CN107936229A - Disaccharides molecular polyhydroxyl connection polycaprolactone forms starlike multi-arm amphipathic nature polyalcohol and preparation method - Google Patents
Disaccharides molecular polyhydroxyl connection polycaprolactone forms starlike multi-arm amphipathic nature polyalcohol and preparation method Download PDFInfo
- Publication number
- CN107936229A CN107936229A CN201711401660.0A CN201711401660A CN107936229A CN 107936229 A CN107936229 A CN 107936229A CN 201711401660 A CN201711401660 A CN 201711401660A CN 107936229 A CN107936229 A CN 107936229A
- Authority
- CN
- China
- Prior art keywords
- hydroxyl
- arm
- disaccharides
- polycaprolactone
- starlike
- 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
Classifications
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
-
- 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
Abstract
The invention discloses disaccharides molecular polyhydroxyl connection polycaprolactone to form starlike multi-arm amphipathic nature polyalcohol and preparation method, it is mainly comprised the following steps：A, silicol is protected：Part protection is carried out to the hydroxyl on two glycan molecules with silane agent, obtains the disaccharides of silanization.B, hydroxyl triggers caprolactone ring-opening polymerisation：Trigger the ring-opening polymerization of caprolactone using remaining unprotected hydroxyl on two glycan molecules.C, the deprotection of hydroxyl：In the solution of polycaprolactone grafted silane disaccharides intermediate product, add excess acid dissolving stirring 1 it is small when more than.Finally obtain using two glycan molecules be head, connection polycaprolactone polymer as arm the amphipathic nature polyalcohol with starlike more arm configurations.The polycaprolactone molecular structure of polyhydroxy head and multi-arm possessed by the starlike multi-arm amphipathic nature polyalcohol has excellent hydrophilic and hydrophobic and physical and chemical performance by polymer, auxiliary agent, dispersant, emulsifying agent etc. can be used as, is had broad application prospects in fields such as biological medicine, chemical industry, the energy.
Description
Technical field
The present invention relates to the preparation of composite material, more particularly to a kind of disaccharides molecular polyhydroxyl connection polycaprolactone forms star
Shape multi-arm amphipathic nature polyalcohol and preparation method thereof.
Background technology
Carbohydrate is a kind of important organic compound widely distributed in nature, is broadly divided into monose, oligosaccharide, polysaccharide
Also combine sugar.Carbohydrate is also a kind of organic molecule with excellent biological property and chemical operability, in molecular structure
With more functional group, such as hydroxyl, this provides many possibilities to sugar in chemical reaction, is allowed in biomaterial
Field possesses very extensive application prospect.Pharmaceutical carrier is in drug controlled release, and medicine is passed through microballoon or micella
Form carries out parcel and enters blood circulation, this requires pharmaceutical carrier to have good biocompatibility, hydrophily, less particle
Size, and property possessed by glycan molecule can meet the requirement of pharmaceutical carrier just.For example be authorized to before us
Chinese patent 201410500077.5 reports a kind of crystallization organic molecule induction magnetic particle in situ and prepares trace nano magnetic
The method of ball, the carbohydrate small molecules such as absorption glucose are can be applied in biomedical sector, and are had very in adsorption process
Strong targeting and accuracy.
Amphipathilic block polymer refers to, the different polymer segment of two or more property is connected together, bag
One section of hydrophilic block is included, also has one section of hydrophobic block, therefore be mainly used for into drug micelles, gene in biomedicine field
Transmit, according to shadow carrier etc., be also used widely in fields such as building, chemical industry, the energy.
The research of existing Amphipathilic block polymer, such as Chinese patent 201510053901.1 report poly- (nitrogen-different
Propylacrylamide)-block-poly- (2- nitrobenzyls methacrylate), Chinese patent 201580027593.3 report from
By the multi-block polymer of based polyalcohol, Chinese patent 201610905174.1 reports the reduction amphipathic block polymerization of response
Thing.But these similar researchs mainly concentrate on the single-stranded linear copolymer of polyesters, and the hydroxyl on single organic molecule
Class hydrophilic radical is on the low side, can reduce it is amphipathic in hydrophily.
The research of existing polyhydroxy carbohydrate amphipathic nature polyalcohol, such as Chinese patent 201310742882.4 report two
Parent's property ursolic acid-polysaccharide conjugate, Chinese patent 201510902697.6 report the Amphiphatic high polymer surface that chitosan is base
Activating agent, Chinese patent 201710058464.1 report amphipathic nature block polymer modified nanometer cellulose, Chinese patent
201510564323.8th, 201610875153.X reports amphipathic polyhydroxy carbohydrate coupling hydrophobic aliphatic chain, Chinese patent
201310742883.9、
201610125193.2,201610205613.8,201710542570.7,201710340577.0 report polysaccharide
Coupling drug prepares amphipathic copolymer, can be applied to targeting micella or medicine carries system.But this polyhydroxy divides greatly
There are the deficiencies of hydrophilic dissolubility is poor, hydrophilic interaction low-response for the polysaccharide organic molecule of son amount.
The research of existing highly branched chain amphipathic nature polyalcohol, for example, Chinese patent 201510377783.X report based on β-
The pH response star polymers of cyclodextrin, Chinese patent 201610397053.0 report the poly- (methacrylic acids of polycaprolactone-b-
Mono methoxy polyethylene glycol ester-co- (p- (metering system acyloxy ethyoxyl) benzaldehyde)) obtain amphipathic four arm star and gather
Compound, Chinese patent 201611035224.1 report fluorescent marker and the star-like polyesters pharmaceutical carrier of temperature-responsive.
For carrier micelle, load medicine glue can be realized by preparing amphipathic nature polyalcohol using hydroxyl numerous in sugar minor structure
Improvement on beam function.But the above-mentioned Chinese patent reported also illustrate that, amphipathic copolymer will be in biological medicine, change
The fields such as work, the energy have the application of bigger, it is necessary to which organic molecule considers more novel, more innovative, more multi-functional knot
Structure feature：
1st, hydrophily and hydrophobicity all obviously amphipathic effects；
2nd, the polymer obtained has extraordinary physical and chemical performance, such as：The stability of solution system, micella particle
Dimensional homogeneity and dispersiveness, have solvent environment very sensitive stimulating responsive etc.；
3rd, the design feature of organic molecule can improve the efficiency of application, such as：Improved as much as possible as carrier micelle
Drugloading rate, the process of carrying can ensure the stabilization of compound system well；, can be with as auxiliary agent, dispersant, emulsifying agent, binder
Strengthen feature, realize simple, economic operability.
The content of the invention
It is an object of the invention to provide a kind of disaccharides molecular polyhydroxyl connection polycaprolactone to obtain amphipathic nature polyalcohol
Preparation method, this amphipathic nature polyalcohol of preparation are hydrophilic head using two glycan molecules as star topology, the connection of multiple hydroxyls
Polycaprolactone polymer be hydrophobic arm, form starlike more arm configurations and amphipathic very excellent polymer.Polymer parent
Hydrophobicity clearly, have extraordinary solution dispersion, size uniform stability, can as the presoma of carrier micelle,
Also can be as the emulsifying agent in the chemical field such as daily, industrial, dispersant, auxiliary agent etc..
The purpose of the present invention realize technical solution be：A kind of preparation method of starlike multi-arm amphipathic nature polyalcohol, uses
Protection-open loop-deprotection three-step approach, carries out part protection to the hydroxyl on two glycan molecules with silane agent, then utilizes two sugars
Remaining unprotected hydroxyl triggers the ring-opening polymerization of caprolactone, then three steps that the hydroxyl through disaccharides protection is deprotected to close on son
Cheng Fa, finally obtains starlike multi-arm amphipathic nature polyalcohol, its specific practice includes：
A, hydroxyl protection
Part protection is carried out to the hydroxyl on two glycan molecules with silane agent：Distilled Dimethyl Asian Maple is added to first dry
In dry three-neck flask, under the protection of nitrogen, by 60 DEG C it is dried 24 it is small when disaccharides be dissolved into Dimethyl Asian Maple；Treat two
After sugar is completely dissolved, silane agent is added in three-neck flask；The temperature for adjusting oil bath is 80 DEG C -120 DEG C, opens stirring, instead
Answer 24 it is small when；After question response terminates, vacuum distillation, removes remaining unreacted silane agent and Dimethyl Asian Maple, obtains part hydroxyl
Base is silylated the disaccharides of protection；
B, ring-opening polymerisation
Trigger the ring-opening polymerization of caprolactone using remaining unprotected hydroxyl on two glycan molecules：A is walked first and is reacted
In obtained part of hydroxyl be silylated the disaccharides of protection with toluene distillation water removal three times；Dried silanization disaccharides is dissolved in
In toluene solvant after water removal, the catalysts of content 0.5%-5%, catalyst dilution with toluene to 1g/ml are then added；
Then, caprolactone is added in three-neck flask, then reaction system is warming up to 120 DEG C -160 DEG C, and reaction 24 is small under magnetic agitation
When；Ring-opening reaction is carried out in being placed on the three-neck flask in the oil bath pan of magnetic stirring function, by ring-opening reaction,
Synthesis obtains the product of the amphipathic nature polyalcohol of the disaccharides g-polycaprolactone of part of hydroxyl silanization protection；
C, hydroxyl is deprotected
The intermediate product of the polycaprolactone grafted silane disaccharides obtained in b step reactions is dissolved in tetrahydrofuran；So
Afterwards, according to the quantity of "-O-SiO3 " group of silanization disaccharides in product, it is 1.1 to be added dropwise with the molar ratio of group:1-1.3:1、
The hydrochloric acid of content 30% is into tetrahydrofuran solution, when persistently stirring 2-3 is small；Cold diethyl ether is added, polycaprolactone is settled out and connects
The product of two glycan molecules of branch；The silane group on copolymer molecule is sloughed through hydroxyl deprotection reaction, exposes protected hydroxyl,
Finally obtain using two glycan molecules as starlike head, the polycaprolactone polymer of connection is the amphiphilic with starlike more arm configurations of arm
Property aggregate target product；In target product, the hydroxyl value of polycaprolactone hydrophobic segment two glycan molecules of connection of hydroxyl connection is：1
Molecule two glycan molecules connection no less than 3 molecules polycaprolactone, the disaccharides hydrophilic segment with polyhydroxy structure with hydroxyl
Radix contains the hydroxyl group no less than 3 molecules for two glycan molecules of 1 molecule.
Further, in the synthetic reaction of a step hydroxyl protections, silane agent is specially hexamethyldisilane amine, trimethyl
Chlorosilane, hexamethyldisilazane, tert-butyl chloro-silicane, tri isopropyl chlorosilane, dimethyl 2 acetoxyl group silane,
One kind in di-t-butyl dichlorosilane, trimethyl hydroxyethylammonium silane, methyldiphenyl base ethoxy silane；Ring-opening polymerisation is walked in b
Synthetic reaction in, catalysts are specially one in the concentrated sulfuric acid, Bronsted acid, lewis acid, stannous octoate, stannous acetate
Kind；In the synthetic reaction of c step hydroxyl deprotections, the amphipathic nature polyalcohol with starlike more arm configurations is specially hydrophilic hydroxyl
Base group and hydrophobic multi-arm connection polycaprolactone molecule respectively the molar ratio with amphipathic nature polyalcohol molecule at least 3:
1。
Further, the catalysts of the b steps are specially the concentrated sulfuric acid, Bronsted acid, lewis acid, stannous octoate, vinegar
One kind in sour stannous.
Further, the average molecular weight that the polycaprolactone that the hydroxyl triggers has is 450-10000.
It is another object of the present invention to a kind of disaccharides molecular polyhydroxyl connection obtained using method as above to gather oneself
Lactone forms starlike multi-arm amphipathic nature polyalcohol, the starlike multi-arm amphipathic nature polyalcohol with two glycan molecules protect after hydroxyl again into
Hydrophilic segment is used as after row deprotection, unprotected multiple hydroxyls trigger ring-opening polymerisation the dredging as polymer of connection caprolactone
A kind of water section, there is provided amphipathic very excellent polymer.
The starlike multi-arm amphipathic nature polyalcohol being prepared using above synthetic method has following characteristics：
(A) there is the disaccharides hydrophilic segment of polyhydroxy structure：The disaccharides of part of hydroxyl is protected by silane agent, completes to draw
After sending out caprolactone polymerization reaction, by acidolysis deprotection reaction, the disaccharides molecular moiety containing multiple hydroxyls is obtained；
(B) the polycaprolactone hydrophobic segment of hydroxyl connection：It is the hydroxyl by not protected on two glycan molecules by silane agent, triggers
The ring-opening polymerization of caprolactone, obtains the polycaprolactone polymer part of multiple hydroxyl connections；
(C) the amphipathic structure of starlike multi-arm：To remain two glycan molecules of part of hydroxyl as the hydrophilic head of star topology,
Using the polycaprolactone polymer of multiple hydroxyls connection as hydrophobic arm, form starlike more arm configurations and amphipathic very excellent gather
Compound.
The disaccharides with polyhydroxy structure, also referred to as disaccharide, in particular to naturally occurring disaccharide or manually conjunction
Into disaccharide；Naturally occurring disaccharide is specifically one kind in sucrose, lactose, maltose；Artificial synthesized disaccharide specifically refers to
The disaccharide formed by dimolecular monose by glycosidic bond；The disaccharides hydrophilic segment with polyhydroxy structure with hydroxyl
Radix contains the hydroxyl group no less than 3 molecules for two glycan molecules of 1 molecule；What the polycaprolactone that the hydroxyl triggers had
Average molecular weight is 450-10000；The polycaprolactone hydrophobic segment of multiple hydroxyls connection connects the hydroxyl of two glycan molecules
Number is no less than the polycaprolactone of 3 molecules for the two glycan molecules connection of 1 molecule；The amphipathic of the amphipathic structure of starlike multi-arm
The average molecular weight that compound has is 760-11000, dispersion degree 1.1-5；The amphipathic structure of starlike multi-arm it is amphipathic
In polymer, the mass percentage content of the disaccharides hydrophilic head construction unit containing polyhydroxy contains multi-arm knot in 3%-45%
The mass percentage content of the polycaprolactone hydrophobic part of structure is in 50%-90%.
Technical scheme makes that there is fine hydrophilic disaccharides to be connected with hydrophobic polycaprolactone direct polymerization,
As hydrophilic segment after being deprotected, unprotected multiple hydroxyls trigger to be connected in oneself hydroxyl after being protected using two glycan molecules
Hydrophobic part of the ring-opening polymerisation of ester as polymer, is a kind of amphipathic very excellent polymer；This amphiphilic prepared
Property polymer be hydrophilic head using two glycan molecules as star topology, the polycaprolactone polymer of multiple hydroxyls connection to be hydrophobic
Arm, forms the polymer of starlike more arm configurations；In this polymer, not only a part of hydroxyl participates in triggering on two glycan molecules
The ring-opening polymerisation of caprolactone, and by making the hydroxyl after protection carry out the certain hydrophilic segment of deprotection reservation again.
Embodiment
The present invention is described in further detail with embodiment the following, but the scope protected of the present invention and unlimited
In embodiment.
Embodiment 1
Hydroxyl protection：
Distilled 20 milliliters of Dimethyl Asian Maple are added in dry three-neck flask first, will under the protection of nitrogen
At 60 DEG C it is dried 24 it is small when 2 grams of sucrose be dissolved into Dimethyl Asian Maple；After sucrose is completely dissolved, add in three-neck flask
Enter 20 milliliters of trim,ethylchlorosilane；The temperature for adjusting oil bath is 100 DEG C, blender is opened, when reaction 24 is small；Question response terminates
After, vacuum distillation, removes remaining unreacted trim,ethylchlorosilane and Dimethyl Asian Maple, obtains part of hydroxyl and be silylated protection
Sucrose.
Ring-opening polymerisation：
Obtained part of hydroxyl is weighed 2 grams by the sucrose that trim,ethylchlorosilane is protected first, three are removed water with toluene distillation
It is secondary；Dried silanization sucrose is dissolved in the strong sulfuric acid response catalysis that content 1% is then added in the toluene solvant after water removal
Agent, concentrated sulfuric acid dilution with toluene to 1g/ml；Then, weigh 10 grams of caprolactone to be added in three-neck flask, then by reaction system
120 DEG C are warming up to, when reaction 24 is small under magnetic agitation；Ring-opening reaction is being placed on in the oil bath pan of magnetic stirring function
Three-neck flask in carry out, by ring-opening reaction, synthesis obtains the sucrose grafting that part of hydroxyl protect by trim,ethylchlorosilane and gathers
The product of the amphipathic nature polyalcohol of caprolactone.
Hydroxyl is deprotected：
First, the intermediate product of the polycaprolactone grafting trim,ethylchlorosilane protection sucrose obtained in ring-opening polymerization claims
5 grams are taken, is dissolved in 30 milliliters of tetrahydrofuran；Then, according to the number of "-O-SiO3 " group of silanization sucrose in product
Amount, it is 1.1 to be added dropwise with the molar ratio of group:1st, the hydrochloric acid of 30%, 35 milliliter of content persistently stirs 2 into tetrahydrofuran solution
Hour；200 milliliters of cold diethyl ether is added, is settled out the product of polycaprolactone grafting sucrose molecule；Hydroxyl deprotection reaction, will
The trimethylchloro-silicane groups on copolymer molecule are sloughed, expose protected hydroxyl.Finally obtain using sucrose molecule to be starlike
Head, connection polycaprolactone polymer be arm the amphipathic nature polyalcohol product with starlike more arm configurations.
Embodiment 2
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the two of addition
Sugar is 3 grams of lactose.
Embodiment 3
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the two of addition
Sugar is 1 gram of sucrose and 1 gram of maltose.
Embodiment 4
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the two of addition
Sugar is the disaccharide that 2 grams of simple sugar glucose is formed by glycosidic bond.
Embodiment 5
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the two of addition
Sugar is the disaccharide that 3 grams of monosaccharides galactose is formed by glycosidic bond.
Embodiment 6
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the two of addition
The disaccharide that sugar is 2 grams of simple sugar glucose and monosaccharide fructose is formed by glycosidic bond.
Embodiment 7
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the silicon of addition
Alkane agent is 20 milliliters of hexamethyldisilane amine.
Embodiment 8
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the silicon of addition
Alkane agent is 20 milliliters of tert-butyl chloro-silicane.
Embodiment 9
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of hydroxyl protection, the silicon of addition
Alkane agent is 20 milliliters of methyldiphenyl base ethoxy silane.
Embodiment 10
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of ring-opening polymerisation, addition it is anti-
Answer the lewis acid that catalyst is content 0.5%.
Embodiment 11
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of ring-opening polymerisation, addition it is anti-
Answer the stannous octoate that catalyst is content 0.5%.
Embodiment 12
This example is substantially the same manner as Example 1, and different is only：In the reactions steps of ring-opening polymerisation, addition it is anti-
Answer the stannous acetate that catalyst is content 1.5%.
Embodiment 13
This example is substantially the same manner as Example 1, and different is only：Hydroxyl deprotection reactions steps in, be added dropwise with
"-O-SiO3 " group molar ratio is 1.2:1st, the hydrochloric acid of 30%, 35 milliliter of content is into tetrahydrofuran solution.
Embodiment 14
This example is substantially the same manner as Example 1, and different is only：Hydroxyl deprotection reactions steps in, be added dropwise with
"-O-SiO3 " group molar ratio is 1.3:1st, the hydrochloric acid of 30%, 35 milliliter of content is into tetrahydrofuran solution.
Claims (7)
1. a kind of preparation method of starlike multi-arm amphipathic nature polyalcohol, using protection-open loop-deprotection three-step approach, uses silane agent
Part protection is carried out to the hydroxyl on two glycan molecules, then triggers caprolactone using remaining unprotected hydroxyl on two glycan molecules
Ring-opening polymerization, then the three-step synthesis method of the deprotection of the hydroxyl through being protected on two glycan molecules, finally obtain starlike multi-arm amphiphilic
Property polymer, its specific practice include：
A, hydroxyl protection
Part protection is carried out to the hydroxyl on two glycan molecules with silane agent：Distilled Dimethyl Asian Maple is added to first dry
In three-neck flask, under the protection of nitrogen, by 60 DEG C it is dried 24 it is small when disaccharides be dissolved into Dimethyl Asian Maple；Treat that disaccharides is complete
After fully dissolved, silane agent is added in three-neck flask；The temperature for adjusting oil bath is 80 DEG C -120 DEG C, opens blender, reaction
24 it is small when；After question response terminates, vacuum distillation, removes remaining unreacted silane agent and Dimethyl Asian Maple, obtains part of hydroxyl
It is silylated the disaccharides of protection；
B, ring-opening polymerisation
Trigger the ring-opening polymerization of caprolactone using remaining unprotected hydroxyl on two glycan molecules：It will be obtained first in a step reactions
To part of hydroxyl be silylated the disaccharides of protection with toluene distillation water removal three times；Dried silanization disaccharides is dissolved in water removal
In toluene solvant afterwards, the catalysts of content 0.5%-5%, catalyst dilution with toluene to 1g/ml are then added；With
Afterwards, caprolactone is added in three-neck flask, then reaction system is warming up to 120 DEG C -160 DEG C, when reaction 24 is small under magnetic agitation；
Ring-opening reaction is carried out in being placed on the three-neck flask in the oil bath pan of magnetic stirring function, by ring-opening reaction, is closed
Into the product of the amphipathic nature polyalcohol for the disaccharides g-polycaprolactone for obtaining the protection of part of hydroxyl silanization；
C, hydroxyl is deprotected
The intermediate product of the polycaprolactone grafted silane disaccharides obtained in b step reactions is dissolved in tetrahydrofuran；Then, root
According to the quantity of "-O-SiO3 " group of silanization disaccharides in product, it is 1.1 to be added dropwise with the molar ratio of group:1-1.3:1st, content
30% hydrochloric acid is into tetrahydrofuran solution, when persistently stirring 2-3 is small；Cold diethyl ether is added, is settled out polycaprolactone grafting two
The product of glycan molecule；The silane group on copolymer molecule is sloughed through hydroxyl deprotection reaction, exposes protected hydroxyl, finally
Obtain using two glycan molecules as starlike head, the polycaprolactone polymer of connection is the amphipathic with starlike more arm configurations of arm
Close target product；In target product, the hydroxyl value of polycaprolactone hydrophobic segment two glycan molecules of connection of hydroxyl connection is：1 molecule
Two glycan molecules connection no less than 3 molecules polycaprolactone, the disaccharides hydrophilic segment with polyhydroxy structure with hydroxyl value
Contain the hydroxyl group no less than 3 molecules for two glycan molecules of 1 molecule.
2. the method according to claim 1 for preparing starlike multi-arm amphipathic nature polyalcohol, it is characterised in that a steps
Silane agent is specially hexamethyldisilane amine, trim,ethylchlorosilane, hexamethyldisilazane, tert-butyl chloro-silicane, three
Isopropyl chloride silane, dimethyl 2 acetoxyl group silane, di-t-butyl dichlorosilane, trimethyl hydroxyethylammonium silane, methyldiphenyl
One kind in base ethoxy silane.
3. the method according to claim 1 for preparing starlike multi-arm amphipathic nature polyalcohol, it is characterised in that the b steps
Catalysts are specially one kind in the concentrated sulfuric acid, Bronsted acid, lewis acid, stannous octoate, stannous acetate.
4. the method according to claim 1 for preparing starlike multi-arm amphipathic nature polyalcohol, it is characterised in that the hydroxyl draws
The average molecular weight that the polycaprolactone of hair has is 450-10000.
5. the starlike multi-arm amphipathic nature polyalcohol that a kind of disaccharides molecular polyhydroxyl connection polycaprolactone is formed, it is characterised in that adopt
It is made with such as power 1 or power 2 or the method for power 3 or power 4.
6. the amphipathic polymerization of starlike multi-arm that disaccharides molecular polyhydroxyl connection polycaprolactone according to claim 5 is formed
Thing, it is characterised in that the average molecular weight that the amphipathic nature polyalcohol of the starlike amphipathic structure of multi-arm has is 760-
11000, dispersion degree 1.1-5.
7. the amphipathic polymerization of starlike multi-arm that disaccharides molecular polyhydroxyl connection polycaprolactone according to claim 5 is formed
Thing, it is characterised in that in the amphipathic nature polyalcohol of the starlike amphipathic structure of multi-arm, the disaccharides hydrophilic head knot containing polyhydroxy
The mass percentage content of structure unit contains in 3%-45%, the mass percent of the polycaprolactone hydrophobic part containing more arm configurations
Amount is in 50%-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711401660.0A CN107936229A (en) | 2017-12-22 | 2017-12-22 | Disaccharides molecular polyhydroxyl connection polycaprolactone forms starlike multi-arm amphipathic nature polyalcohol and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711401660.0A CN107936229A (en) | 2017-12-22 | 2017-12-22 | Disaccharides molecular polyhydroxyl connection polycaprolactone forms starlike multi-arm amphipathic nature polyalcohol and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107936229A true CN107936229A (en) | 2018-04-20 |
Family
ID=61942255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711401660.0A Pending CN107936229A (en) | 2017-12-22 | 2017-12-22 | Disaccharides molecular polyhydroxyl connection polycaprolactone forms starlike multi-arm amphipathic nature polyalcohol and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107936229A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251457A (en) * | 2018-08-24 | 2019-01-22 | 西南交通大学 | Automatically cleaning solar panel film with lotus leaf biomimetic features and preparation method thereof |
| CN114539443A (en) * | 2021-12-28 | 2022-05-27 | 中国科学院海洋研究所 | Acylated marine organism polysaccharide derivative and preparation method and application thereof |
| CN114940894A (en) * | 2022-07-26 | 2022-08-26 | 山东诺尔生物科技有限公司 | Star-shaped temperature-resistant fracturing fluid thickening agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807484A (en) * | 2005-12-29 | 2006-07-26 | 上海交通大学 | Preparation method of glycosyl teminated functionalized polycaprolactone with different branch structure |
| CN101250235A (en) * | 2008-02-03 | 2008-08-27 | 中山大学 | Full biodegradable amphipathic polysaccharides grafts as well as preparation method and use thereof |
-
2017
- 2017-12-22 CN CN201711401660.0A patent/CN107936229A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807484A (en) * | 2005-12-29 | 2006-07-26 | 上海交通大学 | Preparation method of glycosyl teminated functionalized polycaprolactone with different branch structure |
| CN100348640C (en) * | 2005-12-29 | 2007-11-14 | 上海交通大学 | Preparation method of glycosyl teminated functionalized polycaprolactone with different branch structure |
| CN101250235A (en) * | 2008-02-03 | 2008-08-27 | 中山大学 | Full biodegradable amphipathic polysaccharides grafts as well as preparation method and use thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251457A (en) * | 2018-08-24 | 2019-01-22 | 西南交通大学 | Automatically cleaning solar panel film with lotus leaf biomimetic features and preparation method thereof |
| CN114539443A (en) * | 2021-12-28 | 2022-05-27 | 中国科学院海洋研究所 | Acylated marine organism polysaccharide derivative and preparation method and application thereof |
| CN114940894A (en) * | 2022-07-26 | 2022-08-26 | 山东诺尔生物科技有限公司 | Star-shaped temperature-resistant fracturing fluid thickening agent and preparation method thereof |
| CN114940894B (en) * | 2022-07-26 | 2022-09-30 | 山东诺尔生物科技有限公司 | Star-shaped temperature-resistant fracturing fluid thickening agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Effect of surface wettability on the antibacterial activity of nanocellulose-based material with quaternary ammonium groups | |
| Mourya et al. | Chitosan-modifications and applications: Opportunities galore | |
| Turnbull et al. | Design and synthesis of glycodendrimers | |
| CN107936229A (en) | Disaccharides molecular polyhydroxyl connection polycaprolactone forms starlike multi-arm amphipathic nature polyalcohol and preparation method | |
| CN101327328B (en) | Dendrimers targeting nano particle and preparation and application thereof | |
| CN107550921A (en) | Double medicine-carried systems of a kind of nano particle macromolecule injectable composite aquogel and preparation method thereof | |
| CN102002117B (en) | Branched chitosan derivative and preparation method thereof | |
| CN102740895A (en) | Nanoconjugates and nanoconjugate formulations | |
| CN102302782B (en) | Preparation method of hepatoma carcinoma cell-targeted polyamido-amine dendrimer support | |
| CN102406946B (en) | High molecular adriamycin bonded medicament and preparation method thereof | |
| CN101474411B (en) | Anti-tumor prodrug using novel amphipathic hyperbranched polyesters as carrier and preparation method | |
| CN104857521A (en) | Preparation method of bio-based macromolecular vesicles with glucose response | |
| Pelras et al. | Strategies for the synthesis of sequence-controlled glycopolymers and their potential for advanced applications | |
| CN106336501B (en) | Containing sugared amphipathic nature block polymer and preparation method thereof | |
| CN112625183A (en) | High-strength photo-crosslinking antibacterial hydrogel and preparation method thereof | |
| Elsabee et al. | Chemical modifications of chitin and chitosan | |
| Kumar et al. | Role of Chitosan and Chitosan-Based Nanomaterials in Plant Sciences | |
| Bushra et al. | Polysaccharide-based nanoassemblies: From synthesis methodologies and industrial applications to future prospects | |
| CN101440136B (en) | Preparation of amine saccharification chitosan complex | |
| CN105837827B (en) | Epsilon-polylysine-polyethyleneimine-beta cyclodextrin polymer and its preparation method and application | |
| CN105778112A (en) | Ternary brush polymer with amphipathy and pH value responsiveness, and nanoporous capsules | |
| CN104311820B (en) | A kind of method that degradable medicaments carrier is built based on polysaccharide graft poly-aspartate benzyl ester | |
| CN107397962B (en) | Glucan-g-poly (L-lysine) -VAPG nucleic acid vector and preparation method and application thereof | |
| CN110403915A (en) | DNA and the hybridized nucleic acids pharmaceutical carrier of polymer and its preparation method and application | |
| JP5201763B2 (en) | Method for producing mixed fine particle capsules comprising particles having different average particle sizes |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180420 |