CN101612528A - Form the method for coated structure - Google Patents
Form the method for coated structure Download PDFInfo
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- CN101612528A CN101612528A CN200910164646A CN200910164646A CN101612528A CN 101612528 A CN101612528 A CN 101612528A CN 200910164646 A CN200910164646 A CN 200910164646A CN 200910164646 A CN200910164646 A CN 200910164646A CN 101612528 A CN101612528 A CN 101612528A
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Abstract
A kind of method that on porous substrate, forms the room temperature water-soluble polymer coating, its step comprises: form room temperature water-soluble polymer, one or more crosslinking agents, the solvent that is used for room temperature water-soluble polymer such as water, reach one or more the optional pore formers or the solution of multifunctional auxiliary agent; Mixture stirred until all components all dissolve; Solution is joined as solution being dried on the base material as coating before crosslinked in the loose structures such as supatex fabric or perforated membrane and in that coating is carried out.Selection in addition is to carry out partial cross-linked to coating before drying solution.Can form loose structure with room temperature water-soluble polymer coating, the existing convection current that can pass the structure hole of this structure, having again can be by the diffuse flow of coating.
Description
The application is that the name of submitting on August 3rd, 2006 is called the dividing an application of No. 200580003979.7 applications of " method that forms coated structure ".
Background technology
Agarose has been used to prepare gel media, normally in chromatographic isolation and running gel field.Typical implementation method is that the polymer and the aqueous solution are carried out being separated of heat.Why this method can realize it being because polymer has fusing point and gel point.For example for process agarose, polymer must be heated to it more than melting temperature, and this temperature is about 92 ℃ when having water.Polymer melted under this temperature, molten polymer is formed solution by water-soluble thinner then.As long as temperature is higher than the gel point of polymer, it is solvable that polymer just keeps in water, and this gel point is generally more than 30 ℃, is more typically about 43 ℃.Be in and when being lower than gel point, polymer phase separates and becomes and is that hydrogel, this hydrogel are rendered as the just residing Any shape of solution before the gel.In addition, when agarose during near its gel point, the viscosity of solution uprises along with the beginning to form of hydrogel.
For the agarose beads that for example is used for chromatographic media, the solution that heated remains on more than the gel point, and becomes the liquid of immiscible heating through stirring, as mineral oil or vegetable oil, thereby forms bead.Then this two-phase material (agarose beads in the unmixing fluid) is cooled off, reclaim and obtain bead.Described bead then can former state be used for SEC, or further handle by the following method: crosslinked, the various combinations of catching chemicals or crosslinked and chemicals of adding, described chemicals such as affinity chemicals or part, positive charge or negative electrical charge and hydrophobe etc.
Someone attempts utilizing agarose structurally or form coating in the structure, rather than with itself as solid articles.For example, according to Cerro etc., Biotechnol.Prog 2003,19921-927 (Use of Ceramic monoliths as stationary phase in affinitychromatography), by ceramic bulk material being immersed in traditional agarose hot solution, remove unnecessary hot agarose solution in the bulk internal pore with compressed air then, cool off bulk subsequently, make agarose coating become gel, produce the thin agarose coating that only has activity on the surface of described bulk thus on the surface.
A subject matter of this painting method is to apply to be difficult to porous material is worked.In above-mentioned product, agarose must use (therefore needing to use heat-staple base material) under heating status.Another problem is can only produce only to have surface-active thin coating.This may be in part because due to the employed method of removing unnecessary agarose.Also can be because the full-bodied effect that Ago-Gel point and agarose temperature produce during near gel point.In addition, for having than the bulk pore size of the prior art hole base material that is much smaller relatively, it is impossible that the method for prior art is not said, but also be unusual difficulty.For these difficult reasons, being that pressurized passes some porous material and do not stave or damage its loose structure because air is difficult to easily in some cases, as situation for some fabric or perforated membrane.Therefore must use relative porous and hard bulk structure.
WO 00/44928 suggestion forms the agarose solution to temperature stabilization by using high-load (as: 8M) as chaotropic agents such as urea.The agarose of this invention is absorbed into and forms continuous phase in the porous carrier.Add entry carefully, so that form thin gel layer at agarose solution and the interface that added between the water.Gel layer prevents the agarose migration, but allows water and urea molecule further to move to the added water from agarose solution.This process lasts till that always agarose solution becomes gel in the space of porous substrate aperture.
A subject matter of art methods is that its preparation method can cause that the base material aperture stops up in a large number, thereby has seriously limited the convection current by porous carrier.
Needed a kind of just method that can on porous substrate, produce the room temperature water-soluble polymer coating.Particularly, needed is to go up the ability that produces room temperature water-soluble polymer base coating at the less relatively porous substrate of hole (0.01～1000 micron pore-size), it makes to have the good convection current of passing cell structure in described room temperature water-soluble polymer coating self, and has diffuse flow again.
By method of the present invention, be easy on porous substrate, obtain the water miscible polymer coating of room temperature thicker, porous relatively, comprise the surface that can have convection current that the porous material of diffuse flow can be arranged again.
Summary of the invention
The present invention relates to use the method for room temperature water-soluble polymer as coating, manufacturing coated structure.More specifically, the present invention relates to make the coating of room temperature water-soluble polymer, as absorption on the porous substrate or chromatogram coating.
Use the method for the present invention can be to the surface of any base material, comprise irregular material, be included in the layer that applies room temperature water-soluble polymer on its inner surface as porous material, and described water-soluble polymer can not stop up hole in a large number under the room temperature, thereby make convection current can pass described loose structure.In addition, the coating of room temperature water-soluble polymer is enough thick, can be at the inner diffuse flow that produces of room temperature water-soluble polymer layer self.
In one embodiment of the invention, to being used for room temperature water dissolubility polymer, solvent as glucan in this example etc., as adding one or more crosslinking agents, optional one or more pore formers (porogen), wetting agent or part in the water of (68 or 20 ℃) under the room temperature, form the solution of room temperature water dissolubility polymer such as glucan.Room temperature water-soluble polymer is applied to as on the preform constructions such as porous substrate, and solvent is evaporated.Heat coated substrate then at a certain temperature, so that room temperature water-soluble polymer is crosslinked, answer long enough heat time heating time, so that crosslinked polymer is abundant.If used pore former, then should be removed at this moment.In the present embodiment, that chooses use wantonly helps formation continuous coated relatively uniformly as wetting agents such as surfactants.
In another embodiment of the invention, to about room temperature, add one or more crosslinking agents, optional one or more pore formers, wetting agent and/or part in the aqueous solutions of polymers of (68 or 20 ℃), form the solution of room temperature water-soluble polymer.Then compound is coated in as on the preform constructions such as porous substrate.Make room temperature water-soluble polymer partial cross-linked, method both can be under certain temperature coating to be heated, only can make heat time heating time polymer moieties crosslinked, also can be only coating at room temperature to be placed a period of time, and it is partial cross-linked that polymer is taken place.Evaporating solvent then.Make polymer full cross-linked subsequently, method both can be under certain temperature coated substrate to be heated, being enough to heat time heating time make polymer full cross-linked, also can be only coating at room temperature to be placed a period of time, and it is described crosslinked to be enough to standing time make polymer to take place.If used pore former, then should be removed at this moment.In the present embodiment, that chooses use wantonly helps formation continuous coated relatively uniformly as wetting agents such as surfactants.
Description of drawings
Figure 1 shows that a embodiment according to the inventive method.
Figure 2 shows that another embodiment according to the inventive method.
Figure 3 shows that another embodiment according to the inventive method.
Figure 4 shows that another embodiment according to the inventive method.
Figure 5 shows that another embodiment according to the inventive method.
Figure 6 shows that another embodiment according to the inventive method.
The specific embodiment
The present invention relates to form on such as the base material of porous method, so that described base material keeps at least 20% of initial voidage and porosity such as the room temperature water-soluble polymer structure of coating.
Fig. 1 has shown first embodiment of described method with the form of block diagram.This method may further comprise the steps: the solution that a) forms room temperature water-soluble polymer at the solvent that is used for water-soluble polymer such as water, and add one or more crosslinking agents and pore former, b) with this solution-wet porous substrate, randomly remove excessive solution, c) solvent is evaporated from solution, making the surperficial consistent of coating and base material, d) make the full cross-linked room temperature water-soluble polymer of one or more crosslinking agents, and e) base material that applied of rinsing to be to remove the pore former and the crosslinking agent of usefulness not.In addition, optional step comprise as shown in Figure 2 for coating surface interpolation official energy.
Fig. 3 has shown another embodiment of described method with the form of block diagram.This method may further comprise the steps: a) in the solvent such as water of the room temperature water-soluble polymer that preferably contains one or more crosslinking agents and pore former, form the solution of room temperature water-soluble polymer, b) with this solution-wet porous substrate, randomly remove excessive solution, c) make solution only partial cross-linked, d) water is evaporated from solution, make the surperficial consistent of coating and base material, e) making the full cross-linked room temperature water-soluble polymer of coated substrate, and f) base material that applied of rinsing reaches the not crosslinking agent of usefulness to remove pore former.In addition, optional step comprises and is illustrated in figure 4 as coating surface interpolation official energy.
The solution of above-mentioned method for optimizing is formed by room temperature water-soluble polymer, the water that is used for described room temperature water-soluble polymer and/or other solvent, one or more optional pore formers of being used for one or more crosslinking agents of described room temperature water-soluble polymer and being used for coating material.
Preferably at room temperature or near room temperature room temperature water-soluble polymer, water or other solvent, crosslinking agent and optional pore former are mixed.Because the room temperature water-soluble polymer major part is easy to dissolve in water, therefore seldom or not need heating, but add fast process if desired, then can use heating, as long as heat is enough low, can avoids producing any too early crosslinked initiation and get final product.All components can be mixed one and go on foot this process of finishing.Perhaps, also can earlier room temperature water-soluble polymer be added in the solvent of water for example, make the room temperature water-soluble polymer dissolving.Can add crosslinking agent and pore former then.
If solution has passed through heating, preferably make its cooling.
Cooling can be carried out naturally, if desired, also can force cooling solution.This solution is solution stable, non-gelling under the room temperature.
The kind of employed room temperature water-soluble polymer can be determined according to the desired performance of final coating.The agarose of the cellulose of glucan, replacement, low gel point or room temperature gel point and polyvinyl alcohol (PVA) etc. are the representative instances of this base polymer.The ultimate density that should make room temperature water-soluble polymer when preparing described solution be total final solution weight about 0.1%～about 20%, preferred about 1%～about 10%, more preferably from about 2%～about 6%.
Although water is the preferred solvent of room temperature water-soluble polymer, total also can add in final solution weight be up to a spot of cosolvent of 20%, to improve the dissolubility of room temperature water-soluble polymer.The example of suitable cosolvent is dimethylacetylamide or methyl-sulfoxide.Other cosolvent also is well known to those skilled in the art.
Can use industrially to be usually used in containing crosslinked any chemicals such as polyhydric material such as glucan and layer to be carried out crosslinked, the limiting examples of these chemicals has chloropropylene oxide or other multi-functional epoxy compound, various bromyl chemicals or other multifunctional halide; Formaldehyde, gluteraldehyde and other multifunctional aldehyde, two (2-ethoxy) sulfone, dimethyldichlorosilane, dimethylol urea, dimethylol ethylene urea, diisocyanate ester or polyisocyanates etc.
Pore former can be used among the present invention, the effect of pore former can be can played in the present invention although found the solvent of water especially.Yet, preferably use other pore former, because they can provide bigger space (latitude) and can control the formation of coating mesopore and the size of hole.Suitable pore former can be made up of one or more water-soluble polymers, and for instance, it comprises polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, comprises the water-soluble polyacrylamide of the polyacrylamide of replacement, as polydimethylacrylamiin.Believe that these polymer can play " pore former ", because in the porous substrate that applied uses, but their control free permeations are with the amount of the coating volume of dissolving solute.
These pore formers can be in the initial dissolution step mix use with room temperature water-soluble polymer, perhaps can form the back at solution but are dissolved in the solution before it applies again.The cohesion of solution must be noted that not add excessive pore former, because may take place.The ratio of pore former and room temperature water-soluble polymer can be about 0.1～10.Preferred pore former is polyvinyl alcohol and polyacrylamide.
Because these pore formers are water miscible, so after described process finishes, also be easy to remove these pore formers by water-bath or rinse step.
If needs are arranged, also can use non-water-soluble pore former, as long as be used to remove the solvent of pore former or the coating that extract can be beneficial to room temperature water-soluble polymer.
When the formation porous substrate is used coating, after forming, solution selects porous substrate again.
Base material can be such as tablets such as the fiber of fabric, non-woven, mat, felt or films; Perhaps can be three-dimensional structure, as sponge, poly-(HIPES); Or other bulk structure, as honeycomb; Or the porous bead, as controlled cellular glass, expanded polystyrene bead, silica, zirconia etc.Preferred substrates is by Woven fabric, supatex fabric or film formed tablet.
Supatex fabric is the prepared flat porous sheet of fiber of the separation that directly bonded together by by the use of thermal means or chemical method by the fiber that tangles or monofilament.Typically, the medium that provides of nonwoven fabric manufacturers has 1～500 micron average flow hole (MFP) grade.For supatex fabric, loose structure is exactly the fiber that twines, and hole refers to interfibrous tortuous space.For the felted fabric, the implication of hole is similar.Preferred supatex fabric is that its model is FO2463 by the Freudenberg Nonwovens NA manufacturing of Massachusetts Lowell.
Warp thread and weft yarn are interweaved with regular pattern or braiding style with predetermined angle each other and make fabric.Typically weft yarn and warp thread constitute the angle of about 90 degree.Other angle commonly used includes but not limited to 30,45,60 and 75 degree.Cause by weaving method that fibre machinery is interlocked and keep the integrality of fabric.The degree of dangling of fabric (fabric is to the identical ability of complex surface), surface flatness and stability are mainly woven the control of style, as plain weave weave, twill weave, satin weave weave, double cut weave and leno etc.In the case, the hole of base material is interfibrous space, and its tortuous characteristics are not obvious.
The bulk body is the porous materials piece.They can be rectangles, cylindrical or be foamed into other shape.The example is a ceramic bulk material, and it is the rectangle of filling or the ordered structure of triangular capillary.These bulks can be provided by the Corning company of Alabamian Engelhard company and New York Corning.A kind of macromolecule bulk of form is prepared by the sintered plastics particle of the FairburnPorex company manufacturing of Georgia.
Poly (HIPES) [High Internal Phase Emulsion] material is isotropic perforate macromolecule foam stable on the mechanics.The structure of these and other macroporous polymer is seen and is set forth in " Porous polymersand resins for biotechnological and biomedical applications ", H.-P.Hentze and M.Antonietti, Reviews in Molecular Biotechnology 90 (2002) 27-53.
Described base material can be formed by the various materials that comprise glass, plastics, pottery and metal.
Borosilicate glass is an example of suitable glass.It can form the porous bead of glass isolator or sintering, can form sheet material, as can be from the resulting controlled Bio-Glas of the Millipore company of Massachusetts Billerica.
Can use various potteries, these potteries can be based on more common silicate chemistry thing, or rarer chemicals, as yttrium, zirconia and titanium etc., and their mixture.They can form fiber, mat, felt, bulk or film.
Metal comprises sintered sheets and structure, as filter sintered stainless steel or nickel, wire gauze sieve and non-woven mat, fabric and felt, as stainless steel wool.
Preferred substrate is by plastics, more preferably thermoplastic makes.Preferred thermoplastic includes but not limited to polyolefin, as (sheathed) polyethylene/polypropylene fiber of polyethylene, polypropylene, sheath; PVDF, polysulfones, polyether sulfone, polyarylsufone, polyphenylsulphine, polyvinyl chloride, PET and polyamide.
Room temperature water-soluble polymer solution former state ground can be used for coating.Preferably in solution, add coating modified material, improve and control with structure and performance to final coating.
One type coating is material modified comprise can be miscible with described solution volatile organic matter.The example is a monohydric alcohol, as methyl alcohol, ethanol and propyl alcohol.The concentration that they use can reach the muddy slightly solution of generation at the most.These alcohol of higher consumption can produce the precipitation of room temperature water-soluble polymer.Preferred amount for solution in the water equal-volume, more preferably the alcohol of Jia Ruing is about 40%～about 60% of water.Preferred alcohol is methyl alcohol.Also can use mixable ketone, as acetone, but must be careful, because the solubility of room temperature water-soluble polymer in the ketone aqueous mixtures is lower.Also can consider any mixture of two or more these materials.
Another kind of coating modified material comprises nonvolatile mixable organic matter.Its limiting examples comprises glycerine, ethylene glycol, methyl pentanediol, diethylene glycol (DEG), propane diols, triethylene glycol, the methyl of ethylene glycol-, ethyl-, or n-butyl ether, the dimethyl of ethylene glycol-or Anaesthetie Ether, the glycol dinitrate ether acetate, the ethylene glycol diethyl ether acetate, the diethylene glycol (DEG) methyl ether, diethylene glycol monoethyl ether, the diethylene glycol (DEG) n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diethylene glycol dimethyl ether acetate, the diethylene glycol diethyl ether acetate, N-methylmorpholine and N-ethylmorpholine etc.The example of this class material also has low-molecular-weight polyethylene glycol.Also can consider any mixture of two or more these class materials.
In order to obtain best solution coating, can in solution, add one or more surfactants.The various combination of solution kind and base material requires to test, to determine to select for use best surfactant.Found that anion surfactant is available, is preferably anionic fluorinated surfactant.Wherein especially preferred 3M FC-99 and FC-95, perhaps other supplier's counterpart.In the gross weight of solution, the amount of surfactant is preferably about 0.001～about 10%, and more preferably from about 0.01～about 5%.
With coating base material is flooded, for example in coating is bathed, base material is soaked, coating is coated on the porous substrate with any other method known to scraper, nozzle, curtain coater, roll coater, extrusion coater or those of ordinary skills.Remove unnecessary coating, for example by absorb or rock coated substrate, with roll pressed, the surface of coated substrate is scraped, perhaps blow the surface of base material with air or gas.
Remove the solvent of coating by being evaporated to small part then.Preferred solvent is a water, and makes the solvent evaporation by controlled vaporization, so that product is covered with whole base material relatively equably.If desired, can use warm air (preferably its temperature is 20～50 ℃ (preferably are lower than crosslinking agent and can begin to cause polymer crosslinked temperature fast)), microwave drying and vacuum drying oven drying to wait to control and/or accelerate evaporates.This can make the room temperature water-soluble polymer coating form on substrate surface, and the sense of touch of this coating is dry, but wherein still contains residual moisture.
Then, preferably the base material that applied is heated (according to selected crosslinking agent, typically from about 70 to 95 ℃), to cause the crosslinked of room temperature water-soluble polymer.Perhaps, at room temperature can spontaneous in time generation crosslinked.If require like this, the base material that can at room temperature will apply simply leaves standstill appoints crosslinked generation on one side.
Then water and or other can remove the liquid rinse coated substrate of pore former (if having) and untapped crosslinking agent (if having).Rinse step is carried out under about 15 ℃～about 50 ℃, preferred 20 ℃～50 ℃ of temperature usually.Coated substrate is coated with the coating of permeable biomolecule at least in the part of its all surfaces (outer surface and inner surface).Preferably coating is coated on the base material relatively equably.Its whole surface is all covered coats.Also preferred even relatively simultaneously at the thickness of whole base material floating coat.
Described coating can connect one or more senses that comprise part, as A albumen or G albumen, each is natural type or reorganization derivative type, and make them to corroding the more stable A albumen or the modified of G albumen etc., the amino benzimidazole (AMI) of various chemical parts such as 2-, aminomethyl benzimidazole (AMBI), mercaptoethyl pyridine (MEP) or mercaptobenzimidazole (MBI), or the various coating that make are cationic, anionic, close, that dredge or charged chemicals, and are known as forming technical field at medium.
Employedly in the liquid chromatogram be applicable to that functional group of the present invention includes, but are not limited to following group: interaction group, chelate or the chelation group of ion-exchange, biological affinity, hydrophobic grouping, the group that can be used for the covalency chromatogram, close sulphur, the interactional group of so-called π-π, hydrogen bonding and hydrophilic radical etc. are arranged with target compound.
These groups can implement coated with after add and be linked on the base material, or also can join in the initial soln, and utilize crosslinked and it is combined (as illustrated in Figures 5 and 6) with coating.
Can be placed on medium in the fixture then, make one liquid stream (component that contains one or more requirements of catching) medium of flowing through, so that the component that requires is separated with the other parts of liquid.Typically, what catch from liquid is desired component, comprises that the other parts of the liquid of impurity then can flow away.Perhaps, the component of requirement can flow away, and impurity can be by capture medium.Washing medium utilizes the variation of ionic strength or pH value etc. that catches is carried out wash-out to remove any material that does not have combination then.
Need or requirement if having, can on first coating, apply second or overbrushing layer more, to meet the requirements of coating layer thickness etc.
Even coating, base material also have high permeability and good flowing and capacity characteristic.Base material is that the oneself supports, and can be coating platform or structural network are provided.
Selected base material is preferably highly porous, and its inside can have minimum but sufficient wall or solid material like this, with complete and high porosity that structure is provided with flow.The excursion of pore size is at about 0.01～about 1000 microns, preferred 10～300 microns, more preferably from about 30～about 200 microns, also more preferably 30～100 microns, specifically according to fluid and require the composition of therefrom catching and decide.For example, in the application of the protein of catching requirement from a kind of cell soup unlimpid, dissolved cell (broth), the hole of base material should be enough big, makes described soup high velocity stream that the good penetration rate be arranged when base material, and high-caliber catching also can both be arranged at each passage, as greater than 50%.In above-mentioned application, preferred aperture should be about 100～about 300 microns.The application that begins from limpid or clean feed stream, the aperture can be smaller, is about 30～about 60 microns.For the labware that is used for various solution conditions as syringe filter or microtiter plates etc., when the solution that uses is clean and high dilution, preferred littler hole.These apertures are about 0.1 micron～10 microns.
Coating itself in fact also is a porous, so their permeable biomolecule.Preferably in its volume, absorbable biological molecule in the hole that promptly in coating, forms.Coating has enough thickness to form these holes, and there is diffuse flow to flow into wherein, therefore can on the independent capacity in surface, increase the population size of described structure, can also increase the selectivity of catching in some applications, but they are enough thin, so that diffusion length is limited, and can not become and catch or discharge unfavorable factor on the performance of biomolecule.
Typically, described coating constitutes at least 1% of coated substrate cumulative volume.Be preferably about 5%～about 80% of coated substrate cumulative volume.
Use another kind of measuring method, on an average, described coating can with the average diameter of substrate pores never the average diameter of coated substrate reduce about 1%～about 80%, preferred about 10%～about amount of 50%, more preferably from about 20%～about 50%.
Use another kind of measuring method, described coating can with the permeability of base material never the permeability of coated substrate reduce about amount of 5%～about 80%.
The another kind of method of determining the used coating amount is relative (fractional) porosity, and fractional porosity is for guaranteeing to flow through the coated substrate outbalance.Fractional porosity is for the volume of the obtainable coated substrate of positive Treatment Solution and the ratio of the cumulative volume of coated substrate.Higher fractional porosity can give coated substrate higher intrinsic fluid ability.For coated substrate of the present invention, preferred fractional porosity is about 0.35～about 0.55.
The thickness of coating is generally about 1～100 micron, and preferred about 2～about 20 microns, more preferably from about 5～about 15 microns.
Change in the scope that the pore diameter of coating can be used always in chromatogram, or about 1～about 200 nanometers, preferred about 1～about 100 nanometers, 1～50 nanometer more preferably from about.Its size should be enough to make the material of requirement such as protein or other biomolecule or as synthetic molecules such as oligonucleotide etc. by or infiltration wherein.
In preferred embodiments, coating covers on the surface of base material with suitable homogeneous thickness.For this reason, require to carry out routine test, coating solution viscosity, substrate pores size, the method for removing redundant solution and dry run etc. are optimized, to reach this purpose.In general, in case understood the content that the present invention instructed, those skilled in the art just can roughly determine the coating layer thickness that can be optimized the speed of the volume that requires solute and absorption and release.He just can choose pore-size and porosity suitable substrates then, and it is mobile that this thickness can not reduced too much.The routine test and the error experiments of the content of instructing according to the present invention can provide the approach of correctly being filled a prescription with drying means for skilled professional and technical personnel.
In preferred embodiments, all surfaces all are coated with porous coating basically, and preferably it has homogeneous thickness.
Structure of the present invention has the good penetration rate.Permeability is normally defined the flow of fluid and the ratio of institute's applied pressure.The present invention has inherent flowing, even when pressure relatively low (1psi), and under higher relatively flow velocity as 300ml/hr or when higher, still have stable flow rate.Preferred its has the linear relatively permeability of about 1ml/hr～about 500ml/hr in certain pressure limit.
This structure also has good capacity.Usually, this means and be positioned at that following substrate surface is long-pending to be compared that described structure has higher relatively surface and can directly contact with the fluid of the structure of flowing through.Typically, the surface area height at least 25% of the surface area ratio base material that structure of the present invention had itself, preferred 50%, more preferably 75% can increase the breakthrough capacity to capture material like this, makes mass transport (diffusion transport) faster.
Use room temperature soluble polymer solution and method of the present invention, by solution being coated on the surface of object, crosslinked by evaporation subsequently except that desolvating, carrying out then, can act on any surface of polymer coating, comprise surface as irregular materials such as porous materials.After the formation of coating is finished,, can remove pore former and untapped crosslinking agent by for example extracting with fluid composition.
Following examples are for example understood principal character of the present invention.
Embodiment 1: the formation of glucan coating solution
According to following steps, applying hole size with glucan is that about 100 microns, porosity are about 65% polyolefin nonwoven fabric.The preparation coating solution, make this coating solution contain the 15g glucan (500,000MW), as the 1g polyethyleneglycol diglycidylether of crosslinking agent, as the water of the 20g polyacrylamide solution of pore former (in water 10%), 1.5g 1N sodium hydroxid and 62.5g.Supatex fabric is exposed in the above-mentioned glucan coating solution, makes fabric fully by solution-wet.Then wet fabric is placed between two polyethylene films, pushes the redundant solution of removing fabric face gently; From diaphragm, take out fabric then, at room temperature let alone drying.Then the coated fabric of doing was placed in 85 ℃ the stove 4 hours, it is crosslinked that glucan is produced.Rinsing several coated fabric in water is removed any unreacted matters that comprises polyacrylamide then.The fabric that applied is kept in the water.
Embodiment 2: usefulness sulfopropyl (SP) is functionalized to the cross-link dextran coating
The fabric that the cross-link dextran of embodiment 1 was applied is immersed in the sodium hydroxide solution that contains 6g bromo propane sulfonic acid sodium, 94g 1M, temperature with this solution rises to 50 ℃ then, at the functionalization that it was carried out under this temperature 16 hours.With the functionalized coated fabric several of the described sulfopropyl of water rinse, remove unnecessary reactant and alkali; Fabric is kept in the water.After measured, the permeability of modified fabric in the acetic acid of pH4.5 is received buffer solution is 1.78cm
2/ min-psi, electrical conductivity is 8mS.
The combined with protein of the glucan institute coated fabric that embodiment 3:SP is functionalized
The 13mm disk of the fabric that glucan that the SP of embodiment 2 is functionalized applies is immersed in that 6ml pH is 7, electrical conductivity is 2mS and contains in the phosphate buffer that concentration is the 1g/L lysozyme, and fabric was under agitation at room temperature kept in touch 16 hours with protein solution.After 16 hours, the lysozyme concentration in the protein solution is measured, calculated the amount that is combined in the protein on the fabric according to the stereometer of 13mm fabric disk.The combined with protein ability of fabric is 28mg lysozyme/ml fabric after measured.
Embodiment 4: crosslinked agarose coating
6g agarose powder (the XII type obtains from Sigma-Aldrich) is added the 40g water, under 95 ℃ temperature, keep heating, mixture is stirred until the initial soln that forms agarose.Should be cooled to room temperature by free-pouring initial soln, described solution becomes the gel that does not have free-flowing character fully under this temperature.In this gel, add the 15g zinc chloride, this mixture is heated to 95 ℃ once more, form uniform solution up to gel and salt dissolving while stir.Then this solution is cooled to room temperature, solution is keeping free-flowing properties under this temperature.With NaOH or other alkali the pH value of cooling solution is adjusted to 10-14.The cross-linking compounds that (adding) is suitable, as any industrial crosslinked chemicals that are usually used in containing polyhydroxy substance, as agarose, these chemicals are non-limiting instance, the aqueous solution of water-soluble cross-linker comprises chloropropylene oxide or other multi-functional epoxy compound, preferred 1,4-butanediol diglycidyl ether or ethylene glycol diglycidylether, various bromyl chemicals or other multifunctional halide; Formaldehyde, gluteraldehyde and other multifunctional aldehyde, two (2-hydroxyethyl) sulfone, dimethyldichlorosilane, dimethylol urea, dimethylol ethylene urea, diisocyanate ester or polyisocyanates etc.The adding concentration of these crosslinking agents is about 5%.Mix when forming final agarose solution, in this solution, add the methyl alcohol of 39.9g and the Fluorad FC-95 fluorine surfactant (3M company) of 0.1g.This final solution at room temperature remains liquid.
Can apply the aperture according to following steps is that about 100 microns, porosity are about 65% polyolefin nonwoven fabric (the F02463 type originates from the FreudenbergNonwovens NA of Massachusetts Lowell).Employed is as above prepared coating solution.This supatex fabric is exposed in the above-mentioned coating solution, makes this fabric fully wetting by solution.Wet then fabric is placed between two polyethylene films, pushes the redundant solution of removing fabric face gently; From diaphragm, take out fabric then, at room temperature let alone drying.The coated fabric of doing was placed in 85 ℃ the stove 4 hours, it is crosslinked that agarose is produced again.Then with water rinse for several times, to remove any unreacted matters with coated fabric.The fabric that applied is kept in the water.
Claims (28)
1. method that forms the porous substrate of coating, it may further comprise the steps:
A) provide one or more room temperature water-soluble polymer materials, the solvent that is used for room temperature water-soluble polymer, one or more crosslinking agents that are used for room temperature water-soluble polymer, and porous substrate;
B) described room temperature water-soluble polymer, solvent and one or more crosslinking agents are added to together as mixture;
C) described mixture is stirred one sufficiently long period, with the dissolving all components and form the solution of room temperature water-soluble polymer;
D) described room temperature water-soluble polymer solution is coated on the porous substrate;
E) coating on the dry described base material;
F) make described coating crosslinked on base material; And
G) base material of the described coating of rinsing is removed any one or more residual crosslinking agents from coated structure, wherein
Described room temperature water-soluble polymer is selected from following group: glucan, cellulose, agarose and polyvinyl alcohol.
2. the method for claim 1, it also comprises c) and d) between make the partial cross-linked step of coating solution with the method that is selected from following group: be enough to make under the partial cross-linked temperature of room temperature water-soluble polymer solution solution heating a period of time, be enough to make under the partial cross-linked temperature of room temperature water-soluble polymer solution coating protection is stayed following a period of time of room temperature.
3. the method for claim 1, it also comprises other h) step: make the substrate passed extra treatment step that applied.
4. the method for claim 1, it also comprises other h) step: make the substrate passed other treatment step that makes the surface connect one or more chemicals, sense and functional group that applied.
5. the method for claim 4 wherein makes the surface connect one or more chemicals, sense and functional group and is selected from following group: interaction group, chelate or the chelation group of protein ligands, chemical part, ion-exchange group, biological affinity group, hydrophobic grouping, the group that can be used for the covalency chromatogram, close sulphur, with target compound the interactional group of so-called π-π, hydrogen bonding group, hydrophilic radical, and their combination are arranged.
6. the method for claim 1, wherein one or more pore formers are added in the described solution, described one or more pore formers are selected from following group: the polyacrylamide of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyacrylamide, replacement and their mixture.
7. the process of claim 1 wherein that described one or more crosslinking agents are selected from following group: multi-functional epoxy compound, multifunctional titanium dioxide bromine cationic compound, multifunctional halide, multifunctional aldehyde, two (2-hydroxyethyl) sulfone, dimethyldichlorosilane, dimethylol urea, dimethylol ethylene urea, vulcabond, polyisocyanates and their mixture.
8. the process of claim 1 wherein that the described solvent that is used for room temperature water-soluble polymer is selected from following group: the water and the aqueous solution.
9. the process of claim 1 wherein that described porous substrate is selected from following group: glass, plastics, pottery, metal, Woven fabric, supatex fabric, felt, mat, fiber, porous bead, porous sponge, porous bulk and perforated membrane.
10. method that on porous substrate, forms coating chromatogram or absorption, it may further comprise the steps:
A) provide room temperature water-soluble polymer, be used for room temperature water-soluble polymer solvent, be used for one or more crosslinking agents of room temperature water-soluble polymer and be used for one or more pore formers of room temperature water-soluble polymer;
B) by stirring, form room temperature water-soluble polymer, be used for room temperature water-soluble polymer solvent, be used for one or more crosslinking agents of room temperature water-soluble polymer and be used for the solution of room temperature water-soluble polymer of one or more pore formers of room temperature water-soluble polymer;
C) provide porous substrate;
D) with the solution-wet porous substrate of described room temperature water-soluble polymer, make it apply all surface of porous substrate substantially;
E) from the solution evaporating solvent of described coating, on the surface of porous substrate, to form the coating of room temperature water-soluble polymer;
F) be heated to uniform temperature by the base material that will apply and keep one sufficiently long period, it is crosslinked to make room temperature water-soluble polymer pass through one or more crosslinking agents, makes the base material that applied crosslinked, and
G) base material that applied of rinsing is removed any one or more residual crosslinking agents and one or more pore formers from the base material that room temperature water-soluble polymer applied, wherein
Described room temperature water-soluble polymer is selected from following group: glucan, cellulose, agarose and polyvinyl alcohol.
11. the method for claim 10, wherein said solution also comprise one or more wetting agents that are selected from following group: alcohol, volatile organic matter, surfactant and their blend.
12. the method for claim 10, it also is included in d) and e) between by being selected from the method in following group, the step of partial cross-linked described solution after solution being coated to above the base material: be enough to make under the partial cross-linked temperature of room temperature water-soluble polymer solution solution heating a period of time, be enough to make under the partial cross-linked temperature of room temperature water-soluble polymer solution coating protection is stayed following a period of time of room temperature.
13. the method for claim 10, wherein said one or more pore formers are selected from following group: the polyacrylamide of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyacrylamide, replacement and their mixture.
14. the method for claim 10, wherein said one or more crosslinking agents are selected from following group: multi-functional epoxy compound, multifunctional titanium dioxide bromine cationic compound, multifunctional halide, multifunctional aldehyde, two (2-hydroxyethyl) sulfone, dimethyldichlorosilane, dimethylol urea, dimethylol ethylene urea, vulcabond, polyisocyanates and their mixture.
15. the method for claim 10, it also is included in before the step g) official can chemicals be administered to step on the room temperature water-soluble polymer coating of crosslinked mistake.
16. the method for claim 10, its also be included in described room temperature water-soluble polymer solution be coated to before the base material can step from chemicals to its interpolation official.
17. the method for claim 1, it also is included in the step b), before being coated to base material, described room temperature water-soluble polymer solution adds one or more sense chemicals to it, sense and functional group, these chemicals, sense and functional group are selected from following group: protein ligands, the chemistry part, ion-exchange group, biological affinity group, hydrophobic grouping, the group that can be used for the covalency chromatogram, the interaction group of parent's sulphur, chelate or chelation group, with target compound the interactional group of so-called π-π is arranged, the hydrogen bonding group, hydrophilic radical, and their combination.
18. the method for claim 10, it also comprises the step that the official can chemicals be administered to the room temperature water-soluble polymer coating of crosslinked mistake, and wherein said sense chemicals are selected from following group: interaction group, chelate or the chelation group of chemical part, protein ligands, ion-exchange group, biological affinity group, hydrophobic grouping, the group that can be used for the covalency chromatogram, close sulphur, with target compound the interactional group of so-called π-π, hydrogen bonding group, hydrophilic radical, and their combination are arranged.
19. the method for claim 10, wherein said porous substrate are selected from following group: glass, plastics, pottery, metal, Woven fabric, supatex fabric, felt, mat, fiber, porous bead, porous sponge, porous bulk and perforated membrane.
20. the method for claim 10, wherein said solvent evaporates by air movement.
21. being higher than room temperature but being lower than under the crosslinking temperature of room temperature water-soluble polymer in temperature, the method for claim 10, wherein said solvent evaporate by air movement.
22. a method that forms coating chromatogram or absorption on porous substrate, it may further comprise the steps:
A) provide room temperature water-soluble polymer, be used for room temperature water-soluble polymer solvent, be used for one or more crosslinking agents of room temperature water-soluble polymer and be used for one or more pore formers of room temperature water-soluble polymer;
B) by stirring, form room temperature water-soluble polymer, be used for room temperature water-soluble polymer solvent, be used for one or more crosslinking agents of room temperature water-soluble polymer and be used for the solution of room temperature water-soluble polymer of one or more pore formers of room temperature water-soluble polymer;
C) provide porous substrate;
D) with the solution-wet porous substrate of described room temperature water-soluble polymer, make it apply all surface of porous substrate substantially;
E) make coating solution crosslinked on porous substrate top;
F) from the coating solution evaporating solvent, on the surface of porous substrate, to form the coating of room temperature water-soluble polymer;
G) crosslinked fully basically by being selected from the method in following group, making the base material that applied: as to be enough to make under the temperature of room temperature water-soluble polymer solution crosslinking to solution heating a period of time; Coating protection is stayed following a period of time of room temperature being enough to make under the temperature of room temperature water-soluble polymer solution crosslinking, and
H) base material that applied of rinsing is removed any one or more residual crosslinking agents and one or more pore formers from the base material that room temperature water-soluble polymer applied, wherein
Described room temperature water-soluble polymer is selected from following group: glucan, cellulose, agarose and polyvinyl alcohol.
23. the method for claim 22, wherein making the partial cross-linked step e) of solution that applied on porous substrate is to be undertaken by the method that is selected from following group: be enough to make under the partial cross-linked temperature of room temperature water-soluble polymer solution solution heating a period of time, be enough to make under the partial cross-linked temperature of room temperature water-soluble polymer solution coating protection is stayed following a period of time of room temperature.
24. the method for claim 23, its also be included in described room temperature water-soluble polymer solution be coated to before the base material can step from chemicals to its interpolation official.
25. the method for claim 24, wherein said functional compound are the functional groups that is selected from following group: interaction group, chelate or the chelation group of chemical part, protein ligands, ion-exchange group, biological affinity group, hydrophobic grouping, the group that can be used for the covalency chromatogram, close sulphur, the interactional group of so-called π-π, hydrogen bonding group, hydrophilic radical, and their combination are arranged with target compound.
26. the method for claim 22, it also is included in step h) before to crosslinked room temperature water-soluble polymer coating coating official can chemicals step.
27. the method for claim 26, wherein said functional compound are the functional groups that is selected from following group: interaction group, chelate or the chelation group of chemical part, protein ligands, ion-exchange group, biological affinity group, hydrophobic grouping, the group that can be used for the covalency chromatogram, close sulphur, the interactional group of so-called π-π, hydrogen bonding group, hydrophilic radical, and their combination are arranged with target compound.
28. the method for claim 22, wherein said porous substrate are selected from following group: glass, plastics, pottery, metal, Woven fabric, supatex fabric, felt, mat, fiber, porous bead, porous sponge, porous bulk and perforated membrane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54196204P | 2004-02-05 | 2004-02-05 | |
| US60/541,962 | 2004-02-05 | ||
| US60/548,407 | 2004-02-27 |
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| CNB2005800039797A Division CN100540123C (en) | 2004-02-05 | 2005-02-03 | Form the method for coated structure |
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| CN101612528A true CN101612528A (en) | 2009-12-30 |
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| CN200910164646A Pending CN101612528A (en) | 2004-02-05 | 2005-02-03 | Form the method for coated structure |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103702740A (en) * | 2011-06-06 | 2014-04-02 | 瑞士材料试验研究所 | Porous adsorbent structure for adsorption of co2 from a gas mixture |
| CN107847875A (en) * | 2015-08-17 | 2018-03-27 | Emd密理博公司 | Agarose ultrafiltration composite membrane for the separation based on size |
| CN110856804A (en) * | 2018-08-24 | 2020-03-03 | 万华化学集团股份有限公司 | Chlorine-resistant porous membrane and preparation method thereof |
| CN113663535A (en) * | 2020-05-13 | 2021-11-19 | 中国石油化工股份有限公司 | High-performance thin-layer composite membrane and preparation method and application thereof |
| CN113769787A (en) * | 2021-08-24 | 2021-12-10 | 同济大学 | Photocatalytic material based on plastic optical fiber and preparation method and application thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2675538B1 (en) * | 2011-02-16 | 2015-03-25 | Dow Corning Corporation | Method of coating a porous substrate |
| GB201310894D0 (en) * | 2013-06-19 | 2013-07-31 | Univ Singapore | Surface modification of medical or veterinary devices |
| CN106622181B (en) * | 2015-10-30 | 2019-08-02 | 中国科学院大连化学物理研究所 | A kind of immobilized metal affinity chromatography material and its preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000044928A2 (en) * | 1999-01-27 | 2000-08-03 | Halaka Folim G | Materials and methods for the purification of polyelectrolytes |
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2005
- 2005-02-03 CN CNB2005800039797A patent/CN100540123C/en not_active Expired - Fee Related
- 2005-02-03 CN CN200910164646A patent/CN101612528A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000044928A2 (en) * | 1999-01-27 | 2000-08-03 | Halaka Folim G | Materials and methods for the purification of polyelectrolytes |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103702740A (en) * | 2011-06-06 | 2014-04-02 | 瑞士材料试验研究所 | Porous adsorbent structure for adsorption of co2 from a gas mixture |
| CN107847875A (en) * | 2015-08-17 | 2018-03-27 | Emd密理博公司 | Agarose ultrafiltration composite membrane for the separation based on size |
| CN107847875B (en) * | 2015-08-17 | 2021-10-22 | Emd密理博公司 | Agarose ultrafiltration composite membranes for size-based separations |
| US11358102B2 (en) | 2015-08-17 | 2022-06-14 | Emd Millipore Corporation | Agarose ultrafiltration membrane composites for size based separations |
| CN110856804A (en) * | 2018-08-24 | 2020-03-03 | 万华化学集团股份有限公司 | Chlorine-resistant porous membrane and preparation method thereof |
| CN113663535A (en) * | 2020-05-13 | 2021-11-19 | 中国石油化工股份有限公司 | High-performance thin-layer composite membrane and preparation method and application thereof |
| CN113663535B (en) * | 2020-05-13 | 2022-11-18 | 中国石油化工股份有限公司 | High-performance thin-layer composite membrane and preparation method and application thereof |
| CN113769787A (en) * | 2021-08-24 | 2021-12-10 | 同济大学 | Photocatalytic material based on plastic optical fiber and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1913958A (en) | 2007-02-14 |
| CN100540123C (en) | 2009-09-16 |
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