CN101717499A - Multi-arm star polyester/hyperbranched polyglycidyl ether and preparation method thereof - Google Patents
Multi-arm star polyester/hyperbranched polyglycidyl ether and preparation method thereof Download PDFInfo
- Publication number
- CN101717499A CN101717499A CN200910216535A CN200910216535A CN101717499A CN 101717499 A CN101717499 A CN 101717499A CN 200910216535 A CN200910216535 A CN 200910216535A CN 200910216535 A CN200910216535 A CN 200910216535A CN 101717499 A CN101717499 A CN 101717499A
- Authority
- CN
- China
- Prior art keywords
- polyester
- polyglycidyl ether
- arm
- hyperbranched
- arm star
- 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
Images
Abstract
The invention discloses multi-arm star polyester/hyperbranched polyglycidyl ether which comprises biodegradable polyester and polyglycidyl ether, the composed molecular shape takes the shape of a star which comprises a core, a support arm and a hyperbranched part, wherein the core is a residual part after compounds containing at least three hydroxyls are reacted, the support arm is biodegradable polyester, the hyperbranched part is polyglycidyl ether and has a structural general formula as below, wherein R is hyperbranched polyglycidyl ether. The invention also discloses a preparation method of the multi-arm star polyester/hyperbranched polyglycidyl ether. The multi-arm star polyester/hyperbranched polyglycidyl ether not only has biodegradability, but also can satisfy the requirements of control release of different drugs, medical product materials and tissue engineering as the structure simultaneously contains a hydrophobic part and the hydrophilic hyperbranched part, especially a great deal of terminal hydroxyls reserved in the structure can also be bonded with other drugs and various ligands to form a multifunctional medicine carrier.
Description
Technical field
The invention belongs to biodegradable polymer and preparing technical field thereof, be specifically related to a kind of biodegradable multi-arm star polyester/hyperbranched polyglycidyl ether and preparation method thereof.The multi-arm star-shaped polyester/hyperbranched polyglycidyl ether of biological degradation provided by the present invention can be used as medicine sustained release solid support material, medical macromolecular materials and tissue engineering material.
Background technology
Development along with macromolecular structure design and synthetic technology, non-linear branched polymer, as amine dendrimer, hyperbranched polymer, star polymers etc. emerge in an endless stream, because of this base polymer has particular structure, various performances are compared bigger difference with line polymer and are progressed into people's the visual field.Wherein dendrimer and hyperbranched polymer are meant the polymkeric substance with dendritic high branched structure, star polymer then is connected in many equal in length on the nuclear simultaneously or is not waited, forms the formed multi-arm branched polymkeric substance of identical or different polymer chain by an end, has only a main branch point on its structure.The character of star polymer is the various physics of research branched polymer, a kind of ideal model of chemical property between line polymer and hyper branched polymer, also serves many purposes.
Different with linear polymer, characteristics such as star polymer has less atom spatial disposition size, spherical symmetric structure, and intramolecularly does not tangle outward, and intermolecular interaction is less.In addition, because star polymer molecular chain one end is fettered by chemical bond, star polymer in unit volume " free terminal " is though count than linear polymer much less, but the peripheral distribution of its molecule more terminal functionality, according to various objectives surface functional group is carried out modification easily, can further carry out chemically modified, grafting, block etc. it.
Medical macromolecular materials (as suture, stent etc.) and the tissue engineering material used in medicine sustained release solid support material, the body all need to have biocompatibility and biological degradability.For medicine sustained release solid support material, also should have suitable wetting ability and can circulate with blood with the assurance carrier granule, and, also need to bring into specific group or molecule (as folic acid) sometimes, make it have cell or tumor-targeting.Because the polyester material majority is hydrophobicity (as poly(lactic acid), a polycaprolactone), in blood, easily assemble and adsorbed plasma albumen, cause particle in blood circulation, to be eliminated, make the medicine that carries can not arrive target, lower or do not have the effect of treatment.Therefore, amphipathic polyester just has broad application prospects in medicine sustained release field.And the amphipathic polyester of star not only has the characteristics of amphipathic polyester, and, with it with respect to linear molecule functional group more, that be distributed in the molecule periphery, easier relatively introduce target group or molecules.
Usually, the amphipathic polyester of star is to introduce hydrophilic segment again on the basis of synthetic star polyester, and as medicine sustained release solid support material, great majority all are to introduce peg molecule as hydrophilic segment.But such star amphipathic ester molecular structure can not be regulated the length of hydrophilic segment easily because of more single, causes the ratio of hydrophilic and hydrophobic to be not easy to regulate; And the periphery functional group of the star amphipathic ester molecule that obtains how much be limited by the initiation polyester that when beginning use star-shaped molecule functional group what.
In order to obtain more periphery functional group, and the ratio that is easy to regulate hydrophilic and hydrophobic, the research worker begins the star hyper-branched polyester that turns to research amphipathic.CN1486995 discloses the synthetic of a kind of amphipathic star hyper-branched polyester.Detailed process is to use hyperbranched polymer and alpha-halogen carboxylic acid halides by hydroxyl or aminoly form the hyperbranched macromolecular initiator, contain the double bond monomer polymerization with atom transition free radical polymerization reaction (ATRP) initiation then in the presence of catalyzer and part with the carboxylic acid halides reaction, obtain the starlike hyperbranched polymer brush of multi-arm, last is that initiator adopts the polymerization of atom transition free radical polymerization reaction (ATRP) initiation hydroxyl double bond monomer to get in the presence of catalyzer and part with the starlike hyperbranched polymer brush of the multi-arm that obtains again.Though Zhi Bei amphiphilic star-like hyper-branched polyester can provide the big internal space that holds drug molecule in this way, the ratio of also regulating hydrophilic and hydrophobic easily, and the surface also has great amount of hydroxy group functional group.But the polymkeric substance that this invention provides does not have biological degradability, and being used as drug carrier material may Different Organs in vivo gather, so that cause damage or some unpredictalbe adverse consequencess of organ.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, and a kind of new multi-arm star polyester/hyperbranched polyglycidyl ether is provided, this multi-arm star polyester/hyperbranched polyglycidyl ether has biological degradability, can be used as medicine sustained release solid support material, medical macromolecular materials and tissue engineering material.
Another object of the present invention provides a kind of method for preparing above-mentioned star polyester/hyperbranched polyglycidyl ether.
Multi-arm star polyester/hyperbranched polyglycidyl ether provided by the invention, this multi-arm star polyester/hyperbranched polyglycidyl ether is made up of Biodegradable polyester and polyglycidyl ether, the shape of molecule that is constituted is a star, form by core, support arm and hyperbranched three parts, core is the remaining part of compound reaction that contains at least three hydroxyls, support arm is a Biodegradable polyester, and hyperbranched part is a polyglycidyl ether, and its general structure is as follows:
Wherein represent the elliptical support arm, R is a hyperbranched polyglycidyl ether, and its structure is as follows:
The arm number of above-mentioned multi-arm star polyester/hyperbranched polyglycidyl ether is 3～64, and is preferred 3～16, specifically is by the hydroxy number decision of core element.The length of polyester arm be ester units number on every arm 5～200, preferred 10～100, its when perfect condition prepares by the ratio decision of number and the annular lactone or the lactide of hydroxyl.Glycidyl ether unit number on every arm is 2～180, and is preferred 2～80, can regulate according to different application targets.As, for the water miscible material of needs, can design and have the more polymkeric substance of glycidyl ether unit number, if need be dissolved in the polymkeric substance of organic solvent such as methylene dichloride, can design and have the fewer polymkeric substance of glycidyl ether unit number.Ester units number or glycidyl ether unit number and when reaction institute add between the respective quality of material and are easier to conversion.In strict accordance with technological operation the time, the multi-arm star polyester/hyperbranched polyglycidyl ether of synthetic is to be consistent with the structure of design.
The method of the above-mentioned multi-arm star polyester/hyperbranched polyglycidyl ether of preparation provided by the invention, the processing step and the condition of this method are as follows:
(1) synthetic multi-arm star Biodegradable polyester
Contain the compound of at least three hydroxyls and the annular lactone or the lactide of 10～100 parts of purifying mixes with 0.01～10 part, after the vacuum-drying, add again with annular lactone or lactide quality and count 0.01～5% catalyzer, vacuumizing down room temperature～100 ℃ drying 1～24 hour, vacuum sealing tube was in 100～180 ℃ of reactions 1～120 hour again, and the cooling back adopts conventional polyester purification process to carry out the multi-arm star Biodegradable polyester that purifying can obtain having following structure:
Wherein represent the elliptical support arm;
(2) prepare multi-arm star polyester/hyperbranched polyglycidyl ether
After 1～50 part of star Biodegradable polyester vacuum-drying that above-mentioned steps is made, be dissolved in 10～500 parts of exsiccant organic solvents, add 0.1～20 part of catalyst reaction that can form macromole evocating agent 50～130 ℃ of temperature and obtain macromole evocating agent, drip 0.01～50 part of glycidyl ether again, in 0～50 ℃ of reaction of temperature 1～48 hour, cooling back purifying promptly obtained the multi-arm star polyester/hyperbranched polyglycidyl ether of following structure:
Wherein represent the elliptical support arm, R is a hyperbranched polyglycidyl ether, and its structure is as follows:
Above material part is not specifically noted, and is mass parts.
Used purification process is generally dialysis method, selects the dialysis membrane in different apertures for use according to the molecular weight of the multi-arm star polyester/hyperbranched polyglycidyl ether of synthetic.The aperture of selective membrane is general at least greater than the molecular weight of the multi-arm star polyester/hyperbranched polyglycidyl ether of synthetic more than 1000.The synthetic polymkeric substance is put in the dialysis membrane bag of certain pore size, dialysis is 3 days in redistilled water, removes behind the glycidyl ether of homopolymerization promptly.
The used compound that contains at least three hydroxyls is 1 in the aforesaid method, 2, any in 3-glycerol, Pehanorm, trimethylolethane, tetramethylolmethane, dipentaerythritol, polyester-8-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things, polyester-16-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things, polyester-32-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things or the polyester-64-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things.When wishing that kernel is hydrophobic fully, select to contain 6 hydroxyls or following compound as core element; And the compound of selecting to contain 6 above hydroxyls is as core element, and its kernel has just had certain wetting ability.
Used annular lactone is at least a in glycollide, rac-Lactide, the 6-caprolactone in the aforesaid method.Preferred lactide and 6-caprolactone.What deserves to be mentioned is it all is purified when annular lactone or lactide specifically use.
The synthetic used catalyzer of multi-arm star Biodegradable polyester is at least a in tin, zinc, aluminium, magnesium or its inorganic salt, organic salt and/or their oxide compound in the aforesaid method; The catalyzer that can form macromole evocating agent is any in the nucleophilic catalysts such as alkali, basic metal and hydride thereof, amides, organometallics and derivative thereof.
Used organic solvent is tetrahydrofuran (THF), methylene dichloride, trichloromethane, monochloroethane, 1 in the aforesaid method, 2-ethylene dichloride, 1,1,1-trichloroethane, vinyl trichloride, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,4-dioxane, acetone, ethyl acetate, acetonitrile, N, at least a in dinethylformamide and the N,N-dimethylacetamide.
The present invention has the following advantages:
1, owing to containing ester bond in the molecular structure that the invention provides multi-arm star Biodegradable polyester/hyperbranched polyglycidyl ether, thereby and ester bond easily in the presence of water gradually fracture cause the degraded of polyester portion in the molecule, finally cause whole molecular degradation, thereby has a biological degradability, when being used as drug carrier material, just can Different Organs in vivo not gather, more can not cause the damage of organ or bring some unpredictalbe adverse consequencess.
2, owing to the invention provides multi-arm star Biodegradable polyester/hyperbranched polyglycidyl ether, its shape of molecule not only is a star, and comprise hydrophobic part and hydrophilic hyperbranched part in the structure, thereby for polyester material family has increased new kind, also for satisfying the different pharmaceutical sustained release and the differing materials organizational project needs, good biocompatibility provides bigger range of choice.
3, because multi-arm star Biodegradable polyester/hyperbranched polyglycidyl ether provided by the invention has the polyglycidyl ether of hyperbranched hydrophilic layer in the outer end, thereby can be by the iris action of hyperbranched polyglycidyl ether, with medicine " obstruct " in macromole, the charge capacity of medicine is further improved, and the lasting time that discharges is longer.
4, because can regulating the amount of structure, polyester chain length and the hyperbranched polyglycidyl ether of core element easily, preparation method provided by the invention regulates mechanical property, crystallinity, wetting ability and biological degradability, thereby provide bigger internal space for preparing amphipathic multi-arm star hyper-branched polyester, make it easier ratio and the surperficial amount that has hydroxy functional group by regulating hydrophilic and hydrophobic, obtain to be used for material, medical product material and the tissue engineering material of different pharmaceutical Controlled Release System, and the material of other purposes.
5, preparation method provided by the invention is simple, and technological process is easy to control.
Description of drawings
Fig. 1 is the proton magnetic chart spectrum of the multi-arm star polycaprolactone of the embodiment of the invention 2 preparations.The a place is the methyl hydrogen absorption peak on the core compound trimethylolethane among the figure, and the b place is the absorption peak of the methylene radical hydrogen that links with hydroxyl in the terminal caprolactone units, and the c place is near the absorption peak of the methylene radical hydrogen of Sauerstoffatom in the caprolactone units.The arm number calculates by (b/2)/(a/3)=2.94 and obtains when being used to calculate (can be understood as nuclear magnetic spectrum itself have error to cause), and promptly theoretical arm number is 3.Brachium calculates by c/b=24.2 (using the methylene radical of the methylene radical of close Sauerstoffatom in the chain link than last end).
Fig. 2 is the proton magnetic chart spectrum of the multi-arm star polycaprolactone/hyperbranched polyglycidyl ether of the embodiment of the invention 2 preparations.The a place is the methylene radical hydrogen absorption peak that is connected with ester carbonyl group of polycaprolactone among the figure, and 2 such hydrogen are arranged in each caprolactone units.The b place is the methylene radical of hyperbranched polyglycidyl ether and the hydrogen absorption peak of methyne among the figure, and each Racemic glycidol ether unit has 5 hydrogen.The number that every arm contains Racemic glycidol by formula b/5 ÷ (a/24/2) calculates.Because core element shared ratio in polymkeric substance is very little, can not embody in spectrogram.
Fig. 3 is the infared spectrum of the multi-arm star polycaprolactone/hyperbranched polyglycidyl ether of the embodiment of the invention 2 preparations.1729cm in the collection of illustrative plates
-1, 1459cm
-1, 1130cm
-1Absorption peak belongs to the ether-oxygen bond of ester carbonyl group, methylene radical and the ester of polycaprolactone respectively, and 3278cm
-1, 2874cm
-1Absorption peak be because the hydroxyl of hyperbranched polyglycidyl ether, the hydrogen of methyne cause 1130cm
-1The grow of widening than pure polycaprolactone also is because the ether-oxygen bond of polyglycidyl ether causes.Because core element shared ratio in polymkeric substance is very little, can not embody in spectrogram.
Embodiment
Provide embodiment below so that the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the person skilled in the art in this field according to the present invention.
In addition, what deserves to be explained is, below among each embodiment institute add material part and be mass parts.
0.1 part tetramethylolmethane core element is mixed with the rac-Lactide of 30 parts of purifying, after the vacuum-drying, adding 0.03 part of catalyzer zinc powder again mixes, vacuumized room temperature dry 10 hours with oil pump, vacuum sealing tube was in 110 ℃ of reactions 120 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 1 part of multi-arm star Biodegradable polyester vacuum-drying that above-mentioned steps is made, be dissolved in 10 parts of exsiccant dichloromethane solvents, in dry atmosphere, add 0.1 part of sodium methylate reaction and obtain macromole evocating agent in 50 ℃ of temperature, drip 0.01 part of glycidyl ether again, in 0 ℃ of reaction of temperature 48 hours, the cooling back was that 3000 dialysis membrane purifying promptly obtain multi-arm star polyester/hyperbranched polyglycidyl ether with the aperture.
Embodiment 2
0.5 part trimethylolethane core element is mixed with the 6-caprolactone of 35 parts of purifying, after the vacuum-drying, adding the inferior tin of 0.01 part of octoate catalyst again mixes, vacuumize 60 ℃ of dryings 1 hour with oil pump, vacuum sealing tube was in 100 ℃ of reactions 80 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 5 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 25 parts of exsiccant tetrahydrofuran solvents, in dry atmosphere, add 5 parts of potassium methylate reactions and obtain macromole evocating agent in 130 ℃ of temperature, drip 10 parts of glycidyl ethers again, in 20 ℃ of reactions of temperature 30 hours, the cooling back was that 3000 dialysis membrane purifying promptly obtain multi-arm star polyester/hyperbranched polyglycidyl ether with the aperture.
Embodiment 3
10 parts polyester-64-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid core elements are mixed with the rac-Lactide of 100 parts of purifying, after the vacuum-drying, adding 5 parts of catalyzer zinc powders again mixes, vacuumize at 100 ℃ following dry 2 hours with oil pump, vacuum sealing tube was in 180 ℃ of reactions 12 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 2 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 500 parts of exsiccant N, in dinethylformamide and the ethyl acetate solvent (3: 2 mass ratioes), how nak response obtains macromole evocating agent to add 3 parts in 70 ℃ of temperature in dry atmosphere, drip 0.4 part of glycidyl ether again, in 30 ℃ of reactions of temperature 40 hours, the cooling back was that 10000 dialysis membrane purifying promptly obtain multi-arm star polyester/hyperbranched polyglycidyl ether with the aperture.
Embodiment 4
0.05 part tetramethylolmethane core element is mixed with the rac-Lactide and the glycollide (3: 1 mass ratioes) of 70 parts of purifying, after the vacuum-drying, adding 3 parts of catalyzer aluminum ethylates again mixes, 80 ℃ were descended dry 24 hours under vacuum, vacuum sealing tube was in 180 ℃ of reactions 12 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 50 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 500 parts of exsiccant 1, in the 4-dioxane solvent, in dry atmosphere, add 20 parts of nak responses and obtain macromole evocating agent in 130 ℃ of temperature, 0 part of glycidyl ether of Dropwise 5 again, in 30 ℃ of reactions of temperature 40 hours, the cooling back was that 10000 dialysis membrane purifying promptly obtain multi-arm star polyester/hyperbranched polyglycidyl ether with the aperture.
Embodiment 5
0.5 part polyester-16-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching thing core elements are mixed with the 6-caprolactone of 60 parts of purifying, after the vacuum-drying, adding 1 part of catalyzer iron(ic) chloride again mixes, 50 ℃ were descended dry 5 hours under vacuum, vacuum sealing tube was in 140 ℃ of reactions 1 hour, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 7 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 200 parts of exsiccant 1,1,2, in 2-tetrachloroethane and the trichloromethane solvent (1: 1 mass ratio), in dry atmosphere, add 8 parts of potassium methylate reactions and obtain macromole evocating agent, drip 10 parts of glycidyl ethers again in 70 ℃ of temperature, in 50 ℃ of reactions of temperature 1 hour, the cooling back was that 5000 dialysis membrane purifying promptly obtain multi-arm star polyester/hyperbranched polyglycidyl ether with the aperture.
Embodiment 6
0.1 part trimethylolethane core element is mixed with the 6-caprolactone of 10 parts of purifying, after the vacuum-drying, adding 0.01 part of catalyzer tin tetrachloride again mixes, 60 ℃ were descended dry 1 hour under vacuum, vacuum sealing tube was in 120 ℃ of reactions 70 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 5 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 25 parts of exsiccant tetrahydrofuran solvents, in dry atmosphere, add 5 parts of potassium methylate reactions and obtain macromole evocating agent in 130 ℃ of temperature, Dropwise 5 part glycidyl ether again, in 40 ℃ of reactions of temperature 10 hours, the cooling back was that 5000 dialysis membrane purifying promptly obtain multi-arm star polyester/hyperbranched polyglycidyl ether with the aperture.
Embodiment 7
0.25 part trimethylolethane core element is mixed with the 6-caprolactone and the rac-Lactide (2: 1 mass ratioes) of 50 parts of purifying, after the vacuum-drying, adding 0.01 part of catalyzer aluminum ethylate again mixes, 60 ℃ were descended dry 1 hour under vacuum, vacuum sealing tube was in 120 ℃ of reactions 70 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 20 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 200 parts of exsiccant tetrahydrofuran solvents, in dry atmosphere, add 10 parts of potassium methylate reactions and obtain macromole evocating agent in 130 ℃ of temperature, drip 40 parts of glycidyl ethers again, in 40 ℃ of reactions of temperature 10 hours, the cooling back was that 5000 dialysis membrane purifying promptly obtain multi-arm star polyester/hyperbranched polyglycidyl ether with the aperture.
Embodiment 8
5 parts polyester-16-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching thing core elements are mixed with the 6-caprolactone of 55 parts of purifying, after the vacuum-drying, adding 5 parts of catalyzer magnesium powder again mixes, vacuumize at 100 ℃ following dry 2 hours with oil pump, vacuum sealing tube was in 150 ℃ of reactions 10 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 2 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 100 parts of exsiccant N, in the dinethylformamide, in dry atmosphere, add 3 parts of sodium hydrides and obtain macromole evocating agent in 70 ℃ of temperature, drip 0.25 part of glycidyl ether again, in 30 ℃ of temperature reaction 40 hours, the cooling back with the aperture be that 10000 dialysis membrane purifying obtain promptly that 16 arm brachiums are 10, the polyglycidyl ether unit number is 2 multi-arm star polyester/hyperbranched polyglycidyl ether.
Embodiment 9
0.2 part dipentaerythritol core element is mixed with the 6-caprolactone of 52 parts of purifying, after the vacuum-drying, adding the inferior tin of 5 parts of octoate catalysts again mixes, vacuumize at 100 ℃ following dry 2 hours with oil pump, vacuum sealing tube was in 150 ℃ of reactions 10 hours, and the cooling back promptly obtains the multi-arm star Biodegradable polyester with polyester purification process commonly used; After 20 parts of multi-arm star Biodegradable polyesters vacuum-drying that above-mentioned steps is made, be dissolved in 100 parts of exsiccant N, in the dinethylformamide, in dry atmosphere, add 2 parts of potassium for 80 ℃ in temperature, obtain macromole evocating agent, drip 11 parts of glycidyl ethers again, in 60 ℃ of temperature reaction 35 hours, the cooling back with the aperture be that 10000 dialysis membrane purifying obtain promptly that 6 arm brachiums are 100, the glycidyl ether unit number is 80 multi-arm star polyester/hyperbranched polyglycidyl ether.
Claims (10)
1. multi-arm star polyester/hyperbranched polyglycidyl ether, this multi-arm star polyester/hyperbranched polyglycidyl ether is made up of Biodegradable polyester and polyglycidyl ether, the shape of molecule that is constituted is a star, form by core, support arm and hyperbranched three parts, core is the remaining part in compound reaction back that contains at least three hydroxyls, support arm is a Biodegradable polyester, and hyperbranched part is a polyglycidyl ether, and its general structure is as follows:
Wherein represent the elliptical support arm, R is a hyperbranched polyglycidyl ether, and its structure is as follows:
2. multi-arm star polyester/hyperbranched polyglycidyl ether according to claim 1, the arm number of this multi-arm star polyester/hyperbranched polyglycidyl ether is 3～64, and the ester units number on every arm is 5～200, and the glycidyl ether unit number on every arm is 2～180.
3. multi-arm star polyester/hyperbranched polyglycidyl ether according to claim 1 and 2, the arm of this multi-arm star polyester/hyperbranched polyglycidyl ether several 3～16, ester units number on every arm is preferred 10～100, the glycidyl ether unit number preferred 2～80 on every arm.
4. method for preparing each described multi-arm star polyester/hyperbranched polyglycidyl ether in the claim 1～3, the processing step and the condition of this method are as follows:
(1) synthetic multi-arm star Biodegradable polyester
Contain the compound of at least three hydroxyls and the annular lactone or the lactide of 10～100 parts of purifying mixes with 0.01～10 part, after the vacuum-drying, add again with annular lactone or lactide quality and count 0.01～5% catalyzer, vacuumizing down room temperature～100 ℃ drying 1～24 hour, vacuum sealing tube was in 100～180 ℃ of reactions 1～120 hour again, and cooling back purifying gets final product;
(2) prepare multi-arm star polyester/hyperbranched polyglycidyl ether
After 1～50 part of multi-arm star Biodegradable polyester vacuum-drying that above-mentioned steps is made, be dissolved in 10～500 parts of exsiccant organic solvents, add 0.1～20 part of catalyst reaction that can form macromole evocating agent in 50～130 ℃ of temperature and obtain macromole evocating agent, drip 0.01～50 part of glycidyl ether again, in 0～50 ℃ of reaction of temperature 1～48 hour, cooling back purifying promptly obtained multi-arm star polyester/hyperbranched polyglycidyl ether.
Above material part is not specifically noted, and is mass parts.
5. the preparation method of multi-arm star polyester/hyperbranched polyglycidyl ether according to claim 4, the used compound that contains at least three hydroxyls is 1 in this method, 2, any in 3-glycerol, Pehanorm, trimethylolethane, tetramethylolmethane, dipentaerythritol, polyester-8-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things, polyester-16-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things, polyester-32-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things or the polyester-64-hydroxyl-1-carboxyl-two hydroxymethyl propionic acid branching things.
6. according to the preparation method of claim 4 or 5 described multi-arm star polyester/hyperbranched polyglycidyl ethers, used annular lactone is at least a in glycollide, rac-Lactide, the 6-caprolactone in this method.
7. according to the preparation method of claim 4 or 5 described multi-arm star polyester/hyperbranched polyglycidyl ethers, the synthetic used catalyzer of star Biodegradable polyester is at least a in tin, zinc, aluminium, magnesium or its inorganic salt, organic salt and/or their oxide compound in this method; The catalyzer that can form macromole evocating agent is any in alkali, basic metal and hydride thereof, amides, organometallics and the derivative thereof.
8. according to the preparation method of claim 4 or 5 described multi-arm star polyester/hyperbranched polyglycidyl ethers, used organic solvent is tetrahydrofuran (THF), methylene dichloride, trichloromethane, monochloroethane, 1 in this method, 2-ethylene dichloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,4-dioxane, acetone, ethyl acetate, acetonitrile, N, at least a in dinethylformamide and the N,N-dimethylacetamide.
9. the preparation method of multi-arm star polyester/hyperbranched polyglycidyl ether according to claim 6, used organic solvent is tetrahydrofuran (THF), methylene dichloride, trichloromethane, monochloroethane, 1 in this method, 2-ethylene dichloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,4-dioxane, acetone, ethyl acetate, acetonitrile, N, at least a in dinethylformamide and the N,N-dimethylacetamide.
10. the preparation method of multi-arm star polyester/hyperbranched polyglycidyl ether according to claim 7, used organic solvent is tetrahydrofuran (THF), methylene dichloride, trichloromethane, monochloroethane, 1 in this method, 2-ethylene dichloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,4-dioxane, acetone, ethyl acetate, acetonitrile, N, at least a in dinethylformamide and the N,N-dimethylacetamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910216535A CN101717499A (en) | 2009-12-03 | 2009-12-03 | Multi-arm star polyester/hyperbranched polyglycidyl ether and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910216535A CN101717499A (en) | 2009-12-03 | 2009-12-03 | Multi-arm star polyester/hyperbranched polyglycidyl ether and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101717499A true CN101717499A (en) | 2010-06-02 |
Family
ID=42432143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910216535A Pending CN101717499A (en) | 2009-12-03 | 2009-12-03 | Multi-arm star polyester/hyperbranched polyglycidyl ether and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101717499A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446964A (en) * | 2013-08-29 | 2013-12-18 | 西北工业大学 | Preparation method of carboxyl functionalized hyperbranched magnetic mesoporous silica composite microspheres |
| CN103570920A (en) * | 2013-08-13 | 2014-02-12 | 云南民族大学 | Preparation method of multi-arm star-shaped polylactic acid |
| CN105820048A (en) * | 2016-04-08 | 2016-08-03 | 华南理工大学 | Low-viscosity star-shaped hydroxyl polyester as well as preparation method and application thereof |
| CN105968331A (en) * | 2016-05-16 | 2016-09-28 | 华南理工大学 | Low-viscosity heteropoly-arm star hydroxy polyester, and preparation method and application thereof |
| CN107828032A (en) * | 2017-11-17 | 2018-03-23 | 中南大学 | A kind of hyperbranched starlike poly ion liquid and its preparation method and application |
| CN109021229A (en) * | 2018-08-06 | 2018-12-18 | 武汉大学 | A kind of preparation method and applications of sulfur-bearing hyperbranched polyglycidyl ether copolymer |
| CN109069695A (en) * | 2016-03-17 | 2018-12-21 | 泰克细胞有限公司 | Antipollution and/or antithrombotic Medical Devices |
| CN109594144A (en) * | 2018-12-13 | 2019-04-09 | 上海德福伦化纤有限公司 | The fused mass directly spinning method of PLA fiber containing metal-modified cross carboxylate |
| CN110016729A (en) * | 2018-12-13 | 2019-07-16 | 上海德福伦化纤有限公司 | Hollow PLA fiber and preparation method thereof containing metal-modified cross carboxylate |
| TWI690542B (en) * | 2018-12-27 | 2020-04-11 | 財團法人工業技術研究院 | Resin and ink |
| WO2020087222A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Polyglycolic acid resin and production process thereof |
| CN114437325A (en) * | 2020-10-30 | 2022-05-06 | 财团法人工业技术研究院 | Resin and ink |
-
2009
- 2009-12-03 CN CN200910216535A patent/CN101717499A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570920A (en) * | 2013-08-13 | 2014-02-12 | 云南民族大学 | Preparation method of multi-arm star-shaped polylactic acid |
| CN103446964A (en) * | 2013-08-29 | 2013-12-18 | 西北工业大学 | Preparation method of carboxyl functionalized hyperbranched magnetic mesoporous silica composite microspheres |
| CN109069695A (en) * | 2016-03-17 | 2018-12-21 | 泰克细胞有限公司 | Antipollution and/or antithrombotic Medical Devices |
| CN109069695B (en) * | 2016-03-17 | 2021-11-16 | 泰克细胞有限公司 | Anti-contamination and/or anti-thrombosis medical device |
| CN105820048A (en) * | 2016-04-08 | 2016-08-03 | 华南理工大学 | Low-viscosity star-shaped hydroxyl polyester as well as preparation method and application thereof |
| CN105968331A (en) * | 2016-05-16 | 2016-09-28 | 华南理工大学 | Low-viscosity heteropoly-arm star hydroxy polyester, and preparation method and application thereof |
| CN105968331B (en) * | 2016-05-16 | 2019-01-18 | 华南理工大学 | A kind of miscellaneous multi-arm star hydroxyl polyester of low viscosity and the preparation method and application thereof |
| CN107828032A (en) * | 2017-11-17 | 2018-03-23 | 中南大学 | A kind of hyperbranched starlike poly ion liquid and its preparation method and application |
| CN109021229A (en) * | 2018-08-06 | 2018-12-18 | 武汉大学 | A kind of preparation method and applications of sulfur-bearing hyperbranched polyglycidyl ether copolymer |
| WO2020087222A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Polyglycolic acid resin and production process thereof |
| EP3873971A4 (en) * | 2018-10-29 | 2022-06-22 | Pujing Chemical Industry Co., Ltd | Polyglycolic acid resin and production process thereof |
| CN109594144A (en) * | 2018-12-13 | 2019-04-09 | 上海德福伦化纤有限公司 | The fused mass directly spinning method of PLA fiber containing metal-modified cross carboxylate |
| CN110016729B (en) * | 2018-12-13 | 2021-03-23 | 上海德福伦化纤有限公司 | Hollow PLA fiber containing metal modified cross-shaped esterified substance and preparation method thereof |
| CN110016729A (en) * | 2018-12-13 | 2019-07-16 | 上海德福伦化纤有限公司 | Hollow PLA fiber and preparation method thereof containing metal-modified cross carboxylate |
| US10954346B2 (en) | 2018-12-27 | 2021-03-23 | Industrial Technology Research Institute | Resin and ink |
| TWI690542B (en) * | 2018-12-27 | 2020-04-11 | 財團法人工業技術研究院 | Resin and ink |
| CN114437325A (en) * | 2020-10-30 | 2022-05-06 | 财团法人工业技术研究院 | Resin and ink |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101717499A (en) | Multi-arm star polyester/hyperbranched polyglycidyl ether and preparation method thereof | |
| US5665831A (en) | Biocompatible block copolymer | |
| JP5458216B2 (en) | Process for producing biodegradable polylactic acid for medical use by polycondensation from lactic acid catalyzed by creatinine | |
| EP1498147B1 (en) | Absorbable biocompatible block copolymer | |
| TWI440651B (en) | Inorganic decomposition polymerizable polymer with low content of metal catalyst and its preparation method | |
| CN101812227B (en) | Micelle based on non-linear polyethylene glycol-polylactic acid block copolymer and preparation method thereof | |
| JP2009263680A (en) | Biodegradable compound forming polymeric micelle, and method for preparing the same and pharmaceutical composition containing the compound | |
| CN110938200B (en) | Preparation method of amine polyester containing dimethyl pyridine on side chain | |
| CN103204997A (en) | Preparation method of polyactic acid/polyethylene glycol biological hybrid material for PDT (photodynamic therapy) | |
| KR20180068852A (en) | Composition of amphiphilic block copolymer with improved micelle stability and pharmaceutical composition comprising the same | |
| Sun et al. | Self‐assembled micelles prepared from poly (ɛ‐caprolactone)–poly (ethylene glycol) and poly (ɛ‐caprolactone/glycolide)–poly (ethylene glycol) block copolymers for sustained drug delivery | |
| WO2012133608A1 (en) | Biodegradable particle, vascular embolization material and method for producing biodegradable particles | |
| CN103936973A (en) | Multi-functional-group polyethylene oxide-b-aliphatic polyester block copolymers, preparing method thereof and applications thereof | |
| CN101367921A (en) | Method for synthesis of polylactic acid with lactide opened loop | |
| CN101880381A (en) | Segmented copolymer modified by polyethylene glycol 1000 vitamin E succinic acid ester, preparation method and applications thereof | |
| JP2000508017A (en) | Crystal copolymer and method for producing the same | |
| KR101270159B1 (en) | Microsphere containing drug using temperature sensitive copolymer and preparing method thereof | |
| CN102256938A (en) | Thioic acids as building block for polythioesters | |
| KR101745429B1 (en) | Process for purifying an amphiphilic block copolymer, amphiphilic block copolymer obtained therefrom, and pharmaceutical composition containing the same | |
| CN101466758B (en) | Bio-degradable/ absorbable polymer having reduced metal catalyst content, and process for production thereof | |
| CN102807677A (en) | CA-PLGA-TPGS (Cholic Acid-Poly-Lactic-co-Glycolic Acid copolymer-Tocopherol Polyethylene Glycol Succinate) star copolymer as well as preparation method and application thereof | |
| CN105670007A (en) | Method for preparing polyvinyl alcohol-poly trimethylene carbonate-poly lactic acid-glycolic acid double-grafted copolymer micelle | |
| CN105694067A (en) | Method for preparing polyvinyl alcohol-poly (lactic acid-glycolic acid)-polycaprolactone bi-grafted copolymer micelle | |
| CN117427035A (en) | Telmonazole-entrapped mPEG-b-PLLA amphiphilic block copolymer sustained-release drug-loaded micelle and preparation method thereof | |
| CN106554342A (en) | 3,6 dichloromethyl Acetic acid, hydroxy-, bimol. cyclic esters and its production and use |
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 |
Open date: 20100602 |