CN105903270A - Filter material capable of efficiently filtering out leukocyte and thrombocyte and preparation method thereof - Google Patents
Filter material capable of efficiently filtering out leukocyte and thrombocyte and preparation method thereof Download PDFInfo
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- CN105903270A CN105903270A CN201610471087.XA CN201610471087A CN105903270A CN 105903270 A CN105903270 A CN 105903270A CN 201610471087 A CN201610471087 A CN 201610471087A CN 105903270 A CN105903270 A CN 105903270A
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- modified
- filtering material
- polymer
- hematoblastic
- fibroin albumen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
- B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/02—Blood transfusion apparatus
- A61M1/0259—Apparatus for treatment of blood or blood constituents not otherwise provided for
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
- B01D2239/0492—Surface coating material on fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0618—Non-woven
Abstract
The invention relates to a filter material capable of effectively filtering out substances which are contained in a blood preparation for transfusion and cause transfusion side effects and a preparation method thereof, in particular to a filter material capable of efficiently filtering out leukocyte and thrombocyte and a preparation method thereof. The filter material is prepared from a hydrophobic resin fiber filter base material and a modified polymer, wherein the surface of the hydrophobic resin fiber filter base material is coated with the modified polymer. The hydrophobic resin fiber filter base material is polyester fiber non-woven fabric, and the modified polymer is prepared from amidation-modified silk fibroin, polyamide-polyamine-epichlorohydrin and polyurethane at the mass ratio of (0.5-2):(0.05-0.4):1. The filter material has a high filter rate on leukocyte and thrombocyte; besides, the filter material has a low modified polymer elution rate, so that contamination caused by dissolved matter is avoided.
Description
Technical field
The present invention relates to filtering material contained, that cause transfusion adverse effects material in the Blood Preparations for effectively removing blood transfusion
And preparation method thereof, it is specifically related to a kind of efficiently filtrating leukocytes and hematoblastic filtering material and preparation method thereof.
Background technology
Containing substantial amounts of leucocyte in undressed whole blood or blood component preparation, many side effects in input patient body, can be caused,
As: graft versus host disease(GVH disease) after nonhemolytic febrific reaction (NHFR), ARDS (ARDS), blood transfusion
(GVHD), Inefficacy of Platelets Transfusion etc..This is owing to the donor white blood cells repeatedly inputted and receptor occur alloimmunity anti-
Caused by the leukocyte antibody answered and produce.Additionally, the input of leucocyte is also possible to propagate correlated virus, such as human cytomegalovirus
(CMV), human immunodeficiency virus (HIV), human T-lymphocyte virus (HTLV-I) etc..Medical expert exists always both at home and abroad
The method seeking effectively to remove leucocyte, be once used has centrifugal process, washing method, freezing, irradiation method and filtration method,
Wherein filtration method with its safety, simple, quickly, rejection rate advantages of higher accepts by many countries.In filtration method, logical
Cross application non-woven fabrics or there is the method that the porous material in intercommunication space removes leucocyte as filter medium adhesion or absorption
It is widely used.The difference of deformability when utilizing the diameter difference of leucocyte and other haemocytes and pass through filter material, and filter
The difference of Hemadsorption power is made leucocyte separate with other haemocytes by material surface.
Additionally, research shows that blood platelet also can induce body to produce antiplatelet antibody.Antiplatelet antibody is a kind of autoantibody,
Histoorgan nonrecognition to self, can attack the histoorgan of self, thus cause damage, therefore, in order to reduce because of blood transfusion
Platelet and the side effect that causes, people are devoted to that research is a kind of removes hematoblastic means while removing leucocyte the most expeditiously.
There is correlative study attempt the fibre diameter by reducing filter medium or aperture or increase the packed density conduct of filter medium in the past
Improve filter medium and remove leucocyte and the means of blood platelet ability simultaneously.But should there is a problem in that in aforementioned manners,
I.e. hemofiltration process time lengthening and may result in erythrocyte membrane and rupture and haemolysis occurs.
The filter material using filtration method to remove leucocyte is usually is made nonwoven filtration film, preferable filter membrane by the thinnest fibrous material
Should have the following characteristics that fibre diameter aperture ultra-fine, filter material is little, voidage big, surface has excellent adsorptivity and profit
Moist, the most also should have preferable blood compatibility and less expensive price, it is easy to industrialized production and there is certain machinery
Performance etc..The material being currently used for making leukoreduction filter film is broadly divided into two big classes: a class is with polyester fiber, acetate fiber
For the organic synthetic fibers represented, a class is inorganic glass fiber, and what wherein polyester fiber was the most commonly used is poly terephthalic acid fourth
Diol ester, what inorganic glass fiber was the most commonly used is alkali-free glass fibre.But organic synthetic fibers has nature hydrophobic, surface
Tension force is low, is difficult to the feature soaked by blood, causes the rate of filtration slow, and reduces the active surface of filtering material contact blood
Long-pending, make the rejection rate of leucocyte decline, additionally, organic synthetic fibers rough surface, have tiny branch, easy when red blood cell passes
In injured.Glass fibre has the highest surface tension, and wetability is good, and blood is fast easily by, the rate of filtration, smooth surface
Make red blood cell be difficult to when passing injured, and physical property is stable, easily realize copolymer coating, reach to inhale changing the quantity of electric charge
The purpose of attached leucocyte, but the manufacture craft of glass fibre is more complicated, relatively costly.
Prior art many employings surface grafting or coating hydrophilic polymer, to filtering material modifying surface, increase filtering material
Wetability, reduce filtering material surface and blood surface can, increase the effective surface area of filtering material contact blood, thus
Increase the chance catching leucocyte.But the hydrophily on filtering material surface is the highest, blood platelet is more difficult to activate, additionally by water
Can be easy to form water layer at material surface with the hydrogen bond etc. of material, there is suppression plasma protein absorption, especially fibrin
Absorption, thus reduce hematoblastic adhesiveness, retain minimizing to hematoblastic.Additionally, the water solubility of hydrophilic polymer is relatively
By force, dissolution problem can be there is in blood.
Also there is correlation technique to utilize blood cell surface with the feature of negative electrical charge, introduce positive functional groups on filtering material surface,
To increase the adsorption of leucocyte, but this technology is the least to the adsorptivity of haemocyte, and red blood cell also produces one simultaneously
Fixed absorption, is difficult to be given high except leucocyte ability.Therefore, by improving positive functional groups's density, cause blood platelet to live
Change, promote platelet adhesion, thus it is infeasible for increasing blood platelet rejection rate, it is impossible to be used simultaneously as removing leucocyte and blood is little
The coating material of the filtering material of plate.
Chinese patent application CN201180038373.2 discloses for removing material from blood or from blood derivatives
The filter improved and the method being used for obtaining described filter.Described filter comprises the filter cell of receiving stratiform
Housing, layered filter cell comprises multiple layer, and at least one of which of layered filter cell is coated with polyurethane,
The molecular weight of described polyurethane be 12,000 dalton to 18,000 dalton, and the non-woven fabric being coated with polyurethane is mingled with
The stratiform filter element formed in the weaven goods that hydrophily is less, leucocyte and blood platelet are all had by described stratiform filter element
There is the effect that preferably filters.
Chinese patent application CN02816396.6 discloses coating and removes filter raw material polymer and the filter of leucocyte
Material.Described filter raw material are fibrous media or spongy texture thing, and by filtering the coating of raw-material surface
By the unit from hydrophobic polymerizable monomer, the unit from the polymerizable monomer containing basic nitrogen-containing groups with from containing matter
The coating polymer that the unit of the polymerizable monomer of sub-property Neutral hydrophilic part is constituted, improves leucocyte and hematoblastic filter
Except rate.
Summary of the invention
It is an object of the invention to provide contained in a kind of Blood Preparations that can efficiently remove blood transfusion, cause transfusion adverse effects
Leucocyte and hematoblastic filtering material and preparation method thereof.Described filtering material has preferable surface hydrophilic wetability and heat
Water stability, dissolution rate in the hot water is less, and fiber surface is smooth, makes red blood cell be difficult to when passing injured.The present invention carries
The filtering material preparation method of confession is simple, with low cost, does not use any organic solvent, environmentally friendly.
The present invention is by following technical solution to be attained in that
A kind of efficiently filtrating leukocytes and hematoblastic filtering material include hydrophobic resin fiber filter base material and are coated in thin
Polymer-modified on water-base resin fiber filter substrate surface；Described hydrophobic resin fiber filter base material is polyester fiber nonwoven
Cloth, described polymer-modified by amidatioon modify fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with
(0.5～2): (0.05～0.4): the mass ratio composition of 1
Further, described polymer-modified by amidatioon modify fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with
(0.5～1): (0.08～0.2): the mass ratio composition of 1.
Preferably, described polymer-modified by amidatioon modify fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with
The mass ratio composition of 0.8:0.15:1.
Further, described polyester fiber is polyethylene terephthalate, polybutylene terephthalate (PBT), gathers benzene two
One in formic acid propylene glycol ester, poly-2,6-naphthalene naphthalate and polytrimethylene's diol ester.
Preferably, described polyester fiber is polybutylene terephthalate (PBT).
Further, described hydrophobic resin fiber filter base material contains 0.01～10% weight polymer-modified, described modification
Polymer coverage rate on hydrophobic resin fiber filter substrate surface is 80～100%.
Further, the average pore diameter of described filtering material is 5～20 μm.
Filtering material of the present invention can be coated with polymer-modified polyester fiber non-woven fabric by one or more surfaces and form, specifically
Form for polymer-modified polybutylene terephthalate (PBT) fabric nonwoven cloth can be coated with by one or more surfaces.
The amidated products that fibroin albumen is fibroin albumen side chain carboxyl group is modified in the amidatioon that the present invention provides, by changing free carboxylic
The quantity of base, to reach to change the charge on fibroin albumen surface, the adsorptivity of regulation fibroin albumen.Silk is modified in described amidatioon
The condensing agent of fibroin is the carbodiimides with activated carboxylic effect, for example: dicyclohexylcarbodiimide, 1, and 3-bis-is different
Propyl group carbodiimide, N, N'-bis-(2,6-diisopropyl phenyl) carbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide salt
One in hydrochlorate.
Preferably, the condensing agent of fibroin albumen is modified in described amidatioon is 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide hydrochloride
Salt.The accessory substance that described 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride reaction produces has water solubility, can lead to
Cross dialysis to remove.
Additionally, present invention also offers a kind of described amidatioon to modify the preparation method of fibroin albumen, its step is particularly as follows: by silk
Fibroin is dissolved in water, makes the solution that concentration is 10mg/mL, adds the aqueous solution of urea of 1mol/L with the volume ratio of 1:5,
Mixing, then by dilute hydrochloric acid solution regulation pH value to 4.75, is subsequently adding the carbodiimides of 2 times of weight of fibroin albumen,
Reacting 0.5～1h under room temperature, suitably instill dilute hydrochloric acid solution in course of reaction, keep the pH of reactant liquor 4.75, reaction is tied
Shu Hou, adding pH is the acetate buffer of 4.75, decomposes the carbodiimides of excess, then by reactant liquor in deionized water
Dialyse, freeze-drying, to obtain final product.
Fibroin albumen is the natural polymer fibrin obtained after natural silk degumming, has the molecular structure of uniqueness and good biology
Compatibility and mechanical performance.The side chain of fibroin albumen contains amino, hydroxyl, carboxyl isopolarity group, has preferable surface profit
Moist.Fibroin albumen contains the more free carboxyl group being dissociated into anion, and its surface is electronegative in neutral conditions.This
Bright by the carboxyl of fibroin albumen is carried out amidatioon modification, the carboxyl quantity making fibroin albumen can be dissociated into anion reduces, etc.
Electricity point moves to alkalescence direction, and when contacting with neutral blood, and the electrostatic repulsion forces between electronegative haemocyte subtracts
Little, promote the absorption to leucocyte.Additionally, fibroin albumen is modified in amidatioon has the character of similar collagen, to blood platelet
Absorption there is certain facilitation.
Filtrating leukocytes of the present invention and hematoblastic filtering material, i.e. surface are coated with polymer-modified hydrophobic resin
Fiber filter base material is to prepare by infiltration is polymer-modified, and the preparation method of described filtering material comprises the following steps:
(1) take Polyamide-Polyamsne-Epichlorohydrin, polyurethane, amidatioon modification fibroin albumen mixing, add water and make quality
Mark is the solution of 5～20%, is subsequently placed in low-speed agitator, stirs 2～4h, obtain the polymer-modified aqueous solution at 50 DEG C；
(2) hydrophobic resin fiber filter base material is placed in the polymer-modified aqueous solution described in step (1), impregnates 0.5～1h,
It is dried 20h at 60 DEG C, is subsequently placed in 40 DEG C of water washing, continue at vacuum drying oven 60 DEG C to dry 6h, obtain filtering material.
Modified polymer solution system of the present invention is dispersion system, there is not any organic solvent, can avoid organic
Dissolvent residual cause pollution and environmentally friendly.It is coated on hydrophobic resin fiber filter substrate surface and can be effectively filtered out white
Cell and blood platelet, and can effectively remove the unnecessary modified poly not being firmly bound on substrate surface by washing in water
Thing, reduces its dissolution rate in blood, it is to avoid cause relevant pollution further.
Polyamide-Polyamsne-Epichlorohydrin is the thermosetting resin of a kind of water-soluble cationic, and the cation base in its structure can be direct
Being combined with polyester fiber, its epoxy radicals can crosslink with polyester fiber in neutral conditions simultaneously, has certain water-resistance,
It is a discovery of the invention that the water-resistance of Polyamide-Polyamsne-Epichlorohydrin can regulate amidatioon modifies the hydrophilic of fibroin albumen and polyurethane
Property, promoting platelet activation to a certain extent, promote platelet adhesion reaction, himself is with cationic property simultaneously, can promote
Leucocyte is at filtering material Adsorption on Surface.Polyamide-Polyamsne-Epichlorohydrin and polyurethane, polybutylene terephthalate (PBT) are equal
Having preferable compatibility and bridging property, its peptizaiton can make polymer-modified have good mobility and stability, promotes
It is polymer-modified that on hydrophobic resin fiber filter substrate surface, coating is uniformly.
Polyurethane is the polymer on macromolecular structure main chain containing many carbamate groups, has excellent bio-compatible
Property and cohesive, carbamate in its structure is based polar very strong, can dramatically increase hydrophobic resin fiber filter substrate surface
Tension force, reduces its hydrophobicity so that it is hydrophilic and be prone to be spontaneously wet out by water, thus improves the contact surface area of filtering material and blood,
Improve leucocyte and hematoblastic filter effect.
It addition, fibroin albumen is modified in the amidatioon in polymer-modified and Polyamide-Polyamsne-Epichlorohydrin viscosity is poor, particularly
Amidatioon in coating is modified fibroin albumen and is mainly existed with unbodied structure, and fibroin inter-molecular binding force is more weak, in water
Dissolution rate is relatively big, easily causes pollution problem.The excellent cohesive of polyurethane can improve amidatioon and modify fibroin albumen, polyamide
Epoxy polyamine chloropropane and the bond properties of filtering substrate, thus improve the stability of coating, reduce its dissolution rate.Additionally, it is poly-
Urethane and amidatioon are modified and be there is hydrogen bond action between silk fibroin molecular, make amidatioon modify fibroin albumen dispersed, are beneficial to protect
Hold the uniformity of coating.
Meanwhile, amidatioon is modified and be there is also stronger hydrogen bond action between silk fibroin molecular, easily forms little aggregation and uniformly divides
It is dispersed in polyurethane, polybutylene terephthalate (PBT) fiber filter base material and forms new cross-linked network, improve the power of filtering substrate
Learn intensity.
Present invention discover that the indenture on the hydrophobic resin fiber filter base material after being modified polymer coating and groove and surface
On tiny branch all disappear, fiber surface becomes smooth, makes red blood cell be difficult to when filtering filtering material injured, and this may be with
It is relevant that polybutylene terephthalate (PBT) fiber surface is coated with amidatioon modification fibroin protein film.It is coated with additionally, be modified polymer
Polybutylene terephthalate (PBT) fiber average pore diameter after Ceng diminishes, and pore diameter controls in 5～20 μm, effectively
Improve the seizure to leukocyte adhesion efficiency, especially M:L to retain, average pore size referred herein is
The value measured by mercury injection method.In detail, if the amount of mercury injected under the mercury injection pressure of 0.1psia is determined
It is 0%, and the amount of mercury injected under the mercury injection pressure of 180psia is set to 100%, just average pore size is defined as
Corresponding to the aperture that amount of mercury is mercury injection pressure when 50% injected.In filter process, due to erythrocyte surface light
Sliding walk around tunica fibrosa easily by deformation, and leukocyte surface be coarse is easily retained by fiber hole, thus be favorably improved white carefully
Born of the same parents' rejection rate and the red blood cell rate of recovery.
Of the present invention polymer-modified and hydrophobic resin fiber filter base material is respectively provided with excellent biocompatibility, to human body
Toxic reaction will not be produced, will not cause allergic reaction and other bad infringements, in use will not be precipitated with toxic thing
Matter, has higher rejection rate, is simultaneously effective adsorbed by platelet component leucocyte, thus based on transfusions of red cells
In the treatment of blood transfusion of syllabus, efficiently reduce the side effect caused because of platelet transfusion, be particularly suited for following patient: have anaemia,
The patient of the hematologic disease such as aplastic, leukaemia；Tumor post-operation is hemorrhage and needs the patient of blood transfusion after accepting Radiotherapy chemotherapy；
Candidate stem cell and Organ Transplantation Patients；Liver and spleen rapture, craniocerebral trauma, UGB, fibroid, postpartum hemorrhage,
The patients such as hemorrhage of newborn.
Compared with prior art, present invention have an advantage that
(1) the polymer-modified of coating that the present invention provides is modified fibroin albumen, polyamide polyamines epoxy chloropropionate by amidatioon
Alkane and polyurethane are with certain mass ratio composition, between described polymer-modified each component and polymer-modified and filtering substrate
Between be respectively provided with preferable compatibility and bridging property, coated after filtering material significantly improve the rejection rate to leucocyte, and increase
By force to hematoblastic absorption bridging ability, improve and retain hematoblastic, and have and relatively low polymer-modified wash out rate, it is to avoid
Leachable pollutes.
(2) filtering material that the present invention provides has the physical mechanics stability of excellence, in preparation containing filtering material of the present invention
Relevance filtering device production process in and the filtration stage of Blood Preparations all will not cause the problems such as malformation, thus increase
Add leucocyte and hematoblastic filter stability, it is ensured that filtering efficiency.
Detailed description of the invention
Further describe the present invention below by way of detailed description of the invention, but the present invention is not limited only to following example.
Embodiment 1
The filtering material of the embodiment of the present invention 1 includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber
Non-woven fabrics, described polymer-modified by amidatioon modify fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with
The mass ratio composition of 0.8:0.15:1.
Preparation method:
(1) preparation of fibroin albumen is modified in amidatioon: fibroin albumen is dissolved in water, makes the solution that concentration is 10mg/mL,
Volume ratio with 1:5 adds the aqueous solution of urea of 1mol/L, and mixing, then by dilute hydrochloric acid solution regulation pH value to 4.75, so
1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of rear 2 times of weight of addition fibroin albumen, at room temperature reacts 0.5h,
Suitably instilling dilute hydrochloric acid solution in course of reaction, keep the pH of reactant liquor 4.75, after reaction terminates, adding pH is 4.75
Acetate buffer, decompose excess 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, then reactant liquor is being gone
Ionized water is dialysed, freeze-drying, obtain amidatioon and modify fibroin albumen；
(2) preparation of filtering material:
S1: taking Polyamide-Polyamsne-Epichlorohydrin, polyurethane, amidatioon modification fibroin albumen mixing, addition water is made quality and divided
Number is the solution of 15%, is subsequently placed in low-speed agitator, stirs 3h, obtain the polymer-modified aqueous solution at 50 DEG C；
S2: be arranged in the polymer-modified aqueous solution described in S1 by polybutylene terephthalate (PBT) fiber non-woven, impregnates 0.5h,
It is dried 20h at 60 DEG C, is subsequently placed in 40 DEG C of water washing, continue at vacuum drying oven 60 DEG C to dry 6h, obtain filtering material.
Embodiment 2
The filtering material of the embodiment of the present invention 2 includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber,
Described polymer-modified modified fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and the polyurethane matter with 0.5:0.08:1 by amidatioon
Amount is than composition.
Preparation method is with the difference of embodiment 1 with embodiment 1, the present embodiment, polymer-modified in the quality of each component
Than difference.
Embodiment 3
The filtering material of the embodiment of the present invention 3 includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber,
Described polymer-modified modified fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and the polyurethane quality with 1:0.2:1 by amidatioon
Than composition.
Preparation method is with the difference of embodiment 1 with embodiment 1, the present embodiment, polymer-modified in the quality of each component
Than difference.
Embodiment 4
The filtering material of the embodiment of the present invention 4 includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber
Non-woven fabrics, described polymer-modified by amidatioon modify fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with
The mass ratio composition of 0.8:0.15:1.
Preparation method is substantially the same manner as Example 1, but the described polymer-modified mass fraction being configured to the aqueous solution is 5%.
Embodiment 5
The filtering material of the embodiment of the present invention 5 includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber
Non-woven fabrics, described polymer-modified by amidatioon modify fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with
The mass ratio composition of 0.8:0.15:1.
Preparation method is substantially the same manner as Example 1, but the described polymer-modified mass fraction being configured to the aqueous solution is 20%.
Comparative example 1
The filtering material of comparative example 1 of the present invention includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber
Non-woven fabrics, described polymer-modified by fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with the quality of 0.8:0.15:1
Than composition.
Preparation method reference example 1, this comparative example is with the difference of embodiment 1, polymer-modified in amidatioon modify
Fibroin albumen changes fibroin albumen into.
Comparative example 2
The filtering material of comparative example 2 of the present invention includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber
Non-woven fabrics, described polymer-modified modified fibroin albumen and polyurethane by amidatioon and forms with the mass ratio of 0.95:1.
Preparation method reference example 1, this comparative example is with the difference of embodiment 1, polymer-modified many without polyamide
Amine epoxychloropropane, and increase the quality of amidatioon modification fibroin albumen accordingly.
Comparative example 3
The filtering material of comparative example 3 of the present invention includes hydrophobic resin fiber filter base material and is coated in hydrophobic resin fiber
Polymer-modified on filtering substrate surface；Described hydrophobic resin fiber filter base material is polybutylene terephthalate (PBT) fiber
Non-woven fabrics, described polymer-modified by amidatioon modify fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and acrylate with
The mass ratio composition of 0.8:0.15:1.
Preparation method reference example 3, this comparative example is with the difference of embodiment 1, polymer-modified in polyurethane change into
Acrylate.
The physical performance index of the filtering material that embodiment of the present invention 1-5 and comparative example 1-3 prepare
The average pore diameter of filtering material that respectively embodiment of the present invention 1-5 and comparative example 1-3 prepared, contact angle, thickness
Being measured with coating surface coverage rate, result see table.
The physical performance index of the filtering material that table 1 embodiment of the present invention 1-5 and comparative example 1-3 prepare
| Group | Average pore diameter (μm) | Coating surface coverage rate (%) | Contact angle | Thickness (μm) |
| Embodiment 1 | 5.2 | 90 | 45° | 1250 |
| Embodiment 2 | 5.8 | 86 | 43° | 1250 |
| Embodiment 3 | 5.5 | 90 | 47° | 1250 |
| Embodiment 4 | 6.7 | 82 | 50° | 1100 |
| Embodiment 5 | 5.0 | 91 | 44° | 1300 |
| Comparative example 1 | 5.6 | 90 | 59° | 1250 |
| Comparative example 2 | 5.4 | 83 | 35° | 1250 |
| Comparative example 3 | 5.3 | 90 | 46° | 1250 |
Leucocyte and hematoblastic filtering material average pore diameter that the present invention provides are 5.0～6.7 μm, and thickness is
1100～1300 μm, the coverage rate of the surface coating modified polymer of filtering material reaches more than 80%, coated after filtering material
Surface wettability significantly improves, and contact angle is 43 °～50 °.As seen from the above table, divide along with the quality of the polymer-modified aqueous solution
Number increases, and filtering material average pore diameter reduces；Amidatioon in polymer-modified is modified fibroin albumen and is changed fibroin albumen into,
The contact angle of filtering material increases, and sees comparative example 1；Lacking Polyamide-Polyamsne-Epichlorohydrin, the contact angle of filtering material reduces,
See comparative example 2, polymer-modified in polyurethane change acrylate into, the contact angle change of filtering material is inconspicuous, sees contrast
Example 3, shows that the hydrophilic wettability of fibroin albumen modifies fibroin albumen not as good as amidatioon, and Polyamide-Polyamsne-Epichlorohydrin is to acyl
The hydrophilic wettability of amination modification fibroin albumen and polyurethane has regulation effect, acrylate and polyurethane and is respectively provided with preferable parent
Wettability.
Test example one, the rate that the washes out test of filtering material of the present invention
The filtering material prepared embodiment 1-5 and comparative example 1-3 respectively is under conditions of hot water and simulation actual application
Carry out washings test, particularly as follows:
(1) hot water wash out rate test:
The modified polybutylene terephthalate (PBT) fiber non-woven of face coat of learning from else's experience is distributed in after drying to constant weight in 105 DEG C of baking ovens, presses
Sample is vibrated in constant temperature water bath (37 ± 1 DEG C) oscillator and dissolves 60min by the bath raio of 1:100, then leaches sample and puts into 105 DEG C
Baking oven dries to constant weight.The hot water calculating coating washes out rate.The hot water of coating material washes out rate (%)=(m1-m2)/m1× 100,
Wherein m1For the dry mass (g) before sample water-bath, m2For the dry mass (g) after sample water-bath.
(2) rate that the washes out test of simulation actual application:
Take 15g to be arranged in the container of 200ml through the polybutylene terephthalate (PBT) fiber non-woven that face coat is modified, add
Enter normal saline solution as filling liquid, then carry out γ ray sterilization (illuminated line amount 25kGy).In order to reality keeping doctor
Confirm washings within the temperature range of considering when treating apparatus, at 25 DEG C, at 4 DEG C, after keeping 24h, take care of 24h.Observe and preserve
The outward appearance of rear filling liquid, and use ultraviolet specrophotometer to measure the filling liquid maximum absorbance when wavelength is 220～350nm.
The rate that the washes out result of the test of table 2 filtering material of the present invention
The leucocyte of present invention offer and blood platelet filtering material are no matter under hot water conditions or in simulation actual application
Under the conditions of be respectively provided with preferable stability, wash out degree low.The rate that washes out under hot water conditions is 2.22%～3.51%, in simulation
Within the temperature range of considering during actual keeping medical instruments, the absorbance recording filling liquid is 0.040～0.054.As seen from the above table,
When polymer-modified middle polyurethane ratio reduces, the polymer-modified rate that washes out in water increases, and shows that polyurethane changes for increasing
The property polymer bonding force on filtering material surface has important effect.When the mass fraction of the polymer-modified aqueous solution increases,
The rate that washes out in its water increases.From comparative example 1, the amidatioon in polymer-modified is modified fibroin albumen and is changed fibroin egg into
In vain, the polymer-modified rate that washes out in water does not has significant change；From comparative example 2, when polymer-modified shortage polyamide
Epoxy polyamine chloropropane, the polymer-modified rate that washes out in water increases, and shows that Polyamide-Polyamsne-Epichlorohydrin advantageously reduces
Polymer-modified in water, wash out rate；From comparative example 3, polymer-modified in polyurethane change acrylate into, modified
The polymer rate that washes out in water slightly increases, but inconspicuous, shows that acrylate and polyurethane are respectively provided with preferable cohesive.
Test example two, filtering material of the present invention remove leucocyte and hematoblastic performance evaluation
Use the filter containing 8 layers of filtering material of the present invention that 400ml whole blood carries out on-line filtration, evaluate the present invention
Filtering material removes leucocyte and hematoblastic effect, use blood-counter system measure the leucocyte filtered in forward and backward whole blood and
Platelet counts；The assay method wherein remaining leukocyte count is: in the whole blood sampling after filtering to the test tube of polyethylene,
, after the leucocyte dyeing that acridine orange liquid will spill, to be measured with fluorescence microscope.The white blood cell concentration of mensuration is multiplied by recovery
The liquid measure of whole blood, record residue leukocyte count contained in collection bag.
Leucocyte (blood platelet) rejection rate (%)=L0-L1/L0× 100, wherein L0For what unit volume whole blood before filtering contained
Leucocyte (blood platelet) quantity, L1For leucocyte (blood platelet) quantity contained in unit volume whole blood after filtering.
Recording and filtering the quantity of proleukocyte in 400ml whole blood is 2.5 × 109, the quantity filtering thromboblast is 8 × 1010。
Table 3 filtering material of the present invention is to leucocyte and hematoblastic filtration result
Leucocyte in whole blood and blood platelet are had and preferably filter efficiency by the filtering material that the present invention provides, wherein embodiment
The filtering material that 1-5 prepares is up to 99.999% to the rejection rate of leucocyte, and hematoblastic rejection rate is reached more than 90%.When changing
Property polymer in amidatioon modify fibroin albumen and change fibroin albumen into and can reduce filtering material and to leucocyte and hematoblastic filter
Effect, makes the remaining leukocyte count in collection bag increase, and leucocyte and blood platelet rejection rate reduce.When polymer-modified shortage is gathered
Polyamide-polyamino epoxychloropropane, reduces filtering material the most notable to leucocyte and hematoblastic filtration result.When polymer-modified
In polyurethane change acrylate into, worst to leucocyte and hematoblastic filtration result.Result above shows, fibroin albumen warp
After amidatioon processes, its surface charge sexually revises, and promotes leucocyte and hematoblastic absorption, additionally, fibroin egg is modified in amidatioon
In vain compared with fibroin albumen sterically hindered greatly, be conducive to improving the selective absorption to leucocyte；Polyamide-Polyamsne-Epichlorohydrin band
Positive charge and water-resistance is had all to be conducive to improving polymer-modified to leucocyte with hematoblastic absorption；And there is preferable parent equally
The acrylate of wettability and cohesive relatively polyurethane, slightly weakens the filtration result of leucocyte, to hematoblastic filtration result
Poor, show that fibroin albumen is modified in polyurethane and amidatioon, Polyamide-Polyamsne-Epichlorohydrin plays the most collaborative effect, carry
Platelet adhesion is put up a bridge ability by high filtration material, strengthens hematoblastic retaining, and effect is better than acrylate.
Below it is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as the present invention
Restriction, protection scope of the present invention should be as the criterion with claim limited range.Ordinary skill for the art
For personnel, without departing from the spirit and scope of the present invention, it is also possible to make some improvements and modifications, these improvements and modifications
Also should be regarded as protection scope of the present invention.
Claims (10)
1. an efficient filtrating leukocytes and hematoblastic filtering material, it is characterised in that described filtering material includes hydrophobicity tree
Fat fiber filter base material and be coated on hydrophobic resin fiber filter substrate surface polymer-modified；Described hydrophobic resin
Fiber filter base material is polyester fiber non-woven fabric, described polymer-modified is modified fibroin albumen, polyamide polyamines epoxy by amidatioon
Chloropropane and polyurethane are with (0.5～2): (0.05～0.4): the mass ratio composition of 1.
Filtrating leukocytes the most according to claim 1 and hematoblastic filtering material, it is characterised in that described modified poly
Thing is modified fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane with (0.5～1) by amidatioon: (0.08～0.2): the mass ratio of 1
Composition.
Filtrating leukocytes the most according to claim 2 and hematoblastic filtering material, it is characterised in that described modified poly
Thing is modified fibroin albumen, Polyamide-Polyamsne-Epichlorohydrin and polyurethane by amidatioon and is formed with the mass ratio of 0.8:0.15:1.
Filtrating leukocytes the most according to claim 1 and hematoblastic filtering material, it is characterised in that described polyester fiber
For polyethylene terephthalate, polybutylene terephthalate (PBT), PTT, poly-2,6-naphthalene diacid
One in glycol ester and polytrimethylene's diol ester.
Filtrating leukocytes the most according to claim 4 and hematoblastic filtering material, it is characterised in that described polyester fiber
For polybutylene terephthalate (PBT).
Filtrating leukocytes the most according to claim 1 and hematoblastic filtering material, it is characterised in that described hydrophobicity tree
Fat fiber filter base material contains 0.01～10% weight polymer-modified, described polymer-modified at hydrophobic resin fiber filter
Coverage rate on substrate surface is 80～100%.
Filtrating leukocytes the most according to claim 1 and hematoblastic filtering material, it is characterised in that described amidatioon is repaiied
The preparation method of decorations fibroin albumen is: fibroin albumen is dissolved in water, makes the solution that concentration is 10mg/mL, with the body of 1:5
The long-pending aqueous solution of urea than addition 1mol/L, mixing, then by dilute hydrochloric acid solution regulation pH value to 4.75, it is subsequently adding silk
The carbodiimides of 2 times of weight of fibroin, at room temperature reaction 0.5～1h, suitably instills dilute hydrochloric acid solution in course of reaction,
Keeping the pH of reactant liquor 4.75, after reaction terminates, adding pH is the acetate buffer of 4.75, decomposes the carbonization two of excess
Imines, then dialyses in deionized water by reactant liquor, and freeze-drying to obtain final product.
Filtrating leukocytes the most according to claim 7 and hematoblastic filtering material, it is characterised in that described carbonization two is sub-
Amine is 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
Filtrating leukocytes the most according to claim 1 and hematoblastic filtering material, it is characterised in that described filtering material
Average pore diameter be 5～20 μm.
10. according to the arbitrary described filtrating leukocytes of claim 1-9 and the preparation method of hematoblastic filtering material, its feature
It is, comprises the following steps:
(1) take Polyamide-Polyamsne-Epichlorohydrin, polyurethane, amidatioon modification fibroin albumen mixing, add water and make quality
Mark is the solution of 5～20%, is subsequently placed in low-speed agitator, stirs 2～4h, obtain the polymer-modified aqueous solution at 50 DEG C；
(2) hydrophobic resin fiber filter base material is placed in the polymer-modified aqueous solution described in step (1), impregnates 0.5～1h,
It is dried 20h at 60 DEG C, is subsequently placed in 40 DEG C of water washing, continue at vacuum drying oven 60 DEG C to dry 6h, obtain filtering material.
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| CN201610471087.XA CN105903270A (en) | 2016-06-23 | 2016-06-23 | Filter material capable of efficiently filtering out leukocyte and thrombocyte and preparation method thereof |
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| CN201610471087.XA CN105903270A (en) | 2016-06-23 | 2016-06-23 | Filter material capable of efficiently filtering out leukocyte and thrombocyte and preparation method thereof |
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| CN108192437A (en) * | 2017-12-21 | 2018-06-22 | 雅图高新材料有限公司 | It is a kind of to can be used for the wet on wet aqueous high-temperature metal paint and its construction technology for exempting from middle painting system |
| CN111542380A (en) * | 2018-01-22 | 2020-08-14 | Jemp公司 | Direct capture using large bead chromatography media |
| CN114960198A (en) * | 2022-06-10 | 2022-08-30 | 苏州大学 | Anticoagulant protein fiber material in-vivo venous blood and preparation method thereof |
| CN114960198B (en) * | 2022-06-10 | 2024-05-10 | 苏州大学 | Anticoagulation protein fiber material in-vivo venous blood and preparation method thereof |
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| CN108192437A (en) * | 2017-12-21 | 2018-06-22 | 雅图高新材料有限公司 | It is a kind of to can be used for the wet on wet aqueous high-temperature metal paint and its construction technology for exempting from middle painting system |
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| CN114960198B (en) * | 2022-06-10 | 2024-05-10 | 苏州大学 | Anticoagulation protein fiber material in-vivo venous blood and preparation method thereof |
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Application publication date: 20160831 |