CN103275328B - Synthetic method of polyhydroxybutyrate-artemisia sphoerocephala polysaccharide copolymer - Google Patents
Synthetic method of polyhydroxybutyrate-artemisia sphoerocephala polysaccharide copolymer Download PDFInfo
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Abstract
The invention discloses a synthetic method of polyhydroxybutyrate-artemisia sphoerocephala polysaccharide copolymer, and belongs to the field of biomaterials and tissue engineering materials. The method comprises the steps that through a coupling agent reaction, polyhydroxybutyrate macromonomer and artemisia sphoerocephala polysaccharide are subjected to coupling to prepare copolymer, so that performances of polyhydroxybutyrate macromonomer and artemisia sphoerocephala polysaccharide are complementary, hydrophilia of the copolymer is improved, and the application range of polyhydroxybutyrate serving as a drug carrier and a tissue engineering material is widened. The synthetic method disclosed by the invention has a simple structure, requires no special equipment, and is simple, controllable, low in cost and suitable for popularization and application.
Description
Technical field
The invention belongs to biomaterial, tissue engineering material field, relate to a kind of preparation method of the poly butyric ester-biological polyoses multipolymer for pharmaceutical carrier or tissue engineering material, particularly relate to a kind of synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer.
Technical background
Poly-(3-hydroxybutyrate ester) (PHB) is a kind of thermoplastic polyester plastic synthesized by fermentation using bacteria, compare with current general-purpose plastics, PHB has good biocompatibility and biological degradability, its mechanical property is similar to polypropylene, has the special propertys such as optical activity, piezoelectricity, resistance to air loss in addition.PHB can be widely used by Some substitute general-purpose plastics in many aspects as medical material, wrapping material, optical material etc.But, because the price of PHB is high, poor toughness, in the course of processing, easily there is the defects such as decomposition, seriously limit the Application and Development of PHB.At present, two aspects are mainly concentrated at present to the study on the modification of PHB: bio-modification and physical blending.Bio-modification is the link units of the hydroxy fatty acid being introduced other by fermentation using bacteria on the segment of PHB, as poly-(3-hydroxybutyrate ester and 3-hydroxyl valerate), poly-(3-hydroxybutyrate ester and 3-hydroxycaproic ester) etc.These multipolymers are more stable than PHB, and processing characteristics and impact property are all necessarily improved.Compare with bio-modification, physical blending is simple and the low modification mode of cost, the report of this respect is a lot, as PHB/ polyoxyethylene (PEO), PHB/ poly-(6-caprolactone, PCL), PHB/ cellulose propionate (CP), PHB/ cellaburate (CAB) co-mixing system etc.Patent CN1380114A discloses the preparation method of polyhydroxybutyrate/polyglycol porous scaffold material, has prepared the intermingling material being applicable to cartilaginous tissue and cell attachment growth by masterplate method and freeze-drying; Patent CN1312305A discloses a kind of method for toughening of poly butyric ester, adopts gamma-ray irradiation isoprene grafting poly butyric ester, obtains the modifying poly butyric ester material of high percentage of grafting; Patent CN1923890A discloses the intermingling material of polyhydroxy butyrate ester copolymer, poly(lactic acid) and whipping agent for foaming, has certain expansion ratio and totally biodegradable.
Biological polyoses forms the important component of Living organism, and in control cell fission, regulate Growth of Cells and in the organism eubolism that sustains life etc., there is vital role.As the requisite composition of life entity, except participating in vital movement process, polysaccharide also has diversified biological function, as the immunologic injury such as antitumor, anti-infective, immunological enhancement, radioprotective, resisting rheumatoid disease disease, anti-AIDS or immunodeficiency disease and many-sided function and the biological activity such as anti-oxidant.At present, the polysaccharide-modified of poly butyric ester is mainly physical modification, as blending and modifying (the Nattaporn et al. Polymer 52 of cellulose butyl acetate and poly butyric ester, 2011 461-471) and the preparation (Hernane et al. Carbohydrate Polymers 83,2,011 1279 – 1284) etc. of Mierocrystalline cellulose/poly butyric ester blend film.
Round end wormwood artemisia polysaccharide origin in composite family artemisia round end wormwood artemisia (
artemisia sphaerocephala), in its seed, polyose colloidal content is about 20%.Round end wormwood artemisia polysaccharide has the property being different from other biological polysaccharide: more than 115 DEG C high temperature unchangeability, viscosity is 1800 times of gelatin, self water suction 60 times, be insoluble to the diluted acid of heat, diluted alkaline and common solvent, can be dispersed in limited water absorption and swelling state in water, also in limited swelling state in dimethyl sulfoxide (DMSO), be the lac material with extremely strong water-retaining capacity, have high viscosity, high-moisture-retention, good dispersity, film forming properties stablizes the features such as clinging power is strong.Therefore, poly butyric ester chain is introduced hydrophilic round end wormwood artemisia polysaccharide, the wetting ability of poly butyric ester can be improved, obtain the copolymer material that can be used for pharmaceutical carrier or organizational project of better performances.
Summary of the invention
The object of the invention is to for problems of the prior art, a kind of synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer is provided.
The synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer of the present invention, comprises following processing step:
(1) synthesis of polyhydroxybutyrate esterdiol polymeric monomer: be dissolved in by poly butyric ester in chloroform, in 60 ~ 75 DEG C of return stirring 20 ~ 40min, adds anhydrous sulfanilic acid and ethylene glycol, at N
2protective reaction 10 ~ 12 hours; Reaction product with after distilled water agitator treating, suction filtration under the condition of 0.06 ~ 0.08MPa, gained solid ,-60 ~-50 DEG C, lyophilize 24 ~ 36 hours under 1 ~ 5Pa, obtains polyhydroxybutyrate esterdiol polymeric monomer;
The mass volume ratio of described poly butyric ester and chloroform is 10 ~ 15g/150mL; The mass ratio of described poly butyric ester and anhydrous sulfanilic acid is 2:1 ~ 3:1; The volume ratio of described chloroform and ethylene glycol is 3:1 ~ 5:1.
(2) synthesis of polymeric monomer isocyanic ester: be dissolved in ethylene dichloride by polyhydroxybutyrate esterdiol polymeric monomer, in 50 ~ 65 DEG C of return stirrings 20 ~ 40 minutes, adds tolylene diisocyanate, stannous octoate, N successively
2in 50 ~ 60 DEG C of stirring reactions 12 ~ 14 hours under protection, obtain polymeric monomer isocyanic ester; The mass volume ratio of described polyhydroxybutyrate esterdiol polymeric monomer and ethylene dichloride is 2 ~ 3g/50mL; The volume mass of described tolylene diisocyanate and polyhydroxybutyrate esterdiol polymeric monomer is than 0.1 ~ 0.2 mL/ g; Described stannous octoate is 0.05 ~ 0.1 mL/g with the volume mass ratio of polyhydroxybutyrate esterdiol polymeric monomer.
(3) preparation of round end wormwood artemisia polysaccharide soln: join in anhydrous DMF by round end wormwood artemisia polysaccharide, reacts 2 ~ 4 hours under magnetic stirring, obtains round end wormwood artemisia polysaccharide soln at 60 ~ 70 DEG C;
The mass volume ratio of described round end wormwood artemisia polysaccharide and DMF is 0.3 ~ 0.4 g/50mL; Described stirring velocity is 500 ~ 1000 revs/min.
(4) synthesis of poly butyric ester round end wormwood artemisia polysaccharide copolymer: polymeric monomer isocyanic ester is joined in above-mentioned round end wormwood artemisia polysaccharide soln, N
2in 60 ~ 70 DEG C of stirring reactions 24 ~ 48 hours under protection; be cooled to room temperature; absolute ethanol washing; centrifugal; lower sediment thing uses acetone, absolute ethanol washing successively; then suction filtration under 0.06 ~ 0.08MPa, gained solid ,-60 ~-50 DEG C, lyophilize 24 ~ 36 hours under 1 ~ 5Pa, obtains poly butyric ester round end wormwood artemisia polysaccharide copolymer.
The volume ratio of described round end wormwood artemisia polysaccharide soln and polymeric monomer isocyanic ester is 1:2 ~ 1:1; Described centrifugal be under 4000 ~ 5000 revs/min centrifugal 10 ~ 15 minutes.
Analytic explanation is carried out to the structure of the poly butyric ester round end wormwood artemisia polysaccharide copolymer of the present invention's synthesis below.
1, infrared spectrogram
Fig. 1 is the infrared spectrogram of poly butyric ester round end wormwood artemisia polysaccharide copolymer prepared by round end wormwood artemisia polysaccharide and the present invention.In round end wormwood artemisia polysaccharide, 3411 cm
-1with 2933 cm
-1place is the O-H stretching vibration of round end wormwood artemisia polysaccharide, 1052 cm
-1locate to vibrate for the angle of one-level O-H, 1614 cm
-1place is C=O stretching vibration on uronic acid.In poly butyric ester round end wormwood artemisia polysaccharide copolymer, 1728 cm
-1place is the stretching vibration of poly butyric ester chain ester group, 1629 cm
-1place's weak absorbing is the C=O stretching vibration of urethane, 1283 cm
-1place is the stretching vibration of C-O, 2980cm
-1place is the asymmetrical stretching vibration of PHB methyl.898 cm
-1with 825 cm
-1place is 1,2,4-trisubstituted benzene ring=c h bond out-of-plane deformation vibration absorption peak, 3421 cm
-1with 1381 cm
-1for stretching vibration and the flexural vibration of N-H in-OCNH-, the reduction of hydroxyl peak illustrates that round end wormwood artemisia polysaccharide and poly butyric ester are reacted by coupling agent, forms graft copolymer.
2, wetting ability test
At 25 DEG C, use the aqueous phase surface contact angle of DSA100 type contact angle instrument (KRUSS) working sample.Result is: at 25 DEG C, in aqueous phase, contact angle is 54 ° ~ 60 °, illustrates that poly butyric ester round end wormwood artemisia polysaccharide copolymer prepared by the present invention has good wetting ability.
In sum, the present invention compared with prior art tool have the following advantages:
1, the present invention utilizes coupling method in poly butyric ester chain, introduce wetting ability good round end wormwood artemisia polysaccharide, obtained poly butyric ester-biological polyoses multipolymer, effectively improve the wetting ability of poly butyric ester, expand the range of application of poly butyric ester as pharmaceutical carrier and tissue engineering material;
2, preparation method of the present invention is simple, and do not need specific installation, simply controlled, low cost, is applicable to applying.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of poly butyric ester round end wormwood artemisia polysaccharide copolymer prepared by the present invention.
Embodiment
Be further described below by the synthesis of specific embodiment to polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer of the present invention.
embodiment 1
(1) synthesis of polyhydroxybutyrate esterdiol polymeric monomer: take 15g poly butyric ester and be dissolved in 150mL chloroform, 65 DEG C of return stirring 30 min; 30mL ethylene glycol is added, at N after adding 5g anhydrous sulfanilic acid
2the lower reaction of protection 10 hours, adds distilled water agitator treating 6 times, then suction filtration under 0.06MPa, and gained solid ,-60 DEG C, lyophilize 24 hours under 2Pa, obtains polyhydroxybutyrate esterdiol polymeric monomer;
(2) synthesis of polymeric monomer isocyanic ester: take 2g polyhydroxybutyrate esterdiol polymeric monomer and be dissolved in 50mL ethylene dichloride, 60 DEG C of return stirrings 20 minutes, drip 0.5mL tolylene diisocyanate (dripping off for 30 minutes) by constant pressure funnel, add 0.2mL stannous octoate, N
2protection, 60 DEG C of stirring reactions 12 hours, obtain polymeric monomer isocyanic ester;
(3) preparation of round end wormwood artemisia polysaccharide soln: take 0.4g round end wormwood artemisia polysaccharide under room temperature, joins in the anhydrous DMF of 50mL, magnetic stirring apparatus stirs 3 hours (800 revs/min) at 65 DEG C, obtains round end wormwood artemisia polysaccharide soln;
(4) synthesis of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer: 50mL polymeric monomer isocyanic ester constant pressure funnel is added drop-wise in 50mL round end wormwood artemisia polysaccharide soln and (drips off for 30 minutes), N
2protection, stirring reaction 48 hours at 70 DEG C; Completely should be cooled to room temperature, add 300mL absolute ethanol washing, under 4000 revs/min centrifugal 12 minutes, lower sediment thing respectively washs 3 times with 300mL acetone, 400mL absolute ethanol washing successively, then suction filtration under the condition of 0.08MPa, gained solid is-50 DEG C, lyophilize 24 hours under 5Pa, and obtain polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer, at 25 DEG C, in aqueous phase, contact angle is 54 °.
Embodiment 2
(1) synthesis of polyhydroxybutyrate esterdiol polymeric monomer: take 10g poly butyric ester and be dissolved in 150mL chloroform, 75 DEG C of return stirring 20 min; 50mL ethylene glycol is added again, N after adding 4g anhydrous sulfanilic acid
2the lower reaction of protection 12 hours, adds distilled water agitator treating 8 times, suction filtration under the condition of 0.08MPa, and gained solid ,-55 DEG C, lyophilize 28 hours under 1Pa, obtains polyhydroxybutyrate esterdiol polymeric monomer;
(2) synthesis of polymeric monomer isocyanic ester: take 3g polyhydroxybutyrate esterdiol polymeric monomer and be dissolved in 50mL ethylene dichloride, 50 DEG C of return stirrings 40 minutes, drip 0.3mL tolylene diisocyanate (dripping off for 40 minutes) by constant pressure funnel, add 0.15mL stannous octoate, N
2protection, at 50 DEG C, stirring reaction 14 hours, obtains polymeric monomer isocyanic ester;
(3) preparation of round end wormwood artemisia polysaccharide soln: take 0.6g round end wormwood artemisia polysaccharide under room temperature, joins in the anhydrous DMF of 100mL, magnetic stirring apparatus stirs 2 hours (500 revs/min) at 70 DEG C, obtains round end wormwood artemisia polysaccharide soln;
(4) synthesis of poly butyric ester round end wormwood artemisia polysaccharide copolymer: 50mL polymeric monomer isocyanic ester constant pressure funnel is added drop-wise in 100mL round end wormwood artemisia polysaccharide soln and (drips off for 40 minutes), N
2protection, stirring reaction 24 hours at 60 DEG C; React complete and be cooled to room temperature, add 300mL absolute ethanol washing, under 4500 revs/min centrifugal 15 minutes, lower sediment thing respectively washs 3 times with 400mL acetone, 400mL absolute ethanol washing successively, then suction filtration under the condition of 0.07MPa, gained solid is-60 DEG C, lyophilize 36 hours under 1Pa, and obtain poly butyric ester round end wormwood artemisia polysaccharide copolymer, at 25 DEG C, in aqueous phase, contact angle is 58 °.
Embodiment 3
(1) synthesis of polyhydroxybutyrate esterdiol polymeric monomer: take 12g poly butyric ester and be dissolved in 150mL chloroform, 60 DEG C of return stirring 35 min, add 30mL ethylene glycol after adding 4g anhydrous sulfanilic acid, N again
2the lower reaction of protection 11 hours; Add distilled water agitator treating 4 times, suction filtration under the condition of 0.07MPa, gained solid ,-50 DEG C, lyophilize 36 hours under 3Pa, obtains polyhydroxybutyrate esterdiol polymeric monomer;
(2) synthesis of polymeric monomer isocyanic ester: take 2g polyhydroxybutyrate esterdiol polymeric monomer and be dissolved in 50mL ethylene dichloride, 65 DEG C of return stirrings 30 minutes, drip 0.4mL tolylene diisocyanate (dripping off for 35 minutes) by constant pressure funnel, add 0.1mL stannous octoate, N
2protection, at 50 DEG C, stirring reaction 13 hours, obtains polymeric monomer isocyanic ester;
(3) preparation of round end wormwood artemisia polysaccharide soln: take 0.3g round end wormwood artemisia polysaccharide under room temperature, joins in the anhydrous DMF of 50mL, magnetic stirring apparatus stirs 4 hours (1000 revs/min) at 60 DEG C, obtains round end wormwood artemisia polysaccharide soln;
(4) synthesis of poly butyric ester round end wormwood artemisia polysaccharide copolymer: 50mL polymeric monomer isocyanic ester constant pressure funnel is added drop-wise in 50mL round end wormwood artemisia polysaccharide soln and (drips off for 35 minutes), N
2protection, stirring reaction 24 hours at 65 DEG C; React complete and be cooled to room temperature, add 300mL absolute ethanol washing, under 5000 revs/min centrifugal 10 minutes; Lower sediment thing respectively washs 3 times with 200mL acetone, 300mL absolute ethanol washing successively, then suction filtration under the condition of 0.06MPa, gained solid is-55 DEG C, lyophilize 28 hours under 3Pa, and obtain poly butyric ester round end wormwood artemisia polysaccharide copolymer, at 25 DEG C, in aqueous phase, contact angle is 60 °.
Embodiment 4
(1) synthesis of polyhydroxybutyrate esterdiol polymeric monomer: take 15g poly butyric ester and be dissolved in 150mL chloroform, 75 DEG C of return stirring 40min, add 50mL ethylene glycol after adding 5g anhydrous sulfanilic acid, N again
2the lower reaction of protection 11 hours, adds distilled water agitator treating 5 times, suction filtration under 0.07MPa, gained solid at-55 DEG C, 3Pa lyophilize 24 hours, obtain polyhydroxybutyrate esterdiol polymeric monomer;
(2) synthesis of polymeric monomer isocyanic ester: take 3g polyhydroxybutyrate esterdiol polymeric monomer and be dissolved in 50mL ethylene dichloride, 55 DEG C of return stirrings 35 minutes, drip 0.5mL tolylene diisocyanate (dripping off for 30 minutes) by constant pressure funnel, add 0.15mL stannous octoate, N
2at protecting 60 DEG C, stirring reaction 14 hours, obtains polymeric monomer isocyanic ester;
(3) preparation of round end wormwood artemisia polysaccharide soln: take 0.8g round end wormwood artemisia polysaccharide under room temperature, joins in the anhydrous DMF of 100mL, magnetic stirring apparatus stirs 4 hours (700 revs/min) at 60 DEG C, obtains round end wormwood artemisia polysaccharide soln;
(4) synthesis of poly butyric ester round end wormwood artemisia polysaccharide copolymer: 50mL polymeric monomer isocyanic ester constant pressure funnel is added drop-wise in 100mL round end wormwood artemisia polysaccharide soln and (drips off for 30 minutes), N
2stirring reaction 36 hours at protecting 70 DEG C; React complete and be cooled to room temperature, add 450mL absolute ethanol washing, under 4500 revs/min centrifugal 15 minutes, lower sediment thing respectively washs 3 times with 400mL acetone, 200mL absolute ethanol washing successively, then suction filtration under the condition of 0.08MPa, gained solid at-60 DEG C, 5Pa lyophilize 36 hours, obtain poly butyric ester round end wormwood artemisia polysaccharide copolymer, at 25 DEG C, in aqueous phase, contact angle is 52 °.
Comparative example:
The synthesis of polyhydroxybutyrate esterdiol polymeric monomer: take 15g poly butyric ester and be dissolved in 150mL chloroform, 65 DEG C of return stirring 30 min; 30mL ethylene glycol is added, at N after adding 5g anhydrous sulfanilic acid
2the lower reaction of protection 10 hours, adds distilled water agitator treating 6 times, then suction filtration under 0.06MPa, and gained solid is-60 DEG C, lyophilize 24 hours under 2Pa, and obtain polyhydroxybutyrate esterdiol polymeric monomer, at 25 DEG C, in aqueous phase, contact angle is 63 °.Illustrate that the sample wetting ability of non-polysaccharide graft is poor, contact angle is larger.
Claims (10)
1. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer, comprises following processing step:
(1) synthesis of polyhydroxybutyrate esterdiol polymeric monomer: be dissolved in by poly butyric ester in chloroform, in 60 ~ 75 DEG C of return stirring 20 ~ 40min, adds anhydrous sulfanilic acid and ethylene glycol, at N
2protective reaction 10 ~ 12 hours; Reaction product with after distilled water agitator treating, suction filtration under the condition of 0.06 ~ 0.08MPa, gained solid ,-60 ~-50 DEG C, lyophilize 24 ~ 36 hours under 1 ~ 5Pa, obtains polyhydroxybutyrate esterdiol polymeric monomer;
(2) synthesis of polymeric monomer isocyanic ester: be dissolved in ethylene dichloride by polyhydroxybutyrate esterdiol polymeric monomer, in 50 ~ 65 DEG C of return stirrings 20 ~ 40 minutes, adds tolylene diisocyanate, stannous octoate, N successively
2in 50 ~ 60 DEG C of stirring reactions 12 ~ 14 hours under protection, obtain polymeric monomer isocyanic ester;
(3) preparation of round end wormwood artemisia polysaccharide soln: join in anhydrous DMF by round end wormwood artemisia polysaccharide, in 60 ~ 70 DEG C, 500 ~ 1000 revs/min lower stirring reactions 2 ~ 4 hours, obtains round end wormwood artemisia polysaccharide soln;
(4) synthesis of poly butyric ester round end wormwood artemisia polysaccharide copolymer: polymeric monomer isocyanic ester is joined in above-mentioned round end wormwood artemisia polysaccharide soln, N
2in 60 ~ 70 DEG C of stirring reactions 24 ~ 48 hours under protection; be cooled to room temperature; absolute ethanol washing; centrifugal; lower sediment thing uses acetone, absolute ethanol washing successively; then suction filtration under 0.06 ~ 0.08MPa, gained solid ,-60 ~-50 DEG C, lyophilize 24 ~ 36 hours under 1 ~ 5Pa, obtains poly butyric ester round end wormwood artemisia polysaccharide copolymer.
2. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (1), the mass volume ratio of poly butyric ester and chloroform is 10 ~ 15g/150mL.
3. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (1), the mass ratio of poly butyric ester and anhydrous sulfanilic acid is 2:1 ~ 3:1.
4. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (1), the volume ratio of chloroform and ethylene glycol is 3:1 ~ 5:1.
5. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (2), the mass volume ratio of polyhydroxybutyrate esterdiol polymeric monomer and ethylene dichloride is 2 ~ 3g/50mL.
6. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (2), tolylene diisocyanate is 0.1 ~ 0.2 mL/ g with the volume mass ratio of polyhydroxybutyrate esterdiol polymeric monomer.
7. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (2), stannous octoate is 0.05 ~ 0.1 mL/g with the volume mass ratio of polyhydroxybutyrate esterdiol polymeric monomer.
8. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (3), the mass volume ratio of round end wormwood artemisia polysaccharide and DMF is 0.3 ~ 0. 4g/50mL.
9. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, it is characterized in that: in step (4), the volume ratio of round end wormwood artemisia polysaccharide soln and polymeric monomer isocyanic ester is 2:1 or 1:1.
10. the synthetic method of polyhydroxybutyrate-sphoerocephala sphoerocephala polysaccharide copolymer as claimed in claim 1, is characterized in that: in step (4), described centrifugal be under 4000 ~ 5000 revs/min centrifugal 10 ~ 15 minutes.
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| CN1036215A (en) * | 1988-02-03 | 1989-10-11 | 沃纳-兰伯特公司 | Polymer materials by destructurized starch and at least a synthesising thermoplastic copolymer manufacturing |
| CN1380114A (en) * | 2002-03-28 | 2002-11-20 | 天津大学 | Polyhydroxybutyrate/polyglycol porous scaffold material and its preparation method |
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| CN1036215A (en) * | 1988-02-03 | 1989-10-11 | 沃纳-兰伯特公司 | Polymer materials by destructurized starch and at least a synthesising thermoplastic copolymer manufacturing |
| CN1380114A (en) * | 2002-03-28 | 2002-11-20 | 天津大学 | Polyhydroxybutyrate/polyglycol porous scaffold material and its preparation method |
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| 壳聚糖-聚羟基丁酸酯接枝共聚物的制备与表征;孟晓荣等;《中国组织工程研究与临床康复》;20080901;第12卷(第23期);59-63 * |
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