CN101389364A - Silicone containing polymers formed from non-reactive silicone containing prepolymers - Google Patents
Silicone containing polymers formed from non-reactive silicone containing prepolymers Download PDFInfo
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Abstract
The present invention relates to polymer compositions formed from a reactive mixture comprising at least one substantially non-reactive prepolymer comprising silicone containing groups and compatibilizing groups and a hydrophilic component comprising at least one monomer capable of hydrogen bonding with said prepolymer.
Description
Invention field
The present invention relates to the silicone polymer that contains that prepolymers containing by non-activity forms.
Background of invention
The present invention relates to polymeric material.More specifically, the present invention relates to need not extra wetting agent and the prepolymer that can be used for forming the biologic medical apparatus.
Whether a kind of material is applicable to that the biologic medical apparatus depends on many factors, and these factors generally include the wettability of material and are inclined to the bonding of for example biomaterial such as protein and lipid or reaction.In ophthalmic applications such as contact lens and intraocular implant for example, the oxygen flow degree also is an important consideration aspect.
Silicon hydrogel can be the very ideal material that is used for biologic medical apparatuses such as preparation example such as contact lens, because it has good oxygen permeability usually.Yet its hydrophobicity makes apparatus prepared therefrom be difficult to moistening.A kind of method of handling this problem is for being coated with hydrogel with the stronger coating of hydrophilic.This has additionally increased its preparation complexity.In addition, suitable coating compounds thickness, coating uniformity and other factors that may be difficult to select coating material and determine to influence physiological property.
Can be by comprising the surface nature that the big monomer with hydrophobic part, hydrophilic segment, chain-transferring agent and unsaturated end group comes polymeric object such as Change Example such as contact lens at the monomer mixture that is used for preparing polymeric object.Described big monomer can comprise that molecular weight is 500-10, the poly-N-vinyl ketopyrrolidine of 000 (most preferably being 1,000-5,000).Described big monomer polymerization enters hydrogel, has improved the wettability of polymer really.Yet described raising can not reach usually and can prepare glasses by hydrogel and no longer need the degree of hydrophilic coating.
Summary of the invention
The present invention relates to the component of polymer that forms by active mixture, described mixture comprises following component, composed of the following components and composed of the following components substantially: (a) at least a prepolymer and the monomeric hydrophilic component that (b) comprises at least a amide containing that comprises the basic non-activity of siliceous ketone groups and increase-volume (compatibilizing) group, condition is that described active mixture does not contain active prepolymer substantially.
Detailed Description Of The Invention
Polymer of the present invention is by the prepolymer of (a) at least a basic non-activity that comprises siliceous ketone groups and increase-volume group and (b) comprise at least a can formation with the monomeric hydrophilic component of described prepolymer hydrogen bonded, and condition is that described active mixture does not contain active prepolymer substantially.
" biologic medical apparatus " used herein for be designed within mammalian tissues or the body fluid or on (within preferred tissue or the body fluid or on) any goods of using.The example of these apparatuses includes but not limited to conduit, implant, support and ophthalmological instruments, for example intraocular lens and contact lens.In one embodiment, described biologic medical apparatus is an ophthalmological instruments, is specially ophthalmic lens, is specially contact lens most.
Term used herein " lens " and " ophthalmological instruments " refer in eye or the apparatus on the eye.These apparatuses can provide the combination of optical correction, wound protection, drug conveying, diagnostic function, cosmetic potentiation or effect or these character.The term lens include but not limited to soft-contact lens, hard contact lens, intraocular lens, cover lens, the embedded thing of eyes and the embedded thing of optics.
Unless otherwise noted, otherwise all percents in this description are percetage by weight.
Phrase used herein " does not carry out surface treatment " or " not having surface-treated " refers to not have the outer surface to this embodiment apparatus to carry out individual processing to improve the wettability of described apparatus.The example of the processing that can abandon because of the present invention comprises plasma treatment, grafting and coating etc.Yet, can will provide the coating (such as but not limited to antimicrobial coatings) of other character except that enhanced wettability and color or other cosmetic reinforced effects to be used for apparatus of the present invention.
" basic non-activity " used herein refer to prepolymer itself can covalent bond in solidification process or with active mixture in other component covalent bond.Therefore, in one embodiment, described prepolymer does not contain the group that can form covalent bond under curing of selecting for preparation polymer and any required goods prepared therefrom and processing conditions substantially.In one embodiment, prepolymer of the present invention comprises the group that can form covalent bond less than about 10% under selected curing and processing conditions, in another embodiment, and less than about 5% such group, in another embodiment, less than about 1% such group.
Any activity contains the silicone component and can be used for forming prepolymer of the present invention.The suitable silicone component that contains comprises at least one [Si-O-Si] group in monomer, big monomer or prepolymer.Preferably containing Si in the silicone component accounts for the O that links to each other and contains silicone component total molecular weight greater than 20% weight, more preferably greater than 30% weight.The silicone component that contains that preferably has usefulness comprises at least one active group.Can use can be by any group of any reaction pattern reaction.Example comprises the group of reaction, radical polymerization, group transfer polymerization, condensation, esterification, atom transfer radical polymerization, ring-opening polymerisation, anionic polymerisation and the cationic polymerization etc. that can carry out heat, light or visible light initiation.The example that can carry out the active group of radical polymerization comprises acrylate functional groups, methacrylate functional, acrylamide functional group, methacryl amine functional group, N-vinyl lactam functional group, N-vinylamide functional group and styryl functional group.Can be used for visible United States Patent (USP) 3,808,178,4,120,570,4,136,250,4,153,641,4,740,533,5,034,461 and 5,070,215,5,998,498 of example and the EP080539 that contains the silicone component of the present invention.The patent integral body that all this paper are quoted is attached to this paper by reference.The active group of other types known in the art also can use these active groups simultaneously.
The example that can be used as the siliceous one monomers that contains the silicone component is polysiloxane group alkyl shown in the following formula (methyl) acrylic monomers (polysiloxanylalkyl (meth) acrylic monomer):
Formula II
Wherein: R represents H or low alkyl group; X represents O or NR
4Each R
4Independent hydrogen or the methyl represented,
Each R
1-R
3Independent low alkyl group or the phenyl, n represented is 1 or 3-10.
The example of these polysiloxane group alkyl (methyl) acrylic monomerss comprises methacryloxypropyl three (trimethylsiloxy group) silane, methacrylic acid pentamethyl disiloxane base methyl ester (pentamethyldisiloxanyl methylmethacrylate) and methyl two (trimethylsiloxy group) methacryloxy methyl-monosilane.In certain embodiments, preferable methyl acryloxy propyl group three (trimethylsiloxy group) silane.
The another kind of silicone component that contains is poly-(organosiloxane) prepolymer shown in the formula III:
Formula III
Wherein each A independently represents activatory unsaturated group, for example the ester of acrylic or methacrylic acid or amide, have the alkyl of 1-8 carbon atom (in certain embodiments for 1-3 carbon atom) or have the aryl (condition is that an A comprises the activation unsaturated group that can carry out radical polymerization) of 6-10 carbon atom; R
5, R
6, R
7And R
8Each independently is selected from and has 1-18 carbon atom between the carbon atom of (being 1-5 carbon atom in certain embodiments) can have the monovalence alkyl of ehter bond or the monovalence alkyl of halogen replacement, or the monovalence siloxy group;
R
9Representative has the bivalent hydrocarbon radical that can be replaced by ether functional group, hydroxy functional group, ester functional group of 1-22 carbon atom, and m is 0 or more than or equal to 1 integer, preferably 5-400, more preferably 10-300.A particular instance is α, and ω-dimethyl allene acyloxy propyl group gathers-dimethyl siloxane.Another example is mPDMS (the end capped polydimethylsiloxane of the end capped single normal-butyl of monomethyl acryloxy propyl group).
The another kind of useful silicone component that contains comprises that following formula contains the ethylene carbonate or the carbamic acid vinyl acetate monomer of silicone:
Formula IV
Wherein: Y represents O, S or NH; R
SiRepresentative contains the silicone organic group; R representative-(CH
2)
qSi[(CH
2)
sCH
3]
3
-(CH
2)
qSi[OSi(CH
2)
sCH
3]
3；
Hydrogen or methyl; D is 1,2,3 or 4; In certain embodiments, d is 1, and q is 0 or 1.The suitable silicone organic group R that contains
SiComprise following:
Wherein: R
10Be alkyl or fluoroalkyl with 1-6 carbon atom; E is 1-200; Q is 1,2,3 or 4; S is 0,1,2,3,4 or 5.
The ethylene carbonate or the carbamic acid vinyl acetate monomer that contain silicone specifically comprise: 3-[three (trimethylsiloxy group) silicyl] propyl group allyl amino formic acid esters, 3-[three (trimethylsiloxy group) silicyl] propyl vinyl carbamate, trimethyl silyl ethyl vinyl carbonic ester and trimethyl silyl methyl ethylene carbonic ester.
Contain on the main chain that silicone group in the silicone component can be suspended on prepolymer and maybe can be included in the skeleton of prepolymer.
The amount that contains the silicone component in the prepolymer can be based on all active components that are used to prepare described prepolymer, in about 95% weight of about 10-, and about 90% weight of about 20-, the about 80% weight change of about in certain embodiments 30-.
Prepolymer also comprises at least one increase-volume group.Suitable increase-volume group makes prepolymer miscible in hydrophilic component or miscible with hydrophilic component.In certain embodiments, the increase-volume group comprises at least a one-tenth hydrogen bond partner (participant), and in certain embodiments, the increase-volume group comprises at least one hydrogen bond and supplies with group.Suitable increase-volume examples of groups comprises amide, the ammonia of carboxyl, mercaptan, phenol, primary amine, the urea of primary amine, the carbamate of primary amine, hydroxyl and combination thereof.In one embodiment, the increase-volume group comprises at least one hydroxyl, such as but not limited to list or dihydroxy alkyl and polyhydric alcohol.
The increase-volume group can be the part of silicone component, and perhaps it can be independent polymerizable components.The example that comprises the silicone component of increase-volume group comprise 2-acrylic acid, 2-methyl-, 2-hydroxyl-3-[3-[1,3,3,3-tetramethyl-1-[(trimethyl silyl) oxygen base] the disiloxane base] propoxyl group] and propyl ester, hydroxypropyl methyl acrylate ended polydimethylsiloxane, (3-methacryloxy-2-hydroxyl propoxyl group) propyl group three (trimethylsiloxy group) silane, list-(3-methacryloxy-2-hydroxyl propoxyl group) propyl group is end capped, the polydimethylsiloxane of list-butyl end-capping and combination thereof etc.
In another embodiment, by comprise at least one as defined above the independent increase-volume component of increase-volume group and at least one active group the increase-volume group is attached in the prepolymer.Active group can be under the selected polymerizing condition of preparation prepolymer has active any group.If for example prepare prepolymer, can use any active group that can carry out radical polymerization by radical polymerization.Other kind reactive activity groups are known to those skilled in the art.
Suitable increase-volume examples of groups comprises N,N-DMAA (DMA), acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, glycerol methacrylate, 2-hydroxyethyl methacrylamide, methacrylic acid, acrylic acid and hydrophilic vinyl-containing monomers (for example N-vinyl lactam (comprising N-vinyl pyrrolidone (NVP)), N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, N-vinyl formamide, N-2-ethoxy vinyl carbamate and combination thereof) etc.In the embodiment of a use increase-volume component, the increase-volume component is selected from N,N-DMAA (DMA), methacrylic acid 2-hydroxyethyl ester, N-vinyl pyrrolidone (NVP), N-vinyl-N-methylacetamide and combination thereof.
Increase-volume group in the increase-volume component can be suspended on the main chain of prepolymer and maybe can be included in the skeleton of prepolymer.But increase-volume component random dispersion can concentrate on the end of prepolymer in whole prepolymer structure, or in block.By the increase-volume component with contain in the embodiment that the silicone component forms, preferably prepolymer is a random copolymer at some prepolymer.
The amount of increase-volume group should be enough to make prepolymer and hydrophilic component miscible and keep compatible in polymerization process in selected solvent.The suitable amount of increase-volume component comprises that the weight based on all components in the prepolymer is about 50% weight of about 1-, is about 25% weight of about 3-in certain embodiments.
Prepolymer also can comprise other components that can not reduce the required feature of gained prepolymer.
Silicone component and the increase-volume component one formation prepolymer that reacts.Can form prepolymer by any known polyreaction, comprise radical polymerization, anion and cationic polymerization, group transfer polymerization, condensation, atom transfer radical polymerization and ring-opening polymerisation etc.Reaction condition depends on selected component and desired molecule amount.For example, comprise in the embodiment of free radical activity group a pre-polymer component, prepolymer of the present invention can form by following steps: silicone component, increase-volume component and polymerization catalyst are mixed with optional solvent, be suitable for the described mixture of polymerization under the condition of selected catalyst.Thereby finish reaction and make the basic non-activity of gained prepolymer.The suitable response time comprised about 10 seconds-Yue 1 hour, and reaction is generally carried out in inert atmosphere.Perhaps, can comprise for example other components such as chain-transferring agent or end-capping reagent.As the gel permeation chromatography that utilizes refractive index to detect surveys, and the weight average molecular weight of prepolymer of the present invention is about 50, and about 1,000,000 dalton of 000-is 500,000 dalton in certain embodiments, is 200,000 dalton in certain embodiments.
For radical reaction, suitable polymerization catalyst is known in the art, comprises thermal initiator and light trigger.Produce the chemical compound (for example dodecyl peroxide, benzoyl peroxide, isopropyl-off carbonate and azodiisobutyronitrile etc.) and the photoinitiator system (for example aromatics alpha-alcohol ketone, alkoxyl oxygen base Benzoinum, 1-Phenylethanone., acylphosphine oxide, bisacylphosphine oxide, tertiary amine and diketone and composition thereof etc.) of free radical under the temperature that the appropriateness that is included in polymerization initiator improves.The illustrative example of light trigger is 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-third-1-ketone; two (2; 6-dimethoxy benzoyl)-2; 4-4-tri-methyl-amyl phosphine oxide (DMBAPO), two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide (Irgacure819), 2; 4; 6-trimethyl benzyl diphenyl phosphine oxide and 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, the combination of Benzoinum methyl ester and camphorquinone and 4-(N, N-dimethylamino) ethyl benzoate.Commercially available visible light initiator system comprises Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850 (all from Ciba SpecialtyChemicals) and Lucirin TPO initiator (from BASF).Commercially available UV light trigger comprises Darocur 1173 and Darocur 2959 (Ciba Specialty Chemicals).The III volume is used for the photopolymerisable light trigger of radical cation and anion (Photoinitiators forFree Radical Cationic ﹠amp; Anionic Photopolymerization), the 2nd edition, J.V.Crivello ﹠amp; The K.Dietliker work; G.Bradley edits; John Wiley and Sons; NewYork; 1998 disclose spendable these and other light triggers, by reference it are attached to this paper.Use effective amount of initiator to contain the photopolymerization of silicone component and increase-volume component, the about 2 weight portion initiators of for example per 100 parts of about 0.1-of mixture with initiation.Can select heat, visible light, ultraviolet light or other mode initiated polymerizations suitably, this depends on employed polymerization initiator.Perhaps, can for example being to use without light trigger, electron beam causes.Yet when using light trigger, preferred initiator is a bisacylphosphine oxide, for example two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide (Irgacure
) or 1-hydroxycyclohexylphenylketone and two (2,6-dimethoxy benzoyl)-2,4-4-tri-methyl-amyl phosphine oxide DMBAPO) combination, the method for optimizing that polymerization causes is a visible light.Most preferably be two (2,4,6-trimethylbenzene formyl)-phenyl phosphine oxide (Irgacure
).
Can prepolymer with prepolymer is carried out purification before hydrophilic monomer mixes, for example by in solvent, precipitating.Perhaps, can preferably in a kind of aforesaid diluent, form prepolymer, this prepolymer/diluent mixture be mixed with hydrophilic monomer, and need not purification of prepolymer.Can for example form prepolymer/diluent solution, for example by heating or irradiation prepolymer precursor and diluent and suitable initiator with continuity method.A kind of method in back is particularly suitable for High-Speed Automatic preparation method.
By in the presence of selected prepolymer, making at least a hydrophilic component reaction form polymer.Suitable hydrophilic component polymerizable and can with described prepolymer hydrogen bonded.In certain embodiments, the Hansen solubility parameter δ of hydrophilic component is at least about 12, is at least about 14 in certain embodiments, is at least about 15 in certain embodiments.In certain embodiments, hydrophilic component is a hydrophilic monomer.Term used herein " monomer " is for comprising at least one polymerizable groups and utilizing gel permeation chromatography institute lining average molecular weight that refractive index detects for approximately less than 2000 daltonian chemical compounds.Therefore, monomer comprises dimer and oligomer (in some situation), and described oligomer comprises the oligomer by more than one monomeric unit preparation.
The example of suitable hydrophilic component comprises the hydrophilic monomer with at least one polymerizable groups and at least one hydrophilic functional groups.The group of polymerizable groups for reacting by radical polymerization, anion and cationic polymerization, group transfer polymerization, condensation, atom transfer radical polymerization and ring-opening polymerisation etc.Example with polymerizable groups of polymerizable double bond comprises acrylic double bond, the two keys of methacrylic acid, the two keys of acrylamido, the two keys of methacryl amido, the two keys of fumaric acid, the two keys of maleic acid, the two keys of styryl, the two keys of isopropenyl phenyl, the two keys of O-vinyl carbonic ester, the two keys of O-vinyl carbamate, allyl double bonds, the two keys of O-vinyl acetyl group and the two keys of N-vinyl lactam and the two keys of N-vinylamide base.If have two or more polymerizable double bonds in its molecule, then this type of hydrophilic monomer itself can be used as cross-linking agent.
" acrylic type " or " containing acrylic acid " monomer is for comprising acrylic acid groups (CR
12H=CR
13COX) monomer, wherein R
13Be H or CH
3, R
12Be H, alkyl or carbonyl, X is O or N, the polymerization easily of also known described monomer, described monomer is N,N-DMAA (DMA), acrylic acid 2-hydroxyethyl ester, glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid and composition thereof for example.
Hydrophilic component also can be selected from hydrophilic vinyl-containing monomers, for example N-vinyl lactam (comprising N-vinyl pyrrolidone (NVP)), N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, N-vinyl formamide, N-2-ethoxy vinyl carbamate, N-carboxyl-Beta-alanine N-vinyl esters and combination thereof etc.
Can be used for the metathetical polyoxyethylene polyols of functional group that other hydrophilic monomers of the present invention comprise the involved polymerizable double bond of one or more terminal hydroxy groups.Example comprises the metathetical Polyethylene Glycol of functional group of the involved polymerizable double bond of one or more terminal hydroxy groups.Example comprise Polyethylene Glycol and one or a few molar equivalent end-capping group (for example isocyanide acyl group ethyl-methyl acrylate (isocyanatoethyl methacrylate " IEM "), methacrylic anhydride, methacrylic chloride or vinyl benzene formyl chloride etc.) reaction generate polyethylene polyhydric alcohol with one or more polymerisable olefinic end groups, wherein said olefinic end group combines with the polyethylene polyhydric alcohol by for example coupling part such as carbamate groups or ester group.
Further example is a United States Patent (USP) 5,070,215 disclosed hydrophilic carboxylic acid vinyl esters or vinyl carbamate monomer, United States Patent (USP) 4,910,277 disclosed hydrophilic De azolactone monomers and hydrophilic De oxazoline monomer such as 2-ethyl-2-oxazoline for example.Other suitable hydrophilic monomers are apparent to those skilled in the art.
In one embodiment, hydrophilic component comprises the hydrophilic monomer of at least a amide containing or carbamate, in another embodiment, comprises the monomer of at least a amide containing.The example of the hydrophilic monomer of suitable amide containing comprises N, N-DMAA (DMA), 2-hydroxyethyl methacrylamide, N-vinyl pyrrolidone (NVP), N-vinyl-N-methylacetamide (VMA), N-vinyl acetamide, N-vinyl-N-methyl propanamide, N-vinyl-N-methyl-2-methyl propanamide, N-vinyl-2-methyl propanamide, N-vinyl-N, N '-dimethyl urea and combination thereof etc.
In one embodiment, hydrophilic monomer comprises DMA, NVP, VMA or its mixture.
The hydrophilic component that should comprise following amount: when mixing with remaining ingredient, described hydrophilic component has at least about 20% resulting polymers, preferably at least about 25% water content.In certain embodiments, the amount of hydrophilic component based on the weight of all components in the active mixture up to about 60% weight, about 60% weight of about 10-, about 60% weight of about 20-.
Polymer of the present invention is formed by active mixture.Active mixture used herein for the prepolymer that comprises at least a basic non-activity, hydrophilic component and for active mixture is provided or have required character final polymer must or the mixture of ideal any other component.Suitable other components include but not limited to UV absorbent, medicament, nutrient (nutraceutical agent), Antimicrobe compound, reactive dye (reactive tint) but, the pigment copolymerization and not polymerisable dyestuff, releasing agent, wetting agent, increase-volume component, cross-linking agent, chain transfer agents and combination thereof etc.In another embodiment, but other components include but not limited to UV absorbent, medicament, nutrient, Antimicrobe compound, reactive dye, pigment copolymerization and not polymerisable dyestuff, releasing agent, cross-linking agent, chain-transferring agent and combination thereof etc.
In one embodiment, except that prepolymer, active mixture does not contain the silicone component substantially.In another embodiment, except that prepolymer, active mixture comprises weight based on all active components less than 5% weight, less than the silicone component of 1% weight.
Active mixture also can comprise diluent.All components in the suitable diluent lytic activity mixture.Generally speaking, can select suitable diluent by the Hansen solubility parameter of determining prepolymer, hydrophilic component and diluent.
The Hansen solubility parameter is described the interaction between polymeric liquid, can be every kind of solvent and polymer distribution and describes its interactional three parameter group δ
H, δ
PAnd δ
DPolymeric liquid interaction parameter and solubility parameter handbook (Handbook ofPolymer Liquid Interaction Parameters and Solubility Parameter) are seen in the description of this system, CRCPress, Inc.1990 and solubility parameter and other cohesion parameter handbooks (Handbook ofSolubility Parameters and Other Cohesion Parameters), A.F.M.Barton, CRC Press, 1985, table 5.Each three parameter group limits a point in the three-dimensional dissolubility space.
For the liquid as the solvent of given prepolymer/hydrophilic component combination, the HSP parameter that it is desirable to solvent is between the HSP of prepolymer and hydrophilic component parameter.Hansen solubility parameter that can be by the specific prepolymer of dissolubility measurements determination, wherein with the prepolymer sample preservation in multiple different solvents.Whether dissolve by observing prepolymer, swelling or do not change, can in solubility space, mark and draw the dissolubility ball of specific prepolymer, basic as Hansen solubility parameter (Hansen Solubility Parameters); User's manual (a User ' sHandbook), Charles M.Hansen, 43-53 page or leaf, CRC Press 2000 and calculate with CMH ball (CMH ' s Sphere) computer program described.In one embodiment, in three-dimensional solubility space, solvent distance of each in prepolymer and the hydrophilic component should not surpass following value: δ
DAbout 5-is about 10, δ
PAbout 4-is about 12, δ
HAbout 10-about 6.Therefore, should be understood that the polarity of prepolymer and hydrophilic component increases, polarity of solvent to be used also should increase.In certain embodiments, thus may need to select to make its polarity close to prepolymer and hydrophilic component.
In one embodiment, suitable diluent comprises the diluent of while possess hydrophilic property and hydrophobicity.Hydrophilic can utilize Kamlet α value (being also referred to as the α value), characterizes by giving Hydrogen Energy power.The hydrophobicity of diluent can be passed through Hansen solubility parameter δ
PCharacterize.Suitable diluent of the present invention is good hydrogen-bond donor, and its polarity is between prepolymer and hydrophilic component simultaneously." good " used herein hydrogen-bond donor gives hydrogen at least easily as 3-methyl-3-amylalcohol.For some diluent, can measure the hydrogen bond supply capacity by measuring Kamlet α value (" α value " perhaps as used herein).Suitable α value comprises that about 0.05-is about 1, preferably about 0.1-about 0.9.
Should be understood that the character of selected prepolymer and hydrophobic component may influence the character of the diluent that required compatibilization will be provided.For example, if reactant mixture only comprises the component of middle polarity, can use to have moderate δ
PDiluent.Yet if reactant mixture comprises strong polar component, diluent may need to have high δ
P
The example of spendable concrete diluent includes but not limited to 1-ethyoxyl-2-propanol, diisopropylaminoethanol, isopropyl alcohol, 3,7-dimethyl-3-capryl alcohol, 1-decanol, the 1-dodecanol, the 1-capryl alcohol, the 1-amylalcohol, the 2-amylalcohol, the 1-hexanol, the 2-hexanol, sec-n-octyl alcohol, 3-methyl-3-amylalcohol, tert-pentyl alcohol, the tert-butyl alcohol, the 2-butanols, the 1-butanols, 2-methyl-2-amylalcohol, the 2-propanol, the 1-propanol, ethanol, 2-ethyl-1-butanols, 1-tert-butoxy-2-propanol, 3,3-dimethyl-2-butanols, tert-butoxy ethanol, 2-octyl group-1-dodecanol, capric acid, sad, dodecylic acid, 2-(diisopropylaminoethyl) ethanol and composition thereof etc.
The suitable diluent kind includes but not limited to have the alcohol of 2-20 carbon atom, derived from the amide with 10-20 carbon atom and the carboxylic acid with 8-20 carbon atom of primary amine.In certain embodiments, the preferred primary alconol and the tertiary alcohol.Preferred kind comprises the carboxylic acid of the pure and mild 10-20 of having carbon atom with 5-20 carbon atom.
When hydrophilic component comprises vinyl, suitable diluent comprises 3,7-dimethyl-3-capryl alcohol, 1-dodecanol, 1-decanol, 1-capryl alcohol, 1-amylalcohol, 1-hexanol, 2-hexanol, sec-n-octyl alcohol, 1-dodecanol, 3-methyl-3-amylalcohol, 1-amylalcohol, 2-amylalcohol, tert-pentyl alcohol, the tert-butyl alcohol, 2-butanols, 1-butanols, 2-methyl-2-amylalcohol, 2-ethyl-1-butanols, ethanol, 3,3-dimethyl-2-butanols, 2-octyl group-1-dodecanol, capric acid, sad, dodecylic acid and composition thereof etc.
Can use the mixture of diluent.In certain embodiments, maybe advantageously use has diluent of different nature.In addition, should be understood that when using mixture that described mixture can comprise the diluent with the specified character of this paper and not have the diluent of institute's finitude with one or more, perhaps can comprise the diluent that only has a kind of specified character separately.
The consumption of diluent can be all components in the active mixture up to about 50% weight.More preferably the consumption of diluent be in the active mixture all components less than about 45% weight, about 40% weight of more preferably about 15-.
When selected hydrophilic component free redical polymerization, also can use polymerization catalyst.Can use above with regard to the synthetic described any polymerization catalyst of prepolymer.
Also one or more cross-linking agent (being also referred to as cross-linking monomer) can be included in the active mixture.The example of suitable crosslinking agent comprises the monomer with two or more polymerizable double bonds, for example ethylene glycol dimethacrylate (" EGDMA "), trimethylol-propane trimethacrylate (" TMPTMA "), glycerol trimethyl acrylic ester, polyethylene glycol dimethacrylate (wherein the molecular weight of preferred described Polyethylene Glycol up to for example about 5000) and other polyacrylate and polymethacrylates (for example above-mentioned end capped polyoxyethylene polyols that comprises two or more terminal methyl acrylate parts).Use cross-linking agent with constant, for example the active component of per 100 grams is used the about 0.02 mole of cross-linking agent of about 0.0004-in the active mixture.Perhaps, if as cross-linking agent, then can choosing wantonly to reactant mixture, hydrophilic component adds cross-linking agent.The example that can be used as the hydrophilic monomer of cross-linking agent comprises the above-mentioned polyoxyethylene polyols that comprises two or more terminal methyl acrylate parts.
Polymer of the present invention can be used for preparing the medical apparatus and instruments that includes but not limited to ophthalmological instruments, and for example ophthalmic lens and lacrimal ductule embolus (punctual plugs) are specially contact lens in certain embodiments.Polymer of the present invention is the carrier of useful as drug and nutrient compounds also.
Active mixture of the present invention can form by any method (for example jolting or stirring) known to those skilled in the art, and is used to form polymer product or apparatus by known method.When the special thickness of prepolymer, may need to mix for a long time or stir the mixture to form solution, about 100 hours of for example about 2-.In certain embodiments, may or stir the mixture about 70 ℃ of for example about 30-in the high-temperature mixing.
For example, biologic medical apparatus of the present invention can prepare by following steps: polymerization initiator is contained in the active mixture, utilizes appropraite condition to solidify to form product, can this product be configured as suitable shape by car and method such as cut then.Perhaps, active mixture can be placed mold, then be cured as suitable goods.In another embodiment, active mixture can be cast and is cured as other goods, for example film, fiber, sheet material, sheet material, moulding part and mechanograph and the coating that is used for aforementioned any goods.In another embodiment, curable and grind polymer of the present invention with carrier as active agent (for example medicine and nutrient compounds).
Can select suitable polymerizing condition based on the active group on the hydrophilic component.When hydrophilic component comprises the free radical activity group, generally comprise initiator.Suitable initiator comprises thermal initiator and light trigger, and is US 6,822, and 016 is disclosed.With reference to the disclosure of invention and embodiment, it will be understood to those of skill in the art that the polymerizing condition of hydrophilic component and other active function groups.
In one embodiment, active mixture is used to prepare contact lens.The known the whole bag of tricks that is used to process active mixture in the contact lens preparation comprises rotated mold filing and static casting.United States Patent (USP) 3,408,429 and 3,660,545 disclose the rotated mold filing method, United States Patent (USP) 4,113,224 and 4,197,266 disclose static casting method.The method for optimizing for preparing the contact lens that comprises polymer of the present invention is as follows: molding is silicon hydrogel cheaply, and the net shape of aquation lens is accurately controlled.For implementing this method, active mixture placed the mold of (being the swollen polymer of the water) shape that has final required silicon hydrogel, and make reactant mixture stand the condition of monomer polymerization, thereby be prepared as the polymer/diluent mixture of final required product shape.Then, removing diluent, and final water replaces with this polymer/diluent mixture of solvent processing, thus the size and the very close silicon hydrogel of shape of final size of preparation and shape and at first molded polymer/diluent goods.This method can be used for forming contact lens, United States Patent (USP) 4,495, and 313,4,680,336,4,889,664 and 5,039,459 have further described this method, by reference it are attached to this paper.
Biologic medical apparatus of the present invention especially ophthalmic lens has isostatic character, and this makes it very useful.That this type of character comprises is transparent, water content, oxygen permeability and contact angle.Therefore, in one embodiment, the biologic medical apparatus is a water content greater than about 17% contact lens, and water content is greater than about 20% in certain embodiments, and water content is greater than about 25% in other embodiments.
" transparent " used herein refers to not have substantially visible haze.The mist degree of transparent lens is less than about 200%, in certain embodiments less than about 150%.Should be understood that not all goods by polymer formation of the present invention all need transparent.Yet,, can prepare goods with transparency described herein for transparent very important goods (for example ophthalmological instruments).
The suitable oxygen permeability that contains the silicone lens is greater than about 40barrer, in certain embodiments greater than about 60barrer.
In addition, the biologic medical apparatus especially the dynamic contact angle (advancing angle) of ophthalmological instruments and contact lens less than about 90 ℃, in certain embodiments less than about 80 ℃.In certain embodiments, goods of the present invention have the combination of above-mentioned oxygen permeability, water content and contact angle.Think above-mentioned scope all the combination all within the scope of the present invention.
The embodiment of following indefiniteness further describes the present invention.
Embodiment
Wettability is measured by measuring dynamic contact angle or DCA, usually at 23 ℃, uses the borate buffer salt, and utilizes Wilhelmy balance (Wilhelmy balance) to measure.When the belt transect that will shear from the lens middle part immerses with 100 little meter per second speed or pulls out the borate buffer salt, utilize the wetting power between the little balance of Wilhelmy (Wilhelmy microbalance) measurement lens surface and buffer salt.Use following equation
F=2 γ pcos θ or θ=cos
-1(F/2 γ p)
Wherein F is a wetting power, and γ is the surface tension of probe liquid, and p is a sample meniscus girth, and θ is a contact angle.Usually obtain two contact angle-advancing contact angles and receding contact angle from dynamic wetting experiment.Advancing contact angle partly obtains from the wetting experiment that sample is immersed the probe liquid, and what this paper reported is advancing contact angle numerical value.Measure at least four lens of each composition, and the report meansigma methods.
Use the crosshead of constant motion type cupping machine to measure modulus, this cupping machine is equipped with the charge chute that is reduced to initial absolute altitude.Suitable testing machine comprises Instron 1122 types.To grow that 0.522 inch, " ear " are wide 0.276 inch, " neck " wide 0.213 inch Os Canitis shape sample is packed anchor clamps (grip) into, and rupture up to it with the constant speed tension force stretching of 2 inch per minute clocks.The initial mark of measuring samples long (Lo) and sample breakage length (Lf).Measure 12 samples of each composition and average.Initial straight line portion in stress/strain curves is measured stretch modulus.
Following mensuration mist degree: the aquation test lens is placed in the borate buffer salt solution in transparent 20 * 40 * 10mm glass dish under the ambient temperature of smooth black background top, become 66 ° of angles to use optical fiber lamp (Titan Tool Supply Co. optical fiber lamp from the below with the lens ware, have 0.5 ＂ diameter photoconduction, power setting is 4-5.4) illumination, catch lenticular image perpendicular to the lens ware from the top with the video camera (DVC1300C:19130RGB video camera) that places 14mm place, lens platform top with Navitar TV Zoom7000 zoom lens.With EPIX XCAP V1.0 software, by deducting the image of blank ware, subtracting background scattering from lens scatter.By at lens centre 10mm scope integration, be made as 100 1.00 diopter CSI Thin then arbitrarily with haze value
Contrast, the scattered light image after quantitative analysis deducts does not have lens to be made as 0 haze value.Analyze 5 lens, the result is on average obtained haze value in standard C SI lens percentage ratio.
Moisture measurement is as follows: lens to be measured were placed packaging solution (packing solution) 24 hours.There is the swab of sponge that each lens in 3 test lens are taken out from packaging solution with the top, lens are placed on the moisture absorption cleaning piece (blottingwipe) of using the packaging solution moistening.The lens two sides is contacted with cleaning piece.Place weighing plate to weigh test lens with tweezers.Two groups of samples of refabrication are also as above weighed.Dish is weighed 3 times, and meansigma methods is a weight in wet base.
By being placed, specimen disc is preheated to 60 ℃ and keep 30 minutes vacuum drying oven to measure dry weight.Evacuation is until reaching at least 0.4 inch of mercury.Close vacuum valve and pump, dry lens 4 hours.Open vent valve, make drying baker reach normal pressure.The taking-up dish is weighed.Water content is calculated as follows:
Weight in wet base=dish adds the weight of the weight in wet base-pan of a steelyard of lens
Dry weight=dish adds the weight of the dry weight-pan of a steelyard of lens
Water content %=[(weight in wet base-dry weight)/weight in wet base] * 100
The meansigma methods of calculation sample water content and standard deviation, and report.
By the polarography determination oxygen flow degree (Dk) of general description in ISO 9913-1:1996 (E), just in the environment that contains 2.1% oxygen, measure.Produce this environment by the test cabinet that is equipped with input of 1800ml/min nitrogen and the input of 200ml/min air.With po through regulating
2Calculate t/Dk.With barrer report gained Dk value.
Abbreviation below in following examples, using:
SiGMA 2-acrylic acid, the 2-methyl-, 2-hydroxyl-3-[3-[1,3,3,3-tetramethyl-1-[(trimethyl silyl) and the oxygen base] the disiloxane base] propoxyl group] propyl ester
The DMA N,N-DMAA
HEMA methacrylic acid 2-hydroxyethyl ester
MPDMS 800-1000MW (M
n) the end capped polydimethylsiloxane of the end capped single normal-butyl of monomethyl acryloxy propyl group
The NVPN vinyl pyrrolidone
The IPA isopropyl alcohol
MeOH methanol
The EtOAc ethyl acetate
D3O 3,7-dimethyl-3-capryl alcohol
The TEGDMA tetraethylene glycol dimethacrylate
TRIS 3-methacryloxypropyl three (trimethylsiloxy group) silane
CGI819 two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide
DAROCUR 1173 Alpha-hydroxies-α, the alpha-alpha-dimethyl 1-Phenylethanone.
DPMA two (propylene glycol) methyl ether acetas
Embodiment 1-prepolymer A
54g mPDMS, 6g HEMA, 200mg CGI819 and 50ml hexanol are put into each of two amber bottles.Mix after 1 hour,, made these solution degassings with nitrogen filled vacuum chamber releasing vacuum in per 15 minutes by these solution being placed about 80mm Hg vacuum chamber 1 hour.Then in nitrogen atmosphere, room temperature and be higher than the about 14 inches position of solution from above use from the described solution of the radiation of visible light of Philips TL03 fluorescent lamp bulb 1 hour.Merge solution then, make the product precipitation by adding about 500ml MeOH.Decant gained upper strata is by adding MeOH washing lower floor 3 times, jolting, decant upper strata.Lower floor is dissolved in the 200ml ethyl acetate, with about 500ml methanol extraction.Lower floor twice is washed again with 200ml MeOH in the decant upper strata, and decompression is spin-dried for volatile matter and gets 80g prepolymer A colorless solid in 55 ℃ of Rotary Evaporators then.
Prepolymer A (21.1g) is sneaked into formation prepolymer A solution among the 23.9g D3O.
Embodiment 2
Form clear solution by 55.5% (weight) prepolymer A (solid form), 39%DMA, 4%TEGDMA, 1.5%CGI819 and D3O with 70/30 ratio (weight ratio of prepolymer and active component and D3O diluent).Make this admixture degassing 20 minutes at 40mm Hg, then under Philips TL03 lamp, solidified 1 hour in the contact lens mold of 50 ℃, TOPAZ antetheca and polypropylene rear wall.Open mold, take out lens and put it into the IPA of 50:50 (weight) and the solution of water in.Extracted lens 2 hours with IPA, be transferred to then in the solution of the IPA of 75:25,50:50,25:75 and 0:100 and water (keeping 20 minutes in every kind of solution).The performance of gained lens sees the following form 1.
Embodiment 3
Method according to embodiment 2 prepares lens, but uses table 1 prescription, the results are shown in Table 1.
Table 1
| Component | Embodiment 2 | Embodiment 3 |
| Prepolymer A | 55.5% weight | 57% weight |
| DMA | 39% weight | 40% weight |
| TEGDMA | 4% weight | 1.5% weight |
| CGI819 | 1.5% weight | 1.5% weight |
| Monomer diluent ratio (D3O diluent) | 70/30 | 60/40 |
| Dynamic contact angle | 81° | * |
| Mist degree | 59％ | * |
| Modulus | * | 40psi |
| Dk | * | 91 |
| Water content | * | 60.1％ |
*Do not measure
Embodiment 4-prepolymer B solution
The admixture of preparation 54g mPDMS, 5g HEMA, 50mg CGI819 and 50g tert-pentyl alcohol, and be placed in the nitrogen environment several hours.In nitrogen, room temperature, be higher than the about 5 inches position of solution and be used to from the radiation of visible light admixture of Philips TL03 bulb about 1 hour.The gained viscous solution is poured among the 200ml MeOH.After the stirring, the decant upper strata adds 100ml MeOH to lower floor.Stir this mixture once more, the decant upper strata.Add 240ml IPA to form solution to lower floor.Add 250ml MeOH, once more the decant upper strata.Add 200ml IPA with the preparation clear solution to lower floor, then add 400ml MeOH with precipitation polymers, once more the decant upper strata.The volatile matter that is spin-dried on Rotary Evaporators in the lower floor gets transparent, the very heavy-gravity oily product of 21.1g.This grease is dissolved in must 45g prepolymer B solution among the 23.9g D3O.
Embodiment 5-prepolymer C solution
The admixture of preparation 54g TRIS, 5g HEMA, 50mg CGI819 and 50g tert-pentyl alcohol by about 5 minutes of evacuation (30mm Hg) degassing, is filled flask with nitrogen, and storage solution spends the night in nitrogen atmosphere then.In nitrogen, under the room temperature, utilize to place the Philips TL 20W/03T irradiation solution 1 hour that is higher than the about 14 inches positions of solution.The gained viscous solution is poured among the 200ml MeOH.After the stirring, the decant upper strata adds 100mlMeOH to lower floor.Stir this mixture once more, the decant upper strata.Add 150ml IPA to form solution.Add 200ml MeOH, once more the decant upper strata.Add 150ml IPA to lower floor, then add 300ml MeOH, once more the decant upper strata.The volatile matter that is spin-dried on Rotary Evaporators in the lower floor gets transparent, the heavy-gravity oily product of 29.5g.This grease is dissolved in the solution that gets 43% (weight) prepolymer and 57% D3O among the D3O.
Embodiment 6
3.35g prepolymer A solution is mixed the transparent admixture of formation with 1.10g DMA, 40 μ l TEGDMA and 14 μ lDAROCUR1173.By above solution about 5 inches, under room temperature, in the nitrogen, under Philips TL20W/09N fluorescence UV bulb, in TOPAZ/ polypropylene mold, solidified 30 minutes, form lens.Open mold, take out lens and put it in 70/30 the IPA/ water, change fresh solution twice, be placed on then in the borate buffer salt solution.Lens are opaque slightly.
Embodiment 7
3.35g prepolymer A solution is mixed the transparent admixture of formation with 1.10g NVP, 40 μ l TEGDMA and 14 μ lDAROCUR 1173.By above solution about 5 inches, under room temperature, in the nitrogen, under Philips TL 20W/09N fluorescence UV bulb, in TOPAZ/ polypropylene mold, solidified 30 minutes, form lens.Open mold, take out lens and put it in 70/30 the IPA/ water, change fresh solution twice, be placed on then in the borate buffer salt solution.Lens are opaque.
Embodiment 8
3.35g prepolymer B solution is mixed the transparent admixture of formation with 1.10g DMA, 40 μ l TEGDMA and 14 μ lDAROCUR 1173.By solidifying 30 minutes formation lens in TOPAZ/ polypropylene mold and under the Philips TL 20W/09N fluorescence UV bulb.Open mold, take out lens and put it in 70/30 the IPA/ water, change fresh solution twice, be placed on then in the borate buffer salt solution.Lens are opaque.
Embodiment 9-SiGMA pre-polymer solution
When using the de gassed solution of radiation of visible light 29.5g SiGMA, 25mg CGI819 and 25g tert-pentyl alcohol, form insoluble gel, but, when the solution that in room temperature, nitrogen, shines 25g SiGMA, 75mg CGI 819 and 44g isopropyl acetate similarly in the time of 1 hour, then form transparent, heavy-gravity polymer solution with Philips TL03 bulb.Solution is poured in the 100ml acetonitrile into decant gained upper strata.Add 20ml EtOAc to form clear solution.Add the 100ml acetonitrile again, the decant upper strata.Add 35ml EtOAc to form clear solution to lower floor, add the 100ml acetonitrile to precipitate once more.The decant upper strata.Add 20g D3O to lower floor, in Rotary Evaporators, be spin-dried for the solution (" SiGMA pre-polymer solution ") that forms transparent, heavy-gravity slightly 49% prepolymer of 39.4g and 51%D3O then.
Embodiment 10
Form clear solution by 4g SiGMA pre-polymer solution, 1.31g DMA, 0.05g TEGDMA and 10 μ l DAROCUR 1173.By in TOPAZ and polypropylene contact lens mold, utilize Philips 20W/09N UV fluorescent lamp bulb, in nitrogen, 1 hour formation lens of cold curing.Open mold, take out lens, in 70/30 IPA/ water, extract.(changing 2 times) places saline, autoclave sterilization then.The performance of these lens sees Table 2.
Table 2
| Dk | 51 |
| Mist degree | 227+/-21％ |
| Water content | 55.7+/-0.3％ |
| Dynamic contact angle | 70+/-20° |
Embodiment 11
SiGMA and CGI 819 are reacted according to the method for embodiment 9, are that final post precipitation is separated into the transparent thick liquid of 10.5g with polymer, do not add D3O.Spend the night to form clear solution this prepolymer of 1.16g and 0.81g NVP, 0.04g TEGDMA, 0.03g CGI819 and 0.80gEtOAc diluent are mixed.By in ZEONOR and polypropylene contact lens mold, utilize Philips TL 20w/03T fluorescent lamp bulb, in nitrogen, 60 ℃ solidified 1 hour, form lens.Open mold, take out lens, in IPA/ water, extract, place saline then.The medium muddiness of described hydrated lens.
Embodiment 12
According to the method for embodiment 11, form lens by 1.16g SiGMA prepolymer, 0.79g NVP, 0.03g TEGDMA, 0.03g CGI819 and 0.82g DPMA diluent.The gained hydrated lens is muddy slightly.
Embodiment 13
Stir 150g octamethylcy-clotetrasiloxane, 22.6g (3 at 25 ℃, 3, the 3-trifluoro propyl) methyl cyclotrisiloxane, 17.4g1,3,5, the mixture of 7-tetramethyl-ring tetrasiloxane, 0.05g hexamethyl disiloxane, 200g chloroform and 1.5g trifluoromethanesulfonic acid 24 hours becomes neutrality with the purified water repeated washing until the pH of mixture then.After separating water outlet, the evaporated under reduced pressure chloroform.Debris is dissolved in the isopropyl alcohol, uses the methanol redeposition, then the volatile component in the vacuum removal separating liquid gets transparent thick liquid.Described transparent thick liquid is the polysiloxanes with hydrogen silane group.
The mixture of this polysiloxanes of 48g, 11.6g 1-propenol-3,96g isopropyl alcohol, 0.04g potassium acetate, 10mg chloroplatinic acid and 10mg di-tertiary butyl methyl phenol packed into to have in the flask of reflux condenser, 50 ℃ of heated and stirred 3 hours.Filter reaction mixture, the evaporated under reduced pressure isopropyl alcohol is then used the mixture washing of methanol then.Further vacuum is removed volatile component and is got transparent thick liquid.Gained liquid is the polysiloxane prepolymers with alcohol groups.
Embodiment 14
Polysiloxane prepolymers, 39%DMA, 4%TEGDMA, 1.5%CGI819 and D3O by 55.5% (weight) embodiment 13 form transparent active mixture with 70/30 ratio (weight ratio of prepolymer and active component and D3O diluent).Make this active mixture degassing 20 minutes at 40mm Hg, then in TOPAZ antetheca and polypropylene rear wall contact lens mold, under the Philips TL03 light, solidified 1 hour in 5 ℃.Open mold, take out lens and put it into the IPA of 50:50 (weight) and the solution of water in.Extracted lens 2 hours with IPA, be transferred to then in the solution of the IPA of 75:25,50:50,25:75 and 0:100 and water (keeping 20 minutes in every kind of solution).
Claims (25)
1. component of polymer that forms by active mixture, described mixture comprise the prepolymer of (a) at least a basic non-activity that comprises siliceous ketone groups and increase-volume group and (b) comprise at least a can with the monomeric hydrophilic component of described prepolymer hydrogen bonded, condition is that described active mixture does not contain active prepolymer substantially.
2. the polymer of claim 1, that wherein said prepolymer comprises is fluorine-containing at least about 50% weight, the group of silicone or its mixture.
3. the polymer of claim 1, that wherein said prepolymer comprises is fluorine-containing at least about 70% weight, the group of silicone or its mixture.
4. the polymer of claim 1, that wherein said prepolymer comprises is fluorine-containing at least about 90% weight, the group of silicone or its mixture.
5. the polymer of claim 1, the weight average molecular weight of wherein said prepolymer are about 50, and 000-about 1,000,000.
6. the polymer of claim 1, the weight average molecular weight of wherein said prepolymer are about 50, and 000-about 500,000.
7. the polymer of claim 1, the weight average molecular weight of wherein said prepolymer are about 50, and 000-about 200,000.
8. the polymer of claim 1, wherein said prepolymer comprises less than about 1% weight active group.
9. the polymer of claim 1, wherein said hydrophilic component comprises the monomer of at least a amide containing.
10. the polymer of claim 2, wherein said hydrophilic component comprises the monomer at least about 50% weight amide containing.
11. the polymer of claim 9, wherein said hydrophilic component comprises the monomer at least about 75% weight amide containing.
12. the polymer of claim 9, wherein said hydrophilic component comprises the monomer at least about 90% weight amide containing.
13. the polymer of claim 1, wherein said hydrophilic component comprise at least a hydrogen bond partner.
14. being hydrogen bond, the polymer of claim 1, wherein said increase-volume group supply with group.
15. the polymer of claim 1, wherein said increase-volume group are selected from the amide, ammonia, the urea of primary amine, carbamate, hydroxyl and the combination thereof of primary amine of carboxyl, mercaptan, phenol, primary amine.
16. the polymer of claim 1, wherein said increase-volume group comprises hydroxyl.
17. the polymer of claim 1, the oxygen flow degree of wherein said polymer is at least about 30barrer.
18. the polymer of claim 1, the oxygen flow degree of wherein said polymer is at least about 40barrer.
19. the polymer of claim 1, the oxygen flow degree of wherein said polymer is at least about 60barrer.
20. the polymer of claim 1, wherein said hydrophilic component comprise at least a amide monomer, carbamate monomer or its mixture.
21. the polymer of claim 1, wherein said hydrophilic component comprises the monomer of at least a amide containing.
22. the polymer of claim 1, wherein said hydrophilic component is selected from N, N-DMAA, 2-hydroxyethyl methacrylamide, N-vinyl pyrrolidone, N-vinyl-N-methylacetamide, N-vinyl acetamide, N-vinyl-N-methyl propanamide, N-vinyl-N-methyl-2-methyl propanamide, N-vinyl-2-methyl propanamide, N-vinyl-N, N '-dimethyl urea and composition thereof.
23. the polymer of claim 1, wherein said hydrophilic component are selected from N,N-DMAA, N-vinyl pyrrolidone, N-vinyl-N-methylacetamide and composition thereof.
24. a contact lens, described contact lens is by the polymer formation of claim 1.
25. a biologic medical apparatus, described apparatus is formed by the contact lens of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75537105P | 2005-12-30 | 2005-12-30 | |
| US60/755,371 | 2005-12-30 | ||
| US11/608,642 | 2006-12-08 |
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|---|---|---|---|
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| AR (1) | AR058886A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576158A (en) * | 2009-10-01 | 2012-07-11 | 库柏维景国际控股公司 | Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses |
-
2006
- 2006-12-15 CN CNA2006800535058A patent/CN101389364A/en active Pending
- 2006-12-28 AR ARP060105855 patent/AR058886A1/en unknown
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576158A (en) * | 2009-10-01 | 2012-07-11 | 库柏维景国际控股公司 | Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses |
| CN102576158B (en) * | 2009-10-01 | 2014-07-16 | 库柏维景国际控股公司 | Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses |
Also Published As
| Publication number | Publication date |
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| TW200738289A (en) | 2007-10-16 |
| AR058886A1 (en) | 2008-02-27 |
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