CN1222169A - High Moisture Porous Polymers - Google Patents

Abstract

The present invention relates to porous polymers comprising perfluoropolyether units, a process for producing such porous polymers, in particular a process for polymerizing or copolymerizing perfluoropolyether-doped monomers to form porous polymers, comprising perfluoropolyether Articles made of or comprising porous polymers of ether units, such as membranes or ophthalmic devices, and uses of porous polymers comprising perfluoropolyether units as articles, such as membranes or ophthalmic devices. The perfluoropolyether units preferably have the formula (PFPE):—OCH ₂ CF ₂ O(CF ₂ CF ₂ O) _x (CF ₂ O) _y CF ₂ CH ₂ O—(PFPE)where CF ₂ CF ₂ O and CF ₂ O units can be distributed randomly or in blocks throughout the chain and x and y can be the same or different, so that the molecular weight of the perfluoropolyether is 242-4000. Porous polymers comprising one or more perfluoropolyether units have a higher water content when fully swollen in water than the same polymer polymerized under conventional conditions and are suitable for applications such as soft contact lenses.

Description

The porous polymer of high-moisture percentage

The present invention relates to comprise the unitary porous polymer of PFPE, relate to this poromeric production method, be particularly related to a kind of polymerization or copolymerization and be mixed with the monomer of PFPE to form poromeric method, relate to by comprising the unitary porous polymer of PFPE and make or comprise the goods of this polymkeric substance, as film or ophthalmic device, for example contact lens also relates to and comprises the purposes of the unitary porous polymer of PFPE as the goods such as film or ophthalmic device (for example contact lens).

Have found that in many application, it is favourable that polymkeric substance is porous.Desired porosity is relevant with application.For example, membrane filtration depends on the use of microporous polymer, to separate various materials.In addition, the macropore sheet material with polymkeric substance of chemical patience is widely used as the battery separator in electrolytic cell or the accumulate pond.

Can in the technological process of the goods of making desired shape, in polymkeric substance, form the hole, or can after manufacturing process is finished, in goods, form the hole.Known in this area have many methods that hole is introduced in the synthetic polymer, as at WO90/07575, WO91/07687, US-A-5, and 244,799, US-A-5,238,613 or US-A-4, the method described in 799,931.Some method relates to holes after forming polymer or etching.Therefore, as described in WO91/07687, high energy particle or electromagnetic radiation had been used, as going out by Laser emission.These methods take time and effort usually.

Not quite commonly, porosity may be the proper property of polymkeric substance and be kept when polymkeric substance being made the desired shape of application-specific.Particularly advantageous is to introduce hole in the process of polymer formation step.This is normally economical, and in suitable situation, can control porosity and aperture well.

Polymkeric substance based on PFPE has many uniquenesses and desirable performance usually.These performances comprise the resistibility to protein material and the caused fouling of other materials, significant snappiness, the transparency, the high-temperature resistant degree limit and excellent chemical-resistant and oxidation-resistance.The feasible polymkeric substance based on PFPE of these performances is particularly suitable for multiple application and is particularly suitable for as film, if there is the method that can introduce hole economically.In fact, people need to have the mould material of above-mentioned characteristic for a long time.The polytetrafluoroethylene (PTFE) basal lamina material has partly solved these needs.Yet, be easy to by polymerization in situ solidify and form the PFPE based polyalcohol of goods different be that the PTFE sill has the shortcoming that is difficult to make goods.In addition, those pore dimensions that are restricted to a certain extent and the shape and restive described among drawing process such as the US-A-3,953,566 (Gore).

Owing to have above-mentioned performance, the PFPE based polyalcohol is the height desirable material (US-A-4,440,918, US-A-4,818,801) that is used for contact lens and other ophthalmic devices; Tear or nutrient substance shift if this class material can be made porous, and then its availability will greatly improve.

Although these materials have tangible potential advantage, do not have porous PFPE polymkeric substance in the past.

In some polymkeric substance, hole can be the interpenetrating(polymer)networks of perforate, closed pore or its combination.This can obtain by carry out polymerization in the presence of the insoluble material that often is called pore-forming material (porogen).Leach pore-forming material subsequently and in the polymer materials of whole formation, produce the space.Sodium-chlor is a kind of this class material that once was used.A shortcoming of this method is to be difficult to make the effect suspension stabilization of pore-forming material in polyblend.Unsettled suspension may cause heterogeneous and unacceptable product.In many situations, need make the viscosity of this system and the type of pore-forming material reach optimizing completely, to obtain gratifying result.In addition, this program is restricted with regard to the operability of the pore-forming material that is suitable for introducing required pore diameter range.

A kind of convenience and method in common that obtains porous material is the polymerization of microemulsion continuously altogether.Micro-emulsion polymerization relates to the polymerization by the stable isotropic mixture of stable oil phase of tensio-active agent and water.Oil phase contains polymerisable monomer usually, and it is by around the adjacent drops of the stable water of tensio-active agent or polymerization around successive water altogether.Be typically, not with an organic solvent at aqueous phase.

Should understand the porous material that obtained by PFPE and have unique feature in the interaction of itself and other material, one of them is unique low surface energy.Low surface energy and to the adsorptive power lower part of many common materials cause its significant anti-soil power and anti-degradation property and the fluoropolymer availability in requiring didirtresistance or inviscid application.The low surface energy of fluorine-containing chemical and deliquescent result are difficult in water-bearing media and other common media to make stable emulsion and microemulsion.For example, the standard surface promoting agent known of this area crowd is invalid for the stable aqueous microemulsions that contains PFPE.Therefore, the standard method of preparation microemulsion is invalid to the monomer based on PFPE.

An object of the present invention is to provide and comprise the unitary porous polymer of one or more PFPE, when complete swelling in water, the water ratio of this polymkeric substance is higher than the water ratio of polymeric same polymer under normal condition.

Another object of the present invention provides and comprises the unitary porous polymer of one or more PFPE, it is characterized in that the water ratio of described polymkeric substance when complete swelling in water is higher than 23wt%.

A further object of the present invention provides and comprises the unitary porous polymer of one or more PFPE, this polymkeric substance or be homopolymer or for and the multipolymer of hydrophobic comonomer, it is characterized in that the water ratio of described polymkeric substance when complete swelling in water is higher than 5wt%.

Another purpose of the present invention provides by one or more above-mentioned porous polymers and makes or comprise one or more above-mentioned poromeric goods, and these goods for example can be film or ophthalmic device, for example preferred contact lens.

An also purpose of the present invention provides the above-mentioned poromeric method of making.

More particularly, the present invention relates to a kind of porous polymer, this polymkeric substance comprises at least a unitary big monomer of one or more PFPE that has, and it is characterized in that the water ratio of described polymkeric substance is higher than 23wt% when in water fully during balance.The preferable range of water ratio is 25-60wt%, more preferably 30-55wt%.

In addition, the present invention relates to a kind of porous polymer, this polymkeric substance is at least a multipolymer with the unitary big monomeric homopolymer of one or more PFPE or this big monomer and a kind of hydrophobic comonomer, it is characterized in that water ratio is higher than 5wt% when in water fully during balance.The preferable range of water ratio is 5-60wt%, more preferably 10-55wt%, and scope very preferably is 25-52wt%.

In a preferred embodiment, polymerizable components comprises at least a unitary big monomer of at least one PFPE that has.The one skilled in the art should understand a kind of structure that term " PFPE unit " and " PFPE unit " preferably are meant formula PFPE :-OCH ₂CF ₂O (CF ₂CF ₂O) _x(CF ₂O) _yCF ₂CH ₂O-(PFPE) is CF wherein ₂CF ₂O and CF ₂The O unit can be in whole chain random distribution or with block distributed, and wherein x and y can be identical or different, so that the molecular weight of PFPE is 242-4000.X in the preferred formula (PFPE) is 0-20, more preferably 8-12, and preferred y is 0-25, more preferably 10-14.More preferably, x in the formula (PFPE) and y all are not 0, so that x is 1-20, and more preferably 8-12, and y is 1-25, more preferably 10-14.

Preferably have the unitary big monomer of at least one PFPE and include but not limited to those of following formula I, II and III: the big monomer of formula I:

Q-(PFPE-L) _N-1The big monomer of-PFPE-Q (I) formula II:

Q-B-(L-B) _nThe big monomer of-T (II) and formula III:

Q-PFPE-L-M-L-PFPE-Q (III) wherein in these formulas Q can be identical or different and be polymerizable groups, PFPE is the residue of divalent of the defined formula in front (PFPE), L is the difunctionality linking group; N is at least 1; In the big monomer of formula II, each B can be identical or different and for molecular weight is the difunctionality block of 100-4000, and wherein at least one B is the PFPE of formula (PFPE); In the big monomer of formula II, T is can not be by radical polymerization but can contain the monovalence end group of other functionality; And in the big monomer of formula III, M is that the siloxane repeat unit and the molecular weight that comprise the formula IV are preferably 180-6000 and have the double functional copolymer of following end functionality or the residue of multipolymer:

R wherein ¹And R ²Can be identical or different and be selected from hydrogen, alkyl, aryl, haloalkyl etc.R ¹And R ²Be preferably methyl.

As mentioned above, one embodiment of the invention relate to a kind of porous polymer, this polymkeric substance comprises at least a unitary big monomer of one or more PFPE that has, and it is characterized in that the water ratio of described polymkeric substance is higher than 23wt% when in water fully during balance.Preferably one or more have the unitary big monomer of one or more PFPE to this porous polymer, the big monomer of preferred formula I, II or III and one or more hydrophilic polymerized monomers or with the multipolymer of hydrophobicity and hydrophilic polymerized monomeric mixture, hydrophilic polymerized monomeric weight percentage is higher than hydrophobic comonomer in the described mixture.Be preferably based on big monomer and only hydrophilic polymerized polymer of monomers in this article.The example of preferred comonomers provides hereinafter.

Also be as previously mentioned, another embodiment of the present invention relates to a kind of porous polymer, it is at least a multipolymer with the unitary big monomeric homopolymer of one or more PFPE or this big monomer and hydrophobic comonomer, it is characterized in that water ratio is higher than 5wt% when in water fully during balance.In this case, this polymkeric substance or for having the unitary single big monomeric homopolymer of one or more PFPE, or a kind ofly have the unitary big monomeric interpolymer of one or more PFPE or have the unitary big monomer of one or more PFPE for one or more for more than, the big monomer of preferred formula I, II or III and one or more hydrophobic comonomers or with the multipolymer of hydrophobicity and hydrophilic polymerized monomeric mixture, the weight percentage of hydrophobic comonomer is higher than hydrophilic polymerized monomer in the described mixture.Be preferably based on the big monomer and the polymkeric substance of hydrophobic comonomer only in this article.The example of preferred comonomers provides hereinafter.

One of necessary distinctive feature of the present invention is for comprising the water ratio that water ratio that the unitary porous polymer of one or more PFPE had is higher than polymeric same polymer under normal condition when complete swelling in water.This be defined in be interpreted as in the context of the invention porous polymer required for protection after polymerization procedure, do not carry out having really under the situation of any mechanical technology step such as machine drilling or etching step hole and produced thus than high-moisture percentage." normal condition " is interpreted as referring to openly be used for those conditions of the unitary polymkeric substance of aggregate packet perfluoro-polyether.For further specifying " normal condition ", should understand the condition that described condition does not most preferably comprise any promotion porosity, and promote the condition of porosity to be selected for preparation porous polymer of the present invention.

This class promotes that the condition of porosity mainly is to use pore-forming material in polymerization process, by continuous microemulsion altogether begin polymerization or select for use and treat that polymeric component forms homogeneous phase solution but in polymerization process or polymerization finish the solvent of the effect of back demonstration formation disperse phase, described organic solvent disperse phase forms interpenetrating(polymer)networks or is dispersed in the whole mixture in whole mixture.In contrast, " normal condition " mentioned in the context defines a kind of like this polymerization process basically, it is begun by homogeneous phase, for example by treating that the homogeneous phase solution of polymeric component in organic solvent begins, after polymerization finishes, this phase still is homogeneous phase (then formed polymkeric substance is a soluble polymer), or this homogeneous phase changes into solvent phase and polymkeric substance external phase isolating with it (then formed polymkeric substance is the polymkeric substance that is insoluble to selected solvent).The representative instance of " normal condition " provides in Comparative Examples 13 and 14.

In following formula I, II and III, use following definition respectively:

Preferred n is 1-5, and more preferably n is 1-3.Preferred especially wherein n is 1 big monomer.

But Q is for preferably comprising the polymerizable groups of the unsaturated part of olefinic of freedom of entry base polyreaction.Preferred Q is the group of formula A:

P ₁-(Y) _m-(R '-X ₁) _p-(A) P wherein ₁Group for free redical polymerization; Y is-CONHCOO-,-CONHCONH-,-OCONHCO-,-NHCONHCO-,-NHCO-,-CONH-,-NHCONH-,-COO-,-OCO-,-NHCOO-or-OCONH-; M and p are 0 or 1 independently of one another; R ' is for having the divalent group of the organic compound of 20 carbon atoms at the most; X ₁For-NHCO-,-CONH-,-NHCONH ,-COO-, OCO-,-NHCOO-or-OCONH-.

The group P of free redical polymerization ₁For example be to have alkenyl, alkenyl aryl or the alkenyl arylidene alkyl of 20 carbon atoms at the most.Non-limiting examples of alkenyls is a vinyl, allyl group, 1-propylene-2-base, 1-butylene-2-,-3-and-the 4-base, 2-butylene-3-base, and the isomer of pentenyl, hexenyl, octenyl, decene base and undecenyl.The example of alkenyl aryl is ethenylphenyl, vinyl naphthyl or allyl phenyl.The example of alkenyl arylidene alkyl be adjacent-,-or to vinyl benzyl.

P ₁Be preferably and have the alkenyl or the alkenyl aryl of 12 carbon atoms at the most, especially preferably have the alkenyl of 8 carbon atoms at the most, especially have the alkenyl of 4 carbon atoms at the most.

Y is preferably-COO-,-OCO-,-NHCONH-,-NHCOO-,-OCONH-,-NHCO-or-CONH-, preferred especially-COO-,-OCO-,-NHCO-or-CONH-, especially-COO-or-OCO-.

X ₁Preferably-NHCONH-,-NHCOO-or-OCONH-, preferred especially-NHCOO-or-OCONH-.

In preferred embodiments, exponent m and p are not 0 simultaneously.If p is 0, then m is preferably 1.

R ' is preferably alkylidene group, and arylidene has saturated divalence cycloaliphatic groups, arylidene alkylene, alkylidene group arylidene, alkylidene group arylidene alkylene or the arylidene alkylene arylidene of 6-20 carbon atom.

Preferred R ' especially preferably has the divalent group of 8 carbon atoms at the most for to have the divalent group of 12 carbon atoms at the most.In preferred embodiments, R ' is for having the alkylidene group or the arylidene of 12 carbon atoms at the most.The particularly preferred embodiment of R ' is a low-grade alkylidene, especially has the low-grade alkylidene of 4 carbon atoms at the most.

Preferred especially Q is selected from acryl, methacryloyl, styryl, acrylamido, acrylamido alkyl, urethane methacrylic ester or any its substitutive derivative.Most preferably Q is formula A compound, wherein P ₁Be to have the alkenyl of 4 carbon atoms at the most, Y is-COO-that R ' has the alkylidene group of 4 carbon atoms at the most, X ₁Be-NHCOO-and m and p respectively do for oneself 1.

Linking group L can be can with the residue of divalent of any difunctionality part of hydroxyl reaction.The appropriate precursors of L is α, ω-diepoxides, α, ω-vulcabond, α; ω-diisothio-cyanate, α, ω-diacyl halogen, α, ω-dithio acyl halide; alpha, omega-dicarboxylic acid, α, ω-dithionic acid, α; ω-dianhydride, α, ω-dithio isocyanic ester, α, ω-dilactone; α, ω-dialkyl, α, ω-dihalide; α, ω-dialkyl ether, α, ω-dihydroxymethyl acid amides.Preferred linking group is the residue of divalent (C (O)-NH-R-NH-C (O)-) of vulcabond or the corresponding residue of dithio isocyanic ester, and wherein R has the divalent organic group of 20 carbon atoms at the most.

Divalent group R is for example for having the alkylidene group of 20 carbon atoms at the most, arylidene, alkylidene group arylidene, arylidene alkylene or arylidene alkylene arylidene have the saturated divalence cycloaliphatic groups of 6-20 carbon atom or have the cycloalkylidene alkylidene group cycloalkylidene of 7-20 carbon atom.

In preferred embodiments, R is the saturated divalence cycloaliphatic groups that has alkylidene group, arylidene, alkylidene group arylidene, arylidene alkylene or the arylidene alkylene arylidene of 14 carbon atoms at the most or have 6-14 carbon atom.In particularly preferred embodiments, R is the saturated divalence cycloaliphatic groups that has the alkylidene group or the arylidene of 12 carbon atoms at the most or have 6-14 carbon atom.

In preferred embodiments, R is the saturated divalence cycloaliphatic groups that has the alkylidene group or the arylidene of 10 carbon atoms at the most or have 6-10 carbon atom.

In particularly preferred implication, R is by vulcabond deutero-group, for example by hexane 1, the 6-vulcabond, 2,2,4-trimethyl cyclohexane 1,6-vulcabond, tetramethylene diisocyanate, phenylene 1,4-vulcabond, toluene 2, the 4-vulcabond, toluene 2,6-vulcabond, between or to tetramethylxylene diisocyanate, isophorone diisocyanate or hexanaphthene 1,4-vulcabond deutero-group.

Aryl is the carbocyclic aromatic group that does not replace or preferably replaced by low alkyl group or lower alkoxy.Example is a phenyl, tolyl, xylyl, methoxyphenyl, uncle's butoxyphenyl, naphthyl and phenanthryl.

Arylidene is phenylene or naphthylidene preferably, and it is not replace or replaced by low alkyl group or lower alkoxy, and especially 1,3-phenylene, 1,4-phenylene or methyl isophthalic acid, 4-phenylene, 1,5-naphthylidene or 1,8-naphthylidene.

Saturated divalence cycloaliphatic groups is preferably cycloalkylidene, for example inferior cyclohexyl or cyclohexylidene (low-grade alkylidene) are as the cyclohexylidene methylene radical, for not replacing or by one or more low alkyl groups such as methyl substituted, trimethylammonium cyclohexylidene methylene radical for example is as divalence isophorone base.

For the purpose of the present invention, especially represent to have 8 carbon atoms at the most with the term " rudimentary " of group and compound logotype, the preferred group or the compound of 4 carbon atoms at the most, unless otherwise.

Low alkyl group especially has 8 carbon atoms at the most, preferred 4 carbon atoms at the most, and for example be methyl, ethyl, propyl group, butyl, the tertiary butyl, amyl group, hexyl or isohexyl.

Alkylidene group has at the most 12 carbon atoms and can be straight or branched.Suitable example is inferior decyl, octylene, hexylidene, pentylidene, butylidene, propylidene, ethylidene, methylene radical, 2-propylidene, 2-butylidene, 3-pentylidene etc.

Low-grade alkylidene is to have 8 carbon atoms at the most, the preferred especially alkylidene group of 4 carbon atoms at the most.The particularly preferred implication of low-grade alkylidene is propylidene, ethylidene and methylene radical.

Arylene units in alkylidene group arylidene or the arylidene alkylene is preferably not the phenylene that replaces or replaced by low alkyl group or lower alkoxy, and alkylidene unit wherein is preferably low-grade alkylidene, as methylene radical or ethylidene, especially methylene radical.Therefore these groups are preferably phenylene methylene radical or methylene radical phenylene.

Lower alkoxy especially has 8 carbon atoms at the most, preferred 4 carbon atoms at the most, and for example be methoxyl group, oxyethyl group, propoxy-, butoxy, tert.-butoxy or hexyloxy.

The arylidene alkylene arylidene is preferably has 8 at the most in alkylidene unit, especially at the most the phenylene of 4 carbon atoms (low-grade alkylidene) phenylene, for example phenylene ethylidene phenylene or phenylene methylene radical phenylene.

Some examples that derive the preferred vulcabond of residue of divalent L comprise trimethyl hexamethylene diisocyanate (TMHMDI), isophorone diisocyanate (IPDI), methylenediphenyl diisocyanates (MDI) and 1,6-hexamethylene diisocyanate (HMDI).

B block can be monomer, oligomer or polymkeric substance.The molecular weight of each B block and chemical constitution can be identical or different, as long as they fall in the above-mentioned molecular weight ranges.B block can be for hydrophobic or hydrophilic, as long as at least one block has formula (PFPE).Other suitable B block can be derived and got by poly-(alkylene oxide).When one or more B block when being hydrophilic, these blocks autohemagglutination (alkylene oxide) of especially preferably deriving, the autohemagglutination of more preferably deriving (rudimentary alkylene oxide) is most preferably derived from polyoxyethylene glycol.Most preferably B block is selected from block and poly-(alkylene oxide) of formula (PFPE), as long as at least one block has formula (PFPE).In two highly preferred embodiments of the present invention, in the big monomer of formula II, there are two B blocks, these two blocks all have formula (PFPE) or one of them has formula (PFPE), and another autohemagglutination of deriving (alkylene oxide), the autohemagglutination (rudimentary alkylene oxide) of preferably deriving is most preferably derived from polyoxyethylene glycol." autohemagglutination of deriving (alkylene oxide) " in the definition of B block is meant that this B block is that with the different of poly-(alkylene oxide) two are held hydrogen atoms to remove from this poly-(alkylene oxide).For making it to simplify, B represents derived from polyoxyethylene glycol the time-(OCH ₂CH ₂) _aO-, wherein a is the index that representative repeats the unitary number of inferior ethoxyl.

End group T is the monovalence end group, and it can not be by radical polymerization but can contain other functionality.Preferred end group is a hydrogen, alkyl, substituted alkyl, aryl or substituted aryl.Preferred group T is a hydrogen, low alkyl group and phenyl.

The suitable substituent of Q or T can be selected from: alkyl, alkenyl, alkynyl, aryl; halogen, haloalkyl, halogenated alkenyl, halo alkynyl; halogenated aryl, hydroxyl, alkoxyl group, alkenyloxy; aryloxy, halogenated alkoxy, halo alkenyloxy, halo aryloxy; amino, alkylamino, alkenyl amino, alkynyl amino; virtue is amino, acyl group, aroyl, alkenyl acyl; aryl-acyl, amido, alkylsulfonyloxy, alkyl sulfenyl oxygen base; heterocyclic radical, heterocyclic oxy group, heterocyclic radical amino, halogenated heterocyclic base; carbalkoxy, alkylthio, alkyl sulphonyl, arylthio; aryl sulfonyl, amino-sulfonyl, dialkylamino and dialkyl group alkylsulfonyl have 10 carbon atoms at the most.

The double functional copolymer who derives M is contained an independent end functionality of selecting at each end, they can with the precursors reaction of linking group L, thereby form covalent linkage.Preferred end functionality is hydroxyl or amino.This functionality can combine by alkylidene group or other non-reacted spacers with the siloxane unit among the M.Preferred end group partly is a hydroxyalkyl, hydroxy alkoxy alkyl and alkylamino.Especially preferred hydroxyalkyl is hydroxypropyl and hydroxyl butyl; Especially preferred hydroxy alkoxy alkyl is '-hydroxyethoxy ethyl and '-hydroxyethoxy propyl group.Preferred R ¹And R ²Group is a methyl.

The preferred L residue has following formula B in the above-mentioned formula III:

Wherein n is the integer of 5-100; Alk has the alkylidene group of 20 carbon atoms at the most, is not spaced apart or by oxygen at interval; Radicals R ₁, R ₂, R ₃And R ₄Be alkyl independently of one another, aryl or haloalkyl; And X ₃For-O-or-NH-.

In preferred implication, n is the integer of 5-70, preferred especially 8-50, especially 10-28.

In preferred implication, radicals R ₁, R ₂, R ₃And R ₄For to have the low alkyl group of 8 carbon atoms at the most, especially preferably have the low alkyl group of 4 carbon atoms at the most independently of one another, especially have the low alkyl group of 2 carbon atoms at the most.R ₁, R ₂, R ₃And R ₄Another particularly preferred embodiment be methyl.

Preferably in partly each of two low-grade alkylidenes, had the low-grade alkylidene oxygen base low-grade alkylidene of 6 carbon at the most by oxygen alkylidene group at interval, more preferably have the low-grade alkylidene oxygen base low-grade alkylidene of 4 carbon atoms at the most in partly each of two low-grade alkylidenes, example is ethyleneoxy group ethylidene or ethyleneoxy group propylidene.

Haloalkyl is preferably by one or more, the low alkyl group that replaces of 3 halogens such as fluorine, chlorine or bromine especially at the most, and example is a trifluoromethyl, chloromethyl, seven fluorine butyl or bromotrifluoromethanes.

Preferred big monomer is the big monomer with formula I, wherein n is 2-5, L is that wherein R has the alkylidene group of 14 carbon atoms at the most, arylidene, the alkylidene group arylidene, arylidene alkylene or arylidene alkylene arylidene or have the residue of divalent (C (O)-NH-R-NH-C (O)-) of vulcabond of the saturated divalence cycloaliphatic groups of 6-14 carbon atom, and Q is formula A compound, wherein P ₁Be the alkenyl of 4 carbon atoms at the most, Y is-COO-, and R ' is the alkylidene group of 4 carbon atoms at the most, X ₁For-NHCOO-and m and p respectively do for oneself 1.

The preferred big monomer of formula I is such monomer, and wherein n is 2-5, and L is for derived from the residue of divalent of trimethyl hexamethylene diisocyanate (TMHMDI) and Q being the residue derived from methacrylic acid isocyanato ethyl ester.

A preferred embodiment of the present invention relates to the big monomer of formula 1: CH ₂=C (CH ₃) COOC ₂H ₄NHCO-(PFPE-CONH-R-NHCO-) _N-1-PFPE-CONHC ₂H ₄OCOC (CH ₃)=CH ₂

(formula 1) wherein PFPE is the perfluorinated polyether of formula (PFPE) defined herein, and wherein x is that 8-10 and y are 10-14, n＞1.0, and R is the saturated divalence cycloaliphatic groups that has the alkylidene group or the arylidene of 12 carbon atoms at the most or have 6-14 carbon atom.

The big monomer of formula 2: CH is provided in a preferred embodiment of the invention, ₂=C (CH ₃) COOC ₂H ₄NHCO-(PFPE-CONH-R-NHCO-) _N-1-PFPE-CONHC ₂H ₄OCOC (CH ₃)=CH ₂

(formula 2) wherein PFPE is the perfluorinated polyether of formula (PFPE) defined herein, n＞1.0, and R is the tri-methyl hexamethylene part of TMHMDI, and wherein x is 8-10, y is 10-14.

In a preferred embodiment of the invention, provide the big monomer of formula II corresponding to formula 3-6:

CH ₂=C(CH ₃)COOC ₂H ₄NHCO-PFPE-CONH-R-NHCO-PFPE-H????(3)

CH ₂=C(CH ₃)COOC ₂H ₄NHCO-PEG-CONH-R-NHCO-PFPE-H?????(4)

CH ₂=C(CH ₃)COOC ₂H ₄NHCO-PFPE-CONH-R-NHCO-PEG-CH ₃???(5)

CH ₂=C (CH ₃) COOC ₂H ₄NHCO-PFPE-CONH-R-NHCO-PEG-H (6) wherein PFPE has wherein x and y such as the defined formula of preamble (PFPE), R has the alkylidene group of 14 carbon atoms at the most, arylidene, the alkylidene group arylidene, arylidene alkylene or arylidene alkylene arylidene or have the saturated divalence cycloaliphatic groups of 6-14 carbon atom, and PEG is derived from polyoxyethylene glycol.The molecular weight of preferred PEG is 200-2000.

In preferred embodiment of the present invention, provide the big monomer of formula 7-10:

CH ₂=C(CH ₃)COOC ₂H ₄NHCO-PFPE-CONH-R-NHCO-PFPE-H????(7)

CH ₂=C(CH ₃)COOC ₂H ₄NHCO-PEG-CONH-R-NHCO-PFPE-H?????(8)

CH ₂=C(CH ₃)COOC ₂H ₄NHCO-PFPE-CONH-R-NHCO-PEG-CH ₃???(9)

CH ₂=C (CH ₃) COOC ₂H ₄NHCO-PFPE-CONH-R-NHCO-PEG-H (10) wherein PFPE has wherein x and y such as the defined formula of preamble (PFPE), and wherein R is the tri-methyl hexamethylene part of TMHMDI, and PEG is derived from polyoxyethylene glycol.The molecular weight of preferred PEG is 200-2000.Also preferred in this embodiment x be 10 and y be 12.

The preferred big monomer of formula III is so big monomer, and wherein the molecular weight of perfluorinated polyether is 800-4000, and L is the residue of divalent derived from trimethyl hexamethylene diisocyanate (TMHMDI), and Q is the residue derived from methacrylic acid isocyanato ethyl ester.The molecular weight of preferred especially perfluorinated polyether be about 2000 and the molecular weight of M be about 1000.

Preferred big monomer of the present invention has formula 11:

CH ₂=C(CH ₃)-COO-C ₂H ₄-NHCO-PFPE-CONH-R-NHCO-OCH ₂CH ₂CH ₂-Si(CH ₃) ₂-(OSi(CH ₃) ₂) ₁₁-CH ₂CH ₂CH ₂O-CONH-R-????(11)

-NHCO-PFPE-CONH-C ₂H ₄-OCO-C (CH ₃)=CH ₂Wherein PFPE has formula (PFPE), R be the tri-methyl hexamethylene part of TMHMDI (trimethyl hexamethylene diisocyanate) and wherein x be 10 and y be 12.

On the other hand, the invention provides the method for producing polymkeric substance required for protection.These methods can make these highly stable and competent materials with porous form manufacturing and use.Therefore provide a kind of poromeric method defined herein of producing, comprised the steps:

ⅰ) form a kind of mixture that comprises polymerizable components and organic solvent, wherein polymerizable components comprises at least a unitary big monomer of at least one PFPE that has;

ⅱ) the described mixture of polymerization wherein has at least significantly the described organic solvent of ratio be in disperse phase and wherein said organic solvent disperse phase after described polymerization of mixtures immediately and forms interpenetrating(polymer)networks or be dispersed in the whole mixture in whole mixture; And

ⅲ) remove the organic solvent disperse phase.This method is called method A hereinafter.

Also provide second kind to produce poromeric method defined herein, comprised the steps:

1) pore-forming material is dispersed in the monomer component external phase, wherein said monomer component external phase comprises and at least aly has the unitary monomer of at least one PFPE and wherein said pore-forming material and be the optional polyalkylene glycol that replaces;

2) polymerization single polymerization monomer external phase then; And

3) from porous polymer, remove pore-forming material.This method is called method hereinafter with B.

Other disclosures relevant with manufacture method relate to method A and these two kinds of methods of method B, if specifically do not mention additive method.

Polymerizable components comprises at least a unitary big monomer of at least one PFPE that has.Can use the next performance that in porous polymer, provides usefulness of other comonomers, as linking agent and above-mentioned other big monomers.Suitable comonomer also can comprise the comonomer that comprises one or more can the reaction and form the ethylenically unsaturated group of multipolymer.Preferred ethylenically unsaturated group is selected from acryl, methacryloyl, styryl, acrylamido, acrylamido alkyl, urethane methacrylic ester or its any substitutive derivative.Suitable comonomer comprises fluorine-containing and alkyl acrylate and hydrophilic polymerized monomer silicon, can be selected from the material of the available wide region of those skilled in the art, with and composition thereof.Particularly preferred comonomer comprises vinylformic acid dihydro perfluoroalkyl ester such as vinylformic acid dihydro perfluoro capryl ester and vinylformic acid 1,1-dihydro perfluoro butyl ester, vinylformic acid three hydrogen perfluoroalkyl esters, vinylformic acid tetrahydrochysene perfluoroalkyl ester, methacrylic acid three (trimethylsiloxy) propyl ester or vinylformic acid three (trimethylsiloxy) propyl ester, and contain the amine copolymer monomer, as methacrylic acid N, N-dimethylaminoethyl, N,N-DMAA and N, N-dimethylaminoethyl acrylamide.Other suitable comonomers can comprise the polymethylmethacrylate oligomer and the end capped polydimethylsiloxane of ethylenically unsaturated group of many big monomers such as ethenyl blocking.During use, the amount of preferred comonomers in polymeric component is the 1-60wt% of polymeric component, most preferably 2-40%.

Multipolymer can be formed being with or without in the presence of other comonomers by formula I, (II) and (III) big monomeric mixture.Other big monomers (simple function or difunctionality) also can be mixed with or not be mixed with other comonomers.

Can add or not add linking agent such as ethylene glycol dimethacrylate.

When polymerizable components comprised ethylenically unsaturated monomer, polyreaction can use the photochemical method of radical initiator or by the use of thermal means to cause by ionizing radiation.Preferred radical initiator such as benzoin methyl ether, Darocur, Diisopropyl azodicarboxylate, benzoyl peroxide, the peroxide hydrocarbonate (peroxydicarbonates) etc. of using.

Particularly preferred photochemistry radical initiator is benzoin methyl ether and Darocur 1173 (registered trademark of Ciba-Geigy AG).Free radical can be formed by initiator by heat or photochemical method; Also can use redox initiation.

Should to understand " organic solvent " can be mixture and optional can contain in tensio-active agent, water, polarity or the apolar substance one or more.

In method A, organic solvent is preferably polar solvent and is preferably selected from short chain alcohol, amine, ether, nitrile, carboxylic acid and ketone, with and composition thereof.Described short chain alcohol, amine, ether, nitrile, carboxylic acid or ketone can be ring-type, branching or line style; Branched compound is particularly preferred.Carbonatoms in the short chain compound can be 1-12; But preferred 2-8.Preferred organic is to have the amine of 12 carbon atoms at the most, the alcohol of 12 carbon atoms at the most, preferred fluorinated alohol not, the ether of 12 carbon atoms at the most, the nitrile of 12 carbon atoms at the most, the carboxylic acid of 12 carbon atoms and the ketone of 12 carbon atoms at the most at the most.Preferred organic solvent is fluorizated C not ₁-C ₁₀Alkanol is as methyl alcohol, ethanol, Virahol, 3-methyl-2-butanols, hexalin or cyclopentanol, C ₁-C ₁₀Amine is as 3-hexylamine and Isopropylamine, C ₁-C ₁₀Ether such as diisopropyl ether, C ₁-C ₁₀Nitrile such as acetonitrile, C ₁-C ₁₀Carboxylic acid such as acetate and C ₁-C ₁₀Ketone such as pimelinketone or to fluoro benzophenone more preferably have this kind solvent of 7 carbon atoms at the most.Fluorizated C not further preferably ₁-C ₁₀Alkanol, C ₁-C ₁₀Amine, diisopropyl ether, C ₁-C ₁₀Nitrile, C ₁-C ₁₀Carboxylic acid and C ₁-C ₁₀Ketone, even more preferably have this kind solvent of 7 carbon atoms at the most.As organic solvent alcohols particularly preferably, comprise above-mentioned preferred meaning.

Can also use non-polar solvent as organic solvent, but preferred aforementioned polar solvent mix with a small amount of non-polar solvent.This class non-polar solvent can be to have the varsol of 12 carbon atoms at the most, can be ring-type, branching or line style and can be replaced by low alkyl group, lower alkoxy or halogen such as methyl, ethyl, methoxyl group, fluorine or chlorine.Preferred this class non-polar solvent is to have the described varsol of 8 carbon atoms at the most, as hexanaphthene or to the fluoro anisole.If not independent use, then the amount of these non-polar solvents preferably is at most 25% of used total solvent, and more preferably at the most 10%.

Particularly preferred organic solvent is Virahol, diisopropyl ether, 3-hexanol, cyclopentanol, 3-hexylamine and Isopropylamine.

In method B, be used for pore-forming material of the present invention and can be selected from optional (promptly do not replace or replace) polyalkylene glycol that replaces, preferably each can be identical or different alkylidene unit in have those of 7 carbon atoms at the most.Preferred unsubstituted polyalkylene glycol.Preferred pore-forming material is one or more poly-(low-grade alkylidene) glycol, and wherein low-grade alkylidene is illustrated in and has 6 carbon atoms at the most, the preferred alkylidene group of 4 carbon atoms at the most in each alkylidene unit.Have found that polypropylene glycol is a particularly preferred pore-forming material in the inventive method.Pore-forming material can have different molecular weight and preferred molecular weight is lower than 4000, more preferably less than 1000.Have found that pore-forming material preferably at room temperature is in a liquid state.The polyalkylene glycol that replaces is understood to include one of them or two hydroxyls by ether, as lower alkoxy, or ester group, as the displaced polyalkylene glycol of low alkyl group carbonyl oxygen base, thereby the polyalkylene glycol that replaces can be preferably by polyalkylene glycol monoether, polyalkylene glycol diether, polyalkylene glycol monoesters, polyalkylene glycol diester or the representative of polyalkylene glycol monoether monoesters.

Although polypropylene glycol is particularly preferred, also can use other polyalkylene glycols, as polyoxyethylene glycol.

Polymerizable components can mix with other optional components with organic solvent or pore-forming material respectively by any method easily.For example polymerizable components can or stir respectively and mix with other optional components with organic solvent or pore-forming material by jolting.The order that adds each component in mixture is very not crucial.Constituting the various components of polymerizable components mixes before needn't be in adding this mixture.This mixture can maybe can have as out of phase organic solvent or pore-forming material for the homogeneous phase solution form, for example is dispersion liquid, microemulsion or preferably common continuous microemulsion form.In method A, the form of mixture before polymerization is very not crucial, because be that the form of mixture in polymerization process controlled poromeric form.

Mixture can be microemulsion form.Microemulsion is thermodynamically stable and the two-phase system of substantially transparent, and these systems are usually by the Surfactants at Interface layer-stabilizing.Microemulsion is made up of the even spherical droplets that is dispersed in the continuum usually.Particle diameter is generally 10 ^-2About μ m.Microemulsion also can exist with continuous structure altogether, wherein each with continuous interpenetrating(polymer)networks be present in another mutually in.

In method A, can randomly in mixture, add a little performance improvement component before the polymerization.For example, can add other solvents.Other suitable solvents comprise ethyl acetate, dimethyl formamide, water and fluoridize alcohols.In most of the cases, add this kind solvent to reduce soltion viscosity or to make that solution is easier for example to be assigned in the mould.

In method B, can randomly in mixture, add a little performance improvement component before the polymerization.For example, can add solvent.Suitable solvent comprises short-chain alcohols, amine or ethers, and ethyl acetate, dimethyl formamide, water and fluoridize alcohols.In most of the cases, add this kind solvent to reduce soltion viscosity or to make that solution is easier for example to be assigned in the mould.Short chain alcohol, amine or ether can be ring-type, side chain or line style; Preferred especially branched compound.Carbonatoms in the short chain compound can be 1-12; But preferably should be 2-8 by number.Preferred especially Virahol, diisopropyl ether, 3-hexanol, cyclopentanol, 3-hexylamine and Isopropylamine.

Can be with tensio-active agent, the preferred fluorinated tensio-active agent adds in the mixture.The use of tensio-active agent is the effective ways of the size and the density of control punch.The nonionogenic tenside that preferably contains fluorine.Particularly preferred tensio-active agent comprises commercially available fluorinated surfactant, as Zonyl (DuPont) and Fluorad (3M).The ZonylFS300 (DuPont) that is made up of perfluorination hydrophobicity tail groups and poly-(oxyethane) head group of wetting ability is the particularly preferred tensio-active agent that is used for the inventive method.

The another kind of compound that can be used as tensio-active agent in the present invention is the big monomer of formula II disclosed herein.These compounds are disclosed among International Patent Application PCT/EP96/01256 in more detail, and its relevant disclosure (comprising its preferable case) is incorporated this paper into.

This mixture can be by top initiation described any method easily polymerization usually to polymerizable thing component.Suitable polymerizing condition is conspicuous for the one skilled in the art.For example, temperature can be for being lower than normal atmosphere to being higher than normal atmosphere for-100 ℃ to 350 ℃ and pressure.

In method A, it is disperse phase that the organic solvent of remarkable ratio must be arranged after the polymerization immediately.The organic solvent disperse phase can or can be dispersed in drop in the whole polymeric component for the interpenetrating(polymer)networks form in whole polymeric component.

Still in method A, be understood that " significantly the organic solvent of ratio is a disperse phase " is meant that enough organic solvents form the interpenetrating(polymer)networks of organic solvent phase or the dispersion liquid of organic solvent phase mutually.The one skilled in the art is depended on polymeric component and organic solvent with understanding, and a certain proportion of organic solvent can be adsorbed or be retained in the polymeric component and finally and be retained in the porous polymer.Common organic solvent more than 60% is disperse phase immediately after polymerization.Be preferably greater than 80%, the organic solvent more preferably greater than 95% is disperse phase.

In method B, be understood that " significantly the pore-forming material of ratio remains disperse phase " is meant that enough pore-forming materials form interpenetrating(polymer)networks or dispersion.The one skilled in the art is depended on polymeric component and pore-forming material with understanding, and a certain proportion of pore-forming material can be adsorbed or be retained in the polymeric component and finally and be retained in the porous polymer.Common pore-forming material more than 60% is disperse phase immediately after polymerization.Be preferably greater than 80%, the pore-forming material more preferably greater than 95% is disperse phase.

Preferred especially organic solvent phase or pore-forming material form interpenetrating(polymer)networks in generation has poromeric polymeric component of mesh structural porous form.Mesh structural porous form can maybe can be had by perforate, the spongy structure that interconnection polymer spherical particle is formed and a kind ofly has that a row is normal to be the open-celled structure of spheric interconnected pores.

In another preferred embodiment, porous polymer can be for having the unicellular structure that is dispersed in the dispersion hole in the whole polymkeric substance.

Organic solvent or pore-forming material can be removed from porous polymer by any method easily.Suitable removing desolvated or the method for pore-forming material comprises evaporation, solvent extraction, washing or leaching.

The inventive method can be used for producing the material of various apertures and form.Be limited to about 5 μ m on the mean pore size in each hole, be generally 100nm, but also can obtain the hole of the about 10nm of diameter.

The hole can form interpenetrating(polymer)networks.More usefully use perviousness to characterize these forms to the molecule that limits molecular weight.Post-polymerization treatment porous polymer and use perviousness to molecule to characterize common program explanation before the embodiment part of form.

Poromeric form and porosity can be controlled by this that changes organic solvent or pore-forming material and monomer.When organic solvent or pore-forming material ratio are high, obtain the porous sponge shape structure of forming by interconnection polymer spherical particle.Under low ratio, obtain the hole of mesh network.Under lower ratio, obtain the closed pore form.

In method A, have found that the polymerizable components and the ratio of solvent are the porous polymer that generation in about 1: 1.3 has the porous sponge shape structure of being made up of interconnection polymer spherical particle.Under about 1: 0.5 ratio, porous polymer has the hole of mesh network usually.Under about 1: 0.1 ratio, porous polymer has the closed pore form usually.

The useful especially embodiment of the inventive method has organic solvent phase or pore-forming material phase, they are continuous inierpeneirating network structure form, be easy to extract and stay the porous PFPE material with mesh network hole, these holes make fluid and minor diameter particle be easy to pass through porous polymer.

The size in hole and density can be by the ratio control of polymerizable components with organic solvent.Less variation can be undertaken by using aforementioned surfactants.The adding of less water also increases porosity.

As the explanation to a certain degree that preamble is done, can add and comprise one or more comonomers that can enter the ethylenically unsaturated group of reaction formation multipolymer.Preferred ethylenically unsaturated group is selected from acryl, methacryloyl, styryl, acrylamido, acrylamido alkyl or urethane methacrylic ester or its any substitutive derivative.

The comonomer that is present in the polymkeric substance of the present invention can be hydrophilic or hydrophobic or its mixture.Suitable comonomer particularly is generally used for producing those of contact lens and biological medicine material.Hydrophobic comonomer is meant and provides water insoluble usually and can absorb the monomer of the homopolymer of the water that is lower than 10wt%.Similarly, hydrophilic polymerized monomer means and provides water soluble usually and maybe can absorb the monomer of the homopolymer of the water of 10wt% at least.

Suitable hydrophobic comonomer is the C of (being not limited to) vinylformic acid and methacrylic acid ₁-C ₁₈Alkyl ester and C ₃-C ₁₈Cycloalkyl ester, C ₃-C ₁₈Alkyl acrylamide and-Methacrylamide, vinyl cyanide, methacrylonitrile, C ₁-C ₁₈The paraffinic acid vinyl ester, C ₂-C ₁₈Alkene, C ₂-C ₁₈Halogenated olefine, vinylbenzene, (low alkyl group) vinylbenzene, low alkyl group vinyl ether, the C of vinylformic acid and methacrylic acid ₂-C ₁₀Perfluoroalkyl ester and corresponding section fluorizated acrylate and methacrylic ester, the C of vinylformic acid and methacrylic acid ₃-C ₁₂Perfluor alkyl ethide thio-carbonyl-amino ethyl ester, acryloxy-and the methacryloxy alkylsiloxane, N-vinylcarbazole, the C of toxilic acid, fumaric acid, methylene-succinic acid, methylfumaric acid etc. ₁-C ₁₂Alkyl ester.

Vinyl cyanide for example preferably, the ethene with 3-5 carbon atom belongs to the C of unsaturated carboxylic acid ₁-C ₄Alkyl ester or have the vinyl ester of the carboxylic acid of 5 carbon atoms at the most.

Suitable hydrophobic comonomer example is a methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, 2-EHA, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl acrylate, vinyl-acetic ester, propionate, vinyl butyrate, the valeric acid vinyl acetate, vinylbenzene, chloroprene, vinylchlorid, vinylidene chloride, vinyl cyanide, 1-butylene, divinyl, methacrylonitrile, Vinyl toluene, EVE, methacrylic acid perfluoro hexyl ethylenebis dithiocarbamate carbonylamino ethyl ester, isobornyl methacrylate, trifluoroethyl methacrylate, methacrylic acid hexafluoro isopropyl ester, methacrylic acid hexafluoro butyl ester, methacrylic acid three-trimethylsiloxy silyl propyl ester (hereinafter referred to as: three-methacrylic ester), vinylformic acid three-trimethylsiloxy silyl propyl ester (hereinafter referred to as: three-acrylate), 3-methacryloxypropyl pentamethyl disiloxane and two (methacryloxypropyl) tetramethyl disiloxane.

The preferred embodiment of hydrophobic comonomer is methyl methacrylate, three-acrylate, three-methacrylic ester and vinyl cyanide.

Suitable hydrophilic polymerized monomer is that the hydroxyl of (and non exhaustive) vinylformic acid and methacrylic acid replaces lower alkyl esters, acrylamide, Methacrylamide, (low alkyl group)-acrylamide and-Methacrylamide, ethoxylation acrylate and methacrylic ester, (low alkyl group) acrylamide that hydroxyl replaces and-methacryloyl, the low alkyl group vinyl ether that hydroxyl replaces, sodium vinyl sulfonate, Sodium styrene sulfonate, 2-acrylamido-2-methyl propane sulfonic acid, the N-vinyl pyrrole, N-vinyl-2-Pyrrolidone, 2-Yi Xi oxazolin, 2-vinyl-4,4 '-Er Wan oxazolin-5-ketone, 2-and 4-vinylpridine, the ethene that has 3-5 carbon atom altogether belongs to unsaturated carboxylic acid, methacrylic acid and acrylic acid amino (low alkyl group) ester (wherein term " amino " also comprises quaternary ammonium), single (low-grade alkyl amino) (low alkyl group) ester and two (low-grade alkyl amino) (low alkyl group) ester, vinyl carbinol etc.N-vinyl-2-Pyrrolidone for example preferably, acrylamide, Methacrylamide, methacrylic acid and acrylic acid hydroxyl replace lower alkyl esters, (low alkyl group) acrylamide that hydroxyl replaces and-Methacrylamide and the ethene that has 3-5 carbon atom altogether belongs to unsaturated carboxylic acid.

Suitable hydrophilic polymerized monomer example is hydroxyethyl methylacrylate (HEMA), Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid 2-hydroxypropyl ester hydrochloric acid TMA (TriMethylAmine) (Blemer ^QA is for example available from Nippon Oil), dimethylaminoethyl methacrylate (DMAEMA), dimethyl aminoethyl (methyl) acrylamide, acrylamide, Methacrylamide, N,N-DMAA (DMA), vinyl carbinol, vinyl pyridine, glyceral methacrylate, N-(1,1-dimethyl-3-oxo butyl) acrylamide, N-vinyl 2-Pyrrolidone (NVP), vinylformic acid, methacrylic acid etc.

Preferred hydrophilic polymerized monomer is a methacrylic acid 2-hydroxypropyl ester hydrochloric acid TMA (TriMethylAmine), methacrylic acid 2-hydroxyl ethyl ester, dimethylaminoethyl methacrylate, methacrylic acid 2-hydroxypropyl ester hydrochloric acid TMA (TriMethylAmine), N,N-DMAA and N-vinyl-2-Pyrrolidone.

As previously mentioned, suitable comonomer comprises fluorine-containing and alkyl acrylate and hydrophilic polymerized monomer silicon, their optional utilized materials from wide region, and composition thereof.Particularly preferred comonomer comprises vinylformic acid dihydro perfluoroalkyl ester, as vinylformic acid dihydro perfluor monooctyl ester and vinylformic acid 1,1-dihydro perfluor butyl ester, vinylformic acid three hydrogen perfluoroalkyl esters, vinylformic acid tetrahydrochysene perfluoroalkyl ester, methacrylic acid or acrylic acid three (trimethylsiloxy) propyl ester, and the comonomer that contains amine are as methacrylic acid N, the N-dimethylaminoethyl, N,N-DMAA and N, N-dimethyl aminoethyl acrylamide.Each comonomer adds the 0-60wt% of preferable range for filling a prescription in the prescription, most preferably 0-40wt%.Also can use the big monomeric mixture manufacturing of formula I, II or III to contain or do not contain the suitable copolymerizable thing of other comonomers.

If desired, can be by adding linking agent, for example how unsaturated cross-linking comonomer strengthens polymer network.In this case, use crosslinked this term of polymkeric substance.Therefore, the invention still further relates to the cross-linked polymer that comprises formula I, (II) or (III) big monomeric polymerization product, if desired, above-mentioned big monomer is comonomer and at least a cross-linking comonomer polymerization with at least a ethene also.

The example of typical case's cross-linking comonomer is (methyl) allyl acrylate, two (methyl) vinylformic acid low-grade alkylidene diol ester, two (methyl) vinylformic acid gathers (low-grade alkylidene) diol ester, two (methyl) vinylformic acid low-grade alkylidene ester, divinyl ether, divinylsulfone, two-and trivinylbenzene, three (methyl) vinylformic acid trihydroxymethylpropanyl ester, four (methyl) vinylformic acid pentaerythritol ester, dihydroxyphenyl propane two (methyl) acrylate, methylene-bis (methyl) acrylamide, phthalic acid triallyl ester and diallyl phthalate.

If use cross-linking comonomer, then consumption is the 0.05-20% of expection total polymer weight, and preferably this comonomer is 0.1-10%, more preferably 0.1-2%.

According to a further aspect in the invention, provide a kind of ophthalmic device of making by aforementioned porous polymer or multipolymer, preferred contact lens, even more preferably softish contact lens.

Contact lens, also having the softish contact lens is the polymer sheet with surface of different curvature radius.The selection that combines of the refractive index of this radius and polymkeric substance is so that obtain required optical correction and make inner lens surfaces and wearer's cornea shape coupling.They are sold in Sterile Saline usually.Randomly, the surface of lens can apply and modification by the method for using this area crowd to know, as the grafting of plasma polymerization, glow discharge or more hydrophilic polymkeric substance.

As an example, in this lens-like manufacturing, with the polymerisable monomer of appropriate amount, solvent (if needs) and the light trigger formation polyblend that mixes.This polyblend is then with purging with nitrogen gas and aequum is assigned in the recess side of polypropylene molds.Closing molding also clamps, and this assembly is put into the UV radiation chamber that the UV lamp is housed.Carry out the radiation of required time, then the two halves of divided mould.The polymeric lens extract in appropriate solvent (for example isopropyl acetate or the tert-butyl ester/fluorated solvent mixture).Use alcohol (for example Virahol) thoroughly to exchange this solvent then, obtain the product lens also subsequently with the salt solution exchange.

Polymkeric substance produced according to the invention can be made other useful articles or use techniques well known further to process by polymerization in situ.Have at polymkeric substance of the present invention under the condition of visually-clear, they can be used in tissue culturing equipment, opticinstrument, the microslide etc.

Another aspect of the present invention is the porous PFPE with the application as film or strainer of film or sheet-form.This porous PFPE film can form matrix material with another kind of support membrane lamination.This poly-PFPE film can have symmetry or asymmetric pore structure.This class is used the perviousness that may relate to gas or liquid.

Porous polymer of the present invention can be suitable for for example being used for membrane filter and separation field, is used for the industrial biotechnology field and is used for biomedicine field.

The example of membrane filter and separation field is industrial film, as is used for the film of micro-filtration and ultrafiltration, for example is used for food, dairy products, juice or beverage industry, in the membrane distillation of wastewater treatment, automatic reverse osmosis or use osmotic pressure.

The example in industrial biotechnology field is the carrier of synthetic and the bio-ligand or the acceptor of bio-reactor and biosensor, the delayed release device of active compound or electrical condenser.

The example of biomedicine field is an ophthalmic device, as contact lens or cornea,artificial, and dialysis and blood filtration, the biologic implant of sealing, as pancreas islet, the glucose monitor of implantation, delivery tablet and device, wound treatment and wrapping, artificial skin, vascular transplantation, reproducibility template or trauma care piece, (soft) tissue increases, through skin stationary installation or artificial organ.

In whole specification sheets and following claim book, unless requirement is arranged in the literary composition in addition, word " comprises " being interpreted as inferring and comprises described integer or integer group, but do not get rid of any other integer or integer group.

The present invention further specifies in following non-limiting examples.If not otherwise stated, all umbers by weight.Temperature by degree centigrade.The molecular weight of big monomer or polymkeric substance is a number-average molecular weight, except as otherwise noted.

In the embodiment of specification sheets, big monomer (1) is the big monomer of perfluorination of the ethenyl blocking of following formula: CH ₂=C (CH ₃) COOC ₂H ₄NHCO-PFPE-CONHC ₂H ₄OCOC (CH ₃)=CH ₂Wherein PFPE is the PFPE part of 3M test products L-12875, and L-12875 is the PFPE mixture of following formula:

-OCH ₂CF ₂O (CF ₂CF ₂O) _x(CF ₂O) _yCF ₂CH ₂O-is CF wherein ₂CF ₂O and CF ₂The O unit can be in whole chain random distribution or with block distributed and wherein x be that 8-10 and y are 10-14.

In embodiment 25, big monomer (2) is the big monomer of perfluorination of the ethenyl blocking of following formula: CH ₂=C (CH ₃) COOC ₂H ₄NHCO-(PFPE-CONH-R-NHCO-) _0.65-PFPE-CONHC ₂H ₄OCOC (CH ₃)=CH ₂Wherein PFPE such as top big monomer (1) definition, and R is the tri-methyl hexamethylene part of TMHMDI.

Make with the following method:

Measurement of water ratio: poromeric % water ratio (w/w) is measured by the hydration and the dehydrated weight of comparative polymers.At first in vacuum drying oven (0.1mmHg) in 37 ℃ with polymkeric substance dry night, when cooling, weigh then.Classified exchange of solvent method is carried out hydration.The dry polymeric sheet is dipped in the following solution successively, in each solution, placed 0.5 hour when down a kind of in that solvent is become.Per 10 polymer sheets are used the 60ml solvent.

1.100% ethanol

2.75% ethanol/water

3.50% ethanol/water

4.25% ethanol/water

5.100% water

Make polymkeric substance one night of balance or up to constant weight, the starting time of hydrophilic polymer can be longer than 16 hours in water.It is hydration weight to blot the also last weighing of excessive surface-moisture upward that hydrated polymer is placed on the meticulous no velveteen Kimwipes paper of level (Kimberly-Clark).

Perviousness is measured

Method A: with UV spectrography monitoring perviousness

Permeate agent: bovine serum albumin (BSA, molecular weight=67,000).BSA concentration=8mg/ml, in phosphate buffered saline (PBS) (PBS), PBS=20mM phosphoric acid salt, in 0.2M sodium-chlor, pH=7.4

The porosity of synthetic polymer is with static diffuser casing (promptly not stirred solution) research.This method relates to the flat polymer sheet of the hydration of a diameter 20mm (hydration procedures is seen measurement of water ratio) is placed between two Room, and this two Room is that the RUBBER O shape ring of 7.5cm separates by internal diameter.Each chamber volume is about 2.2ml.

The solution of BSA in PBS of 8mg/ml is contained in a chamber, and another chamber only is filled with PBS.In the selected timed interval, use the glass volumetric pipette from the PBS chamber, to take out sample and the UV optical density (A of this solution of measurement under 280nm ₂₈₀).Whether this has determined to have BSA to see through polymer sheet.The high more explanation of optical density reading BSA rate of diffusion is high more and thereby show to have larger aperture and/or than the structure of macropore density.

Method B

The infiltrative more quantitative measurment of BSA uses such device to carry out, and wherein the flat sample of diameter 20mm is fixed between two chambers, and wherein BSA/PBS and PBS solution stir with the speed greater than 200rpm.Stirring purpose is in order to overcome the resistance to mass transfer at the surface boundary layer place that mainly is present in porous material.Use this method to measure polymer sheet to glucose, inulin and I ₁₂₅The perviousness of the BSA of mark.With respect to the aperture is commercial track etching polycarbonate membrane (trade name Poretics) the measurement perviousness of 50nm and 25nm.Embodiment 1:

Following prescription put into polypropylene molds and polyase 13 hour under the radiation of 365nmUV lamp.All umbers by weight.

	A (part)	B (part)
			Big monomer (1)	????1.41	????1.40
Virahol	????1.23	????0.70
			Zonyl?FS-300	????0.06	????0.006
Darocur	????0.008	????0.008

From mould, take out polymkeric substance and generally extract with drying program to remove any not polymeric component.This program is included in the fluorated solvent (PF5060 of 3M Corporation) soaked 4 hours, soaked in isopropyl acetate then 16 hours, soaked in Virahol 4 hours again.After the drying, polymkeric substance is white in color in a vacuum.When white polymer during through the classification solvent change, i.e. ethanol, 75% ethanol/water, 50% ethanol/water, 25% ethanol/water is pure water or salt solution then, they become transparent.The effect of classification solvent change is that water is imported in the porous channel of porous PFPE material; Although the PFPE sill has very hydrophobic character, this also can take place.The water ratio of " hydration " polymkeric substance is respectively 46% and 36% (w/w) through measuring to embodiment 1A and B thus.

The diameter 20mm flat piece of use casting from the thick mould of 0.2mm, with stirred solution chamber commercial measurement polymeric film to iodine 125 (I ¹²⁵) the albuminous perviousness of mark.Record the I of the film that obtains by embodiment 1A and 1B respectively ¹²⁵The albumin rate of permeation is 1.36 * 10 ^-5With 8.60 * 10 ^-6Cm/sec.

The contrast of embodiment 1A and 1B shows that the reduction of Virahol amount has not only reduced the exchange water ratio of polymeric film in the polyblend, and reduces I ¹²⁵The albumin rate of permeation.This explanation embodiment 1B has less hole and the lower such form of hole density.Embodiment 2:

Following prescription put into polypropylene molds and polyase 13 hour under the radiation of 365nmUV lamp.All umbers by weight.

	A (part)	B (part)
			Big monomer (1)	????1.00	????1.00
Virahol	????1.30	????1.00
			Zonyl?FS-300	??????-	????0.30
Darocur	????0.006	????0.005

Carry out the classification exchange of solvent from ethanol to water, record embodiment 2A and have identical water ratio, 53% (w/w) with 2B.The flat polymer sheet of diameter 20mm that use is gone out by the thick mould casting of 0.2mm is by the perviousness of comparative polymers sheet with the diffusion of U.V. spectrography (seeing embodiment 1) monitoring BSA.1.5 after hour, for prescription 2A and 2B, the optical density reading of initial protein-free PBS solution is respectively A ₂₈₀=0.169 and 0.083.Therefore, with (prescription 2B) in the tensio-active agent ZonylFS-300 introducing polyblend albumin rate of permeation is significantly reduced.Detection to the SEM image that produced by embodiment 2A and 2B shows that the material that does not contain tensio-active agent has more open vesicular structure.Embodiment 3:

Put into following prescription in the polypropylene molds (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation of 365nmU.V. lamp.All umbers by weight.

	A (part)	B (part)
			Big monomer (1)	????0.51	????0.31
Methyl alcohol	????0.50	?????-
			3-methyl-2-butanols	??????-	????0.31
Darocur	????0.003	????0.004

Polymer sheet is monitored with the U.V. spectroscopic techniques the perviousness of BSA solution.After 25 hours, the optical density reading of polymer A is A ₂₈₀=0.87, and the optical density of polymer B is A ₂₈₀=0.83 (27 hours), this shows that the porous PFPE can produce by polymerization in the presence of short chain alcohol.The water ratio that records polymer A and B after the hydration is respectively 34.0% (w/w) and 48.8% (w/w).Embodiment 4

Put into following prescription in the polypropylene molds (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation of 365nmU.V. lamp.All umbers by weight.

	A (part)	B (part)
			Big monomer (1)	????0.60	????0.53
The 3-hexanol	????0.30	?????-
			Ethanol	?????-	????0.31
Fluorad(3M)	????0.05	?????-
			Darocur	????0.004	????0.004

Polymeric film is monitored with the U.V. spectroscopic techniques the perviousness of BSA solution.After 25 hours, the optical density reading of polymer A is A ₂₈₀=0.38, and the optical density of polymer B is A ₂₈₀=0.62 (27 hours), this shows that this polymkeric substance is a porous.The water ratio of hydration rear lens B is 35.1% (w/w) after measured.Embodiment 5:

Put into following prescription in the flat polypropylene molds (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation of 365mmU.V. lamp.All umbers by weight.

	A (part)	B (part)
			Big monomer (1)	????0.41	????0.40
Water	????0.21	????0.12
			Fluorad(3M)	????0.09	????0.06
Virahol	????0.60	????0.40
			Ethylene glycol dimethacrylate	????0.04	?????-
Darocur	????0.009	????0.008

Polymeric film is monitored with the U.V. spectroscopic techniques the perviousness of BSA solution.After 47 hours, the optical density reading of polymer A is A ₂₈₀=1.11, and the optical density of polymer B is A after measured ₂₈₀=1.29.The water ratio of hydration post polymerization thing A and B is respectively 63.6% (w/w) and 56.2% (w/w) after measured, and this shows that the existence of water has increased pore volume in the mixture.Embodiment 6:

Put into following prescription in the flat polypropylene molds (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation of 365nmU.V. lamp.All umbers by weight.

	A (part)
		Big monomer (1)	????0.55
Diisopropyl ether	????0.51
		Darocur	????0.005

Polymeric film is monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The water ratio of hydration post polymerization thing A is 35.1% (w/w) after measured.

The scanning electron photomicrograph of lens A (SEM) shows that its structure is made up of the fusion of the about 350nm of diameter, the latex particle of loose interconnection, is distributed with porous channel around the particle.Embodiment 7:

Following prescription put into the polypropylene lens die and at U.V. lamp polyase 13 hour under the radiation that produces under the 365nm wavelength.All umbers by weight.

Big monomer (1)	1.61 part
		PPG-725	0.26 part
Darocur	0.008 part

PPG-725 is that molecular weight is 725 polypropylene glycol.Lens are monitored by U.V. spectroscopic techniques (seeing embodiment 1) the perviousness of BSA solution.After 21 hours, the optical density reading of initial protein free PBS solution is A ₂₈₀=0.066, this was increased to A after 44 hours ₂₈₀=0.117.Embodiment 8:

Following prescription put in the polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. lamp by wavelength 365nm produces.All umbers by weight.

	A (part)
		Big monomer (1)	????0.045
Polypropylene glycol (Mw=192)	????0.28
		Virahol	????0.10

Darocur

????0.007

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The optical density reading of 24 hours rear lens A is A ₂₈₀=0.28.The water ratio of hydration rear lens A is through being measured as 31.8% (w/w).

It is successful equally to prepare porous polymer by prescription A when replacing Virahol with other common organic solvents such as ethanol, ethyl acetate and dimethyl formamide.Embodiment 9: the preparation of microporous polymer sheet

The polymerization that the porous polymer sheet is caused by ultraviolet ray (UV) free radical of the Thermodynamically stable that contains big monomer of formula I (n=1) and Virahol, transparent, homogeneous mixture and synthesizing.The big monomer of formula I (n=1) obtains (PFPE that L-9629 is a kind of usefulness two polymerizable methacrylate functional end-blocking and molecular weight about 2000) by the 3M company of Minn. St.Paul with experiment product L-9629.Following composition is used for the manufacturing of these sheets:

	Weight part
		The big monomer of formula I (n=1)	????54
Virahol	????43
		Zonyl?FS-300(Du?Pont)	????2.25
Darocur?1173(Ciba-Geigy)	????0.15

Big monomer, solvent and tensio-active agent are added in the bottle that glass nut that the magnetic stirring bar that PTFE applies is housed covers.Then this vial is placed on magnetic agitation dish last 10 minute with three kinds of components of thorough mixing.Add radical initiator Darocur 1173 then and continue and mixed 5 minutes.Then the gained mixture is being put into polypropylene flat molds (thick 0.2mm) and polyase 13 hour under the radiation of 365nmUV lamp under the nitrogen.

After polymerization is finished, the flat polymer sheet of gained is taken out from mould and extraction one night (per 10 are used the 60ml solvent) in Virahol.Drain solvent then and replace with isopropyl acetate.After placing 4 hours under 37 ℃, replace these solvents with PF 5060 then.After keeping 4 hours again under 37 ℃, drain PF 5060 and at room temperature place each sheet up to excessive PF 5060 evaporations.In ethanol, preserve each sheet at last.

Obtain the flat sheet-like polymkeric substance with this program with the micropore form." hydration " water ratio (%w/w) of gained porous chips is 52% after measured.Each sheet to the rate of permeation of glucose (molecular weight=181), inulin (molecular weight=5500) and albumin (molecular weight=67000) is after measured:

	Rate of permeation cm/s
		Glucose	????2.1×10 -4
Inulin	????8.3×10 -5
		Albumin	????1.4×10 -5

The perviousness of perfluorination sheet is measured with reference to glucose, inulin and the albumin rate of permeation in the sheet in Nuclepore50nm and Poretics 25nm aperture, and both porositys of PCT/EP94/03680 instruction back are suitable for cornea,artificial wearer (onlay).

	Rate of permeation cm/s
					Glucose	Inulin	Albumin
Nuclepore 50nm	?4.7×10 -4	?1.7×10 -4	?2.2×10 -5
				Poretics?25nm	?4.6×10 -5	?1.1×10 -5	?0.6×10 -6

This porosity of polymkeric substance that shows this embodiment thereby has appropriate porosity and thinks that the cornea wearer provides suitable nutrient substance and high-molecular-weight protein flux between Nuleopore and Poretics film.Embodiment 10:

Obtain the polymkeric substance of embodiment 9 with another micro pore sheet form.Following mixture put into 7 * 10 polypropylene screen moulds and use the program identical by wide range UV lamp polyase 13 hour with embodiment 9.

	Weight part
		The big monomer of formula I (n=1)	????70
Virahol	????35
		Darocur?1173(Ciba-Geigy)	????0.19

Water ratio is 33% after measured.Rate of permeation is as follows:

	Rate of permeation cm/s
		Glucose	????9.18×10 -5
Inulin	????3.21×10 -5
		Albumin	????0.86×10 -5

Detecting this poromeric ox horn film epithelial cell and inoblast adheres to.The result shows that this polymkeric substance supports that corneal epithelial cell and corneal stroma are fibroblastic and adhere to and grow.Embodiment 11:

Obtain the polymkeric substance of embodiment 9 with another micro pore sheet form.Following mixture put into 7 * 10 polypropylene screen moulds and use the program identical by wide range UV lamp polyase 13 hour with embodiment 9.

	Weight part
		The big monomer of formula I (n=1)	????40
Virahol	????40
		Zonyl?FS-300(Du?Pont)	????12
Darocur?1173(Ciba-Geigy)	????0.31

Water ratio is 52% after measured.Rate of permeation is:

	Rate of permeation cm/s
		Glucose	????1.2×10 -4
Inulin	????4.5×10 -5
		Albumin	????0.8×10 -5

Embodiment 12:

By obtain the polymkeric substance of the embodiment 9 of another micropore form with the following mixture of method polymerization of embodiment 9.

	Weight part
		The big monomer of formula I (n=1)	????85
Virahol	????25
		Darocur?1173(Ciba-Geigy)	????0.30

Water ratio is 15% after measured.Rate of permeation is:

	Rate of permeation cm/s
		Glucose	????1.3×10 -5
Inulin	????0.4×10 -5
		Albumin	????9.0×10 -8

Embodiment 13 (contrast):

Following component is placed on polypropylene lens die (thick 0.2mm) and polyase 13 hour under the radiation of 365nmUV lamp.

Big monomer A (referring to as follows)	60 parts
		Benzoin methyl ether	0.3 part
Isopropyl acetate	40 parts

After the demoulding, in 37 ℃ of following extraction polymer sheets 3 hours, putting into isopropyl acetate (IPAc) then spends the night in PF 5060, puts into 50/50 (v/v) mixture 3 hours of IPAc-Virahol (IPA) again, and then puts into fresh IPA 3 hours.Be in the salt solution before the hydration several days on the filter paper in vacuum drying oven under 30 ℃ with each sheet dried overnight.The water ratio of gained transparent polymer sheet be 0.9% and fixedly contact angle be 87 the degree.

This part of embodiment 13 illustrates the preparation of big monomer A.In the 250ml round-bottomed flask, put into the commercially available molecular weight of 24.18g and be 947 hydroxypropyl terminated polydimethylsiloxane and 10.76g and steamed trimethyl hexamethylene diisocyanate.The violent jolting several minutes of mixture adds the 0.04g dibutyl tin laurate then.Jolting mixture 5 minutes again before stirring is spent the night.In first hour, observe gentle heat release.The PFPE (hydroxyl value 55.40) and the 0.10g dilauryl dibutyl tin that in reaction mixture, add the commercially available molecular weight about 2000 of 103.30g then.Behind the violent once more jolting several minutes, mixture is stirred a night.Confirm the disappearance of isocyanate peak with infrared spectra.In mixture, add 7.92g then and newly steam methacrylic acid isocyanato ethyl ester.Violent jolting flask also stirs a night with mixture.Confirm the disappearance of isocyanic ester once more with infrared spectra.The gained viscous fluid has following formula 11.Embodiment 14 (contrast)

Following component put into polypropylene flat molds (thick 0.2mm) and polyase 13 hour under the radiation of 365mmUV lamp.

Big monomers B (referring to as follows)	70 parts
		Isopropyl acetate	30 parts
Benzoin methyl ether	0.3 part

After the demoulding, with the gained sheet in PF 5060 in 37 ℃ the extraction 3 hours, be placed on then in the isopropyl acetate (IPAc) and spend the night, put into 50/50 (v/v) mixture 3 hours of IPAc/ Virahol (IPA) then and put into fresh IPA 3 hours.Be in the salt solution before the hydration several days on the filter paper in vacuum drying oven 30 ℃ of one nights of dry down each sheet.After extraction and the hydration, recording water ratio is 2.4%.

This part of embodiment 14 illustrates the synthetic of big monomers B.In the 250ml round-bottomed flask, add the 150g hydroxyl value and be 55.4 hydroxy-end capped PFPE (then from the 3M company of USA Minnesota State St Paul, trade mark is Z-DOL) and 11.49g and newly steam methacrylic acid isocyanato ethyl ester.Behind the violent jolting mixture several minutes, add the 0.09g dibutyl tin laurate.And then jolting mixture 5 minutes, stir a night afterwards.Write down infrared spectra to confirm the disappearance of isocyanate peak.In mixture, add 15.58g and steamed trimethyl hexamethylene diisocyanate, stir several minutes then, add the 0.10g dibutyl tin laurate again.Behind the violent once more jolting several minutes, mixture is stirred a night.In mixture, add the dry polyoxyethylene glycol (molecular weight 200) of 14.81g then.Stir the mixture behind the several minutes, add the 0.12g dibutyl tin laurate.Violent jolting flask also stirs the mixture a night.Write down infrared spectra once more to confirm the disappearance of isocyanic ester.This program produces a kind of required at high proportion formula 10 big monomeric mixtures that contain.This big monomer is purified with following technology:

Add 50 of 15ml Refrigerant R 113/tert.-butyl acetate in the rough big monomer of 3.0g in bottle: the 50v/v mixture.Big monomer by after the jolting suspension, is transferred to mixed solution in the separating funnel in this solvent mixture.With this solution of 10ml distilled water wash.Lower floor is collected in the round-bottomed flask and removes under high vacuum and desolvate.Then resistates is suspended among the 15g perfluorination paraffin solvents PF 5060 (available from the 3M company of Minn. St Paul).The reservation top layer also removes under high vacuum once more and desolvates.The big monomer that obtains purifying.Embodiment 15:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of 365nm wavelength lamp produces.All umbers by weight.

	Umber
		Big monomer (1)	????100
Virahol	????20
		Acetonitrile	????100
Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.Post-absorption degree reading was A in 24 hours ₂₈₀=0.250.The water ratio of hydration rear lens is 40.0% (w/w) after measured.Embodiment 16:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	Umber
		Big monomer (1)	????100
Acetate	????120
		Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.After 24 hours, the optical density reading of lens is A ₂₈₀=0.559.The water ratio of hydration rear lens is through being measured as 30.9% (w/w).Embodiment 17:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	A (part)	B (part)
			Big monomer (1)	????100	????100
Virahol	????20	????20
			(to fluorobenzene) ketone	????100	????-
To the fluorine anisole	????-	????100
			Darocur	????0.3	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The optical density reading of 24 hours rear lens A is A ₂₈₀=0.28, lens B is A ₂₈₀=0.65.The water ratio of hydration rear lens A and B is respectively 28.0% (w/w) and 31.0% (w/w) after measured.Embodiment 18:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

Component	Part
		Big monomer (1)	????100
????Monocon?400 *	????50
		Virahol	????74.5
????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lenses is A ₂₈₀=0.19.The water ratio of hydration rear lens is through being measured as 31.0% (w/w).

^*Monocon 400 is the polymerisable surfactant according to International Patent Application PCT/EP96/01256, has the big monomeric structure of formula as herein described (10), and wherein PEG is derived from the polyoxyethylene glycol of molecular weight 400.Embodiment 19:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	Part
		Big monomer (1)	????100
????Monocon?200 *	????51
		Virahol	????100
????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lens A is A ₂₈₀=0.26.The water ratio of hydration rear lens is 32% (w/w) after measured.

^*Monocon 200 is the polymerisable surfactants according to International Patent Application PCT/EP96/01256, has the big monomeric structure of formula as herein described (10), and wherein PEG is 200 polyoxyethylene glycol derived from molecular weight.Embodiment 20:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	A (part)	B (part)
			Big monomer (1)	????100	????100
Virahol	????43	????7
			Acetonitrile	????100	????79
Zonyl?FS-300	????21	????20
			Darocur	????0.3	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The optical density reading of 24 hours rear lens A is A ₂₈₀=0.28, lens B is A ₂₈₀=0.32.The water ratio of hydration rear lens A and B is respectively 40.8% (w/w) and 45.2% (w/w) after measured.Embodiment 21:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	(part)
		Big monomer (1)	????100
Virahol	????100
		Pimelinketone	????30
????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.24 hours absorbancy readings are A ₂₈₀=0.52.The water ratio of hydration rear lens is 50% (w/w) after measured.Embodiment 22:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

Component	Part
		Big monomer (1)	????60.3
The 3-hexanol	????47.2
		????Fluorad	????9
????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lenses is A ₂₈₀=0.57.The water ratio of hydration rear lens is 45.7% (w/w) after measured.Embodiment 23:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

Component	Part
		Big monomer (1)	????100
(to fluorobenzene) ketone	????30
		Virahol	????100
????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lenses is A ₂₈₀=1.03.The water ratio of hydration rear lens is 43.0% (w/w) after measured.Embodiment 24:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

Component	Part
		Big monomer (1)	????100
Hexanaphthene	????10
		Virahol	????100
????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lenses is A ₂₈₀=1.06.The water ratio of hydration rear lens is 48.0% (w/w) after measured.Embodiment 25

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

Component	Part
		Big monomer (2)	????102
????Zonyl?FS-300	????120
		Virahol	????50.1
Trifluoroethanol	????30
		????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lenses is A ₂₈₀=0.36.The water ratio of hydration rear lens is 34.3% (w/w) after measured.Embodiment 26:

To comprise that big monomer (1) and hydrophilic polymerized monomeric following prescription are put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	????A
		Big monomer (1)	????0.505
????HEMA	????0.100
		Acetonitrile	????0.400
Virahol	????0.035
		????Darocur	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lenses is A ₂₈₀=0.322.The water ratio of hydration rear lens is 45% (w/w) after measured.Embodiment 27:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	????A	????B
			?Monocon?400 *	????0.511	????0.504
Virahol	????0.504	????0.504
			????HEMA	????0.106	????0.501
????Darocur	????0.3	????0.3

^*The definition of Monocon 400 is referring to embodiment 18.Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lens A is A ₂₈₀=0.157 and lens B be A ₂₈₀=0.227.The water ratio of hydration rear lens A and B is respectively 43% (w/w) and 41% (w/w) after measured.Embodiment 28:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.

	????A
		Big monomer (1)	????0.406
????HEMA	????0.121
		?Monocon?400 *	????0.205
Virahol	????0.304
		????Darocur	????0.3

^*The definition of Monocon 400 is referring to embodiment 18.Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lenses is A ₂₈₀=0.164.The water ratio of hydration rear lens is 31% (w/w) after measured.Embodiment 29:

Following prescription put in the flat polypropylene lens die (thick 0.2mm, diameter 20mm) and polyase 13 hour under the radiation that the U.V. of wavelength 365nm lamp produces.All umbers by weight.Big monomer (X) among this embodiment is 2.9 the big monomer of formula I for n wherein.

	????A	????B
			Big monomer (X)	????0.500	????0.255
Virahol	????0.248	????-
			Hexalin	????-	????0.118
Trifluoroethanol	????0.422	????0.298
			????Darocur	????0.3	????0.3

Lens are monitored by the U.V. spectroscopic techniques the perviousness of BSA solution.The absorbancy reading of 24 hours rear lens A is A ₂₈₀=0.64, lens B is A ₂₈₀=0.33.The water ratio of hydration rear lens A and B is respectively 33% (w/w) and 28% (w/w) after measured.

Claims (19)

1. one kind comprises the unitary porous polymer of one or more PFPE, and when complete swelling in water, its water ratio is greater than the water ratio of polymeric same polymer under normal condition.

2. according to the porous polymer of claim 1, comprise at least a unitary big monomer of one or more PFPE that has, the water ratio that it is characterized in that described polymkeric substance when the abundant balance of water is greater than 23wt%.

3. according to the porous polymer of claim 1,, it is characterized in that water ratio is greater than 5wt% when the abundant balance of water at least a multipolymer with the unitary big monomeric homopolymer of one or more PFPE or this big monomer and hydrophobic comonomer.

4. according to each porous polymer among the claim 1-3, wherein the PFPE unit has formula PFPE:

-OCH ₂CF ₂O (CF ₂CF ₂O) _x(CF ₂O) _yCF ₂CH ₂O-(PFPE) is CF wherein ₂CF ₂O and CF ₂The O unit can be in whole chain random distribution or with block distributed, and wherein x and y can be identical or different, so that the molecular weight of PFPE is 242-4000.

5. according to each porous polymer among the claim 1-4, wherein at least a big monomer has formula I:

Q-(PFPE-L) _N-1-PFPE-Q (I) wherein Q can be identical or different and be polymerizable groups, and PFPE is the part with formula PFPE:

-OCH ₂CF ₂O (CF ₂CF ₂O) _x(CF ₂O) _yCF ₂CH ₂O-(PFPE) is CF wherein ₂CF ₂O and CF ₂The O unit can be in whole chain random distribution or with block distributed, and wherein x and y can be identical or different so that the molecular weight of PFPE is 242-4000, L is the difunctionality linking group; And n is at least 1;

6. according to each porous polymer among the claim 1-4, wherein at least a big monomer has formula II:

Q-B-(L-B) _n-T (II) wherein Q can be identical or different and be polymerizable groups, and L is the difunctionality linking group; N is at least 1; Each B can be identical or different and be the difunctionality block of molecular weight 100-4000, and wherein at least one B is the PFPE of formula (PFPE); PFPE is the part with formula PFPE:

-OCH ₂CF ₂O (CF ₂CF ₂O) _x(CF ₂O) _yCF ₂CH ₂O-(PFPE) is CF wherein ₂CF ₂O and CF ₂The O unit can be in whole chain random distribution or with block distributed, and wherein x and y can be identical or different so that the molecular weight of PFPE is 242-4000, and T is for carrying out polymerization by free radical but can contain the monovalence end group of other functional group.

7. according to each porous polymer among the claim 1-4, wherein at least a big monomer has formula III:

Q-PFPE-L-M-L-PFPE-Q (III) wherein Q can be identical or different and be polymerizable groups, and PFPE is the part with formula PFPE:

-OCH ₂CF ₂O (CF ₂CF ₂O) _x(CF ₂O) _yCF ₂CH ₂O-(PFPE) is CF wherein ₂CF ₂O and CF ₂The O unit can be in whole chain random distribution or with block distributed, and wherein x and y can be identical or different so that the molecular weight of PFPE is 242-4000, L is the difunctionality linking group; M is the residue of double functional copolymer or multipolymer, and this polymkeric substance or multipolymer comprise the siloxane repeat unit of formula IV, and molecular weight is preferably 180-6000 and comprises end as herein described functional group: R wherein ¹And R ²Can be identical or different and be selected from hydrogen, alkyl, aryl, haloalkyl etc.

8. goods comprise each described porous polymer among the claim 1-7.

9. goods according to Claim 8 are ophthalmic device.

10. according to the goods of claim 9, be contact lens.

11. goods according to Claim 8 are film.

12. a poromeric method for preparing claim 1 comprises the steps: ⅰ) form a kind of mixture that comprises polymerizable components and organic solvent, wherein polymerizable components comprises at least a unitary big monomer of at least one PFPE that has; ⅱ) the described mixture of polymerization wherein has at least significantly the described organic solvent of ratio be in disperse phase and wherein said organic solvent disperse phase after described polymerization of mixtures immediately and forms interpenetrating(polymer)networks or be dispersed in the whole mixture in whole mixture; And ⅲ) removes the organic solvent disperse phase.

13. according to the method for claim 12, wherein organic solvent is a diisopropyl ether.

14. poromeric method for preparing claim 1, comprise the steps: 1) pore-forming material is dispersed in the monomer component external phase, wherein said monomer component external phase comprises and at least aly has the unitary monomer of at least one PFPE and wherein said pore-forming material and be the optional polyalkylene glycol that replaces; 2) polymerization single polymerization monomer external phase then; And 3) from porous polymer, remove pore-forming material.

15. according to the method for claim 14, wherein pore-forming material is a polypropylene glycol.

16. goods comprise the porous polymer that can obtain according to the method for claim 12 or 13.

17. goods comprise the porous polymer that can obtain according to the method for claim 14 or 15.

18., be contact lens according to the goods of claim 16.

19., be contact lens according to the goods of claim 17.