CN101003632A - Method for preparing chitosan - grafting polylactic acid - Google Patents
Method for preparing chitosan - grafting polylactic acid Download PDFInfo
- Publication number
- CN101003632A CN101003632A CN 200610117057 CN200610117057A CN101003632A CN 101003632 A CN101003632 A CN 101003632A CN 200610117057 CN200610117057 CN 200610117057 CN 200610117057 A CN200610117057 A CN 200610117057A CN 101003632 A CN101003632 A CN 101003632A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- poly
- chitosan
- grafting
- reaction
- 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
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
This invention discloses a method for preparing chitosan-grafted poly (lactic acid). The method comprises: (1) adding monohydroxyl poly(lactic acid) into a test tube, adding 4,4'-diisocyanate diphenylmethane and DMF, and magnetically stirring in nitrogen atmosphere for reaction to obtain isocyanate-terminated poly(lactic acid); (2) adding chitosan into a test tube, adding DMF, and transferring isocyanate-terminated poly(lactic acid) to the test tube in nitrogen atmosphere; (3) adding dibutyl tin dilaurate into the test tube, magnetically stirring in nitrogen atmosphere for reaction, adding toluene to dissolve after reaction, filtering, and vacuum-drying the residue to obtain chitosan-grafted poly(lactic acid). The grafting degree can be adjusted by the ratio of chitosan to poly (lactic acid), and is up to 3360%. The product has such advantages as no metal, no toxicity and abundant raw materials.
Description
Technical field
The present invention relates to a kind of method of technical field of bioengineering, specifically is a kind of method for preparing chitosan-grafting-poly(lactic acid).
Background technology
Chitosan is by a kind of natural polycation bioactive polysaccharide of 2-amino-2-deoxy-D-glucose by the connection of β-1,4 glycosidic link, can be degraded to glucosamine in vivo, is absorbed by the body, and has good biocompatibility and biodegradability; And have functions such as the regeneration of organs such as promoting extracellular matrix regeneration, hemostasis and wound healing and blood vessel, skin, bone and reparation.But owing to its relatively poor mechanics, moulding processability, so the tegument glycan is difficult to directly as excellent drug carrier and tissue engineering material.Poly(lactic acid) has favorable mechanical and moulding processability, biocompatibility and biodegradability, also has been widely used in biomedical sector.Yet because the high crystalline and the hydrophobicity of poly(lactic acid), its degradation rate is restive and regulate, and is difficult to be used for the solid support material of protein hydrophilic medicament.Therefore, mechanics, the processing characteristics of tegument glycan inherent biological activity and poly(lactic acid) excellence are combined, preparation chitosan-poly(lactic acid) will be to construct an important channel of novel pharmaceutical modified release carrier and tissue engineering material.
Literature search through prior art is found, Wu Yan etc. delivers " Synthesis andcharacterization of a novel amphiphilic chitosan-polylactide graftcopolymer " (synthetic and sign of a kind of amphipathic shell copolymers glycan-grafting-poly(lactic acid) of novelty) on 2005 the 59th phase 165-171 of " Carbohydrate Polymer " (carbon aqueous polymer) magazine page or leaf, propose in this article, method by solution polymerization, with the triethylamine is catalyzer, the graft copolymerization of catalysis rac-Lactide on chitosan.Its deficiency is: polyreaction is to carry out under the heterogeneous conditions, and the percentage of grafting of polyreaction is less than 400%.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method for preparing chitosan-grafting-poly(lactic acid) is provided.Make it adopt the macromole coupled reaction, reasonable in design, easy to operate, production cost is lower and be applicable to the preparation process condition of preparation of industrialization chitosan-grafting-poly(lactic acid).
The present invention is achieved by the following technical solutions, and the present invention is made of the reaction of two steps:
The first step in the test tube that monohydroxy poly(lactic acid) (PLLA) adding thorough drying is crossed, adds 4 then, 4 '-diisocyanate based ditane (MDI) and N, dinethylformamide (DMF) solvent, nitrogen atmosphere lower magnetic force stirring reaction obtains isocyanic ester base polylactic acid (NCO-PLLA).
Described magnetic agitation reaction, the time is 2 hours.
Second step in the test tube that chitosan adding thorough drying is crossed, added DMF then, under the nitrogen atmosphere end group was transferred to test tube for the isocyanic ester base polylactic acid; Again catalyzer dibutyl tin laurate (dibutyl tin laurate: isocyanic ester base polylactic acid=1: 500, mol: mol) join in the test tube nitrogen atmosphere lower magnetic force stirring reaction.After reaction finishes, add toluene dissolving after-filtration, filter residue partial vacuum drying obtains chitosan-grafting-poly(lactic acid).
Described magnetic agitation reaction, the time is 4 hours.
Described toluene, its add-on are 50ml.
Described dibutyl tin laurate, its consumption are 1/500 of isocyanic ester base polylactic acids.
Described temperature of reaction is 80 ℃; The percentage of grafting of reaction can (1/3.75-1/60 g/g) regulates according to the feed ratio of chitosan and poly(lactic acid).
Synthetic route of the present invention is as follows:
The present invention has following advantage:
1) percentage of grafting of product can recently be regulated according to feeding intake of chitosan and poly(lactic acid) easily, and percentage of grafting (3360%) is far above document numerical value (400%);
2) Zhi Bei product containing metal not is nontoxic, is expected in clinical application;
3) catalyzer raw material convenient sources.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail:
Embodiment 1:
The preparation of chitosan-grafting-poly(lactic acid)
Monohydroxy poly(lactic acid) (20.9mg) adds in the test tube that thorough drying crosses, and (0.5mg, 1.4equiv.) and DMF (0.15ml), nitrogen atmosphere lower magnetic force stirring reaction 2h obtains isocyanic ester base polylactic acid (NCO-PLLA) to add MDI then.
Take by weighing chitosan (5.6mg, 0.03mmol GlcN units) in the test tube that the adding thorough drying is crossed, add DMF (0.25ml) then, under the nitrogen atmosphere with NCO-PLLA (20.9mg, 3.75equiv.) be transferred to test tube, again dibutyl tin laurate (2.6 μ g) is joined in the test tube the following 80 ℃ of magnetic agitation heating of nitrogen atmosphere 4h.After reaction finishes, the elimination insolubles, filtrate is in the oil mystery after the sedimentation, and sediment is with 50ml toluene dissolution filter 4h, and filter residue partial vacuum drying obtains chitosan-grafting-poly(lactic acid) (12.7mg, productive rate 35%, poly(lactic acid) graft(ing) degree are 260%).
Embodiment 2:
The preparation of chitosan-grafting-poly(lactic acid)
Monohydroxy poly(lactic acid) (156.6mg) adds in the test tube that thorough drying crosses, and (5.8mg, 1.4equiv.) and DMF (1ml), nitrogen atmosphere lower magnetic force stirring reaction 2h obtains NCO-PLLA to add MDI then.
Take by weighing chitosan (10mg, 0.06mmol GlcN units) in the test tube that the adding thorough drying is crossed, add DMF (0.5ml) then, under the nitrogen atmosphere with NCO-PLLA (156.6mg, 15equiv.) be transferred to test tube, again dibutyl tin laurate (19.8 μ g) is joined in the test tube the following 80 ℃ of magnetic agitation heating of nitrogen atmosphere 4h.After reaction finishes, the elimination insolubles, filtrate is in the oil mystery after the sedimentation, and sediment is with 50ml toluene dissolution filter 4h, and filter residue partial vacuum drying obtains chitosan-grafting-poly(lactic acid) (101.6mg, productive rate 58%, poly(lactic acid) graft(ing) degree are 960%).
Embodiment 3:
The preparation of chitosan-grafting-poly(lactic acid)
The poly(lactic acid) of monohydroxy (140.0mg) adds in the test tube that thorough drying crosses, and (5mg, 1.4equiv.) and DMF (1ml), nitrogen atmosphere lower magnetic force stirring reaction 2h obtains NCO-PLLA to add MDI then.
Take by weighing chitosan (2.3mg, 0.015mmol GlcN units) in the test tube that the adding thorough drying is crossed, add DMF (0.1ml) then, under the nitrogen atmosphere with NCO-PLLA (140.0mg, 60equiv.) be transferred to test tube, again dibutyl tin laurate (17.7 μ g) is joined in the test tube the following 80 ℃ of magnetic agitation heating of nitrogen atmosphere 4h.After reaction finishes, the elimination insolubles, filtrate is in the oil mystery after the sedimentation, and sediment is with 50ml toluene dissolution filter 4h, and filter residue partial vacuum drying obtains chitosan-grafting-poly(lactic acid) (78.9mg, productive rate 55%, poly(lactic acid) graft(ing) degree are 3360%).
Claims (7)
1. a method for preparing chitosan-grafting-poly(lactic acid) is characterized in that, is made of the reaction of two steps:
The first step, the poly(lactic acid) of monohydroxy add in the test tube that thorough drying crosses, and add 4,4 ' then-diisocyanate based ditane and N, the dinethylformamide solvent, and nitrogen atmosphere lower magnetic force stirring reaction obtains the poly(lactic acid) that end group is an isocyanate group;
In second step, chitosan adds in the test tube that thorough drying crosses, and adds N then, and dinethylformamide under the nitrogen atmosphere is that the poly(lactic acid) of isocyanate group is transferred to test tube with end group; The catalyzer dibutyl tin laurate is joined in the test tube, nitrogen atmosphere lower magnetic force stirring reaction after reaction finishes, adds toluene dissolving after-filtration again, and filter residue partial vacuum drying obtains chitosan-grafting-poly(lactic acid).
2. the method for preparing chitosan-grafting-poly(lactic acid) as claimed in claim 1 is characterized in that, in the first step, and described magnetic agitation reaction, the time is 2 hours.
3. the method for preparing chitosan-grafting-poly(lactic acid) as claimed in claim 1 is characterized in that, in second step, and described magnetic agitation reaction, the time is 4 hours.
4. the method for preparing chitosan-grafting-poly(lactic acid) as claimed in claim 1 is characterized in that, in second step, and described toluene, its add-on is 50ml.
5. the method for preparing chitosan-grafting-poly(lactic acid) as claimed in claim 1 is characterized in that, in second step, described dibutyl tin laurate, its consumption are 1/500 of isocyanic ester base polylactic acids.
6. the method for preparing chitosan-grafting-poly(lactic acid) as claimed in claim 1 is characterized in that, in second step, and described reaction, its temperature is 80 ℃.
7. the method for preparing chitosan-grafting-poly(lactic acid) as claimed in claim 1, it is characterized in that, in second step, in the described reaction, its percentage of grafting is recently regulated according to feeding intake of chitosan and poly(lactic acid), and the mass ratio that feeds intake of chitosan and poly(lactic acid) is 1/3.75-1/60.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610117057 CN101003632A (en) | 2006-10-12 | 2006-10-12 | Method for preparing chitosan - grafting polylactic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610117057 CN101003632A (en) | 2006-10-12 | 2006-10-12 | Method for preparing chitosan - grafting polylactic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101003632A true CN101003632A (en) | 2007-07-25 |
Family
ID=38703033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610117057 Pending CN101003632A (en) | 2006-10-12 | 2006-10-12 | Method for preparing chitosan - grafting polylactic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101003632A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284883B (en) * | 2008-05-14 | 2011-02-16 | 西北大学 | Preparation method of polylactic acid-chitose graft copolymer |
| CN101628947B (en) * | 2009-08-14 | 2012-06-06 | 暨南大学 | Chitosan-polylactic acid graft copolymer and preparation method and application thereof |
| CN105001425A (en) * | 2015-07-28 | 2015-10-28 | 大连大学 | Grafted copolymer preparing method based on chitosan and polylactic acid |
| CN106519245A (en) * | 2016-11-22 | 2017-03-22 | 常州工程职业技术学院 | Antibacterial siloxane and preparation method thereof |
| CN107417902A (en) * | 2017-09-13 | 2017-12-01 | 蚌埠学院 | The preparation method and its preparation facilities of a kind of polydactyl acid |
| CN110229343A (en) * | 2019-06-28 | 2019-09-13 | 郑州轻工业学院 | A kind of polylactic acid-metal organic frame composite material and preparation method |
| CN112062932A (en) * | 2020-08-07 | 2020-12-11 | 宁波芬畅凝科香精香料有限公司 | Essence microcapsule and preparation method thereof |
-
2006
- 2006-10-12 CN CN 200610117057 patent/CN101003632A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284883B (en) * | 2008-05-14 | 2011-02-16 | 西北大学 | Preparation method of polylactic acid-chitose graft copolymer |
| CN101628947B (en) * | 2009-08-14 | 2012-06-06 | 暨南大学 | Chitosan-polylactic acid graft copolymer and preparation method and application thereof |
| CN105001425A (en) * | 2015-07-28 | 2015-10-28 | 大连大学 | Grafted copolymer preparing method based on chitosan and polylactic acid |
| CN105001425B (en) * | 2015-07-28 | 2017-11-28 | 大连大学 | A kind of preparation method based on chitosan polylactic acid graft copolymer |
| CN106519245A (en) * | 2016-11-22 | 2017-03-22 | 常州工程职业技术学院 | Antibacterial siloxane and preparation method thereof |
| CN107417902A (en) * | 2017-09-13 | 2017-12-01 | 蚌埠学院 | The preparation method and its preparation facilities of a kind of polydactyl acid |
| CN110229343A (en) * | 2019-06-28 | 2019-09-13 | 郑州轻工业学院 | A kind of polylactic acid-metal organic frame composite material and preparation method |
| CN112062932A (en) * | 2020-08-07 | 2020-12-11 | 宁波芬畅凝科香精香料有限公司 | Essence microcapsule and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101003632A (en) | Method for preparing chitosan - grafting polylactic acid | |
| CN102181060B (en) | Polyvinyl alcohol-polypeptide-polyethylene glycol graft copolymer and preparation method thereof | |
| CN101628947B (en) | Chitosan-polylactic acid graft copolymer and preparation method and application thereof | |
| CN102181061B (en) | Polyurethane-polypeptide graft copolymer and preparation method thereof | |
| Krogman et al. | The influence of side group modification in polyphosphazenes on hydrolysis and cell adhesion of blends with PLGA | |
| JP4680900B2 (en) | Degradable and biocompatible block copolymer | |
| CN103242536A (en) | Method for preparing polypeptide-polylactic acid-polyethyleneglycol dual-graft copolymer | |
| CN110938200B (en) | Preparation method of amine polyester containing dimethyl pyridine on side chain | |
| CN104558504B (en) | A kind of preparation method of polylactic acid poly glycol copolymer | |
| CN106995502B (en) | Bifunctional group modified chitosan derivative and preparation method thereof | |
| CN105237714A (en) | Water response shape memory polyurethane and preparation method therefor | |
| CN108840889A (en) | A kind of application of chitosan oligosaccharide based compound and preparation method thereof | |
| CN101857649A (en) | Method for preparing chitosan oligosaccharide-g-polycaprolactone thermoplastic material | |
| CN110180023B (en) | Preparation method of high-strength biomass tissue engineering scaffold material | |
| CN104892917B (en) | Glucosamine-modified polyethyleneglycol-polylactic acid, preparation method therefor and application thereof | |
| Wang et al. | Chitosan-graft poly (p-dioxanone) copolymers: preparation, characterization, and properties | |
| CN100384883C (en) | Method for preparing chitose graft polycaprolactone | |
| WO2012034544A2 (en) | Method of preparation of highly substituted hyaluronic acid amides | |
| CN107880254B (en) | Poly L-lactic acid cyclodextrin copolymer material and preparation method thereof | |
| Pandit et al. | Alginates production, characterization and modification | |
| US9062159B2 (en) | Poly(lactic-co-glycolic acid) synthesized via copolycondensation catalyzed by biomass creatinine | |
| Sarkar et al. | Modified alginates in drug delivery | |
| CN112979928A (en) | Preparation method of lignin grafted polymer microspheres | |
| WO2003042277A1 (en) | The polyester containing active drugs and having amino acids in the main chain, and its preparation method | |
| Wei et al. | Biodegradable polymers: research and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |