CN104231578A - Completely biodegradable polyester material and preparation and application of completely biodegradable polyester - Google Patents
Completely biodegradable polyester material and preparation and application of completely biodegradable polyester Download PDFInfo
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- CN104231578A CN104231578A CN201410438759.8A CN201410438759A CN104231578A CN 104231578 A CN104231578 A CN 104231578A CN 201410438759 A CN201410438759 A CN 201410438759A CN 104231578 A CN104231578 A CN 104231578A
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Abstract
The invention discloses a completely biodegradable polyester material and preparation and application of the completely biodegradable polyester. The material comprises the following components: 60-98 percent of poly(L-lactic acid) and 2-40 percent of poly(L-lactic acid-caprolactone) copolymer, wherein the molecular weight of the copolymer is 10000-100000, a number ratio of lactic acid units to caprolactone units is (95:5) to (20:80), and the copolymer contains arms of 1-6 specific structures. The preparation method of the material comprises the following steps: dissolving poly(L-lactic acid) into an organic solvent in which polylactic acid can be dissolved, adding the copolymer in a formula amount, and fully stirring, so that the copolymer is completely dissolved; and adding a polymer solution into water or a mixed solution of water/alcohol, separating out the blend by precipitating, filtering, and drying, thereby preparing the to-be-prepared completely biodegradable polyester material. The material can be used for preparing corresponding products in the fields of artificial bones, scaffolds for tissue engineering and interventional medical equipment in biomedicine, and the prepared product has excellent mechanical property and biodegradability.
Description
Technical field
The present invention relates to high-molecular biologic degradable material technical field, more specifically, relating to one can totally biodegradable macromolecular material and preparation method thereof and application.
Background technology
Biodegradated polymer materal is the macromolecular material that after a class executes corresponding function in human body, energy degradation in vivo is also absorbed gradually or drains, and can not forever retain the physiology and life that affect people in vivo as foreign matter.Along with the development of modern medicine, many products resided in for a long time in body that do not need more and more use biodegradated polymer materal.
Degradable high polymer material-poly(lactic acid), be degradable high polymer material conventional in a kind of biomedicine, the size of molecular weight and the height of degree of crystallinity largely affect its mechanical property.Poly(lactic acid) has adjustable intensity, but matter is crisp often has influence on its use range.Although by adding small molecules nucleator [CN200910045012.5] or softening agent [CN201010205306.2] can make Materials Fracture elongation increase, in bio-medical field, small molecules often moves under the effect of body fluid, causes product failure.Use polymeric plasticizer can avoid the migration [CN201210548826.2] as small molecules softening agent, but uses the diamines after the material degradation of vulcabond chain extension may produce toxicity to human body.
Polycaprolactone is also a kind of degradable macromolecule, and biocompatibility is good, and multiple methylene radical in caprolactone units provide flexibility for its molecule.But pure polycaprolactone intensity is bad, and second-order transition temperature is low, be used alone the requirement being difficult to meet medicine equipment goods.Using flexible biodegradable polymer polycaprolactone to form polylactic acid and caprolactone blend to improve the fragility of poly(lactic acid) is a kind of reasonably selection [Engineering Fracture Mechanics 74 (2007) 1872 – 1883].Publication number is CN201210114155.9 patent document, propose poly(lactic acid) and polycaprolactone blended time add poly butylene succinate and diphenylmethanediisocyanate, although add the advantage that each single component material can overcome respective shortcoming, comprehensive each single component material, residual or its degraded product of vulcabond makes it not be applied to biomedical sector.Due to poly(lactic acid) and polycaprolactone two kinds of high molecular poor compatibility, carrying out blended to them, often needing to add compatilizer when not using this kind of chemical coupling agent of vulcabond.In bio-medical field, compatilizer also must be the material of good biocompatibility.Therefore, investigator is had using the segmented copolymer of polyethylene/polypropylene glycol or poly(lactic acid)-polycaprolactone co-polymer as blended property compatilizer.Add the segmented copolymer [Energy Procedia 34 (2013) 542 – 548] of polyethylene/polypropylene glycol or add blended property [the Journal of Applied Polymer Science that poly-(lactic acid-caprol acton) multipolymer all contributes to improving poly(lactic acid) and polycaprolactone, Vol.86,1892 – 1898 (2002)].In any case, these systems all relate to three kinds of different materials, and system is very complicated; Polycaprolactone Partial digestion pure in system is excessively slow; And these researchs are also only limitted to pay close attention to the consistency of co-mixing system, crystalline change, less have the mechanical property change paying close attention to material.
Summary of the invention
For deficiency and the present situation of the biodegradated polymer materal of prior art, object of the present invention aims to provide a kind of polyester material of fully biodegradable, for fields such as the artificial diaphysis in biomedicine, tissue engineering bracket, interventional medical apparatuses to prepare corresponding product, the shortcoming that the product performance prepared of the degraded macromolecular provided to overcome prior art are undesirable.
Basic thought of the present invention is directly mixed with poly(lactic acid) by poly-(Pfansteihl-caprolactone) multipolymer, utilize poly-(Pfansteihl-caprolactone) multipolymer can not degrade slow as pure polycaprolactone, and it is compatible with pure poly(lactic acid), there is provided flexible by the multiple MU (methylene unit) in the caprolactone chain link in multipolymer, thus improve the fragility of blend, and poly-(Pfansteihl-caprolactone) multipolymer itself also can reduce pure polylactic acid crystal, thus material is made to have better mechanical property.
Fully biodegradable polyester material provided by the invention, the poly (l-lactic acid) of its quality 98% ~ 60% and poly-(Pfansteihl-caprolactone) multipolymer of quality 2% ~ 40%, the molecular weight of described poly-(Pfansteihl-caprolactone) multipolymer is 10,000 ~ 100,000, lactic acid units and caprolactone units number are than being 95:5 to 20:80, the arm containing 1 ~ 6 following structure:
N=10 ~ 1000 integer in structural arm, m=5 ~ 200 integer.
In technique scheme of the present invention, described poly-(Pfansteihl-caprolactone) multipolymer preferentially selects poly-(Pfansteihl-caprolactone) multipolymer that lactic acid units and caprolactone units number ratio are 90:10 to 40:60, molecular weight is 10,000 ~ 80,000.Further, described poly-(Pfansteihl-caprolactone) multipolymer is prepared by following method: mixed with 5 ~ 100 parts of annular lactones by 0.01 ~ 1 part of initiator, after vacuum-drying, add the catalyst mix counting 0.01 ~ 5% with annular lactone quality again, at vacuum tightness 0.01 ~ 100mmHg, room temperature ~ 100 DEG C dry 1 ~ 24 hour, vacuum sealing tube, in 100 ~ 180 DEG C of reactions 1 ~ 120 hour, namely obtains degradable poly-(Pfansteihl-caprolactone) multipolymer.
The initiator that poly-(Pfansteihl-caprolactone) multipolymer of preparation uses, preferentially selects the unit alcohol with hydroxyl or polyvalent alcohol.Unit alcohol is the alcohol comprising 4 ~ 16 carbon atoms, as butanols, amylalcohol, hexanol, enanthol etc.; Polyvalent alcohol comprises dibasic alcohol, trivalent alcohol, tetravalent alcohol, five yuan and hexavalent alcohol etc., wherein dibasic alcohol can be ethylene glycol, propylene glycol or, butyleneglycol etc.; Trivalent alcohol can be glycerol, three (methylol) ethane etc.; Tetravalent alcohol can be tetramethylolmethane etc.; Pentavalent alcohol can be Xylitol etc.; Hexavalent alcohol can be dipentaerythritol, N.F,USP MANNITOL, sorbyl alcohol etc.Initiator particularly preferably its mid-boiling point higher than the above-claimed cpd of 150 DEG C.The structures shape of initiator in the structure of poly-(Pfansteihl-caprolactone) multipolymer, when initiator be unit alcohol or dibasic alcohol time, the structure of multipolymer be that linearly multipolymer is an arm or two arms; When initiator be ternary and more than three alcoholic extract hydroxyl groups time, the structure of multipolymer is multi-arm structure.
The annular lactone that poly-(Pfansteihl-caprolactone) multipolymer of preparation uses preferentially selects the annular lactone that lactic acid units and caprolactone units ratio are 95:5 to 20:80, molecular weight is 1 ~ 100,000; Preferentially select the annular lactone that lactic acid units and caprolactone units ratio are 90:10 to 40:60, molecular weight is 1 ~ 80,000 further.
If think prepare poly-(Pfansteihl-caprolactone) multipolymer color comparatively dark, or during to its purity requirement height, purifying can be carried out to poly-(Pfansteihl-caprolactone) multipolymer obtained.The method of purifying can take the normally used method of purifying polyester.
The method of the fully biodegradable polyester material that preparation the invention described above provides, can take poly (l-lactic acid) to be dissolved in 1 ~ 10 times can dissolve in the organic solvent of poly(lactic acid), add poly-(Pfansteihl-caprolactone) multipolymer of formula ratio, after abundant stirring makes polymkeric substance dissolve completely, polymers soln is joined 5 ~ 100 times in the water of polymers soln or water/alcohol mixed solution, blend is precipitated out, after filtration, the dry i.e. obtained completely biodegradable material with toughening effect.Described poly-(Pfansteihl-caprolactone) multipolymer, preferential poly-(Pfansteihl-caprolactone) multipolymer adopting purified process.
In the method preparing fully biodegradable polyester material, described organic solvent preferentially selects methylene dichloride, trichloromethane, monochloroethane, 1,2-ethylene dichloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, acetone, ethyl acetate, tetrahydrofuran (THF), acetonitrile, N, at least one in dinethylformamide, N,N-dimethylacetamide.
Prepare above-mentioned fully biodegradable polyester material, blended for poly (l-lactic acid) and poly-(Pfansteihl-caprolactone), also can adopt polymer blended conventional method, especially larger to molecular weight poly(lactic acid), adopt melt blending more applicable.Concrete operations can be taked, to join in twin screw extruder after the poly (l-lactic acid) of formula ratio and the poly-abundant drying of (Pfansteihl-caprolactone) multipolymer, controlling screw speed is 10 ~ 150 revs/min, extrusion temperature is 130 ~ 200 DEG C, the residence time of material is 1 ~ 15 minute, namely obtains desired product.The controling parameters of melt blending twin screw extruder preferentially selects screw speed to be 10 ~ 100 revs/min, and extrusion temperature is 140 ~ 190 DEG C, and the residence time of material is 1 ~ 10 minute.Preferably first insert vacuum drying oven before melt blending to dry at 45 ~ 100 DEG C, vacuum.
Fully biodegradable polyester material provided by the invention can be used as diaphysis material, tissue engineering bracket material, interventional medical device material etc., can be used for making corresponding medical device goods, as the ligation nail, folder etc. that use in medical operating.The preparation of corresponding medical device goods, directly can adopt and add poly-(Pfansteihl-caprolactone) multipolymer in base material poly (l-lactic acid), after solution blending or blending extrusion machine, add injecting machine material tube, obtain biodegradable medical device goods by injection moulding.
Fully biodegradable polyester material provided by the invention, to join in poly(lactic acid) as the polymer with toughening effect and improve its fragility by gathering (Pfansteihl-caprolactone) multipolymer and keep its intensity, have not been reported in patent or other document.The molecular weight regulating poly(lactic acid) can be further advanced by, add appropriate polyphosphazene polymer (Pfansteihl-caprolactone) multipolymer with toughening effect, obtain a kind of new material for the preparation of the product with degradation property.Until the present invention completes, contriver does not see relevant report in patent documentation or other document yet.
Biodegradable polyester material provided by the invention is a kind of polylactic acid based material, take PLLA as main raw, add poly-(Pfansteihl-caprolactone) multipolymer of the appropriate fully-degradable polymer with toughening effect, by the blended Biodegradable Materials obtained.Poly-(Pfansteihl-caprolactone) multipolymer with toughening effect is joined in poly(lactic acid), improves the fragility of poly(lactic acid), and keep its intensity.Biodegradable polylactic acid sill provided by the invention, amplify in brittle failure face in the Electronic Speculum figure of 500 times and can find out that in intermingling material, two component mixing are very even, the Electronic Speculum figure amplifying 2500 times can find out substantially do not have phase interface between two components, is a kind of Biodegradable Materials of brand new.This material mechanical performance is excellent, and elongation at break improves 10 ~ 200% than the pure PLLA of same molecular amount.The elongation at break of intermingling material and degradation property can regulate according to the ratio of lactic acid units and caprolactone units in poly-(Pfansteihl-caprolactone) multipolymer per-cent in the blend and multipolymer.The present invention, under the complete biodegradable keeping material and high strength prerequisite, effectively improves the snappiness of biodegradable polylactic acid.Therefore, the Biodegradable Materials that the present invention obtains has excellent mechanical property, good biocompatibility and controlled degradation speed, have broad application prospects at biomedical sector, be particularly suitable for preparing complete biodegradable, for the injection-molded item in body as ligation nail clip product.
Biodegradable material provided by the invention, components migrate can not be produced, and there is excellent mechanical property, obviously can improve the toughness of poly(lactic acid) and the defect of fragility difference, elongation at break can reach the poly(lactic acid) 200% of same molecular amount, can be widely used in the various medical devices fields such as diaphysis material, tissue engineering bracket material, interventional medical apparatus (as ligation nail clip etc.) material.The all components raw material Dou Shi food and medicine surveillance authority accreditation that preparation uses, safe and reliable.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrum of poly-(Pfansteihl-caprolactone) multipolymer that the present invention synthesizes;
Fig. 2-1 to Fig. 2-3 is that Electronic Speculum figure is amplified in the brittle failure face of fully biodegradable polyester material of the present invention, the Electronic Speculum figure of wherein Fig. 2-1 to be the Electronic Speculum figure of amplification 500 times, Fig. 2-2 be amplification 2500 times; Fig. 2-3 is Electronic Speculum figure that poly-lactic acid material brittle failure face pure under the same terms amplifies 500 times.
Fig. 3 is the mechanical experimental results graphic representation of complete biodegradable polyester material provided by the invention, and three different curves are results that same sample measures for three times.
In table 1, institute's column data is the mean value of three test results.
Embodiment
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is that following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In following embodiment, the number of each component, per-cent, ratio, unless otherwise indicated, be mass fraction (gram), mass percent, mass ratio.
Embodiment 1
The annular lactone of 0.05 part of nonylcarbinol initiator and the 25 parts of purifying ratio 90:10 of caprolactone monomer (lactic acid monomer with) is mixed, after vacuum-drying, add the catalyst mix counting 0.01% with annular lactone quality again, inflated with nitrogen drives oxygen away, vacuumize, in triplicate, control vacuum tightness 0.05mmHg, vacuum sealing tube, in 130 DEG C of reactions 48 hours, namely obtains degradable poly-(Pfansteihl-caprolactone) multipolymer.The purified rear mensuration number-average molecular weight of products therefrom is 8.1 × 10
4g/mol.
6 parts of/gram of poly (l-lactic acid)s are dissolved in 20mL dichloromethane solvent, add 4 parts of/gram above-mentioned poly-(Pfansteihl-caprolactone) multipolymers produced, after abundant stirring makes polymkeric substance dissolve completely, progressively be added drop-wise in the water/alcohol mixeding liquid of 100mL1:1, blend is precipitated out, filter, dry, obtain the fully biodegradable polyester material with mechanical property.
Embodiment 2
Poly-(Pfansteihl-caprolactone) 20 parts embodiment 1 obtained and poly (l-lactic acid) 180 parts are 80 DEG C of dryings after 5 hours, join in twin screw extruder, controlling screw speed is 15 revs/min, extrusion temperature is 180 DEG C, the residence time of material is 5 minutes, namely obtains the fully biodegradable polyester material with excellent mechanical property.
Embodiment 3
The annular lactone of 0.1 part of three (methylol) ethane initiator and the 50 parts of purifying ratio 90:10 of caprolactone monomer (lactic acid monomer with) is mixed, after vacuum-drying according to poly-(Pfansteihl-caprolactone) interpolymer of method synthesized degradable described in embodiment 1.The purified rear mensuration number-average molecular weight of products therefrom is 5.8 × 10
4g/mol.
7.5 parts of/gram of poly (l-lactic acid)s are dissolved in 30mL dichloromethane solvent, add 2.5 parts of/gram poly-(Pfansteihl-caprolactone) multipolymers, after abundant stirring makes polymkeric substance dissolve completely, progressively be added drop-wise in the water of 200mL, blend is precipitated out, after filtration, dry, obtain the fully biodegradable polyester material with excellent mechanical property.
Embodiment 4
The annular lactone of 0.5 part of three (methylol) ethane initiator and the 100 parts of purifying ratio 50:50 of caprolactone monomer (lactic acid monomer with) is mixed, after vacuum-drying according to poly-(Pfansteihl-caprolactone) of method synthesized degradable described in embodiment 1.The purified rear mensuration number-average molecular weight of products therefrom is 5.7 × 10
4g/mol.
9.8 parts of/gram of poly (l-lactic acid)s are dissolved in 20mL dichloromethane solvent, add 0.2 part of/gram poly-(Pfansteihl-caprolactone) multipolymer, after abundant stirring makes polymkeric substance dissolve completely, progressively be added drop-wise in the water/alcohol mixeding liquid of 300mL1:1, blend is precipitated out, filter, dry, obtain the fully biodegradable polyester material with mechanical property.
Embodiment 5
The annular lactone of 0.5 part of lauryl alcohol initiator and the 50 parts of purifying ratio 50:50 of caprolactone monomer (lactic acid monomer with) is mixed, after vacuum-drying according to poly-(Pfansteihl-caprolactone) of method synthesized degradable described in embodiment 1.The purified rear mensuration number-average molecular weight of products therefrom is 1.8 × 10
4g/mol.
By poly-(Pfansteihl-caprolactone) 66 parts that obtain and poly (l-lactic acid) 134 parts 80 DEG C of dryings after 8 hours, join in twin screw extruder, controlling screw speed is 10 revs/min, extrusion temperature is 182 DEG C, the residence time of material is 5 minutes, namely obtains the fully biodegradable polyester material with mechanical property.
Embodiment 6
95 parts of poly (l-lactic acid)s are dissolved in 200mL trichloromethane solvent, add poly-(Pfansteihl-caprolactone) 5 parts that embodiment 5 obtains, after abundant stirring makes polymkeric substance dissolve completely, progressively be added drop-wise in the water/alcohol mixeding liquid of 1000mL1:1, blend is precipitated out, filter, dry, obtain the fully biodegradable polyester material with mechanical property.
Embodiment 7
The annular lactone of 1.0 parts of dipentaerythritol initiators and the 100 parts of purifying ratio 40:60 of caprolactone monomer (lactic acid monomer with) is mixed, after vacuum-drying according to poly-(Pfansteihl-caprolactone) of method synthesized degradable described in embodiment 1.The purified rear mensuration number-average molecular weight of products therefrom is 2.3 × 10
4g/mol.
9.3 parts of poly (l-lactic acid)s are dissolved in 10mL1,1, in 2,2-tetrachloroethane solvent, add 0.7 part of poly-(Pfansteihl-caprolactone) multipolymer, after abundant stirring makes polymkeric substance dissolve completely, progressively be added drop-wise in the water/alcohol mixeding liquid of 200mL1:1, blend is precipitated out, filter, drying, obtains the fully biodegradable polyester material with mechanical property.
Embodiment 8
The annular lactone of 1 part of n-Heptyl alcohol initiator and the 100 parts of purifying ratio 80:20 of caprolactone monomer (lactic acid monomer with) is mixed, after vacuum-drying according to poly-(Pfansteihl-caprolactone) of method synthesized degradable described in embodiment 1.The purified rear mensuration number-average molecular weight of products therefrom is 1.1 × 10
4g/mol.
By poly-(Pfansteihl-caprolactone) 15 parts that obtain and poly (l-lactic acid) 85 parts 80 DEG C of dryings after 6 hours, join in twin screw extruder, controlling screw speed is 20 revs/min, extrusion temperature is 185 DEG C, the residence time of material is 3 minutes, namely obtains the fully biodegradable polyester material with mechanical property.
Table 1. embodiment 1 ~ 8 prepare Biodegradable Materials correlated performance
Claims (10)
1. a fully biodegradable polyester material, it is characterized in that, composition component comprises the poly (l-lactic acid) of quality 98% ~ 60% and poly-(Pfansteihl-caprolactone) multipolymer of quality 2% ~ 40%, the molecular weight of described poly-(Pfansteihl-caprolactone) multipolymer is 10,000 ~ 100,000, lactic acid units and caprolactone units number are than being 95:5 to 20:80, the arm containing 1 ~ 6 following structure:
N=10 ~ 1000 integer in structural arm, m=5 ~ 200 integer.
2. fully biodegradable polyester material according to claim 1, is characterized in that, the lactic acid units of described poly-(Pfansteihl-caprolactone) multipolymer is with caprolactone units number than being 90:10 to 40:60, and molecular weight is 10,000 ~ 80,000.
3. fully biodegradable polyester material according to claim 1 and 2, it is characterized in that, described poly-(Pfansteihl-caprolactone) multipolymer is prepared by following method: mixed with 5 ~ 100 mass parts annular lactones by 0.01 ~ 1 mass parts initiator, after vacuum-drying, add in the catalyst mix of annular lactone quality 0.01 ~ 5% again, vacuum tightness 0.01 ~ 100mmHg, at 10 DEG C ~ 100 DEG C dry 1 ~ 24 hour, vacuum sealing tube, in 100 ~ 180 DEG C of reactions 1 ~ 120 hour, namely obtains degradable poly-(Pfansteihl-caprolactone) multipolymer.
4. fully biodegradable polyester material according to claim 3, is characterized in that, described initiator is unit alcohol with hydroxyl or polyvalent alcohol.
5. fully biodegradable polyester material according to claim 4, is characterized in that, described initiator is that boiling point is not less than 150 DEG C, with the unit alcohol of hydroxyl or polyvalent alcohol.
6. fully biodegradable polyester material according to claim 1 and 2, is characterized in that, described poly-(Pfansteihl-caprolactone) multipolymer is poly-(Pfansteihl-caprolactone) multipolymer of purified process.
7. the preparation method of the described fully biodegradable polyester material of one of claim 1 to 6, it is characterized in that, poly (l-lactic acid) is dissolved in 1 ~ 10 times can dissolve in the organic solvent of poly(lactic acid), add poly-(Pfansteihl-caprolactone) multipolymer of formula ratio, after abundant stirring makes polymkeric substance dissolve completely, polymers soln is joined 5 ~ 100 times in the water of polymers soln or water/alcohol mixed solution, blend is precipitated out, after filtration, the dry i.e. obtained completely biodegradable material with toughening effect.
8. the preparation method of fully biodegradable polyester material according to claim 7, is characterized in that, described organic solvent is methylene dichloride, trichloromethane, monochloroethane, 1,2-ethylene dichloride, 1，1，1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2, at least one in 2-tetrachloroethane, acetone, ethyl acetate, tetrahydrofuran (THF), acetonitrile, DMF, N,N-dimethylacetamide.
9. the preparation method of the fully biodegradable polyester material that one of claim 1 to 6 is described, the poly (l-lactic acid) of formula ratio and poly-(Pfansteihl-caprolactone) multipolymer is it is characterized in that to insert in twin screw extruder, controlling screw speed is 10 ~ 150 revs/min, extrusion temperature is 130 ~ 200 DEG C, residence time of material be 1 ~ 15 minute blended, extrude and namely prepare fully biodegradable polyester material to be prepared.
10. the application of the described fully biodegradable polyester material of one of claim 1 to 6, is characterized in that preparing the application in diaphysis, tissue engineering bracket, interventional medical device article.
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| CN113403750B (en) * | 2021-06-28 | 2022-02-25 | 运鸿集团股份有限公司 | Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask |
| CN113403750A (en) * | 2021-06-28 | 2021-09-17 | 运鸿集团股份有限公司 | Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask |
| GB2608471B (en) * | 2021-06-28 | 2024-03-27 | China Yunhong Holdings Co Ltd | Method for preparing fully-degradable non-woven fabric by spun-bonding |
| CN116196486A (en) * | 2021-11-30 | 2023-06-02 | 韩国凡特有限公司 | Biodegradable composite material composition for manufacturing stent and preparation method thereof |
| CN114292503A (en) * | 2022-01-10 | 2022-04-08 | 海信容声(广东)冰箱有限公司 | Puncture-resistant biodegradable material and preparation method and application thereof |
| CN114292503B (en) * | 2022-01-10 | 2023-05-02 | 海信容声(广东)冰箱有限公司 | Puncture-resistant biodegradable material and preparation method and application thereof |
| CN114805778A (en) * | 2022-04-15 | 2022-07-29 | 湖南聚仁化工新材料科技有限公司 | Environment-friendly plasticizer and preparation method thereof |
| CN114805778B (en) * | 2022-04-15 | 2023-03-10 | 湖南聚仁化工新材料科技有限公司 | Environment-friendly plasticizer and preparation method thereof |
| CN114907663A (en) * | 2022-05-30 | 2022-08-16 | 冯艳梅 | Blending modified packaging material |
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