CN117801485A - Bioactive polylactic acid/tannin composite material and preparation method thereof - Google Patents
Bioactive polylactic acid/tannin composite material and preparation method thereof Download PDFInfo
- Publication number
- CN117801485A CN117801485A CN202311862762.8A CN202311862762A CN117801485A CN 117801485 A CN117801485 A CN 117801485A CN 202311862762 A CN202311862762 A CN 202311862762A CN 117801485 A CN117801485 A CN 117801485A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- tannin
- composite material
- bioactive
- grafted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001864 tannin Polymers 0.000 title claims abstract description 118
- 239000001648 tannin Substances 0.000 title claims abstract description 118
- 235000018553 tannin Nutrition 0.000 title claims abstract description 118
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 112
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 230000000975 bioactive effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 229920000578 graft copolymer Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 19
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 14
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 10
- 238000012377 drug delivery Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 2
- 229940022769 d- lactic acid Drugs 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000012662 bulk polymerization Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 11
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical group C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000004071 biological effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 210000001519 tissue Anatomy 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001434 poly(D-lactide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004402 polyphenol group Chemical group 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a bioactive polylactic acid/tannin composite material and a preparation method thereof, wherein 70-88% of polylactic acid, 10-20% of tannin and 2-10% of tannin grafted polylactic acid are weighed according to weight percentage; the polylactic acid, the tannin and the tannin grafted polylactic acid are evenly mixed and then added into a double-screw extruder to be subjected to melt blending, extrusion granulation and vacuum drying under certain heating temperature and condition, so that the bioactive polylactic acid/tannin composite material is obtained, the tannin grafted polylactic acid is prepared through bulk polymerization, and the tannin grafted polylactic acid is added into a mixed system of the polylactic acid and the tannin by taking the polylactic acid and the tannin as a compatilizer, so that the dispersion and the compatibility of the tannin in a polylactic acid matrix are promoted, and the stability of the mechanical property of the composite material is ensured.
Description
Technical Field
The invention relates to the technical field of medical polymer composite materials, in particular to a bioactive polylactic acid/tannin composite material and a preparation method thereof.
Background
Polylactic acid has received a great deal of attention in the medical fields of tissue engineering scaffold materials and drug delivery systems, etc. due to its excellent biocompatibility and biodegradability, and has been authenticated by the U.S. food and drug administration (FDI) as a biomaterial implanted into the human body. Polylactic acid has weak biological activity due to poor hydrophilicity and cell adsorption force, and local pH change caused by degradation is easy to cause aseptic inflammation, and the polylactic acid cannot meet the requirements of tissue engineering in certain medical materials, so that the biological activity of the polylactic acid needs to be improved through chemical or physical modification. Among them, blending with a highly bioactive material is one of the simplest and effective methods for obtaining a highly bioactive polylactic acid-based composite material.
Tannins (TA) are natural polyphenols which contain a large number of polyphenol groups and are linked to a polyhydroxy alcohol nucleus via ester bonds, and have excellent hydrophilic, antioxidative, antibacterial properties and other various biological properties due to their special chemical structure. In addition, the biological material is biological with polylactic acid, has biological safety, can effectively improve the biological activity of the polylactic acid by combining with the polylactic acid, and has great application potential in the medical field. The polylactic acid fiber substrate is prepared by adopting an electrostatic spinning technology in the patent CN114438782A, tannic acid and ferric ions are chelated, and cysteine is grafted on the surface to prepare the composite fiber membrane, so that the membrane material has excellent biocompatibility and oxidation resistance, can stimulate cell proliferation and promote osteogenesis, and meets the requirements of bone repair materials, but the preparation process of the product is complex, and is difficult to realize large-scale industrial production.
The direct blending of polylactic acid and tannin is the simplest scheme with industrial production potential, however, due to poor compatibility of polylactic acid and tannin, even under the condition of high filling amount (15%), the dispersibility of tannin in a polylactic acid matrix is still poor, which can lead to unstable biological activity of a composite material of polylactic acid and tannin, and the problem of compatibility can seriously damage the mechanical property of the material, so that the performance of medical products is poor, and the use is affected. For this reason, compatibilizers are often used to improve the compatibility between polylactic acid and tannin. Polylactic acid/tannin composites have been reported to be prepared using reactive extrusion methods using methylene diphenyl diisocyanate (p-MDI) or 3-aminopropyl triethoxysilane (APS) as compatibilizers. The results show that both compatibilizers are effective in improving the compatibility of the mixture, wherein p-MDI is more effective in improving the toughness of the composite. However, since most of the currently used reactive compatibilizers are non-bio-based materials, the risk of the bio-safety of the polylactic acid/tannin composite material is difficult to evaluate, and thus the prepared product is difficult to be applied to the medical field.
Disclosure of Invention
The scheme provides a bioactive polylactic acid/tannin composite material and a preparation method thereof, wherein tannin is introduced into a polylactic acid matrix, so that the bioactivity and hydrophilicity of the polylactic acid-based composite material are improved, the compatibility of the composite material is improved by taking tannin grafted polylactic acid as a compatilizer, the introduction of materials which possibly influence the biosafety is avoided, and the bioactive polylactic acid/tannin composite material can be applied to the biomedical field to overcome the problems and defects of the polylactic acid material in the biomedical aspect in the prior art.
In order to achieve the above purpose, the technical scheme provides a preparation method of a bioactive polylactic acid/tannin composite material, which comprises the following steps:
weighing 70-88% of polylactic acid, 10-20% of tannin and 2-10% of tannin grafted polylactic acid according to weight percentage;
and uniformly mixing polylactic acid, tannin and tannin grafted polylactic acid, adding the mixture into a double-screw extruder, and carrying out melt blending, extrusion granulation and vacuum drying under certain heating temperature and condition to obtain the bioactive polylactic acid/tannin composite material.
In some embodiments, the polylactic acid is one of poly-l-lactic acid, poly-d-lactic acid, and racemic lactic acid. In this embodiment, the polylactic acid is preferably poly-L-lactic acid.
In some embodiments, the tannin grafted polylactic acid is prepared by the following method:
(1) Adding lactide and tannin in a certain proportion into a reactor, adding stannous octoate as a catalyst, catalyzing lactide to carry out ring-opening polymerization under the conditions of nitrogen and 130-200 ℃ for 2-5 hours to prepare a graft copolymer,
(2) And (3) precipitating, purifying and drying the graft copolymer to obtain the tannin grafted polylactic acid.
Specifically, the chemical formula for preparing the graft polymer is shown below:
wherein the grafting reaction takes tannin as an initiator, and takes a plurality of hydroxyl groups on a single Ning Duo phenol group as initiation sites to carry out the grafting reaction, wherein R in the formula is a grafted polylactic acid chain segment.
In some embodiments, the lactide is L-lactide, D-lactide, and mixtures thereof.
In some embodiments, the mass ratio of lactide to tannin is from 2:1 to 20:1, preferably the mass ratio of lactide to tannin is from 2:1 to 11:1. It should be noted that the excessive amount of lactide in the present embodiment can ensure that the hydroxyl group on tannin is completely grafted with polylactic acid chain segment.
In some embodiments, the stannous octoate is used in an amount of 0.01% to 0.05%, preferably, the stannous octoate is used in an amount of 0.01%. The method adopts low-concentration stannous octoate to reduce the content of residual tin element in the polylactic acid product and meet the requirements of medical products.
In some embodiments, the graft copolymer is subjected to precipitation purification to remove unreacted lactide and tannins. Specifically, the precipitation and purification process comprises dissolving the synthesized graft copolymer in dichloromethane to obtain a solution, slowly pouring the solution into methanol for precipitation, taking out the precipitate, drying and crushing to obtain the tannin grafted polylactic acid.
In some embodiments, the twin screw extruder is at a temperature of each zone in order from the feed zone: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 190 ℃ of the temperature of the machine head, 60-80rpm of the screw speed.
In a second aspect, the present disclosure provides a bioactive polylactic acid/tannin composite material, which is prepared according to the preparation method of the bioactive polylactic acid/tannin composite material.
In some embodiments, the bioactive polylactic acid/tannin composite material provided by the present solution has a tensile strength of 55.6-82.6Mpa.
In a third aspect, the present disclosure provides an application of a bioactive polylactic acid/tannin composite material, wherein the bioactive polylactic acid/tannin composite material is applied to the biomedical field, and in particular to a tissue engineering scaffold material and a drug delivery system.
Compared with the prior art, the technical scheme has the following characteristics and beneficial effects:
(1) According to the invention, the tannin grafted polylactic acid is prepared through bulk polymerization, and is added into a mixed system of polylactic acid and tannin by taking the tannin grafted polylactic acid as a compatilizer, so that the dispersion and compatibility of tannin in a polylactic acid matrix are promoted, and the stability of the mechanical property of the composite material is ensured.
(2) The polylactic acid and tannin are blended, so that complementary advantages are realized, and the bioactivity and hydrophilicity of the polylactic acid are obviously improved; the used materials are all bio-based, so that the biological safety of the composite material is ensured, the medical standard is met, and the composite material has great potential in the medical fields of tissue engineering stent materials, drug delivery systems and the like.
(3) The preparation method of the bioactive polylactic acid/tannin composite material is simple and efficient, the production equipment cost is low, the quality of the produced product is high, and the industrial production requirement is met.
Drawings
Fig. 1 is stress-strain curves of comparative example 1, example 2, and example 8.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
The invention is further described below with reference to examples. Main raw material information: PLLA (4032D), nature works LLC, USA, weight average molecular weight 1.7X10 5 g/mol; tannin, chinese Allatin with number average molecular weight of 1701g/mol.
Example 1:
(1) Adding L-lactide and tannin in a ratio of 2:1 in a reactor, adding stannous octoate with 0.03 weight percent as a catalyst, catalyzing lactide to carry out ring-opening polymerization under the conditions of nitrogen and 130 ℃, and reacting for 5 hours to obtain the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight 4937.
(3) 80wt% PLLA, 15wt% TA and 5wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows in sequence from the temperature of each zone of a feeding zone: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Example 2:
(1) Adding L-lactide and tannin in a ratio of 5:1 in a reactor, adding stannous octoate with 0.03 weight percent as a catalyst, catalyzing lactide to carry out ring-opening polymerization under the conditions of nitrogen and 130 ℃, and reacting for 5 hours to obtain the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight of 10082.
(3) 80wt% PLLA, 15wt% TA and 5wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows in sequence from the temperature of each zone of a feeding zone: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Example 3:
(1) Adding L-lactide and tannin in a ratio of 8:1 in a reactor, adding stannous octoate in an amount of 0.03wt% as a catalyst, catalyzing lactide to carry out ring-opening polymerization under the conditions of nitrogen and 130 ℃, and reacting for 5 hours to obtain the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight 14475.
(3) 80wt% PLLA, 15wt% TA and 5wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows in sequence from the temperature of each zone of a feeding zone: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Example 4:
(1) Adding L-lactide and tannin in a ratio of 10:1 in a reactor, adding stannous octoate with 0.03 weight percent as a catalyst, catalyzing lactide to carry out ring-opening polymerization under the conditions of nitrogen and 130 ℃, and reacting for 5 hours to obtain the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight 19828.
(3) 80wt% PLLA, 15wt% TA and 5wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows in sequence from the temperature of each zone of a feeding zone: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Example 5:
(1) Adding L-lactide and tannin in a ratio of 5:1 in a reactor, adding stannous octoate with 0.03 weight percent as a catalyst, catalyzing lactide to carry out ring-opening polymerization under the conditions of nitrogen and 130 ℃, and reacting for 5 hours to obtain the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight of 10053.
(3) 90wt% PLLA, 8wt% TA and 2wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows from the temperature of each zone of a feeding zone in sequence: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Example 6
(1) Adding L-lactide and tannin in a ratio of 5:1 in a reactor, adding stannous octoate with 0.03 weight percent as a catalyst, catalyzing lactide to carry out ring-opening polymerization under the conditions of nitrogen and 130 ℃, and reacting for 5 hours to obtain the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight 11018.
(3) 80wt% PLLA, 10wt% TA and 10wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows from the temperature of each zone of a feeding zone in sequence: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Example 7
(1) Lactide (95% L-lactide, 5% D-lactide) and tannin are added into a reactor in a ratio of 5:1, 0.03wt% stannous octoate is added as a catalyst, and lactide ring-opening polymerization is catalyzed under the conditions of nitrogen and 130 ℃ to react for 5 hours to prepare the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight 6962.
(3) 80wt% PLLA, 15wt% TA and 5wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows in sequence from the temperature of each zone of a feeding zone: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Example 8
(1) D-lactide and tannin are added in a ratio of 5:1 in a reactor, 0.03 weight percent stannous octoate is added as a catalyst, lactide ring-opening polymerization is catalyzed under the conditions of nitrogen and 130 ℃ and the reaction is carried out for 5 hours to prepare the graft copolymer.
(2) Dissolving the graft copolymer synthesized in the step (1) in dichloromethane, slowly pouring the solution into methanol while stirring for precipitation, filtering, taking out the precipitate, drying and crushing to obtain tannin grafted polylactic acid, and measuring to obtain the molecular weight of 10053.
(3) 80wt% PLLA, 15wt% TA and 5wt% of the synthesized compatilizer are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows in sequence from the temperature of each zone of a feeding zone: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃ and 190 ℃ of the temperature of the machine head, the rotating speed of the screw is controlled to be 60rpm, and the bioactive polylactic acid/tannin composite material is obtained by extrusion granulation and drying.
Comparative example 1
84wt% PLLA and 16wt% TA are added into a double-screw extruder, and the heating temperature of the double-screw extruder is controlled to be as follows from the temperature of each zone of a feeding zone in sequence: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 190 ℃ of the temperature of the machine head, 60rpm of the screw, extruding, granulating and drying to obtain the composite material.
The mechanical properties of the composite materials prepared in examples 1 to 8 and comparative example 1 were tested, and the test results are shown in Table 1.
Table 1 shows the test data of the mechanical properties of the polylactic acid composite materials prepared in the examples and comparative examples of the present invention
As can be seen from table 1 and fig. 1, the design of the different molecular weight compatibilizers tannin grafted polylactic acid has a tendency to increase and then decrease. When the designed molecular weight is 5000, the polylactic acid molecular chain on tannin is short (less than 7 repeating units), the molecular chain is active in movement and is not easy to crystallize. When the designed molecular weight becomes large, the mobility of the molecular chain is reduced, a stable crystal structure is easy to form, and the molecular chain can be used as a compatilizer to promote the compatibility of polylactic acid and tannin, so that the mechanical property is enhanced. When the molecular weight of the designed compatilizer is too large, molecular chains are easy to wind and agglomerate, and the tannin component in the compatilizer is too low to improve the compatibility, so that the strength is reduced.
With the increase of the addition amount of the compatilizer, the tensile strength and the elongation at break of the final polylactic acid composite material are increased and then reduced, which shows that a proper amount of compatilizer can obviously increase the tensile strength and the elongation at break of the polylactic acid material, wherein the tensile strength of the embodiment 2 can reach 75.7MPa. The addition of the tannin grafted polylactic acid improves the compatibility of the tannin and the polylactic acid, so that the interaction between molecular chains at the interface of the tannin and the polylactic acid is enhanced, and the energy is better born and transferred. Meanwhile, the tannin can be connected with PLA through hydrogen bond, so that the mechanical property of the composite material is improved. However, when the addition amount of the compatilizer tannin grafted polylactic acid is too large, the compatilizer is agglomerated, so that the matrix structure is destroyed, and the finally prepared polylactic acid composite material is deteriorated in performance.
Since the PLLA and the compatilizer TA-g-PDLA can form the stereocomplex PLA through stereocomplex, the tensile strength of the example 8 reaches 81.5Mpa, which is improved by 59.2 percent compared with the tensile strength of the comparative example.
The present invention is not limited to the above-described preferred embodiments, and any person who can obtain other various products under the teaching of the present invention, however, any change in shape or structure of the product is within the scope of the present invention, and all the products having the same or similar technical solutions as the present application are included.
Claims (10)
1. The preparation method of the bioactive polylactic acid/tannin composite material is characterized by comprising the following steps of:
weighing 70-88% of polylactic acid, 10-20% of tannin and 2-10% of tannin grafted polylactic acid according to weight percentage;
and uniformly mixing polylactic acid, tannin and tannin grafted polylactic acid, adding the mixture into a double-screw extruder, and carrying out melt blending, extrusion granulation and vacuum drying under certain heating temperature and condition to obtain the bioactive polylactic acid/tannin composite material.
2. The method for preparing a bioactive polylactic acid/tannin composite material according to claim 1, wherein the polylactic acid is one of poly-l-lactic acid, poly-d-lactic acid and racemic lactic acid.
3. The method for preparing a bioactive polylactic acid/tannin composite material according to claim 1, wherein the method for preparing tannin grafted polylactic acid is as follows:
(1) Adding lactide and tannin in a certain proportion into a reactor, adding stannous octoate as a catalyst, catalyzing lactide to carry out ring-opening polymerization at 130-200 ℃ under nitrogen, reacting for 2-5h to obtain a graft copolymer, and (2) precipitating, purifying and drying the graft copolymer to obtain the tannin grafted polylactic acid.
4. The method for preparing the bioactive polylactic acid/tannin composite material according to claim 3, wherein the mass ratio of lactide to tannin is 2:1-20:1, and the stannous octoate is 0.01% -0.05%.
5. The method for preparing a bioactive polylactic acid/tannin composite material according to claim 3, wherein the precipitation and purification process comprises dissolving the synthesized graft copolymer in methylene dichloride to obtain a solution, slowly pouring the solution into methanol for precipitation, taking out the precipitate, drying and pulverizing to obtain tannin grafted polylactic acid.
6. The method for preparing a bioactive polylactic acid/tannin composite material according to claim 1, wherein the temperatures of each zone of the twin-screw extruder from the feeding zone are in order: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 190 ℃ of the temperature of the machine head, 60-80rpm of the screw speed.
7. A bioactive polylactic acid/tannin composite material, characterized in that it is prepared by the preparation method of the bioactive polylactic acid/tannin composite material according to any one of claims 1 to 6.
8. The bioactive polylactic acid/tannin composite material according to claim 7, wherein the tensile strength is 55.6 to 82.6Mpa.
9. An application method of the bioactive polylactic acid/tannin composite material is characterized in that the bioactive polylactic acid/tannin composite material of claim 7 is applied to the field of biological medicine.
10. The method of claim 9, wherein the bioactive polylactic acid/tannin composite material is applied to tissue engineering scaffold materials and drug delivery systems.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311862762.8A CN117801485A (en) | 2023-12-29 | 2023-12-29 | Bioactive polylactic acid/tannin composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311862762.8A CN117801485A (en) | 2023-12-29 | 2023-12-29 | Bioactive polylactic acid/tannin composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117801485A true CN117801485A (en) | 2024-04-02 |
Family
ID=90433016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311862762.8A Pending CN117801485A (en) | 2023-12-29 | 2023-12-29 | Bioactive polylactic acid/tannin composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117801485A (en) |
-
2023
- 2023-12-29 CN CN202311862762.8A patent/CN117801485A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Recent progress on chemical modification of cellulose for high mechanical-performance Poly (lactic acid)/Cellulose composite: A review | |
| TWI412384B (en) | Resorbable polyetheresters and their use for preparing of medicinal implants | |
| Corneillie et al. | PLA architectures: the role of branching | |
| Lai et al. | Stiffening, strengthening, and toughening of biodegradable poly (butylene adipate-co-terephthalate) with a low nanoinclusion usage | |
| Bednarek et al. | New polylactide-based materials by chemical crosslinking of PLA | |
| CN104558504B (en) | A kind of preparation method of polylactic acid poly glycol copolymer | |
| CN110624136B (en) | Degradable medical composite material and preparation method and application thereof | |
| CN110938200B (en) | Preparation method of amine polyester containing dimethyl pyridine on side chain | |
| Li et al. | Poly (L-lactic acid) bio-composites reinforced by oligo (D-lactic acid) grafted chitosan for simultaneously improved ductility, strength and modulus | |
| Akopova et al. | A novel approach to design chitosan‐polyester materials for biomedical applications | |
| CN100509063C (en) | Nanometer biological glass particles, composite material of the same and polyester, and preparation method thereof | |
| Liu et al. | Preparation, characterization, and in vitro drug release behavior of biodegradable chitosan-graft-poly (1, 4-dioxan-2-one) copolymer | |
| Wang et al. | Chitosan-graft poly (p-dioxanone) copolymers: preparation, characterization, and properties | |
| CN109810484A (en) | A kind of preparation method of modified polylactic acid material | |
| CN117801485A (en) | Bioactive polylactic acid/tannin composite material and preparation method thereof | |
| CN114409910B (en) | Antibacterial full-biodegradable plastic and preparation method thereof | |
| KR20200083106A (en) | Polyglycolide(PGA)-polylactide(PLA) muliblock copolymer and method of synthesis of the same | |
| Fan et al. | Development and evaluation of a novel biodegradable implants with excellent inflammatory response suppression effect by hot-melt extrusion | |
| CN112679760B (en) | Preparation method of glass fiber reinforced biodegradable polymer composite material | |
| CN114085364A (en) | Synthesis method of high-stability glycolide-trimethylene carbonate block copolymer | |
| KR101692986B1 (en) | Enhanced physical properties of bioasorbable polymer materials by stereocomplex organic filler and manufacturing method | |
| CN111671981A (en) | Absorbable composite material for interface screw sheath and preparation method thereof | |
| KR100817905B1 (en) | Biodegradable aliphatic polyester resin compositionand preparation thereof on the excellence of bionics adapt | |
| EP3656406B1 (en) | Absorbable biomedical composite material and preparation method therefor | |
| CN114940745B (en) | Preparation method of polylactic acid with controllable molecular weight |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |