23 | 1976-06-30 | Redfarn C A | Cross linked polymers |
| GB1545061A (en) * | 1975-03-12 | 1979-05-02 | Loctite Corp | Curable poly(alkylene)ether polyol-based resins having improved properties |
| US4116786A (en) * | 1976-06-08 | 1978-09-26 | Union Carbide Corporation | Radiation curable coating compositions containing an acrylate-capped, polyether urethane and a polysiloxane |
| GB1590413A (en) * | 1976-07-23 | 1981-06-03 | Lord Corp | Radiation curable coating composition |
| GB1590412A (en) * | 1976-08-02 | 1981-06-03 | Lord Corp | Radiation curable compositions |
| GB1599203A (en) * | 1977-02-07 | 1981-09-30 | Goodyear Tire & Rubber | Polyetherurethane composition and polymer prepared by photopolymerization |
| GB1575898A (en) * | 1977-03-21 | 1980-10-01 | Witco Chemical Corp | Crosslinkable polyurethane resins |
| GB2002009A (en) * | 1977-07-12 | 1979-02-14 | Union Carbide Corp | >Radiation curable coating composition |
| GB2010880A (en) * | 1977-12-23 | 1979-07-04 | Armstrong Cork Co | Curable coating compositions and coatings obtained therefrom |
| GB2012290A (en) * | 1978-01-03 | 1979-07-25 | Lord Corp | Actinic radiation curable formulations |
| GB2018263A (en) * | 1978-03-30 | 1979-10-17 | Union Carbide Corp | Acrylyl capped urethane obligomers |
| EP0043073A2 (en) * | 1980-06-25 | 1982-01-06 | E.I. Du Pont De Nemours And Company | Photocurable polyurethane film coatings |
| GB2086927A (en) * | 1980-11-12 | 1982-05-19 | Johnston Christian William | Hydrophilic polyurethane/diacrylate compositions |
| GB2112794A (en) * | 1981-12-31 | 1983-07-27 | Ppg Industries Inc | Polyurea-polyurethane acrylate polymer dispersions |
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2557576A1 (en) * | 1984-01-03 | 1985-07-05 | Gould Francis | Hydrophilic polyurethane acrylate composition, process for its preparation and its use as burn dressing, implant, contraceptive, intrauterine device, cannula, oral application system, gas-permeable membrane, corneal prosthesis, surgical dressing, dialysis membrane, contact lens and coating for boat hulls |
| GB2190037A (en) * | 1986-05-10 | 1987-11-11 | Victaulic Plc | Improvements in or relating to the moulding of plastics products |
| GB2190037B (en) * | 1986-05-10 | 1989-11-29 | Victaulic Plc | Improvements in or relating to the moulding of plastics products |
| US4914173A (en) * | 1986-12-06 | 1990-04-03 | Smith And Nephew Associate Companies Plc | Adhesives, their preparation and use |
| GB2199040A (en) * | 1986-12-06 | 1988-06-29 | Smith & Nephew Ass | Adhesives, their preparation and use |
| JPS63225679A (en) * | 1986-12-06 | 1988-09-20 | スミス アンド ネフュー ピーエルシー | Adhesive, and its production and use |
| JP2619442B2 (en) | 1986-12-06 | 1997-06-11 | スミス アンド ネフュー ピーエルシー | Adhesive, its production method and use |
| GB2199040B (en) * | 1986-12-06 | 1990-01-24 | Smith & Nephew Ass | Adhesives, their preparation and use |
| US4874373A (en) * | 1987-03-03 | 1989-10-17 | Luther Ronald B | Dip formed catheter and assembly |
| WO1989003860A1 (en) * | 1987-10-14 | 1989-05-05 | Tyndale Plains-Hunter, Ltd. | Moisture sensitive elastomer compositions |
| GB2215207A (en) * | 1988-01-28 | 1989-09-20 | Fulmer Yarsley Ltd | Sustained release pharmaceutical dosage units |
| GB2235462A (en) * | 1989-08-15 | 1991-03-06 | Nat Res Dev | Polymeric materials |
| GB2235462B (en) * | 1989-08-15 | 1992-12-16 | Nat Res Dev | Polymeric materials |
| US5261896A (en) * | 1990-01-10 | 1993-11-16 | Rochester Medical Corporation | Sustained release bactericidal cannula |
| US5360402A (en) * | 1990-01-10 | 1994-11-01 | Rochester Medical Corporation | Hand-actuated retention catheter |
| DE9200765U1 (en) * | 1991-01-23 | 1992-04-16 | British Technology Group plc, London | Composition for controlled drug release |
| WO1994004587A1 (en) * | 1992-08-19 | 1994-03-03 | Smith & Nephew Research Ltd | Polymer products |
| GB2284821A (en) * | 1992-08-19 | 1995-06-21 | Smith & Nephew | Polymer products |
| US5725576A (en) * | 1995-06-01 | 1998-03-10 | Mezhotraslevoi Nauchno-Tekhnichesky Komplex "Mikrokhirurgia Glaza" | Polymer material for making an elastic intraocular lens and a lens based on said material |
| US5833890A (en) * | 1995-06-01 | 1998-11-10 | Mezhotraslevoi Nauchno-Tekhnichesky Komplex | Method for making an elastic intraocular lens |
| US6346121B1 (en) * | 1996-08-26 | 2002-02-12 | The Lions Eye Institute Of Western Australia Incorporated | Ocular socket prosthesis |
| US8864730B2 (en) | 2005-04-12 | 2014-10-21 | Rochester Medical Corporation | Silicone rubber male external catheter with absorbent and adhesive |
| US9248058B2 (en) | 2005-04-12 | 2016-02-02 | Rochester Medical Corporation, a subsidiary of C.R. Bard, Inc. | Male external catheter with absorbent and adhesive |
| WO2006120454A1 (en) * | 2005-05-12 | 2006-11-16 | Medtrade Products Limited | Film forming composition |
| US9782514B2 (en) | 2005-05-12 | 2017-10-10 | Med-Trade Products Limited | Film forming compositon |
| DE102007002783A1 (en) | 2007-01-18 | 2008-08-07 | Bayer Materialscience Ag | Hydrogels of hydrophilic polyurethane (meth) acrylates |
| US7947863B2 (en) | 2007-01-18 | 2011-05-24 | Bayer Material Science Ag | Hydrogels of hydrophilic polyurethane (meth)acrylates |
| US10569051B2 (en) | 2011-03-14 | 2020-02-25 | Rochester Medical Corporation, a subsidiary of C. R. Bard, Inc. | Catheter grip and method |
| US9707375B2 (en) | 2011-03-14 | 2017-07-18 | Rochester Medical Corporation, a subsidiary of C. R. Bard, Inc. | Catheter grip and method |
| US11607524B2 (en) | 2011-03-14 | 2023-03-21 | Rochester Medical Corporation | Catheter grip and method |
| US10092728B2 (en) | 2012-11-20 | 2018-10-09 | Rochester Medical Corporation, a subsidiary of C.R. Bard, Inc. | Sheath for securing urinary catheter |
| US10780244B2 (en) | 2012-11-20 | 2020-09-22 | Rochester Medical Corporation, a subsidiary of C. R. Bard, Inc. | Catheter in a bag without additional packaging |
| US9872969B2 (en) | 2012-11-20 | 2018-01-23 | Rochester Medical Corporation, a subsidiary of C.R. Bard, Inc. | Catheter in bag without additional packaging |
| US11730919B2 (en) | 2012-11-20 | 2023-08-22 | Rochester Medical Corporation | Catheter in bag without additional packaging |
| US12311120B2 (en) | 2012-11-20 | 2025-05-27 | Rochester Medical Corporation | Catheter in bag without additional packaging |
| US10857324B2 (en) | 2014-08-26 | 2020-12-08 | C. R. Bard, Inc. | Urinary catheter |
| US10874825B2 (en) | 2014-08-26 | 2020-12-29 | C. R. Bard, Inc. | Urinary catheter |
| US11850370B2 (en) | 2014-08-26 | 2023-12-26 | C. R. Bard, Inc. | Urinary catheter |
| US11547599B2 (en) | 2017-09-19 | 2023-01-10 | C. R. Bard, Inc. | Urinary catheter bridging device, systems and methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2150938B (en) | 1987-04-23 |
| DE3344001A1 (en) | 1985-06-13 |
| GB8332382D0 (en) | 1984-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB2150938A (en) | Hydrophilic polyurethane acrylate compositions | |
| US4780512A (en) | Polyurethane acrylate compositions | |
| US4439585A (en) | Polyurethane diacrylate compositions as carrier for pharmacological agents | |
| US4424305A (en) | Surgical implants formed of polyurethane diacrylate compositions | |
| CA1175596A (en) | Hydrophilic polyurethane diacrylate composition | |
| US4439583A (en) | Polyurethane diacrylate compositions useful in forming canulae | |
| US4408023A (en) | Polyurethane diacrylate compositions useful for contact lenses and the like | |
| US4496535A (en) | Polyurethane polyene compositions | |
| US4454309A (en) | Polyurethane polyene compositions | |
| US4810582A (en) | Hydrophilic polyurethane composition | |
| US4255550A (en) | Polyurethane polymers characterized by carboxylate groups and hydroxyl groups in the polymer backbone | |
| US4798876A (en) | Hydrophilic polyurethane composition | |
| US4131604A (en) | Polyurethane elastomer for heart assist devices | |
| US4136250A (en) | Polysiloxane hydrogels | |
| US4789720A (en) | Hydrophilic polyurethanes prepared from mixed oxyalkylene glycols | |
| CN1950098B (en) | Biodegradable polyurethane and polyurethane ureas | |
| US5728762A (en) | Polyether polyurethane polymers, gels, solutions and uses thereof | |
| US4156066A (en) | Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backbone | |
| JP2993646B2 (en) | Novel prepolymers useful in medical devices | |
| US4451635A (en) | Polyurethane quaternary ammonium salts | |
| GB2111067A (en) | Extrudable polyurethane for prosthetic devices | |
| EP0335664A2 (en) | Fluorinated polyetherurethanes and medical devices therefrom | |
| US4439584A (en) | Gas and ion permeable membranes formed of polyurethane diacrylate compositions | |
| US4490423A (en) | Polyurethane polyene compositions | |
| GB1605079A (en) | Polyurethane polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |