CN1240457A - Porous polyorganosiloxane polymers - Google Patents

Abstract

A hydratable porous polymer comprising a polymerized polyorganosiloxane macromonomer of formula (I): Q-[M-L]c-M-Q wherein c is in the range of from 0 to 5, preferably in the range of from 0 to 3; M may be the same or different and is a difunctional block of molecular weight in the range of from 100 to 8000 and wherein at least one M comprises a residue from a difunctional polymer or copolymer comprising siloxane repeat units of formula (II) where R<1> and R<2> may be the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, alkenyl, alkynyl, aryl, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, heterocyclyl, and haloheterocyclyl; L may be the same or different and is a difunctional group; and Q may be the same or different and is a polymerizable group.

Description

Porous polyorganosiloxane polymers

But but the present invention relates to the porous polyorganosiloxane polymers of hydration and prepare poromeric method of these hydrations.Particularly, but the present invention relates to polymerization or copolymerization and be mixed with the method for the monomer of organopolysiloxane with the porous polyorganosiloxane polymers of formation hydration, but and, comprise film or Ophthalmoligic instrument, for example contact lens by the goods that the porous polyorganosiloxane polymers of hydration makes.

Have been found that in many application it is favourable that polymkeric substance is porous.Required porosity depends on concrete application.For example, membrane filtration depends on the use of microporous polymer, to reach the effect that separates various materials.In the battery of electrolysis or electrical power storage, the macropore sheet of chemicals-resistant polymkeric substance has a wide range of applications as cell partitions.The large pore material (open-celled foams) that utilizes whipping agent to make can be used as cushioning material.Porous material also can be used as the medium of medical compounds administration in field of medicaments, be used in medical implant that cell is sealed or tissue ingrowth, and obtains some mechanical property, as visco-elasticity.

The hole can form in polymkeric substance in the preparation process of desired shape goods, perhaps forms in goods in the preparation back.For example disclose a kind of like this method among the U.S.P.5213721, wherein in the matrix polymer piece, mechanically pierced the hole, then the perforation matrix of gained has been carried out the multiple support and press and press solidly again, be contracted to required aperture until the hole.

Not too commonly, porousness is the internal performance of polymkeric substance, and keeps this porousness when in specific application polymkeric substance being made required shape.Particularly advantageous is to introduce hole in the polymer formation stage.This is normally economical, and under suitable situation, can obtain the good control to porosity and aperture.

Polymkeric substance based on organopolysiloxane has many uniquenesses and perfect performance usually, and this makes these polymkeric substance particularly suitables in many application based on organopolysiloxane.These performances comprise good snappiness, the transparency, highly anti-extreme temperature, good chemical-resistant and scale resistance.Organopolysiloxane also has the characteristic of many ideal films and solubleness aspect, needing to be usually used in during the device of ventilation property and/or medicine drop get.

Polymkeric substance based on organopolysiloxane is the highly desirable material of contact lens and other Ophthalmoligic instrument.Can make the migration of tear or nutritive substance by contact lens or other Ophthalmoligic instrument and keep the porous polymer of its transparent hydration owing to can not prepare, limit these polymkeric substance application in this respect thus based on organopolysiloxane.But the porous polyorganosiloxane of hydration is applicable to that also some other uses, and will be clearly based on their these application of performance.

Organopolysiloxane is celebrated with its hydrophobicity usually.Organopolysiloxane is in use given material and structure usually with water repellency.The equilibrium water content of organopolysiloxane body is very low, and being considered to usually can not hydration.

But have now found that the porous polyorganosiloxane based polyalcohol that can prepare a kind of hydration.In view of the above, but now provide a kind of porous polymer of hydration, this polymkeric substance contains the big monomer of organopolysiloxane of polymeric following formula I:

Q-[M-L] _c-M-Q (I) wherein c is 0～5, preferred 0～3; M can be identical or different, and for molecular weight is 100～8000, more preferably 200～8000 two functional blocks, and wherein at least one M contains to come two functional polymers of siloxane repeat unit of self-contained II or the residue of multipolymer,

R wherein ¹And R ²Can be identical or different, and be selected from hydrogen, the optional alkyl that replaces, alkenyl, alkynyl, aryl, haloalkyl, halogenated alkenyl, halo alkynyl, halogenated aryl, heterocyclic radical and halogenated heterocyclic base; L can be identical or different, and be two functional linking groups; Q can be identical or different, and be polymerisable group.

Have now found that polymkeric substance of the present invention can be hydrated to the water that contains obvious amount.These water are maintained in the internal voids of polymeric matrix.The retainable water-content of polymkeric substance of the present invention has significantly surpassed the water-holding capacity of organopolysiloxane.Typically, the water content of organopolysiloxane body is lower than 0.3 weight %.The water content (seeing embodiment) that has now found that polymkeric substance of the present invention is usually greater than 5 weight %, and more preferably greater than 10 weight % or 15 weight %, and can be made into water content be 25 weight % or bigger.The big monomer of formula I preferably is substantially free of, and does not more preferably contain the PFPE block that is also referred to as " PFPE " block.Further preferably, all variable M contain the unit of formula II, and perhaps more particularly, all variable M are the variable in the formula III of following explanation.

Preferably, polymkeric substance of the present invention is made up of polymeric matrix, has interconnective hole in this polymeric matrix.Depend on used polymerizing condition, various apertures and form all are fine.The size in each hole can be about at the most 5 microns, normally is about 100 nanometers, and the minimum diameter in hole is about 10 nanometers usually.Advantageously, particularly because hole has zigzag path usually, so the transmitance that the porosity of product can the specified molecular weight molecule is represented.

In a second aspect of the present invention, but provide a kind of method of porous polyorganosiloxane polymers of preparation hydration, this method comprises the steps:

I) disperse a kind of pore-forming material (porogen) in the phase-splitting of successive set of monomers, wherein said continuous monomer component contains the big monomer of at least a formula I;

Ii) make successive monomer phase-polymerization subsequently; And

Iii) from porous polymer, remove the pore-forming material.

Below this method be called " pore-forming physical law ".

In a third aspect of the present invention, but provide a kind of method of porous polyorganosiloxane polymers of preparation hydration, this method comprises the steps:

I) form the mixture that contains polymerisable component and a kind of solvent, wherein polymerisable component contains the big monomer of at least a formula I;

Ii) make described polymerization of mixtures, wherein after described polymerization of mixtures, there is at least the remarkable described solvent of ratio be the form of discrete phase immediately, and wherein said discrete solvent phase forms interpenetrating(polymer)networks in whole mixture, perhaps is dispersed in the whole mixture; And

Iii) remove discrete solvent phase.

Below this method be called " two phase process ".

Q is a polymerizable groups, but the ethene that preferably contains freedom of entry base polyreaction belongs to unsaturated part.Preferred Q is the group of formula A,

P ₁-(Y) _m-(R '-X ₁) _p-(A) P wherein ₁It is the group of a 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 each other; R ' is for there being the residue of divalent of the organic compound of 20 carbon atoms at the most; X ₁Be-NHCO-,-CONH-,-NHCONH-,-COO-,-OCO-,-NHCOO-or-OCONH-.

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

Preferably, P ₁Be the alkenyl or the alkenyl aryl of 12 carbon atoms at the most, the preferred especially alkenyl of 8 carbon atoms, the alkenyl of 4 carbon atoms especially at the most at the most.

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

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

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

Preferably, R ' is the alkylidene group of 6～20 carbon atoms, arylidene, saturated divalence cycloaliphatic groups, arylidene alkylene, alkylidene group arylidene, alkylidene group arylidene alkylene or arylidene alkylene arylidene.

Preferably, R ' is the divalent group of 12 carbon atoms at the most, the preferred especially divalent group of 8 carbon atoms at the most.In an embodiment preferred, R ' further is the alkylidene group or the arylidene of 12 carbon atoms at the most.In a particularly preferred embodiment, R ' is a low-grade alkylidene, particularly the low-grade alkylidene of 4 carbon atoms at the most.

Particularly preferably be, Q is selected from acryl, methacryloyl, styryl, acrylamido, acrylamido alkyl, the derivative of carbamate methacrylic ester (urethanemethacrylate) or its any replacement.Most preferably, Q is the compound of formula A, 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-, m and p respectively do for oneself 1.

Among the formula I, preferred c is 1～5, and more preferably c is 1～3.C is that 1 big monomer is particularly preferred, and c is that 0 big monomer also is preferred.

C was at least 1 o'clock, and the big monomer of formula I can contain linking group L.Linking group L can be any can with two functional moieties' of hydroxyl reaction residue of divalent.The suitable precursor of L is α, ω-di-epoxide, 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-dicarboxylic anhydride, α, ω-dilactone; α, ω-dialkyl, α, ω-dihalide; α, ω-dialkyl ether, or α, ω-dihydroxymethyl acid amides.

Preferably, linking group is the residue of divalent (C (O)-NH-R-NH-C (O)-) of vulcabond, or the corresponding residue of diisothio-cyanate, and wherein R is the organic residue of divalence of 20 carbon atoms at the most.

Residue of divalent R for example is the alkylidene group of 20 carbon atoms at the most, arylidene, alkylidene group arylidene, arylidene alkylene or arylidene alkylene arylidene, the saturated divalence cycloaliphatic groups of 6～20 carbon atoms, or the cycloalkylidene alkylidene group cycloalkylidene of 7～20 carbon atoms.

In an embodiment preferred, R is the alkylidene group of 14 carbon atoms at the most, arylidene, alkylidene group arylidene, arylidene alkylene or arylidene alkylene arylidene, or the saturated divalence cycloaliphatic groups of 6～14 carbon atoms.In a particularly preferred embodiment, R is the alkylidene group or the arylidene of 12 carbon atoms at the most, perhaps the saturated divalence cycloaliphatic groups of 6～14 carbon atoms.

In an embodiment preferred, R is the alkylidene group or the arylidene of 10 carbon atoms at the most, perhaps the saturated divalence cycloaliphatic groups of 6～10 carbon atoms.

In a particularly preferred embodiment, R is the residue derived from vulcabond, for example derived from 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 right-tetramethylxylene diisocyanate, isophorone diisocyanate or hexanaphthene 1,4-vulcabond.

Aryl is the carbocyclic aromatic group that does not replace or preferably replaced by low alkyl group or lower alkoxy.Its example is a phenyl, tolyl, xylyl, p-methoxy-phenyl, tert.-butoxy phenyl, naphthyl and phenanthryl.

Preferably, arylidene is phenylene or the naphthylidene that does not replace or replaced by low alkyl group or lower alkoxy, particularly 1, and 3-phenylene, 1,4-phenylene or methyl isophthalic acid, 4-phenylene, 1,5-naphthylidene or 1,8-naphthylidene.

Preferably, saturated divalence cycloaliphatic groups is a cycloalkylidene, for example cyclohexylidene or cyclohexylidene (low-grade alkylidene), for example do not replace or by one or more low alkyl groups, as methyl substituted cyclohexylidene methylene radical, trimethylammonium cyclohexylidene methylene radical for example is as divalence isophorone base.

In the present invention, the term " rudimentary " that is used in combination with residue and compound is meant 8 carbon atoms at the most especially unless add explanation in addition, the preferred residue and the compound of 4 carbon atoms at the most.

Especially, low alkyl group has 8 carbon atoms at the most, and preferably 4 carbon atoms at the most for example are methyl, ethyl, propyl group, butyl, the tertiary butyl, amyl group, hexyl or isohexyl.

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

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

Arylene units in alkylidene group arylidene or 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, and methylene radical particularly.Therefore these residues are preferably phenylene methylene radical or methylene radical phenylene.

Especially, lower alkoxy has 8 carbon atoms at the most, and preferably 4 carbon atoms at the most for example are methoxyl group, oxyethyl group, propoxy-, butoxy, tert.-butoxy or hexyloxy.

Preferably, the arylidene alkylene arylidene is for to have 8 at the most in alkylidene unit, particularly the phenylene of 4 carbon atoms (low-grade alkylidene) phenylene, for example phenylene ethylidene phenylene or phenylene methylene radical phenylene at the most.

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).

The big monomer of formula I contains at least one group M, and this group M is from two functional polymers of the siloxane repeat unit that contains formula II or the residue of multipolymer.The molecular weight of each M and chemical constitution can be identical or different, as long as they all drop in the above-mentioned molecular weight ranges.

Two functional polymers that derive M are contained an independent end functional group of selecting at each end, this end functional group can with the precursors reaction of linking group L, form covalent linkage thus and connect.Preferably end functional group is hydroxyl or amino.These functional groups can be connected with siloxane unit among the M by alkylidene group or other non-reacted spacer groups.Preferred end group partly is hydroxyalkyl, hydroxy alkoxy alkyl and alkylamino.Particularly preferred hydroxyalkyl is hydroxypropyl and hydroxyl butyl; Particularly preferred hydroxy alkoxy alkyl is hydroxyl ethoxy ethyl and hydroxyl-oxethyl propyl group.

Preferably, the radicals R in the formula II repeating unit ¹And R ²Be selected from the alkyl or aryl of 10 carbon atoms at the most, more preferably be selected from low alkyl group, most preferably be methyl.

M residue among the preferred aforesaid formula I has Formula Il I:

Wherein n is 5～100 integer; Alk be not at interval or by oxygen at interval, the alkylidene group of 20 carbon atoms at the most; Radicals R ₁, R ₂, R ₃And R ₄Be selected from alkyl independently of each other, alkenyl, alkynyl, aryl, haloalkyl, halogenated alkenyl, the halo alkynyl, halogenated aryl, heterocyclic radical, halogenated heterocyclic base and the optional derivative that replaces thereof, more preferably these groups are alkyl, aryl or haloalkyl; X ₃For-O-or-NH-.

Preferred n is 5～70 integer, and is preferred especially 8～50, especially 10～28.

Preferably, radicals R ₁, R ₂, R ₃And R ₄Be the low alkyl group of 8 carbon atoms at the most independently of each other, the preferred especially low alkyl group of 4 carbon atoms, the low alkyl group of 2 carbon atoms especially at the most at the most.Further preferred R ₁, R ₂, R ₃And R ₄Be methyl.

Preferably, partly had the low-grade alkylidene of 6 carbon atoms-oxygen base-low-grade alkylidene at the most by oxygen alkylidene group at interval for each low-grade alkylidene, more preferably each low-grade alkylidene partly has the low-grade alkylidene of 4 carbon atoms-oxygen base-low-grade alkylidene at the most, for example ethylidene-oxygen base-ethylidene or ethylidene-oxygen base-propylidene.

Preferably, haloalkyl is by one or more, the low alkyl group that replaces of three halogen atoms such as fluorine, chlorine or bromine at the most particularly, and its example is a trifluoromethyl, chloromethyl, seven fluorine butyl or bromotrifluoromethanes.

Q, R ¹, R ², R ³And R ⁴Suitable substituting group can be selected from the alkyl of 10 carbon atoms at the most, 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; arylamino, acyl group, aroyl, alkenyl acyl; aryl-acyl, amido, alkylsulfonyloxy, aryl sulfinyl oxygen base; heterocyclic radical, heterocyclic oxy group, heterocyclic amino group, halogenated heterocyclic base; alkoxy carbonyl, alkylthio, alkyl sulphonyl, arylthio; aryl sulfonyl, amino-sulfonyl, dialkyl amido and dialkyl group alkylsulfonyl.

Particularly preferred polymkeric substance is aforesaid like this some polymkeric substance, c=0 wherein, and M is that the molecular weight of formula III is 248～8000 the big residues of monomers of organo-siloxane.

Polymerizable components also can comprise and contains one or more comonomers that the ethene that forms multipolymer belongs to unsaturated group that participate in reacting.Preferred ethene belongs to unsaturated group and is selected from acryl, methacryloyl, styryl, acrylamido, acrylamido alkyl, carbamate methacrylic ester, or the derivative of its any replacement.Suitable monomer comprises fluorine-containing and alkyl acrylate and hydrophilic polymerized monomer silicon, and they can be selected from material well-known to those skilled in the art widely, or the mixture of these materials.Particularly preferred comonomer comprises vinylformic acid dihydro perfluoroalkyl ester, as vinylformic acid dihydro perfluoro capryl ester, vinylformic acid 1,1-dihydro perfluoro butyl ester, vinylformic acid three hydrogen perfluoroalkyl esters, vinylformic acid tetrahydrochysene perfluoroalkyl ester, the methacrylic ester or the acrylate of three (trimethylsiloxy) propyl group, hydroxyalkyl methacrylate, as hydroxyethyl methylacrylate, methacrylic acid, and the comonomer that contains amine are as methacrylic acid N, the N-dimethylaminoethyl, N,N-DMAA and N, N-dimethylaminoethyl acrylamide.Based on the weight of prescription, the preferred amounts that single comonomer joins in the big monomer is 0～60 weight %, most preferably 0～40 weight %.Also can have or not have under the situation of other comonomer, use the suitable multipolymer of big monomeric mixture preparation of formula I.Also can have or not have and mix other big monomer (simple function or two functional) under the situation of other comonomer.

The light initiation polymerization of the prescription of other preferred porous polyorganosiloxane polymers two-end capped polydimethylsiloxane of methacrylic acid isocyanato ethyl ester (IEM) by containing formula V gets R by two phase process or pore-forming material legal system _IEM-(OCH ₂CH ₂) _y-O (CH ₂) _z-[Si (CH ₃) ₂O] _x-Si (CH ₃) ₂-(CH ₂) _zO-(CH ₂CH ₂O) _y-R _IEM(V) wherein x, y and z can be identical or different, so that the molecular weight of polydimethylsiloxane is 200～8000, and R wherein _IEMExpression CH ₂=CH (CH ₃)-COO-CH ₂CH ₂-NH-CO-.

Most preferred porous siloxane polymer is that the light initiation polymerization by the prescription of the end capped polydimethylsiloxane of methacrylic acid isocyanato ethyl ester (IEM) that contains formula V makes, x=26 wherein, y=1, z=3 (hereinafter referred to as big monomer 1).

R _IEM-OCH ₂CH ₂-O(CH ₂) ₃-[Si(CH ₃) ₂O] ₂₆-Si(CH ₃) ₂-(CH ₂) ₃O-CH ₂CH ₂O-R _IEM

Big monomer 1

Poromeric form of the present invention and porosity can be by being described in the method control of the present invention second and the third aspect.In the pore-forming physical law, poromeric form usually can be by changing pore-forming material and big monomeric control recently.The increase of pore-forming material proportion causes the volume of voids in the polymeric matrix higher, has improved hole thus and has interconnected to form the possibility of continuous hole from front surface to the rear surface of polymer body.The ratio of pore-forming material is low will to cause forming unicellular structure, and this structure mesoporosity is separated from each other, perhaps its to interconnect degree lower.

Have now found that the pore-forming material is preferred for liquid state at room temperature.It is optional from polyvalent alcohol to be used for pore-forming material of the present invention, polyalkylene glycol and polyamines.Although preferred especially polypropylene glycol also can use other polyalkylene glycol, as polyoxyethylene glycol.The molecular weight of pore-forming material can change, and preferred molecular weight is less than 4000.

Can anyly install easily polymerisable component is mixed with pore-forming material and other optional component.For example, can or stir polymerisable component is mixed with pore-forming material and other optional component by vibration.The order that component joins in the mixture is very not strict.The various components that constitute polymerizable components are unnecessary to mix before mixing mixture.Mixture can be the form of homogeneous phase solution, and perhaps the pore-forming material is a different phase, and for example the form of dispersion, emulsion, microemulsion perhaps preferably is total to continuous microemulsion liquid form.

Can randomly in mixture, add a small amount of modified component before the polymerization.For example, can add solvent control aperture and form.Other suitable solvent comprises ethyl acetate and dimethyl formamide.

Can in mixture, mix tensio-active agent.The use of tensio-active agent is the effective means of control aperture and hole density.

Usually can the initiation by polymerizable components as described below, with this mixture of any method easily polymerization.Suitable polymerizing condition will be conspicuous to those skilled in the art.For example, temperature can be-100～350 ℃, and pressure can be for being lower than normal atmosphere to being higher than normal atmosphere.

Should be understood that significantly the form of discrete phase is held in the pore shaping object quality guarantee of ratio.This pore-forming material that is meant q.s forms interpenetrating(polymer)networks or dispersion.Those skilled in the art will appreciate that and depend on polymeric component and pore-forming material to have a certain amount of pore-forming material to be adsorbed or to be retained in the polymerizable components, and finally adsorb or be retained in the porous polymer.Typically, after polymerization was just finished, it was the form of discrete phase that the pore-forming material more than 60% is arranged.Preferably more than 80% pore-forming material form, more preferably more than 95% pore-forming material form for discrete phase for discrete phase.

Particularly preferably be, the pore-forming material forms interpenetrating(polymer)networks in polymeric component, causes porous polymer to have mesh structural porous form.Mesh structural porous form can be perforate, the spongy structure that is made of interconnected polymer spherical particle, or has interconnected, the open-celled structure that is generally spherical pore in a row.

In another embodiment, porous polymer can be the unicellular structure form that the hole of dispersing is scattered in whole polymkeric substance.

Can from porous polymer, remove the pore-forming material by any mode easily.The suitable mode of desolvating of removing comprises evaporation, with solvent such as Virahol and water exchange subsequently, or with The suitable solvent such as water or Virahol the pore-forming material is washed out from porous polymer simply.

Method of the present invention is applicable to the material of various apertures of preparation and form.Be limited to about 5 microns on the mean pore size in single hole, typically be about 100 nanometers, also can obtain the hole that diameter is about 10 nanometers.

The hole can form interpenetrating(polymer)networks.More advantageously the perviousness with the molecule of specified molecular weight characterizes these forms.This will describe in an embodiment.

The particularly advantageous embodiment of the inventive method is the pore-forming material to be coordinated be successive inierpeneirating network structure form, this pore-forming material can be extracted out at an easy rate mutually, the result stays the porous material with reticulated structure hole, and these reticulated structure holes can make the particle of fluid and minor diameter at an easy rate by this porous polymer.

Although the size in hole and density can also can be made small change by the use of tensio-active agent to the size and the density in hole as mentioned above by the control recently of polymerizable components and pore-forming material.Very the adding of small proportion water also can improve porosity.

In a third aspect of the present invention, two phase process is the porosity and the form of may command organopolysiloxane also.

Can any form easily be mixed with solvent and other optional component by polymerisable component.For example, can or stir polymerisable component is mixed with solvent and other optional component by vibration.The order that component joins in the mixture is very not strict.The various components that constitute polymerizable components are unnecessary to mix before mixing mixture.Mixture can be the form of homogeneous phase solution, and perhaps solvent is a different phase, and for example the form of dispersion, emulsion, microemulsion perhaps preferably is total to continuous microemulsion liquid form.The form of mixture is unimportant before the polymerization, because be that the form of mixture is controlled poromeric form in polymerization process.

Solvent can be organic solvent or water.Organic solvent is preferably selected from alcohol, amine or the polyvalent alcohol of short chain.Short chain alcohol, amine or polyvalent alcohol can be cyclic, branching or linear; Branched compound is particularly preferred.The carbon atom number of short chain compound can be 1～12; Yet preferred carbon atom number is 2～8.Particularly preferably be Virahol, 1-hexanol, 3-hexanol, cyclopentanol, 1, ammediol and ethylene glycol.

Mixture can be the form of microemulsion.Microemulsion is normally by the Surfactants at Interface layer-stabilizing, stable and be the two-phase system that is transparent basically on the thermodynamics.Typically, microemulsion is made up of the drop even and spherical in shape that is scattered in the continuum.Typically, particle diameter is 10 ^-2About micron.Microemulsion also can be total to continuous structure and exist, wherein each mutually all with successive interpenetrating(polymer)networks form be present in another mutually in.

Can randomly in mixture, add a spot of modified component before the polymerization.For example, the solvent that can add other is with control aperture and form.Other suitable solvent comprises ethyl acetate, dimethyl formamide and water.

The polymerization of the present invention second and third aspect method all can cause or cause by radical initiator by ionizing radiation.The preferred radical initiator that uses, as benzoin methylether, Diisopropyl azodicarboxylate, benzoyl peroxide, peroxy dicarbonate (peroxydicarbonate) etc.Particularly preferred radical initiator is Darocur 1173 (registered trademark of Ciba-Geigy SpecialtyChemicals).Can form free radical by initiator by heat or photochemistry mode; Also can use redox initiation.

The preferred method that is used to generate poromeric this third aspect be light trigger, short chain dibasic alcohol (as solvent) and also can be used as solvent the short chain alcohol tensio-active agent in the presence of, carry out the big monomeric polymerization of organopolysiloxane of formula (I).Can change the pore structure and the form of organopolysiloxane significantly by used dibasic alcohol amount in the control microemulsion.High dibasic alcohol content can generate the membrane structure of forming by by the isolating fusion spherical polymer particles of big porous channel.The feature of these films is that they are to the perviousness height of bovine serum albumin (BSA) (MW 67000), and its water-content height.On the contrary, the microemulsion of a small amount of dibasic alcohol generates the lower film of hole density, causes the infiltrative reduction to BSA.

The prescription of organopolysiloxane microemulsion and polymerization can be used non-reacted organic solvent, replace water as Virahol and hexanol.And siloxane microemulsion can not need tensio-active agent to strengthen the stability of microemulsion.Yet, also can add tensio-active agent as a kind of selection.Also can control the porosity of resulting polymers material by the amount that changes short chain dibasic alcohol in the microemulsion simply.

Can be by the porous polymer of any preparation in the method for second and the third aspect that constitute a part of the present invention based on organopolysiloxane.These methods can make these highly stable and durable materials use with the porous form.In addition, the inventive method can provide the polymkeric substance based on siloxanes of the continuous pore structure with sufficient size and density (frequency), and they can allow high molecular biomolecule such as protein and glycoprotein to pass through.

The polymkeric substance that is made by the inventive method is made of polymeric matrix, has interconnective hole in polymeric matrix.According to used polymerizing condition, can obtain various aperture and form.Be limited to about 5 microns on the mean pore size in single hole, be generally 100 nanometers, and general diameter minimum aperture following is limited to about 10 nanometers.More advantageously, and particularly because hole usually has the zigzag path, so the porosity of product is represented with the perviousness of the molecule of specified molecular weight.

Of the present invention second and the third aspect method of introducing continuous pore structure is provided in the organopolysiloxane sill.In application, need low and high-molecular weight nutritive substance and other component accessibke porosity degree in tissue juice as the cornea,artificial.Nutritive substance is very important by the perviousness of implant or onlay (onlay) for the obducent long-term vitality of any epithelium.The unreactiveness of successive pore structure and silicone compositions and good chemical property also make these materials be suitable for and make filtering membrane and similar device.

According to the present invention's content on the other hand, provide a kind of Ophthalmoligic instrument that makes by aforesaid porous polymer or multipolymer, preferred a kind of contact lens, more preferably a kind of soft-contact lens.

Contact lens and soft-contact lens are the different polymkeric substance disks of surface curvature radius.Radius-of-curvature is that the refractive index of conjugated polymer is selected, so that it obtains required optical correction, and the form fit that makes internal surface and wearer's cornea of lens.They are normally sold in Sterile Saline.Randomly, modification can be carried out by coating with method well known in the art in the surface of lens, and these methods for example are plasma polymerization, glow discharge, or a kind of hydrophilic polymers that has more of grafting.

Can also will make other useful goods according to the polymkeric substance that the present invention makes with general forming method well known in the art and complete processing.Transparent polymer of the present invention can be used for tissue culture device, optics, slide etc.

Another aspect of the present invention is with film or sheet form porous polymer to be used as film or strainer.These porous-films can be laminated together to form a kind of mixture with another supporting film.These application can relate to the infiltration of gas or liquid.

Porous polymer of the present invention is specially adapted to medical use, as being used as Ophthalmoligic instrument, delivery device or biomaterial.For example they have the required material property of following application, as percutaneous access device, soft tissue implant, the glucose monitors of implantation, bioimplant of sealing such as pancreas islet, administration is pasted, contact lens, the lasting release of active compound, the fixed ligands that is used for bio-reactor or biosensor, wound healing bandage, and biotechnology and biomedical applications comprise vascular transplantation.

Porous polymer of the present invention also is applicable to broad-spectrum film, comprises industrial film, electrical condenser, household reverse osmosis device, the membrane distillation that carries out with osmotic pressure, and the ultrafiltration in food, milk preparation, fruit juice, lab industry.

In this manual, unless context is indicated in addition, word " contains " and various variant should be understood to described integer or the integer group is included in wherein, but does not get rid of any other integer or integer group.The present invention will be described in further detail by the embodiment of following indefiniteness.Used temperature is degree centigrade.The typical zolymerization method

Under inert atmosphere the polymerizable prescription being incorporated in the circular polypropylene molds (0.2mm is thick, the 20mm diameter), is that the ultra violet lamp of 350nm carried out polymerization in 3 hours by being exposed to wavelength.Equal operating weight part in following composition.

Each component (except the initiator Darocur1173) of prescription is joined in the glass nut phial of the magnetic stirring bar of being furnished with teflon-coating in any order.Then glass vial is placed on the magnetic agitation applicator platform, each component is thoroughly mixed.Add Darocur 1173 after 10 minutes, and continue to mix 5 minutes.This mixture is positioned over carefully the end half one of polypropylene disk mould (20mm diameter, 0.2mm is thick) under nitrogen atmosphere.Then mould lid is put back to original position carefully, note preventing the formation of any air pocket.Promptly repeat this process for remaining serial mould.Then the mould of filling is sandwiched in the framework.The mould that clamps is taken out from nitrogen atmosphere, and place it in the ultraviolet curing case, this curing case is made up of each four glass chassis can placing two frameworks.In the substrate of glass bottom of each dish is two wide range ultraviolet lamps, and it is output as 1.22mW/cm ²Behind the polyase 13 hour, mould is taken out from the ultraviolet curing case.Open mould, peel off the polymkeric substance disk carefully with the tweezers of flat half dog points and finish the demoulding, reach minimum so that polymkeric substance is torn.The polymkeric substance disk of the demoulding is positioned over 60ml to be equipped with in the nut vial of isopropyl acetate (placing 10 polymkeric substance disks in each bottle).Begin to carry out extraction step, purpose is to remove any unpolymerized material from the polymkeric substance disk.Air-tight bottle is placed on incubated overnight in 37 ℃ the water-bath.From water-bath, take out these bottles, and from polymkeric substance the decantation isopropyl acetate.In bottle, charge into Virahol then and it is put back in the water-bath.After 4 hours from polymkeric substance the decantation Virahol, and polymkeric substance finally is kept in the ethanol.

Prepare following porous polymer with above-mentioned general method from listed component.Big monomer 1 is the PDMS of molecular weight 2000, generates terminal double bond (seeing following formula) by polysiloxane and the reaction of methacrylic acid isocyanato ethyl ester and makes its polymerizable.Big monomer 2 is generally identical, and it is based on molecular weight is 1000 PDMS polymkeric substance, i.e. the corresponding lower formula V compound of the value of x.Use following abbreviation: EG: ethylene glycol, IPA: Virahol, Teric G9A8: by the tensio-active agent based on polyoxyethylene (PEO) of ICI Australia Operations Pty Ltd. sale, PPG: (molecular weight is 192 or 725 to polypropylene glycol, as shown), HEMA: hydroxyethyl methylacrylate, MACRO 1: big monomer 1, MACRO 2: big monomer 2.

Poromeric two phase process of preparation and pore-forming physical law have been described in these embodiments, and the performance of resulting polymers.Embodiment 1: non-water microemulsion method

Component	MACRO?1	EG	The 1-hexanol	Darocur?1173
					Weight part	39.8	22.8	34.5	0.5

Embodiment 2: the pore-forming physical law

Component	MACRO?1	PPG-192	IPA	Darocur?1173
					Weight part	44.6	28.2	9.6	0.7

Embodiment 3: non-water microemulsion method

Component	MACRO?1	IPA	1, ammediol	The 1-hexanol	Darocur?1173
						Weight part	44.1	34.8	21.4	10.0	0.4

Embodiment 4: the pore-forming physical law

Component	MACRO?1	PPG-725	HEMA	Darocur?1173
					Weight part	40.3	30.4	10.0	1.4

Embodiment 5: the pore-forming physical law

Component	MACRO?1	PPG-725	HEMA	Darocur?1173
					Weight part	39.8	40.8	10.6	1.3

Embodiment 6: the aqueous microemulsions method

Component	MACRO?1	IPA	Teric?G9A8	Water	Darocur?1173
						Weight part	40.6	6.8	32.1	20.0	1.4

Embodiment 7: the pore-forming physical law

Component	MACRO?1	PPG-725	Darocur?1173
				Weight part	40.4	41.3	1.1

Embodiment 8: non-water microemulsion method

Component	MACRO?2	EG	The 1-hexanol	Darocur?1173
					Weight part	41.8	29.8	29	0.2

Embodiment 9: the pore-forming physical law

Component	MACRO?2	PPG-725	IPA	Darocur?1173
					Weight part	49.6	40.4	9.5	0.5

The polymer property water content

By the hydration weight and the dehydrated weight of comparative polymers disk, determine the poromeric water content of hydration (%w/w).In 37 ℃ vacuum drying oven, dewater by the disk of dried overnight to complete hydration.After the washing step of above-mentioned general polymerization method, handle by the classification exchange of solvent, the polymkeric substance disk is carried out hydration, in solution, keep after 30 minutes, decantation solvent from polymkeric substance, and with following listed following a kind of solvent replacing.Per 10 polymkeric substance disks use the 60ml solvent.Solvent table: 1. 100% ethanol; 2. 75% ethanol/water; 3. 50% ethanol/water;

4. 25% ethanol/water; 5. 100% water; 6. 100% water.

Film with hydration is placed on the Kimwipes paper (Kimberly-Clark) of fine grade (fine grade) then, falls excessive surface-moisture to pat drying, and finally weighs and be designated as hydration weight.

The water content of polymkeric substance is listed in the following table 1 among the embodiment.Table 1: the water content of polymkeric substance among the embodiment

The embodiment sequence number	1	4	5	6	7	8	9
								Water content	34％	34％	42％	50％	42％	55％	28％

Perviousness

By the method for following use static diffusion cell (promptly not stirred solution), by the porosity that the perviousness of bovine serum albumin (BSA) or N,O-Diacetylmuramidase is characterized the product polymkeric substance.

The flat polymkeric substance disk (moisture determination that water breakthrough is legal) that with a diameter is the hydration of 20mm is placed between two chambers, one contains bovine serum albumin (molecular weight is 67000, hereinafter referred to as BSA) or N,O-Diacetylmuramidase (molecular weight is 14000) at phosphate buffered saline (PBS) (in the sodium-chlor of 20mM phosphoric acid salt at 0.2M, pH7.4, hereinafter referred to as PBS) in 8mg/ml solution, and another chamber only charges into PBS.Timed interval place selected takes out sample, and measures the ultraviolet absorptivity (A280) of solution at the 280nm place from the PBS chamber, spread by polymeric film to have determined whether any protein.The optical density reading is high more, illustrates that the protein diffusion is many more, therefore just illustrate that also the aperture of this structure is relatively large, and/or hole density is bigger.The porosity of the sample of being measured by this method is listed in following table 2 and the table 3.Table 2: polymkeric substance is to the porosity of BSA among the embodiment

The embodiment sequence number	1	2	3	4	5	6	7
								Diffusion time	16 hours	24 hours	24 hours	24 hours	24 hours	24 hours	16 hours
A280	0.593	0.272	0.589	0.182	0.317	0.572	0.153

Table 3: polymkeric substance is to the porosity of N,O-Diacetylmuramidase among the embodiment

The embodiment sequence number	8	9
			Diffusion time	24 hours	24 hours
A280	2.49	1.41

Claims (10)

1. But 1. the porous polymer of a hydration, this polymkeric substance contains the big monomer of polymeric organopolysiloxane of formula I,

   Q-[M-L] _c-M-Q (I) wherein c is 0～5, preferred 0～3; M can be identical or different, and for molecular weight is two functional blocks of 100-8000, and wherein at least one M contains to come two functional polymers of siloxane repeat unit of self-contained II or the residue of multipolymer,

   

   R wherein ¹And R ²Can be identical or different, and be selected from hydrogen, the optional alkyl that replaces, alkenyl, alkynyl, aryl, haloalkyl, halogenated alkenyl, halo alkynyl, halogenated aryl, heterocyclic radical and halogenated heterocyclic base; L can be identical or different, and be two functional linking groups; Q can be identical or different, and be a polymerisable group.
2. 2. but the porous polymer of the hydration of claim 1, the equilibrium water content of wherein said polymkeric substance is greater than 5 weight %.
3. 3. but the porous polymer of the hydration of claim 1, c=0 wherein, M are molecular weight is the big residues of monomers of organo-siloxane of 248～8000 formula III, Wherein n is 5～100 integer; Alk be not at interval or by oxygen at interval, the alkylidene group of 20 carbon atoms at the most; Radicals R ₁, R ₂, R ₃And R ₄Be selected from alkyl independently of each other, alkenyl, alkynyl, aryl, haloalkyl, halogenated alkenyl, the halo alkynyl, halogenated aryl, heterocyclic radical, halogenated heterocyclic base and the optional derivative that replaces thereof, wherein more preferably these groups are alkyl, aryl or haloalkyl; X ₃For-O-or-NH-.
4. 4. but method for preparing the porous polyorganosiloxane polymers of hydration, this method comprises the steps:

   I) disperse a kind of pore-forming material in the phase-splitting of successive set of monomers, wherein said continuous monomer component contains the big monomer of at least a formula I;

   Ii) make successive monomer phase-polymerization subsequently; And

   Iii) from porous polymer, remove the pore-forming material.
5. 5. but method for preparing the porous polyorganosiloxane polymers of hydration, this method comprises the steps:

   I) form the mixture that contains polymerisable component and a kind of solvent, wherein polymerisable component contains the big monomer of at least a formula I;

   Ii) make described polymerization of mixtures, wherein after described polymerization of mixtures, there is at least the remarkable described solvent of ratio be the form of discrete phase immediately, and wherein said discrete solvent phase forms interpenetrating(polymer)networks in whole mixture, perhaps is dispersed in the whole mixture; And

   Iii) remove discrete solvent phase.
6. 6. but porous polymer according to the hydration of the method for claim 4 or 5 preparation.
7. 7. the polymkeric substance of claim 1 comprises the purposes in the Ophthalmoligic instrument at medical field.
8. 8. the purposes of the polymkeric substance of claim 1 in industrial circle.
9. 9. Ophthalmoligic instrument, as contact lens, but it contains the polymkeric substance of the hydration of claim 1.
10. 10. but the cornea,artificial of polymkeric substance of containing the hydration of claim 1.