CN103289116B - Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof - Google Patents
Surface-heparinized cellulose ester liquid crystal material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of biological materials and discloses a surface-heparinized cellulose ester liquid crystal material and a preparation method and application thereof. The preparation method of the liquid crystal material comprises the following steps of: (1) preparation of acryloyl-octanoyl-hydroxy propyl cellulose ester liquid crystal: dissolving hydroxy propyl cellulose into an acetone solution, adding acryloyl chloride and reacting; after the reaction is over, cleaning the obtained mixed solution for 3-5 times, and dialyzing and drying; dissolving the obtained product in acetone, dropwise adding octanoyl chloride and reacting; and cleaning, dialyzing and drying to obtain acryloyl-octanoyl-hydroxy propyl cellulose ester; and (2) preparation of surface-heparinized cellulose ester liquid crystal material: dissolving the acryloyl-octanoyl-hydroxy propyl cellulose ester liquid crystal in tetrahydrofuran, fetching the solution to form a film, then adding a sodium hydroxide solution of heparin sodium, reacting and cleaning to obtain the surface-heparinized cellulose ester liquid crystal material.
Description
Technical field
The invention belongs to technical field of biological material, be specifically related to a kind of cellulose esters liquid crystal material and preparation method and application of surface heparinization.
Background technology
For the medicine equipment contacting with blood, while requiring it to contact with blood, do not cause that blood coagulation and thrombocyte stick together cohesion, do not destroy the undesirable actions such as the haemolysis of formed elements in blood, there is blood compatibility.The quality of medicine equipment blood compatibility is directly connected to the effect of its clinical use.In decades, to the novel exploitation without thrombus biomaterial be always in technical field of biological material one have challenging problem, be also the Key technique problem of medicine equipment.
Liquid crystal (LC) is a kind of middle phase between liquid phase and solid phase, has both had mobility and the continuity of liquid, has again order and optical anisotropy that crystal molecule is arranged.Liquid crystal state is prevalent in organism.Much research is verified: cytolemma, polypeptide, nucleic acid, other microbial film in blood vessel and body, especially with the surface of cell membrane of blood Long Term Contact all in mobile lipoid layer liquid crystal state, due to the mobility of biofilm surface, wettability and order just make it have good blood compatibility.The factor of any destruction blood vessel ordered arrangement all can cause the formation of thrombus, and any factor that causes that erythrocyte membrane liquid crystal order degree reduces all can cause microcirculatory having some setbacks.Early stage, liquid crystal biocompatible materials mainly concentrated on using small molecules liquid crystal as disperse phase and polymer matrix Material cladding, but research shows, although this composite structure can improve the describing property of blood of material etc., but there is more serious loss in small molecules liquid crystal, thereby causes the change of colloidal osmotic pressure to cause haemolysis.CN1072021C once prepared different types of polymer/liquid crystal composite membrane and improved the blood compatibility of material, and obtained certain effect.But, if this class matrix material is also had the following disadvantages during for the manufacture of the biomaterial directly contacting with blood and medical device, goods:
1, the anticoagulation function of matrix material and the anticoagulation function of human vas more also do not reach perfect condition, the phenomenon that still exists thrombus to generate while causing material to contact with blood; 2, material surface does not also reach the performance that tunica intima possesses, and biocompatibility between tissue interface also has certain gap, and the regulation and control on material surface liquid crystal farmland still need to improve; 3, be small molecules liquid crystal due to what select in polymer/liquid crystal composite membrane preparation process, and small molecules liquid crystal produce leakage in simulated body fluid environment, causes the anticoagulation function of composite membrane and coating thereof to decline to some extent.
Although current developed polymer/liquid crystal composite membrane has improved the anticoagulation function of substrate material to a certain extent, also has larger gap from the requirement of desirable blood compatibility biological material.Major cause is that small molecules liquid crystal farmland is stable not, being subject to external environment influence can deform (comprising size and orientation), causing material surface liquid crystal state structure to change, cannot be really according to biomaterial is carried out to molecular designing with the pass between surface tissue form and the blood compatibility of material.High molecule liquid crystal molecule is difficult for the features such as stripping more greatly with molecular weight and has caused investigator's attention, and the researchdevelopment of liquid crystal biomaterial turns to Liquid Crystalline Polymeric Materials.
Summary of the invention
In order to overcome the deficiencies in the prior art, primary and foremost purpose of the present invention is the preparation method of the cellulose esters liquid crystal material that a kind of surface heparinization is provided.
Another object of the present invention is to provide a kind of cellulose esters liquid crystal material of the surface heparinization being prepared from by above-mentioned preparation method.This material liquid crystal state can form phase separation structure, be similar to the fluid mosaic model of cytolemma, make the anticoagulation function of material reach the requirement of human vas anticoagulation function, and make the biocompatibility between material surface and tissue interface approach the biocompatibility between tissue.
A further object of the present invention is the application of the cellulose esters liquid crystal material that above-mentioned surface heparinization is provided.
The present invention realizes by following technical proposals:
A preparation method for the cellulose esters liquid crystal material of surface heparinization, comprises the following steps:
(1) preparation of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal: 1～20g hydroxypropylcellulose is dissolved in acetone soln, add 0.5～10mL acrylate chloride, reaction, cleans the mixing solutions obtaining 3-5 time after reaction finishes, dialysis, dry; Then the product obtaining is dissolved in acetone, drips the capryl(yl)chloride of 0.7～14mL, reaction, cleans the solution obtaining 3-5 time, and dialysis is dry, obtains propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal;
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal that 2～25g is obtained is dissolved in 50mL tetrahydrofuran (THF); get this solution film forming of 16mL; then adding 5～50mL mass concentration is the sodium hydroxide solution of the heparin sodium of 2～16mg/mL; reaction; clean, obtain the cellulose esters liquid crystal material of surface heparinization.
The molecular weight of the hydroxypropylcellulose described in step (1) is 80,000～200,000.
Reaction described in step (1) is to react 3～6h under 45～65 DEG C of conditions;
The step of described cleaning is: add deionized water to separate out throw out to mixing solutions, after stirring, leave standstill, remove the aqueous solution, throw out is dissolved in acetone; Wherein, the churning time in described cleaning step is 5h, and time of repose is 15 minutes;
Described dialysis is to dialyse in water, ethanol or tetrahydrofuran (THF);
Described is dried as lyophilize, and the time is 24h.
The time of described dialysis is 8～48h;
Described sublimation drying is 24h.
The temperature of the film forming described in step (2) is 10～35 DEG C;
The sodium hydroxide solution of described heparin sodium is dissolved in aqueous sodium hydroxide solution formulated by heparin sodium; Wherein, in the sodium hydroxide solution of heparin sodium, the mass ratio of heparin sodium and sodium hydroxide is 1:1～1:5.
Described reaction is to react 2～10h under 20～30 DEG C of conditions;
Described cleaning is to use washed with de-ionized water 10 times.
The cellulose esters liquid crystal material of the surface heparinization that a kind of preparation method described above is prepared from: the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 9.2-17.1 μ g/cm
2.
The application of the cellulose esters liquid crystal material of surface heparinization described above in the preparation of biomaterial, medical device or goods.
The principle of the invention is: the present invention is based on Bionic Design theory, on high molecule liquid crystal substrate material by connecting spacerarm, utilize spacerarm with covalent linkage grafting heparin, can ensure that like this stability of heparinization can bring into play again the activity of heparin.The product that the present invention is synthetic, both built the liquid crystal state structure of similar tunica intima, be combined with again the heparin compositions of Effective Anti Blood clotting, after this kind of heparinization liquid crystal state biomimetic material contacts with blood, material surface heparin plays a role first rapidly, by the synergistic effect of heparin and high molecule liquid crystal, effectively stop or delay material surface thrombosis afterwards, promoting material anticoagulation function.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention: reaction conditions of the present invention is gentle and significantly, production energy consumption is low, saves production cost, and the simple and technology maturation of instrument equipment, has good industrial applications prospect; The product that the present invention makes belongs to high molecule liquid crystal, can avoid the stripping of small molecules liquid crystal in application process; And, realize heparinization by spacerarm covalency keyed jointing, can ensure stability and the heparin activity of heparinization.From blood compatibility macromolecular material design angle, the product that the present invention is synthetic, both presented orderly, the mobile liquid crystal state constitutional features of tunica intima, comprise again the heparin component of Effective Anti coagulant property, heparin and high molecule liquid crystal produce synergy, can effectively reduce the interfacial tension between material surface and blood, significantly improve the blood compatibility of material.The synthetic product of the present invention also can with conventional medical polymer, as urethane, polyvinyl chloride, compound polymkeric substance/LC matrix material of preparing such as polysiloxane, makes the liquid crystal state matrix material of good biocompatibility activity.
Brief description of the drawings
The POM image (25 DEG C) of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal prepared by Fig. 1: embodiment 1.
Fig. 2: x-ray diffractometer test result; Wherein, a is hydroxypropylcellulose in embodiment 1; B is propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal prepared by embodiment 1.
Fig. 3: cellulose esters liquid crystal material ATR-FTIR Spectrometry; Wherein, the hydroxypropylcellulose in a: embodiment 1; Propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal in b: embodiment 1; Heparinization propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal in c: embodiment 1.
Fig. 4: the static contact angle test pattern of propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal material.
Fig. 5: platelet adhesion reaction figure; Propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal of a: embodiment 1; Heparinization propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal of b: embodiment 1; Propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction of c: embodiment 1; Heparinization propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction of d: embodiment 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) preparation of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal: by 2g hydroxypropylcellulose (M
w=100,000, buy the company in Aldrich) be dissolved in acetone soln, after dissolving completely, drip wherein 1mL acrylate chloride, under 55 DEG C of conditions, react 4h, reaction finishes backward mixing solutions and adds 200mL deionized water precipitated product, stir after 5h, leave standstill 15 minutes, remove the aqueous solution, precipitated product is dissolved in acetone, add again 200mL deionized water to separate out precipitated product, stir after 5h, leave standstill 15 minutes, remove the aqueous solution, throw out is dissolved in acetone, repeat the above-mentioned deionized water that adds, stir, leave standstill, dewater, throw out is dissolved in after the process 5 times of acetone, at 25 DEG C, 48h dialyses in deionized water, remove remaining acrylate chloride, dry, then the product obtaining is dissolved in acetone, drip the capryl(yl)chloride of 1.4mL, under 55 DEG C of conditions, reaction 4h, adds 200mL deionized water to the mixing solutions of reaction, stirs after 5h, remove the aqueous solution, throw out is dissolved in acetone, then adds 200mL deionized water to separate out product, repeat the above-mentioned deionized water that adds, stir, leave standstill, dewater, throw out is dissolved in after the process 5 times of acetone, at 25 DEG C, the 48h that dialyses in deionized water, lyophilize 24h, obtains propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal.
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: 2.5g propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal is dissolved in 50mL tetrahydrofuran (THF); mixing solutions, get in the culture dish that this mixing solutions of 16mL is 6cm at diameter film forming under the condition of 25 DEG C.By heparin sodium (>=150U/mg, buy the Co. in Shanghai CpG Biotech, Ltd) be dissolved in the aqueous sodium hydroxide solution (mass ratio of heparin sodium and sodium hydroxide is 1:1) of the heparin sodium that in the aqueous sodium hydroxide solution that concentration is 4mg/mL, compound concentration is 4mg/mL, in culture dish, add the aqueous sodium hydroxide solution of this heparin heparin sodium of 10mL, 25 DEG C of reactions were rinsed 10 times repeatedly with deionized water after 7 hours, obtained the cellulose esters liquid crystal material of surface heparinization.Through spectrophotometer test (JINGHUA754PC UV/VS Spectrophotometer, test wavelength: 630nm), the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 9.42 μ g/cm
2.
The POM image of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal is shown in Fig. 1 (instrument: polarizing microscope: Axioskop40, Carl Zeiss, Germany).From POM image, can find out that propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal shows the color texture texture of typical cholesteryl liquid crystal under polarisation.
Fig. 2 is x-ray diffractometer test result; Wherein, a is hydroxypropylcellulose in embodiment 1; B is propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal (instrument: X-ray diffractometer: Dmax-1200, Rigaku) prepared by embodiment 1.Fig. 2 can find out: raw material hydroxypropylcellulose locates to present more sharp-pointed diffraction peak (corresponding to (101) crystal face) in 2 θ=20 °, illustrates that hydroxypropylcellulose exists crystallization to a certain degree.The diffraction peak of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal obviously weakens, and this is because introduces after alkyl by acyl chloride reaction, and the alkyl group side chain of softness has destroyed the intermolecular and intramolecular hydrogen bond of hydroxypropylcellulose, presents non-crystalline state.
Fig. 3 is cellulose esters liquid crystal material ATR-FTIR Spectrometry; Wherein, the hydroxypropylcellulose in a: embodiment 1; Propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal in b: embodiment 1; Heparinization propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal (instrument Fourier infrared spectrograph: EQUINOX-70, Bruker, Germany) in c: embodiment 1.As can be drawn from Figure 3: on hydroxypropylcellulose spectrogram at 3461cm
-1there is wide and strong hydroxyl stretching vibration absorption peak in place; On the spectrogram of product propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal, this absorption peak obviously weakens, and at 1725cm
-1there is the strong stretching vibration absorption peak of the carbonyl that contains unsaturated link(age), 2800-3000cm in place
-1the stretching vibration absorption peak of place's methyl and methylene radical obviously strengthens, and illustrates that acryl and capryloyl are successfully grafted on molecular chain, have replaced the part of hydroxyl on molecular chain by acyl chloride reaction.And on the spectrogram of heparinization propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal, there is 1000cm
-1, 1191cm
-1, 1650cm
-1vibration absorption peak, consistent with the constitutional features of heparin, and 3461cm
-1wide and strong hydroxyl stretching vibration absorption peak further strengthens phenomenons such as (on heparin molecules with hydroxyl) and has illustrated that heparin has been grafted on propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal.
Table 1. contact angle test experiments result (unit/°)
The data of surveying for test average for 10 times, after grafting heparin, the wetting ability on propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal surface obviously improves as shown in Table 1.
The static contact angle test pattern of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal material (contact angle measurement: DSA100, Kruss, Germany) as shown in Figure 4.
Fig. 5: platelet adhesion reaction figure; Propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal of a: embodiment 1; Heparinization propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal of b: embodiment 1; Propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction of c: embodiment 1; Heparinization propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal platelet adhesion reaction of d: embodiment 1.As can be drawn from Figure 5: propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal (a) surface presents staggered stripe texture, heparinization propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal (b) occurs that fragmentarily surface has new material to appear at surface, and the stripe texture of liquid crystal surfactant still exists simultaneously; Carry out platelet adhesion reaction experiment at propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal, experimental result (c) shows that propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal exists certain blood coagulation resisting function to platelet adhesion reaction; Find than the propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal (c) for heparinization and carry out platelet adhesion reaction (d) on heparinization propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal surface; the amount of platelet adhesion reaction reduces; the volume of platelets adhering to also reduces; the surface of liquid crystal film is more smooth, illustrates that the propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal of heparinization has stronger anticoagulation function than propylene acidylate ?decoyl ?hydroxypropylcellulose ester liquid crystal.
Platelet adhesion reaction experimental technique title: directly electron microscopy, reference: J.Yuan, S.C.Lin, J.Shen.Enhanced blood compatibility of polyurethane functionalized with sulfobetaine[J] .Colloids and Surfaces B:Biointerfaces, 2008,66 (1): 90-95.
Experimental procedure:
(1) extract the fresh anti-freezing rabbit of 3.8% Sodium Citrate blood with vacuum test tube, after the centrifugal 15min of 800g, carefully draw each pipe supernatant liquid and mix, be platelet rich plasma (PRP).
(2) before specimen material test, spend the night by PBS solution soaking.
(3) specimen material is immersed in PRP, hatches 60min at 37 DEG C; After taking out, washs gently specimen material the thrombocyte of surface relaxation with PBS solution; In 2.5% glutaraldehyde stationary liquid, fix 2h, after fixing, wash away glutaraldehyde with PBS; Seasoning under room temperature after specimen material takes out.Observe with SEM that thrombocyte sticks at sample surfaces, gathering and deformation.
Embodiment 2
(1) preparation of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal: by 1g hydroxypropylcellulose (M
w=200,000, buy the company in Aldrich) be dissolved in acetone soln, after dissolving completely, drip wherein 0.5mL acrylate chloride, under 65 DEG C of conditions, react 3h, reaction finishes backward mixing solutions and adds 200mL deionized water to separate out precipitated product, stir after 5h, leave standstill 15 minutes, remove the aqueous solution, precipitated product is dissolved in acetone, add again 200mL deionized water to separate out precipitated product, stir after 5h, leave standstill 15 minutes, remove the aqueous solution, throw out is dissolved in acetone, repeat the above-mentioned deionized water that adds, stir, leave standstill, dewater, throw out is dissolved in after the process 5 times of acetone, at 25 DEG C, the 8h that dialyses in ethanol removes remaining acrylate chloride, dry, then the product obtaining is dissolved in acetone, drip the capryl(yl)chloride of 0.7mL, under 65 DEG C of conditions, reaction 3h, adds 200mL deionized water to the mixing solutions of reaction, stirs after 5h, remove the aqueous solution, throw out is dissolved in acetone, then adds 200mL deionized water to separate out product, repeat the above-mentioned deionized water that adds, stir, leave standstill, dewater, throw out is dissolved in after the process 5 times of acetone, at 20 DEG C, the 12h that dialyses in ethanol, lyophilize 24h, obtains propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal.
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: 2g propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal is dissolved in 50mL tetrahydrofuran (THF); mixing solutions, get in the culture dish that this mixing solutions of 16mL is 6cm at diameter film forming under the condition of 10 DEG C.By heparin sodium (>=150U/mg, buy the Co. in Shanghai CpG Biotech, Ltd) be dissolved in the aqueous sodium hydroxide solution (mass ratio of heparin sodium and sodium hydroxide is 1:4) of the heparin sodium that in the aqueous sodium hydroxide solution that concentration is 80mg/mL, compound concentration is 20mg/mL, in culture dish, add the aqueous sodium hydroxide solution of this heparin heparin sodium of 5mL, 30 DEG C of reactions were rinsed 10 times repeatedly with deionized water after 2 hours, obtained the cellulose esters liquid crystal material of surface heparinization.Through spectrophotometer test (JINGHUA754PC UV/VS Spectrophotometer, test wavelength: 630nm), the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 14.7 μ g/cm
2.
Embodiment 3
The preparation of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal: by 20g hydroxypropylcellulose (M
w=80,000, buy the company in Aldrich) be dissolved in acetone soln, after dissolving completely, drip wherein 10mL acrylate chloride, under 45 DEG C of conditions, react 6h, reaction finishes backward mixing solutions and adds 200mL deionized water precipitated product, stir after 5h, leave standstill 15 minutes, remove out the aqueous solution, precipitated product is dissolved in acetone, add again 200mL deionized water to separate out precipitated product, stir after 5h, leave standstill 15 minutes, remove the aqueous solution, throw out is dissolved in acetone, repeat the above-mentioned deionized water that adds, stir, leave standstill, dewater, throw out is dissolved in after the process 3 times of acetone, at 25 DEG C, 8h dialyses in tetrahydrofuran (THF), remove remaining acrylate chloride, dry, then the product obtaining is dissolved in acetone, drip the capryl(yl)chloride of 14mL, under 45 DEG C of conditions, reaction 6h, adds 200mL deionized water to the mixing solutions of reaction, stirs after 5h, remove the aqueous solution, throw out is dissolved in acetone, then adds 200mL deionized water to separate out product, repeat the above-mentioned deionized water that adds, stir, leave standstill, dewater, throw out is dissolved in after the process 3 times of acetone, at 25 DEG C, the 48h that dialyses in tetrahydrofuran (THF), lyophilize 24h, obtains propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal.
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: 25g propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal is dissolved in 50mL tetrahydrofuran (THF); mixing solutions, get in the culture dish that this mixing solutions of 16mL is 6cm at diameter film forming under the condition of 35 DEG C.By heparin sodium (>=150U/mg, buy the Co. in Shanghai CpG Biotech, Ltd) be dissolved in the aqueous sodium hydroxide solution (mass ratio of heparin sodium and sodium hydroxide is 1:2) of the heparin sodium that in the aqueous sodium hydroxide solution that concentration is 60mg/mL, compound concentration is 30mg/mL, in culture dish, add the aqueous sodium hydroxide solution of this heparin heparin sodium of 50mL, 20 DEG C of reactions were rinsed 10 times repeatedly with deionized water after 10 hours, obtained the cellulose esters liquid crystal material of surface heparinization.Through spectrophotometer test (JINGHUA754PC UV/VS Spectrophotometer, test wavelength: 630nm), the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 17.1 μ g/cm
2.
Claims (8)
1. a preparation method for the cellulose esters liquid crystal material of surface heparinization, is characterized in that: comprise the following steps:
(1) preparation of propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal: 1～20g hydroxypropylcellulose is dissolved in acetone soln, add 0.5～10mL acrylate chloride, reaction, cleans the mixing solutions obtaining 3-5 time after reaction finishes, dialysis, dry; Then the product obtaining is dissolved in acetone, drips the capryl(yl)chloride of 0.7～14mL, reaction, cleans the solution obtaining 3-5 time, and dialysis is dry, obtains propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal;
(2) preparation of the cellulose esters liquid crystal material of surface heparinization: propylene acidylate-decoyl-hydroxypropylcellulose ester liquid crystal that 2～25g is obtained is dissolved in 50mL tetrahydrofuran (THF); get this solution film forming of 16mL; then adding 5～50mL mass concentration is the sodium hydroxide solution of the heparin sodium of 2～16mg/mL; reaction; clean, obtain the cellulose esters liquid crystal material of surface heparinization.
2. preparation method according to claim 1, is characterized in that: the molecular weight of the hydroxypropylcellulose described in step (1) is 80,000～200,000.
3. preparation method according to claim 1, is characterized in that: the reaction described in step (1) is to react 3～6h under 45～65 DEG C of conditions;
The step of described cleaning is: add deionized water to separate out throw out to mixing solutions, after stirring, leave standstill, remove the aqueous solution, throw out is dissolved in acetone;
Described dialysis is to dialyse in water, ethanol or tetrahydrofuran (THF);
Described is dried as lyophilize, and the time is 24h.
4. preparation method according to claim 3, is characterized in that: the churning time in described cleaning step is 5h, and time of repose is 15 minutes;
The time of described dialysis is 8～48h.
5. preparation method according to claim 1, is characterized in that: the temperature of the film forming described in step (2) is 10～35 DEG C;
The sodium hydroxide solution of described heparin sodium is dissolved in aqueous sodium hydroxide solution formulated by heparin sodium;
Described reaction is to react 2～10h under 20～30 DEG C of conditions;
Described cleaning is to use washed with de-ionized water 10 times.
6. preparation method according to claim 5, is characterized in that: in the sodium hydroxide solution of described heparin sodium, the mass ratio of heparin sodium and sodium hydroxide is 1:1～1:5.
7. a cellulose esters liquid crystal material for the surface heparinization being prepared from by the preparation method described in claim 1～6 any one, is characterized in that: the heparin grafting content of the unit surface of the cellulose esters liquid crystal material of this surface heparinization is 9.2-17.1 μ g/cm
2.
8. the application of the cellulose esters liquid crystal material of surface heparinization according to claim 7 in the preparation of biomaterial, medical article.
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