USRE27401E - Cross-linked hydrophilic polymers and articles made therefrom - Google Patents
Cross-linked hydrophilic polymers and articles made therefrom Download PDFInfo
- Publication number
- USRE27401E USRE27401E US27401DE USRE27401E US RE27401 E USRE27401 E US RE27401E US 27401D E US27401D E US 27401DE US RE27401 E USRE27401 E US RE27401E
- Authority
- US
- United States
- Prior art keywords
- water
- hydrogel
- acid
- hydrogels
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001477 hydrophilic polymer Polymers 0.000 title description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 13
- 150000007513 acids Chemical class 0.000 abstract description 5
- -1 HYDROXYL GROUP Chemical group 0.000 abstract 2
- 239000000017 hydrogel Substances 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 52
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 23
- 150000005690 diesters Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 239000000470 constituent Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- 210000001519 tissue Anatomy 0.000 description 11
- 150000001298 alcohols Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002504 physiological saline solution Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 210000004400 mucous membrane Anatomy 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- DEWPRFSWNWKLHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCCN(CCO)CCO DEWPRFSWNWKLHF-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229930182555 Penicillin Natural products 0.000 description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229940049954 penicillin Drugs 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- PFUWZSMBSDNGDH-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OC(=O)C(O)C(O)C(O)=O PFUWZSMBSDNGDH-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MZGMQAMKOBOIDR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCO MZGMQAMKOBOIDR-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- YCHXXZUEOABJIB-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.OCCN(CCO)CCO YCHXXZUEOABJIB-UHFFFAOYSA-N 0.000 description 1
- BXYKPNAKWRRWDB-UHFFFAOYSA-N 2-hydroxy-4-methyl-3-oxopent-4-enoic acid Chemical compound CC(=C)C(=O)C(O)C(O)=O BXYKPNAKWRRWDB-UHFFFAOYSA-N 0.000 description 1
- MNZNJOQNLFEAKG-UHFFFAOYSA-N 2-morpholin-4-ylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCOCC1 MNZNJOQNLFEAKG-UHFFFAOYSA-N 0.000 description 1
- GMTJKMKNOIUGPG-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCCCC1 GMTJKMKNOIUGPG-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- ADDIZIHJAQLZCJ-UHFFFAOYSA-N 4-hydroxy-2-(2-hydroxyethyl)butanamide Chemical compound OCCC(C(=O)N)CCO ADDIZIHJAQLZCJ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010015946 Eye irritation Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 231100000013 eye irritation Toxicity 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012907 medicinal substance Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F6/00—Contraceptive devices; Pessaries; Applicators therefor
- A61F6/06—Contraceptive devices; Pessaries; Applicators therefor for use by females
- A61F6/08—Pessaries, i.e. devices worn in the vagina to support the uterus, remedy a malposition or prevent conception, e.g. combined with devices protecting against contagion
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1669—Cellular material
- B01D39/1676—Cellular material of synthetic origin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- 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
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
Definitions
- ABSTRACT OF THE DISCLOSURE A major portion of a monoester of acrylic or methacrylic acid with a bi-functional alcohol which has an esterifimble hydroxyl group and at least one additional hydrophilic functional group is copolymerized in aqueous solution with a small amount of a diester of these acids and of an alcohol which has at least two esterifiable hydroxyl groups until a shape retaining body is obtained.
- This invention relates to a novel cross-linked hydrophilic polymer, to a hydrogel of which it is an essential constituent, and to articles made therefrom.
- hydrogels essentially consisting of 20 to 97% of an aqueous liquid and a crosslinked hydrophilic polymer have desirable physical, optical, and physiological properties.
- the hydrogels of the invention retain a large percentage of water relative to the weight of their dry substance. In their hydrated condition they are elastically deformable under relatively small pressure but virtually immune to plastic deformation. They may be colorless or virtually colorless, and may be optically clear. They form semi-permeable membranes which permit passage of water and certain dissolved materials, but retain others.
- the hydrogels of the invention are compatible with body tissue for extended periods and may be employed for implants in the body separating tissue portions or for objects to be used in contact with mucous membranes, such as contact lenses or pessaries.
- objects made from the hydrogels of the invention may be inserted into cavities in the body through narrow openings to fill the cavities.
- Bacteriostatic, bacteriocidal or otherwise medicinally active substances such as antibiotics may be dissolved in the aqueous constitutent of the hydrogels to provide medication over an extended period.
- the antibiotic or other medicinal substance gradually migrates into adjacent tissue by diffusion.
- the hydrogels of the invention are produced by copolymerizing a hydrophilic monomer capable of forming a linear, or partly linear polymer in aqueous solution with a cross-linking agent in amounts small enough to yield an elastic, soft, transparent hydrogel. If the relative amounts of water and original monomer are such that the polymer may retain the water originally present as a hydrogel throughout the polymerization process, the product is mechanically and optically homogeneous, that is, fully transparent. If the polymer formed is incapable of combining with the entire amount of aqueous liquid present, the polymer separates from a solution phase during polymerization. There is obtained a microporous product.
- Articles having unusual properties may be made from the hydrogel of the invention eiher by polymerizing a suitable mixture in a mold conforming to the desired object, or by first producing a body of polymeric material, and cutting or otherwise shaping it to produce a lens, a pessary, a dialyzer diaphragm, and other articles well known in themselves but acquiring new and useful properties when made from the hydrogel of the invention.
- Preferred starting materials for producing the hydrogels of the invention include the esters of acrylic and methacrylic acid with alcohols having hydrophilic groups which after polymerization impart hydrophilic properties to the polymer obtained.
- a major portion of a monoester of acrylic or methacrylic acid with a bi-functional alcohol which has an esterifiable hydroxyl group and at least one additional hydrophilic functional group is copolymerized in aqueous solution with a small amount of a diester of these acids and of an alcohol which has at least two esterifiable hydroxyl groups until a shape retaining body is obtained.
- the diester preferably does not amount to more than one percent of the monoester so that the copolymer is only sparingly cross-linked.
- the polyfunctional alcohols forming one of the constituent elements of the afore-mentioned monoester, and preferably also the alcohol constituent of the diester should have additional hydrophilic groupsin their molecule which make the esters water soluble even after two or more of the hydroxyl groups are esterified'by the acrylic or methacrylic acid.
- esters are also suitable as monomers in the copolymerization reaction leading to the hydrogels of the invention. These include, but are not limited to the following monomers:
- the corresponding acrylates may be substituted for the methacrylates.
- diesters mentioned above may be replaced by other cross-linking agents of which the following are merely illustrative, it being understood that corresponding acrylic acid derivatives may be substituted for the methacrylic acid derivatives specifically enumerated:
- Triethanolamine dimethacrylate Triethanolamine trimethacrylate, tartaric acid dimethacrylate, triethylene glycol dimethacrylate, the dimethacrylate of bis-hydroxyethylacetamide.
- Hydrogels having a broad range of unusual physical and chemical properties may be obtained by suitable selection of monomers, and particularly by the choice of suitable conditions of concentration in the aqueous solvent.
- the mechanical properties and the ability of retaining water as a homogeneous constituent of the hydrogel are strongly influenced by the proportions of monofunctional monomer and polyfunctional cross-linking agent.
- Hydrogels obtained from derivatives of acrylic and methacrylic acid are distinguished by excellent resistance to chemical attack. Their polymer constituent is not hydrolyzed by the water which is an integral constituent of the hydrogel but it also resists water at elevated temperatures and even at the boiling point so that objects made from the hydrogels of the invention can be repeatedly sterilized by boiling water, by boiling saline solutions, or steam without any deterioration.
- the hydrogels are also resistant to strong chemical agents such as hot fairly concentrated inorganic acids and bases. They are fully resistant to the action of microorganisms and are not attacked by enzymes. Many of them, and particularly those based on esters of acrylic or methacrylic acid may be stored for long periods in dilute aqueous hydrogen peroxide without chemical attack.
- a hydrogel of the invention may be formed with a large number of parallel channels or conduits which are separated by a comparatively thin layer of the polymeric hydrogel.
- the liquids, constituents of which are to be exchanged by dialysis, are passed through adjacent conduits.
- the system of conduits in a diaphragm of the invention may be formed by fibers or sheets made of a substance capable of Ibeing removed from the finished diaphragm. These fibers or sheets are placed in a mold and the polymerization mixture is then poured over them. After polymerization, the insert-forming fibers or sheets are removed as by dissolution in a chemical agent which leaves the hydrogel intact.
- Glass fibers are a preferred insert material, and may be removed after polymerization by means of hydrofluoric acid which does not attack the acrylic and other polymers of this invention. Any excess of hydrofluoric acid, together with the fluosilicic acid formed is washed out by water.
- suitable insert-forming materials are those which can be fused below the boiling point of water such as aliphatic polyesters melting below 100 C. and other low-melting materials such as waxes or alloys. Any residue which cannot be removed by heating is dissolved in a suitable solvent to which the hydrogel is resistant such as ethyl acetate or an acid.
- dialyzer diaphragms made in the afore-descri bed manner are equally suitable for industrial and for medical purposes, such as artificial kidneys. Many other applications will suggest themselves to those skilled in the art.
- An entire article prepared in the manner outlined above is held together by molecular forces, and may thus be described as a single giant molecule skeleton swelled with colloidally retained water. It is not only permeable to water and to certain substances dissolved in water, but it has substantial mechanical strength, the ability to retain its shape, and to elastically recover it after deformation.
- the objects made from the hydrogels of the invention may be boiled in water or aqueous solutions without deterioration, and are thus capable of being sterilized for medical purposes. They are compatible with living tissue and are excellent materials for body implants to fill or divide cavities in the body or, for objects which are to be left in contact with mucous membranes for extended periods, such as contact lenses or pessaries. Under special conditions, they may also find use in ion exchangers.
- the ratio of monomer and water is selected in such a manner that the polymerization mixture divides into two phases during. a period of advanced polymerization, the excess aqueous liquid is not rejected in a continuous layer or in macroscopic bubbles. It collects in minute drops which fill microscopic pores or cavities which are distributed throughout the body of the hydrogel and its mechanical retention is enhanced by the covalent forces of the hydrophilic polymer.
- Water may be partly removed from such articles by exerting pressure on them, but after the pressure is released, air cannot enter the cavities, and the overall volume of the article remains smaller until it is placed in contact with water or an aqueous solution whereupon it swells back to its original size and shape. Water is held in such an article partly by capillary attraction in the cavities, and partly as a constituent of the colloidal system of a hydrogel.
- Hydrogels of the type described from which a portion of the aqueous constituent has been removed by squeezing have absorbent qualities which can be used to advantage in adherent pads or layers for dental prostheses and the like. They also are useful for ultrafiltration.
- the quantity of water or of equivalent aqueous solutions colloidally held in the hydrogel is determined essentially by the amount of cross-linking agent copolymerized. If the water present during polymerization does not satisfy the holding capacity of the hydrogel, additional water or aqueous solution such as physiological saline solution may be absorbed in the hydrogel after polymerization by merely immersing the polymerizate in the aqueous liquid. An increase in cross linking decreases the maximum water content. It is the linear portion of the polymer molecules which retains water most effectively. The water acts very much like a plasticizer and the water content thus influences the mechanical properties of the gel.
- the refractive index of the hydrogels of the invention having a water content of substantially does not differ for all practical purposes from that of human hydrated tissue such as the human eye.
- Contact lenses made from the hydrogels of the invention are practically invisible, and remain invisible even if their surface should be accidentally damaged. They greatly differ in this respect from contact lenses made of methyl methacrylate. From such lenses they also differ by their softness which avoids mechanical eye irritation, and by their permeability to products of tissue metabolism and the like which cannot accumulate at the lens surface.
- Example I Molds conforming to the shapes of contact lenses and of pessaries are filled with an aqueous solution containing 20% by weight of polyvinyl alcohol, 2% adipic acid, and 5% hydrogen chloride to a temperature in the range of 50 to 80 C. until the contents of the molds gel to form a clear soft hydrogel.
- the lenses and pessaries formed are unmolded, thoroughly Washed in running water, and then stored in a solution of a mild antibacterial agent, such as an aqueous solution of 3-5% boric acid.
- a mild antibacterial agent such as an aqueous solution of 3-5% boric acid.
- the boric acid diffuses into the shaped articles and is available as medication to the body tissue with which the lenses or pessaries may be brought into contact.
- Example II A mixture of polyvinyl alcohol esters of methacrylic acid is prepared by reacting 100 equivalents of the alcohol with one equivalent of methacrylic acid anhydride in a manner well known in itself.
- the partly esterified polyvinylalcohol is dissolved in water to form a 25% aqueous solution and polymerized in the presence of potassium persulfate and sodium thiosulfate in a Hat mold to form a clear, soft body which is readily deformed by pressure but elastically recovers its shape when the pressure is released. After removal of water soluble material by thorough washing, the body produced makes a diaphragm.
- Example III An aqueous solution containing 500 parts of triethyleneglycol monomethacrylate having the formula is mixed with a solution of one part of the corresponding dimethacrylate of the formula in 300 parts of ethylene glycol. 100 parts of a 0.5% solution of potassium persulfate in Water are added and the polymerization mixture is poured into a double mold of polycapronamide shaped to conform to a contact lens having a size of 78% of the desired final product.
- the mold is heated to 50 C. for three hours.
- the polymeric body formed in the shape of a lens is washed in running water and stored in physiological saline solution in which it assumes its ultimate shape by swelling.
- the lens may be stored ready for use in the saline solution or in a dilute boric acid solution for long periods.
- Example IV 6 mixture is poured into a mold conforming to a surgical implant of desired shape and heated to an elevated temperature for several hours and until a self-supporting gel-like transparent mass is formed.
- the molding produced is Washed in water and made isotonic by immersion in physiological saline solution.
- Example V An aqueous solution is prepared from 15% (by weight) acrylamide, 10% ethylene glycol monomethacrylate, and
- ethylene glycol dimethacrylate 0.1% ethylene glycol dimethacrylate, the balance being I water.
- One liter of this solution is mixed with 10 ml. of an aqueous 2% solution of sodium thiosulfate and ml. of an aqueous 2% solution of ammonium persulfate.
- the resultant mixture is poured into a mold and polymerizes at room temperature.
- a soft, highly elastic article having the characteristic properties of a gel is obtained. It is washed in running water for several hours to remove watensoluble constituents, and is stored in a solution containing penicillin which gradually diffuses into the body of the hydrogel.
- the block obtained by polymerization may be cut into suitably shaped pieces for medical purposes.
- the penicillin absorbed by the hydrogel will gradually be released to a tissue in contact with the hydrogel.
- the hydrogel formed will be softer and capable of containing a larger percentage of water.
- Example VI An excess amount of ethylene oxide under pressure is forced into a solution of acrylic acid in water. A mixture of polyethylene glycol monoacrylate and diacrylate is obtained. Each molecule of the polyethylene glycol constituent contains an average of 4 to 5 glycol residues. There is a very large excess ofmonoester over the diester.
- the resulting mixture contains water and polyethylene glycol as solvents.
- Polymerization is initiated by addition of 0.1 gram potassium pyrosulfate and 0.5 ml. hydrogen peroxide to each liter of the mixture. The polymerization takes place when the mixture is heated to moderately elevated temperature, or when it is left standing at room temperature.
- a block polymer is obtained which is cut into plate or sheets to suit the intended surgical purpose. These pieces are washed in water and stored in physiological saline solution until needed.
- the corresponding polypropylene glycol esters of acrylic acid are formed and polymerize into a hydrogel of substantially the same properties as those of the copolymer of monoand diesters of polyethylene glycol with acrylic acid.
- acrylic acid may be replaced by methacrylic acid without basic change in the process or in the results achieved.
- Example VII 400 parts of polyethylene glycol methacrylate obtained by absorbing ethylene oxide under pressure in an aqueous solution of methacrylic acid are dissolved in 500 parts of water together with one part of polyethylene glycol dimethacrylate.
- a conventional redox catalyst such as sodium bisulfite and ammonium persulfate, is then added and the polymerization is permitted to take place at moderately elevated temperature in a mold having the shape of a contact lens.
- the polymerizate is washed in water to remove soluble materials and may be employed to replace conventional glasses.
- Example VIII An aqueous solution of polyethylene glycol monomethacrylate and polyethylene glycol dimethacrylate is prepared as in the preceding Example VII.
- Two bundles of differently colored continuous glass fibers are coated with a portion of the solution to which catalyst was added, and the coating is polymerized by gentle heating.
- the coated fibers are then placed in a mold conforming to the shape of a diaphragm and the two ends of all fibers of equal color are connected to respective inlet and outlet pipes.
- the fibers are partly parallel to each other, but they may intersect each other and be superimposed upon each other in any manner.
- the main body of monomer solution is then mixed with the catalyst and poured into the mold where it is per mitted to polymerize.
- the diaphragm with the embedded glass fibers is treated for several hours with hydrofluoric acid to dissolve the glass. It is then washed to remove the residual acid and the fluosilicic acid formed.
- Example IX 20 part of acrylamide, 20 parts of dimethylaminoethyl methacrylate, and 0.1 part of triethanolamine dimethacrylate are dissolved in 60 parts of water and are polymerized in the presence of a redox catalyst containing sodium thiosulfate and potassium persulfate as active constituents. A block of hydrogel is obtained and is cut into small pieces which are employed as ion exchangers.
- hydrogels consisting essentially of a sparingly cross-linked hydrophilic polymer and 20 to 97% of water or other aqueous liquid may be prepared by following the teachings of this disclosure, but substituting other monomers for those specifically named.
- hydrogels consisting of a hydrophilic polymer and an aqueous liquid may be prepared from other monomers by suitably modified methods.
- an unsaturated polymerizable dicarboxylic acid such as itaconic acid
- a glycol such as polyethylene glycol or 1,6 hexamethylene glycol
- Linear water soluble polyamides the chain of which contains a small amount of a polymerizable dicarboxylic acid or of an unsaturated polymerizable diamine may be cross-linked by polymerization.
- a shaped body essentially consisting of a hydrogel of a sparingly cross-linked hydrophilic polymer and of 20 to 97% of an aqueous liquid, said polymer being a copolymer of a major amount of a polymerizable monoester of an olefinic acid selected from the group consisting of acrylic and methacrylic acid, said monoester having a single olefinic double bond, with a minor amount of a polymerizable diester of one of said acids, said diester having at least two olefinic double bonds, said monoesters and diesters being water soluble, said monoester having a hydrophilic functional group.
- a shape-retaining hydrogel body essentially consisting of a sparingly cross-linked hydrophilic copolymer of a water-soluble monoester of an olefinic acid and of a polyfunctional alcohol having an esterifiable hydroxyl group and at least one additional hydrophilic functional group, with a water soluble diester of an olefinic acid and of an alcohol having at least two esterifiable hydroxyl groups, said olefinic acids being selected from the group consisting of acrylic acid and methacrylic acid, and said diester being present in said copolymer in an amount not exceeding one mole percent of said monoester; and of an aqueous liquid.
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- Life Sciences & Earth Sciences (AREA)
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- Oral & Maxillofacial Surgery (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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- General Physics & Mathematics (AREA)
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Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6152270A | 1970-08-05 | 1970-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE27401E true USRE27401E (en) | 1972-06-20 |
Family
ID=22036310
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US27401D Expired USRE27401E (en) | 1970-08-05 | 1970-08-05 | Cross-linked hydrophilic polymers and articles made therefrom |
Country Status (4)
Country | Link |
---|---|
US (1) | USRE27401E (de) |
DE (1) | DE1065621B (de) |
FR (1) | FR1149731A (de) |
NL (2) | NL206587A (de) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4277582A (en) | 1978-03-03 | 1981-07-07 | Ciba-Geigy Corporation | Water-insoluble hydrophilic copolymers |
US4425094A (en) | 1981-05-08 | 1984-01-10 | Dentsply Research & Development Corporation | Method of root canal therapy |
US4450262A (en) | 1982-08-11 | 1984-05-22 | Diamond Shamrock Chemicals Company | Hydrophilic copolymer compositions useful as contact lenses |
US4468229A (en) | 1981-08-12 | 1984-08-28 | Ciba-Geigy Corporation | Tinted contact lenses and a method for their preparation with reactive dyes |
US4553975A (en) | 1981-08-12 | 1985-11-19 | Ciba Geigy Corporation | Tinted contact lenses and a method for their preparation |
EP0188110A1 (de) | 1984-12-18 | 1986-07-23 | T R Developments Ltd | Hydrogelformende Polymere |
US4680336A (en) | 1984-11-21 | 1987-07-14 | Vistakon, Inc. | Method of forming shaped hydrogel articles |
US4822471A (en) | 1988-04-05 | 1989-04-18 | Ionics, Incorporated | Acid efficient membrane for use in electrodialysis for recovery of acid |
US4853227A (en) | 1987-10-23 | 1989-08-01 | Ciba-Geigy Corporation | Transdermal administration of a systemic active agent to a premature neonatal infant |
US4971732A (en) * | 1984-06-28 | 1990-11-20 | Ceskoslovenska Academie Ved | Method of molding an intraocular lens |
US4997897A (en) * | 1990-04-03 | 1991-03-05 | Bausch & Lomb Incorporated | Polymerizable dye |
US5055602A (en) * | 1989-05-02 | 1991-10-08 | Bausch & Lomb Incorporated | Polymerizable dye |
US5064652A (en) * | 1987-04-22 | 1991-11-12 | Michael Bay | Wound dressing |
US5225236A (en) * | 1989-06-28 | 1993-07-06 | Preston Keusch | Composite protective drapes |
US5236592A (en) * | 1990-06-25 | 1993-08-17 | Hospal Industrie | Haemocompatible composite material and method of using thereof |
US5266077A (en) * | 1992-11-09 | 1993-11-30 | Ciba-Geigy Corporation | Method for tinting a hydrophilic contact lens |
US5298033A (en) * | 1989-03-14 | 1994-03-29 | Ciba-Geigy Corporation | Ultraviolet absorbing lenses and methods of manufacturing thereof |
US5480927A (en) * | 1994-05-20 | 1996-01-02 | Ciba Geigy Corporation | Method of increasing the concentration of radiation-absorbing agents in optical and ophthalmic lenses |
US5532289A (en) * | 1995-04-14 | 1996-07-02 | Benz Research And Development Corp. | Contact lens having improved dimensional stability |
US5532287A (en) * | 1994-05-04 | 1996-07-02 | Ciba-Geigy Corporation | Radiation cured drug release controlling membrane |
US5681871A (en) * | 1995-05-24 | 1997-10-28 | Johnson & Johnson Vision Products, Inc. | Method for preparing ultraviolet radiation absorbing contact lenses |
US5959050A (en) | 1995-05-26 | 1999-09-28 | Mosbach; Klaus | Supports useful for molecular imprinting technology |
US6011081A (en) | 1995-04-14 | 2000-01-04 | Benz Research And Development Corp. | Contact lens having improved dimensional stability |
US6020445A (en) | 1997-10-09 | 2000-02-01 | Johnson & Johnson Vision Products, Inc. | Silicone hydrogel polymers |
US6201089B1 (en) | 1998-09-10 | 2001-03-13 | James T Carter | Macroporous hyperhydroxy polymer and articles made therefrom |
US6360129B1 (en) | 1999-12-13 | 2002-03-19 | Cardiac Pacemakers, Inc. | Mannitol/hydrogel cap for tissue-insertable connections |
WO2004097504A1 (en) | 2003-04-24 | 2004-11-11 | Ocular Sciences Inc. | Hydrogel contact lenses and package systems and production methods for same |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3221083A (en) * | 1960-08-18 | 1965-11-30 | American Optical Corp | Optical elements formed of resinous materials and process for making the same |
CH616694A5 (en) * | 1974-06-27 | 1980-04-15 | Ciba Geigy Ag | Process for the preparation of crosslinked, water-insoluble, hydrophilic copolymers |
DE3322993A1 (de) * | 1983-06-25 | 1985-01-03 | Basf Ag, 6700 Ludwigshafen | Verfahren zur acylierung von polyvinylalkoholen und so acylierte produkte enthaltende photopolymerisierbare und/oder photovernetzbare mischungen |
-
0
- NL NL96621D patent/NL96621C/xx active
- DE DENDAT1065621D patent/DE1065621B/de active Pending
- NL NL206587D patent/NL206587A/xx unknown
-
1956
- 1956-04-24 FR FR1149731D patent/FR1149731A/fr not_active Expired
-
1970
- 1970-08-05 US US27401D patent/USRE27401E/en not_active Expired
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4277582A (en) | 1978-03-03 | 1981-07-07 | Ciba-Geigy Corporation | Water-insoluble hydrophilic copolymers |
US4425094A (en) | 1981-05-08 | 1984-01-10 | Dentsply Research & Development Corporation | Method of root canal therapy |
US4468229A (en) | 1981-08-12 | 1984-08-28 | Ciba-Geigy Corporation | Tinted contact lenses and a method for their preparation with reactive dyes |
US4553975A (en) | 1981-08-12 | 1985-11-19 | Ciba Geigy Corporation | Tinted contact lenses and a method for their preparation |
US4450262A (en) | 1982-08-11 | 1984-05-22 | Diamond Shamrock Chemicals Company | Hydrophilic copolymer compositions useful as contact lenses |
US4971732A (en) * | 1984-06-28 | 1990-11-20 | Ceskoslovenska Academie Ved | Method of molding an intraocular lens |
US4680336A (en) | 1984-11-21 | 1987-07-14 | Vistakon, Inc. | Method of forming shaped hydrogel articles |
EP0188110A1 (de) | 1984-12-18 | 1986-07-23 | T R Developments Ltd | Hydrogelformende Polymere |
US5064652A (en) * | 1987-04-22 | 1991-11-12 | Michael Bay | Wound dressing |
US4853227A (en) | 1987-10-23 | 1989-08-01 | Ciba-Geigy Corporation | Transdermal administration of a systemic active agent to a premature neonatal infant |
US4822471A (en) | 1988-04-05 | 1989-04-18 | Ionics, Incorporated | Acid efficient membrane for use in electrodialysis for recovery of acid |
US5298033A (en) * | 1989-03-14 | 1994-03-29 | Ciba-Geigy Corporation | Ultraviolet absorbing lenses and methods of manufacturing thereof |
US5399692A (en) * | 1989-03-14 | 1995-03-21 | Ciba-Geigy Corporation | Ultraviolet absorbing benzophenone sulfonic acid derivatives |
US5055602A (en) * | 1989-05-02 | 1991-10-08 | Bausch & Lomb Incorporated | Polymerizable dye |
US5225236A (en) * | 1989-06-28 | 1993-07-06 | Preston Keusch | Composite protective drapes |
US4997897A (en) * | 1990-04-03 | 1991-03-05 | Bausch & Lomb Incorporated | Polymerizable dye |
US5236592A (en) * | 1990-06-25 | 1993-08-17 | Hospal Industrie | Haemocompatible composite material and method of using thereof |
US5266077A (en) * | 1992-11-09 | 1993-11-30 | Ciba-Geigy Corporation | Method for tinting a hydrophilic contact lens |
US5545442A (en) * | 1994-05-04 | 1996-08-13 | Ciba-Geigy Corporation | Method for using a radiation cured drug release controlling membrane |
US5532287A (en) * | 1994-05-04 | 1996-07-02 | Ciba-Geigy Corporation | Radiation cured drug release controlling membrane |
US5480927A (en) * | 1994-05-20 | 1996-01-02 | Ciba Geigy Corporation | Method of increasing the concentration of radiation-absorbing agents in optical and ophthalmic lenses |
US6265465B1 (en) | 1995-04-14 | 2001-07-24 | Benz Research & Development Corporation | Contact lens having improved dimensional stability |
US6011081A (en) | 1995-04-14 | 2000-01-04 | Benz Research And Development Corp. | Contact lens having improved dimensional stability |
US5532289A (en) * | 1995-04-14 | 1996-07-02 | Benz Research And Development Corp. | Contact lens having improved dimensional stability |
US6555598B2 (en) | 1995-04-14 | 2003-04-29 | Benz Research And Development Corp. | Contact lens having improved dimensional stability |
US6566417B2 (en) | 1995-04-14 | 2003-05-20 | Benz Research And Development Corporation | Contact lens having improved dimensional stability |
US5681871A (en) * | 1995-05-24 | 1997-10-28 | Johnson & Johnson Vision Products, Inc. | Method for preparing ultraviolet radiation absorbing contact lenses |
US5959050A (en) | 1995-05-26 | 1999-09-28 | Mosbach; Klaus | Supports useful for molecular imprinting technology |
US6020445A (en) | 1997-10-09 | 2000-02-01 | Johnson & Johnson Vision Products, Inc. | Silicone hydrogel polymers |
US6201089B1 (en) | 1998-09-10 | 2001-03-13 | James T Carter | Macroporous hyperhydroxy polymer and articles made therefrom |
US6360129B1 (en) | 1999-12-13 | 2002-03-19 | Cardiac Pacemakers, Inc. | Mannitol/hydrogel cap for tissue-insertable connections |
WO2004097504A1 (en) | 2003-04-24 | 2004-11-11 | Ocular Sciences Inc. | Hydrogel contact lenses and package systems and production methods for same |
Also Published As
Publication number | Publication date |
---|---|
NL96621C (de) | |
FR1149731A (fr) | 1957-12-31 |
NL206587A (de) | |
DE1065621B (de) | 1959-09-17 |
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