CN110205344A - A kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof - Google Patents
A kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof Download PDFInfo
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- CN110205344A CN110205344A CN201910479701.0A CN201910479701A CN110205344A CN 110205344 A CN110205344 A CN 110205344A CN 201910479701 A CN201910479701 A CN 201910479701A CN 110205344 A CN110205344 A CN 110205344A
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Abstract
The invention discloses a kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof, the ratio that the dendritic polyhydroxy narrow ditribution polyester is 1:1 according to monomer mole ratio by trihydroxy methyl ethane and suberic acid diethylester or diethylene adipate, is formed by enzyme-catalyzed polymerization.Preparation method is that " one kettle way " is completed in two steps, and polymerization temperature is consistent.First stage is the nitrogen protection under normal pressure stage, continues 12 hours, and second stage is the vacuum reaction stage, and the duration is 24 hours, vacuum degree 10mmHg.The present invention provides a kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof, it is that the narrow ditribution dendritic polyester based on trimethylolethane is obtained by environmentally protective enzyme-catalyzed polymerization method, it is that a kind of structural homogeneity is good, biodegradable dendritic polyester of polyfunctionality, has broad application prospects.
Description
Technical field
The invention belongs to biomedical material technologies, and in particular to a kind of dendritic polyhydroxy narrow ditribution polyester and its
Preparation method.
Background technique
Nano material be usually utilized to improve such as albumen, the physical chemistry and biological property of the medical preparations such as gene, with
The water solubility for reaching enhancing drug, the purpose of increasing the circulation time in vivo of drug and improve the targeting ability of drug.Current
Field of nanometer material technology, the dendritic for possessing ordered structure more and more widely paid close attention to.Branched structure being capable of day
The functional end group being doubled and redoubled with branch quantity so is provided；In addition, the monodisperse characteristic of dendritic makes
Their cavity structure will not disintegrate as linear polymer because of the dilution of concentration.Dendrimers often possesses three-dimensional
Symmetrical dissaving structure；By iteration coupling process (whether divergent iteration coupling or convergent iterations couple), we can be with
Synthesize the stringent controllable product of chemical structure.However, being consumed to obtain the polymer and regular topological structure of higher molecular weight
When and complicated protection-deprotection process is essential.Therefore, for large-scale industrialization production, current method
Too complex and higher cost.In addition, toxic organometallic catalyst used in general chemistry catalysis often allows and is wrapped up
Into being difficult to separate in product；Not only energy consumption is high for pyroreaction (being greater than 150 DEG C) in polymerization process, is also easy to polymerizeing product
Process mesometamorphism.
Therefore, the dendritic polyester for finding a kind of nontoxic mode being produced on a large scale to obtain compound with regular structure be one urgently
Problem to be solved.It is that one kind obtains high functionality branch that biocompatible carbohydrate/polyalcohol, which is introduced into non-polysaccharide structures,
The effective ways of shape " intelligence " material.Traditional chemical method has been successfully used to obtain the specific polyol polyester of structure,
However whether protection and-deprotection procedure cumbersome in the serious crosslinking phenomena in " one kettle way " or multistep reaction, invariably
Illustrate the weak problem of chemical catalysis regioselectivity.In contrast, lipase is due to its outstanding space and structure selectivity,
And mild reaction temperature, it is increasingly becoming a kind of green catalyst being widely studied, to obtain functional polyester.
Moreover, enzymatic has the degree of branching outstanding control force, so as to avoid crosslinking in the course of the polymerization process.In this way, making
Obtain enzyme-catalyzed polymerization becomes to have a extensive future in terms of the controllable dendritic of the preparation degree of branching.But up to the present, also
There is no any report to be related to the Enzyme catalyzed synthesis of narrow ditribution dendritic polyester.
Summary of the invention
Present invention aim to address the above problem, a kind of dendritic polyhydroxy narrow ditribution polyester and its preparation side are provided
Method, largely obtains that a kind of structural homogeneity is good, biodegradable dendritic of polyfunctionality by the method for green environment close friend
Polyester, monomer component are the suberic acid/adipic acid and trimethylolethane of biological nontoxic.
In order to solve the above technical problems, the technical scheme is that a kind of dendritic polyhydroxy narrow ditribution polyester, the tree
Branch type polyhydroxy narrow ditribution polyester is by trihydroxy methyl ethane and suberic acid diethylester or diethylene adipate according to monomer molar
Than the ratio for 1:1, formed by enzyme-catalyzed polymerization.1:1 is optimal proportion, and any monomer excessively can all be unfavorable for obtaining high score
Son amount and narrow ditribution.
In above-mentioned technical proposal, the enzyme is lipase, and full name is Lipase acrylic resin from candida
Antarctica (>=5000U/g), code name Novozyme435.
In above-mentioned technical proposal, the molecular weight distribution of the dendritic polyhydroxy narrow ditribution polyester is between 1.3-1.5.
In above-mentioned technical proposal, in the dendritic polyhydroxy narrow ditribution polyester, wherein one replaces trimethylolethane (T)
Ratio 23%~25%, two replace trimethylolethane (L) ratio 50%~52%, three replace trimethylolethane
(Den) ratio is 24%~26%.T/L/Den totally shows 1/2/1 ratio, the total endgroup content of terminal hydroxyl amount Zhan
96%~98%.
A kind of preparation method of above-mentioned dendritic polyhydroxy narrow ditribution polyester, the dendritic polyhydroxy narrow ditribution polyester pass through
" one kettle way " is prepared in two steps, the specific steps are as follows:
S1: trihydroxy methyl ethane, suberic acid diethylester or diethylene adipate and appropriate solvent by a certain percentage
It is added in reaction vessel, adds sealed reaction vessel after suitable catalyst enzyme, temperature is increased to 80 by nitrogen protection under normal pressure
It DEG C -83 DEG C, reacts 12-13 hours under normal pressure；
S2: keeping temperature-resistant, and after slowly reducing air pressure to 10mmHg continuation Depressor response 24 hours, a large amount of trichlorines are added
Dichloromethane terminates reaction, and filtering removal enzyme granulate is simultaneously concentrated filtrate, after filtrate is dissolved with appropriate chloroform, is slowly added dropwise
Appropriate hexane solution is precipitated, and repeated precipitation 3 times or more, sediment is dried under vacuum to constant weight at a certain temperature, is obtained
Final product dendritic trimethylolethane polyester.
In above-mentioned technical proposal, in the step S1, under conditions of meeting monomer ratio is 1/1,80-83 DEG C of reaction
Temperature is to obtain the necessary condition of high molecular weight, narrow ditribution dendritic polyester.Too low temperature will cause chain growth and be obstructed, excessively high
Temperature can reduce the catalytic activity of enzyme；12-13 hours synthesis under normal pressure time can allow monomer to be fully converted into oligomeric molecule, have
Beneficial to obtaining high molecular weight polyesters during subsequent Depressor response.
In above-mentioned technical proposal, the molecular weight of the dendritic polyhydroxy narrow ditribution polyester is carried out by the input amount of monomer
Control:
For being polymerized trimethylolethane-suberate by trihydroxy methyl ethane and suberic acid diethylester: monomer
When input amount is 5mmol, the weight average molecular weight M of products therefromwIt is 29000~32000, usual weight average molecular weight Mw is 31000,
When monomer input amount is 10mmol, the weight average molecular weight M of products therefromw36000~39000, usual weight average molecular weight Mw exists
38000；
For being polymerized trimethylolethane-adipate ester by trihydroxy methyl ethane and diethylene adipate: monomer
When input amount is 5mmol, the weight average molecular weight M of products therefromw9000~11000, the weight average molecular weight of usual products therefrom
Mw is in 10000, when monomer input amount is 10mmol, the weight average molecular weight M of products therefromwIn 17000~19000, usually gained
The weight average molecular weight Mw of product is 18000；
The molecular weight distribution of all dendritic polyhydroxy narrow ditribution polyester is respectively positioned between 1.3-1.5.
In above-mentioned technical proposal, in the step S1, trihydroxy methyl ethane and catalyst enzyme are dried before use
Processing.
The beneficial effects of the present invention are: the present invention provides a kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof,
It is a kind of pioneer invention, the still not no relevant report about the Enzyme catalyzed synthesis of narrow ditribution dendritic polyester at present.The present invention
It is that the narrow ditribution dendritic polyester based on trimethylolethane, the polyester of acquisition are obtained by environmentally protective enzyme-catalyzed polymerization method
It is that a kind of structural homogeneity is good, biodegradable dendritic polyester of polyfunctionality, has broad application prospects.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of dendritic polyhydroxy narrow ditribution polyester of the present invention；
Fig. 2 is dendritic polyhydroxy narrow ditribution polyester nuclear-magnetism hydrogen stave sign of the present invention；
Fig. 3 is dendritic polyhydroxy narrow ditribution polyester nuclear-magnetism hydrogen stave sign of the present invention.
Specific embodiment
The present invention is described further in the following with reference to the drawings and specific embodiments:
Preparation method step provided by the present invention is simple, below with 5mmol trihydroxy methyl ethane and suberic acid diethyl
It is described in detail for ester copolymerization.
The preparation of dendritic trimethylolethane-suberate, the specific steps are as follows:
S1: 5mmol trimethylolethane (0.601g) and 0.175g (the 10% of reaction monomers gross mass) rouge are weighed respectively
Fat enzyme granulate is dried overnight.Into the trimethylolethane after drying be added 5mmol suberic acid diethylester (1.151g) and
3.504g hexichol ether solvents (2 times of monomer gross mass).After reactant after solvent addition, by the lipase enzyme granule after drying
It is added in reaction flask and seals, then temperature is increased to 80 DEG C of synthesis under normal pressure 12 hours by nitrogen protection；
S2: after slowly reducing air pressure to 10mmHg continuation Depressor response 24 hours, a large amount of chloroform solns is added and terminate
Reaction.Simultaneously filtrate is concentrated in filtering removal enzyme granulate.After filtrate is dissolved with 5ml chloroform, it is molten that 15ml n-hexane is slowly added dropwise
Liquid is precipitated.Three times, sediment overnight vacuum at 40 DEG C is dried to obtain final product dendritic trihydroxy methyl to repeated precipitation
Ethane-suberate.
As shown in Figure 1, being the structural schematic diagram of dendritic polyhydroxy narrow ditribution polyester provided by the invention；According to three hydroxyl first
Polymer architecture is divided into terminal units (T) by the difference of the degree of substitution of base ethane, line type cell (L) and dendroid unit
(Den), each Hydrogen Proton is all marked one by one and is corresponded with the hydrogen spectrum signal peak in Fig. 2-3 in structural unit；
As Figure 2-3, it is levied for dendritic polyhydroxy narrow ditribution polyester nuclear-magnetism hydrogen stave of the present invention；Wherein Fig. 2 is poly-
The nucleus magnetic hydrogen spectrum of (TME- adipic acid), Fig. 3 be poly- (TME- suberic acid) nucleus magnetic hydrogen spectrum, all signal peaks all with the mark of Fig. 1
It corresponds.
GPC and nuclear magnetic data aggregation are as shown in table 1:
1 GPC of table and nuclear magnetic data aggregation
This table is intended to intuitively show the relationship of molecular weight, molecular structure and reaction monomers dosage, TME and suberic acid
Or adipic acid copolymerization, product do not have significant difference in chemical structure, molecular weight distribution.But it is advantageous to improve monomer dosage
In acquisition higher molecular weight, the product of higher algebra.
Those of ordinary skill in the art will understand that the embodiments described herein, which is to help reader, understands this hair
Bright principle, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.This field
Those of ordinary skill disclosed the technical disclosures can make according to the present invention and various not depart from the other each of essence of the invention
The specific variations and combinations of kind, these variations and combinations are still within the scope of the present invention.
Claims (8)
1. a kind of dendritic polyhydroxy narrow ditribution polyester, it is characterised in that: the dendritic polyhydroxy narrow ditribution polyester is by trihydroxy
The ratio that methyl ethane and suberic acid diethylester or diethylene adipate are 1:1 according to monomer mole ratio, passes through enzyme-catalyzed polymerization
It forms.
2. dendritic polyhydroxy narrow ditribution polyester according to claim 1, it is characterised in that: the enzyme is lipase.
3. dendritic polyhydroxy narrow ditribution polyester according to claim 1, it is characterised in that: the dendritic polyhydroxy is narrow
The molecular weight distribution of polyester is distributed between 1.3-1.5.
4. dendritic polyhydroxy narrow ditribution polyester according to claim 1, it is characterised in that: the dendritic polyhydroxy is narrow
It is distributed in polyester, wherein one replaces the ratio of trimethylolethane (T) to replace trimethylolethane (L) 23%~25%, two
Ratio 50%~52%, three replace trimethylolethane (Den) ratio 24%~26%.
5. dendritic polyhydroxy narrow ditribution polyester according to claim 4, it is characterised in that: one replaces trihydroxy methyl second
Alkane/bis- replace trimethylolethane/tri- that the ratio of trimethylolethane is replaced to be 1:2:1, the total endgroup content of terminal hydroxy group content Zhan
97%.
6. a kind of preparation method of any dendritic polyhydroxy narrow ditribution polyester of claim 1-5, it is characterised in that: should
Dendritic polyhydroxy narrow ditribution polyester is prepared in two steps by " one kettle way ", the specific steps are as follows:
S1: trihydroxy methyl ethane, suberic acid diethylester or diethylene adipate and appropriate solvent by a certain percentage is added
In reaction vessel, sealed reaction vessel after suitable catalyst enzyme is added, temperature is increased to 80-83 by nitrogen protection under normal pressure
DEG C synthesis under normal pressure 12-13 hours；
S2: keeping temperature-resistant, and after slowly reducing air pressure to 10mmHg continuation Depressor response 24 hours, a large amount of chloroforms are added
Solution terminates reaction, and simultaneously filtrate is concentrated in filtering removal enzyme granulate, after filtrate is dissolved with appropriate chloroform, is slowly added dropwise appropriate
Hexane solution is precipitated, and several times, sediment is dried under vacuum to constant weight to repeated precipitation at a certain temperature, obtains final produce
Object dendritic trimethylolethane polyester.
7. the preparation method of dendritic polyhydroxy narrow ditribution polyester according to claim 6, it is characterised in that: the branch
The molecular weight of type polyhydroxy narrow ditribution polyester is controlled by the input amount of monomer:
For being polymerized trimethylolethane-suberate by trihydroxy methyl ethane and suberic acid diethylester: monomer is put into
When amount is 5mmol, the weight average molecular weight M of products therefromwIt is 29000~32000, when monomer input amount is 10mmol, gained is produced
The weight average molecular weight M of objectw36000~39000；
For being polymerized trimethylolethane-adipate ester by trihydroxy methyl ethane and diethylene adipate: monomer is put into
When amount is 5mmol, the weight average molecular weight M of products therefromwIn 9000~11000, when monomer input amount is 10mmol, products therefrom
Weight average molecular weight Mw17000~19000；
The molecular weight distribution of all dendritic polyhydroxy narrow ditribution polyester is respectively positioned between 1.3 to 1.5.
8. the preparation method of dendritic polyhydroxy narrow ditribution polyester according to claim 6, it is characterised in that: the step
In S1, trihydroxy methyl ethane and catalyst enzyme are dried before use.
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| CN201910479701.0A CN110205344A (en) | 2019-06-04 | 2019-06-04 | A kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof |
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| CN201910479701.0A CN110205344A (en) | 2019-06-04 | 2019-06-04 | A kind of dendritic polyhydroxy narrow ditribution polyester and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960365A (en) * | 2022-12-01 | 2023-04-14 | 上海交通大学 | Biological terminal hydroxyl hyperbranched polyester, hyperbranched UV (ultraviolet) curing resin, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004050888A1 (en) * | 2002-12-05 | 2004-06-17 | Basf Aktiengesellschaft | Enzymatic production of (meth)acrylic esters that contain urethane groups |
| CN101935391A (en) * | 2010-09-02 | 2011-01-05 | 上海华谊（集团）公司 | Preparation method of high-molecular-weight aliphatic polyester |
-
2019
- 2019-06-04 CN CN201910479701.0A patent/CN110205344A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004050888A1 (en) * | 2002-12-05 | 2004-06-17 | Basf Aktiengesellschaft | Enzymatic production of (meth)acrylic esters that contain urethane groups |
| CN101935391A (en) * | 2010-09-02 | 2011-01-05 | 上海华谊（集团）公司 | Preparation method of high-molecular-weight aliphatic polyester |
Non-Patent Citations (1)
| Title |
|---|
| ZI-KUN RAO等: "Macroscopic Scaffold Control for Lipase-Catalyzed Dendritic Polyol-Polyesters", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960365A (en) * | 2022-12-01 | 2023-04-14 | 上海交通大学 | Biological terminal hydroxyl hyperbranched polyester, hyperbranched UV (ultraviolet) curing resin, and preparation method and application thereof |
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